Uop NAPHTHA HYDROTREATING PROCESS GENERAL OPERATING MANUAL - LIMITED DISTRIBUTION - This material is UOP’s technical information of a confidential nature for use only by personnel within your organization requiring the information. The material shall not be reproduced in any manner or distributed for any purpose whatsoever except by written Permission of UOP and except as authorized under agreements with UOP. August 2003{VOP Nanna ycrouestng Process Tabi of Contans UOP NAPHTHA HYDROTREATING PROCESS GENERAL OPERATING MANUAL TABLE OF CONTENTS INTRODUCTION PROCESS PRINCIPLES A. REACTIONS B. DISCUSSION Sulfur Removal Nitrogen Removal ‘Oxygen Removal Olefin Saturation Halide Removal . Metal Removal ©. REACTION RATES AND HEATS OF REACTION oe rens PROCESS VARIABLES REACTOR PRESSURE TEMPERATURE FEED QUALITY HYDROGEN TO HYDROCARBON RATIO. SPACE VELOCITY CATALYST PROTECTION, AGING, AND POISONS mmoom> ns PagetOP Naphina Hycoreating Process abe of Cotes W. vi. PROCESS FLOW AND CONTROL A B. moo PREFRACTIONATION SECTION REACTOR SECTION 1. Feed System 2. Reactor System 3. Wash Water System 4. Separator System STRIPPING SECTION SPLITTER SECTION ALTERNATE OPERATIONS 1. Stabilizing Naphtha 2. Stripping Sweet Naphtha PROCESS EQUIPMENT Ae“ ToOnNMooOg> REACTORS HEATERS: HEAT EXCHANGERS RECYCLE COMPRESSORS PUMPS FEED SURGE DRUM SEPARATOR OVERHEAD RECEIVERS RECYCLE COMPRESSOR SUCTION DRUM STRIPPER COLUMN SPLITTER COLUMN COMMISSIONING A. PRECOMMISSIONING 1. Vessels 2. Piping 3. Fired Heaters yrs Page?UOP nachna byceraatng Process Table ot Comonts ZOEPSNMMASNMA DENTS 0. 1. Heat Exchangers Pumps Compressors Instrumentation Catalys/Chemical Inventory RELIMINARY OPERATIONS: Commissioning of Utilities Final Inspection of Vessels Pressure Test Equipment Acid Cleaning of Compressor Lines Wash Out Equipment and Break In Pumps Break In Recycle Gas Compressor Service and Calibrate Instruments Dry Out Fired Heaters Reactor Circuit Dry Out Catalyst Loading Purging and Gas Blanketing INITIAL STARTUP 1 2. Discussion Detailed Procedure Vil. NORMAL STARTUP PROCEDURE A B. c. DISCUSSION DETAILED PROCEDURE SUBSEQUENT STARTUP Vill, NORMAL OPERATIONS A. CALCULATIONS 1. Weight Balance 2. Liquid Hourly Space Velocity 3. Hydrogen to Hydrocarbon Ratio 4. Stripper Off Gas ne P9038Yor napa byconsting Process Tate ot Contos 5. Stripper Reflux Ratio 6. Hydrogen Consumption 7. Cumulative Charge 8 Catalyst Life 9. Metals Contamination 10. Water Injection 11. Reactor Pressure Drop 12. Reactor Delta Temperature IX. ANALYTICAL X. TROUBLESHOOTING XI. NORMAL SHUTDOWN A. NORMAL SHUTDOWN PROCEDURE, XI. EMERGENCY PROCEDURES A LOSS OF RECYCLE COMPRESSOR B. REPAIRS WHICH REQUIRE STOPPING COMPRESSOR WITHOUT DEPRESSURING OR COOLING REACTORS C. EXPLOSION, FIRE, LINE RUPTURE, OR SERIOUS LEAK — DO IF POSSIBLE D. INSTRUMENT AIR FAILURE E. POWER FAILURE F. LOSS OF COOLING WATER: XII. SPECIAL PROCEDURES: A. CATALYST LOADING uop rns PagetLUOP Naota Mounting Process Tate of Contents 1. Catalyst Loading Preparation 2, Catalyst Loading Procedure B. | UNLOADING OF UNREGENERATED CATALYST CONTAINING IRON PYRITES, C. CATALYST SKIMMING PROCEDURE D, STEAM-AIR REGENERATION PROCEDURE (FOR S6 AND S-9 HYDROBON® CATALYSTS} E. INERT GAS REGENERATION PROCEDURE (FOR $-6, S-9, $-12, S-15, S- 16, $-18, S-19, S-120, N-204, N-108, AND HC-K HYDROBON® CATALYSTS) F. DESCALING OF HYDROTREATING PROCESS HEATER TUBES 1. Seale Conversion by Buming 2. ‘Scale Removal by Acidizing G PROTECTION OF AUSTENITIC STAINLESS STEEL Introduction 2 General @. Austenitic Stainless Stee! b. Chloride Attack c. Polythionic Acid Attack d. Protection Against Polythionic Acid Attack 3. Purging And Neutralizing a. Purging Nitrogen b. Ammoniated Nitrogen c Soda Ash Solutions 4. Hydrotesting a New Austenitic Stainless Stee! b. Used Austenitic Stainless Steel 5. Special Procedures a. Reactor Charge Heater Tubes Fractionator Heater Tubes Heat Exchangers Reactor Internals Cooling Catalyst After Regeneration 6. References paog uop srs PagesUOP Napa Hyoresing Process Tabi of Contats XIV. XV. SAFETY A. OSHA HAZARD COMMUNICATION STANDARD B. HYDROGEN SULFIDE POISONING c. NICKEL CARBONYL FORMATION D. PRECAUTIONS FOR ENTERING ANY CONTAMINATED OR INERT ATMOSPHERE PREPARATIONS FOR VESSEL ENTRY MSDS SEETS FOR UOP HYDROBON® CATALYSTS, mm EQUIPMENT EVALUATION 105 PagesLUOP Naphina sycoreating Process trrtscon I. INTRODUCTION The UOP Naphtha Hydrotreating Process is a catalytic refining process employing a select catalyst and a hydrogen-rich gas stream to decompose organic sulfur, oxygen and nitrogen compounds contained in hydrocarbon fractions. in addition, hydrotreating removes organo-metallic compounds and saturates olefinic compounds. The hydrotreating process is commonly used to remove Platforming catalyst poisons from straight run or cracked naphthas prior to charging to the Platforming Process Unit. The catalyst used in the Naphtha Hydrotreating Process is composed of an alumina base impregnated with compounds of cobalt or nickel and molybdenum. The feed source and the type of feed contaminants present determine the catalyst type and the operating parameters. This is important to realize when processing non-design type feeds. Volumetric recoveries of products depend on the sulfur and olefin contents, but usually are 100% +2%. ‘Organo-metallic compounds, notably arsenic and lead compounds, are known to be permanent poisons to platinum containing catalyst. The complete removal of these materials by hydrotreating will give longer ultimate catalyst life in the Platforming Unit. Sulfur is a temporary poison to Platforming catalysts and causes an unfavorable change in the product distribution and increase coke laydown. Organic nitrogen is also a temporary poison to Platforming catalyst. It is an extremely potent one, however, and a relatively small concentration of nitrogen in the Piatforming Unit feed will cause a large activity offset as well as deposit ammonium chloride salts in the Platforming Unit cold sections, ‘Oxygen compounds are detrimental to the operation of a Platforming Unit. Any oxygen compounds which are not removed in the hydrotreater will be converted to water in the Platforming Unit, thus affecting the water/chloride balance of the Platiorming catalyst. Olefins can polymerize at Platforming Unit operating conditions which can result in exchanger and reactor fouling. uep nas MOP Waphina Hyeroveeing Process Iteecson The Naphtha Hydrotreating Process makes a major contribution to the ease of ‘operation and economy of Platforming. Much greater flexibility is afforded in choice of allowable charge stocks to the Platforming Unit. Because this unit protects the Platforming catalyst, it is important to maintain consistently good operation in the Hydrotreating Unit. In addition to treating naphtha for Platforming feed, there are uses for the UOP Naphtha Hydrotreating Process in other areas. Naphthas produced from thermal processes, such as delayed coking, FCC, thermal cracking, and visbreaking, are usually high in olefinic content and other contaminants, and may not be stable in storage. These naphthas may be hydrotreated to remove the olefins and reduce ‘organic and metallic contaminants, providing a marketable product. It can be seen that the primary function of the UOP Naphtha Hydrotreating Process can be characterized as a “clean-up” operation. As such, the unit is critical to refinery down stream operation. NOTE: THIS MANUAL IS GENERAL IN NATURE AND CANNOT COVER EVERY POSSIBLE PROCESS OR MECHANICAL VARIATION. ALTHOUGH CARE HAS. BEEN TAKEN TO MAKE THIS MANUAL COMPLETE, MANY ITEMS INCLUDING INSTRUMENTATION AND DETAILED PROCEDURES HAVE NOT BEEN GIVEN. JHE PURPOSE OF THIS MANUAL IS TO PROVIDE GUIDELINES SO THAT THE REFINER CAN PREPARE A MORE DETAILED OPERATIONS HANDBOOK. ue a 2UO Raphi Hytoening Process Process Pmepies i. PROCESS PRINCIPLES The main purpose of the UOP Naphtha Hydrotreating Process is to “clean-up” a naphtha fraction so that it is suitable as charge to a Platforming Unit. There are six basie types of reactions that occur in the hydrotreating unit. A. REACTIONS Conversion of organic sutfur compounds to hydrogen sulfide Conversion of organic nitrogen compounds to ammonia Conversion of organic oxygen compounds to water Saturation of olefins Conversion of organic halides to hydrogen halides Removal of organo-metallic compounds Oae eyo B. DISCUSSION 1. Sulfur Removal For bimetallic Platforming catalyst, the feed naphtha must contain less than 0.5 weight ppm sulfur to optimize the selectivity and stability characteristics of the catalyst. In general, sulfur removal in the hydrotreating process is relatively easy, and for the best operation of a Platforming Unit, the hydrotreated naphtha sulfur content should be maintained well below the 0.5 weight ppm maximum. Commercial operation at 0.2 weight ppm sulfur or less in the hydrotreater product naphtha is common. For higher severity Platforming Units, mainly found in CCR applications, the feed sulfur level is maintained between 0.15 - 0.5 weight ppm. If the sulfur level is below 0.15 weight ppm, then the Platforming feed sulfur content can be increased with the sulfur injection facility located in the Platforming Unit. op nes omUDP nschina Hyarvesing Process Process Pmcptes Typical sulfur removal reactions are shown below. a, (Mercaptan) —- C-C-C-C-C-C-SH + Hz ——* 0-0-0-0-0-C + HS b. (Sulfide) C-C-C-S-C-C-C + 2Hz ——* 2-0-0 + eS c. (Disulfide) C-C-C-S-S-C-C-C + 8Hy ——* 2.0-0-C +2 9S. 4. (Cyclic sulfide) “4 S + 2H, —+ C-C-C-C.0-C +H)8 Tv C—C-C+ 4H, —46.0.0-C-C-C + H,S -C e. _(Thiophenic) It is possible, however, to operate at too high a temperature for maximum sulfur removal. Recombination of hydrogen sulfide with small amounts of olefins or olefin intermediates can then result, producing mereaptans in the product. C-C-C-C = C-C + HeS * C-C-C-0-C-6 l 8 If this reaction is occurring, the reactor temperature must be lowered. Generally, operation at 315-340°C (600-645°F) average reactor temperature will give acceptable rates of the desired hydrogenation reactions and will not result in a significant amount of olefinyhydrogen sulfide recombination. The sulfur recombination reaction typically occurs at temperatures greater than 340°C (645°F). This temperature is dependent upon feedstock composition, operating pressure, uep ris neLUOP apts Mroreating Process Process Pencils and LHSV. Also, this temperature can be achieved within the reactor due to temperature rise from the saturation of olefins, if present. 2. Nitrogen Removal Nitrogen removal is considerably more difficult than sulfur removal in naphtha hydrotreating, The rate of denitrification is only about one-fifth the rate of desulfurization. Most straight run naphthas contain much less nitrogen than sulfur, but attention must be given to ensure that the feed naphtha to Platforming catalyst contains a maximum of 0.5 weight ppm nitrogen and normally much less. Any organic nitrogen that does enter the Platforming Unit will react to ammonia and further with the chloride in the recycle gas to form ammonium chloride. Ammonium chloride will deposit in the recycle gas circuit or stabilizer overhead system. Ammonium chloride salts can be removed by water washing, but will result in downtime or product to slop. Ammonium chloride salts can be minimized by maximizing nitrogen removal in the Naphtha Hydrotreating Unit. Nitrogen removal is much more important when a Naphtha Hydrotreating Unit processes thermally derived naphtha, as these feedstocks normally contain much more nitrogen than a straight run naphtha. Denitrification is favored more by pressure than temperature and thus unit design is, important. If a Naphtha Hydrotreating Unit designed for straight-run naphtha starts processing non straight-run naphtha (except hydrocracked naphtha), there may be incomplete removal of nitrogen. There can be some improvement, usually not a large change, in denitrification with increasing temperature. Equipment design will limit the amount that the pressure can be increased. The ammonia formed in the denitrification reactions, detailed below, is subsequently removed in the hydrotreater reactor effluent wash water. (Pyridir Zu, a (Pyridine) C 45H, ——* C-C--C-C + NHs i Cy & uop nis asOP Nesna Hyaorsing Process Process Principles b. (Quinoline) — G-Pag_Ce, Cy Oo CG + 4, —e 6° "S6-0-C-0-6 + NHy cy LC mo Neel! Ls ¢ cc. (Pyrrole) i—- qc i] I CACC + 4H, —e cogoe +NH, | i c H d. (Methylamine) H—cC—N +H, ——» CH, + NH, H H 3. Oxygen Removal Organically combined oxygen, such as a phenol or alcohol, is removed in the Naphtha Hydrotreating Unit by hydrogenation of the carbon-hydroxyl bond, forming water and the corresponding hydrocarbon. The reaction is detailed below. Oxyegenates are typically not present in naphtha, but when present they are in very low concentrations. Any oxygenates in the product will quantatively convert to water in the Platforming Unit. It is important that the hydrotreater product oxygenate level be reduced sufficiently. uop nas ryUOP Naohina HycansstngPrcenss Process Piles (Phenols) o- Sc ‘Oxyegenate removal is as difficul, if not more, than nitrogen removal. The specific organic oxygen species impacts ease or difficulty of removal. Units normally not designed for oxygen removal may find it difficult to get adequate product quality. Oxygenate removal is favored by high pressure and high temperatures. For high feed concentrations, lower liquid space velocities are required. Processing of such compounds should be done with care. Complete oxygen removal is not normally expected and may only be 50%, However, MTBE has been shown to be essentially removed, but not completely, depending on the feed concentratrions, 4. Olefin Saturation Hydrogenation of olefins is necessary to prevent fouling or coke deposits in downstream units. Olefins can polymerize at the Platforming combined feed exchanger and thus cause fouling. These olefins will also polymerize upstream of the naphtha hydrotreating reactor and cause heat transfer problems. Olefin saturation is almost as rapid as desulfurization. Most straight run naphthas contain only trace amounts of olefins, but cracked naphthas usually have high olefin concentrations. Processing high concentrations of olefins in a Naphtha Hydrotreating Unit must be approached with care because of the high exothermic heat of reaction associated with the saturation reaction, ‘The increased temperature, from processing relatively high amounts of olefins, across the catalyst bed can be sufficient enough to cause sulfur recombination. The olefin reaction is detailed below. a. (Linear olefin) C-C-C-C = C-C +H, ——™ C-C-C-C-C-C (and isomers) uop ens nsLUoP nap hycroreatng Process Process Princes coy, b. (Cyclic olefin) & c 5. Halide Removal Organic halides can be decomposed in the Naphtha Hydrotreating Unit to the corresponding hydrogen halide, which is either absorbed in the reactor effluent water wash or taken overhead in the stripper gas. Decomposition of organic halides is much more difficult than desulfurization. Maximum organic halide removal is thought to be about 90 percent, but is much less at operating conditions set forth for sulfur and nitrogen removal only. For this reason, periodic analysis of the hydrotreated naphtha for chloride content should be made, since this chloride level must be used to set the proper Platforming Unit chloride injection rate. High feed concentrations of chloride can result in corrosion downstream of the reactor. Chloride corrosion control is described in the Process Flow - Wash Water section of this manual. Atypical organic chloride decomposition reaction is shown below. COCCCC-Cl+H, —” HCl+C-C-C-C-6-6 6. Metal Removal Normally the metallic impurities in the naphtha feeds are in the part per billion (ppb) range and these can be completely removed. The UOP Hydrotreating catalysts are capable of removing these compounds at fairly high concentrations, up to 5 weight ppm or more, on an intermittent basis at normal operating conditions. The maximum feed concentration for complete removal is dependent on the metal species and operating conditions. The metallic impurities remain on the Hydrotreating catalyst when removed from the naphtha. Some commonly detected components found on used Hydrotreating Hydrobon® catalyst are arsenic, iron, calcium, magnesium, phosphorous, lead, silicon, copper, and sodium. op nos. wsVOR nate rycorsing Process Process Picfles Removal of metals from the feed normally occurs in plug flow with respect to the catalyst bed, Iron is found concentrated at the top of catalyst beds as iron sulfides. Arsenic, even though it is rarely found in excess of 1 weight ppb in straight run naphthas, is of major importance, because it is a potent Platforming catalyst poison. Arsenic levels of 3 weight percent and higher have been detected on used Hydrotreating catalysts. This arsenic loaded catalyst retained its activity for sulfur removal. Contamination of storage facilities by leaded gasolines and reprocessing of leaded gasolines in crude towers are the common sources of lead on used Hydrotreating catalysts. Sodium, calcium and magnesium are apparently due to contact of the feed with salt water or additives. Improper use of additives to protect fractionator overhead systems from corrosion or to control foaming, such as in Coker Units, account for the presence of phosphorus and silicon, respectively. Removal of metals is essentially complete, at temperatures above 315°C (600°F), up to a metal loading of about 2-3 weight percent of the total catalyst. Some Hydrotreating catalysts have increased capability to remove Silicon, up to 7-8 wt% of the total catalyst. Above the maximum levels, the catalyst begins approaching the equilibrium saturation level rapidly, and metal breakthrough is likely to occur. In this regard, mechanical problems inside the reactor, such as channeling, are especially bad since this results in a substantial overload on a small portion of the catalyst in the reactor. C. REACTION RATES AND HEATS OF REACTION The approximate relative reaction rates for the three major reaction types are: Desulfurization 80-100* Olefin Saturation 80-100" Denitrification 20 *range dependent on specific species. The approximate heats of reaction (in kJ per kg of feed per cubic meter of hydrogen consumed) and relative heats of reaction are: oR ns aLVOP Nephi Hyotery Pracess Process Paciples Relative Heat of Reaction Heat of Reaction Desulfurization at 1 Olefin Saturation 40.6 5 Denitrification 08 04 ‘As can be seen from the above summary, desulfurization is the most rapid reaction taking place, but it is the saturation of olefins which generates the greatest amount of heat. Certainly, as the feed sulfur level increases, the heat of reaction also increases. However, for most of the feedstocks processed, the heat of reaction will just about balance the reactor heat loss, such that the naphtha hydrotreating reactor inlet and outlet temperatures are essentially equal. Conversion of organic chlorides and oxygenated compounds are about as difficult as denitrification. Consequently, more severe operating conditions must be used when these compounds are present. The following table summarizes the physical properties of UOP Hydrotreating catalysts. Refer to section XIV for material data safety sheets on these catalysts uop 75, weLUOP hpi Hy csrasng Process: Precess Poihes TABLE II-1 UOP HYDROBON® CATALYSTS FOR NAPHTHA HYDROTREATING SERVICE Designator Base Form Size ABD Metals. =~ Regeneration in Ibi? S6 Alumina Sphere 16 36 NUMo/Go —Steam/Air 89 Alumina Sphere 16 38 Mo/Co —SteanvAir S12 Alumina Extrudate 116 45 Malo Inert Gas S15 Alumina Extrudate 16 45 NUMo Inert Gas $16 Alumina Extrudate m6 45 NVMo Inert Gas S418 Alumina Sphere 16 45 MolCo Inert Gas S19 Alumina Extrudate 1/18-1/16 41-45 Ni/Mo Inert Gas 8-120 Alumina Cylinder 16 47 MoCo Inert Gas N-108 Alumina Quadlobe 40 MolCo Inert Gas N208 Alumina — Extrudate 20 46 NuMo Inert Gas Ho-K Alumina Quadlobe 120 57 N/Mo. Inert Gas * Sizes may vary ™ Sock loaded op hrs ngLYOP Napa Hycotartng Process Precase Vaiabes lil. PROCESS VARIABLES A. REACTOR PRESSURE The unit pressure is dependent on catalyst life required and feedstock properties. At higher reactor pressures, the catalyst is generally effective for a longer time and reactions are brought to a greater degree of completion. For straight run naphtha desulfurization, 20 to 35 kg/cm2g (300 to 500 psig) reactor pressure is normally used, although design pressure can be higher if feed nitrogen and/or sulfur contents are higher than normal, Cracked naphthas contain substantially more nitrogen and sulfur than straight run naphthas and consequently require higher processing pressures, up to 55 kg/em2g (800 psig). Similarly, higher operating pressures are necessary to completely remove organic halides. Halide contamination of naphtha is usually sporadic in occurrence and is normally due to contamination by crude oil well operators. The selection of the operating pressure is influenced to a degree by the hydrogen to feed ratio set in the design, since both of these parameters determine the hydrogen partial pressure in the reactor. The hydrogen partial pressure can be increased by operation at a higher ratio of gas to feed at the reactor inlet. The extent of substitution is limited by economic considerations. Most units have been designed so that the desulfurization and denitrification reactions go substantially to completion well below the design temperature of the reactors, for the design feedstock. Small variations in pressure or hydrogen gas rate in the unit will not cause changes sufficiently to be reflected by significant differences in product quality. This especially true for denitrification reactions, which are more dependent on the pressure than the desulfurization reactions. Thus, units not designed for nitrogen in the feedstock will have difficulty meeting the Platforming Unit feed requirements. ep nis wr{UOP Naina Hychrmating Process Process Vestine B. TEMPERATURE ‘Temperature has a significant effect in promoting hydrotreating reactions. Its effect, however, is slightly different for each of the reactions that occur. Desulfurization increases as temperature is raised. The desulfurization reaction begins to take place at temperatures as low as 230°C (450°F) with the rate of reaction increasing markedly with temperature. Above 340°C (650°F) there are only slight increases in further removal of sulfur compounds due to temperature. For higher severity Platforming Units, mainly found in CCR applications, the feed sulfur level is maintained between 0.15 - 0.5 weight ppm. If the sulfur level is below 0.15 weight ppm, then the Platforming feed sulfur content can be increased with the sulfur injection facility located in the Platforming Unit. The hydrotreater reactor temperature should be set to completely hydrotreat the naphtha feed and the secondary “fine” sulfur adjustments are made in the Platforming Unit. ‘The decomposition of chloride compounds in low concentrations (<10 weight ppm) will occur at about the same temperature as sulfur compound decomposition. Olefin saturation behaves somewhat similarly to the desulfurization reaction with respect to temperature, except that olefin removal may level off at a somewhat higher temperature. Because this reaction is very exothermic, the olefin content of the feed must be monitored and in some cases limited to keep reactor peak temperature within an acceptable temperature range. At elevated temperatures, an apparent equilibrium condition limits the degree of olefin saturation. This may even cause the residual olefins in the product to be greater at higher temperatures than would be the case at lower operating temperatures. Also, the H2S present can react with these olefins to form mercaptans. In such a case, lowering the reactor temperature can eliminate residual olefins and thus mercaptan formation. With typical olefin concentrations this recombination reaction may occur around 650°F (343°C). Decomposition of oxygen and nitrogen compounds requires a somewhat higher temperature than desulfurization or olefin saturation. The removal of these compounds does not appear to level off at elevated temperatures. Units with uop. nos weOP naphina Hysereeing Process Process Vanenie significant levels of nitrogen or oxygen must be designed for high pressure and low liquid hourly space velocity (LHSV) to ensure complete conversion. The demetalization reactions require a minimum temperature of 315°C (600°F) Above 315°C (600°F), metals removal is essentially complete, Below this temperature, there may be some cases where alll the metals will not be removed. However, a lower temperature may be acceptable for certain metals. Due to the permanent poinsoning of Platforming catalyst, extreme care and monitoring should bbe taken if adjusting the temperature below 315°C (600°F). The recommended minimum reactor inlet temperature to ensure a properly prepared Platforming Unit feed is 315°C (60°F). There are two factors which are important in determining this minimum temperature: First, below the minimum temperature, reaction rates for contaminant removal may be too low. Second, the temperature must be maintained high enough to ensure that the combined feed {recycle or once-through gas plus naphtha) to the charge heater is all vapor. Normal Reactor design temperatures for both straight run (SRN) and cracked naphthas are 399°C (750°F) maximum. Actual operating temperatures will vary, depending upon the feed type, from 285°C (S50°F) to 385°C (650°F). Cracked stocks may require processing at higher temperatures because of the higher sulfur, nitrogen, and olefin contents. For these feeds, the reactor delta T will be in the range of 10-55°C (20-100°F). As the catalyst ages, the product quality may degenerate, which may be corrected by increasing reactor inlet temperature. If increasing the temperature does not improve the product quality, a regeneration or change of catalyst will be required, depending on the history of the operation and catalyst state. In addition to catalyst deterioration, scale and/or polymer formation at the top of the catalyst bed may cause high reactor pressure drops which may result in reactor channeling. This can be corrected by skimming the top of the catalyst bed; and/or unloading, screening and reloading. Higher pressure drop problems should be corrected as soon as possible to minimize the risk of equipment damage and uop ens megUOP nat byoreing Process Process Variales degradation of product quality. Pressure drop is further discussed at the end of this section. C. FEED QUALITY For normal operation, daily changes in hydrotreater reactor inlet temperature to accommodate changes in feed quality should not be necessary. However, in some cases, such as when a refinery is purchasing outside crude from widely different sources, the naphtha quality may change significantly, and adjustment of reactor inlet temperature may be necessary, Changes in the feed olefin content will also affect the heat of reaction and adjustments to the heat balance of the unit may also be required. The final selection of reactor temperature should be based upon product quality. The above relations of feed quality and temperature assume operation within the normal temperature operating ranges given in the preceding section. For units that operate with sweet feed, a minimum sulfur is required to maintain the metals in their proper sulfided state. Sulfur will be desorbed off the catalyst if there is low H,S in the recycle gas. This will allow the metal to reduce to its metal state, which is not condusive to hydrotreating reactions. This reaction is partially reversible. If the sulfur level decreases below 15 wt-ppm sulfur, then sulfur should be injacted into the feed. The same compounds used for fresh catalyst sulfiding can be used for this operation. D. HYDROGEN TO HYDROCARBON RATIO ‘The minimum hydrogen to feed ratio (nm3/m? or SCFB) is dependent on hydrogen consumption, feed characteristics, and desired product quality. For straight run naphthas of moderate sulfur content, 40-75 nm3/m3 (250-400 SCFB) is normally required. Cracked naphthas must be processed at higher Hp uop vers maLUOP Naphia Hytotenog Process Process Venabios ratios [up to 500 nm3/m3 (3000 SCFB)}. As feedstocks vary between these limits, the hydrogen to feed ratio is proportioned between the extremes. Ratios above 500 nmi/m (3000 SCFB) do not contribute to the rate of reactions. The use of low purity hydrogen as makeup gas is limited by economical operation of the recycle compressor. Recycle gas with hydrogen sulfide contents up to 10% and with large quantities of carbon monoxide and nitrogen are not harmful to the catalyst, again when reasonable desutfurization is the only criterion, For nitrogen removal or complete sulfur removal, high hydrogen purity (70% minimum) is necessary, and CO may act as a temporary catalyst poison. The prevention of excessive carbon accumulation on the catalyst requires maintenance of a minimum Hg partial pressure, so impurities present in the makeup gas require higher operating pressures. Lower hydrogen to hydrocarbon ratios can be compensated for by increasing teactor inlet temperature. The approximate relation for these variables is 10°C (48°F) higher reactor temperature requirement for a halving of the hydrogen/feed ratio. This rule assumes operation above the minimum values of 315°C (600°F) reactor inlet temperature and 40 nm3/m3 (250 SCFB) hydrogen ratio. This relation is approximate, and it should again be pointed out that the product quality should dictate the actual reactor temperature utilized. —. SPACE VELOCITY The quantity of catalyst per unit of feed will depend upon feedstock properties, operating conditions, and product quality required. The liquid hourly space velocity (LHSV) is defined as follows: volume of charge per hour volume of catalyst LHSV = With most charge stocks and product objectives, a simplified kinetic expression based on sulfur and/or nitrogen removal determines the initial liquid hourly space velocity. This initial value may be modified due to other considerations, such as size uop nn msUOP Napins Hyaremeatny Process Process Vertes of unit, extended first cycle catalyst service, abnormal levels of feed metals and requirements of other processing units in the refinery flow scheme. Relative ease of conversion for Hydrobon® catalysts indicate that olefins react most easily, sulfur ‘compounds next, then nitrogen and oxygen compounds. There is considerable overlap with several reactions occurring simultaneously and to different degrees. Charge stock variability is so large that only approximate ranges of space velocities can be indicated for the various feed types. SRN is processed at 4-12 LHSV and cracked naphtha at 2-8 LHSV. For daily changes in the LHSV, inlet temperature on the naphtha hydrotreating reactor may be adjusted according to the equation below: LHSV, T= Ts 45in ae (for °F) LHSV, Te Ty. 25m Tae (for °C) where ‘T, = required inlet reactor temperature at LHSV; Te = required inlet reactor temperature at LHSVz The above relation assumes operation between 4 and 12 LHSV and assumes that reactor temperatures are within the limits discussed in Section II. F. CATALYST PROTECTION, AGING, AND POISONS The process variables employed affect the catalyst life by their effect on the rate of carbon deposition on the catalyst. There is a moderate buildup of carbon on the catalyst during the initial days of operation, but the rate of increase in carbon level soon drops to a very low figure under normal processing conditions. This desirable control of the carbon-forming reactions is obtained by maintaining the proper hydrogen to hydrocarbon ratio and by keeping the catalyst temperature at the proper level. uop aris meLUOP naohina Hyoreatng Process Procate Vanabes Temperature is a minor factor in respect to the hydrotreating catalyst life. A higher catalyst temperature increases the rate of the carbon-forming reactions, other factors being equal. It must be remembered that a combination of high catalyst temperature and inadequate hydrogen is very injurious to the catalyst activity. Catalyst deactivation is measured by the decrease in relative effectiveness of the catalyst at fixed processing conditions after a period of catalyst use. The primary causes of catalyst deactivation are: (1) accumulation of coke on the active sites, and, (2) chemical combination of contaminants from the feedstock with the catalyst components. In norma! operation, a carbon level above 5 wi-% may be tolerated without a significant decrease in desulfurization aithough nitrogen removal ability can be decreased. Permanent loss of activity requiring catalyst replacement is usually caused by the gradual accumulation of inorganic species picked up from the charge stock, makeup hydrogen or effluent wash water. Examples of such contaminants are arsenic, lead, calcium, sodium, silicon and phosphorus. Very low concentrations of these species, ppm and/or ppb, will cause deactivation over a long period of service because buildup of deposits depends on the integrated effect of both temperature and time. This effect is important when processing Platforming Unit feed. Hydrobon® catalysts exhibit a high tolerance for metals such as arsenic and lead. Total metals content as high as 2 to 3 wt-% of the catalyst have been observed with the catalyst still effective. However, if the calculated metals content of the catalyst is 0.5 wt- %, the frequency of product analyses should be increased to prevent metal breakthrough to the Platforming catalyst. Organic lead compounds are decomposed by Hydrobon® catalysts and for the most part deposit in the upper portion of the catalyst bed as lead sulfide. Metals are not removed from the catalyst during @ regeneration. When the total metals content, other than silicon, of the catalyst approaches 1 to 2 wt-%, consideration should be given to replacing the catalyst. uop wens weLUOP hagtina Hycroneatng Process Process Varies The only certain method of minimizing the effect of trace metal contaminants on the catalyst is to limit their entry to the system. This is done by careful, conscientious feed analysis and correcting the source of, or conditions, causing the presence of the metal contaminant. Apparent catalyst deactivation may be caused by the accumulation of deposit on top of the catalyst bed. This is seen by increased pressure drop across the reactor. The flow pattem through the balance of the bed is disturbed and product quality is diminished. This condition is easily remedied by skimming a portion of the catalyst, screening and reloading, of replacing with fresh catalyst. The procedure for this is described in Section XIII of this manual. The deposits are generally iron sulfide. ‘The maximum pressure drop that can be sustained is a function of outlet basket design and the product quality. The outlet basket allowable pressure drop ranges from 60-100 psig (4.2 - 7.0 kg/cm’), depending on the design. This can be used as a “general” guideline for when to skim the reactor. Normally the entire measured pressure drop is not taken across the outlet basket, since material deposits are on top of the catalyst bed. The product quality and, in some cases, the recycle gas flow rate may be effected at the higher pressure drop. For hydrogen once-through units the flow rate is even more affected and the allowable pressure drop may be less than units with recycle gas compressors. These changes, along with product quality, need to be considered for all units in determining when to alleviate the pressure drop. Dissolved oxygen, though not a catalyst poison, should be eliminated from the feed. With oxygen in the feed, especially in the presence of olefins, excessive fouling of equipment, particularly the feed-offluent exchangers, can occur. There are anti- fouling agents or dispersents that can be injected to the feed to minimize the effects. Removing the oxygen is the preferred choice. uop Hs we{UOP sapninaHytoreating Process Proceas Fw a Cont IV. PROCESS FLOW AND CONTROL A typical Naphtha Hydrotreating Unit processing a straight run naphtha for Platforming Unit feed will have a reactor section and a stripper section. in addition, some units have a prefractionation section upstream of the reactor section. A naphtha splitter may also be included, downstream of the stripper section, for units that do not process straight run material. A typical Naphtha Hydrotreating Unit with recycle gas is depicted in Figure IV-1, and a once-through hydrogen unit is depicted in Figure 1V-2. A. PREFRACTIONATION SECTION In some special applications, it is desirable to produce a narrow boiling range naphtha cut for feed to the Platforming Unit. An example of this would be an operation aimed at making aromatics, where the end point of the feed to the Platforming Unit is limited to about 160°C (325°F) to concentrate aromatic precursors in the feed. A full boiling range naphtha cut from the crude unit could be processed through a prefractionation section to accomplish this task. The prefractionation section typically consists of two fractionation columns in series. The first column is the prefractionator and the second column is the rerun. Usually, the feed to the prefractionator will be heat exchanged with rerun column bottoms, and a steam heater can be used to provide the remaining heat that is required. The overhead of the second (rerun) column becomes the heartout for processing in the reactor section of the hydrotreater. The heartcut boiling range is controlled by the amount of ight naphtha taken overhead in the prefractionation column and by the amount of heartcut taken overhead in the rerun column, The initial boiling point (I8P) of the heartcut is adjusted in the prefractionator and the final boiling point is adjusted in the rerun column. In the prefractionator, the overhead temperature controller directly sets the amount of overhead liquid product, light naphtha, by controlling net overhead liquid control valve. Increasing this overhead temperature will increase quantity of the overhead product and the increase the endpoint of the overhead product. This in turn controls the initial boiling point of the heartcut. For example, if a 38-204°C (100-400°F) boiling range naphtha is charged to a prefractionation section, the light naphtha is uop prs werWOR napa Hydrening Process Process Pow and Conte! sent overhead and the prefractionator bottoms product now has 82-204°C (180- 400°F) boiling range. The overhead reflux rate is controlled by the prefractionator overhead receiver level controller. As the receiver level increases, the reflux rate increases. For example, when the prefractionator overhead temperature increases above its set point, the net overhead liquid valve closes, thus increasing the overhead receiver level. The high receiver level in tum increases the reflux rate, which decreases the overhead temperature back to its set point. The prefractionator column bottoms are pumped directly to the second (rerun) column without any reheat. The flow rate is set the the prefractionator bottoms level controller. The desired product is taken overhead in the rerun column. The rerun column is also controlled by an overhead temperature controller. increasing the overhead temperature will increase the amount of material taken overhead and will increase its endpoint. Thus, if a heartcut of 82-160°C (180-320°F) is desired, it can be obtained by adjusting the rerun column overhead temperature to set the endpoint. The rerun overhead reflux rate is controlled by the rerun overhead receiver level controller. As the receiver level increases the reflux rate increases. Both columns have reboilers to provide the heat necessary for vaporization of naphtha so that sufficient reflux can be maintained, The overhead product from the prefractionator and the rerun bottoms product are sent to storage for blending or further processing downstream units. A typical prefractionation flow scheme is depicted in Figure IV-3. B. REACTOR SECTION ‘The reactor section can be divided into four systems; feed, reactor, wash water, and separator systems. 1. Feed System Naphtha feed, or feeds, can enter the unit either from intermediate storage or from another process unit. in the case of feed from storage, the tank must be properly uop a8 we(UOP naphina Myroeating Process Procass Rw ana Cont! gas blanketed to prevent oxygen from being dissolved in the naphtha. Even trace quantities of oxygen and/or olefin in the feed can cause polymerization of olefins in the storage tank when stored for long periods or in the combined feed/reactor effluent exchangers if the feed is not prestripped. This results in fouling and a loss of heat transfer efficiency. The feed chloride content should also be monitored. This is important for proper corrosion control, which is described in the wash water section. Typically, the feed(s) are collected in the feed surge drum where the rates are levelled out in the surge capacity of this drum. The feed surge drum is also provided with a water boot to help remove any free water that comes in with the feed. The removal of the sour water, typically to a sour water header, is a manual operation based on an interface level indicator. The feed surge drum pressure is controlled by a split range controller to maintain the pressure some quantity above the bubble point of the naphtha. On a low pressure signal, hydrogen or fuel gas will be added to the drum by opening that control valve. On a high pressure signal, the hydrogen or fuel gas valve will close and the vent vaive to the fuel gas header or relief header will open. At steady state, both valves should be closed. Naphtha is routed out the feed surge drum bottom to the charge pumps. The level of the feed surge Is typically not controlled and is allowed to fluctuate. There is a level indicator on this vessel. At the suction of the charge pumps there is a sulfur injcetion connection, which is for the sulfiding of the catalyst during the intial startup. For units with very tow feed sulfur contents, there may be a normal sulfide injection pump. The sulfide injection rate is set to maintain at least 15-20 weight ppm. This is required to keep the catalyst metals in their optimum state. There is a minimum flow spillback tine from the charge pump discharge back to the feed surge drum to protect this pump from damage. The flow rate to the reactor is set by a flow indicating controller. Low flow will shutdown the feed inlet and combined-feed exchanger control valve to prevent depressuring of the unit. uco fens wesVDP Napnina Hyarevening Process recess Fw and Canto 2. Reactor System Naphtha feed from the charge pump combines with a hydrogen-rich gas stream, and this combined feed enters the combined feed exchangers, usually on the shell side, where it is heated. The combined feed leaving the exchanger is all vapor, and fiows to the charge heater where it is heated to the required reaction temperature. The amount of fuel bumed in the heater is controlled by the temperature of the combined feed leaving the charge heater and flowing to the reactor. The temperature controller resets the charge heater fuel gas pressure controller. In some cases a slip stream of combined feed by-passes the combined feed exchanger. This is done to improve the heater firing control by slightly cooling the total combined feed to the charge heater. The combined feed enters the reactor and flows down through the catalyst bed, When processing straight run naphthta, there is generally very little change in the temperature across the catalyst bed. The reactor effluent enters the combined feed/reactor effluent exchangers, usually on the tube side, where it is cooled. The reactor effluent is then further cooled at the product condenser, in preparation for gas-liquid separation. A wash water injection point is provided in the reactor effluent line to the prduct condenser to dilute any hydrogen chloride present and to prevent salt buildup in the line or the condenser. 3. Wash Water System Water wash injection points are provided to three different locations in the reactor effluent line. The first two are at the combined feed exchanger and the other is just upstream of the product condenser. The wash water is used to dilute any hydrogen chloride that might be present and so that any salt buildup in the combined feed ‘exchangers, process lines or condenser may be washed out. The typical wash water injection point is just after the last combined feed exchanger bundle, but this should be verified by caiculating the dew point and the ammonium chloride desublimation temperature. This water injection should be on a continuous basis. The wash water injection pump injects enough fresh water, typically 3 liquid volume percent of the charge rate, via the flow indicating controller to the system. This. uop rns weUOP Nach Hycrorasing Proeese Proce Flow and Contot amount is sufficient to prevent salt buildup and dilute hydrachloric acid when processing feeds that contain some organic chloride, typically less than 20 weight ppm. If the feed chlorides are high, then altemative chloride corrosion control is required. The wash water tank is supplied from the cold condensate on level control. The separator sour water should be monitored regularly, per the analytical schedule in Section IX, to insure that proper corrosion control is occuring. The goal is to keep the separator sour water between 5.5 — 6.5 pH. Failure to do so can result in corrosion, and possible line rupture, in reactor effiuent piping and equipment as the process stream cools. Achieving the proper pH is normally not difficult when the feed chloride levels are less than 20 weight ppm. Some adjustment to the wash water injection rate can be made to further dilute the hydrogen chloride. However, the rate should not be decreased below 3 liquid volume percent of the feed rate. If the injection point is changed to a “hotter” location then the rate will need to be increased. !t is important that at least 25% of the water injected remains in the liquid phase. If further information on chloride corrosion control is required, please contact uoP. The reactor effluent and injected water flows to a Product Condenser and into the Separator. The product separator is provided with a water boot to collect the water injected. This water is usually pressured, via interface level control, to a sour water stripper for disposal, The waste water quality should be monitored at this point. 4. Separator System Reactor effluent and injected water flows out of the product condenser at a low enough temperature to ensure complete recovery of the naphtha and enters the Separator. A mesh blanket coalescer is provided in the separator to ensure complete separation of gas, hydrocarbon liquid, and water. Pressure Control The reactor circuit pressure is controlled at the Separator by the pressure indicating controller. There are two scenarios, which are discussed, for which the make-up gas is brought into the Naphtha Hydrotreating Unit. The diffferences are dependent on the pressure of the makeup gas. When the presure of the make-up gas is higher uop sa75 weUOP napnna Hycraroniey Process Process lw and Conte than the separator pressure, this pressure controller directly sets the rate of the make-up hydrogen into the unit to replenish the hydrogen consumed by the reactions and keeps the pressure constant (Figure IV-1). Typically the make-up gas comes from the Net Gas Chioride Treaters of the Platforming Unit and is introduced in the reactor effiuent line just upstream of the Product Condenser. The separator also has a hand-controlled valve on the gas effluent line, which is normally closed, that can be used to depressure the unit to the relief header in case of emergency. For units where the make-up hydrogen is at a pressure lower than the separator, ‘the gas must be increased in pressure via a make-up compressor. The Platforming Unit operates at a substantially lower pressure then the Naphtha Hydrotreating Unit and thus the make-up hydrogen must be increased in pressure. The make-up hydrogen is also introduced into the reactor effluent line just upstream of the Product Condenser. The make-up hydrogen is brought in from the Net Gas Chloride Treaters of the Platforming Unit through the Make-up Gas Compressor Drum and Make-up Gas Compressor. The Make-up Gas Compressor Suction Drum contains a monel mesh blanket to remove any entrained liquid droplets before entering the reciprocating compressors. The Separator pressure and Make-up Gas Compressor Drum pressure send a signal to the low signal selector. The low signal selector then controls the spillback valves of the Make-up Gas Compressor. As the signal decreases, the spillback control valve closes and allows more make-up hydrogen to enter the Naphtha Hydrotreating Unit. For example, the Separator pressure becomes too high, then the controller will open the spillback control valves. to reduce the make-up hydrogen flow rate to the unit. There is a water cooled exchanger in the spillback line to prevent overheating of the Make-up Gas Compressor. Recycle Gas There are altemate methods for providing the required hydrogen-rich gas to the reactor. Most common is a Recycle Gas Compressor taking suction from the top of the Product Separator with the discharge joining the naphtha feed upstream of the combined feed/reactor effluent exchanger. This flow scheme is depicted in Figure 1V-1.The gas leaves through the top of the Separator and goes into a Recycle Gas Compressor Suction Drum and on to the Recycle Gas Compressor. The Recycle Gas Compressor Suction Drum contains a monel mesh blanket to remove any entrained liquid droplets before entering the reciprocating compressors. This drum uop 9085 weYOP nptina Hyctmaing Process Procass Flow ans Canta also is equipped with two trays and connections for water addition. These features are to be used during catalyst regeneration. In normal operation, any condensed liquid is manually routed to the Stripper Column in a batchwise fashion. There are typically two single-stage recycle gas reciprocating compressors that can operate between 50-100% of the design recycle gas flow rate. Once-Through Gas In some units, rather than having a Recycle Gas Compressor, a comparable amount of a hydrogen-rich gas stream is brought into the unit on flow control, and flows on a once-through basis through the reactor section to the Product Separator where it is vented on pressure control. This flow scheme is depicted in Figure IV-2. The choice between these flow schemes is made during the design of each unit based upon the availability of a high pressure hydrogen-rich gas stream, and the cost of compression for each stream. C. STRIPPING SECTION The liquid hydrocarbon in the separator is pressured on level contro! through the stripper feed/bottoms exchanger, and the heated material enters near the top of the. stripper. A reboiler, normally a fired heater, is provided to supply the required heat input for generating vapor. This vapor strips hydrogen sulfide, water, light hydrocarbons and dissolved hydrogen from the feed to the stripper, which then passes overhead to the overhead condenser and to the overhead receiver. Normally, no net overhead liquid product is produced, and all of the liquid in the receiver is pumped back to the stripper as reflux. A refluxfeed mole ratio of approximately 0.25 is sufficient to strip the light ends and water from the tower. The reflux is pumped into the stripper on receiver level contra, To increase the amount of reflux, the reboiler heat input must be increased to provide more overhead material. The reboiler firing is controlled by the reboiler stream pressure differential controller, to set the amount of vaporization of the bottom stream. A temperature controller is not used since there is typically little temperuture change in uop ine werUO? Naphiha Hyeorsatng Process Procans Fw ond Core! vaporization, The net overhead gas leaves the receiver on pressure control, usually to amine scrubbing and then to fuel gas. The flow scheme is shown in Figure IV-4. The stripper overhead system is equipped with inhibitor addition facilities to prevent corrosion of the process lines and equipment by hydrogen sulfide in the overhead vapor. The corrosion inhibitor is pumped directly from a drum, diluted with a small slipstream of reflux, and injected directly into the overhead vapor line at the top of the stripper. The stripper bottoms material is pumped through the feed/bottoms exchanger and is usually charged directly to the Platforming Unit. On many units, a small slipstream of stripper bottoms is further cooled in a trim cooler and sent to storage for later use as sweet startup naphtha. The dry, stripped Naphtha Hydrotreating Unit product must meet the following specifications to be acceptable as Platforming Unit feed: Total Sulfur, wt-ppm <05 Total Nitrogen, w-ppm <0.5 Chlorides, wt-ppm <0.5 EP, °F 400 max. “Lead, wt-ppb <20 max. “Arsenic, wt-ppb 1 max. “Iron + Chloride, wt-ppm 1 max. *Copper + Heavy Metals, wi-ppb <25 max. Additionally, water plus total oxygen must be low enough to produce less than 5 mole ppm water in the Platforming Unit recycle gas with no water injection to that unit. ~ Lower limit of detection of the test method. D. SPLITTER SECTION uco nes NeUOP tpt Hyatt Process Procegs Pow and Contat In some special applications, the Stripper bottoms material contains C5 and minus compounds and it will be necessary to fractionate the hydrotreated naphtha before ‘sending to the Platforming Unit. The hydrotreated naphtha is fractionated in the Naphtha Splitter. Light naphtha is typically sent to gasoline blending. The heavy naphtha is sent to the Platforming Unit and should meet the specifications outlined in the previous section, The splitter is designed to split the C5 and C6 components. The tight naphtha product is mostly a C5 fraction, and the heavy naphtha is a C6+ fraction. The C5 fraction is not desired in the Platforming Unit. For greater fixibility, the splitter may also be designed to provide a split between C6 and C7 components. A refiner may ‘want to limit the amount of benzene, methy-cyclopentane and/or cyclohexane in the heavy naphtha product. The amount of C7+ material can also be limited for the light naphtha product. Typically, the Naphtha Splitter feed is preheated by the stripper bottoms material in the stripper feed-bottoms exchanger. The splitter feed is pressured on level control into the splitter. A reboiler, usually steam, is provided to supply the required heat input for the column. The heat input is controlled by the steam condensate flow. The overhead vapor is condensed in an air cooled condenser and trim condenser, and liquid collects in the splitter receiver. The receiver level is controlled by a total net overhead flow controlier. This controller regulates the amount of reflux back to the column. The light naphtha product flow is cascaded to a temperature controller ata top tray of the column. The flow scheme for the splitter is shown in Figure IV-5. The splitter pressure is controlled by a pressure controller on the overhead line. Any off gas or non-condensibles that build in the receiver can be vented to a relief header with a hand control valve. The heavy naphtha product is pumped on level control through the stripper feed-splitter bottoms exchanger to the Platforming Unit. if necessary the heavy naphtha can also be sent to tankage after first being cooled. The heavy naphtha usually passes through a heavy naphtha air cooler and a trim cooler before that material can be safely sent to tankage. op iris wsLUOP Naphina Hyoreaing Process Process Flow and Cont —. ALTERNATE OPERATIONS The hydrotreating columns can also be used for altemate operations when the reactor section is not processing sour naphtha. The columns were designed specifically for two operations. They are 1) to stabilize unstabilized naphtha from ‘storage and 2) to strip any water from the sweet naphtha from storage that will be charged to the Platforming Unit, 1. Stabilizing Naphtha Unstabilized naphtha is charged to the feed surge drum. From the drum the naphtha is pumped to the stripper column on flow (FRC) control. The naphtha bypasses the reactor section and also the stripper cold feed exchanger. The stripper column, which will run at a lower pressure than design, will remove the proper amount of light ends to achieve the RVP specification. The stabilized naphtha is pressured from the bottom of the column through the stripper hot feed exchanger and the “naphtha to storage” cooler and then to the stabilized naphtha storage tanks. 2. Stripping Sweet Naphtha Sweet naphtha from storage is pumped to the stripper or naphtha splitter. This flow is controtled by the level in the bottom of the column. The stripper or splitter will run with total reflux. The stripper column removes the water in the overhead receiver water boot. The splitter column removes water out the overhead receiver off-gas line. The splitter overhead receiver usually does not have a water boot. The dry, sweet naphtha is then pumped directly to the Platforming Unit. uop ores eto.Proonse Flow and Cont [Woe neon Hreruusing Process waLvaH WaONWROXA amavia asad daKTaOD wOLOVEL oxaa vaunayy, wTSNIANOD NaDOuGAK anavnw wossaYsNOD svo mIDAomL SVD 319A03Y HIM NOILOAS HOLOVSY LINN ONLLVSHLOUGAH VHLHdVN TWOldAL LAL S8NDId mtProcess Flew and Cont 1UOP naphinaHyeroveaing Pecess ‘waDKYHOXA ayaa aayrawoo axas VHS NaDONGAH HONOSHL ENO SV9 HONOYHL-JONO HLIM NOILOAS HOLOVAY LINN SNILVAYLOYGAH WHLHdYN TWOldAL @-Al SHNDIA eres‘Process Fan Coot {UOP Napa Hyctomaatig Process aaa Vruntavs, BDVUOLS OL VLLHAYN AAS SWAHOS MO14 NOILVNOLLOVUsSed LINN SNILVSYLOYGAH VHLHdVN TWOldAL €-Al SYNDIS ws, s7H5Process Flow ae Contes YOR naphihe Moreaig Process andr avanntaao 1aN wouvayaas ‘Londowa WALVAA ANOS: HHN WOU aly. © SONITOOD g svo unos You ama" aovaoisor 1 NOISOWNOD MIWHYOALVTa = VHLHdVN To aus NOILO3S ONIddl1S LINN ONILVSYLOYGAH WHLHdWN TWOIdAL Al auNDId 3LUOP Naptia Hyaroveoing Process ‘Proonss Row ana Contet FIGURE IV-5 TYPICAL NAPHTHA HYDROTREATING UNIT SPLITTER SECTION Full Range Naphtha Naphtha ie a | Splitter 6: (D> PDIC LSR Fos ¢ NAPHTHA EYO- te ——_ FIC Heavy Naphtha uep ts as{UOP nanninaMyararcatg Prose Process Equpment V. PROCESS EQUIPMENT A REACTORS The UOP Naphtha Hydrotreating Unit utilizes downflow reactors. Typically this consists of one reactor, but for certain feedstocks two reactors in series are required. In general, the purpose of the hydrotreating reactors is to allow the feed to contact the catalyst at reaction conditions while not allowing the catalyst to leave with the product. Catalyst containment is one of the goals of the design. Process vapors enter through the top of the reactor, via an inlet distributor, and flow down through the catalyst bed and out the bottom of reactor. Typically the naphtha hydrotreating reactor is constructed of Killed carbon steel with an alloy lining. The inlet distributor located at the top of the reactor prevents the vapor from disturbing the catalyst bed and enhances the flow distribution through the catalyst. Usually there are two layers of graded bed material on top of the catalyst bed, This aids in flow distribution and minimizes the pressure drop across the reactor. The depth of each layer is a function of the reactor dimensions and the feed types. The top layer is typically 4 to 6 inches deep (100 mm to 150 mm) and consists of specially shaped inert ceramic material used to filter larger particles from the feed. The second layer ranges from 12 to 24 inches (300 mm to 600 mm) in depth and is another specially shaped material, but includes active metals. ‘At the bottom of each reactor are ceramic support material (balls) of different diameters which help in the flow distribution of the reactor effluent out of the reactor. The varying diameters of the support material are utilized to prevent catalyst migration. An outlet basket prevents the ceramic support material from leaving the reactor. B. HEATERS uop bons vtLUOP Naprene Hycharetig Process Process Eauprent ‘A Charge Healer is used to supply sufficient heat to the combined feed so that the desired reactions can be obtained with the hydrotreating catalyst in the reactors. ‘The Charge Heater is typically a radiant-convection type with one firing zone, with fuel gas-fired bumers located on the floor of the heater box. It is normally a cylindrical updraft type having vertical tubes in the radiant section and sometimes horizontal tubes in the convection section. The combined feed will first flow through the convection section and be preheated, There are a number of passes in the radiant section and each pass contains skin thermocouples. These thermocouples can wam of tube plugging from two-phase flow, mainly during startup. The skin temperature of each pass should be relatively the same. A snuffing steam connection is provided for purging out any combustible gases from the firebox before lighting pilots during startup. The firing pattem of the bumers should be closely observed, and adjusted it necessary. As in all heaters, flames impinging on the tubes should be avoided. A slightly negative pressure at the bridgewalll should be present to provide adequate draft at the bumers. If inadequate draft is available at the bumers, insufficient air may be available through the bumer to complete combustion. This could cause a loss of efficiency, ballooning flame dimensions, or after-buming. As excess air to a bumer declines below acceptable levels, flame dimensions increase; unbumed hydrocarbon will travel a greater distance to come in contact with oxygen and ignite. There is an oxygen analyzer to monitor the excess oxygen content in the flue gas. Ballooning flame dimensions can cause a maldistribution of heat or flame impingement. A further decrease in available air may result in incomplete combustion. Unbumed fuel is useless and lowers efficiency. Unbumed fuel can also ignite in other than burner areas where air can enter the furnace (i.e., lube sheets, inspection doors). This is known as after-buming and can cause tube damage (if ignition occurs in tube areas), refractory damage or structural damage. Dampers located in the stack above the convection section control draft through the heater. Draft gauges (vacuum gauges) are installed in the radiant sections, convection inlets, and before and after the damper to monitor draft through the heater. A negative pressure must be maintained for safe, efficient heater operation. yoo VTS veLUOP naahine Hyorestng Process Process Equant C. HEAT EXCHANGERS Heat exchangers are used to heat and coo! many streams in the Naphtha Hydrotreating Unit. The shell and tube combined feed exchangers (CFE) allow the hot reactor effluent to add heat to the hydrotreating feed before the Charge Heater. The reactor effluent is then cooled further so that hydrogen can be separated from the unit product. The total reactor effluent is condensed by an air cooler and trim cooler. Heat exchangers are used for the reboilers of the Stripper and Splitter Columns. ‘Steam can be used for the Stripper and Splitter Columns, D. RECYCLE COMPRESSORS The Naphtha Hydrotreating Unit has one or two reciprocating, motor-driven recycle compressors. The recycle compressors circulate hydrogen-rich gas through the hydrotreating reactor circuit. Without hydrogen circulation, large amounts of coke will form on the catalyst that will prevent the desired catalytic reactions. It is critical to maintain recycle gas flow when feed is being charged to the unit. =. PUMPS There are many types of pumps used in the Naphtha Hydrotreating Unit. A high- head multi-stage pump is usually used to supply feed to the reactor section that is at much higher pressure than the Feed Surge Drum. Proportioning pumps are used for chemical injection, such as inhibitor or condensate. F, FEED SURGE DRUM The Feed Surge Drum is a pressurized, horizontal killed carbon steel vessel. The naphtha hydrotreating feeds enter through a battle distributor located at the bottom of the Feed Surge Drum and leaves at the opposite end. A level indicator and level uoep nes va{UOP naptime hyaravening Process Process Egmont glass show the hydrocarbon level. Maintaining a liquid seal in the bottom of the drum is important. The liquid outlet line has a vortex breaker. The Feed Surge Drum has a water boot to collect and remove any free water that might be present. G. SEPARATOR ‘The Separator is designed primarily to separate hydrogen from hydrocarbon. The Separator is a horizontal killed carbon steel vessel lined with an alloy, and occasionally concrete, for corrosion protection. The cooled reactor effluent enters through a slot type distributor at one end of the vessel to permit proper mixed phase distribution. The hydrogen and liquid separate and both pass through a vertical monel mesh blanket. The mesh blanket is used as a demister pad to coaiesce, or help remove, entrained hydrocarbon droplets from the gas stream. A level indictor shows the hydrocarbon level and a level controlier controls the flow of hydrocarbon from the separator to the Stripper. Maintaining a liquid seal in the bottom of the separator is important. The liquid outlet line has a vortex breaker. There is also a water-boot to remove the injected water. A level indicator shows the water level and a level controller controls the flow of water from the Separator. Regular sampling of this water should be performed to verify proper corrosion control. H, OVERHEAD RECEIVERS The Stripper and Splitter columns have receivers to collect condensed overhead vapors. The Stripper receiver inlet, has a slotted distributor to permit proper mixed phase distribution. A water boot collects any free water that might be present. There is a level glass and a level control bridle nozzle for the hydrocarbon phase and a level indicator for the water phase. A gas outlet nozzle permits non- condensable gas to go overhead. This valve also acts as the column pressure controller, The liquid outlet lines have a vortex breaker. The Splitter receiver is basically the same as the Stripper receiver with no water boot. A gas outlet nozzle allows off-gas to go to a relief header. This is controlled uop fans vaLUOP nephina Hysiormatng Process ‘Press Eowment by @ hand control valve. A total overhead flow controller typically controls the receiver level. ‘The typical materiai of construction of the Splitter receiver is the same as would be used on the Splitter column, which is carbon steel. The Stripper column and receiver are constructed of killed carbon steel. The overhead receiver design temperature is much higher than its operating temperature. The receiver is designed to withstand temperatures that may develop if the ovethead condenser should fail. L RECYCLE COMPRESSOR SUCTION DRUM The Recycle Compressor Suction Drum is a small vertical vessel designed 10 remove condensable material from the recycle compressor suction stream and thus protect the compressor. The gas stream from the Separator enters the vessel from the side and travels out the top. A partial (monel) mesh blanket is installed to remove entrained jiquid. The 2 bubble cap trays are used during regeneration only. There is a level glass for the liquid hydrocarbon phase. The liquid that is knocked out can be drained manually to the Stripper colurnn. J, STRIPPER COLUMN The stripper column is used to remove light ends, HS and water from the light naphtha product stream. The stripper is typically fabricated out of killed carbon steel with carbon steel or stainless steel valve trays. The top part of the column is narrower than the bottom due to the lower volumes of liquid and vapor in the top section of the column. K. SPLITTER COLUMN yoo ad vsUO Nephina Hydoreating Process Process Equant The Splitter is used to separate the fight naphtha from the heavy naphtha product. The hexane (C6) components and heavier will be taken out the bottoms and sent to the Platforming Unit, tankage or blending system. The pentane (C5) components and lighter will go overhead where they are condensed and the net liquid will be sent to the tankage or blending. The Splitter is typically fabricated out of carbon ‘steel with carbon steel valve trays. ucp ayes veLUOP Naphine Hycroveaing Process Vi. COMMISSIONING A. PRECOMMISSIONING PLANT INSPECTION Sections of the unit should be checked out by both refinery and UOP personnel as soon as the contractor completes work in those areas, Immediately following inspection of those areas, punch lists which indicate the deviations from the UOP- design specifications should be written and distributed to the contractor. In this manner mistakes in construction can be found and corrected early. Inspection of the plant can be basically divided into the following areas: Vessels Piping Heaters Exchangers Pumps Compressors: Instrumentation CatalysChemical Inventory PN MAH aN > A discussion and lists of the major points which must be examined in the inspection of these areas follows: 1. Vessels The actual installations must be compared against the UOP drawings to assure that the vessels will function as intended. The reactor intemals must conform exactly to the UOP design specifications if good distribution is to be attained and catalyst migration is to be avoided. Particular attention must be paid to the following details: uop rs wer{VOR Naphna Hyraraatng Process Comrisioning Specification Check 1. Review UOP design specifications with the vendor drawings to verify agreement on: Pressure, temperature, and vacuum ratings. Shell metallurgy, thickness, and corrosion allowance. Nozzle size and orientation; flange rating, type and finish. ‘Type of lining, thickness and material. Stress relieving and/or heat treatment. Foundation design for full water weight. repo oP 2. Confirm that the vassel has been hydrostatically tested. 3. Verify that all code plate information on the vessel is correct. Internal Inspection a. Reactors 1. Inlet distributors, quench distributors: metallurgy, type, size, opening sizes, freedom to expand. 2. Vaporiliquid distribution trays: metallurgy, vapor pipe dimensions, orientation, and opening sizes; packing; supports; welding; ievelness. 3. Catalyst support grids: metallurgy; grid type and dimensions; screen type and size; supports; welding. 4, Catalyst unloading nozzles: metallurgy, orientation, length. 5. Outlet stools: metallurgy and dimensions. 6. Distributor baskets and support rings: metallurgy; screen type and size; dimensions; quantities. op seins neOP naptinaMycroreaing Pracess Commssoning 7. Thermowells: orientation, length, and metallurgy. b. Other Vessels 1. Vessel trays: spacing; levelness, orientation and dimensions of weirs, downcomers, accumulators, draw-off and twap trays, seal pans, distributors, baffles, nozzles, tray contact devices; metallurgy of trays, contact devices, clips, bolts, nuts and gaskets; freedom of movement of valve caps or other contact devices; number, size, and distribution of tray contact devices or perforated plate holes; proper fit of all intemals and proper welding of support rings or other support devices; liquid tightness of drawoff trays, seal pans and accumulators, all bolting and clips tightened. 2. Mesh blankets and outlet screens: size; location; !evelness; goodness of fit (no bypassing allowable); and metallurgy of blanket, support, tie wires, and grids. 3. Vortex breakers: type, size, and orientation. 4. Baffles: type, orientation, ievelness. 5. Instrument nozzles: location, orientation, cleanliness, thermowell length and metallurgy, baffle size and type. 6. _ Inlet distributors: type, size, orientation, levelness, freedom to expand. 7. Non-fired reboilers: location, orientation, proper supports. 8. Packing: type, size, support, installation. uep aris usOP NaptthaMycroveaing Process Comming 10. Internal ladders and other devices: location, size, orientation, properly secured. Lining and refractory. a, _Hex-steel for concrete lining: clean and properly secured. Lumnite or other specified cement applied according to UOP specifications, with no holes or gaps in the applications. b, Metal linings in good condition. Weld overlays have no gaps or holes in the application. ©. Lining is of the proper thickness and covers the required portion of the vessel. d. Other refractory installed correctly with no gaps or holes in the application. The vessel should be clean (free from trash) and should not have excessive mill scale. External Inspection Manways and nozzles: location, size, flange rating and finish, metallurgy, with proper gaskets, nuts and bolts. Ladders and platforms: correctly positioned, secure and free to expand. Insulation and steam tracing: provided as specified and has expansion joints as required Vessel grounded correctly. nrs weVOP Naphita Hyteating Process commisioning 5. Correct vessel elevation. 6. Valves and instrumentation: easily accessible from grade or platform. 7. Piping: a. Adequate supports and guides for ali connecting lines. b. _ Level and pressure instrument connections drain to a safe location. c. Vents to atmosphere or blowdown provided as specitied. d. Relief valves have been bench tested. e. Check valves exist on utility line connections where hydrocarbon backup could occur. f. Connections available for steaming/purging of the vessel. 8. Fireproofing of structure and supports is complete. 9. Instrumentation: a. Level glass floats center positioned correctly with respect to vessel tangent line, and are readable from grade or platform, b. Through-view level glasses have rear light for illumination. cc. Flange ratings, metallurgy, size, etc. are all correct. ua arias. ves:(U0P Naphiha Hyoreatng Process Commesioning 2 Piping The unit must be constructed in accordance with UOP Piping and Instrumentation Diagrams (P&ID’s), including all details, elevations, dimensions, arrangements, and other notes on the P&lD's. One must be able to startup, shutdown and conduct normal operations on the unit as envisioned in the UOP design. Also, piping for special procedures such as dry-out, special materials preparation, regeneration and/or altemative flow schemes may have been incorporated into the unit's design, and the unit should be able to operate in all of these modes with piping as designed and constructed. If the unit is connected to other process facilities, adequate means must be provided to receive feed from or send products to these facilities without contamination of these streams, Minimize as much as possible the effects of upsets of other process units on the operation of the Naphtha Hydrotreating Unit, especially where contamination of feed or product stream might occur. Check all tankage interconnections to minimize the possibility of stream contamination outside of the battery limits, Check that adequate means of measuring flows, pressures, and temperatures, and sampling of all process streams has been provided. The following items must be checked to ensure conformity to the UOP design specifications: 2 Flanges: rating, facing, and metallurgy; type (typically, 2" and smaller are socket weld, 2-1/2" and larger are weld neck flanges). b. Gaskets: type; metallurgy (materials or retainer, jackets, winding, filler, etc.); thickness, ring size, etc. ¢. Fittings, connections and couplings: rating and metallurgy. d. Vales: rating and metallurgy (body, trim, seats, etc.); packing; seat inserts; bonnet gaskets; grease seals; socket-weld or flange type, rating UuoO 4t7Hs: weUO? Napnins ryattaseng Process Commissioning and facing; installed in correct direction of flow; lubricant provisions; gear operators; extended bonnets; stops; ease of operation. ©. _Bolting: stud or machine bolts; bolt and nut metallurgy; bolt size. f. Pipe: metallurgy, thickness; seamed or seamless; lining. g. Tubing: size and thickness; metallurgy; seamed or seamless. h. Gauge glasses: (1) Through-view types should have rear-mounted lights. (2) Design pressure and temperature. (3) Special materials of construction. (4) Drains to safe location. (5) Visible from grade (or platform, if required). i. Pressure relief valves: (1) Size and style. (2) Lever requirement. (8) _Inlevoutlet flange material, facing and rating. (4) Set pressure — must be bench tested. (8) Metallurgy of nozzle, disc, spring, etc. (6) Type (pilot operated, balanced, etc). (7) Inevoutlet block valves car-sealed open; valve stems installed in horizontal or below. uop nes wrUOP Nagi Hyonating Process Commssienng j. General: (1) Utility systems within the battery limit should fotlow all relevant pipe class specifications in the same detail required for process lines. (2) Package systems (skid-mounted units, etc.) shown on the UOP PAID should follow all relevant pipe class specifications in the same detail required for other process lines. (8) Expansion: review the physical installation to insure that no expansion problems will occur when the unit gets hot and that: (a) Column overhead, reflux, feed and other lines are free to expand. (b) Rotating equipment will not be pulled out of alignment. (c) Sufficient expansion loops have been provided on long hot lines. (d)_ Pipe shoes are free to move in one direction, and are resting on supports of sufficient size that the shoe will not fall off the support. 4 High point vents and low point drains should be installed where necessary. (5) Spectacle blinds should be provided where required. (8) Car-sealed valves should be locked in proper position. (7) Spring hangers should have locking pins removed (after hydrotesting) and necessary adjustments should be made for hot/cold position after startup. uop ayes veeWOP Naptha Hyrcrstng Process Comessioning 3. Fired Heaters The heaters must be inspected to ensure that they can be operated in a safe and efficient manner and that the required heat duty needed for the process can be provided. After all, it is important that the possibility of a tube rupture or other heater mishap is minimized. In particular the following items must be checked: Specification Check All UOP design specifications should be reviewed with vendor drawings to verity agreement on: 1. Conformity to process requirements. 2. Heater type. 3. Tube arrangement, metallurgy, size, and thickness (note that tube metallurgy may be different for radiant, convection, and convection shield tubes). 4, _ Instrumentation connections. 5. Tube supports and support metallurgy. 6. Refractory. 7. Access doors, observations ports, steam smothering connections, and explosion doors. 8. Stack arrangement. uop 7s weLUOP napie Hyer Process commssonng Internal Inspection a. Radiant Section 1. Anangement and symmetry of tube coil with respect to heater wall, bumer rings, and tube spacing. 2. Vertical length of tube coil with respect to supports and guides. 3. Fue! gas, fuel oil and pilot bumer tips are clean and oriented properly. Bumers are properly mounted with clearance for firing and removal. Castable refractory has not been used for bumer blocks. Fuel oil tip sizing is adequate with respect to actuat fuel oil viscosity. 4. Tubeskin thermocouples, if required, are located properly and installed so that they have good contact with the tubeskin. 5. Refractory is in good condition before and after refractory dry-out. No refractory is resting on tubes, 6. Heater shell expansion joints are packed with asbestos wool and clean. 7, Adequate space for tube expansion. 8. Heater shell is sealed to prevent escape of hot gases and entrance of atmospheric moisture during shutdown. 9. Smothering steam and instrumentation connections are not covered by refractory. 10. Heater is clean and free from debris, 11. Heater instrument connections are open — not filled or covered with refractory. woo Se7HtS. Veto.UOP naptts ycrorention Process Commissioning b. Convection Section and Stack If extended surface elements are allowed, the bottom three more rows of convection tubes must be bare. No refractory is on the tubes. Expansion provisions are adequate. Damper is free to move fully open and closed; its position indicator is correct both at the stack and at the damper control; damper is weighted to fail open; the damper, support pipe and bolting are all of the correct metallurgy. Sootblowers, if specified, are provided with provision for inspecting the sootblowing operation. Other checks should be conducted as in the Radiant Section inspection. External Inspection Location with respect to process equipment. Platforms for access to all observation ports, instrumentation, sample connections, sootblowers, and damper connections. ‘Adequate number and arrangement of observation ports to permit visual inspection of the entire length of all wail, hip and shock/shield tubes, and the bumer blocks. Hand firing equipment located adjacent to an observation port from which that bumer can be viewed. Explosion doors located such that heater gases will not flow towards process equipment and platforms. wns verLUOP naphina Hychovesing Process commissioning 6. Explosion doors located such that doors can open completely. 7. Symmetry of extemal piping and crossovers. 8. _ Instrumentation and sampling connections. 9. Damper position indicator visible from damper control; damper controt functioning property. 10. Pocketed crossover connections have flanged drains, 11. Decoking connections as specified. 12. Sufficient smothering steam connections into heater firebox. Box valves on smothering steam are located remote from the heater, with drain valves and/or steam traps upstream of final block valve for condensate removal. Weep holes provided in smothering steam lines at low points. Fuel Systems 1, Fuel fines have battery limit block valves which are remote from the heater and easily accessible. Fuel oil piping and its steam tracing are arranged such that no dead legs or pockets are formed. Fuel lines to bumers can be easity disconnected from bumers for bumer removal, All {fuel lines have been leak tested 2. Fuel oil lines at bumer valves are correctly piped with steam crossovers. All steam lines have adequate traps and condensate drains, 3. Shutdown solenoids for fuel shutoff valves have been set properly. 4, Fuel ol circulating lines are provided. w708 wie_UOP NaphehaHycorating Process Commisoning Heater Instrumentation 1. Alldraft gauge, pyrometer and analyzer connections are as specified. 2. Allheater TRC’s fail upscale during power failure or open circuit. 4, Heat Exchangers Specification Check The UOP design specifications should be reviewed with the vendor drawings to check: 1, Metallurgy of shell, tubes, tubesheet, channel cover, batfle, header box, etc. 2. Tube size and thickness: number of shell and tube passes and direction of flowing streams; max/min allowable velocities. 3. Design temperature, pressure and pressure-drop ratings. 4. Nozzle size, flange type, rating, facing and metallurgy; vent and drain connections. 5. Design differential pressure between shel! and tube sides of the exchanger. Field Inspection In the field the following items should be checked. 1. Name plate verifies UOP specifications. uC0O yas versWOR Noon Hycteatng Process canmsonng 2. Flange size, rating, facing and gaskets. 3. _ Insulation for heat retention and personnel protection. 4. Exchanger properly grounded. 5, Tubular exchangers: a. Elevation b. Slot length of sliding plates adequate for expansion. Exchanger should not be tied down at both ends. Check that sliding ends of mutti-shell exchangers make sense with regard to expansion of exchangers and connecting pipe. c. Piping symmetry for parallel exchangers. d. Non-condensible vents in steam service or in totally condensing systems. @. Water coolers; inlet at bottom of exchangers; inleVoutlet block valves with a thermal relief valve inside the outlet block valve; vent and drain connections inside the block valves. f. Witness a shelltube differential pressure test, if possible (especially important in feed/effluent exchangers). When leak testing piping and equipment, ensure that the design shelltube differential pressure is not exceeded. 6. Air-cooled exchangers: a. "Auto-variable* or "standard-pitch* fans, as specified. b. Motor switches accessible from grade and located near the exchanger. uep Hens. visec. Fan pitch set correctly as determined by fan amperage draw. d. Vibration switch on each fan. @. Proper motorifan rotation. Motors properly grounded. f. Proper elevation and distances from connecting equipment. @. Belt tension on motor drive pulleys is equal and correct. h. Motor amperage can be easily checked. i, Exchanger free to expand. j- — Manifold piping arrangements as shown on UOP P&lD. k. Split header design where specified. |. Free draining requirements, as shown on P&ID. m. Tube fin surfaces are in good condition with no construction debris ‘on top of the fins, Adequate space has been provided for pulling tube bundles, ames vets{UO Naprane Hyarveaing Process Commissonng 5. Pumps Centrifugal Pumps 1. Specification Check The UOP design specifications should be reviewed against the pump curves, and data given by the vendor to confirm agreement on the following: a. Head and capacity. b. Pressure and temperature rating. c. Speed. d. NPSH requirement. . Pump type, materials of construction, flange ratings, seals, bearings, number of stages, lubrication and cooling systems, etc. {Type of driver. g. Balancing lines for multistage pumps must have flanged joints (not unions). 2. Field inspection The following items should be checked in the field: a. Sight flow indicators, inleVoutlet shutoff valves on cooling water lines. b. Thermometers/pressure gauges for gland seat and flushing oil manifolds. c. Restriction orifices (if required) present in seal flush manifold piping. uop N68 veLYOP hapa tycotating Process Commisioning Pedestals on pumps operating over 500°F (260°C) should be water cooled. Cooling water to mechanical seals on pumps operating over 250°F (120°C). Proper direction of rotation. Reciprocating Pumps The vendor information should be checked against the UOP specifications to verify agreement on the following: g. Head and capacity (minimum, normal, maximum). Materials of construction (body/glands, -plungers, diaphragms, packing, intemal check valves). Cooling/lubrication systems. Pressure, temperature ratings. Relief valve setting must be bench tested. Pump speed and stroke. Pulsation suppression devices, if required. Means for calibrating the pump flow rate should be investigated. 07008 verLO? Naphine Hyco Process Commssioning General The following items should be checked for all pumps: a. Piping to be arranged to permit removal or replacement of pump and driver. Piping independently supported from pump: pump will not be pulled out of alignment when lines get hot; no vapor pockets in piping. Suction strainer easily removed for cleaning; strainers fit well so no bypassing can occur; strainers have been installed. Discharge pressure gauge readable from discharge block valve. Suetion/discharge valves easily accessible and operable, and near to the pump. Accessibility of auxiliary piping and controls. Check that NPSH requirements have been met, Warm-up lines provided across discharge check valve when pumping hot fluids. Base plate grouting complete. Steam tracing and insulation provided on suction/discharge lines, pump casing, and process seal flush lines, as required. Minimum flow bypasses (with restriction orifice), if required. All seal oil, warmup, etc. lines have flanged connections and valves to permit removal of pump. Lubrication and cooling systems operate correctly. rms vereUOP napttaPyctoranng Process Conmssonmns m. Adequate means for venting and draining the pump casing are available. n, Vacuum service pumps must have a discharge vent back to the system to allow filing the pump with liquid. ‘©. Pumps and drivers are aligned correctly. P. Check valves are of proper type and installed in the correct direction. q. All drains from pumps and associated piping and instrumentation should be routed to a safe location. 6. Compressors Centrifugal Compressors a. Specification Check ‘The UOP design specifications should be reviewed against the vendor information and drawings to ensure agreement on the following: 1. Design capacity, temperature, pressure and specific gravity. 2. Compression ratio, number of stages. 3. Type of compressor, materials of construction, flange type, rating and facing. 4. Lube and seal oil systems, and estimated seal oil leakage. 5. _ Instrumentation, as supplied, must be in accordance with the UOP design specifications. 6. Piping fumished with the compressor must conform to the same pipe class as connecting lines. uop nes weLUOP napa Myaeating Process Conmasening b. Field Inspection The following items should be checked in the field. 1. Materials of construction; flange type, rating and facing; conformity of compressor piping to applicable pipe specification. 2. Instrumentation for conformity to UOP design specifications, location, operability and access. 3. Lube/seal oil system; operability of all sight flow indicators, instrumenta- tion, pumps (including auto starts), filters, coolers, compressor trips, reservoir, seal oil pot, etc, Check that addition and withdrawal of seaVlube oil to/from the reservoir can be performed easily. 4, General cleanliness of all process and lube/seal oil systems, and of the general compressor area. 5. _ Insulation as required for heat retention and personnel protection. 6. Check for access to sour oil and compressor casing drains, and that those drains are routed to a safe location. 7. Proper supports on suction/discharge piping. uoO yarns veoLUOP Nap Hycoroing Process Commissionng Reciprocating Compressors a, Specification Check The vendor information and drawings should be compared with the UOP design specifications to verify conformity on the following items: 1. Type of compressor, materials of construction, flange type. rating and facing. 2. Number of stages, compression ratio for each stage. 3. Design capacity, pressure, temperature and specific gravity for each cylinder. 4. Compressor speed; piston speed. 5. Lubricated or non-lubricated. 6. Single or double acting; balanced and opposed or dummy crosshead; fixed or variable clearance pockets; auto or manual suction valve unloading. 7. Cooling to cylinder, packing, gearbox, lube oil. 8. _ Lube oil system operation. 9, Pulsation suppression devices; distance piece design; packing and distance piece vent piping. oo aes vetLUOP Naphihe Mytoveaing Process Comms soning b, Field inspection The following items should be checked in the field: 1. Materials of construction; flange type, rating, finish, gasketing. 2. Instrumentation for conformity to UOP design specifications, location, operability and access. 3. Lube oil system/cooling water piping, including sight flow indicators. 4. Distance piece/packing vents piped correctly. 5. Adequate and accessible drains which are routed to a safe location. 6. Single strand steam tracing on the bottom of suction lines and snubbers, as specified; insulation as specified for heat retention and personnel protection. 7. Automatic suction valve unloader operation. 8. Two compartment distance pieces, if required (>30 mol% Ho in process gas). 9. Acidizing requirements have been met and acidized piping is not in contact with the atmosphere (under nitrogen blanket), includes both process and tube oil piping. 10. Provision for suction strainers, if required. vopD 7s veeUO Naoha Hpdrotraaing Process Comnssonig 7 All personnel on site should check to ensure that the instrumentation is provided as specified by UOP; that it is functional; and that a minimum of instrumentation problems will occur when the unit is commissioned. Some of the basic items which must be checked include the following: Instrument type, range, and size. Materials of construction and rating of instrument, accessories, and connecting piping, flanges, and valves. Accessibility of instrument for routine checks and maintenance; rigidly mounted. Installation according to correct UOP drawing details. ‘Accessories (pulsation dampeners, filter/regulators, diaphragm seals, excess flow checks, seal pots). Location of local indicators so they are readable from grade platform or controller assembly, as required. Process requirements of flow, temperature, pressure, differential pressure, specific gravity, etc. Controller type, number of modes, chart type, range, cascades. Power requirements of voltage, frequency; emergency power supply and connections. Calibration of controllers, transmitters, analyzers, special instrumentation. Control valve, block and bypass valve sizes for control valve assemblies. nis weLUOP Nephi Hycemeating Process Conmasining 8. Catalyst/Chemical inventory Catalyst a. It must be verified that sufficient quantities of catalyst, catalyst support material, and other materials (such as asbestos rope, etc.) are on site, are in good condition, and are properly stored (for example, in drums, indoors, and on pallets to prevent contact with moisture). b. {tt must be verified that all equipment required to load the catalyst is on site and in good condition. Chemicats It must be verified that the proper type and quantity of chemicals (such as inhibitors, demulsifiers, soda ash, caustic, etc.) are on site and stored properly. B. PRELIMINARY OPERATIONS Prior to the commissioning of the plant there are several operations that must be conducted by contractor and refinery personnel to prepare the plant for the actual startup; these are: Commissioning of utilities Final inspection of vessels Pressure test equipment Acid cleaning of compressor lines Wash out lines and equipment and break-in pumps Break in compressors Service and calibrate instruments Dry out fired heaters Reactor circuit dry out Catalyst loading Purge and gas blanketing age PN OMe ons #8 uop ts naeYOR Naphena Hyartoing Process Conmssioang tt is important that these operations be carried out as thoroughly and as well as possible to help achieve a smooth and trouble-free startup and later steady normal operation. A discussion detailing the major items to monitor in each of these operations follows. The above outline may be expanded somewhat as follows: 1. Commissioning of Utilities The various utility lines should be tested and placed into service as soon as the construction schedule allows. Pressure tests should be carried out on all steam condensate, air, fuel gas, fuel oil, flare, and nitrogen lines as is done on all process lines. The steam lines should be warmed up gradually to prevent damage by water hammer. At the same time, all steam traps and condensate lines should be placed into service. All turbine inlet and outlet flanges should be blinded off at this time, Scale and construction debris can be conveniently removed from the steam lines by blowing them down as long as necessary with steam. To gauge the effectiveness of the steam blowing (and the amount of scale lettin the lines), target plates should be installed at the blowdown points. The lines should be repeatedly blown down until virtually unmarked target plates are obtained. Condensate fines should be continually checked and traps removed and cleaned if plugged. The other utility lines can be cleaned by blowing with steam or air, or by water flushing if possible. 2. Final Inspection of Vessels Alll vessels should be inspected before final closing and any loose scale, dirt, etc., should be removed. Any line coming directly off of the bottom of a dirty vessel should be removed. It is very important that the internals of the hydrotreating reactor be inspected very carefully. The hydrotreating reactor intemals should be checked for holes and/or op vrs wesVOR Nagi Hydraresing Process Comision damage and repaired as required. The catalyst support basket and unloading sleeve should be checked to ensure correct fit in the nozzles. The product separator should be checked carefully to be sure the cement lining is installed well and that the mesh blanket is securely fastened to the support ring. There should be no gaps in the mesh blanket. 3. Pressure Test Equipment It is normally the contractor's responsibility to hydrostatically pressure test the unit during construction. The following suggestions are made to help the refiner during this stage of startup activity. Before any vessel is filled with water, the foundation design must be checked to see if itis rated for this load. Screens should be placed in the lines before the unit is pressure tested so that the test water can be pumped through the lines for the purpose of washing them. Screens should be placed in a flange between the suction valve and the pump so that the screen may be removed without depressuring any vessels. The flow through the screen should preferably be downward or horizontal. Precautions should be taken to place the screen in a location where the dirt particles will not drop into an inaccessible place in the line when the flow through the pump stops. if this should happen, it would not be possible to remove the dirt upon removal of the soreen. ‘An air pressure test can be placed on the sections of the unit prior to a water test so that any open lines or flanges may be discovered and taken care of before liquid is admitted. It should be remembered that in pressure testing vessels, the test gauge should be placed at the bottom of the vessel so that the liquid head will be taken into account. Before draining any liquid from a vessel, a vent must be opened on top of the vessel to prevent a vacuum from pulling in the vessel sides. uop jones veUOP Nashina Hyceating Process ‘commissioning In pressure testing equipment, particularly in cold weather, care should be taken that the testing of the vessels is not carried out at temperature levels so low that the metal becomes brittle. As metal temperatures decrease, the tending for brittleness increases. Temperatures above 17°C (60°F) are considered satisfactory for testing to eliminate the possibility of cold fracturing of equipment. Such temperatures can be attained by warming the testing medium. It the unit contains any austenitic stainless steel, the chloride content of the test water must be less than 50 wt-ppm. If this is not possible, the test water should have a maximum of 0.5 wt-% sodium nitrate added to it. It will not be practical to test all of the equipment together. Thus, the unit will be divided into sections as governed by the location of the various items of equipment and the test pressures to which each item will be subjected. Suitable blanks must be made up for insertion on nozzles and between fianges to isolate the various sections of equipment as required. Normally, the exchangers, receivers, ete., for the various towers will be tested together with the main vessels. Test pressures will be determined from the pressure vessel summary for the unit. During pressure testing, all safety valves must be blinded off since their normal relieving pressure will be exceeded. It may be convenient to test the heaters and reactors in one group. A field hydrostatic test on the gas compressor ater installation could result in damage to the internals, so the compressors must be isolated from the reactor system. As the heaters are normally tested at a higher pressure than the reactors, it would be simplest to blind off the heaters and test them first and then test the entire system at the reactor test pressure. Blanks can be provided with connections for introduction of water for testing and for venting of air as the system is filled with water. It may be necessary to use thermowell connections and pressure taps for additional vents in the reactor system. At the completion of the hydrostatic test, all water should be removed from the equipment. Where necessary, flanges may be broken to drain low points and the equipment air blown to remove as much water as possible before flanging up. vce aire verUOP Nephi Hycoteatng Process Commissvaing After hydrostatic pressure testing, a tightness test must be conducted to check all flanges and fittings, especially the ones opened during hydrotesting. This final tightness test must be witnessed by UOP representatives and is normally done just prior to startup. 4. Acid Cleaning of Compressor Lines Mill scale, dirt, heavy greases, and other foreign materials that could enter the compressor and result in operating and maintenance problems must be removed from the make-up compressor system. The following items must be acid cleaned: a. Allmake-up gas piping including spillback lines b, Make-up compressor suction drums ¢. Make-up gas coolers and intercoolers The exact procedure to be followed should be supplied by the cleaning contractor, who must accept the responsibility of proposing and carrying out an acceptable and proven procedure for the entire cleaning operation. A discussion and general outline for a typical acid-cleaning operation follows: Preparation 1.a. A list of metals, alloys, and non-metallic materials in the sections to be cleaned, including block valve trims, gaskets, valve packings, nuts, ‘exchanger tubing, as well as major equipment and piping must be made. b. Assurance must be obtained from the cleaning contractor that the chemicals and chemical solutions used in the operation will not be injurious to these materials. uop 715, veU0® Nanhna yaronesting Process Commissioning 2a. 10. A list must be made of the safe operating pressures of all components in the sections to be cleaned. Assurance must be obtained by the cleaning contractor that these pressures will not be exceeded (especially if the safety valves in these sections are going to be blinded off; in this case the cleaning contractor should provide safety valves with his equipment). Spool pieces must be made and substituted for turbine meters and for any valves that must be protected from any chemical solutions. Valves which are removed should be cleaned separately and their openings sealed off. Orifice plates must be removed from the lines. All instrument taps in the system must be disconnected or blocked off. Drain points must be provided in the taps to drain off solution, and all instrument drain valves should be opened. All extemally mounted liquid level instruments, such as displacement type lavel transmitters and gauge glasses, should have all block valves adjacent to the vessei closed and all drain valves opened. Pressure gauges and thermowells should not be in place and their connections should be biocked off. All piping strainer screens must be removed. All high points must be provided with vent valves. These vent valves should be opened periodically during the cleaning operations. Major items of equipment such as compressors, pulsation dampeners, etc., must be blinded off. aes veeLUOP Napnina Myaroveatng Process commesoning 14. Cleaning circulation circuits must be determined. For a three stage make-up compressor system, this might mean four separate circulation circuits, one for each stage and one for the incoming fresh hydrogen line. The Acid-Cleaning Operation The acid-cleaning operations can be generally divided into the following steps: 1 Flushing: All sections should be water flushed to remove ail loose dirt, debris, and other foreign material in the lines. It should be noted that process pumps must not be used to circulate any of the flushing, rinsing, or chemical solutions, All transfer and circulating pumps for handling these solutions must be fumished by the chemical cleaning contractor. 2. Degreasing: All sections should be flushed with a degreasing solution (generally an alkaline solution such as a soda’ ash solution) to remove all grease or oil that may have been applied to the lines and vessels as a rust preventative measure. The cleaning contractor should specify the type and concentration of the solution to be used. During this and other phases of the operation, the contractor may want to heat the circulating solutions. In doing so, reboilers or exchangers must not be used as a means of heating them. All heating is to be external to the systems being cleaned and by equipment furnished by the chemical cleaning contractor. After this step, all sections should be rinsed with water. 3. Chemical Cleaning: All sections must be treated with an acid solution to remove all rust and scale from the metal surface. There are several types of cleaning solutions that can be used to do this step (such as inhibited hydrochloric acid or inhibited phosphoric acid); it is the responsibility of the cleaning contractor to select one which has been proven by experience. A suitable inhibitor must also be chosen to reduce the attack on metal. The contractor should specify the concentration to be used and the percentage of uUoO carts: voLUOP Nestina hytotreting Process Conmissionng metal components (such as iron) to be allowed in solution. Afterwards, the acid circulation should be followed by a water rinse. 4, Neutralizing: Ali sections must be flushed with a neutralizing solution (pethaps a soda ash solution) to neutralize ail traces of acid left in the system. The cleaning contractor should specify the type and concentration of the solution to be used. After this step, all sections should be rinsed with water. 5. Passivating: In order to form an anti-rust skin, a solution with a passivating agent must be circulated through each section. Afterwards, each system is allowed to dry. Note that any passivating agent used must meet with UOP's approval and must be flushed from the system prior to startup. After completing the cleaning operation, the vessels and lines should be inspected to determine the quality of the cleaning. Treated surfaces should be clean, rust-free, and dull gray in color. inline turbine meters, valves, strainers, and all other equipment which was removed must be installed. Afterwards, the make-up system must be nitrogen purged and left under nitrogen pressure until the startup. 5. Wash Out Equipment and Break In Pumps After pressure test has been completed on any vessel with its connected piping, receivers, exchangers, etc., required blanks are pulled and water is circulated for the purpose of removing any dirt, scale, etc. Much of the dirt is picked up in the pump screens where it is taken from the system by removing and cleaning the screen. All possible lines and pumps should be used during the washing procedure for complete cleanout of the system. Of course, no water circulation should be carried out in the gas sections of the unit. a, Vessels and Lines Flushing uop jarvee yorLUOP Waghone Hyramatog Process ‘Commisioning All towers and drums should be manually cleaned before flushing. The fire water system should be flushed first and can be used to supply water for flushing the rest of the plant. Before flushing, open overhead vents on vessels (to avoid vacuum), disconnect pump suctions and discharges, cover pump nozzles, and “drop out” or “roll” control valves and orifice plates. Open compressor headers and blank off compressors. Fill vessels with water and flush lines away from vessels or drums, especially if equipped with intemals that could be fouled. Alt lines not flushed by vessel drainage must be flushed independently. Lines connected to exchangers should not be flushed into exchangers but the joint should be disconnected and the exchanger flange covered with a piece of sheet metal. Alter sufficient flushing, the line can be reconnected and water fiushed through the exchanger to the next section of the jine. Reconnect pump suction lines after inttial flushing and insert 1 mm (20 mesh) screen linings in pump strainer and continue flushing, changing to spare pump and cleaning strainers when plugged. This operation should continue until no debris is collected on the strainers. Any equipment that has had water flushed into it should be opened and cleaned manually. Block valves or other valves not “rolled” or “dropped out” should be checked for closure or rolled out for cleaning as required. All equipment blinds not necessary during startup should be removed during or alter the flushing operation. A mechanical flow diagram should be used as a cleaning “checkoff list. uop wes aeLUOP Nacht Hycroeatng Process Commssoning b, Inspection and Running In of Pumps Prior to unit startup, all centrifugal pumps should be thoroughly checked and run in properly (after pressure testing and water flushing) as indicated in the following outline: CAUTION: Many high head pumps are not designed to pump water. To do so can result in damage to the pump intemals. Check the vendor's specifications before attempting to run in pumps with water. 1. Check to see that all necessary water piping has been made to stuffing boxes, bearing jackets, pedestals and quench glands. Make sure that all necessary lube oil piping is installed, and that this piping is not mistakenly connected to the water system. 2, Check arrangements to vent the pump for priming if the pump is not self- venting. See that special connections such as bleeds and drains are properly installed. 3. Check strainers in pump suction lines. Strainers must be installed before aligning pumps. A 4 mm (three to five mesh) strainer is provided for each Pump suction line during startup. To avoid pump damage during flushing with water, the strainers should temporarily be lined with 1 mm (20 mesh) screen. Remove this screen after water flushing is completed. All strainers should be flagged, and a list similar to the blind list should be kept, so as to prevent a “lost” screen from plugging and upsetting unit operation later on. 4. Check that power or steam is available for running in the pump. Check that pressure gauges and any special instrumentation are in working order. ucp 7s viseUO Nach Hyarteaing Process Commssoning 10. iW 12, 13, Water circulation on motor driven hydrocarbon pumps can result in motor overloading if the full pumping capacity is used. In this type of equipment, the capacity must be reduced by throtiling the discharge during such periods. An ammeter can be used to determine the required throttling. Before lubricating oll-lubricated bearings, check bearing chamber in pumps to see that no slushing compounds or shipping grease is left in the chamber. Mechanical-type pumps should be flushed with water prior to pump operation So no dirt gets into the seal and scores the seal faces. itis extremely important that the proper type and viscosity oil and proper grade of grease is used to lubricate the equipment. Refer to manufacturer's instructions and refinery lubricating schedule for this information. See that the driver rotates the pump in the direction indicated by the arrow on the pump casing, Rotate the pump by hand to see that it is clear before starting. Couple up and align the pumps, then check for cooling water availability and start flow of cooling water to the pumps requiring extemal cooling, before they are run in. Open pump suction valve and close discharge valve (crack discharge valve for high capacity, high head pumps). Make sure the pump js full of liquid. Start the pump. As the pump is motor driven, the pump will come up to speed. Immediately check discharge pressure gauge. If no pressure is shown, stop the pump and find the cause. If the discharge pressure is satisfactory, slowly open the discharge valve and give the desired flow rate. Check the amperage of the motor. Do not run the pump with the discharge block valve closed except for a very short time. Note any unusual vibration or operation condition. Check bearings of pumps and drivers for signs of heating. Recheck all oil levels. tyes. vseVOR Napa yoo Press commssoney 14, Run the pump for approximately one hour, then shut off to make any adjustment necessary and check parts for tightness. Since it is not possible to tun the pump at operating temperature, a final check of alignment must be made during normal operation by switching to the spare pump. 15. Start the pump and run it for at least four hours. 46. Shut the pump down and pull the strainer. Clean the strainer and replace it in the suction line. Remove the temporary fine mesh liner from the strainer after water flushing is complete. On a new unit, the screens are sometimes left in service for the first run on all locations where spare pumps have been provided. When water is used for pressure testing and washing, it is sometimes better to have packing in the pumps for a seal to prevent dirt from ruining the mechanical seal. After the lines and equipment are judged to be clean and alll the pumps have been yun in, the water should be drained from the various systems. Lines containing low spots should be broken at the low spot if no drain is provided. Underground lines, without drains, should be blown free of water. Before draining any vessel, a vent must be opened on that vessel so that a vacuum will not be created on draining. If the towers are to be left standing for a long period of time before steam drying or before operation, an inert gas, such as nitrogen or sweet fuel gas, must be introduced to the vessels to prevent rusting of the internals from oxygen in the air, Of course, no water circulation should be carried out through the gas compressors. It is important that the catalyst and the compressors are not exposed to excessive moisture. uop 17098 wasUOP Nannie Hyatoraing Process Comnsioning 6. Break in Recycle Gas Compressor In hydrotreating process unit service, most reciprocating compressors are non- lubricated type machines. The compressors will be started and operated according to the manufacturer's instructions. NOTE: Before starting any reciprocating compressor, the machine should be barred or jacked over by hand to make certain it is free. a. Prestartup Checks There are several points that must be checked before the compressor is ready to run. 1. The lube oil system must be cleaned and temporary 10 Angstrom fitters with 20 mesh wire screen backings must be installed at the lube oil supply to each bearing. The lube oil is then circulated with the 20 Angstrom filters being frequently replaced. When the filters stay clean, they can be removed and the lube oil system is ready for service. 2. The compressor suction line and the suction snubbers should be acidized. This will remove all scale and fine dirt from the suction line that could be swept into the compressor and damage the valves. 3. All trips and alarms, high discharge temperature, low lube oil pressure, etc., must be checked and be operational. In addition, the auxiliary lube oil pump auto start must be functional. 4, The cooling water to the lube oil cooler and cylinder cooling jacket must be commissioned. 5. The oiler for the packing must be filled, and usually has to be manually cranked to supply oil pressure before the machine can be started. uoO ars vise.OP naphineHysroreaing Precoes conmesering 6. Accold alignment check must be made. After the machine has been run, a hot check must be made. For reciprocating compressors, the method for placing the machine on line should be similar to the following: b. Startup Procedure for the First Compressor 1. Purge the compressor with nitrogen, if hydrogen is to be used, through the suction purge valve to the flare or the atmospheric vent line. As hydrogen may not be available, nitrogen or air probably can be used. Be sure not to over-load the horsepower requirement of the motor. 2. Roll the machine over to ensure complete purging. 3. After nitrogen purging of the machine, introduce hydrogen to the compressor via the hydrogen pressuring line or by cracking open the suction block valve. 4, After partially pressuring the compressor with hydrogen or other gas to be used, roll the machine over and vent the hydrogen to the flare or through the atmospheric vent to displace nitrogen in the machine. 5. Gradually open the compressor suction valve to pressure up the machine to line pressure. 6. Start steam to the steam tracing. Drain the suction line and snubbers of any liquid. 7. Make sure that there are no restrictions to the gas flow from the compressor. Open any upstream flow control valves or spillback control valve prior to starting the machine. 8. If the machine is fully equipped with suction unloader valves, start up the machine as follows: uoD PHS war(VOP naphinabycrouesing Process Commissioning ce. {a) After the machine is pressured with hydrogen, close the small bypass vent line, unload all of the suction valves, and open the compressor discharge line. (b) Check the compressor's lubricating oil fevel in the crank case or reservoir, (c) Start the compressor and check the oil pressure. {d) Let the compressor idle for a few minutes while closely watching the suction temperature. Then close the suction valve loaders to put the machine on line. Follow the manufacturer's loading sequence if he has specified one. Startup Procedure for the Second and Consecutive Compressors Purge the compressor with nitrogen through the suction purge valve to the flare or the atmospheric vent line. Roll the machine over to ensure complete purging. After nitrogen purging of the machine, introduce hydrogen to the compressor via the hydrogen pressuring line or by cracking open the suction block valve. After partially pressuring the compressor with hydrogen, roll the machine over and vent the hydrogen to the flare or through the atmospheric vent to displace the nitrogen in the machine. Gradually open the compressor suction valve to pressure up the machine to line pressure. Start steam to the steam tracing or the in-line jacket heater. Drain the suction line and snubbers of any liquid. If the machine is fully equipped with suction unioader valves, start the second compressor as follows: siete. aeLUOP naphine Hyowening Proosss conmesioing (a) After the machine is pressured with hydrogen, close the small bypass- vent line, unload all of the compressor suction valves, and unblock the compressor discharge line. Since the compressor discharge valves will act as check valves, the gas from the operating machine will not flow back to the suction through the machine which is being started. (b) Check the compressors lubricating oil level in the crackcase of reservoir. (©) Start the machine and check the oll pressure. {d) Let the compressor idle for a few moments while closely watching the suction temperature, then close the suction valve loaders to put the machine online. Follow the manufacturer's loading sequence if he has specified one. 8. When placing the second or additional compressors in operation in booster service, the instrumentation must be in operation in booster service, the instrumentation must be in operation so that excess flow can be spilled back to the suction through normal channels. 9. Load the suction valve loaders as necessary to put the machine in operation fully. d. Maintenance Suggestions for Reciprocating Non-Lubricated Compressors During operation in naphtha hydrotreating service, a fine, gray, powder-like deposit may collect on the intemals of the machines. This material is soluble in hot water. It is non-corrosive when dry, but when exposed to the air, it absorbs moisture readily and then becomes corrdsive not only to iron and carbon steel, but also to all stainless chrome steels, especially it they have been hardened. For protection of the valves, heads, and cylinders, steps must be taken to avoid contact with air whenever possible. Several precautions will assist in this matter. op a8 isoUOe Naphins Hydrating Process Commissioning The valves should be freed of salts as soon as they are removed from the machine. This is easily done by washing in a bucket of hot water which will dissolve off the corrosive powder, The valves can be tested for leakage with water during this procedure. Prolonged soaking in the water should not be done, since the acidic compounds which will build up in the water can also damage the parts. When the valves are removed from the hot water, they will dry very quickly and are then ready for reinstallation. If the valves are to be stored for some time, it is advisable to apply a coating of light oil to the valve faces to prevent possible rusting. This oi] should be removed before the valve is again installed in a machine. In order to inspect the piston and rings, it is necessary to remove the outboard head ‘of the cylinder, remove the road from the crosshead, and pull the piston out far enough to view the rings. The dust should be wiped from the intemal surfaces with alint-free cloth when possible. If the piston is entirely removed, the exposed cylinder bore and valve seating surfaces should be covered with a light coat of oil to avoid contact with air and thus prevent corrosion of the honed and polished surface of the bore. All of this oil should be removed before the piston is again installed. The bore can be plugged. with a pump cup or other similar plus to assist in protection from the atmosphere. A steam hose can be used to remove the powder and scale from the cylinder gas passages, but before doing this, the valve ports must be blocked to avoid getting steam or water on the highly finished cylinder bore surface. It must be emphasized that extreme care be taken if such cleaning is attempted. When the machines are assembled before the rest of the plant is ready for operation, they should be blanketed with gas to avoid contact with air. Close the biock valves and fill the compressors to about 0.3 kg/om2g (5 psig) with nitrogen from a cylinder after purging out all of the air in the system. uop ans. weeo9 actin sytoetg Paces Commies @. Lubricating Oil — Seasonal Changes Naphtha hydrotreating reciprocating compressors are normally installed in outdoor locations. Therefore, the proper weight and quality of lubricating oil in the crankcase must be used during the various seasons of the year and oil should be changed with the seasons, particularly in cold climates. Use the manufacturer's recommended type of oil for the anticipated temperature. 7. Service and Calibrate Instruments. Normally, instrument lead lines will be tested hydrostatically up to block valves when the balance of the unit is tested. Hydrostatic test pressure will not be made on instruments which normally handle gas and no pressure-measuring element should be subjected to test pressures above its range. Also, never pull a vacuum on a pressure instrument or gauge unless it is specifically designed for it. All instrument air piping should be tested at 7 kg/cm?g (100 psig) with compressed air. Soap should be used on all joints to check for leakage. Care should be taken to ensure that this high air pressure is not put on any instruments or control valve diaphragms. Likewise, when pressure testing the unit, care must be taken that the fuel gas pressure balance valves are blinded off to keep high pressure off the diaphragm. Before starting up, all instruments should be serviced and calibrated. This includes carefully measuring all orifice plate bores with a micrometer, 8. Dry Out Fired Heaters: Before a heater is put into service for the first time, it will be necessary to slowly expel the excess moisture from the insulating conerete (setting) by gradually raising its temperature before any appreciable load is put on the heater. To be assured of a tong heater life with minimum maintenance, this work must be done with extreme care. If the heaters are UOP heaters, UOP Heater Specification 2-18 or 2-19 (whichever applies) must be carefully adhered to for the drying operation. If they are non-UOP heaters, the manufacturer's drying procedures should be followed; however, the general procedure utilized is usually similar to the following: uop saris watUO Naphine Hyaveatng Process commssioag a. General Procedure During the initia! heater refractory drying out period, it is preferable that no material be flowing through the tubes, 1. Make a temporary installation of thermocouples through the pipe sleeves in the hip section of the heater. The tips of these thermocouples should extend 150 mm (6 inches) beyond the inside of the insulating concrete, but should not contact the tubes. 2. It is preferable to use gaseous fuel {refinery gas or LPG) for drying out the setting. If no gas is available, liquid fuel may be used, but it should be free of sediment and heated as required to give the proper viscosity (about 200 SSU) for good atomization and clean combustion. 3. Light one or more burners, as required, in each section of the heater and fire slowly, so that the temperature, as indicated by the hip thermocouples, is increased at a rate of about 14°C (25°F) per hour until it reaches 482°C (900°F). Hold this temperature for 10 hours, or 2 hours per inch of refractory thickness, whichever applies. 4. While increasing the temperature, the bumer operation should be rotated frequently in order to distribute the heat as evenly as possible over the entire length of the setting. 5. After the 10-hour holding period, all burners should be shut off and the heater setting allowed to cool slowly by keeping the air inlet doors and stack damper(s) fully closed. 6. Alter drying has been accomplished, the temporary hip thermocouples should be removed and the plugs replaced in the pipe sleeves. If the setting has been dried as outlined above, temperature may be subsequently raised or lowered at any desired rate within the design limits of the heater. b, For Gas-Fired Heaters uop ee vise{YOR nachna Hycroreeing Process Somerisining 1. When unit is shut down, always blind off the fuel gas supply line because gas may leak through the block valves at the heaters and fill a fumace. 2. Before starting to light any pilot bumer, see that all individual bumer block valves are closed and steam out firebox to remove any gas accumulation. Make sure the damper is opened, Steam out the box until a steady plume of steam can be seen rising out of the stack. Stop steaming and pinch in the damper. 3. When all pilot bumers are lit, ight each bumer individually by opening the gas valve to each bumer after the torch is inserted in front of the bumer. After a few bumers are lit, it will be necessary to open the damper to provide enough draft to light the remainder of the bumers. 4, Bumers should be fired to produce a blue flame with a yellow tip, obtained by regulating the primary and secondary air supply. The heaters should be checked frequently for dirty bumers which might give either too long, too short, or a misdirected flame. There must be some excess of air to the bumers so that an increase in fuel gas flow will have sutficient air to produce complete combustion. 5. _ If for any reason the fires in a heater go out: (a) Shut off gas supply immediately by closing the block valves at the fuel gas control valves. Bypass and pilot lines which might be open around the control valves must also be closed. {b) Put snuffing steam in the firebox. (©) Close alt individual bumer valves. 6. As in all heaters, care should be taken that no flame impingement on the tubes is permitted. uop nates vag[UOP napa Hycroreaing Process Commesoning c. For Oil-Fired Heaters 1. When the unit is shut down and before entering heaters, always double block the oil supply line on both the supply and retum headers and pull the oil guns from the bumers as oil may ieak through the block valves at the heaters and fill a furnace. 2. Before starting to light any pilot bumers, see that all individual oil guns are removed from the bumers, and steam out the firebox and header to remove any gas accumulation. Make sure that the dampers are opened slightly. 3. Oil bumers without gas pilots should be lighted from a regulation torch. When there is a gas pilot, light it first and then light the oil from the pilot. Have fuel oil circulating through the fuel oil return at normal operating temperature. 4. Bumers should be fired to produce a yellow.flame with a good pattem obtained by regulating the primary and secondary air supply. The furnaces should be checked frequently for dirty burners which might give either too long, too short, or a misdirected flame. There should be some excess air to the bumers so that an increase in fuel flow will have sufficient air to produce complete combustion. 5. Iffor any reason the fires in the fumace go out, then: (a) Shut off the fuel supply immediately. Do this by closing the main block valve in the fuel supply to the fumace. This will take care of any bypass lines which might be open around the control valves. Be sure the check valve on the fuel oil return does not ieak allowing fuel to back into the firebox. (b) Put snuffing steam in the firebox, (0) Block in the pilot gas line. close individual bumer valves. uop nas VidLUOP NaphinaHytctmating Process Commissioning 6. 9 As in all heaters, care should be taken that no flame impingement on the tubes is permitted. Safe Procedure for Lighting Oil Burners: Push the oil gun forward, and then tum on steam by fully opening the steam block vaive and the steam control valve. Close off when the steam is dry. Make sure the oil block valve is closed, then open the steam bypass valve to clean and warm the bumer. When condensate has been removed and the steam is dry (dry steam is invisible), close the bypass steam valve. Adjust atomizing steam valve for a small flow of steam, ‘Open oil block valve gradually until the oil starts buming. The oil will ignite from the pilot gas flame or an oil torch. Take care to see that unbumed oil is not put into the firebox. Accumulated oil will become hazardous as the firebox heats up. Adjust the atomizing steam vaive and cil valve to obtain correct flame pattem. Never let the flame touch the tubes. Reactor Circuit Dry Out tis not necessary for the reactor circuit to be bone dry, but any free water should be removed. Drain all low points in the system and air blow the lines as dry as possible. individual charge heater passes should be blown clear separately to ensure that no liquid pockets are present. Small amounts of moisture are not harmful to the catalyst, but care must be taken so it does not become wet. 7s. ws\UOP Neptta Hyaravsuing Process commisining 40. Catalyst Loading For the catalyst loading to go smoothly, well-thought out planning and thorough preparation must be done prior to the actual loading. It must be determined how the catalyst will be loaded and what materials, equipment, and personnel will be required to do the loading. (See Catalyst Loading discussion in Section XIII.) 11. Purging and Gas Blanketing It must be remembered that oil or flammable gas should never be charged into process lines or vessels indiscriminately. The unit must be purged before admitting hydrocarbons. There are many ways to purge the unit and ambient conditions may dictate the procedure to be followed: nitrogen or inert gas purging, displacement of air by liquid filling followed by gas blanketing, or steaming followed by gas blanketing. For the remainder of the unit other than the reactor section, steam purging followed by fue! gas blanketing can be used to air free the unit. The following steps will briefly outline this method. Potential problems or hazards could develop during the steam purge are as follows: a. Collapse due to vacuum: some of the vessels are not designed for vacuum. This equipment must not be allowed to stand blocked in with steam since the condensation of the steam will develop a vacuum. Thus, the vessel must be vented during steaming and immediately followed up with fuel gas purge at the conclusion of the steamout. b. Flange and gasket leaks: thermal expansion and stress during warm-up of equipment along with dirty flange faces can cause small leaks at flanges and gasket joints. These must be corrected at this time. c. Water hammering: care must be taken to prevent “water hammering” when steam purging the unit. Severe equipment damage can result from water hammering uop aris viasLUOP Nepean biycotaatng rocoss Conmaseoning Block in the cooling water to all coolers and condensers. Shut down fans on fin-fan coolers and condensers. Open high point vents and low point drains on the vessels to be steam purged. Start introducing steam into the bottom of the columns, towers, and at low points of the various vessels. It may be necessary to make up additional steam connections to property purge some piping which may be “dead-ended.” Thoroughly purge all equipment and associated piping of air. Be sure to open sufficient drains to drain condensate which will accumulate in low spots and receivers. When purging is completed, close ail vents and drains. Start introducing fuel gas into all vessels and cut back the steam flow until it is stopped completely when the systems are pressured. Regulate the fuel gas flow and the reduction of steam so that a vacuum due to condensing steam is not created in any vessel or that the refinery fuel gas system pressure is not appreciably reduced. Cc. INITIAL STARTUP: 1, Discussion This procedure is designed to prepare UOP Hydrobon® catalyst for service in the fastest and safest manner without sacrificing catalyst activity or cycle length. If the procedure Is not followed, catalyst activity or cycle length may be diminished, or equipment may be damaged, The procedure has been prepared for a startup with fresh or freshly regenerated catalyst. It is not intended to apply to individual units and refinery situations. THE PURPOSE OF THIS PROCEDURE |S TO PROVIDE GUIDELINES FOR THE REFINER WHEN HE iS PREPARING SPECIFIC PROCEDURES FOR AN INDIVIDUAL UNIT. op nous vrUO? WapninsHycciraaing Process Commissioning Fresh or freshly regenerated Hydrobon® Hydrotreating catalyst is a complex of metal and nonmetal oxides. During normal operation, the catalyst exists as a complex of nonmetal oxides and metal sulfides. Conversion of the metals from oxides to sulfides during startup must be done in a careful, prescribed manner in order to achieve optimum catalyst activity. An improper startup can result in depressed catalyst activity, reduced catalyst stability and possible temperature runaways. ‘The startup naphtha used to sulfide the Hydrobon® catalyst should be straight run material with a maximum end point of 205°C (400°F) and a bromine number of 1 or less. This minimizes the possibility of polymerization taking place in the reactor at lower temperatures, and avoids excessive heat of reaction due to olefin hydrogenation during sulfiding. In the event that the startup naphtha is quite low in sulfur, organic sulfur may be added to the feed to the unit in order to reduce the time required for sulfiding. Typically the sulfiding procedure should take 8 - 12 hours. If the time is too short it will be difficult to properly monitor the H2S in the recycle gas and insure that all the metal sites were properly sulfided. Too long a sulfiding period can start to affect the catalyst and may have some impact on the metal oxide state. The objective is to conduct the sulfiding in a controlled, orderly fashion. Sulfur compounds added to the charge for accelerated sulfiding may be any light, liquid, organie sulfur compound (e.g., dimethyl sulfide, propyl or butylmercaptan) which will easily decompose in the system. HoS may be used in place of a liquid sulfur compound, but the source must be examined for detrimental contaminants such as olefinic gases, suifur oxides, carbon oxides, and ammonia, which may damage the catalyst. The total detrimental contaminants in the H,S-tich gas should be limited to a maximum of 0.1 mol%. Disulfides, such as carbon disulfide, are not recommended for sulfiding, since there is a safety and handling problem. Also carbon disulfide (CSz) may not hydrogenate completely at sulfiding temperatures, resulting in excessive coking of the catalyst. There is also evidence that a temperature runaway is more likely than when using other sulfides. op. teens ieLUOP haphinaHyarovsatng Process Cornistoning The following table is a list of common sulfiding agents and their associated properties. $A-200 DMS DMDS. NPS. (UOP) ‘Sulfur, wt% 40 51 68. 37 Specitic Gravity @ 60°F 1.045 0.854 1.06 1.03 Thermal Decomposition] 320 482 392 320 Temp, °F Since feed must be started to the unit while the system is relatively cold, the reactor charge heater flow will be two phase during the period temperatures are being increased. For units with a multiple pass charge heater, a coil could be damaged if it were blocked by a liquid pocket and the heater firing continued. To ensure that the feed to the heater becomes single phase (all vapor) at relatively low temperatures, the reactor inlet pressure is initially limited to 14 kg/em?g (200 psig) When a Platforming Unit is the only potential source of hydrogen for startup and the Naphtha Hydrotreating Unit will be supplying charge for the Platforming Unit, a sweet, stripped, low-sulfur naphtha should be stored prior to the unit shutdown for startup purposes. It is strongly recommended that a hydrotreated naphtha be made available, but when this is not possible, straight run naphtha may be used, subject to the following limitations: Total sulfur 100 wt ppm maximum Total nitrogen 1 wt ppm maximum Arsenic 5 wt ppb maximum Lead 25 wt ppb maximum Halides 1 wt ppm maximum Distillation endpoint 205°C (400°F) maximum Bromine No. 1 maximum Aromatics 15 vol-% maximum op wats vas(UOP Nach Fycronsatng Process commesaning The above stock may also be used for sulfiding the Hydrobon® catalyst if a sufficient amount is available, particularly if it is planned to sulfide using additional organic suifur or H2S. The charge stock to the Platforming Unit should be as free of water as possible during the startup, The Naphtha Hydrotreating Unit fractionation or stripping section should be in service with reflux if possible, preferably at about the design rate prior to routing naphtha to the Platforming Unit. PRECAUTION: HYDROGEN SULFIDE (HS) IS A POISONOUS GAS During sulfiding of the hydrotreating catalyst, hydrogen sulfide will be released to the gas and liquid streams of the unit as sulfur-bearing compounds are decomposed. Hydrogen sulfide may also be utilized as additional sulfur in the sulfiding step. The safety procedures for handling H2S should be reviewed with the appropriate operating personnel before starting the unit. Make certain that each person in the operating area is familiar with the dangers of H2S, approved methods for handling it, and first aid in case of HS poisoning. PRECAUTION Organic sulfur-bearing compounds which may be used for adding sulfur to the Naphtha Hydrotreater charge are dangerous materials. Make certain that each person in the operating area is familiar with the dangers of the materials being used, approved methods for handling them and appropriate first aid procedures in case of contact with the materials. 2. Detailed Procedure -— Fresh or Freshly Regenerated Hydrobon® Catalyst Naphtha Hydrotreating Unit NOTE: This procedure is general in nature and is not intended to cover every possible mechanical and process combination. Before proceeding with a startup, each unit should be examined and a detailed procedure should be prepared to deal with that specific unit. Particular care should be taken not to exceed equipment limitations. uop saris. viseUOP Napie Hyowtog Process Comisstoning 4, Remove oxygen from the fractionation or stripping section of the unit following the suggested procedure described in the commissioning section of the manual or normal refinery practices. 2. Establish acceptable startup naphtha charge to the fractionation or stripping section, and establish heat input (if possible) to allow a sufficient reflux/feed volume ratio (0.25 on a stripper) to remove essentially all water from the bottoms product. Slowly heat-up of the column bottoms at a rate of 20°C (35°F) per hour. When the temperature approaches 100°C (212°F) reduce the heat-up rate to 10°C (18°F) per hour to allow any water in naphtha to expand slowly. After most of the water has been sent overhead, then the temperature can be increased to the required. 3. fan associated Platforming Unit is the only source of makeup hydrogen to the naphtha hydrotreater, the Platforming Unit must be placed on stream. If hydrogen-rich makeup gas is to be supplied from an independent source, ensure that a sufficient supply is available. Hydrogen will be used to pressure the reactor circuit, after the last vacuum, up to the various operating pressures detailed below. During the sulfiding procedure some hydrogen will be dissolved in the naphtha stream and thus some hydrogen will be lost out of the Stripper column. Hydrogen-rich makeup gas supplied from an independent source should be at least 75 mol-% hydrogen, and should be sufficient to maintain the hydrogen to hydrocarbon at a minimum of 35 nm3/m3 (200 SCFB) with the reactor products separator at 28 kg/cm2g (400 psig) (or at design if the design pressure is lower). It should contain less than 0.5 mok% sulfur and carbon oxides, less than 0.5 mol-% unsaturated hydrocarbons, and less than 50 mol ppm halides. 4, Evacuate the reactor section to 500-600 mm of mercury (20-25 in. of Hg) vacuum, and hold for at least 30 minutes to check the tightness of the unit. Vacuum loss should be less than 25-50 mm of Hg/hour (1-2 inches of Ha/hour). Break the vacuum with nitrogen to 0.3 kg/em2g (5 psig). Evacuate uop vans wise[BOP nachna Yyaranesig Process Commissioning 5. and purge with nitrogen a second time. Pull a third vacuum and break with hydragen, NOTE: Any time the unit has been opened (i.e., for maintenance or catalyst regeneration), a pressure test should be conducted to ensure the tightness of the unit. Pressure the reactor section to 14 kg/cm2g (200 psig) with hydrogen, and establish once-through or recycle gas flow at the maximum possible rate. {f reactor temperatures are between ambient and 150°C (00°F), charge startup naphtha to the reactor section at approximately one-half of the design charge rate. Continue the bypass flow to the stripper. If any reactor temperature is above 150°C (300°F), cool the reactor with gas flow so that all catalyst temperatures are below 150°C (300°F) before bringing startup naphtha into the unit if the catalyst is fresh or freshly regenerated. When a liquid level is established in the reactor products separator, discontinue routing startup naphtha directly to the stripper section. Make the transition smoothly so that downstream units are not upset. Maintain the naphtha hydrotreater feed rate at approximately one-half of the design charge ate. For a hydrotreater startup with an independent source of makeup hydrogen, it is preferable to circulate the naphtha used for sulfiding from the stripping section, through cooling and back to the feed section, making up naphtha as necessary. This minimizes the production of off-specification material during the startup. Purge the reactor charge heater firebox and light fires following normal refinery practice. Increase the reactor inlet temperature to 230°C (450°F) at approximately 30°C/hr (50°F/hr). Maintain a minimum hydrogen to hydro- carbon ratio of 35 nmS/m3 (200 SCFB) and maintain the reactor products separator pressure at 14 kg/emég (200 psig). NOTE: Throughout this phase of the sulfiding, monitor the separator boot for water accumulation. When water Is detected, drain it from the separator. nrms vseUDP nach Hyung Process Commissioning 10. NOTE: For those units with a multiple-pass reactor charge heater, the individual charge heater pass outlet temperatures should be checked at least every 5 minutes as the heater outlet temperature is increased. If one or more pass outlet temperatures lag behind, this could indicate a liquid seal or pocket obstructing flow. This may cause localized overheating of the tube(s). If this ‘occurs, shock the system momentarily by changing the charge flow abruptly. If the seal persists, lower temperatures and shock the system again by abruptly changing the charge rate. If the seat persists, stop heater firing, stop the naphtha charge and make certain the pass is cleared before restarting charge to the unit. Ensure that the heater is not overfired during any of these activities. A iiquid seal can be broken or prevented by adjusting the flow so that the charge heater delta P is greater than the head developed by a liquid pocket in any pass. After the reactor inlet and outlet temperatures have been stabilized at 230°C (450°F), increase the reactor products separator pressure to the normal operating level or 28 kg/cm2g (400 psig), whichever is lower. ‘At 230°C (450°F), sulfiding will take place using the native sulfur in the charge. If this proves to be a time-consuming operation (assume 90% desulfurization of the native sulfur), additional sulfur in the form of an organic sulfur compound may be added to the feed, or H2S may be added to the gas to the reactor. The total amount of sulfur charged to the catalyst (native plus added) should not exceed 0.25 wt-% of the naphtha charge at this point, However, to extend the sulfiding periad for better control, the total amount of sulfur injected should be controlled at 0.08 ~ 0.10 wt% of the naphtha charge, depending on the catalyst metal loading. Calculate the sulfur injection rate required, for the actual catalyst loaded, so that the sulfiding step takes 8-12 hours. Hold the reactor inlet temperature at 230°C (450°F) and maintain a minimum hydrogen to hydrocarbon ratio of 35 nm?/m3 (200 SCFB). Increase the feed rate to design, or the maximum available. saris esoLVOP Aaohihe Hytorecing Process Commissioning 11. 12. 13. 14, 15. NOTE: In the event of a rapid reactor outlet or catalyst temperature rise above 250°C (480°F), stop sulfur addition (whether H2S or organic sulfur is to be added) to the unit immediately and reduce the firing in the reactor charge heater. If necessary, stop the charge to the unit to limit the temperature rise. When temperature control is regained, adjust the reactor inlet temperature to 230°C (450°F), and slowly restart sulfur addition to the unit. When unspiked start-up oil is used for catalyst sulfiding and if the conditions indicate very little desulfurization is taking place at 230°C (450°F) catalyst temperatures, then the bed peak temperature can be increased slowly up to a maximum of about 250°C (480°F). It should not be necessary to exceed a 230°C (450°F) catalyst peak temperaure if an organic sulfiding compound is being added. During the sulfiding period, increase the stripping section reflux ratios as much as possible to remove any H28, water, or light mercaptans which might otherwise contaminate the product. If necessary, the operating pressure of the fractionation or stripping section should be reduced to obtain sufficient material for reflux. If additional sulfur is used, after the unit has stabilized at 0.08 — 0.10 wi% (maximum 0.25 wt-%) sulfur in the reactor feed, smoothly increase the amount of added sulfur until the total sulfur being charged to the catalyst is 0.15 — 0.20 wt% (maximum 0.50 wt-%) of the naphtha charge. Maintain 230°C (450°F) reactor inlet temperature and continue sulfiding. Drain water from the reactor products separator and the fractionation or stripping section water boots as it accumulates. Continue sulfiding at these conditions for a period of 1-2 hours. Increase the reactor inlet temperature to 290°C (550°F) at a rate of 17°C (30°F) per hour. NOTE: Do not exceed 17°C (30°F) temperature rise across any catalyst bed. five eseUOP Napa Hyrssang Process commsning 16. The catalyst can be considered sulfided when the total amount of sulfur injected has reached the maximum shown in the following Table. Sulfur Level, Based on Hydrobon® Catalyst Loaded Catalyst Weight S6 6.0 wt-% So 6.0 wt-% $12 B.5 Wt-% S-12H 9.0 wt-% $127 B85 Wt-% S-15 4.5 wt-% S16 8.5 we% $-18 6.0 WE-% S-19H 9.0 wt-% S-19T 10.5 w1-% ‘S-19M 8.5 wIH-% $120 9.6 we% N-204 7.2 we% N-108 9.4 we% HC-K 11.3 wt-% 17. Establish normal plant operation in the following sequence: a. Adjust naphtha charge to the desired rate. b. Increase the reactor inlet temperature to 315°C (600° temperature as required to produce on-specification product. Adjust c. Increase the reactor products separator pressure to normal, if this was not done in Step 9. d. Increase the hydrogan-to-hydrocarbon ratio to normal, if this was not already done. uoo 17985 vss1UOP Napnina Hyeatng Process Commssnng e. For units that process charge different from the startup naphtha, normai charge can now be routed to the unit and startup naphtha stopped. The change should not be made abruptly to avoid upsets, and control of the reactor temperatures is maintained. {. _ Establish water injection to the reactor products condenser, just after the last combined-feed exchanger bundle, at a rate equal to 3 liquid volume- % of the charge rate. uoO 497005 VEEUOP Nachina Hyctaxting Proce Nema Sane Vil. NORMAL STARTUP A. Discussion This procedure is designed to prepare UOP Hydrobon® catalyst for service in the fastest and safest manner without sacrificing catalyst activity or cycle length. If the procedure is not followed, catalyst activity or cycle length may be diminished, or ‘equipment may be damaged. The procedure has been prepared for a startup with fresh or freshly regenerated catalyst. It is not intended to apply to individual units and refinery situations. THE PURPOSE OF THIS PROCEDURE |S TO PROVIDE GUIDELINES FOR THE REFINER WHEN HE IS PREPARING SPECIFIC PROCEDURES FOR AN INDIVIDUAL UNIT. Fresh or freshly regenerated Hydrobon® Hydrotreating catalyst is a complex of metal and nonmetal oxides. During normal operation, the catalyst exists as a complex of nonmetal oxides and metal sulfides. Conversion of the metals from oxides to sulfides during startup must be done in a careful, prescribed manner in order to achieve optimum catalyst activity. An improper startup can result in depressed catalyst activity, reduced catalyst stability and possible temperature runaways. The startup naphtha used to sulfide the Hydrobon® catalyst should be straight run material with a maximum end point of 205°C (400°F) and a bromine number of 1 or less. This minimizes the possibility of polymerization taking place in the reactor at lower temperatures, and avoids excessive heat of reaction due to olefin hydrogenation during sulfiding, In the event that the startup naphtha is quite tow in sulfur, organic sulfur may be added to the feed to the unit in order to reduce the time required for sulfiding. Typically the sulfiding procedure should take 8 - 12 hours. If the time is too short it will be difficult to properly monitor the HeS in the recycle gas and insure that all the metal sites were properly sulfided. Too long a sulfiding period can start to affect the Platforming catalyst and may have some impact on the metal oxide state. The objective is to conduct the sulfiding in a controlled, orderly fashion. uop Hes vm{UOP Naoki Hyorteatng Process Noma! simp Sulfur compounds added to the charge for accelerated sulfiding may be any light, liquid, organic sulfur compound (e.g., dimethyl sulfide, propyl or butyimercaptan) which will easily decompose in the system. H2S may be used in place of a liquid sulfur compound, but the source must be examined for detrimental contaminants such as olefinic gases, sulfur oxides, carbon oxides, and ammonia, which may damage the catalyst. The total detrimental contaminants in the H2S-rich gas should be limited to a maximum of 0.1 mol-%. Disulfides, such as carbon disulfide, are not recommended for sulfiding, since there is a safety and handling problem. Also carbon disulfide (CS2) may not hydrogenate completely at sulfiding temperatures, resulting in excessive coking of the catalyst. There is also evidence that a temperature runaway is more likely than when using other sulfides. The following table is a list of common sulfiding agents and their associated properties. ‘SA-200 DMs OMDS TNPS (UOP) Sulfur, wt% 40 51 68 7 Specific Gravity @ 60°F 4.045 0.854 1.06 4.03 Thermal Decomposition] 320 482 392 320 Temp, °F Since feed must be started to the unit while the system is relatively cold, the reactor charge heater flow will be two phase during the period temperatures are being increased, For units with a multiple pass charge heater, a coil could be damaged if it were blocked by a liquid pocket and the heater firing continued. To ensure that the feed to the heater becomes single phase (all vapor) at relatively low temperatures, the reactor inlet pressure is initially limited to 14 kg/cm2g (200 psig). When a Platforming Unit is the only potential source of hydrogen for startup and the Naphtha Hydrotreating Unit will be supplying charge for the Platforming Unit, a sweet, stripped, low-sulfur naphtha should be stored prior to the unit shutdown for startup purposes. It is strongly recommended that a hydrotreated naphtha be made uee hme vueOP Nephina Mycareating Paces Noma! Stare available, but when this is not possible, straight run naphtha may be used, subject to the following limitations: Total sulfur * 100 wt ppm maximum Total nitrogen 1 wt ppm maximum: Arsenic 5 wt ppb maximum Lead 25 wt ppb maximum Halides 4 wt ppm maximum Distillation endpoint 205°C (400°F) maximum Bromine No. 1 maximum Aromatics 15 vol-% maximum The above stock may also be used for sulfiding the Hydrobon® catalyst if a ‘sufficient amount is available, particularly if it is planned to sulfide using additional organic sulfur or HpS. The charge stock to the Platforming Unit should be as free of water as possible during the startup. The Naphtha Hydrotreating Unit fractionation or stripping section should be in service with reflux if possible, preferably at about the design rate prior to routing naphtha to the Platforming Unit. PRECAUTION: HYDROGEN SULFIDE (H2S) IS A POISONOUS GAS: During sulfiding of the hydrotreating catalyst, hydragen sulfide will be released to the gas and liquid streams of the unit as sulfur-bearing compounds are decomposed. Hydrogen sulfide may also be utilized as additional sulfur in the sulfiding step. The safety procedures for handling H»S should be reviewed with the appropriate operating personnel before starting the unit. Make cettain that each person in the operating area is familiar with the dangers of HoS, approved methods for handiing it, and first aid in case of H2S poisoning. PRECAUTION Organic sulfur-bearing compounds which may be used for adding sulfur to the Naphtha Hydrotreating Unit charge are dangerous materials. Make certain that op 10705 msUO Nephi Hycrorartng Process ‘Norma! Stamp each person in the operating area is familiar with the dangers of the materials being used, approved methods for handling them and appropriate first aid procedures in case of contact with the materials. B. Detailed Procedure - Fresh or Freshly Regenerated Hydrobon® Catalyst Naphtha Hydrotreating Unit NOTE: This procedure is general in nature and is not intended to cover every possible mechanical and process combination, Before proceeding with a startup, each unit should be examined and a detailed procedure should be prepared to deal with that specific unit. Particular care should be taken not to exceed equipment limitations. 1. Remove oxygen from the fractionation or stripping section of the unit following the suggested procedure described in the commissioning section of the manual or normal refinery practices. 2, Establish acceptable startup naphtha charge to the fractionation or stripping section, and establish heat input (if possible) to allow a sufficient refluxfeed volume ratio (0.25 on a stripper) to remove essentially all water from the bottoms product. Slowly heat-up of the column bottoms at a rate of 20°C (85°F) per hour. When the temperature approaches 100°C (212°F) reduce the heat-up rate to 10°C (18°F) per hour to allow any water in naphtha to expand slowly. After most of the water has been sent overhead, then the temperature can be increased to the required. 3. _ If-an associated Platforming Unit is the only source of makeup hydrogen to the Naphtha Hydrotreating Unit, the Platforming Unit must be placed on stream. If hydrogen-rich make-up gas is to be supplied from an independent source, ensure that a sufficient supply is available. Hydrogen will be used to pressure the reactor circuit, after the last vacuum, up to the various operating pressures detailed below. During the sulfiding procedure some hydrogen will tbe dissolved in the naphtha stream and thus some hydrogen will be lost out of the Stripper Column. uop rs viaLUOP nzpniha Mysroraetny recess omal Sie Hydrogen-rich make-up gas supplied from an independent source should be at least 75 mok% hydrogen, and should be sufficient to maintain the hydrogen to hydrocarbon ratio at a minimum of 35 nm8/m$ (200 SCFB) with the reactor products separator at 28 kg/cm?g (400 psig) (or at design if the design pressure is lower). it should contain less than 0.5 mol-% sulfur and carbon oxides, less than 0.5 mol-% unsaturated hydrocarbons, and less than 50 mol ppm halides. 4. Evacuate the reactor section to 500-600 mm of mercury (20-25 in. of Hg) vacuum, and hold for at least 30 minutes to check the tightness of the unit. Vacuum loss should be less than 25-50 mm of Hyhour (1-2 inches of Hg/hour), Break the vacuum with nitrogen to 0.3 kg/em?g (5 psig). Evacuate and purge with nitrogen a second time. Pull a third vacuum and break with hydrogen. NOTE: Any time the unit has been opened (ie., for maintenance or catalyst regeneration), a pressure test should be conducted to ensure the tightness of the unit, 5. Pressure the reactor section to 14 kg/em2g (200 psig) with hydrogen, and establish once-through or recycle gas tlow at the maximum possible rate. 6. If reactor temperatures are between ambient and 150°C (300°F), charge startup naphtha to the reactor section at approximately one-half of the design charge rate. Continue the bypass flow to the stripper. If any reactor temperature is above 150°C (300°F), cool the reactor with gas flow so that all catalyst temperatures are below 150°C (300°F) before bringing startup naphtha into the unit if the catalyst is fresh or freshly regenerated. 7. When a liquid level is established in the reactor products separator, discontinue routing startup naphtha directly to the stripper section. Make the transition smoothly so that downstream units are not upset. Maintain the naphtha hydrotreating feed rate at approximately one-half of the design charge rate. For a hydrotreating startup with an independent source of make- up hydrogen, it is preferable to circulate the naphtha used for sulfiding from the stripping section, through cooling and back to the feed section, making up uop ns vesUOP Mecha Hreouening Process Noma Sane 10. naphtha as necessary. This minimizes the production of off-specification material during the startup. Purge the reactor charge heater firebox and light fires following normal refinery practice. Increase the reactor inlet temperature to 230°C (450°F) at approximately 30°C/hr (50°F/hr). Maintain a minimum hydrogen to hydro- carbon ratio of 35 nm3/m3 (200 SCFB) and maintain the reactor products separator pressure at 14 kg/om2g (200 psig). NOTE: Throughout this phase of the suffiding, monitor the separator boot for water accumulation. When water is detected, drain it from the separator. NOTE: For those units with a multiple-pass reactor charge heater, the individual charge heater pass outlet temperatures should be checked at least every 5 minutes as the heater outlet temperature is increased. If one or more pass outlet temperatures lag behind, this could indicate a liquid seal or pocket obstructing flow. This may cause localized overheating of the tube(s). If this occurs, shock the system momentarily by changing the charge flow abruptly. If the seal persists, lower temperatures and shock the system again by abruptly changing the charge rate. If the seal persists, stop heater firing, stop the naphtha charge and make certain the pass is cleared before restarting charge to the unit, Ensure that the heater is not overfired during any of these activities. A liquid seal can be broken or prevented by adjusting the flow so that the charge heater detta P is greater than the head developed by a liquid pocket in any pass. After the reactor inlet and outlet temperatures have been stabilized at 230°C (450°F), increase the reactor products separator pressure to the normal operating level or 28 kg/em2g (400 psig), whichever is lower. ‘At 230°C (450°F), sulfiding will take place using the native sulfur in the charge. If this proves to be a time-consuming operation (assume 90% desulfurization of the native sulfur), additional sulfur in the form of an organic sulfur uoO 197s vies(WOP machina Hycrarearag Process ‘Nama’ Sip 1. 12. 13. compound may be added to the feed, or HeS may be added to the gas to the reactor. The total amount of sulfur charged to the catalyst (native plus added) should not exceed 0.25 wt-% of the naphtha charge at this point. However, to extend the sulfiding period for better control, the total amount of sulfur injected should be controlled at 0.08 - 0.10 wt% of the naphtha charge, depending on the catalyst metal loading. Calculate the sulfur injection rate required, for the actual catalyst loaded, so that the sulfiding step takes 8-12 hours. Hold the reactor inlet temperature at 230°C (450°F) and maintain a minimum hydrogen to hydrocarbon ratio of 35 nm%/m? (200 SCFB). Increase the feed rate to design, or the maximum available. NOTE: In the event of a rapid reactor outlet or catalyst temperature rise above 250°C (480°F), stop sulfur addition (whether H2S or organic sulfur is to be added) to the unit immediately and reduce the firing in the reactor charge heater. If necessary, stop the charge to the unit to limit the temperature rise. When temperature control is regained, adjust the reactor inlet temperature to 230°C (450°F), and slowly restart sulfur addition to the unit. When unspiked start-up oil is used for catalyst sulfiding and if the conditions indicate very ttle desulfurization is taking place at 230°C (450°F) catalyst temperatures, then the bed peak temperature can be increased slowly up to a maximum of about 250°C (480°F). It should not be necessary to exceed a 230°C (450°F) catalyst peak temperaure if an organic sulfiding compound is being added. During the sulfiding period, increase the stripping section reflux ratios as much as possible to remove any HeS, water, or light mercaptans which might otherwise contaminate the product. If necessary, the operating pressure of the fractionation or stripping section should be reduced to obtain sufficient material for reflux. If additional sulfur is used, after the unit has stabilized at 0.08 - 0.10 wt% (maximum 0.25 wt-%) sulfur in the reactor feed, smoothly increase the amount ‘of added sulfur until the total sulfur being charged to the catalyst is 0.15 - 0.20 uop nme verLVOP Nephina Mcroreating Process ‘Nomal me wi% (maximum 0.50 wt-%) of the naphtha charge. Maintain 230°C (450°F) reactor inlet temperature and continue sulfiding. Drain water from the reactor products separator and the fractionation or stripping section water boots as it accumulates. 14. Continue sulfiding at these conditions for a period of 1-2 hours. 15. Increase the reactor inlet temperature to 290°C (S50°F) at a rate of 17°C (80°F) per hour. NOTE: Do not exceed 17°C (30°F) temperature rise across any catalyst bed. 16. The catalyst can be considered sulfided when the total amount of sulfur injected has reached the maximum shown in the following Tabte. uop 7s vineUDP Napa Hy crouestng Process Nea Stat ‘Sulfur Level, Based on Hydrobon® Catalyst Loaded Catalyst Weight S-6 6.0 wt-% S39 6.0 wt-% $-12 85 wt-% S-12H 9.0 WI-% $-12T 8.5 wi-% S45 45 Wt-% S-16 8.5 Wt-% S18 6.0 WI-% S-419H 9.0 wt-% S-19T 10.5 wt-% S-19M 8.5 wt% S120 9.6 wt-% N-204, 7.2 wt-% N-108 9.4 Wt-% HC-K 11.3 Wt-% 17. Establish normal plant operation in the following sequence: a. Adjust naphtha charge to the desired rate. b. Increase the reactor inlet temperature to 315°C (600°F). Adjust temperature as required to produce on-specification product. ¢. Increase the reactor products separator pressure to normal, if this was not done in Step 9. d. Increase the hydrogen-to-hydrecarbon ratio to normal, if this was not already done. €. For units that process charge different from the startup naphtha, normal charge can now be routed to the unit and startup naphtha stopped. The ucp nes. veoOP nepaineHycworsatng Process Normal Starup change should not be made abruptly so that upsets are avoided, and control of the reactor temperatures is maintained. . Establish water injection to the reactor products condenser, just after the last combined-feed exchanger bundle, at a rate equal to 3 liquid volume-% of the charge rate. C. SUBSEQUENT STARTUP The procedure used for the initial startup should be followed except that sulfiding is not required for used catalyst so those steps should be omitted. It is not necessary to cool the reactor beds to less than 290°C (550°F) before cutting in the feed if the catalyst is already sulfided. The procedure to use is as follows: 1 Pressure the reactor section to 14 kg/em2g (200 psig) with Hz and establish once-through or recycle gas flow at the maximum possible rate. If the reactor temperatures are between ambient and 290°C (550°F), charge startup naphtha to the reactor at about one-half of the design rate. Purge the charge heater firebox with steam and light fires following normal refinery practices. Increase the reactor temperatures to 315°C (600°F) at about 40°C (75°F) per hour. NOTE: The reactor inlet temperatures will decrease sharply when oil is cut into the unit. Do not overfire the charge heater in an attempt to hold the existing reactor temperature. NOTE: For those units with a multiple-pass reactor charge heater, the individual charge heater pass outlet temperatures should be checked at least every 5 minutes as the heater outlet temperature is increased. If one or more serts veo‘LOP Naghine Hobeaing Process Noma! Stame pass outlet temperatures lag behing, this could indicate a liquid seal or pocket obstructing flow. This may cause localized overheating of the tube(s). If this occurs, shock the system momentarily by changing the charge flow abruptly. If the seal persists, lower temperatures and shook the system again by abruptly changing the charge rate. If the seal persists, stop heater firing, stop the naphtha charge and make certain the pass is cleared before restarting charge to the unit. Ensure that the heater is not overfired during any of these acti A liquid seal can be broken or prevented by adjusting the flows so that the charge heater delta P is greater than the head developed by a liquid pocket in any pass. 4, After the reactor iniet and outlet temperatures have exceeded 260°C (500°F), increase the reactor products separator pressure to the normal operating level, 5. Establish normal plant operation by increasing the charge rate to normal, increasing the reactor inlet temperatures as required to produce on-spec product, and switching to normal feed if sweet naphtha was used for startup. Restart water injection to the products condenser, just after the last combined- feed exchanger bundle, at a rate equal to 3 liquid volume-% of the charge rate. uop a7H5 vertUOP naphia Hycanenting Process ‘Nonmal Opsatens Vill. NORMAL OPERATIONS The Naphtha Hydrotreating Unit is fairly simple to monitor from a calculation and data review standpoint. The chapter describes calculations that are typically done in a Naphtha Hydrotreating Unit. This does not include the Splitter section. A. CALCULATIONS Before any calculations are performed, the data should be reviewed to verify the unit was lined out during the period of time the calculations will cover. Usually, this is 24 hours. Good practice dictates that calculations be performed routinely, such as once a day, so that changes in performance can be quickly noted. Also, engineers find it very useful to have some data and calculations plotted in order to monitor trends and maintain a unit operating history. Before the unit's performance can be properly monitored, the unit must first weight balance. Kilograms of liquid and gas in should equal kilograms out. A good balance is one where the percentage of kgs of products divided by the kgs of feeds equals 100 percent, plus or minus 2% maximum. If itis outside this range, the engineer will have to try to evaluate which indicator(s) is reading wrong and have it corrected, On the Naphtha Hydrotreating Unit there can be one to multiple naphtha feed streams and hydrogen make-up. The products typically consist of two streams: the stripper off-gas and stripper bottoms. if there is not a flow meter on the stripper bottoms, the product flow meter(s) from downstream vessels (splitter, intermediate tanks, Platforming Unit feed, etc.) should be used. Water injection and sour water product are not considered in the weight balance. Water and oil do not mix. The first step of the calculations is to correct the feed and product flows to their actual mass flows at standard conditions. The averages on the logsheets are only approximations of the actual value. Liquid streams have to be corrected for changes in density as measured at a standard temperature due to variations in flowing temperatures. Gases have to be corrected for variations in specific gravity, uop 1985 vetLUOP aphiheHychoveeting Process Norma! Operavone ‘operating pressure and operating temperatures. The corrected flows are then used to check the unit weight balance and for other calculations as is noted below. The following calculations are typically performed on the Naphtha Hydrotreating Unit daily: 1. Weight Balance kgfhr products 4, kg/hr feed An acceptable weight balance is within 98 to 102 weight %. 2. Liquid Hourly Space Velocity (hr) volume of charge per hour Lusv = s volume of catalyst 3. Hydrogen to Hydrocarbon Ratio Nm3/hr of hydrogen recycle gas mS/hr of naphtha charge 4. Stripper Offgas NmS/hr of stripper offgas: m9/hr of naphtha charge 5. Stripper Reflux Ratio m3/hr of reflux m/hr of naphtha charge uop nenis vueVOP Nisha Hyuratening Process Norma Operations 6. Hydrogen Consumption (Nm*hr H, makeup) - (Nm*/hr hydrogen out of the unit) mihr of naphtha charge 7. Cumulative Charge Total m3 of charge to the unit. Usually, calculated from beginning of a run to a regeneration. If the unit has more than 1 feed source, the individual rates should be recorded as well. 8 Catalyst Life cumulative charge,m* kg of catalyst Catalyst life is measured from original startup to catalyst replacement. 9. Metals Contamination wt% metals in charge xkg charge kg of catalyst 107? Usually, kg of charge is the total from the last time a metals analysis was performed on the feed to the latest one. The total metals contamination is then the summation of the incremental contaminations between analyses. See Section Ill, Part F tor more information. 10, Water Injection m3/nr of water mower x 100 mhr of naphtha charge The typical continuous water injection target is 3 liquid volume percent of the charge rate. This is for when the water is injected just after the last combined- feed exchanger bundle. If the water is injected further upstream where the ucp jars vans2OP Napa yorousaing Process anne! Operators 1. 12. process temperature is higher, then the water rate must be increased. The goal is to maintain at least 25% of the injected water in the liquid phase. The injection rate may require adjustments based on the separator water analysis. The separator water should be analyzed 3 times per day to insure it has the following qualities: pH 6.0 +05 (avoid 6.8 - 7.3 range) Iron 2 wt-ppm or less Chloride Less than 500 wt-ppm Ifthe pH decreases below 5.5, then increase the water injection rate to bring the pH up to the desired range. Note that different water rates change the acceptable level of iron. It is the mass of iron being removed that is important to monitor. If increased water injection does not bring the pH into the proper range, then a “basic” water injection may be required. Contact UOP for further details. Reactor pressure drop Reactor inlet pressure — reactor outlet pressure ‘The maximum pressure drop of the reactor is typically set by the allowable pressure drop across the outlet basket. This is for guideline purposes only. For older units this is typically 60 psig (4.2 kg/cm’) and about 100 psig (7 kg/cm?) for newer designs. However, the pressure drop usually occurs at the top of the reactor bed. Thus, product quality and hydrogen flow are usually the limiting factor. Reactor delta Temperature Reactor outlet temperature - reactor inlet temperature For most straight run naphthas, there will be no temperature rise across the teactor, and may actually show a loss of temperature depending on heat loss, Naphthas that contain olefins, such as cracked naphthas, will exhibit a temperature rise. The magnitude will depend on the amount of olefins wwe vueUO Naphta Hracmeaing Process Norma! Operations present. As the olefin content increases so does the exotherm. As the outlet temperature approaches 343°C (650°F) then sulfur recombination can occur. uop tes, warsWOR Natit Hytacing Process Labortony Test Method Scheie IX. ANALYTICAL Included in this section is the laboratory test method schedule for the Naphtha Hydrotreating Unit. This laboratory schedule is general in nature and is customized for each customer depending on the equipment included in the design. Please refer to the 934 specifications in the UOP Schedule A books for your unit. uoo ys. meLUOP naphina Hyaotening Process Lavoratry Test Motbod Sendo LABORATORY TEST METHOD SCHEDULE Naphtha Hydrotreating Unit Sample Stream Name Test Method Frequency Number Test Name Number Normal Startup 1 Charge to NHT (Reactor Feed) Gravity ASTMD40520r = 1/D 3D ASTM D 1298 API ASTM D 287 wD 3/D Distillation ASTM D 86 uD 3D Color ASTM D 156 3D 3D ‘Sulfur ASTM D 4045 uD 3/D Chloride UOP 588 Occas. /D Nitrogen ASTM D 4629 Occas. uD Composition (PONA) UOP 880 Occas. —Oceas. Arsenic UOP 946 Occas. /D Lead UOP 952 Occas. uD Bromine Number UOP 304 Occas. wD Dissolved Oxygen UOP 678 Occas. —Occas. Trace Metals UOP 389 Occas. Occas. Mercury UOP 938 Occas. Occas. 2 Recycle Gas (Separator Off-Gas) Relative Density UOP 114 VD aD Composition UOP 539 aw uD 3 Stripper Off-Gas Relative Density UOP 114 vd aD Composition UOP 539 aw uD 4 Stripper Overhead Liquid Composition (requires UOP 551 Occas. v> high pressure sampler) HS UOP 212 Occas. 1/D uop 978 KeeUOP Nope Meaning Process Labora Test Med Scheie Sample Stream Name Test Method Frequency Number Test Name Number Normai Startup 5 Stripper Bottoms Relative Density ASTMD40520r —-3/D 3/D ASTM D 1298 API ASTM D 287 3/D 3D Distillation ASTM D 86 3/D 3D Color ASTM D 156 3/D 3/D Suttur ASTM D 4045, V0 0 Chloride UOP 395 1w 41D Nitrogen ASTM D 4629 Ww 0 Composition (PONA) UOP 880 1W ve) Composition (Ce) UOP 551 Occas. 1/0 Arsenic UoP 298 1M Ww Lead UOP 350 1M 1 Copper uoP 144 1M Ww Water Content UoP 481 Occas. 1 Bromine Number UOP 304 17M 1 Silicones UOP 787 Ww Ww Fluoride uoP 619 1M 1 6 Naphtha Splitter Overhead ‘Composition UOP 551 Asreq. 1/D. Relative Density ASTM D 4052 or 31D ASTM D 1298 API ASTM D 287 3D 3D Distillation ASTM D 86 3D 3D 7 Naphtha Splitter Bottoms Composition UOP 880 Asreq. 1/D Relative Density ASTMD40820r = -/D. 3D ASTM D 1298 API ASTM D 287, 3/D 3D Distillation ASTMD 86 3/D 3D Nitrogen ASTM D 4629 Asteq. As req. 8 Make-Up Hydrogen Relative Density UOP 114 7) 3D Composition UoP 539 1D 10 9 Charge Heater Flue Gas ‘Oxygen Content Orsat Occas. Orcas. ueo hens maJOP Nephi Hcoesing Proase aboatn Test Mate Schoo Sample Stream Name Test Method Frequency Number Test Name Number Normal Startup 10 Stripper Reboiler Heater Flue Gas Oxygen Content Orsat Occas. Occas. W Naphtha Splitter Reboiler Heater Flue Gas Oxygen Content Orsat Oceas. Occas. 12 Product Separator Water pH, Iron, Copper UOP 314 Occas. = 1/W Hs. UOP 740 Occas., Occas. HS UOP 683 Occas. Oceas. Chlorides UOP 456 Occas. Occas. 13 Stripper Overhead Receiver Water PH, Iron, Copper UOP 314 Occas. Ww REGENERATION CASE 14 Recycle Gas COz by Orsat UOP 172 As Required Oz Portable Anal. As Required Hos. Detector Tube As Required 802 Detector Tube As Required 15 Reactor Effluent Gas COp by Orsat uoP 172 As Required Oz Portable Anal. As Required 16 Spent Caustic Percent NaQH UOP 210 As Required pH (pH Meter) ASTM D 1293 As Required pH Litmus Paper As Required Total Solids APHA 2540-A Ww Settleable Solids APHA 2540-F iw 7 Circulating Caustic Percent NaQH UOP 210 As Required pH (pH Meter) ASTM D 1293 As Required pH Litmus Paper As Required Total Solids APHA 2540-A uw Settleable Solids APHA 2540-F IW aes wet(YO Naphna Hyoraeaing Process Troubleshooting X. TROUBLESHOOTING No information is provided in this section. Please refer to the Process Principles and Process Variables sections for potential resolutions. If further assistance is required, please contact UOP. uoOD THs a{UOP Waphiha Hyactering Process Noma! Suton XI. NORMAL SHUTDOWN A. NORMAL SHUTDOWN PROCEDURE The following shutdown procedures cover normal planned complete shutdowns of the Naphtha Hydrotreating Unit such as would be required for a complete catalyst change and/or the periodic cleaning and inspection of vessels. Variations of this procedure may be required from time to time because of special operating conditions which may arise. 1. _ Notify operating foreman and other operating units concemed as to the exact time when shutdown activity will begin. Changes in fuel gas composition, steam demand, etc., may affect other units. Pumpers, tank farm, and others who may be involved should be notified. 2. Reduce the hydrotreating reactor(s) inlet temperature to 316°C (600°F) and the charge to about 50% of design. The Platforming Unit must be fed sweet naphtha at this time, or it must be shut down also. 3. Cut charge out of the unit and continue to sweep the unit with gas to remove hydrocarbons. 4. The prefractionator and rerun columns should be cooled down by stopping reboiler heat input, and should be left under positive fuel gas pressure. If entry into the columns is required, at a minimum, they must be drained, steamed out, blinded off from other equipment, and air purged for safe entry. 5. After approximately one hour of gas sweeping at a minimum reactor(s) temperature of 260°C (600°F), begin reducing reactor(s) temperatures by 30-40°C (50-75°F) per hour to 65°C (150°F) or 38°C (100°F) if the catalyst is to be dumped unregenerated. uce peotts etOP Nacht Hycrorsatng Process oad Shawn 10. If the catalyst is to be regenerated, the reactor(s) can be left at 260°C (50°F) when the gas flow is shut down. More specific procedures are given in the Regeneration Section of the Section Xlil Special Procedures. Block in the product separator level contro! valve when liquid stops accumulating. Drain the separator and ail reactor section low points to remove all hydrocarbons. The stripper and splitter should be cooled down and drained if any maintenance work is required. Shut down stripper bottoms and/or splitter bottoms pump. ‘Shut down the recycle gas or once-through gas flow when the reactor is cool. The unit may be depressured to about 1 kg/em2g (15 psig) pending maintenance, hs weBOP naphne Hyarreaang Process morgen Procedures Xl. EMERGENCY PROCEDURES Emergencies must be recognized and acted upon immediately. The operators should carefully study, in advance, the steps to be taken in such situations. While some of the emergencies listed in this section may not result in a unit shutdown, they could cause serious trouble on the unit if not handled property. In addition, damage to the catalyst might occur. Hard and fast rules cannot be made to cover all situations which might arise. The folowing outline lists those situations which might arise and suggested means of handling the situation. Because the Naphtha Hydrotreating Unit and Platforming Unit are so intimately connected, an emergency in one unit will usually cause an emergency in the other. A. LOSS OF RECYCLE COMPRESSOR 1. Stop Naphtha Hydrotreating Unit charge heater fires immediately and cut steam through the fumace boxes for its cooling effect. The charge heater should should down automatically on low recycle gas flow. 2. Switch the Platforming Unit to sweet naphtha feed, bypassing the hydrotreater, so it can continue to run. If this is not possible, shut down the Platforming Unit in the normal manner. 3. Shut off Naphtha Hydrotreating Unit charge pumps and block in. 4. Block in Naphtha Hydrotreating Unit offgas valves so that the system pressures are maintained. Block in tiquid levels. NOTE: The above four steps must be performed as quickly as possible. 5. Start the compressor as quickly as possible. Remember that with no flow through the heater, the material in the tubes may become excessively hot, and if it was put through the reactors, could result in damage to the catalyst. Thus, when the compressor is started after such a shutdown, immediately check the uop ainis autLOR Napnins Hyomeaieg Prcess emergency Procativos reactor inlet temperatures; if over 343°C (650°F), stop recycle flow and continue cooling the heater with purging steam until the reactor inlet temperatures, with recycle gas flowing, are below 343°C (650"F). 6. When the compressor is again in service, come back on stream in normal manner. 7. Ifa compressor cannot be started within an hour, the hydrotreating reactor pressure should be bled off gradually to the fuel gas system or flare until 7.0 kg/cm2g (100 psig) of pressure is released. This is done to purge out hydrocarbons present in the reactor as much as possible and minimize coking. B. REPAIRS WHICH REQUIRE STOPPING COMPRESSOR WITHOUT DEPRESSURING OR COOLING REACTORS 1. Drop reactor(s) temperature to 315°C (600°F) by’cutting back on heater outlet temperatures while reducing reactor charge rate to one-haif. Cut out reactor charge. Block in separator and columns as in normal shutdown. 2. Ifunit has been operating at a low pressure, it would be proper to increase the unit pressure before the shutdown, so that leakage during the down period will not be so great as to require extra outside hydrogen to be purchased and used in the subsequent startup. However, DO NOT EXCEED DESIGN PRESSURE FOR THE UNIT. 3. Continue firing heaters and circulate recycle gas for one hour while reducing reactor inlets to 260-290°C (500-550°F). 4. Cut fires from all heaters and stop compressor. ucp yeas SuneVOP Mepis Hyctestng Procass Emergency Procedures c. EXPLOSION, FIRE, LINE RUPTURE, OR SERIOUS LEAK — DO IF POSSIBLE Cut fire from all heaters. If heaters or control valve are beyond reach, main gas valve can be used. ‘Stop reactor charge pumps. Stop other pumps, if possible. Leave compressor running if possible while other items are attended to since it will contribute little extra pressure to the system. Shut down compressor. Depressure plant. Use of separator safety relief valve will depressure the separator and the system. Shut down balance of plant as circumstances permit or require. If leak or line rupture is in a heater, add snutffing steam to cool down firebox AFTER THE SOURCE OF COMBUSTIBLES HAS BEEN ELIMINATED. DO NOT CLOSE THE HEATER DAMPER as it may force the fire out of the heater. Purge unit of hydrocarbon as soon as possible. DO NOT EVACUATE. INSTRUMENT AIR FAILURE Locate reason for failure. If in air drier system, bypass that section. This can then be repaired when possible. nents waUOP npn Mycoreating Process Emergarey Procedves 3. If air cannot be obtained, the alternatives are a plant shutdown, or operation of the various controls on hand control. Action will depend upon the desires of the supervisor. 4. Due to the possibility of instrument air being used for breathing equipment and/or pneumatic instruments venting in the control room, do not add nitrogen to the instrument air system. 5. Be familiar with action of all control valves — memorize ail actions on air failure. —. POWER FAILURE Emergency procedures during a power failure will vary greatly, depending on: (1) the extent of the failure, (2) which utilities may be affected by a failure, and (3) the length of the failure. In general, the first consideration in case of a power failure, is to bring the plant to a safe standby condition. Of aimost equal importance, however, is the protection of the catalyst. 1. If the charge pump and recycle compressor are motor driven, they will stop. Be sure the charge heater fires trip out and that the individual bumer fuel valves are blocked in, if the compressor is turbine driven, it should be run long enough to sweep hydrocarbons from the system and cool down the reactor and charge heater before it is shut down. 2, Ifthe stripper reboiler pump is motor driven, be sure the fires trip out and the individual bumers are blocked in. 3. When power is restored, follow the procedure for startup after a recycle compressor failure. uEp pens. vatVOP Naphna Myrousatng Process F. LOSS OF COOLING WATER Watch condenser and cooler temperatures, especially on recycle gas compressor system. A shutdown may be necessary if temperatures rise too much. Do not jeopardize the recycle gas compressor by allowing lube oil temperatures to increase above 70°C (160°F). If this occurs, follow emergency procedure for shutdown of the unit. wesLUOP Napttha Mcroreeing Process Spedal Preesores XII, SPECIAL PROCEDURES ‘A. CATALYST LOADING 1. Catalyst Loading Preparation Loading of the reactor(s) is normally the last item attended to before the unit starts up. Reactor loading consists of the following: Planning and preparation including a loading diagram Installation and inspection of the bottom internals Loading of the catalyst support material Loading of the catalyst Loading of the catalyst graded bed material installation of the inlet distributor and bolting up of the reactor PAR ONa 2, Catalyst Loading Procedure It must first be decided how the catalyst is to be lifted to the top of the reactors. It could be lifted in its original drums by a monorail or pulley system, but the quickest and probably best way is to lift the catalyst by a crane if one is available. If a crane is used, the loading time can be greatly reduced by constructing two large transfer hoppers to move the catalyst from the ground level to the top of the reactors. In this case a transfer hopper loading platform must be constructed in a convenient place close to the reactors, The loading platform can be constructed of scaffolding and wooden planks or of any other convenient material. The platform area should be at least large enough to accommodate enough drums to load ane hopper and to allow working room for the personnel who will do the loading. Regardless of the way the catalyst will be lifted, a convenient, temporary storage place near the reactor must be found for the catalyst. The catalyst should be stored on pallets and completely covered by canvas to give a certain measure of Protection against the elements. A forklift or some other means of moving the uop 08 ameUOP hacia Hycboteotng Process ‘Speci Procodes catalyst from this site to the loading platform (or to any other place) should be available. The catalyst loading path, both on the ground and through the air, must be checked s0 that it is entirely free from obstruction. To assure this, it may be necessary to remove or modify the reactor superstructure, the piping support, or the piping itself. Failure to obtain a clear loading path could result in a slow and hazardous loading procedure. A typical lay-out for the catalyst loading is shown in Figure XIll-1. A list must be made of all the accessory equipment which will be needed to do the loading. A partial list of some of the items that will be needed follows: 1. One crane (not necessary but very helpful if available) and safety hitch for the crane hook. 2. One forklift. 3. Two large transfer hoppers (also not necessary, but desirable) and separate lifting cables for each hopper. 4, One transter hopper loading platform if transfer hoppers are to be used. 5. One loading hopper to rest above the reactor. 6. _Explosion-proof light inside the reactor (and also flashlights). 7. Ceramic rope to protect the manway ring joint and to fill crevices created between cerlain reactor internals. 8. Ceramic gasket or wooden cover to protect the reactor manway and elbow flange gasket surfaces. 9. Canvas for covering the catalyst drums and for covering the reactor inlets between loading intervals as protection against rain, snow, etc. uco ams weLUOP Machina yctsreating Process Sect Proosaures 10. A safe ladder to enter and leave the reactor. 11. Loading socks of correct diameter and sufficient length to do the loading in the manner planned. 12. Wooden boards to stand on while inside the reactor and to level the catalyst and catalyst support material. 13. A vacuum eductor to remove catalyst dust. 14. Dust masks for the personnel who will be working with the catalyst. Fresh air masks may be desirable for the personnel who will be doing the actual loading inside the reactors. 15. Measuring tapes for both small and large measurements (such as catalyst loading outages). 16. Chalk, crayons, or other types of markers to mark the reactor walls. 17. Wooden covers or other means (such as plastic and tape) to the reactor baskets. Cover the reactor baskets. 18. Miscellaneous hand tools such as pliers, screwdriver, etc. 19. Air hose to supply air to the dense loading machine (if the catalyst is to be dense loaded). 20. A planned loading diagram is prepared and supplied to the loading supervisor. The bottom intemals consist of the outlet basket, the catalyst loading sleeve and the catalyst unloading support plate. The outlet basket is constructed of perforated piate and, in newer designs consists of multuple sections that are fitted together once inside the reactor. The slots in the plate are usually 10 mm by 40 mm oblong ‘slots on 25 mm centers with 13 mm between the ends of the slots. The entire outlet basket should be inspected for deviations from the project specification and for uoep ns ams.2OP nophihaHyereaing Process Seca Precetii structural weaknesses. For older designs, the basket is centered over the outlet nozzle by four equally spaced lugs, which fit inside the outlet nozzle. For newer designs, the outlet collector is attached to the bottom head with three hold down legs. Verity that the bottom centering ring, which is cut to the bottom head radius, is flush along the bottom and there will be proper containment. The catalyst unloading sleeve is made of 1.5 mm (16 ga.) plate. It is loosely fit into the catalyst unloading nozzle. into the catalyst unloading nozzle is fitted the catalyst support plate. A ceramic rope must be placed on top of the plate to plug the unloading nozzle. The removable support plate rests on three equally spaced lugs. This support plate allows the removal of the nozzle blank flange and the installation of an extemal unloading spout prior to the actual removal of any catalyst. ‘Once the bottom internals are in place, the loading can begin. Be sure to record all the amounts and types of material loaded and construct an “as loaded” diagram similar to Figure XIll-2. Begin loading the the catalyst support material as follows (Project Specifications take precedence for actual dimensions): 1. 19 mm (3/4") diameter ceramic balls are loaded to a level height above the outlet basket as shown in Figure XIll-2. Typically 100 mm above the outlet basket top. 2. A level layer of 6 mm (1/4") diameter ceramic balls are placed on top of the 19 mm balls as shown in Figure XIll-2. 3. A level layer of 3 mm (1/8") spherical Hydrobon® catalyst base, ceramic balls or NMRS, is usually placed on the 6 mm balls as shown in Figure XIll-2. When loading each layer of the catalyst support material, care must be taken so that the previous layer of bails is not disturbed. Cratering of any layer may cause migration of the balls resulting in the migration of the catalyst bed. The catalyst unloading nozzle is also filled with 6 mm (1/4") balls to within 100 mim (4 in.) of the top. The remaining 100 mm (4") space is filled with 3 mm (1/8") catalyst base or ceramic balls. An alternate is that the sleeve may be yoo 7s xdUOP Raohina Hyaoroaing Process ‘Space! Procooures completely filled with 3 mm spherical Hydrobon® catalyst base or ceramic balls. Catalyst should not be used due to coking potential. 4. The UOP Hydrotreating catalyst may be sock loaded or “dense” loaded by using UOP's dense loading machine. Dense loading has the primary advantage of being able to load more catalyst into the same reactor volume. In general, there are only a few differences in the sock loading and dense loading procedures. In dense loading, the dense loading machine is anchored either above or inside the reactor. A loading sock attached to the loading hopper feeds the loading machine with catalyst. The operator of the machine regulates it so that the catalyst is loaded uniformly and so that the level rises evenly. Even when dense loading, it will probably be necessary to level the bed after reaching the desired catalyst height. Afterwards, an outage measurement should be taken and recorded. If the sock loading method is used, the sock should only extend to the reactor top tangent line when connected to the hopper in the reactor inlet manway. The catalyst must be loaded slowly at first to prevent cratering of the support material. The sock should be kept moving in a figure eight pattem to prevent the catalyst from forming hills. it is important to keep the catalyst bed as level as possible during loading so the loaded catalyst density is uniform throughout the bed. 5. During the loading of the catalyst, an accurate count of the drums loaded and the drum lot numbers must be recorded. It is advisable to retain a composite catalyst sample for future reference composed of about 1 07, of catalyst from each drum loaded. 6. Load catalyst to the specified level. 7. Load the bottom layer of graded bed material (usally TK-550) to the depth ‘specified, typically 300 mm (12 inches), but can be as much as 600 mm (24 inches). ucop samt msUO naghins Hyctotetng Process Speci Proceeras 8. Load the top layer of graded bed material (usually TK-10) to the depth specified, typically 150 mm (6 inches). The loading should be calculated such that the distance from the top of the TK-10 to the bottom of the inlet distributor is not less than that indicated in the following table: Reactor ID Height of Open Space 4-6 18” minimum 65'-8' 15" minimum >8.5° 42" minimum 9. A catalyst loading diagram (as loaded) similar to Figure Xill-2 should be drawn and retumad for reference. NOTE: While loading the last layers of catalyst and the graded bed materials, careful measurements must be taken. This is especially true if loading different types of catalyst in a reactor. The top layer of the top graded bed material (TK-10) must not be above the reactor tangent line. The minimum distance from the top of the graded bed material to the bottom of the inlet distributor is as shown in the loading diagram. Catalyst should be leveled before the graded bed material. B. UNLOADING OF UNREGENERATED CATALYST CONTAINING IRON PYRITES. The following precautions are recommended for use during unloading of unregenerated hydrotreating catalyst. The main concer is that no oxygen be allowed to contact the catalyst inside the reactors, since this can result in spontaneous combustion of the iron pyrites. The temperature generated by this ‘combustion can be quite high, and left unchecked can result in severe damage to the catalyst and reactor intemals, Of secondary, but no less importance, is protection of personnel and proper handling of catalyst during unloading. All Personnel involved with the unloading must be properly informed of the dangers involved and the proper safety measures. op 718 ewesLUOP mpi Hycttbng Process Spiel Prcerres 1. Follow the shutdown procedure as outlined in the procedures section. Be very careful to drain all residual hydrocarbons from the system low points, the ‘separator and the feed line down stream of the feed flow control valve. 2. After all residual hydrocarbons have been drained from the system, cut out the heater fires and cool the reactor beds to less than 66°C (150°F) preferably to 57°C (135°F). At temperatures above this level, combustion of iron pyrites is greatly accelerated and more difficult to control. If the catalyst is to be screened during unloading, the catalysts beds should be cooled to less than 54°C (130°F). 3. After cooling the beds to 66°C (150°F), the unit should be evacuated and purged with No at least twice. The unit should then be properly isolated and a ‘small No purge established at the compressor discharge or preferably at the inlet to each reactor. Do not open the reactors at the top until all catalyst has been unloaded. 4. Connect the unloading nozzle and be sure that a full opening but positive shutoff valve is installed. This is best accomplished by using a ball-ype or slide valve. 5. Remove all combustible materials from the area. 6. Be sure that several COz extinguishers are available. 7. Use only metal drums for unloading, and dump directly into drums if possible. It is best to soreen the catalyst after it has had time to cool to ambient temperature. Each drum should be either purged with Nz during unloading or a piece of dry ice placed at the bottom of each drum. Should the catalyst be screened at the same time as it is being dumped from the reactors, nitrogen should be purged through the dumping nozzle to the top of the first screen to provide additional protection from pyrite ignition. op nas xmOP nphinaMycteating Process Special Procesuas Do not seal the drum air tight since this could result in sudden rupture of the drum should combustion occur. Burning of catalyst in the drums is not serious and can be quickly extinguished with nitrogen or CO. 8. Its expected that some “sparking” of the pyrites will take place in any event. Therefore, all workmen in the area must be supplied with face and eye protection. In addition, they should wear long sleeve shirts with collars and cutts tightly buttoned. 9. Maintain a positive flow of Np out of the unloading nozzle throughout the unloading. If the catalyst becomes bridged in the unloading nozzle or is not free flowing, break the plug with a blast of Nz or steam. Do not allow air to be drawing into the reactor. 10. If ignition of pyrites takes place inside a reactor, stop unloading in that reactor and increase the Nz purge to maximum untii buming has stopped. . CATALYST SKIMMING PROCEDURE The amount of catalyst to skim off is dependent on the amount of fines deposited in the catalyst. The extent of this is difficult to determine without seeing the condition of the catalyst, but generally has been in the 1 meter (3 feet) range. The catalyst should be inspected as it is skimmed and continue until fines are no longer ‘observed. If the depth of catalyst skimmed is insufficient then the skimming operation may not be successful. Follow the procedure above for “UNLOADING OF UNREGENERATED CATALYST CONTAINING IRON PYRITES” but do not unload the catalyst from the bottom. Since the top layers collect most of the iron and other inorganic material, special Precautions and care must be taken when handling this material. The catalyst can be vacuumed out from the top of the reactor. The reactor should be under a nitrogen atmosphere, especially for nickel containing catalyst. This is best performed by catalyst handling companies that specialize in this operation. uop 117085 aneYOP naprina Myctoeating Process ‘Specs Prcecires There are several catalyst handling companies who are experienced with catalyst Joading and unloading in an inert atmosphere. If “fresh” catalyst is being added, suifiding of this new catalyst is required during the restart. NAPHTHA HYDROTREATING CATALYST REGENERATION During operation, carbon will gradually accumulate on the catalyst. The rate of accumulation will depend upon the type of feedstock and the type of operation to which the catalyst is being subjected. The rate at which the carbon accumulates will inerease if heavier feedstocks are used or if improper operating conditions are employed. The accumulated carbon, polymer, or metals deposited on the catalyst by the feed will eventually cause the catalyst to become deactivated to the point where it will not produce acceptable product quality. When the catalyst does become deactivated, it must either be discarded or regenerated. If carbon is the prime cause of the deactivation, the activity can be substantially restored by buming off the carbon under carefully controlled conditions. It must also be noted that the process of buming off the carbon does not remove the metals that have been deposited on the catalyst. If metals are the reason for the deactivation, then that catalyst must be discarded. Special precautions must be followed throughout the procedures if there is austenitic stainless steel in the reactor section of the unit. Water in the liquid phase plus oxygen should never be allowed to come in contact with austenitic stainless steel since there will be a light deposit of iron sulfide on the metal. If water, oxygen, and suffur come in contact with austenitic stainless steel, the areas of stress, such as welds, could suffer from stress cracks. This hazard should at all times be considered by the supervisor and operating personnel who will be conducting the regeneration. op saris moLUOP napama hyctoreanng Process ‘Spec Proved The temperature of austenitic stainless steel should be kept above the dew point of water when water and oxygen are both present to prevent stress cracking due to polythionic acid. Neutralization is not recommended uniess absolutely necessary, such as when austenitic tube bundles are to be pulled for maintenance. NOTE: (Only for austenitic stainless steel) If, for any reason, it is necessary to open the reactor system prior to regeneration, the unit must first be properly evacuated and purged with dry nitrogen. The nitrogen blanket should then be maintained with a smali nitrogen purge in the section to be opened to prevent air and moisture from entering. Other sections should be blinded at this time. NOTE: For the purpose of naphtha hydrotreating catalyst regeneration with austenitic stainless steel in the reactor section, nitrogen containing 100 mol-ppm or less of oxygen must be used. There are two basic procedures for regeneration of Hydrobon® catalyst: steam-air or inert gas. The steam-air procedure is still commonly used. However, the steam- air procedure should only be used for S-6 and S-9 Hydrobon® catalysts as an activity loss may result in the other catalyst formulations. For other UOP Hydrobon® catalysts, these must be regenerated using the inert gas technique to ensure no loss of activity. All of the Hydrobon® catalysts can be regenerated by the inert gas procedure, and it is commonly used on units that are designed with recycle gas rather than once-through gas. Throughout both procedures, the steps shown in capital letters are intended specifically for units with austenitic stainless steel in the reactor circuit. These steps may be omitted on units without austenitic stainless steel. uop nos sas9(VOR Naha Pycoratinn Process ‘Sond Procedures Cc. STEAM-AIR REGENERATION PROCEDURE (FOR S-6 AND S-9 HYDROBON® CATALYSTS) Shutdown 1. Cut the feed out of the unit, and increase the flow of hydrogen through the reactor section to the maximum available. 2. Raise the reactor inlet temperature to 370-400°C (700-750°F), continuing maximum hydrogen flow over the catalyst. Do not exceed the reactor design temperature. 3. Hold until the reactor outlet temperature is 400°C (750°F) or slightly higher for at least one hour, and until the accumulation of hydrocarbon in the separator and reactor section low points is zero (nil). 4 Stop the flow of hydrogen to the reactor. IMMEDIATELY REDUCE CHARGE HEATER FIRES AS NECESSARY TO MAINTAIN 290-315°C (700-750°F) FIREBOX TEMPERATURES, AS MEASURED BY THERMOCOUPLES PLACED IN THE HIP SECTIONS OF THE HEATER BELOW ANY CONVECTION COILS THAT MAY EXIST. ONLY FUEL GAS FIRING SHOULD BE USED FOR THIS OPERATION BECAUSE OF THE DIFFICULTY IN CONTROLLING AND MAINTAINING SUFFICIENTLY SMALL FLAMES WHEN BURNING FUEL OIL. BE CAREFUL AT THIS POINT TO PREVENT OVERFIRING THE CHARGE HEATER. If the heater coils and reactor are not austenitic steel, the heater firing should be stopped. 5. Depressure, evacuate and purge with nitrogen in the normal manner. BE SURE THAT PURGING NITROGEN GETS HEATED IN THE CHARGE HEATER BEFORE PASSING THROUGH THE REACTOR IF THE REACTOR CONTAINS AUSTENITIC STEEL. uop anes meatJOP naphineMycretaatng Process Special Procroes 6. AFTER EVACUATION AND PURGING IS COMPLETED, REDUCE THE CHARGE HEATER FIRES TO MAINTAIN 205°C (400°F) FIREBOX TEMPERATURES IF THE COILS ARE FABRICATED FROM AUSTENITIC STAINLESS STEEL. AFTER EVACUATION AND PURGING OF HYDROGEN IS COMPLETE, A LOW NITROGEN PURGE SHOULD BE CONTINUED TO PREVENT AIR FROM ENTERING THE SYSTEM WHILE PREPARING FOR REGENERATION. REDUCE THE CHARGE HEATER FIRES TO MAINTAIN 205°C (400°F) FIREBOX TEMPERATURES IF THE COILS ARE FABRICATED FROM AUSTENITIC STAINLESS STEEL. IF THE REACTOR CONTAINS AUSTENITIC STAINLESS STEEL INTERNALS, IT WILL BE NECESSARY TO MAINTAIN 290-315°C (550-600°F) CHARGE HEATER: FIREBOX TEMPERATURES TO ASSURE PREHEATING THE PURGING. NITROGEN. Otherwise, it is most convenient to merely maintain small gas pilots in the interim while mechanical preparations are being made prior to beginning the regeneration. Preparations Be prepared to hook up all required regeneration equipment rapidly to avoid any unnecessary loss of heat from the reactor. Maintain low nitrogen purge during the following mechanical preparations. Disconnect the effluent line from the reactor at the designated location, and hook up a temporary vent line to atmosphere at a safe location to dispose of the steam and waste gases during regeneration. A thermocouple should be maintained or installed as necessary at the reactor outlet for temperature indication during regeneration. Blind off the combined feed line ahead of the reactor charge heater and connect the regeneration steam line. ss. ae?UOP Nesnma Hyarzeeing Process Seed Pressures 4. Hook up the regeneration air manifold to the combined feed tine between the heater and the reactor. The line should be sized so that it will provide enough air to give an oxygen content of up to 2.0 mol-% in the steam-air mixture during regeneration, The air line is provided with an FRC assembly to measure and control the quantity of air being used 5. Connect the sample cooler and the measuring apparatus to the regeneration vent gas line from the reactor. Regeneration BEFORE ADMITTING STEAM TO A REACTOR CONTAINING AUSTENITIC STAINLESS STEEL INTERNALS, IT MUST BE ASSURED THAT THE CATALYST BED TEMPERATURE IS ABOVE 205°C (400°F) TO PREVENT ANY CONDENSATION OF STEAM IN THE REACTOR. 1. Drain the regeneration steam lines of condensate to assure the availability of dry saturated steam for regeneration. 2, Raise the charge heater firebox temperature, as measured by thermocouple(s) placed in the hip section, to about 260°C (500°F). Slowly establish a flow of steam to the reactor 0.225 kg/hr (0.5 Ib/hr) per pound of catalyst in the reactor, adjusting the heater fires simultaneously as necessary to hold the heater transfer temperature above 260°C (500°F). Be careful to avoid overfiring the heater. NOTE: Until steam flow is established through the heater tubes, the heater transfer temperature can not be used to control the firing. 3. Increase the steam flow rate to the maximum possible and simultaneously increase the reactor inlet temperature at 28°C/hr (50°F/hr) to 288°C (550°F). Do not exceed 3.5 kg/cm? (50 psi) pressure drop across the reactor; reduce the steam flow rate if necessary. Again, be careful to avoid overfiring the heater. uop v8 xia.OP Nephi Hycreatig Process Spec! Proewdires When the reactor inlet temperature has been held at 288°C (550°F) for at least one hour, cut in enough air so that there will be approximately 0.5 mol-% oxygen in the steam-air mixture. Take two or three volume samples of the condensate and the waste gas to verify the accuracy of the steam and air meters. If the meter readings are verified and the reactor outlet temperature is less than 370°C (700°F), slowly raise the air rate to give 1.0 mol-% of oxygen in the steam-air mixture, Verify this figure by taking volume samples of condensate and waste gas. Continue taking volume samples every two hours to check the accuracy of the meters. An Orsat or sniffer tube should also be used every two hours to check the ‘CO content of the waste gas. Keep a record of the reactor outlet temperatures and if it appears that this temperature is going to exceed 370°C (700°F) at any time during the tegeneration, the reactor inlet temperature or oxygen content should be adjusted accordingly. Continue analyzing the waste gas for COp content and when this figure falls below 10% and the delta T is zero, raise the reactor(s) inlet temperature to 343°C (650°F) at the rate of 42°C (75°F) per hour. Hold 343°C (650°F) reactor inlet temperature until the COz content of the waste gas falls below 2 mol%. At this time, the regeneration can be considered complete as long as the reactor(s) outlet temperature has cooled to the same as the reactor inlet temperature. If not, continue maintaining these conditions as necessary. After completion of regeneration, stop the air addition. REDUCE THE HEATER FIRES TO MAINTAIN 205°C (400°F) FIREBOX TEMPERATURES IF THE COILS ARE AUSTENITIC STAINLESS STEEL. IF THE REACTORS CONTAIN AUSTENITIC STAINLESS STEEL INTERNALS, FIRE THE CHARGE HEATER TO MAINTAIN 260°C (500°F) REACTOR INLET TEMPERATURE WHILE COOLING THE CATALYST WITH STEAM. hes maLVOP Nepniha Hyctoreatng Process ‘Spec Procooures W. COOL THE CATALYST WITH STEAM TO A REACTOR OUTLET TEMPERATURE OF 290°C (550°F). It the charge heater and reactors are not austenitic steel, stop the charge heater firing and cool the catalyst to 232°C (450°F). Stop the steam and immediately follow with a large flow of nitrogen to rapidly purge the steam from the reactors. IF THE REACTORS CONTAIN AUSTENITIC STAINLESS STEEL INTERNALS, MAINTAIN 290-315°C (650-600°F) CHARGE HEATER FIREBOX TEMPERATURES UNTIL ALL THE STEAM HAS BEEN PURGED FROM THE REACTOR. Maintain nitrogen purges to prevent air from entering the system while disconnecting regeneration equipment and piping the plant for normal processing. Dump and Screen Catalyst After the first regeneration, it is advisable to dump and screen catalyst. This will give an indication of the completeness of the regeneration plus an indication of the amount of fines and scale that can be expected on future regenerations. Even though a catalyst regeneration has been conducted, small amounts of iron sulfide scale can still remain in the system. Therefore, with austenitic stainless stee! in the heater/ reactors, it is necessary to cool the catalyst with nitrogen to prevent steam from condensing in the system. Coo! the catalyst with nitrogen flow until the reactor has dropped to about 50°C (120°F). Cooling to about 50°C (120°F) is necessary to allow safe handling of the catalyst, and to cool the reactors sufficiently to allow personnel to enter to clean and inspect the reactor, and to reload catalyst. (F THE REACTORS CONTAIN AUSTENITIC STAINLESS STEEL INTERNALS, MAINTAIN A NITROGEN BLANKET IN THE REACTOR WHILE DUMPING AND SCREENING CATALYST, TO PREVENT AIR FROM ENTERING THE REACTORS. ns 25UOP Naphina Hychutn Process Soest Process AFTER THE CATALYST HAS BEEN DUMPED FROM A REACTOR CONTAINING AUSTENITIC STAINLESS STEEL, UNHEAD THE TOP OF THE REACTOR. THOROUGHLY WASH THE INSIDE REACTOR WALLS AND INTERNALS WITH A COPIOUS AMOUNT OF SODA ASH SOLUTION, AS EXPLAINED IN THE "PROTECTION OF AUSTENITIC STAINLESS STEEL" APPENDIX F BEFORE ALLOWING AIR TO ENTER THE REACTOR. AFTER THE REACTOR HAS BEEN THOROUGHLY NEUTRALIZED, AIR CAN BE ALLOWED TO ENTER THE REACTOR TO DRY IT OUT PRIOR TO ENTRY. AFTER WASHING WITH THE SODA ASH SOLUTION, ALLOW THE SURFACES TO DRY WITH A FINE DEPOSIT OF SODA ASH. DO NOT RINSE THIS RESIDUE OFF WITH WATER, BUT LET IT REMAIN AS A PROTECTIVE FILM. ANY CATALYST THAT REMAINED IN THE BOTTOM OF THE REACTOR WHILE WASHING WITH SODA ASH SOLUTION SHOULD BE CONSIDERED CONTAMINATED WITH SODIUM AND SHOULD BE DISCARDED AND REPLACED WITH FRESH CATALYST. Alter cleaning out the bottom of the reactor, install reactor intemals, catalyst support material, and catalyst as recommended in Section V. Start up the unit in the normal manner, treating the regenerated catalyst in the same manner as fresh catalyst. Emergency Procedures During Steam-Air Regeneration 1 If, at any time, the catalyst temperatures become excessive, block in the air injection control valve immediately. If steam flow is interrupted and cannot be immediately resumed, then do the following: a. Block in air injection immediately. aries ese_YOP Natta Hyeroteting Process ‘Speci Process b. If heater/reactors are not austenitic stainless steel, cut out heater fires. C IF HEATER/REACTORS ARE AUSTENITIC STAINLESS STEEL AND STEAM CAN BE RESTORED WITHIN ONE-HALF HOUR, MAINTAIN FIREBOX TEMPERATURES AT 288-343°C (550-650°F) AS MEASURED BY THERMOCOUPLES PLACED IN THE HIP SECTIONS OF THE HEATERS BELOW ANY CONVECTION COILS THAT MAY EXIST. d. IF HEATER/REACTORS ARE AUSTENITIC STAINLESS STEEL AND STEAM CANNOT BE RESTORED WITHIN ONE-HALF HOUR, CUT IN HIGH NITROGEN PURGE RATE THROUGH HEATER AND REACTOR. MAINTAIN FIREBOX TEMPERATURES AT 205°C {400°F) IF FIREBOX COILS ARE AUSTENITIC AND 290-315°C (550- 600°F) IF REACTOR INTERNALS ARE AUSTENITIC. 3. In general, whatever the emergency, take steps to prevent condensation of water in any austenitic system while oxygen is present, Also, avoid pumping caustic into the catalyst beds. D. INERT GAS REGENERATION PROCEDURE {FOR S-6, S-9, S-12, S-15, S-16, S-18, S-19, S-120, N-204, N-108 AND HC-K HYDROBON® CATALYSTS) ‘Shutdown 1. Shut down the unit in the normal manner following the procedure detailed earlier. Continue recycle gas circulation for at least one hour 260°C: (500°F) and until no more liquid accumulates in the product separator and the reactor section low points. Shut down the charge heater and then the recycle compressor. IF THE CHARGE HEATER COIL IS AUSTENITIC STAINLESS STEEL, MAINTAIN 205°C (400°F) FIREBOX TEMPERATURE. Drain all liquid hydrocarbon from the system. uoD Its. xm