43 44 45 46 47 CHEMICAL CLEANI |G PROCEDURE ILED OPERATIONAL PROCEDURE TABLE OF CONTENTS INTRODUCTION OUTLINE CHEMICAL CLEANING PROCEDURE APPENDIX A- SAFETY RULES APPENDIX B- ANALYTICAL METHODS, ON LINE INHIBITOR TEST SULFAMIC ACID DISSOLVED IRON CITRIC ACID Ph MEASUREMENT INHIBITOR CORROSION TEST COPPER APPENDIX C- OPERATIONAL LOGINTRODUCTION A chemical cleaning treatment is performed on the boiler water circuits to remove from the intemal surfaces’ impurities such as water hardness scale and treatments, excessive iron oxide formation, silica compounds, copper-based compounds and other debris, and to establish a satisfactory magnetite layer. Such a procedure ensures that optimum boiler water and steam conditions are achieved and reducing corrosion on heat exchange surfaces. The method of cleaning on this project is by chemical cleaning and passivation of the economizer and boiler steam generating sections. The supetheater is excluded from the acid cleaning process and will be protected from chemical ingress during cleaning by water wedging/plugging.12 13 14 15 22 23 24 25 32 33 34 (CHEMICAL CLEA! iG PROCEDURE Operation Stage 1 -Preliminary Checks Check all chemicals and other materials are present in sufficient quantity and quality to perform the clean. A sample of the Inhibitor (Aquacure IC 600) to be retained for corrosion test analysis if required. Sample Coupons to be installed into the cleaning circuit at agreed location if required. (not usually done on in service cleans.) Complete erection of temporary cleaning pumps and pipework. Test run pumps. Connect up other utilities (demineralized water, compressedair & nitrogen.) Fill temporary pipework only with demineralized water. Apply hydraulic pressure test to the temporary lines to 1 % times the system static head. (ca 4,5 bar). Repair leaks as necessary. Test steam, water, air and nitrogen lines for integrity, and repair leaks as required. Stage 2- Initial Filling Fill boiler with demineralized water to normal working level via economizer with makeup water pumps. Commence filling superheater with demineralized water using make up water pumps. When at normal working level stop filling, continue back flushing superheaters until a rise in drum level is observed. Fill and prove all temporary and permanent pipework to the system static head (ca bar). Repair leaks as necessary. Establish circulation of economizer and boiler by temporary chemical cleaning, pumps. Drain all system Stage 3 - Iron Oxide Removal Fill the boiler via Economiser with make-up water pump and feed water pump of boiler unit 2. Then stop pumps. Circulate water until water temperature is measured 72 °C at circulation tank, Backflush superheater until a rise in drum level is observed then lower drum level to accommodate addition of chemicals as required. Check the temperature of system has stabilized between 68 and 73°C, then inject chemicals to give concentrations of 5-6% Sulfamic acid (12000 - 14000 kg) 0,2% Aquacure IC 600 (200kg) Backflush superheater until rise in drum level is observed, then continue as necessary to raise the level in the drum to required cleaning level. (Approximately up to half drum), After two hours add Ammonium Bifluoride (S00kg) to give a 0.5% solution, Circulate the solution until the dissolved iron concentration stabilises, or to give a minimum overall contact time of six hours. If the iron level exceeds 10000 ppm a second iron removal should be43 44 45 g = considered. If the iron level exceeds 15000 ppm the boiler should be drained and a second iron removal stage done. Stop circulation and drain boiler and economizer to the chemical water pit. Neutralize and treat effluent in the pit until acceptable for discharge, then pump to Effluent point at waste water treatment plant, Stage 4 — Citrie Acid Rinse Commence filling boiler with demineralized water via economizer and via superheater with make-up water pumps to open drains for approximately 10 minutes then close drains and fill to NWL. Establish circulation of boiler and Economiser and inject chemicals to give: 0.2% Citric Aci Ammonia to pH 3 (200 kg anhydrous) 4.0 (approx. 200-250 liters) imately 1 hour, then stop circulating pumps. Circulate solution for appro» Drain boiler and Economiser to the chemical waste water pit. Neutralize and treat effluent in the pit until acceptable for discharge, then pump to effluent point at waste water treatment plant. Stage 5 — Flush with Demin Water Fill boiler with demineralized water via Economiser to open drains for 10 min. (or until effluent condition is satisfactory), then close drains and fill to NWL. Circulate boiler section only then stop circulation and drain boiler section only to waste. (leaving economizer) Refill boiler with demineralized water to NWL via economizer. Circulate boiler section only for 10-15 minutes and check that condu water is satisfactory. (less than 100pS cm-1) If water condition is unsatisfactory at this point, drain boiler section, refill, circulate and check until a satisfactory conductivity is achieved, leave boiler full and circulating, If there is a lot of insoluble debris in the boiler it may be necessary to manually clean the drums. ty of ‘Neutralise and treat effluent in the pit until acceptable for discharge, then pump to effluent point at waste water treatment plant. Stage 6- Copper Removal/ Passivation Fill the boiler via economizer with make-up water pump and feed water pump of boiler unit 2 and circulate water and down temperature of circulating system to 55°C and as measured temporary chemical cleaning pumps and stop the take water from feed water pumps of boiler unit 2. Backflush superheater until a rise in drum level is observed then lower drum level to accommodate chemicals as required, Check the temperature has stabilized between 50 and 55 °C, then inject chemicals to give the following 1.0% w/w Citric acid (1000 kg anhydrous) ‘Ammonia to pH 3.5-4.0 (approx. 200 liters 25%)64 65 6.6 67 68 4 12 13 14 15 8.2 9.0 O4 92 93 94 95 9.6 97 NOTE: Circulate or up to one hour. Add further Ammonia solution (approx. 2200 liters 25%) to raise pH to 9.5 to 10. Inject chemicals to give the following: 0.5% wiw Sodium Nitrite (500kg) Circulate for a further 4-6 hours until the dissolved copper concentration is stable. Stop pump circulation. Open vents and drain boiler and economizer to effluent neutralization tank until completely empty. Neutralization and treat effluent in the pit until acceptable for discharge, then pump to effluent point at waste water treatment plant Stage 7- Ammonia Rinse Refill boiler with demineralized water to NWL via economizer. Add chemicals, 25-50 liters Ammonia to pH 10.0-10.2 Circulate boiler for 15 minutes. Stop circulation and drain, Stage 8- Inspection Disconnect temporary connections from boiler pressure parts, open both steam drum doors and allow internal parts to ventilate and dry out from heat in the metal Inspect at steam drum, remove sample coupons (if used), and manually remove and debris lying in low-flow areas. Inspect at other terminal points as agreed. On acceptance, release boiler for pressure parts reinstatement. SITE ANALYSIS METHODS On-line Inhibitor Test Sulfamic Acid Dissolved Iron Citrie Acid Ph Measurements Inhibitor Corrosion Test Copper In order to conduct these Site Analysis methods, we need the support from LISCO Chemical Laboratory with LISCO manpowerAPPENDIX A SAFETY RULES Storage All chemical products must be stored and labelled in accordance with the instructions on the safety sheet. Chemicals must not be stored together with inflammable material and gas cylinders. Do not store acids and alkalis together. Do not store strong acids and organic substances together. Do not store strongly oxidizing substances together with oxidizable substances. Ethers and other peroxide-building substances must be stored in the dark and cool, in tightly sealed containers, Chemical containers must be stored with closed lids when they are not being used. Refrigerators and freezers for storage of chemicals must be of such a type that is specially made for this purpose. Chemicals and similar items must not be stored in refrigerators or freezers that are intended to store food. Chemical stores must not have open floor drains. If there is a floor drain, it must be equipped with protection to prevent leakage. This means for example tight fitting lids, a manual opening and closing function in the drain or other comparable arrangement. Equipment for handling and cleaning up spillage must be in readiness and suitable for the chemicals that are stored. It is suitable to have equipment placed outside the chemical store. Itis important for the fire classification of storage lockers and rooms to match the types and amounts of chemicals stored therein. Combustible material must be stored in fireproof cupboards or in separate spaces. Labelling Chemicals must normally be stored in their original packaging. If you need smaller amounts ofa chemical, the new packaging must be suitable for the substance. Labelling must be in accordancewiththeoriginalpackaging,Itmustalwaysbepossibletoknowwhatsubstancethe packaging contains and what risks there may be. Handling of chemicals Always read the safety data sheet and the text on the packaging carefully when you are about to use a product with which you are not completely familiar with the risks. Contact the environmental coordinator if you are unsure about handling methods. Use personal protection equipment (¢.g., gloves, face mask) where necessary. Surplus chemicals and hazardous waste must be dealt with in accordance with the information in the safety data sheet. First Aid equipment must be available. Workplaces must be cleaned regularly. There must not be chemical spills on the floor. Personal hygiene Smoking is forbidden in the factory area outside specially assigned smoking areas. If you smoke, remember to wash your hands before lighting up a cigarette. Otherwise, chemical substances can be transferred by skin contact or breathed in. Immediately wash off chemical traces from the skin. Read the safety data sheet or ask your immediate superior if you are not sure what needs to be done, Food products must not be stored or eaten in premises where chemicals are handled, Work clothes must be kept clean. If you have been in contact with chemicals, take a shower before you go home. 6APPENDIX B_ ANALYTICAL METHODS SYSTEM: Site Analysis Method TOPIC: ON-LINE INHIBITOR TEST REFERENCE: Inhibit/S/01 METHOD: Qualitative test for Inhibitor efficiency in acid cleaning solutions. Introduction Inhibitors are added to acids during chemical cleaning to reduce the rate at which the acid attacks the metal in the system, normally to negligible levels (say 1-2% of uninhibited corrosion rate). Normally the only metal normally requiring protection in chemical cleaning is iron, in the form of carbon steel. When an acid e.g Hydrochloric Acid, reacts with iron it produces hydrogen gas. 2HCI+Fe AFE Ch +H2 Thus the production of appreciable amounts of hydrogen indicate that the acid is attacking the steel in the system The inhibitor test consists of the addition of a small ball of clean steel wool to a sample of the acid solution. If the inhibition is poor then hydrogen will be evolved. The hydrogen bubbles formed will normally adhere to the surface of the wire or become trapped in the body of the ball. Since the ball of steel! wool has a very large area for its weight, once a few bubbles have formed it will tend to float to the surface. Equipment Steel Wool NOTE: The most suitable grade is 00 (fine). Coarser grades have a lower surface area to weight ratio and are therefore less sensitive. New stee! wool is normally covered by a protective layer of grease or oil and this must be removed before use. This is most easily done by washing several times in a volatile solvent. e.g., Acetone or Genklene. After cleaning the wool is highly susceptible to rust and must be stored in a dry sealed container with some silica-gel dessicant. Procedure Tear off a portion of the clean steel wool and roll into a ball about the size of a small pea. Drop the ball into a beaker containing 50-100 cm? of the hot acid solution, ensure the ball is fully wetted and observe for two minutes, (NOTE: For citric acid solutions, the test. temperature should not be more than 80° C as above this the ball may float even in a fully inhibited solution.) Evaluation of Results In normal conditions if the ball remains submerged then the inhibition is satisfactory. Ifit rises to the surface, or refuses to sink, then the inhibition is not satisfactory, the most frequent causes being- 9.7.1 Poor mixing of inhibitor with the acid solution. 9.1.2 Too high and acid strength due to poor mixing or excessive acid addition rates. 9.1.3 Wrong inhibitor for the acid being used.9.7.4 Wrong materials being handled, caused normally by using unmarked or wrongly marked containers. ‘The preliminary action to be taken if the inhibitor test fails is as follows Stop acid addition. Carry out another test on a fresh sample. Check for causes. Notes It should be appreciated that as there are so many variables involved in this test, the results should not always be treated at face value, For more accurate estimations chemical analysis for metal or corrosion tests on sample metal coupons should be undertaken for a particular system. The following points should be noted in particular. Citric Acid cleaning solutions sometimes give rise to misleading results, floating and/or bubbling at|-Sminutes after addition of the ball is not necessarily indicative of poor inhibition, although addition of extra inhibitor to the system should be considered. Quite often at high Iron concentrations, i.e, >5000 ppm a “Ferric iron corrosion”, Reaction occurs at the metal surface which restricts the normal inhibitor bonding thus allowing some acid attack on the surface giving a rise to hydrogen gas, even in a fully inhibited solution. This phenomenon is normally quiteindicativeoftheconditionsinthesystembeingcleanedandthereforeshoulditoccur,the acid solution should be drained as rapidly as possible. Thetestisonlyindicativeoftheinhibitionofthesteelwoolinthebeaker.Care should be taken that the solution flow in the cleaning system does not exceed the maximum flow velocity for acid cleaning of 5 feet (1.5 meters) per second in any area; even a fully inhibited solution will be very corrosive to carbon steel at velocities above this The test temperature is not necessarily that in the whole system. The test would not give waming of, for instance, break up of inhibition on boiler furnace tubes should be inadvertently fired during an acid clean. SYSTEM: Site Analysis Method TOPIC: DISSOLVED IRON REFERENCE: Fe/S/O1 METHOD: Colorimetric determination of Total Iron in process solutions using thioglycollic acid. ‘Theoretical Considerations Thioglycollic Acid (HS.CH:COOH) reacts with ferrous ions in alkaline solution to give a magenta coloration, the intensity of which is directly proportional to the Ferrous Iron concentrationofthesolution. Thioglycollicacidalsoactsasareducingagent,convertingferric ions(Fe*)toferrousions(Fe™*).Hencethetotalironconcentrationofasolutioncanbefound using the following method. Chemical Reagents Concentrated Ammonia solution (0,880 Analar) Thioglycollic Acid (Mercaptoacetic) G.P.R Standard Iron Solution (1000 ppm Fe)Apparatus Spectrophotometer capable of measuring at approx. 550 nm (550x10-°m) e.g WPA E1 colorimeter fitted with No. 5 filter at Hi-intensity. WPA HC 600 with 560 filter or Lovibond Comparator with cells and a 3/6 standard disc. 100 cm? volumetric flasks Micromaster or Eppendorf pipettes and disposable tips. Plastic filter funnel No. 1 filter papers Wash bottle for demineralised water Procedure Ifa colorimeter is to be used switch on and allow to warm up for at least 15 minutes. Filter the sample if necessary to remove suspended solids and allow to cool. Take 100 microliter of sample (or other quantity-see Notes below) using micromasterpipette and transfer to 100 cm? volumetric flask. ‘Add 20-30 cm? water, then 2 drops of Thioglycollic Acid and mix. ‘Addanexcess(approx.0,5cm?)ofAmmoniasolution,makeuptothe100cm?mark with water and mix thoroughly. The colour should develop almost immediately. Transfer sufficient quantity of the colour solution to a 1cm. glass cell. Zero the colorimeter to 0(%absorbance)or100(%transmittance)withasimilarcellcontainingdemineralisedwater, then measure the transmittance T or absorbance A as per the colorimeter instructions. At the end of sampling session, switch off the colorimeter. For the Lovibond Comparator add the colour solution to one glass cell to approx 2/3 full and add demineralized water to the other cell. Place the cells in the instrument with the coloured cell in the centre. Holding the device up to the light rotate the disc until the nearest match is made between the two coloured circles. Read off the absorbance A from the bottom right- hand number hole. Colorimeter Standardization For the first in a set of readings it is recommended to standardize the colorimeter as follows: Conduct the above determination but using a suitable volume (often 200ul) of Standard1000 ppm Fe solution to give a midpoint reading. Read the transmittance Ts or absorbance As. Calculation Calculate the Standardization Factor Q by the formula: 2000 2000 or (2-logTs As From the standardization factor the Iron concentration of the sample may be calculated as: For 100 ul sample taken Ppm Iron = (2-logT) x Q Or ppm Iron = Ax Qx 100/V For the Lovibond Comparator fitted with 3/6 disc the reading corresponds directly to mg. of iron in the coloured solution. To calculate Iron concentration in the sample.For 100ul sample taken: ppm Iron = A x100000 For a volume V ul sample taken: Ppm Iron = A x 100000000/ V SYSTEM: Site Analysis Method TOPIC: CITRIC ACID REFERENCE: CAIS/OL METHOD: Determination of % Citric Acid in process solutions by Cation Exchange / Volumetric technique. Theoretical Considerations Citric Acid (C. OH. COOH. (CH2COOH),) is a complexing acid and finds wide use in chemical cleaning. Inprocessesitisnecessarytodetermineitsconcentrationinbothacidicandalkaline solutions. As citric acid is rarely employed on its own, but usually as a salt, e.g. monoammonium citrate (in acidic processes) and tri ammonium citrate (in alkaline passivations/copperstripprocesses),thenallcitratesmustbeconvertedbacktothefreeacid form. Thismaybeachievedbyusingacationexchangeresinwhichhastheeffectofremoving ammonium ions and replacing them with hydrogen ions, thus giving free citric acid, Likewise, iron citrates are converted to citric acid by the absorption of the ferrous and ferric ionsbytheresin.Thereforethetotalcitricacidcanbefoundbystandardtitrationwithsodium hydroxide using phenolphthalein indicator. if ammonium bifluoride, sodium bromate or sodium nitrate are present the ion-exchange treatment will result in the formation of HF, HBrO3 and HNO, respectively, and these acids will contribute to the overall acidity acting against the NaOH, hence corrections need to be made if necessary. Chemical Reagents Cationic exchange resin (in Hydrogen H* form) e.gZerolit 325, Dowex 50-W-X8(H) Standard Sodium Hydroxide solution 0.5 molar (0.5N) Phenolphthalein indicator Apparatus 250 em? & 100 em? conical flasks Reservoir bottle & 10 cm’ auto burette for 0.5M NaOH. Pipettes 10 & 20cm! and safety pipette filler 2x Plastic filter funnel No. I filter papers 25 em’ plastic measuring cylinder Glass wool Wash bottle for demineralized water Procedure Filter the sample if necessary, to remove suspended solids and allow to cool. ‘Add a slurry of resin to the measuring cylinder until, after settling, the resin volume reaches approximately 10 cm®. Transfer the resin to a clean 100cm* conical flask, rinsing a few times 10with demineralized water if necessary. When all the resin has been transferred, decant off excess water from the resin. Using a safety pipette filler, pipette 10cm? (for 2-3% acid cleans) or 20 cm*(for citric rinses and passivation’s) of the sample on to the resin in the flask. Swirl gently to mix and allow to stand for 5 minutes, occasionally swirling the flask to thoroughly mix the contents (Flask A.) Place a small plug of glass wool lightly in the mouth of another clean plastic filter funnel or a filter paper and place the funnel in a 250 cm? conical flask(Flask B). Decant the solution from Flask A through the funnel into Flask B taking care to keep as much resin as possible in Flask ‘A. Rinse the walls of the funnel with 2-3 cm? water into Flask B. ‘Add 10-20 cm? water to Flask A, swirl briefly and again decant through the plugged funnel as above info Flask B. Rinse funnel again with 2-3 cm? water. Wash the resin twice more as above. If any beads of resin have collected in the funnel, rinse them thoroughly, allowing the funnel to empty between rinsing’s. Finally place the empty funnel in Flask A. Add 3-6 drops phenolphthalein indicator to the solution in Flask B, zero the auto burette and titrate against the standard sodium hydroxide solution. Allow the solution to just turn pink andthenstoptitrating PlacethepluggedfunnelinFlaskB,addafurther10-20cm?waterinto the resin in Flask A, swirl briefly and again decant through the funnel into Flask B. Continue titrating dropwise as above until the solution turns pink once more. If three drops or less of Sodium Hydroxide solution are required the end point has been reached, if not perform another 10-20 cm? rinse. Note the final burette reading Vem? Empty Flask B of the solution and rinse out well. Once again rinse the resin in Flask A and discard the rinse water. Finally discard any resin in the funnel, then place the empty funnelin Flask B. Drain excess water from the resin. The resin may be used for the next determination. Calculation For a solution containing only citric acid, ammonia and dissolved iron, the cidric acid concentration is found as follows: Total Citric Acid (%w/v) = V cm? x 0,32 (for 10cm? sample) Total Citric Acid (%w/v) = V cm? x 0,16 (for 20cm? sample) Free Citric Acid (%w/v) = Total Citric Acid — (3,4 x Iron*) * See notes below. Ammonium Bifluoride present TOPIC: pH MEASUREMENTS. REFERENCE: pHIS/O1 METHOD: Determination of pH of Chemical Cleaning solutions. Theoretical Considerations The pH ofa solution is a measure of its acidity or alkalinity. The pH scale runs from O (very acidic) to 14 (very alkaline). At pH 7 acidity is equal to alkalinity, i.e. the solution is neutral. Technicallypl Tisdefinedasminusonemultipliedbythelogarithmtobase I Oofthellydrogen ion concentration, i.e.:- pH ~ logio [H'] Since it is a logarithm, it is a pure number and therefore has no units. ulThe precise measurement of pH is conveniently carried out electrically and many commercial electronic pH meters are available. The method used relies on placing two different electrodes in the solution to be measured and measuring the voltage produced between them. One electrode is known as a "reference" electrode while the other is a "glass" electrode. The glass electrode is the one which produces a varying output, depending on the pH of the solution. In most modern meters the two electrodes are combined in a single unit often referred to as a “combination pH electrode". This is the type used with the WPA El Suitcase Laboratory kit. Due to ageing effects in the electrode(s) itis essential to set up a pH meter to read correctly by using solutions whose pl is accurately known, Such solutions are known as buffer solutions. Once set up, the calibration will last for about 24 hours, but less if the instrument is repeatedly switched on or off, Accuracy When ammonium bifluoride has been added to cleaning solution, there in will convert it to HP acid which contributes towards the total titration value. The correction is 2,244 x (Yew/w Bifluoride added.) The correction is as % Citric Acid and is to be subtracted from the Total Citric Acid as calculated above. For 10 cm? sample containing 0.5% w/w Ammonium Bifluoride Total Cittic Acid (%ow/v) = (V em x 0,32)- 1,122 Notes The calculation for free citric acid is based on the reaction between iron scale and citric acid producing Ferrous Hydrogen Citrate (monoammonium Fe II citrate) CHy COO" Fe* CHy This is certainly what is formed with an excess of citric acid, Calculations based on forming thisproduetshowanlronsaturationlevelof8820ppm((.87%w/w)for3%citricacidsolution, However thisisnotthesaturationlimitforcitricacidasfurtherreactioncantakeplaceleading to the tri ferrous dicitrate salt. This gives a true saturation level of 13000 ppm Fe (1.3% wiw) for a 3% citric acid solution, In addition to the above in the presence of oxidizing conditions a corrosive reaction known as “ferric ion corrosion’’ can occur. This is particulary severe in solutions of high Iron concentrations, say above 6000-7000 ppm (0,6-0,7 % w/w) when it tends to become self- supporting. Fe(III) citrate + 02 AFe(III) citrate COO" NH. 2(Fe(Ill) citrate) + Fe &3(Fe(II) citrate) ‘The first reaction above occurs more easily the higher the pH of the solution becomes. The overall reaction is unaffected by the presence of inhibitors and in fact as it is a metal surface reaction it can, in some cases, interfere with normal “surface coating” action of the inhibitor giving the appearance of inhibitor breakdown. For the above reasons it is not good practice to exceed 7000 ppm Fe during a 3% w/w citric acid clean, nor to allow the free citric acid level to fall below 0.5% w/w. It is neither good practicetosupplementthestrengthof” dirty” acidsolutionsbyadditionoffurthercitricacid, as has been common practice in the past. The solution should be drained and the acid stage repeated, if agreed with the client. 12SYSTEM: Site Analysis Method There is a theoretical maximum accuracy for pH measurements of about 0.01. With an analogue indicator such as that fitted to the WPA meter, the reading accuracy is only about 0.1, This is probably the highest accuracy that could be expected from such an instrument and a figure of 0.2 is more realistic. Temperature has a marked effect on the measurement of pH andwithasimpleapparatusitisimportanttomakemeasurementsonsolutionsatapproximately the same temperature as the buffer solutions used for calibrations. CertainpHmetersarefittedwith" Temperaturecompensated" electrodesorhaveaTemperature adjustmentscale.Forthebestaccuracy however, itisalwaysbesttouseasettemperature(say 20°C) for all readings. Apparatus and reagents Suitable pH meter and electrode such as WPA Suitcase Laboratory with E1/F pH module and pH electrode. 100cm3 glass or plastic beakers Wash bottle for demineralized water pH Buffer solutions, pH 4, 7 & 10 Thermometer Procedure Standardization (This normally only needs to be done once at the start of an analysis session or if a new pH range is being measured.) ConnectpHelectrodetothepHmeter Switchonandperformbatterycheckifne stabilise for 10 minutes before taking readings. Select the pH buffer nearest in pH to the sample to be measured and pour approx 50 cm3 in a clean 100 cm3. Remove the electrode cover, fit protective skirt if necessary, then rinse the electrode with a jet of demineralized water. Place electrode gently in the Standard Buffer solution, stir gently and allow the meter reading tosettleforabout3 seconds. UsingtheadjustingknobonthepHmodulesetthemetertoread the correct pH value on the meter scale. Record also the solution temperature. ssary.Allow to Sample Reading Pour about 50 cm3 of the sample into another clean 100 cm3 beaker and measure the temperature. Coolifnecessarytogiveatemperatureof5°Cofthebuffersolutiontemperature, Place electrode gently in the sample solution, stir gently and allow the meter reading to settle for about 30 seconds. Read the pH directly on the meter scale. If the reading is more than + 2 pH units away from the buffer reading, then itis likely that a better choice of buffer can be made. Remove the electrode, rinse thoroughly with demineralized water then immerse in a beaker containing demineralized water. Care of Electrodes CombinationpHelectrodesaresensitive,fragileandexpensive. Wheninuse,theglassbulbon the electrode tip must never be touched and the protective plastic skirt around the tip must always be fitted. The glass tip must never be allowed to dry out and when not in use the plastic skirt should be removed and replaced with the rubber cap supplied, filled with demineralized water or pH 7 buffer solution for storage (take care not to touch the glass bulb with the fingers when doing this). If necessary clean the tip carefully by wiping gently with a fine paper tissue, then rinse thoroughly with demineralized water. Store with the bulb facing downwards if possible. 13SYSTEM: Site Analysis Method TOPIC: INHIBITOR CORROSION TEST InhibCorr/S/01 Quantitative evaluation of corrosion rate of an Inhibited Acid cleaning solution, Introduction Inhibitors are added to acids during chemical cleaning to reduce the rate at which the acid attacks the metal in the system, normally to negligible levels (say 1 - 2% of uninhibited corrosion rate). Normally the only metal normally requiring protection in chemical cleaning is iron, in the form of carbon steel. When an acid e.g. Hydrochloric Acid, reacts with iron it produces hydrogen gas:~ 2HCI + Fe => FeCb + H2 Thus the production of appreciable amounts of hydrogen indicate that the acid is attacking the steel in the system, Abriefmethodtocheckforthisreactioninapoorlyinhibitedsolutionisthesimple"wirewoo!" test (ref. Method sheet Inhib/S/01). However when a batch of inhibitor is of suspect quality, or its identity cannot be certain (e.g. missing or defaced labels on containers), then the following laboratorymethodmaybeusedtoestablishthecorrosionrateoftheacid/inhibitorcombination. The following method is given for a standard cleaning solution, i.e. Hydro chloric Acid inhibited with Armohib 28 at 70°C, however it may be adapted for other combinations, e.g. Citric Acid inhibited with Stannine LTP at 90°C (further details available on request). Apparatus Combination Magnetic stirrer/hotplate with thermostatic control* ‘Thermostatic immersion type contact thermometer (adjustable +20 -+100°C)* (*iftheabovearenotavailableastandardtemperatureadjustablestirrerhotplatecanbeused, however the temperature should be checked and adjusted continually to be in the required range) Magnetic stirrer follower Weighing balance (accurate to 4 decimal places, i.e. to 0.0001g, 0.1mg) 800cm? glass beaker Retort stand, 2 x bosses & clamps Eppendorf Micropipette, 100 - 100011 + disposable tips Stainless steel wire Wash bottle for demineralized water Carbon steel standard test coupons Reagents Hydrochloric Acid 5% w/w solution Armohib 28 inhibitor (taken from batch to be tested) Acetone or Methanol (50ml) Method Set up the stitrer/hotplate and stand with the beaker & magnetic follower. Set the contact thermometer to 70°C and suspend using one of the clamps in the beaker. Add Hydrochloric Acid to the 500ml mark (or sufficient to fully cover the test coupons) ensuring the tip of the thermometer is immersed. Commence heating and stirring slowly. 14Allow the solution temperature to balance at 70°C +/- 5°C. In the meantime prepare a new corrosion test coupon by degreasing thoroughly with a little acetone or methanol, drying thoroughly and weighing on the balance, recording the initial weight. Add 0.2%wiw of the inhibitor to be tested (100011 using the micropipette) and allow to mix thoroughly. Suspend the coupon in the stirring solution by means of a piece of stainless steel wire attached to the retort clamp. Ensure the coupon is fully immersed and does not interfere with the magnetic stirrer follower. Note the start time. Continue heating & stirring as above checking the liquid level. Occasionally add water to the 500m! mark to make up for evaporation loss. After 4 hours exactly, remove the coupon and wash immediately with demineralised water followedbyacetoneormethanolanddryagain. Reweighimmediately(orwithinS-10minutes) and note the final weight. Measure the dimensions of the coupon and calculate its surface area (in m?) Calculation & Evaluation of Results ‘The corrosion rate of the acid/inhibitor combination can be found as follows:- Corrosion rate in gm-*h"? = (Initial weight (g) - Final weight (g) Surface area(m*) x 4 A satisfactory corrosion rate would be less than 2 gn may be achieved, If the corrosion rate exceeds 2, the inhibitor may not be satisfactory and should not be used for thechemicalclean.Inthiscasethechemicalsuppliermustalwaysbeinformed.Iftheevaluation is uncertain, repeat the test on a separate sample of the inhibitor with a new test coupon. 2h, in practice less than 1 gm-*h"* SYSTEM: Site Analysis Method TOPIC: Copper REFERENCE: cwS/01 METHOD: Colorimetric determination of Copper in process solutions using Biscyclo hexanone Oxaldi hydrazone Reagent ‘Theoretical Considerations BiscyclohexanoneOxaldihydrazone(BCHorBCODH:Cy4H22Na02)reactswithcopperionsin ammonical solution to give a blue coloured complex. The intensity (depth) of colour is proportional to the amount of copper ions in solution(i.e. the copper concentration). High iron contentinthesamplewillpreventtheformationofthecoppercomplex,henceafluoridebuffer is, added to overcome this. Chemical Reagents BiscyclohexanoneOxaldihydrazone, Dissolve 0.25g BCH in 100 cm* of 50%w/w Ethanol (Ethyl Alcohol CzHsOH) - water solution. Allow to cool. Buffer solution, Dissolve 50g Citric Acid (A.R. Grade) in 200cm? distilled water. Solution (Solution A). Dissolve 25g ammonium fluoride, NH4F (A.R. Grade) in 100cm3 in a plastic beaker(Solution8).AddsolutionAandBto1 50cm?0.880Ammonia(A.R.Grade-35%wiw); mix, cool and dilute to $00em® with distilled water. Caution: Ammonia is Toxic, Fluorides are toxic and corrosive. Standard Copper Solution (1000 ppm Cu) 15Apparatus Spectrophotometer capable of measuring at approx. 59Snm (595 x 10%s m) e.g: El colorimeter fitted with No. 7 filter at Lo-intensity 100cm* volumetric flasks Micromaster or Eppendorf pipettes and disposable tips Plastic filter funnel No. 1 filter papers Wash bottle for demineralised water Procedure If a colorimeter is to be used switch on and allow to warm up for at least 15 minutes. Filter the sample if necessary to remove suspended solids and allow to cool. ‘Take 100 microlitres (111) of sample (or other quantity - see Notes below) using micromaster pipette and transfer to 100cm* volumetric flask. Add 20 - 30cm? water, then 10cm? buffer solution and mix. Pipette Sem* of BCH reagent into the flask, mix and make up to 100cm3 with distilled water. Allow to stand for 10 minutes exactly before measurement. Transfer sufficient quantity of the colour solution to a | cm. glass cell. Zero the colorimeter to © (% absorbance) or 100 (% transmittance) with a similar cell containing demineralized water, then measure the transmittance T or absorbance A as per the colorimeter instructions. At the end of a sampling session, switch off the colorimeter. Colorimeter Standardization For the first in a set of readings it is recommended to standardize the colorimeter as follows:- Conduct steps to 4.7 above but using 100,11 of Standard 1000 ppm Copper solution, Read the transmittance Ts or absorbance As Calculations Calculate the Standardization Factor Q by the formula:~ Q = 1000 or — 1000 (2-logTs) As From the standardization factor the Copper concentration of the sample may be calculated as:~ For 1001 sample taken:-ppm Copper = (2 - log T) x Q or: ppm Copper = A xQ For a volume V ul of sample taken:~ ppm Copper = (2 - log T) x Q x 100/V or: ppm Copper = A x Q x 100 Notes For initial Copper removal stage (500-2000ppm) take 10011 sample For Second Copper removal stage (20-400ppm) take S00uI-Sc 16CHEMICAL CLEANING PROCEDURE / Operational og Comments Devons Trai [Retain ssampe of bor Armanib or Ise ap apply hydrate tat on tensoray ppEwOR iahen at aprox 3/7 vein te ro, ap AN [continu ing ad backtushngsopereatrs vt seen ram ve! fat ast sme bserved 7lbetom of sem runtnsmay be permanent our as apron i? dr or rene hours Mesure every 30 mies or as stn caver So Lieor ad ithe tank 18‘ag. 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When 0.010 225-50 tres, 20‘The List of Chemicals required for Boiler Chemical cleaning according to the above procedure is given below: S.No | Chemical Quantity ( Approx.) 1 | 5-6% Sulfamic Acid 12000 - 14000 Kg 2 | 0.2% Aquacure IC 600 200 Kg 3 | Ammonium Bifluoride 500 Kg 4a | 0.2% Citric Acid 200 Kg anhydrous 4b | 1.0% wiw Citric Acid 1000 Kg anhydrous 5 | Ammonia Solution 2750 Liters 6 | 0.5% wiw Sodium Nitrate 500 Kg 2