TECHNOLOGIES FOR CLEAN AND

RENEWABLE ENERGY PRODUCTION

IMPURITIES REMOVAL FROM LIQUID FUELS
DR. PRASENJIT MONDAL
CHEMICAL ENGINEERING DEPARTMENT

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 Contents

 Impurities and need of their removal

 Processes for impurities removal
• Sulphur compounds removal (Sweetening process)
• Sulphur, nitrogen and metal removal (Hydro treatment)

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 Impurities and need of their removal
• Fractions or streams produced by crude distillation, cracking, and other refinery
processes often contain small amounts of impurities such as organic compounds
containing sulfur, nitrogen and oxygen; dissolved metals and inorganic salts; and
soluble salts dissolved in emulsified water.
• Impurities removal needed to achieve the quality of finish products (colour, orour,
oxygen stability etc.) as well as to prepare feedstocks for other processes such as
polymerization and reforming) in which catalysts would be harmed by impurities.
• Impurities may be removed by chemical reagents, by catalysts, and by adsorption
on clays or similar materials.
• Removal of Sulphur compounds (sweetening) is most important for refiners and
is carried out by alkali extraction (caustic sweetening) and hydrotreatment
• A variety of intermediate and finished products, including middle distillates,
gasoline, kerosene, jet fuel, and sour gases are dried and sweetened

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 Sulphur and nitrogen compounds in petroleum products
Sulphur compounds Nitrogen compounds

Thiols (mercaptans) RSH Pyrole C4H5N

Non Basic
Sulfides RSR’ Indole C8H7N

Disulfides RSSR’ Carbazole C12H9N

Cyclic sulfides Benzo(a)carbazole C16H11N

Thiophene
Benzothiophene Pyridine C5H5N

Dibenzothiophene Quiniline C9H7N Basic

Naphtanobenzothiophene Indoline C8H9N

Benzo(f)quinolone C13H9N

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Processes for impurities removal Sweetening processes

• Caustic wash
• Doctor treatment
• Copper sweetening
• Merox process

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 Caustic wash
The process consists of mixing a water solution of lye (sodium hydroxide or caustic soda) with a
petroleum fraction.
The treatment is carried out as soon as possible after the petroleum fraction is distilled, since
contact with air forms free sulfur, which is very corrosive and difficult to remove.
The lye reacts with any hydrogen sulfide present to form sodium sulfide, which is soluble in
water. Mercaptans are converted as follows.
RSH + NaOH ---> NaSR + H2O
Caustic solutions ranging from 5 to 20% w/w are used at 20 to 45°C and 5 to 40 psi. High
temperatures and strong caustic are usually avoided because of the risk of color body
formation and stability loss. Caustic-product treatment ratios vary from 1:1 to 1:10.
Spent lye is the term given to a lye solution in which about 65% of the sodium hydroxide
content has been used by reaction with hydrogen sulfide, light mercaptans, organic acids, or
mineral acids.
A lye solution that is spent, as far as hydrogen sulfide is concerned, may still be used to remove
mineral or organic acids from petroleum products
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 Doctor treatment
Doctor Sweetening
It is the treatment with sodium plumbite solution (Na2PbO2) and elemental sulfur
to convert mercaptan to disulfide.
2RSH + Na2PbO2 ----> Pb(SR)2 + 2NaOH
2Pb(SR)2 + XS --> RSSR + RSxR + 2PbS
Pb(SR)2 + 1/2O2 --> RSSR + PbO
Disadvantages
• Too much elemental sulfur added cause excess formation of polysulfides which
leads product to fail copper strip corrosion test.
• If sulfur added is less, lead mercaptide remains in oil and its oxidation to lead
oxide causes failure to pass water tolerance test.

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 Copper sweetening
It is the treatment with copper chloride to convert mercaptan to disulfide
4RSH + 2CuCl2 ---> 2CuSR + 4HCl + RSSR
RSH + CuCl ---> CuSR + HCl
2CuSR + 2CuCl2 ---> RSSR + 4CuCl
2CuSR + O2 ---> 2CuO + RSSR

Disadvantage
• Some oil soluble cuprous mercaptide remains in treated oil
• Copper chloride reacts with naphthenic acids, phenols and other polar
compounds to form oil-soluble copper compounds
• Oil soluble cuprous mercaptide oxidization to copper oxide causing failure to pass
water tolerance test.

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 Merox process

• Merox is one of the most successful treating processes licensed by UOP

introduced in 1958.
• Completely replaced the older processes
• Success attributed due to simplicity, diversity and economy.
Mercaptan Reduction can be accomplished in Two Ways
• Extraction of low molecular weight mercaptans from LPG or light straight run
naphtha (LSRN) with alkali and subsequent catalytic oxidation to disulfides.
• Conversion of high molecular weight mercaptans present in heavy naphtha, FCC
gasoline, ATF and kerosene into disulfides.

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 Reactions in Mercaptan Reduction

RSH + NaOH NaSR + H2O (1)

Oil Aqueous Aqueous
Phase Phase Phase

4NaSR + O2 + 2H2O  4NaOH + 2RSSR (2)

Aqueous Phase Oil Phase
(insoluble in caustic)
4RSH + O2  2RSSR + 2H2O
Reaction (1) is Favourable
i) For low molecular wt. mercaptans
ii) Low temperature
iii) High caustic concentration

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 Extraction merox process

Image provided courtesy of Honeywell UOP ©2019 11

 Caustic prewash
 The petroleum fraction is subjected to pretreatment for removing hydrogen
sulfide and catalyst toxins. This treatment increases the process efficiency and
reduces catalyst consumption.
H2S + NaOH  Na2S + 2H2O
Na2S + H2S  2NaHS
The following reactions could occur in oxidizer
2Na2S + 2O2 + H2O  Na2S2O3 + 2NaOH
2NaHS + 2O2  Na2S2O3 + H2O
Na2S + 2O2  Na2SO4
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Air Injection :
It supplies oxygen for oxidation reaction in the oxidizer. Stoichiometric
requirement is 0.84 Nm3/kg of RSH-sulfur. Necessary to have excess air in the
range of 110-200%. Increasing air rate causes rapid and complete caustic
regeneration. With very high air rate :
• Dissolved oxygen could cause sweetening in extractor.
• Spent air will have higher oxygen leading to increased corrosion and hazard.
• Settling of catalyst.
Air = 1.5 x 0.84 (F) (SG) (RSH)/1000
where Air = Air injection rate Nm3/hr
F = LPG flow rate, m3/hr
SG = Specific gravity of LPG at 15.5oC
RSH = Mercaptan sulfur, ppmw
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 Catalyst for merox reaction
• Merox WS is a totally water-soluble and specially formulated catalyst for use in
extractive or liquid-liquid sweetening
• Form Liquid Solution
• Sp. gravity at15oC 1.16 + 0.01
• Freezing pt. oC 0
• Active ingredient 1 Kg / gallon (3.8 ltr)
• Merox FB catalyst is developed for in-situ impregnation of the fixed-bed
sweetening version of the UOP Merox process. Merox FB catalyst is as water
slurry ready for use in the fixed bed Merox reactor impregnation step.
• Form Liquid Dispersion
• Sp. gravity at15oC 1.15 + 0.01
• Freezing pt. oC 0 ; Active ingredient 2.5 Kg / 2.5 gallon (9.5 ltr)
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 Examples of Applications of the Merox Process
Stream Applicable Treatment
LPG Extraction for Mercaptan Removal
Light Straight run naphtha Extraction /
Liquid-Liquid Sweetening
Visbreaker Gasoline Fixed Bed Sweetening
FCC Gasoline Fixed Bed Sweetening or
Liquid-Liquid Sweetening
Full Boiling Range Fixed Bed Sweetening
straight run naphtha
Kerosene, Aviation Fixed Bed Sweetening
Turbine Fuel
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 Hydro treating/Hydro processing
Hydroprocessing : Thermal conversion process in which hydrogen is used to
accomplish the objectives of the refiner
Hydrotreating: A process in which H2 is used to convert heteroatom constituents into
their heteroatom hydrogen analogues and hydrocarbons
R-S-R1 + H2 RH R1H + H2S
Hydrocracking: Thermal decomposition is extensive and H2 assists in the removal of
the heteroatoms (S & N) as well as mitigating the coke formation which normally
accompanies thermal cracking of high molecular weight polar constituent.

Major differences between hydrotreating and hydrocracking are the time at which
the feedstock remains at reaction temperature and the extent of decomposition of
non heteroatom constituent and products

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 Hydrodenitrogenation
• Hydrodesulfurisation
RSH + H2 RH + H2S
(Mercaptan)
RSR + 2H2 2RH + H2S
(Sulphide)
RSSR + 3H2 2RH + 2H2S
H2S Combustion CO2 + SO2

Heterocyclic ring-opening pathways

during HDN in the presence of an
acid−base pair as illustrated by the
conversion of indole
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Substitution reaction leading to denitrogenation during HDN in the presence of H2S
The catalysts
• Tungsten and molybdenum sulfides (active components) supported on alumina,
and their properties are modified by adding cobalt or nickel (hydrogenation
promoters).
• Co/Mo is more selective for sulfur removal while Ni/Mo is more selective for
nitrogen removal.
• This is the case because Ni/Mo catalysts have higher hydrogenation activity than
Co/Mo catalysts.
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 Metal removal
• The metals found are sodium, potassium, lithium, calcium, strontium, copper,
silver, vanadium, manganese, tin, lead, cobalt, titanium, gold, chromium and
nickel.
• The concentration of the vanadium varies from as low as 0.1 ppm to as high as
1200 ppm, while that of nickel commonly varies from trace to 150 ppm.
• Vanadium and nickel are thought to occur in petroleum in two forms; porphyrinic
and nonporphyrinic. Little is known about the nature of nonporphyrins. However,
the porphyrins have been extensively studied
• The heavy metals (Me) in crude oil residue are
agglomerated in asphaltenes in the form of porphyrin
compounds. The molecular weight of this type of
compound varies between 420 and 520 i.e., from
C27N4 – C33N4
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 • The physical method is essentially deasphalting. The chemical method includes
thermal processes such as visbreaking and coking; and chemical treatment.
• In the deasphalting process, the lighter oils are physically separated from heavier
asphaltenes by mixing the heavy oil/residue with a very low boiling solvent such as
propane, butane or isobutene. The thermal processes are basically the reshuffling
of the hydrogen distribution in the residue to produce lighter products containing
more hydrogen while the asphaltenes and metals are removed in the form of coke
or visbreaking residue.
• The basic chemical concept of demetallization is to selectively remove the metal
from the organic moiety with minimal conversion of the remaining petroleum. The
deme-tallization of metalloporphyrins by acid is a reversible reaction and can be
represented by the following equation:
PM + HX PH + MX
• Catalytic hydroprocessing is a hydrogenation process used to remove compounds
containing nitrogen, sulfur, oxygen and/or metals from liquid petroleum fractions.

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Thanks…

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