THIONOL
Introduction Sulphur compounds are naturally existing in natural gas and crude Sulphur occurrence in small quantities is undesirable and should be treated. to: Comply with environmental standards & regulations Reduce toxic exposure and health risk level Reduce operational risks at refineries; storage tanks facilities, terminals and transport vessels Control odors Reduce corrosion Maximize profitability by meeting fuel and crude oil specification Increasing the value and open markets of the products ($CASH)
Introduction- Crude & Sulphur There are basically* four type of crudes around the world: - Light sweet 30-40 API, 0.5% Sulphur - Light sour 30-40 API, < 1.5% Sulphur - Heavy sour 15-30 API, 1.5% < Sulphur < 3.1% - Extra heavy 9-15 API, > 3% Sulphur Tengiz 46.4 0.51% Kazakhstan Saharan Blend 45 0.09% Algeria Sulphur compounds include Thiophene Diethyl disulfide Sulfur dioxide 1-Propanethiol 2-methyl-1-propanethiol Benzothiophene Methanethiol Ethylmethyl sulfide Diethyl Sulfide Methyl Benzothiophene Ethanethiol 2-Butanethiol 1-Butanethiol Other methyl Benzothiophenes Dimethyl sulfide H2S Dimethyl disulfide C2 thiophenes Carbon disulfide 1-Propanethiol 2-methylthiophene Dibenzothiophene 2-propanethiol Ethylmethyl sulfide 3-methylthiophene Carbonyl sulfide 2-methyl-2propanethiol 2-Butanethiol
Introduction- Crude & Sulphur The level of Sulphur in the past two decades has steadily been increasing due to the production (use) of heavier crude and cheaper high sulfur crude which has forced the refining industry to go for additional facilities like Ultra-de-sulphurization for gasoline and diesel to meet the stringent requirements of Sulphur emission standards. Sulphur content in the crude varies widely depending on the origin The variation is considerable and this impacts the processing schemes as well as the product slate Worldwide Crude Quality: Source: Samanti R.K Refining challenges and Trends on Petroleum refining and petrochemicals, June 6, 2012.
Introduction- Sulphur in fuel v When fuel is burned the Sulphur combines with oxygen (SOx) to create emissions that contribute to decrease air quality and have negative environmental and health effects. v Due to increasing environmental concerns, stringent limits on Sulphur levels in fuel are being implemented worldwide to achieve the target of allowed Sulphur content: 15-30ppm. v Deep hydrodesulphurization is required which is an additional capital cost as well as an energy intensive changing step and loss of hydrocarbon. The evolution of EU fuel specifications for sulfur content-ppm Year Product 1994 1996 2000 2005 2008 Gasoline 2000 2000 350 50 30 (all blends) Diesel 1000 500 150 15 10
Definition- Sulphur Contaminants 1. Mercaptan Sulphur: Class of organic compounds which are composed of an aryl OR alkyl group and a thiol group. Ø Aryl compounds contain an aromatic ring with one or more functional group(s) or substituents. The aromatic ring can be phenyl, naphthyl, tolyl or xylyl group. - Phenyl considered as the simplest member of aryl group. Ø An alkyl compound is an organic functional group that contains only carbon and hydrogen atoms, which are arranged in a chain -They have general formula CnH2n+1 - Methyl CH3 (derived from methane) is considered as simplest member of alkyl group
Definition- Sulphur Contaminants- continue Ø Thiol is a compound that contains the functional group composed of a sulfur atom and a hydrogen atom (-SH). Ø Methyl Mercaptan is considered the simplest form: CH3-SH Ø Other examples: Ethanethiol C2H5SH [ethyl mercaptan] 1-Propanethiol C3H7SH [n-propyl mercaptan] 2-Propanethiol CH3CH(SH)CH3 [2C3 mercaptan] Allyl mercaptan CH2=CHCH2SH [2-propenethiol] Butanethiol C4H9SH [n-butyl mercaptan] tert-butyl mercaptan (CH3)3CSH [t-butyl mercaptan] Pentanethiols C5H11SH [pentyl mercaptan]
Definition- Sulphur Contaminants- continue 2- H2S Hydrogen Sulfide Ø Hydrogen sulfide occurs naturally in crude oil, Natural Gas, Propane, LPG and can be generated from refining processes, including hydro-cracking, hydrolysis and elemental sulfur production. Ø Hydrogen sulfide is the chemical compound with the formula H 2 S. It is a colorless gas with the characteristic foul odor of rotten eggs. Ø Molar mass: 34.1 g/mol Ø Boiling point: -60 C Ø Density: 1.36 kg/m³ Ø Melting point: -82 C Ø Soluble in: Water & oil
Sulphur Contaminants Treatment There have been many attempts to provide processes for the removal of mercaptan contaminants. Ø Early processes included treatment of the hydrocarbon fractions with caustic, clays, and hydro-treating. Ø Treatment with purely chemical reactions such as scrubbing with mono or diethanolamine (Methyldiethanolamine, Diglycolamine and Di-isopropanolamine) or counter current extraction using a hot potassium carbonate solution Amine systems are unfortunately high in operation cost Characterized by corrosive nature of the absorbing liquids used Inability to sufficiently remove all mercaptan.
Sulphur Contaminants Treatment Caustic Wash - The Main Process in the Oil Industry Traditional caustic wash is the main treatment practice associated with mercaptan removal from sour crude in the world so far. Caustic wash is used in two different methods: 1. Catalytically air oxidation for caustic recovery 2. Without regeneration of spent caustic, (nowadays is almost out of practice due to ecological and economical issues). Caustic recovery results in massive liquid wastage These wastage are characterized as difficult to waste.
Sulphur Contaminants Treatment Merox for Extraction/Sweetening of mercaptans Conventional Merox for extraction of mercaptans from LPG, propane, butanes or light naphthas Conventional Merox for sweetening jet fuels and kerosenes with caustic Merox for extraction of mercaptans from refinery and natural gases Minalk Merox for sweetening of naphthas. This process continuously injects less caustic amounts into the feed naphtha. Caustic-free Merox for sweetening jet fuels and kerosenes. This process injects small amounts of ammonia and water (rather than caustic). Caustic-free Merox for sweetening of naphthas. This process injects small amounts of ammonia and water (rather than caustic) into the feed naphtha to provide the required alkalinity.
Reactions of Mercaptans The caustic solution reacts with mercaptans and extracts them. The reaction that takes place in the extractor is: Ø RSH + NaOH NaSR (Mercaptide) + H2O 1 In the above reaction, RSH is a mercaptan and R signifies an organic group such as a methyl, ethyl, propyl or other group. For example, the ethyl mercaptan (ethanethiol) has the formula C2H5SH. The second step is referred to as regeneration and it involves heating and oxidizing of the caustic solution leaving the extractor. The oxidations results in converting the extracted mercaptans to organic disulfides (RSSR) which are liquids that are waterinsoluble and are then separated and decanted from the aqueous caustic solution. The reaction that takes place in the regeneration step is: Ø 4NaSR + O2 + 2H2O 2RSSR + 4NaOH. 2
Reactions of Mercaptans In all of the Merox versions, the overall oxidation reaction that takes place in converting mercaptans to disulfides is: 4 RSH + O 2 2RSSR + 2H 2 O Reversible reaction
UOP Merox Gas Treating Process
Disadvantages of caustic treatment Main disadvantage of caustic treatment is the disposal of spent caustic Environmentally not-friendly Difficult to dispose spent caustic waste government regulations High capital costs Complicated process Not applicable to black oil and heavy crude- Limited application; Negative impact on quality of treated product: Formation of water-oil emulsions Advantages: Low cost of caustic.
Caustic waste spill effect -The Crisis in Cote d'ivoire state (published in international media - 2006) Vessel Probo Koala registered in Panama Chartered by the Dutch-based oil and commodity shipping company Trafigura Beheer BV Offloaded spent caustic waste at the Ivorian port of Abidjan The waste was then dumped by a local contractor at 12 sites in and around of Abidjan in August 2006. Result of this dump were 17 deaths and about 30 thousands of casualties.
Caustic waste spill effect -The Crisis in Cote d'ivoire state (published in international media - 2006) continue The damage was caused by 500 ton of spent caustic waste, which is considerably little quantity!
THIONOL series The invention relates to a process for scavenging hydrogen sulfide and mercaptan (thiol) contaminants from oil distillates, gas condensate and crude oil. The process of the present invention finds applicability for use in treating a large number of fluids including hydrocarbons, water, combinations of liquid and gaseous phases, and the like. Other fluids treated with THIONOL invented series include hydrocarbons such as refinery fuel gas, LPG, light catalytically cracked gasoline (LCCG), straight run gasoline, natural gasoline and heavier hydrocarbon distillates including kerosene, fuel oil and the like.
THIONOL series (continue) Ø Advantages of this technology are simplicity of implementation and operation, and relatively low cost of treatment $$$$$$$$ Ø THIONOL for selective oxidation of mercaptans in all types of hydrocarbon materials: Crude oil Gas condensate Liquefied gases Residual fuel (fuel oil, heating oil) Gasoline fractions Kerosene fraction Diesel fraction Products recycling
THIONOL reaction mechanism Reduction of active sulfur compounds is directly performed in hydrocarbon media by THIONOL conversion of mercaptan RSH and hydrogen sulfide H 2 S to disulfides. Oxidation of hydrogen sulfide and mercaptan with THIONOL reagent takes place in hydrocarbon media directly, and can be set in refinery production line, buffer tanks, settlers and storage tanks. Unlike many known processes THIONOL does not require water caustic which allows us to propose:- caustic free technology of hydrogen sulfide and mercaptan removal
THIONOL- Advantages ü THIONOL is nontoxic, nonflammable and noncorrosive ü THIONOL doesn t have a negative impact on characteristics of treated fuel ü Reduction of hydrogen sulfide and mercaptan content is provided by direct conversion into less noxious/toxic sulfides 2nH2S + thionol nhssh +(2H)n thionol 2nRSH + thionol nrssr+(2h)n thionol ü THIONOL yields irreversible conversion of hydrogen sulfide and mercaptans ü Average consumption of THIONOL is 1-3 ppm per 1 ppm of active sulfur depending on treatment conditions (temperature, contact time, use of air to support oxidation). ü Reduce Operational and Capital costs. ü THIONOL is non-triazine and non-amine based product
THIONOL series applications THIONOL is water and oil soluble additive that can be used for following processes: ü Hydrogen Sulfide Removal From Crude Oil And Oil Products ü Methyl Ethyl Mercaptan Removal From Crude Oil And Oil Products ü Hydrogen Sulfide Removal From Water ü Kerosene Sweetening ü Copper Corrosion Improvement In Distillates.
THIONOL For Water Injection Treatment Interaction of iron ions with H 2 S builds up scale flakes: 1 to 3 mm Formation permeability drop occurs due to the accumulation of iron sulfide in the capillaries and pores of oil zone formation. Removal of hydrogen sulfide from injected water by adding reagent THIONOL- less than 2 ppm, thus: Prevents iron sulphide flakes Reduces formation of sulfide slick at "oil-water boundary and therefore reduces the amount/cost of demulsifiers. THIONOL doesn t contain heavy metal and can be used at any ph THIONAL reaction products are water-soluble THIONOL is compatible with production chemicals (CI, DE, OS, BIO..)
Hydrogen Sulfide Removal From Crude Oil And Oil Products Commonly used Methods for removing Hydrogen Sulfide from Crude Oil and Oil Products as follow: 1. Stripping Columns 2. Catalytic oxidative methods by atmospheric oxygen in presence of cobalt catalyst and ammonia 3. Scavengers treatment (triazine, formaldehyde). Ø Disadvantage of the first two methods is the high losses of oil in form of hydrocarbon vapor thus reducing the quality of treated Crude Oil / Oil Product Ø Disadvantage of the most commonly used scavengers are high toxicity, low efficiency and corrosiveness effect of the reaction
THIONOL:- Hydrogen Sulfide Removal From Crude Oil And Oil Products ü The scavenger Thionol is used for binding hydrogen sulfide with a procedure that does not require any special equipment. ü Thionol is not a triazine or formaldehyde based product. ü THIONOL is water and oil - soluble liquid additive. ü THIONOL is waste-free and environmentally friendly. ü THIONOL technology is applicable in refineries and oil fields. ü Reactions of reduction hydrogen sulfide are irreversible Traditional Scavenger THIONOL Method Of Application Dosing Into Flow Dosing Into Flow Rate Of Dosage (Chemical ppm / H2S ppm) 3/1 1/1 Harmful Contaminant Formaldehyde/ triazine No Air Pollution Formaldehyde/ triazine No Gel Formation In Pipeline Yes No Diagram of THIONOL treatment Fuel For Treatment Static Mixer Storage Tank THIONOL
Methyl Ethyl Mercaptan Removal From Crude Oil And Oil Products Ø Alkaline treatments are the most widely used for removal of methyl and ethyl mercaptans. Disadvantages of alkaline De-Mercaptanization: üformation sulfur-alkaline waste- disposal problems ü High water consumption for the manufacture of alkaline solution ühigh losses of treated oil due to air supply. ühigh level of capital expenditures ülong period of reaching the project indicators ünot able to treat the heavy weighted mercaptans
THIONOL:- Methyl Ethyl Mercaptan Removal From Crude Oil And Oil Products Advantages of the THIONOL vs alkaline De-Mercaptanization ü Effective & easy to implement with No capital expenditures $$$ ü No requirement of changing the parameters of the treated crude oil (temperature, pressure, etc.). ü In most cases does not require air for oxidation (which eliminate the flaring of spent air with alkali -emissions of acid gases (SO 2 = acidic rain ). ü Waste-free (No requirement for Sulfur-alkaline waste disposal) $$$ ü Capability to remove light and heavy mercaptan (C5). ü Doesn t not contain any toxic or aggressive ingredients (caustic alkaline, formaldehyde, triazine, etc.). ü The average consumption of THIONOL is 1-3 ppm per 1 ppm of active S Diagram of THIONOL treatment Fuel For Treatment THIONOL Static Mixer Storage Tank
The rate of the THIONOL reaction 600 500 ppm methyl ethyl mercaptan 400 300 200 100 0 1 2 3 4 5 6 7 8 9 10 11 time/hour Dosage 1/2 Dosage 1/1 Dosage 1/3
Kerosene sweetening ü Kerosene shall meet the requirements of total sulfur levels less than 0.2% weight, and content of mercaptan less than 0.003% for jet fuel and 0.001% - for military jet fuel. ü THIONOL is used for irreversible conversion of the mercaptans into neutral compound; ü THIONOL sweetening is much cheaper than hydro treating (which is the most common method used for Kerosene sweetening).. ü Switching to THIONOL sweetening process liberates hydro treating facilities for production of low-sulfur motor fuels without extra investment resources.
Kerosene sweetening (continue) In order that the final products conform to the international standards with sweetening light products (e.g. kerosene), a conveniently administered catalyst THIONOL supported on activated carbon. In this case, the neutralization of the mercaptans and hydrogen sulfide occurs in a fixed bed reactor (filter) For sweetening oil, residual fuel oil and other types of raw oil, it is more convenient to use the direct THIONOL catalyst in the form of liquid oil soluble additives - reagent.
Copper Corrosion Improvement in Distillates ü The sulfur compounds which remain in the oil after treatment process cause corrosion of metallurgy. Test on the copper plate is designed to evaluate relative grade of corrosiveness of fuel. ü Copper corrosion test is a qualitative assessment of corrosiveness of fuel on a copper strip. Tests are carried out in accordance with ASTM D130. ü We offer a model of THIONOL assigned to improve copper corrosion test to fulfill strict requirements.
Stages of Implementation Laboratory tests ü ü ü In average 100 scavenger tests made per oil sample Huge results data base available for a quicker THIONOL type selection: H2S Ethyl Mercaptan (C2H5SH) Methyl Mercaptan (CH3SH) Industrial scale tests, no risks Industrial risk is limited i.e. storage tank Short term of preparations: 1-3 months
H2S Scavengers Reduction Efficiency-Tests (1 to 1 ppm) Dragon Oil study Scavenger-1 PRE-H2S POST-H2S (5min) POST-H2S (15min) POST-H2S (30min) Composition Composition Composition Composition POST-H2S (5min) % Reduction in H2S POST-H2S (15min) % Reduction in H2S POST-H2S (30min) % Reduction in H2S Component ppm ppm ppm ppm H2S 6729 2930 182.7 46.91 56.46% 97.28% 99.30% Scavenger-3 PRE-H2S POST-H2S POST-H2S POST-H2S POST-H2S POST-H2S POST-H2S Composition Composition Composition Composition % Reduction in H2S % Reduction in H2S % Reduction in H2S Component ppm ppm ppm ppm H2S 6792 1396 909 546 79.45% 86.62% 91.96% Scavenger-4 PRE-H2S POST-H2S POST-H2S POST-H2S POST-H2S POST-H2S POST-H2S % Reduction in % Reduction in % Reduction in Composition Composition Composition Composition Component H2S H2S H2S ppm ppm ppm ppm H2S 7113 1532 1360 800 78.46% 80.88% 88.75% Scavenger-5 PRE-H2S POST-H2S POST-H2S POST-H2S POST-H2S POST-H2S POST-H2S % Reduction in % Reduction in % Reduction in Composition Composition Composition Composition Component H2S H2S H2S ppm ppm ppm ppm H2S 6742 4597 3300 3001 31.82% 51.05% 55.49% Results Summary Scavenger-1 Scavenger-3 Scavenger-4 Scavenger-5 time (min) % H2S removal % H2S left % H2S removal % H2S left % H2S removal % H2S left % H2S removal % H2S left 0 0 100 0 100 0 100 0 100 5 56.46 43.54 79.45 20.55 78.46 21.54 31.82 68.18 15 97.28 2.72 86.62 13.38 80.88 19.12 51.05 48.95 30 99.3 0.7 91.96 8.04 88.75 11.25 55.49 44.51
SUMMARY CHART (Bottle no 4.01/SSB 33256-MB; H2S @ 4000psi) 100% H2S % Reduction VS. Time 90% 80% Scavenger-1 Scavenger-3 Scavenger-4 Scavenger-5 70% 60% % H2S 50% 40% 30% 20% 10% 0% 0 5 10 15 20 25 30 35 Time (Min)
Technologies comparison Table. Hydrogen Sulfide Method Of Treatment Health Hazard (Carcinogen) Insoluble Product Of Reactions. Deposits In Pipelines And Reservoirs. Formalfehyde Based Reagents Yes Triazine Based Reagents No Conventional Caustic Treatment (Merox) Health Hazard Of Direct Conact Physical methods of treatment (blow-off by clean natural gas, desorption steam stripping, fractionating the light naphtha with subsequent caustic treattment and so on) Health Hazard Of Direct Conact THIONOL Yes Yes No No No In Crude Oil Applicable Applicable Applicable Applicable Applicable In Petroleum Limited Not Applicable Associated Gas Efficiency Not Applicable Not Applicable Applicable In Water (Effluent Brine, Oilfield Waters, Sewage Not Applicable Not Applicable Not Applicable Not Applicable Applicable Waste Water Mercaptan Not Applicable Poor Efficiency Applicable Not Applicable Applicable Capex High Cost. Low Cost. Low Cost. Low Cost. Erection Of High Cost. Erection Of Conventional Conventional Conventional Special Facilities Special Facilities Is Dosing Dosing Dosing Is Needed. Equipment. Equipment. Needed. Equipment. Liquid Waste No No Other Problems Malodorous Smell Of Treated Oil. Deposits Formation In Pipelines, Reservoirs, Distillation Column In Refinery Malodorous Smell Of Treated Oil. Deposits Formation In Pipelines, Reservoirs, Distillation Column In Refinery Difficult to dispose wastes. Special Facilities For Spent Caustic Disposal Are Needed wastes. Erection Of Gas Purification Plant Is Needed. No No No