WO2024023215A1 - Method for scavenging mercaptans in a hydrocarbon fluid - Google Patents
Method for scavenging mercaptans in a hydrocarbon fluid Download PDFInfo
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- WO2024023215A1 WO2024023215A1 PCT/EP2023/070838 EP2023070838W WO2024023215A1 WO 2024023215 A1 WO2024023215 A1 WO 2024023215A1 EP 2023070838 W EP2023070838 W EP 2023070838W WO 2024023215 A1 WO2024023215 A1 WO 2024023215A1
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- WIPO (PCT)
- Prior art keywords
- ethanol
- mercaptans
- scavenging
- amount
- alkaline reagent
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 30
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 28
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 27
- 230000002000 scavenging effect Effects 0.000 title claims abstract description 23
- 239000012530 fluid Substances 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 14
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 6
- 239000010941 cobalt Substances 0.000 claims abstract description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003209 petroleum derivative Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000010779 crude oil Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 239000010763 heavy fuel oil Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 12
- 239000002516 radical scavenger Substances 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- -1 light naphthas Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003518 caustics Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 235000013844 butane Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- ZRKMQKLGEQPLNS-UHFFFAOYSA-N 1-Pentanethiol Chemical compound CCCCCS ZRKMQKLGEQPLNS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 150000002019 disulfides Chemical class 0.000 description 3
- 239000003915 liquefied petroleum gas Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 101100078001 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MSC2 gene Proteins 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 101150117600 msc1 gene Proteins 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000008427 organic disulfides Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
- C07C7/14891—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds alcohols
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/06—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of alkaline solutions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/10—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
Definitions
- the present invention relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition.
- a method for scavenging mercaptans in a hydrocarbon fluid comprising contacting the hydrocarbon fluid with an aqueous scavenging composition.
- Mercaptans can cause many problems ranging from malodors to metal corrosion. Because of the volatility of mercaptans, they tend to evolve into vapor spaces, where their offensive odors create problems in and around storage areas and throughout pipelines and shipping systems used for transportation.
- the treatment of a hydrocarbon fluid containing undesirable acidic species such as mercaptans is known and can be performed using either an extraction or a conversion process.
- a catalytic chemical process was developed by UOP, referred to as the Merox process, which is used in oil refineries and natural gas processing plants to remove mercaptans from LPG, propane, butanes, light naphthas, kerosene and jet fuel by converting them to liquid hydrocarbon disulfides.
- the Merox process requires an alkaline environment which, in some process versions, is provided by an aqueous solution of sodium hydroxide (NaOH), a strong base, commonly referred to as caustic. In other versions of the process, the alkalinity is provided by ammonia, which is a weak base.
- the conversion processes are known as “sweetening” processes because they results in products which no longer have the sour, foul odors of mercaptans and hydrogen sulfide.
- the liquid hydrocarbon disulfides may remain in the sweetened products. These may be used as part of the refinery or natural gas processing plant fuel, or they may be processed further.
- Mercaptan scavengers are commercially available to sweeten fuels.
- a successful scavenger is based on IVKAZTM, which is a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide; and further comprising caustic soda (50%) and ethanol, employed in amounts of 0.6 mg, 0.84 I and 0.2 I.
- This scavenger is pumped into a hydrocarbon fluid, and together with the ethanol acts to oxidize the common mercaptans into disulfides.
- an oxidizing agent may be present.
- the sour liquid hydrocarbon may contain entrained oxygen or air in sufficient concentration to accomplish the desired sweetening.
- the oxidizing agent may also be used during the regeneration process.
- a description of the demercaptanization of gas condensate with IVKAZ catalyst in a pilot plant scale is described by Maryam Ghaedian et al, in Petroleum & Coal 54(4), 379-384, 2012, Available online at www.vurup.sk/petroleum-coal. Further information may be found in RU2241732, which provides a method for purification of hydrocarbonaceous raw material or commercial hydrocarbon fractions from mercaptans, in particular from high-boiling tertiary mercaptans. The method realizes oxidation of mercaptans by oxygen-bearing gas in an alkaline medium in presence of a phthalocyanine catalyst, ethanolamine and a promoting additive.
- the current invention relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide, and optionally a source of oxygen, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1 :3 to 1 :4, and the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.0 to 1.5 mg/l, preferably from 1.1 to 1.3 mg/l.
- the current method is similar to the conventional Merox process for extraction and removal of mercaptans from crude oil, crude oil emulsions, oilfield condensate, petroleum residua and refined fuels including liquefied petroleum gases (LPG), such as propane, butanes and mixtures of propane and butanes.
- LPG liquefied petroleum gases
- the hydrocarbon fluids to which the method herein may be applied include, but are not limited to, crude oil, oil field condensates (e.g. naphtha, etc.), residual fuels, petroleum distillates (e.g. gasoline, kerosene, diesel, etc.) light hydrocarbons (e.g. propane, butane, etc.), aromatic solvents (e.g.
- the hydrocarbon fluids may contain oxygenated compounds such as alcohols, esters, glycols, ethers and the like and mixtures thereof.
- the aqueous caustic solution containing the scavenger catalyst reacts with mercaptans in the hydrocarbon fluids and extracts them. The reaction that takes place in the extractor is:
- RSH is a mercaptan and R signifies an organic group such as a methyl, ethyl, propyl or other group.
- 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 water-insoluble and are then separated and decanted from the aqueous caustic solution.
- RSSR organic disulfides
- the regenerated "lean" caustic solution is recirculated back to the top of the extractor to continue extracting mercaptans.
- the net overall Merox reaction covering the extraction and the regeneration step may be expressed as:
- the scavenging method of the present invention can be carried out at normal atmospheric or elevated pressure. Also, the scavenging method of the present invention can be carried out at temperatures in the range of -50° C. through 900° C., in the range of -50° C. through room temperature, in the range of room temperature through 900° C., and at room temperature. Preferably, the temperature is in the range of -20° C. through 100° C. The method can even be carried out at higher temperatures, although such temperatures are not characteristic in petroleum extraction and treatment, or for the scavenging of petroleum products downstream from heat exchangers of the installation.
- the temperature limits of the hydrocarbon raw material being processed in systems for treatment of crude petroleum or gas, or in feeding petroleum products from a plant downstream from a cooler are usually in the range of 30° C. to 60° C.
- the scavenger composition of the present invention can be used at temperatures of raw material being processed in this range of 30° C. to 60° C.
- the scavenger composition of the present invention can even be used at product extraction temperatures up to 90° C. or more.
- the scavenger composition of the present invention can also be used at lower temperatures, for example, down to -5° C., under conditions of storage of petroleum in reservoirs in cold climate conditions.
- the scavenger composition of the present invention can also be used at even lower temperatures, and the inventors do not restrict the present invention to a particular indicated temperature below which the method is not applicable.
- the treatment time increases at lower temperatures. To shorten the treatment time, it may be necessary to increase the expenditure of reagent.
- the applicability of the method will depend on the conditions of each particular case, and the inventors do not herein restrict the area of application of the composition of the present invention to a lower temperature limit of -5° C., but rather indicate that this is a low temperature as a reference point for the primary range of applications.
- the current invention accordingly relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1 :3 to 1 :4; and the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.0 to 1.5 mg/l.
- an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulf
- alkaline reagent is caustic soda, more preferably is caustic soda at 50%mass (having a density of about 1.15 g/ml).
- the ratio of alkaline reagent to ethanol, by mass is from 1 :3.2 to 1 :3.6, more preferably from 1 :3.3 to 1 :3.5, still more preferably from 1 :3.40 to 1.3.45.
- this corresponds to about 0.3I caustic soda on about 0.75I ethanol (both ⁇ 0.05 I).
- the ratio is therefore 1 : 3.43
- the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.1 to 1.3 mg/l. For instance, on about 0.75I ethanol ( ⁇ 0.05I) about 0.9 mg phthalocyanine catalyst ( ⁇ 0.05 mg) may be used.
- the phthalocyanine catalyst preferably comprises 70-75 %mass disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with 20-25% mass disodium sulfate and further comprising 0.1-0.5 %mass potassium bromide as promoting additive.
- the catalyst that is employed is the catalyst that is available as IVKAZ® catalyst, which is an improved Russian analogue of the Merox WS (manufactured by Honeywell UOP, USA).
- test results are not yet optimized. Still, it may be seen from Table 1 that the mercaptan levels using MSC2 as compared to the higher dosage levels of MSC1 were equal or even better.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1:3 to 1:4; and the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.0 to 1.5 mg/l.
Description
Title: METHOD FOR SCAVENGING MERCAPTANS IN A HYDROCARBON FLUID
Technical Field
The present invention relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition. As a result, light mercaptans in sour hydrocarbon are separated and heavy mercaptans are catalytically oxidized to disulfide oils using an aqueous treatment solution containing a chelated polyvalent metal catalyst.
Background Art
Mercaptans can cause many problems ranging from malodors to metal corrosion. Because of the volatility of mercaptans, they tend to evolve into vapor spaces, where their offensive odors create problems in and around storage areas and throughout pipelines and shipping systems used for transportation. The treatment of a hydrocarbon fluid containing undesirable acidic species such as mercaptans is known and can be performed using either an extraction or a conversion process.
A catalytic chemical process was developed by UOP, referred to as the Merox process, which is used in oil refineries and natural gas processing plants to remove mercaptans from LPG, propane, butanes, light naphthas, kerosene and jet fuel by converting them to liquid hydrocarbon disulfides. The Merox process requires an alkaline environment which, in some process versions, is provided by an aqueous solution of sodium hydroxide (NaOH), a strong base, commonly referred to as caustic. In other versions of the process, the alkalinity is provided by ammonia, which is a weak base.
The conversion processes are known as “sweetening” processes because they results in products which no longer have the sour, foul odors of mercaptans and hydrogen sulfide. The liquid hydrocarbon disulfides may remain in the sweetened products. These may be used as part of the refinery or natural gas processing plant fuel, or they may be processed further.
The most common mercaptans removed are:
Methanethiol - CH3SH [m-mercaptan]
Ethanethiol - C2H5SH [e- mercaptan]
1 -Propanethiol - C3H7SH [n-P mercaptan]
• 2-Propanethiol - CH3CH(SH)CH3 [2C3 mercaptan]
• Butanethiol - C4H9SH [n-butyl mercaptan]
• tert-Butyl mercaptan - C(CH3)3SH [t-butyl mercaptan]
• Pentanethiol - C5H11SH [pentyl mercaptan]
In particular, high molecular weight mercaptans (C4 and higher) are difficult to convert.
Mercaptan scavengers are commercially available to sweeten fuels. A successful scavenger is based on IVKAZ™, which is a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide; and further comprising caustic soda (50%) and ethanol, employed in amounts of 0.6 mg, 0.84 I and 0.2 I. This scavenger is pumped into a hydrocarbon fluid, and together with the ethanol acts to oxidize the common mercaptans into disulfides. Additionally, an oxidizing agent may be present. However, the sour liquid hydrocarbon may contain entrained oxygen or air in sufficient concentration to accomplish the desired sweetening. The oxidizing agent may also be used during the regeneration process.
A description of the demercaptanization of gas condensate with IVKAZ catalyst in a pilot plant scale is described by Maryam Ghaedian et al, in Petroleum & Coal 54(4), 379-384, 2012, Available online at www.vurup.sk/petroleum-coal. Further information may be found in RU2241732, which provides a method for purification of hydrocarbonaceous raw material or commercial hydrocarbon fractions from mercaptans, in particular from high-boiling tertiary mercaptans. The method realizes oxidation of mercaptans by oxygen-bearing gas in an alkaline medium in presence of a phthalocyanine catalyst, ethanolamine and a promoting additive.
Basu B et al, “Merox and related metal phthalocyanine catalyzed oxidation processes” Catalysis Reviews, Vol. 35, No. 4, 571-609 (1993) explains that alkyl and aromatic mercaptans are among important organic sulfur compounds distributed in petroleum products. The mercaptans cause foul odor and are corrosive toward metals. In addition, mercaptans may cause oxidative deterioration as well as inhibit the performance of various additives (TEL, antioxidants) in finished products. Therefore, it is necessary to remove them, either by extractive processes or by converting them into innocuous disulfides. Such processes are usually referred to as “sweetening.” Likewise US3352777 describes the oxidation of mercaptans, wherein in the US patent the acceleration of the rate of oxidation of mercaptans in contact with phthalocyanine catalyst is achieved by means of a specific salt. Whereas the use of an alcohol is mentioned, these documents d not disclose that further improvement may be achieved with a reduced amount of scavenger.
Further information may be fund in Vil’danov, A.F., Bazhirova, N.G., Mazgarov, A.M. et al. Experience with the operation of units at the Omsk Oil Refinery for removing sulfur compounds from the butane-butylene fraction and waste water with the use of homogeneous and heterogeneous catalysts. Chem Technol Fuels Oils 49, 204-210 (2013). https://doi . orq/10.1007/s 10553-013-0432-x. In this paper data is reported that attests to the successful operation of the butane-butylene fraction demercaptanizing unit of the gas fractionating section of the KT-1/1 plant and the unit for demercaptanizing the unsaturated stabilizer overhead stream (reflux) of the gas purifying and gas fractionating section of the catalytic cracking plant 43-103. In the demercaptanization process, the alkali solution was regenerated using homogeneous catalyst of the trademark IVKAZ.
There remains a need for enhanced reduction of mercaptans in fuels, in particular high molecular weight mercaptans (C4 and higher) with a reduced amount of scavenger as additive.
Summary of the Invention
The current invention relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide, and optionally a source of oxygen, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1 :3 to 1 :4, and the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.0 to 1.5 mg/l, preferably from 1.1 to 1.3 mg/l.
Detailed description of the invention
The current method is similar to the conventional Merox process for extraction and removal of mercaptans from crude oil, crude oil emulsions, oilfield condensate, petroleum residua and refined fuels including liquefied petroleum gases (LPG), such as propane, butanes and mixtures of propane and butanes. More specifically, the hydrocarbon fluids to which the method herein may be applied include, but are not limited to, crude oil, oil field condensates (e.g. naphtha, etc.), residual fuels, petroleum distillates (e.g. gasoline, kerosene, diesel, etc.) light hydrocarbons (e.g. propane, butane, etc.), aromatic solvents (e.g. toluene, xylene, etc.) and paraffinic solvents (e.g. pentane, heptane, etc.), renewable fuels such as biodiesel, and mixtures thereof. Further, the hydrocarbon fluids may contain oxygenated compounds such as alcohols, esters, glycols, ethers and the like and mixtures thereof.
The aqueous caustic solution containing the scavenger catalyst reacts with mercaptans in the hydrocarbon fluids and extracts them. The reaction that takes place in the extractor is:
2 RSH + 2 NaOH 2 NaSR + 2 H2O
In the above reaction, RSH is a mercaptan and R signifies an organic group such as a methyl, ethyl, propyl or other group.
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 water-insoluble and are then separated and decanted from the aqueous caustic solution. The reaction that takes place in the regeneration step is:
4NaSR + O2 + 2H2O 2RSSR + 4NaOH.
After decantation of the disulfides, the regenerated "lean" caustic solution is recirculated back to the top of the extractor to continue extracting mercaptans.
The net overall Merox reaction covering the extraction and the regeneration step may be expressed as:
4 RSH + O2 2 RSSR + 2 H2O.
Technical details of the demercaptanization process may also be found in the article in Petroleum & Coal 54(4), 379-384, 2012, mentioned above. Moreover, methods for scavenging mercaptans from hydrocarbons are disclosed in various patents, such as US8679203B2, RU2656100C2, or LIS20210198583 and references described therein, which involve adding to the hydrocarbon fluid an effective scavenging amount of an aqueous scavenging composition.
The scavenging method of the present invention can be carried out at normal atmospheric or elevated pressure. Also, the scavenging method of the present invention can be carried out at temperatures in the range of -50° C. through 900° C., in the range of -50° C. through room temperature, in the range of room temperature through 900° C., and at room temperature. Preferably, the temperature is in the range of -20° C. through 100° C. The method can even be carried out at higher temperatures, although such temperatures are not characteristic in petroleum extraction and treatment, or for the scavenging of petroleum products downstream from heat exchangers of the installation. Keeping in mind that the temperature limits of the hydrocarbon raw material being processed in systems for treatment of crude petroleum or gas, or in feeding petroleum products from a plant downstream from a cooler, are usually in the range of 30° C. to 60° C., the scavenger composition of the present invention can be used at temperatures of raw material being processed in this range of 30° C. to 60° C. When being supplied to the well, the scavenger composition of the present invention can even be used at
product extraction temperatures up to 90° C. or more. The scavenger composition of the present invention can also be used at lower temperatures, for example, down to -5° C., under conditions of storage of petroleum in reservoirs in cold climate conditions. The scavenger composition of the present invention can also be used at even lower temperatures, and the inventors do not restrict the present invention to a particular indicated temperature below which the method is not applicable. However, the treatment time increases at lower temperatures. To shorten the treatment time, it may be necessary to increase the expenditure of reagent. Thus, the applicability of the method will depend on the conditions of each particular case, and the inventors do not herein restrict the area of application of the composition of the present invention to a lower temperature limit of -5° C., but rather indicate that this is a low temperature as a reference point for the primary range of applications.
It will be appreciated that it is not necessary for all of the mercaptans present in the hydrocarbon fluids to be reacted and/or removed for the method herein to be considered successful. The method has accomplished a goal when the amounts of mercaptan are reduced as a consequence of being contacted with the scavenging composition described herein.
The current invention accordingly relates to a method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1 :3 to 1 :4; and the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.0 to 1.5 mg/l.
Preferably, alkaline reagent is caustic soda, more preferably is caustic soda at 50%mass (having a density of about 1.15 g/ml).
Preferably, the ratio of alkaline reagent to ethanol, by mass, is from 1 :3.2 to 1 :3.6, more preferably from 1 :3.3 to 1 :3.5, still more preferably from 1 :3.40 to 1.3.45. When using Caustic Soda at 50%mass, this corresponds to about 0.3I caustic soda on about 0.75I ethanol (both ± 0.05 I). In other words, .0.31 NaOH (50%) is 0.3 x 1.15 x 50% = 0.1725 g whereas 0.75I EtOH equals 0.75 x 0.789 = 0.59175. The ratio is therefore 1 : 3.43
Preferably, the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.1 to 1.3 mg/l. For instance, on about 0.75I ethanol (± 0.05I) about 0.9 mg phthalocyanine catalyst (± 0.05 mg) may be used.
The phthalocyanine catalyst preferably comprises 70-75 %mass disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with 20-25% mass disodium sulfate and further comprising 0.1-0.5 %mass potassium bromide as promoting additive. Preferably, the catalyst that is employed is the catalyst that is available as IVKAZ® catalyst, which is an improved Russian analogue of the Merox WS (manufactured by Honeywell UOP, USA).
The invention is illustrated by the following examples.
Examples
Three different hydrocarbon fractions containing mercaptans were tested.
As shown in Table 1 , a commercial mercaptan scavenger, MSC1 , or the mercaptan scavenger according to the invention, MSC2, was used in the indicated dosages. The liquid phase mercaptan (RH) proportion after 48 and 96 hours was noted. The results are listed in Table 1.
Table 1
Results
The test results are not yet optimized. Still, it may be seen from Table 1 that the mercaptan levels using MSC2 as compared to the higher dosage levels of MSC1 were equal or even better.
Claims
CLAIMS A method for scavenging mercaptans in a hydrocarbon fluid, comprising contacting the hydrocarbon fluid with an aqueous scavenging composition comprising an alcohol, an aqueous alkaline reagent and an effective scavenging amount of a phthalocyanine catalyst comprising disulfoacid of cobalt dichlorodihydroxyphthalocyanine mixed with disodium sulfate and potassium bromide, and optionally a source of oxygen, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1 :3 to 1 :4; and the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.0 to 1.5 mg/l. The method of claim 1 , wherein the alkaline reagent is caustic soda, more preferably is caustic soda at 50%mass, having a density of about 1.15 g/ml. The method of claim 1 or 2, wherein the ratio of alkaline reagent to ethanol, by mass, is from 1 :3.2 to 1 :3.6, more preferably from 1 :3.3 to 1 :3.5, still more preferably from 1 :3.40 to 1.3.45. The method of claim 2, wherein the alkaline reagent is caustic soda at 50%mass, used in an amount of 0.3 ± 0.05 I caustic soda to 0.75± 0.05 I ethanol. The method of anyone of claims 1-4, wherein the phthalocyanine catalyst is dissolved in ethanol in an amount of 1.1 to 1.3 mg/l. The method of anyone of claims 1-4, wherein the phthalocyanine catalyst is dissolved in ethanol in an amount of 0.9 ± 0.05 mg phthalocyanine catalyst on 0.75 ± 0.05 I ethanol. The method of anyone of claims 1-6, wherein the method is applied to crude oil, oil field condensates, residual fuels, petroleum distillates, light hydrocarbons, aromatic solvents and paraffinic solvents, renewable fuels, and mixtures thereof. The method of claim 7, wherein the hydrocarbon liquid is prewashed to remove any H2S.
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