US20030019793A1 - Mercaptan removal from petroleum streams (law950) - Google Patents
Mercaptan removal from petroleum streams (law950) Download PDFInfo
- Publication number
- US20030019793A1 US20030019793A1 US10/247,993 US24799302A US2003019793A1 US 20030019793 A1 US20030019793 A1 US 20030019793A1 US 24799302 A US24799302 A US 24799302A US 2003019793 A1 US2003019793 A1 US 2003019793A1
- Authority
- US
- United States
- Prior art keywords
- aqueous
- stream
- petroleum
- mercaptans
- phase transfer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000003208 petroleum Substances 0.000 title claims abstract description 46
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title claims description 18
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003444 phase transfer catalyst Substances 0.000 claims description 75
- 238000000034 method Methods 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 150000002019 disulfides Chemical class 0.000 claims description 14
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 13
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000908 ammonium hydroxide Substances 0.000 claims description 7
- -1 quaternary ammonium halides Chemical class 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 239000002609 medium Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 150000003983 crown ethers Chemical class 0.000 claims description 2
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 2
- HJHUXWBTVVFLQI-UHFFFAOYSA-N tributyl(methyl)azanium Chemical compound CCCC[N+](C)(CCCC)CCCC HJHUXWBTVVFLQI-UHFFFAOYSA-N 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 150000003573 thiols Chemical class 0.000 abstract description 34
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000008346 aqueous phase Substances 0.000 description 24
- 238000000605 extraction Methods 0.000 description 24
- 239000002585 base Substances 0.000 description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 22
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 13
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 12
- 235000001508 sulfur Nutrition 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- 239000003518 caustics Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- XKKTWZRDROMNNJ-UHFFFAOYSA-N CN(C)(C)C Chemical compound CN(C)(C)C XKKTWZRDROMNNJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001768 cations Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000622 liquid--liquid extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 150000003577 thiophenes Chemical class 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical class CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000001172 liquid--solid extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000003408 phase transfer catalysis Methods 0.000 description 1
- 229940068917 polyethylene glycols Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
- C10G19/04—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions containing solubilisers, e.g. solutisers
Definitions
- This invention relates to the removal of thiols (mercaptans) from petroleum streams. Specifically, mercaptans of the five-carbon molecular weight range and above can be removed from petroleum streams. Removal of light thiols (less than C 5 molecular weight), an enhancement to base assisted extractive processes such as extractive Merox®, may also be improved.
- the normal extractive process is less effective.
- the thiols are extracted from the petroleum stream into an aqueous caustic solution in the absence of air.
- the aqueous and petroleum streams are then separated.
- the extracted mercaptans in the aqueous stream are then catalytically oxidized with air and converted to disulfides. These disulfides are separated from the aqueous stream and disposed of into a waste stream.
- the limitation to this process is the solubility of the thiol in aqueous caustic. Thiols with chain lengths beyond five carbons are too oleophilic to be extracted into the aqueous phase and therefore cannot be fully removed by this process.
- 2,059,075 describes the addition of “substantial” amount of quaternary ammonium hydroxide to aqueous caustic to enhance mercaptan extraction.
- Other agents such as propyleneglycol (U.S. Pat. No. 2,183,801), butyleneglycols (U.S. Pat. No. 2,152,166), triethyleneglycol (U.S. Pat. No. 2,212,105) have been cited.
- species containing greater than six carbons were noted as being “unsuitable”.
- the preferred range of use for these solubilizers is from 25-75 wt % relative to the aqueous caustic.
- the instant process describes a method for removal of mercaptans from petroleum streams comprising the steps of:
- the process may also comprise steps of:
- FIG. 1 is a plot of n-octylthiol (C8-thiol) removal as a function of the amount of quaternary ammonium salt added to 10 wt % sodium hydroxide solutions for two different quaternary ammonium salts in the absence of air.
- FIG. 2 depicts thiol removal by use of impregnated molecular sieves in the presence of air (sweetening).
- substantial absence of oxygen means no more than that amount of oxygen which will be present in a refinery process despite precautions to exclude the presence of oxygen. Typically, 10 ppm or less, preferably 2 ppm or less oxygen will be the maximum amount present. Preferably, the process will be run in the absence of oxygen.
- This invention includes the removal of thiols (mercaptans) from petroleum streams, specifically, mercaptans comprising mercaptans of five carbon molecular weight and above. Lower molecular weight mercaptans and mercaptans which contain non-linear alkyl chains may also be removed during the process.
- thiols mercaptans
- the invention includes the use of a basic phase transfer catalyst (PTC) in water or a combination of phase transfer catalyst and aqueous base to remove mercaptans from petroleum streams.
- the streams may have previously undergone other forms of sulfur removal for non-mercaptan type species such as thiophenes and aliphatic sulfides.
- Such processes include, processes known in the art such as, for example, SCANfining as taught by U.S. Pat. No. 5,985,136, herein incorporated by reference, hydrodesulfurization, etc.
- the streams may also have previously undergone caustic extraction to reduce the short-chain thiol concentration prior to the instant treatment such as extractive Merox®.
- the extracting medium may consist essentially of or consist of aqueous base and phase transfer catalyst.
- the phase transfer catalyst is sufficiently basic (capable of deprotonating a mercaptan with a pKa of ⁇ 16) in water, it may be used alone to accomplish the extraction.
- Quaternary ammonium hydroxide salts such as tetrabutylammonium hydroxide, are examples of the latter.
- Suitable basic phase transfer catalyst or PTC in combination with aqueous base may dramatically reduce the presence of C5+ thiols (at least about 70, preferably, at least about 75% removal).
- phase-transfer catalyst allows for the extraction of these higher molecular weight mercaptans ( ⁇ C5+) into the aqueous caustic at a rapid rate.
- the aqueous phase can then be separated from the feedstream by known techniques.
- lower molecular weight mercaptans, if present, are also removed during the process.
- phase transfer catalysts which can be utilized in the instant invention can be supported or unsupported.
- the attachment of the PTC to a solid substrate facilitates its separation and recovery and reduces the likelihood of contamination of the product petroleum stream with PTC.
- Typical materials used to support PTC are polymers, silicas, aluminas and carbonaceous supports.
- the PTC and aqueous base will be supported on or contained within the pores of a solid state material to accomplish the mercaptan extraction.
- the bed can be regenerated by flushing with air and a stripper solvent to wash away the disulfide which would be generated. If necessary, the bed could be re-activated with fresh base/PTC before being brought back on stream.
- This swing bed type of operation may be advantageous relative to liquid-liquid extractions in that the liquid-liquid separation steps would be replaced with solid-liquid separations typical of solid adsorbent bed technologies.
- Embodiments of the invention include liquid-liquid extraction where aqueous base and water soluble PTC are utilized to accomplish the extraction, or basic aqueous PTC is utilized.
- an “extractive” process whereby the thiols are first extracted from the petroleum feedstream in the substantial absence of air into an aqueous phase and the mercaptan-free petroleum feedstream is then separated from the aqueous phase and passed along for further refinery processing can be conducted.
- the aqueous phase may then subjected to aerial oxidation to form disulfides from the extracted mercaptans. Separation and disposal of the disulfide would allow for recycle of the aqueous phase.
- the disulfide is readily separated by extraction with an organic extractant in which the disulfides are soluble. Such extractants are easily selected by the skilled artisan and can include for example a reformate stream.
- the extraction step can be conducted in air, the loss of thiol is concurrent with generation of disulfide.
- the thiol is transported from the organic phase into the aqueous phase, prior to conversion to disulfide then back into the petroleum phase.
- the extracting medium will consist essentially of aqueous base and PTC or aqueous basic PTC. In a sweetening process, no catalysts other than the PTC(s) will be present.
- the porous supports may be selected from, molecular sieves, polymeric beads, carbonaceous solids and inorganic oxides for example.
- a second adsorbent bed will be swung into operation. Regeneration of the first bed will be accomplished by introduction of oxygen (air) into the bed along with an organic phase which will provide a suitable extractant stream for the disulfide which should form upon oxidation of the mercaptide anions. Such extractants are easily chosen by the skilled artisan. Pressure and heat could be used to stimulate the oxidative process. If necessary, the stripped bed could be regenerated by re-saturation with fresh base/PTC solution before being swung back into operation. Neither the base nor the PTC are consumed in this process, other than by losses due to contaminants. The advantage of using a supported PTC is that the mercaptans are trapped within the pores of the support facilitating separation.
- Bases preferred are strong bases, e.g., sodium, potassium and ammonium hydroxide, and sodium and potassium carbonate, and mixtures thereof. These may be used as an aqueous solution of sufficient strength, typically base will be up to or equal to 50 wt % of the aqueous medium, preferably about 15% to about 25 wt % when used in conjunction with onium salt PTCs and 30-50 wt % when used in conjunction with polyethyleneglycol type PTCs.
- strong bases e.g., sodium, potassium and ammonium hydroxide, and sodium and potassium carbonate, and mixtures thereof. These may be used as an aqueous solution of sufficient strength, typically base will be up to or equal to 50 wt % of the aqueous medium, preferably about 15% to about 25 wt % when used in conjunction with onium salt PTCs and 30-50 wt % when used in conjunction with polyethyleneglycol type PTCs.
- the phase transfer catalyst is present in a sufficient concentration to result in a treated feed having a decreased mercaptan content.
- a catalytically effective amount of the phase transfer catalyst will be utilized.
- the phase transfer catalyst may be miscible or immiscible with the petroleum stream to be treated. Typically, this is influenced by the length of the hydrocarbyl chains in the molecule; and these may be selected by one skilled in the art. While this may vary with the catalyst selected, typically concentrations of about 0.01 to about 10 wt. %, preferably about 0.05 to about 1 wt % based on the amount of aqueous solution will be used.
- Phase transfer catalysts suitable for use in this process include the types of PTCs described in standard references on PTC, such as Phase Transfer Catalysis: Fundamentals, Applications and Industrial Perspectives by Charles M. Starks, Charles L. Liotta and Marc Halpern (ISBN 0-412-04071-9 Chapman and Hall, 1994). These reagents are typically used to transport a reactive anion from an aqueous phase into an organic phase in which it would otherwise be insoluble. This “phase-transferred” anion then undergoes reaction in the organic phase and the phase transfer catalyst then returns to the aqueous phase to repeat the cycle, and hence is a “catalytic” agent.
- the PTC transports the hydroxide anion, ⁇ OH, into the petroleum stream, where it reacts with the thiols in a simple acid base reaction, producing the deprotonated thiol or thiolate anion.
- This charged species is much more soluble in the aqueous phase and hence the concentration of thiol in the petroleum stream is reduced by this chemistry.
- PTC PTC
- onium salts such as quaternary ammonium and quaternary phosphonium halides, hydroxides and hydrogen sulfates for example.
- the phase transfer catalyst is a quaternary ammonium hydroxide
- the quaternary ammonium cation will have the formula:
- Cw, Cx, Cy, and Cz represent alkyl radicals with carbon chain lengths of w, x, y and z carbon atoms respectively.
- the preferred quaternary ammonium salts are the quaternary ammonium halides.
- the four alkyl groups on the quaternary cation are typically alkyl groups with total carbons ranging from four to forty, but may also include cycloalkyl, aryl, and arylalkyl groups.
- Some examples of useable onium cations are tetrabutyl ammonium, tetrabutylphosphonium, tributylmethyl ammonium, cetyltrimethyl ammonium, methyltrioctyl ammonium, and methyltricapryl ammonium.
- PTC PTC have been found effective for hydroxide transfer.
- crown ethers such as 18-crown-6 and dicyclohexano-18-crown-6 and open chain polyethers such as polyethyleneglycol 400.
- open chain polyethers such as polyethyleneglycol 400.
- Partially-capped and fully-capped polyethyleneglycols are also suitable. This list is not meant to be exhaustive but is presented for illustrative purposes. Supported or unsupported PTC and mixtures thereof are utilizable herein.
- the amount of aqueous medium to be added to said petroleum stream being treated will range from about 5% to about 200% by volume relative to petroleum feed.
- process temperatures of from 25° C. to 180° C. are suitable, lower temperatures of less than 25° C. can be used depending on the nature of the feed and phase transfer catalyst used.
- the pressure should be sufficient pressure to maintain the petroleum stream in the liquid state. Oxygen must be excluded, or be substantially absent, during the extraction and phase separation steps to avoid the premature formation of disulfides, which would then redissolve in the feed. Oxygen is necessary for a sweetening process.
- the stream is then passed through the remaining refinery processes, if any.
- the base and PTC or basic PTC may then be recycled for extracting additional mercaptans from a fresh petroleum stream.
- the mixture of PTC and base may consist essentially of or consist of PTC and base.
- basic PTCs they may consist essentially of or consist of basic PTC's.
- the invention will be practiced in the absence of any catalyst other than the phase transfer catalyst such as those used to oxidize mercaptans, e.g. metal chelates as described in U.S. Pat. Nos. 4,124,493; 4,156,641; 4,206,079; 4,290,913; and 4,337,147. Hence in such cases the PTC will be the only catalyst present.
- Extractions of n-octylthiol in hexane were conducted in the absence of air by mixing together equal volumes of an aqueous phase and a thiol/hexane phase as described in Example 1.
- the aqueous phase consisted of 2.5 N sodium hydroxide (about 10 wt %) in water with a variable concentration of benzyltrimethylammonium hydroxide (BZTMOH).
- BZTMOH benzyltrimethylammonium hydroxide
- Example 4 The procedure of Example 4 was repeated, except that after mixing the two deaerated solutions for four minutes and allowing them to phase separate, three quarters of the aqueous phase was removed from the flask by syringe, leaving behind all of the original “feedstream” and one quarter of the aqueous extractant phase. All of the aqueous phase was not removed so as to avoid any possibility of removing any of the original organic phase.
- the octane thiol had been nearly quantitatively extracted from the pentane phase (1000 ppm to 20 ppm). The portion of the aqueous phase which had been removed was then combined with fresh pentane of equal volume to the original feedstream and mixed in air overnight.
- TBAOH tetrabutylammonium hydroxide
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention relates to reducing the amount of thiols (mercaptans) in petroleum streams, specifically, mercaptans above the five carbon molecular weight range.
Description
- This application is a divisional of U.S. patent application Ser. No. 09/551,010 filed Apr. 18, 2000.
- This invention relates to the removal of thiols (mercaptans) from petroleum streams. Specifically, mercaptans of the five-carbon molecular weight range and above can be removed from petroleum streams. Removal of light thiols (less than C5 molecular weight), an enhancement to base assisted extractive processes such as extractive Merox®, may also be improved.
- To prepare fuels, which satisfy regulatory sulfur limits, it is necessary to process the fuels to remove various sulfur species. For example, long chain mercaptans are not native to crude, but are produced during the hydrotreatment of olefin-containing petroleum streams to remove sulfur species such as thiophenes. The byproduct, hydrogen sulfide, from the hydrodesulfurization process reacts with olefins present in the feeds to produce longer chain, higher molecular weight mercaptans. Normally, short chain (less than C5) mercaptans are easily and cheaply removed from such streams by base assisted extractive processes such as extractive Merox®. However, due to the insolubility of the longer chain mercaptans in caustic, the normal extractive process is less effective. In the extractive process, the thiols are extracted from the petroleum stream into an aqueous caustic solution in the absence of air. The aqueous and petroleum streams are then separated. Once isolated from the petroleum stream, the extracted mercaptans in the aqueous stream are then catalytically oxidized with air and converted to disulfides. These disulfides are separated from the aqueous stream and disposed of into a waste stream. The limitation to this process is the solubility of the thiol in aqueous caustic. Thiols with chain lengths beyond five carbons are too oleophilic to be extracted into the aqueous phase and therefore cannot be fully removed by this process.
- A large body of art exists in the patent literature describing additives used in conjunction with aqueous base to overcome the limitation due to the insolubility of long-chain mercaptans. All of these additives are added in substantial quantities (>10 wt % of aqueous phase) in order to modify the “solvent power” of the caustic solution. In more modem terminology, these additives alter the solvent parameters of the aqueous caustic. The additive's impact on solvent properties are proportional to the quantity added and therefore substantial quantities of additive are required to produce the substantive change required. In the literature these are commonly referred to as “solubilizing agents” or “solutizers.” For example U.S. Pat. No. 2,059,075 describes the addition of “substantial” amount of quaternary ammonium hydroxide to aqueous caustic to enhance mercaptan extraction. Other agents such as propyleneglycol (U.S. Pat. No. 2,183,801), butyleneglycols (U.S. Pat. No. 2,152,166), triethyleneglycol (U.S. Pat. No. 2,212,105) have been cited. In the ethyleneglycol family of additives, species containing greater than six carbons were noted as being “unsuitable”. Typically the preferred range of use for these solubilizers is from 25-75 wt % relative to the aqueous caustic. The use of such large quantities of expensive reagents and attendant problems of separation from extracted petroleum, undesirable decomposition and byproducts at operating conditions, etc, in using such large quantities, have precluded their widespread use in commercial practice.
- One of these classes of additives, quaternary ammonium halides, has been found to be effective in low concentration for a sweetening process when used in conjunction with oxygen, oxidation catalyst and alkali metal hydroxide (U.S. Pat. No. 4,124,493). Subsequent patents (U.S. Pat. Nos. 4,156,641 US 4,206,079, US 4,290,913 and US 4,337,147) disclose the use of quaternary ammonium hydroxides in conjunction with a mercaptan oxidizing catalyst as components of solid oxidation catalyst composites to be used in the presence of oxygen for sweetening applications.
- Another approach to reducing the sulfur content of petroleum streams has been to conduct bulk solvent extraction on the stream, such as is described in U.S. Pat. No. 2,792,332. This approach leads to losses of 20% of the original feed volume, which is unacceptable in many cases.
- Other mercaptan removal or destruction processes are available, however, they remove sulfurs at the cost of saturating olefins, thereby decreasing the octane of the fuel being produced. For example, non-selective high-pressure catalytic hydrodesulfurization can be used to hydrogenate all olefins and ultimately reduce mercaptans but at a very high-octane loss.
- Thus, what is needed in the art is a process for removing mercaptans, especially ≧C5+ mercaptans, while maintaining octane.
- The instant process describes a method for removal of mercaptans from petroleum streams comprising the steps of:
- (a) extracting said petroleum stream, in the substantial absence of oxygen, with an aqueous medium comprising an aqueous base and a catalytically effective amount of a phase transfer catalyst or an aqueous solution of a catalytically effective amount of a basic phase transfer catalyst to remove said mercaptans from said petroleum stream;
-
- where q=1/w+1/x+1/y+1/z and wherein q≧1.0 and wherein, Cw, Cx, Cy, and Cz represent alkyl radicals with carbon chain lengths of w, x, y and z carbon atoms respectively.
- The process may also comprise steps of:
- (c) subjecting said aqueous stream to oxidation to convert mercaptide anions contained therein to disulfides;
- (d) separating said disulfides and recovering an aqueous stream having disulfides removed therefrom;
- (e) recycling said aqueous stream to said step (a) wherein said aqueous stream contains said base and said phase transfer catalyst or said basic phase transfer catalyst of said step (a).
- FIG. 1 is a plot of n-octylthiol (C8-thiol) removal as a function of the amount of quaternary ammonium salt added to 10 wt % sodium hydroxide solutions for two different quaternary ammonium salts in the absence of air.
- FIG. 2 depicts thiol removal by use of impregnated molecular sieves in the presence of air (sweetening).
- As used herein, substantial absence of oxygen means no more than that amount of oxygen which will be present in a refinery process despite precautions to exclude the presence of oxygen. Typically, 10 ppm or less, preferably 2 ppm or less oxygen will be the maximum amount present. Preferably, the process will be run in the absence of oxygen.
- This invention includes the removal of thiols (mercaptans) from petroleum streams, specifically, mercaptans comprising mercaptans of five carbon molecular weight and above. Lower molecular weight mercaptans and mercaptans which contain non-linear alkyl chains may also be removed during the process.
- The invention includes the use of a basic phase transfer catalyst (PTC) in water or a combination of phase transfer catalyst and aqueous base to remove mercaptans from petroleum streams. The streams may have previously undergone other forms of sulfur removal for non-mercaptan type species such as thiophenes and aliphatic sulfides. Such processes include, processes known in the art such as, for example, SCANfining as taught by U.S. Pat. No. 5,985,136, herein incorporated by reference, hydrodesulfurization, etc. The streams may also have previously undergone caustic extraction to reduce the short-chain thiol concentration prior to the instant treatment such as extractive Merox®.
- In conducting the instant process, the extracting medium may consist essentially of or consist of aqueous base and phase transfer catalyst. However, if the phase transfer catalyst is sufficiently basic (capable of deprotonating a mercaptan with a pKa of <16) in water, it may be used alone to accomplish the extraction. Quaternary ammonium hydroxide salts, such as tetrabutylammonium hydroxide, are examples of the latter.
- The use of suitable basic phase transfer catalyst or PTC in combination with aqueous base may dramatically reduce the presence of C5+ thiols (at least about 70, preferably, at least about 75% removal).
- The addition of a phase-transfer catalyst allows for the extraction of these higher molecular weight mercaptans (≧C5+) into the aqueous caustic at a rapid rate. The aqueous phase can then be separated from the feedstream by known techniques. Likewise, lower molecular weight mercaptans, if present, are also removed during the process.
- The phase transfer catalysts which can be utilized in the instant invention can be supported or unsupported. The attachment of the PTC to a solid substrate facilitates its separation and recovery and reduces the likelihood of contamination of the product petroleum stream with PTC. Typical materials used to support PTC are polymers, silicas, aluminas and carbonaceous supports.
- In one embodiment of this invention, the PTC and aqueous base will be supported on or contained within the pores of a solid state material to accomplish the mercaptan extraction. After saturation of the supported PTC bed with mercaptide in the substantial absence of oxygen, the bed can be regenerated by flushing with air and a stripper solvent to wash away the disulfide which would be generated. If necessary, the bed could be re-activated with fresh base/PTC before being brought back on stream. This swing bed type of operation may be advantageous relative to liquid-liquid extractions in that the liquid-liquid separation steps would be replaced with solid-liquid separations typical of solid adsorbent bed technologies.
- Embodiments of the invention include liquid-liquid extraction where aqueous base and water soluble PTC are utilized to accomplish the extraction, or basic aqueous PTC is utilized. A liquid-liquid extraction with aqueous base and supported PTC where the PTC is present on the surface or within the pores of the support, for example a polymeric support; and liquid-solid extraction where both the basic aqueous PTC or aqueous base and PTC are held within the pores of the support.
- Thus an “extractive” process whereby the thiols are first extracted from the petroleum feedstream in the substantial absence of air into an aqueous phase and the mercaptan-free petroleum feedstream is then separated from the aqueous phase and passed along for further refinery processing can be conducted. The aqueous phase may then subjected to aerial oxidation to form disulfides from the extracted mercaptans. Separation and disposal of the disulfide would allow for recycle of the aqueous phase. The disulfide is readily separated by extraction with an organic extractant in which the disulfides are soluble. Such extractants are easily selected by the skilled artisan and can include for example a reformate stream.
- If it is desired to conduct a sweetening process, the extraction step can be conducted in air, the loss of thiol is concurrent with generation of disulfide. This indicates a “sweetening process”, in that the total sulfur remains essentially constant in the feedstream, but the mercaptan sulfur is converted to disulfide. Furthermore, the thiol is transported from the organic phase into the aqueous phase, prior to conversion to disulfide then back into the petroleum phase. We have found this oxidation of mercaptide to disulfide to occur readily at room temperature without the addition of any other oxidation catalyst. When conducting a sweetening process, the extracting medium will consist essentially of aqueous base and PTC or aqueous basic PTC. In a sweetening process, no catalysts other than the PTC(s) will be present.
- When utilizing a supported PTC, the porous supports may be selected from, molecular sieves, polymeric beads, carbonaceous solids and inorganic oxides for example.
- Applicants believe that, higher molecular weight mercaptans are extracted from the petroleum feedstream into the basic solution which is contained within the pores of an appropriate solid support such as a “molecular sieve”. This is achieved by bringing into contact the solid-supported aqueous basic solution with the petroleum stream by conventional methods such as are used in solid adsorbent technologies well known in the art. Upon contact, the mercaptide anion should be generated and transported into the aqueous phase within the pores of the molecular sieves. The mercaptan-free petroleum effluent stream is now ready for normal processing. With time, the capacity of the bed will be exceeded and the thiol content of the effluent will rise. At this point the bed will need to be regenerated. A second adsorbent bed will be swung into operation. Regeneration of the first bed will be accomplished by introduction of oxygen (air) into the bed along with an organic phase which will provide a suitable extractant stream for the disulfide which should form upon oxidation of the mercaptide anions. Such extractants are easily chosen by the skilled artisan. Pressure and heat could be used to stimulate the oxidative process. If necessary, the stripped bed could be regenerated by re-saturation with fresh base/PTC solution before being swung back into operation. Neither the base nor the PTC are consumed in this process, other than by losses due to contaminants. The advantage of using a supported PTC is that the mercaptans are trapped within the pores of the support facilitating separation.
- Bases preferred are strong bases, e.g., sodium, potassium and ammonium hydroxide, and sodium and potassium carbonate, and mixtures thereof. These may be used as an aqueous solution of sufficient strength, typically base will be up to or equal to 50 wt % of the aqueous medium, preferably about 15% to about 25 wt % when used in conjunction with onium salt PTCs and 30-50 wt % when used in conjunction with polyethyleneglycol type PTCs.
- The phase transfer catalyst is present in a sufficient concentration to result in a treated feed having a decreased mercaptan content. Thus, a catalytically effective amount of the phase transfer catalyst will be utilized. The phase transfer catalyst may be miscible or immiscible with the petroleum stream to be treated. Typically, this is influenced by the length of the hydrocarbyl chains in the molecule; and these may be selected by one skilled in the art. While this may vary with the catalyst selected, typically concentrations of about 0.01 to about 10 wt. %, preferably about 0.05 to about 1 wt % based on the amount of aqueous solution will be used.
- Phase transfer catalysts (PTCs) suitable for use in this process include the types of PTCs described in standard references on PTC, such asPhase Transfer Catalysis: Fundamentals, Applications and Industrial Perspectives by Charles M. Starks, Charles L. Liotta and Marc Halpern (ISBN 0-412-04071-9 Chapman and Hall, 1994). These reagents are typically used to transport a reactive anion from an aqueous phase into an organic phase in which it would otherwise be insoluble. This “phase-transferred” anion then undergoes reaction in the organic phase and the phase transfer catalyst then returns to the aqueous phase to repeat the cycle, and hence is a “catalytic” agent. In the invention, it is believed that, the PTC transports the hydroxide anion, −OH, into the petroleum stream, where it reacts with the thiols in a simple acid base reaction, producing the deprotonated thiol or thiolate anion. This charged species is much more soluble in the aqueous phase and hence the concentration of thiol in the petroleum stream is reduced by this chemistry.
- A wide variety of PTC would be suitable for this application. These include onium salts such as quaternary ammonium and quaternary phosphonium halides, hydroxides and hydrogen sulfates for example. When the phase transfer catalyst is a quaternary ammonium hydroxide, the quaternary ammonium cation will have the formula:
- where q=1/w+1/x+1l/y+1/z and wherein q≧1.0. Preferably, q≧3. In this formula, Cw, Cx, Cy, and Cz represent alkyl radicals with carbon chain lengths of w, x, y and z carbon atoms respectively. The preferred quaternary ammonium salts are the quaternary ammonium halides.
- The four alkyl groups on the quaternary cation are typically alkyl groups with total carbons ranging from four to forty, but may also include cycloalkyl, aryl, and arylalkyl groups. Some examples of useable onium cations are tetrabutyl ammonium, tetrabutylphosphonium, tributylmethyl ammonium, cetyltrimethyl ammonium, methyltrioctyl ammonium, and methyltricapryl ammonium. In addition to onium salts, other PTC have been found effective for hydroxide transfer. These include crown ethers such as 18-crown-6 and dicyclohexano-18-crown-6 and open chain polyethers such as
polyethyleneglycol 400. Partially-capped and fully-capped polyethyleneglycols are also suitable. This list is not meant to be exhaustive but is presented for illustrative purposes. Supported or unsupported PTC and mixtures thereof are utilizable herein. - The amount of aqueous medium to be added to said petroleum stream being treated will range from about 5% to about 200% by volume relative to petroleum feed.
- While process temperatures of from 25° C. to 180° C. are suitable, lower temperatures of less than 25° C. can be used depending on the nature of the feed and phase transfer catalyst used. The pressure should be sufficient pressure to maintain the petroleum stream in the liquid state. Oxygen must be excluded, or be substantially absent, during the extraction and phase separation steps to avoid the premature formation of disulfides, which would then redissolve in the feed. Oxygen is necessary for a sweetening process.
- Following the extraction of the mercaptans, and separation of the mercaptan free petroleum stream, the stream is then passed through the remaining refinery processes, if any. The base and PTC or basic PTC may then be recycled for extracting additional mercaptans from a fresh petroleum stream.
- The mixture of PTC and base may consist essentially of or consist of PTC and base. When using basic PTCs, they may consist essentially of or consist of basic PTC's. Preferably, the invention will be practiced in the absence of any catalyst other than the phase transfer catalyst such as those used to oxidize mercaptans, e.g. metal chelates as described in U.S. Pat. Nos. 4,124,493; 4,156,641; 4,206,079; 4,290,913; and 4,337,147. Hence in such cases the PTC will be the only catalyst present.
- The following examples are illustrative and are not meant to be limiting in any way.
- Fifty milliliters of a model petroleum stream consisting of 200 wppm of n-octylthiol in hexane was deaerated by twenty cycles of evacuation and argon refilling. This was then mixed with a similarly deaerated fifty milliliters of an aqueous solution containing 20 wt % sodium hydroxide. After 15 minutes of mixing under argon, the mixer was stopped and the phases were allowed to separate. A sample of the organic phase was analyzed by gas chromatography and showed a loss of 2% of the original n-octylthiol and no formation of disulfide. The estimated error for these measurements is +/−5%. This experiment demonstrates essentially no extraction of thiol from the organic phase by sodium hydroxide alone. For comparison, the experiment was repeated exactly, except that 800 wppm (relative to the aqueous phase weight) of cetyltrimethylammonium bromide (CTAB) was added to the aqueous phase. This time, the product organic phase showed 81% thiol extraction with no disulfide formation. The phase transfer agent, CTAB, is required to achieve significant long-chain thiol extraction.
- The same procedure as that described in Example 1 was performed, except that the concentration of sodium hydroxide was reduced to 10 wt % and a series of different CTAB concentrations was added to ascertain the impact of CTAB concentration on thiol removal. The CTAB concentration added in three separate experiments was 200, 400 and 800 wppm relative to the weight of the aqueous phase. The amount of n-octylthiol removed was 20%, 34% and 47% respectively. An extraction with 10 wt % sodium hydroxide with no added CTAB produced a 2% thiol removal.
- Extractions of n-octylthiol in hexane were conducted in the absence of air by mixing together equal volumes of an aqueous phase and a thiol/hexane phase as described in Example 1. The aqueous phase consisted of 2.5 N sodium hydroxide (about 10 wt %) in water with a variable concentration of benzyltrimethylammonium hydroxide (BZTMOH). Four separate experiments at the following concentrations of BZTMOH were conducted: 20 wt %, 10 wt %, 1 wt % and 1000 wppm relative to the total aqueous phase weight. This basic quaternaryammonium hydroxide and experimental conditions were those reported in U.S. Pat. No. 2,059,075. The following percentages of n-octylthiol removal were determined by gas chromatographic analysis: 34%, 8%, 2% and 0% respectively. The results of these extractions and those from Example 2 are plotted together in FIG. 1. Clearly, the quat salt cited in this patent is not effective as a phase transfer catalyst, but rather is acting as a solutizer and is only effective in high concentrations.
- The results are shown in FIG. 1.
- The same procedure as in Example 1 was followed except for the substitution of a highly branched mercaptan, 2-Methyl-2-propanethiol (tert-butyl mercaptan), for the n-octylthiol. Sixty-four percent thiol removal was achieved.
- The requirement for air to form disulfide was demonstrated as follows. A model feed containing 1000 ppm octanethiol in pentane was deaerated on a Schlenck line under an argon atmosphere by three freeze-pump-thaw cycles. This should reduce the oxygen content to less than 10 ppm. An aqueous solution containing 10 wt % tetrabutylammonium hydroxide and 10 wt % sodium hydroxide was degassed by purging with nitrogen for one hour. Equal volumes of the two phases were combined under strictly airless conditions, mixed vigorously for one minute and then allowed to separate for five minutes. A sample was then removed by syringe for gc analysis. The thiol concentration dropped from 1000 ppm to 242 ppm with only a very slight increase in disulfide concentration (from 6 to 8 ppm). The flask containing the two phases was then bubbled briefly with air (15 sec), restoppered, stirred for one minute and allowed to separate for five minutes. Gas chromatographic analysis of the organic phase now shows further extraction of thiol (242 ppm to 132 ppm) but most significantly, a sharp increase in disulfide content (8 ppm to 144 ppm). Further stirring of the solution under air overnight resulted in nearly complete thiol removal (7 ppm) and conversion to disulfide (477 ppm). This result clearly demonstrates the ability to extract C5+ mercaptans from a petroleum feedstream in the absence of air and the necessity of air for the conversion of thiol to disulfide.
- The procedure of Example 4 was repeated, except that after mixing the two deaerated solutions for four minutes and allowing them to phase separate, three quarters of the aqueous phase was removed from the flask by syringe, leaving behind all of the original “feedstream” and one quarter of the aqueous extractant phase. All of the aqueous phase was not removed so as to avoid any possibility of removing any of the original organic phase. The octane thiol had been nearly quantitatively extracted from the pentane phase (1000 ppm to 20 ppm). The portion of the aqueous phase which had been removed was then combined with fresh pentane of equal volume to the original feedstream and mixed in air overnight. GC analysis of the pentane solution showed a 282 ppm disulfide concentration. This experiment demonstrates that the thiol removed from the feedstream is extracted quantitatively into the aqueous phase. Exposure of this aqueous phase (which now contains mercaptides) to air converts these mercaptides to disulfides, which are then readily extracted out of the aqueous phase into a suitable organic solvent (pentane in this example) for disposal.
- Two airless (oxygenless) extractions of a real feed containing 73% mercaptan sulfur and 27% non-mercaptan sulfur were conducted. The feed chosen was a hydrotreated intermediate catalytic cracked naphtha (ICN). Two different phase transfer agents were employed separately. One was 40 wt % tetrabutylammonium hydroxide in water and the second was 1000 wppm of cetyltrimethylammonium bromide in a 10 wt % sodium hydroxide in water solution. Extraction under argon at room temperature with a 1:1 volume ratio by mixing vigorously for five minutes reduced the total sulfur content by 72 and 77% respectively as determined by X-ray fluorescence spectroscopy (XRF). Hence 100±5% mercaptan sulfur was removed.
- Examples 8, 9, and 10 were conducted in the presence of air.
- A series of room temperature extractions of a model petroleum stream consisting of 200 ppm n-octyl thiol in pentane were conducted. Separate equal volume extractions with 20 wt % sodium hydroxide in water and with polyethyleneglycol 400 (PEG) did not remove any of the n-octylthiol from the pentane solution. However, extraction with a combination of sodium hydroxide and PEG led to a greater than 90% extraction of thiol from the pentane solution and conversion to disulfide.
- As a follow-up, an alternative phase-transfer catalyst, tetrabutylammonium hydroxide (TBAOH) which combines both the PTC functionality and the high basicity in one molecule was tested. Extraction with 40 wt % aqueous TBAOH, by stirring or shaking for 5 minutes at room temperature, led to removal of thiol from the pentane to less than our detection limit (<5 ppm) with commensurate production of disulfide.
- Three types of impregnated molecular sieves were produced by separately soaking dehydrated beads (Davidson Molecular Sieves, Type 13A) in three different solutions: pure distilled water, 10 wt % NaOH in water and 5000 wppm cetyltrimethylammonium bromide (CTAB) plus 10 wt % NaOH together in water. These molecular sieves were filtered after a thirty minute soak and rinsed quickly with distilled water to remove any excess aqueous solution from the surface of the beads. The beads (4 g) were then loaded into glass vials and approximately 3 mls of 500 wppm octylthiol in pentane model feed was added. This was sufficient to fill the voids within the column of beads to maximize solution-to-bead contact. The vials were shaken every 5 minutes. Samples of the pentane solution were removed at 30 minutes and at four hours and analyzed by gc. The results are shown in FIG. 2. As expected, water soaked beads showed little impact on thiol concentration over four hours. Both the NaOH only and combined NaOH and CTAB beads produced zero thiol solutions after four hours, with the CTAB containing beads showing significantly higher initial thiol removal rates. In all cases, corresponding increases in disulfide were detected by gc.
- The results are shown in FIG. 2.
Claims (20)
1. A method for removal of mercaptans from petroleum streams comprising the steps of:
(a) extracting said petroleum stream, in the substantial absence of oxygen, with an aqueous medium comprising an aqueous base and a catalytically effective amount of a phase transfer catalyst or an aqueous solution of a catalytically effective amount of a basic phase transfer catalyst to remove said mercaptans from said petroleum stream;
(b) Separating and recovering an aqueous stream containing mercaptide anions and a petroleum stream having a reduced amount of mercaptans, and wherein when said phase transfer catalyst is a quaternary ammonium hydroxide, said quaternary ammonium cation has the formula:
where q=1/w+1/x+1/y+1/z and wherein q≧1.0, and wherein Cw, Cx, Cy, and Cz represent alkyl radicals with carbon chain lengths of w, x, y and z carbon atoms respectively.
2. The process of claim 1 further comprising the step of processing said petroleum feedstream.
3. The process of claim 1 further comprising the steps of:
(c) subjecting said aqueous stream to oxidation to convert mercaptide anions contained therein to disulfides;
d) separating said disulfides and recovering an aqueous stream having disulfides removed therefrom;
(e) recycling said aqueous stream to said step (a) wherein said aqueous stream contains said base and said phase transfer catalyst or said basic phase transfer catalyst of said step (a).
4. The process of claim 1 wherein said phase transfer catalyst is selected from the group consisting essentially of onium salts, crown ethers, open chain polyethers, and mixtures thereof.
5. The process of claim 4 wherein said onium salts are selected from the group consisting of quaternary ammonium hydroxides, quaternary ammonium halides, quaternary ammonium hydrogen sulfates and mixtures thereof.
6. The process of claim 4 wherein said phase transfer catalyst is selected from polyethylene glycol, tetrabutylammonium hydroxide, cetyltrimethylammonium bromide, and tetrabutylphosphonium, tributylmethyl ammonium, methyltrioctyl ammonium and methyltricapryl ammonium salts, and mixtures thereof.
7. The process of claim 1 wherein said base is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, and mixtures thereof.
8. The process of claim 1 wherein said PTC is supported or unsupported.
9. The process of claim 8 , wherein when said PTC is a supported PTC, said support is selected from the group consisting essentially of molecular sieves, polymers, carbonaceous supports, inorganic oxides and mixtures thereof.
10. The process of claim 9 wherein said inorganic oxides are selected from the group consisting essentially of silicas, aluminas, and mixtures thereof.
11. The process of claim 8 wherein said support is regenerated by introduction of oxygen (air) and an organic extractant into the support.
12. The process of claim 1 wherein said PTC is added in amounts of about 0.01 to about 10 wt. % of said aqueous medium.
13. The process of claim 12 wherein said base is added in amounts of up to about 50 wt % of said aqueous stream.
14. The process of claim 11 wherein said process is a swing bed process.
15. The process of claim 1 wherein prior to said step (a) said petroleum stream has been treated to remove non-mercaptan sulfur species.
16. The process of claim 1 wherein said mercaptans are ≧C5 + molecular weight mercaptans.
17. A method for sweetening mercaptan containing petroleum streams comprising the steps of:
(a) mixing said petroleum stream, in the presence of a sufficient amount of oxygen to oxidize the mercaptans contained in said petroleum stream to disulfides, with a medium consisting essentially of an aqueous base and a phase transfer catalyst (PTC) or an aqueous solution of a basic phase transfer catalyst to reduce the amount of said mercaptans from said petroleum stream
(b) Separating and recovering an aqueous stream and a petroleum stream having mercaptans converted to disulfides therein.
18. The process of claim 1 wherein at least about 70% mercaptan removal is obtained.
19. The process of claim 1 wherein said process is run in the absence of any additional mercaptan oxidizing catalyst.
20. The process of claim 1 wherein said aqueous medium is used in an amount of from about 5 to about 200% by volume of said petroleum stream.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/247,993 US20030019793A1 (en) | 2000-04-18 | 2002-09-20 | Mercaptan removal from petroleum streams (law950) |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/551,010 US6488840B1 (en) | 2000-04-18 | 2000-04-18 | Mercaptan removal from petroleum streams (Law950) |
US10/247,993 US20030019793A1 (en) | 2000-04-18 | 2002-09-20 | Mercaptan removal from petroleum streams (law950) |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/551,010 Division US6488840B1 (en) | 2000-04-18 | 2000-04-18 | Mercaptan removal from petroleum streams (Law950) |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030019793A1 true US20030019793A1 (en) | 2003-01-30 |
Family
ID=24199453
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/551,010 Expired - Fee Related US6488840B1 (en) | 2000-04-18 | 2000-04-18 | Mercaptan removal from petroleum streams (Law950) |
US10/247,993 Abandoned US20030019793A1 (en) | 2000-04-18 | 2002-09-20 | Mercaptan removal from petroleum streams (law950) |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/551,010 Expired - Fee Related US6488840B1 (en) | 2000-04-18 | 2000-04-18 | Mercaptan removal from petroleum streams (Law950) |
Country Status (7)
Country | Link |
---|---|
US (2) | US6488840B1 (en) |
EP (1) | EP1285051A4 (en) |
JP (1) | JP2004501216A (en) |
AU (1) | AU2001243548A1 (en) |
CA (1) | CA2404902A1 (en) |
NO (1) | NO20024977L (en) |
WO (1) | WO2001079380A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9302204B2 (en) | 2012-08-14 | 2016-04-05 | Uop Llc | Process for purifying a disulfide oil and an apparatus relating thereto |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7799210B2 (en) * | 2004-05-14 | 2010-09-21 | Exxonmobil Research And Engineering Company | Process for removing sulfur from naphtha |
US20060151359A1 (en) * | 2005-01-13 | 2006-07-13 | Ellis Edward S | Naphtha desulfurization process |
US7842181B2 (en) | 2006-12-06 | 2010-11-30 | Saudi Arabian Oil Company | Composition and process for the removal of sulfur from middle distillate fuels |
US8142646B2 (en) | 2007-11-30 | 2012-03-27 | Saudi Arabian Oil Company | Process to produce low sulfur catalytically cracked gasoline without saturation of olefinic compounds |
WO2009105749A2 (en) | 2008-02-21 | 2009-08-27 | Saudi Arabian Oil Company | Catalyst to attain low sulfur gasoline |
US9005432B2 (en) | 2010-06-29 | 2015-04-14 | Saudi Arabian Oil Company | Removal of sulfur compounds from petroleum stream |
US8535518B2 (en) | 2011-01-19 | 2013-09-17 | Saudi Arabian Oil Company | Petroleum upgrading and desulfurizing process |
US10752847B2 (en) | 2017-03-08 | 2020-08-25 | Saudi Arabian Oil Company | Integrated hydrothermal process to upgrade heavy oil |
US10703999B2 (en) | 2017-03-14 | 2020-07-07 | Saudi Arabian Oil Company | Integrated supercritical water and steam cracking process |
US10093868B1 (en) * | 2017-11-15 | 2018-10-09 | Baker Hughes, A Ge Company, Llc | Ionic liquid-based hydrogen sulfide and mercaptan scavengers |
US10526552B1 (en) | 2018-10-12 | 2020-01-07 | Saudi Arabian Oil Company | Upgrading of heavy oil for steam cracking process |
US10822549B2 (en) | 2019-01-18 | 2020-11-03 | Baker Hughes Holdings Llc | Methods and compounds for removing non-acidic contaminants from hydrocarbon streams |
US11491466B2 (en) | 2020-07-24 | 2022-11-08 | Baker Hughes Oilfield Operations Llc | Ethyleneamines for regenerating adsorbent beds for sulfur compound removal |
US11331649B2 (en) | 2020-07-24 | 2022-05-17 | Baker Hughes Oilfield Operations Llc | Regenerated adsorbent beds for sulfur compound removal |
CN115340480A (en) * | 2022-08-16 | 2022-11-15 | 中国科学院上海高等研究院 | Method for removing mercaptan in sulfurized olefin |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6013175A (en) * | 1994-03-03 | 2000-01-11 | Baker Hughes, Inc. | Quaternary ammonium hydroxides as mercaptan scavengers |
Family Cites Families (49)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1796621A (en) | 1926-08-27 | 1931-03-17 | Gyro Process Co | Process of refining hydrocarbon oils |
US1968842A (en) | 1930-11-03 | 1934-08-07 | Atiantic Refining Company | Treatment of hydrocarbons |
US1973499A (en) | 1930-11-22 | 1934-09-11 | Universal Oil Prod Co | Treatment of hydrocarbon oils |
US2059075A (en) | 1936-05-18 | 1936-10-27 | Shell Dev | Process of sweetening a sour hydrocarbon distillate |
US2152166A (en) | 1936-09-28 | 1939-03-28 | Shell Dev | Process of separating mercaptans contained in a hydrocarbon distillate |
US2152720A (en) | 1936-09-28 | 1939-04-04 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2160632A (en) | 1937-05-07 | 1939-05-30 | Shell Dev | Process for removing acid components from hydrocarbon solutions |
US2152721A (en) | 1937-05-26 | 1939-04-04 | Shell Dev | Process for the removal of mercaptans from hydrocarbon distillates |
US2152723A (en) | 1937-11-01 | 1939-04-04 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2186398A (en) | 1939-02-07 | 1940-01-09 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2212107A (en) | 1939-02-07 | 1940-08-20 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2212106A (en) | 1939-02-07 | 1940-08-20 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2183801A (en) | 1939-02-07 | 1939-12-19 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2212105A (en) | 1939-02-07 | 1940-08-20 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2168078A (en) | 1939-02-07 | 1939-08-01 | Shell Dev | Process for removing acid components from hydrocarbon distillates |
US2297866A (en) | 1939-09-25 | 1942-10-06 | Universal Oil Prod Co | Treatment of hydrocarbon oil |
US2309651A (en) | 1941-02-13 | 1943-02-02 | Atlantic Refining Co | Treatment of hydrocarbon oil |
US2437348A (en) | 1944-11-04 | 1948-03-09 | Universal Oil Prod Co | Process for the refining of hydrocarbon oil containing mercaptans |
US2425777A (en) | 1945-08-22 | 1947-08-19 | Standard Oil Co | Process for the extraction of mercaptans from hydrocarbon oil |
US2593851A (en) | 1948-03-20 | 1952-04-22 | Cities Service Refining Corp | Method of removing mercaptans from hydrocarbons |
US2570277A (en) | 1949-02-24 | 1951-10-09 | Standard Oil Dev Co | Sweetening process |
US2634230A (en) | 1949-11-29 | 1953-04-07 | Standard Oil Co | Desulfurization of olefinic naphtha |
US2608519A (en) | 1949-11-29 | 1952-08-26 | Standard Oil Co | Desulfurization of olefinic naphtha |
US2776929A (en) | 1950-08-22 | 1957-01-08 | Exxon Research Engineering Co | Gasoline sweetening process |
US2792332A (en) | 1953-12-04 | 1957-05-14 | Pure Oil Co | Desulfurization and dearomatization of hydrocarbon mixtures by solvent extraction |
US3708421A (en) * | 1971-09-20 | 1973-01-02 | C Rippie | Process to remove mercaptan sulfur from sour oils |
US4124493A (en) | 1978-02-24 | 1978-11-07 | Uop Inc. | Catalytic oxidation of mercaptan in petroleum distillate including alkaline reagent and substituted ammonium halide |
US4206079A (en) | 1978-02-24 | 1980-06-03 | Uop Inc. | Catalytic composite particularly useful for the oxidation of mercaptans contained in a sour petroleum distillate |
US4290913A (en) | 1978-07-24 | 1981-09-22 | Uop Inc. | Catalytic composite useful for the treatment of mercaptan-containing sour petroleum distillate |
US4337147A (en) | 1979-11-07 | 1982-06-29 | Uop Inc. | Catalytic composite and process for use |
US4298463A (en) * | 1980-07-11 | 1981-11-03 | Uop Inc. | Method of treating a sour petroleum distillate |
US4626341A (en) | 1985-12-23 | 1986-12-02 | Uop Inc. | Process for mercaptan extraction from olefinic hydrocarbons |
US4753722A (en) | 1986-06-17 | 1988-06-28 | Merichem Company | Treatment of mercaptan-containing streams utilizing nitrogen based promoters |
US4705620A (en) * | 1986-12-16 | 1987-11-10 | Uop Inc. | Mercaptan extraction process |
US4824818A (en) | 1988-02-05 | 1989-04-25 | Uop Inc. | Catalytic composite and process for mercaptan sweetening |
US4897180A (en) * | 1988-02-05 | 1990-01-30 | Uop | Catalytic composite and process for mercaptan sweetening |
US4908122A (en) * | 1989-05-08 | 1990-03-13 | Uop | Process for sweetening a sour hydrocarbon fraction |
US4913802A (en) * | 1989-05-08 | 1990-04-03 | Uop | Process for sweetening a sour hydrocarbon fraction |
US4923596A (en) * | 1989-05-22 | 1990-05-08 | Uop | Use of quaternary ammonium compounds in a liquid/liquid process for sweetening a sour hydrocarbon fraction |
US5273646A (en) | 1990-08-27 | 1993-12-28 | Uop | Process for improving the activity of a mercaptan oxidation catalyst |
US5167797A (en) | 1990-12-07 | 1992-12-01 | Exxon Chemical Company Inc. | Removal of sulfur contaminants from hydrocarbons using n-halogeno compounds |
US5346609A (en) | 1991-08-15 | 1994-09-13 | Mobil Oil Corporation | Hydrocarbon upgrading process |
US5271835A (en) * | 1992-05-15 | 1993-12-21 | Uop | Process for removal of trace polar contaminants from light olefin streams |
US5582714A (en) | 1995-03-20 | 1996-12-10 | Uop | Process for the removal of sulfur from petroleum fractions |
US6013598A (en) | 1996-02-02 | 2000-01-11 | Exxon Research And Engineering Co. | Selective hydrodesulfurization catalyst |
WO1999061566A2 (en) * | 1998-05-28 | 1999-12-02 | Interline Hydrocarbon, Inc. | Method for obtaining base oil and removing contaminants and additives from used oil products |
US5985136A (en) | 1998-06-18 | 1999-11-16 | Exxon Research And Engineering Co. | Two stage hydrodesulfurization process |
US6238551B1 (en) * | 1999-02-16 | 2001-05-29 | Miami University | Method of removing contaminants from petroleum distillates |
US6007701A (en) * | 1999-02-16 | 1999-12-28 | Miami University | Method of removing contaminants from used oil |
-
2000
- 2000-04-18 US US09/551,010 patent/US6488840B1/en not_active Expired - Fee Related
-
2001
- 2001-03-09 AU AU2001243548A patent/AU2001243548A1/en not_active Abandoned
- 2001-03-09 JP JP2001577364A patent/JP2004501216A/en active Pending
- 2001-03-09 EP EP01916533A patent/EP1285051A4/en not_active Withdrawn
- 2001-03-09 CA CA002404902A patent/CA2404902A1/en not_active Abandoned
- 2001-03-09 WO PCT/US2001/007650 patent/WO2001079380A2/en not_active Application Discontinuation
-
2002
- 2002-09-20 US US10/247,993 patent/US20030019793A1/en not_active Abandoned
- 2002-10-16 NO NO20024977A patent/NO20024977L/en not_active Application Discontinuation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6013175A (en) * | 1994-03-03 | 2000-01-11 | Baker Hughes, Inc. | Quaternary ammonium hydroxides as mercaptan scavengers |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9302204B2 (en) | 2012-08-14 | 2016-04-05 | Uop Llc | Process for purifying a disulfide oil and an apparatus relating thereto |
Also Published As
Publication number | Publication date |
---|---|
WO2001079380A2 (en) | 2001-10-25 |
WO2001079380A3 (en) | 2002-02-14 |
NO20024977L (en) | 2002-12-06 |
JP2004501216A (en) | 2004-01-15 |
US6488840B1 (en) | 2002-12-03 |
AU2001243548A1 (en) | 2001-10-30 |
EP1285051A4 (en) | 2005-01-12 |
EP1285051A2 (en) | 2003-02-26 |
NO20024977D0 (en) | 2002-10-16 |
CA2404902A1 (en) | 2001-10-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6488840B1 (en) | Mercaptan removal from petroleum streams (Law950) | |
US7244352B2 (en) | Selective hydroprocessing and mercaptan removal | |
EP3891126B1 (en) | Oxidized disulfide oil solvent compositions | |
US7276152B2 (en) | Oxidative desulfurization and denitrogenation of petroleum oils | |
Eßer et al. | Deep desulfurization of oil refinery streams by extraction with ionic liquids | |
EP1315785B1 (en) | Process for removing low amounts of organic sulfur from hydrocarbon fuels | |
CN101611119B (en) | Oxidative desulfurization and denitrogenation of petroleum oils | |
US7790021B2 (en) | Removal of sulfur-containing compounds from liquid hydrocarbon streams | |
US20070227951A1 (en) | Novel Process for Removing Sulfur from Fuels | |
EA016125B1 (en) | Diesel oil desulfurization by oxidation and extraction | |
WO2013049177A1 (en) | Selective liquid-liquid extraction of oxidative desulfurization reaction products | |
WO2005066313A2 (en) | Reactive extraction of sulfur compounds from hydrocarbon streams | |
JP2006514145A (en) | Organic sulfur oxidation method | |
US20040154959A1 (en) | Method for desulphurizing a hydrocarbon mixture | |
RU2408657C2 (en) | Method of purifying hydrocarbon mixtures from sulphur-containing heterocyclic compounds | |
JP2004501217A (en) | Caustic extraction of mercaptans | |
US20230331668A1 (en) | Odso acid medium, odso acid mixture medium, and uses thereof | |
US20240175105A1 (en) | Leaching agent composition and method of removing metal from catalyst material | |
WO2015057108A1 (en) | Method for cleaning liquid motor fuels of sulfur-containing compounds | |
Syntyhaki et al. | Research Article Assessment of the Oxidative Desulfurization of Middle Distillate Surrogate Fuels with Spectroscopic Techniques | |
FR2840917A1 (en) | Process for elimination of sulfur and nitrogen compounds from fluid catalytic cracking petrol and middle distillate hydrocarbon cuts by alkylation and extraction with a non-aqueous polar ionic solvent | |
CN111040804A (en) | Method for desulfurizing fuel oil by catalytic oxidation of ionic liquid | |
KR100566487B1 (en) | Sweetening Process of Petroleum Hydrocarbons | |
DeLancey | i, United States Patent (10) Patent No.: US 8877013 B2 | |
EA019364B1 (en) | Method for purification of hydrocarbon feed stock from sulfur compounds |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: DAINIPPON SCREEN MFG. CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:YAMAMOTO, TAKEHARU;TAKEDA, KAZUYA;REEL/FRAME:014036/0633 Effective date: 20030415 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO PAY ISSUE FEE |