US20020134705A1 - Process for reducing the level of elemental sulfur in hydrocarbon streams - Google Patents
Process for reducing the level of elemental sulfur in hydrocarbon streams Download PDFInfo
- Publication number
- US20020134705A1 US20020134705A1 US10/022,936 US2293601A US2002134705A1 US 20020134705 A1 US20020134705 A1 US 20020134705A1 US 2293601 A US2293601 A US 2293601A US 2002134705 A1 US2002134705 A1 US 2002134705A1
- Authority
- US
- United States
- Prior art keywords
- mercaptan compound
- stream
- hydrocarbon
- pipeline
- treated
- 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 41
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 41
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 mercaptan compound Chemical class 0.000 claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 239000003502 gasoline Substances 0.000 claims abstract description 14
- 238000009835 boiling Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000001983 dialkylethers Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- WYLQOLGJMFRRLX-UHFFFAOYSA-N 2-methoxy-2-methylpentane Chemical compound CCCC(C)(C)OC WYLQOLGJMFRRLX-UHFFFAOYSA-N 0.000 claims description 2
- WICKZWVCTKHMNG-UHFFFAOYSA-N 2-methyl-2-propan-2-yloxybutane Chemical compound CCC(C)(C)OC(C)C WICKZWVCTKHMNG-UHFFFAOYSA-N 0.000 claims description 2
- FITVQUMLGWRKKG-UHFFFAOYSA-N 2-methyl-2-propoxypropane Chemical compound CCCOC(C)(C)C FITVQUMLGWRKKG-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical group COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 claims description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000446 fuel Substances 0.000 abstract description 9
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 10
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229920001021 polysulfide Polymers 0.000 description 3
- 239000005077 polysulfide Substances 0.000 description 3
- 150000008117 polysulfides Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- GAZXPZNJTZIGBO-UHFFFAOYSA-N Dipropyl trisulfide Chemical compound CCCSSSCCC GAZXPZNJTZIGBO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
Definitions
- This invention relates to a process for reducing the level of elemental sulfur from sulfur-containing hydrocarbon streams, particularly refined fuel streams such as gasoline that is transported through a pipeline.
- a mercaptan compound is mixed with the stream prior to, or after, the stream is pipelined.
- U.S. Pat. No. 4,149,966 discloses a method for removing elemental sulfur from refined hydrocarbon fuels by adding an organo-mercaptan compound plus a copper compound capable of forming a soluble complex with the mercaptan and sulfur and contacting the fuel with an adsorbent material to remove the resulting copper complex and substantially all the elemental sulfur.
- the mercaptan is mixed with the hydrocarbon stream prior to its being transported through a pipeline.
- the mercaptan is mixed with the hydrocarbon stream after it has been transported through a pipeline.
- the hydrocarbon streams can contain quantities of elemental sulfur as high as 1000 mg sulfur per liter, typically from about 10 to about 100 mg per liter, more typically from about 10 to 60 mg per liter, and most typically from about 10 to 30 mg per liter. Such streams can be effectively treated in accordance with this invention to reduce the elemental sulfur contamination to less than about 10 mg per liter, preferably to less than about 5 mg sulfur per liter, or lower.
- Preferred hydrocarbon streams are those streams that have become contaminated with elemental sulfur as a result of being transported in a pipeline that was previously used to transport sour hydrocarbon streams, such as sour petroleum crudes. Residual sulfur from the sour crudes will contaminate the pipeline.
- Illustrative ethers are methyl tertiary-butyl ether, methyl tertiary-amyl ether, methyl tertiary-hexyl ether, ethyl tertiary-butyl ether, n-propyl tertiary-butyl ether, and isopropyl tertiary-amyl ether. Mixtures of these ethers and hydrocarbon streams may also be treated in accordance with this invention.
- This amount of mercaptan compound will typically range from about 1 wppm to about 1000 wppm, preferably from about 10 wppm to about 100 wppm. In terms of mole ratios, the amount of mercaptan compound will range from about 0.2 to about 20 moles of mercaptan per mole of elemental sulfur in the refined hydrocarbon stream, or the estimated moles of elemental sulfur that will be picked-up by the stream during its transport through a pipeline.
- the process of the present invention involves the addition of an effective amount of mercaptan to the hydrocarbon stream to be treated.
- the mercaptan can be added at any time, such as prior to, during, or after the hydrocarbon stream has been transported through a pipeline. It is preferred to mix the mercaptan with the stream prior to its being transported through a pipeline.
- Conditions at which the stream is treated with the mercaptan will be relatively mild conventional conditions. That is, the mercaptan is added when either or both the product stream and mercaptan are at a temperature from about ambient temperature (about 22° C.) to about 100° C., or higher.
- Substantially atmospheric pressures are suitable, although pressures may, for example, range up to about 1000 psig.
- the contact time will be an effective contact time. Contact times may vary widely depending on the particular hydrocarbon product stream to be treated, the amount of elemental sulfur present, and the particularly mercaptan used. The contact time will be chosen to affect the desired degree of mixing and subsequent elemental sulfur reduction. In most cases, contact times ranging from about a few hours to a few days will be adequate. The reaction proceeds faster with aliphatic mercaptans than with aromatic mercaptans. Lower carbon number mercaptans will react faster than the higher carbon number mercaptans.
- the mercaptan be adequately mixed with the hydrocarbon product stream to be treated. For example, if the mercaptan is added prior to the product stream being pipelined, the transportation of the product stream through the pipeline will provide adequate mixing of the mercaptan with the hydrocarbon product stream. If the mercaptan is added to the product stream after it is pipelined, then it is preferred to use a suitable mixing device, such as a static mixer, wherein the mercaptan is injected into a moving flow of hydrocarbon product stream prior to entry into the static mixer.
- a suitable mixing device such as a static mixer
- Propyl mercaptan was added to an amber glass bottle containing gasoline with 24 mg/l of elemental sulfur. The molar ratio of propyl mercaptan to elemental sulfur was 1.5. The solution was mixed for one minute by shaking. The elemental sulfur level in the mixture was monitored over time. After 5 days the elemental sulfur level dropped from 24 to 1 mg/l as shown in Table 2 below. TABLE 2 Effect of Propyl Mercaptan Addition to Gasoline Containing Elemental Sulfur Time Temperature S° S° Conv.
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)
Abstract
A process for reducing the level of elemental sulfur from sulfur-containing hydrocarbon streams, particularly refined fuel streams such as gasoline that is transported through a pipeline. A mercaptan compound is mixed with the stream prior to, or after, the stream is pipelined.
Description
- This application claims benefit of U.S. Provisional Patent Application Serial No. 60/258,711 filed on Dec. 28, 2000.
- This invention relates to a process for reducing the level of elemental sulfur from sulfur-containing hydrocarbon streams, particularly refined fuel streams such as gasoline that is transported through a pipeline. A mercaptan compound is mixed with the stream prior to, or after, the stream is pipelined.
- It is well known that elemental sulfur in hydrocarbon streams, such as petroleum streams, is corrosive and damaging to metal equipment, particularly copper and copper alloys. Sulfur and sulfur compounds may be present in varying concentrations in refined petroleum streams, such as in gasoline boiling range streams. Additional contamination will typically take place as a consequence of transporting the refined stream through pipelines that contain sulfur contaminants remaining in the pipeline from the transportation of sour hydrocarbon streams, such as petroleum crudes. The sulfur has a particularly corrosive effect on equipment such as brass valves, gauges and in-tank fuel pump copper commutators.
- Various techniques have been reported for removing elemental sulfur from petroleum products. For example, U.S. Pat. No. 4,149,966 discloses a method for removing elemental sulfur from refined hydrocarbon fuels by adding an organo-mercaptan compound plus a copper compound capable of forming a soluble complex with the mercaptan and sulfur and contacting the fuel with an adsorbent material to remove the resulting copper complex and substantially all the elemental sulfur.
- U.S. Pat. No. 4,011,882 discloses a method for reducing sulfur contamination of refined hydrocarbon fluids transported in a pipeline for the transportation of sweet and sour hydrocarbon fluids by washing the pipeline with a wash solution containing a mixture of light and heavy amines, a corrosion inhibitor, a surfactant and an alkanol containing from 1 to 6 carbon atoms.
- U.S. Pat. No. 5,618,408 teaches a method for reducing the amount of sulfur and other sulfur contaminants picked-up by refined hydrocarbon products, such as gasoline and distillate fuels, which are pipelined in a pipeline used to transport heavier sour hydrocarbon streams. The method involves controlling the level of dissolved oxygen in the refined hydrocarbon stream that is to be pipelined.
- The removal of elemental sulfur from pipelined fuels is also addressed in U.S. Pat. No. 5,250,181 which teaches the use of an aqueous solution containing a caustic, an aliphatic mercaptan, and optionally a sulfide to produce an aqueous layer containing metal polysulfides and a clear fluid layer having a reduced elemental sulfur level. U.S. Pat. No. 5,199,978 teaches the use of an inorganic caustic material, an alkyl alcohol, and an organo mercaptan, or sulfide compound, capable of reacting with sulfur to form a fluid-insoluble polysulfide salt reaction product at ambient temperatures.
- While such methods have varying degrees of success, there still exists a need in the art for increasing the economics and efficiency of elemental sulfur removal from hydrocarbon streams that pick-up sulfur when transported in pipelines.
- In accordance with the present invention, there is provided a process for reducing the level of elemental sulfur in a hydrocarbon stream containing same, which process comprises treating said hydrocarbon stream with an effective amount of a mercaptan compound.
- In a preferred embodiment of the present invention the mercaptan is mixed with the hydrocarbon stream prior to its being transported through a pipeline.
- In another preferred embodiment of the present invention the mercaptan is mixed with the hydrocarbon stream after it has been transported through a pipeline.
- In still another preferred embodiment of the present invention the mercaptan is selected from the group consisting of aliphatic and aromatic mercaptans.
- In yet another preferred embodiment of the present invention the mercaptan is used in a concentration from about 1 to about 1000 wppm.
- Hydrocarbon streams that are treated in accordance with the present invention are preferably refined hydrocarbon streams containing elemental sulfur, particularly those wherein the sulfur has been, or will be, picked-up when the stream is transported through a pipeline. Preferred streams are also those wherein the elemental sulfur is detrimental to the performance of the intended use of the hydrocarbon stream. The preferred streams to be treated in accordance with the present invention are naphtha boiling range streams that are also referred to as gasoline boiling range streams. Naphtha boiling range streams can comprise any one or more refinery streams boiling in the range from about 10° C. to about 230° C., at atmospheric pressure. The naphtha stream generally contains cracked naphtha that typically comprises fluid catalytic cracking unit naphtha (FCC catalytic naphtha, or cat cracked naphtha), coker naphtha, hydrocracker naphtha, resid hydrotreater naphtha, debutanized natural gasoline (DNG), and gasoline blending components from other sources from which a naphtha boiling range stream can be produced. FCC catalytic naphtha and coker naphtha are generally more olefinic naphthas since they are products of catalytic and/or thermal cracking reactions. Non-limiting examples of hydrocarbon feed streams boiling in the distillate range include diesel fuels, jet fuels, heating oils, and lubes. Such streams typically have a boiling range from about 150° C. to about 600° C., preferably from about 175° C. to about 400° C.
- The hydrocarbon streams can contain quantities of elemental sulfur as high as 1000 mg sulfur per liter, typically from about 10 to about 100 mg per liter, more typically from about 10 to 60 mg per liter, and most typically from about 10 to 30 mg per liter. Such streams can be effectively treated in accordance with this invention to reduce the elemental sulfur contamination to less than about 10 mg per liter, preferably to less than about 5 mg sulfur per liter, or lower. Preferred hydrocarbon streams are those streams that have become contaminated with elemental sulfur as a result of being transported in a pipeline that was previously used to transport sour hydrocarbon streams, such as sour petroleum crudes. Residual sulfur from the sour crudes will contaminate the pipeline. Non-limiting examples of such streams that can be treated in accordance with the present invention include gasoline, jet fuel, diesel fuel, kerosene and dialkyl ethers containing same. Alkyl ethers are typically used to improve the octane rating of gasoline. These ethers are typically dialkyl ethers having 1 to 7 carbon atoms in each alkyl group. Illustrative ethers are methyl tertiary-butyl ether, methyl tertiary-amyl ether, methyl tertiary-hexyl ether, ethyl tertiary-butyl ether, n-propyl tertiary-butyl ether, and isopropyl tertiary-amyl ether. Mixtures of these ethers and hydrocarbon streams may also be treated in accordance with this invention.
- The mercaptan that is mixed with the sulfur-containing stream is an organo mercaptan that includes a relatively wide variety of compounds having the general formula RSH, where R represents an organic radical that may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or arylalkyl having from 1 to about 16 carbon atoms. Thus, the radical may be, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, amyl, n-octyl, decyl, dodecyl, octadecyl, phenyl, benzyl, and the like. Most preferably, RSH is an alkyl mercaptan containing 2 to 5 carbon atoms. The concentration of mercaptan that is added to the stream to be treated will be an effective amount. That is, an amount that will be capable of reducing the level of elemental sulfur by a predetermined amount, preferably by at least about 80 wt. %, more preferably by at least about 90 wt. %, and most preferably by at least about 95 wt. %, of the elemental contaminants. This amount of mercaptan compound will typically range from about 1 wppm to about 1000 wppm, preferably from about 10 wppm to about 100 wppm. In terms of mole ratios, the amount of mercaptan compound will range from about 0.2 to about 20 moles of mercaptan per mole of elemental sulfur in the refined hydrocarbon stream, or the estimated moles of elemental sulfur that will be picked-up by the stream during its transport through a pipeline.
- In general, the process of the present invention involves the addition of an effective amount of mercaptan to the hydrocarbon stream to be treated. The mercaptan can be added at any time, such as prior to, during, or after the hydrocarbon stream has been transported through a pipeline. It is preferred to mix the mercaptan with the stream prior to its being transported through a pipeline. Conditions at which the stream is treated with the mercaptan will be relatively mild conventional conditions. That is, the mercaptan is added when either or both the product stream and mercaptan are at a temperature from about ambient temperature (about 22° C.) to about 100° C., or higher. Substantially atmospheric pressures are suitable, although pressures may, for example, range up to about 1000 psig. The contact time will be an effective contact time. Contact times may vary widely depending on the particular hydrocarbon product stream to be treated, the amount of elemental sulfur present, and the particularly mercaptan used. The contact time will be chosen to affect the desired degree of mixing and subsequent elemental sulfur reduction. In most cases, contact times ranging from about a few hours to a few days will be adequate. The reaction proceeds faster with aliphatic mercaptans than with aromatic mercaptans. Lower carbon number mercaptans will react faster than the higher carbon number mercaptans.
- It is preferred that the mercaptan be adequately mixed with the hydrocarbon product stream to be treated. For example, if the mercaptan is added prior to the product stream being pipelined, the transportation of the product stream through the pipeline will provide adequate mixing of the mercaptan with the hydrocarbon product stream. If the mercaptan is added to the product stream after it is pipelined, then it is preferred to use a suitable mixing device, such as a static mixer, wherein the mercaptan is injected into a moving flow of hydrocarbon product stream prior to entry into the static mixer.
- The following examples are illustrative of the invention and are not to be taken as limiting in any way.
- Thiophenol was added to a tank containing gasoline with 21 mg/l of elemental sulfur (S°). The molar ratio of thiophenol to elemental sulfur was 2.0. The solution was mixed for 5 minutes using a recirculation pump. The elemental sulfur level in the mixture was monitored over time. After 16 days the elemental sulfur level dropped from 21 to 9.8 mg/l as shown in Table 1 below.
TABLE 1 Effect of Thiophenol Addition to Gasoline Containing Elemental Sulfur Time Temperature S° S° Conv.* Total Sulfur (Days) (° C.) (mg/l) (%) (mg/l) 0 12-15 21.3 0 108 2.0 12-15 18.8 11.7 — 9.9 12-15 11.2 47.4 — 15.9 0 9.8 54.0 120 20.8 23 9.8 54.0 — - Sulfur species analysis of the mixture after 21 days showed the presence of diphenol-disulphide that was not present in the fresh feed.
- Propyl mercaptan was added to an amber glass bottle containing gasoline with 24 mg/l of elemental sulfur. The molar ratio of propyl mercaptan to elemental sulfur was 1.5. The solution was mixed for one minute by shaking. The elemental sulfur level in the mixture was monitored over time. After 5 days the elemental sulfur level dropped from 24 to 1 mg/l as shown in Table 2 below.
TABLE 2 Effect of Propyl Mercaptan Addition to Gasoline Containing Elemental Sulfur Time Temperature S° S° Conv. Total Sulfur (Days) (° C.) (mg/l) (%) (mg/l) 0 22 24.1 0 96 3.0 24 3.4 85.9 — 4.0 25 3.9 83.8 — 5.0 23 1.1 95.4 86 6.0 222 1.1 95.4 — 9.8 23 1.1 95.4 86 - Sulfur species analysis of the mixture after 10 days showed the presence of dipropyl-disulphide and dipropyl-trisulphide that were not present in the fresh feed. Although the sulfur speciation data indicates the formation of polysulfides the exact mechanism is not understood.
Claims (14)
1. A process for reducing the level of elemental sulfur in hydrocarbon stream containing same, which process comprises treating said hydrocarbon stream with an effective amount of a mercaptan compound.
2. The process of claim 1 wherein said hydrocarbon stream is treated with said mercaptan compound prior to being transported through a pipeline.
3. The process of claim 1 wherein said hydrocarbon stream is treated with said mercaptan compound while being transported through a pipeline.
4. The process of claim 1 wherein said hydrocarbon product stream is treated with said mercaptan compound after being transported through a pipeline.
5. The process of claim 1 wherein said mercaptan compound is represented by the formula RSH, where R represents an organic radical that may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or arylalkyl having from 1 to about 16 carbon atoms.
6. The process of claim 1 wherein said mercaptan compound is used in a concentration of from about 1 to about 1000 wppm.
7. The process of claim 1 wherein the hydrocarbon product stream is selected from the group consisting of gasoline boiling range streams and distillate boiling range streams.
8. The process of claim 1 wherein the hydrocarbon product stream is a dialkyl ether having 1 to 7 carbon atoms in each alkyl group.
9. The process of claim 8 wherein the dialkyl ether is selected from the group consisting of methyl tertiary-butyl ether, methyl tertiary-amyl ether, methyl tertiary-hexyl ether, ethyl tertiary-butyl ether, n-propyl tertiary-butyl ether, and isopropyl tertiary-amyl ether.
10. The process of claim 1 wherein the sulfur content of the hydrocarbon product stream before being treated with the mercaptan compound is up to about 1000 mg/l.
11. A process for reducing the level of elemental sulfur in naphtha boiling range streams containing same, which process comprises treating said naphtha boiling range stream with an effective amount of a mercaptan compound represented by the formula RSH, where R represents an organic radical that may be alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl or arylalkyl having from 1 to about 16 carbon atoms.
12. The process of claim 11 wherein said hydrocarbon stream is treated with said mercaptan compound prior to being transported through a pipeline.
13. The process of claim 11 wherein said hydrocarbon stream is treated with said mercaptan compound while being transported through a pipeline.
14. The process of claim 11 wherein said mercaptan compound is used in a concentration of from about 1 to about 1000 wppm.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/022,936 US20020134705A1 (en) | 2000-12-28 | 2001-12-17 | Process for reducing the level of elemental sulfur in hydrocarbon streams |
| CA002366234A CA2366234A1 (en) | 2000-12-28 | 2001-12-27 | Process for reducing the level of elemental sulfur in hydrocarbon streams |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US25871100P | 2000-12-28 | 2000-12-28 | |
| US10/022,936 US20020134705A1 (en) | 2000-12-28 | 2001-12-17 | Process for reducing the level of elemental sulfur in hydrocarbon streams |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20020134705A1 true US20020134705A1 (en) | 2002-09-26 |
Family
ID=26696523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/022,936 Abandoned US20020134705A1 (en) | 2000-12-28 | 2001-12-17 | Process for reducing the level of elemental sulfur in hydrocarbon streams |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20020134705A1 (en) |
| CA (1) | CA2366234A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438193A (en) * | 2018-09-25 | 2019-03-08 | 安徽海德化工科技有限公司 | A kind of method of methyl tertiary butyl ether(MTBE) purifying crude |
-
2001
- 2001-12-17 US US10/022,936 patent/US20020134705A1/en not_active Abandoned
- 2001-12-27 CA CA002366234A patent/CA2366234A1/en not_active Abandoned
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438193A (en) * | 2018-09-25 | 2019-03-08 | 安徽海德化工科技有限公司 | A kind of method of methyl tertiary butyl ether(MTBE) purifying crude |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2366234A1 (en) | 2002-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU719046B2 (en) | Bisoxazolidine hydrogen sulfide scavenger | |
| US6027636A (en) | Sulfur removal from hydrocarbon fluids by mixing with organo mercaptan and contacting with hydrotalcite-like materials, alumina, bayerite or brucite | |
| US5160045A (en) | Process for removing elemental sulfur from fluids | |
| US5618408A (en) | Method for reducing elemental sulfur pick-up by hydrocarbon fluids in a pipeline (law177) | |
| AU2009233811B2 (en) | Quick removal of mercaptans from hydrocarbons | |
| US7566687B2 (en) | Methods and compositions for removing sulfur from liquid hydrocarbons | |
| US20020134705A1 (en) | Process for reducing the level of elemental sulfur in hydrocarbon streams | |
| US5525233A (en) | Process for the removal of elemental sulfur from fluids by mixing said fluid with an immiscible solution of alcoholic caustic and an inorganic sulfide or hydrosulfide | |
| US20060011518A1 (en) | Process for reducing the level of elemental sulfur in hydrocarbon streams | |
| EP1713885B1 (en) | Hydrocarbons having reduced levels of mercaptans and method and composition useful for preparing same | |
| CA2512063C (en) | Process for reducing the level of elemental sulfur in hydrocarbon streams | |
| US5336277A (en) | Composition for reducing in-tank fuel pump copper commutator wear and method | |
| US5200062A (en) | Process for removing elemental sulfur from fluids | |
| US7713409B2 (en) | Method for reducing the level of elemental sulfur and total sulfur in hydrocarbon streams | |
| US8658028B2 (en) | Removal of elemental sulfur in pipelines using static mixers | |
| US7632396B2 (en) | Method for reducing the level of elemental sulfur and total sulfur in hydrocarbon streams | |
| CA2587420C (en) | Method for reducing the amount of sulfur pick-up by hydrocarbon streams transported through a pipeline | |
| US20020139714A1 (en) | Method for reducing the level of elemental sulfur and total sulfur in hydrocarbon streams | |
| US20060281637A1 (en) | Methods and compositions for removing sulfur from liquid hydrocarbons | |
| US20090230027A1 (en) | Methods and compositions for removing sulfur from liquid hydrocarbons | |
| CA2249696C (en) | Sulfur removal from hydrocarbon fluids by mixing with organo mercaptan and contacting with hydrotalcite-like materials, alumina, bayerite or brucite | |
| CA2105134C (en) | Process for removing elemental sulfur from fluids | |
| WO2024023215A1 (en) | Method for scavenging mercaptans in a hydrocarbon fluid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: EXXONMOBIL RESEARCH & ENGINEERING CO., NEW JERSEY Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FEIMER, JOSEPH L.;FALKINER, ROBERT J.;LECLAIR, DAVID;REEL/FRAME:012723/0866;SIGNING DATES FROM 20020207 TO 20020218 |
|
| STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |