CA1091608A - Removal of carbonyl sulfide from liquid hydrocarbon streams - Google Patents
Removal of carbonyl sulfide from liquid hydrocarbon streamsInfo
- Publication number
- CA1091608A CA1091608A CA283,981A CA283981A CA1091608A CA 1091608 A CA1091608 A CA 1091608A CA 283981 A CA283981 A CA 283981A CA 1091608 A CA1091608 A CA 1091608A
- Authority
- CA
- Canada
- Prior art keywords
- hydrocarbon stream
- carbonyl sulfide
- potassium hydroxide
- methanol
- recited
- 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.)
- Expired
Links
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
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
-
- 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
Abstract
APPLICATION FOR UNITED STATES PATENT
REMOVAL OF CARBONYL SULFIDE FROM
LIQUID HYDROCARBON STREAMS
ABSTRACT OF THE DISCLOSURE
Carbonyl sulfide is removed from propane and other similar liquefied petroleum gas products by mix-ing liquid methanol with the untreated liquefied gas and then contacting the liquid mixture with solid potassium hydroxide.
REMOVAL OF CARBONYL SULFIDE FROM
LIQUID HYDROCARBON STREAMS
ABSTRACT OF THE DISCLOSURE
Carbonyl sulfide is removed from propane and other similar liquefied petroleum gas products by mix-ing liquid methanol with the untreated liquefied gas and then contacting the liquid mixture with solid potassium hydroxide.
Description
~ ~91~OB
BA CKGROUND OF THE _NVEN~ ION
BA CKGROUND OF THE _NVEN~ ION
2 The present invention concerns removing carbonyl
3 sulfide (COS) ~rom liquid hydrocarbon streams and, particu-
4 larly, ~rom propane and other simil~r liquefied petroleum gas streams ( LPG) .
6 In oil and gas production operations carbonyl 7 sulfide sometimes occurs in propane and other related 8 liquefied petroleum gas products. I~ the carbonyl sul~ide 9 comes in contact with water in tank cars, pipelines, sto-rage caverns etc. used to transport or store the liquified 11 gas products it may convert to hydrogen sul~ide (H2S) in 12 the presence o~ a heavy metal catalyst such as iron or 13 aluminum. I~ more than one PP~ (parts per million by 14 volume) o~ hydrogen sul~ide is produced ~rom the resulting reaction the lique~ied gas products will not meet the Gas 16 Producers Association (GPA) copper strip corrosion test 17 specification. Carbonyl sul~ide is a stable unreactive 18 compound that is very di~icult to reduce to concentration 19 levels below one PP~ using conventional amine and mole~
Gular sieve processes. The present invention is designed 21 to reduce the carbonyl sul~ide content o~ a lique~ied 22 petroleum gas product to less than one PP~ expediently, 2~ economically, and with negligible energy consumption.
2~ ~UMM~RY OF THE INVENTION
In accordance with the invention a liqui~ied 26 petroleum gas product containing carbonyl sul~ide i9 27 mixed with liquid methanol (CH30H) and then contacted 28 with solid potassium hydroxide (KOH) to remove carbonyl 29 sul~ide from the lique~ied gas product. The overall reaction is:
31 KOH + C~30H + COS ~ H20 + KSCOOCH3 1(~9i~08 DESCRIPTION OF TIIE PREFERR~[) EME~ODIMl~NTS
.... ..
2 Referring to the sole Figure in which the process 3 of the invention is illustrated liquid methanol is pumped 4 by means of a pump 9 through a conduit lO into a mixer ll, which may be a static mixer as shown. An LP~stre~m is 6 fed into mixer ll through a conduit 13 and the two streams 7 are mixed or blended together. The mixed stream flows 8 into the bottom of one of the contacting towers 14 through 9 conduits 15 and 16. Each tower 14 contains a bed of solid potassium hydroxide 18 supported by a suitable screen l9.
ll The liquid mixture flows upward through the solid potassium 12 hydroxide bed 18 where the carbonyl sulfide is removed in 13 the reaction between potassium hydroxide, methanol and 14 carbonyl sulfide to yield the reaction products water and KSCOOCH3. Those products are periodically drawn off the 16 bottom of each tower through conduits 21 and 22. The 17 treated LPG stream is removed from the top of each tower 18 through lines 23 and 24.
l9 The process has been used to successfully treat propane streams containing as high as 400 PPMV carbonyl 21 sul~ide. Methanol consumption for the process averages 22 5 to lO mols per mol of carbonyl sul~ide in the ~eed 23 gtream. Methanol consumption is reduced to as low as 3 2l~ mols per mol of carbonyl sulfide if multiple beds or towers in series are used. Potassium hydroxide consump-26 tion averages 1.2 to 1.5 mols per mol of carbonyl sulfide.
27 The reaction products produced are 2.5 pounds per pound of 28 carbonyl sulfide. The process will operate over a wide 29 range of temperatures and pressures as long as the propane remains in the liquid phase. However, methanol consump-31 tion decreases with decreasing temperature. Total energy 32 consumption for the process is only 0.02 ~ horsepower ~/?~ - 3 -7~ G
6 0 ~
1 (BHP) to pump methanol ~or a typical plant treating 2 8000 barrels per day (B/D) of propane which contains 3 1 00 PP~ o~ carbonyl sulfide.
L~ The two contacting towers 14 are installed in parallel so that one column can be removed ~rom operation 6 to replenish the potassium hydroxide supply after it has 7 been consumed. If the untreated LPG stream contains 8 greater than about 100 PP~ o~ carbonyl sul~ide then two 9 contacting towers in series or multiple beds in the same tower may be used with methanolbeing injected into the 11 LPG stream upstream of each tower or bed. The solid 12 potassium hydroxide provides good contact with the LPG
13 stream while minimizing losses of potassium hydroxide and 14 consumption of methanol. In addition, using solid potas-sium hydroxide produces an LPG produc-t that meets GPA dry-16 ness specifications. The use of solid potassium hydroxide 17 tends to minimize the consumption o~ methanol because only 18 enough methanol is needed for injection to wet the outer l~ surface o~ the potassium hydroxide. As the LPG-methanol mixture progresses up the tower 14 it comes in contact 2~ with potassium hydroxide that has progressi~ely ~ewer ~2 reaction products on the surface thereo~ -thereby provlding ~ ~ more e~icient remov~l process o~ the carbonyl sul~ide.
24 ln a solution tank the methanol and LPG mixture would come ~5 ln contact w~th essentially a constant composltion solu-26 tion and consume greater amounts o~ methanol. Also, solid 27 potassium hydroxide, as opposed to a solution o~ potassium 28 hydroxide, is employed because the reaction products, in-29 cluding water, would remain in a solution o~ potassium hydroxide and cause the LPG to become wet. In addition 31 any water in the system might lead to the formation of 32 undesired hydrogen sulfide by the reaction between the 33 water and the carbonyl sulfide.
~ 4 -r~ 10~160B
1 Solid potassium hydroxide is available in 2 flake, granular and walnut size; however, plugging of 3 the bed is reduced when the latter is used and it, there-4 fore, is preferred. Channeling through the bed is re-duced by using a vessel height to diameter ratio of 3 or 6 higher based on bed height (not vessel height). Superfi-7 cial velocity, i.e. velocity of the liquid hydrocarbon 8 stream through an empty vessel, should be below about one 9 foot per minute to minimize carryover and achieve low con-sumption of methanol and potassium hydroxide. Such low 11 velocities were employed in the illustrative successful 12 treatment of propane streams given above. The low pro-13 pane stream velocity also allows time for the reac-tion 14 products to settle to the bottom of the towers.
The potassium hydroxide-methanol process of the 16 invention provides essentially 100 percent removal of 17 carbonyl sul~ide from liquid hydrocarbon streams and has 1~ the advantages o~ a simple design, low capital cost, 19 quick installation, low operating costs (minimal energy input for pumping methanol), minimal utility requ:lrements ~1 and dry ef~luent liquid hydrocarbons without downætream ~2 dehydration.
~3 More informàtion relating to the background, 2~ ~dvantages, operation and other features of the invention are disclosed in a paper, entitled "Treating Propane for 26 Removal of Carbonyl Sul~ide" by M. B. Mick presented to 27 the National Gas Processors Association, March 24, 1976 28 and published on pages 114-125 of the Proceedings of the 29 Fifty-Fifth Annual Convention of the Gas Processors Association, March 22-24, 1976.
1~91~0~
1 Changes and modi~ications may be made in the 2 illustrative embodiments of the invention shown and 3 described herein without departing ~rom the scope of the 4 invention as defined in the appended claims.
Having ~ully described the nature, objects, 6 method and advantages o~ our invention we claim:
6 In oil and gas production operations carbonyl 7 sulfide sometimes occurs in propane and other related 8 liquefied petroleum gas products. I~ the carbonyl sul~ide 9 comes in contact with water in tank cars, pipelines, sto-rage caverns etc. used to transport or store the liquified 11 gas products it may convert to hydrogen sul~ide (H2S) in 12 the presence o~ a heavy metal catalyst such as iron or 13 aluminum. I~ more than one PP~ (parts per million by 14 volume) o~ hydrogen sul~ide is produced ~rom the resulting reaction the lique~ied gas products will not meet the Gas 16 Producers Association (GPA) copper strip corrosion test 17 specification. Carbonyl sul~ide is a stable unreactive 18 compound that is very di~icult to reduce to concentration 19 levels below one PP~ using conventional amine and mole~
Gular sieve processes. The present invention is designed 21 to reduce the carbonyl sul~ide content o~ a lique~ied 22 petroleum gas product to less than one PP~ expediently, 2~ economically, and with negligible energy consumption.
2~ ~UMM~RY OF THE INVENTION
In accordance with the invention a liqui~ied 26 petroleum gas product containing carbonyl sul~ide i9 27 mixed with liquid methanol (CH30H) and then contacted 28 with solid potassium hydroxide (KOH) to remove carbonyl 29 sul~ide from the lique~ied gas product. The overall reaction is:
31 KOH + C~30H + COS ~ H20 + KSCOOCH3 1(~9i~08 DESCRIPTION OF TIIE PREFERR~[) EME~ODIMl~NTS
.... ..
2 Referring to the sole Figure in which the process 3 of the invention is illustrated liquid methanol is pumped 4 by means of a pump 9 through a conduit lO into a mixer ll, which may be a static mixer as shown. An LP~stre~m is 6 fed into mixer ll through a conduit 13 and the two streams 7 are mixed or blended together. The mixed stream flows 8 into the bottom of one of the contacting towers 14 through 9 conduits 15 and 16. Each tower 14 contains a bed of solid potassium hydroxide 18 supported by a suitable screen l9.
ll The liquid mixture flows upward through the solid potassium 12 hydroxide bed 18 where the carbonyl sulfide is removed in 13 the reaction between potassium hydroxide, methanol and 14 carbonyl sulfide to yield the reaction products water and KSCOOCH3. Those products are periodically drawn off the 16 bottom of each tower through conduits 21 and 22. The 17 treated LPG stream is removed from the top of each tower 18 through lines 23 and 24.
l9 The process has been used to successfully treat propane streams containing as high as 400 PPMV carbonyl 21 sul~ide. Methanol consumption for the process averages 22 5 to lO mols per mol of carbonyl sul~ide in the ~eed 23 gtream. Methanol consumption is reduced to as low as 3 2l~ mols per mol of carbonyl sulfide if multiple beds or towers in series are used. Potassium hydroxide consump-26 tion averages 1.2 to 1.5 mols per mol of carbonyl sulfide.
27 The reaction products produced are 2.5 pounds per pound of 28 carbonyl sulfide. The process will operate over a wide 29 range of temperatures and pressures as long as the propane remains in the liquid phase. However, methanol consump-31 tion decreases with decreasing temperature. Total energy 32 consumption for the process is only 0.02 ~ horsepower ~/?~ - 3 -7~ G
6 0 ~
1 (BHP) to pump methanol ~or a typical plant treating 2 8000 barrels per day (B/D) of propane which contains 3 1 00 PP~ o~ carbonyl sulfide.
L~ The two contacting towers 14 are installed in parallel so that one column can be removed ~rom operation 6 to replenish the potassium hydroxide supply after it has 7 been consumed. If the untreated LPG stream contains 8 greater than about 100 PP~ o~ carbonyl sul~ide then two 9 contacting towers in series or multiple beds in the same tower may be used with methanolbeing injected into the 11 LPG stream upstream of each tower or bed. The solid 12 potassium hydroxide provides good contact with the LPG
13 stream while minimizing losses of potassium hydroxide and 14 consumption of methanol. In addition, using solid potas-sium hydroxide produces an LPG produc-t that meets GPA dry-16 ness specifications. The use of solid potassium hydroxide 17 tends to minimize the consumption o~ methanol because only 18 enough methanol is needed for injection to wet the outer l~ surface o~ the potassium hydroxide. As the LPG-methanol mixture progresses up the tower 14 it comes in contact 2~ with potassium hydroxide that has progressi~ely ~ewer ~2 reaction products on the surface thereo~ -thereby provlding ~ ~ more e~icient remov~l process o~ the carbonyl sul~ide.
24 ln a solution tank the methanol and LPG mixture would come ~5 ln contact w~th essentially a constant composltion solu-26 tion and consume greater amounts o~ methanol. Also, solid 27 potassium hydroxide, as opposed to a solution o~ potassium 28 hydroxide, is employed because the reaction products, in-29 cluding water, would remain in a solution o~ potassium hydroxide and cause the LPG to become wet. In addition 31 any water in the system might lead to the formation of 32 undesired hydrogen sulfide by the reaction between the 33 water and the carbonyl sulfide.
~ 4 -r~ 10~160B
1 Solid potassium hydroxide is available in 2 flake, granular and walnut size; however, plugging of 3 the bed is reduced when the latter is used and it, there-4 fore, is preferred. Channeling through the bed is re-duced by using a vessel height to diameter ratio of 3 or 6 higher based on bed height (not vessel height). Superfi-7 cial velocity, i.e. velocity of the liquid hydrocarbon 8 stream through an empty vessel, should be below about one 9 foot per minute to minimize carryover and achieve low con-sumption of methanol and potassium hydroxide. Such low 11 velocities were employed in the illustrative successful 12 treatment of propane streams given above. The low pro-13 pane stream velocity also allows time for the reac-tion 14 products to settle to the bottom of the towers.
The potassium hydroxide-methanol process of the 16 invention provides essentially 100 percent removal of 17 carbonyl sul~ide from liquid hydrocarbon streams and has 1~ the advantages o~ a simple design, low capital cost, 19 quick installation, low operating costs (minimal energy input for pumping methanol), minimal utility requ:lrements ~1 and dry ef~luent liquid hydrocarbons without downætream ~2 dehydration.
~3 More informàtion relating to the background, 2~ ~dvantages, operation and other features of the invention are disclosed in a paper, entitled "Treating Propane for 26 Removal of Carbonyl Sul~ide" by M. B. Mick presented to 27 the National Gas Processors Association, March 24, 1976 28 and published on pages 114-125 of the Proceedings of the 29 Fifty-Fifth Annual Convention of the Gas Processors Association, March 22-24, 1976.
1~91~0~
1 Changes and modi~ications may be made in the 2 illustrative embodiments of the invention shown and 3 described herein without departing ~rom the scope of the 4 invention as defined in the appended claims.
Having ~ully described the nature, objects, 6 method and advantages o~ our invention we claim:
Claims (5)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for removing carbonyl sulfide from an essentially water-free liquid hydrocarbon stream, the improvement comprising:
mixing said hydrocarbon stream containing carbonyl sulfide with liquid methanol;
passing said mixed methanol-hydrocarbon stream upwardly through a bed of solid potassium hydroxide arranged in a reaction vessel, said potassium hydroxide, methanol and carbonyl sulfide reacting to form reaction products H2O and KSCOOCH3;
the superficial velocity of said hydrocarbon stream being less than about one foot per minute; and separating said reaction products from said treated hydrocarbon stream by downward flow of said reaction products and upward flow of said treated hydrocarbon stream in said vessel to provide essentially 100% removal of said carbonyl sulfide from said liquid hydrocarbon stream.
mixing said hydrocarbon stream containing carbonyl sulfide with liquid methanol;
passing said mixed methanol-hydrocarbon stream upwardly through a bed of solid potassium hydroxide arranged in a reaction vessel, said potassium hydroxide, methanol and carbonyl sulfide reacting to form reaction products H2O and KSCOOCH3;
the superficial velocity of said hydrocarbon stream being less than about one foot per minute; and separating said reaction products from said treated hydrocarbon stream by downward flow of said reaction products and upward flow of said treated hydrocarbon stream in said vessel to provide essentially 100% removal of said carbonyl sulfide from said liquid hydrocarbon stream.
2. A process as recited in claim 1, including periodically removing said reaction products from said vessel.
3. A process as recited in claim 2, in which the particles of said solid potassium hydroxide are walnut size.
4. A process as recited in claim 3, in which said bed of potassium hydroxide is cylindrically shaped and has a height to diameter ratio of three or more.
5. A process as recited in claim 1, in which said carbonyl sulfide in said separated treated hydrocarbon stream is less than one part per million by volume.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/713,171 US4290879A (en) | 1976-08-10 | 1976-08-10 | Removal of carbonyl sulfide from liquid hydrocarbon streams |
| US713,171 | 1976-08-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1091608A true CA1091608A (en) | 1980-12-16 |
Family
ID=24865070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA283,981A Expired CA1091608A (en) | 1976-08-10 | 1977-08-03 | Removal of carbonyl sulfide from liquid hydrocarbon streams |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4290879A (en) |
| AU (1) | AU506963B2 (en) |
| CA (1) | CA1091608A (en) |
| GB (1) | GB1555889A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4835338A (en) * | 1987-08-31 | 1989-05-30 | Aluminum Company Of America | Process for removal of carbonyl sulfide from organic liquid by adsorption using alumina adsorbent capable of regeneration |
| US6099815A (en) * | 1999-03-23 | 2000-08-08 | The Sulfatreat Company | Method for removing carbonyl sulfide from fluids using carbon monoxide |
| FR2888247B1 (en) * | 2005-07-11 | 2009-11-20 | Inst Francais Du Petrole | PROCESS FOR REMOVING CARBON OXYSULFIDE FROM A LIQUID HYDROCARBON LOAD |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2028335A (en) * | 1931-04-10 | 1936-01-21 | Standard Oil Dev Co | Process for desulphurizing a petroleum oil distillate |
| US2146353A (en) * | 1936-04-13 | 1939-02-07 | Shell Dev | Process for desulphurization of hydrocarbons |
| US3000817A (en) * | 1958-03-26 | 1961-09-19 | Exxon Research Engineering Co | Method of sweetening petroleum distillate |
| US3812200A (en) * | 1972-08-23 | 1974-05-21 | Sun Oil Co | Process for reactivation of soda-lime |
-
1976
- 1976-08-10 US US05/713,171 patent/US4290879A/en not_active Expired - Lifetime
-
1977
- 1977-08-03 CA CA283,981A patent/CA1091608A/en not_active Expired
- 1977-08-04 GB GB32730/77A patent/GB1555889A/en not_active Expired
- 1977-08-08 AU AU27695/77A patent/AU506963B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AU2769577A (en) | 1979-02-15 |
| AU506963B2 (en) | 1980-01-31 |
| US4290879A (en) | 1981-09-22 |
| GB1555889A (en) | 1979-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4171349A (en) | Desulfurization process and installation for hydrocarbon reservoir fluids produced by wells | |
| CA1163423A (en) | Method for removal of sulfur compounds from a gas stream | |
| US2904511A (en) | Method and apparatus for producing purified water from aqueous saline solutions | |
| US2356407A (en) | System for forming and storing hydrocarbon hydrates | |
| US2798772A (en) | Transportation of sulfur | |
| US4083696A (en) | Process for desulfurizing pipelined coal | |
| CA1091608A (en) | Removal of carbonyl sulfide from liquid hydrocarbon streams | |
| US3676981A (en) | Treatment of hydrocarbon gases | |
| CN105400544A (en) | Method for preparing alkylate oil by using multistage circulating flow reactor | |
| CN111905549B (en) | Absorb H2S desulfurization solution, desulfurization system and desulfurization method | |
| Demmink et al. | Oxidative absorption of hydrogen sulfide by a solution of ferric nitrilotriacetic acid complex in a cocurrent down flow column packed with SMV-4 static mixers | |
| RU2385180C1 (en) | Method to purify hydrocarbon gases | |
| WO2017188847A1 (en) | A device, process, and catalyst intended for desulfurization/demercaptanization/dehydration of gaseous hydrocarbons | |
| CN110028991A (en) | A kind of wet oxidation desulfurization oxygen spray regeneration technology and device | |
| US9062260B2 (en) | Removing unstable sulfur compounds from crude oil | |
| US2264220A (en) | Treatment of hydrocarbon oils | |
| Saha et al. | Absorption of carbon dioxide in alkanolamines in the presence of fine activated carbon particles | |
| US3630666A (en) | Precontacting hydrogen sulfide containing gas streams with rich sulfinol | |
| Sakke Tira et al. | Optimization of Water Scrubbing Method for Enhancement of Biogas Quality through Base Solutions Addition | |
| CN210826084U (en) | Wet process hydrogen sulfide removal device for coal gas | |
| CA2520046C (en) | Process for reducing the level of sulfur compounds from liquid hydrocarbon streams | |
| Wainwright et al. | Selective absorption of hydrogen sulfide from synthesis gas | |
| CN112473339B (en) | Energy-saving efficient desulfurization process adopting fiber membrane countercurrent amine washing | |
| US2914467A (en) | Sweetening process including reactivation of copper chloride catalyst | |
| US9708550B2 (en) | Extraction of sulphur-containing compounds in a first pretreatment reactor operating in batch mode followed by a second pretreatment reactor of the piston type |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |