EP0215911A1 - Absorption selective de sulfure d'hydrogene a partir de gaz contenant egalement du gaz carbonique - Google Patents
Absorption selective de sulfure d'hydrogene a partir de gaz contenant egalement du gaz carboniqueInfo
- Publication number
- EP0215911A1 EP0215911A1 EP86902174A EP86902174A EP0215911A1 EP 0215911 A1 EP0215911 A1 EP 0215911A1 EP 86902174 A EP86902174 A EP 86902174A EP 86902174 A EP86902174 A EP 86902174A EP 0215911 A1 EP0215911 A1 EP 0215911A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon dioxide
- hydrogen sulfide
- absorption solution
- gas stream
- amine compound
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/16—Hydrogen sulfides
- C01B17/167—Separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1462—Removing mixtures of hydrogen sulfide and carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Definitions
- the present invention is directed to an improved process for the selective absorption of hydrogen sulfide (H2S) from gas streams, such as natural or synthesis gas streams, which also contain carbon dioxide (CO2).
- gas streams such as natural or synthesis gas streams, which also contain carbon dioxide (CO2).
- a process for removal of hydrogen sulfide from gas streams comprising hydrogen sulfide and carbon dioxide by contacting the gas stream with a substantially anhydrous absorption solution comprising at least one amine compound selected from the group consisting of tertiary amines and hindered amines, present in an amount sufficient to absorb the hydrogen sulfide contained in the gas stream at a temperature above the dew point of water in the gas stream, to selectively remove hydrogen sulfide substantially to the essential exclusion of carbon dioxide, and stripping the absorbed hydrogen sulfide from the substantially anhydrous absorption solution to regenerate the amine for recycle.
- the process is carried out at ambient temperature and atmospheric pressure or above, with the temperature preferably ranging from ambient to about 15 ⁇ °F. If operated at elevated pressure, physically absorbed carbon dioxide can be desorbed effectively by pressure reduction after the absorption stage.
- the absorption solution may be 100% amine, it is convenient to provide a solution diluted with a low-cost diluent for the amine, which diluent has only physical absorptivity for carbon dioxide and other constituents of the gas such as COS, CS2 and mercaptans, and does not chemically bind carbon dioxide.
- the physical absorptivity of the diluent is preferably about 5 volumes or less carbon dioxide per volume of diluent at a temperature of 77°F and a partial pressure of CO2 of one atmosphere. However, if more removal of CO2 from the feed gas is desired, solvents of higher absorptivity for CO2 may be employed.
- the ratio of the amount of physical solvent in the mixture to the amount of amine in the mixture can be adjusted so that the required amount of CO2 and H2S are absorbed simultaneously from the gas undergoing treatment.
- the pressure of the treating solution is then reduced and the absorbed C0 2 and other physically absorbed gases are flashed from the absorbant solution.
- the absorbed H2 which is chemically bonded to the amine or other H2 reactant, is not desorbed until the solution is stripped in the heated stripping column.
- the H2 and CO2 are thereby effectively separated for more economical processing of the H2S in a Claus plant.
- the absorption solution can contain up to about 5% by weight water, for, at this concentration the rate of absorption of carbon dioxide by the water, for forming carbonates and bicarbonates, is very low.
- the small amount of water may be beneficially used as a stripping vapor in the stripping of hydrogen sulfide from the absorption solution.
- the amine chemically absorbs hydrogen sufide. Any carbon dioxide absorbed is, for all practical purposes, absorbed physically.
- the spent solution may first be formed to a pressure-reduction zone, where carbon dioxide and other physically absorbed constituents are removed by flashing, and then to a recovery zone, where the hydrogen sulfide is stripped from the solution by application of heat, with or without prior elimination of carbon dioxide.
- the stripping carrier gas may comprise the small amount of. water present in the solution, which water is condensed and recycled to maintain water balance in the solution.
- the hydrogen sulfide is extracted in a concentrated form for passage through a sulfur-recovery unit, such as a Claus plant.
- the object is to remove hydrogen sulfide substantially to the exclusion of carbon dioxide, as the former is highly toxic and the latter is innocuous.
- absorption tower i ⁇ a sour feed gas 12 containing hydrogen sulfide as the most undesirable impurity, but also containing carbon dioxide and other minor constituents such as COS, CS2 and mercap- tans.
- Absorber 10 is normally a multi-plate absorption column where, as shown, the absorption solution is intro ⁇ quizd by line 14 countercurrent to the flow of gas. Purified gas leaves by line 16 at the top of the column, and spent absorbent leaves by line 18 at the base of the column.
- Spent absorbent after being heated in 'exchanger 20 with return stripped absorbent from heated stripping column 24, is passed by line 22 to the top of heated stripping column 24.
- Heat is applied at the base of the stripping column, conveniently through reboiler 26, to furnish the heat required to desorb the absorbed hydrogen sulfide and to vaporize water to act as carrier vapor for hydrogen sulfide.
- Pressure-reduction flash zone 30 may be employed ahead of heated stripping column 24, in cases where it is desired to release physically absorbed carbon dioxide and other physically dissolved constituents.
- Regenerated absorption solution from heated strip ⁇ ping column 24 is returned by pump 36 through cooler 38 to absorption tower 10, and condensate from knock-out drum 29 is returned by pump 32 to heated stripping column 24.
- a concentrated hydrogen sulfide stream is passed by ' line 34 to a sulfur-recovery system, such as a Claus plant.
- the absorption solution be water-free, or substantially water-free, with a water concentration of up to about 5% by volume being tolerable.
- the amine employed be a tertiary amine, a hindered amine, or mixtures thereof, and, if a diluent for the amine is employed, such diluent is no more than a physical absorbent for carbon dioxide, preferably a physical absorbent wherein the capacity is not more than about 5 volumes of gaseous carbon dioxide, at 77°F and one atmosphere partial pressure of carbon dioxide per liquid volume of physical absorbent. Solu ⁇ tions meeting such criteria are effectively precluded from enabling significant reaction of carbon dioxide with the amine. ,
- tertiary amines there may be mentioned triethanolamine, methyldiethanol- amine, and the like.
- a "sterically hindered amine” is a primary amine in which the amino group is attached to a tertiary carbon atom, or a secondary amine in which the amino group is attached to a secondary or tertiary carbon atom.
- the amine acts as a chemical absorbent for hydrogen sulfide, and strongly bonds hydrogen sulfide to the amine following the formation of hydrosulfides. Reaction is very rapid.
- the flow and concentration rates of the a ine are adjusted, in terms of the hydrogen sulfide con ⁇ centration of the stream to be purified, to essentially enable absorption equilibrium to be reached. This is accomplished by sufficient contact time with a solution sufficiently lean along the length of the column to substantially absorb all the hydrogen sulfide present in the sour gas stream, thereby yielding a sweet gas for further processing.
- an absorption solution of 100% amine may be employed, it is convenient to dilute the amine with a non- chemical absorbent for carbon dioxide.
- a non- chemical absorbent for carbon dioxide There may be employed, for instance, physical absorbents for carbon dioxide which, at the normal temperatures of operation, i.e., ambient or above, have a relatively low solubility for carbon dioxide, e.g., about 5 or less volumes (gas) per volume liquid. Lower-than-ambient temperatures may also be employed to increase the amount of carbon dioxide taken up by the physical absorbent that will become part of the hydrogen sulfide separated in the stripper 24. However, the CO2 can be separated from the H2S by flash ⁇ ing zone 30.
- glycols such as diethylene glycol, tri ⁇ ethylene glycol, and ethylene glycol
- glycol esters such as monoalkyl and dialkyl ethers of diethylene glycol, triethylene glycol ethers, polyethylene glycol ethers and the like.
- N-methyl pyrrolidone ethylene glycol diacetate, diethylene glycol diacetate, triethyl phosphate, butyl carbitol acetate, methyl cellusolve acetate, propylene glycol methyl ether.
- tributyl phosphate dipropylene glycol methyl ether, tripropylene glycol methyl ether, carbitol, diethyl ⁇ ene glycol diethyl ether, propylene carbonate, dimethyl sulfolane, dimethoxy tetraglycol, mixtures of ethylene carbonate, benzyl alcohol, and the like.
- the amount of diluent solvent utilized may be up to about 90% by weight, based on the weight of the diluent solvent and the amine, and provide a combined solution which has a sufficiently low viscosity to enable flow through the absorption column at and below ambient temperatures. It may be desirable that the feed gas be pretreated with a dessicant to remove as much water vapor as possible. This is because it is desirable to operate the absorption column under substantially anhydrous conditions, and it is nor- mally inevitable that some moisture will be taken up by the solution, as the diluent for the amine will normally be hygroscopic, or some water condensation or retention may occur.
- the absorption column At a tem ⁇ perature above the dew point of water in the gas stream undergoing purification, to prevent condensation. This limits water take-up to that which may result in conse ⁇ quence of the hygroscopicity of the solution employed.
- maintaining a water-content level of about 5% by volume of absorption solution or less can be beneficial. This will essentially eliminate the formation of carbonates and bicarbonates, because the rate of reaction is low, yet there is a sufficient amount of water to enable its effective use in stripping hydrogen sulfide from the absorption solution.
- the advantage of the practice of the process of the instant invention is a materially sharper selectivity of hydrogen sulfide to the exclusion of chemically bound carbon dioxide.
- hydrogen sulfide beyond that which chemically bonds with the amine, is absorbed in the diluent solvent by physical solubility and may be recovered in the stripping column.
- the sweetened gas stream may, if desired, be separately processed for carbon dioxide removal using chemical solvents. What is unique, however, is the achievement of separation at extremely low cost using conventional absorbents and relying on substantially anhydrous conditions to achieve the desired result.
- the lean absorption solution contains 23.8% methyldiethanola- mine, the balance ' being anhydrous diethylene glycol.
- the absorption solution temperature is 40°C.
- the process gas stream is passed countercurrent to the absorption solution.
- the absorption solution is then passed to a flash zone, where the physically absorbed carbon dioxide is released through a reduction in pressure; the balance of the absorption solution is then passed through a stripping zone, where the absorbed hydrogen sulfide is released by heating as a concentrated hydrogen sulfide stream for processing to sulfur; and the lean absorption solution is recycled back to the absorption column.
Abstract
Une solution pratiquement anhydre d'une amine tertiaire et/ou d'une amine entravée est utilisée pour l'absorption sélective de sulfure d'hydrogène à partir d'un flux gazeux (10) contenant aussi du gaz carbonique. Un solvant physique peut être utilisé comme diluant de l'amine. La solution d'absorption contenant le sulfure d'hydrogène est acheminée jusqu'à la colonne d'extraction (24) et la solution d'absorption extraite est recyclée vers l'absorbeur (10).
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US71168085A | 1985-03-14 | 1985-03-14 | |
US711680 | 1985-03-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0215911A1 true EP0215911A1 (fr) | 1987-04-01 |
Family
ID=24859069
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86902174A Withdrawn EP0215911A1 (fr) | 1985-03-14 | 1986-03-13 | Absorption selective de sulfure d'hydrogene a partir de gaz contenant egalement du gaz carbonique |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0215911A1 (fr) |
WO (1) | WO1986005474A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11383197B2 (en) | 2018-02-14 | 2022-07-12 | Taminco Bvba | Contaminant removal process |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63111918A (ja) * | 1986-10-30 | 1988-05-17 | Toho Chem Ind Co Ltd | 酸性ガス吸収剤用組成物 |
US4770862A (en) * | 1987-05-26 | 1988-09-13 | Shell Oil Company | Removal of hydrogen sulfide from supercritical carbon dioxide |
EP0322924A1 (fr) * | 1987-12-31 | 1989-07-05 | Union Carbide Corporation | Elimination sélectone de H2S de mélanges de fluides utilisant la triéthanolamine de haute pureté |
ES2054049T5 (es) * | 1988-05-24 | 1997-12-16 | Elf Aquitaine | Liquido absorbente de gases acidos que contiene una alcanol-amina terciaria y un activador de absorcion del co2, y su aplicacion a la desacidificacion de gas conteniendo co2 y eventualmente otros gases acidos. |
FR2631853B1 (fr) * | 1988-05-24 | 1992-01-24 | Elf Aquitaine | Liquide absorbant des gaz acides renfermant une composante alcanolamine tertiaire et un activateur d'absorption du co2 et son application a la desacidification de gaz contenant co2 et eventuellement d'autres gaz acides |
US5700438A (en) * | 1996-08-05 | 1997-12-23 | Miller; John C. | Process for removal of H2S from gas processing streams |
US7083662B2 (en) | 2003-12-18 | 2006-08-01 | Air Products And Chemicals, Inc. | Generation of elevated pressure gas mixtures by absorption and stripping |
US20120061613A1 (en) * | 2010-09-10 | 2012-03-15 | Battelle Memorial Institute | System and process for capture of acid gasses at elevated-pressure from gaseous process streams |
US8652237B2 (en) * | 2010-12-17 | 2014-02-18 | Battelle Memorial Institute | System and process for capture of H2S from gaseous process streams and process for regeneration of the capture agent |
CN105637070A (zh) | 2013-10-30 | 2016-06-01 | 陶氏环球技术有限责任公司 | 用于选择性h2s去除的混合溶剂调配物 |
WO2015065842A1 (fr) | 2013-10-30 | 2015-05-07 | Dow Global Technologies Llc | Formulations de solvant hybrides pour l'élimination du soufre organique total et l'élimination des gaz acides totaux |
US10130907B2 (en) | 2016-01-20 | 2018-11-20 | Battelle Memorial Institute | Capture and release of acid gasses using tunable organic solvents with aminopyridine |
US10940432B2 (en) | 2016-04-27 | 2021-03-09 | Dow Global Technologies Llc | Process for selective removal of acid gases from fluid streams using a hybrid solvent mixture |
US10456739B2 (en) | 2016-11-14 | 2019-10-29 | Battelle Memorial Institute | Capture and release of acid gasses using tunable organic solvents with binding organic liquids |
US10933367B2 (en) | 2017-03-03 | 2021-03-02 | Dow Global Technologies Llc | Process for separating hydrogen sulfide from gaseous mixtures using a hybrid solvent mixture |
US11167241B2 (en) | 2017-03-06 | 2021-11-09 | Dow Global Technologies Llc | Energy efficient process for separating hydrogen sulfide from gaseous mixtures using a hybrid solvent mixture |
US11253811B2 (en) | 2017-03-07 | 2022-02-22 | Dow Global Technologies Llc | Process for reducing energy consumption in the regeneration of hybrid solvents |
EP3978099A4 (fr) * | 2019-05-28 | 2023-06-14 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Procédé de traitement de gaz, et dispositif de traitement de gaz |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2425886A1 (fr) * | 1978-05-16 | 1979-12-14 | Elf Aquitaine | Procede de purification de gaz residuaires industriels renfermant en faibles concentrations des composes soufres |
IT1132170B (it) * | 1980-07-04 | 1986-06-25 | Snam Progetti | Processo di separazione selettiva di idrogeno solforato da miscele gassose contenenti anche anidride carbonica |
US4539189A (en) * | 1984-01-23 | 1985-09-03 | Chevron Research Company | Method for removing sulfides from industrial gas |
-
1986
- 1986-03-13 WO PCT/US1986/000527 patent/WO1986005474A1/fr unknown
- 1986-03-13 EP EP86902174A patent/EP0215911A1/fr not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO8605474A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11383197B2 (en) | 2018-02-14 | 2022-07-12 | Taminco Bvba | Contaminant removal process |
Also Published As
Publication number | Publication date |
---|---|
WO1986005474A1 (fr) | 1986-09-25 |
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Legal Events
Date | Code | Title | Description |
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LI LU NL SE |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 19861216 |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: RIESENFELD, FRED, CHARLES |