GB2202522A - Removing H2S and CO2 from a gas mixture including H2S and CO2 - Google Patents
Removing H2S and CO2 from a gas mixture including H2S and CO2 Download PDFInfo
- Publication number
- GB2202522A GB2202522A GB08702649A GB8702649A GB2202522A GB 2202522 A GB2202522 A GB 2202522A GB 08702649 A GB08702649 A GB 08702649A GB 8702649 A GB8702649 A GB 8702649A GB 2202522 A GB2202522 A GB 2202522A
- Authority
- GB
- United Kingdom
- Prior art keywords
- absorbent
- gas stream
- produce
- regenerated absorbent
- gas
- 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- Withdrawn
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/105—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur
- C10K1/106—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids containing metal compounds other than alkali- or earth-alkali carbonates, -hydroxides, oxides, or salts of inorganic acids derived from sulfur containing Fe compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/124—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing metal compounds other than alkali- or earth-alkali carbonates, hydroxides- or oxides- or salts of inorganic acids derived from sulfur
- C10K1/125—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors containing metal compounds other than alkali- or earth-alkali carbonates, hydroxides- or oxides- or salts of inorganic acids derived from sulfur containing Fe compounds
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Removing H2S and CO2 from a gas mixture comprises contacting the gas mixture in absorber (2) at elevated pressure with liquid absorbent, removing purified gas and loaded absorbent from the absorber (2), flashing the loaded absorbent to produce a first off-gas stream and a partly regenerated absorbent, regenerating in regenerator (15) a part of the partly regenerated absorbent to produce a second off-gas stream and a regenerated absorbent, introducing regenerated absorbent into the upper part of the absorber (2), introducing the remaining partly regenerated absorbent into the absorber (2) at an intermediate level, and contacting the first off-gas stream and/or the second off-gas stream in contactor (20) with an aqueous solution containing an oxidizing reactant to produce purified gas and an aqueous solution containing reduced reactant and elemental sulphur. <IMAGE>
Description
REMOVING H2S AND CO FROM A GAS MIXTURE INCLUDING AND AND C02 The present invention relates to a process for removing H2S and C02 from a gas mixture including H2S and CO2. In particular the invention relates to a process for removing removing these sour components from a gas mixture comprising hydrocarbons, between 10 and 50% by volume C02 and only a small amount of H2S, wherein for example the ratio of H2S to C02 is between 10 6 and 0.1, An example of such a gas mixture is natural gas.
It is an object of the present invention to provide a simple process for deep H2S removal and bulk CO removal and for sulphur recovery.
To this end the process for removing H2 S and C02 from a gas mixture including H2S and C02 according to the invention comprises the steps of
a) contacting the gas mixture in a contact zone at elevated pressure countercurrently with liquid and regeneratable absorbent to produce a purified gas stream and loaded absorbent;
b) removing the purified gas stream and loaded absorbent from the contact zone;
c) flashing the loaded absorbent in at least one step by releasing the pressure to a level below the pressure in the contact zone to produce a first off-gas stream and a partly regenerated absorbent;
d) regenerating at least a part of the partly regenerated absorbent to produce a second off-gas stream and a regenerated absorbent, and introducing regenerated absorbent into an upper part of the contact zone;;
e) supplying directly the first off-gas stream and/or the second off-gas stream to a sulphur recovery unit; and
f) removing in the sulphur recovery unit H2S from the off-gas stream(s) to produce a purified gas.
Partly regenerated absorbent is regenerated by heating and/or stripping with steam.
In order to reduce the amount of heat required to regenerate partly regenerated absorbent, step d) may comprise regenerating a part of the partly regenerated absorbent to produce a second off-gas stream and a regenerated absorbent, introducing regenerated absorbent into the upper part of the contact zone, and introducing the remaining partly regenerated absorbent into the contact zone at a level which is between the level at which the gas mixture is introduced into the contact zone and the level at which regenerated absorbent is introduced.
The off-gas stream(s) will comprise a considerable amount of
C02. Therefore it is preferred to remove H2S from the off-gas stream(s) by contacting the gas stream(s) in a second contact zone with aqueous reactant solution containing an effective amount of an oxidizing reactant to produce purified gas and an aqueous solution containing reduced reactant and elemental sulphur.
The invention will now be elucidated in more detail by way of example with reference to the Figure showing schematically a flow diagram of the process according to the invention.
A hydrocarbon-containing gas mixture comprising CH , 250 ppmv
4, (parts by million by volume) H2S and 15 %v C02 is supplied through inlet conduit 1 to a contact zone in the form of absorber 2. In absorber 2 the gas mixture is contacted at a pressure between 0.5 and 15 MPa and at a temperature between 10 and 70 0C countercurrently with liquid and regeneratable absorbent supplied to the absorber 2 through conduit 3 to produce a purified gas stream and loaded absorbent. The purified gas stream is removed from the absorber 2 through outlet conduit 5, and loaded absorbent is removed through conduit 6. Purified gas contains about 2 ppmv H2S and 1.5 %v CO2.
Loaded absorbent is supplied through conduit 6, which is provided with a pressure reduction valve 9, to vessel 10. The pressure in vessel 10 is maintained at a level below the pressure in the absorber 2 and above the total partial pressure of CO2 and
H2S before flashing, upstream the pressure reduction valve 9, at the prevailing temperature, and the loaded absorbent is flashed to produce a hydrocarbon-containing first off-gas stream and a partly regenerated absorbent. The hydrocarbon-containing first off-gas stream is removed from the vessel 10 through conduit 11, and partly regenerated absorbent is passed through conduit 12 to a regenerator 15.
The regenerator 15 is provided with a conventional reboiler system 16, a gas outlet conduit 17 and a liquid outlet connected to conduit 3. Partial regenerated absorbent is regenerated to produce a second off-gas stream, which is removed from the regenerator 15 through the gas outlet conduit 17, and regenerated absorbent, which is supplied to the top of the absorber 2 through conduit 3.
The second off-gas stream, which includes more than 80 %v CO2 and less than 2 %v H2S is directly supplied to a sulphur recovery unit through outlet conduit 17. In the sulphur recovery unit H2S is removed from the off-gas stream to produce a purified gas.
To remove H2S from the off-gas stream, the off-gas stream is
2 supplied to a second contact zone, in the form of contactor 20, and aqueous reactant solution containing an effective amount of an oxidizing reactant is supplied to the contactor 20 through conduit 21. In the contactor 20 the off-gas stream is contacted at a temperature between 10 and 80 0C an at a pressure between 0.1 and 15 MPa with the aqueous reactant solution to produce purified gas, which is removed through conduit 23, and an aqueous solution containing reduced reactant and elemental sulphur, which solution is removed through conduit 24.
Sulphur is separated from the aqueous solution in sulphur separator 26, and removed from separator 26 through conduit 27. To regenerate the reduced reactant, the sulphur-free aqueous solution containing reduced reactant is supplied through conduit 28 to reactant regenerator 29. In the reactant regenerator 29 the aqueous solution is contacted at a temperature between 10 and 80 0C with a free-oxygen containing gas, such as air, supplied to the reactant regenerator 29 through conduit 30. Suitably the amount of oxygen is between 20 and 500 per cent excess. A gaseous mixture having a reduced oxygen content is removed from the reactant regenerator 29 through conduit 32, and regenerated aqueous reactant solution is supplied to the contactor 20 through conduit 21.
An advantage of the process according to the invention is that it does not involve enriching the off-gas stream, because the above described conversion of H2S to elemental sulphur is not adversely affected by the presence of C02 in the off-gas stream.
To remove traces of H2S from the hydrocarbon-containing first off-gas stream, this stream may be contacted with liquid and regeneratable absorbent in a separate contactor (not shove) to produce a substantially H2S-free hydrocarbon-containing stream and loaded absorbent. In a suitable embodiment, regenerated absorbent is supplied to the separate contactor, and loaded absorbent is added to the partly regenerated absorbent downstream the vessel 10.
In an alternative embodiment of the invention the pressure in vessel 10 is maintained at a level which is below the total partial pressure of CO2 and H2S before flashing, upstream the pressure reduction valve 9, at the prevailing temperature, and the loaded absorbent is flashed to produce a first off-gas stream, and a partly regenerated absorbent. The first off-gas stream is removed from the vessel 10 through conduit 11, and partly regenerated absorbent is passed through conduit 12 to the regenerator 15, where the partly regenerated absorbent is regenerated as described above.
The first off-gas stream, which includes more than 80 %v CO2 and less than 2 %v H2S is passed through connecting conduit 40 directly to the contactor 20 of the sulphur recovery unit. In the sulphur recovery unit H2 S is removed from both the first off-gas stream and the second off-gas stream to produce a purified gas as described above.
When the loaded absorbent is heated before or during flashing to a temperature between 80 and 120 0C the first off-gas stream will contain substantially all H2 S as removed from the gas mixture which was supplied to the absorber 2. The H2S-content of the second off-gas will then be so low that no removal of H2S therefrom in the sulphur recovery unit is required. Therefore in this embodiment only the first off-gas stream is passed to the sulphur recovery unit.
To reduce the amount of heat required to regenerate in regenerator 15 the partly regenerated absorbent, a part of the partly regenerated absorbent is regenerated in regenerator 15 to produce a second off-gas stream and a regenerated absorbent. Regenerated absorbent is introduced into the upper part of the absorber 2 through conduit 3. The remaining part of the partly regenerated absorbent is introduced into the absorber 2 through conduit 45 at a level which is between the level at which the gas mixture is introduced into the absorber 2 and the level at which regenerated absorbent is introduced.
To obtain a purified gas having the same low H2S-content and C02-content the total amount of absorbent passing through conduits 3 and 45 is larger than the amount of regenerated absorbent when all absorbent was regenerated. However, the amount of absorbent supplied to the regenerator 15 is smaller.
The amount of absorbent supplied to the regenerator 15 is suitably between 5 to 30 % of the total amount of absorbent removed from the vessel 10, and preferably between 10 to 20 %.
The ratio of the distance between the level at which the gas mixture is introduced into the absorber 2 and the level at which partly regenerated absorbent is introduced to the distance between the level at which the gas mixture is introduced into the absorber 2 and the level at which regenerated absorbent is introduced is suitably in the range of from .4 to .8.
The loaded absorbent from the absorber 2 can be flashed in two stages, at first by releasing the pressure to a level which is above the total partial pressure of CO2 and H2 S before flashing at the prevailing temperature to produce a hydrocarbon-containing gas stream and a partly purified absorbent, and subsequently flashing the partly purified absorbent by releasing the pressure to a level below the total partial pressure of C02 and H2S before subsequent flashing at the prevailing temperature to produce the first off-gas stream and the partly regenerated absorbent. The first off-gas stream is passed to the contactor 20 of the sulphur recovery unit, and at least a part of the partly regenerated absorbent is passed to the regenerator 15.
In each of the two stages flashing can be carried out in two or more steps.
To remove traces of H2S from the hydrocarbon-containing gas stream, this stream may be contacted with liquid and regeneratable absorbent in a separate contactor (not shown) to produce a substantially H2S-free hydrocarbon-containing stream and loaded absorbent. In a suitable embodiment, regenerated absorbent is supplied to the separate contactor, and loaded absorbent is added to the partly regenerated absorbent downstream the vessel 10.
Suitably, the liquid and regeneratable absorbent is an aqueous solution comprising a chemical solvent or a mixture of chemical solvents. A suitable chemical solvent is an amine, for example a tertiary amine, such as methyl diethanol amine (MDEA).
The liquid and regeneratable absorbent may further comprise a physical solvent such as sulfolane.
The liquid and regeneratable absorbent suitably comprises an aqueous solution of 10-60% by mass MDEA. The liquid and regeneratable absorbent may further contain 15-55% by mass sulfolane.
The aqueous reactant solution comprises suitably a coordination complex of Fe(III) with an organic acid, for example nitrilotriacetic acid (NTA), ethylenediamine tetra acetic acid (EDTA).
In an attractive embodiment the aqueous reactant solution comprises an ammonium form of a coordination complex of Fe(III) with NTA and an ammonium form of a coordination complex of Fe(II) with NTA. The aqueous reactant solution may further comprise aqueous ammonia. The pH of the solution is suitably between 5 and 8.5, and the molar ratio of the coordination complex of Fe(III) with NTA to the ammonium form of a coordination complex of Fe(II) with NTA is suitably between 0.2 and 6. The aqueous reactant solution comprises about 2-15 mol of an ammonium form of a coordination complex of Fe(III) with NTA per mol H2S to be removed.
The absorber, the regenerator, the contactor or the reactant regenerator can be a column provided with a plurality of contact trays, or a column provided with suitable packing material.
Claims (6)
1. Process for removing H2S and CO2 from a gas mixture including
H2S and CO2 comprising the steps of
a) contacting the gas mixture in a contact zone at elevated pressure countercurrently with liquid and regeneratable absorbent to produce a purified gas stream and loaded absorbent;
b) removing the purified gas stream and loaded absorbent from the contact zone;
c) flashing the loaded absorbent in at least one step by releasing the pressure to a level below the pressure in the contact zone to produce a first off-gas stream and a partly regenerated absorbent;
d) regenerating at least a part of the partly regenerated absorbent to produce a second off-gas stream and a regenerated absorbent, and introducing regenerated absorbent into an upper part of the contact zone;
e) supplying directly the first off-gas stream and/or the second off-gas stream to a sulphur recovery unit; and
f) removing in the sulphur recovery unit H2S from the off-gas stream(s) to produce a purified gas.
2. Process as claimed in claim 1, wherein step d) comprises regenerating a part of the partly regenerated absorbent to produce a second off-gas stream and a regenerated absorbent, introducing regenerated absorbent into the upper part of the contact zone, and introducing the remaining partly regenerated absorbent into the contact zone at a level which is between the level at which the gas mixture is introduced into the contact zone and the level at which regenerated absorbent is introduced.
3. Process as claimed in claims 1 or 2, wherein removing H2S from the off-gas stream(s) comprises contacting the off-gas stream(s) in a second contact zone with aqueous reactant solution containing an effective amount of an oxidizing reactant to produce purified gas and an aqueous solution containing reduced reactant and elemental sulphur.
4. Process as claimed in any one of the claims 1-3, wherein step c) comprises flashing the loaded absorbent in at least one step by releasing the pressure to a level below the partial pressure of CO
L and H2S before flashing at the prevailing temperature to produce the first off-gas stream and the partly regenerated absorbent.
5. Process as claimed in any one of the claims 1-3, wherein step c) comprises flashing the loaded absorbent in at least one step by releasing the pressure to a level which is above the total partial pressure of CO2 and H2 S before flashing at the prevailing temperature to produce a hydrocarbon-containing gas stream and a partly purified absorbent, and subsequently flashing the partly purified absorbent in at least one step by releasing the pressure to a level below the total partial pressure of CO2 and H2S before subsequent flashing at the prevailing temperature to produce the first off-gas stream and the partly regenerated absorbent.
6. Process for removing H2S and CO2 from a gas mixture including H2S and CO2 substantially as described hereinbefore with reference to the drawing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08702649A GB2202522A (en) | 1987-02-06 | 1987-02-06 | Removing H2S and CO2 from a gas mixture including H2S and CO2 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08702649A GB2202522A (en) | 1987-02-06 | 1987-02-06 | Removing H2S and CO2 from a gas mixture including H2S and CO2 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8702649D0 GB8702649D0 (en) | 1987-03-11 |
| GB2202522A true GB2202522A (en) | 1988-09-28 |
Family
ID=10611799
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08702649A Withdrawn GB2202522A (en) | 1987-02-06 | 1987-02-06 | Removing H2S and CO2 from a gas mixture including H2S and CO2 |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2202522A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0375077A2 (en) * | 1988-12-23 | 1990-06-27 | Shell Internationale Researchmaatschappij B.V. | Removing hydrogen sulphide from a gas mixture |
| WO2010136425A1 (en) * | 2009-05-26 | 2010-12-02 | Basf Se | Process for recovery of carbon dioxide from a fluid stream, in particular from syngas |
| WO2013049114A1 (en) * | 2011-09-26 | 2013-04-04 | Eig, Inc. | Simultaneous high efficiency capture of co2 and h2s from pressurized gas |
-
1987
- 1987-02-06 GB GB08702649A patent/GB2202522A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0375077A2 (en) * | 1988-12-23 | 1990-06-27 | Shell Internationale Researchmaatschappij B.V. | Removing hydrogen sulphide from a gas mixture |
| EP0375077A3 (en) * | 1988-12-23 | 1990-11-22 | Shell Internationale Research Maatschappij B.V. | Removing hydrogen sulphide from a gas mixture |
| WO2010136425A1 (en) * | 2009-05-26 | 2010-12-02 | Basf Se | Process for recovery of carbon dioxide from a fluid stream, in particular from syngas |
| US8795415B2 (en) | 2009-05-26 | 2014-08-05 | Basf Se | Process for recovery of carbon dioxide from a fluid stream, in particular from syngas |
| WO2013049114A1 (en) * | 2011-09-26 | 2013-04-04 | Eig, Inc. | Simultaneous high efficiency capture of co2 and h2s from pressurized gas |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8702649D0 (en) | 1987-03-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |