EP2307120A1 - Process for removing acid gases from a gas stream - Google Patents
Process for removing acid gases from a gas streamInfo
- Publication number
- EP2307120A1 EP2307120A1 EP09776842A EP09776842A EP2307120A1 EP 2307120 A1 EP2307120 A1 EP 2307120A1 EP 09776842 A EP09776842 A EP 09776842A EP 09776842 A EP09776842 A EP 09776842A EP 2307120 A1 EP2307120 A1 EP 2307120A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- absorbent
- gas stream
- detergent
- physical
- acid gases
- 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- Withdrawn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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/408—Cyanides, e.g. hydrogen cyanide (HCH)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/502—Carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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 invention relates to a method for removing acid gases from a gas stream, in particular from a natural gas stream, synthesis gas stream or the like, wherein the acid gases from the gas stream are absorbed by at least one absorbent and wherein as absorbent a mixture of a physical detergent, a chemical detergent and water is used.
- DE 10 2005 050 385 A1 discloses a method for removing carbon dioxide from gas streams.
- the absorbent used is a mixture of a primary or secondary amine in an aqueous solution, a physical solvent (for example acetylmorpholine, N-formylmorpholine) and optionally other amines.
- the proportion of morpholine in the absorbent is up to 25 wt .-%.
- a disadvantage of the known processes, especially when there are high sour gas partial pressures, is that the proportion of the physically active absorbent must be reduced by the proportion of the chemical detergent and the water in the absorbent, so that the capacity of the physically acting absorption medium is reduced.
- a further disadvantage is that due to the water content in the absorbent, especially at high sour gas partial pressures, increasing corrosion in the devices in which the processes are carried out can be expected.
- the invention has the technical problem of providing a method with which sour gas components can be easily and easily removed from a gas stream and with which the above-described corrosion problems are reliably avoided.
- the invention teaches a method for removing acid gases from a gas stream, in particular from a natural gas stream, synthesis gas stream or the like of the type mentioned, which is characterized in that the absorbent more than 70 wt .-% of the physical detergent and contains at most 5 wt .-% of water that is used as a physical detergent, a morpholine derivative and that a chemical detergent is used based on at least one aliphatic amine compound.
- acid gases or sour gas components include carbon monoxide (CO), carbon dioxide (CO 2 ), hydrocyanic acid (HCN), hydrogen sulphide (H 2 S), carbon disulphide (CS 2 ), carbonyl sulphide (COS) and mercaptans.
- the sour gas-containing gas stream is passed through an absorber column, in which the liquid absorbent flows counter to the gas stream.
- the absorbent By the opposite directions of flow of the acid gas-containing gas stream and the absorbent intimate mixing of the gas or gas stream and the absorbent is achieved, so that the sour gas components are absorbed by the absorbent.
- the regeneration of the absorbent is conveniently carried out in a stripping column.
- the absorbent largely contains at least one physical detergent. It is possible that the physical detergent consists of one and preferably two morpholine derivatives. Also, a plurality or a plurality of morpholine derivatives may be contained in the physical detergent.
- the chemical detergent contains at least one aliphatic amine compound.
- the combination of the physical detergent and the chemical detergent makes it possible to absorb acid gases, in particular H 2 S, down to the ppm range.
- the chemical detergent contains at least two amine compounds.
- the absorbent contains more than 80% by weight of the physical detergent. In a preferred embodiment of the method of the invention, the absorbent contains about 85% to about 98%, and more preferably about 95%, by weight of the physical detergent.
- the aim is a low water content of the absorbent.
- the absorbent contains less than 3% by weight of water. It is within the scope of the invention that the absorbent has a water content of about 1 wt .-% or even less than 1 wt .-%.
- the absorbent may contain from 0.1% to 30% by weight of the aliphatic amine compounds, with a proportion of the aliphatic amine compounds of from 0.1% to 25% by weight being particularly advantageous. According to a preferred embodiment, the absorbent contains up to 10% by weight of the aliphatic amine compound, in particular up to 5% by weight of the aliphatic amine compound. The percentages by weight of the physical detergent contained in the absorbent, of the water and of the chemical detergent or of the aliphatic amine compound always add up to 100% by weight.
- NFM N-formylmorpholine
- NAM N-acetylmorpholine
- the absorbent is largely a mixture of NFM and NAM.
- the amine compound has at least one component selected from the group "methyldiethanolamine (MDEA), diethanolamine (DEA), polyethylene glycol-substituted amine". It is recommended that the amine and expediently carries two polyethylene glycol substituents. It is also possible that the amine is provided with three polyethylene glycol substituents.
- the invention is based on the finding that with the process according to the invention, acid gases are simply and reliably removed from a gas stream. It is essential to the invention that a removal of the acid gases is functionally reliable down to the ppm range. It has been found that the method according to the invention can be used for a large number of gas streams with different sour gas components and sour gas compositions. Furthermore, synthesis gas, in particular acid-converted synthesis gas, can be desulfurized with the process according to the invention in a surprisingly selective manner, thus achieving more selective and less expensive desulfurization than a purely physical solvent.
- the invention is based on the finding that the height of the absorber or stripper columns can be significantly reduced by means of the method according to the invention in comparison with the methods known from practice. Furthermore, the process according to the invention, in particular in the selective desulfurization of synthesis gases behind an acidic conversion, has an unexpectedly low amount of solvent circulation. It has have shown that the partial pressure differences for the physical absorption of the acid gases or of the acid gas components in the absorbent according to the invention are favorably influenced by the addition of the amine compound. In this way, particularly difficult to remove sulfur compounds can be reliably absorbed from the gas stream. It should be noted that the low water content ensures that corrosion in installations in which the method according to the invention is carried out is reliably avoided.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008031552A DE102008031552A1 (en) | 2008-07-07 | 2008-07-07 | Process for removing acid gases from a gas stream |
PCT/EP2009/004609 WO2010003558A1 (en) | 2008-07-07 | 2009-06-26 | Process for removing acid gases from a gas stream |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2307120A1 true EP2307120A1 (en) | 2011-04-13 |
Family
ID=41077711
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09776842A Withdrawn EP2307120A1 (en) | 2008-07-07 | 2009-06-26 | Process for removing acid gases from a gas stream |
Country Status (10)
Country | Link |
---|---|
US (1) | US8702846B2 (en) |
EP (1) | EP2307120A1 (en) |
KR (1) | KR101447765B1 (en) |
CN (1) | CN102089061A (en) |
AU (1) | AU2009267461A1 (en) |
BR (1) | BRPI0915687A2 (en) |
CA (1) | CA2729862A1 (en) |
DE (1) | DE102008031552A1 (en) |
RU (1) | RU2506985C2 (en) |
WO (1) | WO2010003558A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103980954B (en) * | 2014-05-28 | 2016-02-03 | 西南化工研究设计院有限公司 | The removal methods of benzene hydrocarbon in a kind of coke-oven gas |
US9782719B1 (en) * | 2016-08-09 | 2017-10-10 | Nrgtek, Inc. | Solvents and methods for gas separation from gas streams |
US9962656B2 (en) | 2016-09-21 | 2018-05-08 | Nrgtek, Inc. | Method of using new solvents for forward osmosis |
FR3045401B1 (en) * | 2015-12-17 | 2018-02-02 | IFP Energies Nouvelles | ABSORBENT SOLUTION BASED ON HYDROXYLIC DERIVATIVES OF 1,6-HEXANEDIAMINE AND METHOD FOR REMOVING ACIDIC COMPOUNDS FROM A GASEOUS EFFLUENT |
US10143970B2 (en) | 2016-08-09 | 2018-12-04 | Nrgtek, Inc. | Power generation from low-temperature heat by hydro-osmotic processes |
US9956522B2 (en) | 2016-08-09 | 2018-05-01 | Nrgtek, Inc. | Moisture removal from wet gases |
US20180126336A1 (en) | 2016-11-04 | 2018-05-10 | Nrgtek, Inc. | Renewable Energy Storage Methods and Systems |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1132170B (en) * | 1980-07-04 | 1986-06-25 | Snam Progetti | SELECTIVE SEPARATION PROCESS OF HYDROGEN SULFURATED FROM GASEOUS MIXTURES CONTAINING ALSO CARBON DIOXIDE |
DE3314182C2 (en) * | 1983-04-19 | 1985-08-08 | Heinrich 2915 Saterland Geesen | Method for locating a leak in the sealing of a flat roof and measuring device for carrying out the method |
US5347003A (en) * | 1993-03-05 | 1994-09-13 | Quaker Chemical Corporation | Methods for regenerating a sulfur scavenging compound from a product of a sulfur scavenging reaction |
DE19753903C2 (en) * | 1997-12-05 | 2002-04-25 | Krupp Uhde Gmbh | Process for the removal of CO¶2¶ and sulfur compounds from technical gases, in particular from natural gas and raw synthesis gas |
EP1022046A1 (en) * | 1999-01-22 | 2000-07-26 | Krupp Uhde GmbH | Process for removing carbon dioxide, sulphur compounds, water and aromatic and higher aliphatic hydrocarbons from technical gases |
KR20120019511A (en) * | 2003-03-21 | 2012-03-06 | 다우 글로벌 테크놀로지스 엘엘씨 | Improved composition and method for removal of carbonyl sulfide from acid gas containing same |
MX276488B (en) * | 2003-07-22 | 2010-06-09 | Dow Global Technologies Inc | Regeneration of acid gas-containing treatment fluids. |
JP2007533431A (en) * | 2003-11-10 | 2007-11-22 | ビーエーエスエフ アクチェンゲゼルシャフト | Method for obtaining an acid gas stream under high pressure by removing acid gas from a fluid stream |
DE10352878A1 (en) * | 2003-11-10 | 2005-06-16 | Basf Ag | Removing acid gases from a fluid stream comprises contacting the fluid stream with a liquid absorbent and regenerating the absorbent by heating to produce a compressed acid gas stream |
DE102004042418B4 (en) * | 2004-09-02 | 2008-04-30 | Clariant Produkte (Deutschland) Gmbh | Absorption liquid, its use and method for purifying gases |
DE102005043142A1 (en) * | 2004-10-22 | 2006-04-27 | Basf Ag | Deacidifying a fluid stream comprises absorbing acid gases in an absorbent comprising a polyamine and an aliphatic or alicyclic amine |
FR2877858B1 (en) * | 2004-11-12 | 2007-01-12 | Inst Francais Du Petrole | METHOD FOR DEACIDIFYING A GAS WITH A FRACTIONED REGENERATION ABSORBENT SOLUTION |
DE102005050385A1 (en) * | 2005-10-20 | 2007-04-26 | Basf Ag | Absorbent and method for removing carbon dioxide from gas streams |
AU2007260028B2 (en) * | 2006-06-13 | 2011-09-08 | Basf Se | Removal of carbon dioxide from flue gases |
-
2008
- 2008-07-07 DE DE102008031552A patent/DE102008031552A1/en not_active Withdrawn
-
2009
- 2009-06-26 BR BRPI0915687A patent/BRPI0915687A2/en not_active IP Right Cessation
- 2009-06-26 WO PCT/EP2009/004609 patent/WO2010003558A1/en active Application Filing
- 2009-06-26 RU RU2011104093/05A patent/RU2506985C2/en not_active IP Right Cessation
- 2009-06-26 CN CN2009801262511A patent/CN102089061A/en active Pending
- 2009-06-26 EP EP09776842A patent/EP2307120A1/en not_active Withdrawn
- 2009-06-26 AU AU2009267461A patent/AU2009267461A1/en not_active Abandoned
- 2009-06-26 KR KR1020107029775A patent/KR101447765B1/en not_active IP Right Cessation
- 2009-06-26 CA CA2729862A patent/CA2729862A1/en not_active Abandoned
- 2009-06-26 US US12/994,859 patent/US8702846B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO2010003558A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR101447765B1 (en) | 2014-10-06 |
WO2010003558A1 (en) | 2010-01-14 |
KR20110031166A (en) | 2011-03-24 |
DE102008031552A1 (en) | 2010-01-14 |
RU2506985C2 (en) | 2014-02-20 |
BRPI0915687A2 (en) | 2019-09-24 |
AU2009267461A1 (en) | 2010-01-14 |
CN102089061A (en) | 2011-06-08 |
US8702846B2 (en) | 2014-04-22 |
US20110088554A1 (en) | 2011-04-21 |
CA2729862A1 (en) | 2010-01-14 |
RU2011104093A (en) | 2012-08-20 |
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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 |
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17P | Request for examination filed |
Effective date: 20110128 |
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AX | Request for extension of the european patent |
Extension state: AL BA RS |
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DAX | Request for extension of the european patent (deleted) | ||
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: THYSSENKRUPP UHDE GMBH |
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Owner name: THYSSENKRUPP INDUSTRIAL SOLUTIONS AG |
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Effective date: 20150204 |
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STAA | Information on the status of an ep patent application or granted ep patent |
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18D | Application deemed to be withdrawn |
Effective date: 20150615 |