EP2307120A1 - Procédé pour éliminer les gaz acides d'un flux gazeux - Google Patents

Procédé pour éliminer les gaz acides d'un flux gazeux

Info

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Withdrawn
Application number
EP09776842A
Other languages
German (de)
English (en)
Inventor
Johannes Menzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ThyssenKrupp Industrial Solutions AG
Original Assignee
Uhde GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Uhde GmbH filed Critical Uhde GmbH
Publication of EP2307120A1 publication Critical patent/EP2307120A1/fr
Withdrawn legal-status Critical Current

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

La présente invention concerne l'élimination de gaz acides dans un flux gazeux, notamment dans un flux de gaz naturel, dans un flux de gaz de synthèse ou analogues, ces gaz acides étant absorbés à partir du flux gazeux par au moins un agent absorbant. Comme agent absorbant, on utilise un mélange composé d'un détergent physique, d'un détergent chimique et d'eau. L'agent absorbant présente plus de 60 % en poids de détergent physique, et on utilise comme détergent physique un dérivé morpholinique ainsi qu'un détergent chimique à base d'au moins un composé aminé aliphatique.
EP09776842A 2008-07-07 2009-06-26 Procédé pour éliminer les gaz acides d'un flux gazeux Withdrawn EP2307120A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008031552A DE102008031552A1 (de) 2008-07-07 2008-07-07 Verfahren zum Entfernen von Sauergasen aus einem Gasstrom
PCT/EP2009/004609 WO2010003558A1 (fr) 2008-07-07 2009-06-26 Procédé pour éliminer les gaz acides d’un flux gazeux

Publications (1)

Publication Number Publication Date
EP2307120A1 true EP2307120A1 (fr) 2011-04-13

Family

ID=41077711

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09776842A Withdrawn EP2307120A1 (fr) 2008-07-07 2009-06-26 Procédé pour éliminer les gaz acides d'un flux gazeux

Country Status (10)

Country Link
US (1) US8702846B2 (fr)
EP (1) EP2307120A1 (fr)
KR (1) KR101447765B1 (fr)
CN (1) CN102089061A (fr)
AU (1) AU2009267461A1 (fr)
BR (1) BRPI0915687A2 (fr)
CA (1) CA2729862A1 (fr)
DE (1) DE102008031552A1 (fr)
RU (1) RU2506985C2 (fr)
WO (1) WO2010003558A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980954B (zh) * 2014-05-28 2016-02-03 西南化工研究设计院有限公司 一种焦炉煤气中苯族烃的脱除方法
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 (fr) * 2015-12-17 2018-02-02 IFP Energies Nouvelles Solution absorbante a base de derives hydroxyles de la 1,6-hexanediamine et procede d'elimination de composes acides d'un effluent gazeux
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

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IT1132170B (it) * 1980-07-04 1986-06-25 Snam Progetti Processo di separazione selettiva di idrogeno solforato da miscele gassose contenenti anche anidride carbonica
DE3314182C2 (de) * 1983-04-19 1985-08-08 Heinrich 2915 Saterland Geesen Verfahren zum Orten einer Leckstelle in der Abdichtung eines Flachdachs und Meßgerät zur Durchführung des Verfahrens
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 (de) * 1997-12-05 2002-04-25 Krupp Uhde Gmbh Verfahren zur Entfernung von CO¶2¶ und Schwefelverbindungen aus technischen Gasen, insbesondere aus Erdgas und Roh-Synthesegas
EP1022046A1 (fr) * 1999-01-22 2000-07-26 Krupp Uhde GmbH Procédé pour élimination de dioxide de carbone, des composés soufrés, l'eau et des hydrocarbures aromatiques et aliphatiques supérieures de gaz techniques
MXPA05010039A (es) * 2003-03-21 2005-10-26 Dow Global Technologies Inc Composicion mejorada y metodo para eliminar sulfuro de carbonilo del gas acido que lo contiene.
BRPI0412767A (pt) * 2003-07-22 2006-09-26 Dow Global Technologies Inc regeneração de fluidos de tratamento contendo gás ácido
JP2007533431A (ja) 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 酸性ガスを流体の流れから除去することによって高い圧力下にある酸性ガス流を取得する方法
DE10352878A1 (de) * 2003-11-10 2005-06-16 Basf Ag Verfahren zur Gewinnung eines unter hohem Druck stehenden Sauergasstroms durch Entfernung der Sauergase aus einem Fluidstrom
DE102004042418B4 (de) * 2004-09-02 2008-04-30 Clariant Produkte (Deutschland) Gmbh Absorptionsflüssigkeit, deren Verwendung und Verfahren zum Reinigen von Gasen
DE102005043142A1 (de) * 2004-10-22 2006-04-27 Basf Ag Verfahren zum Entsäuern eines Fluidstroms und Absorptionsmittel hierfür
FR2877858B1 (fr) * 2004-11-12 2007-01-12 Inst Francais Du Petrole Procede de desacidification d'un gaz avec une solution absorbante a regeneration fractionnee
DE102005050385A1 (de) 2005-10-20 2007-04-26 Basf Ag Absorptionsmittel und Verfahren zum Entfernen von Kohlendioxid aus Gasströmen
US7887620B2 (en) * 2006-06-13 2011-02-15 Basf Se Removal of carbon dioxide from flue gases

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Also Published As

Publication number Publication date
CA2729862A1 (fr) 2010-01-14
BRPI0915687A2 (pt) 2019-09-24
CN102089061A (zh) 2011-06-08
KR20110031166A (ko) 2011-03-24
RU2506985C2 (ru) 2014-02-20
WO2010003558A1 (fr) 2010-01-14
US20110088554A1 (en) 2011-04-21
DE102008031552A1 (de) 2010-01-14
RU2011104093A (ru) 2012-08-20
AU2009267461A1 (en) 2010-01-14
US8702846B2 (en) 2014-04-22
KR101447765B1 (ko) 2014-10-06

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