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EP0560039B1 - Procédé pour purifier un gaz provenant de la gazéification des matériaux carbonés - Google Patents

Procédé pour purifier un gaz provenant de la gazéification des matériaux carbonés Download PDF

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Publication number
EP0560039B1
EP0560039B1 EP19930101536 EP93101536A EP0560039B1 EP 0560039 B1 EP0560039 B1 EP 0560039B1 EP 19930101536 EP19930101536 EP 19930101536 EP 93101536 A EP93101536 A EP 93101536A EP 0560039 B1 EP0560039 B1 EP 0560039B1
Authority
EP
European Patent Office
Prior art keywords
gas
stage
hydrogen sulphide
gasification
scrubbing
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.)
Revoked
Application number
EP19930101536
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German (de)
English (en)
Other versions
EP0560039A1 (fr
Inventor
Manfred Dr. Gross
Ulrich Dr. Meisl
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.)
Krupp Koppers GmbH
Original Assignee
Krupp Koppers 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
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6453288&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0560039(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Krupp Koppers GmbH filed Critical Krupp Koppers GmbH
Publication of EP0560039A1 publication Critical patent/EP0560039A1/fr
Application granted granted Critical
Publication of EP0560039B1 publication Critical patent/EP0560039B1/fr
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Classifications

    • 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
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • 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
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials

Definitions

  • the invention relates to a method for cleaning a gas obtained by gasification of carbon-containing material, in particular fine-grained to dusty coal, which is to be burned in the combustion chamber of a gas turbine of a power plant.
  • the gas generated during the gasification of carbonaceous material contains nitrogen and sulfur compounds, such as ammonia (NH3), hydrogen cyanide (HCN), hydrogen sulfide (H2S) and carbon oxysulfide (COS), which in the gas turbine produce nitrogen oxides (NO x ) and sulfur dioxide ( SO2) are implemented.
  • NH3 ammonia
  • HCN hydrogen cyanide
  • H2S hydrogen sulfide
  • COS carbon oxysulfide
  • SO2 sulfur dioxide
  • the invention is therefore based on the object of providing a method for purifying a gas obtained by gasifying carbon-containing material, in which the nitrogen and sulfur compounds mentioned above are removed from the gas to such an extent that the purified gas can be removed without Damage to the environment can be used as fuel gas for the gas turbine of a power plant.
  • the resulting waste products should not pose a burden on the environment and should at the same time be used as widely as possible.
  • the process can also be modified in accordance with the main claim in such a way that instead of process steps d) and e) the hydrogen sulfide driven off from the washing solution is processed together with the exhaust gas from the two-stage stripping to sulfuric acid, the Exhaust gas from the sulfuric acid plant is released into the atmosphere.
  • the raw gas coming from the gasification system is introduced via line 1 into the circuit water scrubber 2 used for dedusting the gas.
  • the ammonia and hydrogen cyanide present in the gas are almost completely washed out as well as the hydrogen sulfide partially, so that the gas after the cycle water wash still has the following residual levels: NH3 0.02 vol% CN 50 ppmV
  • the pressure required to carry out the cycle water scrubbing 2 is normally already predetermined, since the upstream gasification is carried out under pressure.
  • the application of pressure enables the apparatus required for gas treatment to be kept correspondingly small.
  • the required temperature can normally be set during the cooling of the raw gas following the gasification.
  • Gas washers of conventional design which can be provided with internals, can be used to carry out the cycle water scrubbing 2.
  • the washing water is circulated over the solids separator 4, which is indicated in the flow diagram by the double arrow 3.
  • the entrained dust is separated in the solids separation 4 in a manner known per se, e.g. by filtration and / or sedimentation, separated from the wash water.
  • the wash water then returns to the cycle water wash 2.
  • a small partial flow of the same is drawn off after the solid separation 4 and fed to the two-stage stripping 6 via line 5.
  • the amount of the partial stream withdrawn via line 5 is dependent on the pollutant content, in particular on the chloride content, of the fuel used for the gasification. To the extent necessary, the amount of wash water withdrawn from the circuit replaced by fresh water.
  • a series connection of a stripper stage 7 operating in an acidic environment and a stripper stage 8 operating in a basic environment is provided. First, in the stripping stage 7 working in the acidic environment, the acidic components are driven off from the wash water.
  • the washing water running out of the stripper stage 7 is transferred to the stripper stage 8.
  • the ammonium ions contained in the wash water are added according to the reaction equation by adding lye NH4+ + OH ⁇ ⁇ NH3 + H2O converted into molecular ammonia, which is also driven out of the wash water by increasing the temperature.
  • the lye required for this, such as sodium hydroxide solution, is metered in via line 10 to stripper stage 8.
  • the correspondingly treated wash water can either be returned to the cycle water wash 2, or it is discharged from the process and to a wastewater treatment facility fed. Both options are not shown in the flow diagram.
  • the two stripper stages 7 and 8 can either be carried out in separate columns connected in series, or both stages are combined to form a structural unit, the wash water running out of the stripper stage 7 being metered in with the alkali required for the stripper stage 8.
  • the two-stage stripping 6 is carried out in stripping columns of conventional design, in which the temperature increase required for the removal of the pollutants from the wash water is brought about either by a bottom circulation boiler.
  • the pollutants driven off from the wash water, ie HCN, H2S and NH3 are fed via lines 11 and 12 to the Claus system 13.
  • the pollutant streams emerging from the two stripper stages 7 and 8 can also be combined and led to the Claus system 13 via a common line.
  • the dedusted gas emerging from the cycle water scrubber 2 is meanwhile fed to the carbon oxysulfide removal 15 via the line 14.
  • the carbon oxysulfide present in the gas which is difficult to wash out with water or other common solvents, is converted into hydrogen sulfide by catalytic hydrolysis.
  • the carbon oxysulfide reacts in the gas phase with water vapor according to the following reaction equation: COS + H2O ⁇ H2S + CO 2
  • the catalyst used for this reaction contains aluminum oxide as an active component.
  • the gas then passes via line 16 to the hydrogen sulfide scrubbing 17, in which the hydrogen sulfide present in the gas is washed out absorptively with a selectively acting washing solution.
  • the hydrogen sulfide present in the gas can be removed to a residual content of approx. 7 ppm, while the co-absorption of the other gas components is only slight.
  • An amine solution such as, for example, an aqueous methyldiethanolamine solution can be used as a particularly suitable washing solution.
  • the treated gas is of sufficient purity and can therefore be fed via line 18 to the combustion chamber of the gas turbine.
  • the hydrogen sulfide wash 17 usually consists of an absorption and a desorption column. In the latter, the loaded washing solution is regenerated by stripping off the hydrogen sulfide taken up. This produces a gas stream with a high H2S concentration, which reaches the Claus system 13 via line 19.
  • the gas flows from lines 11, 12 and 19 are further treated according to a modified Claus process, which also allows the catalytic decomposition of the nitrogen compounds (NH 3 and HCN) supplied via line 11 and 12.
  • the following reactions take place: 1. 2 NH3 ⁇ N2 + 3 H2 2.
  • the resulting elemental sulfur is withdrawn in liquid form from the Claus plant 13 via the line 20 and can be used for further use.
  • the Claus plant 13 is a known plant which consists of an incinerator for carrying out reactions 1, 2 and 3 and a one- or multi-stage Claus reactor for carrying out reaction 4.
  • a catalyst layer for decomposing the nitrogen compounds according to reactions 1 and 2 is provided in the incinerator. Since the H2S concentration of the gas stream supplied via line 19 is relatively high, the system volumes of the Claus system 13 can be kept correspondingly small.
  • the residual Claus gas can also be fed to an afterburning system, the waste gas resulting from the afterburning being blown off into the atmosphere.
  • a further variant of the method according to the invention is that the gas streams from the lines 11, 12 and 19 are not worked up further in the Claus plant 13 but in a sulfuric acid plant with the production of sulfuric acid.
  • the exhaust gas from the sulfuric acid plant is released into the atmosphere.
  • a raw gas from a coal pressure gasification was treated, which in about 180,000 m3 / h 0.300 vol .-% H2S 0.030 vol .-% COS 0.020 vol% NH3 0.005 vol .-% HCN contains and is dedusted under a pressure of 25 bar.
  • the circuit water scrubber 2 used for dedusting is charged with 20,000 kg / h of circuit water. In addition to the solids contained in the gas, ammonia and hydrogen cyanide are almost completely washed out as well as hydrogen sulfide and carbon dioxide from the gas.
  • the gas which has been cooled down to 40 ° C., is then treated in the hydrogen sulfide wash 17 with a circulating methyldiethanolamine washing solution, the residual H2S content in the desulfurized gas being reduced to approximately 7 ppm H2S.
  • the desulfurized gas can then be warmed up in the heat exchange with the gas stream in line 16 and leaves the system via line 18 at approximately 130 ° C. and a pressure of 22.5 bar.
  • the hydrogen sulfide released during the regeneration of the washing solution is conducted at 40 ° C. and 1.5 bar via line 19 to the Claus system 13.
  • 830 kg / h of liquid sulfur are generated from the gas streams entering via the lines 11, 12 and 19 and are discharged via line 20 in the liquid state.
  • the nitrogen compounds present in the gas are catalytically decomposed in the Claus plant 13.
  • the residual Claus gas is withdrawn via line 21 and, after catalytic hydrogenation via line 23, is mixed with the gas stream in line 14.

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  • 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)
  • Organic Chemistry (AREA)
  • Industrial Gases (AREA)
  • Treating Waste Gases (AREA)

Claims (3)

  1. Procédé pour purifier un gaz provenant de la gazéification de matériaux carbonés, en particulier de charbon allant d'une structure à grains fins à une structure pulvérulente, qui doit être brûlé dans la chambre de combustion d'une turbine à gaz d'une centrale électrique, caractérisé par les opérations de base suivantes:
    a) Le gaz provenant de l'installation de gazéification est soumis à l'aide d'un dispositif de lavage à l'eau en circuit fermé à une opération de dépoussiérage à une pression comprise entre 15 et 25 bar ainsi qu'à une température comprise entre 110 et 150° C, lors de laquelle, on enlève simultanément par lavage presqu'entièrement l'ammoniaque et l'acide cyanhydrique ainsi qu'au moins partiellement l'acide sulfhydrique contenus dans le gaz, un courant partiel de l'eau de lavage étant à chaque fois retiré du circuit et étant soumis, après dépôt des matières solides entraînées, à un strippage à deux étapes en milieu acide et en milieu basique;
    b) l'oxysulfure de carbone contenu dans le gaz est converti par hydrolyse catalytique en acide sulfhydrique;
    c) l'acide sulhydrique encore présent dans le gaz est éliminé du gaz à l'aide d'un lavage sélectif, le gaz purifié étant alors dirigé vers la turbine à gaz, alors que l'acide sulfhydrique est expulsé de la solution de lavage chargée;
    d) on fait réagir l'acide sulfhydrique expulsé de la solution de lavage chargée conjointement avec le gaz de rejet produit dans l'étape a) en provenance du strippage à deux étapes dans une installation Claus pour former du soufre élémentaire, les composés d'azote présents dans le gaz de rejet étant simultanément décomposés catalytiquement; et
    e) le gaz restant Claus produit au cours de l'étape d) est soumis à un traitement ultérieur, le gaz restant étant soit hydrogéné catalytiquement et ensuite à nouveau additionné au courant de gaz avant l'introduction dans l'étape b) (hydrogénation de COS), soit acheminé en direction d'une installation de post-combustion, le gaz de rejet qui se dégage dans celle-ci étant relâché dans l'atmosphère.
  2. Procédé selon la revendication 1, caractérisé en ce que, à la place d'utiliser les étapes d) et e), on fait réagir l'acide sulfhydrique expulsé de la solution de lavage chargée conjointement avec le gaz de rejet produit dans l'étape a) en provenance du strippage à deux étapes pour former de l'acide sulfurique, le gaz de rejet en provenance de l'installation d'acide sulfurique étant relâché dans l'atmosphère.
  3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on utilise, pour le lavage d'acide sulfhydrique dans l'étape c), une solution d'amine à action sélective, comme par exemple une solution aqueuse de méthyldiéthanolamine.
EP19930101536 1992-03-05 1993-02-02 Procédé pour purifier un gaz provenant de la gazéification des matériaux carbonés Revoked EP0560039B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4206943 1992-03-05
DE19924206943 DE4206943A1 (de) 1992-03-05 1992-03-05 Verfahren zur reinigung eines durch vergasung von kohlenstoffhaltigem material gewonnenen gases

Publications (2)

Publication Number Publication Date
EP0560039A1 EP0560039A1 (fr) 1993-09-15
EP0560039B1 true EP0560039B1 (fr) 1995-11-02

Family

ID=6453288

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19930101536 Revoked EP0560039B1 (fr) 1992-03-05 1993-02-02 Procédé pour purifier un gaz provenant de la gazéification des matériaux carbonés

Country Status (4)

Country Link
EP (1) EP0560039B1 (fr)
DE (2) DE4206943A1 (fr)
DK (1) DK0560039T3 (fr)
ES (1) ES2080538T3 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4321542C1 (de) * 1993-06-29 1994-09-01 Bfi Entsorgungstech Verfahren zur getrennten Entfernung von Schwefelverbindungen und CO¶2¶ aus Gas
NL1002134C2 (nl) * 1996-01-19 1997-07-22 Stork Comprimo Bv Werkwijze voor het verwijderen van zwavelbevattende verontreinigingen, aromaten en koolwaterstoffen uit gas.
NL1002135C2 (nl) * 1996-01-19 1997-07-22 Stork Comprimo Bv Werkwijze voor het verwijderen van zwavelbevattende verontreinigingen, aromaten en koolwaterstoffen uit gas.
DE102004062687A1 (de) 2004-12-21 2006-06-29 Uhde Gmbh Verfahren zum Erzeugen von Wasserstoff und Energie aus Synthesegas
US8551199B2 (en) * 2009-04-03 2013-10-08 General Electric Company Method and apparatus to recycle tail gas
US11530131B1 (en) 2021-11-16 2022-12-20 Saudi Arabian Oil Company Methods and systems of sub-dew point sulfur recovery with interstage membrane units

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4254094A (en) * 1979-03-19 1981-03-03 Air Products And Chemicals, Inc. Process for producing hydrogen from synthesis gas containing COS
US4356161A (en) * 1981-08-24 1982-10-26 Shell Oil Company Process for reducing the total sulfur content of a high CO2 -content feed gas
DE3923840C1 (en) * 1989-07-19 1991-01-17 Rheinische Braunkohlenwerke Ag, 5000 Koeln, De Prodn. of fuel gas - by partial combustion of carbonaceous materials, cooling, removing suspended solid matter, etc.
DE3926575A1 (de) * 1989-08-11 1991-02-14 Metallgesellschaft Ag Verfahren zum reinigen von rohbrenngas aus der vergasung fester brennstoffe

Also Published As

Publication number Publication date
DK0560039T3 (da) 1996-03-04
ES2080538T3 (es) 1996-02-01
EP0560039A1 (fr) 1993-09-15
DE59300836D1 (de) 1995-12-07
DE4206943A1 (de) 1993-09-09

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