WO2014108423A1 - Procédé de production de gaz de synthèse à partir de charbon - Google Patents

Procédé de production de gaz de synthèse à partir de charbon Download PDF

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Publication number
WO2014108423A1
WO2014108423A1 PCT/EP2014/050190 EP2014050190W WO2014108423A1 WO 2014108423 A1 WO2014108423 A1 WO 2014108423A1 EP 2014050190 W EP2014050190 W EP 2014050190W WO 2014108423 A1 WO2014108423 A1 WO 2014108423A1
Authority
WO
WIPO (PCT)
Prior art keywords
loog
hydrogenation
sulphide
cobalt
catalysts
Prior art date
Application number
PCT/EP2014/050190
Other languages
English (en)
Inventor
Michael Rieger
Jan SCHÖNEBERGER
Holger Thielert
Original Assignee
Thyssenkrupp 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
Priority claimed from DE201310009885 external-priority patent/DE102013009885A1/de
Application filed by Thyssenkrupp Uhde Gmbh filed Critical Thyssenkrupp Uhde Gmbh
Priority to CN201480004324.0A priority Critical patent/CN104903428B/zh
Priority to JP2015551202A priority patent/JP2016505695A/ja
Priority to US14/760,117 priority patent/US9677018B2/en
Priority to KR1020157021202A priority patent/KR102055036B1/ko
Priority to PL14702755T priority patent/PL2943556T3/pl
Priority to EP14702755.1A priority patent/EP2943556B1/fr
Publication of WO2014108423A1 publication Critical patent/WO2014108423A1/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
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • 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 belongs to the field of coke making technology and relates to a new process for the removal of carbon sulphides from coke oven gas and to a new catalyst and its application.
  • Coke oven gas (synonym : coking gas) is obtained from dry distillation of hard coal in coke oven plants.
  • the gas typically contains approx. 55 %-wt hydrogen, 25 %-wt methane, 10 %-wt nitrogen and 5 %-wt. carbon monoxide. Due to this, coke oven gas is generally qualified as a synthesis gas for chemical reactions; disadvantageous, however, are the contents of carbonyl sulphide and carbon disulphide, which must previously be re- moved as they act as catalyst poisons in subsequent reactions, for example. The consequence is that the catalysts must frequently be cleaned or even exchanged, which directly involves effort and cost and is also unwanted because of the turnaround of the plant.
  • One method to free coke oven gas from unwanted carbon sulphides is to subject the gas to a catalytic hydrogenation and to convert the sulphur compounds into hydrogen sulphide. Although this gas is also unwanted, it can be washed out easily by means of aqueous lye, for example, ammonia solution.
  • German patent application DE 1545470 Al suggests to hydrogenate carbon sulphides over cobalt molybdenum, nickel molybdenum or nickel cobalt molybdenum catalysts to hydrogen sul- phide, which is then to be separated.
  • the reaction temperature in the examples is above 550 °C.
  • German patent application DE 2647690 Al (Parsons), which proposes to hydrogenate sulphur-bearing carbon compounds over catalysts on the basis of cobalt, molybdenum, iron, chromium, vanadium, thorium, nickel, tungsten and/or uranium and to remove the hydrogen sulphide obtained in an extraction column by means of an alkali hydroxide solution.
  • the sulphides of the above metals are proposed as concrete catalysts.
  • a disadvantage involved is, however, that in this case as well the catalysts require a minimum temperature of 260 °C and the hydrogenation must preferably be carried out at significantly higher temperatures, partly even above 400 °C. This is not desired especially for reasons of energy cost; in addition, such temperatures will change the composition of the gas, i.e. methanation will take place already.
  • Aim of the present invention therefore was to improve the existing processes in so far as the carbon sulphides and organic sulphur compounds (e.g. thiophenes), if any, are transformed virtually quantitatively to hydrogen sulphide but at temperatures which are significantly lower. Furthermore, the process was intended to ensure keeping the mass ratio of carbon oxides to methane unchanged, i.e. preventing methanation.
  • carbon sulphides and organic sulphur compounds e.g. thiophenes
  • Subject matter of the invention is a process for the production of synthesis gas from coke, in which
  • the gas mixture is subjected to hydrogenation at a temperature in the range of 200 to 280 °C over a sulphidic cobalt molybdenum catalyst provided on an aluminium oxide carrier material, and
  • the sulphidic cobalt molybdenum catalysts known for hydrogenation of carbon sulphides feature a high activity and selectivity even below 280 and preferably below 260°C if they are deposited on aluminium oxide carrier material. Carbon sulphides are actually hydrogenated to hydrogen sulphide at at least 95 %-vol. without observing an influence of the hydrogenation on the ratio of carbon oxides to methane.
  • Hydrogenation of the pyrolysis gases may be done in the manner customary, for which mainly fixed-bed reactors have proved best suited, as the catalysts are provided in the form of lumps as bulk layer or fixed packing. Since bulk material leads to channelling more easily and hence to an inhomogeneous flow distribution, preference is given to the embodiment in which the catalysts are arranged in packings inside the reactor.
  • the advantage of the hydrogenation in the fixed-bed reactor is that high space/time yields can be achieved, which is why the process according to the invention can also be carried out at high GSHV values of approx. 500 to approx. 1500 and preferably ap- prox. 1000 to approx. 1200 l/h.
  • Another advantage is provided in that no special measures are required for the product discharge, as the reactants - i.e. pyrolysis gas and hydrogen - are preferably introduced jointly at the bottom of the reactor, pass through the catalyst bed leading to hydrogenation and leave the reactor as products at the top.
  • a specific advantage of the process is that the sulphur compounds are hydrogenated over the catalysts to be used according to the invention, so that the reaction is possible at significantly more moderate conditions and effects the complete conversion of the carbon sulphides, without any signs of methanation.
  • the reaction temperature ranges between 200 and 280 and with regard to an adequate reaction velocity preferably between 240 and 260 °C.
  • the reactor may be heated from the outside - which results in a higher energy consumption - or the reaction components may be heated before introducing them into the reactor, with the mixing being possibly done in a nozzle which works, for example, by the Venturi principle.
  • reaction may take place in the range of 1 to 15 bar, i.e. at atmospheric pressure or under pressure. Preference is given to an em bodiment which uses a pressure in the range of approx. 5 to approx. 10 bar, as this is of benefit to yield and reaction velocity.
  • 'sulphidic cobalt molybdenum catalysts' mainly refers to catalysts which contain molybdenum sulphide as the actual catalyst and cobalt as the promoter. Catalysts of that kind are produced in known manner by joint sulphidation of the respective oxides, where the Mo0 3 is converted completely to MoS 2 . When the latter is applied to the aluminium oxide carrier, it is either bonded flat to the surface ('basal bonding') or to one edge only ('edge bonding').
  • the cobalt is available in three forms: first as Co 9 S 8 crystals deposited on the carrier, as Co 2+ ions on the edges of the MoS 2 plates ('CoMo phase') and as Co 2+ ions on the tetrahedral positions in the aluminium oxide lattice.
  • the preferred catalysts are hence composed predominantly, i.e. of more than 50 %-mole, preferably of more than 70 %-mole and most preferably of more than 90 %-mole, of molybdenum sulphide and contain the cobalt in sulphidic form as a promoter, the quantity in %-mole result- ing as the difference to 100. From this it follows that in a likewise preferred embodiment the catalysts do not contain any other metals, especially no other transition metals.
  • Aluminium oxides of especially high specific surface area come into consideration as suitable carriers for the sulphidic cobalt molybdenum catalysts, the aluminium oxides preferably featuring the following characteristics:
  • V 37A of 75 ml/lOOg, preferably 80 ml/lOOg and most preferably 85 ml/lOOg;
  • Aluminium oxide carriers of the type mentioned are sufficiently known from the state of the art.
  • European patent documents EP 1385786 Bl and EP 1385787 Bl (Axens) describe a process for their manufacture, in which a hydrargillite-type aluminium oxide is ground, undergoes hydrothermal treatment with an aqueous solution of aluminium nitrate and formic acid at 200 °C for 6 hours, the resulting product then being calcined at 400 to 1300. The carrier material is then extruded and is thus ready for loading.
  • the two documents mentioned are related to by reference.
  • the hydrogenation gases are, for this purpose, preferably passed through an absorption column, where they are treated, for ex- ample, in counter current with an aqueous base such as caustic soda or ammonia.
  • other devices may be used for the purification of gases as, for example, venturi scrubbers.
  • the purified product is available without restriction as a high-quality synthesis gas for further chemical reactions.
  • Another subject matter of the invention relates to the use of sulphidic cobalt molybdenum catalysts provided on aluminium oxide carriers for the hydrogenation of carbon sulphides to hydrogen sulphide.
  • cobalt molybdenum catalysts are used that, with reference to the metal com ponents, predominantly consist of molybdenum sulphide and contain cobalt sulphide as a promoter only.
  • carriers for the cobalt molybdenum catalysts are aluminium oxides that feature a high specific area surface and at the same time feature the following characteristics:
  • V 37A 75 ml/lOOg, preferably 80 ml/lOOg and most preferably 85 ml/lOOg;
  • the present invention also encompasses a method for preparing hydrogen sulphide, wherein carbon sulphides are subjected to hydrogenation in the presence of a working amount of sulphidic cobalt molybdenum catalysts provided on aluminium oxide carriers.
  • carbon sulphides are subjected to hydrogenation in the presence of cobalt molybdenum catalysts which, with reference to the metal components, predominantly consist of molybdenum sulphide and contain cobalt sulphide as a promoter only.
  • cobalt molybdenum catalysts which, with reference to the metal components, predominantly consist of molybdenum sulphide and contain cobalt sulphide as a promoter only.
  • aluminium oxide carriers meeting the following characteristics:
  • V 37A of at least 75 ml/lOOg, preferably 80 ml/lOOg and most preferably 85 ml/lOOg;
  • a pilot plant for fixed-bed hydrogenation was equipped with a bulk layer of commercially available lumpy sulphidic cobalt molybdenum catalyst on an aluminium oxide carrier. Subsequently, different coking gases were introduced at the bottom of the column. The only difference between these so-called feed gases was the amount of carbon sulphides, in particular carbon disulphide.
  • the hydrogenation was performed at a temperature of 220 °C and a pressure of 10 bar.
  • the GHSV was about 1200 l/h.
  • the product gas was analysed for sulphur in the gas chromatograph and the fractions of hydrogen sulphide and carbon sulphides were determined by means of the retention periods. Table 1 sums up the results.
  • the conversion rates refer to the hydrogenation of the CS 2 fraction.

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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)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Industrial Gases (AREA)

Abstract

La présente invention concerne un procédé de production de gaz de synthèse à partir de coke, dans lequel (a) du charbon est soumis à une pyrolyse à sec, aboutissant à la production d'un mélange gazeux contenant de l'hydrogène, du méthane, de l'azote et du monoxyde de carbone comme principaux constituants et des sulfures de carbone comme constituants mineurs, (b) le mélange gazeux est soumis à une hydrogénation à une température allant de 200 à 280 °C sur un catalyseur cobalt-molybdène sulphidique prévu sur un matériau porteur à base d'oxyde d'aluminium et (c) le sulfure d'hydrogène issu de l'hydrogénation étant séparé du mélange gazeux.
PCT/EP2014/050190 2013-01-09 2014-01-08 Procédé de production de gaz de synthèse à partir de charbon WO2014108423A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201480004324.0A CN104903428B (zh) 2013-01-09 2014-01-08 由无烟煤生产合成气的工艺方法
JP2015551202A JP2016505695A (ja) 2013-01-09 2014-01-08 無煙炭から合成ガスを生成する方法
US14/760,117 US9677018B2 (en) 2013-01-09 2014-01-08 Process for the production of synthesis gas from hard coal
KR1020157021202A KR102055036B1 (ko) 2013-01-09 2014-01-08 경탄으로부터 합성 가스를 생성하는 방법
PL14702755T PL2943556T3 (pl) 2013-01-09 2014-01-08 Sposób uwodorniania siarczku węgla z użyciem katalizatora siarczkowego kobaltowo-molibdenowego na nośniku z tlenku glinu
EP14702755.1A EP2943556B1 (fr) 2013-01-09 2014-01-08 Procédé d'hydrogénation de sulfure de carbone à l'aide d'un catalyseur sulfuré au cobalt et au molybdène sur support alumine

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE102013000173 2013-01-09
DE102013000173.0 2013-01-09
DE102013010473 2013-06-03
DE102013010473.4 2013-06-03
DE201310009885 DE102013009885A1 (de) 2013-01-09 2013-06-06 Verfahren zur Herstellung von Synthesegas aus Steinkohle
DE102013009885.8 2013-06-06

Publications (1)

Publication Number Publication Date
WO2014108423A1 true WO2014108423A1 (fr) 2014-07-17

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PCT/EP2014/050190 WO2014108423A1 (fr) 2013-01-09 2014-01-08 Procédé de production de gaz de synthèse à partir de charbon

Country Status (6)

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EP (1) EP2943556B1 (fr)
JP (1) JP2016505695A (fr)
KR (1) KR102055036B1 (fr)
CN (1) CN104903428B (fr)
PL (1) PL2943556T3 (fr)
WO (1) WO2014108423A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101641045B1 (ko) * 2015-09-30 2016-07-20 주식회사 포스코 강판의 산화 방지층 형성장치 및 방법

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1018630A (en) * 1963-11-13 1966-01-26 Shell Int Research Process for the purification of hot gases obtained by partial combustion and containing soot and carbonyl sulphide
DE1545470A1 (de) 1966-10-05 1970-02-05 Pichler Dr Phil Helmut Verfahren zur Umwandlung von Koksofengas in ein gegen Erdgas austauschbares Gas
GB1332337A (en) * 1970-09-21 1973-10-03 Shell Int Research Reducing total sulphur content of claus offgases
GB1404581A (en) * 1971-09-01 1975-09-03 Shell Int Research Process for the removal of soot and sulphur compounds from the crude gas generated by the partial combustion of a carbonaceous fuel
DE2647690A1 (de) 1975-12-29 1977-07-14 Parsons Co Ralph M Verfahren zur entschwefelung von koksofengas
US4085199A (en) * 1976-06-08 1978-04-18 Bethlehem Steel Corporation Method for removing hydrogen sulfide from sulfur-bearing industrial gases with claus-type reactors
US4336233A (en) * 1975-11-18 1982-06-22 Basf Aktiengesellschaft Removal of CO2 and/or H2 S and/or COS from gases containing these constituents
JPS59145288A (ja) 1983-02-07 1984-08-20 Nippon Steel Chem Co Ltd 軽油の水添精製法
JPS59230092A (ja) 1978-12-26 1984-12-24 シエブロン・リサ−チ・コンパニ− 潤滑油組成物
US4863489A (en) * 1989-02-03 1989-09-05 Texaco Inc. Production of demercurized synthesis gas, reducing gas, or fuel gas
WO1993013184A1 (fr) * 1991-12-30 1993-07-08 Gastec N.V. Procede de traitement des gaz obtenu par gazeification du charbon, gazeification des residus, gazeification des dechets ou gazeification de l'huile
WO2004105922A1 (fr) * 2003-05-29 2004-12-09 Shell Internationale Research Maatschappij B.V. Procede d'elimination du so2, du hcn and du h2s et eventuellement du cos, du s2 et du nh3 d'un courant de gaz
EP1385787B1 (fr) 2001-04-04 2006-05-03 Axens Agglomeres d'alumine, leur procede de preparation, et leurs utilisations comme support de catalyseur ou adsorbant
EP1385786B1 (fr) 2001-04-10 2010-01-06 Axens Adsorbants contenant des agglomeres d'alumine et leurs procedes de preparation
EP2412667A1 (fr) * 2010-07-27 2012-02-01 Air Products And Chemicals, Inc. Procédé et appareil de traitement ajustable d'un gaz acide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101050389A (zh) * 2007-05-11 2007-10-10 湖北省化学研究院 煤制燃气中hcn与cos的净化方法

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1018630A (en) * 1963-11-13 1966-01-26 Shell Int Research Process for the purification of hot gases obtained by partial combustion and containing soot and carbonyl sulphide
DE1545470A1 (de) 1966-10-05 1970-02-05 Pichler Dr Phil Helmut Verfahren zur Umwandlung von Koksofengas in ein gegen Erdgas austauschbares Gas
GB1332337A (en) * 1970-09-21 1973-10-03 Shell Int Research Reducing total sulphur content of claus offgases
GB1404581A (en) * 1971-09-01 1975-09-03 Shell Int Research Process for the removal of soot and sulphur compounds from the crude gas generated by the partial combustion of a carbonaceous fuel
US4336233A (en) * 1975-11-18 1982-06-22 Basf Aktiengesellschaft Removal of CO2 and/or H2 S and/or COS from gases containing these constituents
DE2647690A1 (de) 1975-12-29 1977-07-14 Parsons Co Ralph M Verfahren zur entschwefelung von koksofengas
US4085199A (en) * 1976-06-08 1978-04-18 Bethlehem Steel Corporation Method for removing hydrogen sulfide from sulfur-bearing industrial gases with claus-type reactors
JPS59230092A (ja) 1978-12-26 1984-12-24 シエブロン・リサ−チ・コンパニ− 潤滑油組成物
JPS59145288A (ja) 1983-02-07 1984-08-20 Nippon Steel Chem Co Ltd 軽油の水添精製法
US4863489A (en) * 1989-02-03 1989-09-05 Texaco Inc. Production of demercurized synthesis gas, reducing gas, or fuel gas
WO1993013184A1 (fr) * 1991-12-30 1993-07-08 Gastec N.V. Procede de traitement des gaz obtenu par gazeification du charbon, gazeification des residus, gazeification des dechets ou gazeification de l'huile
EP1385787B1 (fr) 2001-04-04 2006-05-03 Axens Agglomeres d'alumine, leur procede de preparation, et leurs utilisations comme support de catalyseur ou adsorbant
EP1385786B1 (fr) 2001-04-10 2010-01-06 Axens Adsorbants contenant des agglomeres d'alumine et leurs procedes de preparation
WO2004105922A1 (fr) * 2003-05-29 2004-12-09 Shell Internationale Research Maatschappij B.V. Procede d'elimination du so2, du hcn and du h2s et eventuellement du cos, du s2 et du nh3 d'un courant de gaz
EP2412667A1 (fr) * 2010-07-27 2012-02-01 Air Products And Chemicals, Inc. Procédé et appareil de traitement ajustable d'un gaz acide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101641045B1 (ko) * 2015-09-30 2016-07-20 주식회사 포스코 강판의 산화 방지층 형성장치 및 방법

Also Published As

Publication number Publication date
KR20150103738A (ko) 2015-09-11
CN104903428B (zh) 2019-01-18
KR102055036B1 (ko) 2019-12-11
PL2943556T3 (pl) 2020-09-21
JP2016505695A (ja) 2016-02-25
EP2943556A1 (fr) 2015-11-18
CN104903428A (zh) 2015-09-09
EP2943556B1 (fr) 2020-04-08

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