EP2943556B1 - Verfahren zur hydrierung von carbonsulfide unter verwendung von einem sulfidierten kobalt- und molybdän-katalysator auf einem aluminiumoxid-träger - Google Patents

Verfahren zur hydrierung von carbonsulfide unter verwendung von einem sulfidierten kobalt- und molybdän-katalysator auf einem aluminiumoxid-träger Download PDF

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Publication number
EP2943556B1
EP2943556B1 EP14702755.1A EP14702755A EP2943556B1 EP 2943556 B1 EP2943556 B1 EP 2943556B1 EP 14702755 A EP14702755 A EP 14702755A EP 2943556 B1 EP2943556 B1 EP 2943556B1
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EP
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Prior art keywords
cobalt
hydrogenation
catalysts
molybdenum
sulphidic
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EP14702755.1A
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English (en)
French (fr)
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EP2943556A1 (de
Inventor
Michael Rieger
Jan SCHÖNEBERGER
Holger Thielert
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ThyssenKrupp Industrial Solutions AG
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ThyssenKrupp Industrial Solutions AG
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Priority claimed from DE201310009885 external-priority patent/DE102013009885A1/de
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Priority to PL14702755T priority Critical patent/PL2943556T3/pl
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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.
  • 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 removed 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.
  • a common method to free industrial gas from unwanted carbon sulphides is the catalytic hydrolysis of such compounds as described in DE 26 47 690 A1 , EP 2 412 667 A1 , GB 1 332 337 A , US 4 336 233 A , US 4 863 489 A , WO 2004/105922 A1 , and WO 93/13184 A1 .
  • One further 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.
  • a catalytic hydrogenation of gas mixtures is known in which carbonyl sulphide is hydrogenated using catalyst materials such as alumina, bauxite, activated clays, aluminium phosphate, thoria and magnesium chloride while carbon disulphide is hydrogenated using a catalyst containing at least one metal from Groups VI and/or VIII of the Periodic System of the Elements, either as such or in chemically bound form.
  • catalyst materials such as alumina, bauxite, activated clays, aluminium phosphate, thoria and magnesium chloride
  • carbon disulphide is hydrogenated using a catalyst containing at least one metal from Groups VI and/or VIII of the Periodic System of the Elements, either as such or in chemically bound form.
  • Cobalt-molybdenum-aluminium catalysts for hydrogenation of carbonyl sulphide and carbon disulphide are also known from US 4 336 233 and EP 2 412 667 A1 , respectively.Related processes are already known according to prior
  • German patent application DE 1545470 A1 suggests to hydrogenate carbon sulphides over cobalt molybdenum, nickel molybdenum or nickel cobalt molybdenum catalysts to hydrogen sulphide, which is then to be separated.
  • the reaction temperature in the examples is above 550 °C.
  • German patent application DE 2647690 A1 (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 hard coal, in which
  • 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 approx. 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 embodiment 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 MoO 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 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 resulting 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:
  • Aluminium oxide carriers of the type mentioned are sufficiently known from the state of the art.
  • European patent documents EP 1385786 B1 and EP 1385787 B1 (Axens ), for example, 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 example, 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.
  • a further subject matter of the present invention is the use of sulphidic cobalt molybdenum catalysts provided on aluminum oxide carriers for the hydrogenation of carbon sulphides to hydrogen sulphide, wherein sulphidic cobalt molybdenum catalysts are used which contain molybdenum sulphide as the actual catalyst and cobalt as the promoter, wherein said catalysts are composed of more than 50 %-mole of molybdenum sulphide and said catalysts contain the cobalt in sulphidic form, the quantity in %-mole of said cobalt in sulphidic form resulting as the difference to 100, wherein molybdenum sulphide has been obtained by sulphidation of the respective oxide, wherein the MoO 3 has been converted completely to MoS 2 , wherein after sulphidation the cobalt is present 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 (
  • 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.
  • the 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:
  • 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.

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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)

Claims (12)

  1. Verfahren zur Herstellung von Synthesegas aus Steinkohle, wobei
    (a) Steinkohle trockener Pyrolyse unterzogen wird, um ein Gasgemisch zu erzeugen, das Wasserstoff, Methan, Stickstoff und Kohlenmonoxid als Hauptbestandteile und Kohlenstoffsulfide als Nebenbestandteile enthält,
    (b) das Gasgemisch Hydrierung bei einer Temperatur in dem Bereich von 200 bis 280 °C über einem sulfidischen Cobalt-Molybdän-Katalysator, der auf einem Aluminiumoxidträgermaterial bereitgestellt ist, unterzogen wird, und
    (c) der durch Hydrierung erhaltene Schwefelwasserstoff von dem Gasgemisch abgetrennt wird,
    wobei sulfidische Cobalt-Molybdän-Katalysatoren verwendet werden, die Molybdänsulfid als den eigentlichen Katalysator und Cobalt als den Promotor enthalten,
    wobei die Katalysatoren aus mehr als 50 mol-% Molybdänsulfid bestehen und die Katalysatoren das Cobalt in sulfidischer Form enthalten, wobei die Menge des Cobalts in sulfidischer Form in mol-% den Unterschied zu 100 bildet,
    wobei Molybdänsulfid durch Sulfidierung des entsprechenden Oxids erhalten worden ist,
    wobei das MoO3 vollständig zu MoS2 umgewandelt worden ist,
    wobei das Cobalt nach der Sulfidierung in drei Formen vorhanden ist: zuerst als Co9S8-Kristalle, die auf dem Träger abgeschieden sind, als Co2+-Ionen an den Kanten der MoS2-Platten ("CoMo-Phase") und als Co2+-Ionen an den tetraedrischen Positionen in dem Aluminiumoxidgitter.
  2. Verfahren gemäß Anspruch 1, wobei die Katalysatoren aus mehr als 70 mol-% Molybdänsulfid bestehen.
  3. Verfahren gemäß Anspruch 2, wobei die Katalysatoren aus mehr als 90 mol-% Molybdänsulfid bestehen.
  4. Verfahren gemäß Anspruch 1, wobei Synthesegase mit einem Gehalt von 10 bis 200 ppm Kohlenstoffsulfiden verwendet werden.
  5. Verfahren gemäß Anspruch 1, wobei Hydrierung in einem Temperaturbereich zwischen 240 und 260 °C durchgeführt wird.
  6. Verfahren gemäß Anspruch 1, wobei Hydrierung bei einem Druck von 1 bis 15 bar durchgeführt wird.
  7. Verfahren gemäß Anspruch 6, wobei Hydrierung bei einem Druck von 5 bis 10 bar durchgeführt wird.
  8. Verfahren gemäß Anspruch 1, wobei die Hydrierung bei einem GHSV von 500 bis 1500 l/h durchgeführt wird.
  9. Verfahren gemäß wenigstens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass Hydrierung in einem Festbettreaktor durchgeführt wird.
  10. Verfahren gemäß Anspruch 9, wobei die in dem Festbettreaktor verwendeten Katalysatoren als Masseschicht oder Packung bereitgestellt werden.
  11. Verfahren gemäß Anspruch 1, wobei das Hydrierungsprodukt nach dem Verlassen des Reaktors durch eine Absorptionssäule geleitet wird, in der der Schwefelwasserstoff mit einer basischen Flüssigkeit ausgewaschen wird.
  12. Verwendung von sulfidischen Cobalt-Molybdän-Katalysatoren, die auf Aluminiumoxidträgern bereitgestellt sind, zur Hydrierung von Kohlenstoffsulfiden zu Schwefelwasserstoff,
    wobei sulfidische Cobalt-Molybdän-Katalysatoren verwendet werden, die Molybdänsulfid als den eigentlichen Katalysator und Cobalt als den Promotor enthalten,
    wobei die Katalysatoren aus mehr als 50 mol-% Molybdänsulfid bestehen und die Katalysatoren das Cobalt in sulfidischer Form enthalten, wobei die Menge des Cobalts in sulfidischer Form in mol-% den Unterschied zu 100 bildet,
    wobei Molybdänsulfid durch Sulfidierung des entsprechenden Oxids erhalten worden ist,
    wobei das MoO3 vollständig zu MoS2 umgewandelt worden ist,
    wobei das Cobalt nach der Sulfidierung in drei Formen vorhanden ist: zuerst als Co9S8-Kristalle, die auf dem Träger abgeschieden sind, als Co2+-Ionen an den Kanten der MoS2-Platten ("CoMo-Phase") und als Co2+-Ionen an den tetraedrischen Positionen in dem Aluminiumoxidgitter.
EP14702755.1A 2013-01-09 2014-01-08 Verfahren zur hydrierung von carbonsulfide unter verwendung von einem sulfidierten kobalt- und molybdän-katalysator auf einem aluminiumoxid-träger Active EP2943556B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL14702755T PL2943556T3 (pl) 2013-01-09 2014-01-08 Sposób uwodorniania siarczku węgla z użyciem katalizatora siarczkowego kobaltowo-molibdenowego na nośniku z tlenku glinu

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102013000173 2013-01-09
DE102013010473 2013-06-03
DE201310009885 DE102013009885A1 (de) 2013-01-09 2013-06-06 Verfahren zur Herstellung von Synthesegas aus Steinkohle
PCT/EP2014/050190 WO2014108423A1 (en) 2013-01-09 2014-01-08 Process for the production of synthesis gas from hard coal

Publications (2)

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EP2943556A1 EP2943556A1 (de) 2015-11-18
EP2943556B1 true EP2943556B1 (de) 2020-04-08

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

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KR101641045B1 (ko) * 2015-09-30 2016-07-20 주식회사 포스코 강판의 산화 방지층 형성장치 및 방법

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Also Published As

Publication number Publication date
EP2943556A1 (de) 2015-11-18
PL2943556T3 (pl) 2020-09-21
WO2014108423A1 (en) 2014-07-17
CN104903428B (zh) 2019-01-18
CN104903428A (zh) 2015-09-09
KR20150103738A (ko) 2015-09-11
JP2016505695A (ja) 2016-02-25
KR102055036B1 (ko) 2019-12-11

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