WO2010054948A2 - Gazéification du charbon avec catalyse intégrée - Google Patents

Gazéification du charbon avec catalyse intégrée Download PDF

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Publication number
WO2010054948A2
WO2010054948A2 PCT/EP2009/064471 EP2009064471W WO2010054948A2 WO 2010054948 A2 WO2010054948 A2 WO 2010054948A2 EP 2009064471 W EP2009064471 W EP 2009064471W WO 2010054948 A2 WO2010054948 A2 WO 2010054948A2
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WO
WIPO (PCT)
Prior art keywords
transition metal
synthesis gas
metal compound
gasification
conversion
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.)
Ceased
Application number
PCT/EP2009/064471
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German (de)
English (en)
Other versions
WO2010054948A3 (fr
Inventor
Alexander Weck
Ekkehard Schwab
Jochen Steiner
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2010054948A2 publication Critical patent/WO2010054948A2/fr
Publication of WO2010054948A3 publication Critical patent/WO2010054948A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/466—Entrained flow processes
    • 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
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts

Definitions

  • the invention relates to a process for the production of synthesis gas with the addition of volatile transition metal compounds by gasification of organic substances and subsequent conversion of the synthesis gas.
  • the synthesis gas obtained during the gasification of organic substances has a hydrogen / carbon monoxide ratio (H 2 / CO ratio) which is unsuitable for use in most other synthesis reactions.
  • H 2 / CO ratio hydrogen / carbon monoxide ratio
  • synthesis gases having an H 2 / CO ratio of 3: 1 to 0.8: 1 are obtained.
  • Conversion equilibrium refers to the equilibrium reaction between carbon monoxide and water on one side and carbon dioxide and hydrogen on the other side. This reaction is slightly exothermic towards carbon dioxide and hydrogen and is also referred to as a water gas reaction.
  • the synthesis gas must first be subjected to elaborate purification steps, since the minor constituents the downstream conversion reaction by deposits of condensable secondary constituents or by catalyst poisoning affect. These include the separation of hydrogen sulphide and the condensable secondary constituents as well as the dedusting of the synthesis gas. For this purpose, it is necessary to cool the escaping synthesis gas to temperatures of below 100 0 C to separate the condensable secondary components.
  • the dedusting is usually done by an upstream dry dedusting followed by a wet dedusting.
  • Secondary constituents are, for example, molten and condensable constituents, such as condensable aliphatic and aromatic hydrocarbons and inorganic substances, such as ash, water, and non-condensable aliphatic and aromatic hydrocarbons, carbon dioxide and unconverted residual carbon.
  • the purified synthesis gas must also be reheated.
  • the entire process cycle therefore includes the steps of heating for the gasification reaction, cooling for purification, and then reheating for the conversion reaction. With these temperature changes, an energy loss is necessarily connected.
  • the object of the present invention is to provide a process for the production of synthesis gas having an H 2 / CO ratio of> 1: 1, which is technically and economically easy to carry out and overcomes the disadvantages of the prior art described above and without intermediate Abküh - Lungs- and cleaning steps requires.
  • the object is achieved by a process for the production of synthesis gas comprising the steps
  • the method according to the invention overcomes the disadvantages of the prior art described above.
  • the inventive method is technically and economically easy to carry out and comes without intermediate cooling and cleaning steps. While in the process described in the prior art, the conversion of the synthesis gas is carried out only after extensive purification steps in a downstream reactor with a fixed catalyst, the catalyst formation in the process according to the invention in step A) and / or B) takes place in situ from a volatile transition metal compound , so that consuming intermediate stored cleaning steps can be saved. The conversion reaction can therefore be carried out immediately after the formation of the synthesis gas.
  • step A) of the process according to the invention all gasifiable organic substances can be used.
  • examples include fossil fuels such as lignite, hard coal (coal, coal, anthracite, coke), pitch coal, Shungitkohle, Wealdenkohle, petroleum, petroleum residues and natural gas, renewable biomass such as wood and peat called. It is also possible to use waste and garbage in the gasification reaction.
  • lignite coal (fumed coal, simmering coal, anthracite coal, coke), pitch coal, shungite coal and whale sink are used as the organic substance.
  • lignite coal (fumed coal, simmering coal, anthracite coal, coke), pitch coal, shungite coal and whale sink are used as the organic substance.
  • brown and hard coal is particularly preferred.
  • the gasification of the organic material in step A) to form synthesis gas can be carried out in any gasification reactor.
  • Gasification reactors are also referred to as carburetors. These are known to the person skilled in the art, for example, entrained-flow gasifiers such as the Shell, Texaco or Prenflo carburetor can be used. be set.
  • fluidized bed gasifiers such as the Winkler gasifier can be used, in which finely divided solids such as lignite are gasified.
  • the Lurgi fixed bed gasifier for coal gasification and the Koppers Totzek carburetor or carburetor are suitable for the steam reforming technology work.
  • Preferred carburettor types are fly-by-gas carburetors such as Shell, Siemens, Texaco or Prenflo carburettors.
  • the gasification of the organic substance takes place under known conditions known to the person skilled in the art (step A) within the gasification zone of the gasification reactor.
  • the gasification zone is the part of the reactor in which the formation of synthesis gas from the organic substances to be gasified takes place within the gasification reactor.
  • the process according to the invention is carried out with the addition of at least one volatile transition metal compound.
  • the addition of the volatile transition metal compound can be carried out in step A).
  • Suitable volatile transition metal compounds are compounds which, under the reaction conditions in step A), form a catalyst which catalyzes the water gas shift reaction (water gas shift active catalyst (WGS catalyst)).
  • WGS catalyst water gas shift active catalyst
  • the WGS catalyst is preferably formed in finely particulate form.
  • the resulting catalyst particles preferably have sizes of less than 50 ⁇ m.
  • Volatile transition metal compounds in the context of the present invention are compounds which are present under the reaction temperatures in step A) in the gaseous state.
  • Suitable transition metal compounds are, for example, transition metal carbonyls of groups V to VIII of the Periodic Table of the Elements, ie carbonyls of vanadium, niobium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, or mixtures thereof.
  • Preferred transition metal carbonyls are vanadium hexacarbonyl V (CO) 6, chromium hexacarbonyl Cr (CO) 6, molybdenum hexacarbonyl Mo (CO) 6, tungsten hexacarbonyl W (CO) 6 , dimangandecacarbonyl Mn 2 (CO) i O , iron pentacarbonyl Fe (CO) 5 , dieisenno - Nacarbonyl Fe 2 (CO) 9 , triene dodecacarbonyl Fe 3 (CO) i 2 , ruthenium pentacarbonyl Ru (CO) 5 , triruthenium dodecacarbonyl Ru 3 (CO) i 2 , hexaruthenium hexadecacarbonyl Ru 6 (CO) 16 , dicobalt octacarbonyl Co 2 (CO) 8 Tetracobalt dodecacarbonyl Co 4 (CO) i 2 , hexacobalt he
  • transition metal carbonyls of iron such as iron pentacarbonyl Fe (CO) 5 , diisone nonacarbonyl Fe 2 (CO) 9 , triene dodecacarbonyl Fe 3 (CO) 2 and mixtures thereof.
  • iron pentacarbonyl Fe (CO) 5 is particularly preferred.
  • the volatile transition metal compounds form a WGS catalyst under the reaction conditions in step A).
  • WGS catalysts are meant those compounds which catalyze the equilibrium reaction between carbon monoxide and water vapor to carbon dioxide and hydrogen. Such catalysts are also referred to as CO shift catalysts or water gas shift catalysts. It is believed that under the reaction conditions in step A) the transition metal compounds are converted to the corresponding elemental transition metals or their oxides which catalyze the water gas shift reaction.
  • the WGS catalysts are obtained in fine particulate form.
  • step B) of the process according to the invention the synthesis gas formed in step A) is subjected to a conversion. This preferably takes place without intervening purification or work-up steps.
  • the synthesis gas formed in the gasification zone is fed without intermediate purification or work-up steps to a conversion zone in which the conversion of carbon monoxide and water vapor to carbon dioxide and hydrogen takes place.
  • an indirect heat exchanger preferably for steam generation, may be connected between the gasification zone and the conversion zone.
  • the conversion zone is designed so that, adapted to the design of the gasifier, the residence times of the synthesis gas from step A) in the conversion zone can be adjusted between 0.1 to 60 s. Preferred are residence times in the range of 1 to 10 s.
  • the conversion zone has a first region into which the crude synthesis gas formed in step A) is introduced and converted. Further, the conversion zone optionally has a water or steam supply, which is designed so that the water can be injected finely distributed.
  • the water or steam supply is preferably in the gasification zone, but the water or steam feeds can also be distributed over the conversion zone.
  • the total amount of water used in the gasifier and / or in the conversion zone is between 0.1 and 1 kg, preferably between 0.2 and 0.5 kg, in each case per kg of carbon present in the organic substance, which is used in the gasifier becomes.
  • the synthesis gas and the steam, or the injected water flow in cocurrent.
  • the conversion zone has a second region in which the gas mixture can be further cooled.
  • the cooling is carried out by external cooling or by supplying water or low-temperature steam in this area by one or more feeds, the water is preferably injected.
  • the conversion zone is preferably constructed very simply and can be designed, for example, as a simple tube.
  • the gasification and conversion zones are in the same reactor, i. Step A) and Step B) are carried out successively in the same reactor, preferably in the gasification reactor.
  • the process according to the invention is carried out with the addition of at least one volatile transition metal compound.
  • the addition of the volatile transition metal compounds may be carried out in step B) instead of the addition of a transition metal compound in step A) or in addition to the addition of a transition metal compound in step A). It is also possible that the addition of the volatile transition metal compound takes place only in step A).
  • Suitable volatile transition metal compounds are compounds which under the reaction conditions in step B) form a catalyst which catalyzes the water gas shift reaction.
  • the WGS catalyst is preferably formed in finely particulate form. Preferably, the resulting catalyst particles are smaller than 50 microns.
  • Volatile transition metal compounds in the context of the present invention are compounds which form a WGS catalyst under the reaction temperatures in step B). Suitable transition metal compounds for the addition in step B) are described above under step A).
  • the WGS catalysts are transported together with the synthesis gas and can, if desired, be separated off from the synthesis gas in step C) by customary workup and / or purification steps known to those skilled in the art.
  • Preferred is a method in which the water gas shift-active catalyst is discharged from the gasification reactor and / or the conversion zone and in step C) is separated from the converted synthesis gas.
  • Corresponding purification steps are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry; Chapter “Gasproduction”, paragraphs 1.5 to 1.5.2 (pages 18-20) and 4.3 to 5.1.6 (pages 59-82), "Online Edition", 2007, Wiley-VCH Verlag GmbH & Co.KG aA , Weinheim.
  • the solid by-products are not contaminated by additional toxic substances so that the solid by-products can be readily disposed of.
  • these by-products are used in road construction as well as concrete and cement substitutes.
  • formation of the WGS catalyst from the volatile transition metal compounds carbon monoxide, which is reacted in step B) with water to hydrogen.
  • the volatile transition metal compounds are added in at least one of steps A) and / or B).
  • the volatile transition metal compounds are added in quantities of not more than 100 ppm, preferably in amounts of from 0.1 to 80 ppm, more preferably in amounts of from 1 to 50 ppm, and in particular in amounts of from 1 to 20 ppm (in each case based on that in step A) formed synthesis gas). If the addition of the transition metal compound in step A) (variant I), the volatile transition metal compound is introduced into the gasification reactor.
  • the manner of addition is not problematic and depends on the type of process used. Thus, the addition, in the event that gaseous organic substances are gasified, be supplied together with the gaseous substances.
  • liquid or solid organic substances are supplied to the reactor by means of a carrier gas
  • the addition of the volatile transition metal compound takes place through a separate feed line.
  • the separate feed of the liquid transition metal compound is, of course, also possible in the case of the use of gaseous organic substances or liquid or solid organic substances which are fed to the reactor with the aid of a carrier gas.
  • the volatile transition metal compound in step B) (variant II).
  • the volatile transition metal compound is metered into the synthesis gas leaving the reactor or fed directly into the conversion zone.
  • a volatile transition metal compound is added in step A) and in step B), wherein the addition can be carried out according to the methods described for variants I and II.
  • an iron carbonyl is used as the transition metal compound.
  • Fe (CO) 5 iron pentacarbonyl is used as the transition metal compound.
  • the iron carbonyl according to variant I is preferably added to the gasification reactor in step A). From the iron carbonyl is formed in the gasification reactor, a WGS catalyst containing elemental iron and / or iron oxides. The WGS catalyst thereby falls in fine particulate form, so that it is discharged together with the synthesis gas from the gasification reactor. The WGS catalyst generated in the gasifier is then introduced into the above-described conversion zone together with the synthesis gas.
  • This is preferably constructed very simple and can be formed for example as a simple tube.
  • the generated in the gasification reactor WGS catalyst catalyses in the conversion reactor, the adjustment of the equilibrium of the water gas shift reaction.
  • the equilibrium is in the temperature range of the effluent from the gasifier synthesis gas, ie at temperatures in the range of 1200 - 1600 0 C on the side of carbon monoxide and water. With decreasing temperature, the equilibrium shifts to the side of carbon dioxide and hydrogen.
  • the rate of equilibration so that from temperatures below 800 0 C, the equilibration dwell times requires that complicate economic operation of the conversion reactor.
  • the WGS catalyst is distributed in fine particulate form in the synthesis gas.
  • the equilibrium of the water-gas shift reaction at temperatures less than 800 0 C in a sufficient overall speed.
  • the process according to the invention makes it possible to cool the synthesis gas containing the WGS catalyst in the conversion reactor in such a way that the water gas shift reaction conversion curve follows the cooling curve within the residence time zone.
  • the syngas containing the WGS catalyst in finely particulate form is cooled rapidly to temperatures ⁇ 600 ° C. at the outlet of the conversion zone.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Industrial Gases (AREA)

Abstract

L'invention concerne un procédé de fabrication de gaz de synthèse comportant les étapes suivantes A) formation de gaz de synthèse par gazéification de matières organiques, B) conversion du gaz de synthèse de l'étape A), et C) éventuellement lavage du gaz de synthèse converti de l'étape B), au moins un composé volatil de métaux de transition étant additionné au procédé dans au moins une des étapes A) et B).
PCT/EP2009/064471 2008-11-12 2009-11-02 Gazéification du charbon avec catalyse intégrée Ceased WO2010054948A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP08168940.8 2008-11-12
EP08168940 2008-11-12

Publications (2)

Publication Number Publication Date
WO2010054948A2 true WO2010054948A2 (fr) 2010-05-20
WO2010054948A3 WO2010054948A3 (fr) 2010-07-29

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PCT/EP2009/064471 Ceased WO2010054948A2 (fr) 2008-11-12 2009-11-02 Gazéification du charbon avec catalyse intégrée

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014183847A1 (fr) * 2013-05-16 2014-11-20 Ecoloop Gmbh Procédé de purification de gaz de synthèse

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989480A (en) * 1974-09-05 1976-11-02 The United States Of America As Represented By The United States Energy Research And Development Administration Decomposition of carbohydrate wastes
JPS51111205A (en) * 1975-03-26 1976-10-01 Univ Tohoku Method of gasification accompanied by liquid ammonia treatment of the carbonnaceous substance
JPS581790A (ja) * 1981-06-26 1983-01-07 Yasukatsu Tamai 石炭の接触ガス化方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014183847A1 (fr) * 2013-05-16 2014-11-20 Ecoloop Gmbh Procédé de purification de gaz de synthèse

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