EP2193184A1 - Procédé de purification du gaz brut d'une gazéification de combustible solide - Google Patents

Procédé de purification du gaz brut d'une gazéification de combustible solide

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Publication number
EP2193184A1
EP2193184A1 EP08802648A EP08802648A EP2193184A1 EP 2193184 A1 EP2193184 A1 EP 2193184A1 EP 08802648 A EP08802648 A EP 08802648A EP 08802648 A EP08802648 A EP 08802648A EP 2193184 A1 EP2193184 A1 EP 2193184A1
Authority
EP
European Patent Office
Prior art keywords
sorbent
solid
gas
raw gas
solids
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Withdrawn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
EP08802648A
Other languages
German (de)
English (en)
Inventor
Johannes Kowoll
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 EP2193184A1 publication Critical patent/EP2193184A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/06—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 adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/08—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 adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds according to the "moving bed" method
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • B01D53/06—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 adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10—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 adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • 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
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • 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
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • 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
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
    • 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
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
    • 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
    • C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
    • C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
    • C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
    • C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
    • 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
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0073—Selection or treatment of the reducing gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/20—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2047—Hydrofluoric acid
    • 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
    • B01D2257/302—Sulfur oxides
    • 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
    • B01D2257/308—Carbonoxysulfide COS
    • 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
    • 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
    • C10J2300/0903—Feed preparation
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • 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
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0943—Coke
    • 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
    • C10J2300/0996—Calcium-containing inorganic materials, e.g. lime
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • 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
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Definitions

  • the invention relates to a method for purifying a dust-containing gas, which is prepared in a gasification reaction of solid carbonaceous materials by reaction with an oxygen or water vapor and oxygen-containing gas at elevated temperature, wherein a crude gas is obtained, mainly from carbon monoxide and hydrogen, and the actual purification step is carried out by adding a solid sorbent to the hot gas stream immediately after production.
  • the resulting purified gas is a synthesis gas and is used for chemical syntheses, for hydrogen production and for the production of metals from metal ores by the direct reduction process.
  • the preparation of the raw gas required for this purpose is usually carried out at a temperature of 1200 to 2500 0 C in a suitable reactor.
  • a suitable reactor There are several types and embodiments for this purpose.
  • the solid carbonaceous material is placed in a reaction vessel equipped with feeders for the fuel and the oxygen-containing reaction gas.
  • the raw gas and solid impurities which usually consist of ash or slag depending on the composition of the fuel, are produced in a chemical reaction.
  • the crude gas and solid impurities can leave the reactor by separate reaction guides. The raw gas obtained then leads even smaller amounts of solid and liquefied accompanying substances with it.
  • the raw gas is carried out of the reactor and passed into a reaction space, where it is mixed to dissipate the high internal energy with colder gas and cooled down.
  • This process is also called quenching process.
  • Conventional apparatuses are those in which the raw gas is passed into a reactor chamber directed downwards or upwards, also called a quenching space, for mixing with the colder gas and mixed with the gas.
  • the liquefied slag particles contained therein solidify and are continued with the raw gas in the form of slag particles.
  • the cleaning process depending on the application of the synthesis gas may be different.
  • the raw gas exported from the quench chamber has, depending on the starting material and manufacturing process, a temperature of 600 ° C to 1000 0 C.
  • the gas is cooled and purified for many purposes.
  • this is energy intensive and associated with high investment and running costs, especially if the synthesis gas for the subsequent use needs to be reheated.
  • An example is the production of iron by the direct reduction process, in which a synthesis gas, which comprises predominantly hydrogen and carbon monoxide, is used for the production of pig iron by reduction of iron ore.
  • the synthesis gas must be used at high temperatures to effectively reduce the iron ore.
  • the production of iron by the direct reduction process is often carried out, since this manufacturing method also allows the operation of small plants, which can thus produce at low cost. Even chemical syntheses often require a hot syngas.
  • the addition of limestone has the consequence that the flow temperature of most slags is significantly lowered.
  • the flow temperature of slags in ordinary gasification reactions may be 1200 ° C or above.
  • the flow temperature drops to values of 500 to 600 0 C.
  • the slag solidifies much later in the process and can be easily discharged.
  • the cleaning of the slagging gasifier can therefore be carried out at much prolonged intervals. In this procedure, the dedusting of the raw gas must be carried out before the addition of the sorbent and before the sintering of the slag to avoid clogging of the dust filter.
  • the crude gas obtained is usually first cooled to 1000 to 600 0 C, then dedusted and freed in a subsequent step of sulfur compounds and halogens.
  • the invention has for its object to provide a coal gasification process available, which manages without cooling the quenched gas and still provides a largely by-products liberated synthesis gas.
  • the synthesized gas produced should be able to be made available at a high temperature, without having to make use of further process steps of cooling, cleaning and reheating.
  • the cleaning and absorption of pollutants in the raw gas should be done easily and without energy-intensive cooling.
  • the synthesis gas thus produced should also be as free as possible of sulfur compounds.
  • the object is achieved in that the crude gas obtained from the coal gasification process after the gasification process and during or immediately after the process of quenching a solid absorbent for acidic and sulfur-containing impurities is added.
  • the method is particularly suitable for a coal gasification process in which the raw gas and the slag are carried out separately from the gasification reaction vessel, so that the raw gas obtained from the outset contains only slightly admixed solid or liquefied foreign components.
  • the added absorbent can be any of the solids that are preferred to be basic in order to obtain the desired effect. In order to allow a better chemical absorption of non-acid sulfur-containing gases from the raw gas obtained, metal salts may be added to the basic absorbent, in particular iron ores to develop the desired effect.
  • Claimed is in particular a process for the preparation and purification of a raw gas with synthesis gas character, wherein • the raw gas is produced by gasification of a solid carbonaceous material with an oxygen-containing or water vapor and oxygen-containing gas in a suitable reactor, wherein
  • Fuel comprises acidic or basic or sulfur-containing or halogen-containing gaseous pollutants, and •
  • the raw gas may also include solid, ash or slag-containing substances, where
  • the raw gas is passed from the gasification reactor in a downwardly or upwardly leading reaction space, where a colder gas or a vaporized liquid or a liquid is added, whereby the raw gas can react to dissipate the high internal energy, and which is characterized that
  • the dusty raw gas is added during or after the addition of the colder gas or vaporized liquid for cleaning with a solid sorbent, which is entrained with the raw gas in the gas flow direction and transported and reacts with the acidic or basic or sulfur-containing or halogen-containing substances within a short time and converting these substances into a solid and bound form.
  • the sorbent is added together with the gas for cooling.
  • a suitable addition point for this is the space immediately behind the outlet opening of the gasification reactor.
  • the addition is advantageously in the form of a smoke, wherein smoke denotes a heterogeneous mixture of solid and gas.
  • the smoke is formed by a mixture of solid sorbent and the gas or steam to cool the raw gas.
  • the smoke is introduced by way of example through an opening at the edge of the carburetor exit into the gas stream, whereby the smoke is entrained with the raw gas stream and the sorbent contained therein can react with the pollutants contained in the raw gas.
  • the reaction of the sorbent with the steam is usually fast.
  • By swirling the smoke is distributed throughout the gas stream.
  • By adding in the edge area of the cool smoke shields the surrounding wall against the radiant heat of the raw gas obtained. This minimizes the heat loss of the raw gas.
  • the sorbent is added separately from the gas or steam for cooling the raw gas, with separate therefor Feeding devices are provided. Suitable addition points for this purpose is also the space immediately behind the outlet opening of the gasification reactor. The smoke then forms only when the sorbent is mixed with the gases.
  • the delivery of the solid sorbent into the gas is preferably carried out pneumatically in all cases. But it can be performed arbitrarily, for example by a conveyor belt.
  • Suitable solid, carbonaceous fuels for the gasification reaction are all solid, carbonaceous materials that can form a carbon monoxide and hydrogen-containing crude gas with an oxygen or water vapor and oxygen-containing gas by a gasification reaction.
  • the fuel is preferably coal or petroleum coke. It is also possible to use a preferably pretreated, cellulose-containing biological fuel. Examples include wood or pressed plant material.
  • the supplied reaction gas usually comprises oxygen or water vapor and oxygen. But it may also contain other gases, carbon dioxide being exemplified here.
  • the gasification reaction generally produces a crude gas which essentially contains carbon monoxide, hydrogen or else carbon dioxide and which is suitable for synthesis gas production.
  • the crude gas obtained is mixed with a colder medium to dissipate the high internal energy.
  • Typical media for carrying out the quenching process are cooled synthesis gas, recycled process gases, steam, nitrogen or carbon dioxide.
  • the crude gas thus obtained has a temperature of 600 to 1000 0 C at a pressure of 0.3 to 7 MPa in a typical embodiment of the invention after mixing with the quench gas. At this temperature, the sorbent is added to the crude gas obtained, so that the sorption process can develop optimal activity.
  • the reaction time of the absorption process is short and is usually less than 1 s.
  • the sorbent should have a solid and fine-grained, possibly also powdery form for the addition.
  • a preferred grain size on addition is 1 to 0.01 mm, and ideally 0.1 to 0.03 mm.
  • the sorbent is then injected with a delivery gas.
  • the sorbent is mixed with the quench medium or the foreign gas prior to addition by suitable devices and then injected with the medium to be pumped into the quench chamber.
  • the sorbent is added directly behind the quench to the cooled raw gas.
  • the addition of sorbent to the cooled raw gas is particularly advantageous if the proportion of impurities in the raw gas is lower, since then a comparatively shorter reaction distance is needed.
  • the sorbent contains compounds which react quickly and intensively with the added acidic and sulfur-containing constituents.
  • examples of such compounds are calcium and magnesium carbonates as mono- or polybasic salts, dolomite or limestone being mentioned as natural representatives of these salts.
  • the salts can be used in natural or calcined form.
  • transition-containing components can be added to the sorbents.
  • transition metal compounds are zinc or iron salts, such as zinc or iron ore.
  • a preferred transition metal additive for absorbing the sulfur compounds is iron oxide or iron ore.
  • solid, oxidizing substances to the sorbent which react with the sulfidic constituents to form sulfates and thereby convert them into insoluble solids.
  • calcium sulfide can be converted into easily separable and recoverable calcium sulfate.
  • solid oxidizing sorbents are peroxides or persulfates.
  • quenching medium may not react with the sorbent. If the sorbent is added separately from the quench medium, the delivery medium must be inert to the sorbent.
  • Typical acidic or basic gases from the gasification process are hydrogen sulfide (H 2 S), carbon dioxide sulfide (COS), sulfur dioxide (SO 2 ), hydrogen chloride (HCl) or hydrogen fluoride (HF).
  • H 2 S hydrogen sulfide
  • COS carbon dioxide sulfide
  • SO 2 sulfur dioxide
  • HCl hydrogen chloride
  • HF hydrogen fluoride
  • the basic sorbent reacts with the acidic constituents to form calcium or magnesium salts.
  • the transition metal-containing salts react with the hydrogen sulfide to sulfides or hydrogen sulfides.
  • the crude gas is passed through a particle bed which contains the sorbent in particulate form, for example as pellets.
  • the bed of particles must be periodically cleaned or regenerated to purify it from the fly ash ingredients or cooled slag constituents trapped in the particle bed.
  • the particles in the particle bed should have a larger average particle size than the fly ash.
  • the particles in the particle bed have an average particle size greater than 0.2 mm.
  • the synthesis gas prepared and purified according to the invention can be used for all purposes in which a purified synthesis gas is needed. It is preferably used in the direct reduction of metal ores. Possible applications are also the synthesis of chemicals or the provision of hydrogen. A subsequent process which makes use of a synthesis gas prepared and purified according to the invention is expressly claimed.
  • the crude gas obtained with the reacted sorbent without a further purification step.
  • examples include iron production processes by direct reduction starting from a low-sulfur iron, especially when the proportion of sorbent in the raw gas is low.
  • the resulting synthesis or generator gas is required in a substantially freed state from solids.
  • the solids thus obtained must be removed from the bound, absorbed pollutants by a further process step from the raw gas.
  • filter devices can be used which are customary for the solids filtration of gases.
  • the filter device should be designed such that the temperature of the gas obtained is only slightly changed by the solids purification process.
  • the resulting solid contains the loaded sorbent and the ash constituents entrained in the coal gasification process and solidified slag particles.
  • the process step of solids deposition takes place after the quenching process and after the addition of the sorbent. It is also possible to carry out a solid separation several times in the course of the process. This is particularly useful if the raw gas is heavily solids laden after production by coal gasification. For this one can perform a solid separation after the coal gasification reaction and another after the addition of the sorbent. In general, however, especially when using advantageous coal gasification reactors, only a solid separation after the process of sorption is necessary.
  • the sorbent is added directly to the process of solids separation. This is particularly advantageous if the entrained pollutants to be absorbed in the raw gas are solid or solidified nature. Then the sorption takes place in the solids separator and the sorbed components are discharged from the process with the other constituents. By adding the sorbent, the sinterability of the fly ash is lowered, which allows separators to be used at a significantly higher temperature.
  • the separated solid is usually separated after the discharge in its constituents.
  • various methods exist such as the use of classifying devices.
  • the solid or solidified by-products obtained in the form of ash or slag and the reacted sorbent or a predominantly the reacted sorbent particle fraction.
  • the ash and slag can be recycled or disposed of.
  • the sorbent may be reused by suitable regeneration procedures. Examples of suitable regeneration processes are washing, drying and calcining. Suitable steps for the regeneration of the solid sorbent may also be hydrogenation, wherein the bound sulfur can be removed as hydrogen sulfide.
  • the regeneration of the basic sorbent can also be carried out by passing a water vapor or oxygen-containing gas.
  • the thus regenerated sorbent can then be recycled back into a process for re-sorption. It is also possible to reuse the sorbent in the coal gasification reaction. For this purpose, it is either added directly to the coal gasification reactor or pretreatment for the fuel. For this purpose, the sorbent is finely ground, for example, with the fuel or dried. But it is also possible to give the sorbent in a subsequent process.
  • the flow temperature of most slags is lowered, whereby the gasification or smelting temperature can be reduced and the efficiency of the gasification or smelting is increased.
  • the sorption material can act as slag remover after the regeneration during iron production and can favorably influence the smelting process.
  • the subsequent process can itself produce a gas laden with solids. This is advantageously passed again into a solids separator and cleaned. The resulting solid may be combined with the separated solid from the coal gasification reaction and also fed to the stated purposes.
  • the loading of the reacted sorbent at a correct dosage is such that regeneration is inevitable for reuse.
  • the loading of the sorbent for example, when using a clean coal only small, then a large part can be reused without further regeneration.
  • the use of the sorbent is then supplied for the same purposes as would be the case with regeneration, for example for reuse in the coal gasification process or for use in a sequential process.
  • the sorbent may also be ground or dried prior to reuse.
  • a device which is suitable for carrying out the process according to the invention is also claimed. Claimed is in particular a device for carrying out the method according to the invention, wherein
  • It consists of a refractory reaction vessel which is suitable for the calcination of solid, carbon-containing fuels by reaction with an oxygen or water vapor and oxygen-containing gas, and
  • This reaction vessel is followed by a reaction space, which is equipped with feeders for a solid sorbent and gaseous or vaporous substances for cooling the raw gas, and
  • the solid sorbent and gaseous and vaporous material supply means are designed in the form of at least one opening which opens outwards in the direction of the gas stream and comprises means for pressurizing the sorbent in admixture with the cooling gas under pressure into the gas stream Promote and initiate product gases.
  • the opening for adding the solid sorbent is designed such that an addition of the sorbent into the gas stream of the raw gas takes place in the flow direction. If the addition of the sorbent together with the raw gas in the form of a smoke, so the opening is also designed so that an addition of the smoke takes place in the flow direction.
  • the shape of the opening on the carburetor wall side preferably prefers a slot, but it can also be a collar or an annular nozzle.
  • the shaping can be arbitrary, in order to allow a feed of the roughness or of the sorbent into the raw gas stream in the flow direction.
  • the device according to the invention also includes, by way of example, atomizing devices, screw conveyors or gas pressure pumps.
  • the claimed device also includes a gasification reactor, which is equipped with at least one opening for separate discharge of the solid reaction product and at least one further opening for separate discharge of the gaseous reaction product.
  • a gasification reactor which is equipped with at least one opening for separate discharge of the solid reaction product and at least one further opening for separate discharge of the gaseous reaction product.
  • the gasification reactor in a preferred embodiment, includes a separate orifice for carrying out the slag and other resulting solids, which are then sent for further use or disposal.
  • the gasification reactor also contains a separate opening for the execution of the raw gas, whereby special devices ensure that the raw gas contains as few slag and ash constituents as possible.
  • part of a device according to the invention may be mills, dryers or fluidized bed devices for fuel pretreatment.
  • reaction space which serves to mix the raw gas with a quench medium to dissipate the high internal energy after the gasification process.
  • nozzles for introducing the quenching medium and the sorbent are introduced into the reaction space. If the sorbent is fed in the quench space after the addition of the quench medium, the quench space contains additional injection or introduction devices for feeding the sorbent.
  • the nozzles are advantageously provided with a mixing device for the addition of the solid sorbent in the gas or vapor stream.
  • the nozzles are equipped in front of the mixing device with a suitable sorbent feeding means. These may be, for example, screw conveyors or pneumatic propulsion conveyors.
  • a suitable sorbent feeding means may be, for example, screw conveyors or pneumatic propulsion conveyors.
  • sorbent nozzle or conveyors for the sorbent in the process flow also be mounted behind the quench or in a downstream solids separator.
  • part of a device according to the invention may be mills, dryers or fluidized beds for sorbent pretreatment.
  • the apparatus includes a solids separator, into which the raw gas passes after the reaction with the sorbents and in which the solid components are filtered out of the gas.
  • the apparatus may contain other apparatus which allow, for example, a solid treatment of the separated solids. These include, for example, classifying devices such as sifter or sifter devices which can separate ash or slag constituents from the abreacted sorbent.
  • Suitable Feststoffabscheidervoriquesen are in particular centrifugal, also called cyclones.
  • suitable solids separator devices may also be temperature-resistant cloth filters, ceramic filter elements, filter candles or an electric deduster.
  • the process step of the solids separation usually takes place directly behind the quenching and sorption process. It is also possible to give the solids-laden, hot raw gas via pipelines in the process step of the solids separation. It is also possible to carry out the solids separation by filtration. This process step is preferably carried out before the addition of the sorbent, since the sintering temperature of the slag otherwise drops and this clogs the filtration devices.
  • the apparatus may also contain apparatuses which allow regeneration of the sorbent after separation of the solid from the sorbent.
  • apparatuses which allow regeneration of the sorbent after separation of the solid from the sorbent.
  • These include, for example, washing kettles or drying and quenching facilities. These device components are usually located in the process flow behind the quench and behind the solids separation.
  • the regenerated sorbent is returned in a preferred embodiment of the invention by suitable devices back into the process of coal gasification. This can be done at the point of fuel pretreatment or directly into the coal gasification reactor.
  • the device for carrying out the method according to the invention may also contain devices which allow further use of the sorbent in a subsequent process. If the subsequent process in turn produces a gas laden with solids, then the device according to the invention can also contain apparatuses for separating solids and recycling the separated solid.
  • the gas obtained from the quenching process before or after the separation of solids it is possible to subject the gas obtained from the quenching process before or after the separation of solids to a washing process with a washing liquid.
  • the crude gas provided with solids or laden sorbent may preferably be washed with water to wash out loaded sorbent or solid from the raw gas.
  • washing liquids are ethanolamines or alkylated polyalkylene glycols.
  • the invention enables efficient and rapid purification of a synthesis or generator gas originating from a coal gasification process by adding a solid sorbent immediately after the coal gasification reaction.
  • a rapid reaction of the added sorbent with raw gases containing acidic or sulfur-containing or halogen-containing substances or a combination of these substances these interfering substances can be removed quickly and efficiently from the raw gas. This eliminates the energy and time consuming associated with a cooling washing process and the subsequent reheating of the gas.
  • the resulting sorbent can be inexpensively used or regenerated.
  • FIG. 1 shows a process flow according to the invention for carrying out a process with the addition of a solid sorbent to a crude gas stream of a gasification reaction.
  • FIG. 2 shows a device according to the invention for adding a solid sorbent to the crude gas stream of a gasification reaction.
  • FIG.1 shows a greatly simplified scheme for performing the method with the addition of the sorbent to the raw gas stream in the mixing chamber during quenching.
  • the solid carbonaceous fuel (1) is placed in a device for grinding and drying (2) to prepare for the gasification process.
  • the thereby resulting small-particle or fine-grained fuel is added via suitable conveyors (2a) in a gasification reactor.
  • a further supply line and devices for spraying an oxygen or water vapor and oxygen-containing reaction gas (3) is introduced into the gasification reactor (4), in which the actual gasification reaction takes place for the production of synthesis gas.
  • the reactor (4) is equipped in an advantageous embodiment with a separate discharge device for solid and liquefied gasification products, which allow the resulting in the gasification process slag with the other solid components separately from the raw gas from the reactor (5).
  • the crude gas obtained is passed from the reactor in vertically downwardly directed flow into a mixing or quenching chamber (6). It is also possible to constructively connect the mixing or quenching chamber to the reactor. In the quench the hot raw gas is provided to dissipate the high internal energy with a lower tempered foreign gas (7).
  • the sorbent can be mixed again in the pretreatment with the fuel (13a) and added to the gasification reaction (2a). If the sorbent is suitable, it is also possible to add it directly to the gasification reactor (13b).
  • the dedusted raw gas (12) of the coal gasification reaction is passed to the subsequent process (17). There it is used in various processes. It is possible to use the loaded sorbent depending on the nature of the subsequent process (16). During the follow-up process, some of the gas is consumed while the sorptive onsffen changes only little. The remainder of the solids or dust-containing gas (18) is subjected to another purification by solids separation (19). The resulting solid can be given depending on the nature and loading in the process of solid regeneration (19a).
  • the sorbent-laden solid is discharged after use in the subsequent process (20).
  • the fresh sorbent (8) is added immediately after the mixing or quenching in the process or placed in the solids separator, the rest of the plant design changes little.
  • FIG. Fig. 2 shows the exit opening of a gasification reactor (4a) which carries out the raw gas (21) in an upward direction from the gasification reactor.
  • the raw gas passes through a constriction (4b), which increases the velocity of the gas stream.
  • Behind the constriction is an opening (23) through which the solid sorbent (8) is introduced together with an inert gas in the form of a smoke (22).
  • the smoke is entrained with the raw gas (9) and thereby performs a cleaning effect.
  • the smoke is entrained with the purified raw gas along the pipe to Rohgasausment (24).
  • Gasification reactor a outlet opening of a gasification reactor b constriction at the outlet opening of the gasification reactor

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Abstract

L'invention concerne un procédé et un dispositif de production et de purification d'un gaz brut pour la production de gaz de synthèse à partir d'un combustible solide carboné par une réaction de gazéification du carbone, sachant que : le combustible est, juste après la production, mélangé à un agent de trempe (7) pour évacuer l'énergie interne élevée et, encore dans la chambre de mélange (6) ou en aval de la chambre de mélange, est amené en contact avec un agent de sorption (8) comprenant un composé basique solide de métal alcalinoterreux ou un composé de métal de transition, de sorte que les composants acides ou basiques ou sulfureux ou halogénés présents dans le gaz brut et issus de la réaction de gazéification sont absorbés; et un dispositif (10) séparateur de substance solide se trouve après le dispositif d'apport de l'agent de sorption, dispositif (10) avec lequel les composants solides ou solidifiés sont évacués du système, et l'agent de sorption basique et contenant un métal de transition peut être régénéré dans le mélange ou après une séparation des composants de cendres et de scories, et recyclé dans le processus, de sorte qu'on peut renoncer pour la purification du gaz brut à une réfrigération dépensière en énergie du gaz brut, et que ce gaz de synthèse ainsi purifié peut être utilisé dans un processus consécutif sans autre réchauffement.
EP08802648A 2007-09-26 2008-09-26 Procédé de purification du gaz brut d'une gazéification de combustible solide Withdrawn EP2193184A1 (fr)

Applications Claiming Priority (2)

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DE102007046260A DE102007046260A1 (de) 2007-09-26 2007-09-26 Verfahren zur Reinigung des Rohgases aus einer Feststoffvergasung
PCT/EP2008/008194 WO2009043540A1 (fr) 2007-09-26 2008-09-26 Procédé de purification du gaz brut d'une gazéification de combustible solide

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BR (1) BRPI0817286A2 (fr)
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CN102259835B (zh) * 2011-06-20 2013-03-27 中国科学院广州能源研究所 一种基于熔融盐特性的粗合成气净化提质方法
GB2513154B (en) * 2013-04-17 2015-10-28 Tetronics International Ltd Precious Metal Recovery
CN103657368B (zh) * 2013-12-30 2015-12-23 昆明理工大学 一种同时脱硫脱硝脱汞干法烟气净化方法及装置
US9810146B2 (en) * 2014-07-17 2017-11-07 Saudi Arabian Oil Company Calcium sulfate looping cycles for sour gas combustion and electricity production
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AU2008306154B2 (en) 2013-02-21
US8529792B2 (en) 2013-09-10
AU2008306154B9 (en) 2013-03-21
AU2008306154A1 (en) 2009-04-09
WO2009043540A1 (fr) 2009-04-09
BRPI0817286A2 (pt) 2015-03-10
KR101566335B1 (ko) 2015-11-05
WO2009043540A4 (fr) 2009-05-22
ZA201000342B (en) 2010-12-29
US20140044601A1 (en) 2014-02-13
CN101802143B (zh) 2015-08-26
CN101802143A (zh) 2010-08-11
KR20100063812A (ko) 2010-06-11
US20100311847A1 (en) 2010-12-09
CA2734601A1 (fr) 2009-04-09
DE102007046260A1 (de) 2009-04-09
RU2010116168A (ru) 2011-11-10
CA2694584A1 (fr) 2009-04-09
CA2734601C (fr) 2016-11-08

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