WO2012068930A1 - Medium to low temperature pyrolysis system for upgrading the quality of coal or biomass, and method of producing upgraded coal, high calorific value pyrolysis gas and tar or liquefied synthetic oil by using the system - Google Patents

Medium to low temperature pyrolysis system for upgrading the quality of coal or biomass, and method of producing upgraded coal, high calorific value pyrolysis gas and tar or liquefied synthetic oil by using the system Download PDF

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Publication number
WO2012068930A1
WO2012068930A1 PCT/CN2011/080840 CN2011080840W WO2012068930A1 WO 2012068930 A1 WO2012068930 A1 WO 2012068930A1 CN 2011080840 W CN2011080840 W CN 2011080840W WO 2012068930 A1 WO2012068930 A1 WO 2012068930A1
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transfer material
coal
heat carrier
oxygen transfer
catalytic
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PCT/CN2011/080840
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French (fr)
Chinese (zh)
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刘科
崔哲
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北京低碳清洁能源研究所
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Publication of WO2012068930A1 publication Critical patent/WO2012068930A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/16Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
    • C10B49/18Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form according to the "moving bed" type
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B49/00Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
    • C10B49/16Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10BDESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L9/00Treating solid fuels to improve their combustion
    • C10L9/08Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1011Biomass
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/4043Limiting CO2 emissions
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/20Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00Technologies relating to oil refining and petrochemical industry
    • Y02P30/40Ethylene production

Definitions

  • the present invention relates to the comprehensive utilization and conversion of coal or biomass, in particular to a chemical cycle reaction system for pyrolysis upgrading of coal or biomass, and more particularly to low temperature pyrolysis of coal or biomass.
  • coal pyrolysis and upgrading technology has become a near-cost conversion of coal to fuels and chemicals at low cost.
  • researchers at home and abroad have proposed different coal ⁇ ⁇ process routes through the improvement of the process.
  • processes that have reached the scale of pilot and semi-industrialization, but these processes are mainly focused on the improvement of pyrolysis reactors.
  • the ENFCAL LFC (Liquid from the Coal) process was commercialized in 1992.
  • ENCOAL's LFC process by pyrolysis, a high-quality dry half of 0.5 tons of calorific value of 26.5 million joules/kg can be obtained from 1 ton of high-moisture, low-quality coal with a calorific value of 18-20 megajoules/kg.
  • Coke, ie upgraded coal and 0.07 high quality coal tar The advantage of this method is that the moisture in the high moisture coal is effectively removed by drying.
  • the process consumes a large amount of gas and requires external introduction of fuel, such as natural gas, to supply energy, which increases operating costs. And energy consumption also reduces overall efficiency.
  • US 2010/0037516 discloses a process for the thermal upgrading of carbonaceous materials which is primarily a reduction in water content, which is carried out in a high pressure steam environment to remove moisture and by-products therefrom. It also involves improvements to the design of the pyrolyzer, such as the use of various water/solid separation devices, and improves the relative position of the heating medium inlet nozzle and the outlet of the process chamber to prevent the heating shield from flowing toward the container exhaust outlet. A short circuit has occurred.
  • No. 6,558,441 discloses a upgrading process for low quality coal comprising pyrolysis of coal in a liquid phase, for example in an organic solvent, at 400-450 °C. The method finally obtains three products of upgraded coal, pyrolysis gas and oil.
  • US7008459 discloses a method and apparatus for coal pyrolysis pretreatment comprising a pretreatment vessel, a preheater and a deaerator. The method is to pyrolyze and purify coal under anaerobic conditions and in an environment where oxygen is generated during coal heating.
  • US 2008/0134666 A1 discloses a system and method using a non-mixed fuel processor that uses three reactors in which coal reacts with water vapor and is initially gasified to include hydrogen, carbon monoxide and a synthesis gas of a gas such as carbon dioxide, which further reacts with water vapor to form carbon dioxide and hydrogen, and the carbon dioxide is adsorbed by the carbon dioxide adsorbent material in the second reactor, so that the gas discharged from the first reactor is mainly rich Hydrogen gas.
  • a metal or metal oxide as an oxygen transfer material such as FeO, undergoes a strongly exothermic oxidation reaction with the heated hot air. The oxygen transfer material is combined with oxygen and sent to the second reactor.
  • the hot air in the third reactor forms a nitrogen-rich gas after depletion of oxygen, and such high temperature inert hot gas is discharged from the third reactor. It can then be used to generate electricity.
  • the waste carbon dioxide adsorbent material entering the second reactor undergoes thermal decomposition to release the dioxide dioxide under the action of a large amount of heat brought into the second reactor by the oxygen-containing high-temperature oxygen transfer material.
  • some of the coke produced in the coal which is not completely vaporized also enters the second reactor from the first reactor, and further vaporizes to react with the oxygen-transporting material from the third reactor to form carbon dioxide and water vapor. .
  • the oxygen-transferring material that combines oxygen from the third reactor into the second reactor is reduced at this time, releases oxygen and then changes to the oxygen-transporting material without oxygen, and the third reaction from the second reactor.
  • a further oxidation reaction cycle is carried out in the device to combine oxygen.
  • the gas thus released from the second reactor will be a carbon dioxide rich gas. Recycling and reducting the adsorbent material and the oxygen transfer material by regenerating and reducing the carbon dioxide adsorbent material and the oxygen transfer material in the second reactor, and entering the first reactor and the third reactor, respectively,
  • a hydrogen-rich gas, a dioxide-rich gas, and a nitrogen-rich gas are each discharged from the first, second, and third reactors.
  • pyrolysis is only to remove water as much as possible or to be pyrolyzed while maintaining oxygen isolation.
  • the pyrolysis temperature cannot be too high, for example, it cannot be higher than 450. C, or in order to achieve the desired pyrolysis and quality improvement, the existing pyrolysis furnace structure has to be improved; and coal conversion requires three high-temperature reactors, and its operation and cost are high; three high-temperature reactors
  • the operating temperature must be close to or above 1000 ° C, especially in the third reactor up to 1200 ° C - 1550. C, the complexity and operational insecurity of the system is significantly increased.
  • the object of the present invention is to overcome the above-mentioned deficiencies in the upgrading and conversion of coal and biomass, and to provide a system and method for efficiently and economically utilizing coal and retaining and recovering useful components in coal. More particularly, the present invention relates to a low temperature pyrolysis upgrading system for coal or biomass and a method for producing upgraded coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil using the system.
  • the coal refers to all kinds of coal, carbonaceous biomass, petroleum coke, carbonaceous solid waste and/or carbonaceous sludge, carbonaceous slag, etc.
  • the catalytic-heat carrier-oxygen transfer material refers to a material which simultaneously has a function of chemical conversion, heat transfer or heat transfer, and oxygen transfer during a pyrolysis reaction, wherein the material can be combined with coal during pyrolysis
  • the sulphur reaction in the reaction forms a catalyst for promoting the hydro-hydrogenation reaction of the coal and/or the hydrocracking reaction of the coal tar; and the large amount of the reaction tropic generated by the oxidization of the material in the regenerator is introduced into the pyrolysis furnace, thereby Maintaining the pyrolysis temperature of the pyrolysis furnace; finally, the oxygen combined in the regenerator is released in the pyrolysis furnace to reduce oxygen, thereby transferring oxygen from the regenerator to the pyrolysis furnace to provide a pyrolysis reaction The oxygen required.
  • a low temperature pyrolysis system for coal comprising: a fixed bed, a vibrating bed, or a moving bed type medium and low temperature pyrolysis furnace, including a raw coal inlet, a water vapor inlet, a ⁇ co coal, and a waste Catalyst-heat carrier-oxygen transfer material mixture outlet, pyrolysis gas output line, and at least one medium-low temperature between the original *A port and the ⁇ coal outlet in the medium-low temperature pyrolysis furnace a pyrolysis zone, wherein the raw coal reacts with the oxygen-providing catalytic-heat carrier-oxygen transfer material in the medium-low temperature pyrolysis zone to be pyrolyzed at a medium-low temperature, and generates methane, carbon monoxide, carbon dioxide, hydrogen, and water.
  • At least one catalyst-heat carrier-oxygen transfer material connected to the pyrolysis furnace via at least one solid-solid separator and spent catalytic-heat carrier-oxygen transfer material delivery conduit, regenerated catalytic-heat carrier-oxygen transfer material delivery conduit a regenerator, wherein the spent catalyst in the catalytic-heat carrier-oxygen transfer material regenerator-heat carrier-oxygen transfer material is regenerated by oxidation reaction with an oxygen-carrying gas fed into the regenerator, and the regenerated catalytic-heat carrier - the oxygen transfer material is recycled back to the pyrolysis furnace via a regenerative catalytic-heat carrier-oxygen transfer material delivery conduit, and the oxygen-carrying gas that is lost by oxidation or oxygen is removed from its outlet;
  • a condenser that communicates with the pyrolysis furnace via the pyrolysis gas output pipe, wherein the tar gas or synthetic oil gas is condensed to become tar or liquefied synthetic oil, and is separated from the pyrolysis gas phase.
  • the catalytic-heat carrier-oxygen transfer material is an iron, a sample, and/or an oxide, more preferably FeO, Fe2 ⁇ 3, and/or Fe3 ⁇ 4 or
  • the raw coal may also be a mixture of raw coal and coal direct liquefaction catalyst, in which one or more heat exchangers may be provided in the pyrolysis furnace and/or the catalytic-heat carrier-oxygen transfer material regenerator to remove excess heat Transferring the above system, one or more cyclones, cyclone cascades, filters, and the like may also be provided in the pyrolysis furnace, catalytic-heat carrier-oxygen transfer material regenerator, and/or solid-solid separator.
  • a separator for separating the gas therein from the solid particles wherein the oxygen-depleted oxygen or the oxygen-carrying oxygen-removed gas in the catalytic-heat carrier-oxygen transfer material regenerator can be used to heat the heat exchanger
  • the pyrolysis furnace or the water vapor required thereof may be arranged with one or more carbon dioxide adsorbents in the condenser to capture carbon dioxide and increase the heat of the pyrolysis gas, and the raw coal is in the middle and low temperature pyrolysis zone.
  • the catalyst required for the coal-to-hydrogenation liquefaction reaction or the coal tar hydrocracking reaction is preferably a sulfide of iron, more preferably FeS or FeSi-x (wherein 1-X is about 0.7-0.9).
  • the raw coal entering the medium and low temperature pyrolysis furnace has a particle size of about 5 to 15 cm, more preferably 5 to 15 cm, and the catalytic-heat carrier-oxygen transfer material regenerator comprises the spent catalytic-heat carrier.
  • an oxygen transfer material is lifted from a lower portion of the regenerator to a riser at the upper portion of the regenerator, and an exchange may be included between the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material and the solid-solid separator a plurality of screens connected in series to classify the mixture particles, and further comprising at least two conveyors between the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material and the solid-solid separator , respectively, conveying the sieve and the undersize of the sieve, the minimum diameter of the sieve mesh is greater than or equal to the maximum diameter of the waste catalytic-heat carrier-oxygen transfer material particles, so as to at least make the waste catalytic-heat carrier-
  • the oxygen transfer material passes through the screen, and the separation medium of the solid-solid separator may be high pressure water vapor and/or circulating pyrolysis gas, and the high pressure water vapor and/or circulating pyrolysis gas leaves the solid-solid separator, and is solid
  • the solid fine particles and/or fine dust can be injected into the pyrolysis furnace through the water vapor inlet, wherein the raw coal particles entering the pyrolysis furnace through the raw coal inlet and the regenerated catalytic-heat carrier-oxygen transfer material conveying pipeline are circulated
  • the regenerated catalytic-heat carrier-oxygen transfer material particles in the reheat furnace can be uniformly mixed in a pyrolysis furnace to be uniformly mixed.
  • the method comprises the following steps in sequence : and the heat-heat carrier-oxygen transfer material, while passing ⁇ water vapor, and making the medium-low temperature pyrolysis furnace; the medium-low temperature pyrolysis zone reaches 250. C-750. Medium and low temperature pyrolysis temperature of C;
  • the medium-low temperature pyrolysis component and the catalytic-heat carrier-oxygen transfer material in the raw coal react in the medium-low temperature pyrolysis zone to form pyrolysis gas including methane, carbon monoxide, carbon dioxide, hydrogen and water vapor, and medium and low temperature Pyrolysis of coal char oil or synthetic oil and gas, at the same time, the raw coal is subjected to medium and low temperature pyrolysis to remove water, low and medium temperature volatiles and become high calorific value of upgraded coal;
  • the solid-solid separator separates the coal and the waste catalytic-heat carrier-oxygen transfer material by using a gravity difference between the upgraded coal and the waste catalytic-heat carrier-oxygen transfer material;
  • the spent catalytic-heat carrier-oxygen transfer material is transported to the catalytic-heat carrier-oxygen transfer material regenerator via the spent catalytic-heat carrier-oxygen transfer material delivery conduit;
  • the spent catalytic-heat carrier-oxygen transfer material is regenerated in the regenerator by oxidation reaction with an oxygen-carrying gas introduced into the regenerator;
  • Regenerated catalytic-heat carrier-oxygen transfer material is transported from the regenerator to the medium-low temperature pyrolysis furnace via the regenerated catalytic-heat carrier-oxygen transfer material delivery conduit for recycling the catalytic-heat carrier
  • An oxygen transfer material the substance passes through a condenser, and the 'medium-low temperature pyrolysis coal gas synthesis oil body is condensed to convert coal tar or liquefied synthetic oil to be separated from the pyrolysis gas phase.
  • the oxygen-carrying gas is air
  • the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material is discharged from the pyrolysis furnace and passed through a 3 ⁇ 4 solid-solid separator.
  • a plurality of screens in series to fractionate the mixture of particles, the sieves in the mixture that do not pass through the screen and the sieves that pass through the screen can be transported by respective conveyor belts, in the catalytic-heat carrier-oxygen transfer
  • the oxygen-carrying gas in the material regenerator that loses oxygen or is deoxidized by the oxidation reaction can be used to drive a steam boiler or a steam turbine to generate electricity.
  • FIG. 1 is a schematic view showing the operation principle of a low temperature pyrolysis upgrading system for coal or biomass according to the present invention. Some of the components are optional. detailed description
  • Figure 1 shows a general and exemplary embodiment of the low temperature pyrolysis upgrading system of the present invention.
  • the system includes a medium-low temperature moving bed pyrolysis furnace (100) and catalysis.
  • a heat carrier-oxygen transfer material regenerator (200) said catalytic-heat carrier-oxygen transfer material regenerator
  • the bottom portion has a water vapor inlet (102), and the upper portion of the pyrolysis furnace, preferably the top, has a pyrolysis gas outlet or output line (111).
  • OTM - Oxygen Transfer Material physical and chemical changes occur, which are pyrolyzed by medium and low temperature to form coke or upgraded coal, and coal pyrolysis gas.
  • the coal pyrolysis gas mainly contains methane, carbon monoxide, carbon dioxide and hydrogen. , steam, and a small amount of hydrogen sulfide gas, while the above pyrolysis gas also contains gaseous coal tar.
  • the main component of coke or upgraded coal is carbon.
  • the sulfide contained in the coal is pyrolyzed by medium and low temperature to form a sulfide gas mainly composed of H2S, and then the following reaction occurs:
  • the coal in the medium-low temperature pyrolysis furnace undergoes pyrolysis and chemical reaction to form coke or upgraded coal solids and coal pyrolysis gas containing gaseous coal tar, while the fresh oxygen-carrying catalytic-heat carrier-oxygen transfer material is in the middle.
  • the waste catalytic-heat carrier-oxygen transfer material which is reduced to oxygen release or oxygen-free in the low temperature pyrolysis furnace, discharged from the pyrolysis furnace through the solid-solid separator and separated from the coal, passed through the waste catalytic-heat carrier-oxygen
  • the transfer material transfer line (103) enters its regenerator (200) and is regenerated by the following chemical reactions:
  • OTM-o + ⁇ 2 OTM+o 10
  • the regenerated oxygen-carrying catalytic-heat carrier-oxygen transfer material is recycled to the pyrolysis furnace (100) through a regenerative catalytic-heat carrier-oxygen transfer material transfer line (104). Medium, and a large amount of heat is input thereto to maintain its pyrolysis temperature, and is once again reduced to achieve its chemical cycle.
  • the mixture of coke or upgraded coal and spent catalytic-heat carrier-oxygen transfer material formed in the above pyrolysis furnace is discharged and pyrolyzed through the mixture outlet (109) located at the lower portion of the pyrolysis furnace (100), preferably at the bottom. Outside the furnace,
  • the coal pyrolysis gas formed in the pyrolysis furnace is also discharged outside the pyrolysis furnace via a coal pyrolysis gas outlet or outlet pipe (116) located at the upper portion, preferably at the top of the pyrolysis furnace, and the coal pyrolysis gas contains no condensation separation Coal tar or synthetic oil gas.
  • Pyrolysis furnaces typically operate at temperatures from 250 to 750. C, preferably 300-700. C, more preferably 350-650 ° C, particularly preferably 400-600 ° C, most preferably 450-550 ° C; and the working pressure of the pyrolysis furnace is usually not much larger than 60 Bar, preferably 20-60 Bar, more preferably It is 25-55 Bar, particularly preferably 30-50 Bar, most preferably 35-45 Bar, for example 40 Bar.
  • Water vapor preferably high pressure steam
  • Water vapor is typically injected into the pyrolysis furnace from the lower or bottom portion of the pyrolysis furnace via a high pressure nozzle to promote the water gas reaction therein.
  • the water vapor temperature and its amount here are not specifically determined as long as it can bring the temperature of the pyrolysis furnace to the required working temperature and allow the water gas reaction to proceed normally, for example, 200-750.
  • C which may also be the same or similar to the operating temperature in the pyrolysis furnace.
  • the operating temperature in the catalytic-heat carrier-oxygen transfer material regenerator is typically from 450 to 1000.
  • C preferably 500-900 ° C, more preferably 550-850 ° C, particularly preferably 550-800.
  • C most preferably 550-750 ° C, such as 600. C or 700 ° C; and the working pressure of the pyrolysis furnace is usually not much larger than 60 Bar, It is preferably 20-60 Bar, more preferably 25-55 Bar, particularly preferably 30-50 Bar, most preferably 35-45 Bar, for example 40 Bar.
  • the oxygen-releasing or anaerobic waste catalytic-heat carrier-oxygen transfer material at the bottom of the regenerator (200) is carried by the hot air blown from the bottom (201) through the riser (202) to the upper portion of the regenerator (200).
  • a strong exothermic oxidation reaction with oxygen in the hot air occurs and is oxidized to oxygen-carrying fresh or regenerated catalytic-heat carrier-oxygen transfer material, regenerated catalytic-heat carrier-oxygen transfer material transport
  • the line (104) is recycled back to the pyrolysis furnace (100), and the dirty or depleted oxygen is removed through its outlet (203) located at the top or top of the regenerator (200).
  • the temperature and the amount of the above hot air are not particularly limited as long as they ensure that the regenerator (200) reaches the required operating temperature and the oxidation reaction therein proceeds smoothly.
  • the hot air is preferably injected into the bottom of the regenerator (200) via a high pressure nozzle.
  • the above catalytic-heat carrier-oxygen transfer material is usually an oxide of a metal oxide such as iron, nickel, zinc or another metal, and is preferably an oxide of Fe, and particularly preferably FeO, Fe Os and/or Fe3 ⁇ 4 And a mixture thereof, most preferably Fe203.
  • FeS is a good catalyst for coal direct liquefaction reaction and coal tar hydrocracking reaction.
  • coal tar formed by coal and/or medium and low temperature pyrolysis is in the pyrolysis furnace (100) at a high pressure of 20-60 Bar.
  • the following hydrogenation reaction will occur with the hydrogen contained in the coal pyrolysis gas:
  • the tar in the coal and/or coal pyrolysis gas is converted into synthetic petroleum. If the amount of FeS obtained by the above reaction is insufficient to promote the above-described hydroliquefaction reaction to proceed continuously or sufficiently, a certain proportion of a catalyst such as FeS or FeSi-x may be mixed in the raw coal added to the medium-low temperature pyrolysis furnace (100). 1-X is about 0.7-0.9) to promote the completion of the above hydroliquefaction reaction.
  • the coal pyrolysis gas discharged from the medium-low temperature pyrolysis furnace is separated from the coal tar or the liquefied synthetic oil by a tar collecting device usually including a condenser, thereby becoming pure coal pyrolysis gas.
  • the above pyrolysis gas contains hydrogen, methane, carbon monoxide and carbon dioxide. Passing the above pyrolysis gas through a filter composed of a carbon dioxide adsorbent material to obtain a purer coal pyrolysis gas whose main components are hydrogen, methane and carbon monoxide, and the coal pyrolysis gas filtered out above is free of impurities, thereby High quality gaseous fuel with very high calorific value.
  • the raw coal loses moisture and low-temperature volatiles after medium-low temperature pyrolysis, and then turns into coke or upgraded coal, and its calorific value is also greatly improved.
  • the tar or liquefied synthetic oil separated from the coal pyrolysis gas is a good chemical raw material or liquid fuel.
  • the usual raw coal, especially the inferior coal is converted into upgraded coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil by the low-temperature pyrolysis upgrading system of the present invention, and the utilization value and thermal efficiency thereof are greatly improved.
  • the catalytic-heat carrier-oxygen transfer material may have various forms because of the oxidation of Fe which is usually used as the above-mentioned catalytic-heat carrier-oxygen transfer material.
  • the following reactions occur in the medium-low temperature pyrolysis furnace (100) and the regenerator (200): Under the reducing atmosphere of the pyrolysis furnace (100), the iron oxide undergoes the following reaction:
  • coal pyrolysis gas discharged from the above pyrolysis furnace and the dirty air discharged from the above regenerator usually contain dust of solid particles, preferably such gas is passed through a gas-solid or gas-liquid separator, for example
  • a gas-solid or gas-liquid separator for example
  • the cyclone 114, the cyclone cascade, the diaphragm, and/or the filter shown in Fig. 1 are used to achieve gas-solid separation, and the separated solid dust can be subjected to conventional water quenching treatment.
  • the coal pyrolysis gas after gas-solid separation is usually between 250 and 750 C.
  • one or more heat exchangers such as water or air, may be passed through a coiled or multi-tube heat exchanger to reduce the temperature thereof to a condensed separation coal tar or hydrogenation
  • the temperature of the liquefied synthetic oil for example 22-35. C, the above temperatures will be apparent to those of ordinary skill in the art and can be derived from the related prior art literature or proprietary device specifications.
  • the coal pyrolysis gas preferably gas-solid separated and cooled, classically contains a coal tar or liquefied synthetic oil collection device of the condenser (300) as shown in Fig. 1, and is separated into pure coal pyrolysis gas and Coal tar or hydrogenated liquefied synthetic oil.
  • compressed air pressurized by a compressor (not shown) is used as a heat exchange medium of the heat exchanger, and compressed air heated by the above heat exchanger can be used as the above regenerator (200)
  • the desired source of hot air is sprayed directly onto the bottom of the regenerator (200) via a high pressure nozzle.
  • the temperature of the oxygen-depleted or oxygen-free dirty air discharged from the top of the regenerator (200) can reach 400-1000 ° C, and one or more heat exchangers (not shown) can also be used to lower the temperature, but preferably Ground, the high temperature and high pressure air can be sent to the expander and drive the steam boiler or steam turbine for power generation.
  • the generated steam can also be directly injected into the steam source required by the medium and low temperature pyrolysis furnace (100) through the high pressure nozzle. To the lower or bottom of the pyrolysis furnace, or to the separation medium for the solid-solid separator described above.
  • the coal is pyrolyzed in the region at low temperatures, and the same water gas reaction also occurs in this region.
  • the raw coal and the catalytic-heat carrier-oxygen transfer material are thoroughly mixed, and high-pressure and high-temperature steam are also injected into the region from the lower or bottom portion of the pyrolysis furnace (100) to form coal, catalytic-heat carrier. - a mixture of oxygen transfer material, and water vapor.
  • a mixture of upgraded coal or coke and spent catalytic-heat carrier-oxygen transfer material that completes the low-temperature pyrolysis and chemical reaction is discharged from the outlet (109) to the pyrolysis furnace (100) and passed through a solid-solid separator (400).
  • the solid-solid separation is carried out, and the separation of the waste catalyst-heat carrier-oxygen transfer material after the separation of the coal or the coke is reduced to become a solid product of the coal, and the waste after separation from the coal or coke
  • the catalytic-heat carrier-oxygen transfer material is regenerated by the spent catalytic-heat carrier-oxygen transfer material transfer line (103) into its regenerator (200).
  • the above solid-solid separator utilizes the difference in gravity to achieve separation of different types of solid particles. Specifically, due to the different specific gravity of different types of solid particles, they may be fluidized under the fluidization or blowing force of the gaseous separation medium. The floating height and the drop are also different, and the separation of different kinds of solid particles can be achieved by using the height difference or the drop.
  • Such solid-solid separators are well known to those of ordinary skill in the art, and more details can be obtained by reviewing related literature or equipment specifications in the prior art.
  • the present invention may alternatively be a fluidized bed type, such as a fountain bed type solid-solid separator; a cyclone type solid-solid separator, or other type of solid-solid separator may also be used.
  • the mixture is passed through one or more before the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material is discharged from the pyrolysis furnace (100) and before entering the solid-solid separator (400).
  • a mesh (110) in series and the mixture particles are subjected to one or more classifications, and the mesh (110) has a mesh diameter of at least equal to or greater than a maximum diameter of the waste catalytic-heat carrier-oxygen transfer material particles.
  • the mixture in the above solid-solid separator has catalyzed a mixture of the heat carrier-oxygen transfer material particles and the upgraded coal fine particles having a particle size equivalent thereto.
  • the upgraded coal particles having a particle size larger than the spent catalytic-heat carrier-oxygen transfer material particles have been intercepted by the above-mentioned screen and formed into high quality upgraded coal.
  • the screen described above is preferably a vibrating screen capable of withstanding high temperatures of about 250-750 ° C and having sufficient strength and resistance to deformation at the elevated temperatures described above.
  • the above screens can be prepared using a variety of materials, for example based on Fe, Co And / or Ni high temperature alloy.
  • the classified particles may be transported by respective conveyors, such as conveyors (113) and (115) shown in FIG.
  • the separation medium entering the solid-solid separator via the separation medium inlet (401) may be high pressure steam and/or recycled pyrolysis gas, more preferably oxygen from the aforementioned regenerator (200).
  • the separator may be injected into the pyrolysis furnace (100) through a water vapor inlet (102) after removal of solid fine particles or dust by a gas-solid separation apparatus such as a X-ray machine (403).
  • the solid or solid separator (400) is discharged from the overflow outlet (not shown) in the middle or side, and a small portion of the coke powder is separated from the solid-solid separator by the separation medium gas, through the gas-solid separation device,
  • a cyclone (403) is separated from a separation medium gas, such as high-pressure steam or a circulating pyrolysis gas, and the coke-coke powder obtained by a gas-solid separation device such as a cyclone (403) can be recovered from the bottom, After the coke breeze is pressed, it can be sold as a by-product.
  • a certain proportion of the above-mentioned coke breeze may be intentionally mixed into the above-mentioned waste catalytic-heat carrier-oxygen transfer material particles, which together with the waste catalytic-heat carrier-oxygen transfer material particles
  • the regenerator (200) is then combusted with a hot oxygen-carrying gas, such as oxygen in the hot air, introduced into the regenerator (200) to vent heat of combustion to supplement the heat so that the regenerator is
  • a hot oxygen-carrying gas such as oxygen in the hot air
  • the catalyst-heat carrier-oxygen transfer material particles have a particle size of from 1 to 1000 microns, and the coal or coke particles have a particle size of from 5 to 15 cm, for example from 5 to 15 cm.
  • the temperature and pressure of the medium-low temperature pyrolysis furnace (100) are within a range suitable for medium-low temperature pyrolysis of coal, for example, 200. C-900. C, especially 250. C-750. C; 1 atmosphere - 100 bar, especially 20-60 bar.
  • the atmosphere in the medium-low temperature pyrolysis furnace (100) is a reducing atmosphere
  • the atmosphere in the regenerator (200) is an oxidizing atmosphere
  • the two reactors require atmospheric isolation.
  • Water vapor (not shown) may be used as an atmosphere isolating medium to isolate the atmospheres of the two from each other.
  • the residence time of the coal in the medium and low temperature pyrolysis furnace (100) generally depends on the type and operating conditions of the low temperature pyrolysis furnace in the coal used. These process parameters can be found in the manuals or product specifications of the relevant equipment, as well as in the prior art documents well known to those skilled in the art.
  • the time in which the coal stays is about 30 minutes to 3 hours, for example, about 1 hour to 2 hours, and preferably about 1 hour and 30 minutes.
  • the oxygen-depleted or anaerobic dirty air discharged from the upper or top of the catalytic-heat carrier-oxygen transfer material regenerator (200) will contain a certain amount of solid dust particles, which may include catalytic-heat carrier-oxygen transfer material fine particles. Or dust.
  • the above-mentioned solid-gas or liquid-gas separation equipment such as a machine, a cyclone cascade, a filter, and/or a diaphragm, is used to discharge the oxygen-depleted or anaerobic dirty air entrained with these solid fine particles or dust. Perform one or more stages of solid-gas separation before performing heat utilization. ,
  • lignite having the following chemical composition was broken into particles having the following particle size distribution by a conventional crushing apparatus.
  • the catalytic-heat carrier-oxygen transfer material is Fe203, which has the following particle size distribution:
  • Catalytic-heat carrier - Oxygen transfer material > 10 ⁇ m
  • the particle size of the above particles is determined by a sieving method or a specific surface area method.
  • the chemical composition of lignite is as follows (dry basis): c HONS ash volatiles
  • the moisture content of lignite is not limited, but the moisture content of lignite is 30.99%.
  • the calorific value is 17,541 joules / gram.
  • the lignite feedstock may also be preheated and pre-dried to a moisture content of less than 12% by weight and a temperature of 120. C or so.
  • the pyrolysis residence time of lignite in a medium-low temperature pyrolysis furnace is about 1 hour and 45 minutes.
  • the above lignite granules of C are fed into the known fluidized bed type pyrolysis furnace (100) from the upper or top portion via a known lock system at a flow rate of 1000 kg / hr.
  • the pyrolysis zone (105) of (100) has an operating temperature of approximately 400-550 e C and a working pressure of approximately 35 bar. From the lower portion of the above-mentioned medium-low temperature pyrolysis furnace (100), a flow rate of 1000 m 3 /hr through the high pressure nozzle will be about 200-300. The water vapor of C is sprayed into the medium-low temperature pyrolysis furnace (100), and the regenerated catalytic-heat carrier-oxygen transfer material delivery line (104) is used to regenerate the catalytic-heat carrier-oxygen transfer material at a flow rate of 180 kg/hr. Fe203 is added to the above-mentioned medium-low temperature pyrolysis zone (105) in the pyrolysis furnace
  • the catalytic-heat carrier-oxygen transfer material of C is uniformly collided and uniformly mixed, and then low-temperature pyrolysis begins to occur in the presence of water vapor.
  • the temperature of the pyrolysis zone (105) in the pyrolysis furnace (100) gradually becomes stable.
  • the coal is decomposed by moisture at medium and low temperature, and the volatile matter of medium and low temperature becomes coke or semi-coke, and pyrolysis gas containing gaseous tar is produced, and Fe203 is reduced and releases oxygen, thereby becoming waste catalysis mainly of Fe/FeO.
  • Heat carrier - oxygen transfer material is uniformly collided and uniformly mixed, and then low-temperature pyrolysis begins to occur in the presence of water vapor.
  • the temperature of the pyrolysis zone (105) in the pyrolysis furnace (100) gradually becomes stable.
  • the coal is decomposed by moisture at medium and low temperature, and the volatile matter of medium and low temperature becomes coke or semi-coke, and pyr
  • the temperature of the mixture was about 400.
  • the semi-coke/waste catalytic-heat carrier-oxygen transfer material mixture after pyrolysis is discharged from its outlet and sieved by a vibrating screen (110) with a mesh diameter of 1 ⁇ m, based on the screen M made of high temperature resistant alloy and exhibits excellent strength and deformation resistance at around 400 ° C. Since the semi-coke particle diameter is much larger than the particle diameter of the waste catalytic-heat carrier-oxygen transfer material, semi-coke and waste catalyst -
  • the heat carrier-oxygen transfer material mixture is divided into two streams.
  • the semi-coke is deactivated and passivated to cool down to form a high quality semi-coke product - upgraded coal.
  • Waste catalytic-heat carrier-oxygen transfer material and particle size smaller than the mesh diameter The mixture of semi-coke particles is separated from each other into a known fluidized bed type solid-solid separator.
  • the density of the spent catalyst-heat carrier-oxygen transfer material Fe or FeO is greater than 5 g / cm 3 ; Density of 1.2 g / cm 3 , passing through the solid-solid separator
  • the fluidization force of the chemical bed, the dense waste catalytic-heat carrier-oxygen transfer material is enriched in the bottom of the fluidized bed type separator.
  • the semi-coke particles are then separated from the separator by the fluidized separation medium, water vapor, from the top of the separator, thereby achieving separation of the two solids.
  • a hot air of about 300 ° C at a flow rate of about 100 cubic meters per hour is injected into the bottom of the regenerator (200 ) with a high pressure nozzle, and the catalytic-heat carrier-oxygen transfer material regenerator (200) is operated at a temperature of 800-1000 °. C, the pressure is 35 bar, and between the catalytic-heat carrier-oxygen transfer material regenerator (200) and the medium-low temperature pyrolysis furnace (100), the atmosphere is isolated by steam.
  • the temperature of the hot air can be raised to about 1000 ° C. After it reaches the operating temperature and the exothermic reaction has begun, the temperature of the hot air can be lowered. To 300. C, in the regenerator (200), the spent catalytic-heat carrier-oxygen transfer material and the oxygen in the hot air entering the regenerator (200) through the air inlet (201) are oxidized, the reaction releases a large amount of heat, and The spent catalytic-heat carrier-oxygen transfer material is regenerated from Fe/FeO to Fe2 ⁇ 3.
  • the oxygen-free air and the regenerated catalytic-heat carrier-oxygen transfer material at 800-1000 ° C are separated from each other.
  • the regenerated catalytic-heat carrier-oxygen transfer material is injected into the pyrolysis furnace (100) from the top through its delivery conduit (104); and the oxygen-free air is discharged from its outlet (203). Since the catalytic-heat carrier-oxygen transfer material is gradually worn and lost, it needs to be appropriately supplemented according to the specific situation.
  • the source of the above hot air in the regenerator (200) may be derived from a heat exchanger (not shown) in which the heat exchange shield exchanges heat with the pyrolysis gas.
  • the air can be pressurized by a compressor and injected into the above heat exchanger as a heat exchange medium, and then heated to 300.
  • the hot air of C is discharged from the heat exchanger and injected into the bottom of the regenerator (200).
  • Oxygen-depleted or oxygen-free dirty air exhausted from the upper or top of the regenerator (200) may be sent through a cyclone, a cyclone cascade, a filter, and/or a diaphragm (not shown) for solid-gas separation.
  • a cyclone a cyclone cascade, a filter, and/or a diaphragm (not shown) for solid-gas separation.
  • Into the expansion B ⁇ (not shown) to drive a steam boiler (not shown) or a steam turbine (not shown) for power generation.
  • the water vapor/semi-coke standing gas mixture obtained from the top of the solid-solid separator is separated by a gas-solid separation device such as a cyclone. Then about 200-30 (TC steam as the loose wind of the pyrolysis furnace A steam inlet (102) from the lower side wall of the pyrolysis furnace (100) is injected into the pyrolysis furnace. In the pyrolysis furnace (100), water vapor reacts with coal and semi-coke for a portion of the gasification reaction to produce hydrogen gas and carbon monoxide.
  • the hydrogen produced by the gasification reaction exists in a proton state instantaneously, and has a strong activity, and can undergo a hydrocracking reaction with the macromolecular oil-tar component in the coal pyrolysis product under the action of the hydrocracking reaction catalyst.
  • a synthetic oil of small molecules is produced.
  • J3 »J is recycled from the bottom and sold as a by-product.
  • the pyrolysis gas discharged from the upper portion of the pyrolysis furnace (100) may contain small molecule gases such as hydrogen, carbon monoxide, carbon dioxide, methane, water vapor, etc., and some coal tar components such as alkanes, alkenes, aromatic hydrocarbons, and the like.
  • the solid fine particles or ash entrained by it is filtered through a solid-gas separation device, such as a cyclone (117), and then passed to a tar or liquefied synthetic oil recovery unit including a condenser (300) and a heat exchanger (not shown).
  • the heat exchanger has its temperature lowered to 70 C-150 e C and then passed through a condenser (300) which further reduces the gas temperature to 22.
  • liquid coal distillate can be used as a product, and the light component-pure pyrolysis product can be burned to provide system energy or sold as a product.
  • the calorific value of the above-mentioned upgraded coal was measured to be 25,731 joules/gram, and it was found that the heat value of the coal was greatly improved by the above treatment.
  • the calorific value of the above coal pyrolysis gas dehydration is about 17,500 kJ/m 3 , which is known to be a gaseous fuel having a relatively high calorific value.
  • Elemental analysis, in weight%, the elemental composition of medium and low temperature pyrolysis coal tar is as follows:
  • the lignite particles crushed in the above Example 1 are mixed with pyrrhotite (Fe(ix)S) having the same or similar particle diameter (wherein (1-x) is generally about 0.8) in a weight ratio of 99:1.
  • the resulting mixture was injected into the medium-low temperature pyrolysis furnace (100) in the same manner as in Example 1.
  • the medium-low temperature pyrolysis furnace 100
  • the tar produced by coal or coal pyrolysis will be cracked and hydrogenated with hydrogen in the pyrolysis gas to form a low molecular weight. Liquefied synthetic oil.
  • the calorific value of the above pyrolysis gas after dehydration is about 15,900 kJ/m 3 , which is known to be a gaseous fuel having a relatively high calorific value.
  • the elemental composition of the above synthetic oil is as follows:
  • Example 2 CHNS o metal 82% 14% 1.0% 0.8% 1.3% 0.9%
  • Example 2 the same process conditions as in Example 1 were employed, wherein the raw material composition, process parameters, product composition and the like not mentioned were the same as in Example 1. Same as unless otherwise stated.
  • the determination of the chemical composition or elemental composition of the above lignite, upgraded coal, pyrolysis gas, coal tar or liquefied synthetic oil is carried out by methods well known to those skilled in the art.
  • the measurement is carried out by spectrometry, industrial analysis, and/or elemental analysis.
  • the catalytic-heat carrier-oxygen transfer material is used as a heat carrier. Heat transfer by solid-solid contact with raw coal particles and causes the occurrence of a pyrolysis reaction. Since no gas-solid heat transfer method is used, a large amount of gas can be saved.
  • the degree of pulverization of raw coal in the moving bed of the pyrolysis furnace is also much lower than that of the most commonly used fluidized bed. While reducing energy consumption, it also guarantees the quality of semi-coke-quality coal.

Abstract

Disclosed are a medium to low temperature pyrolysis system for upgrading the quality of coal or biomass, and a method of producing upgraded coal, high calorific value pyrolysis gas and tar or liquefied synthetic oil by using the system. The system and method enable effective capture of carbon dioxide. The system includes a medium to low temperature pyrolysis oven which is preferably of a moving bed type, and at least a catalysis-heat carrier-oxygen transfer material regenerator in connection with the medium to low temperature pyrolysis oven, a solid-solid separator and a condenser. In the medium to low temperature pyrolysis oven, raw coal is subjected to medium to low temperature pyrolysis, and upgraded coal, high calorific value pyrolysis gas and gas of tar or liquefied synthetic oil are produced. The gas of tar or liquefied synthetic oil is condensed to become tar or liquefied synthetic oil. In the catalysis-heat carrier-oxygen transfer material regenerator, the saturated spent catalysis-heat carrier-oxygen transfer material is oxidized and regenerated, and is returned to the medium to low temperature pyrolysis oven, thus achieving the regeneration and recycling of the catalysis-heat carrier-oxygen transfer material.

Description

一种煤或生物质中低温热解提质系统和利用该系统生产 提质煤、 高热值热解气和焦油或液化合成油的方法  Low-temperature pyrolysis upgrading system for coal or biomass and method for producing upgraded coal, high calorific value pyrolysis gas and tar or liquefied synthetic oil by using same
技术领域 Technical field
本发明涉及煤或生物质的综合利用和转化, 具体地说,涉及一种煤或生 物质热解提质的化学循环反应系统, 更具体地说, 涉及一种煤或生物质中 低温热解^^系统和利用该系统生产^ ^煤、 高热值热解气和煤焦油或液 化合成油的方法。 背景技术  The present invention relates to the comprehensive utilization and conversion of coal or biomass, in particular to a chemical cycle reaction system for pyrolysis upgrading of coal or biomass, and more particularly to low temperature pyrolysis of coal or biomass. ^^ System and method for producing ^ ^ coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil using the system. Background technique
在众多传统煤和生物质转化技术、 例如煤燃烧, 煤气化, 煤热解等技 术中,煤的热解提质技术因其可低成本地将煤简单地转化为燃料和化学品, 成为近期国际上煤利用研究的一个热点。 国内外研究者通过对工艺过程的 改进, 提出了不同的煤^ ^工艺路线。 目前, 有几种 ^^工艺已经达到了 中试和半工业化的规模水平, 但这些工艺主要集中在对热解反应器的改进 上。  In many traditional coal and biomass conversion technologies, such as coal combustion, coal gasification, coal pyrolysis and other technologies, coal pyrolysis and upgrading technology has become a near-cost conversion of coal to fuels and chemicals at low cost. A hot spot in coal research in the world. Researchers at home and abroad have proposed different coal ^ ^ process routes through the improvement of the process. At present, there are several types of processes that have reached the scale of pilot and semi-industrialization, but these processes are mainly focused on the improvement of pyrolysis reactors.
美国 ENCOAL公司的 LFC ( Liquids From Coal )工艺已经在 1992 年^商业化生产。 在 ENCOAL的 LFC工艺中,通过热解 , 可从 1 吨热值为 18-20百万焦耳 /千克的高水分低品质煤中得到 0.5吨热值为 26.5 百万焦耳 /千克的高品质干燥半焦、即提质煤和 0.07 优质煤焦油。此方法 的优点是高水分煤中的水分通过干燥被有效去除。 然而, 由于其对煤的干 ^^热解是以气-固接触的方式进行的, 所以工艺过程中耗气量大, 且需要 从外部引入燃料、 例如天然气等提供能量, 这就增加了运行成本和能耗, 也降低了总体效率。  The ENFCAL LFC (Liquid from the Coal) process was commercialized in 1992. In ENCOAL's LFC process, by pyrolysis, a high-quality dry half of 0.5 tons of calorific value of 26.5 million joules/kg can be obtained from 1 ton of high-moisture, low-quality coal with a calorific value of 18-20 megajoules/kg. Coke, ie upgraded coal and 0.07 high quality coal tar. The advantage of this method is that the moisture in the high moisture coal is effectively removed by drying. However, since the pyrolysis of coal is carried out by means of gas-solid contact, the process consumes a large amount of gas and requires external introduction of fuel, such as natural gas, to supply energy, which increases operating costs. And energy consumption also reduces overall efficiency.
US2010/0037516公开了一种主要是减少含水量的热提质碳质材料的 方法,其是在高压蒸汽环境下进行热提质,从而除去其中的水分和副产物。 其中也涉及对热解器设计的改进, 例如使用各种水 /固分离设备, 并改进加 热介质入口喷嘴和工艺腔的出气口的相对位置, 以避免加热介盾在向容器 排气出口流动时出现短路。 US6558441公开了一种低品质煤的提质方法, 其包括在 400-450°C下 使煤在液相中、 例如在有机溶剂中进行热解。 该方法最终可获得提质煤、 热解气以及油品三种产品。 US 2010/0037516 discloses a process for the thermal upgrading of carbonaceous materials which is primarily a reduction in water content, which is carried out in a high pressure steam environment to remove moisture and by-products therefrom. It also involves improvements to the design of the pyrolyzer, such as the use of various water/solid separation devices, and improves the relative position of the heating medium inlet nozzle and the outlet of the process chamber to prevent the heating shield from flowing toward the container exhaust outlet. A short circuit has occurred. No. 6,558,441 discloses a upgrading process for low quality coal comprising pyrolysis of coal in a liquid phase, for example in an organic solvent, at 400-450 °C. The method finally obtains three products of upgraded coal, pyrolysis gas and oil.
US7008459公开了一种煤热解预处理的方法和设备, 该设备包括预处 理容器、 预加热器和除氧器。 该方法是在无氧条件下, 和在去除煤加热时 产生的氧的环境下对煤进行热解提质的。  US7008459 discloses a method and apparatus for coal pyrolysis pretreatment comprising a pretreatment vessel, a preheater and a deaerator. The method is to pyrolyze and purify coal under anaerobic conditions and in an environment where oxygen is generated during coal heating.
US2008/0134666A1公开了一种使用非混合燃料处理器的系统和方法, 该方法使用了三个反应器, 在第一个反应器中, 煤与水蒸汽反应, 被初步 气化成包括氢气、 一氧化碳和二氧化碳等气体的合成气, 一氧化碳又进一 步与水蒸汽反应形成二氧化碳和氢气, 而二氧化碳被二氧化碳吸附剂材料 吸附后 第二个反应器中, 这样从第一个反应器中排出的气体主要是富 含氢气的气体。在第三个反应器中,作为氧转移材料的金属或金属氧化物、 例如 FeO与被通入的热空气发生强放热的氧化反应。氧转移材料与氧结合 后被输送至第二反应器中, 在第三反应器中的热空气在耗尽氧后形成富含 氮的气体, 这样的高温惰性热气体从第三反应器中排出后可用于发电。 而 进入第二反应器中的废二氧化碳吸附剂材料在结合氧的高温氧转移材料进 入第二反应器而带入的大量热量作用下, 发生热分解释放出二氧化破。 同 时煤中未被完全气化而产生的一些焦炭也从第一反应器中进入第二反应器 中, 进一步气化后与来自第三反应器的结合氧的氧转移材料反应生成二氧 化碳和水蒸汽。 而从第三反应器进入第二反应器中的结合氧的氧转移材料 此时被还原, 释放氧后重新变为未结合氧的氧转移材料, 并从第二个反应 器中 第三个反应器中进行再一次氧化反应循环, 以便结合氧。 这样从 第二个反应器中释放出的气体将是富含二氧化碳的气体。 通过二氧化碳吸 附剂材料以及氧转移材料在第二反应器中的再生和被还原, 并各自进入第 一反应器和第三反应器, 实现了吸附剂材料和氧转移材料的循环和再生利 用, 同时从第一、 第二和第三反应器中各自排出富含氢的气体、 富含二氧 化破的气体和富含氮的气体。  US 2008/0134666 A1 discloses a system and method using a non-mixed fuel processor that uses three reactors in which coal reacts with water vapor and is initially gasified to include hydrogen, carbon monoxide and a synthesis gas of a gas such as carbon dioxide, which further reacts with water vapor to form carbon dioxide and hydrogen, and the carbon dioxide is adsorbed by the carbon dioxide adsorbent material in the second reactor, so that the gas discharged from the first reactor is mainly rich Hydrogen gas. In the third reactor, a metal or metal oxide as an oxygen transfer material, such as FeO, undergoes a strongly exothermic oxidation reaction with the heated hot air. The oxygen transfer material is combined with oxygen and sent to the second reactor. The hot air in the third reactor forms a nitrogen-rich gas after depletion of oxygen, and such high temperature inert hot gas is discharged from the third reactor. It can then be used to generate electricity. The waste carbon dioxide adsorbent material entering the second reactor undergoes thermal decomposition to release the dioxide dioxide under the action of a large amount of heat brought into the second reactor by the oxygen-containing high-temperature oxygen transfer material. At the same time, some of the coke produced in the coal which is not completely vaporized also enters the second reactor from the first reactor, and further vaporizes to react with the oxygen-transporting material from the third reactor to form carbon dioxide and water vapor. . And the oxygen-transferring material that combines oxygen from the third reactor into the second reactor is reduced at this time, releases oxygen and then changes to the oxygen-transporting material without oxygen, and the third reaction from the second reactor. A further oxidation reaction cycle is carried out in the device to combine oxygen. The gas thus released from the second reactor will be a carbon dioxide rich gas. Recycling and reducting the adsorbent material and the oxygen transfer material by regenerating and reducing the carbon dioxide adsorbent material and the oxygen transfer material in the second reactor, and entering the first reactor and the third reactor, respectively, A hydrogen-rich gas, a dioxide-rich gas, and a nitrogen-rich gas are each discharged from the first, second, and third reactors.
上述文献中所涉及的煤^^和转化工艺存在很多需要改进的地方, 例 如, 热解提质仅是尽可能地去除含水量或在保持与氧隔绝状态下热解, 而 热解温度又不能太高, 例如不能高于 450。C, 或者为了达到理想的热解提 质效果, 不得不对现有的热解炉结构进行改进; 而煤转化需要三个高温反 应器, 其运行和造价成^艮高; 三个高温反应器的运行温度均须接近或超 过 1000°C, 尤其第三反应器甚至高达 1200°C-1550。C, 这样系统的复杂性 和运行不安全性显著增加。 There are many areas for improvement in the coal and conversion processes involved in the above documents. For example, pyrolysis is only to remove water as much as possible or to be pyrolyzed while maintaining oxygen isolation. The pyrolysis temperature cannot be too high, for example, it cannot be higher than 450. C, or in order to achieve the desired pyrolysis and quality improvement, the existing pyrolysis furnace structure has to be improved; and coal conversion requires three high-temperature reactors, and its operation and cost are high; three high-temperature reactors The operating temperature must be close to or above 1000 ° C, especially in the third reactor up to 1200 ° C - 1550. C, the complexity and operational insecurity of the system is significantly increased.
上述所提及的专利文献在此全文引入以作参考。  The above mentioned patent documents are hereby incorporated by reference in its entirety.
迄今为止,还没有一种煤热解提质的化学循环反应系统, 其中能够在中 温或低温的热解温度下去除煤中水分和挥发分、 并通过催化-热载体 -氧转 移材料在反应系统中的化学循环,获取提质煤、 高热值的合成气、 和煤焦油 或液化合成油的系统。 发明内容  So far, there is no chemical cycle reaction system for coal pyrolysis and upgrading, which can remove moisture and volatiles in coal at a medium or low temperature pyrolysis temperature, and pass the catalytic-heat carrier-oxygen transfer material in the reaction system. The chemical cycle in which a system for upgrading coal, high calorific value of syngas, and coal tar or liquefied synthetic oil is obtained. Summary of the invention
本发明的目的旨在克服煤和生物质提质和转化过程中的上述不足, 并 提供一种高效、经济地利用煤,并保留和回收煤中有用组分的系统和方法。 更具体地说, 本发明涉及一种煤或生物质中低温热解提质系统和利用该系 统生产提质煤、 高热值热解气和煤焦油或液化合成油的方法。  SUMMARY OF THE INVENTION The object of the present invention is to overcome the above-mentioned deficiencies in the upgrading and conversion of coal and biomass, and to provide a system and method for efficiently and economically utilizing coal and retaining and recovering useful components in coal. More particularly, the present invention relates to a low temperature pyrolysis upgrading system for coal or biomass and a method for producing upgraded coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil using the system.
在本发明中, 所述煤指所有种类的煤、 含碳生物质、 石油焦、 碳质固 体废弃物和 /或碳质泥以及碳质渣等  In the present invention, the coal refers to all kinds of coal, carbonaceous biomass, petroleum coke, carbonaceous solid waste and/or carbonaceous sludge, carbonaceous slag, etc.
在本发明中, 催化-热载体-氧转移材料是指在热解反应过程中同时具 化、 热传递或热转移、 和氧转移功能的材料, 其中该材料在热解过程 中即可与煤中的硫分反应生成促进煤加氢液化反应和 /或煤焦油加氢裂化 反应的催化剂; 又可将该材料在其再生器中因氧化而产生的大量反应热带 入到热解炉中, 从而维持热解炉的热解温度; 最后还可在热解炉中因被还 原而释放出在再生器中结合的氧, 从而将氧从再生器中转移到热解炉中, 以便提供热解反应所需的氧。  In the present invention, the catalytic-heat carrier-oxygen transfer material refers to a material which simultaneously has a function of chemical conversion, heat transfer or heat transfer, and oxygen transfer during a pyrolysis reaction, wherein the material can be combined with coal during pyrolysis The sulphur reaction in the reaction forms a catalyst for promoting the hydro-hydrogenation reaction of the coal and/or the hydrocracking reaction of the coal tar; and the large amount of the reaction tropic generated by the oxidization of the material in the regenerator is introduced into the pyrolysis furnace, thereby Maintaining the pyrolysis temperature of the pyrolysis furnace; finally, the oxygen combined in the regenerator is released in the pyrolysis furnace to reduce oxygen, thereby transferring oxygen from the regenerator to the pyrolysis furnace to provide a pyrolysis reaction The oxygen required.
根据本发明的一个方面, 提供一种煤中低温热解^^系统, 包括: 固定床、 震动床、 或移动床型中低温热解炉, 包括原煤入口、 水蒸气 入口、 ^^煤和废催化-热载体-氧转移材料的混合物出口、 热解气输出管 道、 和至少一个在中低温热解炉内位于原 *A口和^ ^煤出口之间的中低 温热解区, 其中原煤在所述中低温热解区中与提供氧的催化-热载体 -氧转 移材料发生反应而被中低温热解, 并生成包括甲烷, 一氧化碳、二氧化碳、 氢气、 和水蒸气的热解气、 以及焦油或合成油气; 和 According to an aspect of the invention, a low temperature pyrolysis system for coal is provided, comprising: a fixed bed, a vibrating bed, or a moving bed type medium and low temperature pyrolysis furnace, including a raw coal inlet, a water vapor inlet, a ^co coal, and a waste Catalyst-heat carrier-oxygen transfer material mixture outlet, pyrolysis gas output line, and at least one medium-low temperature between the original *A port and the ^^ coal outlet in the medium-low temperature pyrolysis furnace a pyrolysis zone, wherein the raw coal reacts with the oxygen-providing catalytic-heat carrier-oxygen transfer material in the medium-low temperature pyrolysis zone to be pyrolyzed at a medium-low temperature, and generates methane, carbon monoxide, carbon dioxide, hydrogen, and water. Pyrolysis gas of steam, and tar or synthetic oil and gas; and
至少一个经固 -固分离器和废催化 -热载体-氧转移材料输送管道, 再生 催化 -热载体-氧转移材料输送管道而与所述热解炉相连通的催化 -热载体- 氧转移材料再生器, 其中 ^催化-热载体-氧转移材料再生器中的废催化- 热载体-氧转移材料与被输入所述再生器中的携氧气体发生氧化反应而被 再生,再生催化-热载体 -氧转移材料经再生催化-热载体 -氧转移材料输送管 道被循环回所述热解炉中, 而经氧化反应损失氧或被去除氧的携氧气体从 其出口被排出;  At least one catalyst-heat carrier-oxygen transfer material connected to the pyrolysis furnace via at least one solid-solid separator and spent catalytic-heat carrier-oxygen transfer material delivery conduit, regenerated catalytic-heat carrier-oxygen transfer material delivery conduit a regenerator, wherein the spent catalyst in the catalytic-heat carrier-oxygen transfer material regenerator-heat carrier-oxygen transfer material is regenerated by oxidation reaction with an oxygen-carrying gas fed into the regenerator, and the regenerated catalytic-heat carrier - the oxygen transfer material is recycled back to the pyrolysis furnace via a regenerative catalytic-heat carrier-oxygen transfer material delivery conduit, and the oxygen-carrying gas that is lost by oxidation or oxygen is removed from its outlet;
上述固 -固分离器, 其中被排出所述热解炉的^ ^煤和废催化 -热载体- 氧转移材料的混合物依靠粒径差和 /或重力差在所述固-固分离器中被分 离,分离后的废催化-热载体-氧转移材料经废催化 -热载体-氧转移材料输送 管道^催化-热载体-氧转移材料再生器中再生; 和  The solid-solid separator described above, wherein a mixture of the coal discharged from the pyrolysis furnace and the spent catalytic-heat carrier-oxygen transfer material is subjected to a particle size difference and/or a gravity difference in the solid-solid separator Separation, separation of spent catalytic-heat carrier-oxygen transfer material by waste catalytic-heat carrier-oxygen transfer material delivery pipe ^catalytic-heat carrier-oxygen transfer material regenerator regeneration;
经上述热解气输出管道而与所述热解炉相连通的冷凝器, 其中所述焦 油气体或合成油气体经冷凝而变为焦油或液化合成油, 并与所述热解气相 分离。  A condenser that communicates with the pyrolysis furnace via the pyrolysis gas output pipe, wherein the tar gas or synthetic oil gas is condensed to become tar or liquefied synthetic oil, and is separated from the pyrolysis gas phase.
优选地, 在上述煤热解提质系统中, 催化-热载体 -氧转移材料为铁、 樣、 和 /或辞的氧化物、 更优选为 FeO、 Fe2〇3、 和 /或 Fe3〇4或其混合物, 原煤也可是原煤和煤直接液化催化剂的混合物, 在所述热解炉和 /或催化- 热载体-氧转移材料再生器中可设置一个或多个热转换器, 以便将多余的热 量转移出上述系统, 在所述热解炉、 催化-热载体-氧转移材料再生器、 和 / 或固-固分离器中也可设置一个或多个旋风机、 旋风机级联、 过滤器、 和 / 或隔膜, 以便将其中的气体与固体颗粒分离, 在催化-热载体 -氧转移材料 再生器中经氧化反应损失氧或被去除氧的携氧气体可被用于经热交换器而 加热所述的热解炉或其所需要的水蒸气, 可在冷凝器中布置一层或多层二 氧化碳吸附剂, 从而捕捉二氧化碳、 并提高所述热解气的热, 原煤在中低 温热解区中被脱去水分、 中低温挥发分, 从而变为热值被提高的提质煤, 原煤中的硫分与催化-热载体-氧转移材料在中低温热解炉中发生反应可形 成煤加氢液化反应或煤焦油加氢裂化反应所需的催化剂, 所述的催化剂优 选是铁的硫化物, 更优选是 FeS或 FeSi-x(其中 1-X约为 0.7-0.9)。 Preferably, in the above coal pyrolysis upgrading system, the catalytic-heat carrier-oxygen transfer material is an iron, a sample, and/or an oxide, more preferably FeO, Fe2〇3, and/or Fe3〇4 or The mixture, the raw coal may also be a mixture of raw coal and coal direct liquefaction catalyst, in which one or more heat exchangers may be provided in the pyrolysis furnace and/or the catalytic-heat carrier-oxygen transfer material regenerator to remove excess heat Transferring the above system, one or more cyclones, cyclone cascades, filters, and the like may also be provided in the pyrolysis furnace, catalytic-heat carrier-oxygen transfer material regenerator, and/or solid-solid separator. And/or a separator for separating the gas therein from the solid particles, wherein the oxygen-depleted oxygen or the oxygen-carrying oxygen-removed gas in the catalytic-heat carrier-oxygen transfer material regenerator can be used to heat the heat exchanger The pyrolysis furnace or the water vapor required thereof may be arranged with one or more carbon dioxide adsorbents in the condenser to capture carbon dioxide and increase the heat of the pyrolysis gas, and the raw coal is in the middle and low temperature pyrolysis zone. Was taken off the water , Low temperature volatile, heat value is increased so as to become the upgraded coal, coal and sulfur in the catalytic - heat carrier - reacting the oxygen transfer material in the low temperature pyrolysis furnace may be formed The catalyst required for the coal-to-hydrogenation liquefaction reaction or the coal tar hydrocracking reaction is preferably a sulfide of iron, more preferably FeS or FeSi-x (wherein 1-X is about 0.7-0.9).
同样优选地,进入中低温热解炉中的原煤粒径约为 5亳米 -15厘米,更 优选为 5厘米 -15厘米,催化-热载体 -氧转移材料再生器包含将废催化 -热载 体-氧转移材料从再生器的下部提升至再生器上部的提升管,在所述提质煤 和废催化-热载体 -氧转移材料的混合物出口与固-固分离器之间还可包括一 个或多个串联的筛网, 以将所述混合物颗粒分级, 在所述提质煤和废催化- 热载体-氧转移材料的混合物出口与固-固分离器之间可进一步包括至少两 个传送机, 以各自传送所述筛网的筛上物和筛下物, 筛网的筛孔最小直径 大于或等于废催化 -热载体-氧转移材料颗粒的最大直径, 以便至少使废催 化-热载体-氧转移材料通过所述筛网, 固 -固分离器的分离介质可是高压水 蒸汽和 /或循环热解气,所述高压水蒸汽和 /或循环热解气离开固 -固分离器、 经固 -气分离除去固体细颗粒和 /或微尘后可通过水蒸气入口被注入到热解 炉中, 其中经原煤入口进入热解炉中的原煤颗粒和经再生催化 -热载体-氧 转移材料输送管道被循环回热解炉中的再生催化 -热载体-氧转移材料颗粒 可在热解炉中发生强烈碰撞而被均匀混合。  Also preferably, the raw coal entering the medium and low temperature pyrolysis furnace has a particle size of about 5 to 15 cm, more preferably 5 to 15 cm, and the catalytic-heat carrier-oxygen transfer material regenerator comprises the spent catalytic-heat carrier. - an oxygen transfer material is lifted from a lower portion of the regenerator to a riser at the upper portion of the regenerator, and an exchange may be included between the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material and the solid-solid separator a plurality of screens connected in series to classify the mixture particles, and further comprising at least two conveyors between the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material and the solid-solid separator , respectively, conveying the sieve and the undersize of the sieve, the minimum diameter of the sieve mesh is greater than or equal to the maximum diameter of the waste catalytic-heat carrier-oxygen transfer material particles, so as to at least make the waste catalytic-heat carrier- The oxygen transfer material passes through the screen, and the separation medium of the solid-solid separator may be high pressure water vapor and/or circulating pyrolysis gas, and the high pressure water vapor and/or circulating pyrolysis gas leaves the solid-solid separator, and is solidified. - gas separation The solid fine particles and/or fine dust can be injected into the pyrolysis furnace through the water vapor inlet, wherein the raw coal particles entering the pyrolysis furnace through the raw coal inlet and the regenerated catalytic-heat carrier-oxygen transfer material conveying pipeline are circulated The regenerated catalytic-heat carrier-oxygen transfer material particles in the reheat furnace can be uniformly mixed in a pyrolysis furnace to be uniformly mixed.
根据本发明的另一个方面, 提供一种利用上述煤或生物质中低温热解 提质系统生产提质煤、 高热值热解气和焦油或液化合成油的方法: 该方法 按顺序包括以下步骤: 和催 -热载体-氧 ^移材料, 同时通 λ水蒸气, 并使中低温热解炉;的中 低温热解区达到 250。C-750。C的中低温热解温度;  According to another aspect of the present invention, there is provided a method for producing upgraded coal, high calorific value pyrolysis gas and tar or liquefied synthetic oil using the above-mentioned coal or biomass low temperature pyrolysis upgrading system: the method comprises the following steps in sequence : and the heat-heat carrier-oxygen transfer material, while passing λ water vapor, and making the medium-low temperature pyrolysis furnace; the medium-low temperature pyrolysis zone reaches 250. C-750. Medium and low temperature pyrolysis temperature of C;
原煤中的中低温热解组分和催化-热载体-氧转移材料在所述中低温热 解区中发生反应, 形成包括甲烷、 一氧化碳、 二氧化碳、 氢气和水蒸气的 热解气, 以及中低温热解煤焦油气或合成油气, 同时原煤经中低温热解脱 去水分、 中低温挥发分而变为高热值的提质煤;  The medium-low temperature pyrolysis component and the catalytic-heat carrier-oxygen transfer material in the raw coal react in the medium-low temperature pyrolysis zone to form pyrolysis gas including methane, carbon monoxide, carbon dioxide, hydrogen and water vapor, and medium and low temperature Pyrolysis of coal char oil or synthetic oil and gas, at the same time, the raw coal is subjected to medium and low temperature pyrolysis to remove water, low and medium temperature volatiles and become high calorific value of upgraded coal;
从 ^^煤和废催化-热载体-氧转移材料的混合物出口排出所形成的提 质煤和废催化-热载体-氧转移材料的混合物, 从热解气输出管道排出所述 热解气和中低温热解煤焦油气体或合成油气体的混合物; 所述固-固分离器利用提质煤和废催化-热载体-氧转移材料的重力差将 ^^煤和废催化-热载体 -氧转移材料分离; Discharging a mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material from the mixture outlet of the ^^ coal and the spent catalytic-heat carrier-oxygen transfer material, and discharging the pyrolysis gas from the pyrolysis gas output pipe and a medium-low temperature pyrolysis coal tar gas or a mixture of synthetic oil gases; The solid-solid separator separates the coal and the waste catalytic-heat carrier-oxygen transfer material by using a gravity difference between the upgraded coal and the waste catalytic-heat carrier-oxygen transfer material;
所述废催化 -热载体-氧转移材料经所述废催化-热载体-氧转移材料输 送管道而被输送至催化 -热载体-氧转移材料再生器中;  The spent catalytic-heat carrier-oxygen transfer material is transported to the catalytic-heat carrier-oxygen transfer material regenerator via the spent catalytic-heat carrier-oxygen transfer material delivery conduit;
所述废催化-热载体-氧转移材料在所述再生器中与被通入所述再生器 中的携氧气体发生氧化反应而被再生;  The spent catalytic-heat carrier-oxygen transfer material is regenerated in the regenerator by oxidation reaction with an oxygen-carrying gas introduced into the regenerator;
再生催化-热载体 -氧转移材料经所述再生催化-热载体-氧转移材料输 送管道从所述再生器中被输送至所述中低温热解炉中, 以便循环使用所述 催化-热载体-氧转移材料; 和 物经过冷凝器, 所述'中低温热解煤焦 气体 合成油 ^体经冷凝而变 煤 焦油或液化合成油, 从而与所述热解气相分离。  Regenerated catalytic-heat carrier-oxygen transfer material is transported from the regenerator to the medium-low temperature pyrolysis furnace via the regenerated catalytic-heat carrier-oxygen transfer material delivery conduit for recycling the catalytic-heat carrier An oxygen transfer material; the substance passes through a condenser, and the 'medium-low temperature pyrolysis coal gas synthesis oil body is condensed to convert coal tar or liquefied synthetic oil to be separated from the pyrolysis gas phase.
优选地, 在上述方法中, 携氧气体是空气, 提质煤和废催化 -热载体- 氧转移材料的混合物从所述热解炉中排出后、在 ¾ 固-固分离器之前可通 过一个或多个串联的筛网, 以将所述混合物颗粒分级, 混合物中未通过筛 网的筛上物和通过筛网的筛下物可分别由各自的传送带运输,在催化 -热载 体-氧转移材料再生器中经氧化反应损失氧或被去除氧的携氧气体可被用 于驱动蒸汽锅炉或汽轮机, 从而发电。 附图说明  Preferably, in the above method, the oxygen-carrying gas is air, and the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material is discharged from the pyrolysis furnace and passed through a 3⁄4 solid-solid separator. Or a plurality of screens in series to fractionate the mixture of particles, the sieves in the mixture that do not pass through the screen and the sieves that pass through the screen can be transported by respective conveyor belts, in the catalytic-heat carrier-oxygen transfer The oxygen-carrying gas in the material regenerator that loses oxygen or is deoxidized by the oxidation reaction can be used to drive a steam boiler or a steam turbine to generate electricity. DRAWINGS
图 1为本发明煤或生物质中低温热解提质系统操作原理的示意图.其中 有些组件是任选的。 具体实施方式  BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the operation principle of a low temperature pyrolysis upgrading system for coal or biomass according to the present invention. Some of the components are optional. detailed description
下面参考附图进一步解释和描述本发明, 以使本领域普通技术人员清 楚理解本发明的实质和内涵。 但描述仅仅是示范性的, 不意味着对本发明 构成任何限制。  The invention is further explained and described in detail below with reference to the accompanying drawings, in which FIG. However, the description is merely exemplary and does not imply any limitation to the invention.
图 1表示了本发明煤中低温热解提质系统的一个概括性和示范性的实 施方式。 如图 1所示, 该系统包括一个中低温移动床热解炉(100 )和催化 -热载体 -氧转移材料再生器(200 ) , 所述催化-热载体 -氧转移材料再生器BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a general and exemplary embodiment of the low temperature pyrolysis upgrading system of the present invention. As shown in Figure 1, the system includes a medium-low temperature moving bed pyrolysis furnace (100) and catalysis. a heat carrier-oxygen transfer material regenerator (200), said catalytic-heat carrier-oxygen transfer material regenerator
( 200 )通过固-固分离器和废催化-热载体-氧转移材料输送管线(103 ) 、 以及再生催化-热载体-氧转移材料输送管线(104 )与所述热解炉 (100 ) 相连通。 在所述热解炉的下部, 优选为底部具有水蒸气入口 (102 ), 而在 所述热解炉上部、优选为顶部具有热解气出口或输出管线(111 )。 同时在 所述热解炉中部或上部具有原煤入口(101 ), 而在所述热解炉下部或底部 具有 煤和饱和的废催化-热载体 -氧转移材料的混合物出口 (109 )。 在 催化-热载体 -氧转移材料再生器的底部、 中部和顶部分别具有热空气入口(200) being connected to the pyrolysis furnace (100) by a solid-solid separator and a waste catalytic-heat carrier-oxygen transfer material transfer line (103), and a regenerated catalytic-heat carrier-oxygen transfer material transfer line (104) through. In the lower portion of the pyrolysis furnace, preferably, the bottom portion has a water vapor inlet (102), and the upper portion of the pyrolysis furnace, preferably the top, has a pyrolysis gas outlet or output line (111). At the same time, there is a raw coal inlet (101) in the middle or upper portion of the pyrolysis furnace, and a mixture outlet (109) of coal and saturated spent catalytic-heat carrier-oxygen transfer material at the lower or bottom of the pyrolysis furnace. Hot air inlet at the bottom, middle and top of the catalytic-heat carrier-oxygen transfer material regenerator
( 201 ) 、 提升管 (202 )和脏空气出口 (203 ) 。 (201), riser (202) and dirty air outlet (203).
一定粒度、例如 5亳米 -15厘米的原煤从所述热解炉的中部或上部进入 所述热解炉中,在水蒸汽和催化-热载体 -氧转移材料 (在以下反应式中简写 为 OTM - Oxygen Transfer Material )的存在下, 发生物理和化学变化, 被中低温热解, 从而形成焦或提质煤, 以及煤热解气, 煤热解气中主要含 有甲烷、 一氧化碳、 二氧化碳、 氢气、 水蒸气、 和少量的硫化氢气体, 同 时上述热解气中还含有气态煤焦油。 焦或提质煤的主要成分是碳。  A certain particle size, for example, 5 to 15 cm of raw coal enters the pyrolysis furnace from the middle or upper portion of the pyrolysis furnace, in water vapor and catalytic-heat carrier-oxygen transfer material (abbreviated in the following reaction formula) In the presence of OTM - Oxygen Transfer Material , physical and chemical changes occur, which are pyrolyzed by medium and low temperature to form coke or upgraded coal, and coal pyrolysis gas. The coal pyrolysis gas mainly contains methane, carbon monoxide, carbon dioxide and hydrogen. , steam, and a small amount of hydrogen sulfide gas, while the above pyrolysis gas also contains gaseous coal tar. The main component of coke or upgraded coal is carbon.
来自催化-热载体 -氧转移材料再生器( 200 )的新鲜或再生催化-热载体 -氧转移材料经再生催化-热载体-氧转移材料输送管线( 104 ) 上述中低 温热解炉中,在向热解炉中输入大量的热量的同时, 发生如下反应:  Fresh or regenerated catalytic-heat carrier-oxygen transfer material from catalytic-heat carrier-oxygen transfer material regenerator (200) via regenerated catalytic-heat carrier-oxygen transfer material transfer line (104) in the above medium and low temperature pyrolysis furnace, While inputting a large amount of heat into the pyrolysis furnace, the following reaction occurs:
OTM+o + C → CO + OTM-o  OTM+o + C → CO + OTM-o
CO + OTM+o→ CO2 + OTM-o  CO + OTM+o→ CO2 + OTM-o
OTM+o + H2 H2O +OTM-0  OTM+o + H2 H2O +OTM-0
同时, 原煤在所述热解炉中发生如下水煤气反应:  At the same time, the raw coal undergoes the following water gas reaction in the pyrolysis furnace:
CHo.8 (煤) + Η2θ→ CO + 1.4H2  CHo.8 (coal) + Η2θ→ CO + 1.4H2
CO + Η2θ C02 + Η2  CO + Η2θ C02 + Η2
CO + 3H2 CH4 + Η2θ  CO + 3H2 CH4 + Η2θ
2CO + 2Η2 CH4 + C02  2CO + 2Η2 CH4 + C02
煤中含有的硫化物经中低温热解形成主要为 H2S 的硫化物气体,接着 发生如下反应:  The sulfide contained in the coal is pyrolyzed by medium and low temperature to form a sulfide gas mainly composed of H2S, and then the following reaction occurs:
H2S + ΟΤΜ+ο→ Η2θ + S02 + OTM-o (8) 或 H2S + OTM+o→ H2O + OTM-oS (9) H2S + ΟΤΜ+ο→ Η2θ + S02 + OTM-o (8) Or H2S + OTM+o→ H2O + OTM-oS (9)
这样,在中低温热解炉中的煤经热解和化学反应形成焦或提质煤固体 以及含气态煤焦油的煤热解气,同时新鲜携氧的催化-热载体-氧转移材料在 中低温热解炉中被还原为释氧的或无氧的废催化-热载体-氧转移材料,排 出热解炉经固-固分离器与^ ^煤分离后, 通过废催化-热载体 -氧转移材料 输送管线(103 )进入其再生器(200 ) 中, 并发生以下化学反应而被再生:  In this way, the coal in the medium-low temperature pyrolysis furnace undergoes pyrolysis and chemical reaction to form coke or upgraded coal solids and coal pyrolysis gas containing gaseous coal tar, while the fresh oxygen-carrying catalytic-heat carrier-oxygen transfer material is in the middle. The waste catalytic-heat carrier-oxygen transfer material which is reduced to oxygen release or oxygen-free in the low temperature pyrolysis furnace, discharged from the pyrolysis furnace through the solid-solid separator and separated from the coal, passed through the waste catalytic-heat carrier-oxygen The transfer material transfer line (103) enters its regenerator (200) and is regenerated by the following chemical reactions:
OTM-o + Ο2 OTM+o (10) 再生后的携氧催化 -热载体-氧转移材料又通过再生催化-热载体 -氧转 移材料输送管线(104 )被循环回上述热解炉(100 ) 中,并向其中输入大量 热量以维持其热解温度的同时, 被再一次还原, 从而实现其化学循环。  OTM-o + Ο2 OTM+o (10) The regenerated oxygen-carrying catalytic-heat carrier-oxygen transfer material is recycled to the pyrolysis furnace (100) through a regenerative catalytic-heat carrier-oxygen transfer material transfer line (104). Medium, and a large amount of heat is input thereto to maintain its pyrolysis temperature, and is once again reduced to achieve its chemical cycle.
在上述热解炉中形成的焦或提质煤和废催化-热载体-氧转移材料的混 合物经位于热解炉 (100 )下部、 优选底部的所述混合物出口 (109 ) 而被 排出热解炉外,  The mixture of coke or upgraded coal and spent catalytic-heat carrier-oxygen transfer material formed in the above pyrolysis furnace is discharged and pyrolyzed through the mixture outlet (109) located at the lower portion of the pyrolysis furnace (100), preferably at the bottom. Outside the furnace,
在热解炉中形成的煤热解气经位于热解炉上部、 优选顶部的煤热解气 出口或输出管道 ( 116 )也被排出热解炉外, 该煤热解气中含有尚未冷凝分 离的煤焦油或合成油气体。  The coal pyrolysis gas formed in the pyrolysis furnace is also discharged outside the pyrolysis furnace via a coal pyrolysis gas outlet or outlet pipe (116) located at the upper portion, preferably at the top of the pyrolysis furnace, and the coal pyrolysis gas contains no condensation separation Coal tar or synthetic oil gas.
热解炉的工作温度通常为 250-750。C, 优选为 300-700。C, 更优选为 350-650°C , 特别优选为 400-600 °C, 最优选为 450-550 °C ; 而热解炉的工作 压力通常不大与 60Bar, 优选为 20-60Bar, 更优选为 25-55Bar, 特别优选 为 30-50Bar, 最优选为 35-45Bar, 例如为 40Bar。  Pyrolysis furnaces typically operate at temperatures from 250 to 750. C, preferably 300-700. C, more preferably 350-650 ° C, particularly preferably 400-600 ° C, most preferably 450-550 ° C; and the working pressure of the pyrolysis furnace is usually not much larger than 60 Bar, preferably 20-60 Bar, more preferably It is 25-55 Bar, particularly preferably 30-50 Bar, most preferably 35-45 Bar, for example 40 Bar.
水蒸汽、 优选为高压水蒸汽通常经高压喷嘴从热解炉的下部或底部被 注入到热解炉中以促进其中的水煤气反应。 对此处的水蒸汽温度及其用量 不做特别的 P艮定, 只要其能够使热解炉的温度达到所要求的工作温度和使 水煤气反应正常进行就行,例如为 200-750。C,其也可与热解炉中的工作温 度相同或相似。  Water vapor, preferably high pressure steam, is typically injected into the pyrolysis furnace from the lower or bottom portion of the pyrolysis furnace via a high pressure nozzle to promote the water gas reaction therein. The water vapor temperature and its amount here are not specifically determined as long as it can bring the temperature of the pyrolysis furnace to the required working temperature and allow the water gas reaction to proceed normally, for example, 200-750. C, which may also be the same or similar to the operating temperature in the pyrolysis furnace.
催化-热载体 -氧转移材料再生器中的工作温度通常为 450-1000。C, 优 选为 500-900 °C, 更优选为 550-850 °C, 特别优选为 550-800。C, 最优选为 550-750°C , 例如 600。C或 700°C; 而热解炉的工作压力通常不大与 60Bar, 优选为 20-60Bar, 更优选为 25-55Bar, 特别优选为 30-50Bar, 最优选为 35-45Bar, 例如为 40Bar。 The operating temperature in the catalytic-heat carrier-oxygen transfer material regenerator is typically from 450 to 1000. C, preferably 500-900 ° C, more preferably 550-850 ° C, particularly preferably 550-800. C, most preferably 550-750 ° C, such as 600. C or 700 ° C; and the working pressure of the pyrolysis furnace is usually not much larger than 60 Bar, It is preferably 20-60 Bar, more preferably 25-55 Bar, particularly preferably 30-50 Bar, most preferably 35-45 Bar, for example 40 Bar.
再生器(200 )底部的释氧或无氧废催化 -热载体-氧转移材料被从 底部(201 )吹入的热空气携带经提升管(202 )上升至再生器(200 )的上 部, 在向上运动的过程中, 与热空气中的氧气发生强放热的氧化反应, 并 被氧化为携氧的新鲜或再生催化-热载体-氧转移材料,经再生催化 -热载体- 氧转移材料输送管线(104 )被循环回热解炉(100 ) 中, 而损耗或耗尽氧 的脏空气则经位于再生器(200 )上部或顶部的其出口 (203 )排除。  The oxygen-releasing or anaerobic waste catalytic-heat carrier-oxygen transfer material at the bottom of the regenerator (200) is carried by the hot air blown from the bottom (201) through the riser (202) to the upper portion of the regenerator (200). During the upward movement, a strong exothermic oxidation reaction with oxygen in the hot air occurs and is oxidized to oxygen-carrying fresh or regenerated catalytic-heat carrier-oxygen transfer material, regenerated catalytic-heat carrier-oxygen transfer material transport The line (104) is recycled back to the pyrolysis furnace (100), and the dirty or depleted oxygen is removed through its outlet (203) located at the top or top of the regenerator (200).
这里, 不对上述热空气的温度和用量作特别的限定, 只要其保证再生 器(200 )达到所要求的工作温度和使其中的氧化反应顺利进行就行。 上述 热空气优选经高压喷嘴被喷入到再生器(200 )的底部。  Here, the temperature and the amount of the above hot air are not particularly limited as long as they ensure that the regenerator (200) reaches the required operating temperature and the oxidation reaction therein proceeds smoothly. The hot air is preferably injected into the bottom of the regenerator (200) via a high pressure nozzle.
上述催化-热载体 -氧转移材料通常为金属氧化物、 例如铁, 镍, 锌或 者其他金属的氧化物, 而优选为 Fe的氧化物, 而特别优选为 FeO、 Fe Os 和 /或 Fe3〇4和其混合物, 最优选为 Fe203。  The above catalytic-heat carrier-oxygen transfer material is usually an oxide of a metal oxide such as iron, nickel, zinc or another metal, and is preferably an oxide of Fe, and particularly preferably FeO, Fe Os and/or Fe3〇4 And a mixture thereof, most preferably Fe203.
当上述催化-热载体-氧转移材料为 Fe203时, 在热解炉(100 ) 中其将 与煤热解气中的 H2S发生以下反应: When the above catalytic-heat carrier-oxygen transfer material is Fe 2 03, it will react with H2S in the coal pyrolysis gas in the pyrolysis furnace (100):
Fe203 + H2S + H2→ H2O + FeS ( 9, ) 众所周知, 中低温热解煤焦油是人造石油的重要来源之一, 经高压加 氢裂化可制得包括汽油、 柴油等液化合成油的产品。  Fe203 + H2S + H2 → H2O + FeS ( 9, ) It is well known that medium-low temperature pyrolysis coal tar is one of the important sources of artificial petroleum. High-pressure hydrocracking can produce products including liquefied synthetic oils such as gasoline and diesel.
而 FeS是煤直接液化反应以及煤焦油加氢裂化反应的良好催化剂, 在 FeS 的催化作用下, 煤和 /或中低温热解形成的煤焦油在热解炉 (100 ) 中 在 20-60Bar高压下将与煤热解气中含有的氢气发生以下加氢反应:  FeS is a good catalyst for coal direct liquefaction reaction and coal tar hydrocracking reaction. Under the catalysis of FeS, coal tar formed by coal and/or medium and low temperature pyrolysis is in the pyrolysis furnace (100) at a high pressure of 20-60 Bar. The following hydrogenation reaction will occur with the hydrogen contained in the coal pyrolysis gas:
CxHy (煤焦油或煤) + H2 → CH2 (合成油 ) ( 11 ) 其中 y/x约为 0.8。  CxHy (coal tar or coal) + H2 → CH2 (synthetic oil) (11) where y/x is approximately 0.8.
经过上述加氢反应, 煤和 /或煤热解气中的焦油被转变为人造合成石 油。 如果上述反应获得的 FeS数量不足以促使上述加氢液化反应连续进行 或充分进行, 可在加入到中低温热解炉(100 )中的原煤中混入一定比例的 催化剂, 例如 FeS或 FeSi-x ( 1-X约 0.7-0.9 ) , 以促使上述加氢液化反应 完成。 从中低温热解炉中排出的煤热解气经通常包括冷凝器的焦油收集设备 被分离出煤焦油或液化合成油, 从而变成纯的煤热解气。 上述热解气含有 氢气, 甲烷, 一氧化碳和二氧化碳。 将上述热解气通过由二氧化碳吸附剂 材料组成的过滤器将得到主要成分为氢气, 甲烷和一氧化碳的更纯的煤热 解气, 上述过滤掉二氧化碳的煤热解气由于不含杂质, 因而是热值非常高 的优质气态燃料。 Through the above hydrogenation reaction, the tar in the coal and/or coal pyrolysis gas is converted into synthetic petroleum. If the amount of FeS obtained by the above reaction is insufficient to promote the above-described hydroliquefaction reaction to proceed continuously or sufficiently, a certain proportion of a catalyst such as FeS or FeSi-x may be mixed in the raw coal added to the medium-low temperature pyrolysis furnace (100). 1-X is about 0.7-0.9) to promote the completion of the above hydroliquefaction reaction. The coal pyrolysis gas discharged from the medium-low temperature pyrolysis furnace is separated from the coal tar or the liquefied synthetic oil by a tar collecting device usually including a condenser, thereby becoming pure coal pyrolysis gas. The above pyrolysis gas contains hydrogen, methane, carbon monoxide and carbon dioxide. Passing the above pyrolysis gas through a filter composed of a carbon dioxide adsorbent material to obtain a purer coal pyrolysis gas whose main components are hydrogen, methane and carbon monoxide, and the coal pyrolysis gas filtered out above is free of impurities, thereby High quality gaseous fuel with very high calorific value.
原煤在热解炉中经中低温热解失去水分和中低温挥发分后变为焦或提 质煤, 其热值也大幅度提高。  In the pyrolysis furnace, the raw coal loses moisture and low-temperature volatiles after medium-low temperature pyrolysis, and then turns into coke or upgraded coal, and its calorific value is also greatly improved.
与煤热解气冷凝分离的焦油或液化合成油是很好的化工原料或液体燃 料。  The tar or liquefied synthetic oil separated from the coal pyrolysis gas is a good chemical raw material or liquid fuel.
这样, 通常的原煤、 尤其是劣质煤经本发明煤中低温热解提质系统而 被转变为提质煤、 高热值热解气和煤焦油或液化合成油, 其利用价值和热 效率被大大提高。  In this way, the usual raw coal, especially the inferior coal, is converted into upgraded coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil by the low-temperature pyrolysis upgrading system of the present invention, and the utilization value and thermal efficiency thereof are greatly improved. .
当上述催化-热载体-氧转移材料是 Fe的氧化物时,这种催化 -热载体-氧 转移材料可能会存在多种形态,因为通常作为上述催化-热载体 -氧转移材料 的 Fe的氧化物在中低温热解炉( 100 )和再生器( 200 )中会发生以下反应: 在热解炉(100)的还原气氛下, 铁的氧化物会发生以下反应:  When the above catalytic-heat carrier-oxygen transfer material is an oxide of Fe, the catalytic-heat carrier-oxygen transfer material may have various forms because of the oxidation of Fe which is usually used as the above-mentioned catalytic-heat carrier-oxygen transfer material. The following reactions occur in the medium-low temperature pyrolysis furnace (100) and the regenerator (200): Under the reducing atmosphere of the pyrolysis furnace (100), the iron oxide undergoes the following reaction:
CxHy (coal)+ FeO → CO2 + H2O+ Fe (12) 或 CxHy (coal)+ Fe2〇3→ CO2 + H2O+ Fe (13) CxHy (coal)+ FeO → CO2 + H2O+ Fe (12) or CxHy (coal)+ Fe2〇3→ CO2 + H2O+ Fe (13)
FeO + H2 = Fe + H2O (14)FeO + H2 = Fe + H2O (14)
Fe203 + H2 = 2FeO+ H2O (15)Fe203 + H2 = 2FeO+ H2O (15)
Fe203 + 3H2 = 2Fe+ 3H2O (16)Fe203 + 3H2 = 2Fe+ 3H2O (16)
2Fe304+ 3H2 = 3Fe203 + Η2θ (17)2Fe304+ 3H2 = 3Fe203 + Η2θ (17)
FeO + CO= FeO+ CO2 (18)FeO + CO= FeO+ CO2 (18)
Fe203 + CO = 2FeO+ CO2 (19)Fe203 + CO = 2FeO+ CO2 (19)
Fe203 + 3CO = 2Fe+ 3C02 (20)Fe203 + 3CO = 2Fe+ 3C02 (20)
2Fe304+ 3CO = 3Fe203 + C02 (21) 而在再生器(200) 中, 在氧化气氛下, Fe会发生以下反应: 2Fe304+ 3CO = 3Fe203 + C02 (21) In the regenerator (200), Fe undergoes the following reaction in an oxidizing atmosphere:
2Fe + 02 = 2FeO ( 22 ) 4FeO + θ2 = 2Fe203 ( 23 )2Fe + 02 = 2FeO ( 22 ) 4FeO + θ2 = 2Fe203 ( 23 )
4Fe + 3 θ2 = 2Fe203 ( 24 )4Fe + 3 θ2 = 2Fe203 ( 24 )
3Fe + 2 θ2 = Fe304 ( 25 )3Fe + 2 θ2 = Fe304 ( 25 )
6FeO + θ2 = 2Fe304 ( 26 ) 上述氧化反应均为强放热反应, 其间将会产生大量热量, 从而将再生 器(200 )的工作温度维持在 400-1000。C的范围之内。上述反应具有不同的 反应温度, 例如在 520-1000 °C的反应温度下, Fe主要被氧化为 Fe203。 6FeO + θ2 = 2Fe304 ( 26 ) The above oxidation reactions are all strongly exothermic, during which a large amount of heat is generated, thereby maintaining the operating temperature of the regenerator (200) at 400-1000. Within the scope of C. The above reaction has different reaction temperatures, for example, Fe is mainly oxidized to Fe203 at a reaction temperature of 520 to 1000 °C.
由于从上述热解炉中排出的煤热解气体和从上述再生器中排出的脏空 气通常会含有固体颗粒的粉尘, 优选地, 使这样的气体通过气 -固或气-液 分离器, 例如图 1所示的旋风机 114、 旋风机级联、 隔膜、 和 /或过滤器, 以实现气-固分离, 分离后的固体粉尘可进行常规的水淬处理。  Since the coal pyrolysis gas discharged from the above pyrolysis furnace and the dirty air discharged from the above regenerator usually contain dust of solid particles, preferably such gas is passed through a gas-solid or gas-liquid separator, for example The cyclone 114, the cyclone cascade, the diaphragm, and/or the filter shown in Fig. 1 are used to achieve gas-solid separation, and the separated solid dust can be subjected to conventional water quenching treatment.
气-固分离后的煤热解气体通常在 250-750 C之间。 优选地, 可用一个 或多个热交换器(未示出) , 例如水或空气可流经其间的盘管式或多管式 热交换器将其温度降低到适合于冷凝分离煤焦油或加氢液化合成油的温 度, 例如 22-35。C, 上述温度对于本领域普通技术人员来说是显而易见的, 并可从相关的现有技术文献或专有设备说明书中得到。  The coal pyrolysis gas after gas-solid separation is usually between 250 and 750 C. Preferably, one or more heat exchangers (not shown), such as water or air, may be passed through a coiled or multi-tube heat exchanger to reduce the temperature thereof to a condensed separation coal tar or hydrogenation The temperature of the liquefied synthetic oil, for example 22-35. C, the above temperatures will be apparent to those of ordinary skill in the art and can be derived from the related prior art literature or proprietary device specifications.
优选地被气 -固分离和冷却的煤热解气体经典型地含有如图 1所示的冷 凝器(300 )的煤焦油或液化合成油收集设备, 而被分离成纯的煤热解气和 煤焦油或加氢液化合成油。  The coal pyrolysis gas, preferably gas-solid separated and cooled, classically contains a coal tar or liquefied synthetic oil collection device of the condenser (300) as shown in Fig. 1, and is separated into pure coal pyrolysis gas and Coal tar or hydrogenated liquefied synthetic oil.
更优选地, 在上述热交换器中, 使用经压缩机(未示出)增压的压缩 空气作为热交换器的热交换介质, 被上述热交换器加热的压缩空气可作为 上述再生器( 200 )所需的热空气来源, 经高压喷嘴被直接喷到所述再生器 ( 200 )的底部。  More preferably, in the above heat exchanger, compressed air pressurized by a compressor (not shown) is used as a heat exchange medium of the heat exchanger, and compressed air heated by the above heat exchanger can be used as the above regenerator (200) The desired source of hot air is sprayed directly onto the bottom of the regenerator (200) via a high pressure nozzle.
从上述再生器 ( 200 ) 的顶部排出的耗氧或无氧的脏空气温度可达 400-1000 °C , 同样也可用一个或多个热交换器(未示出)来降低其温度, 但优选地, 该高温高压空气可被送入膨胀机中, 并驱动蒸汽锅炉或汽轮机 用于发电, 所产生的蒸汽也可作为中低温热解炉(100 )所需的蒸汽来源经 高压喷嘴被直接注入到所述热解炉的下部或底部、或用于上述固-固分离器 的分离介貭。 实际上,在中低温热解炉( 100 )中存在至少一个中低温热解区( 105 ), 该热解区为固定床、 震动床、 或移动床型结构, 而优选为移动床型结构, 煤在该区域被中低温热解, 同样水煤气反应也发生在该区域。 在该区域, 原煤和催化-热载体 -氧转移材料被充分混合, 高压和高温水蒸汽也从热解 炉(100 )的下部或底部被注入到该区域中, 从而形成煤、 催化 -热载体-氧 转移材料, 和水蒸汽的混合物。 The temperature of the oxygen-depleted or oxygen-free dirty air discharged from the top of the regenerator (200) can reach 400-1000 ° C, and one or more heat exchangers (not shown) can also be used to lower the temperature, but preferably Ground, the high temperature and high pressure air can be sent to the expander and drive the steam boiler or steam turbine for power generation. The generated steam can also be directly injected into the steam source required by the medium and low temperature pyrolysis furnace (100) through the high pressure nozzle. To the lower or bottom of the pyrolysis furnace, or to the separation medium for the solid-solid separator described above. In fact, there is at least one medium-low temperature pyrolysis zone (105) in the medium-low temperature pyrolysis furnace (100), which is a fixed bed, a vibrating bed, or a moving bed type structure, and is preferably a moving bed type structure. The coal is pyrolyzed in the region at low temperatures, and the same water gas reaction also occurs in this region. In this region, the raw coal and the catalytic-heat carrier-oxygen transfer material are thoroughly mixed, and high-pressure and high-temperature steam are also injected into the region from the lower or bottom portion of the pyrolysis furnace (100) to form coal, catalytic-heat carrier. - a mixture of oxygen transfer material, and water vapor.
完成中低温热解和化学反应的提质煤或焦和废催化 -热载体-氧转移材 料的混合物从其出口( 109 )被排出热解炉( 100 ),并通过固-固分离器( 400 ) 进行固-固分离, 与废催化-热载体 -氧转移材料分离后的^^煤或焦经飩化 失活降温变为^^煤固体产品, 而与 ^^煤或焦分离后的废催化 -热载体- 氧转移材料经废催化-热载体-氧转移材料输送管线(103 )进入其再生器 ( 200 ) 中被再生。  A mixture of upgraded coal or coke and spent catalytic-heat carrier-oxygen transfer material that completes the low-temperature pyrolysis and chemical reaction is discharged from the outlet (109) to the pyrolysis furnace (100) and passed through a solid-solid separator (400). The solid-solid separation is carried out, and the separation of the waste catalyst-heat carrier-oxygen transfer material after the separation of the coal or the coke is reduced to become a solid product of the coal, and the waste after separation from the coal or coke The catalytic-heat carrier-oxygen transfer material is regenerated by the spent catalytic-heat carrier-oxygen transfer material transfer line (103) into its regenerator (200).
上述固-固分离器是利用重力差来实现不同种类固体颗粒分离的,具体 地说,由于不同种类固体颗粒比重不同,在气态分离介质的流化力或吹力作 用下,它们的流化或漂浮高度以及落差也不同,利用这种高度差或落差就可 实现不同种类固体颗的分离。这类固-固分离器为本领域普通技术人员所熟 知, 并可通过查阅现有技术中的相关文献或设备说明书获取更多详情。 本 发明可选用流化床型、 例如喷泉床型固 -固分离器; 也可选用旋风型固-固 分离器、 或其它类型的固 -固分离器。  The above solid-solid separator utilizes the difference in gravity to achieve separation of different types of solid particles. Specifically, due to the different specific gravity of different types of solid particles, they may be fluidized under the fluidization or blowing force of the gaseous separation medium. The floating height and the drop are also different, and the separation of different kinds of solid particles can be achieved by using the height difference or the drop. Such solid-solid separators are well known to those of ordinary skill in the art, and more details can be obtained by reviewing related literature or equipment specifications in the prior art. The present invention may alternatively be a fluidized bed type, such as a fountain bed type solid-solid separator; a cyclone type solid-solid separator, or other type of solid-solid separator may also be used.
优选地, 在提质煤和废催化-热载体 -氧转移材料的混合物被排出热解 炉(100 )之外、 而进入上述固-固分离器(400 )之前, 使该混合物通过一 个或多个串联的筛网 (110 ) , 而对所述混合物颗粒进行一次或多次分级, 而上述筛网 (110 )的筛孔最小直径大于或等于废催化-热载体 -氧转移材料 颗粒的最大直径, 以便至少使废催化 -热载体-氧转移材料通过所述筛网。 这样 上述固-固分离器中的混合物已 催化-热载体-氧转移材料颗粒 和粒径与其相当的提质煤细颗粒的混合物。 粒径大于废催化-热载体 -氧转 移材料颗粒的提质煤颗粒已被上述筛网截流, 并形成高品质的提质煤。 上 述筛网优选为振动筛,能承受约 250-750°C的高温,并在上述高温下具有足 够的强度和抗变形能力。 可使用多种材料制备上述筛网、例如基于 Fe、 Co 和 /或 Ni的耐高温合金。上述提质煤和废催化-热载体-氧转移材料的混合物 在分级后, 分级颗粒可由各自的传送机、 例如图 1所示的传送机(113 )和 ( 115 )运输。 Preferably, the mixture is passed through one or more before the mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material is discharged from the pyrolysis furnace (100) and before entering the solid-solid separator (400). a mesh (110) in series, and the mixture particles are subjected to one or more classifications, and the mesh (110) has a mesh diameter of at least equal to or greater than a maximum diameter of the waste catalytic-heat carrier-oxygen transfer material particles. In order to at least pass the spent catalytic-heat carrier-oxygen transfer material through the screen. Thus the mixture in the above solid-solid separator has catalyzed a mixture of the heat carrier-oxygen transfer material particles and the upgraded coal fine particles having a particle size equivalent thereto. The upgraded coal particles having a particle size larger than the spent catalytic-heat carrier-oxygen transfer material particles have been intercepted by the above-mentioned screen and formed into high quality upgraded coal. The screen described above is preferably a vibrating screen capable of withstanding high temperatures of about 250-750 ° C and having sufficient strength and resistance to deformation at the elevated temperatures described above. The above screens can be prepared using a variety of materials, for example based on Fe, Co And / or Ni high temperature alloy. After fractionation of the above mixture of upgraded coal and spent catalytic-heat carrier-oxygen transfer material, the classified particles may be transported by respective conveyors, such as conveyors (113) and (115) shown in FIG.
同样优选地, 经由分离介质入口 (401 )进入上述固-固分离器的分离 介质可为高压水蒸汽和 /或循环热解气, 更优选地为来自前述由再生器 ( 200 )排出的耗氧或无氧高温脏空气驱动的高压蒸气锅炉的水蒸气和 /或 由冷凝器(300 )排出的热解气, 上述水蒸汽和 /或循环热解气经由分离介 质出口 (402 ) 离开固-固分离器后可经气-固分离设备、 例如^ X机(403 ) 除去固体细颗粒或粉尘后、 经水蒸气入口 (102 )被注入到热解炉 (100 ) 中。  Also preferably, the separation medium entering the solid-solid separator via the separation medium inlet (401) may be high pressure steam and/or recycled pyrolysis gas, more preferably oxygen from the aforementioned regenerator (200). Or water vapor of a high-pressure steam boiler driven by an oxygen-free high-temperature dirty air and/or pyrolysis gas discharged from a condenser (300), the water vapor and/or circulating pyrolysis gas leaving the solid-solid via a separation medium outlet (402) The separator may be injected into the pyrolysis furnace (100) through a water vapor inlet (102) after removal of solid fine particles or dust by a gas-solid separation apparatus such as a X-ray machine (403).
上述废催化 -热载体-氧转移材料颗粒和粒径与其相当的提质煤细颗粒- 焦粉的混合物经上述固-固分离器(400 )分离后, 绝大多数的焦粉由例如 位于上述固-固分离器(400 ) 中部或侧边的其溢流出口 (未示出)排出, 而一小部分焦粉会随分离介质气体离开固-固分离器后, 经气-固分离设备、 例如旋风机(403 )而与分离介质气体、例如高压水蒸汽或循环热解气实现 分离, 由气-固分离装置、 例如旋风机(403 )得到的焦微粒-焦粉可从底部 回收, 上述焦粉进行压块后可作为副产品出售。  After the above waste catalytic-heat carrier-oxygen transfer material particles and the mixture of the upgraded coal fine particle-coke powder having the same particle diameter and the above-mentioned solid-solid separator (400) are separated, most of the coke powder is, for example, located above. The solid or solid separator (400) is discharged from the overflow outlet (not shown) in the middle or side, and a small portion of the coke powder is separated from the solid-solid separator by the separation medium gas, through the gas-solid separation device, For example, a cyclone (403) is separated from a separation medium gas, such as high-pressure steam or a circulating pyrolysis gas, and the coke-coke powder obtained by a gas-solid separation device such as a cyclone (403) can be recovered from the bottom, After the coke breeze is pressed, it can be sold as a by-product.
需要注意的是: 在某些情况下, 可故意在上述废催化-热载体-氧转移 材料颗粒中混入一定比例的上述焦粉, 所述焦粉随废催化-热载体-氧转移 材料颗粒一起 所述再生器(200 ) 中后, 会与通入再生器(200 ) 中的 热携氧气体、例如热空气中的氧气一起燃烧,从而放出燃烧热以补充热量, 以便使所述再生器中的化学反应得以连续进行,或维持整个系统的热平衡。  It should be noted that: in some cases, a certain proportion of the above-mentioned coke breeze may be intentionally mixed into the above-mentioned waste catalytic-heat carrier-oxygen transfer material particles, which together with the waste catalytic-heat carrier-oxygen transfer material particles The regenerator (200) is then combusted with a hot oxygen-carrying gas, such as oxygen in the hot air, introduced into the regenerator (200) to vent heat of combustion to supplement the heat so that the regenerator is The chemical reaction is carried out continuously or maintains the thermal equilibrium of the entire system.
在本发明的一个优选实施方式中, 催化-热载体-氧转移材料颗粒的粒 度为 1至 1000微米, 而煤或焦颗粒的粒度为 5亳米到 15厘米, 例如 5厘 米 -15厘米。 中低温热解炉(100 )的温度和压力在适合于煤的中低温热解 的范围内, 例如 200。C-900。C, 特别是 250。C-750。C; 1大气压 -100巴, 特 别是 20-60巴。  In a preferred embodiment of the invention, the catalyst-heat carrier-oxygen transfer material particles have a particle size of from 1 to 1000 microns, and the coal or coke particles have a particle size of from 5 to 15 cm, for example from 5 to 15 cm. The temperature and pressure of the medium-low temperature pyrolysis furnace (100) are within a range suitable for medium-low temperature pyrolysis of coal, for example, 200. C-900. C, especially 250. C-750. C; 1 atmosphere - 100 bar, especially 20-60 bar.
由于中低温热解炉 (100 ) 中的气氛是还原气氛, 而再生器(200 ) 中 的气氛是氧化气氛, 在中低温热解炉( 100 )和再生器( 200 )经管线( 103 ) 和( 104 )相连通的情况下, 两个反应器需要气氛隔离。 可将水蒸汽(未示 出)作为气氛隔离介质而将二者的气氛相互隔离。 Since the atmosphere in the medium-low temperature pyrolysis furnace (100) is a reducing atmosphere, and the atmosphere in the regenerator (200) is an oxidizing atmosphere, in the medium-low temperature pyrolysis furnace (100) and the regenerator (200) via the pipeline (103) In the case of communication with (104), the two reactors require atmospheric isolation. Water vapor (not shown) may be used as an atmosphere isolating medium to isolate the atmospheres of the two from each other.
煤在中低温热解炉( 100 )中停留的时间通常取决于所用煤中低温热解 炉的类型和操作条件。 这些工艺参数可从相关设备的使用手册或产品说明 书中查到, 也可从本领域普通技术人员所熟知的现有技术文献中查阅到。 对于移动床类型的煤中低温热解炉而言,通常煤在其中停留的时间约为 30 分钟 -3小时, 例如约 1小时 -2小时, 而优选约为 1小时 30分钟。  The residence time of the coal in the medium and low temperature pyrolysis furnace (100) generally depends on the type and operating conditions of the low temperature pyrolysis furnace in the coal used. These process parameters can be found in the manuals or product specifications of the relevant equipment, as well as in the prior art documents well known to those skilled in the art. For a moving bed type coal medium to low temperature pyrolysis furnace, usually the time in which the coal stays is about 30 minutes to 3 hours, for example, about 1 hour to 2 hours, and preferably about 1 hour and 30 minutes.
从催化-热载体 -氧转移材料再生器(200 )上部或顶部排出的耗氧或无 氧脏空气会含有一定量的固体粉尘颗粒,这些固体颗粒可能包括催化 -热载 体-氧转移材料细颗粒或粉尘。 优选地, 用常规固-气或液-气分离设备、 如 机、 旋风机级联、 过滤器、 和 /或隔膜对上述夹带这些固体细颗粒或粉 尘的耗氧或无氧脏空气在排放或进行热利用之前进行一级或多级固 -气分 离处理。 ,  The oxygen-depleted or anaerobic dirty air discharged from the upper or top of the catalytic-heat carrier-oxygen transfer material regenerator (200) will contain a certain amount of solid dust particles, which may include catalytic-heat carrier-oxygen transfer material fine particles. Or dust. Preferably, the above-mentioned solid-gas or liquid-gas separation equipment, such as a machine, a cyclone cascade, a filter, and/or a diaphragm, is used to discharge the oxygen-depleted or anaerobic dirty air entrained with these solid fine particles or dust. Perform one or more stages of solid-gas separation before performing heat utilization. ,
下面用详细的示范性实施例进一步描述本发明, 但这些实施例不构成 对本发明的任何限制。 实施例  The invention is further described by the following detailed examples, which are not intended to limit the invention. Example
实施例 1 Example 1
采取如图 1所示的煤热解 ^^的系统来实施本发明生产^ ^煤、 高热 值热解气和煤焦油或液化合成油的方法  The method for producing coal of coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil by using the system of coal pyrolysis shown in FIG. 1
首先, 将以下化学组成的褐煤用常规的破碎设备破碎成具有以下粒径 分布的颗粒。  First, lignite having the following chemical composition was broken into particles having the following particle size distribution by a conventional crushing apparatus.
15厘米 > 100重量%烟煤颗粒粒径 > 5厘米 催化-热载体-氧转移材料为 Fe203,其具有如下粒径分布:  15 cm > 100% by weight of bituminous coal particles > 5 cm The catalytic-heat carrier-oxygen transfer material is Fe203, which has the following particle size distribution:
1亳米 > 100重量%催化-热载体 -氧转移材料 > 1微米 1 亳 > 100% by weight of catalytic-heat carrier - oxygen transfer material > 1 micron
100微米 > 95重量%催化-热载体 -氧转移材料 > 10微米 上述颗粒的粒径用筛分法或比表面积法确定。 100 μm > 95% by weight Catalytic-heat carrier - Oxygen transfer material > 10 μm The particle size of the above particles is determined by a sieving method or a specific surface area method.
以重量%计,褐煤的化学组成如下 (干基): c H O N S 灰分 挥发分 In terms of % by weight, the chemical composition of lignite is as follows (dry basis): c HONS ash volatiles
64.18 4.45 16.86 0.99 0.33 13.19 43.39 通常,对褐煤的水分含量不做限定,但此时褐煤的水分含量为 30.99%。 热值是 17,541焦耳 /克。任选地, 也可对褐煤原料进行预热和预干燥, 使其 水分含量为 12重量%以下, 温度达到 120。C左右。 褐煤在中低温热解炉中 的热解停留时间约为 1小时 45分钟。  64.18 4.45 16.86 0.99 0.33 13.19 43.39 Generally, the moisture content of lignite is not limited, but the moisture content of lignite is 30.99%. The calorific value is 17,541 joules / gram. Optionally, the lignite feedstock may also be preheated and pre-dried to a moisture content of less than 12% by weight and a temperature of 120. C or so. The pyrolysis residence time of lignite in a medium-low temperature pyrolysis furnace is about 1 hour and 45 minutes.
将预热至 120。C的上述褐煤颗粒以 1000公斤 /小时的流量从上部或顶 部经已知的锁斗系统喂入已知流动床型热解炉 (100)中。 中低温热解炉 It will be warmed up to 120. The above lignite granules of C are fed into the known fluidized bed type pyrolysis furnace (100) from the upper or top portion via a known lock system at a flow rate of 1000 kg / hr. Medium and low temperature pyrolysis furnace
( 100 ) 的热解区 (105 ) 的工作温度是大约 400-550eC, 工作压力是大约 35巴。从上述中低温热解炉( 100 )的下部经高压喷嘴以 1000立方米 /小时 的流量将大约 200-300。C的水蒸气喷入到中低温热解炉(100 ) 中, 经再生 催化-热载体-氧转移材料输送管道( 104 )以 180公斤 /小时的流量将再生催 化-热载体 -氧转移材料 -Fe203加入到上述中低温热解区(105)中,在热解炉The pyrolysis zone (105) of (100) has an operating temperature of approximately 400-550 e C and a working pressure of approximately 35 bar. From the lower portion of the above-mentioned medium-low temperature pyrolysis furnace (100), a flow rate of 1000 m 3 /hr through the high pressure nozzle will be about 200-300. The water vapor of C is sprayed into the medium-low temperature pyrolysis furnace (100), and the regenerated catalytic-heat carrier-oxygen transfer material delivery line (104) is used to regenerate the catalytic-heat carrier-oxygen transfer material at a flow rate of 180 kg/hr. Fe203 is added to the above-mentioned medium-low temperature pyrolysis zone (105) in the pyrolysis furnace
( 100 )中, 褐煤颗粒和 800-1000。C的催化-热载体-氧转移材料发生强烈碰 撞而被均匀混合, 并随后在水蒸气的存在下开始发生中低温热解。 随着混 合物向下移动并持续发生热解反应, 热解炉 (100 ) 中的热解区(105)的温 度逐渐趋于稳定。煤经中低温热解脱去水分和中低温挥发分变为焦或半焦, 并产生含有气态焦油的热解气,同时 Fe203被还原并释放出氧, 从而变为主 要为 Fe/FeO的废催化-热载体-氧转移材料。在热解炉底部的上述混合物出 口处, 混合物温度约为 400。 ( 。 热解后的半焦 /废催化-热载体 -氧转移材料 混合物从其出口处被排出, 并由一个震动筛 (110)进行筛分, 筛孔直径为 1 亳米, 筛网用基于 M的耐高温合金制成, 并在 400。C左右表现出优异的强 度和抗变形能力。 由于半焦颗粒直径远大于废催化-热载体-氧转移材料的 颗粒直径, 半焦和废催化 -热载体-氧转移材料混合物被分成两股物流。 半 焦经过失活钝化降温, 形成高品质的半焦产品-提质煤。 废催化 -热载体-氧 转移材料和粒径小于筛孔直径的半焦微粒的混合物进入一个已知流化床型 固-固分离器中进行彼此分离。 由于废催化-热载体 -氧转移材料 Fe或 FeO 的密度大于 5g/cm3; 而半焦颗粒的密度为 1.2g/cm3, 经过固-固分离器中流 化床的流化力作用, 密度大的废催化-热载体-氧转移材料富集于流化床型 分离器底部。而半焦微粒则被流化分离介质 -水蒸气从分离器顶部带离分离 器, 从而实现两种固体的分离。 (100), lignite pellets and 800-1000. The catalytic-heat carrier-oxygen transfer material of C is uniformly collided and uniformly mixed, and then low-temperature pyrolysis begins to occur in the presence of water vapor. As the mixture moves downward and the pyrolysis reaction continues, the temperature of the pyrolysis zone (105) in the pyrolysis furnace (100) gradually becomes stable. The coal is decomposed by moisture at medium and low temperature, and the volatile matter of medium and low temperature becomes coke or semi-coke, and pyrolysis gas containing gaseous tar is produced, and Fe203 is reduced and releases oxygen, thereby becoming waste catalysis mainly of Fe/FeO. - Heat carrier - oxygen transfer material. At the outlet of the above mixture at the bottom of the pyrolysis furnace, the temperature of the mixture was about 400. (The semi-coke/waste catalytic-heat carrier-oxygen transfer material mixture after pyrolysis is discharged from its outlet and sieved by a vibrating screen (110) with a mesh diameter of 1 亳m, based on the screen M made of high temperature resistant alloy and exhibits excellent strength and deformation resistance at around 400 ° C. Since the semi-coke particle diameter is much larger than the particle diameter of the waste catalytic-heat carrier-oxygen transfer material, semi-coke and waste catalyst - The heat carrier-oxygen transfer material mixture is divided into two streams. The semi-coke is deactivated and passivated to cool down to form a high quality semi-coke product - upgraded coal. Waste catalytic-heat carrier-oxygen transfer material and particle size smaller than the mesh diameter The mixture of semi-coke particles is separated from each other into a known fluidized bed type solid-solid separator. The density of the spent catalyst-heat carrier-oxygen transfer material Fe or FeO is greater than 5 g / cm 3 ; Density of 1.2 g / cm 3 , passing through the solid-solid separator The fluidization force of the chemical bed, the dense waste catalytic-heat carrier-oxygen transfer material is enriched in the bottom of the fluidized bed type separator. The semi-coke particles are then separated from the separator by the fluidized separation medium, water vapor, from the top of the separator, thereby achieving separation of the two solids.
经过上述水蒸气的流化分离后, 废催化-热载体-氧转移材料被冷却到 After the fluidized separation of the above water vapor, the spent catalytic-heat carrier-oxygen transfer material is cooled to
200-300°C, 并经废催化-热载体-氧转移材料输送管道( 103 ) 再生器底 部( 200 )的底部。 用高压喷嘴将流量约 100立方米 /小时的约 300°C的热空 气注入到再生器(200 ) 的底部, 催化-热载体 -氧转移材料再生器(200 ) 的工作温度为 800-1000 °C, 压力是 35巴, 在催化 -热载体-氧转移材料再生 器(200 )和中低温热解炉(100 )之间, 用水蒸气进行气氛隔离。 在再生 器(200 ) 的操作初期, 为了保持其工作温度, 可将热空气的温度提高至 1000°C左右, 在其达到工作温度、 并且放热反应已开始进行后, 可降低热 空气的温度至 300。C, 在再生器(200 ) 中, 废催化-热载体-氧转移材料和 经空气入口 (201 )进入再生器(200 ) 中的热空气中的氧进行氧化反应, 反应释放出大量热量, 并使废催化-热载体-氧转移材料由 Fe/FeO 变为 Fe2〇3而被再生。 在再生器(200 )顶部的扩大段, 无氧空气和 800-1000°C 的再生催化 -热载体-氧转移材料相互分离。再生催化-热载体-氧转移材料经 其输送管道(104 )被从顶部注入热解炉 (100 ) 中; 而无氧空气则由其出 口 (203 )排出。 因为催化-热载体 -氧转移材料会逐渐磨损和损失, 因此需 要根据具体情况进行适当补充。 200-300 ° C, and through the waste catalytic - heat carrier - oxygen transfer material delivery pipe (103) at the bottom of the regenerator bottom (200). A hot air of about 300 ° C at a flow rate of about 100 cubic meters per hour is injected into the bottom of the regenerator (200 ) with a high pressure nozzle, and the catalytic-heat carrier-oxygen transfer material regenerator (200) is operated at a temperature of 800-1000 °. C, the pressure is 35 bar, and between the catalytic-heat carrier-oxygen transfer material regenerator (200) and the medium-low temperature pyrolysis furnace (100), the atmosphere is isolated by steam. At the beginning of the operation of the regenerator (200), in order to maintain its operating temperature, the temperature of the hot air can be raised to about 1000 ° C. After it reaches the operating temperature and the exothermic reaction has begun, the temperature of the hot air can be lowered. To 300. C, in the regenerator (200), the spent catalytic-heat carrier-oxygen transfer material and the oxygen in the hot air entering the regenerator (200) through the air inlet (201) are oxidized, the reaction releases a large amount of heat, and The spent catalytic-heat carrier-oxygen transfer material is regenerated from Fe/FeO to Fe2〇3. In the enlarged section at the top of the regenerator (200), the oxygen-free air and the regenerated catalytic-heat carrier-oxygen transfer material at 800-1000 ° C are separated from each other. The regenerated catalytic-heat carrier-oxygen transfer material is injected into the pyrolysis furnace (100) from the top through its delivery conduit (104); and the oxygen-free air is discharged from its outlet (203). Since the catalytic-heat carrier-oxygen transfer material is gradually worn and lost, it needs to be appropriately supplemented according to the specific situation.
再生器(200 )中的上述热空气的来源可来自其中热交换介盾与热 解气进行热交换的热交换器(未示出) 。 可用压缩机将空气增压后作为热 交换介质注入到上述热交换器中, 之后被加热到 300。C的热空气从热交换 器中排出、 并被注入到再生器(200 )底部。  The source of the above hot air in the regenerator (200) may be derived from a heat exchanger (not shown) in which the heat exchange shield exchanges heat with the pyrolysis gas. The air can be pressurized by a compressor and injected into the above heat exchanger as a heat exchange medium, and then heated to 300. The hot air of C is discharged from the heat exchanger and injected into the bottom of the regenerator (200).
从再生器( 200 )的上部或顶部排出的耗氧或无氧的脏空气可经旋风机、 旋风机级联、 过滤器、 和 /或隔膜(未示出)进行固 -气分离后, 送入到膨 B ^ (未示出) 中以驱动蒸汽锅炉 (未示出)或汽轮机 (未示出)用于发 电。  Oxygen-depleted or oxygen-free dirty air exhausted from the upper or top of the regenerator (200) may be sent through a cyclone, a cyclone cascade, a filter, and/or a diaphragm (not shown) for solid-gas separation. Into the expansion B ^ (not shown) to drive a steam boiler (not shown) or a steam turbine (not shown) for power generation.
从固-固分离器顶部得到的水蒸气 /半焦樹立混合气经过一个气-固分离 装置、例如旋风机进行分离。然后约 200-30(TC水蒸气作为热解炉的松动风 从热解炉 (100 )的下部侧壁水蒸气入口 (102 )被注入热解炉中。 在热解 炉(100 )中, 水蒸气与煤和半焦会进行一部分气化反应, 产生氢气和一氧 化碳。 气化反应生成的氢在瞬间以质子态存在, 其具有艮强的活性, 可在 加氢裂化反应催化剂的作用下与煤热解产物中的大分子油-焦油组份进行 加氢裂解反应, 生成小分子的合成油品。 由气-固分离装置得到的半焦微粒The water vapor/semi-coke standing gas mixture obtained from the top of the solid-solid separator is separated by a gas-solid separation device such as a cyclone. Then about 200-30 (TC steam as the loose wind of the pyrolysis furnace A steam inlet (102) from the lower side wall of the pyrolysis furnace (100) is injected into the pyrolysis furnace. In the pyrolysis furnace (100), water vapor reacts with coal and semi-coke for a portion of the gasification reaction to produce hydrogen gas and carbon monoxide. The hydrogen produced by the gasification reaction exists in a proton state instantaneously, and has a strong activity, and can undergo a hydrocracking reaction with the macromolecular oil-tar component in the coal pyrolysis product under the action of the hydrocracking reaction catalyst. A synthetic oil of small molecules is produced. Semi-coke particles obtained by a gas-solid separation device
J3 »J从底部回收后进行压块作为副产品出售。 J3 »J is recycled from the bottom and sold as a by-product.
从热解炉(100 )上部排出的热解气可包含小分子气体、 如氢气, 一氧 化碳, 二氧化碳, 甲烷, 水蒸气等, 和一些烷烃, 烯烃, 芳香烃等煤焦油 组分。 经过一个固气分离装置、 例如旋风机(117 )滤掉其夹带的固体细颗 粒或灰分, 然后进入包括冷凝器(300 )和热交换器(未示出)的焦油或液 化合成油回收装置, 热交换器使其温度被降低至 70 C-150eC, 之后再使其 经过冷凝器( 300 ),冷凝器将上述气体温度进一步降低到 22。C-35。C,从而得 到液相的煤馏出油 -煤焦油和轻组份气相-纯热解气产物。 液相煤馏出油可 作为产品,轻组分 -纯热解气产物可视情况燃烧提供系统能量或者作为产品 出售。 The pyrolysis gas discharged from the upper portion of the pyrolysis furnace (100) may contain small molecule gases such as hydrogen, carbon monoxide, carbon dioxide, methane, water vapor, etc., and some coal tar components such as alkanes, alkenes, aromatic hydrocarbons, and the like. The solid fine particles or ash entrained by it is filtered through a solid-gas separation device, such as a cyclone (117), and then passed to a tar or liquefied synthetic oil recovery unit including a condenser (300) and a heat exchanger (not shown). The heat exchanger has its temperature lowered to 70 C-150 e C and then passed through a condenser (300) which further reduces the gas temperature to 22. C-35. C, thereby obtaining a liquid distillate-coal tar and a light component gas phase-pure thermal degassing product. The liquid coal distillate can be used as a product, and the light component-pure pyrolysis product can be burned to provide system energy or sold as a product.
以重量%计, 提质煤的化学组成如下:  In terms of % by weight, the chemical composition of the upgraded coal is as follows:
表 2
Figure imgf000019_0001
Table 2
Figure imgf000019_0001
上述提质煤的热值经测量为 25731焦耳 /克,由此可知,经过上述处理, 煤的热值有了大幅度的提高。  The calorific value of the above-mentioned upgraded coal was measured to be 25,731 joules/gram, and it was found that the heat value of the coal was greatly improved by the above treatment.
以摩尔%计, 上述纯煤热解气的化学组成如下:  In mole %, the chemical composition of the above pure coal pyrolysis gas is as follows:
表 3
Figure imgf000019_0002
table 3
Figure imgf000019_0002
上述煤热解气脱水后的热值约为 17500千焦耳 /立方米, 由此可知, 其 为一种热值较高的气体燃料。  The calorific value of the above coal pyrolysis gas dehydration is about 17,500 kJ/m 3 , which is known to be a gaseous fuel having a relatively high calorific value.
以重量%计, 上述中低温热解煤焦油的化学组成如下: 表 4 The chemical composition of the above medium-low temperature pyrolysis coal tar is as follows: Table 4
Figure imgf000020_0001
Figure imgf000020_0001
经元素分析, 以重量%计, 中低温热解煤焦油的元素组成如下:  Elemental analysis, in weight%, the elemental composition of medium and low temperature pyrolysis coal tar is as follows:
表 5
Figure imgf000020_0002
实施例 2
table 5
Figure imgf000020_0002
Example 2
将上述实施例 1 中破碎的褐煤颗粒与粒径相等或相似的磁黄铁矿 ( Fe(i-x)S ) (式中 ( 1-x )一般为 0.8左右) 以 99: 1的重量比例混合后, 所形成的混合物用与实施例 1相同的方法被注入到中低温热解炉( 100 )中。 在上述磁黄铁矿以及煤热解过程中产生的 FeS的催化作用下, 煤或煤热解 所产生的焦油将发生裂解, 并与热解气中的氢气发生加氢反应, 从而形成 低分子量的液化合成油。  The lignite particles crushed in the above Example 1 are mixed with pyrrhotite (Fe(ix)S) having the same or similar particle diameter (wherein (1-x) is generally about 0.8) in a weight ratio of 99:1. The resulting mixture was injected into the medium-low temperature pyrolysis furnace (100) in the same manner as in Example 1. Under the catalytic action of FeS produced in the pyrrhotite and coal pyrolysis process, the tar produced by coal or coal pyrolysis will be cracked and hydrogenated with hydrogen in the pyrolysis gas to form a low molecular weight. Liquefied synthetic oil.
最终, 以摩尔%计, 煤热解气的化学组成如下:  Finally, in mole%, the chemical composition of coal pyrolysis gas is as follows:
表 6
Figure imgf000020_0003
Table 6
Figure imgf000020_0003
上述热解气脱水后的热值约为 15900千焦耳 /立方米, 由此可知, 其仍 为一种热值较高的气体燃料。  The calorific value of the above pyrolysis gas after dehydration is about 15,900 kJ/m 3 , which is known to be a gaseous fuel having a relatively high calorific value.
以重量%计, 合成油的化学组成如下:  In terms of % by weight, the chemical composition of the synthetic oil is as follows:
表 7
Figure imgf000020_0004
Table 7
Figure imgf000020_0004
经元素分析, 以重量%计, 上述合成油的元素组成如下:  By elemental analysis, the elemental composition of the above synthetic oil is as follows:
表 8  Table 8
C H N S o 金属 82% 14% 1.0% 0.8% 1.3% 0.9% 在实施例 2中, 采用与实施例 1相同的工艺条件, 其中未提及的原料 组成、 工艺参数、 以及产物组成等等均与实施例 1中相同, 除非另有说明。 CHNS o metal 82% 14% 1.0% 0.8% 1.3% 0.9% In Example 2, the same process conditions as in Example 1 were employed, wherein the raw material composition, process parameters, product composition and the like not mentioned were the same as in Example 1. Same as unless otherwise stated.
上述褐煤、 提质煤、 热解气、 煤焦油或液化合成油的化学组成或元素 组成的测定用本领域普通技术人员所熟知的方法进行。 例如, 用光谱法、 工业分析法和 /或元素分析法进行测定。  The determination of the chemical composition or elemental composition of the above lignite, upgraded coal, pyrolysis gas, coal tar or liquefied synthetic oil is carried out by methods well known to those skilled in the art. For example, the measurement is carried out by spectrometry, industrial analysis, and/or elemental analysis.
在本发明煤或生物质热解^ ^系统以及利用该系统生产^ ^煤、 高热 值热解气和煤焦油或液化合成油的方法中, 催化 -热载体-氧转移材料作为 热的载体, 通过与原煤颗粒的固 -固接触传热并导致热解反应的发生。 由于 没有使用气-固传热方式, 可以节省大量的气体。 在热解炉移动床中的原煤 颗粒粉碎程度也远低于当前最常采用的流化床方式。 在降低能耗的同时, 也保证了半焦-提质煤的产品质量。  In the coal or biomass pyrolysis system of the present invention and the method for producing ^ ^ coal, high calorific value pyrolysis gas and coal tar or liquefied synthetic oil by using the system, the catalytic-heat carrier-oxygen transfer material is used as a heat carrier. Heat transfer by solid-solid contact with raw coal particles and causes the occurrence of a pyrolysis reaction. Since no gas-solid heat transfer method is used, a large amount of gas can be saved. The degree of pulverization of raw coal in the moving bed of the pyrolysis furnace is also much lower than that of the most commonly used fluidized bed. While reducing energy consumption, it also guarantees the quality of semi-coke-quality coal.
尽管已表示和描述了本发明的几个实施方式, 但本发明不被限制为所 描述的实施方式。 相反, 本领域普通技术人员应当意识到在不脱离本发明 原则和实质的情况下, 可对这些实施方式进行任何变通和改进, 本发明保 护范围由所附的权利要求及其等同物所确定。  Although a few embodiments of the invention have been shown and described, the invention is not limited to the described embodiments. Rather, it is to be understood by those of ordinary skill in the art that the present invention may be modified and modified by the appended claims and equivalents thereof.

Claims

权利要求书 Claim
1、 一种煤中低温热解^^系统, 包括: 1. A medium-low temperature pyrolysis system for coal, comprising:
固定床、 震动床、 或移动床型中低温热解炉, 包括原煤入口、 水蒸气 入口、 ^^煤和废催化-热载体-氧转移材料的混合物出口、 热解气输出管 道、 和至少一个在中低温热解炉内位于原 *A口和^ ^煤出口之间的中低 温热解区, 其中原煤在所述中低温热解区中与提供氧的催化-热载体 -氧转 移材料发生反应而被中低温热解, 并生成包括甲烷, 一氧化碳、二氧化碳、 氢气、 和水蒸气的热解气、 以及焦油或合成油气;  Fixed bed, vibrating bed, or moving bed type medium and low temperature pyrolysis furnace, including raw coal inlet, water vapor inlet, ^^ coal and waste catalytic-heat carrier-oxygen transfer material mixture outlet, pyrolysis gas output pipeline, and at least one In the medium-low temperature pyrolysis furnace, the medium-low temperature pyrolysis zone between the original *A port and the ^ ^ coal outlet, wherein the raw coal occurs in the medium-low temperature pyrolysis zone and the catalytic-heat carrier-oxygen transfer material providing oxygen The reaction is pyrolyzed by medium and low temperature, and generates pyrolysis gas including methane, carbon monoxide, carbon dioxide, hydrogen, and water vapor, and tar or synthetic oil and gas;
至少一个经固 -固分离器和废催化 -热载体-氧转移材料输送管道, 再生 催化 -热载体-氧转移材料输送管道而与所述热解炉相连通的催化 -热载体- 氧转移材料再生器, 其中 ^催化-热载体-氧转移材料再生器中的废催化- 热载体-氧转移材料与被输入所述再生器中的携氧气体发生氧化反应而被 再生,再生催化-热载体 -氧转移材料经再生催化-热载体 -氧转移材料输送管 道被循环回所述热解炉中, 而该携氧气体经氧化反应损失氧或被去除氧后 从其出口被排出;  At least one catalyst-heat carrier-oxygen transfer material connected to the pyrolysis furnace via at least one solid-solid separator and spent catalytic-heat carrier-oxygen transfer material delivery conduit, regenerated catalytic-heat carrier-oxygen transfer material delivery conduit a regenerator, wherein the spent catalyst in the catalytic-heat carrier-oxygen transfer material regenerator-heat carrier-oxygen transfer material is regenerated by oxidation reaction with an oxygen-carrying gas fed into the regenerator, and the regenerated catalytic-heat carrier - the oxygen transfer material is recycled to the pyrolysis furnace via a regenerative catalytic-heat carrier-oxygen transfer material delivery conduit, and the oxygen-carrying gas is depleted of oxygen by oxidation reaction or is removed from its outlet after being removed from oxygen;
上述固 -固分离器, 其中被排出所述热解炉的^ ^煤和废催化 -热载体- 氧转移材料的混合物依靠粒径差和 /或重力差在所述固-固分离器中被分 离,分离后的废催化-热载体-氧转移材料经废催化 -热载体-氧转移材料输送 管道^催化-热载体-氧转移材料再生器中再生; 和  The solid-solid separator described above, wherein a mixture of the coal discharged from the pyrolysis furnace and the spent catalytic-heat carrier-oxygen transfer material is subjected to a particle size difference and/or a gravity difference in the solid-solid separator Separation, separation of spent catalytic-heat carrier-oxygen transfer material by waste catalytic-heat carrier-oxygen transfer material delivery pipe ^catalytic-heat carrier-oxygen transfer material regenerator regeneration;
经上述热解气输出管道而与所述热解炉相连通的冷凝器, 其中所述焦 油气体或合成油气体经冷凝而变为焦油或液化合成油, 并与所述热解气相 分离。  A condenser that communicates with the pyrolysis furnace via the pyrolysis gas output pipe, wherein the tar gas or synthetic oil gas is condensed to become tar or liquefied synthetic oil, and is separated from the pyrolysis gas phase.
2、 根据权利要求 1的系统, 其中所述催化-热载体 -氧转移材料为铁、 镍、 和 /或辞的氧化物。  2. A system according to claim 1 wherein said catalytic-heat carrier-oxygen transfer material is an oxide of iron, nickel, and/or.
3、 根据权利要求 2的系统, 其中所述铁的氧化物为 FeO、 Fe2〇3、 和 /或 Fe3〇4或其混合物。  3. A system according to claim 2, wherein said iron oxide is FeO, Fe2?3, and / or Fe3?4 or a mixture thereof.
4、根据权利要求 1的系统, 其中, 所述的原煤 煤和煤直接液化催 化剂的混合物。 4. The system of claim 1 wherein said mixture of raw coal and coal direct liquefaction catalyst.
5、根据权利要求 1的系统,其中在所述热解炉和 /或催化-热载体 -氧转 移材料再生器中设置一个或多个热转换器, 以便将多余的热量转移出上述 系统。 The system of claim 1 wherein one or more heat exchangers are provided in said pyrolysis furnace and/or catalytic-heat carrier-oxygen transfer material regenerator to transfer excess heat out of said system.
6、 根据权利要求 1的系统, 其中在所述热解炉、 催化-热载体-氧转移 材料再生器、 和 /或固-固分离器中设置一个或多个旋风机、 旋风机级联、 过滤器、 和 /或隔膜, 以便将其中的气体与固体颗粒分离。  6. The system of claim 1 wherein one or more cyclones, cyclone cascades are disposed in said pyrolysis furnace, catalytic-heat carrier-oxygen transfer material regenerator, and/or solid-solid separator, A filter, and/or a separator, to separate the gas therein from the solid particles.
7、 根据权利要求 1的系统, 其中在所述催化 -热载体-氧转移材料再生 器中经氧化反应损失氧或被去除氧的所述携氧气体被用于经热交换器而加 热所述的热解炉或其所需要的水蒸气。  7. The system according to claim 1, wherein said oxygen-carrying gas which is oxygen-reduced by oxidation reaction or oxygen-removed in said catalytic-heat carrier-oxygen transfer material regenerator is used to heat said heat exchanger The pyrolysis furnace or the water vapor it needs.
8、根据权利要求 1的系统,其中在所述冷凝器中布置一层或多层二氧 化碳吸附剂, 从而捕捉二氧化碳、 并提高所述热解气的热值。  8. A system according to claim 1 wherein one or more layers of carbon dioxide adsorbent are disposed in said condenser to capture carbon dioxide and increase the calorific value of said pyrolysis gas.
9,根据前述权利要求 1的系统,其中原煤在中低温热解区中被脱去水 分、 中低温挥发分, 从而变为热值被提高的提质煤。  A system according to any of the preceding claims, wherein the raw coal is dehydrated, medium and low temperature volatiles in the medium and low temperature pyrolysis zone, thereby becoming a upgraded coal having an increased calorific value.
10、 根据权利要求 1 的系统, 其中原煤中的硫分与催化-热载体 -氧转 移材料在所述中低温热解炉中发生反应形成煤加氢液化反应或煤焦油加氢 裂化反应所需的催化剂。  10. The system according to claim 1, wherein the sulfur in the raw coal is reacted with the catalytic-heat carrier-oxygen transfer material in the medium-low temperature pyrolysis furnace to form a coal hydroliquefaction reaction or a coal tar hydrocracking reaction. Catalyst.
11、 根据权利要求 10的系统, 其中所述的催化剂是铁的硫化物。  11. A system according to claim 10 wherein said catalyst is a sulfide of iron.
12、 其中进入所述中低温热解炉中的原煤粒径为 5厘米 -15厘米。  12. The raw coal entering the medium-low temperature pyrolysis furnace has a particle size of 5 cm to 15 cm.
13、 根据权利要求 1 的系统, 其中所述催化 -热载体-氧转移材料再生 器包含将所述废催化 -热载体-氧转移材料从所述再生器的下部提升至所述 再生器上部的提升管。  13. The system of claim 1 wherein said catalytic-heat carrier-oxygen transfer material regenerator comprises lifting said spent catalytic-heat carrier-oxygen transfer material from a lower portion of said regenerator to an upper portion of said regenerator Lift tube.
14、 根据权利要求 1 的系统, 其中在所述^ ^煤和废催化 -热载体-氧 转移材料的混合物出口位于所述热解炉的底部。  14. The system of claim 1 wherein the mixture outlet of said coal and spent catalytic-heat carrier-oxygen transfer material is located at the bottom of said pyrolysis furnace.
15、 根据权利要求 1 的系统, 其中在所述^ ^煤和废催化 -热载体-氧 转移材料的混合物出口与固-固分离器之间还包括一个或多个串联的筛网, 以将所述混合物颗粒分级。  15. The system of claim 1 wherein one or more screens in series are included between the mixture outlet of the coal and spent catalytic-heat carrier-oxygen transfer material and the solid-solid separator to The mixture particles are fractionated.
16、 根据权利要求 15的系统, 其中在所述^ ^煤和废催化 -热载体-氧 转移材料的混合物出口与固 -固分离器之间进一步包括至少两个传送机,以 各自传送所述筛网的筛上物和筛下物。 16. The system of claim 15 further comprising at least two conveyors between said mixture of said coal and spent catalytic-heat carrier-oxygen transfer material and said solid-solid separator to each deliver said Sieve and undersize of the screen.
17、根据权利要求 15的系统,其中所述筛网的筛孔最小直径大于或等 于废催化-热载体-氧转移材料颗粒的最大直径, 以便至少 催化 -热载体- 氧转移材料通过所述筛网。 17. The system of claim 15 wherein said screen has a mesh having a minimum diameter greater than or equal to a maximum diameter of the spent catalytic-heat carrier-oxygen transfer material particles such that at least the catalytic-heat carrier-oxygen transfer material passes through said sieve network.
18、根据权利要求 1的系统, 其中所述固-固分离器的分离介质是高压 水蒸汽和或 /循环热解气。  18. The system of claim 1 wherein the separation medium of the solid-solid separator is high pressure water vapor and/or recycled pyrolysis gas.
19、根据权利要求 1的系统, 其中所述的高压水蒸汽和 /或循环热解气 离开固 -固分离器、 经固 -气分离除去固体细颗粒和 /或微尘后通过所述的水 蒸 口被注入到所述的热解炉中。  19. The system of claim 1 wherein said high pressure water vapor and/or circulating pyrolysis gas exits the solid-solid separator and is passed through said water after solid-gas separation to remove solid fine particles and/or fine dust. A steaming port is injected into the pyrolysis furnace.
20、 根据权利要求 1的系统, 其中经所述原 * 口 所述热解炉中 的原煤颗粒和经再生催化-热载体 -氧转移材料输送管道被循环回所述热解 炉中的再生催化-热载体 -氧转移材料颗粒在热解炉中发生强烈碰撞而被均 匀混合。  20. The system according to claim 1, wherein the raw coal particles in the pyrolysis furnace and the regenerated catalytic-heat carrier-oxygen transfer material delivery conduit are recycled back to the pyrolysis furnace in the pyrolysis furnace. - The heat carrier-oxygen transfer material particles are uniformly collided in the pyrolysis furnace and uniformly mixed.
21、一种使用根据前 利要求 1-20任何之一的煤中低温热解 ^^系 统生产提质煤、 高热值热解气和焦油或液化合成油的方法: 该方法按顺序 包括以下步骤: 和催 -热载体-氧 ^移材料, 同时通 λ水蒸气, 并使中低温热解炉;的中 低温热解区达到 250。C-750。C的中低温热解温度;  21. A method of producing upgraded coal, high calorific value pyrolysis gas and tar or liquefied synthetic oil using a low temperature pyrolysis system according to any one of the preceding claims 1-20: the method comprises the following steps in sequence : and the heat-heat carrier-oxygen transfer material, while passing λ water vapor, and making the medium-low temperature pyrolysis furnace; the medium-low temperature pyrolysis zone reaches 250. C-750. Medium and low temperature pyrolysis temperature of C;
原煤中的中低温热解组分和催化-热载体-氧转移材料在所述中低温热 解区中发生反应, 形成包括甲烷、 一氧化碳、 二氧化碳、 氢气和水蒸气的 热解气, 以及中低温热解煤焦油气或合成油气, 同时原煤经中低温热解脱 去水分、 中低温挥发分而变为高热值的提质煤;  The medium-low temperature pyrolysis component and the catalytic-heat carrier-oxygen transfer material in the raw coal react in the medium-low temperature pyrolysis zone to form pyrolysis gas including methane, carbon monoxide, carbon dioxide, hydrogen and water vapor, and medium and low temperature Pyrolysis of coal char oil or synthetic oil and gas, at the same time, the raw coal is subjected to medium and low temperature pyrolysis to remove water, low and medium temperature volatiles and become high calorific value of upgraded coal;
从 ^^煤和废催化-热载体-氧转移材料的混合物出口排出所形成的提 质煤和废催化-热载体-氧转移材料的混合物, 从热解气输出管道排出所述 热解气和中低温热解煤焦油气体或合成油气体的混合物;  Discharging a mixture of the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material from the mixture outlet of the ^^ coal and the spent catalytic-heat carrier-oxygen transfer material, and discharging the pyrolysis gas from the pyrolysis gas output pipe and a medium-low temperature pyrolysis coal tar gas or a mixture of synthetic oil gases;
所述固-固分离器利用提质煤和废催化-热载体-氧转移材料的重力差将 ^^煤和废催化-热载体 -氧转移材料分离;  The solid-solid separator separates the coal and the spent catalytic-heat carrier-oxygen transfer material by using a gravity difference between the upgraded coal and the spent catalytic-heat carrier-oxygen transfer material;
所述废催化 -热载体-氧转移材料经所述废催化-热载体-氧转移材料输 送管道而被输送至催化 -热载体-氧转移材料再生器中; 所述废催化-热载体-氧转移材料在所述再生器中与被通入所述再生器 中的携氧气体发生氧化反应而被再生; The spent catalytic-heat carrier-oxygen transfer material is transported to the catalytic-heat carrier-oxygen transfer material regenerator via the spent catalytic-heat carrier-oxygen transfer material delivery conduit; The spent catalytic-heat carrier-oxygen transfer material is regenerated in the regenerator by oxidation reaction with an oxygen-carrying gas introduced into the regenerator;
再生催化-热载体 -氧转移材料经所述再生催化-热载体-氧转移材料输 送管道从所述再生器中被输送至所述中低温热解炉中, 以便循环使用所述 催化-热载体-氧转移材料; 物经过冷凝器, 所述中低温热解煤焦油气体或合成油气体经冷凝而变为煤 焦油或液化合成油, 从而与所述热解气相分离。  Regenerated catalytic-heat carrier-oxygen transfer material is transported from the regenerator to the medium-low temperature pyrolysis furnace via the regenerated catalytic-heat carrier-oxygen transfer material delivery conduit for recycling the catalytic-heat carrier An oxygen transfer material; the medium passes through a condenser, and the medium-low temperature pyrolysis coal tar gas or synthetic oil gas is condensed to become coal tar or liquefied synthetic oil, thereby being separated from the pyrolysis gas phase.
22、 根据权利要求 21所述的方法, 其中携氧气体是空气。  22. The method of claim 21 wherein the oxygen carrying gas is air.
23、 根据权利要求 21所述的方法, 其中所述^ ^煤和废催化 -热载体- 氧转移材料的混合物从所述热解炉中排出后、在 ¾ 固-固分离器之前通过 一个或多个串联的筛网, 以将所述混合物颗粒分级。  23. The method according to claim 21, wherein the mixture of the coal and the spent catalytic-heat carrier-oxygen transfer material is discharged from the pyrolysis furnace, passed through a or before the 3⁄4 solid-solid separator A plurality of screens in series are used to fractionate the mixture of particles.
24、根据权利要求 23所述的方法,其中所述混合物中未通过所述筛网 的筛上物和通过所述筛网的筛下物分别由各自的传送带运输。  24. A method according to claim 23 wherein the oversize of the mixture that does not pass through the screen and the undersize that passes through the screen are separately transported by respective conveyor belts.
25、 根据权利要求 21所述的方法, 其中在所述催化 -热载体-氧转移材 料再生器中经氧化反应损失氧或被去除氧的所述携氧气体被用于驱动蒸汽 锅炉或汽轮机, 从而发电。  25. The method according to claim 21, wherein said oxygen-carrying gas which is oxygen-removed by oxidation reaction or oxygen-removed in said catalytic-heat carrier-oxygen transfer material regenerator is used to drive a steam boiler or a steam turbine, Thereby generating electricity.
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