CN102313283B - Coal chemical looping combustion method by using pressurized two-circuit circulating fluidized bed - Google Patents
Coal chemical looping combustion method by using pressurized two-circuit circulating fluidized bed Download PDFInfo
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- CN102313283B CN102313283B CN201110252874.2A CN201110252874A CN102313283B CN 102313283 B CN102313283 B CN 102313283B CN 201110252874 A CN201110252874 A CN 201110252874A CN 102313283 B CN102313283 B CN 102313283B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/725—Redox processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
- C10J3/485—Entrained flow gasifiers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1606—Combustion processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Fluidized-Bed Combustion And Resonant Combustion (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention relates to a coal chemical looping combustion method by using pressurized two-circuit circulating fluidized bed, which comprises the following steps: 1) coal particles and a gasifying agent enters from a bottom area of the pressurized high density circulating fluidized bed fuel reactor (1), a gasification reaction is carried out, then a gasified product and a regenerated oxygen carrier returned from a recycles inlet C are performed an oxidation reduction reaction, the gasified product is oxidized to CO2 and H2O by the oxygen carrier; 2) the flue gas generated by the reaction carries an inactivated oxygen carrier to depart from the fuel reactor (1) and enters into a cyclone separator (2), the inactivated oxygen carrier is separated and enters into an air reactor (5), flue gas enters into an auxiliary loop II; flue gas separated from an major loop I enters into a cross flow moving bed fuel reactor (11) of the auxiliary loop II transversally through an exhaust pipe (10) and a valve (9), and the flue gas is oxidized by the oxygen carrier with high activity; the reduced oxygen carrier particles enter into a return feeder (16), and are returned into an air reactor (17) to recapture the oxygen carrying capability under the effect of the fluidized gas which is entered from an air intake G of the feeder.
Description
Technical field
The invention belongs to the clean burning of coal and efficiently utilize field, relating to a kind of method of pressurized double-loop circulating fluidized bed coal chemistry chain burning.
Technical background
Carbon dioxide (CO
2) be a kind of greenhouse gases to eco-environmental impact maximum.The burning of fossil fuel has produced a large amount of CO
2, cause the rising of earth's surface and lower atmosphere layer temperature, and caused global warming, human survival and social development have been produced and had a strong impact on.Therefore, the discharge of minimizing and control carbon dioxide has become the common recognition of the whole society.China take coal and is that main energy resource structure has determined reduction of discharging CO
2one of main contents of sustainable development from now on will be become.
Burning chemistry chains (CLC) is a kind of burning theory of novelty, energy releasing mechanism is to react without flame chemistry, fuel is not directly and air catalytic combustion, but with oxygen carrier, the cycle alternation between two reactors (air reactor and fuel reactor) reacts to realize the combustion process of fuel, has broken flame combustion concept since ancient times.Oxygen carrier carries out oxidation reaction in air reactor, then in fuel reactor, carries out reduction reaction with fuel, generates CO
2and H
2o, by condensation, can obtain highly purified CO
2.The major advantage that CLC compares traditional combustion mode is the CO that fuel combustion produces
2not by N
2dilution, so separation of C O
2energy consumption low.In addition CLC is in NOx zero-emission, and high thermal efficiency aspect also has superiority.
Summary of the invention
technical problem:the object of the present invention is to provide a kind of method of pressurized double-loop circulating fluidized bed coal chemistry chain burning, overcome the problem of the conventional valuable oxygen carrier of the insoluble soft of CLC system easy loss in reaction unit, reach coal combustion efficiency high, CO
2exit concentration is high, the little object of valuable oxygen carrier loss.
technical scheme:the method that the present invention proposes the burning of a kind of pressurized double-loop circulating fluidized bed coal chemistry chain, this device consists of two closed circuit I of major-minor and II, and two loops are by recirculating fluidized bed, cyclone separator, revert system, and cross-flow moving bed composition.Particularly, in major loop I, in recirculating fluidized bed fuel reactor, realize
The flameless combustion course of reaction that the coal gasification of high granule density, high circulating ratio and high particle flux and gasification product and oxygen carrier occur; In the I of loop, in cross-flow moving bed air reactor, realize the process of oxygen carrier again of oxygen carrier; And in the I of loop, in cyclone separator, realized the effective separated of oxygen carrier and flue gas.For the II of loop, cross-flow moving bed fuel reactor has realized the process that burns away of reducibility gas in flue gas, and in the II of loop, recirculating fluidized bed air reactor has been realized the process of oxygen carrier again of oxygen carrier.The gaseous product of coal and oxygen carrier burning is discharged from the outlet of the cross-flow moving bed fuel reactor of loop II, and its main component is CO
2with the mixture of water vapour, go out highly purified CO through condensation is just separable
2.
Flow process can be sketched and be:
1) coal particle and gasifying agent enter from the bottom section of pressurization high density circulating fluidized bed fuel reactor, generating gasification reaction, and then gasification product and the regeneration oxygen carrier generation redox reaction returned from returning charge entrance C, gasification product is become CO by oxygen carrier oxidating
2and H
2o;
2) flue gas that reaction produces carries inactivation oxygen carrier and leaves fuel reactor, enters cyclone separator, and inactivation oxygen carrier is separated and enters air reactor, and flue gas enters subloop II;
3) in major loop I, the isolated inactivation oxygen carrier of cyclone separator enters in cross-flow moving bed air reactor from top, air enters from the air intake E of cross-flow moving bed air reactor side, cross-flow contact there is redox reaction in both, the oxidation by air of inactivation oxygen carrier obtains and lives again, and reacted tail gas is discharged from air reactor exhaust outlet F; Oxygen carrier after regeneration enters material returning device, under the effect of the fluidizing gas entering from material returning device air inlet D, gets back to fuel reactor and continues reaction;
4) in major loop I, isolated flue gas laterally enters the cross-flow moving bed fuel reactor of subloop II through blast pipe, valve, by wherein high activity oxygen carrier oxidating; The oxygen carrier granule being reduced enters material returning device, returns to air reactor and recapture oxygen carrying capability under the effect of the fluidizing gas being entered by material returning device air inlet G; The gaseous product of moving bed fuel reactor outlet is CO
2and H
2o, rejects H through condensation
2after O, obtain highly purified CO
2.
Described fuel reactor adopts pressurized operation mode, have high density solid-gas volume ratio be greater than 0.1, high circulating ratio 50~100 and high particle flux and >200kg/m
2the feature of s.
Described exhaust outlet is connected with cross-flow moving bed reactor by valve, the flue gas that blast pipe is discharged therein with high activity oxygen carrier generation redox reaction, improved efficiency of combustion and outlet CO
2concentration.
The gas of discharging from cross-flow moving bed reactor 11 exhaust outlets is removed H through condensation
2after O, just can obtain highly purified CO
2.
beneficial effect:compare with existing conventional CLC system, the present invention has following characteristic and advantage:
1, this device consists of major and minor two closed circuit I and II, two loops are by recirculating fluidized bed, cyclone separator, revert system, and cross-flow moving bed composition, a valve is arranged in major loop I and subloop II junction, can select to close or open valve according to the difference of the activity of oxygen carrier and hardness, make major loop I participate in separately reaction or major minor loop participates in reaction simultaneously, be used for the burning chemistry chains reaction of one or both oxygen carriers collocation, have well selective.
There is the unreacted reducibility gas of part in the flue gas that 2, in the I of loop, cyclone separator is discharged, during by cross-flow moving bed in the II of loop, reducibility gas can continue to react with high-performance oxygen carrier granule and oxidized, thereby improves total combustion efficiency and the CO of coal
2exit concentration.
3, the high performance valuable oxygen carrier of soft (for example NiO) is placed in the II of loop and is reacted, because the power of subloop II and system dimension are much smaller than major loop I, so in subloop II, the loss of valuable oxygen carrier is far away
Be less than the cheap oxygen carrier in major loop I, guaranteed economic benefit.
4, cross-flow moving bed in major loop I have less bedside and a larger ventilation cross section, and a bed air resistance was reduced, and the disposal ability of gas strengthens, and can effectively realize the process of oxygen carrier again of inactivation oxygen carrier.In addition, compare with fluidized bed air reactor, cross-flow moving bed air reactor is simple in structure, and it is convenient to control.
5, in major loop I, pressurization high density circulating fluidized bed fuel reactor is combined to utilization with cross-flow moving bed air reactor, realize respectively the combustion reaction process of coal/oxygen carrier and the oxygen carrier course of reaction of oxygen carrier.By pressurization, promote the reduction reaction in fuel reactor, solved two reactor internal cause reaction rates and had the differential and rate-matched problem that causes of quantity.
6, system adopts pressurized operation, major loop fuel reactor to have high density (Gu-gas volume ratio be greater than 0.1), high circulating ratio (50~100), high material flux (>200kg/m
2s) feature, the material particles time of staying is long, and gas-solid reaction (as coal gasification reaction, the reaction of gasification product reduction oxygen carrier) is violent, has significantly improved burning of coal efficiency.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of pressurized double-loop circulating fluidized bed coal chemistry chain combustion method,
In major loop I, pressurization high density circulating fluidized bed fuel reactor 1, cyclone separator 2, dipleg 3, fresh oxygen carrier granule dispenser 4, cross-flow moving bed air reactor 5, flase floor 6, inactivation oxygen carrier granule removal device 7, material returning device 8, valve 9, blast pipe 10; Coal particle entrance A, gasification agent inlet B, major loop returning charge entrance C, major loop I material returning device air inlet D, major loop I air intake E, major loop I air reactor exhaust outlet F,
In subloop II, cross-flow moving bed 11, fresh oxygen carrier granule dispenser 12, inactivation oxygen carrier granule removal device 13, flase floor 14, dipleg 15, material returning device 16, tedge air reactor 17, cyclone separator 18, cyclone separator blast pipe 19, valve 20; Subloop II material returning device air inlet G, subloop II returning charge entrance H, subloop II cyclone separator blast pipe I, subloop II fuel reactor entrance J, subloop II fuel reactor outlet K, subloop II air reactor air inlet L.
The specific embodiment
Referring to Fig. 1, describe coal pressurization high density circulating fluidized bed burning chemistry chains separation of C O of the present invention in detail
2method, the oxygen carrier in major loop I be take iron ore, and (main component is Fe
2o
3) be example, the oxygen carrier in subloop II be take NiO as example.
1) air distribution plate that in major loop I, fuel reactor bed body bottom is arranged is gasification agent inlet, and bed body both sides are coal particle entrance and returning charge entrance.The steam that adds device heating through electricity is as gasifying agent and fluidizing agent; from the gasification agent inlet B of fuel reactor 1 bottom, enter, carry the coal particle entering from coal particle entrance A, the returning charge that contains high concentration oxygen carrier iron ore entering from returning charge entrance C and the coal entering from returning charge entrance D and oxygen carrier fine-grained mixture and move upward.In this process, gasifying agent reacts with coal generating gasification, generates coal gas, and main component is CO and H
2.Coal gas and oxygen carrier generation redox reaction, the oxygen in oxygen carrier passes to coal gas, makes CO be oxidized to CO
2, H
2be oxidized to H
2and oxygen carrier loses partial oxygen and generates tri-iron tetroxide O(steam).Oxygen carrier generation redox reaction, consumes CO and H
2, also promoted coal gasification reaction.
2) reacted solid particle (oxygen loss oxygen carrier granule and carbon containing coal ash) is taken out of by flue gas, enter with fuel reactor and export the cyclone separator 2 being connected, because particle diameter is larger, most of inactivation oxygen carrier granule is separated gets off to enter the cross-flow moving bed air reactor 5 being connected with dipleg 3, and carbon containing coal ash and a small amount of inactivation oxygen carrier fine grained export and enter subloop II from blast pipe 10 with flue gas.
3), in cross-flow moving bed air reactor 5, the isolated inactivation oxygen carrier of cyclone separator 2 carries out oxygen carrier reaction.Inactivation oxygen carrier granule enters from the top of cross-flow moving bed air reactor 5, air evenly enters after flase floor 6 from air intake E, cross-flow contact there is redox reaction in both, inactivation oxygen carrier oxidation by air regeneration, and reacted tail gas is discharged from air reactor exhaust outlet F.Oxygen carrier after regeneration enters material returning device 8, under the effect of the steam assist gas entering from material returning device air inlet D, gets back to fuel reactor 1 and continues reaction.The shuttling movement of material between the cross-flow moving bed air reactor 5-of fuel reactor 1-cyclone separator 2-material returning device 8 formed main circulation loop I.When oxygen carrier oxygen carrying capability obviously declines, from fresh oxygen carrier granule dispenser 4, supplement corresponding fresh oxygen carrier, meanwhile, the oxygen carrier of permanent deactivation and lime-ash are discharged from inactivation oxygen carrier granule removal device 7.
4) when valve 9 is opened, carry carbon containing coal ash and by cyclone separator blast pipe 10 levels, enter the cross-flow moving bed reactor 11 in subloop II with a small amount of fine grain flue gas of inactivation oxygen carrier, carry out redox reaction, product CO with the NiO particle slowly falling from cross-flow moving bed top inlet
2and H
2o(gas) admixture of gas is discharged from cross-flow moving bed fuel reactor outlet K, through condensation, rejects steam, obtains highly purified CO
2.
The Ni particle being reduced enters material returning device 16 through dipleg 15, under the effect of the steam assist gas entering from air inlet G, is back to tedge air reactor 17, regains oxygen carrying capability with the air reaction entering from air inlet L.The shuttling movement of material between fuel reactor 11-cyclone separator 18-material returning device 16-air reactor 17 formed secondary closed circuit II.When oxygen carrier oxygen carrying capability obviously declines, from fresh oxygen carrier granule dispenser
12 supplement corresponding fresh oxygen carrier, and meanwhile, the oxygen carrier of permanent deactivation is discharged from inactivation oxygen carrier granule removal device 13.
Claims (2)
1. the method that pressurized double-loop circulating fluidized bed coal chemistry chain burns, is characterized in that the method is specially:
1) coal particle and gasifying agent enter from the bottom section of pressurization high density circulating fluidized bed fuel reactor (1), generating gasification reaction, then gasification product and the regeneration oxygen carrier generation redox reaction returned from returning charge entrance C, gasification product is become CO by oxygen carrier oxidating
2and H
2o;
2) flue gas that reaction produces carries inactivation oxygen carrier and leaves pressurization high density circulating fluidized bed fuel reactor (1), enters cyclone separator (2), and inactivation oxygen carrier is separated and enters cross-flow moving bed air reactor (5), and flue gas enters subloop II;
3) in major loop I, the isolated inactivation oxygen carrier of cyclone separator (2) enters in cross-flow moving bed air reactor (5) from top, air enters from the air intake E of cross-flow moving bed air reactor (5) side, cross-flow contact there is redox reaction in both, the oxidation by air of inactivation oxygen carrier obtains and lives again, and reacted tail gas is discharged from cross-flow moving bed air reactor exhaust outlet F; Oxygen carrier after regeneration enters material returning device (8), under the effect of the fluidizing gas entering from material returning device air inlet D, gets back to pressurization high density circulating fluidized bed fuel reactor (1) and continues reaction;
4) in major loop I, isolated flue gas laterally enters the cross-flow moving bed fuel reactor (11) of subloop II through blast pipe (10), valve (9), by high activity oxygen carrier oxidating wherein; The oxygen carrier granule being reduced enters material returning device (16), returns to air reactor (17) and recapture oxygen carrying capability under the effect of the fluidizing gas being entered by material returning device air inlet G; The gaseous product of cross-flow moving bed fuel reactor (11) outlet is CO
2and H
2o, rejects H through condensation
2after O, obtain highly purified CO
2;
Described pressurization high density circulating fluidized bed fuel reactor (1) adopts pressurized operation mode, have high density solid-gas volume ratio be greater than 0.1, high circulating ratio 50~100 and high particle flux be >200kg/m
2the feature of s.
2. the method that pressurized double-loop circulating fluidized bed coal chemistry chain according to claim 1 burns, it is characterized in that described blast pipe (10) outlet is connected with cross-flow moving bed fuel reactor (11) by valve (9), the flue gas that blast pipe is discharged therein with high activity oxygen carrier generation redox reaction, improved efficiency of combustion and outlet CO
2concentration.
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CN103062787B (en) * | 2012-12-15 | 2015-07-22 | 华中科技大学 | Method and device for burning pulverized coal with self-heating oxygen generation function |
CN106423132A (en) * | 2016-09-22 | 2017-02-22 | 新奥科技发展有限公司 | Catalyst for catalytic coal gasification as well as catalytic coal gasification method and device |
CN107937035B (en) * | 2017-11-30 | 2023-09-26 | 陕西延长石油(集团)有限责任公司 | Pulverized coal pressurized gasification device and method with two sections of double-circulation fluidized bed coupled |
CN110065943B (en) * | 2019-04-22 | 2021-08-10 | 东南大学 | Coal gasification CO separation2Apparatus and separation method thereof |
CN114574250B (en) * | 2022-04-14 | 2023-05-02 | 河南大学 | Method and device for preparing clean synthetic gas by biomass chemical chain gasification |
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