CN107143848B - A kind of coal gasification burning chemistry chains system in situ of coupling chemistry chain oxygen - Google Patents
A kind of coal gasification burning chemistry chains system in situ of coupling chemistry chain oxygen Download PDFInfo
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- CN107143848B CN107143848B CN201710422550.6A CN201710422550A CN107143848B CN 107143848 B CN107143848 B CN 107143848B CN 201710422550 A CN201710422550 A CN 201710422550A CN 107143848 B CN107143848 B CN 107143848B
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 203
- 239000001301 oxygen Substances 0.000 title claims abstract description 201
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 200
- 239000003245 coal Substances 0.000 title claims abstract description 56
- 238000002309 gasification Methods 0.000 title claims abstract description 47
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 26
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 239000000446 fuel Substances 0.000 claims abstract description 76
- 239000000126 substance Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 51
- 239000007789 gas Substances 0.000 claims description 48
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- 239000003546 flue gas Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 238000010926 purge Methods 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 8
- 238000011069 regeneration method Methods 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 7
- 238000002955 isolation Methods 0.000 claims description 7
- 238000007906 compression Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 2
- 239000003034 coal gas Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract 4
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000004449 solid propellant Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23D—BURNERS
- F23D14/00—Burners for combustion of a gas, e.g. of a gas stored under pressure as a liquid
-
- 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
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0959—Oxygen
-
- 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
- C10J2300/0953—Gasifying agents
- C10J2300/0969—Carbon dioxide
-
- 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
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
-
- 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
-
- 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
- C10J2300/1612—CO2-separation and sequestration, i.e. long time storage
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Carbon And Carbon Compounds (AREA)
- Industrial Gases (AREA)
Abstract
本发明属于能源清洁燃烧和高效利用相关技术领域，公开了一种耦合化学链制氧的原位煤气化化学链燃烧系统，该系统由一套化学链制氧子系统和一套原位煤气化化学链燃烧子系统耦合而成，其中所述化学链制氧子系统包括释氧反应器、吸氧反应器、第一四通阀和第二四通阀，所述原位煤气化化学链燃烧子系统包括燃料反应器、空气反应器和冷凝器，同时对这些组件之间的耦合关系及其工作方式进行了改进和设计。通过本发明，能够以结构紧凑、便于操控的方式，高效率地将化学链制氧子系统制取的包含少量O2的CO2/H2O混合气化剂通入原位煤气化化学链燃烧子系统的燃料反应器中，加速煤焦的气化反应速率，从而达到提高整体煤化学链燃烧转化效率的目的。
The invention belongs to the technical field of clean combustion and efficient utilization of energy, and discloses an in-situ coal gasification chemical chain combustion system coupled with chemical chain oxygen production. The system comprises a set of chemical chain oxygen production subsystems and a set of in-situ coal gasification A chemical chain combustion subsystem is coupled, wherein the chemical chain oxygen production subsystem includes an oxygen release reactor, an oxygen absorption reactor, a first four-way valve and a second four-way valve, and the in-situ coal gasification chemical chain combustion The subsystem includes fuel reactor, air reactor and condenser, and the coupling relationship between these components and their working methods are improved and designed. By means of the present invention, the CO 2 /H 2 O mixed gasification agent containing a small amount of O 2 produced by the chemical chain oxygen production subsystem can be passed into the in-situ coal gasification chemical chain with high efficiency in a compact structure and convenient operation. In the fuel reactor of the combustion subsystem, the gasification reaction rate of coal char is accelerated, so as to achieve the purpose of improving the overall coal chemical chain combustion conversion efficiency.
Description
Technical field
The invention belongs to clean energy burning and correlative technology field efficiently is utilized, more particularly, to a kind of couplingization
Learn the coal gasification burning chemistry chains system in situ of chain oxygen.
Background technique
Burning chemistry chains (Chemical Looping Combustion, CLC) technology is a kind of novel using energy source side
Formula, it is by transporting the circulation of oxygen in fuel reactor and air reactor by means of the carrier of oxygen, by a traditional " step
Formula " combustion process is decomposed into two relatively independent redox reaction processes, realizes the cascade utilization of energy.Meanwhile
In fuel reactor, fuel is aoxidized under the atmosphere of isolation air by the carrier of oxygen, and CO is contained only in reactor tail gas2And H2O leads to
Crossing simple moisture condensation process can be obtained high-purity CO2, to realize high-efficiency low energy consumption CO2Interior separation.
For the burning chemistry chains of the solid fuels such as coal, currently compare there are two types of tending to by the way of, namely in situ
Coal gasification burning chemistry chains (In-situ Gasification Chemical Looping Combustion, iG-CLC) and change
It learns chain oxygen decoupling burning (Chemical Looping with Oxygen Uncoupling, CLOU).But both modes
It all has some limitations in application process.Specifically, for iG-CLC: on the one hand, due to coal (especially high-order
Coal) and gasifying medium (H2O、CO2Or H2O/CO2Gaseous mixture) gasification reaction rate it is slower so that the burning of whole coal chemistry chain turns
Change rate-constrained in During Char Gasification at a slow speed, to reduce efficiency of combustion and CO2Arresting efficiency；On the other hand, due to
IG-CLC process combusts are inefficient, fuel reactor exiting flue gas (predominantly CO2/H2O contain a small amount of uncombusted gas in)
Body is unfavorable for CO2Compression purifying post-processing.For CLOU, application process need to be used can be in suitable temperature ranges and indifferent gas
Have the carrier of oxygen of release gaseous oxygen ability under atmosphere, and the copper-based carrier of oxygen price of current most chemical chain oxygen decoupling application prospect
Expensive and high temperature easy-sintering (compared to iron based oxygen carrier most common in iG-CLC) turns although the burning of coal chemistry chain can be improved
Change rate (due to gaseous state O in fuel reactor2Presence), but simultaneously but also the circular flow increased costs of the carrier of oxygen.This
Outside, during the burning chemistry chains of the solid fuels such as coal, environment locating for the carrier of oxygen is compared with using more severe, coal when gaseous fuel
Ash can all inevitably lead to the carrier of oxygen in the deposition and the carrier of oxygen of carrier of oxygen particle surface and the separation process of coal ash
Loss.Therefore, the more expensive carrier of oxygen of price is directly applied to the burning chemistry chains of the solid fuels such as coal is in the process uneconomical
's.
Summary of the invention
For the above insufficient or Improvement requirement of the prior art, the present invention provides a kind of original positions of coupling chemistry chain oxygen
Coal gasification burning chemistry chains system, wherein by combining coal combustion and CO2The unique characteristics for trapping technique, exist to its integral system
It is studied and is redesigned in internal structure and layout, and specific set-up mode and working principle etc. are improved,
It accordingly not only can effectively overcome the defect that gasification rate of coal is limited in conventional iG-CLC system, while also solve traditional coal chemistry
Chain burning technology is not easy the problem of reconciling between low operating cost and high coal conversion rate, more actual test show with
The prior art compares the full combustion and Efficient Conversion that can ensure that coal gasifies in situ during burning chemistry chains.
To achieve the above object, it is proposed, according to the invention, provide a kind of coal gasification chemical chain in situ of coupling chemistry chain oxygen
Combustion system, the system by a set of chemical chain oxygen subsystem and a set of coal gasification burning chemistry chains subsystems couple in situ and
At, it is characterised in that:
The chemical chain oxygen subsystem includes oxygen release reactor (R2), oxygen-absorbing reaction device (R1), the first four-way valve (W1)
With the second four-way valve (W2), the original position coal gasification burning chemistry chains subsystem includes fuel reactor (R3), air reactor
(R4) and condenser (C)；
The entrance of the oxygen release reactor (R2) is via first four-way valve (W1) and the fuel reactor (R3)
Outlet is connected, and is consequently for receiving the CO for coming from the fuel reactor (R3)2+H2O gaseous mixture f2 ", and as fluidized gas
Or purge gass provide reaction atmosphere for the carrier of oxygen (oxidation state) oxygen release；The oxygen release reactor (R2) is via the second four-way valve (W2)
It is connected with the entrance of the fuel reactor (R3), and has the O of certain oxygen concentration to its output2+CO2+H2O gaseous mixture f4；
The entrance of the oxygen-absorbing reaction device (R1) is via the first four-way valve (W1) input air f1, using in air
The carrier of oxygen (reduction-state) after oxygen and oxygen release reacts to realize the regeneration of its oxygen carrying capability；The oxygen-absorbing reaction device (R1)
Outlet be then connected with second four-way valve (W2), and export oxygen debt air f3 outward；
The entrance of the fuel reactor (R3) is connected with second four-way valve (W2) to introduce the O2+CO2+H2O is mixed
Gas f4 is closed, and makes the coal particle rapid conversion of the fuel reactor inner containment, in the process, gas as gasifying agent
Change product and carrier of oxygen particle reacts and generates CO2+H2Then O gaseous mixture f2 gives defeated via the outlet of the fuel reactor
Out；Wherein, a part of CO2+H2O gaseous mixture f2' is directly entered the condenser (C) and removes vapor therein, thus obtains
Obtain the CO of high-purity2Air-flow f5；The CO of another part2+H2O gaseous mixture f2 " is then delivered to the oxygen release reactor (R2), is used in combination
Fluidized gas or purge gass needed for forming above-mentioned carrier of oxygen oxygen release；
The air reactor (R4) keeps atmosphere isolation with the fuel reactor (R3) but structure is connected, and for making
It obtains and obtains oxygen in air atmosphere from the reduction aspect carrier granular that fuel reactor conveying comes and realize regeneration, then weigh
It is newly back in the fuel reactor (R3), thus executes cyclic oxidation reduction reaction next time；In addition, the air reaction
The outlet of device (R4) is for being discharged oxygen debt air f3.
By conceiving above, chemical chain air separation (CLAS) technology is allowed for first as a kind of novel oxygen skill processed
Art can directly produce pure oxygen or O2/CO2Gaseous mixture, and its oxygen energy consumption processed is only current state-of-the-art deep cooling technology
22% or so, the oxygen release reaction of the carrier of oxygen is the endothermic reaction in CLAS technology at the same time, and oxygen-absorbing reaction is exothermic reaction, accordingly
Oxygen generation system can be made to reach thermal balance by the heat during coupling carrier of oxygen oxygen release and oxygen uptake --- in the case, this
Invention by chemical chain oxygen subsystem therein construction especially key component specific set-up mode improvement, accordingly
Can be in mode compact-sized, convenient for manipulation, expeditiously obtaining includes a small amount of O2CO2/H2O hybrid gasification agent is passed through iG-
In CLC fuel reactor, accelerate the gasification reaction rate of coal tar, improves whole coal chemistry chain burning conversion efficiency to reach
Purpose.Secondly, the present invention is (main by flue gas caused by coal gasification burning chemistry chains subsystem (iG-CLC) in situ by proposing
It is CO2/H2O, it is also possible to contain a small amount of unburnt gas) fluidized gas or purge gass as oxygen release reactor, oxygen accordingly can be achieved
Carrier discharges gaseous state O under proper temperature (such as 950 DEG C, avoid the high temperature sintering of the carrier of oxygen as far as possible) and oxygen debt atmosphere2(balance point
Pressure is general lower, is 4.7%) O of a small amount of unburnt gas by reacting with the carrier of oxygen or with release in flue gas such as at 950 DEG C2
Reaction generates CO2And H2The overwhelming majority is CO in the flue gas of oxygen release reactor outlet by O2And H2O；These contain O2Flue gas one
Flue gas of the part as iG-CLC fuel reactor, to accelerate Char Gasification Rate in iG-CLC fuel reactor, another part
It can be used for compressing purifying, and since the amount of unburnt gas (being foreign gas for compression purifying process) is less, thus
Energy consumption and cost can be significantly reduced.
Preferably, the chemical chain oxygen subsystem is preferably that two fixed bed forms in parallel or two are in parallel
Bubbling bed form or be by two atmosphere isolation reactor group at interconnected fluidized bed form.
Preferably, the fuel reactor of the coal gasification burning chemistry chains subsystem in situ, air reactor are preferred
Form interconnected fluidized bed form.
Between the two preferably for above-mentioned chemical chain oxygen subsystem, coal gasification burning chemistry chains subsystem in situ
For coupled modes, preferably set as follows: the O that the outlet of the oxygen release reactor (R2) is exported2+CO2+H2O gaseous mixture f4 quilt
All it is passed into the fuel reactor (R3)；A part of CO that the outlet of the fuel reactor (R3) is exported2+H2O is mixed
Close the CO that gas be used to obtain high-purity2Air-flow, the CO of another part2+H2O gaseous mixture is then transported to the oxygen release reactor
(R2) in, and fluidized gas or purge gass needed for being used to form above-mentioned carrier of oxygen oxygen release.
Between the two preferably for above-mentioned chemical chain oxygen subsystem, coal gasification burning chemistry chains subsystem in situ
It for coupled modes, can also preferably set as follows: the CO that the outlet of the fuel reactor (R3) is exported2+H2O gaseous mixture
It is all passed into the oxygen release reactor (R2), and makes a small amount of unburnt gas included in it anti-in the oxygen release
It answers and is fully converted to CO in device2And H2O；In addition, a part of O that the outlet of the oxygen release reactor (R2) is exported2+CO2+H2O
Gaseous mixture is passed into the fuel reactor as fluidized gas, and another part directly carries out CO2Compression purifying.
Between the two preferably for above-mentioned chemical chain oxygen subsystem, coal gasification burning chemistry chains subsystem in situ
It for coupled modes, can also preferably set as follows: a part of CO that the outlet of the fuel reactor (R3) is exported2+H2O
Gaseous mixture is passed into the oxygen release reactor as fluidized gas or purge gass；What the outlet of the oxygen release reactor (R2) was exported
A part of O2+CO2+H2O gaseous mixture is then passed through in the fuel reactor as fluidized gas；In addition, by the fuel reactor
Both remainder flue gases that the outlet of outlet exported remainder flue gas, the oxygen release reactor is exported are mixed
It closes, and utilizes gaseous state O2By the unburnt gas completely burned in the fuel reactor flue gas.
Preferably, the carrier of oxygen particle in the chemical chain oxygen subsystem is preferably the copper-based carrier of oxygen, further preferably
For the CuO@TiO with nucleocapsid structure2-Al2O3The carrier of oxygen；The carrier of oxygen in the original position coal gasification burning chemistry chains subsystem
Particle is preferably iron based oxygen carrier, the further preferably cheap iron ore carrier of oxygen.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, mainly have below
Technological merit:
It 1, not only can effective coupling by the improvement of internal structure and specific set-up mode to whole system in the present invention
Close chemical chain oxygenerating technology and coal gasification chemical chain burning technology in situ, but also make full use of that CLAS technology produced it is low at
This O2/CO2/H2O gaseous mixture for coal gasification course in iG-CLC, thus solve tradition iG-CLC process gasification rate of coal by
While limit problem, additionally it is possible to be obviously improved its efficiency of combustion and CO2Arresting efficiency, and finally realize whole coal chemistry chain burning
The raising of conversion rate；
2, due to by iG-CLC system fuel reactor tail gas (predominantly CO in the present invention2/H2O, also containing a small amount of uncombusted
Gas) it is introduced into the oxygen release reactor of CLAS system, accordingly using the carrier of oxygen or gaseous state O2Unburnt gas is sufficiently converted
For CO2And H2O reduces subsequent CO2Compress the energy consumption and cost of purification unit；
3, gaseous state oxygen source is provided for coal gasification course using chemical chain oxygen generation system, is improving the same of gasification rate of coal
When, greatly reduce oxygen energy consumption processed.And the oxygen generation system can be according to iG-CLC process to O2/CO2/H2The demand of O gaseous mixture
Load increase and decrease (by the amount of filler etc. of the carrier of oxygen in control temperature of reactor and reactor) freely is carried out, system flexibility is more
It is high；
4, through the invention, using the copper-based carrier of oxygen, (price general charged is more expensive, such as with the CuO@TiO of nucleocapsid structure2-
Al2O3The carrier of oxygen) (and not contacted with solid fuels such as coals directly) release gaseous state under conditions of reaction environment is relatively mild
Oxygen, the O that then will be produced2It is passed into the iG-CLC with iron based oxygen carrier (such as iron ore carrier of oxygen, cheap) as bed material
In the fuel reactor of system, can accordingly it realize different carrier of oxygen functions maximumlly simultaneously, it is thus also avoided that by such price
The more expensive carrier of oxygen directly applies to the burning chemistry chains process of coal, thus reduces the economic cost of carrier of oxygen circular flow.
Detailed description of the invention
Fig. 1 is according to chemical chain oxygen constructed by the preferred embodiment for the present invention and coal gasification burning chemistry chains coupling in situ
The overall construction schematic diagram of collaboration system；
In all the appended drawings, identical appended drawing reference is used to denote the same element or structure, in which:
R1- oxygen-absorbing reaction device；R2- oxygen release reactor；R3- fuel reactor；R4- air reactor；The first four-way of W1-
Valve；The second four-way valve of W2-；C- condenser；F1- air；Total CO caused by f2- fuel reactor R32+H2O gaseous mixture；f2'-
Into the CO of condenser C2+H2O gaseous mixture；F2 "-enters the CO of oxygen release reactor R2 by the first four-way valve W12+H2O mixing
Gas；F3- is oxygen debt air；(or entering fuel reactor R3's) O that f4- oxygen release reactor R2 is generated2+CO2+H2O gaseous mixture；f5-
High-purity CO after condenser C2Air-flow；Liquid water of the f6- after condenser C；The Me- reduction-state carrier of oxygen；MeO- oxidation state oxygen
Carrier.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is described in detail.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below each other it
Between do not constitute conflict and can be combined with each other.
Fig. 1 is according to chemical chain oxygen constructed by the preferred embodiment for the present invention and coal gasification burning chemistry chains coupling in situ
The overall construction schematic diagram of collaboration system.As shown in fig. 1, the system is mainly by a set of chemical chain oxygen subsystem and a set of original position
Coal gasification burning chemistry chains subsystems couple forms, while having carried out specific aim to the specific set-up mode in its inside and working principle
Research and improvement, corresponding expectation is while solving the problems, such as that tradition iG-CLC process gasification rate of coal is limited, additionally it is possible into
One step promotes its efficiency of combustion and CO2Arresting efficiency.Its key component will be made and more specifically be illustrated below.
Described chemical chain oxygen subsystem mainly include oxygen release reactor R2, oxygen-absorbing reaction device R1, the first four-way valve W1 and
Second four-way valve W2, the original position coal gasification burning chemistry chains subsystem mainly includes fuel reactor R3, air reactor R4
With condenser C etc..For example, two reactors in chemical chain oxygen subsystem may be designed as fixed bed or bubbling bed or serial stream
Change bed；Two reactors constitute interconnected fluidized bed in coal gasification burning chemistry chains subsystem in situ, are achieved in the carrier of oxygen
Circulation of the grain between reactor transports.
Below by by taking the first coupled modes that demonstration of the present invention provides as an example, to further explain said modules
Between mutual set-up mode especially working principle.
(such as copper-based carrier of oxygen preferably has nucleocapsid structure to the aerobic carrier granular of inner containment of the oxygen release reactor R2
CuO@TiO2-Al2O3The carrier of oxygen), its entrance via the first four-way valve W1 and the fuel reactor R3 outlet phase
Even, it is consequently for receiving the CO from fuel reactor R32+H2O gaseous mixture f2 ", and be oxygen as fluidized gas or purge gass
Carrier (oxidation state) oxygen release provides reaction atmosphere；Oxygen release reactor R2 is connected and the fuel reactor via the second four-way valve W2
(R3) entrance is connected, and has the O of certain oxygen concentration to its output2+CO2+H2O gaseous mixture f4；To be carried using copper-based oxygen
For body, oxygen release temperature are 950 DEG C, O in the gaseous mixture2Concentration reaches as high as 4.7vol.%.
The inner containment of the oxygen-absorbing reaction device R1 has hypoxemia gesture carrier of oxygen particle, its entrance is via first four-way
Valve W1 input air f1 is reacted using the carrier of oxygen (reduction-state) after the oxygen and oxygen release in air to realize its oxygen carrier energy
The regeneration of power；The outlet of oxygen-absorbing reaction device R1 is then connected with the second four-way valve W2, and exports oxygen debt air f3 outward.
In operation, when the suction in R1 and R2/oxygen release reaction carries out complete, four-way valve W1 and W2 can be switched simultaneously.
At this point, the redox state of the carrier of oxygen and reaction atmosphere all realize exchange, therefore two reactors in reactor R1 and R2
Function also exchanged (reactor of oxygen uptake before becomes oxygen release, and the reactor of oxygen release becomes oxygen uptake before), finally
Reach and has continuously produced O2+CO2+H2The purpose of O gaseous mixture f4.
In addition, the entrance of the fuel reactor R3 is connected to introduce the oxygen-containing O with the second four-way valve W22+
CO2+H2O gaseous mixture f4, and make as gasifying agent the coal particle rapid conversion of the fuel reactor inner containment, herein
In the process, gasification product (such as CO, H2And CH4Deng) and carrier of oxygen particle (it can be iron based oxygen carrier, such as cheap iron ore
The stone carrier of oxygen) reacting generates CO2+H2O gaseous mixture f2, is then exported via the outlet of the fuel reactor；Wherein,
It may be selected the CO of a part2+H2O gaseous mixture f2' is directly entered the condenser C and removes vapor therein, thus to obtain
The CO of high-purity2Air-flow f5；The CO of another part2+H2O gaseous mixture f2 " is then delivered to the oxygen release reactor R2, and is used for shape
At fluidized gas or purge gass needed for above-mentioned carrier of oxygen oxygen release；
The air reactor R4 and the fuel reactor R3 keep atmosphere isolation but structure is connected, and for so that from
The reduction-state carrier of oxygen particle that fuel reactor conveying comes obtains oxygen in air atmosphere and realizes regeneration, then returns again
It is back in the fuel reactor R3, thus executes cyclic oxidation reduction reaction next time；In addition, air reactor R4
Outlet is for being discharged oxygen debt air f3.
It is worth mentioning that above-mentioned two subsystem is the case where basic module and its usage mode holding are basically unchanged
Under, the coupled modes between them can be multiplicity, and it is equally constituted where key improvements of the invention, specifically such as
Under:
(1) O of the outlet oxygen release reactor R22+CO2+H2O gaseous mixture is all passed through fuel reactor R3, and fuel is in O2/
CO2/H2Quick-gasifying and efficient burning are realized under O atmosphere；A part of CO of fuel reactor outlet2+H2O gaseous mixture is (containing a small amount of
Unburnt gas) it is passed through fluidized gas (if using interconnected fluidized bed) or purge gass of the oxygen release reactor as carrier of oxygen oxygen release
(if using fixed bed in parallel or bubbling bed), unburnt gas is by the carrier of oxygen or O2It is completely oxidized to CO2And H2O, oxygen release reaction
Device outlet generates O2+CO2+H2O gaseous mixture；Another part CO of fuel reactor outlet2+H2O gaseous mixture is purified through overcompression
To high-purity CO2。
(2) CO of fuel reactor outlet2+H2O gaseous mixture (containing a small amount of unburnt gas) is all passed through oxygen release reactor,
Unburnt gas is fully converted to CO in oxygen release reactor2And H2O；A part of O of oxygen release reactor outlet2+CO2+H2O mixing
Gas is passed through in fuel reactor as fluidized gas, and another part directly carries out CO2Compression purifying.
(3) a part of CO of fuel reactor outlet2+H2O gaseous mixture (containing a small amount of unburnt gas) is passed through oxygen release reaction
Device is as fluidized gas or purge gass；A part of O of oxygen release reactor outlet2+CO2+H2O gaseous mixture is passed through fuel reactor conduct
Fluidized gas；Fuel reactor is exported into remainder flue gas and oxygen release reactor outlet remainder flue gas mixes, utilizes gaseous state
O2By the unburnt gas completely burned in fuel reactor flue gas, subsequent CO is reduced2Compress the cost of purifying.It is anti-for air
Device and oxygen-absorbing reaction device are answered, the carrier of oxygen realizes the regeneration of its oxygen carrying capability by the oxygen captured in air.
Below the worked of above system according to the invention will be further elaborated with by taking the first coupled modes as an example
Journey.
For the chemical chain oxygen subsystem using fixed bed in parallel or bubbling bed configuration, which can
Summary are as follows: in oxygen release reactor R2, carrier of oxygen particle (can be the copper-based carrier of oxygen, such as with the CuO of nucleocapsid structure
TiO2-Al2O3The carrier of oxygen) in CO2+H2O is discharged under O atmosphere f2 "2, oxygen release reactor outlet flue gas is O2+CO2+H2O gaseous mixture f4
(to use the copper-based carrier of oxygen, oxygen release temperature for 950 DEG C, O in gaseous mixture2Concentration reaches as high as 4.7vol.%)；It is same with this
When, the carrier of oxygen in oxygen-absorbing reaction device R1 realizes the regeneration of oxygen carrying capability and reacting with the oxygen in air f1.When anti-
When answering suction/oxygen release fully reacting of the carrier of oxygen in device R1 and R2, while switching four-way valve W1 and W2, is reacted in reactor R1 and R2
Atmosphere is exchanged, and the function of two reactors also achieves exchange at this time, continuously produces O to reach2+CO2+H2O mixing
The purpose of gas f4.
In addition, the O that chemical chain oxygen generation system is produced2+CO2+H2O gaseous mixture f4 needs not move through condensation, and it is anti-to be introduced directly into fuel
It answers in device R3, coal particle is in O2/CO2/H2Gasification (or burning) rapidly, gasification product (such as CO, H under the atmosphere that O coexists2And CH4
Deng) with reactor in carrier of oxygen particle (can be iron based oxygen carrier, such as the cheap iron ore carrier of oxygen) react
Generate CO2+H2O gaseous mixture f2.The CO of generation2+H2O gaseous mixture a part of (f2') is directly entered condenser C, by removing moisture removal
Available high-purity CO2Air-flow f5；Another part CO2+H2The oxygen release that O gaseous mixture (f2 ") then introduces chemical chain oxygen generation system is anti-
Device is answered, the purge gass as carrier of oxygen oxygen release process.The carrier of oxygen particle Me being reduced in fuel reactor R3 is transported to sky
In solid/liquid/gas reactions device R4, reacts with air f1 and be regenerated as MeO.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.For example, above-mentioned chemical chain oxygen subsystem is matched using fixed bed in parallel or bubbling bed
It sets, in addition several coupled modes also can be realized flexibly, belong to proposed systematic difference scope.In addition, working as chemical chain oxygen
When subsystem uses interconnected fluidized bed system, too big influence is equally had no on process mentioned above.
Claims (5)
1. a kind of coal gas chemical chain combustion system in situ of coupling chemistry chain oxygen, the system is by a set of chemical chain oxygen subsystem
It is formed with a set of coal gasification burning chemistry chains subsystems couple in situ, it is characterised in that:
The chemical chain oxygen subsystem includes oxygen release reactor (R2), oxygen-absorbing reaction device (R1), the first four-way valve (W1) and
Two four-way valves (W2), and the carrier of oxygen particle in the chemical chain oxygen subsystem uses the copper-based carrier of oxygen；The original position coal gas
Changing burning chemistry chains subsystem includes fuel reactor (R3), air reactor (R4) and condenser (C), and the original position coal gas
The carrier of oxygen particle changed in burning chemistry chains subsystem uses iron based oxygen carrier；
The entrance of the oxygen release reactor (R2) via first four-way valve (W1) and the fuel reactor (R3) outlet
It is connected, is consequently for receiving the CO from the outlet the fuel reactor (R3)2+H2O gaseous mixture f2 ", and as fluidized gas
Or purge gass provide reaction atmosphere for carrier of oxygen oxygen release；The outlet of the oxygen release reactor (R2) via the second four-way valve (W2) with
The entrance of the fuel reactor (R3) is connected, and has the O of certain oxygen concentration to its output2+CO2+H2O gaseous mixture f4；
The entrance of the oxygen-absorbing reaction device (R1) utilizes the oxygen in air via the first four-way valve (W1) input air f1
It is reacted with the carrier of oxygen after oxygen release to realize the regeneration of its oxygen carrying capability；The outlet of the oxygen-absorbing reaction device (R1) then with institute
It states the second four-way valve (W2) to be connected, and exports oxygen debt air f3 outward；
The entrance of the fuel reactor (R3) is connected with second four-way valve (W2) to introduce the O2+CO2+H2O gaseous mixture
F4, and make as gasifying agent the coal particle rapid conversion of the fuel reactor inner containment；In the process, gasification produces
Object and carrier of oxygen particle, which react, generates CO2+H2O gaseous mixture f2, is then exported via the outlet of the fuel reactor:
Wherein, a part of CO2+H2O gaseous mixture f2' is directly entered the condenser (C) and removes vapor therein, thus to obtain
The CO of high-purity2Air-flow f5；The CO of another part2+H2O gaseous mixture f2 " is then delivered to the oxygen release reactor (R2), and conduct
Above-mentioned fluidized gas or purge gass；
The air reactor (R4) and the fuel reactor (R3) keep atmosphere isolation but structure is connected, and for so that from
The reduction-state carrier of oxygen particle that fuel reactor conveying comes obtains oxygen in air atmosphere and realizes regeneration, then returns again
It is back in the fuel reactor (R3), thus executes cyclic oxidation reduction reaction next time；In addition, the air reactor
(R4) outlet is for being discharged oxygen debt air f3.
2. the system as claimed in claim 1, which is characterized in that the chemical chain oxygen subsystem is two fixed beds in parallel
Form or two bubbling bed forms in parallel or be by two atmosphere isolation reactor group at interconnected fluidized bed shape
Formula；The fuel reactor of the original position coal gasification burning chemistry chains subsystem, air reactor are two fixations in parallel
Bed form or two bubbling bed forms in parallel or be by two atmosphere isolation reactor group at it is interconnected fluidized bed
Form.
3. system as claimed in claim 1 or 2, which is characterized in that for above-mentioned chemical chain oxygen subsystem, coal gasification in situ
For the coupled modes of burning chemistry chains subsystem between the two, set as follows: the outlet institute of the oxygen release reactor (R2)
The O of output2+CO2+H2O gaseous mixture f4 is all passed into the fuel reactor (R3)；The fuel reactor (R3)
Export a part of CO exported2+H2O gaseous mixture be used to obtain the CO of high-purity2Air-flow, the CO of another part2+H2O mixing
Gas is then transported in the oxygen release reactor (R2), and fluidized gas or purging needed for being used to form above-mentioned carrier of oxygen oxygen release
Gas.
4. system as claimed in claim 1 or 2, which is characterized in that for above-mentioned chemical chain oxygen subsystem, coal gasification in situ
For the coupled modes of burning chemistry chains subsystem between the two, set as follows: the outlet institute of the fuel reactor (R3)
The CO of output2+H2O gaseous mixture is all passed into the oxygen release reactor (R2), and is made a small amount of unburned included in it
Gas to the greatest extent is fully converted to CO in the oxygen release reactor2And H2O；In addition, the outlet of the oxygen release reactor (R2) is exported
A part of O2+CO2+H2O gaseous mixture is passed into the fuel reactor as fluidized gas, and another part directly carries out CO2's
Compression purifying.
5. system as claimed in claim 1 or 2, which is characterized in that for above-mentioned chemical chain oxygen subsystem, coal gasification in situ
For the coupled modes of burning chemistry chains subsystem between the two, set as follows: the outlet institute of the fuel reactor (R3)
A part of CO of output2+H2O gaseous mixture is passed into the oxygen release reactor as fluidized gas or purge gass；The oxygen release reactor
(R2) a part of O that outlet is exported2+CO2+H2O gaseous mixture is then passed through in the fuel reactor as fluidized gas；In addition,
The remainder that the outlet of remainder flue gas, the oxygen release reactor that the outlet of the fuel reactor is exported is exported
Divide both flue gases to be mixed, and utilizes gaseous state O2By the unburnt gas completely burned in the fuel reactor flue gas.
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| CN108954303A (en) * | 2018-05-10 | 2018-12-07 | 哈尔滨理工大学 | Integral type fixes bed chemical chain combustion apparatus |
| CN108680017B (en) * | 2018-05-28 | 2019-10-18 | 中石化（洛阳）科技有限公司 | Heating furnace system and heating furnace equipment |
| CN108413421B (en) * | 2018-05-30 | 2023-09-29 | 华中科技大学 | Oxygen-free combustible waste gas removing equipment |
| CN111477285A (en) * | 2020-04-24 | 2020-07-31 | 华中科技大学 | Method for obtaining thermal neutral oxygen carrier in chemical looping combustion process |
| CN112029540A (en) * | 2020-07-27 | 2020-12-04 | 新奥科技发展有限公司 | Chemical looping coal gasification system and method |
| CN112555834A (en) * | 2020-12-15 | 2021-03-26 | 苏州西热节能环保技术有限公司 | Garbage incineration system and method coupled with chemical chain air separation technology |
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