CN109652145A - The device and method of fluidized bed coal catalytic gasification methane with nozzle - Google Patents
The device and method of fluidized bed coal catalytic gasification methane with nozzle Download PDFInfo
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- CN109652145A CN109652145A CN201710946346.4A CN201710946346A CN109652145A CN 109652145 A CN109652145 A CN 109652145A CN 201710946346 A CN201710946346 A CN 201710946346A CN 109652145 A CN109652145 A CN 109652145A
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- 238000002309 gasification Methods 0.000 title claims abstract description 128
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003245 coal Substances 0.000 title claims abstract description 49
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 143
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 22
- 239000003250 coal slurry Substances 0.000 claims abstract description 21
- 239000007921 spray Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 238000000746 purification Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 11
- 230000005484 gravity Effects 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 230000008676 import Effects 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001845 chromium compounds Chemical class 0.000 claims description 2
- 230000005496 eutectics Effects 0.000 claims description 2
- 238000005243 fluidization Methods 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 150000002816 nickel compounds Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052799 carbon Inorganic materials 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000002956 ash Substances 0.000 description 23
- 239000010881 fly ash Substances 0.000 description 16
- 239000008187 granular material Substances 0.000 description 16
- 239000003345 natural gas Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 241001672694 Citrus reticulata Species 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
- C10J3/56—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS 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
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
-
- 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
- C10J2200/00—Details of gasification apparatus
- C10J2200/15—Details of feeding means
- C10J2200/152—Nozzles or lances for introducing gas, liquids or suspensions
-
- 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
- C10J2300/0956—Air or oxygen enriched air
-
- 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
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- 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
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1662—Conversion of synthesis gas to chemicals to methane (SNG)
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of fluidized bed coal catalytic gasification methane device and method with nozzle, solve the problems, such as that efficiency of carbon con version existing in the prior art is low, methane production is low, energy consumption is high, operating cost is high, raw material is added to fluidized-bed gasification furnace using the feeding structure of opposed type nozzle in the present invention, it is characterized in that gasified raw material uses coal slurry, it mainly comprises the steps of: that coal slurry enters burner hearth by the nozzle of fluidized-bed gasification furnace lower layer space, is reacted with the oxygen-containing gas (not containing water vapor) from gas distributor and generate synthesis gas；Synthesis gas reacts after entering upper space with the catalyst generation catalytic production of methane that upper space nozzle sprays into, and generates the product gas of methane rich.Product gas is purified, separates, by CO+H therein2And CO2Circulation is passed through the process that burner hearth promotes methanation reaction and gasification reaction, reduces the energy consumption of whole system, saves the input cost of vapor, and effectively improve efficiency of carbon con version and methane production, can be used for technical field of coal chemical industry.
Description
Technical field
The invention belongs to the technical fields of catalytic coal gasifaction methane.More particularly to a kind of fluidized bed coal catalysis with nozzle
The device and method of vaporizing system methane.
Background technique
Natural gas is good fuel and important industrial chemicals, is had the advantages that safe and reliable, environmentally protective.With me
The fast development of state's economy and the quickening of urbanization paces, the demand to natural gas increasingly increase.The natural gas in China itself
To be unable to reach the demand of natural gas, imbalance between supply and demand becomes increasingly conspicuous yield, and supply gap, which has only, to be relied on import and made up, pole
The energy security in China is affected in big degree.China be again one with coal be main energy resource structure country, it is following very
It will not change in long a period of time, according to statistics, in the non-renewable energy consumption structure in China, coal has reached 66%.With petroleum
Resource it is increasingly in short supply, effective use coal resources have become a strategy of China's energy sustainable development.It converts coal into
Natural gas is the important channel that Coal Clean efficiently utilizes, and because of its energy transformation ratio height, is suitble to China's national situation, becomes current coal
One of research hotspot of chemical field.
Existing natural gas from coal technology can be divided into: two-step method and two kinds of one-step method.Two-step method natural gas from coal technology category
It is that coal is first converted into synthesis gas (CO+H in more traditional technology2), then carry out the method that methanation obtains SNG, need through
Go through following steps: gasification, transformation cooling, purification, methane synthesis etc..One-step method natural gas from coal technology is using coal as raw material
Direct synthesizing methane is realized gasification, transformation and methanation reaction process by catalyst in gasification furnace, is obtained rich in methane
Synthesis gas.Two-step method natural gas from coal technology needs are realized in different reactors, thus cause the temperature of each reaction process
It is not matched that with pressure, in internal system circulation, heat loss is more, reduces the efficient energy conversion of system.And one-step method coal
Preparing natural gas technology efficiently solves the above problem, realizes logistics and the coupling of heat, economy with higher and feasible
Property, thus become the important research direction in natural gas from coal field.
United States Patent (USP) US4077778 proposes a kind of technique of coal one-step method methane, using alkali carbonate or alkali
Metal hydroxides is catalyst, by superheated steam control reaction in furnace temperature at 700 DEG C or so, and and coal dust in catalyst
Under the action of reacted, directly obtain methane-rich gas.Superheated steam is heated to 850 DEG C or so by the process requirement, energy consumption
Higher, efficiency of carbon con version is lower, maintaining reaction temperature is difficult under conditions of no outer heat supply, and the technology is still in research and development rank
Section.The patent CN102465047B of Chinese Xin Ao group proposes a kind of technique of catalytic coal gasifaction one-step method methane, by gas
Change furnace and be divided into synthesis gas generation section, coal methanation section and synthesis gas methanation section, makes burning, gasification, methanation reaction and pyrolysis
Reaction segmentation carries out, and improves methane production.However in gasification furnace, structure is complicated, and the recovery difficult of catalyst is big, at high cost, and
And the technology there is no industrialized unit.
Existing one-step method natural gas from coal technology is in research and development or amplification stage, and industrialization has not yet been formed.How
The gasification efficiency of gasification furnace is further increased, investment and operating cost are reduced, it is natural as one-step method coal system to simplify chamber structure
The development key of gas technology.
Summary of the invention
Present invention mainly solves the technical issues of first is that efficiency of carbon con version is low in the prior art, methane production is low, energy consumption is high,
The high problem of operating cost, the invention proposes the device of the fluidized bed coal catalytic gasification methane with nozzle, which is flowing
It is added to nozzle material-feeding system in the main structure of fluidized bed reactor, so that coal slurry is got enter into fluidized-bed reactor, and then in gas
The addition for reducing vapor in agent, reduces operating cost, improves efficiency of carbon con version and methane production.
The two of technical problem solved by the invention are a kind of fluidized bed coals with nozzle corresponding with technical problem one
The method of catalytic gasification methane.
In order to solve the technical problem one, the present invention provides a kind of fluidized bed coal catalytic gasification methane device with nozzle,
It is characterized by comprising fluidized-bed gasification furnace 1, first jet 2, second nozzle 3, gas-solid separating device 4, ash buckets 5, gas purification
Separative unit 6, slag bucket 7；1 bottom of fluidized-bed gasification furnace is connected with slag bucket 7,1 lower layer space of fluidized-bed gasification furnace and upper layer are empty
Between be respectively equipped at the top of first jet 2 and second nozzle 3, fluidized-bed gasification furnace 1 connection gas-solid separating device 4, gas solid separation dress
Set 4 solid outlets connection ash bucket 5,4 gas vent of gas-solid separating device is connected with gas purification separative unit 6.
In above-mentioned technical proposal, first jet 2 uses dual channel structure, wherein a side runner passes through for recyclegas I, separately
One side runner coal supply slurry B and delivery of carrier gas pass through, and wherein recyclegas I is CO2；Second nozzle 3 uses dual channel structure, wherein
One side runner passes through for recyclegas II, and another side runner passes through for catalyst C and delivery of carrier gas, wherein recyclegas II is
CO and H2Gaseous mixture.
In above-mentioned technical proposal, first jet 2 and second nozzle 3 are all made of two opposed arrangements of nozzle, and are respectively perpendicular
Horizontal plane arrangement in the middle part of 1 lower layer space of fluidized-bed gasification furnace and in the middle part of upper space.
In above-mentioned technical proposal, 1 bottom of fluidized-bed gasification furnace is equipped with the import of oxygen-containing gas A, and the import of oxygen-containing gas A is adopted
Gas is introduced with gas distributor structure, gas distributor selects one kind of single tube jetting type, multitube jetting type；Single tube is selected to penetrate
When streaming gas distributor, gas distributor is arranged perpendicular to 1 bottom of fluidized-bed gasification furnace；Select the distribution of multitube jetting type gas
When device, gas distributor is arranged perpendicular to 1 bottom sides of fluidized-bed gasification furnace.
In order to solve the technical problem two, the present invention provides a kind of fluidized bed coal catalytic gasification methanol method with nozzle,
Characterized by comprising the following steps:
Coal slurry B and recyclegas I (F) are atomized by the lower layer space that first jet 2 sprays into fluidized-bed gasification furnace 1, and with
Violent burning occurs for oxygen-containing gas A contact, gasification reaction generates synthesis gas and lime-ash G, lime-ash drop into slag because of self gravity
It in bucket 7 and is collected, and synthesis gas flow is upwardly into the upper space of fluidized-bed gasification furnace 1, and from second nozzle 3
Methanation reaction occurs for the catalyst C of penetrating, generates and is rich in CH4Product gas (E), be rich in CH4Product gas (E) carry it is few
It measures tiny solid particle and is fed through gas-solid separating device 4, after separation, a small amount of tiny solid particle is sent to ash bucket 5
And be collected, and it is rich in CH4Product gas (E) then enter gas purification separative unit 6 evolve, separation, obtain recyclegas
II (D), product gas (E) and recyclegas I (F)；Wherein, recyclegas II (D) is sent into second nozzle 3, fluidized bed of going forward side by side
1 upper space of gasification furnace further promotes methanation reaction；Recyclegas I (F) is sent into first jet 2, fluidized bed of going forward side by side gas
Change 1 lower layer space of furnace and promotes gasification reaction.
The oxygen-containing gas (A) is selected from any one of oxygen or air.
It include coal, water and K in the coal slurry (B)2CO3, coal and K2CO3Initial feed average grain diameter be respectively less than
250μm；The concentration of coal slurry is 45-60%.
The catalyst (C) is catalyst for methanation in presence of sulfur, and average grain diameter is less than 250 μm, selected from being supported on silica
On nickel compound containing or/and eutectic containing chromium compound.
The operation temperature of the fluidized-bed gasification furnace (1) is 800-950 DEG C.
Advantages of the present invention brief introduction
The present invention will gasify and methanation reaction is coupled in one, main in the lower layer space gasification reaction section of fluidized bed
Burning and gasification reaction are carried out, high-temperature synthesis gas is generated, is passed through the gas that circulating air adjusts the area in the upper space of fluidized bed
Body composition, and catalyst is supplemented by nozzle, main forced mathaneization reaction improves methane production.In addition, passing through product
CO in gas2Recycle, realize logistics coupling, increase gas production capacity, improve efficiency of carbon con version.
Using technical solution of the present invention, fluidized bed feed coal feeds the form for being all made of coal slurry, and uses nozzle material-feeding,
Contact effect of the coal with gasifying agent is improved, efficiency of carbon con version is improved；In addition, due to containing certain mass score in coal slurry
Moisture saves the raw material cost of investment in operational process so that the vapor of required offer is reduced in gasifying agent.This hair
Bright technical solution can make reactor outlet efficiency of carbon con version up to 96%, and methane concentration reaches 25%, realize logistics and heat
Coupling, while reducing the addition of vapor in gasifying agent, production cost is largely reduced, before there is good application
Scape.
Detailed description of the invention
Attached drawing Fig. 1 is the schematic diagram of the fluidized bed coal catalytic gasification methane device provided by the invention with nozzle.
In figure, 1- fluidized-bed gasification furnace；2- first jet；3- second nozzle；4- gas-solid separating device；5- ash bucket；6- gas
Body purification separation unit；7- slag bucket；A- oxygen-containing gas；B- coal slurry；C- catalyst；D- recyclegas II；E- product gas；F- circulation
Gas I；G- lime-ash.
Coal slurry B and recyclegas I (F) is sprayed into 1 lower layer space of fluidized-bed gasification furnace by first jet 2 and is atomized, and with
Burning occurs for oxygen-containing gas, gasification reaction generates synthesis gas, and synthesis gas occurs under the action of catalyst C after entering upper space
Methanation reaction generates the product gas for being rich in methane E, after product gas is separated, purified, wherein product gas (E) is collected, and is followed
Ring gas I (F) enters 1 lower layer space of fluidized-bed gasification furnace as gasifying agent and assists gasification reaction, and recyclegas II (D) enters stream
Change the reaction of 1 upper space forced mathaneization of bed gasification furnace.
Specific embodiment
The features of the present invention is described in detail with reference to the accompanying drawings and examples.
[embodiment 1]
In the embodiment, oxygen-containing gas (A) uses air, and introduces fluidized bed by single tube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized gasification furnace bottom.It is 45% coal slurry raw material that the embodiment, which selects concentration,
It is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 800 DEG C of operation temperature, reaction generates
Lime-ash fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and sprays into from second nozzle
SiO2The contact of/Ni catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries in furnace
Tiny fly ash granule enters gas-solid separation equipment and is separated, and fly ash granule is sent to ash bucket collection, and product gas continues
Gas purification separative unit is sent to be further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into second nozzle,
Fluidized bed of going forward side by side gasification furnace upper space further promotes methanation reaction；CO2It is sent into first jet, fluidized bed of going forward side by side gas
Change furnace lower layer space and promotes gasification reaction；CH4Then collected as product key product therein.The efficiency of carbon con version of whole system
It is 91%, the content of methane reaches 18% in gasification furnace exported product gas, and see Table 1 for details for result.
[embodiment 2]
In the embodiment, oxygen-containing gas (A) uses air, and introduces fluidized bed by multitube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized-bed gasification furnace bottom sides.It is 45% coal slurry that the embodiment, which selects concentration,
Raw material is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 800 DEG C of operation temperature, reaction
The lime-ash of generation is fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and in from second nozzle
The SiO of penetrating2The contact of/Ni catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries furnace
Interior tiny fly ash granule enters gas-solid separation equipment and is separated, and fly ash granule is sent to ash bucket and collects, and product gas quilt
Continue to be sent to gas purification separative unit and is further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into second
Nozzle, fluidized bed of going forward side by side gasification furnace upper space further promote methanation reaction；CO2It is sent into first jet, goes forward side by side and becomes a mandarin
Change bed gasification furnace lower layer space and promotes gasification reaction；CH4Then collected as product key product therein.The carbon of whole system
Conversion ratio is 92%, and the content of methane reaches 19% in gasification furnace exported product gas, and see Table 1 for details for result.
[embodiment 3]
In the embodiment, oxygen-containing gas (A) uses air, and introduces fluidized bed by multitube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized-bed gasification furnace bottom sides.It is 60% coal slurry that the embodiment, which selects concentration,
Raw material is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 800 DEG C of operation temperature, reaction
The lime-ash of generation is fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and in from second nozzle
The SiO of penetrating2The contact of/Ni catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries furnace
Interior tiny fly ash granule enters gas-solid separation equipment and is separated, and fly ash granule is sent to ash bucket and collects, and product gas quilt
Continue to be sent to gas purification separative unit and is further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into second
Nozzle, fluidized bed of going forward side by side gasification furnace upper space further promote methanation reaction；CO2It is sent into first jet, goes forward side by side and becomes a mandarin
Change bed gasification furnace lower layer space and promotes gasification reaction；CH4Then collected as product key product therein.The carbon of whole system
Conversion ratio is 92%, and the content of methane reaches 21% in gasification furnace exported product gas, and see Table 1 for details for result.
[embodiment 4]
In the embodiment, oxygen-containing gas (A) uses air, and introduces fluidized bed by multitube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized-bed gasification furnace bottom sides.It is 60% coal slurry that the embodiment, which selects concentration,
Raw material is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 950 DEG C of operation temperature, reaction
The lime-ash of generation is fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and in from second nozzle
The SiO of penetrating2The contact of/Ni catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries furnace
Interior tiny fly ash granule enters gas-solid separation equipment and is separated, and fly ash granule is sent to ash bucket and collects, and product gas quilt
Continue to be sent to gas purification separative unit and is further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into second
Nozzle, fluidized bed of going forward side by side gasification furnace upper space further promote methanation reaction；CO2It is sent into first jet, goes forward side by side and becomes a mandarin
Change bed gasification furnace lower layer space and promotes gasification reaction；CH4Then collected as product key product therein.The carbon of whole system
Conversion ratio is 95%, and the content of methane reaches 24% in gasification furnace exported product gas, and see Table 1 for details for result.
[embodiment 5]
In the embodiment, oxygen-containing gas (A) uses oxygen, and introduces fluidized bed by multitube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized-bed gasification furnace bottom sides.It is 60% coal slurry that the embodiment, which selects concentration,
Raw material is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 950 DEG C of operation temperature, reaction
The lime-ash of generation is fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and in from second nozzle
The SiO of penetrating2The contact of/Ni catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries furnace
Interior tiny fly ash granule enters gas-solid separation equipment and is separated, and fly ash granule is sent to ash bucket and collects, and product gas quilt
Continue to be sent to gas purification separative unit and is further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into second
Nozzle, fluidized bed of going forward side by side gasification furnace upper space further promote methanation reaction；CO2It is sent into first jet, goes forward side by side and becomes a mandarin
Change bed gasification furnace lower layer space and promotes gasification reaction；CH4Then collected as product key product therein.The carbon of whole system
Conversion ratio is 96%, and the content of methane reaches 24% in gasification furnace exported product gas, and see Table 1 for details for result.
[embodiment 6]
In the embodiment, oxygen-containing gas (A) uses oxygen, and introduces fluidized bed by multitube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized-bed gasification furnace bottom sides.It is 60% coal slurry that the embodiment, which selects concentration,
Raw material is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 950 DEG C of operation temperature, reaction
The lime-ash of generation is fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and in from second nozzle
The SiO of penetrating2The contact of/Cr catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries furnace
Interior tiny fly ash granule enters gas-solid separation equipment and is separated, and fly ash granule is sent to ash bucket and collects, and product gas quilt
Continue to be sent to gas purification separative unit and is further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into second
Nozzle, fluidized bed of going forward side by side gasification furnace upper space further promote methanation reaction；CO2It is sent into first jet, goes forward side by side and becomes a mandarin
Change bed gasification furnace lower layer space and promotes gasification reaction；CH4Then collected as product key product therein.The carbon of whole system
Conversion ratio is 96%, and the content of methane reaches 25% in gasification furnace exported product gas, and see Table 1 for details for result.
[embodiment 7]
In the embodiment, oxygen-containing gas (A) uses oxygen, and introduces fluidized bed by multitube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized-bed gasification furnace bottom sides.It is 60% coal slurry that the embodiment, which selects concentration,
Raw material is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 950 DEG C of operation temperature, reaction
The lime-ash of generation is fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and in from second nozzle
The SiO of penetrating2The contact of/(Cr+Ni) catalyst occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries
Tiny fly ash granule in furnace enter gas-solid separation equipment and separated, fly ash granule is sent to ash bucket collection, and product
Gas, which continues to be sent to gas purification separative unit, to be further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Circulation is sent into
Second nozzle, fluidized bed of going forward side by side gasification furnace upper space further promote methanation reaction；CO2It is sent into first jet, is gone forward side by side
Fluidized bed gasification furnace lower layer space promotes gasification reaction；CH4Then collected as product key product therein.Whole system
Efficiency of carbon con version be 96%, the content of methane reaches 25% in gasification furnace exported product gas, and see Table 1 for details for result.
[comparative example 1]
Using the gasification reactor apparatus for the catalytic coal gasifaction methane that Xin Ao group proposes, fluidized-bed reaction used is tested
Device operation temperature is 900 DEG C, and catalyst is potassium carbonate, and gasifying agent is the mixture of oxygen and vapor.Test obtained outlet
Methane content 19% in gas component, efficiency of carbon con version 85%, see Table 1 for details for result.
[comparative example 2]
Using Xin Ao group PDU gasification reactor apparatus, raw material uses lignite coal dust, and adds potassium carbonate as catalyst,
Gasifying agent is the mixture of oxygen and vapor, 800 DEG C of operation temperature, methane content in the exit gas component to gasify
14%, but its efficiency of carbon con version is 90%, and see Table 1 for details for result.
[comparative example 3]
In the embodiment, oxygen-containing gas (A) uses air, and introduces fluidized bed by single tube jetting type gas distributor
Gasification furnace, gas distributor are arranged perpendicular to fluidized gasification furnace bottom.It is 45% coal slurry raw material that the embodiment, which selects concentration,
It is put into gasification furnace lower layer space by first jet, and issues raw gasification reaction in 800 DEG C of operation temperature, reaction generates
Lime-ash fallen into slag bucket due to self gravity；And synthesis gas is then upwardly into upper space, and and SiO2/ Ni catalyst connects
Touching occurs catalytic production of methane reaction, generates and be rich in CH4Product gas.Product gas carries the entrance of the tiny fly ash granule in furnace
It is separated to gas-solid separation equipment, fly ash granule is sent to ash bucket collection, and product gas continues to be sent to gas purification separation
Unit is further processed to obtain CO+H2、CH4And CO2, wherein CO+H2Nozzle is not used, fluidisation is only entered by pipeline
Bed gasification furnace upper space further promotes methanation reaction；CO2It is sent into first jet, fluidized bed of going forward side by side gasification furnace lower layer is empty
Between promote gasification reaction；CH4Then collected as product key product therein.The efficiency of carbon con version of whole system is 91%, gas
The content for changing methane in outlet of still product gas reaches 14%, and see Table 1 for details for result.
Table 1
Claims (10)
1. a kind of fluidized bed coal catalytic gasification methane device with nozzle, it is characterised in that: including fluidized-bed gasification furnace (1),
First jet (2), second nozzle (3), gas-solid separating device (4), ash bucket (5), gas purification separative unit (6), slag bucket (7)；
Fluidized-bed gasification furnace (1) bottom is connected with slag bucket (7), fluidized-bed gasification furnace (1) lower layer space and upper space are respectively equipped with
Gas-solid separating device (4) are connected at the top of first jet (2) and second nozzle (3), fluidized-bed gasification furnace (1), gas-solid separating device
(4) solid outlet connection ash bucket (5), gas-solid separating device (4) gas vent are connected with gas purification separative unit (6).
2. the fluidized bed coal catalytic gasification methane device according to claim 1 with nozzle, it is characterised in that: the first spray
Mouth (2) uses dual channel structure, wherein a side runner passes through for recyclegas I (F), another side runner coal supply slurry (B) and conveying
Carrier gas passes through, and wherein recyclegas I (F) is CO2。
3. the fluidized bed coal catalytic gasification methane device according to claim 1 with nozzle, it is characterised in that: the second spray
Mouth (3) uses dual channel structure, wherein a side runner passes through for recyclegas II (D), another side runner is for catalyst (C) and defeated
Carrier gas is sent to pass through, wherein recyclegas II (D) is CO and H2Gaseous mixture.
4. the fluidized bed coal catalytic gasification methane device according to claim 1 with nozzle, it is characterised in that: the first spray
Mouth (2) and second nozzle (3) are all made of two opposed arrangements of nozzle, and are respectively perpendicular to fluidized-bed gasification furnace (1) lower layer space
Horizontal plane arrangement in the middle part of middle part and upper space.
5. the fluidized bed coal catalytic gasification methane device according to claim 1 with nozzle, it is characterised in that: fluidized bed
Gasification furnace (1) bottom is equipped with the import of oxygen-containing gas (A), and the import of oxygen-containing gas (A) introduces gas using gas distributor structure
Body, gas distributor select one kind of single tube jetting type, multitube jetting type.
6. a kind of fluidized bed coal catalytic gasification methanol method with nozzle, using any one band described in claim 1-5
The fluidized bed coal catalytic gasification methane device of nozzle, which comprises the following steps:
Coal slurry (B) and recyclegas I (F) are atomized by the lower layer space that first jet (2) spray into fluidized-bed gasification furnace (1), and
The violent burning of generation is contacted with oxygen-containing gas (A), gasification reaction generates synthesis gas and lime-ash (G), lime-ash are fallen because of self gravity
Enter in slag bucket (7) and be collected, synthesis gas flow is upwardly into the upper space of fluidized-bed gasification furnace (1), with from
Methanation reaction occurs for the catalyst (C) that second nozzle (3) sprays into, and generates and is rich in CH4Product gas (E), be rich in CH4Product
Gas (E) carries a small amount of tiny solid particle and is fed through gas-solid separating device (4), after separation, a small amount of tiny solid
Particle is sent to ash bucket (5) and is collected, and is rich in CH4Product gas (E) then enter gas purification separative unit (6) into
Change, separation, obtains recyclegas II (D), product gas (E) and recyclegas I (F)；Wherein, recyclegas II (D) circulation is sent
Enter second nozzle (3), fluidized bed of going forward side by side gasification furnace (1) upper space further promotes methanation reaction；Recyclegas I (F)
It is sent into first jet (2), fluidized bed of going forward side by side gasification furnace (1) lower layer space promotes gasification reaction.
7. the fluidized bed coal catalytic gasification methanol method according to claim 6 with nozzle, it is characterised in that: oxygenous
Body (A) is selected from any one of oxygen or air.
8. the fluidized bed coal catalytic gasification methanol method according to claim 6 with nozzle, it is characterised in that: coal slurry
It (B) include coal, water and K in2CO3；Coal and K2CO3Initial feed average grain diameter be respectively less than 250 μm；The concentration of coal slurry is
45-60%.
9. the fluidized bed coal catalytic gasification methanol method according to claim 6 with nozzle, it is characterised in that: catalyst
It (C) is catalyst for methanation in presence of sulfur, average grain diameter selected from the nickel compound containing being supported on silica or/and contains less than 250 μm
The eutectic of chromium compound.
10. the fluidized bed coal catalytic gasification methanol method according to claim 6 with nozzle, it is characterised in that: fluidisation
The operation temperature of bed gasification furnace (1) is 800-950 DEG C.
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| CN112961705A (en) * | 2021-02-04 | 2021-06-15 | 中国华能集团清洁能源技术研究院有限公司 | Gasification furnace for directly preparing methane/methanol by coal gasification |
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| CN106590761A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Fluidized bed reaction device and reaction method for coal catalytic gasification for producing methane-rich synthetic gas |
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| CN112961705A (en) * | 2021-02-04 | 2021-06-15 | 中国华能集团清洁能源技术研究院有限公司 | Gasification furnace for directly preparing methane/methanol by coal gasification |
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