CN105907430A - Device for producing synthesis gas through biomass gasification and method of device - Google Patents
Device for producing synthesis gas through biomass gasification and method of device Download PDFInfo
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- CN105907430A CN105907430A CN201610450149.9A CN201610450149A CN105907430A CN 105907430 A CN105907430 A CN 105907430A CN 201610450149 A CN201610450149 A CN 201610450149A CN 105907430 A CN105907430 A CN 105907430A
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- gasification
- gas
- biomass
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- 238000002309 gasification Methods 0.000 title claims abstract description 131
- 239000002028 Biomass Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 19
- 239000007789 gas Substances 0.000 claims abstract description 90
- 238000002407 reforming Methods 0.000 claims abstract description 63
- 238000000197 pyrolysis Methods 0.000 claims abstract description 60
- 238000011069 regeneration method Methods 0.000 claims abstract description 58
- 230000008929 regeneration Effects 0.000 claims abstract description 57
- 239000000571 coke Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims description 33
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 230000008676 import Effects 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000011269 tar Substances 0.000 claims description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 16
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003546 flue gas Substances 0.000 claims description 10
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 7
- 238000007781 pre-processing Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- 239000007792 gaseous phase Substances 0.000 claims description 6
- 239000001095 magnesium carbonate Substances 0.000 claims description 6
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 6
- 239000002154 agricultural waste Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 238000006057 reforming reaction Methods 0.000 claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 229910020634 Co Mg Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 3
- 229910018496 Ni—Li Inorganic materials 0.000 claims description 3
- 229910018505 Ni—Mg Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000003134 recirculating effect Effects 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 230000032258 transport Effects 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 239000011285 coke tar Substances 0.000 claims 1
- 239000011286 gas tar Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000001833 catalytic reforming Methods 0.000 abstract description 3
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 239000003337 fertilizer Substances 0.000 abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000004523 catalytic cracking Methods 0.000 abstract 1
- 235000011164 potassium chloride Nutrition 0.000 abstract 1
- 239000001103 potassium chloride Substances 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 239000010902 straw Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009719 regenerative response Effects 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
- C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
- C10K3/023—Reducing the tar content
-
- 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
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
- C10J3/60—Processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/82—Gas withdrawal means
- C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0906—Physical processes, e.g. shredding, comminuting, chopping, sorting
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0903—Feed preparation
- C10J2300/0909—Drying
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/0916—Biomass
- C10J2300/092—Wood, cellulose
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a device for producing synthesis gas through biomass gasification and a method of the device. The device mainly comprises a pyrolysis reactor, a gasification reactor, a reforming reactor, a regeneration reactor and heat pipes. In the technological process, biomass is firstly pretreated with a sylvite solution, the pretreated biomass is subjected to pyrolysis in the pyrolysis reactor, coke is gasified in the gasification reactor, the gasification reactor and the regeneration reactor generate hydrogen-rich gas through circulation bed material heat loading and CO2 absorption, and the hydrogen-rich gas enters the reforming reactor to carry out hydrogenation catalytic cracking and reforming on pyrolysis gas. Therefore, the synthesis gas with low tar and high-concentration H2 and CO is obtained through step-by-step pyrolysis, gasification, reforming and regenerative combustion at mild reaction temperature, meanwhile, potassium-rich agricultural fertilizer is by-produced, stepped transfer of heat in the biomass thermo-chemical conversion process is achieved, the energy utilization efficiency is improved, and economic additional value is increased.
Description
Technical field
The present invention relates to method and the apparatus system thereof of a kind of gasification of biomass, belong to biomass resource utilization field.
Background technology
Gasification of biomass is one of important channel of biomass thermal chemical conversion utilization, and the synthesis gas produced can not only be used for gas
Fuel, it is possible to as the intermediate product of the chemical products such as methanol, dimethyl ether, FT artificial oil, biomass gasification technology has
There is important actual application value.The subject matter of biomass thermal chemical conversion approach is that (1) utilizes air direct at present
Synthesis gas exists during gasification a large amount of N2, cause flow rate low, poor quality；(2) there is tar in gasification product,
Not only affect GAS QUALITY, and affect the properly functioning of upstream device, when carrying out tar catalytic reforming, be easily caused catalysis
Agent carbon distribution inactivates, thus constrains the application of biomass gasifying hydrogen making technology.
In order to avoid air direct gasification causes there is a large amount of N in synthesis gas2So that GAS QUALITY declines, and grinds in recent years
The person of studying carefully uses the mode of indirect heating, improves effective ingredient and the calorific value of synthesis gas, and main technical method includes:
(1) classification gasification method is utilized to be separated, by inertia or catalyst bed with coke burning by the pyrolytic gasification of biomass
Expecting that pyrolysis and gasification for biomass provide heat, in order to reduce tar content, pyrolytic gasification product is further weighed
Whole purification.(2) by classification gasification method, utilizing coke to carry out gasification and obtain highly purified hydrogen, pyrolysis gas burns
Heat is provided, and avoids the generation of tar.
In order to overcome the coal-tar middle oil conversion of biomass gasification process not exclusively and reforming catalyst carbon distribution inactivation, improve biomass
The gasification utilization rate of carbon and system effectiveness, the present invention proposes a kind of new classification gasification apparatus and method.
Summary of the invention
Technical problem: according in the limitation of prior art, it is an object of the invention to provide a kind of biomass graded gasification and produce conjunction
Becoming the devices and methods therefor of gas, to solve, existing biomass gasified synthesis gas calorific value is low, tar content is high, it is tired to convert removing
Difficult problem, proposes one and produces without tar, high concentration by realizing biomass thermal chemical conversion under gentle reaction temperature
H2With biomass gasification device and the method thereof of CO synthesis gas, and can coproduction obtain rich in the chemical fertilizer by-product of potassium.
Technical scheme: the device of a kind of gasification of biomass producing synthesis gas of the present invention includes pyrolysis reactor, gasification reaction
Device, reforming reactor, regeneration reactor, the first heat-transfer pipe, the second heat-transfer pipe, the first gas-solid separator, the second gas-solid
Separator, coke batcher, feed pipe and connecting line；In first reactor, pyrolysis reactor is placed in gasification
Reactor top, is separated by division board between pyrolysis reactor and gasification reactor, is connected by coke batcher and feed pipe
Connecing, the two ends of the first heat-transfer pipe are respectively placed in pyrolysis reactor and gasification reactor, are provided with charging on pyrolysis reactor
Mouthful, the first gas outlet；Gasification reactor is provided with gasifying medium inlet, the second gas outlet, and the first circulation bed is entered
Mouth and circulation bed outlet；
In a second reactor, reforming reactor be placed in regeneration reactor top, reforming reactor and regeneration reactor it
Between separated by division board, the two ends of the second heat-transfer pipe are respectively placed in reforming reactor and regeneration reactor, reforming reactor
It is provided with gas feed, the 3rd gas outlet, the charge door of catalyst and discharging opening；Regeneration reactor is provided with material and enters
Mouth, the second circulation bed import, and air intlet and flue gas/material outlet；The gas feed of reforming reactor is positioned at
The bottom of reforming reactor；
The circulation bed outlet of gasification reactor is connected with the second circulation bed import of regeneration reactor；Gasification reactor
Gas outlet connects the import of the first gas-solid separator, the first gas outlet of pyrolysis reactor and the first gas-solid separator
Gaseous phase outlet connects the gas feed of reforming reactor；Flue gas/the material outlet of regeneration reactor connects the second gas-solid separator
Import, the solid outlet of the second gas-solid separator connect gasification reactor first circulation bed import.
Described discharge nozzle, discharge nozzle import and discharge nozzle outlet are respectively placed in pyrolysis reactor and gasification reactor.
Pyrolysis reactor and reforming reactor are fixed bed or moving-burden bed reactor, and gasification reactor is bubbling fluidized bed or spray
Fluidized bed, regeneration reactor is recirculating fluidized bed or transports bed.
Gasification reactor and regeneration reactor are filled with circulation bed, and circulation bed is followed in 2 described reactors
Ring；Reforming reactor is filled with reforming catalyst.
The outlet of feed pipe extend in the filling bed of gasification reactor.
The gasification process substep of a kind of biomass gasification device of the present invention carries out biomass pyrolysis process, pyrolysis gas/tar
Reforming process and coke gasification process, the method comprises the steps:
1) first the biomass of natural drying are crushed to below 1mm, after utilizing potassium salt soln dipping biomass, bakee dry
Dry to moisture content less than 20%, it is thus achieved that preprocessing biomass；
2) preprocessing biomass pyrolysis reactor described in charging aperture enters is pyrolyzed, and produces pyrolysis after pyrolytic reaction
Gas and coke, pyrolysis gas is entered reforming reactor, solid by the first gas outlet through the gas feed of reforming reactor
Material coke controls to enter gasification reactor through feed pipe by coke batcher；
3) coke carries out gasification reaction with the steam entering gasification reactor in gasification reactor, generates gaseous product
H2, CO and CO2, and CO2React with the MgO/CaO in circulation bed, be cured as MgCO3/CaCO3；
4) gaseous product of gasification reactor is entered the first gas-solid separator by the second gas outlet, the biology carried by gas
Reforming reactor, isolated biology is entered by gaseous phase outlet by reforming reactor gas access after matter lime-ash isolation of purified
Matter lime-ash is exported discharger by lime-ash；
5) enter in the pyrolysis gas of reforming reactor that macromole tar is under catalyst bed effect, and from gasification reaction
The hydrogen-rich gas H of device2O、H2, CO and CO2Carry out reforming reaction and hydrocracking, be eventually converted into H2、CO、CO2、
CH4Micro-molecular gas product；
6) biomass are entered regeneration reactor with air/oxygen burnt by material inlet and the air intlets of regeneration reactor,
Circulation bed MgCO in gasification reactor3/CaCO3Regeneration reactor calcination and regeneration is returned by regeneration reactor bed import,
MgCO therein3/CaCO3It is decomposed into MgO/CaO and CO2, the circulation bed after calcining after the second gas-solid separator by gas
Changing Reactor inlet and enter back into gasification reactor, thus circulation bed circulates in two reactors, and by regeneration reactor
Heat bring gasification reactor into；
7) flue gas that regeneration reactor generates is after the second gas-solid separator, enters heat exchanger heating supply gasification reactor
Feedwater, discharger after cooling.
Described preprocessing biomass includes agricultural wastes, forestry waste；The potassium salt soln that pretreatment uses includes
KNO3、K2CO3, wherein potassium salt is 8%～30% with the quality proportioning of biomass.
Circulation bed in gasification reactor and regeneration reactor is MgCO3/CaCO3/MgO/CaO/Al2O3/SiO2Mixing
Thing, particle diameter is 1mm～3mm；Catalyst feed in reforming reactor be Ni-Li, Ni-Mo, Ni-Mg or Co-Li,
Co-Mo, Co-Mg are the composite catalyst of active component.
Heat in gasification reactor is passed to pyrolysis reactor by the first described heat pipe；Second heat pipe is by regeneration reactor
Heat pass to reforming reactor, the heat transfer medium in the first heat pipe and the second heat pipe is Na or K and mixture thereof.
The temperature of described pyrolysis reactor 400～600 DEG C, gasification reactor at 600～750 DEG C, regeneration reactor is
800～900 DEG C；Reforming reactor 600～800 DEG C.
Beneficial effect: biomass pyrolysis process is separated by the present invention with coke gasification process, utilizes in coke displacement steam
Hydrogen obtain hydrogen-rich gas, enter reforming reactor by this hydrogen-rich gas and promote the hydrocracking of tar and catalytic reforming,
Thus the tar during critical heat is vented one's spleen efficiently, it is thus achieved that the synthesis gas of low tar；
The reforming catalyst of tar of the present invention utilizes under hydrogenation, it is to avoid the carbon distribution of catalyst, improves making of catalyst
Use the life-span.
The present invention utilizes potassium salt that biomass carry out pretreatment, K therein2O not only catalytic coke gasifies at a lower temperature and obtains
Take hydrogen-rich gas, and reacted lime-ash is rich in K2O can improve the attached of biomass trans-utilization as farmland fertilizer
Value added.
Accompanying drawing explanation
Fig. 1 is technical process and the system and device schematic diagram of the present invention.
Pyrolysis reactor 1, gasification reactor 2, reforming reactor 3, regeneration reactor 4, the first heat-transfer pipe 5, second
Heat-transfer pipe 6, the first gas-solid separator 7, the second gas-solid separator 8, coke batcher 9, feed pipe 10.
Detailed description of the invention
Below in conjunction with the accompanying drawings the devices and methods therefor of a kind of gasification of biomass of the present invention is described in detail.
The method of the gasification of biomass producing synthesis gas of the present invention is the generation in order to avoid tar, promotes that coke is relatively low
At a temperature of realize Efficient Conversion, first biomass have been carried out potassium salt pretreatment, and classification have been carried out under mild reaction conditions
The reformation of biomass pyrolytic, coke gasification and tar, tar is hydrogenated with by the hydrogen-rich gas utilizing coke gasification to obtain
Cracking and reformation, thus obtain high concentration H2With the synthesis gas of CO, promote tar conversion, improve coke gasification utilization rate.
The device of the gasification of biomass producing synthesis gas of the present invention, including pyrolysis reactor 1, gasification reactor 2, reforms anti-
Answering device 3, regeneration reactor 4, the first heat-transfer pipe 5, the second heat-transfer pipe 6, the first gas-solid separator 7, the second gas-solid divides
From device 8, coke batcher 9, discharge nozzle 10 and connecting line.In first reactor, pyrolysis reactor 1 is put
In gasification reactor 2 top, separated by division board between pyrolysis reactor 1 and gasification reactor 2, by coke feed
Machine 9 and discharge nozzle 10 connect；In a second reactor, reforming reactor 3 is placed in regeneration reactor 4 top, weight
Separated by division board between whole reactor 3 and regeneration reactor 4；And first to be respectively placed in pyrolysis anti-the two ends of heat-transfer pipe 5
Answer device 1 and gasification reactor 2；And second the two ends of heat-transfer pipe 6 be respectively placed in reforming reactor 3 and regeneration reactor 4.
Wherein, pyrolysis reactor includes charging aperture 1A, gas outlet 1B；Gasification reactor 2 includes gasifying medium inlet 2A,
Gas outlet 2C, circulation bed import 2B and circulation bed outlet 2D；In a second reactor, reforming reactor 3
Including gas feed 3A, gas outlet 3C, the charge door 3B and discharging opening 3D of catalyst；Regeneration reactor 4 includes
Material inlet 4A, circulates bed import 4B, and air intlet 4C and flue gas/material outlet 4D；Reforming reactor 3
Gas feed 3A be positioned at the bottom of reforming reactor 3.
It addition, the import 10A of discharge nozzle 10 and outlet 10B is respectively placed in pyrolysis reactor 1 and gasification reactor 2,
And inside is equipped with coke dispenser 9；
The circulation bed outlet 2D of gasification reactor 2 is connected with the circulation bed import 4B of regeneration reactor 4；Gasified reverse
The gas outlet 2C answering device 2 connects the import 7A of the first gas-solid separator 7, the first gas outlet of pyrolysis reactor 1
The gaseous phase outlet 7B of 1B and the first gas-solid separator 7 connects the gas feed 3A of reforming reactor 3；Regeneration reactor 4
Flue gas/material outlet 4D meet the import 8A, the solid outlet 8C of the second gas-solid separator 8 of the second gas-solid separator 8
Meet the first circulation bed import 2B of gasification reactor 2.
Preferably pyrolysis reactor 1 and reforming reactor 3 are fixed bed or moving-burden bed reactor, and gasification reactor 2 is drum
Bubble fluid bed or spouted fluidized bed, regeneration reactor 4 is for recirculating fluidized bed or transports bed；And gasification reactor 2 and again
Raw reactor 4 is filled with circulation bed, and circulation bed circulates in 2 described reactors；Preferably pyrolysis is anti-
The outlet 10B answering the discharge nozzle 10 of device 1 extend in the filling bed of gasification reactor 2；Preferably reforming reactor
3 are filled with reforming catalyst；
A kind of biomass gasification method that the present invention provides, comprises the steps:
First the biomass of natural drying are included that agricultural wastes, forestry waste etc. are crushed to 1mm by step one
Hereinafter, potassium salt soln such as KNO is utilized3、K2CO3Deng, it is 8%～30% according to the quality proportioning of potassium salt Yu biomass
Dipping biomass, the biomass after dipping bakee and are dried to moisture content less than 20%, it is thus achieved that preprocessing biomass；
Step 2, the biomass of pretreatment pyrolysis reactor 1 described in charging aperture 1A enters is pyrolyzed, through heat
Producing pyrolysis gas and coke after solving reaction, pyrolysis gas is entered through the gas of reforming reactor 3 by gas outlet 1B
Mouth 3A enters reforming reactor 3, and coke batcher 9 controls the biomass time of staying in pyrolysis reactor, so
Rear solid material coke enters gasification reactor 2 by discharge nozzle 10；
Step 3, coke carries out gasification reaction, water with the steam entering gasification reactor 2 in the gasification reactor 2
Steam with the mass ratio of biomass is: 0.3～2, generates gaseous product H2, CO and CO2, and CO2With circulation
MgO/CaO in bed reacts, and is cured as MgCO3/CaCO3；
Step 4, the gaseous product of gasification reactor 2 is entered the first gas-solid separator 7 by exporting 2C, is taken by gas
Reformation is entered by gaseous phase outlet 7B by reforming reactor 3 gas access 3A after the biomass lime-ash isolation of purified of band
Reactor 3, isolated biomass lime-ash is exported 7C discharger by lime-ash；
Step 5, in the pyrolysis gas of entrance reforming reactor 3, macromole tar is under catalyst bed effect, with next
The gas H of autopneumatolysis reactor 42O、H2, CO and CO2Carry out reforming reaction and hydrocracking, be eventually converted into
H2、CO、CO2、CH4Micro-molecular gas product；
Step 6, biomass are entered regeneration with air/oxygen by the material inlet 4A and air intlet 4C of regeneration reactor 4
Reactor 4 burns, circulation bed MgCO in gasification reactor 23/CaCO3Entered by regeneration reactor bed
Mouth 4B returns regeneration reactor calcination and regeneration, MgCO therein3/CaCO3It is decomposed into MgO/CaO and CO2, forge
Circulation bed after burning is entered back into gasification reactor 2 by gasification reactor import 2B after the second gas-solid separator 8,
Thus circulation bed circulates in two reactors, and brings the heat of regeneration reactor 4 into gasification reactor 2；
Step 7, the flue gas that regeneration reactor 4 generates, after the second gas-solid separator 8, enters heat exchanger heating supply
The feedwater of gasification reactor 2 generates steam, discharger after flue gas cooling.
Wherein, heat in gasification reactor 2 is passed to pyrolysis reactor 1 by the first heat pipe 5；Second heat pipe 6 will regeneration
The heat of reactor 4 passes to reforming reactor 3.Heat transfer medium in preferred first heat pipe 5 and the second heat pipe 6 is
Na or K and mixture thereof；
Preferably the temperature of pyrolysis reactor 1 400～600 DEG C, gasification reactor 2 at 600～750 DEG C, regenerative response
Device 4 is at 800～900 DEG C, and reforming reactor 3 is at 600～800 DEG C；
Circulation bed in preferred gasification reactor 2 and regeneration reactor 4 is MgCO3/CaCO3/Al2O3
/MgO/CaO/SiO2Mixture, particle diameter is 1mm～3mm；
Preferably the catalyst feed in reforming reactor 3 is Ni-Li, Ni-Mo, Ni-Mg or Co-Li, Co-Mo, Co-Mg
Composite catalyst for active component；
Under the conditions of You Xuan, the synthesis gas of gaseous product is mainly composed of the H of 50%～75%2, 10%～the CO of 30%, 5%～
25%CO2With minimal amount of CH4；Tar content is less than 500mg/Nm3；The K of biomass lime-ash2O content is more than 40%,
Can be as agrochemical side-product.
Example 1: wheat straw biomass
Agricultural wastes straw is raw material, and gasifying process is described above: straw is crushed to about 0.3-0.6mm, utilizes 100g
K2CO3Configuration solution 2000mL, impregnates the straw 1h after 1000g crushes, is then fed into exsiccator and is dried to containing under room temperature
Water less than 10%；Pretreated straw feeding pyrolysis reactor, pyrolysis reaction temperature 600 DEG C, gasification temperature 700 DEG C,
Reforming reaction temperature 750 DEG C, combustion reaction temperature 900 DEG C, gasification reactor is sent into steam/straw mass ratio 0.5, is followed
Ring bed is Al2O3And CaCO3/ CaO, the two proportioning 1: 5, CaCO3/ CaO circulating load and biomass quality proportioning 4: 1,
Reforming catalyst is 15%Ni-3%Li/Al2O3；The synthesis gas that gasification reformation obtains, through the gas componant of cooling and purifying
H2: 65.9%, CO:19.5%, CO2: 14.1%, CH4＜ 0.25%, gas yield: 1.02Nm3/ kg, tar
＜ 500mg/Nm3, lime-ash K2O content～50%.
Example 2: wheat straw biomass
Agricultural wastes straw is raw material, and gasifying process is described above: straw is crushed to about 0.3-0.6mm, utilizes 150g
K2CO3Configuration solution 3000mL, impregnates the straw 1h after 1000g crushes, is then fed into exsiccator and is dried to containing under room temperature
Water less than 10%；Pretreated straw sends into pyrolysis reactor, reaction temperature 700 DEG C, gasification temperature 750 DEG C, weight
Whole reaction temperature 750 DEG C, combustion reaction temperature 900 DEG C, gasification reactor sends into steam/straw mass ratio 0.4, circulation
Bed is Al2O3And CaCO3/ CaO, the two proportioning 2: 1, CaCO3/ CaO circulating load and biomass quality proportioning 2: 1,
Reforming catalyst is 15%Ni-10%Mg/Al2O3；The synthesis gas that gasification reformation obtains, the gas through cooling and purifying becomes
Divide H2: 60.2%, CO:24.2%, CO2: 15.2%, CH4＜ 0.3%, gas yield: 1.03Nm3/ kg, tar
＜ 400mg/Nm3, lime-ash K2O content～60%.
Claims (10)
1. the device of a gasification of biomass producing synthesis gas, it is characterised in that: this device includes pyrolysis reactor (1),
Gasification reactor (2), reforming reactor (3), regeneration reactor (4), the first heat-transfer pipe (5), the second heat-transfer pipe (6),
First gas-solid separator (7), the second gas-solid separator (8), coke batcher (9), feed pipe (10) and connection
Pipeline；In first reactor, pyrolysis reactor (1) is placed in gasification reactor (2) top, pyrolysis reactor (1)
And separated by division board between gasification reactor (2), connected by coke batcher (9) and feed pipe (10), the
The two ends of one heat-transfer pipe (5) are respectively placed in pyrolysis reactor (1) and gasification reactor (2), at pyrolysis reactor
(1) charging aperture (1A), the first gas outlet (1B) it are provided with；Gasification reactor (2) is provided with gasifying medium inlet
(2A), the second gas outlet (2C), the first circulation bed import (2B) and circulation bed outlet (2D)；
In a second reactor, reforming reactor (3) is placed in regeneration reactor (4) top, reforming reactor (3)
And separated by division board between regeneration reactor (4), the two ends of the second heat-transfer pipe (6) are respectively placed in reforming reactor (3)
With in regeneration reactor (4), reforming reactor (3) is provided with gas feed (3A), the 3rd gas outlet (3C), catalysis
The charge door (3B) of agent and discharging opening (3D)；Regeneration reactor (4) is provided with material inlet (4A), the second circulation bed
Import (4B), and air intlet (4C) and flue gas/material outlet (4D)；The gas feed (3A) of reforming reactor (3)
It is positioned at the bottom of reforming reactor (3)；
Circulation bed outlet (2D) of gasification reactor (2) circulates bed import (4B) with the second of regeneration reactor (4)
Connect；The gas outlet (2C) of gasification reactor (2) connects the import (7A) of the first gas-solid separator (7), pyrolysis
First gas outlet (1B) of reactor (1) is connected reforming reaction with the gaseous phase outlet (7B) of the first gas-solid separator (7)
The gas feed (3A) of device (3)；Flue gas/the material outlet (4D) of regeneration reactor (4) connects the second gas-solid separator (8)
Import (8A), the solid outlet (8C) of the second gas-solid separator (8) connect gasification reactor (2) first circulation bed
Import (2B).
Biomass gasification device the most according to claim 1, it is characterised in that: described discharge nozzle (10), discharging
Pipe import (10A) and discharge nozzle outlet (10B) are respectively placed in pyrolysis reactor (1) and gasification reactor (2).
Biomass gasification device the most according to claim 1, it is characterised in that: pyrolysis reactor (1) and reformation
Reactor (3) is fixed bed or moving-burden bed reactor, and gasification reactor (2) is bubbling fluidized bed or spouted fluidized bed,
Regeneration reactor (4) is recirculating fluidized bed or transports bed.
Biomass gasification device the most according to claim 1, it is characterised in that: gasification reactor (2) and regeneration
Reactor (4) is filled with circulation bed, and circulation bed circulates in 2 described reactors；Reforming reactor
(3) it is filled with reforming catalyst.
Biomass gasification device the most according to claim 1 and 2, it is characterised in that: the outlet of feed pipe (10)
(10B) it extend in the filling bed of gasification reactor (2).
The gasification process of a kind of biomass gasification device the most according to claim 1, it is characterised in that: the method is divided
Step carries out biomass pyrolysis process, pyrolysis gas/coke tar reforming process and coke gasification process, and the method comprises the steps:
1) first the biomass of natural drying are crushed to below 1mm, after utilizing potassium salt soln dipping biomass, bakee dry
Dry to moisture content less than 20%, it is thus achieved that preprocessing biomass；
2) preprocessing biomass pyrolysis reactor (1) described in charging aperture (1A) enters is pyrolyzed, through pyrolytic reaction
Rear generation pyrolysis gas and coke, pyrolysis gas by the first gas outlet (1B) through the gas feed of reforming reactor (3)
(3A) entering reforming reactor (3), solid material coke is controlled through feed pipe (10) by coke batcher (9)
Enter gasification reactor (2)；
3) coke carries out gasification reaction with the steam entering gasification reactor (2) in gasification reactor (2), generates
Gaseous product H2, CO and CO2, and CO2React with the MgO/CaO in circulation bed, be cured as MgCO3/CaCO3；
4) gaseous product of gasification reactor (2) is entered the first gas-solid separator (7) by the second gas outlet (2C), will
Entered by reforming reactor gas access (3A) by gaseous phase outlet (7B) after the biomass lime-ash isolation of purified that gas carries
Reforming reactor (3), isolated biomass lime-ash is exported (7C) discharger by lime-ash；
5) enter in the pyrolysis gas of reforming reactor (3) that macromole tar is under catalyst bed effect, and from gas
Change the hydrogen-rich gas H of reactor2O、H2, CO and CO2Carry out reforming reaction and hydrocracking, be eventually converted into H2、CO、
CO2、CH4Micro-molecular gas product；
6) biomass are entered regeneration instead with air/oxygen by material inlet (4A) and the air intlet (4C) of regeneration reactor (4)
Device (4) is answered to burn, circulation bed MgCO in gasification reactor (2)3/CaCO3By regeneration reactor bed import
(4B) regeneration reactor calcination and regeneration, MgCO therein are returned3/CaCO3It is decomposed into MgO/CaO and CO2, after calcining
Circulation bed is entered back into gasification reactor (2) by gasification reactor import (2B) after the second gas-solid separator (8), by
This circulation bed circulates in two reactors, and brings the heat of regeneration reactor (4) into gasification reactor (2)；
7) flue gas that regeneration reactor (4) generates is after the second gas-solid separator (8), enters heat exchanger heating supply gas
Change the feedwater of reactor (2), discharger after cooling.
The gasification process of a kind of biomass gasification device the most according to claim 6, it is characterised in that: described
Preprocessing biomass includes agricultural wastes, forestry waste；The potassium salt soln that pretreatment uses includes KNO3、K2CO3,
Wherein potassium salt is 8%～30% with the quality proportioning of biomass.
The gasification process of a kind of biomass gasification device the most according to claim 6, it is characterised in that gasified reverse
Answering the circulation bed in device (2) and regeneration reactor (4) is MgCO3/CaCO3/MgO/CaO/Al2O3/SiO2Mixture,
Particle diameter is 1mm～3mm；Catalyst feed in reforming reactor (3) be Ni-Li, Ni-Mo, Ni-Mg or Co-Li, Co-Mo,
Co-Mg is the composite catalyst of active component.
The gasification process of a kind of biomass gasification device the most according to claim 6, it is characterised in that described
Heat in gasification reactor (2) is passed to pyrolysis reactor (1) by the first heat pipe (5)；Second heat pipe (6) is by anti-for regeneration
It is Na or K that the heat answering device (4) passes to the heat transfer medium in reforming reactor (3), the first heat pipe and the second heat pipe
And mixture.
The gasification process of a kind of biomass gasification device the most according to claim 6, it is characterised in that described
The temperature of pyrolysis reactor (1) 400～600 DEG C, gasification reactor (2) at 600～750 DEG C, regeneration reactor (4)
It it is 800～900 DEG C；Reforming reactor 600～800 DEG C.
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