CN101747947A - Gasification complex reaction device of pyrolysis fluidized bed of biomass moving bed - Google Patents
Gasification complex reaction device of pyrolysis fluidized bed of biomass moving bed Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 152
- 238000002309 gasification Methods 0.000 title claims abstract description 100
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 78
- 239000002028 Biomass Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims description 29
- 238000007599 discharging Methods 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 4
- 230000009466 transformation Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 56
- 239000002956 ash Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 239000011269 tar Substances 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 230000007812 deficiency Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002737 fuel gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
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- 230000005587 bubbling Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
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- 210000002985 organ of corti Anatomy 0.000 description 1
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- 238000010079 rubber tapping Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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Abstract
A gasification complex reaction device of a pyrolysis fluidized bed of a biomass moving bed is provided with a moving bed pyrolysis reaction section with a feeding hole and a gas outlet, and one end of the device is communicated with a fluidized bed gasification reaction section with a gasifying agent input pipe and an ash exhaust port at the bottom, and both pyrolysis and gasification reaction are carried out at the moving bed pyrolysis reaction section and the fluidized bed gasification reaction section. In the invention, the moving bed pyrolysis and the fluidized bed gasification are organically combined together, and the material transformation efficiency is high; and gasification and biomass are in retrograde motion with low outlet temperature and high thermal efficiency.
Description
Technical field
The present invention relates to a kind of biomass pyrolytic and gasifying biomass complex reaction device, particularly a kind of biomass gasification device that is used for realizing simultaneously biomass pyrolytic and gasifying biomass production combustible fuel gas.
Background technology
The major technique means that biomass produce biomass energy are biomass gasification reactions, and gasifying biomass is to utilize oxygen or oxygen carrier to cook vaporized chemical, the hydrocarbon in the solid biomass are generated the process of inflammable gas.In this process, also be attended by the reaction of carbon and water vapour and the reaction of carbon and hydrogen.
The primitive reaction of biomass gasification process comprises the drying (100～150 ℃) of raw material, pyrolysis (＞160 ℃), reduction reaction (reaction of carbon dioxide reduction, the reaction of aqueous vapour reducing, methane formation reaction and carbon monodixe conversion reaction), oxidizing reaction (charcoal and oxygen generation oxidizing reaction generate carbonic acid gas and carbon monoxide).
Solid biomass used equipment of when gasification is the core of gasifying biomass, comprises two types of fixed bed gasifiers and fluidized-bed gasifiers, and that fixed bed gasifiers and fluidized-bed gasifier all have is multiple multi-form.
The compound gasifying reactor that fixed bed gasifiers can be divided into downdraft gasifier, updraft type gasifier, flat-absorpting type gasifier and this mutation of three types and mutually combine and constitute.Its advantage is that gasifier is simple in structure, and is easy to operate, safe and reliable to operation, and the coal-tar middle oil content of output gas is few etc.Its deficiency is that dissimilar fixed bed gasifiers has different requirements to raw material, and temperature distributing disproportionation is even in the output gas tapping temperature height, gasifier, and throughput can not fluctuate in a big way, and continuous operations are indifferent.
Fluidized-bed gasifier can be divided into bubbling bed gasifier, circulating fluidized bed gasifier, double-fluidized-bed gasifier and carry a gasifier by gasifier structure and gasification.Compare with fixed bed, temperature is even in the fluidized-bed, and gas-solid mixes improvement, and the transmission of heat and quality is quickened, and reaction is violent, the gasification intensity height, and throughput can fluctuate in a big way, is applicable to the occasion of continuous operation.Its deficiency is a system complex, and the carry-over in the output gas is more, and operation control and detection means are complicated, and facility investment is big.
Existing document CN1446880A has openly reported " a kind of biomass gasification method nuclear machinery of negative-pressure firing ", adopt induced draft fan to be connected with smoke pipe or gas exit, form a subnormal ambient at inside reactor, guarantee to produce and to carry out continuously, gas leak can not take place, guaranteed the safety of producing.But can take a large amount of unreacted carbon particles under the condition of negative pressure in the product gas out of, reduce prepared using efficient and factor of created gase.
Existing document CN1221777A has openly reported a kind of " method and the device of calorific value gas in the oxygen gasified of biological generation ", this reactor adopts circulating fluidized bed, quick fluidisation under oxygen-enriched atmosphere, heating and gasification, through gas solid separation, get back to and continue reaction in the stove by recirculation outside bed for unreacted charcoal.Though oxygen-enriched atmosphere has improved conversion of raw material down, oxygen level improves in the product gas, causes product gas calorific value limited.
Existing document CN101161777A has openly reported a kind of " novel biomass solid particle analgesic reactor ", this device can be under the condition of secluding air, by the vibration of regulating pyrolysis reactor, the angle of inclination and the Heating temperature of bottom wall, can realize pyrolytic gasification, pyrolysis liquefaction and pyrolysis charring as requested to biomass solid particle, do not need to feed fluidized carrier gas, inside does not need the mounted movable parts yet.Under the secluding air condition, a large amount of carbon residue of residue after the biomass material pyrolysis, and product tolerance is limited; Material gasification efficient is not high, and product gas calorific value is low.
Existing document CN1274739A has openly reported a kind of " calorific value gasification system in the biomass ", and this system comprises that mainly CO system, separator and secondary combustible gas water cooler etc. fall in vapourizing furnace, catalytic pyrolysis.Biomass material is sent into vapourizing furnace through lift, through dividing wall type heating and calorific value inflammable gas during the pyrolytic gasification reaction conversions becomes, after falling the CO system by catalytic pyrolysis, through separator and secondary combustible gas water cooler, dehydration and remove residue tar and the impurity that contains in the combustion gas, tar enters the tar settling pool, and the inflammable gas of production is most of for the user, a small amount of inflammable gas burns to the vapourizing furnace heat supply through burner and combustion chamber, and the semicoke that vapourizing furnace is discharged is the field also.
Existing biomass gasification device uses the reactor assembly of single type, simultaneously, for mostly adopting air, pure oxygen, the transformation efficiency that improves biomass material cooks vaporized chemical, though this measure can improve the transformation efficiency of biomass, but increased the content of nitrogen in the product gas or oxygen, reduced the calorific value of product gas.
All there is certain deficiency owing to utilize fixed bed and fluidized-bed that biomass are gasified, and existing gasifying reactor is not all brought fixed-bed reactor and fluidized-bed reactor advantage into play, therefore, on the biogas metallization processes, press for fixed bed gasifiers and fluidized-bed gasifier advantage are separately brought into play, further improve the ability of gasifying biomass.
Apparatus of the present invention mainly solve the reasonable reunification of biomass pyrolytic and two self-contained process of gasifying biomass, make full use of the characteristic of biomass in biomass pyrolytic and two processes of gasifying biomass, in conjunction with fixed bed and fluidized-bed advantage separately, further improve the gentle gasification calorific value of biomass heat energy transformation efficiency, dispersive, low-grade, Wood Adhesives from Biomass low value-added, that be difficult for transportation is high-grade, cleaning, fuel gas product high added value, that can transport at a distance.In addition, because biomass material sulfur-bearing and nitrogen content are all lower, the ash content share is also less, SO in the combustion processes
X, NO
XAll much smaller with the dust emissions amount than fossil oil.Simultaneously, biomass are utilized in the process at it, are zero to the clean quantity discharged of the carbonic acid gas of atmospheric environment, can not cause and aggravate Greenhouse effect as fossil oil.Meet the requirement of environmental protection and carbon dioxide discharge-reduction.
Summary of the invention
The present invention utilizes electrically heated that moving bed pyrolysis and fluidized-bed gasification are organically combined, biomass are carried out pyrolysis and gasification reaction, to overcome single use moving-bed or fluidized-bed biomass are carried out the deficiency of gasification reaction, and a kind of biomass moving bed pyrolysis and fluidized-bed gasification complex reaction device are provided.
A kind of biomass moving bed pyrolysis of the present invention and fluidized-bed gasification complex reaction device, comprise resistance heater, spiral conveyer, moving bed pyrolysis device and fluidized-bed gasifier, its described set composite is provided with: one one end has the moving bed pyrolysis conversion zone of material inlet and pneumatic outlet, the other end is communicated with the fluidized-bed gasification conversion zone that a bottom has ash discharge passage and vaporized chemical input tube, and moving bed pyrolysis conversion zone and fluidized-bed gasification conversion zone carry out pyrolysis and gasification complex reaction.
In a kind of complex reaction device of the present invention, the upper left quarter of its described moving bed pyrolysis conversion zone is provided with material inlet and pneumatic outlet, and the right-hand member bottom is communicated with the fluidized-bed gasification conversion zone by connecting passage; Be provided with spiral propeller I in the described moving bed pyrolysis conversion zone; Right-hand part is outside equipped with resistance heater I; Described fluidized-bed gasification conversion zone bottom is provided with ash discharge passage and vaporized chemical input tube, and the vaporized chemical input tube is communicated with the vaporized chemical sparger, and ash discharge passage lower end is provided with spiral propeller II and passes through ash discharging hole) ash discharge; Described fluidized-bed gasification conversion zone is outside equipped with resistance heater II.
Apparatus of the present invention adopt the resistance heater heating, can be according to the variation flexible temperature of reaction of the gentle gasification of raw material; When temperature of reaction is low, input speed can be slowed down, pyrolysis and gasification time lengthening, gas output speed reduces; When temperature of reaction is higher, input speed can be accelerated, pyrolysis and gasification time shorten, and gas output speed raises; In addition, can be according to the real-time start-stop car of the situation of raw material supply and gas consumption, convenient, flexible.
The present invention organically is incorporated into moving bed pyrolysis and entrained flow gasification together, and is little with proportion before the biomass straw pyrolysis, be difficult to move to need mobile pyrolysis, and residual charcoal ventilation property difference needs the characteristics of fluidized-bed gasification to be complementary after the pyrolysis, has improved the transformation efficiency of material.Gasification gas in this course and biomass material drive in the wrong direction and move, and temperature out is low, the thermo-efficiency height, and product gas dustiness is low, is easy to purify.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Among the figure: 1: material inlet; 2: pneumatic outlet; 3: the moving bed pyrolysis conversion zone; 4: spiral propeller I; 5: connecting passage; 6: the fluidized-bed gasification conversion zone; 7: the vaporized chemical sparger; 8: the vaporized chemical input tube; 9: spiral propeller II; 10: ash discharging hole; 11: the ash discharge passage; 12: resistance heater II; 13: resistance heater I;
Embodiment
By embodiment a kind of gasification complex reaction device of pyrolysis fluidized bed of biomass moving bed that the present invention proposes is described in further detail below in conjunction with accompanying drawing, the person of ordinary skill in the field can understand and realize technical solutions according to the invention, and also can reach described effect of the present invention.
Embodiment
Referring to Fig. 1, implement a kind of gasification complex reaction device of pyrolysis fluidized bed of biomass moving bed of the present invention, comprise moving bed pyrolysis conversion zone and fluidized-bed gasification conversion zone.Raw material is entered the moving bed pyrolysis conversion zone 3 of screw propulsion by material inlet 1, biomass thermal dehydration drying, fugitive constituent is separated out in pyrolysis, finish with pyrolysis, under the effect of spiral propeller I 4, enter fluidized-bed gasification conversion zone 6 from moving bed pyrolysis conversion zone 3 for 5 mouthfuls through connecting passage, in fluidized-bed gasification conversion zone 6, enter, enter the vaporized chemical generating gasification reaction of rising again through vaporized chemical sparger 7 with bottom vaporized chemical input tube 8.Remaining gasification residue (ash content) enters ash discharge spiral organ II9 from ash discharge passage 11 behind the gasification reaction, under the prograding of spiral propeller II9, ash is discharged from ash discharging hole 10.
Unreacted solid materials of High Temperature Gas gasification, part that produces at fluidized-bed gasification conversion zone 6 and part of ash etc. enter moving bed pyrolysis conversion zone 3 by connecting passage 5, on the one hand and pyrolysis gas generation secondary reaction, participate in pyrolytic reaction; On the other hand with moving bed pyrolysis conversion zone 3 in material carry out heat exchange, improve Btu utilization efficient.Gasification gas and pyrolysis gas are mixed into product gas, are sent to purification section, output products gas after purifying again from pneumatic outlet 2 discharges after the retrograde heat exchange of product gas and material.
By regulating the speed of input speed and vaporized chemical input, guarantee that fluidized-bed gasification conversion zone 6 materials inside are in fluidized state, also can control the residence time of material simultaneously in fluidized-bed gasification conversion zone 6 inside.
According to the difference of raw material water content, by the pyrolysis temperature of resistance heater II 12 control moving bed pyrolysis conversion zones 3; By spiral propeller I 4 control input speeds.
The tar that moving bed pyrolysis conversion zone 3 produces enters fluidized-bed gasification conversion zone 6 with the pyrolysis carbon residue, or Pintsch process or secondary participation gasification reaction, improve the utilising efficiency of raw material, reduce the tar content in the product gas, alleviate the burden of subsequent product gas purification section, reduce the cost of investment of product gas purification section.
The temperature of reaction of the moving bed pyrolysis conversion zone 3 of screw propulsion material is 500～700 ℃, and temperature of reaction is by resistance heater II 12 controls.
The temperature of reaction of fluidized-bed gasification conversion zone 6 is 700～900 ℃, and temperature of reaction is by resistance heater I 13 controls.
The resistance heater II 12 of the moving bed pyrolysis conversion zone 3 of screw propulsion material is separate with resistance heater I 13 temperature controls of fluidized-bed gasification conversion zone 6.
Implement a kind of biomass moving bed pyrolysis of the present invention and fluidized-bed gasification set composite, this device adopts resistance heater I 13 and resistance heater II 12 is heated to be biomass pyrolytic and gasification provides heat; The reaction unit leading portion is a moving bed pyrolysis conversion zone 3, and back segment is to connect by connecting passage 5 between 6, two sections of the fluidized-bed gasification conversion zones.Biomass are at first carried out pyrolytic reaction at moving bed pyrolysis conversion zone 3, carbon residue after the pyrolysis carries out gasification reaction at fluidized-bed gasification conversion zone 6 then, and pneumatic outlet 2 is positioned at moving bed pyrolysis conversion zone 3, the gasification gas of fluidized-bed gasification conversion zone 6 carries out heat exchange through moving bed pyrolysis section 3 and material, the air outlet gas temperature reduces, and has improved heat utilization efficiency.
Vaporized chemical adopts water vapour (can sneak into the part air), enters fluidized-bed gasification conversion zone 6 by fluidized-bed gasification conversion zone 6 bottoms through vaporized chemical sparger 7, has reduced the oxygen level in the product gas.Carbon monoxide in the product gas, methane and hydrogen content increase, the calorific value height of product gas; Ashes are discharged out of the furnace through ash discharging hole 10 by the bottom.
Biomass material is in the 3 main generation biomass thermal decomposition reactions of moving bed pyrolysis conversion zone; When temperature was lower than 150 ℃, the organic thermal decomposition rate of biomass was very slow, and chemical constitution also changes hardly, and this process mainly is a moisture evaporation.Along with spiral propeller I 4 advances moving ahead of material, temperature raises gradually, and pyrolysis begins obviously, and organic composition also begins to change; Be higher than 200 ℃, hemicellulose begins to decompose, and generates CO
2With gases such as CO; When being higher than 400 ℃, violent thermolysis takes place in biomass, produces a large amount of gas, CO during it is formed
2Reduce gradually with CO, and CH
4And H
2Increase Deng beginning, discharged the most of volatiles in the biomass material this moment, and raw material is finished the pyrolysis charring process basically.Therefore, the temperature of reaction of moving bed pyrolysis conversion zone 3 is designed to 500～700 ℃, purpose is in order to allow biomass material as much as possible fully discharge fugitive constituent, and pyrolysis charring is complete.
Biomass material is finished the pyrolysis charring process at moving bed pyrolysis conversion zone 3, and its pyrolysis carbon residue enters fluidized-bed gasification conversion zone 6 and carries out gasification reaction.This device adopts water vapour (can mend into the part air) to be the vaporized chemical gasification, and this gasification is mainly carried out the reaction of aqueous vapour reducing, reaction, methane formation reaction and the carbon monodixe conversion reaction of carbon dioxide reduction, and its principal reaction equation is:
The reaction of aqueous vapour reducing:
C+H
2O
(g)＝CO+H
2；ΔH＝+118.628kJ/mol (1)
C+2H
2O
(g)＝CO
2+2H
2；ΔH＝+75.114kJ/mol (2)
The reaction of carbon dioxide reduction:
C+CO
2＝2CO；ΔH＝+162.142kJ/mol (3)
The reaction that methane generates:
2C+2H
2O＝CH
4+CO
2(g)；ΔH＝-677.286kJ/mol (4)
C+2H
2＝CH
4；ΔH＝-752.400kJ/mol (5)
CO+3H
2＝CH
4+H
2O
(g)；ΔH＝-2035.66kJ/mol (6)
CO
2+4H
2＝CH
4+H
2O
(g)；ΔH＝-827.514kJ/mol (7)
The carbon monodixe conversion reaction:
CO+H
2O
(g)＝CO
2+H
2；ΔH＝-43.514kJ/mol (8)
(1) and (2) two reactions all be thermo-negative reaction, so the temperature increase all will help the carrying out of aqueous vapour reducing reaction.But generate CO and CO
2Reaction equilibrium constant be different.When temperature is lower than 700 ℃, generate CO
2Reaction constant is unfavorable for the generation of CO than generating the big of CO under this temperature, help CO
2Generation.The reverse be true when temperature is higher than 700 ℃, the reaction that helps generating CO is carried out.And along with the increase of temperature, the reaction equilibrium constant lift velocity of (1) formula is fast, and the reaction equilibrium constant lift velocity of (2) formula is slow, and hence one can see that, improves temperature and helps improving CO content and reduce CO
2Content; In addition, when temperature was lower than 700 ℃, the speed of reaction of water vapour and charcoal was very slow.(3) formula is the intensive thermo-negative reaction, thereby temperature is higher, CO
2Reduction will heal thoroughly, the formation of CO will be more.Effective CO
2Reduction temperature is more than 800 ℃, with the rising of temperature, CO
2Content sharply reduce.In the time of 900 ℃, the equilibrium composition of (3) formula is: CO=97.88%, CO
2=2.12%.(4) formula is a strong exothermic reaction, and methane is stable compound, and when temperature was higher than 600 ℃, methane was not just stable, thereby reaction will be to the direction CH that decomposes
4=C+2H
2Carry out; (5), (6) and (7) be the thermopositive reaction that generates methane, in the time of 800 ℃, C+H
2Consisting of of reaction mixture: CH
4=4.41%, H
2=95.59%.(8) formula is the CO of gasifying stage generation and the reaction between the water vapour, provides the required H of methanation reaction in the gasification
2The primitive reaction in source; But when temperature was higher than 850 ℃, the positive reaction speed of this reaction was higher than reversed reaction speed, and this reaction could be carried out smoothly when requiring temperature of reaction to be higher than 900 ℃ usually.Therefore, fluidized-bed gasification conversion zone temperature of reaction being designed to 700～900 ℃, is in order to improve H in the product gas on the one hand
2, CO and CH
4Content, reduce CO
2Content, the calorific value of raising product gas; Be in order to reduce requirement, to have reduced cost of investment on the other hand to device materials.
When mending the part air in the vaporized chemical, oxidizing reaction can take place in gasification:
C+O
2＝CO
2；ΔH＝-408.177kJ/mol (9)
2C+O
2＝2CO；ΔH＝-246.034kJ/mol (10)
Remove and generate CO
2Outward, owing to be the burning of limit oxygen, the supply of oxygen is inadequate, thereby incomplete combustion reaction generation simultaneously, generates carbon monoxide, emits heat simultaneously.When outside heat supply can not be satisfied the required heat of gasification reaction, can in vaporized chemical, mend and go into air, utilize the oxidizing reaction liberated heat to provide a part of heat for gasification reaction.
This device is implemented gasification at fluidized-bed gasification conversion zone 6.Vaporized chemical enters fluidized-bed gasification conversion zone 6 by vaporized chemical input tube 8 through vaporized chemical sparger 7.Gasification reaction mainly contains (1) in fluidized-bed gasification conversion zone 6 lower floors, (2) and (4) reaction is carried out; When mending air in the vaporized chemical, reaction (9) and (10) is also carried out simultaneously.Mainly contain (3), (5), (6) on fluidized-bed gasification conversion zone 6 upper stratas, (7) and (8) reaction is carried out.Gasification reaction gained gasification gas is followed hot-fluid and is entered moving bed pyrolysis conversion zone 3 together.Reacted ash content is dropped into ash discharge passage 11 and is discharged from ash discharging hole 10 through spiral propeller 9.This design down because gasification gas is consistent with direction of heat flow, so needn't consume very big power during work; In addition, the ash discharge path 10 is owing to the cooling that is subjected to air intake, and is safe and reliable.
This device is implemented pyrolytic process at moving bed pyrolysis conversion zone 3, and this conversion zone leading portion is a drying zone, and back segment is a pyrolysis zone.In pyrolysis zone, in moving bed pyrolysis conversion zone 3, provide a part of heat for pyrolytic process from the High Temperature Gas gasification of fluidized-bed gasification conversion zone 6 on the one hand, improve efficiency of utilization; High Temperature Gas gasification and pyrolysis gas and partial thermal decomposition tar carry out secondary reaction on the other hand, simultaneously, gasification gas and pyrolysis gas obtain filtering when flowing through moving bed pyrolysis conversion zone 3, can make ash content minimizing in the pneumatic outlet gas, alleviate the burden of follow-up gas sweetening operation.At drying zone, gasification gas and pyrolysis gas and biomass material carry out heat exchange, make the moisture evaporation in the biomass, become dry material, effectively utilize gas waste-heat, reduce the temperature of exit gas, improve thermo-efficiency.
Apparatus of the present invention are made up of for two sections moving bed pyrolysis conversion zone and fluidized-bed gasification conversion zone.Have spiral propeller in the moving bed pyrolysis conversion zone, wherein the left side is provided with opening for feed and pneumatic outlet, and right-hand part is provided with resistance heater.Moving bed pyrolysis conversion zone bottom is connected with fluidized-bed gasification conversion zone top, and fluidized-bed gasification conversion zone bottom is provided with vaporized chemical input tube and ash discharging hole, and fluidized-bed gasification conversion zone outside is provided with resistance heater; The vaporized chemical input tube is connected with the vaporized chemical sparger, and the lower end of ash discharge passage is provided with spiral propeller and passes through the ash discharging hole ash discharge.
Claims (5)
1. gasification complex reaction device of pyrolysis fluidized bed of biomass moving bed, its described set composite is provided with: one one end has the moving bed pyrolysis conversion zone (3) of material inlet (1) and pneumatic outlet (2), the other end is communicated with the fluidized-bed gasification conversion zone (6) that a bottom has ash discharge passage (11) and vaporized chemical input tube (8), and moving bed pyrolysis conversion zone (3) and fluidized-bed gasification conversion zone (6) carry out pyrolysis and gasification complex reaction.
2. a kind of complex reaction device as claimed in claim 1, the upper left quarter of its moving bed pyrolysis conversion zone (3) are provided with material inlet (1) and pneumatic outlet (2), and the right-hand member bottom is communicated with fluidized-bed gasification conversion zone (6) by connecting passage (5).
3. a kind of set composite as claimed in claim 1 or 2 is provided with spiral propeller I (4) in its moving bed pyrolysis conversion zone (3); Right-hand part is outside equipped with resistance heater I (13).
4. a kind of complex reaction device as claimed in claim 1, its fluidized-bed gasification conversion zone (6) bottom is provided with ash discharge passage (11) and vaporized chemical input tube (8), vaporized chemical input tube (8) is communicated with vaporized chemical sparger (7), and ash discharge passage (11) lower end is provided with spiral propeller II (9) by ash discharging hole (10) ash discharge.
5. as claim 1 or 4 described a kind of complex reaction devices, its fluidized-bed gasification conversion zone (6) is outside equipped with resistance heater II (12).
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