CN103923705A - Device and method for preparing hydrogen-rich gas by gasifying biomass - Google Patents
Device and method for preparing hydrogen-rich gas by gasifying biomass Download PDFInfo
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- CN103923705A CN103923705A CN201410112624.2A CN201410112624A CN103923705A CN 103923705 A CN103923705 A CN 103923705A CN 201410112624 A CN201410112624 A CN 201410112624A CN 103923705 A CN103923705 A CN 103923705A
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- 239000007789 gas Substances 0.000 title claims abstract description 112
- 239000001257 hydrogen Substances 0.000 title claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 74
- 239000002028 Biomass Substances 0.000 title claims abstract description 72
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000000197 pyrolysis Methods 0.000 claims abstract description 81
- 238000002485 combustion reaction Methods 0.000 claims abstract description 73
- 238000002309 gasification Methods 0.000 claims abstract description 71
- 239000000571 coke Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 104
- 230000008676 import Effects 0.000 claims description 37
- 239000002918 waste heat Substances 0.000 claims description 21
- 239000000428 dust Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000003546 flue gas Substances 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 235000011194 food seasoning agent Nutrition 0.000 claims description 7
- 239000002154 agricultural waste Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 238000013459 approach Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 210000000952 spleen Anatomy 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000010802 sludge Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 16
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 238000005202 decontamination Methods 0.000 abstract 1
- 230000003588 decontaminative effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000010902 straw Substances 0.000 description 7
- 239000011269 tar Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011285 coke tar Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- 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
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Abstract
The invention discloses device and method for preparing hydrogen-rich gas by gasifying biomass. The device mainly comprises a pyrolysis reactor, a combustion reactor, a gasification reactor, a gas-solid separator, a gas cooler and an exhaust heat boiler, wherein the pyrolysis reactor is arranged in the combustion reactor. In a process course, the biomass is firstly pyrolyzed in the pyrolysis reactor to generate pyrolysis gas and coke, the pyrolysis gas is directly combusted to provide heat for biomass pyrolysis and gasification, and the coke is subjected to gasification reaction with water vapor to obtain the hydrogen-rich gas. The device and method disclosed by the invention realize the separation of the pyrolysis process and coke gasification process of the biomass and can be used for displacing the hydrogen contained in the water vapor by sufficiently utilizing fixed carbon contained in the biomass. According to the device and method, the obtained hydrogen-rich gas mainly contains H2, CO2 and a small amount of CO, so that the conventionally gasified hydrogen-rich gas product is prevented from being mixed with low-carbon hydrocarbon gas and tar, and the subsequent decontamination and purification utilization are simple, convenient and economic.
Description
Technical field
The invention discloses a kind of biomass and produce method and the apparatus system thereof of rich hydrogen body, relate to biomass resource utilization field.
Background technology
Hydrogen Energy is a kind of clean energy of high-quality, and the product in energy conversion process is water, can really realize the zero release of pollutent.Because Hydrogen Energy is a kind of secondary energy, must obtain through the conversion of primary energy source.Hydrogen is mainly to be transformed and produced by the thermochemistry of the fossil oils such as Sweet natural gas, coal, oil at present, although technology maturation, conversion process energy expenditure is large, and efficiency of conversion is low, and cost is high, and switching process is accompanied by a large amount of CO
2discharge.In short supply along with fossil energy, ecotope increasingly serious, therefore utilizes reproducible biomass, seeks to clean, the hydrogen manufacturing new technology of economy, Sustainable development caused world's extensive concern.
Biomass thermal chemical conversion hydrogen manufacturing is one of biomass hydrogen preparation technological approaches most with prospects, wherein mainly comprises biomass gasifying hydrogen making, biomass pyrolytic catalytically reforming hydrogen producing, several modes of biomass supercritical water gasification hydrogen production.And the conventional coal-tar middle oil content of biomass gasifying hydrogen making gaseous product is high, easily cause equipment to stop up, in order to promote coke gasification, promote the carrying out of coke tar cracking and reforming reaction, conventionally adopt catalytic gasification and catalytic tar to reform to improve transformation efficiency and the hydrogen productive rate of biomass hydrogen preparation, no matter but pyrolysis catalytic reformation hydrogen production or catalytic gasification hydrogen manufacturing all face the easy carbon distribution inactivation of catalyzer, and tar is difficult to complete transition problem, and contains more CO, CO in the rich hydrogen product gas obtaining
2, CH
4and small molecules C
nh
metc. various ingredients, subsequent purification complexity.Biomass supercritical water gasification technique it is advantageous that to have high gasification efficiency and hydrogen selectivity, but the deposition of tar, coke also easily occurs, and the shortcoming such as investment is large, severe reaction conditions, equipment are perishable.In recent years, investigator you can well imagine out the chemical chain gasification hydrogen manufacturing new technology based on circulation oxygen carrier and carbon carrier based on chemical chain technical point.Gasification technology based on circulation oxygen carrier is mainly taking metal oxide as thermophore and circulate between the different reactors burning of gasification hydrogen-producing and the chemical chain of realizing biomass of oxygen carrier, realizes CO when making system produce hydrogen-rich gas
2near zero release.Chemical chain gasification based on circulation carbon carrier is taking CaO as thermophore with CO
2absorption agent, thereby realize the biomass gasifying hydrogen making of system near zero release.Although hydrogen-rich gas prepared by these novel procesies separates the gasification of biomass and combustion processes, but in hydrogen-rich gas, still contain multiple gases component, still have the problem of further removal tar and purification, and the control of the preparation of oxygen carrier and operation operation still needs long runtime verification.
The problem still existing based on above-mentioned biomass gasifying hydrogen making, and consider in biomass self only 6wt.% left and right of H content, biomass thermal chemical conversion hydrogen manufacturing is mainly to change H by carbon
2hydrogen in O obtains, and therefore water vapour is best gasifying medium.Because the steam gasification of biomass is endothermic processes, therefore in order to provide gasification required heat, avoiding again in air rare gas element nitrogen to be blended in gaseous product affects GAS QUALITY, the present invention proposes a kind of new apparatus and method.
Summary of the invention
Technical problem: the devices and methods therefor that the object of this invention is to provide a kind of biomass and produce hydrogen-rich gas, many to solve in existing gasifying biomass product component, purify complicated, and tar content is high, conversion removes difficult problem, proposes a kind of biomass gasification device and method thereof of producing the hydrogen-rich gas of without tar, easily purifying by biomass thermal chemical conversion.
Summary of the invention: for solving the problems of the technologies described above, the invention provides a kind of gasifying biomass and produce the device of hydrogen-rich gas, this device comprises pyrolysis reactor, combustion reactor, gasifying reactor, the first cyclonic separator, the second cyclonic separator, gas cooler, waste heat boiler, material feeder, bed material bunker, variable valve and connecting pipeline, pyrolysis reactor is built in combustion reactor; Wherein,
Pyrolysis reactor comprises opening for feed, pyrolysis gas outlet and coke export; Combustion reactor comprises the import of air/circulation bed material, secondary air inlet and the outlet of flue gas/circulation bed material; Gasifying reactor comprises coke import, water vapour import, gasification product outlet, the outlet of the first circulation bed material/lime-ash, the outlet of the second circulation bed material/lime-ash;
Wherein, the outlet of combustion reactor flue gas/circulation bed material is connected with the first cyclonic separator import, the coke export of combustion reactor is connected with material feeder import, material feeder outlet is directly connected with the import of gasifying reactor coke, the dipleg of the first cyclonic separator directly inserts in gasifying reactor, and the first cyclonic separator exhanst gas outlet is connected with the hot gas approach of waste heat boiler;
The gaseous product outlet of gasifying reactor connects the second cyclonic separator import, the second cyclonic separator pneumatic outlet is connected with the hot gas import of gas cooler, the solid-state lime-ash outlet of the second cyclonic separator is connected with the returning charge mouth of gasifying reactor, the first circulation bed material/lime-ash outlet of gasifying reactor is connected with the import of bed material bunker by connecting pipeline with the outlet of the second circulation bed material/lime-ash, and the outlet of bed material bunker is connected with the import of combustion reactor air/circulation bed material by carrier pipe;
Gas cooler is connected with the feed-water inlet of waste heat boiler to water out, and the superheated vapour outlet of waste heat boiler connects the water vapour import of gasifying reactor by pipeline.
Preferably, pyrolysis reactor is downdraft moving-bed, and opening for feed is positioned at the top of pyrolysis reactor, and pyrolysis gas outlet and coke export are all positioned at pyrolysis reactor bottom; Pyrolysis reactor is placed in combustion reactor reactant inner and two reactors blending does not occur;
Combustion reactor is for transporting bed, and the import of combustion reactor air/circulation bed material is positioned at the bottom of combustion reactor, and secondary air inlet is positioned at the middle and lower part of combustion reactor;
Gasifying reactor is bubbling bed or spouted bed, water vapour import is positioned at the bottom of gasifying reactor, the outlet of the first circulation bed material/lime-ash is positioned at gasifying reactor bottom, the outlet of the second circulation bed material/lime-ash is positioned at gasifying reactor bottom, the first circulation bed material/lime-ash outlet of gasifying reactor, is equipped with respectively variable valve on the connecting pipeline between the outlet of the second circulation bed material/lime-ash and bed material bunker.
The present invention also provides a kind of gasifying biomass to produce the method for hydrogen-rich gas, and the method comprises the steps:
Step 1: will send into pyrolysis reactor by the opening for feed on pyrolysis reactor top through biomass broken, seasoning, 500 DEG C～750 DEG C of temperature of reaction, inertia/reducing atmosphere issues heat-dissipating solution, and Wood Adhesives from Biomass Heat of Formation is vented one's spleen and coke;
Step 2: the pyrolysis gas that pyrolysis reactor produces directly enters combustion reactor bottom by pyrolysis gas outlet, and coke directly enters material feeder by coke export, sends into gasifying reactor by material feeder;
Step 3: pyrolysis gas enters combustion reactor and burns with the air of sending into, bed material in heating flame reactor, and provide heat to built-in pyrolysis reactor, by wind, secondary air flow adjustment, control the internal circulating load of bed material and combustion reactions actuator temperature at 800 DEG C～1000 DEG C; High hotbed material is carried and is sent into gasifying reactor through the dipleg of the first cyclonic separator and provide heat for coke gasification by combustion product gases;
Step 4: coke reacts with water vapour generating gasification in gasifying reactor, gasification reaction temperature is controlled between 650 DEG C～800 DEG C, and the hydrogen-rich gas of gasifying reactor outlet enters gas cooler and will wherein after water vapor condensation separation, obtain dry hydrogen-rich gas after the second tornado dust collector dedusting;
Step 5: the solid lime-ash of gasifying reactor and bed material are discharged by the first circulation bed material/lime-ash outlet of bottom and the second circulation bed material/lime-ash outlet of bottom, return to bed material bunker by transfer line, the solid ash content that the second tornado dust collector separate returns to gasifying reactor or discharger by the returning charge mouth of gasifying reactor after exporting discharge;
Step 6: the bed material that air carries bed material bunker enters combustion reactor together by combustion reactor bottom;
Step 7: gasification feedwater is introduced into after the preliminary heating of gas cooler, enters waste heat boiler and is further heated as superheated vapour; An overheated steam part is sent into gasifying reactor, part steam supply/heat supply outside device;
Step 8: the high-temperature flue gas of the first tornado dust collector outlet enters waste heat boiler, discharger after heated feed water.
Preferably, the hydrogen-rich gas composition of producing: H
2: 60～85%, CO
2: 10%～35% and CO:5%～10%.
Preferably, export steam temperature at 400 DEG C～600 DEG C through gas cooler and waste heat boiler heating.
Preferably, the working pressure of reactor is normal pressure, and pyrolysis reactor > combustion reactor > gasifying reactor.
Preferably, the residence time in gasifying reactor by returning charge valve control coke.
Preferably, described biomass are any or its arbitrary combination in other carbonaceous refuses such as agricultural wastes, forestry waste and the dewatered sludge after seasoning, and the biomass particle diameter after fragmentation is at 1mm～10mm.
Preferably, the mixture that described bed material is inert heat carrier and catalyzer is the effect of gasification reaction heat supply in gasification reaction process, and promotes the gasification reaction of coke and water vapour.
Preferably, described inert heat carrier is Al
2o
3, SiO
2, any in lime-ash, described catalyzer is K
2cO
3, NiO, CaO, Fe
2o
3in any one or arbitrarily several combination.
Beneficial effect:
Method of the present invention by the gasification of biomass pyrolysis process and coke separately, makes full use of the hydrogen in the fixed carbon replacing water steam in biomass, in the hydrogen-rich gas of acquisition, is mainly H
2and CO
2, and a small amount of CO, has avoided being mixed with lower carbon number hydrocarbons gas in the hydrogen-rich gaseous product of conventional gasification, make follow-up purification, utilize easy.
Biomass pyrolysis reactor of the present invention is built in combustion reactor, pyrolysis gas at high temperature directly enters combustion reactor burning, burning heat release is again directly for pyrolytic process provides heat, and without the coal-tar middle oil composition of pyrolysis gas is carried out to special secondary treatment, both take full advantage of the energy of tar, solved again the upstream device fault that the coal-tar middle oil condensation of pyrolysis gas brings.
The burning heat release of pyrolysis gas is offered coke gasification by the circulation that coke gasification of the present invention is expected by bed, both realized gasifying biomass from heat supply, avoided again the rare gas element of biomass combustion process to sneak in gasification product.
Brief description of the drawings
Fig. 1 is technological process of the present invention and system and device schematic diagram.
In figure, illustrate: 1-pyrolysis reactor; 2-combustion reactor; 3-gasifying reactor; 4-the first cyclonic separator; 5-the second cyclonic separator; 6-gas cooler; 7-waste heat boiler; 8-material feeder; 9-bed material bunker; 10-variable valve.
Embodiment
Below in conjunction with drawings and the embodiments, patent of the present invention is described in further detail:
The method that gasifying biomass of the present invention is produced hydrogen-rich gas is by the gasification of the pyrolytic process of biomass and coke separately, first in the pyrolysis reactor that is built in combustion reactor, there is thermo-cracking in biomass, the pyrolysis gas wherein obtaining provides heat by the gasification of burning form biomass pyrolysis process and coke, and pyrolysis coke enters in gasifying reactor and reacts (C+H with gasifying medium water vapour generating gasification
2o → CO+H
2, CO+H
2o → H
2+ CO
2, C+2H
2o → H
2+ 2CO
2), utilize the bed heating in combustion reactor to expect to provide heat for gasification reaction simultaneously.
Biomass gasification device of the present invention comprises pyrolysis reactor 1, combustion reactor 2, gasifying reactor 3, the first cyclonic separators 4 and the second cyclonic separator 5, gas cooler 6, waste heat boiler 7, material feeder 8, bed material bunker 9, variable valve 10 and connecting pipeline.Wherein, pyrolysis reactor 1 comprises opening for feed 1A, pyrolysis gas outlet 1B and coke export 1C, and pyrolysis reactor 1 is built in combustion reactor 2; Combustion reactor 2 comprises air/bed material import 2A, secondary air inlet 2B and flue gas/bed material outlet 2C; Gasifying reactor 3 comprises coke import 3A, water vapour import 3B, gasification product outlet 3C, the first circulation bed material/lime-ash outlet 3D1, the second circulation bed material/lime-ash outlet 3D2, returning charge mouth 3E; Wherein combustion reactor 2 flue gases/circulation bed material outlet 2C is connected with the first cyclonic separator 4 import 4A, the coke export 1C of pyrolysis reactor 1 is connected with material feeder 8 import 8A, material feeder 8 exports 8B and is directly connected with gasifying reactor 3 import 3A, the dipleg 4B of the first cyclonic separator 4 directly inserts in gasifying reactor 3, and the first cyclonic separator 4 exhanst gas outlet 4C are connected with the hot gas approach 7A of waste heat boiler 7; The hydrogen-rich gaseous product outlet 3C of gasifying reactor 3 connects the second cyclonic separator 5 import 5A, the second cyclonic separator outlet 5B is connected with the hot gas import 6A of water cooler 6, the second cyclonic separator outlet 5C is connected with gasifying reactor returning charge mouth 3E, the Solid Bed material of gasifying reactor 3 is connected with bed material bunker 9 import 9A by connecting pipeline with 3D2 through slag-drip opening 3D1, and bed material bunker 9 exports 9B and is connected with combustion reactor 2 import 2A by carrier pipe.
In addition, pyrolysis reactor 1 is downdraft moving-bed, and biomass feed inlet 1A is positioned at the top of pyrolysis reactor 1, and pyrolysis gas outlet 1B and coke export are all positioned at pyrolysis reactor 1 bottom; Pyrolysis reactor 1 is placed in combustion reactor 2 reactant inner and two reactors blending does not occur; Combustion reactor 2 is for transporting bed, and/wind air intlet 2A of bed material of combustion reactor 2 is positioned at the bottom of combustion reactor 2, and secondary air air intlet 2B is positioned at the middle and lower part of combustion reactor 2.Gasifying reactor 3 is bubbling bed or spouted bed, gasifying medium water vapour import 3B is positioned at the bottom of gasifying reactor 3, the first circulation bed material/lime-ash outlet 3D1 is positioned at gasifying reactor 3 bottoms, the second circulation bed material/lime-ash outlet (3D2) is positioned at gasifying reactor 3 bottoms, on the connecting pipeline between deslagging outlet 3D1,3D2 and the bed material bunker (9) of gasifying reactor 3, variable valve 10 is housed.
Gasifying biomass provided by the invention is produced the method for hydrogen-rich gas, and the method comprises the steps:
Step 1: will send into pyrolysis reactor 1 by the opening for feed 1A on pyrolysis reactor 1 top through biomass broken, seasoning, 500 DEG C～750 DEG C of temperature of reaction, inertia/reducing atmosphere issues heat-dissipating solution, and Wood Adhesives from Biomass Heat of Formation is vented one's spleen and coke;
Step 2: the pyrolysis gas that pyrolysis reactor 1 produces directly enters combustion reactor 2 bottoms by pyrolysis gas outlet 1B, and coke directly enters material feeder 8 by coke export 1C, sends into gasifying reactor 3 by material feeder 8;
Step 3: pyrolysis gas enters combustion reactor 2 and burns with the air of sending into, bed material in heating flame reactor 3, and provide heat to built-in pyrolysis reactor 1, by wind, secondary air flow adjustment, control the internal circulating load of bed material and combustion reactor 2 temperature at 800 DEG C～1000 DEG C; High hotbed material is carried and is sent into gasifying reactor 3 through the dipleg 4B of the first cyclonic separator 4 and provide heat for coke gasification by combustion product gases;
Step 4: coke reacts with water vapour generating gasification in gasifying reactor 3, gasification reaction temperature is controlled between 650 DEG C～800 DEG C, and the hydrogen-rich gas that gasifying reactor 3 exports enters gas cooler 6 and will wherein after water vapor condensation separation, obtain dry hydrogen-rich gas after the second tornado dust collector 5 dedustings;
Step 5: the solid lime-ash of gasifying reactor 3 and bed material are discharged by the first circulation bed material/lime-ash outlet 3D1 of bottom and the second circulation bed material/lime-ash outlet 3D2 of bottom, return to a solid ash content that material bunker 9, the second tornado dust collector 5 separate by transfer line and return to gasifying reactor 3 or discharger by exporting after 5C discharges by the returning charge mouth 3E of gasifying reactor 3;
Step 6: the bed material that air carries bed material bunker 9 enters combustion reactor 2 together by combustion reactor 2 bottoms;
Step 7: gasification feedwater is introduced into after the preliminary heating of gas cooler 6, enters waste heat boiler 7 and is further heated as superheated vapour; An overheated steam part is sent into gasifying reactor, part steam supply/heat supply outside device;
Step 8: the high-temperature flue gas that the first tornado dust collector 4 export 4C enters waste heat boiler 7, discharger after heated feed water.
The hydrogen-rich gas composition of producing: H
2: 60～85%, CO
2: 10%～35% and CO:5%～10%.
Export steam temperature at 400 DEG C～600 DEG C through gas cooler 6 and waste heat boiler heating.
The working pressure of reactor is normal pressure, and pyrolysis reactor 1> combustion reactor 2> gasifying reactor 3.
Control the residence time of coke in gasifying reactor 3 by returning charge valve 10.
Described biomass are any or its arbitrary combination in other carbonaceous refuses such as agricultural wastes, forestry waste and the dewatered sludge after seasoning, and the biomass particle diameter after fragmentation is at 1mm～10mm.
The mixture that described bed material is inert heat carrier and catalyzer is the effect of gasification reaction heat supply in gasification reaction process, and promotes the gasification reaction of coke and water vapour.
Described inert heat carrier is Al
2o
3, SiO
2, any in lime-ash, described catalyzer is K
2cO
3, NiO, CaO, Fe
2o
3in any one or arbitrarily several combination.
Concrete, in above-mentioned device, it is as follows that gasifying biomass is produced the processing step of hydrogen-rich gas: first send into pyrolysis reactor 1 through biomass broken, seasoning by pyrolysis reactor 1 upper inlet 1A, in inertia/reducing atmosphere, 500 DEG C～750 DEG C generation thermo-crackings of temperature of reaction, Wood Adhesives from Biomass Heat of Formation is vented one's spleen and coke; Wherein pyrolysis gas directly enters combustion reactor 2 bottoms by lower part outlet 1B, the air (wind) of sending into bottom 2A, there is combustion reactions in the air (secondary air) that middle and lower part 2B sends into, by wind, secondary air flow adjustment, control an internal circulating load of material and combustion reactor 2 temperature at 800 DEG C～1000 DEG C, bed material in heating flame reactor 3 thus, and provide heat to built-in pyrolysis reactor 1, significantly reduce the thermosteresis of pyrolysis, combustion processes.The coke of pyrolysis reactor 1 is sent into gasifying reactor 3 and is preheating to 400～600 DEG C of water vapour generating gasification and reacts by screw feeder 8 by lower part outlet 1C in addition, meanwhile, high hotbed material is carried after the first cyclonic separator 4 gas solid separation by combustion product gases, send into gasifying reactor 3 by dipleg 4B and provide heat for coke gasification, the temperature of controlling gasifying reactor 3 by bed material internal circulating load size is between 650 DEG C～800 DEG C, the hydrogen-rich gas that gasification produces enters gas cooler 6 and will wherein after water vapor condensation separation, obtain dry hydrogen-rich gas after the second tornado dust collector 5 dedustings, gaseous constituent: H
2: 60～85%, CO
2: 10%～35% and CO:5%～10%.The part lime-ash that gas carries returns to gasifying reactor 3 or discharger after the second tornado dust collector 5; Another part solid lime-ash of gasifying reactor 3 and bed material are discharged by lower part outlet 3D1 or outlet at bottom 3D2, control the height of gasifying reactor 3 dense-phase bed by returning charge valve 10, regulate the residence time of coke gasification; Bed material and part lime-ash return to bed material bunker 9 by transfer line, and then enter combustion reactor 3.Gasifying biomass is in service is atmospheric gasification, and the working pressure of reactor keeps: pyrolysis reactor 1> combustion reactor 2> gasifying reactor 3.
In order to reduce the gasification reaction temperature of coke, improve gasification reaction speed and coke gasification transformation efficiency, the bed material adopting not only has inert heat carrier Al
2o
3, SiO
2and lime-ash, and being mixed with a certain proportion of catalyzer, catalyzer is K
2cO
3/ Al
2o
3, NiO/Al
2o
3, CaO/Al
2o
3, Fe
2o
3/ Al
2o
3in any one or arbitrarily several combination, catalyzer and inert bed material mass ratio are 0.2～1.Not only realize the transmission of heat between two reactors by bed material in the circulation between combustion reactor 2 and gasifying reactor 3, and realize calcining and the regeneration of catalyzer, and can eliminate carbon distribution.
In order to make full use of the high temperature sensible heat of high-temperature flue gas and hydrogen-rich gas in biomass gasification process, by hydrogen-rich gas water cooler 6 and waste heat boiler 7, feedwater is heated to 400～600 DEG C, wherein part water vapour is sent into gasifying reactor 3 as gasifying medium, and the superheated vapour of remainder is for outward supplying heat.
Embodiment 1
Agricultural wastes cornstalk is raw material, and gasifying process is described above: cornstalk is crushed to 1mm left and right, water ratio <10%, 750 DEG C of pyrolysis reaction temperature under normal pressure, 950 DEG C of combustion reaction temperatures, 750 DEG C of gasification temperatures, water vapour/cornstalk mass ratio 2.5, circulation bed material is Al
2o
3and K
2cO
3, the two proportioning 4:1, gasification hydrogen-rich gas is through condensed composition H
2: 63.9%, CO:8.3%, CO
2: 27.7%, CH
4<0.1%, gas yield: 1.35Nm
3/ kg cornstalk.
Embodiment 2
Agricultural wastes straw is raw material, and gasifying process is described above: straw is crushed to 1mm left and right, water ratio <10%, 700 DEG C of pyrolysis reaction temperature under normal pressure, 950 DEG C of combustion reaction temperatures, 700 DEG C of gasification temperatures, water vapour/straw mass ratio 2, circulation bed material is Al
2o
3and K
2cO
3, the two proportioning 4:1, gasification hydrogen-rich gas is through condensed composition H
2: 63.1%, CO:5.8%, CO
2: 30.9%, CH
4<0.2%, gas yield: 1.01Nm
3/ kg.
Embodiment 3
Agricultural wastes straw is raw material, and gasifying process is described above: straw is crushed to 1mm left and right, water ratio <10%, 700 DEG C of pyrolysis reaction temperature under normal pressure, 950 DEG C of combustion reaction temperatures, 700 DEG C of gasification temperatures, water vapour/straw mass ratio 2, circulation bed material is Al
2o
3, K
2cO
3with CaO mixture, three's proportioning 3:1:1, gasification hydrogen-rich gas is through condensed composition H2:80.6%, CO:3.8%, CO
2: 15.5%, CH
4<0.1%, gas yield: 0.9Nm
3/ kg straw.
Should understand above-described embodiment only for the embodiment of technical solution of the present invention is described, limit the scope of the invention and be not used in.After having read the present invention, amendment and the replacement of those skilled in the art to various equivalents of the present invention all falls within the protection domain that the application's claim limits.
Reference
[1] present Research of hydrogen-rich gas is produced in biomass pyrolytic and gasification, chemical industry progress, 2013,32 (7): 1534-541
[2] Xie Jianjun, cloudy beautiful, Wu creates it, a kind of by biomass-making gasification installation and the method for hydrogen-rich synthetic gas, 201010214480.3
[3] Dong Changqing, Jiang Jingzhou, Yang Yong's equality, a kind of biomass gasification hydrogen-producing system and method, 201010118131.1
[4] Wang Qinhui, Luo Zhongyang, Fang Mengxiang etc., the solid fuel anaerobic gasification hydrogen production process of near zero release, 200310108667.5.
Claims (10)
1. a gasifying biomass is produced the device of hydrogen-rich gas, it is characterized in that: this device comprises pyrolysis reactor (1) combustion reactor (2), gasifying reactor (3), the first cyclonic separator (4), the second cyclonic separator (5), gas cooler (6), waste heat boiler (7), material feeder (8), bed material bunker (9), variable valve (10) and connecting pipeline, pyrolysis reactor (1) is built in combustion reactor (2); Wherein,
Pyrolysis reactor (1) comprises opening for feed (1A), pyrolysis gas outlet (1B) and coke export (1C); Combustion reactor (2) comprises air/circulation bed material import (2A), secondary air inlet (2B) and flue gas/circulation bed material outlet (2C); Gasifying reactor (3) comprises coke import (3A), water vapour import (3B), gasification product outlet (3C), the first circulation bed material/lime-ash outlet (3D1), the second circulation bed material/lime-ash outlet (3D2);
Wherein, combustion reactor (2) flue gas/circulation bed material outlet (2C) is connected with the first cyclonic separator (4) import (4A), the coke export (1C) of combustion reactor (2) is connected with material feeder (8) import (8A), material feeder (8) outlet (8B) is directly connected with gasifying reactor (3) coke import (3A), the dipleg (4B) of the first cyclonic separator (4) directly inserts in gasifying reactor (3), and the first cyclonic separator (4) exhanst gas outlet (4C) is connected with the hot gas approach (7A) of waste heat boiler (7);
The gaseous product outlet (3C) of gasifying reactor (3) connects the second cyclonic separator (5) import (5A), the second cyclonic separator outlet (5B) is connected with the hot gas import (6A) of gas cooler (6), the outlet (5C) of the second cyclonic separator (5) is connected with the returning charge mouth (3E) of gasifying reactor (3), the the first circulation bed material/lime-ash outlet (3D1) of gasifying reactor (3), the second circulation bed material/lime-ash outlet (3D2) is connected with bed material bunker (9) import (9A) by connecting pipeline respectively, bed material bunker (9) outlet (9B) is connected with combustion reactor (2) air/circulation bed material import (2A) by carrier pipe,
Gas cooler (6) is connected to water out (6D) with the feed-water inlet (7B) of waste heat boiler (7), the superheated vapour outlet of waste heat boiler (7) connects the water vapour import (3B) of gasifying reactor (3) by pipeline.
2. gasifying biomass according to claim 1 is produced the device of hydrogen-rich gas, it is characterized in that: pyrolysis reactor (1) is downdraft moving-bed, opening for feed (1A) is positioned at the top of pyrolysis reactor (1), and pyrolysis gas outlet (1B) and coke export (1C) are all positioned at pyrolysis reactor (1) bottom; Pyrolysis reactor (1) is placed in combustion reactor (2) reactant inner and two reactors blending does not occur;
Combustion reactor (2) is for transporting bed, and combustion reactor (2) air/circulation bed material import (2A) is positioned at the bottom of combustion reactor (2), and secondary air inlet (2B) is positioned at the middle and lower part of combustion reactor (2);
Gasifying reactor (3) is bubbling bed or spouted bed, water vapour import (3B) is positioned at the bottom of gasifying reactor (3), the outlet of the first circulation bed material/lime-ash (3D1) and the second circulation bed material/lime-ash outlet (3D2) lays respectively at bottom and the bottom of gasifying reactor (3), and two outlets with bed expect, on the connecting pipeline between bunker (9), variable valve (10) is housed respectively.
3. gasifying biomass is produced a method for hydrogen-rich gas, it is characterized in that, the method comprises the steps:
Step 1: will send into pyrolysis reactor (1) by the opening for feed (1A) on pyrolysis reactor (1) top through biomass broken, seasoning, 500 DEG C～750 DEG C of temperature of reaction, inertia/reducing atmosphere issues heat-dissipating solution, and Wood Adhesives from Biomass Heat of Formation is vented one's spleen and coke;
Step 2: the pyrolysis gas that pyrolysis reactor (1) produces directly enters combustion reactor (2) bottom by pyrolysis gas outlet (1B), and coke directly enters material feeder (8) by coke export (1C), sends into gasifying reactor (3) by material feeder (8);
Step 3: pyrolysis gas enters combustion reactor (2) and burns with the air of sending into, bed material in heating flame reactor (3), and provide heat to built-in pyrolysis reactor (1), by wind, secondary air flow adjustment, control the internal circulating load of bed material and combustion reactor (2) temperature at 800 DEG C～1000 DEG C; High hotbed material is carried and is sent into gasifying reactor (3) through the dipleg (4B) of the first cyclonic separator (4) and provide heat for coke gasification by combustion product gases;
Step 4: coke reacts with water vapour generating gasification in gasifying reactor (3), gasification reaction temperature is controlled between 650 DEG C～800 DEG C, and the hydrogen-rich gas of gasifying reactor (3) outlet enters gas cooler (6) and will wherein after water vapor condensation separation, obtain dry hydrogen-rich gas after the second tornado dust collector (5) dedusting;
Step 5: the solid lime-ash of gasifying reactor (3) and bed material are discharged by the outlet of the first circulation bed material/lime-ash (3D1) and the second circulation bed material/lime-ash outlet (3D2), return to bed material bunker (9) by transfer line, the solid ash content that the second tornado dust collector (5) separate returns to gasifying reactor (3) or discharger by exporting after (5C) discharges by the returning charge mouth (3E) of gasifying reactor (3);
Step 6: the bed material that air carries bed material bunker (9) enters combustion reactor (2) together by combustion reactor (2) bottom;
Step 7: gasification feedwater is introduced into after the preliminary heating of gas cooler (6), enters waste heat boiler (7) and is further heated as superheated vapour; An overheated steam part is sent into gasifying reactor, part steam supply/heat supply outside device;
Step 8: the high-temperature flue gas of the first tornado dust collector (4) outlets (4C) enters waste heat boiler (7), discharger after heated feed water.
4. gasifying biomass according to claim 3 is produced the method for hydrogen-rich gas, it is characterized in that, the hydrogen-rich gas composition of producing: H
2: 60～85%, CO
2: 10%～35% and CO:5%～10%.
5. gasifying biomass according to claim 3 is produced the method for hydrogen-rich gas, it is characterized in that, exports steam temperature at 400 DEG C～600 DEG C through gas cooler (6) and waste heat boiler heating.
6. gasifying biomass according to claim 3 is produced the method for hydrogen-rich gas, it is characterized in that, the working pressure of reactor is normal pressure, and pyrolysis reactor (1) > combustion reactor (2) > gasifying reactor (3).
7. gasifying biomass according to claim 3 is produced the method for hydrogen-rich gas, it is characterized in that, controls the residence time of coke in gasifying reactor (3) by returning charge valve (10).
8. gasifying biomass according to claim 3 is produced the method for hydrogen-rich gas, it is characterized in that, described biomass are any or its arbitrary combination in other carbonaceous refuses such as agricultural wastes, forestry waste and the dewatered sludge after seasoning, and the biomass particle diameter after fragmentation is at 1mm～10mm.
9. gasifying biomass according to claim 3 is produced the method for hydrogen-rich gas, it is characterized in that, the mixture that described bed material is inert heat carrier and catalyzer is the effect of gasification reaction heat supply in gasification reaction process, and promotes the gasification reaction of coke and water vapour.
10. gasifying biomass according to claim 9 is produced the method for hydrogen-rich gas, it is characterized in that, described inert heat carrier is Al
2o
3, SiO
2, any in lime-ash, described catalyzer is K
2cO
3, NiO, CaO, Fe
2o
3in any one or arbitrarily several combination.
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