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CN101225315B - Method and device for biomass compound gasification - Google Patents

Method and device for biomass compound gasification Download PDF

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Publication number
CN101225315B
CN101225315B CN2007100326754A CN200710032675A CN101225315B CN 101225315 B CN101225315 B CN 101225315B CN 2007100326754 A CN2007100326754 A CN 2007100326754A CN 200710032675 A CN200710032675 A CN 200710032675A CN 101225315 B CN101225315 B CN 101225315B
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gasification
coke
biomass
zone
composite
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CN101225315A (en
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吴创之
阴秀丽
周肇秋
马隆龙
蔡建渝
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Jiangsu Zhongke Dragon Energy System Co Ltd
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Guangzhou Institute of Energy Conversion of CAS
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Abstract

本发明公开了一种生物质复合气化方法和装置,通过将流化床和气流床相耦合,将热解、气化、部分氧化过程在同一反应器内复合。生物质首先在500-600℃条件下发生热解反应,生成焦炭;大颗粒焦炭在焦炭气化区发生部分氧化反应和气化反应,为热解区提供热量并生成可燃气体;热解区释放出的带细小焦炭颗粒的反应气体和催化剂向上快速流经重组分气化区,在二次气化剂作用下发生部分氧化反应,焦油重组分在1000℃以上高温和催化剂作用下同时发生热裂解和催化裂解反应,转化为轻质可燃气体;未反应的焦炭通过气固分离和固体回流装置返回炉内。本发明具有气化效率高、焦油含量低、气体组分调控能力强、运行稳定、易于放大的特点。

Figure 200710032675

The invention discloses a biomass compound gasification method and device. By coupling a fluidized bed and an air flow bed, the processes of pyrolysis, gasification and partial oxidation are compounded in the same reactor. Biomass first undergoes pyrolysis reaction at 500-600°C to generate coke; large-particle coke undergoes partial oxidation and gasification reactions in the coke gasification zone, providing heat for the pyrolysis zone and generating combustible gas; the pyrolysis zone releases The reaction gas with fine coke particles and the catalyst flow upward quickly through the heavy component gasification zone, and partial oxidation reaction occurs under the action of the secondary gasification agent, and the heavy component of the tar is simultaneously thermally cracked and decomposed under the action of the catalyst at a high temperature above 1000°C. Catalytic cracking reaction, converted into light combustible gas; unreacted coke is returned to the furnace through gas-solid separation and solid reflux device. The invention has the characteristics of high gasification efficiency, low tar content, strong control ability of gas components, stable operation and easy enlargement.

Figure 200710032675

Description

A kind of method of biomass combined gasification and device
Technical field
The present invention relates to the biomass gasification technology field, relate in particular to remove in a kind of stove the method and the device of the integration biomass combined gasification of tar.
Background technology
Because petroleum resources is day by day deficient, environmental pollution and Greenhouse effect problem serious day by day, obtain the higher-grade liquid fuel and chemical becomes a kind of development trend just gradually from abundant biomass agriculture and forestry organic waste material resource (as stalk etc.), at home and abroad cause and show great attention to.Biomass gasification technology can become high-grade geseous fuel with various depleted Wood Adhesives from Biomass, is to produce liquid fuel, chemical by the thermochemistry path for transformation, and be used to generate electricity, the main core technology of air feed and heat supply.The market outlook of biomass-based liquid fuel and chemical will finally depend on the competitiveness of cost, and efficient, economic biogas metallization processes is a development biomass indirect liquefaction technology key link, so must solve the bottleneck problem that present gasification technology exists, reduce tar content, improve gasification efficiency and aerogenesis quality.
At different industrial uses, biomass gasification technology has been carried out a large amount of research and developments both at home and abroad, develop different biogas metallization processes such as fixed bed, fluidized-bed, air flow bed.Fixed bed gasification technological reaction speed is slow, treatment capacity is little, is difficult for amplifying; The fluidized bed gasifying process speed of response is fast, and treatment capacity is big, helps scale operation, so obtained using widely; And the research of air flow bed mainly rests on the verification experimental verification stage.No matter adopt which kind of gasifying process, the generation of tar is the common problem of gasification technology.Tar is gaseous state when high temperature, mix fully with inflammable gas, and be condensed into liquid state when low temperature, and its separation and processing be difficulty very.The existence of tar has not only reduced gasification efficiency, gas heating value, and more seriously tar is condensed into liquid state when low temperature, and gas pipe line is stopped up in easy and combinations such as water, coke, influences the normal operation of equipment for gasification; The tar that is condensed into fine drop is difficult to burn, and is easy to generate particles such as carbon black when burning, and gas-fired equipment is caused great infringement.The existence of tar greatly reduces the utility value of synthetic gas, has stoped the high-end applications of gasification technology, is the bottleneck problem of the efficient large-scale application of gasification technology.
Industrial tar removal method commonly used mainly is that stove is removed outward at present, as dry type filtration, wet scrubbing, catalytic pyrolysis etc.Though filtration and method for washing are simple to operate, cost is lower, efficient is not high, for preventing secondary pollution, need to increase extra treating plant and sewage treatment equipment, not only occupation of land is bigger, has also increased cost of investment, and the tar of disposing can not utilize, and causes the waste of the energy.Catalytic pyrolysis is simple because of system, capacity usage ratio is high, and the biological fuel gas component is had promotor action and becomes the focus of domestic and international research, but needs to consume a large amount of additional energies, also needs extra utility appliance, has increased the complicacy and the investment of system; Simultaneously,, also do not form business-like special-purpose catalyst series, especially also have bigger distance from commercialization aspect the work-ing life of catalyzer because problems such as catalyst deactivation, mechanical wear and application cost are mainly used in experimental study at present.
Tar also can suppress in vapourizing furnace promptly that tar produces and is target product gas with the tar converted in-situ that produces by the method removed in the stove, realizes not containing tar in the crude synthesis gas in the vapourizing furnace.Remove in the stove and can realize, reduce the purpose that vapourizing furnace exports the coal-tar middle oil content of combustion gas thereby reach by optimizing methods such as adding catalyzer in gasification furnace structure design, optimization gasification operating parameters, the vapourizing furnace.This method is the focus and the Future Development direction of research at present.
Both at home and abroad the development trend of gasification technology be that exploitation is efficient, low tar, gasifying process that combustion gas component ability of regulation and control is stronger.At the effective elimination of tar and the high-end utilization of combustion gas, carried out the research of novel gasifying process both at home and abroad.As: Technical University Of Denmark has designed two-stage gasifier, and the coal-tar middle oil content of gained combustion gas reduces greatly; Germany Choren company has proposed the technology of mild pyrolysis and high temperature pyrolysis two-step method making high quality synthetic gas, contains tar in the synthetic gas hardly.These apparatus features be with many reactors in series on a successive flow process, fuel drying and pyrolysis in the indirect heating type cracker earlier, the cracked product and then lane between cracker and coke gasification device carries out partial oxidation, product gas flow is through the coke bed of heat, thereby makes the coke tar cracking in the product gas and reach lower content.
Granted publication number has disclosed a kind of agricultural waste material treatment facility for the patent of invention of CN1116383 " a kind of combined biomass vaporization furnace and gas preparation method thereof " and by the method for solid carbon-contg material production combustion gas, its goal of the invention provides a kind of Rural areas combustion gas preparation facilities and method that be suitable for, small-sized, as described in content in the specification sheets, fixed bed downdraft vapourizing furnace be provided with a biomass carbonization stove nearby, yet the simple superposition that disclosed this composite gasification furnace only is multiple device in the patent specification.
Granted publication number is the patent of invention " a kind of low-tar biomass gasifying method and device " of CN1272404C, it is characterized in that this device comprises a pyrolysis reactor and a pyrolysis gasification device, the pyrolysis product in the pyrolysis reactor enters a placed in-line pyrolysis gasification device.Described gasifier is a fixed bed downdraft vapourizing furnace.This invention realizes with pyrolysis by two placed in-line reactors and gasifies two processes separately that obtain the lower inflammable gas of tar content, but amplify at reactor, aspects such as operation stability all can't satisfy the needs of industrial application.
Publication number is the gasifying furnace device that the patent application " combined biomass vaporization furnace and thermal cracker " of CN1664066 discloses a kind of combined type, but from this patent specification, can know, this composite gasification furnace also only is the simple superposition of multiple arrangement, described in patent specification, its main technical scheme is that this main equipment is made of two vapourizing furnaces, also comprise quadruplet U type catalyst converter, composition such as gas blower and blast regulator.
Publication number is that the patent application " a kind of biomass combined gasification furnace " of CN101021336 is a kind of biomass gasification fired small-sized stove and accessory that makes.As described in this patented invention purpose, its technical superiority that will gasify and partly gasify two kinds of stove and accessorys entirely organically combines, a kind of biomass combined gasification furnace that need not use blower fan is provided, is not difficult to find out from the accompanying drawing of this patent, this combined gasification furnace also is the simple superposition of multiple arrangement.
Therefore, mostly the gasifying process that removes tar at present in the stove is to utilize the series connection of several reactors to realize also not having incorporate biomass combined gasification equipment, even there is so-called combined gasification furnace structure at present, also be the simple superposition and the serial connection of several devices, do not have creativeness.
Summary of the invention
The objective of the invention is removing and the high-end utilization of combustion gas at tar, a kind of integration biomass combined gasification method and apparatus of low tar is provided, promptly utilize " multistage " gasification notion, biomass pyrolytic, coke gasification, heavy constituent gasification are separated relatively, realize the control of parameter subregion and optimize coupling.Promptly, reduce tar content by the control of heavy constituent gasification; The control of biomass coke gasification improves gasification efficiency; By the control of gasification condition subregion, realize the orientation regulation and control of gaseous fraction.And the structure of utilizing fluidized-bed and air flow bed to be coupled, realizing the integrated design of the multistage gasification of biomass, institute is responded can carry out in a cover reaction unit.
For reaching above purpose, the present invention realizes by following technical scheme: a kind of method of biomass combined gasification, this method comprises the following steps: that (1) biomass material adds composite gasification furnace from the opening for feed that is positioned at pyrolysis zone, pyrolytic reaction takes place under 500-600 ℃ of temperature, biomass discharge volatilization gas, and generate solid coke; (2) the coke macrobead flows into the coke gasification district in the composite gasification furnace downwards, and under the effect of a vaporized chemical, small part coke generation oxidizing reaction reaches more than 1000 ℃ coke gasification district temperature, and most of coke then generating gasification reaction generates inflammable gas; (3) the mobile high-temperature gas form biomass pyrolysis district that makes progress from the coke gasification district provides biomass pyrolytic required heat, keeps the pyrolysis zone temperature at 500-600 ℃; (4) the biomass pyrolytic district discharge with the reactant gases of tiny coke granule and the catalyzer heavy constituent gasification zone of upwards flowing through fast, under second gasification agent effect, partial oxidation reaction takes place, heavy constituent gasification zone temperature reaches more than 1000 ℃, make the tar heavy constituent in the volatile matter that thermo-cracking and catalytic cracking reaction take place under high temperature and catalyst action simultaneously, the tar heavy constituent are converted into the lightweight inflammable gas, both reduce the coal-tar middle oil content of crude synthesis gas, improved gas yield and gasification efficiency again.(5) the unreacted coke in heavy constituent gasification zone and be entrained in catalyst fines in the gas and receive cyclonic separator by the escape pipe on top and carry out gas solid separation, simultaneously by cyclonic separator bottom reflux, send solid particulate back to the coke gasification district, improve the efficiency of carbon conversion of system.
A described vaporized chemical and second gasification agent are one or more in air or oxygen or water vapour or the oxygen enrichment.
In above-mentioned steps (1), at the charging opening adding catalyzer of pyrolysis zone, the orientation that the adding of catalyzer helps gaseous fraction generates.
Biomass combined gasification method of the present invention can realize by the device of the following stated, a kind of low-tar biomass combined gasification equipment, described combined gasification equipment comprises composite gasification furnace, comprises fluidized-bed of being made up of pyrolysis zone and coke gasification district and the air flow bed that is made of the heavy constituent gasification zone in the described composite gasification furnace.The sectional area in described heavy constituent gasification zone and coke gasification district is less than the sectional area of described pyrolysis zone.Described pyrolysis zone is provided with biomass feed inlet, and described coke gasification district is provided with the vaporized chemical input aperture one time, and described heavy constituent gasification zone is provided with second gasification agent input aperture.Described biomass combined gasification equipment also includes gas solid separation and the solids backflow device that is connected with described composite gasification furnace.In this device, heavy constituent gasification zone and coke gasification district are the high-temperature zone, temperature reaches more than 1000 ℃, the biomass pyrolytic district is middle warm area, temperature is about 500 ℃-600 ℃, by adding different vaporized chemicals, and the temperature of same district not in the control stove, regulate the component of combustion gas, in a stove, realize the control and the optimization of different operating modes.
Biomass combined gasification method of the present invention is a mode of utilizing fluidized-bed and air flow bed to be coupled, and pyrolysis, gasification, partial oxidation process is compound in same reactor, realizes the control of parameter subregion and optimizes.The characteristics that this technology has the gasification efficiency height, tar content is low, the gaseous fraction ability of regulation and control is strong, load performance strong, the raw material suitability is strong, stable, be easy to amplify.This gasification process can reach following technical indicator: gasification efficiency 〉=80%, efficiency of carbon conversion 〉=98%, tar content≤20mg/Nm 3And stable, continuous, applicable to multiple field, as generating, heat supply, air feed, synthetic liquid fuel etc.
Description of drawings
Fig. 1 is an embodiment of the invention apparatus structure synoptic diagram;
Description of reference numerals: 1, composite gasification furnace, 2, pyrolysis zone, 3, the heavy constituent gasification zone, 4, the coke gasification district, 5, vaporized chemical input apertures, 6, second gasification agent input aperture, 7, biomass feed inlet, 8, gas solid separation and solids backflow device.
Embodiment
Below in conjunction with accompanying drawing and embodiment content of the present invention is described further:
See also shown in Figure 1, a kind of biomass combined gasification method, biomass material adds composite gasification furnaces 1 from the opening for feed 7 that is positioned at pyrolysis zone 2, under 500-600 ℃ of temperature pyrolytic reaction takes place, biomass discharge volatilization gas, and generate solid coke; The coke macrobead flows into the coke gasification district 4 in the composite gasification furnace 1 downwards, one time vaporized chemical is added by a vaporized chemical input aperture 5, under the effect of a vaporized chemical, small part coke generation oxidizing reaction, coke gasification district temperature is reached more than 1000 ℃, and most of coke then generating gasification reaction generates inflammable gas; From the coke gasification district 4 upwards mobile high-temperature gas form biomass pyrolysis district 2 provide biomass pyrolytic required heat, the temperature of keeping pyrolysis zone 2 is at 500-600 ℃; Biomass after pyrolysis zone 2 reaction, discharge with the reactant gases of tiny coke granule and the catalyzer heavy constituent gasification zone 3 of upwards flowing through fast, the second gasification agent is added by second gasification agent input aperture 6, under second gasification agent effect, partial oxidation reaction takes place, heavy constituent gasification zone 3 temperature reach more than 1000 ℃, make the tar heavy constituent in the volatile matter under high temperature and catalyst action condition thermo-cracking and catalytic pyrolysis take place simultaneously, the tar heavy constituent are converted into the lightweight inflammable gas.Unreacted coke returns coke gasification district 4 by gas solid separation and solids backflow device 8 and further participates in reaction, and inflammable gas is from the top output of gas solid separation and solids backflow device 8.

Claims (7)

1.一种生物质复合气化的方法,其特征在于,该方法包括下列步骤:1. A method for composite gasification of biomass, characterized in that the method may further comprise the steps: (1)生物质原料从位于热解区的进料口加入复合气化炉内,在500-600℃温度下发生热解反应,生物质释放出挥发气体,并生成固体焦炭;(1) Biomass raw materials are fed into the composite gasifier from the feed port located in the pyrolysis zone, and a pyrolysis reaction occurs at a temperature of 500-600 ° C, and the biomass releases volatile gas and generates solid coke; (2)焦炭大颗粒向下流入复合气化炉内的焦炭气化区,在一次气化剂的作用下,少部分焦炭发生氧化反应,使焦炭气化区温度达到1000℃以上,大部分焦炭则发生气化反应生成可燃气体;(2) Large coke particles flow downward into the coke gasification zone in the composite gasifier. Under the action of the primary gasification agent, a small part of the coke undergoes an oxidation reaction, making the temperature of the coke gasification zone reach above 1000 °C, and most of the coke Gasification reaction occurs to generate flammable gas; (3)自焦炭气化区向上流动的高温气体为生物质热解区提供生物质热解所需的热量,维持热解区温度在500-600℃;(3) The high-temperature gas flowing upward from the coke gasification zone provides the heat required for biomass pyrolysis in the biomass pyrolysis zone, and maintains the temperature in the pyrolysis zone at 500-600°C; (4)生物质热解区释放出的带细小焦炭颗粒的反应气体和催化剂向上快速流经焦油重组分气化区,在二次气化剂的作用下,发生部分氧化反应,重组分气化区温度达到1000℃以上,使挥发分中的焦油重组分在高温和催化剂作用下同时发生热裂解和催化裂解反应,焦油重组分转化为轻质可燃气体;(4) The reaction gas with fine coke particles and the catalyst released from the biomass pyrolysis zone quickly flow upward through the gasification zone of the heavy components of tar, and under the action of the secondary gasification agent, partial oxidation reaction occurs, and the heavy components are gasified The temperature of the zone reaches above 1000°C, so that the heavy tar components in the volatile matter undergo thermal cracking and catalytic cracking reactions at the same time under the action of high temperature and catalyst, and the heavy tar components are converted into light combustible gases; (5)重组分气化区未反应的焦炭以及夹带在气体中的催化剂细颗粒通过上部的出气管接到旋风分离器进行气固分离,燃气通过旋风分离器上部排出,固体颗粒通过旋风分离器下部回流装置被送回焦炭气化区。(5) The unreacted coke in the heavy component gasification zone and the catalyst fine particles entrained in the gas are connected to the cyclone separator through the upper gas outlet pipe for gas-solid separation, the gas is discharged through the upper part of the cyclone separator, and the solid particles pass through the cyclone separator The lower reflux unit is sent back to the coke gasification zone. 2.根据权利要求1所述的生物质复合气化的方法,其特征在于:所述一次气化剂和二次气化剂为空气或氧气或水蒸气或富氧中的一种或几种。2. The method for composite gasification of biomass according to claim 1, characterized in that: the primary gasification agent and the secondary gasification agent are one or more of air or oxygen or water vapor or oxygen-enriched . 3.根据权利要求1或2所述的生物质复合气化的方法,其特征在于:在上述步骤(1)中,在热解区的进料口加入催化剂。3. The method for composite gasification of biomass according to claim 1 or 2, characterized in that: in the above step (1), a catalyst is added to the feed port of the pyrolysis zone. 4.一种用于实现权利要求1所述生物质复合气化方法的复合气化装置,其特征在于:所述复合气化装置包括复合气化炉(1),所述复合气化炉(1)内包括由热解区(2)和焦炭气化区(4)组成的流化床以及由重组分气化区(3)构成的气流床。4. a composite gasification device for realizing the biomass composite gasification method described in claim 1, characterized in that: the composite gasification device comprises a composite gasifier (1), and the composite gasifier ( 1) includes a fluidized bed composed of a pyrolysis zone (2) and a coke gasification zone (4) and an air-flow bed composed of a heavy component gasification zone (3). 5.根据权利要求4所述的生物质复合气化方法的复合气化装置,其特征在于:所述重组分气化区(3)和焦炭气化区(4)的截面积小于所述热解区(2)的截面积。5. The composite gasification device of the biomass composite gasification method according to claim 4, characterized in that: the cross-sectional area of the heavy component gasification zone (3) and the coke gasification zone (4) is smaller than the thermal The cross-sectional area of solution area (2). 6.根据权利要求4所述的生物质复合气化方法的复合气化装置,其特征在于:在所述热解区(2)上设置有生物质进料口(7),在所述焦炭气化区(4)上设置有一次气化剂输入口(5),在所述重组分气化区(3)上设置有二次气化剂输入口(6)。6. The composite gasification device of the biomass composite gasification method according to claim 4, characterized in that: a biomass feed port (7) is provided on the pyrolysis zone (2), and a biomass feed port (7) is arranged on the coke The gasification zone (4) is provided with a primary gasification agent input port (5), and the heavy component gasification zone (3) is provided with a secondary gasification agent input port (6). 7.根据权利要求4至6中任一所述的生物质复合气化方法的复合气化装置,其特征在于:还包括有与所述复合气化炉(1)连接的气固分离和固体回流装置(8)。 7. according to the composite gasification device of the biomass composite gasification method described in any one of claims 4 to 6, it is characterized in that: also comprise the gas-solid separation and solid that are connected with described composite gasifier (1) Backflow device (8). the
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WO2005113732A1 (en) * 2004-05-18 2005-12-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Device and method for generating a tar-free lean gas by gasifying biomass

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CN1673317A (en) * 2004-03-23 2005-09-28 财团法人电力中央研究所 Carbonization and gasification of biomass and power generation system
WO2005113732A1 (en) * 2004-05-18 2005-12-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Device and method for generating a tar-free lean gas by gasifying biomass
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