CN101962574B - Clean synthesis gas and preparation method thereof - Google Patents
Clean synthesis gas and preparation method thereof Download PDFInfo
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- CN101962574B CN101962574B CN201010500769.1A CN201010500769A CN101962574B CN 101962574 B CN101962574 B CN 101962574B CN 201010500769 A CN201010500769 A CN 201010500769A CN 101962574 B CN101962574 B CN 101962574B
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Abstract
The invention relates to a preparation method of clean synthesis gas. The method comprises the following steps of: mixing dried biomass particles and dried coal powder uniformly to obtain the mixed particles; and feeding the mixed particles into an entrained flow gasifier by dense phase pneumatic transmission mode, and performing co-gasification on the mixed particles and a gasification agent to generate the clean synthesis gas. The invention also relates to the clean synthesis gas prepared by the method. In the preparation method of the clean synthesis gas, the co-gasification temperature of the entrained flow gasifier is high, the obtained synthesis gas dose not contain harmful ingredients, such as tar, phenol and the like, so the problem that the volatile content of the biomass is high and energy density is low, so secondary pollution is caused by decoking due to high the tar content of the synthesis gas which is gasified independently is solved; meanwhile, the use ratio of the biomass is increased, CO2 emission reduction is facilitated, large-scale, high-efficiency, clean and economic use of the biomass can be realized.
Description
Technical field
The present invention relates to a kind of clean synthetic gas and preparation method thereof.
Background technology
In various renewable energy sources, biomass energy is the carbon resource that unique renewable, alternative fossil energy converts gaseous state, liquid state and solid fuel and other industrial chemicals or product to.The conversion using technology of biomass energy mainly comprises thermochemistry switch technology and biochemical transformations technology, and the gasifying biomass in the thermochemistry switch technology is biomass energy higher-grade utilization development one of the most practical technology, it is also one of biomass energy switch technology realized the earliest commercial applications.
But biomass gasify separately and have some shortcomings: 1. biomass seasonal and the dispersiveness that distributes thereof, limited continuity and the mass-producing of gasifying biomass; 2. because the particle formed after the biomass pulverizing has irregularity, make when adopting fluidized-bed gasification, be difficult for the stable bed of material of formation in fluidized-bed gasification furnace, need to add a certain amount of inertia heavy constituent bed material as river sand, quartz sand etc., increased energy consumption; 3. biomass are high volatile matter and oxygen level, easily generate more tar while making biomass no matter adopt fixed bed or fluidized-bed to gasify separately, not only reduced the quality of gasification efficiency and the synthetic gas of biomass, and the steady running of gasification has also been caused to disadvantageous effect.
In gasification of coal technique, gasification process commonly used has three kinds: moving-bed (fixed bed), fluidized-bed and air flow bed.Exploitation biomass and coal be gasification technology altogether, if adopt the mode of fixed bed and fluidized-bed, although improve a lot utilizing on scale, gasification efficiency with biomass fixed-bed comparing with fluidized-bed gasification merely, with the direction of utilizing on a large scale of coal, runs counter to.The coal gas fluidized bed gasification has larger coal and granularity adaptability and better technical feature, is the combustion gas of coal-based large capacity, high effect cleaning and one preferred technique prepared by synthetic gas, is core, the tap and crucial of coal-based Poly-generation technology.
Summary of the invention
Technical problem to be solved by this invention is to have overcome in existing biomass gasification method because the biomass volatile content is high, energy density is low, the coal-tar middle oil content of synthetic gas that causing gasification to generate is high and carry out decoking and easily cause the defects such as secondary pollution, and a kind of new clean synthetic gas and preparation method thereof is provided.The method can improve the utilization ratio of biomass and the transformation efficiency of coal, contributes to CO
2reduce discharging, and can realize extensive, efficient, the clean and economic utilization of biomass.
One of purpose of the present invention is to provide a kind of preparation method of clean synthetic gas, and it comprises the steps: dry biological particles and dry coal dust evenly are mixed to get to composite grain; Mode by Dense Phase Pneumatic Conveying feeds this composite grain in air flow bed, by this composite grain and the vaporized chemical generating clean synthetic gas that gasifies altogether.
Wherein, described biomass, for all organic substances that directly or indirectly utilizes green plants photosynthesis to form, comprise plant, animal and microorganism and excretion and metabolite etc. except fossil oil.Biomass in the present invention are preferably agriculture and forestry organic waste material, more preferably comprise one or more in stalk, wood chip, fuel wood, weeds, husk, shell, bagasse and corn cob.
Wherein, described drying can adopt this area ordinary method to realize, preferably by the heat of 150～250 ℃, carries rare gas element in the present invention and realizes.
Wherein, the particle diameter to described biological particles in the present invention has carried out preferably, is preferably below 3mm.The water ratio of the biological particles of described drying can be selected according to this area general knowledge, is preferably below 10wt%, and better is below 4wt%.
Wherein, the mean particle size of described coal dust can be selected the regular particle size of entrained flow gasification, is preferably below 0.1mm.The water ratio of the coal dust of described drying can be selected according to this area general knowledge, is preferably below 10wt%, and better is below 4wt%.
Wherein, in described composite grain, the content of dry biological particles is preferably 0.1～40wt%.
Wherein, the biological particles of described drying and dry coal dust can realize by rare gas element even the mixing in transport pipeline.
Wherein, the pressure of described Dense Phase Pneumatic Conveying can be selected according to this area general knowledge, is preferably 0.05～6.0MPa.The carrier gas of described Dense Phase Pneumatic Conveying can be selected the conventional carrier gas of this area, is preferably nitrogen and/or carbonic acid gas.In described Dense Phase Pneumatic Conveying, the ratio of described composite grain and described carrier gas can be selected according to this area ordinary method, and the present invention is preferably 2～10kg composite grain/kg carrier gas.
Wherein, described vaporized chemical preferably includes oxygen-containing gas, described oxygen-containing gas preferably using oxygen, oxygen level in the form of the oxygen-rich air more than 50% or air as vaporized chemical of the present invention.Wherein, the ratio of described composite grain and described oxygen-containing gas is preferably 0.002～3.5kg composite grain/Nm
3oxygen-containing gas, that better is 0.3～3.5kg composite grain/Nm
3oxygen-containing gas.Preferably, in described vaporized chemical, also can comprise water vapor, now, the ratio of described water vapor and described composite grain is preferably 0.5kg water vapor/below the kg composite grain, but does not comprise 0kg water vapor/kg composite grain.
Wherein, the described pressure of gasification altogether can be selected according to this area general knowledge, and the present invention is 0.01～5.0MPa preferably.The described temperature of gasification altogether can be selected according to this area general knowledge, preferably 1000～1700 ℃ of the present invention.The time of described altogether gasification, better was 2～10 seconds so that altogether till gasification fully, be preferably 0.1～100 second.
In the present invention one, preferably in embodiment, described preparation method adopts following concrete steps to carry out:
(1) raw materials pretreatment, mixing and feed: it is below 3mm that biomass material is crushed to grain diameter, and simultaneously by 150～250 ℃ of heat, carrying rare gas element, to be dried to water ratio be below 10.0wt%, obtains dry biological particles; By coal, through ball mill grinding to mean particle size, be below 0.1mm, simultaneously by 150～250 ℃ of heat, carrying rare gas element, to be dried to water ratio be below 10.0wt%, obtains dry coal dust; Respectively dry biological particles and dry coal dust are relied on to transporting of rare gas element, realize both even mixing in pipeline, obtain composite grain; Mode by described composite grain by Dense Phase Pneumatic Conveying feeds in the vapourizing furnace of air flow bed;
(2) air flow bed gasifies altogether: in described vapourizing furnace, described composite grain and described vaporized chemical are entered in described vapourizing furnace by two passages that are connected with the nozzle of vapourizing furnace respectively; At the temperature of the pressure of 0.01～5.0MPa and 1000～1700 ℃, the disperse mixing with vaporized chemical under the carrying of vaporized chemical of this composite grain, gasify 2～10 seconds altogether; Obtain clean synthetic gas, and the lime-ash of melting is discharged to vapourizing furnace; Wherein, described biomass, composite grain and vaporized chemical are all with aforementioned; The condition of described Dense Phase Pneumatic Conveying and gasification altogether and optimum condition are all with aforementioned.
Preferably, in step (1), before carrying out Dense Phase Pneumatic Conveying, described composite grain is separated in a cloth envelop collector with described rare gas element, the rare gas element after separating is discharged to system.
Two of purpose of the present invention is to provide a kind of clean synthetic gas made by above-mentioned preparation method, and it mainly comprises CO, H
2, CO
2and N
2deng gas, the CO that the volume fraction of those gases is 10～68%, 2～35% H
2, 0.01～25% CO
2, 0.1～75% N
2.
Rare gas element of the present invention can be the rare gas element of the various routines in this area, is generally nitrogen, argon gas etc.
Raw material of the present invention, equipment and reagent is commercially available obtaining all unless otherwise indicated.
In the present invention, but above-mentioned optimum condition arbitrary combination on the basis that meets this area general knowledge obtains the preferred embodiments of the invention.
Positive progressive effect of the present invention is:
(1) in the preparation method of clean synthetic gas of the present invention, the temperature gasified altogether due to air flow bed is high, do not contain the objectionable constituent such as tar, phenol in the synthetic gas of gained, biomass have been overcome because volatile content is high, energy density is low, the coal-tar middle oil content of synthetic gas that causes independent gasification to generate is high and decoking easily causes the problem of secondary pollution, also improved the utilization ratio of biomass, contributed to CO simultaneously
2reduce discharging, and can realize extensive, efficient, the clean and economic utilization of biomass.
(2) contain more basic mineral in the biomass inorganic components, can reduce the discharge of gasification temperature, promotion vapourizing furnace slag tap.
(3) in biomass, alkali metal content is high, and to char gasification, reaction has katalysis, while therefore gasifying altogether with coal, can accelerate the char gasification speed of reaction, thereby improves the transformation efficiency of coal.
The accompanying drawing explanation
The air flow bed that Fig. 1 is biomass and coal in embodiment 1～3 is the gasifying process schematic flow sheet altogether.
Embodiment
Below with embodiment, further illustrate the present invention, but the present invention is not limited.
Embodiment 1
Adopt the flow process of Fig. 1.Biomass are the discarded pine of wood-working factory.
The preparation method of clean synthetic gas is:
1, will discard pine and be crushed to 2～3mm in pulverizer 1, being dried to water ratio by 150 ℃ of hot nitrogen carrier gases is 10.0wt%, obtains dry pine sawdust simultaneously; It is 0.1mm that coal is ground to mean particle size through ball mill 2, and being dried to water ratio by 150 ℃ of hot nitrogen carrier gases is 10.0wt%, obtains dry coal dust simultaneously;
2, dry pine sawdust and dry coal dust are completed to even mixing respectively under the rolling action of nitrogen in pipeline 3 and pipeline 4 arrival pipelines 5, obtain composite grain, wherein dry pine sawdust accounts for 40% of composite grain quality;
3, by composite grain in the interior gas solid separation that realizes of cloth envelop collector 6, the nitrogen after separating is discharged to system, this composite grain enters batch can 8 through pipeline 7; Under the carrying of carrier gas, through pipeline 9, in the mode of Dense Phase Pneumatic Conveying, the nozzle 1001 by vapourizing furnace feeds in vapourizing furnace 10 composite grain in batch can 8; Wherein, Dense Phase Pneumatic Conveying pressure is 6.0MPa, and delivery of carrier gas is N
2, composite grain and N
2ratio be 10kg composite grain/kg N
2; The feed flow rate that composite grain feeds vapourizing furnace is 80t/h;
4, vaporized chemical is fed in vapourizing furnace 10, at vapor pressure, be under 5.0MPa, the gasification temperature condition that is 1000 ℃, this composite grain and vaporized chemical carry out common gasification reaction, the mean residence time of material in vapourizing furnace is 2 seconds, the clean synthetic gas generated after reaction is discharged vapourizing furnace by venting port 1002, and the melting slag of generation is discharged by slag-drip opening 1003; Wherein, vaporized chemical is oxygen, and the flow of oxygen is 23117Nm
3/ h (3.5kg composite grain/Nm
3oxygen).
The clean gas composition obtained is (butt, volume): H
2: 30.36%, CO:46.84%, CO
2: 10.81%, N
2: 7.50%, CH
4: 3.84%, H
2s:0.50%, COS:0.03%, H
3n:0.03%, Ar:0.09%.Efficiency of carbon conversion is 99.30%; The synthetic gas Lower heat value is 9.53MJ/Nm
3.
Adopt the flow process identical with embodiment 1.Biomass are straw.
The preparation method of clean synthetic gas is:
1, straw is crushed in pulverizer 1 to the 3mm left and right, being dried to water ratio by 250 ℃ of hot nitrogen carrier gases is 0.0wt%, obtains dry straw particle simultaneously; It is 65 μ m that coal is ground to mean particle size through ball mill 2, and being dried to water ratio by 250 ℃ of hot nitrogen carrier gases is 0.0wt%, obtains dry coal dust simultaneously;
2, dry straw particle and dry coal dust are completed to even mixing respectively under the rolling action of nitrogen in pipeline 3 and pipeline 4 arrival pipelines 5, obtain composite grain, wherein the content of straw particle is 5% of composite grain quality;
3, by composite grain in the interior gas solid separation that realizes of cloth envelop collector 6, the nitrogen after separating is discharged to system, this composite grain enters batch can 8 through pipeline 7; Under the carrying of carrier gas, through pipeline 9, in the mode of Dense Phase Pneumatic Conveying, the nozzle 1001 by vapourizing furnace feeds in vapourizing furnace 10 composite grain in batch can 8; Wherein, Dense Phase Pneumatic Conveying pressure is 0.05MPa, and delivery of carrier gas is CO
2, composite grain and CO
2ratio be 8kg composite grain/kg CO
2; The feed flow rate that composite grain feeds vapourizing furnace is 12t/h;
4, vaporized chemical is fed in vapourizing furnace 10, at vapor pressure, be under 0.01MPa, the gasification temperature condition that is 1200 ℃, this composite grain and vaporized chemical carry out common gasification reaction, the mean residence time of material in vapourizing furnace is 5 seconds, the clean synthetic gas generated after reaction is discharged vapourizing furnace by venting port 1002, and the melting slag of generation is discharged by slag-drip opening 1003; Wherein, vaporized chemical is air and water vapor, and the flow of air is 39470Nm
3/ h (0.3kg composite grain/Nm
3air), the flow of water vapor is 600kg/h (0.05kg water vapor/kg composite grain).
The clean gas composition obtained is (butt, volume): H
2: 8.69%, CO:26.97%, CO
2: 5.06%, N
2: 59.11%, CH
4: 0.02%, H
2s:0.13%, COS:0.02%.Efficiency of carbon conversion is 99.00%; The synthetic gas Lower heat value is 4.18MJ/Nm
3.
Embodiment 3
Adopt the flow process identical with embodiment 1.The mixture that biomass are straw and pine (1: 1, weight).
The preparation method of clean synthetic gas is:
1, biomass are crushed to 1～2mm in pulverizer 1, being dried to water ratio by 220 ℃ of hot nitrogen carrier gases is 4.0wt%, obtains dry biological particles simultaneously; It is 58 μ m that coal is ground to mean particle size through ball mill 2, and being dried to water ratio by 220 ℃ of hot nitrogen carrier gases is 4.0wt%, obtains dry coal dust simultaneously;
2, dry biological particles and dry coal dust are completed to even mixing respectively under the rolling action of nitrogen in pipeline 3 and pipeline 4 arrival pipelines 5, obtain composite grain, wherein the quality of biological particles accounts for 0.1% of composite grain quality;
3, by composite grain in the interior gas solid separation that realizes of cloth envelop collector 6, the nitrogen after separating is discharged to system, this composite grain enters batch can 8 through pipeline 7; Under the carrying of carrier gas, through pipeline 9, in the mode of Dense Phase Pneumatic Conveying, the nozzle 1001 by vapourizing furnace feeds in vapourizing furnace 10 composite grain in batch can 8; Wherein, Dense Phase Pneumatic Conveying pressure is 4.0MPa, and delivery of carrier gas is N
2, composite grain and N
2ratio be 2kg composite grain/kg N
2; The feed flow rate that composite grain feeds vapourizing furnace is 40t/h;
4, vaporized chemical is fed in vapourizing furnace 10, at vapor pressure, be under 3.5MPa, the gasification temperature condition that is 1700 ℃, this composite grain and vaporized chemical carry out common gasification reaction, the mean residence time of material in vapourizing furnace is 8 seconds, the clean synthetic gas generated after reaction is discharged vapourizing furnace by venting port 1002, and the melting slag of generation is discharged by slag-drip opening 1003; Wherein, vaporized chemical is 80% oxygen-rich air and water vapor, and the flow of 80% oxygen-rich air is 37766Nm
3/ h (1.1kg composite grain/Nm
3oxygen-rich air), the flow of water vapor is 20000kg/h (0.5kg water vapor/kg composite grain).
The clean gas composition obtained is (butt, volume): H
2: 21.03%, CO:42.98%, CO
2: 11.68%, N
2: 24.05%, H
2s:0.24%, COS:0.02%.Efficiency of carbon conversion is 99.10%; The synthetic gas Lower heat value is 6.14MJ/Nm
3.
Claims (7)
1. the preparation method of a clean synthetic gas is characterized in that: it comprises the steps: dry biological particles and dry coal dust evenly are mixed to get to composite grain; Mode by Dense Phase Pneumatic Conveying feeds this composite grain in air flow bed, by this composite grain and the vaporized chemical generating clean synthetic gas that gasifies altogether; The particle diameter of described biological particles is below 3mm; The water ratio of the biological particles of described drying is below 10wt%; The mean particle size of described coal dust is below 0.1mm; The water ratio of the coal dust of described drying is below 10wt%; In described composite grain, the content of the biological particles of described drying is 0.1～40wt%;
The pressure of described Dense Phase Pneumatic Conveying is 0.05～6.0MPa; The carrier gas of described Dense Phase Pneumatic Conveying is nitrogen and/or carbonic acid gas; The ratio of described composite grain and described carrier gas is 2～10kg composite grain/kg carrier gas;
Described vaporized chemical comprises oxygen-containing gas and water vapor; The ratio of described composite grain and described oxygen-containing gas is 0.002～3.5kg composite grain/Nm
3oxygen-containing gas; The ratio of described water vapor and described composite grain is 0.5kg water vapor/below the kg composite grain, but does not comprise 0kg water vapor/kg composite grain;
The described pressure of gasification altogether is 0.01～5.0MPa; The described temperature of gasification altogether is 1000～1700 ℃; The described time of gasification altogether is 2～10 seconds.
2. preparation method as claimed in claim 1, it is characterized in that: described biomass are agriculture and forestry organic waste material; Described drying is carried rare gas element by the heat of 150～250 ℃ and is realized.
3. preparation method as claimed in claim 2, it is characterized in that: described biomass comprise one or more in stalk, wood chip, fuel wood, weeds, husk, shell, bagasse and corn cob.
4. preparation method as claimed in claim 1 or 2, it is characterized in that: the water ratio of the biological particles of described drying is below 4wt%; The water ratio of the coal dust of described drying is below 4wt%.
5. preparation method as claimed in claim 1 is characterized in that: described oxygen-containing gas using oxygen, oxygen level in the form of the oxygen-rich air more than 50% or air as described vaporized chemical.
6. preparation method as claimed in claim 1, it is characterized in that: the ratio of described composite grain and described oxygen-containing gas is 0.3～3.5kg composite grain/Nm
3oxygen-containing gas.
7. preparation method as described as any one in claim 1～3, it is characterized in that: described preparation method adopts following concrete steps to carry out:
(1) raw materials pretreatment, mixing and feed: it is below 3mm that biomass material is crushed to grain diameter, and simultaneously by 150～250 ℃ of heat, carrying rare gas element, to be dried to water ratio be below 10.0wt%, obtains dry biological particles; By coal, through ball mill grinding to mean particle size, be below 0.1mm, simultaneously by 150～250 ℃ of heat, carrying rare gas element, to be dried to water ratio be below 10.0wt%, obtains dry coal dust; Respectively dry biological particles and dry coal dust are relied on to transporting of rare gas element, realize both even mixing in pipeline, obtain composite grain; Mode by described composite grain by Dense Phase Pneumatic Conveying feeds in the vapourizing furnace of air flow bed;
(2) air flow bed gasifies altogether: in described vapourizing furnace, described composite grain and vaporized chemical are entered in described vapourizing furnace by two passages that are connected with the nozzle of described vapourizing furnace respectively; At the temperature of the pressure of 0.01～5.0MPa and 1000～1700 ℃, the disperse mixing with vaporized chemical under the carrying of vaporized chemical of this composite grain, gasify 2～10 seconds altogether; Obtain clean synthetic gas, and the lime-ash of melting is discharged to vapourizing furnace.
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| CN102154034B (en) * | 2011-03-20 | 2013-08-14 | 中国烟草总公司郑州烟草研究院 | Co-transformation catalytic gasification method for tobacco straw waste and coal |
| CN103074113B (en) * | 2013-02-26 | 2014-05-07 | 昆明理工大学 | Method for preparing gas by using biomass and coal |
| CN103604285B (en) * | 2013-12-02 | 2016-06-29 | 中南林业科技大学 | A kind of biomass wood flour drying system and biomass wood flour drying means |
| CN111471489A (en) * | 2020-04-01 | 2020-07-31 | 华东理工大学 | Method and device for preparing synthesis gas from carbon-containing solid waste |
| CN113698961A (en) * | 2020-05-22 | 2021-11-26 | 中国石油化工股份有限公司 | Method for catalytic gasification by using natural potassium and sodium elements in coal |
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| CN101003754A (en) * | 2006-01-19 | 2007-07-25 | 神华集团有限责任公司 | Entrained flow gasification stove, and gasification method |
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