CN102220150B - Method for preparing high-quality gas by biomass pyrolysis desulphurization and decarbonization - Google Patents
Method for preparing high-quality gas by biomass pyrolysis desulphurization and decarbonization Download PDFInfo
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- CN102220150B CN102220150B CN2011101255292A CN201110125529A CN102220150B CN 102220150 B CN102220150 B CN 102220150B CN 2011101255292 A CN2011101255292 A CN 2011101255292A CN 201110125529 A CN201110125529 A CN 201110125529A CN 102220150 B CN102220150 B CN 102220150B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention relates to a method for preparing high-quality gas by biomass pyrolysis desulphurization and decarbonization, which is characterized by comprising the following steps that: (1) a biomass material and calcium oxide are added indo a jacketed pyrolyzer according to proportion to carry out biomass pyrolysis, tar catalytic pyrolysis and calcium oxide CO2 absorption reaction; (2) a pipeline passed by a gas phase product produced by pyrolysis penetrates through a combustor, and the gas phase product is indirectly heated under the temperature of 900-1,000 DEG C, and tar is further subject to pyrolysis, so that the high-quality gas can be obtained; (3) carbon residues and carbonic acid calcium which are produced by the pyrolysis are transmitted into the combustor through a transmitting device, and the heat produced by the combustion is used for carbonic acid calcium decomposition; and (4) flue gas produced by the combustion enters into a cyclone separator with regenerated calcium oxide, high-temperature flue gas after gas-solid separation enters the interlayer of the jacketed pyrolyzer to provide heat for the pyrolysis and tar cracking reaction, and the regenerated calcium oxide is transmitted into the jacketed pyrolyzer to be recycled. The method has the advantages that the process is simple, and the high-quality gas with multi purposes can be obtained by continuous operation.
Description
Technical field
The present invention relates to a kind of biomass pyrolytic decoking decarburization and prepare high-quality combustion gas method, belong to biomass thermal chemical conversion field.
Background technology
Than fossil energy, biomass energy has cleaning, environmental protection and characteristics such as renewable, and the utilization of biomass energy will go from bad to worse significant to alleviating the nervous and environment of power supply.It is that the thermal transition of a kind of important biomolecule mass-energy utilizes mode that biomass pyrogenation gasification is produced gas technology, traditional biomass pyrogenation gasification technology, the combustion gas of producing is mainly used in driving the combustion machine and produces power, electric power, perhaps be used for domestic cooking, industrial furnace burning, but these purposes are subjected to by product tar and CO in the biomass pyrolysis process
2Restriction, the existence of tar not only reduces pyrolysis efficient, and serious to equipment damage, and CO
2Existence will reduce the energy density of gas products, and can increase the energy consumption of its subsequent disposal, also cause process economy to be difficult to traditional fuel gas competition simultaneously.Combustion gas high-quality, that composition is desirable is produced in directional thermal decomposition gasification decoking decarburization by biomass, and the economy that improves the pyrolytic gasification process is the development trend in this field.
Biomass pyrogenation gasification is produced pyrolytic gasification process need high temperature in the gas technology, and removing of by product tar also needs high-temperature catalytics more, existing most of technology adopts electrically heated or other thermals source that heat is provided, as the endogenous pyrogen of the high-temperature flue gas (up to 2000 ℃) behind patent " a kind of biomass high temperature pyrolysis and gasification and high temperature pyrolysis gas catalytic purification system " (200810137286) employing liquefied petroleum gas (LPG) or the Sweet natural gas high-temperature and low-oxygen combustion as pyrolysis oven, pyrolysis artifact matter pyrolysis gas institute tar content is few, and the pyrolysis temperature degree of pyrolysis oven outlet reaches 1200 ℃, sprays into ground dolomite and carry out catalytic pyrolysis and further reduce tar in cat cracker.On technology, a large amount of external heat sources have lost whole energy utilization efficiency, have reduced the economy of technology.The removal method of tar has mechanical means, method such as catalytic pyrolysis and thermo-cracking, wherein to remove the tar method be the domestic and international more technology of research to catalytic pyrolysis, patent " a kind of biological matter pyrolysis gasifying detarring catalyst and preparation method thereof " (CN 100434162C) invented a kind of by the rhombspar attapulgite clay through pulverizing, particulate state or column or ring-type catalyzer that moulding and activation obtain, the tar clearance reaches more than 90%, the effect of catalytic pyrolysis is fine, but this method is with the same easy inactivation of catalyzer that all is faced with of other catalytic cracking methods, problems such as life-span weak point and cost height.The heating gas partial combustion that patent " a kind of removing biomass pyrolytic gasifying tar oil method and device " (CN 1821346A) utilizes oxygen and gasification/pyrolysis oven to come out provides pyrolysis fuel oil required heat, and coke tar cracking is micromolecular hydrocarbon polymer and H in the extremely short time
2, CO, CH
4Deng, tar content significantly reduces.This method has been avoided the easy inactivation of catalyzer and the high problem of cost, but the higher economy that reduces system of oxygen preparation expense.Simultaneously, CO in the combustion gas of traditional biological matter pyrolytic gasification technology acquisition
2Content higher, CO in the synthetic gas that obtains as patent " the distributed oxygen-rich gasification of a kind of biomass prepares the method and apparatus of synthetic gas " (CN 101164866A)
2Content reach about 20% a large amount of CO
2Existence reduced the energy density of gas products, and can increase the energy consumption of its subsequent disposal.
In sum, existing gasifying biomass pyrolysis gas producing technology also exists certain deficiency in some aspects, and the economy of technology also need improve.Further explore and in biomass pyrolytic, realize the autothermal energy supply and realize tar and CO simultaneously
2Remove, form the processing method of better economy, will be conducive to improve energy utilization efficiency, obtain high-quality combustion gas, further promote the development of biomass energy utilization technologies.
Summary of the invention
The objective of the invention is to adopt self-heating biomass pyrolysis and calcium oxide decoking decarburization technique, in pyrolysis, realize tar and CO
2Remove, obtain high-quality in calorific value gas.
The present invention can be used for setting, dwarf thicket, shrub, non-wooden cane and seasonal growing plant etc. are main agriculture and forestry organic waste material biomass material, and is applied widely.Its process characteristic is biomass pyrolytic, CO
2Absorb and catalytic cracking of tar etc. is reflected at carries out in the same process, and the calcium oxide absorption agent absorbs the CO of generation synchronously
2And promote the tar catalyzed conversion, can effectively reduce the coal-tar middle oil and CO of combustion gas of acquisition
2Content, not only eliminated tar to the infringement of equipment and the pollution of environment, and improved efficiency gas in the follow-up use of pyrolysis gas greatly, this technology can be obtained the different combustion gas of component with the ratio of calcium oxide by regulating biomass simultaneously, be applicable to alcohol ether synthetic with different purposes such as fuel cell, the what is more important system can carry out self-heated pyrolysis, need not external heat source.
A kind of biomass pyrolytic decoking decarburization prepares the method for high-quality combustion gas, it is characterized in that it is made up of following steps: (1) with biomass material and calcium oxide according to 1:(0.2～1) ratio add in the jacketed type pyrolyzer, carry out biomass pyrolytic, catalytic cracking of tar and calcium oxide at 600～750 ℃ and absorb CO
2Reaction; (2) pipeline of the gas-phase product process that produces of pyrolysis runs through the combustion chamber, under 900～1000 ℃ of temperature by indirect heating, the further cracking of tar, thus obtain high-quality combustion gas; (3) carbon residue and the calcium carbonate of pyrolysis generation are delivered to combustion chambers burn by e Foerderanlage, and the heat that burning produces decomposes for calcium carbonate; (4) flue gas that produces of the burning calcium oxide that carries regeneration enters cyclonic separator, high-temperature flue gas after the gas solid separation enters jacketed type pyrolyzer interlayer and provides heat for the reaction of pyrolysis and coke tar cracking, and the calcium oxide of regeneration is then carried back the recycle of jacketed type pyrolyzer.
The concrete characteristics of this programme also have, and biomass, carbon residue, calcium oxide and calcium carbonate are all carried by helical twist cage, have increased the stability of systemic circulation.The combustion chamber is pulled out the whistle by the cylindrical burner hearth in top and bottom and is formed, and the two flange connects, and pulls out whistle structure and sees accompanying drawing 2, and this chamber structure is conducive to the burning of carbon residue and biomass powder.Flue gas is drawn by induced draft fan on the top, combustion chamber, and the bottom adopts gas blower to blast air, and the two combines to make and keeps in the combustion chamber 10 not having pressing or the minute-pressure state, and it is stable reinforced to be conducive to carbon residue strand cage.The chuck outer wall of inner tube of jacketed type pyrolyzer increases fin and is conducive to enhance heat transfer.
Self-heating biomass pyrolysis decoking decarburization of the present invention prepares high-quality combustion gas method and may further comprise the steps: (1) biomass powder material and quality are admitted to pyrolyzer for its lime powder of 0.2～1 times by doser, under 600～750 ℃ of temperature condition, biomass generation thermo-cracking and partial gasification reaction, the cracking under the katalysis of calcium oxide and calcium carbonate of by product tar, CO
2The CaO that then is added into absorbs and solidifies, and the heat of pyrolysis reactor is provided by the heat that carbonation reaction and the burning of pyrolysis carbon residue discharge.The principal reaction that takes place in the pyrolyzer is as follows:
CaO and CO
2Carbonation reaction be thermopositive reaction, can reduce the process heat of pyrolysis input; And CO
2Minimizing each reaction is carried out towards micromolecular directions such as generating hydrogen, the gas volume productive rate is reduced reduces sensible heat loss; The minimizing of tar has improved the effective transformation efficiency of biomass, has reduced hazardness; Therefore the Energy efficiency of whole technology improves greatly, and the combustion gas quality of acquisition significantly promotes.
(2) pyrolysis product that produces in the pyrolyzer carries out gas solid separation in separator, gas after the separation connects heating through the combustion chamber high temperature interval, contained tar generation second pyrolysis, the high-quality combustion gas that finally obtains are drawn to collect by vacuum pump and are utilized, and carbon residue and CaCO
3Falling into carbon residue collects.
(3) carbon residue and CaCO
3Send into the combustion chamber by the strand cage, in combustion chamber carbon residue and air generation combustion reactions, the heat that burning discharges is supplied with calcium carbonate and is decomposed required heat.The temperature of combustion chamber can reach between 900-1000 ℃, and calcium carbonate decomposes the generation calcium oxide under this temperature condition;
(4) calcium oxide of combustion heat flue gas and regeneration enters cyclonic separator and separates, and CaO is as CO
2Receptor send back to pyrolysis reactor again, and hot flue gas enters the chuck of pyrolysis reactor and heats, and guarantees pyrolyzer internal reaction institute heat requirement.(5) total system can realize self-heated pyrolysis under the good situation of insulation, if system's thermosteresis is too much, can replenishes a part of biological material and enter combustion chambers burn institute's heat requirement is provided.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention adopts the mode of the heat release of calcium oxide absorption reaction and by product carbon residue combustion product gases heating pyrolyzer can keep higher and stable pyrolyzer temperature, and system can self-heating move, thereby has improved system's heat utilization efficiency, has reduced running cost.
2, the present invention adopts calcium oxide cheap and easy to get as absorption agent, and calcium oxide can further reduce production costs by absorbing and the recycle of regeneration integrated technique.
3, the present invention adopts calcium oxide to absorb the CO that pyrolysis produces synchronously
2, be conducive in the pyrolyzer W-response to producing H
2, CO and CH
4Carry out etc. micromolecular direction, improved the energy density of combustion gas.
4, the present invention has realized the decoking decarburization simultaneously, reduces the content of the coal-tar middle oil and CO2 of product combustion gas.Obtain CO in the product gas with other biological matter pyrolytic gasification technology
2Volume content is compared up to 28%, CO in present method product gas
2Volume content can reach 3.5%, CO
2Specific absorption is more than 80%, and tar content is at 45 mg/Nm
3Below, can satisfy the requirement that equipment is used in most of combustion gas, therefore, the present invention not only can eliminate tar to the infringement of equipment and the pollution of environment, and has improved the combustion gas quality greatly.
5, the present invention adopts the means of adjusting biomass and calcium oxide ratio can realize component ratio in the pyrolysis aerogenesis, be applicable to alcohol ether synthetic with different purposes such as fuel cell.
Description of drawings
Fig. 1 is reaction process synoptic diagram of the present invention; Among the figure: 1-doser, 2-induced draft fan, 3-jacketed type pyrolyzer, 4-fly-ash separator, 5-carbon residue collector, 6-carbon residue strand cage, 7-vacuum pump, 8-gas outlet, 9-gas blower, 10-combustion chamber, 11-ash discharging hole, 12-cyclonic separator, 13-calcium oxide strand cage.Fig. 2 pulls out whistle synoptic diagram; Among the figure: 14-air intlet pipe, 15-pipe hole, 16-air distribution plate, 17-flange.
Embodiment
Embodiment 1
Be raw material (water content 10%) with the wood chip powder about 50 orders, at first the lime powder (about 100 orders) with 0.7 times of quality mixes, mix the back and add jacketed type pyrolyzer 3 by doser 1, biomass pyrolytic, calcium oxide absorb CO under 600-700 ℃ of condition
2Carried out 10-20 minute with the catalytic tar scission reaction is collaborative; Separate by fly-ash separator 4 with solid matters such as pyrolysis carbon residue and calcium carbonate at jacketed type pyrolyzer 3 afterbody pyrolysis gas and to purify, then through 10 high-temperature zones, combustion chamber, tar macromole in the pyrolysis gas carries out second pyrolysis at 900-1000 ℃, and the gas tar oil content that obtains is at 40 mg/Nm
3Below, each volume concentration of gas phase approximate range is H
241%, CH
427%, CO 16%, CO
23.5%, fuel gases calorific value reaches 17MJ/Nm
3The high-quality combustion gas that obtains is finally drawn to collect by vacuum pump 7 and is utilized.
Fall into carbon residue collector 5 at solid matters such as jacketed type pyrolyzer 3 afterbody pyrolysis carbon residues and calcium carbonate, be delivered in the combustion chamber 10 by carbon residue strand cage 6; In combustion chamber 10, carbon residue produces the high temperature that can reach more than 900 ℃ with the air mixed burning of being introduced by induced draft fan 2 and gas blower 9, and calcium carbonate is decomposed into calcium oxide under this temperature; Ash content after the calcium oxide of regeneration and the burning enters cyclonic separator 12 with high-temperature flue gas, and the flue gas after the separation enters the pyrolyzer interlayer and supplies with the required heat of pyrolysis, then draws discharging by induced draft fan 2; The calcium oxide that falls in the cyclonic separator 12 and ash content are delivered to 3 recycles of jacketed type pyrolyzer by calcium oxide strand cage 13; Along with the increase of cycle index, the amount of the calcium oxide of ash content and inefficacy constantly increases in the system, then can be by ash discharging hole 11 part of draining, thus reach the steady running of system.
Embodiment 2
The lime powder (about 100 orders) of the wood dust about 50 orders (water content 10%) and 0.5 times of quality mixes the adding pyrolyzer, other step and embodiment 1 identical repeating no more, and the gas tar oil amount that obtains is at 40 mg/Nm
3Below, each volume concentration of gas phase approximate range is H
238%, CH
428%, CO 20%, CO
24.5%, fuel gases calorific value reaches 17.3MJ/Nm
3
Embodiment 3
The lime powder (about 100 orders) of the powdered rice hulls about 80 orders (water content 11%) and 0.3 times of quality mixes the adding pyrolyzer, other step and embodiment 1 identical repeating no more, and the gas tar oil amount that obtains is at 45 mg/Nm
3Below, each volume concentration of gas phase approximate range is H
230%, CH
427%, CO 25%, CO
26.5%, fuel gases calorific value reaches 16.9MJ/Nm
3
Claims (4)
1. a biomass pyrolytic decoking decarburization prepares the method for high-quality combustion gas, it is characterized in that it is made up of following steps: the wood chip powder with 50 order water content 10% is raw material, at first mix with 0.7 times of quality, 100 purpose lime powders, mix the back and add the jacketed type pyrolyzer by doser, biomass pyrolytic, calcium oxide absorb CO under 600-700 ℃ of condition
2Carried out 10-20 minute with the catalytic tar scission reaction is collaborative; Separate by fly-ash separator with the calcium carbonate solid matter with the pyrolysis carbon residue at jacketed type pyrolyzer afterbody pyrolysis gas and to purify, pass through the combustion chamber high temperature district then, tar macromole in the pyrolysis gas carries out second pyrolysis at 900-1000 ℃, and the gas tar oil content that obtains is at 40 mg/Nm
3Below, each volume concentration of gas phase scope is H
241%, CH
427%, CO 16%, CO
23.5%, fuel gases calorific value reaches 17MJ/Nm
3The high-quality combustion gas that obtains is finally drawn to collect by vacuum pump and is utilized;
Fall into the carbon residue collector at jacketed type pyrolyzer afterbody pyrolysis carbon residue and calcium carbonate solid matter, be delivered in the combustion chamber by carbon residue strand cage; In the combustion chamber, carbon residue produces the high temperature that can reach more than 900 ℃ with the air mixed burning of being introduced by induced draft fan and gas blower, and calcium carbonate is decomposed into calcium oxide under this temperature; Ash content after the calcium oxide of regeneration and the burning enters cyclonic separator with high-temperature flue gas, and the flue gas after the separation enters the pyrolyzer interlayer and supplies with the required heat of pyrolysis, then draws discharging by induced draft fan; The calcium oxide that falls in the cyclonic separator and ash content are delivered to the recycle of jacketed type pyrolyzer by calcium oxide strand cage; Along with the increase of cycle index, the amount of the calcium oxide of ash content and inefficacy constantly increases in the system, by the ash discharging hole part of draining, thereby reaches the steady running of system.
2. biomass pyrolytic decoking decarburization as claimed in claim 1 prepares the method for high-quality combustion gas, it is characterized in that the combustion chamber pulls out the whistle by the cylindrical burner hearth in top and bottom and form, and the two flange connects.
3. biomass pyrolytic decoking decarburization as claimed in claim 1 prepares the method for high-quality combustion gas, it is characterized in that being drawn by induced draft fan at top, combustion chamber flue gas, and the bottom adopts gas blower to blast air, and the two combines to make and keeps in the combustion chamber not having pressing or the minute-pressure state.
4. biomass pyrolytic decoking decarburization as claimed in claim 1 prepares the method for high-quality combustion gas, it is characterized in that the chuck outer wall of inner tube of jacketed type pyrolyzer increases fin.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106047385A (en) * | 2016-07-20 | 2016-10-26 | 昆明理工大学 | Ammonium polyphosphate microcapsule and boric acid added biomass pyrolysis process |
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| CN106947510A (en) * | 2017-04-28 | 2017-07-14 | 神雾科技集团股份有限公司 | The system and method that a kind of biomass graded sub-prime is utilized |
| CN109140427A (en) * | 2018-09-30 | 2019-01-04 | 西安鑫顶天装备智能科技有限公司 | A kind of combustion gas fission device |
| CN109603841B (en) * | 2019-01-15 | 2019-10-25 | 武汉轻工大学 | A kind of decoking denitrating catalyst and its preparation method and application |
| CN113477239A (en) * | 2021-06-18 | 2021-10-08 | 华中科技大学 | Method for reforming volatile components by using high-calcium solid waste based CaO and product thereof |
| CN113477238B (en) * | 2021-06-18 | 2023-02-24 | 华中科技大学 | Organic acid modified CaO catalyst, and preparation method and application thereof |
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