CN208917131U - A kind of directional catalyzing cracker - Google Patents
A kind of directional catalyzing cracker Download PDFInfo
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- CN208917131U CN208917131U CN201821422638.4U CN201821422638U CN208917131U CN 208917131 U CN208917131 U CN 208917131U CN 201821422638 U CN201821422638 U CN 201821422638U CN 208917131 U CN208917131 U CN 208917131U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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
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Abstract
A kind of directional catalyzing cracker, reaction atmosphere in the reaction tube of upper section furnace, which tiles by first gas distributor to catalyst bed, carries out the activation of reaction gas, reaction atmosphere is under the action of catalyst, it generates free radicals, free radical is contacted with the free radical that the raw material pyrolysis in raw material bed generates, obtained gaseous products tile by third gas distributor to catalyst A bed, catalyst A bed carries out catalytic pyrolysis to the gaseous products of pyrolytic reaction, product after catalytic pyrolysis enters catalyst B bed and carries out shape selective catalysis, product after shape selective catalysis enters condensing unit and is condensed, obtained tar liquid.The raw materials such as coal, biomass are pyrolyzed to improve tar yield process and orient corresponding product distributed process and be integrated into a set of technique by the utility model, simplify integrated artistic process, it is environmentally friendly, reduce Energy Consumption Cost, improve production efficiency, and it is easy to mass production scale, it is suitable for industrial application.
Description
Technical field
The utility model belongs to field of energy and chemical technology, is related to a kind of directional catalyzing cracker.
Background technique
Pyrolysis of coal is the committed step of coal trans-utilization, the technical process such as burning of coal, gasification, liquefaction will occur or
Undergo pyrolytic process.But coal tar low yield, heavy components content height, and heavy group again that traditional pyrolysis of coal obtains
Point have the characteristics that higher boiling, high viscosity, separation are difficult, in target product all kinds of products distributions in a jumble and also relative amount compared with
It is low, therefore all kinds of products cannot be effectively enriched with.
Biomass is mainly made of cellulose, hemicellulose, lignin etc., and pyrolysis is also biomass thermal chiral process
In most basic process, be the synthesis of its liquefaction, gasification and combustion process, due to three big cellulose contents in different biomass materials
Difference, so there are larger difference, Bu Nengjin for the content for the bio oil that biomass pyrolysis process generates, ingredient and product distribution
Row effectively further directly utilizes.
Therefore, the pyrolytic tars yields such as coal, biomass, orientation regulation tar product distribution, so that target tar produces are improved
The upgrading of article matter, generating has high added value tar product, to the efficient of China's coal chemical industry, Biochemical Industry and national energy
Using with important and profound significance.
Pyrolysis of coal acquisition tar yield is low, is limited by low hydrogen-carbon ratio in coal.During pyrolysis of coal, dividing greatly in texture of coal
The continuous depolymerization of minor structure, the macromolecular radical being variously formulated, hydroperoxyl radical etc..Studies have shown that burnt during pyrolysis of coal
The formation of oil is related by thermal cracking and the cracking stabilization of free radical with organic macromolecule in coal.Excessive cracking is possible to will form
The combination of gaseous product, free radical and small molecule is likely to form tar, and the combination between free radical is likely to form tar,
Macromolecular may be re-formed to exist in the form of solid semicoke.Therefore, during pyrolysis of coal, hydrogen-rich is applied by outside
Small molecule free radical, so that the free radical that coal cracking generates is stablized, it is the effective way for improving tar yield.
High hydrogen price, so that the raw materials such as coal, biomass pass through hydropyrolysis, to improve the pyrolysis coke of corresponding raw material
Yield and the quality cost with higher of oil, constrain their practicability.Methane is the main component of natural gas, and source is wide
It is general, possess high hydrogen-to-carbon ratio, and cheap, be ideal hydrogen-rich gas, therefore can be using methane as coal, life
The reaction atmosphere of the raw materials such as substance pyrolysis.But the study found that 800 DEG C hereinafter, methane does not react substantially with coal, first
Alkane is equivalent to inert atmosphere in pyrolytic process, can not improve coal tar oil yield because methane under the conditions of non-catalytic very
Stablize and is difficult to activate.
Pyrolysis of coal forms tar product, and heavy components content is higher, and oxygenatedchemicals is more, so tar low quality.
Therefore regulation is oriented to pyrolysis of coal tar, then can get higher yields has high added value target product.
Currently, improve coal, the raw materials pyrolytic tar yield such as biomass and to the raw materials pyrolytic tar product such as coal, biomass into
Row orientation regulation, generally all carries out in two sets independent systems respectively, result in this way integrated artistic complication, energy consumption at
This height, the problems such as product utilization rate is low, production efficiency is low.Using both ends formula fixed bed, the raw materials such as coal, biomass heat is improved
While solving tar yield, shape selective catalysis can be also carried out to the raw materials pyrolytic tar product such as coal, biomass, and then it is burnt to orient regulation
The device and method of oil product are but rarely reported.
Utility model content
In order to overcome the problems of the above-mentioned prior art, the purpose of this utility model is to provide a kind of directional catalyzings
Cracker while can be improved the raw materials pyrolytic tar products collection efficiency such as coal, biomass, can also orient regulation coal, biology
The distribution of the raw materials pyrolytic tar product such as matter, to obtain the dreamboat tar product with high added value.
To achieve the goals above, used technical solution is as follows for the utility model:
A kind of directional catalyzing cracker, including feeder, for improve pyrolysis of coal reaction tar yield upper section furnace,
For carrying out the lower section furnace and temperature and pressure control device that type is selected in catalysis to pyrolytic tar；Upper section furnace and lower section furnace are
Cylindrical body, and two sections of upper section furnaces and lower section furnace are coaxial up and down, and center vertical is provided with reaction tube in upper section furnace and lower section furnace；For
Device of air is connected with upper section furnace, and feeder, upper section furnace and lower section furnace are connected with temperature and pressure control device.
The utility model, which further improves, to be, feeder includes the first carrier gas bottle, the second carrier gas bottle, third carrier gas
It bottle, the first carrier gas flux control valve, the second carrier gas flux control valve, third carrier gas flux control valve, mixed gas tank and is used for
Regulate and control the total carrier gas flux controller of system of the total flow of reaction gas；Outlet the first carrier gas flux control valve of first carrier gas bottle
It is connected with mixed gas tank entrance, outlet the second carrier gas flux control valve of the second carrier gas bottle is connected with mixed gas tank entrance, the
The outlet of three carrier gas bottles is connected through third carrier gas flux control valve with mixed gas tank entrance, and mixed gas tank is exported through the total carrier gas of system
Flow controller is connected with upper section furnace entrance.
The utility model, which further improves, to be, temperature and pressure control device is controlled including the first carrier gas flux
Device, the second carrier gas flux controller, third carrier gas flux controller, upper section furnace middle portion temperature controller, upper section furnace upper temp
Controller, upper section furnace temperature of lower controller, lower section furnace middle portion temperature controller, lower section furnace upper temp controller and lower section
Furnace temperature of lower controller；First carrier gas flux controller is connected with the first carrier gas flux control valve, the control of the second carrier gas flux
Device is connected with the second carrier gas flux control valve, and third carrier gas flux controller is connected with third carrier gas flux control valve；Upper section furnace
The outer position of upper, middle and lower three of furnace body, be separately connected signal wire temperature in the middle part of the upper section furnace into temperature and pressure control device
Spend controller, upper section furnace upper temp controller, upper section furnace temperature of lower controller, the outer upper, middle and lower three of the furnace body of lower section furnace
Position is separately connected signal wire to lower section furnace middle portion temperature controller, lower section furnace upper temp controller, lower section furnace temperature of lower
Controller.
The utility model, which further improves, to be, in the reaction tube in upper section furnace, from top to bottom equipped with gas distributor,
Catalyst bed, the first solids distribution device, raw material bed, the second solids distribution device and second gas distributor；Wherein, gas
For distributor for making reaction gas uniformly be distributed in catalyst bed, catalyst bed is used for activating reaction gas, the first solid point
Cloth device and the second solids distribution device are respectively used to tiling catalyst bed and raw material bed, and second gas distributor is for making to be pyrolyzed
Gaseous product stream after reaction is into the reaction tube of lower section furnace.
The utility model, which further improves, to be, in the reaction tube in lower section furnace, from top to bottom equipped with third gas point
Cloth device, catalyst A bed, third solids distribution device, catalyst B bed, the 4th solids distribution device and the 4th gas distributor；
Wherein, third gas distributor for the gaseous product distribution after making pyrolytic reaction in catalyst A bed, use by catalyst A bed
In the gaseous products of catalytic pyrolysis pyrolytic reaction, third solids distribution device and the 4th solids distribution device are respectively used to tiling catalyst
A bed and catalyst B bed, the 4th gas distributor are used to that the gaseous products after reaction to be made to flow to condensing unit.
The utility model, which further improves, to be, further includes the cooling device being arranged in below lower section furnace.
The utility model, which further improves, to be, cooling device includes spiral condensing unit, circulating condensing liquid conveying
Pump, tar collector, gas collector and product detection device；It is provided with spiral condensing unit below lower section furnace,
And spiral condensing unit entrance is connected with lower section outlet of still, and spiral condensing unit outlet is divided into two-way, all the way through gas
Body product reservoir is connected with phase chromatograph-mass spectrometer, is provided with secondary liquid condensed product storage tank below gaseous product storage tank,
And secondary liquid condensed product storage tank is connected with gaseous product storage tank, and another way is through tar collector and product detection device
It is connected.
The utility model, which further improves, to be, spiral condensing unit is also connected with circulating condensing liquid delivery pump.
The utility model, which further improves, to be, the reaction tube inlet in upper section furnace is also connected with plunger pump.
Compared with prior art, the utility model has the following beneficial effects:
The utility model is by setting feeder, the upper section furnace for improving pyrolysis of coal reaction tar yield and is used for
Catalysis is carried out to pyrolytic tar and selects the lower section furnace of type, between reaction gas needed for can reasonably regulating and controlling reaction, between reaction solution,
Or the charge proportion between reaction gas and reaction solution, so that feeding manner is not influenced by sample introduction sample form, input mode
Flexibly, operating condition is mild, and equipment investment is smaller.Compared to the N of same condition2Or the tar yield under inert atmosphere, the dress
Set the yield that can significantly improve the raw materials pyrolytic tar product such as coal, biomass, and greatly improve oil quality.
Further, due in the reaction tube in upper section furnace, from top to bottom equipped with gas distributor, catalyst bed, the
One solids distribution device, raw material bed, the second solids distribution device and second gas distributor, in the reaction tube in lower section furnace, from
Third gas distributor, catalyst A bed, third solids distribution device, catalyst B bed, the 4th solids distribution are housed up to lower
Device and the 4th gas distributor, so the distribution of the raw materials pyrolytic tar products such as regulation coal, biomass can be effectively directed.
Original sample coal passes through the process unit and method, and the light aromatics relative amount such as BTXN (benzene,toluene,xylene, naphthalene) is big in product
Width increases；Biomass passes through the process unit and method, and the relative amounts increment such as PCX (phenol, cresols, xylenol) is aobvious in product
Write, it is seen that the present apparatus can the target product to these high added values be effectively enriched with.
The raw materials such as coal, biomass are pyrolyzed by the utility model improves tar yield process and the corresponding product point of orientation regulation
Cloth process conformity simplifies integrated artistic process into a set of technique, environmentally friendly, reduces Energy Consumption Cost, improves
Production efficiency, and it is easy to mass production scale, it is suitable for industrial application.Pass through the pyrolysis such as orientation regulation coal, biomass
The distribution of tar product improves the temperature, pressure and orientation goal of regulation and control tar product of products collection efficiency area (fixed bed upper section furnace)
The segmentation Reasonable Regulation And Control of the temperature in distributed area (fixed bed lower section furnace), pressure, so that integrated artistic flexible operation, having preferably
Controllability.
Detailed description of the invention
Fig. 1 is the single unit system structural schematic diagram of the utility model.
Fig. 2 is the structural front view of upper section furnace, lower section furnace.
Fig. 3 is the structure right view of upper section furnace, lower section furnace.
Fig. 4 is spiral condensing unit structural schematic diagram.
Fig. 5 is the total ion chromatogram (N of the pyrolysis of coal gaseous state tar product of embodiment 12For reaction gas).
Fig. 6 is the total ion chromatogram of the pyrolysis of coal gaseous state tar product of embodiment 2.
Fig. 7 is the total ion chromatogram of the pyrolysis of coal gaseous state tar product of embodiment 3.
Fig. 8 is that the corn stover of embodiment 4 is pyrolyzed the total ion chromatogram of gaseous state tar product.
Fig. 9 is that the corn stover of embodiment 5 is pyrolyzed the total ion chromatogram of gaseous state tar product.
Figure 10 is that the corn stover of embodiment 6 is pyrolyzed the total ion chromatogram of gaseous state tar product.
Description of symbols, 1. first carrier gas bottles；2. the second carrier gas bottle；3. third carrier gas bottle；4. the first carrier gas flux control
Valve processed；5. the second carrier gas flux control valve；6. third carrier gas flux control valve；7. mixed gas tank；8. the total carrier gas flux control of system
Device processed；9. upper section furnace；10. lower section furnace；11. reaction tube fixed disassembly device；12. first gas distributor；13. catalyst bed
Layer；14. the first solids distribution device；15. raw material bed；16. the second solids distribution device；17. second gas distributor；18. third
Gas distributor；19. catalyst A bed；20. third solids distribution device；21. catalyst B bed；22. the 4th solids distribution
Device；23. the 4th gas distributor；24. spiral condensing unit；25. circulating condensing liquid delivery pump；26. tar collector；
27. incubator；28. gaseous product storage tank；29. secondary liquid condensed product storage tank；30. product detection device；31. the first carrier gas
Flow controller；32. the second carrier gas flux controller；33. third carrier gas flux controller；34. upper section furnace middle portion temperature controls
Device；35. upper section furnace upper temp controller；36. upper section furnace temperature of lower controller；37. lower section furnace middle portion temperature controller；
38. lower section furnace upper temp controller；39. lower section furnace temperature of lower controller；40. heating tape temperature controller；41. heat preservation
Case temperature controller；42. controller power source master switch；43. upper section furnace and lower section furnace battery main switch；44. incubator, heating
Charged master switch；45. flow controller battery main switch；46. backup temperature controller；47. two sections furnace door handle
Hand；48. spiral condenser pipe；49. plunger pump；50. gaseous products channel；51. condensate outlet；52. condensate liquid import.
Specific embodiment
The embodiments of the present invention are described in detail with reference to the accompanying drawing, utility model is further described, these
Embodiment is only exemplary explanation the utility model, and be should not be understood as limiting the present invention.
Referring to Fig. 1, a kind of directional catalyzing cracker of the utility model includes feeder, anti-for improving pyrolysis of coal
It answers the upper section furnace 9 of tar yield, the lower section furnace 10, condensing unit and temperature and pressure control that type is selected in catalysis is carried out to pyrolytic tar
Device device processed.Wherein, feeder includes the first carrier gas bottle 1, the second carrier gas bottle 2, third carrier gas bottle 3, the first carrier gas flux control
Valve 4 processed, the second carrier gas flux control valve 5, third carrier gas flux control valve 6, for what different proportion reaction gas was uniformly mixed
The total carrier gas flux controller 8 of the system of mixed gas tank 7 and the total flow for regulating and controlling reaction gas；It is equipped with inside mixed gas tank 7
Gas distributor；Outlet the first carrier gas flux control valve 4 of first carrier gas bottle 1 is connected with 7 entrance of mixed gas tank, the second carrier gas
Outlet the second carrier gas flux control valve 5 of bottle 2 is connected with 7 entrance of mixed gas tank, and the outlet of third carrier gas bottle 3 is through third carrier gas
Flow control valve 6 is connected with 7 entrance of mixed gas tank, and the outlet of mixed gas tank 7 is through the total carrier gas flux controller 8 of system and upper section furnace 9
Entrance is connected, and upper section furnace 9 is located at 10 top of lower section furnace；Feeder, upper section furnace 9 and lower section furnace 10 with temperature and pressure control
Device device processed is connected.Cooling device is arranged below lower section furnace 10.
Referring to figs. 2 and 3, be divided into upper, middle and lower inside upper section furnace 9 and lower section furnace 10, top, middle part and
The difference of the bed and catalyst that are arranged in lower part, can control the different reaction temperature in upper, middle and lower accordingly.
Temperature and pressure control device includes the first carrier gas flux controller 31, the second carrier gas flux controller 32, the
Three carrier gas flux controllers 33, upper section furnace middle portion temperature controller 34, upper section furnace upper temp controller 35, upper section furnace lower part temperature
Spend controller 36, lower section furnace middle portion temperature controller 37, lower section furnace upper temp controller 38, lower section furnace temperature of lower controller
39, heating tape temperature controller 40, incubator temperature controller 41, controller power source master switch 42, upper section furnace and lower section furnace electricity
Source master switch 43, incubator, heating tape battery main switch 44, flow controller battery main switch 45 and backup temperature controller
46.First carrier gas flux controller 31 is connected with the first carrier gas flux control valve 4, the second carrier gas flux controller 32 and second
Carrier gas flux control valve 5 is connected, and third carrier gas flux controller 33 is connected with third carrier gas flux control valve 6.
Gas can be CH in first carrier gas bottle 1, the second carrier gas bottle 2 and third carrier gas bottle 34、CO2、CO、O2Etc. high-purity
Gas, reaction process can be individually with CH4For reaction gas, or use CH4It forms with other gases and uniformly mixes in certain proportion
Gas, as reaction gas needed for reaction.The feeder can flexibly regulate and control to be mixed between various reaction gas or reaction gas
Ratio, to improve W-response efficiency.
Referring to figure 1, figure 2 and figure 3, upper section furnace 9 and 10 shape of lower section furnace are cylindrical body of the same size, and on two sections
Section furnace 9 and about 10 lower section furnace are coaxial, are in same plumb line, and center vertical is provided with reaction in upper section furnace 9 and lower section furnace 10
It manages, is provided with two sections furnace door handle 47 on upper section furnace 9 and lower section furnace 10, fire door can pass through two sections furnace door
Handle 47 is the handle in respective furnace body center, opens 0 ° to 180 ° around plumb line, is located at upper section furnace 9 and lower section furnace 10 for dismounting
Furnace stay body center reaction tube, reaction tube tube body in upper section furnace 9 and lower section furnace 10 by reaction tube fixed disassembly device 11
It is fixed on furnace body center, raw material bed 15 and catalyst bed 13 etc. needed for reaction tube is provided with reaction.The furnace of upper section furnace 9
The external position of upper, middle and lower three, is separately connected upper section furnace middle portion temperature control of the signal wire into temperature and pressure control device
Device 34 processed, upper section furnace upper temp controller 35, upper section furnace temperature of lower controller 36, are respectively used on real-time monitoring upper section furnace
Portion, middle part, temperature of lower parameter.The outer position of upper, middle and lower three of the furnace body of lower section furnace 10, is separately connected signal wire to lower section furnace
Middle portion temperature controller 37, lower section furnace upper temp controller 38, lower section furnace temperature of lower controller 39, are respectively used to adjust in real time
Control lower section furnace top, middle part, temperature of lower parameter.
In reaction tube in upper section furnace 9, from top to bottom equipped with gas distributor 12, catalyst bed 13, the first solid point
Cloth device 14, raw material bed 15, the second solids distribution device 16 and second gas distributor 17.Wherein, gas distributor 12 can make
Reaction gas is uniformly distributed in catalyst bed 13, and catalyst bed 13 is used for activating reaction gas, 14 He of the first solids distribution device
Second solids distribution device 16, which is respectively used to tiling catalyst bed 13 and raw material bed 15, second gas distributor 17, can make to be pyrolyzed
Gaseous products uniform flow after reaction carries out next step correlated response into the reaction tube of lower section furnace 10.
Upper section furnace 9 is provided with reaction above the reaction tube inlet in upper section furnace 9 for improving raw material pyrolytic tar yield
Conductance tracheae, reaction gas gas-guide tube are connected with plunger pump 49, and reaction gas is for air guide tube needed for the offer reaction into reacting furnace
Reaction gas, plunger pump 49 react required reaction solution, reaction solution CH for providing3OH or naphthane etc., when reaction solution is
CH3When OH, under suitable process conditions, CH3OH is directly pyrolyzed, CH3OH is under oxidant effect, by catalysis
Agent activation and catalytic reforming, CH3OH and excessive water vapor reaction, these reaction process can provide a large amount of hydroperoxyl radical, with
The free radical fragment that pyrolysis of coal generates is combined, and then improves the yield of pyrolysis of coal tar product.
In reaction tube in lower section furnace 10, third gas distributor 18, catalyst A bed 19, third are housed from top to bottom
Solids distribution device 20, catalyst B bed 21, the 4th solids distribution device 22 and the 4th gas distributor 23.Wherein, third gas
Distributor 18 can make the gaseous products after pyrolytic reaction uniformly be distributed in catalyst A bed 19, and catalyst A bed 19 is used for
The gaseous products of catalytic pyrolysis pyrolytic reaction, third solids distribution device 20 and the 4th solids distribution device 22 are respectively used to tiling catalysis
Agent A bed 19 and catalyst B bed 21, the 4th gas distributor 23 can make the gaseous products after reaction, and uniformly flow direction is spiral
Condensing unit 24, is condensed.
Referring to fig. 4, condensing unit includes spiral condensing unit 24, circulating condensing liquid delivery pump 25, tar collector
26 (tar liquid product reservoirs), attemperator 27, gas collector 28, product detection device 30；It is set below lower section furnace 10
It is equipped with spiral condensing unit 24, and spiral 24 entrance of condensing unit is connected with the outlet of lower section furnace 10, it is spiral to condense
Be gaseous products channel 50 in device 24, the spiral outlet of condensing unit 24 is divided into two-way, all the way through gaseous product storage tank 28 with
Product detection device 30 is connected, and gaseous product storage tank 28 is arranged in incubator 27, is provided with two below gaseous product storage tank 28
Secondary liquid condensed product storage tank 29, and secondary liquid condensed product storage tank 29 is connected with gaseous product storage tank 28, secondary liquid
Condensed product storage tank 29 is arranged outside incubator 27, and another way is connected through tar collector 26 with product detection device 30.
In addition, spiral condensing unit 24 is also connected with circulating condensing liquid delivery pump 25；Condensation is provided on spiral condensing unit 24
Liquid outlet 51 and condensate liquid import 52.
Referring to Fig. 1 and Fig. 4, the condensate liquid in spiral condensing unit 24 recycle by circulating condensing liquid delivery pump 25 defeated
It send, condenser pipe in spiral condensing unit 24, helically formula rises shape, spiral cold around the transfer pipeline of gaseous products
Solidifying pipe both enhances condensation effect, in turn simplifies device preparation, reduces costs, embody preferable economy.
Through the condensed liquid tar of spiral condensing unit 24, it is collected into tar collector 26, it is uncooled
Or uncondensable gaseous products enter gaseous product storage tank 28, and to be connected to secondary liquid downwards cold for gaseous product storage tank 28
Solidifying product reservoir 29, for collecting the tar product of time condensation.The outside of gaseous product storage tank 28 is equipped with incubator 27, is used for
The injector temperature regulation of product detection device 30 is provided.
Reaction gas in the utility model is directly with CH4For reaction gas, or the CH mixed with certain volume ratio4And CO2It is mixed
Conjunction gas is reaction gas, or with CH4It is reaction gas with excessive vapor, or with CH4With small amounts agent O2For reaction gas, specifically such as
Under:
Specifically, the reaction gas in the utility model can be directly with CH4For reaction gas, the catalyst for being passed through upper section bed is living
Change bed 13, under the effect of the catalyst further activation, the CH after activation4Reaction gas generate hydroperoxyl radical, methylene from
By base and methyl free radicals etc. with CH4The air-flow of reaction gas passes through the bed for the gaseous state tar that the raw materials such as coal, biomass are pyrolyzed
Layer, the free radical fragment generated with raw material pyrolysis are contacted, and the steady rate and efficiency of free radical are improved, to improve
The raw materials pyrolytic tar yield such as coal, biomass.
Reaction gas in the utility model can be with (1~2): the CH of 1 volume ratio mixing4And CO2Gaseous mixture be anti-
Atmosphere is answered, so that CH4And CO2Catalytic reforming occurs and generates hydrogen-rich free radical component, is generated with raw materials pyrolysis such as coal, biomass
Free radical fragment is contacted, and stablizes the free radical fragment that pyrolysis of coal generates in time, and then improve the pyrolysis of the raw materials such as coal, biomass
The yield of tar.
Reaction gas in the utility model is with CH4It is reaction atmosphere with excessive vapor, methane and vapor reaction are made
Carbon monoxide and hydrogen, carbon monoxide and vapor further reacts and obtains carbon dioxide and hydrogen, the process of these reactions
The middle free radical intermediate for generating a large amount of hydrogen-rich, the free radical fragment that the pyrolysis of the raw materials such as these free bodies and coal, biomass generates
In conjunction with the raw materials pyrolytic tar yield such as raising coal, biomass.Wherein, CH4Percent by volume is pressed with the gaseous mixture of excessive vapor
Meter, CH4It is 10%~20%, vapor is 80%~90%.
Reaction gas in the utility model is with CH4With small amounts agent O2For reaction atmosphere, portion of methane is by catalysis oxidation
Hydrogen-rich component can be generated, the free radical fragment that the pyrolysis of the raw materials such as coal, biomass generates further is stabilized, improves corresponding tar
Yield.Wherein, CH4With small amounts agent O2Gaseous mixture press volume percentage, CH4It is 80%~90%, oxidant O2For
10%~20%.
The utility model can using dissociated methanol gas as reaction atmosphere, can also with dissociated methanol gas and oxygen collectively as
Reaction atmosphere, can also (methanol be liquid, is entered in upper section furnace by plunger pump 49, is pyrolyzed as gas, into one with dissociated methanol gas
Step with corresponding reaction gas mixing, reacted as reaction atmosphere with raw material) and vapor collectively as reaction atmosphere, specifically
It is as follows:
Directly using methanol as reaction solution, pre- thermalization processing is carried out by upper section furnace, reaction temperature is heated to, by catalyst
After bed 13 activates, generate free radical fragment that a large amount of hydroperoxyl radical is timely generated with the raw materials pyrolysis such as coal, biomass into
Row contact and combination, can effectively improve the raw materials pyrolytic tar yield such as coal, biomass.
The reaction solution methanol can carry out partial oxidation reaction with oxygen, carry out catalysis weight by catalyst bed 13
Whole reaction forms hydrogen, and the hydroperoxyl radical in reaction process can be generated free radicals with raw materials pyrolysis such as coal, biomass and be tied
It closes, and the reaction is exothermic reaction, can provide heat for pyrolytic reaction, reduces the cost of process flow, while effectively
Improve the yield of raw material pyrolytic tar product.
Ratio between the reaction solution methanol and oxygen are as follows: enter the substance of the methanol and oxygen in upper section furnace 9
Amount ratio be (2~5): 1.
The reaction solution methanol can be reacted with vapor, carry out catalytic reforming reaction by catalyst bed 13
Form hydrogen, form a large amount of hydrogen free bodies in reforming process, the classes of compounds fragment that can be formed with raw material thermal decomposition product into
Row combines, and improves pyrolytic tar products collection efficiency.
Ratio between the reaction solution methanol and vapor are as follows: the ratio of the amount of the substance of methanol and vapor be (1~
1.5): 1.
The substantially process flow of the utility model is: with CH4Or CH4It is formed in certain proportion with other gases uniformly
For gaseous mixture is as reaction atmosphere, by CH4Or CH4Homogeneous mixture is formed in certain proportion with other gases, as anti-
Answer required reaction gas, be adjusted to suitable flow and enter upper section furnace 9, by first gas distributor 12 uniformly tiling to urging
Agent bed 13 carries out the activation of reaction gas, activation temperature (i.e. upper section reaction in furnace pipe upper temp) are as follows: and 600 DEG C~800 DEG C,
Reaction pressure is 0.1MPa~1MPa.CH4In catalyst, (catalyst includes: the catalysis of carried metal, alkali metal, transition metal
Any one in agent, catalyst carrier include molecular sieve, oxide, semicoke etc. any one) under effect, generate methyl or Asia
The free radicals such as methyl, these free radicals in raw material bed 15 coal or the free radical that generates of the raw materials pyrolysis such as biomass contact,
The steady rate and efficiency of free radical can be improved, to improve the raw materials pyrolytic tar yield such as coal, biomass.Either by anti-
Answer liquid CH3OH pyrolysis, CH3OH and oxidizer catalytic reformation, CH3OH is reacted with vapor, which can equally provide largely
Hydroperoxyl radical, the free radical fragment generated with raw materials pyrolysis such as coal, biomass is combined, and then is improved raw material pyrolytic tar and produced
The yield of object.Obtained gaseous products uniformly tile by third gas distributor 18 to catalyst A bed 19, catalyst A
Bed 19 carries out catalytic pyrolysis to the gaseous products of pyrolytic reaction, and the product after catalytic pyrolysis is carried out into catalyst B bed 21
Further shape selective catalysis orients regulation product, and then obtains ideal target product, and the product after shape selective catalysis enters condensation
Device is condensed, and obtained tar liquid is collected in tar collector 26, and gaseous products then enter gaseous product storage tank
28, the tar liquid and gaseous products collected are sent into product detection device 30 and carry out on-line real-time measuremen analysis, product inspection
It surveys result and timely feedbacks the related process parameters given temperature and pressure control device, and then adjust each process section in real time, realize
The optimization of technological parameter.Wherein, when raw material is coal, target product is benzene,toluene,xylene and naphthalene；When raw material is biomass,
Target product is phenol, cresols, xylenol.
Catalyst packet for the mixture that priming reaction liquid or priming reaction liquid and reaction gas are mixed in a certain proportion
It includes: Cu/CeO2、CuO/CeO2、Cu/ZnO/ZrO2、Cu/ZnO/Al2O3Equal Cu series catalysts；Ni/CeO2、Ni/CeO2-ZrO2Deng
Ni series catalysts；And Pd/ZnO, Pd/La2O3、Pd/SiO2、Pd/ZrO2Equal noble metals series catalysts.
The mixture that reaction solution or reaction solution and reaction gas are mixed in a certain proportion, carries out by catalyst bed 13
Priming reaction, priming reaction temperature (upper section bed reaction tubes upper temp) are as follows: 200 DEG C~500 DEG C, reaction pressure are as follows:
0.01MPa~0.1MPa.
The raw materials such as coal, biomass pyrolysis temperature (upper section bed reaction tubes temperature of lower) are as follows: 300 DEG C~800 DEG C, reaction pressure
Power is 0.1MPa~1MPa.
The catalyst quality ratio of the raw material (coal or biomass) and activating reaction gas (reaction solution) are as follows: (0.5~2): 1.
The process that catalytic pyrolysis and orientation regulation are carried out to the pyrolytic tar product of raw material includes: raw material pyrolytic tar
Product catalyst cracks segment process method and raw material pyrolytic tar product orientation regulation segment process method, specific as follows:
Raw material pyrolytic tar product catalyst cracks segment process method are as follows:
Lower section furnace 10 described in the utility model is selected type for carrying out catalysis to raw material pyrolytic tar, is produced to orient regulation
Object is distributed, and in the reaction tube in lower section furnace, is sequentially arranged with third gas distributor 18, catalyst A bed 19, solid from top to bottom
Distributor 20, catalyst B bed 21, solids distribution device 22, the 4th gas distributor 23, catalyst A bed 19 are used for pyrolysis
The catalytic pyrolysis of tar, catalyst B bed 21 is for being oriented regulation to catalytic pyrolysis product.
The gaseous state tar product that yield is improved through upper section furnace, as reaction gas flow enters lower section bed, by catalyst A bed
Macromolecular substances in gaseous state tar product are further cracked into compared with small-molecule substance, promote coal by 19 progress catalytic pyrolysis
Pyrolizing heavy tar conversion is with tar light oil and gas, to realize the optimization of tar quality.
The catalytic pyrolysis section, gaseous state catalytic cracking of tar temperature are as follows: 600 DEG C~800 DEG C, reaction pressure 0.1MPa
~1 MPa.
The catalyst of the catalyst A bed 19 includes: predominantly carbon-supported catalysts or aluminium oxide catalyst, with half
Coke, active carbon, activated carbon fibre, carbon nanotube, graphene or aluminium oxide etc. are catalyst carrier, in these supported on carriers
The different types of metal ion such as Co, Ni, Cu, Zn, Fe, Mg, Ce, Zr, Ga of different proportion.
The mass ratio of the catalyst of the raw material and catalyst A bed 19 are as follows: (0.5~4): 1.
Raw material pyrolytic tar product orientation regulation segment process method are as follows:
Gaseous state tar product passes through catalyst A bed 19, after carrying out catalytic pyrolysis, as reaction gas flow enters catalyst B
Bed 21, the catalyst positioned at catalyst B bed 21 carry out shape selective catalysis to gaseous state tar product, and then orient regulation tar and produce
The distribution of object.
The catalyst of the catalyst B bed 21 specifically includes that molecular sieve catalyst or carried molecular sieve catalysis
Agent.Molecular sieve catalyst includes: ZSM-5, ZSM-11, USY, HY and beta-molecular sieve etc..The metal ion of load specifically includes that
Mo and Ni etc..
The carried molecular sieve catalyst of the catalyst B bed 21, can individually load certain mass score Mo or
Ni metal ion, or Mo the and Ni metal ion of certain mass score is loaded simultaneously.
The orientation regulates and controls section, gaseous state catalytic cracking of tar temperature are as follows: and 400 DEG C~600 DEG C, reaction pressure 0.1MPa
~1 MPa.
The orientation of the raw material and B bed 21 regulates and controls catalyst quality ratio are as follows: (0.5~2): 1.
Upper section furnace 9 and lower section furnace 10 described in the utility model, up and down coaxially, the reaction tube of two sections furnace are located in furnace body
Between, upper lower same diameter, and communicate up and down, centre is separated by with gas distribution grid and sieve plate.The outside of two-stage furnace is connected with temperature control respectively
Device and pressure controller processed are respectively used to the temperature and pressure of upper and lower part of control upper section reaction in furnace pipe, in lower section furnace
The temperature and pressure of the upper and lower part of reaction tube.
The lower section of lower section furnace 10 connects condensing unit 24, and condensing unit is used to condense the gaseous products after shape selective catalysis,
It is closed condensation tank body 24 outside condensing unit, inside is spiral condensation fluid catheter, and the condensation fluid catheter is imported and exported, with
External circulating condensing liquid delivery pump 25 is connected.
Condensing unit further connects tar collector 26 and gas collector 28, is respectively used to collect condensable coke
Oily and uncondensable gaseous product, and tar and gas collector 28 then connection product detection device 30, for tar and
The on-line checking of the constituent of gaseous product and analysis.
The product detection device 30 of the utility model be gas chromatography-mass spectrometry, gas chromatography-mass spectrometry with should
Temperature and pressure control device 31~46 in device is connected, for timely feedbacking product detection result to temperature and pressure
Control device 31~46, and then the related process parameters of each process section are adjusted in real time, realize the optimization of technological parameter.
The following are the embodiments under different technology conditions.
Embodiment 1
Using northern Shensi chemical plant low-order coal as raw material, Industrial Analysis and elemental analysis are shown in Table 1.Experiment coal 5g, instead
Should gas be N2, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY (also referred to as HY molecular sieve catalytic
Agent), HY dosage 2g；The temperature of pyrolysis of coal is 800 DEG C, reaction pressure are as follows: 0.1MPa；Catalytic cracking catalyst is Al2O3,
Al2O3Dosage 2g, catalytic pyrolysis section temperature are 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst,
Mo/Ni/HZSM-5 dosage is 2g, and orientation regulation section temperature is 500 DEG C, reaction pressure are as follows: 0.1MPa.Pyrolysis of coal tar yield
It is 5.63%.The component of all kinds of products of coal is distributed referring to table 2, as shown in Table 2, the catalytic pyrolysis product of the coal after orientation regulation
Total relative amount of middle BTXN is 8.84%.Fig. 5 is the total ion chromatogram (N of pyrolysis of coal gaseous state tar product2For reaction
Gas), as shown in Figure 5, after orientation regulation, the GC/MS peak type of target product is larger and relatively independent, i.e., target product is had
The separation and enrichment of effect.
The Industrial Analysis and elemental analysis of 1 low-order coal of table
* minusing
The component of all kinds of products of 2 coal of table is distributed (N2For reaction gas)
Embodiment 2
Using northern Shensi chemical plant low-order coal as raw material, Industrial Analysis and elemental analysis are shown in Table 1.Experiment coal 5g, instead
Should gas be CH4, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 2g；Pyrolysis of coal
Temperature is 800 DEG C, reaction pressure are as follows: 0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 2g, catalytic pyrolysis section temperature
It is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 2g, and orientation is adjusted
Controlling section temperature is 500 DEG C, reaction pressure are as follows: 0.1MPa.Pyrolysis of coal tar yield is 8.81%.The component of all kinds of products of coal point
Cloth is referring to table 3, and as shown in Table 3, total relative amount of BTXN is in the catalytic pyrolysis product of the coal after orientation regulation
32.94%.Fig. 6 is the total ion chromatogram of pyrolysis of coal gaseous state tar product, it will be appreciated from fig. 6 that after orientation regulation, target product
GC/MS peak type it is larger and relatively independent, i.e., target product is efficiently separated and is enriched with.
The component of all kinds of products of 3 coal of table is distributed (CH4For reaction gas)
Embodiment 3
Using northern Shensi chemical plant low-order coal as raw material, Industrial Analysis and elemental analysis are shown in Table 1.Experiment coal 5g, instead
Answering liquid is CH3OH, catalyst activation temperature are 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 2g；Pyrolysis of coal
Temperature be 800 DEG C, reaction pressure are as follows: 0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 2g catalytic pyrolysis Duan Wen
Degree is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 2g, orientation
Regulating and controlling section temperature is 500 DEG C, reaction pressure are as follows: 0.1MPa.Pyrolysis of coal tar yield is 9.93%.The component of all kinds of products of coal
Distribution is referring to table 4, and as shown in Table 4, total relative amount of BTXN is in the catalytic pyrolysis product of the coal after orientation regulation
19.01%.Fig. 7 is the total ion chromatogram of pyrolysis of coal gaseous state tar product, as shown in Figure 7, after orientation regulation, target product
GC/MS peak type it is larger and relatively independent, i.e., target product is efficiently separated and is enriched with.
The component of all kinds of products of 4 coal of table is distributed (reaction solution CH3OH)
Embodiment 4
Using corn stover as raw material, Industrial Analysis and elemental analysis are shown in Table 5.Experiment corn stover 4g, reaction gas
For N2, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 1g；Corn stover pyrolysis
Temperature be 800 DEG C, reaction pressure are as follows: 0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 1g, catalytic pyrolysis Duan Wen
Degree is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, Mo/Ni/HZSM-5 dosage is 1g, orientation
Regulating and controlling section temperature is 500 DEG C, reaction pressure are as follows: 0.1MPa.The pyrolytic tar yield of corn stover is 4.35%.Corn stover
All kinds of products component be distributed referring to table 6, as shown in Table 6, orientation regulation after corn stover catalytic pyrolysis product in PCX
Total relative amount is 14.04%.Fig. 8 is the total ion chromatogram that corn stover is pyrolyzed gaseous state tar product, can by Fig. 8
Know, orientation regulation after, the GC/MS peak type of target product is larger and relatively independent, i.e., target product obtained efficiently separating and
Enrichment.
The Industrial Analysis and elemental analysis of 5 corn stover of table
* minusing
The component of all kinds of products of 6 corn stover of table is distributed (N2For reaction gas)
Embodiment 5
Using corn stover as raw material, Industrial Analysis and elemental analysis are shown in Table 5.Experiment corn stover 4g, reaction gas
For CH4, catalyst activation temperature is 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 1g；Corn stover pyrolysis
Temperature be 800 DEG C, reaction pressure are as follows: 0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 1g, catalytic pyrolysis Duan Wen
Degree is 600 DEG C；Catalyst for orienting regulation tar product is Mo/Ni/HZSM-5, and Mo/Ni/HZSM-5 dosage is 1 g, fixed
It is 500 DEG C to regulation section temperature, reaction pressure are as follows: 0.1MPa.The pyrolytic tar yield of corn stover is 8.29%.Corn stover
All kinds of products component be distributed referring to table 7, as shown in Table 7, orientation regulation after corn stover catalytic pyrolysis product in PCX
Total relative amount is 31.01%.Fig. 9 is the total ion chromatogram that corn stover is pyrolyzed gaseous state tar product, can by Fig. 9
Know, orientation regulation after, the GC/MS peak type of target product is larger and relatively independent, i.e., target product obtained efficiently separating and
Enrichment.
The component of all kinds of products of 7 corn stover of table is distributed (CH4For reaction gas)
Embodiment 6
Using corn stover as raw material, Industrial Analysis and elemental analysis are shown in Table 5.Experiment corn stover 4g, reaction solution
For CH3OH, catalyst activation temperature are 600 DEG C, and the catalyst for activating reaction gas is HY, HY dosage 1g；Corn stover heat
The temperature of solution is 800 DEG C, reaction pressure are as follows: 0.1MPa；Catalytic cracking catalyst is Al2O3, Al2O3Dosage 1g, catalytic pyrolysis section
Temperature is 600 DEG C；It is Mo/Ni/HZSM-5 for orienting regulation tar product catalyst, 5 dosage of Mo/Ni/HZSM- is 1g, fixed
It is 500 DEG C to regulation section temperature, reaction pressure are as follows: 0.1MPa.The pyrolytic tar yield of corn stover is 9.92%.Corn stover
All kinds of products component be distributed referring to table 8, as shown in Table 8, orientation regulation after corn stover catalytic pyrolysis product in PCX
Total relative amount is 29.42%.Figure 10 is the total ion chromatogram that corn stover is pyrolyzed gaseous state tar product, can by Figure 10
Know, orientation regulation after, the GC/MS peak type of target product is larger and relatively independent, i.e., target product obtained efficiently separating and
Enrichment.
The component of all kinds of products of 8 corn stover of table is distributed (reaction solution CH3OH)
Claims (9)
1. a kind of directional catalyzing cracker, which is characterized in that including feeder, for improving pyrolysis of coal reaction tar yield
Upper section furnace (9), for carrying out catalysis to pyrolytic tar select the lower section furnace (10) and temperature and pressure control device of type；On
Section furnace (9) and lower section furnace (10) are cylindrical body, and two sections of upper section furnaces (9) and lower section furnace (10) are coaxial up and down, upper section furnace (9)
Lower section furnace (10) interior center vertical is provided with reaction tube；Feeder is connected with upper section furnace (9), feeder, upper section furnace (9)
And lower section furnace (10) is connected with temperature and pressure control device.
2. a kind of directional catalyzing cracker according to claim 1, which is characterized in that feeder includes the first carrier gas
Bottle (1), the second carrier gas bottle (2), third carrier gas bottle (3), the first carrier gas flux control valve (4), the second carrier gas flux control valve
(5), the total carrier gas stream of the system of third carrier gas flux control valve (6), mixed gas tank (7) and the total flow for regulating and controlling reaction gas
Amount controller (8)；Outlet the first carrier gas flux control valve (4) of first carrier gas bottle (1) is connected with mixed gas tank (7) entrance,
Outlet the second carrier gas flux control valve (5) of second carrier gas bottle (2) is connected with mixed gas tank (7) entrance, third carrier gas bottle (3)
Outlet be connected through third carrier gas flux control valve (6) with mixed gas tank (7) entrance, mixed gas tank (7) outlet always carried through system
Air-flow amount controller (8) is connected with upper section furnace (9) entrance.
3. a kind of directional catalyzing cracker according to claim 2, which is characterized in that temperature and pressure control device
Including the first carrier gas flux controller (31), the second carrier gas flux controller (32), third carrier gas flux controller (33), upper section
Furnace middle portion temperature controller (34), upper section furnace upper temp controller (35), upper section furnace temperature of lower controller (36), lower section furnace
Middle portion temperature controller (37), lower section furnace upper temp controller (38) and lower section furnace temperature of lower controller (39)；First
Carrier gas flux controller (31) is connected with the first carrier gas flux control valve (4), and the second carrier gas flux controller (32) is carried with second
Flow control valves (5) are connected, and third carrier gas flux controller (33) is connected with third carrier gas flux control valve (6)；Upper section furnace
(9) the outer position of upper, middle and lower three of furnace body, is separately connected signal wire in the upper section furnace into temperature and pressure control device
Portion's temperature controller (34), upper section furnace upper temp controller (35), upper section furnace temperature of lower controller (36), lower section furnace (10)
The outer position of upper, middle and lower three of furnace body, be separately connected signal wire to lower section furnace middle portion temperature controller (37), lower section furnace top
Temperature controller (38), lower section furnace temperature of lower controller (39).
4. a kind of directional catalyzing cracker according to claim 1, which is characterized in that the reaction tube in upper section furnace (9)
It is interior, from top to bottom equipped with gas distributor (12), catalyst bed (13), the first solids distribution device (14), raw material bed (15),
Second solids distribution device (16) and second gas distributor (17)；Wherein, gas distributor (12) is for keeping reaction gas uniform
Be distributed in catalyst bed, catalyst bed (13) is used for activating reaction gas, the first solids distribution device (14) and the second solid
Distributor (16) is respectively used to tiling catalyst bed (13) and raw material bed (15), and second gas distributor (17) is for making heat
Gaseous product stream after solution reaction is into the reaction tube of lower section furnace (10).
5. a kind of directional catalyzing cracker according to claim 1, which is characterized in that the reaction tube in lower section furnace (10)
It is interior, third gas distributor (18), catalyst A bed (19), third solids distribution device (20), catalyst B are housed from top to bottom
Bed (21), the 4th solids distribution device (22) and the 4th gas distributor (23)；Wherein, third gas distributor (18) is used for
For gaseous product distribution after making pyrolytic reaction in catalyst A bed (19), catalyst A bed (19) is anti-for catalytic pyrolysis pyrolysis
The gaseous products answered, third solids distribution device (20) and the 4th solids distribution device (22) are respectively used to tiling catalyst A bed
(19) and catalyst B bed (21), the 4th gas distributor (23) are used to that the gaseous products after reaction to be made to flow to condensing unit.
6. a kind of directional catalyzing cracker according to claim 5, which is characterized in that further include being arranged in lower section furnace
(10) cooling device below.
7. a kind of directional catalyzing cracker according to claim 6, which is characterized in that cooling device includes spiral cold
Solidifying device (24), circulating condensing liquid delivery pump (25), tar collector (26), gas collector (28) and product detection
Device (30)；Be provided with spiral condensing unit (24) below lower section furnace (10), and spiral condensing unit (24) entrance with
Lower section furnace (10) outlet is connected, and the outlet of spiral condensing unit (24) is divided into two-way, all the way through gaseous product storage tank (28) with
Product detection device (30) is connected, and is provided with secondary liquid condensed product storage tank (29) below gaseous product storage tank (28), and
Secondary liquid condensed product storage tank (29) is connected with gaseous product storage tank (28), and another way is through tar collector (26) and product
Detection device (30) is connected.
8. a kind of directional catalyzing cracker according to claim 7, which is characterized in that spiral condensing unit (24) is also
It is connected with circulating condensing liquid delivery pump (25).
9. a kind of directional catalyzing cracker according to claim 1, which is characterized in that the reaction tube in upper section furnace (9)
Entrance is also connected with plunger pump (49).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913179A (en) * | 2018-08-31 | 2018-11-30 | 西北大学 | A kind of directional catalyzing cracker and technique |
| CN111234857A (en) * | 2020-02-11 | 2020-06-05 | 西安石油大学 | Method for regulating and controlling composition of biomass pyrolysis product by using methane catalytic activation process |
| CN111635785A (en) * | 2020-05-30 | 2020-09-08 | 肖孟辉 | Medium temperature pyrolysis device structure of living beings pyrolysis gas tar |
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2018
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913179A (en) * | 2018-08-31 | 2018-11-30 | 西北大学 | A kind of directional catalyzing cracker and technique |
| CN111234857A (en) * | 2020-02-11 | 2020-06-05 | 西安石油大学 | Method for regulating and controlling composition of biomass pyrolysis product by using methane catalytic activation process |
| CN111635785A (en) * | 2020-05-30 | 2020-09-08 | 肖孟辉 | Medium temperature pyrolysis device structure of living beings pyrolysis gas tar |
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