CN108913179B - Directional catalytic cracking device and process - Google Patents

Directional catalytic cracking device and process Download PDF

Info

Publication number
CN108913179B
CN108913179B CN201811013130.3A CN201811013130A CN108913179B CN 108913179 B CN108913179 B CN 108913179B CN 201811013130 A CN201811013130 A CN 201811013130A CN 108913179 B CN108913179 B CN 108913179B
Authority
CN
China
Prior art keywords
gas
catalyst
furnace
reaction
bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811013130.3A
Other languages
Chinese (zh)
Other versions
CN108913179A (en
Inventor
孙鸣
刘永琦
马明明
李亚波
么秋香
代成义
郝青青
马晓迅
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NORTHWEST UNIVERSITY
Original Assignee
NORTHWEST UNIVERSITY
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NORTHWEST UNIVERSITY filed Critical NORTHWEST UNIVERSITY
Priority to CN201811013130.3A priority Critical patent/CN108913179B/en
Publication of CN108913179A publication Critical patent/CN108913179A/en
Application granted granted Critical
Publication of CN108913179B publication Critical patent/CN108913179B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/04—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of powdered coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

A directional catalytic cracking device and process, wherein the reaction atmosphere in the reaction tube of the upper furnace is flatly paved to a catalyst bed layer through a first gas distributor to activate reaction gas, the reaction atmosphere generates free radicals under the action of a catalyst, the free radicals are contacted with free radicals generated by pyrolysis of raw materials in the raw material bed layer, the obtained gaseous products are flatly paved to a catalyst A bed layer through a third gas distributor, the catalyst A bed layer carries out catalytic cracking on the gaseous products of pyrolysis reaction, the products after catalytic cracking enter a catalyst B bed layer to carry out shape-selective catalysis, and the products after shape-selective catalysis enter a condensing device to be condensed, so as to obtain liquid tar. The invention integrates the process of improving the tar yield by pyrolyzing raw materials such as coal, biomass and the like and the process of directionally regulating and controlling the corresponding product distribution into one set of process, simplifies the whole process flow, is environment-friendly, reduces the energy consumption cost, improves the process production efficiency, is easy for large-scale production, and is suitable for industrialized popularization and application.

Description

Directional catalytic cracking device and process
Technical Field
The invention belongs to the technical field of energy and chemical industry, and relates to a directional catalytic cracking device and a directional catalytic cracking process.
Background
Coal pyrolysis is a key step of coal conversion and utilization, and the technological processes of combustion, gasification, liquefaction and the like of coal all need to occur or undergo pyrolysis. However, the coal tar obtained by traditional coal pyrolysis has low yield and high heavy component content, and the heavy component has the characteristics of high boiling point, high viscosity, difficult separation and the like, and various products in the target product are distributed in disorder and have low relative content, so that various products cannot be effectively enriched.
Biomass mainly consists of cellulose, hemicellulose, lignin and the like, pyrolysis is the most basic process in the biomass thermochemical processing process, and is the synthesis of liquefaction, gasification and combustion processes, and the content of three-major-element in different biomass raw materials is different, so that the content, the components and the product distribution of bio-oil generated in the biomass pyrolysis process have great difference, and cannot be further and effectively utilized directly.
Therefore, the yield of pyrolysis tar such as coal, biomass and the like is improved, the distribution of tar products is directionally regulated and controlled, the quality of target tar products is improved, and the tar products with high added value are generated, so that the method has important and profound significance for the coal chemical industry, the biochemical industry and the efficient utilization of national energy sources in China.
The yield of tar obtained by pyrolysis of coal is low and is limited by the low hydrogen-carbon ratio in the coal. In the process of pyrolysis of coal, macromolecular structures in the coal structure are continuously depolymerized to form macromolecular free radicals, hydrogen free radicals and the like in different forms. Studies have shown that tar formation during pyrolysis of coal is related to thermal pyrolysis of organic macromolecules in the coal and stabilization of the pyrolysis radicals. Excessive cleavage may form gaseous products, the combination of free radicals with small molecules may form tar, while the combination of free radicals may form tar, and the large molecules may be reformed to exist in the form of solid semicoke. Therefore, in the process of pyrolysis of coal, hydrogen-rich small molecular free radicals are externally applied, so that the free radicals generated by pyrolysis of coal are stable, and the method is an effective way for improving the yield of tar.
The high price of hydrogen ensures that the raw materials such as coal, biomass and the like have higher cost by hydropyrolysis to improve the yield and quality of pyrolysis tar of the corresponding raw materials, and restricts the practicability of the raw materials. Methane is a main component of natural gas, has wide sources, high hydrogen-carbon atomic ratio and low price, and is an ideal hydrogen-rich gas, so that methane can be used as a reaction atmosphere for pyrolysis of raw materials such as coal, biomass and the like. However, it was found that below 800 ℃ methane does not substantially react with coal, the methane corresponds to an inert atmosphere during pyrolysis and does not increase the coal tar yield because methane is very stable under non-catalytic conditions and difficult to activate.
Coal pyrolysis forms tar products, which have higher heavy component content and higher oxygen-containing compounds, so the quality of the tar is low. Therefore, the target product with high added value and high yield can be obtained by directionally regulating and controlling the coal pyrolysis tar.
At present, the improvement of the yield of raw material pyrolysis tar such as coal, biomass and the like and the directional regulation and control of raw material pyrolysis tar products such as coal, biomass and the like are generally carried out in two independent systems respectively, so that the problems of complex overall process, high energy consumption cost, low product utilization rate, low process production efficiency and the like are caused. The device and the method for directionally regulating and controlling the tar products have been reported only rarely by utilizing the fixed beds at two ends, improving the yield of the pyrolysis tar of the raw materials such as coal, biomass and the like, and simultaneously performing shape-selective catalysis on the tar products of the pyrolysis of the raw materials such as coal, biomass and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a directional catalytic pyrolysis device and a directional catalytic pyrolysis process, which can improve the yield of raw material pyrolysis tar products such as coal, biomass and the like, and can directionally regulate and control the distribution of the raw material pyrolysis tar products such as the coal, the biomass and the like, so that an ideal target tar product with high added value is obtained.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a directional catalytic cracking device comprises a gas supply device, an upper-stage furnace for improving the yield of tar in a coal pyrolysis reaction, a lower-stage furnace for performing catalytic shape selection on the pyrolysis tar, a cooling device and a temperature and pressure controller device; the upper section furnace and the lower section furnace are both cylinders, and the upper section furnace and the lower section furnace are coaxial up and down, and the centers in the upper section furnace and the lower section furnace are vertically provided with reaction pipes; the air supply device is connected with the upper-stage furnace, and the air supply device, the upper-stage furnace and the lower-stage furnace are connected with the temperature and pressure controller device; the cooling device is arranged below the lower-stage furnace.
The invention is further improved in that the gas supply device comprises a first gas carrying cylinder, a second gas carrying cylinder, a third gas carrying cylinder, a first gas carrying flow control valve, a second gas carrying flow control valve, a third gas carrying flow control valve, a mixed gas tank and a system total gas carrying flow controller for regulating and controlling the total flow of the reaction gas; the outlet of the first gas carrying cylinder is connected with the inlet of the mixed gas cylinder through a first gas carrying flow control valve, the outlet of the second gas carrying cylinder is connected with the inlet of the mixed gas cylinder through a second gas carrying flow control valve, the outlet of the third gas carrying cylinder is connected with the inlet of the mixed gas cylinder through a third gas carrying flow control valve, and the outlet of the mixed gas cylinder is connected with the inlet of the upper furnace through a system total gas carrying flow controller.
The invention is further improved in that the temperature and pressure controller device comprises a first carrier gas flow controller, a second carrier gas flow controller, a third carrier gas flow controller, an upper furnace middle temperature controller, an upper furnace upper temperature controller, an upper furnace lower temperature controller, a lower furnace middle temperature controller, a lower furnace upper temperature controller and a lower furnace lower temperature controller; the first carrier gas flow controller is connected with the first carrier gas flow control valve, the second carrier gas flow controller is connected with the second carrier gas flow control valve, and the third carrier gas flow controller is connected with the third carrier gas flow control valve; the upper, middle and lower parts outside the furnace body of the upper furnace are respectively connected with a signal wire to the upper furnace middle temperature controller, the upper furnace upper temperature controller and the upper furnace lower temperature controller in the temperature and pressure controller device, and the upper, middle and lower parts outside the furnace body of the lower furnace are respectively connected with the signal wire to the lower furnace middle temperature controller, the lower furnace upper temperature controller and the lower furnace lower temperature controller.
The invention is further improved in that a gas distributor, a catalyst bed layer, a first solid distributor, a raw material bed layer, a second solid distributor and a second gas distributor are arranged in a reaction tube in the upper furnace from top to bottom; the gas distributor is used for uniformly distributing the reaction gas in a catalyst bed, the catalyst bed is used for activating the reaction gas, the first solid distributor and the second solid distributor are respectively used for tiling the catalyst bed and a raw material bed, and the second gas distributor is used for enabling the gaseous product after the pyrolysis reaction to flow into a reaction tube of the lower furnace.
The invention is further improved in that a third gas distributor, a catalyst A bed, a third solid distributor, a catalyst B bed, a fourth solid distributor and a fourth gas distributor are arranged in a reaction tube in the lower furnace from top to bottom; the third gas distributor is used for distributing gaseous products after pyrolysis reaction on a catalyst A bed, the catalyst A bed is used for catalyzing the gaseous products of pyrolysis reaction, the third solid distributor and the fourth solid distributor are respectively used for tiling the catalyst A bed and the catalyst B bed, and the fourth gas distributor is used for enabling the gaseous products after reaction to flow to the condensing device.
The invention is further improved in that the cooling device comprises a spiral condensing device, a circulating condensate conveying pump, a tar collecting device, a gas collecting device and a product detecting device; a spiral condensing device is arranged below the lower-stage furnace, an inlet of the spiral condensing device is communicated with an outlet of the lower-stage furnace, an outlet of the spiral condensing device is divided into two paths, one path is connected with a phase chromatography mass spectrometer through a gas product storage tank, a secondary liquid condensing product storage tank is arranged below the gas product storage tank, the secondary liquid condensing product storage tank is connected with the gas product storage tank, and the other path is connected with the phase chromatography mass spectrometer through a liquid tar product storage tank; the spiral condensing device is also connected with a circulating condensate delivery pump.
In the directional catalytic cracking process, the reaction atmosphere in the reaction tube of the upper furnace is tiled to a catalyst bed layer through a first gas distributor to activate the reaction gas, wherein the activation temperature is as follows: the reaction pressure is 0.1 MPa-1 MPa at 600-800 ℃, free radicals are generated under the action of a catalyst in the reaction atmosphere and are in contact with free radicals generated by pyrolysis of raw materials in a raw material bed layer, the obtained gaseous products are tiled to a catalyst A bed layer through a third gas distributor, the catalyst A bed layer carries out catalytic pyrolysis on the gaseous products of the pyrolysis reaction, the products after the catalytic pyrolysis enter a catalyst B bed layer for shape-selective catalysis, and the products after the shape-selective catalysis enter a condensing device for condensation, so that liquid tar is obtained; wherein the raw material is coal or biomass.
A further improvement of the invention is that the reaction atmosphere is CH 4 、CH 4 And CO 2 Is a mixed gas of CH 4 And water vapor mixture, CH 4 And O 2 A mixture of methanol cracking gas and oxygen or a mixture of methanol cracking gas and water vapor; wherein CH is 4 And CO 2 CH in the mixed gas of (2) 4 And CO 2 The volume ratio of (1-2): 1, a step of; CH (CH) 4 In the mixed gas with water vapor, CH is calculated by volume percent 4 10-20% of water vapor 80-90%; CH (CH) 4 And O 2 In volume percent, CH 4 80 to 90 percent of O 2 10% -20%; in the mixture of methanol and oxygen, the ratio of the amounts of the substances of methanol and oxygen is (2 to 5): 1, a step of; in the mixture of methanol and water vapor, the ratio of the amounts of the methanol and water vapor is (1 to 1.5): 1.
the invention is further improved in that the temperature of catalytic cracking is 600-800 ℃ and the pressure is 0.1-1 MPa; the mass ratio of the raw materials to the catalyst on the catalyst A bed 19 is as follows: (0.5-4): 1.
the invention is further improved in that the temperature of the shape selective catalysis is 400-600 ℃ and the pressure is 0.1-1 MPa; the mass ratio of the raw materials to the catalyst on the catalyst B bed 21 is as follows: (0.5-2): 1.
compared with the prior art, the invention has the following beneficial effects:
according to the invention, by arranging the gas supply device, the upper-stage furnace for improving the tar yield of the coal pyrolysis reaction and the lower-stage furnace for catalyzing and shape-selecting the pyrolysis tar, the feeding proportion between reaction gases, between reaction liquids or between the reaction gases and the reaction liquids required by the reaction can be reasonably regulated, so that the feeding mode is not influenced by the form of a sample injection sample, the sample injection mode is flexible, the operation condition is mild, and the equipment investment is small. Compared with N under the same condition 2 Or the yield of tar under inert atmosphere, the device can obviously improve the yield of tar products generated by pyrolysis of raw materials such as coal, biomass and the like, and greatly improve the quality of oil products.
Further, the gas distributor, the catalyst bed, the first solid distributor, the raw material bed, the second solid distributor and the second gas distributor are arranged in the reaction tube in the upper furnace from top to bottom, and the third gas distributor, the catalyst A bed, the third solid distributor, the catalyst B bed, the fourth solid distributor and the fourth gas distributor are arranged in the reaction tube in the lower furnace from top to bottom, so that the distribution of raw material pyrolysis tar products such as coal, biomass and the like can be effectively and directionally regulated. The relative content of light aromatic hydrocarbon such as BTXN (benzene, toluene, xylene and naphthalene) in the product is greatly increased by the process device and the method; through the process device and the method, the content increment of PCX (phenol, cresol, xylenol) and the like in the products is obvious, so that the device can effectively enrich the target products with high added values.
The invention integrates the process of improving the tar yield by pyrolyzing raw materials such as coal, biomass and the like and the process of directionally regulating and controlling the corresponding product distribution into one set of process, simplifies the whole process flow, is environment-friendly, reduces the energy consumption cost, improves the process production efficiency, is easy for large-scale production, and is suitable for industrialized popularization and application. The distribution of pyrolysis tar products such as coal, biomass and the like is directionally regulated, so that the temperature and pressure of a product yield zone (a fixed bed upper-section furnace) and the temperature and pressure of a target tar product distribution zone (a fixed bed lower-section furnace) are directionally regulated in a sectional and reasonable mode, and the whole process is flexible in operation and has good controllability.
Drawings
Fig. 1 is a schematic view of the whole device structure of the present invention.
Fig. 2 is a front view of the structure of the upper furnace and the lower furnace.
Fig. 3 is a right side view of the structure of the upper furnace and the lower furnace.
Fig. 4 is a schematic structural view of a spiral condensing unit.
FIG. 5 is a total ion flow chromatogram of the gaseous tar product of coal pyrolysis of example 1 (N 2 Is reaction gas).
Fig. 6 is a total ion flow chromatogram of the coal pyrolysis gaseous tar product of example 2.
Fig. 7 is a total ion flow chromatogram of the coal pyrolysis gaseous tar product of example 3.
Fig. 8 is a total ion flow chromatogram of the corn stover pyrolysis gaseous tar product of example 4.
Fig. 9 is a total ion flow chromatogram of the corn stover pyrolysis gaseous tar product of example 5.
Fig. 10 is a total ion flow chromatogram of the corn stover pyrolysis gaseous tar product of example 6.
Reference numerals illustrate, 1. A first gas carrying cylinder; 2. a second gas carrying cylinder; 3. a third gas carrying cylinder; 4. a first carrier gas flow control valve; 5. a second carrier gas flow control valve; 6. a third carrier gas flow control valve; 7. a mixing gas tank; 8. a system total carrier gas flow controller; 9. an upper furnace; 10. a lower furnace; 11. the reaction tube disassembly and assembly fixing device; 12. a first gas distributor; 13. a catalyst bed; 14. a first solids distributor; 15. a raw material bed layer; 16. a second solids distributor; 17. a second gas distributor; 18. a third gas distributor; 19. a catalyst A bed; 20. a third solids distributor; 21. a catalyst B bed; 22. a fourth solids distributor; 23. a fourth gas distributor; 24. a screw type condensing device; 25. a circulating condensate delivery pump; 26. a liquid tar product storage tank; 27. an insulation box; 28. a gas product storage tank; 29. a secondary liquid condensation product storage tank; 30. a gas chromatograph mass spectrometer; 31. a first carrier gas flow controller; 32. a second carrier gas flow controller; 33. a third carrier gas flow controller; 34. a temperature controller in the middle of the upper furnace; 35. an upper temperature controller of the upper furnace; 36. a temperature controller at the lower part of the upper furnace; 37. a temperature controller in the middle of the lower furnace; 38. a lower furnace upper temperature controller; 39. a lower temperature controller of the lower furnace; 40. a heating belt temperature controller; 41. a temperature controller of the incubator; 42. a controller power supply main switch; 43. a main power switch of the upper furnace and the lower furnace; 44. a heat preservation box and a heating belt power supply main switch; 45. a flow controller power supply main switch; 46. a standby temperature controller; 47. an upper furnace door handle and a lower furnace door handle; 48. a spiral condenser tube; 49. a plunger pump; 50. a gaseous product channel; 51. a condensate outlet; 52. and a condensate inlet.
Detailed Description
The invention is further illustrated by the following detailed description of embodiments of the invention, which are merely exemplary of the invention and are not to be construed as limiting the invention.
Referring to fig. 1, a directional catalytic cracking apparatus of the present invention includes a gas supply device, an upper furnace 9 for improving the yield of tar produced in a coal pyrolysis reaction, a lower furnace 10 for catalytic shape selection of pyrolysis tar, a condensing device, and a temperature and pressure controller device. The gas supply device comprises a first gas carrying bottle 1, a second gas carrying bottle 2, a third gas carrying bottle 3, a first gas carrying flow control valve 4, a second gas carrying flow control valve 5, a third gas carrying flow control valve 6, a mixing gas bottle 7 for uniformly mixing the reactant gases with different proportions and a system total gas carrying flow controller 8 for regulating and controlling the total flow of the reactant gases; the gas distributor is arranged in the mixed gas tank 7; the outlet of the first gas carrying cylinder 1 is connected with the inlet of a mixed gas tank 7 through a first gas carrying flow control valve 4, the outlet of the second gas carrying cylinder 2 is connected with the inlet of the mixed gas tank 7 through a second gas carrying flow control valve 5, the outlet of the third gas carrying cylinder 3 is connected with the inlet of the mixed gas tank 7 through a third gas carrying flow control valve 6, the outlet of the mixed gas tank 7 is connected with the inlet of an upper furnace 9 through a system total gas carrying flow controller 8, and the upper furnace 9 is positioned above a lower furnace 10; the air supply device, the upper furnace 9 and the lower furnace 10 are all connected with a temperature and pressure controller device. The cooling device is disposed below the lower furnace 10.
Referring to fig. 2 and 3, the inside of the upper furnace 9 and the lower furnace 10 is divided into an upper part, a middle part and a lower part, and different reaction temperatures of the upper part, the middle part and the lower part can be correspondingly controlled according to different beds and catalysts arranged in the upper part, the middle part and the lower part.
The temperature and pressure controller means includes a first carrier gas flow controller 31, a second carrier gas flow controller 32, a third carrier gas flow controller 33, an upper stage furnace middle temperature controller 34, an upper stage furnace upper temperature controller 35, an upper stage furnace lower temperature controller 36, a lower stage furnace middle temperature controller 37, a lower stage furnace upper temperature controller 38, a lower stage furnace lower temperature controller 39, a heating zone temperature controller 40, an incubator temperature controller 41, a controller power supply total switch 42, upper stage furnace and lower stage furnace power supply total switches 43, an incubator, a heating zone power supply total switch 44, a flow controller power supply total switch 45, and a standby temperature controller 46. The first carrier gas flow controller 31 is connected to the first carrier gas flow control valve 4, the second carrier gas flow controller 32 is connected to the second carrier gas flow control valve 5, and the third carrier gas flow controller 33 is connected to the third carrier gas flow control valve 6.
The gas in the first gas carrying bottle 1, the second gas carrying bottle 2 and the third gas carrying bottle 3 can be CH 4 、CO 2 、CO、O 2 The reaction process can be independently carried out by CH 4 For the reaction gas, or with CH 4 And the mixed gas and other gases are uniformly mixed according to a certain proportion to be used as reaction gas required by the reaction. The gas supply device can flexibly regulate and control various reaction gases or the mixing proportion between the reaction gases, thereby improving the overall reaction efficiency.
Referring to fig. 1, 2 and 3, the upper furnace 9 and the lower furnace 10 are cylindrical with the same size, the upper furnace 9 and the lower furnace 10 are coaxial up and down and are in the same straight line, the inner centers of the upper furnace 9 and the lower furnace 10 are vertically provided with reaction tubes, the upper furnace 9 and the lower furnace 10 are respectively provided with an upper furnace door handle 47 and a lower furnace door handle 47, the furnace doors can be opened by 0-180 degrees around the straight line through the upper furnace door handle 47 and the lower furnace door handle 47 which are handles in the center of the respective furnace body, the reaction tubes positioned in the furnace cylinder centers of the upper furnace 9 and the lower furnace 10 are used for disassembling and assembling, the reaction tube bodies in the upper furnace 9 and the lower furnace 10 are fixed in the furnace body center by the reaction tube disassembling and assembling fixing device 11, and the raw material bed layer 15, the catalyst bed layer 13 and the like required by the reaction are arranged in the reaction tubes. The upper, middle and lower parts outside the furnace body of the upper furnace 9 are respectively connected with a signal wire to an upper furnace middle part temperature controller 34, an upper furnace upper part temperature controller 35 and an upper furnace lower part temperature controller 36 in the temperature and pressure controller device, and are respectively used for regulating and controlling the upper, middle and lower temperature parameters of the upper furnace in real time. The upper, middle and lower parts outside the furnace body of the lower furnace 10 are respectively connected with signal wires to a lower furnace middle part temperature controller 37, a lower furnace upper part temperature controller 38 and a lower furnace lower part temperature controller 39, and are respectively used for regulating and controlling the temperature parameters of the lower furnace upper part, middle part and lower part in real time.
The reaction tube in the upper furnace 9 is provided with a gas distributor 12, a catalyst bed 13, a first solid distributor 14, a raw material bed 15, a second solid distributor 16 and a second gas distributor 17 from top to bottom. Wherein, the gas distributor 12 can uniformly distribute the reaction gas in the catalyst bed 13, the catalyst bed 13 is used for activating the reaction gas, the first solid distributor 14 and the second solid distributor 16 are respectively used for flatly laying the catalyst bed 13 and the raw material bed 15, and the second gas distributor 17 can uniformly flow the gaseous product after the pyrolysis reaction into the reaction tube of the lower furnace 10 for carrying out the next related reaction.
The upper furnace 9 is used for improving the yield of raw material pyrolysis tar, a reaction gas guide pipe is arranged above the inlet of the reaction pipe in the upper furnace 9, the reaction gas guide pipe is connected with a plunger pump 49, the reaction gas guide pipe is used for providing reaction gas required by the reaction in the reaction furnace, the plunger pump 49 is used for providing reaction liquid required by the reaction, and the reaction liquid is CH 3 OH or tetrahydronaphthalene, when the reaction solution is CH 3 OH, CH under suitable process conditions 3 OH direct pyrolysis, CH 3 Under the action of oxidant, OH is catalytically reformed and CH by activating catalyst 3 OH reacts with excessive steam, and the reaction process can provide a large amount of hydrogen radicals which are combined with radical fragments generated by pyrolysis of coal, so that the yield of tar products of pyrolysis of coal is improved 。
The reaction tube in the lower furnace 10 is equipped with a third gas distributor 18, a catalyst a bed 19, a third solid distributor 20, a catalyst B bed 21, a fourth solid distributor 22, and a fourth gas distributor 23 from top to bottom. The third gas distributor 18 can uniformly distribute the gaseous products after the pyrolysis reaction on the catalyst a bed 19, the catalyst a bed 19 is used for catalyzing the gaseous products of the pyrolysis reaction, the third solid distributor 20 and the fourth solid distributor 22 are respectively used for tiling the catalyst a bed 19 and the catalyst B bed 21, and the fourth gas distributor 23 can uniformly flow the gaseous products after the reaction to the spiral condensing device 24 for condensing.
Referring to fig. 4, the condensing device comprises a screw type condensing device 24, a circulating condensate delivery pump 25, a tar collecting device 26, a heat preservation device 27, a gas collecting device 28 and a product detecting device 30; the lower furnace 10 is provided with a spiral condensing device 24 below, the inlet of the spiral condensing device 24 is communicated with the outlet of the lower furnace 10, a gaseous product channel 50 is arranged in the spiral condensing device 24, the outlet of the spiral condensing device 24 is divided into two paths, one path is connected with a phase chromatography mass spectrometer 30 through a gas product storage tank 28, the gas product storage tank 28 is arranged in an insulation box 27, a secondary liquid condensation product storage tank 29 is arranged below the gas product storage tank 28, the secondary liquid condensation product storage tank 29 is connected with the gas product storage tank 28, the secondary liquid condensation product storage tank 29 is arranged outside the insulation box 27, and the other path is connected with the phase chromatography mass spectrometer 30 through a liquid tar product storage tank 26. In addition, the spiral condensing device 24 is also connected with a circulating condensate delivery pump 25; the screw-type condensing device 24 is provided with a condensate outlet 51 and a condensate inlet 52.
Referring to fig. 1 and 4, condensate in the spiral condensing device 24 is circularly conveyed by a circulating condensate conveying pump 25, and a condensing pipe in the spiral condensing device 24 is spirally ascending and surrounds a conveying pipeline of gaseous products, so that the condensing effect is enhanced, the device preparation is simplified, the cost is reduced, and better economical efficiency is embodied.
The liquid tar condensed by the spiral condensing device 24 enters the liquid tar product storage tank 26 for collection, the uncondensed or uncondensable gaseous product enters the gas product storage tank 28, and the gas product storage tank 28 is connected with the secondary liquid condensation product storage tank 29 downwards for collecting the secondary condensed tar product. An incubator 27 is arranged outside the gas product storage tank 28 and is used for providing sample injection temperature regulation and control of the gas chromatography-mass spectrometer 30.
The reaction gas in the invention is directly CH 4 Is a reaction gas or CH mixed in a certain volume proportion 4 And CO 2 The mixed gas is reaction gas or CH 4 And excess water vapor as reaction gas, or CH 4 And a small amount of an oxidizing agent O 2 The reaction gas is specifically as follows:
specifically, the reaction gas in the invention can be directly CH 4 The reaction gas is introduced into a catalyst activation bed layer 13 of the upper bed, and is further activated under the action of the catalyst, and the activated CH 4 The hydrogen radicals, methylene radicals, methyl radicals and the like generated by the reaction gas follow CH 4 The gas flow of the reaction gas is contacted with free radical fragments generated by raw material pyrolysis through a bed layer of gaseous tar generated by raw material pyrolysis such as coal, biomass and the like, so that the stable rate and efficiency of free radicals are improved, and the yield of the raw material pyrolysis tar such as coal, biomass and the like is improved.
The reaction gas in the present invention may be (1-2): 1 by volume ratio of mixed CH 4 And CO 2 The mixture gas of (2) is a reaction atmosphere, so that CH 4 And CO 2 Generating hydrogen-rich free radical components through catalytic reforming, contacting with free radical fragments generated by pyrolysis of raw materials such as coal, biomass and the like, and stabilizing the free radical fragments generated by pyrolysis of the coal in time, so that the yield of pyrolysis tar of the raw materials such as the coal, biomass and the like is improved.
The reaction gas in the invention is CH 4 And excessive steam is used as reaction atmosphere, carbon monoxide and hydrogen produced by the reaction of methane and steam are further reacted to obtain carbon dioxide and hydrogen, a large amount of hydrogen-rich free radical intermediates are produced in the reaction process, and the free radicals are combined with free radical fragments produced by pyrolysis of raw materials such as coal, biomass and the like to improve the performance of the coal, Biomass and other raw material pyrolysis tar yield. Wherein CH is 4 And excess water vapor in volume percent, CH 4 10-20% and 80-90% of water vapor.
The reaction gas in the invention is CH 4 And a small amount of an oxidizing agent O 2 In order to produce a reaction atmosphere, partial methane is catalyzed and oxidized to generate hydrogen-rich components, so that free radical fragments generated by pyrolysis of raw materials such as coal, biomass and the like are further stabilized, and the corresponding tar yield is improved. Wherein CH is 4 And a small amount of an oxidizing agent O 2 In volume percent, CH 4 80 to 90 percent of oxidant O 2 10 to 20 percent.
The invention can use methanol cracking gas as reaction atmosphere, can use methanol cracking gas and oxygen together as reaction atmosphere, can also use methanol cracking gas (methanol is liquid, enters the upper furnace through the plunger pump 49, is pyrolyzed into gas, is further mixed with corresponding reaction gas, and reacts with raw materials as reaction atmosphere) and water vapor together as reaction atmosphere, and is concretely as follows:
methanol is directly used as reaction liquid, the reaction liquid is preheated by an upper furnace and heated to the reaction temperature, and after the reaction liquid is activated by a catalyst bed layer 13, a large amount of hydrogen free radicals are generated to timely contact and combine with free radical fragments generated by pyrolysis of raw materials such as coal, biomass and the like, so that the yield of pyrolysis tar of the raw materials such as coal, biomass and the like can be effectively improved.
The reaction liquid methanol can be subjected to partial oxidation reaction with oxygen, and is subjected to catalytic reforming reaction through the catalyst bed layer 13 to form hydrogen, the hydrogen free radicals in the reaction process can be combined with free radicals generated by pyrolysis of raw materials such as coal, biomass and the like, and the reaction is exothermic, so that heat can be provided for the pyrolysis reaction, the cost of a process flow is reduced, and meanwhile, the yield of raw material pyrolysis tar products is effectively improved.
The ratio of the reaction liquid methanol to the oxygen is as follows: the ratio of the amounts of methanol and oxygen introduced into the upper furnace 9 is (2 to 5): 1.
the reaction liquid methanol can react with water vapor, and is subjected to catalytic reforming reaction through the catalyst bed layer 13 to form hydrogen, a large amount of hydrogen free bodies are formed in the reforming process, and the hydrogen free bodies can be combined with various compound fragments formed by pyrolysis products of raw materials, so that the yield of pyrolysis tar products is improved.
The ratio of the reaction liquid methanol to the water vapor is as follows: the ratio of the amounts of methanol and water vapor is (1 to 1.5): 1.
the general process flow of the invention is as follows: by CH 4 Or CH 4 The mixture gas is mixed with other gases in a certain proportion to form a uniform mixture gas as a reaction atmosphere, and CH is used as an example 4 Or CH 4 And the mixed gas and other gases are formed into uniform mixed gas according to a certain proportion, the mixed gas is used as reaction gas required by reaction, the mixed gas is regulated to a proper flow to enter the upper furnace 9, and the mixed gas is uniformly paved to the catalyst bed 13 through the first gas distributor 12 to activate the reaction gas, wherein the activation temperature (namely, the upper temperature of a reaction tube in the upper furnace) is as follows: 600-800 ℃ and the reaction pressure is 0.1-1 MPa. CH (CH) 4 Under the action of the catalyst (the catalyst comprises any one of a catalyst loaded with metal, alkali metal and transition metal, and the catalyst carrier comprises any one of molecular sieve, oxide, semicoke and the like), free radicals such as methyl or methylene are generated, and the free radicals are contacted with free radicals generated by pyrolysis of raw materials such as coal or biomass in the raw material bed layer 15, so that the stable rate and efficiency of the free radicals can be improved, and the yield of raw material pyrolysis tar such as coal and biomass is improved. Or from the reaction solution CH 3 OH pyrolysis, CH 3 Catalytic reforming of OH and oxidant, CH 3 OH reacts with steam, and the process can also provide a large amount of hydrogen free radicals, and the hydrogen free radicals are combined with free radical fragments generated by pyrolysis of raw materials such as coal, biomass and the like, so that the yield of raw material pyrolysis tar products is improved. The obtained gaseous product is evenly spread to a catalyst A bed layer 19 through a third gas distributor 18, the catalyst A bed layer 19 carries out catalytic pyrolysis on the gaseous product of pyrolysis reaction, the product after catalytic pyrolysis enters a catalyst B bed layer 21 to carry out further shape-selective catalysis to directionally regulate and control the product, the ideal target product is further obtained, the product after shape-selective catalysis enters a condensing device to be condensed, the obtained liquid tar is collected in a liquid tar product storage tank 26, and the gas The gaseous products enter a gas product storage tank 28, the collected liquid tar and gaseous products are sent to a gas chromatograph-mass spectrometer 30 for online real-time detection and analysis, and the detection results of the products are fed back to a temperature and pressure control device in time, so that the relevant process parameters of each process section are regulated in real time, and the optimization of the process parameters is realized. Wherein, when the raw material is coal, the target products are benzene, toluene, xylene and naphthalene; when the raw material is biomass, the target products are phenol, cresol and xylenol.
The catalyst for activating the reaction liquid or the mixture of the reaction liquid and the reaction gas in a certain ratio comprises: cu/CeO 2 、CuO/CeO 2 、Cu/ZnO/ZrO 2 、Cu/ZnO/Al 2 O 3 A Cu-based catalyst; ni/CeO 2 、Ni/CeO 2 -ZrO 2 Ni-based catalyst; pd/ZnO, pd/La 2 O 3 、Pd/SiO 2 、Pd/ZrO 2 Noble metal catalysts.
The reaction liquid or the mixture of the reaction liquid and the reaction gas mixed in a certain proportion is subjected to an activation reaction through the catalyst bed layer 13, and the activation reaction temperature (the upper temperature of a reaction tube in the upper section bed) is as follows: 200-500 ℃, and the reaction pressure is as follows: 0.01MPa to 0.1MPa.
The pyrolysis temperature (the lower temperature of the reaction tube in the upper bed) of the raw materials such as coal, biomass and the like is as follows: the reaction pressure is 0.1 MPa-1 MPa at 300-800 ℃.
The mass ratio of the catalyst of the raw material (coal or biomass) to the activated reaction gas (reaction liquid) is as follows: (0.5-2): 1.
The process method for carrying out catalytic pyrolysis and directional regulation on pyrolysis tar products of raw materials comprises the following steps: the technical method of the catalytic cracking section of the raw material pyrolysis tar product and the technical method of the directional regulation section of the raw material pyrolysis tar product are as follows:
the catalytic cracking section process method of the raw material pyrolysis tar product comprises the following steps:
the lower furnace 10 is used for catalyzing and shape-selecting raw material pyrolysis tar, so that product distribution is directionally regulated and controlled, a third gas distributor 18, a catalyst A bed layer 19, a solid distributor 20, a catalyst B bed layer 21, a solid distributor 22 and a fourth gas distributor 23 are sequentially arranged in a reaction tube in the lower furnace from top to bottom, the catalyst A bed layer 19 is used for catalyzing and cracking pyrolysis tar, and the catalyst B bed layer 21 is used for directionally regulating and controlling catalytic cracking products.
The gaseous tar product with the yield increased by the upper furnace enters the lower bed along with the reaction gas flow, and is subjected to catalytic pyrolysis by the catalyst A bed layer 19, so that macromolecular substances in the gaseous tar product are further cracked into smaller molecular substances, and the coal pyrolysis heavy tar is promoted to be converted into light tar and gas, thereby realizing the optimization of tar quality.
The catalytic cracking section has the following catalytic cracking temperature of gaseous tar: 600-800 ℃ and the reaction pressure is 0.1-1 MPa.
The catalyst of the catalyst A bed 19 comprises: mainly comprises a carbon-based catalyst or an alumina catalyst, semicoke, activated carbon fiber, carbon nano tube, graphene or alumina and the like are used as catalyst carriers, and different types of metal ions such as Co, ni, cu, zn, fe, mg, ce, zr, ga and the like with different proportions are loaded on the carriers.
The mass ratio of the raw materials to the catalyst of the catalyst A bed 19 is as follows: (0.5-4): 1.
the process method of the directional regulation section of the raw material pyrolysis tar product comprises the following steps:
after the gaseous tar product passes through the catalyst A bed 19 and is subjected to catalytic pyrolysis, the gaseous tar product is subjected to shape-selective catalysis by the catalyst positioned in the catalyst B bed 21 along with the reaction gas flow entering the catalyst B bed 21, so that the distribution of the tar product is directionally regulated and controlled.
The catalyst of the catalyst B bed 21 mainly comprises: molecular sieve catalysts or supported molecular sieve catalysts. The molecular sieve catalyst comprises: ZSM-5, ZSM-11, USY, HY, beta molecular sieves, and the like. The loaded metal ions mainly comprise: mo, ni, and the like.
The supported molecular sieve catalyst of the catalyst B bed 21 can be independently supported with a certain mass fraction of Mo or Ni metal ions or simultaneously supported with a certain mass fraction of Mo and Ni metal ions.
The directional regulation section has the following catalytic cracking temperature of gaseous tar: the reaction pressure is 0.1 MPa-1 MPa at 400-600 ℃.
The mass ratio of the raw materials to the catalyst of the directional regulation and control of the B bed layer 21 is as follows: (0.5-2): 1.
the upper furnace 9 and the lower furnace 10 are coaxial up and down, the reaction pipes of the upper furnace and the lower furnace are positioned in the middle of the furnace body, have the same diameter up and down and are communicated up and down, and the middle is separated by a gas distribution plate and a sieve plate. The outside of the two-stage furnace is respectively connected with a temperature controller and a pressure controller which are respectively used for controlling the temperature and the pressure of the upper part and the lower part of the reaction tube in the upper-stage furnace and the temperature and the pressure of the upper part and the lower part of the reaction tube in the lower-stage furnace.
The lower part of the lower furnace 10 is connected with a condensing device 24, the condensing device is used for condensing the gaseous products after shape-selective catalysis, the outside of the condensing device is a closed condensing tank 24, the inside of the condensing device is a spiral condensate conduit, and an inlet and an outlet of the condensate conduit are communicated with an external circulating condensate conveying pump 25.
The condensing device is further connected to a tar collecting device 26 and a gas collecting device 28 for collecting condensable tar and non-condensable gas products, respectively, while the tar and gas collecting device 28 is connected to a product detecting device 30 for on-line detection and analysis of the constituent components of the tar and gas products.
The product detection device 30 is a gas chromatography-mass spectrometer which is connected with the temperature and pressure control devices 31-46 in the device and is used for feeding back the product detection result to the temperature and pressure control devices 31-46 in time, so that the relevant process parameters of each process section are regulated in real time, and the optimization of the process parameters is realized.
The following are examples under different process conditions.
Example 1
The industrial analysis and the element analysis of the low-rank coal of a certain chemical plant in the north of Shaanxi are shown in Table 1. 5g of experimental coal, and N as reaction gas 2 The catalyst activation temperature is 600 ℃, the catalyst used for activating the reaction gas is HY (also called HY molecular sieve catalyst),the HY consumption is 2g; the temperature of the pyrolysis of the coal is 800 ℃, and the reaction pressure is: 0.1MPa; the catalytic cracking catalyst is Al 2 O 3 ，Al 2 O 3 The dosage is 2g, and the temperature of the catalytic cracking section is 600 ℃; the catalyst for directionally regulating and controlling the tar product is Mo/Ni/HZSM-5, the dosage of the Mo/Ni/HZSM-5 is 2g, the temperature of a directional regulating section is 500 ℃, and the reaction pressure is as follows: 0.1MPa. The yield of coal pyrolysis tar was 5.63%. Referring to Table 2, the distribution of the components of various products of the coal is shown in Table 2, and the total relative content of BTXN in the catalytic cracking products of the coal after directional control is 8.84%. FIG. 5 is a total ion flow chromatogram of a gaseous tar product from coal pyrolysis (N 2 As the reaction gas), as can be seen from fig. 5, after directional regulation, the GC/MS peak of the target product is relatively large and independent, i.e., the target product is effectively separated and enriched.
TABLE 1 Industrial analysis and elemental analysis of Low rank coal
* Differential subtraction
Table 2 component distribution of various products of coal (N 2 Is reaction gas
Example 2
The industrial analysis and the element analysis of the low-rank coal of a certain chemical plant in the north of Shaanxi are shown in Table 1. 5g of experimental coal, and CH as reaction gas 4 The catalyst activation temperature is 600 ℃, the catalyst used for activating the reaction gas is HY, and the HY consumption is 2g; the temperature of the pyrolysis of the coal is 800 ℃, and the reaction pressure is: 0.1MPa; the catalytic cracking catalyst is Al 2 O 3 ，Al 2 O 3 The dosage is 2g, and the temperature of the catalytic cracking section is 600 ℃; the catalyst for directionally regulating and controlling the tar product is Mo/Ni/HZSM-5, the dosage of the Mo/Ni/HZSM-5 is 2g, the temperature of a directional regulating section is 500 ℃, and the reaction pressure is as follows: 0.1MPa. The yield of coal pyrolysis tar was 8.81%. The component distribution of each type of product of the coal is shown in table 3,as can be seen from Table 3, the total relative BTXN content in the directionally regulated coal catalytic cracking product was 32.94%. Fig. 6 shows a total ion flow chromatogram of a gaseous tar product of coal pyrolysis, and as can be seen from fig. 6, after directional regulation, the GC/MS peak of the target product is relatively large and independent, i.e., the target product is effectively separated and enriched.
TABLE 3 component distribution (CH) of various products of coal 4 Is reaction gas
Example 3
The industrial analysis and the element analysis of the low-rank coal of a certain chemical plant in the north of Shaanxi are shown in Table 1. 5g of experimental coal, and the reaction solution is CH 3 OH, the catalyst activation temperature is 600 ℃, the catalyst used for activating the reaction gas is HY, and the HY consumption is 2g; the temperature of the pyrolysis of the coal is 800 ℃, and the reaction pressure is: 0.1MPa; the catalytic cracking catalyst is Al 2 O 3 ，Al 2 O 3 The temperature of the catalytic cracking section with the dosage of 2g is 600 ℃; the catalyst for directionally regulating and controlling the tar product is Mo/Ni/HZSM-5, the dosage of the Mo/Ni/HZSM-5 is 2g, the temperature of a directional regulating section is 500 ℃, and the reaction pressure is as follows: 0.1MPa. The yield of coal pyrolysis tar was 9.93%. Referring to table 4, the distribution of the components of each product of the coal is shown in table 4, and the total relative content of BTXN in the catalytic cracking product of the coal after directional control is 19.01%. Fig. 7 shows a total ion flow chromatogram of a gaseous tar product of coal pyrolysis, and as can be seen from fig. 7, after directional regulation, the GC/MS peak of the target product is relatively large and independent, i.e., the target product is effectively separated and enriched.
TABLE 4 distribution of the components of various products of coal (reaction liquid CH 3 OH)
Example 4
The corn stalks are used as raw materials, and the industrial analysis and the element analysis are shown in Table 5. Corn for experiment 4g of straw and N as reaction gas 2 The catalyst activation temperature is 600 ℃, the catalyst used for activating the reaction gas is HY, and the HY consumption is 1g; the pyrolysis temperature of the corn straw is 800 ℃, and the reaction pressure is as follows: 0.1MPa; the catalytic cracking catalyst is Al 2 O 3 ，Al 2 O 3 The dosage is 1g, and the temperature of the catalytic cracking section is 600 ℃; the catalyst for directionally regulating and controlling the tar product is Mo/Ni/HZSM-5, the dosage of the Mo/Ni/HZSM-5 is 1g, the temperature of a directional regulating section is 500 ℃, and the reaction pressure is as follows: 0.1MPa. The pyrolysis tar yield of the corn straw is 4.35%. Referring to table 6, the distribution of the components of each product of the corn straw is shown in table 6, and the total relative content of PCX in the catalytic cracking product of the corn straw after directional control is 14.04%. Fig. 8 shows a total ion flow chromatogram of a gaseous tar product of pyrolysis of corn straw, and as can be seen from fig. 8, after directional regulation, the GC/MS peak of the target product is relatively large and independent, i.e. the target product is effectively separated and enriched.
TABLE 5 Industrial and elemental analysis of corn stover
* Differential subtraction
TABLE 6 component distribution of various products of corn stover (N 2 Is reaction gas
Example 5
The corn stalks are used as raw materials, and the industrial analysis and the element analysis are shown in Table 5. Corn stalk 4g for experiment, reaction gas CH 4 The catalyst activation temperature is 600 ℃, the catalyst used for activating the reaction gas is HY, and the HY consumption is 1g; the pyrolysis temperature of the corn straw is 800 ℃, and the reaction pressure is as follows: 0.1MPa; catalytic crackingThe catalyst is Al 2 O 3 ，Al 2 O 3 The dosage is 1g, and the temperature of the catalytic cracking section is 600 ℃; the catalyst for directionally regulating and controlling the tar product is Mo/Ni/HZSM-5, the dosage of the Mo/Ni/HZSM-5 is 1g, the temperature of the directionally regulating section is 500 ℃, and the reaction pressure is as follows: 0.1MPa. The pyrolysis tar yield of the corn straw is 8.29%. Referring to table 7, the distribution of the components of each product of the corn straw is shown in table 7, and the total relative content of PCX in the catalytic cracking product of the corn straw after directional regulation is 31.01%. Fig. 9 shows a total ion flow chromatogram of a gaseous tar product of pyrolysis of corn straw, and as can be seen from fig. 9, after directional regulation, the GC/MS peak of the target product is relatively large and independent, i.e. the target product is effectively separated and enriched.
TABLE 7 component distribution of various products of corn stover (CH 4 Is reaction gas
Example 6
The corn stalks are used as raw materials, and the industrial analysis and the element analysis are shown in Table 5. 4g of corn stalk for experiments, and the reaction solution is CH 3 OH, the catalyst activation temperature is 600 ℃, the catalyst used for activating the reaction gas is HY, and the HY consumption is 1g; the pyrolysis temperature of the corn straw is 800 ℃, and the reaction pressure is as follows: 0.1MPa; the catalytic cracking catalyst is Al 2 O 3 ，Al 2 O 3 The dosage is 1g, and the temperature of the catalytic cracking section is 600 ℃; the catalyst for directionally regulating and controlling the tar product is Mo/Ni/HZSM-5, the dosage of the Mo/Ni/HZSM-5 is 1g, the temperature of a directional regulating section is 500 ℃, and the reaction pressure is as follows: 0.1MPa. The pyrolysis tar yield of the corn straw is 9.92%. Referring to table 8, the distribution of the components of various products of the corn stalks is shown in table 8, and the total relative content of PCX in the catalytic cracking products of the corn stalks after directional control is 29.42%. Fig. 10 shows a total ion flow chromatogram of a gaseous tar product of pyrolysis of corn straw, and as can be seen from fig. 10, after directional regulation, the GC/MS peak of the target product is relatively large and independent, i.e. the target product is effectively separated and enriched.
TABLE 8 component distribution of various products of corn stover (reaction solution CH) 3 OH)
/>

Claims (8)

1. The directional catalytic cracking device is characterized by comprising a gas supply device, an upper-stage furnace (9) for improving the yield of tar in a coal pyrolysis reaction, a lower-stage furnace (10) for performing catalytic shape selection on the pyrolysis tar, a cooling device and a temperature and pressure controller device; the upper-stage furnace (9) and the lower-stage furnace (10) are both cylinders, the upper-stage furnace (9) and the lower-stage furnace (10) are coaxial up and down, and the centers in the upper-stage furnace (9) and the lower-stage furnace (10) are vertically provided with reaction pipes; the air supply device is connected with the upper-stage furnace (9), and the air supply device, the upper-stage furnace (9) and the lower-stage furnace (10) are connected with the temperature and pressure controller device; the cooling device is arranged below the lower-stage furnace (10);
A gas distributor (12), a catalyst bed (13), a first solid distributor (14), a raw material bed (15), a second solid distributor (16) and a second gas distributor (17) are arranged in a reaction tube in the upper furnace (9) from top to bottom; the gas distributor (12) is used for uniformly distributing the reaction gas in the catalyst bed, the catalyst bed (13) is used for activating the reaction gas, the first solid distributor (14) and the second solid distributor (16) are respectively used for tiling the catalyst bed (13) and the raw material bed (15), and the second gas distributor (17) is used for enabling the gaseous product after the pyrolysis reaction to flow into the reaction tube of the lower furnace (10);
a third gas distributor (18), a catalyst A bed (19), a third solid distributor (20), a catalyst B bed (21), a fourth solid distributor (22) and a fourth gas distributor (23) are arranged in the reaction tube in the lower furnace (10) from top to bottom; the third gas distributor (18) is used for distributing gaseous products after pyrolysis reaction on a catalyst A bed (19), the catalyst A bed (19) is used for catalyzing the gaseous products of pyrolysis reaction, the third solid distributor (20) and the fourth solid distributor (22) are respectively used for tiling the catalyst A bed (19) and a catalyst B bed (21), the catalyst B bed (21) is used for directionally regulating and controlling the distribution of tar products, and the supported molecular sieve catalyst of the catalyst B bed (21) is used for independently supporting Mo or Ni metal ions with a certain mass fraction or simultaneously supporting Mo and Ni metal ions with a certain mass fraction; a fourth gas distributor (23) for flowing the gaseous product after the reaction to the condensing means;
The upper, middle and lower parts outside the furnace body of the upper furnace (9) are respectively connected with a signal wire to an upper furnace middle part temperature controller (34), an upper furnace upper part temperature controller (35) and an upper furnace lower part temperature controller (36) in the temperature and pressure controller device, and the upper, middle and lower parts outside the furnace body of the lower furnace (10) are respectively connected with a signal wire to a lower furnace middle part temperature controller (37), a lower furnace upper part temperature controller (38) and a lower furnace lower part temperature controller (39).
2. A directional catalytic cracking unit according to claim 1, characterized in that the gas supply means comprises a first gas cylinder (1), a second gas cylinder (2), a third gas cylinder (3), a first carrier gas flow control valve (4), a second carrier gas flow control valve (5), a third carrier gas flow control valve (6), a mixing gas cylinder (7) and a system total carrier gas flow controller (8) for regulating the total flow of the reaction gas; the outlet of the first gas carrying cylinder (1) is connected with the inlet of a mixed gas cylinder (7) through a first gas carrying flow control valve (4), the outlet of the second gas carrying cylinder (2) is connected with the inlet of the mixed gas cylinder (7) through a second gas carrying flow control valve (5), the outlet of the third gas carrying cylinder (3) is connected with the inlet of the mixed gas cylinder (7) through a third gas carrying flow control valve (6), and the outlet of the mixed gas cylinder (7) is connected with the inlet of an upper furnace (9) through a system total gas carrying flow controller (8).
3. A directional catalytic cracking unit according to claim 2, wherein the temperature and pressure controller means comprises a first carrier gas flow controller (31), a second carrier gas flow controller (32), a third carrier gas flow controller (33), an upper furnace middle temperature controller (34), an upper furnace upper temperature controller (35), an upper furnace lower temperature controller (36), a lower furnace middle temperature controller (37), a lower furnace upper temperature controller (38) and a lower furnace lower temperature controller (39); the first carrier gas flow controller (31) is connected with the first carrier gas flow control valve (4), the second carrier gas flow controller (32) is connected with the second carrier gas flow control valve (5), and the third carrier gas flow controller (33) is connected with the third carrier gas flow control valve (6).
4. A directional catalytic cracking unit according to claim 1, characterized in that the cooling unit comprises a screw type condensing unit (24), a circulating condensate transfer pump (25), a liquid tar product storage tank (26), a gas product storage tank (28) and a gas chromatography mass spectrometer (30); a spiral condensing device (24) is arranged below the lower-stage furnace (10), the inlet of the spiral condensing device (24) is communicated with the outlet of the lower-stage furnace (10), the outlet of the spiral condensing device (24) is divided into two paths, one path is connected with a gas chromatography mass spectrometer (30) through a gas product storage tank (28), a secondary liquid condensing product storage tank (29) is arranged below the gas product storage tank (28), the secondary liquid condensing product storage tank (29) is connected with the gas product storage tank (28), and the other path is connected with the gas chromatography mass spectrometer (30) through a liquid tar product storage tank (26); the spiral condensing device (24) is also connected with a circulating condensate delivery pump (25).
5. A directional catalytic cracking process based on the device of claim 1, characterized in that the reaction atmosphere in the reaction tube of the upper furnace (9) is tiled to the catalyst bed (13) through the first gas distributor (12) to activate the reaction gas, and the activation temperature is: the reaction pressure is between 0.1 and 1MPa at 600 and 800 ℃, free radicals are generated under the action of a catalyst in the reaction atmosphere and are in contact with free radicals generated by pyrolysis of raw materials in a raw material bed layer (15), the obtained gaseous products are tiled to a catalyst A bed layer (19) through a third gas distributor (18), the catalyst A bed layer (19) carries out catalytic pyrolysis on the gaseous products of the pyrolysis reaction, the products after the catalytic pyrolysis enter a catalyst B bed layer (21) for shape-selective catalysis, and the products after the shape-selective catalysis enter a condensing device for condensation, so that liquid tar is obtained; wherein the raw material is coal or biomass.
6. The process according to claim 5, wherein the reaction atmosphere is CH 4 、CH 4 And CO 2 Is a mixed gas of CH 4 And water vapor mixture, CH 4 And O 2 A mixture of methanol cracking gas and oxygen or a mixture of methanol cracking gas and water vapor; wherein CH is 4 And CO 2 CH in the mixed gas of (2) 4 And CO 2 The volume ratio of (1-2): 1, a step of; CH (CH) 4 In the mixed gas with water vapor, CH is calculated by volume percent 4 10-20% of water vapor 80-90%; CH (CH) 4 And O 2 In volume percent, CH 4 80 to 90 percent of O 2 10% -20%; in the mixture of methanol and oxygen, the ratio of the amounts of the substances of methanol and oxygen is (2 to 5): 1, a step of; in the mixture of methanol and water vapor, the ratio of the amounts of the methanol and water vapor is (1 to 1.5): 1.
7. the directional catalytic cracking process according to claim 5, wherein the catalytic cracking temperature is 600-800 ℃ and the pressure is 0.1-1 MPa; the mass ratio of the raw materials to the catalyst on the catalyst A bed (19) is as follows: (0.5-4): 1.
8. the directional catalytic cracking process according to claim 5, wherein the shape selective catalytic temperature is 400-600 ℃ and the pressure is 0.1-1 MPa; the mass ratio of the raw material to the catalyst on the catalyst B bed (21) is as follows: (0.5-2): 1.
CN201811013130.3A 2018-08-31 2018-08-31 Directional catalytic cracking device and process Active CN108913179B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811013130.3A CN108913179B (en) 2018-08-31 2018-08-31 Directional catalytic cracking device and process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811013130.3A CN108913179B (en) 2018-08-31 2018-08-31 Directional catalytic cracking device and process

Publications (2)

Publication Number Publication Date
CN108913179A CN108913179A (en) 2018-11-30
CN108913179B true CN108913179B (en) 2024-01-16

Family

ID=64407412

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811013130.3A Active CN108913179B (en) 2018-08-31 2018-08-31 Directional catalytic cracking device and process

Country Status (1)

Country Link
CN (1) CN108913179B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110208451B (en) * 2019-04-26 2022-05-24 合肥工业大学 Online detection system and method for bipolar miniature fixed bed reactor combined with photoionization mass spectrometry
CN110066671A (en) * 2019-05-13 2019-07-30 华南理工大学 The biomass microwave catalytic pyrolysis method and its integrated apparatus of catalyst regeneration
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
CN111849535B (en) * 2020-07-27 2022-01-04 天津大学 Pyrolysis and catalysis integrated experimental device and method
CN112410058B (en) * 2020-11-06 2022-09-02 重庆大学 Pyrolysis device and pyrolysis method for hydrocarbon raw material

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4724064A (en) * 1983-11-17 1988-02-09 Betz Laboratories, Inc. Composition and method for coke retardant during hydrocarbon processing
JP2011236394A (en) * 2010-05-10 2011-11-24 Nippon Sozai Kk Woody gas producer
WO2013040886A1 (en) * 2011-09-23 2013-03-28 北京神雾环境能源科技集团股份有限公司 Revolving bed retort and method for increasing tar yield of coal carbonization by activating endogenous pyrolysis gas
CN103571541A (en) * 2012-07-30 2014-02-12 新奥科技发展有限公司 Catalytic gasification method for co-production of methane and tar
CN104046374A (en) * 2014-06-12 2014-09-17 江苏大学 Device and method for quickly preparing bio-oil by catalytically cracking biomass pyrolysis vapor on line
CN106147817A (en) * 2015-04-17 2016-11-23 中国科学院过程工程研究所 A kind of catalysis method for pyrolysis of biomass and/or coal
CN106675610A (en) * 2017-02-28 2017-05-17 西北大学 Device and method for performing in-situ catalytic modification on volatile components obtained during rapid pyrolysis and coupling pyrolysis of coal
CN107670699A (en) * 2016-08-01 2018-02-09 北京华石联合能源科技发展有限公司 A kind of heavy oil floating bed hydrogenation catalyst using complex carrier

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104910941B (en) * 2015-05-14 2017-11-03 神雾科技集团股份有限公司 A kind of revolving bed coal is catalyzed method for pyrolysis
CN208917131U (en) * 2018-08-31 2019-05-31 西北大学 A kind of directional catalyzing cracker

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4724064A (en) * 1983-11-17 1988-02-09 Betz Laboratories, Inc. Composition and method for coke retardant during hydrocarbon processing
JP2011236394A (en) * 2010-05-10 2011-11-24 Nippon Sozai Kk Woody gas producer
WO2013040886A1 (en) * 2011-09-23 2013-03-28 北京神雾环境能源科技集团股份有限公司 Revolving bed retort and method for increasing tar yield of coal carbonization by activating endogenous pyrolysis gas
CN103571541A (en) * 2012-07-30 2014-02-12 新奥科技发展有限公司 Catalytic gasification method for co-production of methane and tar
CN104046374A (en) * 2014-06-12 2014-09-17 江苏大学 Device and method for quickly preparing bio-oil by catalytically cracking biomass pyrolysis vapor on line
CN106147817A (en) * 2015-04-17 2016-11-23 中国科学院过程工程研究所 A kind of catalysis method for pyrolysis of biomass and/or coal
CN107670699A (en) * 2016-08-01 2018-02-09 北京华石联合能源科技发展有限公司 A kind of heavy oil floating bed hydrogenation catalyst using complex carrier
CN106675610A (en) * 2017-02-28 2017-05-17 西北大学 Device and method for performing in-situ catalytic modification on volatile components obtained during rapid pyrolysis and coupling pyrolysis of coal

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Mo-Fe/C催化裂解乙醇协同制备氢气和多壁碳纳米管;刁金香等;化工新型材料;第46卷(第7期);全文 *
凹凸棒石粘土催化裂解生物质焦油模型化合物的实验研究;彭书传;宋磊;张先龙;周凯华;陈天虎;;矿物学报;第30卷(第03期);全文 *
府谷煤CO2催化气化反应性的研究;闫小霞等;化工进展;第35卷(第11期);全文 *
甲醇水蒸气重整与煤热解耦合对热解产物分布的影响;张小琴等;煤炭技术;第37卷(第8期);第290-292页 *

Also Published As

Publication number Publication date
CN108913179A (en) 2018-11-30

Similar Documents

Publication Publication Date Title
CN108913179B (en) Directional catalytic cracking device and process
US8864984B2 (en) Catalytic pyrolysis of solid biomass and related biofuels, aromatic, and olefin compounds
Ma et al. Controlling the selectivity to chemicals from lignin via catalytic fast pyrolysis
Xu et al. High pressure hydropyrolysis of coals by using a continuous free-fall reactor☆
CN102559273B (en) Microwave plasma biomass gasification fixed-bed gasification furnace and process
US20090165378A1 (en) Fractional catalytic pyrolysis of biomass
Chen et al. Studies of fast co-pyrolysis of oil shale and wood in a bubbling fluidized bed
Fan et al. Directional synthesis of ethylbenzene through catalytic transformation of lignin
MX2014002032A (en) Method for producing fluid hydrocarbons.
JP2011514927A5 (en)
CN101475143B (en) Biomass hydrogen production in water vapour atmosphere and series fluidized bed apparatus system thereof
Hong et al. Selective production of green light olefins by catalytic conversion of bio‐oil with Mg/HZSM‐5 catalyst
CN208917131U (en) A kind of directional catalyzing cracker
US10174258B2 (en) Two-stage biomass pyrolysis
Burhenne et al. Technical demonstration of the novel Fraunhofer ISE biomass gasification process for the production of a tar-free synthesis gas
CN103275757A (en) Oil-gas coupling poly-generation method in coal chemical engineering industry
Fan et al. Catalytic upgrading of biomass pyrolysis volatiles to bio-fuel under pre-plasma enhanced catalysis (PPEC) system
Zhang et al. Low temperature catalytic gasification of pig compost to produce H2 rich gas
CN213803649U (en) Device for preparing gasoline by catalytic hydrogenation of carbon dioxide
Ma et al. Hydrogen Production from Bio‐Char via Steam Gasification in a Fluidized‐Bed Reactor
US8536234B2 (en) Process for generation of synthetic fuel from carbonaceus substances
García et al. Hydrogen production from catalytic biomass pyrolysis
KR101032178B1 (en) Gasification system for converting carbonaceous feedstock into synthesis gas and method thereof
CN112300825B (en) Biomass hydro-catalysis rapid pyrolysis device and method based on hydrogen overflow
Nugraha et al. The combined process of pyrolysis and catalytic cracking of rice straw using ZSM-5 and γ-Al2O3 catalyst prepared by physically mixing

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant