System and method for catalytic pyrolysis of broken - bond reforming of bacterial residue to prepare aviation fuel precursors

Abstract

The present invention discloses a system and method for catalytic pyrolysis of broken - bond reforming of mushroom residue to prepare aviation fuel precursors. The intake system includes a carrier gas inlet, a nitrogen gas cylinder, an air cylinder, a nitrogen mass flowmeter, an air mass flowmeter and a flow controller; the multi - stage pyrolysis catalytic system includes a mushroom residue pusher, a primary heating section, a secondary heating section, a tertiary heating section, a pyrolysis carbon collection tube, a broken - bond catalyst bed, a shape - selective catalyst bed, a pyrolysis reactor and a temperature controller; the product collection system includes a four - stage condenser, a drying tube and a gas collection bag. The method involves rapid pyrolysis of mushroom residue in the primary heating section, preliminary broken - bond deoxidation in the secondary heating section to form stable small - molecule products and match the pore channels of the shape - selective catalyst, and aromatization conversion into aromatic aviation fuel precursors in the pore channels of the shape - selective catalyst in the tertiary heating section. It solves the problems in traditional catalytic pyrolysis, such as wide molecular weight distribution of mushroom residue pyrolysis intermediate products, mismatch with the pore channels of microporous shape - selective catalysts, and low yield of target products.

Description

Technical Field

[0001] The present invention relates to a system and method for catalytic pyrolysis of broken - bond reforming of microbial residue to prepare aviation fuel precursors, belonging to the technical field of comprehensive utilization of biomass. Background Art

[0002] Waste microbial residue is a solid waste formed by fermentation. In addition, waste microbial residue has a high water content, high collection and transportation costs, backward treatment capacity, low utilization efficiency, and easy accumulation or incineration, which can cause pollution to relevant enterprises and water bodies, resulting in waste of resources and environmental pollution. Therefore, high - value utilization is an inevitable trend for the utilization of waste microbial residue. Biomass such as waste microbial residue is a renewable resource with a huge output. Catalytic pyrolysis of waste microbial residue to prepare aviation fuel precursors in a targeted manner is an efficient solid - waste conversion route, which can realize the resource - based and energy - based utilization of waste microbial residue.

[0003] Waste microbial residue has a high protein content. The primary pyrolysis products have large molecular weights and are unstable, and are prone to secondary condensation to produce heavy tar, blocking the reactor pipeline. The catalytic pyrolysis of waste microbial residue by zeolite catalyst can catalytically convert glucosamine residue to prepare aromatics, but there are still problems such as low yield of target liquid products and many by - products. In addition, pyrolyzed large - molecule oxygen - containing compounds are prone to polymerization and coking at strong acid sites. Coke will deposit on the surface of the molecular sieve, covering the active sites of the catalyst and blocking the catalyst pores, which has a negative impact on the shape - selective deoxygenation performance of the catalyst. The molecular diameter of large - molecule microbial residue pyrolysis does not match the pore diameter of the shape - selective catalyst, making it difficult to be effectively converted. Moreover, the process of bond breaking in microbial residue pyrolysis is extremely complex, and the composition and distribution of products are affected by many factors. It is necessary to develop a multifunctional catalyst and device system for the efficient conversion of waste microbial residue. Summary of the Invention

[0004] Technical Problem: Aiming at the deficiencies in the prior art, the present invention provides a system and method for catalytic pyrolysis of broken - bond reforming of microbial residue to prepare aviation fuel precursors. Combining the functional characteristics of a multi - pore bond - breaking catalyst and a micro - pore reforming catalyst, the pyrolyzed large - molecules of waste microbial residue are step - by - step broken - bond deoxygenated and shape - selectively converted, realizing the efficient conversion of waste microbial residue into aviation fuel precursors. At the same time, it solves the problems of rapid coking of the catalyst and secondary polymerization of pyrolysis products to form tar blocking the reactor in the traditional catalytic pyrolysis process.

[0005] Technical Solution: The present invention is a system and method for catalytic pyrolysis of broken - bond reforming of microbial residue to prepare aviation fuel precursors. The system for catalytic pyrolysis of broken - bond reforming of microbial residue to prepare aviation fuel precursors includes an air - intake system, a multi - stage pyrolysis catalytic system, and a product collection system;

[0006] The intake system includes a nitrogen gas cylinder, an air cylinder, a nitrogen mass flowmeter, an air mass flowmeter, and a flow controller; the outlet of the nitrogen gas cylinder is connected to the inlet of the nitrogen mass flowmeter, the outlet of the air cylinder is connected to the inlet of the air mass flowmeter, the flow controller is respectively connected to the nitrogen mass flowmeter and the air mass flowmeter, and the outlets of the nitrogen mass flowmeter and the air mass flowmeter are merged through valves and then connected to the carrier gas inlet;

[0007] The multi-stage pyrolysis catalytic system includes a bacterial residue pusher, a carrier gas inlet, a first-stage heating section, a second-stage heating section, a third-stage heating section, a pyrolysis carbon collection tube, a bond-breaking catalyst bed, a shape-selective catalyst bed, a pyrolysis reactor, and a temperature controller; the outlets of the bacterial residue pusher and the carrier gas inlet are connected to the inlet of the pyrolysis reactor, and the inlet of the pyrolysis reactor, the pyrolysis carbon collection tube, the bond-breaking catalyst bed, the shape-selective catalyst bed, and the outlet of the pyrolysis reactor are sequentially connected. The first-stage heating section, the second-stage heating section, and the third-stage heating section are sequentially arranged outside the pyrolysis carbon collection tube, the bond-breaking catalyst bed, and the shape-selective catalyst bed, and the temperature controller is respectively connected to the pyrolysis carbon collection tube, the bond-breaking catalyst, and the shape-selective catalyst bed;

[0008] The product collection system includes a four-stage condenser, a drying tube, and a gas collection bag. The inlet of the four-stage condenser is connected to the outlet of the pyrolysis reactor, the inlet of the drying tube is connected to the outlet of the four-stage condenser, and the outlet of the drying tube is connected to the gas collection bag.

[0009] The method for catalytic pyrolysis of waste microbial bacterial residue to prepare aviation fuel precursor by bond-breaking and reforming in the system of the present invention includes the following steps:

[0010] S1. After the system device is started, open the nitrogen gas cylinder, adjust the nitrogen gas flow through the flow controller and the nitrogen mass flowmeter. The nitrogen gas enters the pyrolysis reactor through the carrier gas inlet to evacuate the air in the reactor and maintain an inert atmosphere environment; heat the first-stage heating section, the second-stage heating section, and the third-stage heating section to a predetermined temperature and stabilize them through the temperature controller;

[0011] S2. Use the bacterial residue pusher to pump the waste microbial bacterial residue into the pyrolysis reactor at a predetermined speed. After the bacterial residue is pyrolyzed in the first-stage heating section (3), the solid product remains in the pyrolysis carbon collection tube, and the pyrolysis gas enters the second-stage heating section area, where it is preliminarily bond-broken and deoxidized through the bond-breaking catalyst bed, and then enters the third-stage heating section area, where it is reformed into an aviation fuel precursor through the shape-selective catalyst bed;

[0012] S3. The product at the outlet of the pyrolysis reactor is condensed by the four-stage condenser, and the non-condensed gas enters the drying tube (17) to remove the doped water vapor. Finally, the non-condensed pyrolysis gas enters the gas collection bag;

[0013] S4. After the pyrolysis reaction is completed, take out the pyrolysis carbon collection tube and weigh the mass of the solid product, and collect the catalysts in the bond-breaking catalyst bed and the shape-selective catalyst bed (8);

[0014] S5. Open the air cylinder, adjust the air flow through the flow controller and air mass flowmeter, heat the pyrolysis reactor to a predetermined temperature through the temperature controller, remove the residual heavy tar on the reactor wall by combustion, and weigh the mass of the reactor before and after the reaction to obtain the mass of the heavy tar catalytically pyrolyzed from the waste microbial residue.

[0015] The waste microbial residue is crushed particles with a mesh number of 40 - 80 and dried at 90 - 110 °C.

[0016] The lower part of the pyrolysis carbon collection tube is provided with holes, quartz wool is placed at the bottom, and the top is at the same height as the inside of the pyrolysis reactor.

[0017] The bond-breaking catalyst bed uses natural or synthetic acidic or alkaline solid catalysts, including activated carbon catalysts with large - medium - micro interconnected hierarchical pores, and the bed thickness is 10 - 20 mm.

[0018] The shape-selective catalyst bed uses molecular sieve catalysts, including HY, HZSM - 5, H-β, with a silica-alumina ratio of 25 - 80, a catalyst particle size of 40 - 50 mesh, and a bed thickness of 5 - 10 mm.

[0019] The nitrogen flow rate is 60 - 180 ml / min, and the pyrolysis gas stays in the pyrolysis reactor for 2 - 6 s.

[0020] The outlet of the residue pusher (1) is inclined upward with an inclination angle of 10 - 30°, and the raw material feeding speed is controlled; the waste microbial residue is pumped into the pyrolysis reactor at a feeding speed of 10 - 40 mg / min.

[0021] The temperature range of the first-stage heating section area is 550 - 700 °C, the temperature of the second-stage heating section area is 450 - 600 °C, and the temperature of the third-stage heating section area is 550 - 600 °C.

[0022] The bottom of the pyrolysis reactor (9) is wrapped with heating tapes, with two layers of heating tapes, and the temperature range is 150 - 300 °C, to prevent the condensation of aviation fuel precursors at the reactor outlet.

[0023] Beneficial effects: The pyrolysis gas of agricultural and forestry waste biomass such as waste microbial residues contains a large number of macromolecular products. When directly pyrolyzed or catalytically pyrolyzed in one step using microporous shape-selective catalysts, these macromolecules are difficult to be directly converted. By using a hierarchical pore bond-breaking catalyst, the macromolecules with a wide molecular weight distribution in the pyrolysis gas of the waste microbial residue are preliminarily bond-broken and deoxygenated into small molecules with a uniform molecular weight matching the pore channels of the microporous shape-selective catalyst, and then the pyrolysis gas enters the shape-selective catalyst bed for catalytic reforming to obtain high-yield aviation fuel precursors, significantly reducing the coking and carbon deposition of the pyrolysis gas on the reforming catalyst. Specifically, the following advantages are also included:

[0024] 1. The system structure of the present invention is simple and the device is compact. The multi-stage reaction system device is combined into the same reactor. The pyrolysis liquid of waste microbial bacterial residue does not need to be condensed and then gasified and upgraded again, and there is no need to separately set a catalytic reforming device after pyrolysis, reducing energy consumption and equipment costs.

[0025] 2. The present invention selects activated carbon with large-medium-small interconnected multi-stage pores as the catalyst, which can realize the initial bond-breaking and deoxidation of macromolecules in the pyrolysis of waste microbial bacterial residue. Pyrolysis vapors with different molecular weights can be enriched into small molecules adapted to the pore channels of the microporous catalyst, significantly reducing the secondary polycondensation reaction of pyrolysis gas and the yield of heavy tar, and avoiding reactor blockage.

[0026] 3. The present invention selects microporous catalysts such as HY, HZSM-5, and H-β with a silica-alumina ratio of 25-80 and a catalyst particle size of 40-50 mesh as the shape-selective reforming catalyst, forming a cascade catalysis with the bond-breaking catalyst. The bond-breaking products are adapted to the microporous catalyst, and the waste microbial bacterial residue can be efficiently converted into aviation fuel precursors with a carbon yield of 14.8%. Brief Description of the Drawings

[0027] Figure 1 It is a schematic structural diagram of the system of the present invention.

[0028] Figure 2 It is a scanning electron microscope image of the porous activated carbon bond-breaking catalyst used in the preparation of the present invention.

[0029] Figure 1 It includes: bacterial residue pusher 1, carrier gas inlet 2, primary heating section 3, secondary heating section 4, tertiary heating section 5, pyrolytic carbon collection tube 6, bond-breaking catalyst bed 7, shape-selective catalyst bed 8, pyrolysis reactor 9, nitrogen gas cylinder 10, air cylinder 11, nitrogen gas mass flowmeter 12, air mass flowmeter 13, flow controller 14, temperature controller 15, four-stage condenser 16, drying tube 17, gas collection bag 18. Detailed Embodiments

[0030] The present invention will be described in detail below with reference to the drawings and specific embodiments.

[0031] As Figure 1 shown, the system for preparing aviation fuel precursors by bond-breaking-reforming cascade catalysis pyrolysis of waste microbial bacterial residue adopted in this embodiment includes an intake system, a multi-stage pyrolysis catalytic system, and a product collection system;

[0032] The intake system includes a nitrogen gas cylinder 10, an air cylinder 11, a nitrogen mass flowmeter 12, an air mass flowmeter 13, and a flow controller 14; the outlet of the nitrogen gas cylinder 10 is connected to the inlet of the nitrogen mass flowmeter 12, the outlet of the air cylinder 11 is connected to the inlet of the air mass flowmeter 13, the flow controller 14 is respectively connected to the nitrogen mass flowmeter 12 and the air mass flowmeter 13, and the outlets of the nitrogen mass flowmeter 12 and the air mass flowmeter 13 are merged through valves and then connected to the carrier gas inlet 2; it is used to provide an inert reaction atmosphere for the pyrolysis reaction of the multi-stage pyrolysis catalytic system; the air cylinder, the air mass flowmeter, and the carrier gas inlet are connected to provide an air atmosphere for the tar combustion reaction;

[0033] The multi-stage pyrolysis catalytic system includes a bacterial residue pusher 1, a carrier gas inlet 2, a first-stage heating section 3, a second-stage heating section 4, a third-stage heating section 5, a pyrolysis carbon collection tube 6, a bond-breaking catalyst bed 7, a shape-selective catalyst bed 8, a pyrolysis reactor 9, and a temperature controller 15; the outlets of the bacterial residue pusher 1 and the carrier gas inlet 2 are connected to the inlet of the pyrolysis reactor 9, and the inlet of the pyrolysis reactor 9, the pyrolysis carbon collection tube 6, the bond-breaking catalyst bed 7, the shape-selective catalyst bed 8, and the outlet of the pyrolysis reactor 9 are sequentially connected. The first-stage heating section 3, the second-stage heating section 4, and the third-stage heating section 5 are sequentially arranged outside the pyrolysis carbon collection tube 6, the bond-breaking catalyst bed 7, and the shape-selective catalyst bed 8. The temperature controller 15 is respectively connected to the pyrolysis carbon collection tube 6, the bond-breaking catalyst bed 7, and the shape-selective catalyst bed 8; the pyrolysis reactor 9 and the pyrolysis carbon collection tube 6 for collecting the pyrolysis residue carbon of the waste microbial bacterial residue, the bond-breaking catalyst bed 7 for the preliminary bond-breaking and deoxidation of the waste microbial bacterial residue, the shape-selective catalyst bed 8 for further reforming the pyrolysis vapor after bond-breaking catalysis into the precursor of aviation fuel, the temperature controller 15 for controlling the temperature in the three heating zones of the heating furnace, the bacterial residue pusher and the carrier gas inlet are connected to the inlet of the pyrolysis reactor, and the nitrogen gas flow of the carrier gas inlet can ensure that the bacterial residue raw material is blown into the first-stage heating section 3 of the pyrolysis reactor.

[0034] The product collection system includes a four-stage condenser 16, a drying tube 17, and a gas collection bag 18. The inlet of the four-stage condenser 16 is connected to the outlet of the pyrolysis reactor 9, the inlet of the drying tube 17 is connected to the outlet of the four-stage condenser 16, and the outlet of the drying tube 17 is connected to the gas collection bag 18, which is used to collect liquid products such as the precursor of aviation fuel. The inlet and outlet of the drying tube are respectively connected to the four-stage condenser and the gas collection bag. The drying tube is used to remove the moisture generated by pyrolysis, and the gas collection bag is used to collect the non-condensable gas generated by pyrolysis.

[0035] The working process of the present invention specifically includes:

[0036] (1) Load a certain mass of waste microbial residue into the residue pusher, place the bond-breaking catalyst, a natural or synthetic acidic or alkaline solid catalyst, in the bond-breaking catalyst bed with a bed thickness of 10 - 20 mm; place the molecular sieve catalyst (HY, HZSM-5, H-β) with a silica-alumina ratio of 25 - 80 and a particle size of 40 - 50 mesh in the shape-selective catalyst bed with a bed thickness of 5 - 10 mm; place quartz wool at the bottom of the pyrolysis carbon collection tube, place it at the upper end of the pyrolysis reactor, assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0037] (2) Turn on the system power supply, start the gas supply system and the multi-stage pyrolysis catalytic system, open the nitrogen gas cylinder and adjust the nitrogen gas flow rate to 60 - 180 ml / min through the flow controller and the nitrogen gas mass flowmeter. The nitrogen gas enters the pyrolysis reactor through the carrier gas inlet to evacuate the air in the reactor and maintain an inert atmosphere environment; heat the first heating section, the second heating section, and the third heating section to 550 - 700 °C, 450 - 600 °C, and 550 - 600 °C respectively through the temperature controller and stabilize; start the heating belt at the bottom of the pyrolysis reactor (9) and set the temperature to 150 - 300 °C.

[0038] (3) Connect a four-stage condensation device, a drying tube, and a gas collection bag behind the pyrolysis reactor. Use the residue pusher to pump the waste microbial residue into the pyrolysis reactor at a predetermined speed of 10 - 30 mg / min. The solid product after pyrolysis of the residue in the first heating section remains in the pyrolysis carbon collection tube, and the pyrolysis gas enters the second heating section area, is initially bond-broken and deoxidized through the bond-breaking catalyst bed, and then enters the third heating section area and is reformed into an aviation fuel precursor through the shape-selective catalyst bed (8).

[0039] (4) The product at the outlet of the pyrolysis reactor is condensed after passing through the four-stage condenser. The non-condensable gas enters the drying tube and the doped water vapor is removed. Finally, the non-condensable pyrolysis gas enters the gas collection bag; after the pyrolysis reaction is completed, take out the pyrolysis carbon collection tube, weigh the mass of the solid product, and collect the catalysts in the bond-breaking catalyst bed and the shape-selective catalyst bed.

[0040] (5) Open the air cylinder, adjust the air flow rate through the flow controller and the air mass flowmeter, heat the pyrolysis reactor to a predetermined temperature through the temperature controller, remove the heavy tar remaining on the reactor wall by combustion, and weigh the mass of the reactor before and after the reaction to obtain the mass of the heavy tar in the catalytic pyrolysis of the waste microbial residue.

[0041] The specific implementation process is as follows:

[0042] Example 1:

[0043] The process of preparing an aviation fuel precursor by the bond-breaking-reforming cascade catalytic pyrolysis of waste microbial residue in this example is as follows:

[0044] (1) Weigh 500 mg of the dried waste microbial residue with a particle size of 60 - 80 mesh and put it into the residue feeder. Weigh 100 mg of the multi - pore activated carbon bond - breaking catalyst and place it in the bond - breaking catalyst bed with a bed thickness of 10 mm. Weigh 200 mg of the zeolite catalyst HZSM - 5 with a silica - alumina ratio of 30 and a particle size of 40 mesh and place it in the shape - selective catalyst bed with a bed thickness of 8 mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0045] (2) Start the gas supply system and the multi - stage pyrolysis catalytic system. Adjust the nitrogen flow rate to 120 ml / min. Heat the first - stage heating section, the second - stage heating section, and the third - stage heating section to 600 °C, 500 °C, and 550 °C respectively and keep them stable. Set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200 °C.

[0046] (3) Connect the four - stage condensation device, the drying tube, and the gas collection bag. After the system is stable, pump the waste microbial residue into the pyrolysis reactor at a predetermined speed of 20 mg / min. The solid product after pyrolysis of the residue in the first - stage heating section remains in the pyrolysis carbon collection tube, and the pyrolysis gas enters the second - stage heating section for preliminary bond - breaking and deoxidation, and then enters the third - stage heating section for reforming into the precursor of aviation fuel.

[0047] (4) The products at the outlet of the pyrolysis reactor pass through the four - stage condenser, the drying tube, and the gas collection bag in sequence. Collect the products in the condenser and the gas collection bag respectively for analysis. After the pyrolysis system cools down, collect the catalysts in the bond - breaking catalyst bed and the shape - selective catalyst bed for analysis.

[0048] (5) After the reaction, introduce air and raise the temperature of the pyrolysis reactor to 700 °C to remove the residual heavy tar on the reactor wall by combustion, and weigh the mass of the reactor before and after the reaction.

[0049] Through analysis and testing, the carbon yields of benzene, toluene, and xylene, the precursors of aviation fuel, can reach 14.8%. The carbon deposition yield of the multi - pore activated carbon bond - breaking catalyst is 0.34 wt.%, the carbon deposition yield of the zeolite catalyst HZSM - 5 is 1.24 wt.%, and the tar yield is 0.14 wt.%.

[0050] Example 2:

[0051] The process of preparing the precursor of aviation fuel by the step - by - step catalytic pyrolysis of waste microbial residue bond - breaking - reforming is as follows:

[0052] (1) Implement it in the same way as step (1) in Example 1, with the difference that the bond - breaking catalyst and the shape - selective catalyst are not placed.

[0053] (2) Implement it in the same way as step (2) in Example 1.

[0054] (3) Implement it in the same way as step (3) in Example 1.

[0055] (4) It is implemented in the same way as step (4) in Example 1.

[0056] (5) It is implemented in the same way as step (5) in Example 1.

[0057] Through analysis and testing, the carbon yield of benzene, toluene and xylene as jet fuel precursors can reach 1.35%, and the tar yield is 2.67 wt.%.

[0058] Example 3:

[0059] The process of preparing jet fuel precursors by bond-breaking and reforming cascade catalytic pyrolysis of waste microbial residue in this example is as follows:

[0060] (1) It is implemented in the same way as step (1) in Example 1, except that the bond-breaking catalyst is not placed.

[0061] (2) It is implemented in the same way as step (2) in Example 1.

[0062] (3) It is implemented in the same way as step (3) in Example 1.

[0063] (4) It is implemented in the same way as step (4) in Example 1.

[0064] (5) It is implemented in the same way as step (5) in Example 1.

[0065] Through analysis and testing, the carbon yield of benzene, toluene and xylene as jet fuel precursors can reach 11.5%, the carbon deposition yield of molecular sieve catalyst HZSM-5 is 3.37 wt.%, and the tar yield is 2.35 wt.%.

[0066] Example 4:

[0067] The process of preparing jet fuel precursors by bond-breaking and reforming cascade catalytic pyrolysis of waste microbial residue in this example is as follows:

[0068] (1) It is implemented in the same way as step (1) in Example 1, except that 200 mg of molecular sieve catalyst Hβ with a silicon-aluminum ratio of 30 and a particle size of 40 mesh is weighed and placed in the shape-selective catalyst bed, and the bed layer thickness is 8 mm.

[0069] (2) It is implemented in the same way as step (2) in Example 1.

[0070] (3) It is implemented in the same way as step (3) in Example 1.

[0071] (4) It is implemented in the same way as step (4) in Example 1.

[0072] (5) It is implemented in the same way as step (5) in Example 1.

[0073] After analysis and testing, the carbon yields of benzene, toluene, and xylene as jet fuel precursors can reach 10.5%, the carbon deposition yield of the molecular sieve catalyst Hβ is 0.87 wt.%, and the tar yield is 0.08 wt.%.

[0074] Example 5:

[0075] The process of preparing jet fuel precursors by bond-breaking and reforming cascade catalytic pyrolysis of waste microbial residue in this example is as follows:

[0076] (1) It is implemented in the same way as step (1) in Example 1, except that 200 mg of molecular sieve catalyst HY with a silica-alumina ratio of 30 and a particle size of 40 mesh is weighed and placed in the shape-selective catalyst bed, and the bed thickness is 8 mm.

[0077] (2) It is implemented in the same way as step (2) in Example 1.

[0078] (3) It is implemented in the same way as step (3) in Example 1.

[0079] (4) It is implemented in the same way as step (4) in Example 1.

[0080] (5) It is implemented in the same way as step (5) in Example 1.

[0081] After analysis and testing, the carbon yields of benzene, toluene, and xylene as jet fuel precursors can reach 9.5%, the carbon deposition yield of the molecular sieve catalyst HY is 1.14 wt.%, and the tar yield is 0.09 wt.%.

[0082] Example 6:

[0083] The process of preparing jet fuel precursors by bond-breaking and reforming cascade catalytic pyrolysis of waste microbial residue in this example is as follows:

[0084] (1) It is implemented in the same way as step (1) in Example 1.

[0085] (2) It is implemented in the same way as step (2) in Example 1, except that the temperature of the secondary heating section is 600 °C.

[0086] (3) It is implemented in the same way as step (3) in Example 1.

[0087] (4) It is implemented in the same way as step (4) in Example 1.

[0088] (5) It is implemented in the same way as step (5) in Example 1.

[0089] After analysis and testing, the carbon yields of benzene, toluene and xylene as jet fuel precursors can reach 12.36%, the carbon deposition yield of the multi - pore activated carbon bond - breaking catalyst is 0.21 wt.%, the carbon deposition yield of the molecular sieve catalyst HZSM - 5 is 0.82 wt.%, and the tar yield is 0.08 wt.%.

[0090] Example 7:

[0091] The process of using waste microbial residue for bond - breaking - reforming cascade catalytic pyrolysis to prepare jet fuel precursors in this example is as follows:

[0092] (1) Implement it in the same way as step (1) in Example 1.

[0093] (2) Implement it in the same way as step (2) in Example 1.

[0094] (3) Implement it in the same way as step (3) in Example 1, except that the waste microbial residue is pumped into the pyrolysis reactor at a feeding rate of 40 mg / min.

[0095] (4) Implement it in the same way as step (4) in Example 1.

[0096] (5) Implement it in the same way as step (5) in Example 1.

[0097] After analysis and testing, the carbon yields of benzene, toluene and xylene as jet fuel precursors can reach 10.68%, the carbon deposition yield of the multi - pore activated carbon bond - breaking catalyst is 0.53 wt.%, the carbon deposition yield of the molecular sieve catalyst HZSM - 5 is 2.55 wt.%, and the tar yield is 1.38 wt.%.

[0098] The above specific examples are only preferred embodiments of the present invention, and do not impose any limitation on the technical scope of the present invention. Any minor modification, equivalent change and modification made to the above examples based on the technical essence of the present invention are equally included in the patent protection scope of the present invention.

Claims

1. A method for preparing aviation fuel precursor by bond-breaking reforming and catalytic pyrolysis of fungus residue, characterized by: The following steps are included: S1. After the system device used in the method is started, the nitrogen cylinder (10) is opened, and the nitrogen flow rate is adjusted by the flow controller (14) and the nitrogen mass flow meter (12). The nitrogen enters the pyrolysis reactor (9) through the carrier gas inlet (2) to evacuate the air in the reactor and maintain an inert atmosphere. The first heating section (3), the second heating section (4), and the third heating section (5) are heated to a predetermined temperature and stabilized by the temperature controller (15). S2. The waste microbial residue is pumped into the pyrolysis reactor (9) at a predetermined speed using a residue pusher (1). After the residue is pyrolyzed in the primary heating section (3), the solid product remains in the pyrolysis carbon collection pipe (6). The pyrolysis gas enters the secondary heating section (4), passes through the bond-breaking catalyst bed (7), undergoes initial bond breaking and deoxygenation, and then enters the tertiary heating section (5), where it is reformed into an aviation fuel precursor through the shape-selective catalyst bed (8). S3. The product at the outlet of the pyrolysis reactor (9) passes through a four-stage condenser (16) where the liquid phase product is condensed. The non-condensable gas enters a drying tube (17) and removes the doped water vapor. Finally, the non-condensable pyrolysis gas enters a gas collection bag (18). S4. After the pyrolysis reaction is completed, the pyrolysis carbon collection tube (6) is removed and the mass of the solid product is weighed, and the catalyst of the bond-breaking catalyst bed (7) and the shape-selective catalyst bed (8) is collected; S5. Open the air cylinder (12), adjust the air flow rate using the flow controller (14) and the air mass flowmeter (13), heat the pyrolysis reactor (9) to a predetermined temperature using the temperature controller (15), remove the heavy tar remaining on the reactor wall by combustion, and weigh the reactor mass before and after the reaction to obtain the mass of heavy tar produced by catalytic pyrolysis of the waste microbial residue; The fungus residue is crushed waste microorganism residue particles with a mesh size of 40-80 mesh and dried at 90-110°C; The pyrolysis carbon collection tube (6) has a hole at the bottom, quartz wool is placed at the bottom, and the top is at the same height as the inside of the pyrolysis reactor (9); The bond-breaking catalyst bed (7) uses a natural or synthetic acidic or alkaline solid catalyst, including an activated carbon catalyst with large-medium-micro through-hole multi-level pores, and the bed thickness is 10-20 mm.

2. The method for preparing aviation fuel precursor by bond-breaking reforming and catalytic pyrolysis of fungus residue according to claim 1, characterized in that: The shape-selective catalyst bed (8) uses a molecular sieve catalyst, including HY, HZSM-5 or H-β, with a molecular sieve silicon-aluminum ratio of 25-80, a catalyst particle size of 40-50 meshes, and a bed thickness of 5-10 mm.

3. The method for preparing aviation fuel precursor by bond-breaking reforming and catalytic pyrolysis of fungus residue according to claim 1, characterized in that: The nitrogen flow rate is 60-180 ml / min, and the pyrolysis gas stays in the pyrolysis reactor (9) for 2-6 s.

4. The method for preparing aviation fuel precursor by bond-breaking reforming and catalytic pyrolysis of fungus residue according to claim 1, characterized in that: The outlet of the bacterial residue pusher (1) is tilted upward at an angle of 10-30 degrees; the waste microbial residue is pumped into the pyrolysis reactor (9) at a feed rate of 10-40 mg / min.

5. The method for preparing aviation fuel precursor by bond-breaking reforming and catalytic pyrolysis of fungus residue according to claim 1, characterized in that: The temperature range of the primary heating section (3) is 550-700°C, the temperature of the secondary heating section (4) is 450-600°C, and the temperature of the tertiary heating section (5) is 550-600°C.

6. The method for preparing aviation fuel precursor by bond-breaking reforming and catalytic pyrolysis of fungus residue according to claim 1, characterized in that: The bottom of the pyrolysis reactor (9) is wrapped with a heating tape, which is wrapped in two layers and has a temperature range of 150-300 °C to prevent the aviation fuel precursor from condensing at the reactor outlet.

Images