System and method for preparing aviation oil precursor from microbial biomass residue by means of bond-breaking and reforming and catalytic pyrolysis

Abstract

Disclosed in the present invention are a system and method for preparing an aviation oil precursor from a microbial biomass residue by means of bond-breaking and reforming and catalytic pyrolysis. A gas inlet system comprises a carrier gas inlet, a nitrogen cylinder, an air cylinder, a nitrogen mass flow meter, an air mass flow meter, and a flow controller; a multi-stage pyrolysis catalysis system comprises a microbial biomass residue pusher, 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; a product collection system comprises a fourth-stage condenser, a drying tube, and a gas collection bag. The method comprises: rapidly pyrolyzing a microbial biomass residue in a first-stage heating section; performing preliminary bond breaking and deoxidizing in a second-stage heating section to form a stable small-molecule product matching a shape-selective catalyst pore channel; and in a third-stage heating section, after entry into the shape-selective catalyst pore channel, performing aromatization for conversion into an aromatic hydrocarbon aviation oil precursor. The present invention solves the problems that intermediate products from microbial biomass residue pyrolysis show wide molecular weight distribution and do not match microporous shape-selective catalyst pore channels, target product yield is low and the like in traditional catalytic pyrolysis.

Description

A system and method for preparing aviation fuel precursors by bond-breaking reforming catalytic pyrolysis of bacterial residue. Technical Field

[0001] This invention relates to a system and method for preparing aviation fuel precursors by catalytic pyrolysis of bacterial residue bond breaking reforming, belonging to the field of biomass comprehensive utilization technology. Background Technology

[0002] Waste microbial inoculum residue is a solid waste formed during fermentation. my country is a major producer of microbial pharmaceuticals, with a huge annual output of waste microbial inoculum residue. Furthermore, waste microbial inoculum residue has a high moisture content, high collection and transportation costs, outdated processing capacity, and low utilization efficiency. Accumulation or incineration easily causes pollution to related enterprises and water bodies, resulting in serious resource waste and environmental pollution problems. Therefore, high-value utilization is an inevitable trend for waste microbial inoculum residue. my country is a major consumer of aviation fuel, which is traditionally produced mainly through petroleum refining. However, my country's petroleum resources are highly dependent on imports, posing a serious threat to national energy security. Waste microbial inoculum residue and other biomass are renewable resources with huge production volumes. Directed catalytic pyrolysis of waste microbial inoculum residue to prepare aviation fuel precursors is an efficient solid waste conversion pathway that can realize the resource and energy utilization of waste microbial inoculum residue.

[0003] Waste microbial residue has a high protein content, and its initial pyrolysis products have large and unstable molecular weights, easily leading to secondary condensation and the formation of heavy tar, which clogs reactor pipes. While zeolite catalysts can be used to catalytically pyrolyze waste microbial residue to convert glucosamine residue into aromatics, low yields of the target liquid product and a large number of byproducts remain. Furthermore, the large oxygen-containing compounds in the pyrolysis readily polymerize and coke at strong acid sites, and the coke deposits on the molecular sieve surface, covering the catalyst's active sites and clogging the catalyst pores, negatively impacting the catalyst's shape-selective deoxygenation performance. The mismatch between the molecular diameter of the pyrolyzed microbial residue and the pore size of the shape-selective catalyst hinders effective conversion. Moreover, the bond-breaking process in the pyrolysis of microbial residue is extremely complex, and the composition and distribution of the products are influenced by multiple factors. Therefore, the development of multifunctional catalysts and equipment systems for the efficient conversion of waste microbial residue is necessary.

[0004] Summary of the Invention

[0005] This invention addresses the shortcomings of existing technologies by providing a system and method for preparing aviation fuel precursors through catalytic pyrolysis of microbial residue. Combining the functional characteristics of hierarchical porous catalysts and microporous reforming catalysts, the invention enables the pyrolysis of waste microbial residue to achieve the efficient conversion of waste microbial residue into aviation fuel precursors through stepwise bond breaking, deoxygenation, and shape selection. Simultaneously, it solves the problems of rapid catalyst coking and secondary polymerization of pyrolysis products forming tar and clogging the reactor during traditional catalytic pyrolysis processes.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is as follows:

[0007] A system for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond breaking reforming includes an air intake system, a multi-stage pyrolysis catalytic system, and a product collection system.

[0008] The air intake system includes a nitrogen cylinder, an air cylinder, a nitrogen mass flow meter, an air mass flow meter, and a flow controller; the outlet of the nitrogen cylinder is connected to the inlet of the nitrogen mass flow meter, the outlet of the air cylinder is connected to the inlet of the air mass flow meter, the flow controller is connected to both the nitrogen mass flow meter and the air mass flow meter, and the outlets of the nitrogen mass flow meter and the air mass flow meter are combined through valves and then connected to the carrier gas inlet;

[0009] The multi-stage pyrolysis catalytic system includes a bacterial residue pusher, a carrier gas inlet, a primary heating section, a secondary heating section, a tertiary heating section, a pyrolysis carbon collection pipe, a bond-breaking catalyst bed, a shape-selective catalyst bed, a pyrolysis reactor, and a temperature controller. The outlet of the bacterial residue pusher and the carrier gas inlet is connected to the inlet of the pyrolysis reactor. The inlet of the pyrolysis reactor, the pyrolysis carbon collection pipe, the bond-breaking catalyst bed, the shape-selective catalyst bed, and the outlet of the pyrolysis reactor are connected in sequence. The primary heating section, the secondary heating section, and the tertiary heating section are sequentially arranged outside the pyrolysis carbon collection pipe, the bond-breaking catalyst bed, and the shape-selective catalyst bed. The temperature controller is connected to the pyrolysis carbon collection pipe, the bond-breaking catalyst bed, and the shape-selective catalyst bed, respectively.

[0010] 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.

[0011] A method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond-breaking reforming is implemented using the aforementioned system for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond-breaking reforming, and includes the following steps:

[0012] S1. After the system is started, the nitrogen cylinder is opened, and the nitrogen flow rate is adjusted by the flow controller and the nitrogen mass flow meter. The nitrogen enters the pyrolysis reactor through the carrier gas inlet to purge the air in the reactor and maintain an inert atmosphere. The primary heating section, the secondary heating section and the tertiary heating section are heated to the predetermined temperature and stabilized by the temperature controller.

[0013] S2. Use a microbial residue pusher to pump the waste microbial residue into the pyrolysis reactor at a predetermined speed. After the microbial residue is pyrolyzed in the first heating section (3), the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section area, and is initially deoxygenated by the bond-breaking catalyst bed. Then it enters the third heating section area and is reformed into aviation fuel precursor by the shape-selective catalyst bed.

[0014] S3. The product from the outlet of the pyrolysis reactor is condensed by the four-stage condenser. The non-condensable gas enters the drying tube (17) and removes the doped water vapor. Finally, the non-condensable pyrolysis gas enters the gas collection bag.

[0015] S4. After the pyrolysis reaction is completed, take out the pyrolysis carbon collection tube, weigh the solid product, and collect the catalysts of the bond-breaking catalyst bed and the shape-selective catalyst bed (8);

[0016] S5. Open the air cylinder, adjust the air flow rate through the flow controller and air mass flow meter, heat the pyrolysis reactor to the predetermined temperature through the temperature controller, remove the heavy tar remaining on the reactor wall by combustion, and weigh the reactor before and after the reaction to obtain the mass of heavy tar catalytically pyrolyzed from the waste microbial residue.

[0017] The waste microbial residue is pulverized into particles with a mesh size of 40-80 and dried at 90-110℃.

[0018] The bottom of the pyrolysis carbon collection pipe is perforated, and quartz wool is placed at the bottom. The top is at the same height as the inside of the pyrolysis reactor.

[0019] The bond-breaking catalyst bed uses natural or synthetic acidic or basic solid catalysts, including activated carbon catalysts with large-medium-micro interconnected hierarchical pores, with a bed thickness of 10-20 mm.

[0020] Shape-selective catalyst beds use molecular sieve catalysts, including HY, HZSM-5, and H-β, with a silicon-to-aluminum ratio of 25-80, catalyst particle size of 40-50 mesh, and bed thickness of 5-10 mm.

[0021] The nitrogen flow rate is 60-180 ml / min, and the pyrolysis gas stays in the pyrolysis reactor for 2-6 seconds.

[0022] The outlet of the microbial residue pusher (1) is tilted upward at an angle of 10-30° to control the feed rate of the raw materials; the waste microbial residue is pumped into the pyrolysis reactor at a feed rate of 10-40 mg / min.

[0023] The temperature range of the first-stage heating section is 550-700℃, the temperature range of the second-stage heating section is 450-600℃, and the temperature range of the third-stage heating section is 550-600℃.

[0024] The bottom of the pyrolysis reactor (9) is wrapped with a heating belt, which is wrapped in two layers and has a temperature range of 150-300℃ to prevent the aviation fuel precursor from condensing at the reactor outlet.

[0025] A multi-level porous catalyst structure with interconnected macro-meso-micropores was constructed using a template method. Biomass pyrolysis macromolecules first enter the catalyst macropores, where they undergo bond cleavage under the influence of acid / base active sites. The resulting intermediates are further transferred to mesopores and micropores, forming smaller molecular weight compounds. Most of these compounds can enter the shape-selective catalyst channels and undergo aromatization under the influence of active sites, forming aviation fuel precursors. The tandem use of the bond-breaking catalyst and the shape-selective catalyst avoids direct contact between biomass pyrolysis vapors and strong acid sites on the shape-selective catalyst surface, reducing the polymerization and coking of oxygen-containing macromolecules on the catalyst's outer surface and preventing catalyst channel blockage. Beneficial effects:

[0026] The pyrolysis gas from agricultural and forestry waste biomass, such as waste microbial inoculum residue, contains a large number of macromolecular products. These macromolecules are difficult to directly convert during direct pyrolysis or one-step catalytic pyrolysis using a microporous shape-selective catalyst. By using a multi-level porous bond-breaking catalyst, the macromolecules with a wide molecular weight distribution in the pyrolysis gas from waste microbial inoculum residue are initially broken down and deoxygenated into smaller molecules with uniform molecular weight that match the pore size of the microporous shape-selective catalyst. Then, the pyrolysis gas enters a shape-selective catalyst bed for catalytic reforming to obtain a high-yield aviation fuel precursor, significantly reducing coking and carbon deposition on the reforming catalyst. Specifically, it also includes the following advantages:

[0027] 1. The system structure of this invention is simple and the device is compact. It combines a multi-stage reaction system into a single reactor. The waste microbial residue pyrolysis liquid does not need to be condensed and then re-gasified for upgrading. It also eliminates the need to set up a separate catalytic reforming device after pyrolysis, thus reducing energy consumption and equipment costs.

[0028] 2. This invention selects activated carbon with a multi-level pore structure of large, medium and micro-sized interconnections as a catalyst, which can realize the initial bond breaking and deoxygenation of macromolecules in the pyrolysis of waste microbial residue. Pyrolysis vapors of different molecular weights can be enriched into small molecules that are compatible with the microporous catalyst channels. The secondary condensation reaction of pyrolysis gas and the yield of heavy tar are significantly reduced, and reactor blockage can be avoided.

[0029] 3. This invention selects microporous catalysts such as HY, HZSM-5, and H-β with a silicon-to-aluminum ratio of 25-80 and a catalyst particle size of 40-50 mesh as shape-selective reforming catalysts. These catalysts form a cascade catalysis with bond-breaking catalysts. The bond-breaking products are adapted to the microporous catalysts, which can realize the efficient conversion of waste microbial residue into aviation fuel precursors with a carbon yield of 14.8%. Attached Figure Description

[0030] Figure 1 is a schematic diagram of the system of the present invention.

[0031] Figure 2 is a scanning electron microscope image of the porous activated carbon bond-breaking catalyst used in the preparation of this invention.

[0032] Figure 1 shows: 1. Mushroom residue pusher; 2. Carrier gas inlet; 3. Primary heating section; 4. Secondary heating section; 5. Tertiary heating section; 6. Pyrolysis carbon collection pipe; 7. Bond-breaking catalyst bed; 8. Shape-selective catalyst bed; 9. Pyrolysis reactor; 10. Nitrogen cylinder; 11. Air cylinder; 12. Nitrogen mass flow meter; 13. Air mass flow meter; 14. Flow controller; 15. Temperature controller; 16. Quadruple condenser; 17. Drying pipe; 18. Gas collection bag. Detailed Implementation

[0033] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0034] As shown in Figure 1, the system for preparing aviation fuel precursors by bond-breaking reforming of waste microbial residue in this embodiment includes an air intake system, a multi-stage pyrolysis catalytic system, and a product collection system.

[0035] The air intake system includes a nitrogen cylinder 10, an air cylinder 11, a nitrogen mass flow meter 12, an air mass flow meter 13, and a flow controller 14. The outlet of the nitrogen cylinder 10 is connected to the inlet of the nitrogen mass flow meter 12, and the outlet of the air cylinder 11 is connected to the inlet of the air mass flow meter 13. The flow controller 14 is connected to both the nitrogen mass flow meter 12 and the air mass flow meter 13. The outlets of the nitrogen mass flow meter 12 and the air mass flow meter 13 are combined through valves and then connected to the carrier gas inlet 2. This system provides an inert reaction atmosphere for the pyrolysis reaction in the multi-stage pyrolysis catalytic system. The air cylinder, the air mass flow meter, and the carrier gas inlet are connected to provide an air atmosphere for the tar combustion reaction.

[0036] The multi-stage pyrolysis catalytic system includes a bacterial residue pusher 1, a carrier gas inlet 2, a primary heating section 3, a secondary heating section 4, a tertiary heating section 5, a pyrolysis carbon collection pipe 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. The inlet of the pyrolysis reactor 9, the pyrolysis carbon collection pipe 6, the bond-breaking catalyst bed 7, the shape-selective catalyst bed 8, and the outlet of the pyrolysis reactor 9 are connected in sequence. The primary heating section 3, the secondary heating section 4, and the tertiary heating section 5 are sequentially arranged outside the pyrolysis carbon collection pipe 6, the bond-breaking catalyst bed 7, and the shape-selective catalyst bed 8. Heating section 5 and temperature controller 15 are respectively connected to pyrolysis carbon collection pipe 6, bond-breaking catalyst bed 7, and shape-selective catalyst bed 8; pyrolysis reactor 9, pyrolysis carbon collection pipe 6 for collecting pyrolysis residue carbon from waste microbial residue, bond-breaking catalyst bed 7 for preliminary bond-breaking and deoxygenation of waste microbial residue, shape-selective catalyst bed 8 for further reforming of pyrolysis steam after bond-breaking catalysis into aviation fuel precursor, temperature controller 15 for controlling the temperature of the three heating zones of the heating furnace, residue pusher and carrier gas inlet are connected to the inlet of pyrolysis reactor, and nitrogen flow from carrier gas inlet can ensure that residue raw material is blown into the first heating section 3 of pyrolysis reactor.

[0037] 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. It is used to collect liquid products such as aviation fuel precursors. The inlet and outlet of the drying tube are connected to the four-stage condenser and the gas collection bag, respectively. The drying tube is used to remove moisture generated by pyrolysis, and the gas collection bag is used to collect non-condensable gases generated by pyrolysis.

[0038] The working process of this invention specifically includes:

[0039] (1) Load a certain mass of waste microbial residue into the residue pusher, place the bond-breaking catalyst (natural or synthetic acid or basic 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 silicon-aluminum 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 pipe, place it at the top of the pyrolysis reactor, assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0040] (2) Turn on the system power, start the gas supply system and the multi-stage pyrolysis catalytic system, open the nitrogen cylinder and adjust the nitrogen flow rate to 60-180 ml / min through the flow controller and nitrogen mass flow meter. Nitrogen enters the pyrolysis reactor through the carrier gas inlet to purge the air in the reactor and maintain an inert atmosphere. Heat the first heating section, the second heating section and the third heating section to 550-700℃, 450-600℃ and 550-600℃ respectively through the temperature controller and stabilize them. Start the bottom heating belt of the pyrolysis reactor (9) and set the temperature to 150-300℃.

[0041] (3) Connect a four-stage condenser, a drying pipe and a gas collection bag after the pyrolysis reactor. Use a microbial residue pusher to pump the waste microbial residue into the pyrolysis reactor at a predetermined speed of 10-30 mg / min. After the microbial residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section area, and is initially deoxygenated by the bond breaking catalyst bed. Then it enters the third heating section area and is reformed into aviation fuel precursor by the shape-selective catalyst bed (8).

[0042] (4) The product at the outlet of the pyrolysis reactor is condensed by the liquid phase after passing through the four-stage condenser. The non-condensable gas enters the drying tube and removes the doped water vapor. Finally, the non-condensable pyrolysis gas enters the gas collection bag. After the pyrolysis reaction is completed, the pyrolysis carbon collection tube is taken out and the mass of the solid product is weighed. The catalysts of the bond-breaking catalyst bed and the shape-selective catalyst bed are collected.

[0043] (5) Open the air cylinder, adjust the air flow rate through the flow controller and air mass flow meter, heat the pyrolysis reactor to the predetermined temperature through the temperature controller, remove the heavy tar remaining on the reactor wall by combustion, and weigh the reactor before and after the reaction to obtain the mass of heavy tar catalytically pyrolyzed by waste microbial residue.

[0044] The specific implementation process is as follows:

[0045] Example 1:

[0046] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0047] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of multi-level porous activated carbon bond-breaking catalyst and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of molecular sieve catalyst HZSM-5 with a silicon-aluminum ratio of 30 and a particle size of 40 mesh and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0048] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first heating section, the second heating section and the third heating section to 600℃, 500℃ and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0049] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 20 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0050] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0051] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700°C. The heavy tar remaining on the reactor wall is removed by combustion. The reactor mass before and after the reaction is weighed.

[0052] Analysis and testing showed that the carbon yield of aviation fuel precursors benzene, toluene, and xylene could reach 14.8%, the carbon yield of hierarchical porous activated carbon bond-breaking catalyst was 0.34 wt.%, the carbon yield of molecular sieve catalyst HZSM-5 was 1.24 wt.%, and the tar yield was 0.14 wt.

[0053] Example 2:

[0054] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0055] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of multi-level porous activated carbon bond-breaking catalyst and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of molecular sieve catalyst Hβ with a silicon-aluminum ratio of 30 and a particle size of 40 mesh and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0056] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first heating section, the second heating section and the third heating section to 600℃, 500℃ and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0057] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 20 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0058] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0059] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700°C. The heavy tar remaining on the reactor wall is removed by combustion. The reactor mass before and after the reaction is weighed.

[0060] Analysis and testing showed that the carbon yield of aviation fuel precursors benzene, toluene, and xylene could reach 10.5%, the carbon yield of molecular sieve catalyst Hβ was 0.87 wt.%, and the tar yield was 0.08 wt.%.

[0061] Example 3:

[0062] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0063] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of multi-level porous activated carbon bond-breaking catalyst and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of molecular sieve catalyst HY with a silicon-aluminum ratio of 30 and a particle size of 40 mesh and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0064] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first heating section, the second heating section and the third heating section to 600℃, 500℃ and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0065] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 20 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0066] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0067] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700℃. The heavy tar remaining on the reactor wall is removed by combustion, and the reactor mass before and after the reaction is weighed. After analysis and testing, the carbon yield of the aviation fuel precursors benzene, toluene and xylene can reach 9.5%, the carbon yield of the molecular sieve catalyst HY is 1.14 wt.%, and the tar yield is 0.09 wt.%.

[0068] Example 4:

[0069] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0070] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of multi-level porous activated carbon bond-breaking catalyst and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of molecular sieve catalyst HZSM-5 with a silicon-aluminum ratio of 30 and a particle size of 40 mesh and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0071] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first-stage heating section, the second-stage heating section, and the third-stage heating section to 600℃, 600℃, and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0072] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 20 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0073] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0074] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700°C. The heavy tar remaining on the reactor wall is removed by combustion. The reactor mass before and after the reaction is weighed.

[0075] Analysis and testing showed that the carbon yield of aviation fuel precursors benzene, toluene, and xylene reached 12.36%, the carbon yield of hierarchical porous activated carbon bond-breaking catalyst was 0.21 wt.%, the carbon yield of molecular sieve catalyst HZSM-5 was 0.82 wt.%, and the tar yield was 0.08 wt.

[0076] Example 5:

[0077] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0078] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of multi-level porous activated carbon bond-breaking catalyst and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of molecular sieve catalyst HZSM-5 with a silicon-aluminum ratio of 30 and a particle size of 40 mesh and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0079] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first heating section, the second heating section and the third heating section to 600℃, 500℃ and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0080] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 40 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0081] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0082] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700℃. The heavy tar remaining on the reactor wall is removed by combustion, and the reactor mass before and after the reaction is weighed. Analysis and testing show that the carbon yield of the aviation fuel precursors benzene, toluene, and xylene can reach 10.68%, the carbon yield of the hierarchical porous activated carbon bond-breaking catalyst is 0.53 wt.%, the carbon yield of the molecular sieve catalyst HZSM-5 is 2.55 wt.%, and the tar yield is 1.38 wt.

[0083] Comparative Example 1:

[0084] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0085] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of porous silicon and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of porous silicon and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0086] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first heating section, the second heating section and the third heating section to 600℃, 500℃ and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0087] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 20 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0088] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0089] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700°C. The heavy tar remaining on the reactor wall is removed by combustion. The reactor mass before and after the reaction is weighed.

[0090] Analysis and testing showed that the carbon yield of the aviation fuel precursors benzene, toluene, and xylene can reach 1.35%, and the tar yield is 2.67 wt.%.

[0091] Comparative Example 2:

[0092] The process for preparing aviation fuel precursors using the bond-breaking and reforming stepwise catalytic pyrolysis of waste microbial residue in this embodiment is as follows:

[0093] (1) Weigh 500mg of dried 60-80 mesh waste microbial residue and put it into the residue pusher. Weigh 100mg of porous silicon and place it in the bond-breaking catalyst bed with a bed thickness of 10mm. Weigh 200mg of molecular sieve catalyst HZSM-5 with a silicon-aluminum ratio of 30 and a particle size of 40 mesh and place it in the shape-selective catalyst bed with a bed thickness of 8mm. Assemble the pyrolysis reactor and place it in the middle of the heating furnace.

[0094] (2) Start the gas supply system and the multi-stage pyrolysis catalytic system, adjust the nitrogen flow rate to 120 ml / min, and heat the first heating section, the second heating section and the third heating section to 600℃, 500℃ and 550℃ respectively and stabilize them; set the temperature of the heating belt at the bottom of the pyrolysis reactor to 200℃.

[0095] (3) After connecting the four-stage condenser, drying pipe and gas collection bag and waiting for the system to stabilize, the waste microbial residue is pumped into the pyrolysis reactor at a predetermined rate of 20 mg / min. After the residue is pyrolyzed in the first heating section, the solid products remain in the pyrolysis carbon collection pipe. The pyrolysis gas enters the second heating section for preliminary bond breaking and deoxygenation, and then enters the third heating section to be reformed into aviation fuel precursor.

[0096] (4) The product from the outlet of the pyrolysis reactor passes through a four-stage condenser, a drying tube and a gas collection bag in sequence; the products from the condenser and the gas collection bag are collected and analyzed respectively, and the catalysts from the bond-breaking catalyst bed and the shape-selective catalyst bed are collected and analyzed after the pyrolysis system is cooled.

[0097] (5) After the reaction is complete, air is introduced and the temperature of the pyrolysis reactor is raised to 700°C. The heavy tar remaining on the reactor wall is removed by combustion. The reactor mass before and after the reaction is weighed.

[0098] Analysis and testing showed that the carbon yield of aviation fuel precursors benzene, toluene, and xylene reached 11.5%, the carbon yield of molecular sieve catalyst HZSM-5 was 3.37 wt.%, and the tar yield was 2.35 wt.%.

[0099] Conclusion Analysis:

[0100] Analysis of the experimental results of Examples 1 to 5 and Comparative Examples 1 to 2 shows that the carbon yields of benzene, toluene and xylene, the aviation fuel precursors used in the examples with bond-breaking catalysts and shape-selective catalysts, are significantly higher than those in the comparative examples, while the carbon deposit yields and tar yields are lower than those in the comparative examples.

[0101] The above specific embodiments are merely preferred embodiments of the present invention and do not constitute any limitation on the technical scope of the present invention. Any minor modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention are similarly included within the patent protection scope of the present invention.

Claims

1. A system for preparing aviation fuel precursors by catalytic pyrolysis of bacterial residue bond-breaking reforming, characterized in that: This includes an air intake system, a multi-stage pyrolysis catalytic system, and a product collection system; The air intake system includes a nitrogen cylinder (10), an air cylinder (11), a nitrogen mass flow meter (12), an air mass flow meter (13), and a flow controller (14); the outlet of the nitrogen cylinder (10) is connected to the inlet of the nitrogen mass flow meter (12), the outlet of the air cylinder (11) is connected to the inlet of the air mass flow meter (13), and the flow controller (14) is connected to the nitrogen mass flow meter (12) and the air mass flow meter (13) respectively. The outlets of the nitrogen mass flow meter (12) and the air mass flow meter (13) are connected to the carrier gas inlet (2) after being combined by valves. The multi-stage pyrolysis catalytic system includes a bacterial residue pusher (1), a carrier gas inlet (2), a primary heating section (3), a secondary heating section (4), a tertiary heating section (5), a pyrolysis carbon collection pipe (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). The inlet of the pyrolysis reactor (9), the pyrolysis carbon collection pipe (6), the bond-breaking catalyst bed (7), the shape-selective catalyst bed (8), and the outlet of the pyrolysis reactor (9) are connected in sequence. The primary heating section (3), the secondary heating section (4), and the tertiary heating section (5) are sequentially arranged outside the pyrolysis carbon collection pipe (6), the bond-breaking catalyst bed (7), and the shape-selective catalyst bed (8). The temperature controller (15) is connected to the pyrolysis carbon collection pipe (6), the bond-breaking catalyst bed (7), and the shape-selective catalyst bed (8) respectively. 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).

2. A method for preparing aviation fuel precursors by catalytic pyrolysis of bacterial residue bond-breaking reforming, characterized in that, The system described in claim 1 is implemented by comprising the following steps: S1. After the system device 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 vent the air in the reactor and maintain an inert atmosphere environment. The primary heating section (3), the secondary heating section (4), and the tertiary heating section (5) are heated to the 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 microbial residue pusher (1). After the microbial residue is pyrolyzed in the first heating section (3), the solid products remain in the pyrolysis carbon collection pipe (6). The pyrolysis gas enters the second heating section (4) area, and is initially deoxygenated by the bond breaking catalyst bed (7). Then it enters the third heating section (5) area and is reformed into aviation fuel precursor by the shape-selective catalyst bed (8). S3. The product from the outlet of the pyrolysis reactor (9) is condensed in the liquid phase after passing through the four-stage condenser (16). The non-condensable gas enters the drying tube (17) and removes the doped water vapor. Finally, the non-condensable pyrolysis gas enters the gas collection bag (18). S4. After the pyrolysis reaction is complete, remove the pyrolysis carbon collection tube (6), weigh the solid product, and collect the broken-bond catalyst bed (7) and Catalysts in shape-selective catalyst beds (8); S5. Open the air cylinder (12), adjust the air flow through the flow controller (14) and the air mass flow meter (13), heat the pyrolysis reactor (9) to the predetermined temperature through the temperature controller (15), remove the heavy tar remaining on the reactor wall by combustion, and weigh the reactor before and after the reaction to obtain the mass of heavy tar catalytically pyrolyzed by waste microbial residue.

3. The method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond-breaking reforming according to claim 2, characterized in that: The bacterial residue is pulverized waste microbial residue particles with a mesh size of 40-80 mesh, dried at 90-110℃.

4. The method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond-breaking reforming according to claim 2, characterized in that: The bottom of the pyrolysis carbon collection pipe (6) is perforated, and quartz wool is placed at the bottom. The top is at the same height as the inside of the pyrolysis reactor (9).

5. The method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond breaking reforming according to claim 2, characterized in that: The bond-breaking catalyst bed (7) uses natural or synthetic acidic or basic solid catalysts, including activated carbon catalysts with large-medium-micro interconnected multi-level pores, with a bed thickness of 10-20 mm.

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

7. The method for preparing aviation fuel precursors by catalytic pyrolysis of bacterial residue bond breaking reforming according to claim 2, 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 seconds.

8. The method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond breaking reforming according to claim 2, characterized in that: The outlet of the microbial residue pusher (1) is inclined upward at an angle of 10-30°; the waste microbial residue is pumped into the pyrolysis reactor (9) at a feed rate of 10-40 mg / min.

9. The method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond-breaking reforming according to claim 2, characterized in that: The temperature range of the first heating section (3) is 550-700℃, the temperature range of the second heating section (4) is 450-600℃, and the temperature range of the third heating section (5) is 550-600℃.

10. The method for preparing aviation fuel precursors by catalytic pyrolysis of fungal residue bond-breaking reforming according to claim 2, characterized in that: The bottom of the pyrolysis reactor (9) is wrapped with a heating belt, which is wrapped in two layers and has a temperature range of 150-300℃ to prevent the aviation fuel precursor from condensing at the reactor outlet.

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