Pyrolysis-graded catalysis experiment system and method

Abstract

The invention provides a pyrolysis-grading catalysis experiment system and method, and belongs to the technical field of heavy carbon resource thermochemical treatment. The tubular furnace is provided with a pyrolysis area and a catalysis area which are independently controlled in temperature along a heat conduction pipe, and a sample introduction assembly with double gas transmission paths is inserted into the tubular furnace; the assembly comprises a sample injection lining pipe with a material fixing groove and a sealing switching component, flow division of inner pipe carrier gas and annular space carrier gas is achieved, the inert atmosphere is ensured, and backflow is prevented. A heat tracing temperature control device is arranged on a transmission section between an outlet of the tubular furnace and the condensing device, so that condensation and retention of products are prevented. The second-stage condensing device is matched with gradient cooling (ice-water bath and salt ice bath), and fractional condensation and collection of products are optimized. The device solves the problems of difficulty in partitioned temperature control, poor air tightness, transmission condensation and product loss, can accurately simulate rapid temperature rise, is suitable for pyrolysis, graded catalysis and coupling conversion experiments of heavy carbon resources such as coal, biomass and plastic, and has the advantages of convenience in operation and high product collection efficiency.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of thermal chemical processing of heavy carbon resources, and relates to a pyrolysis-grading catalysis experimental system and method. BACKGROUND

[0002] Pyrolysis catalysis has wide application potential in the field of high-value utilization of heavy carbon resources. The two-stage pyrolysis-catalysis experimental device commonly adopted in the laboratory is a combination of a pyrolysis furnace and a catalytic furnace, which is easy to cause condensation at the connection between the two furnaces, and the pyrolysis volatiles of the raw material are difficult to enter the downstream catalytic furnace. At present, for a one-stage tubular furnace, the raw material and the catalyst are pre-placed in the reaction tube and are placed in layers, which can realize the pyrolysis-catalysis grading conversion of the raw material, but the target temperature is often reached by programmed heating, which is difficult to completely simulate the rapid heating process in the industry. In order to simulate the rapid heating process, the catalyst bed is pre-placed, and after the furnace temperature rises to the target temperature, the raw material is placed in a basket or a porcelain boat and pushed into the furnace, which is easy to cause the sample to fall off and is difficult to guarantee the air tightness. In addition, the pyrolysis and catalysis regions of the one-stage tubular furnace often cannot realize separate temperature control, and cannot respectively reach the optimal pyrolysis and catalysis temperatures. SUMMARY

[0003] The purpose of the present application is to solve the above-mentioned problems existing in the prior art, and to provide a pyrolysis-grading catalysis experimental system and method.

[0004] The purpose of the present application can be achieved by the following technical scheme: a pyrolysis-grading catalysis experimental system, a one-stage partition temperature control tubular furnace, a filter, a two-stage condensing device and a gas treatment device are sequentially arranged according to the process flow, the one-stage partition temperature control tubular furnace is connected by a heat conduction pipe from the furnace inlet to the furnace outlet, the heat conduction pipe is a quartz pipe, a pyrolysis zone and a catalysis zone are sequentially arranged along the inlet-outlet direction in the furnace cavity around the outer periphery of the heat conduction pipe, the pyrolysis zone is provided with an independent heating temperature control device one, and the catalysis zone is provided with an independent heating temperature control device two; the pyrolysis zone and the catalysis zone form a heating zone;

[0005] A sample feeding assembly with double gas conveying paths is inserted into the one-stage partition temperature control tubular furnace, the sample feeding assembly includes a sample feeding inner lining pipe, the sample feeding inner lining pipe is connected to the heat conduction pipe, the sample feeding inner lining pipe is provided with a material fixing groove, the material fixing groove is located in the catalysis zone, the sample feeding inner lining pipe penetrates the furnace inlet to form a front pipe section, the pipe opening of the front pipe section is a gas inlet, the outer periphery of the front pipe section is sleeved with a sealing adapter member, the annular gap between the sealing adapter member and the front pipe section is connected to the annular gap between the heat conduction pipe and the sample feeding inner lining pipe, and a gas inlet is formed in the sealing adapter member.

[0006] The double gas conveying path includes one gas conveying path from the gas inlet to the sample inlet lining pipe and another gas conveying path from the gas inlet to the annular gap between the sealing adapter and the pre-pipe section and then to the annular gap between the heat conducting pipe and the sample inlet lining pipe.

[0007] The one-stage partition temperature control tube furnace is provided with a pre-condensation transmission section between the furnace outlet and the secondary condensing device, and the pre-condensation transmission section is provided with a pre-condensation transmission heat tracing temperature control device.

[0008] Preferably, the first independent heating temperature control device comprises a first heating wire, a first thermocouple and a first temperature controller, the first heating wire is wound around the outer periphery of the heat conducting pipe, the first thermocouple contacts the first heating wire, and the first heating wire and the first thermocouple are connected to the first temperature controller outside the furnace cavity through an electric circuit; the second independent heating temperature control device comprises a second heating wire, a second thermocouple and a second temperature controller, the second heating wire is wound around the outer periphery of the heat conducting pipe, the second thermocouple contacts the second heating wire, and the second heating wire and the second thermocouple are connected to the second temperature controller outside the furnace cavity through an electric circuit.

[0009] The first heating wire is powered to heat the heat conducting pipe in the corresponding area, the temperature of the first heating wire is monitored in real time by the first thermocouple and fed back to the first temperature controller, and the first temperature controller adjusts the heating temperature of the first heating wire in a timely manner according to the set temperature. The second heating wire is powered to heat the heat conducting pipe in the corresponding area, the temperature of the second heating wire is monitored in real time by the second thermocouple and fed back to the second temperature controller, and the second temperature controller adjusts the heating temperature of the second heating wire in a timely manner according to the set temperature.

[0010] Preferably, the sample inlet lining pipe and the heat conducting pipe pass through the furnace outlet to form an output port, the output port is connected to the filter through an adapter, the filter is connected to the secondary condensing device through a pre-condensation transmission pipe, and the output port, the adapter, the filter and the pre-condensation transmission pipe form the pre-condensation transmission section; the pre-condensation transmission heat tracing temperature control device comprises a heating belt, a third thermocouple and a third temperature controller, the heating belt is wound around the outer periphery of the output port, the adapter, the filter and the pre-condensation transmission pipe, the third thermocouple contacts the heating belt, and the heating belt and the third thermocouple are connected to the third temperature controller through an electric circuit.

[0011] Preferably, the gas inlet of the sample injection inner liner tube is connected to a carrier gas channel one through an adapter, a gas valve one is arranged on the carrier gas channel one, the sample injection inner liner tube is connected to the sealing adapter through an adapter two, the connection end of the sealing adapter and the adapter two is a sealing end, and the sealing adapter is connected to the inlet of a one-segment partition temperature control tube furnace; the gas inlet of the sealing adapter is connected to a carrier gas channel two through an adapter two, and a gas valve two is arranged on the carrier gas channel two; the inlet part of the heat conduction tube extends into the sealing adapter, and the gas inlet arranged on the sealing adapter is located in the front side area of the inlet part of the heat conduction tube, that is, the gas inlet is not blocked by the heat conduction tube. The material fixing groove is an annular groove formed by the inwardly recessed outer wall of the sample injection inner liner tube, and the annular groove is protruded radially by the inner wall of the sample injection inner liner tube to reduce the pipe diameter. The material fixing groove is specifically arranged in the middle and rear segment of the sample injection inner liner tube, the raw material and the catalyst are arranged in the pipe cavity in the front segment of the material fixing groove, and the raw material and the catalyst are prevented from moving or being blown out by the carrier gas through the reduced pipe diameter.

[0012] Preferably, the filter comprises a filter shell, the filter shell is filled with filter medium, and the filter medium specifically adopts a glass fiber filter sheet, and the outer periphery of the filter shell is bound with a clamp to form a seal.

[0013] Preferably, the secondary condensing device comprises a plurality of serially connected condensing collection containers, the condensing collection containers are filled with a collection liquid and 2mm quartz beads, the filter is connected to the first condensing collection container through a pre-condensation transmission pipe, the pipe opening of the pre-condensation transmission pipe is below the liquid level of the collection liquid, the adjacent condensing collection containers are connected through an inverted U-shaped pipe, the U-shaped pipe has a long input pipe and a short output pipe, the long input pipe extends below the liquid level of the collection liquid, and the short output pipe is above the liquid level of the collection liquid. It is ensured that the pyrolysis or pyrolysis-catalysis products of the raw material are fully condensed in the secondary condensing device, and the solvent cannot be flushed out of the condensing collection bottle. The condensing collection container comprises a bottle body, the top opening of the bottle body is sealed by a silica gel plug, and the U-shaped pipe penetrates into the bottle body through the silica gel plug. The first condensing collection container is placed in an ice water condensing tank, and the remaining condensing collection containers are placed in a salt ice condensing tank.

[0014] Preferably, the gas treatment device comprises a three-way joint, a gas collection bag and a tail gas pipe, the inlet of the three-way joint is connected to the gas outlet pipe of the last condensing collection container, one outlet of the three-way joint is connected to the gas collection bag through a gas valve three, and the other outlet of the three-way joint is connected to the tail gas pipe through a gas valve four.

[0015] A pyrolysis-grading catalysis experiment method, which adopts the system in Embodiment 1 and specifically comprises the following steps:

[0016] S1 loading: load the material into the sample inner lining tube, ensure that the material is located in the heating zone, and the material is located at the end of the material fixing groove away from the outlet; an isolation layer is arranged between the material and the material fixing groove;

[0017] S2 reaction preparation: after loading, close the gas valve three at the front end of the gas collection bag, open the gas valve four at the front end of the tail gas pipe; connect the sample inner lining tube with the carrier channel one, open the gas valve one of the carrier gas channel one, so that the gas in the carrier gas channel one enters the sample inner lining tube; ensure that the sample in the sample inner lining tube is in an inert atmosphere, and at the same time, check whether the gas flow in the sample inner lining tube is smooth to prevent blockage.

[0018] Start the independent heating temperature control device one to heat the temperature of the pyrolysis zone to T1; start the independent heating temperature control device two to heat the temperature of the catalytic zone to T2; start the pre-condensation transmission heating temperature control device to heat the temperature of the heating belt to T3;

[0019] Open the gas valve two of the carrier gas channel two to make the gas in the carrier gas channel two enter the heat conduction tube; ensure that the inside of the heat conduction tube is in an inert atmosphere to avoid the mixing of oxygen and cause oxidation side reactions, and at the same time, prevent the backflow of pyrolysis volatiles in the sample inner lining tube to the gap between the quartz tube and the sample inner lining tube;

[0020] S3 heating reaction: after the reaction preparation is completed, push the sample inner lining tube loaded with the material into the heat conduction tube for heating reaction; the volatiles or pyrolysis-catalysis reaction products pass through the filter to filter out solid particles, powders or heavy components, pass through the secondary condensation device to condense and collect organic products, and then pass through the subsequent gas collection bag to collect small molecule gas products.

[0021] S4 post-processing: after the heating reaction is completed, close the independent heating temperature control device one, the independent heating temperature control device two and the pre-condensation transmission heating temperature control device; after the temperature of the furnace cavity of the one-stage partition temperature control tube furnace decreases to room temperature, close the gas valve one of the carrier gas channel one, close the gas valve two of the carrier gas channel two, close the gas valve three at the front end of the gas collection bag and open the gas valve four at the front end of the tail gas pipe, and take out the sample inner lining tube.

[0022] When the material is only a pyrolysis raw material, the heating temperatures of the independent heating temperature control device one and the independent heating temperature control device two are set to be the same;

[0023] When the material is a mixture of a pyrolysis raw material and a catalyst, the heating temperatures of the independent heating temperature control device one and the independent heating temperature control device two are set to be the same;

[0024] When the material includes a pyrolysis raw material and a single-stage catalyst, the pyrolysis raw material is located in the pyrolysis zone, the single-stage catalyst is located in the catalytic zone, an isolation layer is arranged between the pyrolysis raw material and the single-stage catalyst, and an isolation layer is arranged between the single-stage catalyst and the material fixing groove;

[0025] When the material comprises pyrolysis raw material, secondary or multi-stage catalyst, the pyrolysis raw material is located in the pyrolysis zone, the secondary or multi-stage catalyst is located in the catalytic zone, and the isolation layer is arranged between different stages of catalysts; the isolation layer is arranged between the pyrolysis raw material and the first-stage catalyst; and the isolation layer is arranged between the last-stage catalyst and the material fixing groove.

[0026] Preferably, the material of the isolation layer is selected from porous inert isolation materials, such as quartz wool.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] Accurate partition temperature control and rapid heating simulation are achieved: by arranging the pyrolysis zone and the catalytic zone with independent temperature control (respectively configuring heating wires, thermocouples and temperature controllers) in the one-stage tubular furnace, the defect that the prior art cannot control the temperature in different zones is solved. The pyrolysis zone and the catalytic zone can be independently set to a temperature, and at the same time, through the way of rapidly pushing the high-temperature reaction zone by the sample inlet lining tube, the industrial rapid heating process is simulated, and the matching degree of the experiment and the actual working condition is significantly improved.

[0029] Breakthrough in sampling safety and airtightness bottleneck: the innovative design of the sample inlet lining tube integrates the material fixing groove, which can firmly fix the raw material and the catalyst; the double gas conveying path design (inner tube gas flow path + annular gas flow path) combined with the sealing adapter member completely solves the problems of backflow of carrier gas and penetration of oxygen while ensuring the inert atmosphere, and significantly improves the system airtightness and operation reliability.

[0030] Eliminate the risk of transmission condensation and product loss: the heating temperature control device (heating belt + thermocouple + temperature controller) is arranged in the transmission section before condensation, the temperature of the filter and the transmission pipeline is maintained at a set value, which effectively prevents the condensation and retention of pyrolysis volatiles and catalytic products in the transmission process, ensures the complete collection of products and avoids pipeline blockage.

[0031] Optimize multi-stage catalysis and product collection efficiency: the material loading adopts a layered isolation design (such as quartz wool isolation layer), which supports the staged arrangement of pyrolysis raw material and multi-stage catalyst, realizes continuous pyrolysis-catalysis reaction; the secondary condensation device is designed with a U-shaped tube series structure and a liquid-submerged gas inlet, combined with gradient cooling (ice water bath + salt ice bath), so that organic products are efficiently condensed and enriched in the collection liquid, and small molecule gases are accurately captured by the gas collection bag.

[0032] Improve system integration and operation convenience: the pyrolysis, catalysis, filtration, condensation and gas treatment modules are integrated into a coherent process, and through partition temperature control, sample push-in operation and automatic heating management, the experimental steps are greatly simplified, and human errors are reduced.

[0033] Wide range of applications: The sample introduction method of this invention is suitable for different types of raw materials, including heavy carbon resource samples such as solid blocks, powders, slurries and liquids, such as fossil fuels, biomass, plastics, solid waste, oil sludge and coal-water slurry; This invention can control the temperature of the pyrolysis zone and the catalytic zone separately, and can carry out isothermal pyrolysis-catalysis experiments as well as low temperature pyrolysis-high temperature catalysis experiments; This invention can also carry out gasification, pyrolysis-gasification and pyrolysis-oxidation coupling experiments, and the multi-purpose experimental switching is convenient. Attached Figure Description

[0034] Figure 1 This is a structural diagram of the pyrolysis-stage catalytic experimental system in this invention.

[0035] Figure 2 This is a schematic diagram of the loading of the sample inlet liner tube in this invention.

[0036] exist Figure 1 The structure includes: 1. Carrier gas channel one; 2. Gas valve one; 3. Adapter one; 4. Sample inlet liner; 5. Material fixing groove; 6. Adapter two; 7. Sealing adapter component; 8. Carrier gas channel two; 9. Gas valve two; 10. One-stage zone temperature-controlled tubular furnace; 11. Heat conduction tube; 12. Pyrolysis zone; 13. Heating wire one; 14. Thermocouple one; 15. Temperature controller one; 16. Catalytic zone; 17. Heating wire two; 18. 19. Thermocouple 2; 20. Temperature controller 2; 21. Adapter; 22. Filter; 23. Clamp; 24. Pre-condenser transfer pipe; 25. Heating belt; 26. Thermocouple 3; 27. Temperature controller 3; 28. Condensation collection container; 29. ​​U-tube; 30. Ice water condensation tank; 31. Salt ice condensation tank; 32. Gas outlet pipe; 33. T-junction; 34. Gas collection bag; 35. Gas valve 4; 36. Exhaust pipe. Detailed Implementation

[0037] The following are specific embodiments of the present invention, which are described in conjunction with the accompanying drawings. However, the present invention is not limited to these embodiments.

[0038] Example 1

[0039] like Figure 1 As shown, a pyrolysis-stage catalytic experimental system is arranged sequentially according to the process flow, including a single-stage zone-controlled temperature-controlled tubular furnace 10, a filter 21, a secondary condenser, and a gas treatment device. The single-stage zone-controlled temperature-controlled tubular furnace 10 has a heat transfer pipe 11 running from the furnace inlet to the outlet. Around the outer periphery of the heat transfer pipe 11, along the inlet and outlet directions, the furnace cavity is arranged with a pyrolysis zone 12 and a catalytic zone 16. The pyrolysis zone 12 is equipped with an independent heating and temperature control device one, and the catalytic zone 16 is equipped with an independent heating and temperature control device two. The heat transfer pipe 11 is a quartz tube. The pyrolysis zone 12 and the catalytic zone 16 constitute the heating zone.

[0040] A one-stage partition temperature control tube furnace 10 is inserted with a sample injection assembly having a double gas delivery path, the sample injection assembly includes a sample injection inner liner tube 4, the sample injection inner liner tube 4 penetrates the heat conduction tube 11, the sample injection inner liner tube 4 is provided with a material fixing groove 5, the material fixing groove 5 is located in the catalytic zone 16, the sample injection inner liner tube 4 penetrates the furnace inlet to form a pre-pipe section, the pre-pipe section is provided with a first gas inlet, the pre-pipe section is sleeved with a sealing adapter member 7, the sealing adapter member 7 is connected with the pre-pipe section, the annular gap between the sealing adapter member 7 and the pre-pipe section is connected with the annular gap between the heat conduction tube 11 and the sample injection inner liner tube 4, and the sealing adapter member 7 is provided with a second gas inlet.

[0041] A condensation pre-transmission section is formed between the furnace outlet of the one-stage partition temperature control tube furnace 10 and the secondary condensation device, and the condensation pre-transmission section is provided with a condensation pre-transmission heat tracing temperature control device.

[0042] The independent heating temperature control device one includes a heating wire one 13, a thermocouple one 14 and a temperature controller one 15, the heating wire one 13 is wound on the outer periphery of the heat conduction tube 11, the thermocouple one 14 contacts the heating wire one 13, and the heating wire one 13 and the thermocouple one 14 are connected with the temperature controller one 15 outside the furnace cavity through a circuit; the independent heating temperature control device two includes a heating wire two 17, a thermocouple two 18 and a temperature controller two 19, the heating wire two 17 is wound on the outer periphery of the heat conduction tube 11, the thermocouple two 18 contacts the heating wire two 17, and the heating wire two 17 and the thermocouple two 18 are connected with the temperature controller two 19 outside the furnace cavity through a circuit.

[0043] The output port is connected with the filter 21 through the adapter 20, the filter 21 is connected with the secondary condensation device through the condensation pre-transmission tube 23, and the output port, the adapter 20, the filter 21 and the condensation pre-transmission tube 23 form the condensation pre-transmission section; the condensation pre-transmission heat tracing temperature control device includes a heating belt 24, a thermocouple three 25 and a temperature controller three 26, the heating belt 24 is wound on the outer periphery of the output port, the adapter 20, the filter 21 and the condensation pre-transmission tube 23, the thermocouple three 25 contacts the heating belt 24, and the heating belt 24 and the thermocouple three 25 are connected with the temperature controller three 26 through a circuit.

[0044] The gas inlet of the sample injection inner liner tube 4 is connected with the carrier gas channel one 1 through the adapter one 3, the carrier gas channel one 1 is provided with the gas valve one 2, the sample injection inner liner tube 4 is connected with the sealing adapter member 7 through the adapter two 6, the connection end of the sealing adapter member 7 and the adapter two 6 is a sealing end, and the sealing adapter member 7 is connected with the furnace inlet of the one-stage partition temperature control tube furnace 10; the gas inlet of the sealing adapter member 7 is connected with the carrier gas channel two 8 through the adapter two, and the carrier gas channel two 8 is provided with the gas valve two 9; the material fixing groove 5 is an annular groove formed by the inward recess of the outer tube wall of the sample injection inner liner tube 4, and the annular groove is protruded from the inner tube wall of the sample injection inner liner tube 4 to reduce the pipe diameter.

[0045] The filter 21 comprises a filter shell filled with filter medium, and a hoop 22 is bound to the outer periphery of the filter shell to form a seal.

[0046] The secondary condensing device comprises a plurality of serially connected condensing collection containers 27, each of which is filled with a collection liquid, and the filter 21 is connected to the first condensing collection container 27 through a pre-condensing transmission pipe 23, the pipe opening of which is below the liquid level of the condensing liquid, and the serially connected condensing collection containers 27 are connected through inverted U-shaped pipes 28, each of which has a long input pipe and a short output pipe, the long input pipe of which extends below the liquid level of the condensing liquid, and the short output pipe of which is above the liquid level of the condensing liquid; the first condensing collection container 27 is placed in an ice-water condensing tank 29, and the remaining condensing collection containers 27 are placed in a salt-ice condensing tank 30.

[0047] The gas treatment device comprises a three-way pipe 32, a gas collection bag 34, and a tail gas pipe 36, the inlet of the three-way pipe 32 is connected to the gas outlet pipe 31 of the last condensing collection container 27, one outlet of the three-way pipe 32 is connected to the gas collection bag 34 through a gas valve three 33, and the other outlet of the three-way pipe 32 is connected to the tail gas pipe 36 through a gas valve four 35.

[0048] Example 2

[0049] A pyrolysis-grading catalysis experimental method, which uses the experimental system in Example 1, specifically comprises the following steps:

[0050] S1 loading: load the material into the sample inner lining pipe 4 according to the loading requirements, and ensure that the material is located in the heating zone; all the material is located at the end of the material fixing groove 5 away from the furnace outlet, and a separation layer is arranged between the material and the material fixing groove 5;

[0051] S2 pre-reaction preparation: after the loading is completed, close the gas valve three 33 at the front end of the gas collection bag 34, and open the gas valve four 35 at the front end of the tail gas pipe 36; connect the sample inner lining pipe 4 and the carrier channel one 1, open the gas valve one 2 of the carrier channel one 1, and make the gas in the carrier channel one 1 enter the sample inner lining pipe 4;

[0052] Start the independent heating temperature control device one 15 to heat the temperature of the pyrolysis zone 12 to T1; start the independent heating temperature control device two 19 to heat the temperature of the catalysis zone 16 to T2; and start the pre-condensing transmission heat tracing temperature control device 26 to heat the temperature of the heating belt 24 to T3;

[0053] Open the gas valve two 9 of the carrier channel two 8 to make the gas in the carrier channel two 8 enter the heat conduction pipe 11;

[0054] S3 heating reaction: after the pre-reaction preparation is completed, push the sample inner lining pipe 4 loaded with the material into the heat conduction pipe 11 to perform the heating reaction;

[0055] S4 post-processing: after the reaction is completed, turn off the independent heating temperature control device 15, the independent heating temperature control device 19 and the pre-condensation transmission heating temperature control device 26; after the temperature of the furnace cavity of the one-section partition temperature control tube furnace 10 drops to room temperature, close the gas valve 2 on the carrier gas passage 1, close the gas valve 9 on the carrier gas passage 8, close the gas valve 33 in front of the gas collection bag 34 and open the gas valve 35 in front of the tail gas pipe 36, and take out the sample inlet lining pipe 4.

[0056] As shown in Figure 2 When the material is only pyrolysis raw material, the material is located in the heating zone, and the heating temperatures of the independent heating temperature control device one and the independent heating temperature control device two are set to be the same; when the material is a mixture of pyrolysis raw material and catalyst, the material is located in the heating zone, and the heating temperatures of the independent heating temperature control device one and the independent heating temperature control device two are set to be the same; when the material includes pyrolysis raw material and single-stage catalyst, the pyrolysis raw material is located in the pyrolysis zone 12, the single-stage catalyst is located in the catalytic zone 16, and a separation layer is arranged between the pyrolysis raw material and the single-stage catalyst; when the material includes pyrolysis raw material, two-stage or multi-stage catalyst, the pyrolysis raw material is located in the pyrolysis zone 12, and the two-stage or multi-stage catalyst is located in the catalytic zone 16, and a separation layer is arranged between different stages of catalyst; a separation layer is arranged between the pyrolysis raw material and the first-stage catalyst; and a separation layer is arranged between the last-stage catalyst and the material fixing groove 5.

[0057] Example three

[0058] According to the method in Example 2, a pyrolysis experiment was carried out: the material was only pyrolysis raw material-lignin, and the pyrolysis experiment was carried out for lignin to explore the composition and distribution of volatile pyrolysis products. The pyrolysis zone 12 and the catalytic zone 16 were set to the same temperature, and the temperature of the temperature control instrument one 15 and the temperature control instrument two 19 was set to 400-1000 DEG C; the temperature of the temperature control instrument three 26 was set to 250 DEG C; the ice water condensation tank 29 was set to 0 DEG C; the salt ice condensation tank 30 was set to -20 DEG C; the condensation collection container 27 was filled with 2mm quartz beads and methanol; the filter 21 was filled with glass fiber; the pre-condensation transmission pipe 23, the U-shaped pipe 28 and the exhaust pipe 31 were all made of stainless steel; the gas flow of the carrier gas passage one 1 and the carrier gas passage two 8 was set to 100mL / min, and the inert gas was nitrogen;

[0059] During the experiment, lignin was pyrolyzed rapidly in the heating zone to generate pyrolysis volatiles, which were then first collected by the filter 21 into the ice water condensation tank 29 to collect heavy pyrolysis volatiles; then through the salt ice condensation tank 30 to collect light pyrolysis volatiles, and finally by the gas collection bag 34 to collect small molecule gas products. The composition and relative content of the organic pyrolysis volatiles collected by condensation were analyzed by gas chromatography mass spectrometry, and the composition and relative content of the small molecule gas products were analyzed by gas chromatography. After the experiment, the pyrolysis residue was weighed to calculate the amount of coke generated. The experimental results show that the lignin conversion rate is more than 45%, the main components of the organic volatiles include phenol, aromatic hydrocarbon, ketone, guaiacol derivative, alkane and olefin, and the small molecule gas products mainly include CO, CH4, C2H4, C2H6 and C3H8. The experiment successfully verifies the pyrolysis conversion capacity of the system for biomass and the collection capacity of the secondary condensing device for tar components. The experimental raw materials can be expanded to coal, plastic, heavy oil and oil sludge and other heavy carbon resource raw materials.

[0060] Example Four

[0061] In-situ catalytic pyrolysis experiment: lignin was used as raw material for in-situ catalytic pyrolysis experiment to explore the feasibility of converting lignin into high value-added aromatic hydrocarbons and phenolic products by in-situ catalytic pyrolysis. Lignin powder and HZSM-5 molecular sieve catalyst were physically mixed uniformly and placed in the heating zone; wherein the temperature of the pyrolysis zone 12 and the catalytic zone 16 was set to the same value, the temperature of the temperature controller one 15 and the temperature controller two 19 was set to 550℃; the temperature of the temperature controller three 26 was set to 250℃; the ice water condensation tank 29 was set to 0℃; the salt ice condensation tank 30 was set to -20℃; the condensation collection container 27 was filled with 2mm quartz beads and methanol; the filter 21 was placed with glass fiber; the condensation front transmission pipe 23, the U-shaped pipe 28 and the gas outlet pipe 31 were all made of stainless steel; the gas flow of the carrier gas channel one 1 and the carrier gas channel two 8 was set to 100mL / min, and the inert gas was nitrogen;

[0062] During the experiment, lignin catalytically generated pyrolysis products in situ, which were then first collected by filter 21 into ice water condensation tank 29 to collect heavy pyrolysis volatiles; then collected by salt ice condensation tank 30 to collect light pyrolysis volatiles, and collected by gas collection bag 34 to collect small molecule gas products. The composition and relative content of the organic pyrolysis volatiles collected by condensation were analyzed by gas chromatography mass spectrometry, and the composition and relative content of the small molecule gas products were analyzed by gas chromatography. After the experiment, the pyrolysis residue was weighed to calculate the amount of coke generated. The experimental results showed that the main products were single-ring aromatic hydrocarbon products such as benzene, toluene and xylene, and the relative content of single-ring aromatic hydrocarbons was 16%. The experiment successfully verified the in-situ catalytic conversion capacity of the system for biomass, and the collection capacity of the secondary condensing device for tar components. The experimental raw materials can be expanded to coal, plastic, heavy oil and oil sludge and other heavy carbon resource raw materials.

[0063] Example Five

[0064] The non-in-situ pyrolysis-catalysis experiment was carried out according to the method in Example 2: the material was pyrolysis raw material-lignin and single catalyst-HZSM-5 molecular sieve catalyst. The non-in-situ pyrolysis-catalysis experiment was carried out with lignin as raw material to explore the feasibility of converting lignin pyrolysis volatiles into high value-added aromatic hydrocarbons and phenolic products. The temperature of temperature controller one 15 was set to 550°C; the temperature of temperature controller two 19 was set to 600°C; the temperature of temperature controller three 26 was set to 250°C; the temperature of ice water condensation tank 29 was 0°C; the temperature of salt ice condensation tank 30 was -20°C; 2mm quartz beads and methanol were placed in condensation collection container 27; glass fiber was placed in filter 21; condensation front transmission pipe 23, U-shaped pipe 28 and gas outlet pipe 31 were all made of stainless steel; the gas flow of carrier gas channel one 1 and carrier gas channel two 8 was both set to 100mL / min, and the inert gas was nitrogen.

[0065] During the experiment, lignin was pyrolyzed rapidly in the pyrolysis zone 12 to generate initial pyrolysis volatiles, and then entered the catalytic zone 16 to undergo cracking, deoxidation and aromatization reactions; the generated catalytic reforming products first entered the ice water condensation tank 29 through the filter 21 to collect heavy pyrolysis volatiles; then through the salt ice condensation tank 30 to collect light pyrolysis volatiles, and the small molecule gas products were collected by the gas collection bag 34. The composition and relative content of the organic pyrolysis volatiles collected by condensation were analyzed by gas chromatography mass spectrometry, and the composition and relative content of the small molecule gas products were analyzed by gas chromatography. After the experiment, the pyrolysis residue was weighed to calculate the amount of coke generated. The experimental results show that the main products are single-ring aromatic hydrocarbon products such as benzene, toluene and xylene, the relative content of single-ring aromatic hydrocarbons is 19%, and the carbon deposition rate of the catalyst is 6%. The experiment successfully verifies the selective catalytic conversion ability of the system for biomass pyrolysis volatiles, and the collection ability of the condensation collection system for tar composition. The experimental raw materials can be expanded to coal, plastic, heavy oil and oil sludge and other heavy carbon resource raw materials.

[0066] Example Six

[0067] The non-in-situ pyrolysis-catalytic experiment was carried out according to the method in Example 2: the material was pyrolysis raw material-lignin, and the catalyst included the first-stage catalyst-basic catalyst and the second-stage catalyst-HZSM-5 molecular sieve catalyst; the non-in-situ pyrolysis-catalytic experiment was carried out with lignin as the raw material to explore the feasibility of the pyrolysis volatiles of lignin being converted into high-value-added aromatic hydrocarbons and phenolic products by staged catalytic conversion. The temperature setting of temperature controller one 15 was 550°C; the temperature settings of temperature controller two 19 were all 600°C; the temperature setting of temperature controller three 26 was 250°C; the temperature of ice water condensation tank 29 was 0°C; the temperature of salt ice condensation tank 30 was -20°C; 2mm quartz beads and methanol were placed in the condensation collection container 27; glass fiber was placed in the filter 21; the pre-condensation transmission pipe 23, the U-shaped pipe 28 and the gas outlet pipe 31 were all made of stainless steel; the gas flow of carrier gas channel one 1 and carrier gas channel two 8 were both set to 100mL / min, and the inert gas was nitrogen.

[0068] During the experiment, the generated catalytic products firstly enter the ice water condensation tank 29 through the filter 21 to collect heavy pyrolysis volatiles; then pass through the salt ice condensation tank 30 to collect light pyrolysis volatiles, and use the gas collection bag 34 to collect small molecule gas products. The composition and relative content of the organic pyrolysis volatiles collected by condensation are analyzed by using a gas chromatograph mass spectrometer, and the composition and relative content of the small molecule gas products are analyzed by using a gas chromatograph analyzer. After the experiment is completed, the pyrolysis residue is weighed to calculate the coke generation amount. The experimental results show that after the lignin pyrolysis volatiles are subjected to the staged catalysis, the relative content of the monocyclic aromatic hydrocarbons (benzene, toluene, xylene) is 7%, and the relative content of the phenolic products is 47%. The carbon deposition rate of the catalyst is 4%. The experiment verifies the staged catalytic conversion capacity of the system on the biomass pyrolysis volatiles. The experimental raw materials can be expanded to coal, plastic, heavy oil and oil sludge and other heavy carbon resource raw materials.

[0069] The above embodiments can be combined with each other or mixed and matched with other embodiments based on design requirements and reliability considerations, that is, the technical features in different embodiments can be freely combined to form more feasible implementation solutions. The protection scope of the present application is not limited to the specific embodiments listed, and any reasonable changes or equivalent replacements based on the inventive concept should be covered within the scope of the claims of the present application.

[0070] The experimental system and method of the present application is not only suitable for the catalytic conversion of heavy carbon resources, but also can be expanded to other similar thermochemical treatment processes, such as the pyrolysis, catalytic-pyrolysis, oxidation, gasification and coupling treatment processes of biomass, coal and waste plastic raw materials, etc. Any related experiment or industrial application using the core design idea of the present application belongs to the protection scope of the present patent.

[0071] Those skilled in the art can properly adjust the size, material, temperature range and operation method of the device without departing from the technical principles of the present application, and these adjustments should be considered as equivalent embodiments of the present application.

[0072] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application, and it should be understood that the above are only specific embodiments of the present application and are not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A pyrolysis-fractionation catalytic experimental system, characterized in that a one-stage partition temperature-controlled tubular furnace, a filter, a two-stage condensing device, and a gas treatment device are sequentially arranged according to a process flow. The one-section partition temperature control tube furnace is provided with a heat conduction pipe penetrating from the furnace inlet to the furnace outlet, and a furnace cavity surrounding the heat conduction pipe is sequentially provided with a pyrolysis zone and a catalysis zone along the inlet and outlet directions. The one-section partition temperature control tube furnace is provided with a sample feeding assembly with double gas feeding paths, which comprises a sample feeding inner lining pipe penetrating the heat conduction pipe and provided with a material fixing groove in the catalysis zone. The one-section partition temperature control tube furnace is provided with a condensation front transmission segment between the furnace outlet and the two-stage condensation device.

2. The pyrolysis - fractionation catalysis experimental system of claim 1, wherein, The independent heating and temperature control device one comprises a heating wire one, a thermocouple one and a temperature controller one, the heating wire one is wound around the outer periphery of the heat conduction pipe, the thermocouple one contacts the heating wire one, and the heating wire one and the thermocouple one are connected to the temperature controller one outside the furnace cavity through an electric circuit.

3. The pyrolysis - fractionation catalysis experimental system of claim 1, wherein, The output port of the sample feeding inner lining pipe and the heat conduction pipe penetrating the furnace outlet forms an output port, the output port is connected to the filter through an adapter, the filter is connected to the two-stage condensation device through a condensation front transmission pipe, and the output port, the adapter, the filter and the condensation front transmission pipe form the condensation front transmission segment.

4. The pyrolysis-stage catalyst experimental system of claim 1, wherein, The gas inlet of the sample feeding inner lining pipe is connected to a carrier gas channel one through an adapter one, a gas valve one is arranged on the carrier gas channel one, the sample feeding inner lining pipe is connected to the sealing adapter member through an adapter head two, the connection end of the sealing adapter member and the adapter head two is a sealing end, and the sealing adapter member is connected to the furnace inlet of the one-section partition temperature control tube furnace. The gas inlet of the sealing adapter member is connected to a carrier gas channel two through an adapter two, and a gas valve two is arranged on the carrier gas channel two.

5. The pyrolysis - fractionation catalysis experimental system of claim 1, wherein, The material fixing groove is an annular groove formed by the inward recess of the outer tube wall of the sample feeding inner lining pipe, and the annular groove is protruded from the inner tube wall of the sample feeding inner lining pipe to reduce the pipe diameter. The filter comprises a filter shell, the filter shell is filled with filter medium, and the outer periphery of the filter shell is bound with a clamp to form a seal.

6. The pyrolysis - fractionation catalysis experimental system of claim 3, wherein, The secondary condensing device comprises several serially connected condensing collection containers, which are filled with collection liquid, and the filter is connected to the first condensing collection container through a pre-condensation transmission pipe, the pipe opening of which is below the liquid level of the collection liquid, and the adjacent condensing collection containers are connected through an inverted U-shaped pipe, which has a long input pipe and a short output pipe, the long input pipe of which is below the liquid level of the collection liquid, and the short output pipe of which is above the liquid level of the collection liquid; the first condensing collection container is placed in an ice water condensing tank, and the remaining condensing collection containers are placed in a salt ice condensing tank.

7. The pyrolysis - fractionation catalysis experimental system of claim 6, wherein, The gas treatment device comprises a tee, a gas collection bag and a tail gas pipe, the inlet of the tee is connected to the gas outlet pipe of the last condensing collection container, one outlet of the tee is connected to the gas collection bag through a gas valve three, and the other outlet of the tee is connected to the tail gas pipe through a gas valve four.

8. A pyrolysis-staged catalytic experimental method, characterized by, Specifically comprising the following steps: S1 loading: loading the material into the sample inner lining pipe, ensuring that the material is located in the heating zone, and the material is located at the end of the material fixing groove away from the furnace outlet; an isolation layer is arranged between the material and the material fixing groove; S2 pre-reaction preparation: after the loading is completed, close the gas valve three at the front end of the gas collection bag, and open the gas valve four at the front end of the tail gas pipe; connect the sample inner lining pipe and the carrier channel one, and open the gas valve one of the carrier gas channel one, so that the gas in the carrier gas channel one enters the sample inner lining pipe; Start the independent heating temperature control device one to heat the temperature of the pyrolysis zone to T1; start the independent heating temperature control device two to heat the temperature of the catalytic zone to T2; start the pre-condensation transmission heat tracing temperature control device to heat the temperature of the heating belt to T3; Open the gas valve two of the carrier gas channel two to make the gas in the carrier gas channel two enter the heat conduction pipe; S3 heating reaction: after the pre-reaction preparation is completed, push the sample inner lining pipe loaded with the material into the heat conduction pipe for heating reaction; S4 post-treatment: after the heating reaction is completed, close the independent heating temperature control device one, the independent heating temperature control device two and the pre-condensation transmission heat tracing temperature control device; after the temperature of the furnace cavity of the one-stage partition temperature control pipe furnace decreases to room temperature, close the gas valve one on the carrier gas channel one, close the gas valve two on the carrier gas channel two, close the gas valve three at the front end of the gas collection bag and open the gas valve four at the front end of the tail gas pipe, and take out the sample inner lining pipe.

9. The pyrolysis - fractionation catalytic experimental method according to claim 8, characterized in that, When the material is only a pyrolysis raw material, the heating temperatures of the independent heating temperature control device one and the independent temperature control device two are set to be the same; When the material is a mixture of a pyrolysis raw material and a catalyst, the heating temperatures of the independent heating temperature control device one and the independent heating temperature control device two are set to be the same; When the material comprises a pyrolysis raw material and a single-stage catalyst, the pyrolysis raw material is located in the pyrolysis zone, the single-stage catalyst is located in the catalytic zone, an isolation layer is arranged between the pyrolysis raw material and the single-stage catalyst, and an isolation layer is arranged between the single-stage catalyst and the material fixing groove; When the material comprises a pyrolysis raw material and a two-stage or multi-stage catalyst, the pyrolysis raw material is located in the pyrolysis zone, the two-stage or multi-stage catalyst is located in the catalytic zone, isolation layers are arranged between different stages of the catalyst, an isolation layer is arranged between the pyrolysis raw material and the first-stage catalyst, and an isolation layer is arranged between the last-stage catalyst and the material fixing groove.

10. The pyrolysis-toll catalyst experimental method according to claim 8, wherein, The material of the isolation layer is selected from porous isolation materials.

Images