CN107987866B - Device and method for efficiently depolymerizing solid waste by microwaves and co-producing bio-oil and biochar - Google Patents
Device and method for efficiently depolymerizing solid waste by microwaves and co-producing bio-oil and biochar Download PDFInfo
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- CN107987866B CN107987866B CN201810036853.9A CN201810036853A CN107987866B CN 107987866 B CN107987866 B CN 107987866B CN 201810036853 A CN201810036853 A CN 201810036853A CN 107987866 B CN107987866 B CN 107987866B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
Abstract
The invention discloses a device and a method for efficiently depolymerizing and co-producing bio-oil and biochar by using solid waste microwaves, wherein the device comprises an air inlet system for providing reaction gas and carrier gas, a preheating system is connected to the outlet end of the air inlet system, a heat-preserving and filtering system is connected to the outlet end of the preheating system, a reaction system is connected to the outlet end of the heat-preserving and filtering system, a product collecting system is connected to the outlet end of the reaction system, a product heat-preserving system is arranged on a pipeline between the reaction system and the product collecting system, and a microwave generating system is sleeved outside the preheating system, the heat-preserving and filtering system and the reaction system. The invention adopts a two-stage conversion method of microwave depolymerization and catalytic pyrolysis, so that the solid waste can be efficiently reduced, harmless and recycled into high-value liquid product bio-oil and solid product pyrolytic carbon.
Description
Technical Field
The invention belongs to the field of waste resource utilization, and particularly relates to a device and a method for efficiently depolymerizing solid waste by microwaves to co-produce bio-oil and biochar.
Background
In recent years, human activities have led to a dramatic increase in the amount of emissions of various types of waste, including industrial waste, agricultural waste, forestry waste, household waste, town and paper sludge, rubber waste, tires waste, and the like. The effective utilization rate of the wastes is low, and the traditional incineration and burial cannot meet the increasingly severe environmental protection requirements, so that the search for efficient conversion and effective utilization ways of waste resources is particularly critical.
The thermal cracking technology has the advantages of wide raw material adaptability, high treatment speed, clean and pollution-free treatment process and the like, and becomes one of the effective ways of recycling the wastes. However, the conventional thermal cracking process is characterized by relatively complex conversion of thermal cracking process and poor controllability of products due to the fact that heat energy is conducted from the surface of the raw material to the inside at a relatively low heat transfer rate, which restricts the further development of the technology. The microwave thermal cracking mode can realize simultaneous internal and external heating of materials under the auxiliary action of microwave absorption medium by means of microwave dielectric heating, can effectively overcome the defects existing in conventional thermal cracking, prevents coking and carbonization in the thermal cracking process and secondary reaction, and is beneficial to efficient and full conversion of waste resources. However, there is no professional microwave thermal cracking device at present, and in particular, there is no two-stage catalytic device capable of precisely controlling the products of the microwave thermal cracking process.
Disclosure of Invention
The invention aims to provide a device and a method for efficiently depolymerizing and co-producing bio-oil and biochar by using solid waste microwaves, which are used for solving the problems in the prior art.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the utility model provides a device of high-efficient depolymerization of solid waste microwave coproduction bio-oil and biochar, including the air intake system that is used for providing reaction gas and carrier gas, air intake system's exit end is connected with preheating system, preheating system's exit end is connected with heat preservation filtration system, heat preservation filtration system's exit end is connected with reaction system, reaction system's exit end is connected with the product collecting system, and be provided with the product heat preservation system on the pipeline between reaction system and the product collecting system, preheating system, heat preservation filtration system and reaction system's outside cover are equipped with microwave generation system.
Further, the air inlet system comprises an air inlet pipe formed by collecting a reaction air pipe and a carrier air pipe, and the outlet end of the air inlet pipe is connected with a preheating system; the preheating system comprises a spiral preheating pipe connected to the outlet end of the air inlet pipe, a preheating silicon carbide sleeve is sleeved on the outer side of the preheating pipe, and the outlet end of the preheating pipe is connected with the heat-preserving filtering system.
Further, the heat preservation and filtration system comprises a filtration and heat preservation plug connected to the outlet end of the preheating pipe, wherein temperature-resistant quartz heat preservation cotton is arranged in the filtration and heat preservation plug, and the outlet end of the filtration and heat preservation plug is connected with the reaction system; the reaction system comprises a cracking reactor connected to the outlet end of the filtering heat preservation plug and a catalytic reactor arranged at the outlet end of the cracking reactor, wherein the outlet end of the catalytic reactor is connected with a gas valve, and a product collecting system is connected between the outlet end of the catalytic reactor and the gas valve.
Further, the cracking reactor is a hollow column body with a semicircular section, the upper end of the hollow column body is a solid waste inlet, one end of the hollow column body is provided with a cracking reactor air inlet, and the cracking reactor air inlet is connected with the outlet end of the filtering heat-preserving plug;
the catalytic reactor comprises a hollow cylindrical reactor body, wherein one end of the reactor body is provided with an end cover, a plurality of catalytic reactor air inlets are uniformly distributed on the end cover, and the other end of the reactor body is provided with a catalytic reactor air outlet.
Further, the microwave generating system comprises a microwave box body arranged outside the preheating system, the heat preservation filtering system and the reaction system and a microwave feed-in system arranged on the microwave box body, a front-end microwave suppression device and a rear-end microwave suppression device are respectively arranged on two sides of the microwave box body, and a sealing end is arranged at the free end of the front-end microwave suppression device.
Further, the product heat preservation system comprises a heat preservation silicon carbide sleeve sleeved on the outlet end pipeline of the catalytic reactor and an electric heating heat preservation device, the heat preservation silicon carbide sleeve is sleeved on the part of the outlet end pipeline of the catalytic reactor, which is positioned in the microwave box, and the electric heating heat preservation device is sleeved on the part of the outlet end pipeline of the catalytic reactor, which is positioned outside the microwave box.
Further, the product collecting system comprises a collecting pipeline connected between the outlet end of the catalytic reactor and the gas valve, the outlet end of the collecting pipeline is connected with a primary biological oil collecting device, the distillation outlet of the primary biological oil collecting device is connected with a secondary biological oil collecting device, and a condensing pipe is sleeved on the collecting pipeline.
A method for efficiently depolymerizing solid waste microwave to co-produce bio-oil and biochar adopts the device, and comprises the following steps:
step one: crushing solid waste into particles with the particle size of 0.5-10 mm, and placing the particles in a cracking reactor; placing a catalyst with the particle size of 2-10 mm into a catalytic reactor, and introducing carrier gas to remove air in a reaction system, wherein the flow rate of the carrier gas corresponding to each gram of solid waste is 5-30 mL/min;
step two: opening an electric heating heat preservation device, wherein the temperature is 250-350 ℃, opening a gas valve, then opening a microwave generation system, the microwave frequency is 2.45GHz, the microwave power is 200-400W, reacting for 5-10 minutes, and discharging water and low-molecular compounds generated by initial cracking reaction;
step three: introducing reaction gas, opening condensed water in a condensing pipe, controlling the temperature to be 2-5 ℃, adding dry ice acetone bath in a secondary biological oil collecting device, closing a gas valve, adjusting the microwave power to be 800-1200W, heating a cracking reactor to 400-700 ℃, keeping the corresponding catalytic reactor temperature to be 350-650 ℃ at the moment, and reacting for 15-30 minutes at the temperature, wherein the reaction gas is methanol, formaldehyde or methane gas, and the flow rate of the reaction gas corresponding to each gram of solid waste is 0.1-2 mL/min;
step four: after the reaction is finished, closing the microwave generation system, closing the electric heating heat preservation device, stopping introducing reaction gas, stopping introducing carrier gas when the temperature in the cracking reactor is reduced to below 150 ℃, closing condensed water in the condensing pipe, and performing reduced pressure distillation on the first-stage biological oil mixed liquid collected in the first-stage biological oil collecting device under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.085 to-0.095 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device; the remaining product in the cleavage reactor is biochar.
Further, the solid waste is one or more of agriculture and forestry waste, household garbage, sludge and waste rubber; the carrier gas is helium; the catalyst is one of zeolite catalyst and active carbon supported metallic catalyst.
Further, the cracking reactor material is formed by mixing 80-90% of recrystallized silicon carbide and 10-20% of metal oxide absorbent in percentage by mass, wherein the metal oxide absorbent is one of ferric oxide, cupric oxide, magnesium oxide, calcium oxide and nickel oxide; the catalytic reactor material is recrystallized silicon carbide.
Compared with the prior art, the invention has the following beneficial technical effects:
the device designs a reaction gas and carrier gas two-stage gas inlet system, combines the cracking reactor and the catalytic reactor, well realizes the on-line catalytic reforming of the thermal cracking steam of the solid waste, can realize the automatic temperature adjustment under the same microwave energy through the wave-absorbing characteristic points of the self materials of the cracking reactor and the catalytic reactor, and is beneficial to improving the quality of the biological oil of the final product. The designed product collecting system can realize the graded enrichment of components with different molecular weights and boiling points in the product in a two-stage grading mode.
In the method, reaction gas is added in the reaction process, and methanol, formaldehyde and methane in the reaction gas can well absorb microwave energy and convert the microwave energy into free radicals to form 'high-activity free radical sites', so that the high-activity free radical sites are combined with the active end of pyrolysis steam to inhibit secondary reaction; meanwhile, the reaction gas can be well carried with thermal cracking steam to be removed from the reaction system and mixed into the biological oil in a solvent form, so that the biological oil is prevented from adhering to the pipe wall of the device, and the solvent can be separated from the biological oil in a reduced pressure distillation mode and recycled, so that clean and cyclic production and utilization are realized.
Further, the cracking reactor material is formed by mixing 80-90% of recrystallized silicon carbide and 10-20% of metal oxide absorbent by mass, and the catalytic reactor material is recrystallized silicon carbide, so that the reaction temperature of the cracking section and the catalytic section can be well controlled. The metal oxide is added into the material of the pyrolysis reactor, so that the microwave absorption efficiency of the pyrolysis reactor can be well accelerated, and the heating rate and the pyrolysis efficiency of the pyrolysis reaction are improved; the catalytic reactor is made of recrystallized silicon carbide, and the temperature of the catalytic reaction section is lower than that of the cracking reaction section on the premise of not changing the microwave frequency, so that the secondary catalysis of cracking steam is facilitated, and the occurrence of secondary reaction is reduced.
Further, when the reaction starts, firstly opening a gas valve, then opening a microwave generating system, wherein the microwave frequency is 2.45GHz, the microwave power is 200-400W, the reaction lasts for 5-10 minutes, and water and low-molecular compounds generated by the initial cracking reaction are discharged; the mode can greatly reduce the oxygen content (removed in the forms of water, carbon dioxide, carbon monoxide and the like) in agricultural and forestry waste and the like, thereby being beneficial to improving the heat value of the biological oil and improving the distribution of components in the biological oil.
Drawings
FIG. 1 is a flow chart of the apparatus of the present invention;
FIG. 2 is a schematic diagram of a cleavage reactor;
FIG. 3 is a schematic of a catalytic reactor.
The device comprises a 1-air inlet pipe, a 2-sealed end socket, a 3-front end microwave inhibition device, a 4-preheating silicon carbide sleeve, a 5-preheating pipe, a 6-microwave box body, a 7-filtering heat preservation plug, an 8-cracking reactor, a 9-microwave feed system, a 10-catalytic reactor, a 11-heat preservation silicon carbide sleeve, a 12-rear end microwave inhibition device, a 13-electric heating heat preservation device, a 14-gas valve, a 15-condenser pipe, a 16-primary biological oil collection device, a 17-secondary biological oil collection device, an 18-cracking reactor air inlet, a 19-catalytic reactor end cover, a 20-catalytic reactor air inlet and a 21-catalytic reactor air outlet.
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 1 to 3, a device for efficiently depolymerizing and co-producing bio-oil and biochar by using solid waste microwaves mainly comprises an air inlet system, a preheating system, a heat preservation and filtration system, a reaction system, a microwave generation system, a product heat preservation system and a product collection system.
The air inlet system consists of two air inlet pipes 1 of reaction gas and carrier gas, the material is a quartz pipe, and the outlet of the air inlet pipe 1 is connected with the preheating system.
The preheating system consists of a preheating silicon carbide sleeve 4 and a preheating pipe 5. The preheating silicon carbide sleeve 4 is made of recrystallized silicon carbide and is a hollow sleeve, and the preheating pipe 5 is sleeved in the preheating silicon carbide sleeve 4; the preheating pipe 5 is made of quartz pipe and is spiral, the inlet of the preheating pipe 5 is connected with the outlet of the air inlet pipe 1, and the outlet of the preheating pipe 5 is connected with the heat preservation and filtration system.
The heat preservation and filtration system consists of a filtration and heat preservation plug 7, wherein the filtration and heat preservation plug is made of a quartz tube, temperature-resistant quartz heat preservation cotton is added into the filtration and heat preservation plug, an inlet of the filtration and heat preservation plug 7 is connected with the preheating tube 5, and an outlet of the filtration and heat preservation plug 7 is connected with the reaction system.
The reaction system consists of a cracking reactor 8 and a catalytic reactor 10. The cracking reactor 8 is made of 80-90% of recrystallized silicon carbide and 10-20% of metal oxide absorbent by mass, wherein the metal oxide absorbent is one of ferric oxide, cupric oxide, magnesium oxide, calcium oxide and nickel oxide; the cracking reactor 8 is semicircular, the upper end is open, solid waste is added from the upper end, the cracking reactor air inlet 18 is connected with the outlet of the filtering heat-preserving plug 7, and gas generated by the cracking reactor 8 volatilizes from the upper end and enters the catalytic reactor 10. The material of the catalytic reactor 10 is recrystallized silicon carbide, one end of the catalytic reactor 10 is provided with a catalytic reactor end cover 19, the catalytic reactor end cover 19 is provided with a catalytic reactor air inlet hole 20, the other end of the catalytic reactor 10 is provided with a catalytic reactor air outlet 21, and the catalytic reactor air outlet 21 is connected with a product heat preservation system. The reaction system energy is provided by a microwave generating system.
The microwave generating system consists of a microwave box 6, a microwave feed-in system 9, a front-end microwave suppression device 3, a rear-end microwave suppression device 12 and a sealing end head 2. The sealing end head 2 and the front end microwave suppression device 3 play a role in gas sealing through a sealing gasket. The front end microwave suppression device 3 and the rear end microwave suppression device 12 are connected with the microwave box body 6 and are round hollow sleeves made of stainless steel. The microwave feed system 9 mainly provides microwave power, 4. Microwave frequency: 2.45GHz,2. Microwave output power: 0.01-1.45 KW is continuously adjustable.
The product heat preservation system consists of a heat preservation silicon carbide sleeve 11 and an electric heating heat preservation device 13. The heat-preserving silicon carbide sleeve 11 is used for preserving heat of the inner pipe of the microwave box 6, and is made of recrystallized silicon carbide; the electric heating heat preservation device 13 carries out heat preservation on an outer pipeline of the microwave box body 7, and an outlet of the outer pipeline is connected with the gas valve 14 and the product collection system. The gas valve 14 is used to control the discharge of the microwave depolymerization generated gas.
The product collecting system consists of a condensing pipe 15, a primary biological oil collecting device 16 and a secondary biological oil collecting device 17. The medium of the condensing tube 15 is water with the temperature of 2-5 ℃, the outlet of the condensing tube 15 is connected with the primary biological oil collecting device 16, the primary biological oil collecting device 16 is connected with the secondary biological oil collecting device 17, and the secondary biological oil collecting device 17 is internally provided with a cooling medium which is dry ice acetone bath.
A method for efficiently depolymerizing solid waste microwave to co-produce bio-oil and biochar mainly comprises the following steps:
1. crushing solid waste into particles with the particle size of 0.5-10 mm, and placing the particles in a cracking reactor 8; the catalyst having a particle diameter of 2 to 10mm is placed in the catalytic reactor 10. Introducing carrier gas for 10 minutes to remove air in the reaction system, wherein the flow rate of the carrier gas corresponding to each gram of solid waste is 5-30 mL/min; the solid waste is one or more of agriculture and forestry waste, household garbage, sludge and waste rubber; the carrier gas is helium; the catalyst is one of zeolite catalyst and active carbon supported metallic catalyst.
2. The electric heating and heat preserving device 13 is started, the temperature is 250-350 ℃, the gas valve 14 is opened, then the microwave generating system is started, the microwave frequency is 2.45GHz, the microwave power is 200-400W, the reaction is carried out for 5-10 minutes, and water and low molecular compounds generated by the initial cracking reaction are discharged.
3. And (3) introducing reaction gas, opening condensed water in a condensing pipe 15, controlling the temperature to be 2-5 ℃, adding dry ice acetone bath into a secondary biological oil collecting device 17, closing a gas valve 14, adjusting the microwave power to be 800-1200W, heating a cracking reactor to 400-700 ℃, and keeping the corresponding catalytic reactor at the temperature of 350-650 ℃ for reaction for 15-30 minutes. The reaction gas is methanol or formaldehyde gas, and the flow rate of carrier gas corresponding to each gram of solid waste is 0.1-2 mL/min.
4. After the reaction is finished, the microwave generating system is closed, the electric heating and heat preserving device is closed, the introduction of the reaction gas is stopped, and when the temperature in the cracking reactor 8 is reduced to be lower than 150 ℃, the introduction of the carrier gas is stopped, and the condensed water in the condensing pipe 15 is closed. The first-stage biological oil collecting device 16 is used for collecting a first-stage biological oil mixed solution, the first-stage biological oil mixed solution is subjected to reduced pressure distillation (the temperature is 20 ℃, the relative vacuum degree is-0.085 to-0.095 Mpa), and when no fraction is distilled out, the residual liquid is the first-stage biological oil; the secondary biological oil is collected by the secondary biological oil collecting device 17; the microwave device is turned on and the remaining product in the cleavage reactor 8 is biochar.
The invention is described in detail below with reference to examples:
example 1
10g of corn stalks are crushed into grains with the grain diameter of 0.5-2 mm and placed in a cracking reactor 8 which consists of 80 percent of recrystallized silicon carbide and 20 percent of ferric oxide; HZSM-5 zeolite catalyst with the particle size of 2mm is placed in a catalytic reactor 10 made of recrystallized silicon carbide, and helium with the flow rate of 50mL/min is introduced to remove air in a reaction system. The electric heating heat preservation device 13 is started, the temperature is 250 ℃, the gas valve 14 is opened, then the microwave generation system is started, the microwave frequency is 2.45GHz, the microwave power is 200W, the reaction is carried out for 10 minutes, then methanol reaction gas with the flow of 1mL/min is introduced, condensed water in the condensing tube 15 is started, the temperature is controlled to be 2 ℃, dry ice acetone bath is added into the secondary biological oil collecting device 17, the gas valve 14 is closed, the microwave power is adjusted to be 800W, the temperature of the cracking reactor 8 is raised to 550 ℃, the corresponding catalytic reactor temperature is 500 ℃, and the reaction is kept for 20 minutes at the temperature. After the reaction is finished, closing the microwave generation system, closing the electric heating and heat preserving device 13, stopping introducing methanol reaction gas, stopping introducing helium when the temperature in the cracking reactor 8 is reduced below 150 ℃, closing condensed water in the condensing pipe 15, and performing reduced pressure distillation on the first-stage biological oil mixed solution collected in the first-stage biological oil collecting device 16 under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.085 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device 17; the remaining product in the cleavage reactor 8 is biochar. The bio-oil yield (first orderBio-oil + secondary bio-oil) is 67%, the heating value is 32MJ/kg; the yield of the biochar is 12 percent, and the specific surface area is 960m 2 /g。
Example 2
The invention is described by taking waste plastic as an example as follows:
10g of waste plastic is crushed into particles with the particle size of 2-5 mm and is placed in a cracking reactor 8 which consists of 90 percent of recrystallized silicon carbide and 10 percent of copper oxide; the SBA-15 zeolite catalyst with the grain diameter of 5mm is placed in a catalytic reactor 10 made of recrystallized silicon carbide, and helium with the flow of 300mL/min is introduced to remove air in a reaction system. The electric heating heat preservation device 13 is started, the temperature is 350 ℃, the gas valve 14 is opened, then the microwave generation system is started, the microwave frequency is 2.45GHz, the microwave power is 400W, the reaction is carried out for 5 minutes, then methane reaction gas with the flow of 20mL/min is introduced, condensed water in the condensation pipe 15 is started, the temperature is controlled to be 5 ℃, dry ice acetone bath is added into the secondary biological oil collecting device 17, the gas valve 14 is closed, the microwave power is adjusted to be 1200W, the temperature of the cracking reactor 8 is raised to 700 ℃, the corresponding catalytic reactor temperature is 650 ℃, and the reaction is kept for 15 minutes at the temperature. After the reaction is finished, closing the microwave generation system, closing the electric heating and heat preserving device 13, stopping introducing methane reaction gas, stopping introducing helium when the temperature in the cracking reactor 8 is reduced below 150 ℃, closing condensed water in the condensing pipe 15, and performing reduced pressure distillation on the first-stage biological oil mixed solution collected in the first-stage biological oil collecting device 16 under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.095 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device 17; the remaining product in the cleavage reactor 8 is biochar. The yield of the obtained biological oil (primary biological oil and secondary biological oil) is 48 percent, and the calorific value is 43MJ/kg; the yield of the biochar is 18 percent, and the specific surface area is 810m 2 /g。
Example 3
Taking paper sludge raw materials as an example to describe the implementation process of the invention as follows:
10g of papermaking sludge is crushed into 0.5 to 3mm of grain diameter and then placedIn a cracking reactor 8 composed of 85% of recrystallized silicon carbide and 15% of magnesium oxide material; the HY zeolite catalyst with the particle size of 10mm is placed in a catalytic reactor 10 made of recrystallized silicon carbide, and helium with the flow rate of 100mL/min is introduced to remove air in a reaction system. The electric heating heat preservation device 13 is started, the temperature is 300 ℃, the gas valve 14 is opened, then the microwave generation system is started, the microwave frequency is 2.45GHz, the microwave power is 300W, the reaction is carried out for 5 minutes, then formaldehyde reaction gas with the flow of 10mL/min is introduced, condensed water in the condensation pipe 15 is started, the temperature is controlled to be 3 ℃, dry ice acetone bath is added into the secondary biological oil collecting device 17, the gas valve 14 is closed, the microwave power is adjusted to be 1000W, the temperature of the cracking reactor 8 is raised to 400 ℃, the corresponding catalytic reactor temperature is 350 ℃, and the reaction is kept for 30 minutes at the temperature. After the reaction is finished, closing the microwave generation system, closing the electric heating and heat preserving device 13, stopping introducing formaldehyde reaction gas, stopping introducing helium when the temperature in the cracking reactor 8 is reduced below 150 ℃, closing condensed water in the condensing pipe 15, and performing reduced pressure distillation on the first-stage biological oil mixed solution collected in the first-stage biological oil collecting device 16 under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.09 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device 17; the remaining product in the cleavage reactor 8 is biochar. The yield of the obtained biological oil (primary biological oil and secondary biological oil) is 35 percent, and the calorific value is 22MJ/kg; the yield of the biochar is 47 percent, and the specific surface area is 75m 2 And/g, the component is calcium carbonate.
Example 4
Taking larch and waste tire mixed raw materials as an example to describe the implementation process of the invention as follows:
5g of larch and 5g of waste tires are crushed into particles with the particle size of 5-10 mm and then mixed together, and placed in a cracking reactor 8 which is composed of 87% of recrystallized silicon carbide and 13% of calcium oxide; pd/C catalyst with the particle size of 5mm is placed in a catalytic reactor 10 made of recrystallized silicon carbide, and helium with the flow rate of 150mL/min is introduced to remove air in a reaction system. The electric heating and heat preserving device 13 is started, and the temperature is 32The gas valve 14 is opened at 0 ℃, then the microwave generating system is opened, the microwave frequency is 2.45GHz, the microwave power is 350W, the reaction is carried out for 7 minutes, then methanol reaction gas with the flow of 15mL/min is introduced, the condensed water in the condensing pipe 15 is opened, the temperature is controlled to be 5 ℃, dry ice acetone bath is added into the secondary biological oil collecting device 17, the gas valve 14 is closed, the microwave power is adjusted to 900W, the temperature of the cracking reactor 8 is increased to 450 ℃, the corresponding catalytic reactor temperature is 400 ℃, and the reaction is kept for 25 minutes at the temperature. After the reaction is finished, closing the microwave generation system, closing the electric heating and heat preserving device 13, stopping introducing methanol reaction gas, stopping introducing helium when the temperature in the cracking reactor 8 is reduced below 150 ℃, closing condensed water in the condensing pipe 15, and performing reduced pressure distillation on the first-stage biological oil mixed solution collected in the first-stage biological oil collecting device 16 under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.092 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device 17; the remaining product in the cleavage reactor 8 is biochar. The yield of the obtained biological oil (primary biological oil and secondary biological oil) is 55 percent, and the calorific value is 38MJ/kg; the yield of the biochar is 31 percent, and the specific surface area is 1530m 2 /g。
Example 5
Taking alkali lignin as an example to describe the implementation process of the invention is as follows:
crushing 10g of alkali lignin into particles with the particle size of 1-3 mm, mixing the particles together, and placing the particles in a cracking reactor 8 which consists of 80% of recrystallized silicon carbide and 20% of nickel oxide; fe with particle size of 10mm 2 O 3 The catalyst/C was placed in a catalytic reactor 10 of recrystallized silicon carbide, and helium gas was introduced at a flow rate of 180mL/min to exclude air from the reaction system. Opening an electric heating heat preservation device 13, wherein the temperature is 270 ℃, opening a gas valve 14, then opening a microwave generation system, wherein the microwave frequency is 2.45GHz, the microwave power is 350W, reacting for 10 minutes, then introducing methanol reaction gas with the flow of 3mL/min, opening condensed water in a condensing tube 15, controlling the temperature to be 2 ℃, adding dry ice acetone bath into a secondary biological oil collecting device 17, closing the gas valve 14, and regulatingThe microwave power is saved by 1200W, the temperature of the cracking reactor 8 is raised to 600 ℃, the corresponding catalytic reactor temperature is 550 ℃, and the reaction is kept for 30 minutes at the temperature. After the reaction is finished, closing the microwave generation system, closing the electric heating and heat preserving device 13, stopping introducing methanol reaction gas, stopping introducing helium when the temperature in the cracking reactor 8 is reduced below 150 ℃, closing condensed water in the condensing pipe 15, and performing reduced pressure distillation on the first-stage biological oil mixed solution collected in the first-stage biological oil collecting device 16 under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.088 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device 17; the remaining product in the cleavage reactor 8 is biochar. The yield of the obtained biological oil (primary biological oil and secondary biological oil) is 49%, and the calorific value is 36MJ/kg; the yield of the biochar is 40 percent, and the specific surface area is 1210m 2 /g。
Claims (5)
1. The device for efficiently depolymerizing and co-producing the bio-oil and the biochar by utilizing the solid waste microwaves is characterized by comprising an air inlet system for providing reaction gas and carrier gas, wherein the outlet end of the air inlet system is connected with a preheating system, the outlet end of the preheating system is connected with a heat preservation and filtration system, the outlet end of the heat preservation and filtration system is connected with a reaction system, the outlet end of the reaction system is connected with a product collection system, a product heat preservation system is arranged on a pipeline between the reaction system and the product collection system, and the outer sides of the preheating system, the heat preservation and filtration system and the reaction system are sleeved with a microwave generation system;
the air inlet system comprises an air inlet pipe (1) formed by collecting a reaction air pipe and a carrier air pipe, and the outlet end of the air inlet pipe (1) is connected with a preheating system; the preheating system comprises a spiral preheating pipe (5) connected to the outlet end of the air inlet pipe (1), a preheating silicon carbide sleeve (4) is sleeved on the outer side of the preheating pipe (5), and the outlet end of the preheating pipe (5) is connected with the heat-preserving filtering system;
the heat-preserving and filtering system comprises a filtering heat-preserving plug (7) connected to the outlet end of the preheating pipe (5), wherein temperature-resistant quartz heat-preserving cotton is arranged in the filtering heat-preserving plug (7), and the outlet end of the filtering heat-preserving plug (7) is connected with the reaction system; the reaction system comprises a cracking reactor (8) connected to the outlet end of the filtering heat-preserving plug (7) and a catalytic reactor (10) arranged at the outlet end of the cracking reactor (8), wherein the outlet end of the catalytic reactor (10) is connected with a gas valve (14), and a product collecting system is connected between the outlet end of the catalytic reactor (10) and the gas valve (14);
the cracking reactor (8) is a hollow column body with a semicircular section, the upper end of the hollow column body is provided with a solid waste inlet, one end of the hollow column body is provided with a cracking reactor air inlet (18), and the cracking reactor air inlet (18) is connected with the outlet end of the filtering heat-preserving plug (7);
the catalytic reactor (10) comprises a hollow cylindrical reactor body, one end of the reactor body is provided with an end cover (19), a plurality of catalytic reactor air inlets (20) are uniformly distributed on the end cover (19), and the other end of the reactor body is provided with a catalytic reactor air outlet (21);
the microwave generation system comprises a microwave box body (6) arranged outside the preheating system, the heat preservation and filtration system and the reaction system and a microwave feed-in system (9) arranged on the microwave box body (6), wherein a front-end microwave suppression device (3) and a rear-end microwave suppression device (12) are respectively arranged on two sides of the microwave box body (6), and a sealing end (2) is arranged at the free end of the front-end microwave suppression device (3);
the cracking reactor (8) is formed by mixing 80-90% of recrystallized silicon carbide and 10-20% of metal oxide absorbent in percentage by mass, wherein the metal oxide absorbent is one of ferric oxide, copper oxide, magnesium oxide, calcium oxide and nickel oxide; the material of the catalytic reactor (10) is recrystallized silicon carbide.
2. The device for efficiently depolymerizing and co-producing biological oil and biological carbon by utilizing solid waste microwaves according to claim 1, wherein the product heat preservation system comprises a heat preservation silicon carbide sleeve (11) and an electric heating heat preservation device (13) which are sleeved on an outlet end pipeline of the catalytic reactor (10), the heat preservation silicon carbide sleeve (11) is sleeved on a part of the outlet end pipeline of the catalytic reactor (10) positioned in the microwave box (6), and the electric heating heat preservation device (13) is sleeved on a part of the outlet end pipeline of the catalytic reactor (10) positioned outside the microwave box (6).
3. The device for efficiently depolymerizing and co-producing bio-oil and biochar by utilizing solid waste microwaves according to claim 2, wherein the product collecting system comprises a collecting pipeline connected between an outlet end of the catalytic reactor (10) and the gas valve (14), the outlet end of the collecting pipeline is connected with a primary bio-oil collecting device (16), a distillation outlet of the primary bio-oil collecting device (16) is connected with a secondary bio-oil collecting device (17), and a condensing pipe (15) is sleeved on the collecting pipeline.
4. A method for efficiently depolymerizing solid waste microwave to co-produce bio-oil and biochar, which adopts the device of claim 3, and is characterized by comprising the following steps:
step one: crushing solid waste into particles with the particle size of 0.5-10 mm, and placing the particles in a cracking reactor (8); placing a catalyst with the particle size of 2-10 mm into a catalytic reactor (10), and introducing carrier gas to remove air in a reaction system, wherein the flow rate of the carrier gas corresponding to each gram of solid waste is 5-30 mL/min;
step two: opening an electric heating heat preservation device (13), wherein the temperature is 250-350 ℃, opening a gas valve (14), then opening a microwave generation system, wherein the microwave frequency is 2.45GHz, the microwave power is 200-400W, reacting for 5-10 minutes, and discharging water and low-molecular compounds generated by initial cracking reaction;
step three: introducing reaction gas, opening condensed water in a condensing pipe (15), controlling the temperature to be 2-5 ℃, adding dry ice acetone bath into a secondary biological oil collecting device (17), closing a gas valve (14), adjusting the microwave power to be 800-1200W, heating a cracking reactor (8) to 400-700 ℃, at the moment, keeping the corresponding catalytic reactor temperature to be 350-650 ℃, and reacting for 15-30 minutes at the temperature, wherein the reaction gas is methanol, formaldehyde or methane gas, and the reaction gas flow rate corresponding to each gram of solid waste is 0.1-2 mL/min;
step four: after the reaction is finished, closing the microwave generation system, closing the electric heating heat preservation device (13), stopping introducing reaction gas, stopping introducing carrier gas when the temperature in the cracking reactor (8) is reduced to below 150 ℃, closing condensed water in the condensing pipe (15), and performing reduced pressure distillation on the first-stage biological oil mixed solution which is collected in the first-stage biological oil collecting device (16) under the conditions that the temperature is 20 ℃ and the relative vacuum degree is-0.085 to-0.095 Mpa, wherein the residual liquid is the first-stage biological oil when no fraction is distilled out; the secondary biological oil is collected by the secondary biological oil collecting device (17); the remaining product in the cracking reactor (8) is biochar.
5. The method for efficiently depolymerizing and co-producing bio-oil and biochar by using solid waste microwave according to claim 4, wherein the solid waste is one or more of agricultural and forestry waste, household garbage, sludge and waste rubber; the carrier gas is helium; the catalyst is one of zeolite catalyst and active carbon supported metallic catalyst.
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| CN109500062B (en) * | 2018-12-13 | 2021-04-20 | 南京工业大学 | Preparation method of waste tire resource material improved by excess sludge |
| CN110437856A (en) * | 2019-07-30 | 2019-11-12 | 华南理工大学 | A kind of combustible solid wastes by utilizing rapid pyrolysis method and device based on zeolite porous media and more physical chemistry fields |
| CN110437861A (en) * | 2019-07-30 | 2019-11-12 | 华南理工大学 | It is a kind of based on microwave-assisted and zeolite catalyst combustible solid wastes by utilizing high temperature pyrolysis method and apparatus |
| CN112938982A (en) * | 2021-02-18 | 2021-06-11 | 陕西科技大学 | Method for preparing liquid oil and silicon carbide through microwave-assisted depolymerization of rice hulls |
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| CN114199666B (en) * | 2021-11-22 | 2023-08-15 | 中国石油大学(北京) | Design, construction and debugging of efficient and controllable online microwave reaction system |
| CN115557466B (en) * | 2022-09-27 | 2023-07-21 | 杭州慕皓新能源技术有限公司 | Device for producing hydrogen through pyrolysis |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106586956A (en) * | 2016-12-21 | 2017-04-26 | 天津大学 | Method and apparatus for out-of-furnace microwave catalytic cracking of biomass gasification tar |
| CN106635110A (en) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues |
| CN107337585A (en) * | 2017-07-21 | 2017-11-10 | 陕西科技大学 | A kind of method that lignin microwave depolymerization prepares single phenolic compound |
| CN207811678U (en) * | 2018-01-15 | 2018-09-04 | 陕西科技大学 | A kind of device of solid waste microwave efficient depolymerization co-producing bio-oil and charcoal |
-
2018
- 2018-01-15 CN CN201810036853.9A patent/CN107987866B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106635110A (en) * | 2016-10-27 | 2017-05-10 | 陕西科技大学 | Method for preparing liquid product containing rich phenols and alcohols through microwave catalytic thermal cracking of forestry and agricultural residues |
| CN106586956A (en) * | 2016-12-21 | 2017-04-26 | 天津大学 | Method and apparatus for out-of-furnace microwave catalytic cracking of biomass gasification tar |
| CN107337585A (en) * | 2017-07-21 | 2017-11-10 | 陕西科技大学 | A kind of method that lignin microwave depolymerization prepares single phenolic compound |
| CN207811678U (en) * | 2018-01-15 | 2018-09-04 | 陕西科技大学 | A kind of device of solid waste microwave efficient depolymerization co-producing bio-oil and charcoal |
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