CN111117683A - Microwave continuous frequency modulation and biomass pyrolysis product cooperation gaseous hydrogenation device and use method thereof - Google Patents
Microwave continuous frequency modulation and biomass pyrolysis product cooperation gaseous hydrogenation device and use method thereof Download PDFInfo
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- CN111117683A CN111117683A CN202010063346.1A CN202010063346A CN111117683A CN 111117683 A CN111117683 A CN 111117683A CN 202010063346 A CN202010063346 A CN 202010063346A CN 111117683 A CN111117683 A CN 111117683A
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention discloses a microwave continuous frequency modulation and biomass pyrolysis product cooperation gaseous hydrogenation device and a using method thereof, and belongs to the technical field of biomass resource utilization. The device comprises a temperature control system, a pyrolysis reaction system and a gaseous hydrogenation reaction system, can realize the active depolymerization of biomass and the gaseous hydrogenation of pyrolysis products thereof in a microwave reactor with continuously adjustable frequency, and has simple structure and convenient operation. The microwave with continuously variable emission frequency is adopted to cooperate with the gaseous hydrogenation of the biomass pyrolysis product, the microwave with continuously variable frequency can activate the hydrogen bond of the active carrier gas, and can form resonance with the molecules of the gaseous product under certain optimal emission frequency so as to directionally break the bond, so that the gaseous hydrogenation of the biomass pyrolysis product is realized under low pressure or even normal pressure.
Description
Technical Field
The invention belongs to the technical field of biomass resource utilization, and particularly relates to a microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device and a using method thereof.
Background
The energy and environmental problems are increasingly prominent due to the large consumption of traditional fossil energy, and the key problem to be solved urgently is to seek renewable alternative energy to guarantee the energy safety. Among various renewable energy sources, biomass energy is the only carbonaceous resource that can be directly converted into liquid fuel, and therefore, the technology for preparing high-grade liquid fuel by utilizing lignocellulose biomass through thermochemical conversion is always the focus and hot spot of research in the field of biomass energy utilization. However, the bio-oil prepared by the conventional fast pyrolysis technology usually contains abundant high-activity oxygen-containing substances (such as acids, aldehydes, ketones, esters and the like), which are the main reasons for the defects of poor stability, high viscosity, strong acidity and the like, so that the bio-oil cannot be directly used as a fuel. Therefore, there is a need for upgrading bio-oils to reduce oxygen content and increase the content of products such as hydrocarbons to achieve the goal of replacing gasoline or aviation fuel.
In the aspect of catalytic deoxidation and upgrading of the pyrolysis bio-oil based on C-O bond targeting, the method generally refers to Hydrodeoxygenation (HDO) reaction carried out on liquid bio-oil. The upgrading process is carried out with H2Or hydrogen donor solvent is used as active medium and is carried out in a high-pressure reaction kettle at certain temperature and pressure, so that the oxygen element in the biological oil can be replaced by H under the premise of extremely low carbon element loss2And removing O in a form. The noble metal or noble metal-based bifunctional oxide has higher activity under low hydrogen pressure and high tolerance to acid environment, so that the noble metal or noble metal-based bifunctional oxide becomes a research hotspot in the field of HDO catalysts, but the high cost of the noble metal or noble metal-based bifunctional oxide limits large-scale commercial popularization and application. Meanwhile, the bio-oil obtained by pyrolysis or catalytic pyrolysis condensation is heated and pressurized again to carry out HDO reaction in the high-pressure reaction kettle, so that not only is secondary consumption of energy caused, but also high repolymerization of active oxygen-containing compounds in the bio-oil is promoted, and the catalyst can be quickly deactivated and possibly block the reactor to cause reaction interruption.
In order to achieve the goal of integrating biomass cracking and deep hydrodeoxygenation, in recent years, a biomass fast Catalytic Fast Hydropyrolysis (CFHP) technology has attracted much attention. With conventional inertness (N)2) Different from the biomass catalytic pyrolysis reaction under the normal pressure atmosphere, the pressurized catalytic hydrogenolysis adopts H2As an active carrier gas, the biomass is subjected to catalytic cracking and on-line hydrogenation of gaseous products under a certain reaction pressure, and the process can be considered to be integrated with the rapid catalytic pyrolysis and hydrodeoxygenation processes of the biomass. Specifically, a large amount of unsaturated free radicals are generated in the biomass pyrolysis process, and can be saturated under the hydrogen supply effect of an external hydrogen source, so that secondary reaction is avoided, the polarity and the oxygen content of pyrolysis oil can be reduced, deep deoxidation of pyrolysis products can be realized under the condition of adding a proper HDO catalyst, the pressure range of a reactor can be flexibly selected, and the aim of effectively hydrogenating the pyrolysis products can be fulfilled.
In addition, the conventional biomass thermochemical conversion and hydrodeoxygenation upgrading process of the high-pressure reaction kettle thereof adopt an electric heating mode for heating, compared with microwave heating, the conventional biomass thermochemical conversion and hydrodeoxygenation upgrading process generally has the defects of high energy consumption, low speed, uneven heating and the like, and the directional fracture of the C-O, C-C bonds of the biomass macromolecules is difficult to realize. Thus, the manner in which microwave-assisted heating is used has received a great deal of attention in thermochemical conversion of biomass. However, the microwave emitting frequency of the currently used microwave heating method is generally 2.45GHz, mainly because the intrinsic resonance frequency of water molecules is consistent with the microwave emitting frequency, and thus the water molecules can be caused to resonate, thereby having higher heating efficiency. The three components of the biomass and the pyrolysis product thereof are different from water molecules, and the intrinsic resonance frequency of the three components is obviously different from that of the water molecules, so that the conventional microwave radiation frequency of 2.45GHz cannot cause the three components to break the resonance bonds, and the biomass pyrolysis gaseous product contains a series of different substances such as alcohols, esters, phenols, aldehydes, olefins, aromatic hydrocarbons and the like, and the molecular resonance frequency of the gaseous product is different from that of the water molecules, so that the 'resonance' broken bond hydrogenation cannot be realized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device, which is a two-stage reaction system for biomass active depolymerization and online hydrogenation of a gaseous product of the biomass active depolymerization in a continuous frequency conversion microwave reactor, and has the advantages of simple structure, convenient operation and high efficiency in realizing the gaseous hydrogenation of the biomass pyrolysis product. The invention aims to solve another technical problem of providing a using method of a microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device, wherein microwaves with continuously changed frequencies can not only activate hydrogen bonds of active carrier gas, but also form resonance with gaseous product molecules under certain optimal emission frequency so as to directionally break bonds, and online hydrogenation of the gaseous product is realized under low pressure or even normal pressure.
The technical scheme is as follows: in order to solve the problems, the technical scheme adopted by the invention is as follows:
a microwave continuous frequency modulation and biomass pyrolysis product gas hydrogenation device comprises a gas source, a temperature control system, a pyrolysis reaction system and a gas hydrogenation reaction system; the gas source comprises an inert gas source and a reactive gas source; a plurality of probes are arranged in the temperature control system;
the pyrolysis reaction system is a first-stage fixed bed cracking reactor, an air inlet of the first-stage fixed bed cracking reactor is connected with a gas source, and a preheater is arranged between the first-stage fixed bed cracking reactor and the gas source; the feed inlet of the first-stage fixed bed cracking reactor is connected with a solid feed hopper; a probe of the temperature control system extends into the first-stage fixed bed cracking reactor; a pyrolysis catalyst bed layer is arranged in the first-stage fixed bed cracking reactor;
the gaseous hydrogenation reaction system comprises a microwave continuous frequency modulation power supply, a microwave resonant cavity, a second-stage quartz tube fixed bed hydrogenation reactor and a condensation system; the gas outlet of the first-stage fixed bed cracking reactor is connected with a second-stage quartz tube fixed bed hydrogenation reactor; a microwave feed port is arranged on the microwave resonant cavity, and the microwave continuous frequency modulation power supply is connected with the microwave feed port; the second-stage quartz tube fixed bed hydrogenation reactor is arranged in the microwave resonant cavity, a catalyst filling screen spacer is arranged in the second-stage quartz tube fixed bed hydrogenation reactor, an infrared thermometer is arranged at the catalyst filling screen spacer, and the infrared thermometer is connected with a temperature control system; the condensing system is connected with an outlet of the second-stage quartz tube fixed bed hydrogenation reactor, and an air collecting bag is arranged at an outlet of the condensing system.
The microwave continuous frequency modulation is cooperated with the biomass pyrolysis product gaseous hydrogenation device, and gas flow meters are arranged on a connecting pipeline of the inert gas source and the preheater and a connecting pipeline of the active reaction gas source and the preheater; and an inert gas pipeline is arranged between the inert gas source and the biomass feed hopper, and inert gas purging is carried out on the solid biomass raw material before feeding.
The microwave continuous frequency modulation is cooperated with a biomass pyrolysis product gaseous hydrogenation device, and a feed valve is arranged between the solid feed hopper and the first-stage fixed bed cracking reactor.
The microwave continuous frequency modulation is cooperated with the biomass pyrolysis product gaseous hydrogenation device, and an online detection system is arranged between the second-stage quartz tube fixed bed hydrogenation reactor and the condensation system.
The microwave continuous frequency modulation is cooperated with the biomass pyrolysis product gaseous hydrogenation device, and the online detection system is a gas phase-mass spectrometer.
The microwave continuous frequency modulation is cooperated with the biomass pyrolysis product gaseous hydrogenation device, and the infrared thermometer is in a non-contact type.
According to the microwave continuous frequency modulation and biomass pyrolysis product gaseous hydrogenation device, a feed inlet of a first-stage fixed bed cracking reactor is connected with a liquid feed pump, when a biomass raw material is liquid, the liquid feed pump is started to feed the liquid, at the moment, a solid feed hopper is in a closed state, when the biomass raw material is solid, the solid feed hopper is adopted to feed the liquid, and the liquid feed pump is in a closed state; and a preheater is arranged between the liquid feed pump and the feed inlet of the first-stage fixed bed cracking reactor and is used for preheating the biomass liquid raw material before feeding.
The microwave continuous frequency modulation is cooperated with a biomass pyrolysis product gaseous hydrogenation device, and the solid feed hopper and the first-stage fixed bed cracking reactor are both connected with a pressure sensor.
The microwave continuous frequency modulation is cooperated with the gaseous hydrogenation device for the biomass pyrolysis product, the microwave continuous frequency modulation power supply is composed of different frequency modulation modules, the microwave emission frequency is continuously adjustable between 2.45GHz and 8GHz, and the output power is freely adjusted between 200W and 500W: the frequency adjustment range is 0.1-1000 MHz.
The use method of the microwave continuous frequency modulation synergetic biomass pyrolysis product gaseous hydrogenation device specifically comprises the following steps:
1) arranging a pyrolysis catalyst in a catalyst bed layer in a first-stage fixed bed reactor, uniformly arranging a hydrogenation catalyst in the center of a quartz tube in a second-stage quartz tube fixed bed hydrogenation reactor, and adding a biomass raw material into a solid feed hopper; then, preheating inert gas by a preheater and then purging a first-stage fixed bed cracking reactor and a second-stage quartz tube fixed bed hydrogenation reactor;
2) after the purging is finished, a carrier gas valve is switched to an active reaction carrier gas source, the temperature of the first-stage fixed bed cracking reactor is raised, a microwave continuous frequency modulation power supply is started, continuously variable microwaves enter a microwave resonant cavity through a microwave feed port, a hydrogenation catalyst arranged at the center of a quartz tube is selectively heated, the temperature of the contact part of the hydrogenation catalyst and the wall surface of the quartz tube is monitored in real time through an infrared thermometer, and the step 3 is carried out when the temperatures of the first-stage fixed bed cracking reactor and the second-stage quartz tube fixed bed hydrogenation reactor reach the reaction temperature;
3) opening a feeding valve of a solid feeding hopper, allowing the biomass raw material to enter a first-stage fixed bed cracking reactor, then performing rapid catalytic cracking to generate a gaseous product mainly containing aromatic hydrocarbons, allowing the gaseous product to enter a second-stage quartz tube fixed bed hydrogenation reactor in a gaseous form, and performing hydrogenation reaction under the action of a hydrogenation catalyst and microwaves with continuously changed frequencies;
4) and the product components generated by the hydrogenation reaction are detected in real time by an online detection system arranged at the outlet of the quartz tube reactor, the product after the reaction is condensed by a condensation system and then collected into a liquid product, and the non-condensable gaseous product is collected into a gas collection bag for subsequent offline analysis.
Has the advantages that: compared with the prior art, the invention has the advantages that:
the device comprises a temperature control system, a pyrolysis reaction system and a gaseous hydrogenation reaction system, can realize the active depolymerization of biomass and the gaseous hydrogenation of pyrolysis products thereof in a microwave reactor with continuously adjustable frequency, and has simple structure and convenient operation. The microwave with continuously variable emission frequency is adopted to cooperate with the gaseous hydrogenation of the biomass pyrolysis product, the microwave with continuously variable frequency can activate the hydrogen bond of the active carrier gas, and can form resonance with the molecules of the gaseous product under certain optimal emission frequency so as to directionally break the bond, so that the gaseous hydrogenation of the biomass pyrolysis product is realized under low pressure or even normal pressure.
Drawings
FIG. 1 is a schematic structural diagram of a microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device.
Detailed Description
The invention is further illustrated by the accompanying drawings and specific examples, which are intended to be illustrative only and not limiting of the scope of the invention, and various equivalent modifications of the invention will become apparent to those skilled in the art after reading the present patent application and are intended to fall within the scope of the appended claims.
Example 1
A microwave continuous frequency modulation and biomass pyrolysis product gas hydrogenation device, as shown in figure 1. As shown in FIG. 1, the apparatus comprises a gas source, a temperature control system 5, a pyrolysis reaction system, and a gaseous hydrogenation reaction system; the gas source comprises an inert gas source 1 and a reactive gas source 2; a plurality of probes are arranged in the temperature control system 5;
the pyrolysis reaction system is a first-stage fixed bed cracking reactor 6, a feed inlet, an air inlet and an air outlet are arranged on the first-stage fixed bed cracking reactor 6, the air inlet of the first-stage fixed bed cracking reactor 6 is connected with a gas source, and gas flow meters are arranged on a connecting pipeline of the inert gas source 1 and the preheater 3 and a connecting pipeline of the active reaction gas source 2 and the preheater 3 and used for accurately controlling the flow rates of the inert gas and the active reaction gas; a preheater 3 is arranged between the first-stage fixed bed cracking reactor 6 and the gas source and is used for heating inert gas and active reaction gas; the solid feed hopper 4 and the liquid feed pump 16 are both connected with a feed inlet of the first-stage fixed bed cracking reactor 6, different feeding devices are selected according to the type of the biomass raw material, a preheater 3 is arranged between the liquid feed pump 16 and the feed inlet of the first-stage fixed bed cracking reactor 6, the liquid raw material is preheated before feeding, and a feed valve is arranged between the solid feed hopper 4 and the first-stage fixed bed cracking reactor 6 and used for accurately controlling the feeding time and the feeding amount; a probe of the temperature control system 5 extends into the first-stage fixed bed cracking reactor 6 to monitor the temperature change condition of the pyrolysis reactor in real time; a pyrolysis catalyst bed layer 7 is arranged in the first-stage fixed bed cracking reactor 6; the solid feed hopper 4 is connected with a uniform pressure sensor 18 of the first-stage fixed bed cracking reactor 6;
the gaseous hydrogenation reaction system comprises a microwave continuous frequency modulation power supply 9, a microwave resonant cavity 11, a second-stage quartz tube fixed bed hydrogenation reactor 8 and a condensing system 12; the gas outlet of the first-stage fixed bed cracking reactor 6 is connected with a second-stage quartz tube fixed bed hydrogenation reactor 8; a microwave feed port 10 is arranged on the microwave resonant cavity 11, a microwave continuous frequency modulation power supply 9 is connected with the microwave feed port 10, the continuously adjustable microwave frequency modulation power supply 9 consists of different frequency modulation modules, the microwave transmitting frequency is continuously adjustable between 2.45GHz and 8GHz, the output power is freely adjusted between 200W and 500W, and the frequency adjusting amplitude is 0.1 MHz to 1000 MHz; the second-stage quartz tube fixed bed hydrogenation reactor 8 is arranged in the microwave resonant cavity 11, a catalyst filling screen spacer 13 is arranged in the second-stage quartz tube fixed bed hydrogenation reactor 8, a non-contact infrared thermometer 14 is arranged at the catalyst filling screen spacer 13, and the infrared thermometer 14 is connected with the temperature control system 5; the condensing system 12 is connected with an outlet of the second-stage quartz tube fixed bed hydrogenation reactor 8, an air collecting bag 17 is arranged at an outlet of the condensing system 12, a condensable part in a hydrogenation product is condensed by the condensing system 12 to obtain bio-oil, and a non-condensable part enters the air collecting bag 17 for further detection and analysis; an online detection system 15 is arranged between the outlet of the second-stage quartz tube fixed bed hydrogenation reactor 8 and the condensing system 12, and the online detection system 15 can be a gas phase-mass spectrometer for online detection and analysis of the components of the hydrogenation product.
The use method of the microwave continuous frequency modulation synergetic biomass pyrolysis product gaseous hydrogenation device specifically comprises the following steps:
(1) arranging a pyrolysis catalyst in a catalyst bed layer in a first-stage fixed bed reactor, uniformly arranging a hydrogenation catalyst in the center of a quartz tube in a second-stage quartz tube fixed bed hydrogenation reactor 8, and adding a biomass raw material into a solid feed hopper 4; then preheating 3 times by using inert gas through a preheater and then blowing and sweeping a first-stage fixed bed cracking reactor 6 and a second-stage quartz tube fixed bed hydrogenation reactor 8;
(2) after the purging is finished, a carrier gas valve is switched to an active reaction carrier gas source 2, the temperature of the first-stage fixed bed cracking reactor is raised, a microwave continuous frequency modulation power supply is started, continuously variable microwaves enter a microwave resonant cavity through a microwave feed port, a hydrogenation catalyst arranged at the center of a quartz tube is selectively heated, the temperature of the contact part of the hydrogenation catalyst and the wall surface of the quartz tube is monitored in real time through a non-contact infrared thermometer, and the step 3 is carried out when the temperatures of the first-stage fixed bed cracking reactor 6 and the second-stage quartz tube fixed bed hydrogenation reactor 8 reach the reaction temperature;
(3) opening a feeding valve of a solid feeding hopper 4, allowing the biomass raw material to enter a first-stage fixed bed cracking reactor 6, then performing rapid catalytic cracking to generate a gaseous product mainly containing aromatic hydrocarbons, allowing the gaseous product to enter a second-stage quartz tube fixed bed hydrogenation reactor 8 in a gaseous form, and performing hydrogenation reaction under the microwave action of a hydrogenation catalyst and continuous frequency change;
(4) and the product components generated by the hydrogenation reaction are detected in real time by an online detection system arranged at the outlet of the quartz tube reactor, the product after the reaction is condensed by a condensation system and then collected into a liquid product, and the non-condensable gaseous product is collected into a gas collection bag for subsequent offline analysis.
The microwave with continuously variable emission frequency is adopted to cooperate with the gaseous hydrogenation of the biomass pyrolysis product, the microwave with continuously variable frequency can activate the hydrogen bond of the active carrier gas, and can form resonance with the molecules of the gaseous product under certain optimal emission frequency so as to directionally break the bond, so that the gaseous hydrogenation of the biomass pyrolysis product is realized under low pressure or even normal pressure.
Claims (10)
1. A microwave continuous frequency modulation and biomass pyrolysis product gas hydrogenation device is characterized by comprising a gas source, a temperature control system (5), a pyrolysis reaction system and a gas hydrogenation reaction system; the gas source comprises an inert gas source (1) and a reactive gas source (2); a plurality of probes are arranged in the temperature control system (5);
the pyrolysis reaction system is a first-stage fixed bed cracking reactor (6), an air inlet of the first-stage fixed bed cracking reactor (6) is connected with a gas source, and a preheater (3) is arranged between the first-stage fixed bed cracking reactor (6) and the gas source; the feed inlet of the first-stage fixed bed cracking reactor (6) is connected with a solid feed hopper (4); a probe of the temperature control system (5) extends into the first-stage fixed bed cracking reactor (6); a pyrolysis catalyst bed layer (7) is arranged in the first-stage fixed bed cracking reactor (6);
the gaseous hydrogenation reaction system comprises a microwave continuous frequency modulation power supply (9), a microwave resonant cavity (11), a second-stage quartz tube fixed bed hydrogenation reactor (8) and a condensation system (12); the gas outlet of the first-stage fixed bed cracking reactor (6) is connected with a second-stage quartz tube fixed bed hydrogenation reactor (8); a microwave feed port (10) is formed in the microwave resonant cavity (11), and the microwave continuous frequency modulation power supply (9) is connected with the microwave feed port (10); the second-stage quartz tube fixed bed hydrogenation reactor (8) is arranged in the microwave resonant cavity (11), a catalyst filling screen spacer (13) is arranged in the second-stage quartz tube fixed bed hydrogenation reactor (8), an infrared thermometer (14) is arranged at the catalyst filling screen spacer (13), and the infrared thermometer (14) is connected with the temperature control system (5); the condensing system (12) is connected with an outlet of the second-stage quartz tube fixed bed hydrogenation reactor (8), and an air collecting bag (17) is arranged at an outlet of the condensing system (12).
2. The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device according to claim 1, wherein gas flow meters are arranged on a connecting pipeline of the inert gas source (1) and the preheater (3) and a connecting pipeline of the active reaction gas source (2) and the preheater (3); an inert gas pipeline is arranged between the inert gas source (1) and the solid feed hopper (4).
3. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device according to claim 1, wherein a feed valve is arranged between the solid feed hopper (4) and the first stage fixed bed cracking reactor (6).
4. The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device according to claim 1, wherein an online detection system (15) is arranged between the outlet of the second stage quartz tube fixed bed hydrogenation reactor (8) and the condensation system (12).
5. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device according to claim 4, wherein the online detection system (15) is a gas phase-mass spectrometer.
6. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation apparatus according to claim 1, wherein the infrared thermometer (14) is non-contact.
7. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device according to claim 1, wherein a feed port of the first stage fixed bed cracking reactor (6) is connected with a liquid feed pump (16), and a preheater (3) is arranged between the liquid feed pump (16) and the feed port of the first stage fixed bed cracking reactor (6).
8. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device according to claim 1, wherein the solid feed hopper (4) and the first stage fixed bed cracking reactor (6) are both connected with a pressure sensor (18).
9. The microwave continuous frequency modulation and biomass pyrolysis product gaseous hydrogenation device according to claim 1, wherein the microwave continuous frequency modulation power supply (9) is composed of different frequency modulation modules, the microwave emission frequency is continuously adjustable between 2.45GHz and 8GHz, the output power is freely adjustable between 200W and 500W, and the frequency adjustment amplitude is 0.1 MHz to 1000 MHz.
10. The use method of the microwave continuous frequency modulation cooperative biomass pyrolysis product gaseous hydrogenation device as claimed in claim 1 is characterized by comprising the following steps:
1) a pyrolysis catalyst is arranged in a catalyst bed layer in a first-stage fixed bed reactor, a hydrogenation catalyst is uniformly arranged at the center of a quartz tube in a second-stage quartz tube fixed bed hydrogenation reactor (8), a biomass raw material is added into a solid feed hopper (4), and then an inert gas is preheated by a preheater and then used for purging a first-stage fixed bed cracking reactor (6) and the second-stage quartz tube fixed bed hydrogenation reactor (8);
2) after purging is finished, a carrier gas valve is switched to an active reaction gas source (2), the temperature of a first-stage fixed bed cracking reactor (6) is raised, a microwave continuous frequency modulation power supply (9) is started, continuously variable microwaves enter a microwave resonant cavity (11) through a microwave feed port, a hydrogenation catalyst arranged at the center of a quartz tube is selectively heated, the temperature of the contact part of the hydrogenation catalyst and the wall surface of the quartz tube is monitored in real time through an infrared thermometer (14), and when the temperatures of the first-stage fixed bed cracking reactor (6) and a second-stage quartz tube fixed bed hydrogenation reactor (8) reach reaction temperatures, the step 3 is carried out;
3) opening a feeding valve of a solid feeding hopper (4), allowing the biomass raw material to enter a first-stage fixed bed cracking reactor (6) and then to be subjected to rapid catalytic cracking to generate a gaseous product mainly containing aromatic hydrocarbons, and allowing the gaseous product to enter a second-stage quartz tube fixed bed hydrogenation reactor (8) in a gaseous form to perform hydrogenation reaction under the microwave action of a hydrogenation catalyst and continuous frequency change;
4) the product components generated by the hydrogenation reaction are detected in real time by an online detection system (15) arranged at the outlet of the quartz tube reactor, the product after the reaction is condensed by a condensation system (12) and then collected into a liquid product, and the non-condensable gaseous product is collected into a gas collection bag for subsequent off-line analysis.
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| CN115340882A (en) * | 2021-05-15 | 2022-11-15 | 陕西青朗万城环保科技有限公司 | Method for generating gas based on microwave pyrolysis and control system thereof |
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| CN115340882B (en) * | 2021-05-15 | 2024-04-19 | 陕西青朗万城环保科技有限公司 | Method for generating gas based on microwave pyrolysis and control system thereof |
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