CN111117683B - Microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device and application method thereof - Google Patents
Microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device and application method thereof Download PDFInfo
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- CN111117683B CN111117683B CN202010063346.1A CN202010063346A CN111117683B CN 111117683 B CN111117683 B CN 111117683B CN 202010063346 A CN202010063346 A CN 202010063346A CN 111117683 B CN111117683 B CN 111117683B
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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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- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
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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
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- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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Abstract
The invention discloses a microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device and a use 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 the advantages of simple structure and convenient operation. According to the invention, 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 gaseous product molecules at certain optimal emission frequency so as to directionally break bonds, so that the gaseous hydrogenation of the biomass pyrolysis product is realized at low pressure even normal pressure, and compared with the conventional hydrogenation process of liquid biological oil, the method has the advantages of low reaction energy consumption, high hydrogenation efficiency and the like.
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 use method thereof.
Background
The great consumption of traditional fossil energy causes increasingly outstanding energy and environmental problems, and the search for renewable alternative energy sources to ensure energy safety becomes a key problem to be solved urgently. Among the renewable energy sources, biomass energy is the only carbonaceous resource that can be directly converted into liquid fuel, so the technology for preparing high-grade liquid fuel by thermochemical conversion of lignocellulose biomass has been 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 generally contains rich high-activity oxygen-containing substances (such as acids, aldehydes, ketones, esters and the like), which are 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 fuel. Therefore, it is required to upgrade bio-oil to reduce oxygen content and increase hydrocarbon content, etc. products, thereby achieving the goal of replacing gasoline or aviation fuel.
In terms of catalytic deoxygenation and upgrading of pyrolyzed bio-oil based on c—o bond targeting, it is generally referred to as Hydrodeoxygenation (HDO) reactions performed on liquid bio-oil. The upgrading process uses H 2 Or hydrogen-supplying solvent is used as active medium, and is carried out in high-pressure reactor under a certain temp. and pressure, so that the oxygen element in the biological oil can be used as H under the precondition of less loss of carbon element in the biological oil 2 O is removed in the form of a catalyst. The higher activity of noble metal or noble metal-based difunctional oxides at low hydrogen pressure and the high tolerance to acidic environments become research hotspots in the field of HDO catalysts, but the higher cost limits the large-scale popularization and application in commerce. Meanwhile, the biological oil obtained by pyrolysis or catalytic pyrolysis condensation is heated and pressurized again to carry out HDO reaction in a high-pressure reaction kettle, thereby not only generating two energy sourcesThe secondary consumption, which promotes a high degree of repolymerization of the active oxygenates in the bio-oil, can lead to rapid deactivation of the catalyst and possible blockage of the reactor leading to reaction interruption.
In order to achieve the goal of integrating biomass pyrolysis with hydrodeoxygenation, biomass rapid catalytic hydropyrolysis (Catalytic fast hydropyrolysis, CFHP) technology has attracted considerable attention in recent years. Inert to the tradition (N) 2 ) Different biomass catalytic pyrolysis reactions under normal pressure atmosphere, and H is adopted for pressurized catalytic hydrogenolysis 2 As an active carrier gas, the biomass is subjected to catalytic pyrolysis and gaseous product on-line hydrogenation under a certain reaction pressure, and the catalytic pyrolysis and hydrodeoxygenation process of the biomass can be considered to be integrated. Specifically, a large amount of unsaturated free radicals are generated in the biomass pyrolysis process, and the biomass pyrolysis process can be saturated under the hydrogen supply action of an external hydrogen source, so that secondary reaction is avoided, the polarity and 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 quality improvement processes of the high-pressure reaction kettle are all heated by adopting an electric heating mode, and compared with microwave heating, the method has the defects of high energy consumption, low speed, uneven heating and the like, and the directional fracture of the C-O, C-C bond of the biomass macromolecules is difficult to realize. Therefore, the manner of microwave-assisted heating has gained widespread attention in terms of thermochemical conversion of biomass. However, the microwave heating mode commonly used at present has a microwave emission frequency of 2.45GHz, mainly because the intrinsic resonance frequency of water molecules is consistent with the microwave emission frequency, so that the microwave heating mode can cause "resonance" of water molecules, thereby having higher heating efficiency. The biomass three components and pyrolysis products thereof are different from water molecules, and the intrinsic resonance frequency of the biomass three components and pyrolysis products thereof is obviously different from that of the water molecules, so that the conventional microwave radiation frequency of 2.45GHz can not cause the resonance to break bonds, and the biomass pyrolysis gaseous products comprise a series of different substances such as alcohols, esters, phenols, aldehydes, olefins, aromatic hydrocarbons and the like, and the molecular resonance frequency of the biomass pyrolysis gaseous products is inconsistent with that of the water molecules, so that the resonance broken bond hydrogenation can not be realized.
Disclosure of Invention
The invention aims to solve the technical problem of providing a microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device which is a double-stage reaction system for active depolymerization of biomass and online hydrogenation of gaseous products thereof under a continuous variable frequency microwave reactor, and has the advantages of simple structure, convenient operation and high efficiency for realizing the gaseous hydrogenation of biomass pyrolysis products. The invention aims to solve the other technical problem of providing a use method of the microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device, wherein microwaves with continuously changing frequencies can activate hydrogen bonds of active carrier gas, and can form resonance with gaseous product molecules at an optimal emission frequency so as to directionally break bonds, so that on-line hydrogenation of the gaseous products is realized at low pressure 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 gaseous hydrogenation device for a biomass pyrolysis product through microwave continuous frequency modulation collaboration comprises a gas source, a temperature control system, a pyrolysis reaction system and a gaseous 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 pyrolysis reactor, an air inlet of the first-stage fixed bed pyrolysis reactor is connected with a gas source, and a preheater is arranged between the first-stage fixed bed pyrolysis reactor and the gas source; the feed inlet of the first-stage fixed bed cracking reactor is connected with a solid feed hopper; the 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 pyrolysis 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; the microwave resonant cavity is provided with a microwave feed port, 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 the 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 the outlet of the condensing system.
The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device is characterized in that a gas flowmeter is 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; 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 cooperated biomass pyrolysis product gaseous hydrogenation device is characterized in that a feed valve is arranged between the solid feed hopper and the first-stage fixed bed pyrolysis reactor.
The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device is characterized in that 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 cooperated biomass pyrolysis product gaseous hydrogenation device is characterized in that the online detection system is a gas phase-mass spectrometer.
The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device is characterized in that the infrared thermometer is non-contact.
The feeding port of the first-stage fixed bed cracking reactor is connected with a liquid feeding pump, when biomass raw materials are liquid, the liquid feeding pump is started to feed liquid, at the moment, the solid feeding hopper is in a closed state, and when the biomass raw materials are solid, the solid feeding hopper is used for feeding, and the liquid feeding pump is in a closed state; a preheater is arranged between the liquid feed pump and the feed inlet of the first-stage fixed bed cracking reactor, and the preheater performs preheating treatment on the biomass liquid raw material before feeding.
The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device, and the solid feed hopper and the first-stage fixed bed pyrolysis reactor are both connected with a pressure sensor.
The microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device comprises different frequency modulation modules, the microwave emission frequency is continuously adjustable between 2.45 and 8GHz, and the output power is freely adjustable between 200 and 500W: the frequency adjustment amplitude is 0.1-1000 MHz.
The application method of the microwave continuous frequency modulation synergistic 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 biomass raw materials into a solid feed hopper; then inert gas is preheated by a preheater and then is used for purging a first-stage fixed bed cracking reactor and a second-stage quartz tube fixed bed hydrogenation reactor;
2) Switching a carrier gas valve to an active reaction carrier gas source after purging is finished, starting to heat the first-stage fixed bed cracking reactor, starting a microwave continuous frequency modulation power supply, enabling continuously variable microwaves to enter a microwave resonant cavity through a microwave feed port, selectively heating a hydrogenation catalyst arranged at the center of a quartz tube, monitoring the temperature of the contact part of the hydrogenation catalyst and the wall surface of the quartz tube in real time through an infrared thermometer, and entering the step 3 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 feed hopper, quickly catalyzing and cracking biomass raw materials after the biomass raw materials enter a first-stage fixed bed cracking reactor to generate gaseous products mainly comprising aromatic hydrocarbons, then entering a second-stage quartz tube fixed bed hydrogenation reactor in a gaseous form, and carrying out hydrogenation reaction under the action of a hydrogenation catalyst and microwaves with continuously changing frequencies;
4) The product components generated by the hydrogenation reaction are detected in real time through an online detection system arranged at the outlet of the quartz tube reactor, the products after the reaction are condensed by a condensing system and then are collected into liquid products, and the non-condensable gaseous products are collected into a gas collecting bag for subsequent offline analysis.
The beneficial effects are 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 the advantages of simple structure and convenient operation. According to the invention, 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 gaseous product molecules at certain optimal emission frequency so as to directionally break bonds, so that the gaseous hydrogenation of the biomass pyrolysis product is realized at low pressure even normal pressure, and compared with the conventional hydrogenation process of liquid biological oil, the method has the advantages of low reaction energy consumption, high hydrogenation efficiency and the like.
Drawings
FIG. 1 is a schematic diagram of a microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device.
Detailed Description
The present invention will be further illustrated with reference to the attached drawings and specific examples, which are to be understood as being illustrative only of the present patent and not limiting the scope of the present patent, and various modifications to the equivalent versions of the present patent will fall within the scope of the appended claims after reading the present patent.
Example 1
A microwave continuous frequency modulation cooperated biomass pyrolysis product gaseous hydrogenation device is shown in figure 1. As can be seen from fig. 1, the device comprises a gas source, a temperature control system 5, a pyrolysis reaction system and a gaseous hydrogenation reaction system; the gas sources comprise 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 formed in 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 on a connecting pipeline of the active reaction gas source 2 and the preheater 3 and are 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 a 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 the feed inlet of the first-stage fixed bed cracking reactor 6, different feed devices are selected according to the types of biomass raw materials, 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 materials are preheated before being fed, 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 feed time and the feed quantity; the probe of the temperature control system 5 stretches into the first-stage fixed bed cracking reactor 6, and the temperature change condition of the pyrolysis reactor is monitored 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 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; the microwave resonant cavity 11 is provided with a microwave feed port 10, the 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 emission frequency is continuously adjustable between 2.45 and 8GHz, the output power is freely adjusted between 200 and 500W, and the frequency adjustment amplitude is 0.1 to 1000MHz; 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 the outlet of the second-stage quartz tube fixed bed hydrogenation reactor 8, a gas collecting bag 17 is arranged at the outlet of the condensing system 12, the condensable part in the hydrogenation product is condensed by the condensing system 12 to obtain biological oil, and the non-condensable part enters the gas collecting bag 17 for further detection and analysis; an on-line 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 on-line detection system 15 can be a gas phase-mass spectrometer for on-line detection analysis of hydrogenation product components.
The application method of the microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device specifically comprises the following steps:
(1) The pyrolysis catalyst is arranged in a catalyst bed layer in the first-stage fixed bed reactor, the hydrogenation catalyst is uniformly arranged at the center of a quartz tube in the second-stage quartz tube fixed bed hydrogenation reactor 8, and the biomass raw material is added into a solid feed hopper 4; then inert gas is used for purging the first-stage fixed bed cracking reactor 6 and the second-stage quartz tube fixed bed hydrogenation reactor 8 after 3 times of preheating by a preheater;
(2) Switching a carrier gas valve to an active reaction carrier gas source 2 after purging is finished, starting to heat the first-stage fixed bed cracking reactor, starting a microwave continuous frequency modulation power supply, enabling continuously variable microwaves to enter a microwave resonant cavity through a microwave feed port, selectively heating a hydrogenation catalyst arranged at the center of a quartz tube, monitoring the temperature of the contact part of the hydrogenation catalyst and the wall surface of the quartz tube in real time through a non-contact infrared thermometer, and entering a step 3 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 feed hopper 4, quickly catalyzing and cracking biomass raw materials after entering a first-stage fixed bed cracking reactor 6 to generate gaseous products mainly comprising aromatic hydrocarbons, and then entering a second-stage quartz tube fixed bed hydrogenation reactor 8 in a gaseous form to carry out hydrogenation reaction under the action of a hydrogenation catalyst and microwaves with continuously changing frequency;
(4) The product components generated by the hydrogenation reaction are detected in real time through an online detection system arranged at the outlet of the quartz tube reactor, the products after the reaction are condensed by a condensing system and then are collected into liquid products, and the non-condensable gaseous products are collected into a gas collecting bag for subsequent offline analysis.
According to the invention, 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 gaseous product molecules at certain optimal emission frequency so as to directionally break bonds, so that the gaseous hydrogenation of the biomass pyrolysis product is realized at low pressure even normal pressure, and compared with the conventional hydrogenation process of liquid biological oil, the method has the advantages of low reaction energy consumption, high hydrogenation efficiency and the like.
Claims (8)
1. The gaseous hydrogenation device for the biomass pyrolysis product is characterized by comprising 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 pyrolysis reactor (6), an air inlet of the first-stage fixed bed pyrolysis reactor (6) is connected with a gas source, and a preheater (3) is arranged between the first-stage fixed bed pyrolysis 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); the probe of the temperature control system (5) stretches 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 feed inlet 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 inlet 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 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); the microwave resonant cavity (11) is provided with a microwave feed port (10), 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 the outlet of the second-stage quartz tube fixed bed hydrogenation reactor (8), and a gas collecting bag (17) is arranged at the outlet of the condensing system (12); the microwave continuous frequency modulation power supply (9) consists of different frequency modulation modules, the microwave emission frequency is continuously adjustable between 2.45 and 8GHz, the output power is freely adjusted between 200 and 500W, and the frequency adjustment amplitude is 0.1 to 1000MHz.
2. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation device according to claim 1 is characterized in that gas flow meters are arranged on a connecting pipeline of the inert gas source (1) and the preheater (3) and on 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 apparatus 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 collaborative biomass pyrolysis product gaseous hydrogenation apparatus according to claim 1, wherein an online detection system (15) is arranged between an outlet of the second-stage quartz tube fixed bed hydrogenation reactor (8) and a condensing system (12).
5. The microwave continuous frequency modulation collaborative biomass pyrolysis product gaseous hydrogenation apparatus 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 apparatus 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).
8. The method for using the microwave continuous frequency modulation synergistic biomass pyrolysis product gaseous hydrogenation device as claimed in claim 1, which is characterized by comprising the following steps:
1) The pyrolysis catalyst is arranged in a catalyst bed layer in the first-stage fixed bed reactor, the hydrogenation catalyst is uniformly arranged at the center of a quartz tube in the second-stage quartz tube fixed bed hydrogenation reactor (8), biomass raw materials are added into a solid feed hopper (4), and then inert gas is preheated by a preheater and then the first-stage fixed bed cracking reactor (6) and the second-stage quartz tube fixed bed hydrogenation reactor (8) are purged;
2) Switching a carrier gas valve to an active reaction gas source (2) after purging is finished, starting to heat a first-stage fixed bed cracking reactor (6), starting a microwave continuous frequency modulation power supply (9), enabling continuously variable microwaves to enter a microwave resonant cavity (11) through a microwave feed port, selectively heating a hydrogenation catalyst arranged in the center of a quartz tube, monitoring the temperature of the contact part of the hydrogenation catalyst and the wall surface of the quartz tube in real time through an infrared thermometer (14), and entering a step 3 when the temperature 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) Starting a feeding valve of a solid feed hopper (4), quickly catalyzing and cracking biomass raw materials after entering a first-stage fixed bed cracking reactor (6) to generate gaseous products mainly containing aromatic hydrocarbons, and then entering a second-stage quartz tube fixed bed hydrogenation reactor (8) in a gaseous form to carry out hydrogenation reaction under the action of a hydrogenation catalyst and microwaves with continuously changing frequency;
4) The product components generated by the hydrogenation reaction are detected in real time through an online detection system (15) arranged at the outlet of the quartz tube reactor, the products after the reaction are condensed by a condensation system (12) and then are collected into liquid products, and the non-condensable gaseous products are collected into a gas collecting bag for subsequent offline analysis.
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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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19631201A1 (en) * | 1996-08-02 | 1998-02-05 | Biotecon Ges Fuer Biotechnologische Entwicklung & Consulting Mbh | Conversion of organic materials into fuels |
| CN102329654A (en) * | 2011-08-30 | 2012-01-25 | 张建超 | Biomass gasification device and process |
| CN102946655A (en) * | 2012-11-13 | 2013-02-27 | 中国石油大学(北京) | Microwave heating device capable of being continuously operated and resisting high temperature and high pressure and application thereof |
| 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 |
| CN108117878A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | Biomass microwave is pyrolyzed the method and system of preparing synthetic gas |
| CN109337702A (en) * | 2018-10-18 | 2019-02-15 | 中国科学院上海高等研究院 | Microwave-assisted biomass pyrolytic preparation is rich in the method and device of phenolic compound |
| CN109837103A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of biomass thermal chemical conversion integrated system and application |
| CN110292899A (en) * | 2019-04-19 | 2019-10-01 | 东南大学 | High temperature microwave reaction kettle combined apparatus and reaction method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11021661B2 (en) * | 2012-02-21 | 2021-06-01 | Battelle Memorial Institute | Heavy fossil hydrocarbon conversion and upgrading using radio-frequency or microwave energy |
-
2020
- 2020-01-19 CN CN202010063346.1A patent/CN111117683B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19631201A1 (en) * | 1996-08-02 | 1998-02-05 | Biotecon Ges Fuer Biotechnologische Entwicklung & Consulting Mbh | Conversion of organic materials into fuels |
| CN102329654A (en) * | 2011-08-30 | 2012-01-25 | 张建超 | Biomass gasification device and process |
| CN102946655A (en) * | 2012-11-13 | 2013-02-27 | 中国石油大学(北京) | Microwave heating device capable of being continuously operated and resisting high temperature and high pressure and application thereof |
| CN108117878A (en) * | 2016-11-28 | 2018-06-05 | 中国石油化工股份有限公司 | Biomass microwave is pyrolyzed the method and system of preparing synthetic gas |
| 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 |
| CN109837103A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of biomass thermal chemical conversion integrated system and application |
| CN109337702A (en) * | 2018-10-18 | 2019-02-15 | 中国科学院上海高等研究院 | Microwave-assisted biomass pyrolytic preparation is rich in the method and device of phenolic compound |
| CN110292899A (en) * | 2019-04-19 | 2019-10-01 | 东南大学 | High temperature microwave reaction kettle combined apparatus and reaction method |
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