CN112662413A - Device and method for high-value utilization of biomass based on photo-thermal coupling - Google Patents
Device and method for high-value utilization of biomass based on photo-thermal coupling Download PDFInfo
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Abstract
The invention belongs to the technical field related to biomass energy utilization, and discloses a device and a method for high-value utilization of biomass based on photo-thermal coupling. The device comprises a carrier gas protection unit, a heating unit, a photocatalytic cracking unit and a condensation collection unit, wherein the carrier gas protection unit is used for forming carrier gas circulation; the heating unit comprises a thermal reactor, a loading hanging basket and a heating device, wherein the loading hanging basket is suspended in the thermal reactor and is used for loading biomass to be treated, and the heating device is arranged outside the thermal reactor and is used for heating the thermal reactor; the photocatalytic cracking unit comprises a vacuum reactor, spoilers and an integrated light source, wherein the spoilers are arranged in a staggered manner, the spoilers are loaded with photocatalysts, and the integrated light source is used as a light source; the condensing and collecting unit is used for collecting biomass light pyrolysis oil and combustible gas generated by cracking. The method has the remarkable advantages of low energy consumption, reduction of carbon deposition in the reaction process, improvement of the quality of products obtained by biomass pyrolysis and the like.
Description
Technical Field
The invention belongs to the technical field of biomass energy utilization, and particularly relates to a device and a method for utilizing biomass in a high-value mode based on photo-thermal coupling.
Background
The biomass energy has the characteristics of cleanness, reproducibility, wide distribution, carbon neutrality and the like. The development of biomass energy utilization technology is beneficial to optimizing the energy supply structure of China and relieving the increasingly severe environmental problems. The biomass resource reserves in China are abundant, the annual output of biomass raw materials which can be used as energy reaches 50 hundred million tons, and the annual output is about 24 hundred million tons compared with standard coal, so that the biomass energy-saving coal has great economic value. Therefore, the research and development of the biomass high-efficiency transformation technology have great significance for solving the problems of agriculture, farmers and the like, improving the ecological environment, promoting the sustainable development of social economy, guaranteeing the national energy supply safety and the like.
Biomass has the characteristics of raw material dispersion, small collection radius and high transportation and storage cost, and the biomass is generally converted into biomass pyrolysis oil (bio-oil), combustible gas and biomass coke by using a pyrolysis technology at present, so that the utilization rate of the raw material is 95%. But the biomass thermal conversion and utilization process has the problems of large energy consumption, low product calorific value, easy coking when being heated and the like. Based on the above, the invention combines two reactions of thermal cracking and photocatalytic cracking, so that the energy consumption required by the thermal cracking of biomass is reduced, the obtained biomass light pyrolysis oil and combustible gas are upgraded, and the device and the method for high-value utilization of biomass based on photo-thermal coupling are provided.
Disclosure of Invention
Aiming at the defects or improvement requirements in the prior art, the invention provides a device and a method for utilizing biomass at high value based on photo-thermal coupling, the high-value utilization of the biomass is realized through the overall structural layout of the device and the structural design of important parts, and the collection function of light volatile components and combustible gas obtained by biomass pyrolysis can be further realized through the design.
In order to achieve the above objects, according to one aspect of the present invention, there is provided an apparatus for high-value utilization of biomass based on photothermal coupling, the apparatus comprising a carrier gas protecting unit, a heating unit, a photocatalytic cracking unit, and a condensation collecting unit, wherein,
the carrier gas protection unit is connected with the heating unit and the photocatalytic cracking unit to form carrier gas circulation;
the heating unit is arranged above the photocatalytic cracking unit and comprises a thermal reactor, a loading basket and a heating device, the loading basket is suspended in the thermal reactor and used for loading biomass to be treated, and the heating device is arranged outside the thermal reactor and used for heating the thermal reactor;
the photocatalytic cracking unit comprises a vacuum reactor, spoilers and an integrated light source, wherein the spoilers are arranged on the inner wall of the vacuum reactor and are arranged in a staggered manner, the spoilers are loaded with photocatalysts, and the integrated light source is arranged outside the vacuum reactor and is used as a light source;
the condensation collection unit is arranged below the photocatalytic cracking unit, volatile components generated by pyrolysis of biomass to be treated in the heating unit enter the photocatalytic cracking unit to be subjected to photocatalytic cracking under the driving of carrier gas, and biomass light pyrolysis oil and combustible gas generated by cracking are collected by the condensation collection unit.
Further preferably, the device further comprises a control unit, wherein the control unit is simultaneously connected with the carrier gas protection unit, the heating unit and the photocatalytic cracking unit and independently controls each unit.
Further preferably, the condensation collection unit comprises a condensation device and a gas storage tank, the condensation device is used for collecting the biomass light pyrolysis oil, and the gas storage tank is used for collecting combustible gas obtained by biomass pyrolysis.
According to another aspect of the invention, there is provided a method for photothermal coupling pyrolysis of biomass by using the above apparatus, the method comprising the following steps:
s1, placing the biomass to be treated in the loading hanging basket, preparing the spoiler, and starting the carrier gas protection unit, the heating unit and the photocatalytic cracking unit;
s2, pyrolyzing the biomass to be treated to obtain volatile components, allowing the volatile components to flow from top to bottom in a carrier gas to enter the photocatalytic cracking unit, and performing catalytic cracking reaction under the irradiation of a photocatalyst and a light source;
and the biomass light pyrolysis oil and combustible gas generated by catalytic cracking of S3 enter the condensation collection unit to be collected.
Further preferably, the biomass to be treated is cellulosic biomass, such as cotton, corn stover or straw.
Further preferably, the carrier gas is inert gas or nitrogen, and the flow rate is 200mL/min to 400 mL/min.
Further preferably, the temperature of biomass pyrolysis is 250-400 ℃, and the heating rate is not more than 10 ℃/s.
Further preferably, the spoiler is formed by mixing titanium dioxide and quartz crystal in a mass ratio of not less than 1: 1 to obtain a round rod with the diameter not more than 10mm, wherein the round rod is the required spoiler, and the titanium dioxide is a photocatalyst.
Further preferably, the wavelength range of the light source is controlled within 300nm to 380 nm.
Generally, compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. according to the invention, a thermal-thermal coupling is formed by coupling a pyrolysis reaction and a photocatalytic reaction, wherein the pyrolysis can generate a large amount of water, necessary conditions are provided for the later photocatalysis, the photocatalytic reaction conditions are mild, the reaction process can be regulated, target volatile components can be effectively cracked by catalysts with different structures, light effective components are obtained, carbon deposition in the process is avoided, the thermal-thermal coupling can effectively reduce the temperature required by the reaction, the product selectivity is improved, the reaction conditions are reduced, coking and carbon deposition are avoided, the optimal effect can be achieved by coupling the two, and the defect is not available;
2. according to the invention, the hanging basket loaded in the heating unit is suspended, so that biomass feeding is facilitated, and meanwhile, the volatile component release position can be adjusted according to different requirements, so that the device has the advantage of high flexibility; the turbulence plates in the photocatalytic cracking unit are distributed in a staggered manner, so that the contact area of volatile matters and the photocatalyst can be effectively increased, and the optimal cracking effect is achieved;
3. according to the invention, the low-temperature slow pyrolysis of the cellulose biomass is utilized, the volatile matter of the cellulose biomass has low macromolecular substances and high moisture, so that the volatile matter is used as a self-oxygen supply source in the photocatalytic cracking;
4. the invention provides a device for high-valued utilization of biomass based on photo-thermal coupling, which can greatly reduce energy consumption required by cracking, prepare light biomass pyrolysis oil convenient to transport, store and reprocess, and prepare combustible gas with higher purity, thereby effectively improving the utilization efficiency of biomass;
5. the reaction conditions are mild, accurate and controllable, and are different from the violent reaction conditions such as high temperature and high pressure required by conventional thermochemical upgrading, the reaction temperature is lower, the reaction pressure is normal pressure, and meanwhile, the violent degree of the reaction can be accurately changed by controlling the heating temperature in the heating unit and the integrated light source in the photocatalytic cracking unit.
Drawings
FIG. 1 is a schematic diagram of a photothermal coupling based biomass upgrading apparatus constructed in accordance with a preferred embodiment of the present invention;
FIG. 2 is a graph showing the variation of the content of small molecular substances and the content of combustible gases in the light tar obtained by condensation, constructed according to the preferred embodiment 1 of the present invention.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
1.1-gas cylinder, 1.2-mass flowmeter, 2.1-thermal reactor, 2.2-loading basket, 2.3-temperature control device, 3.1-spoiler, 3.2-integrated light source, 3.3-vacuum reactor, 4-control unit, 5.1-condensing device and 5.2-gas storage tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the device for high-value utilization of biomass based on photothermal coupling provided by the present invention comprises a carrier gas protection unit 1, a heating unit 2, a photocatalytic cracking unit 3, a control unit 4 and a condensation collection unit 5, wherein:
the carrier gas protection unit 1 connects the gas cylinder 1.1 and the mass flowmeter 1.2 into a passage, and brings the protective gas into the heating unit 2;
the heating unit 2 comprises a thermal reactor 2.1, a loading hanging basket 2.2, a heating device 2.3 and a temperature control device 2.4, wherein biomass is placed in the loading hanging basket 2.2 in advance, the loading hanging basket 2.2 is fixed in a heating center of the thermal reactor 2.1 through an iron wire clamping position, and in the pyrolysis process, protective gas carries volatile obtained by pyrolysis of the biomass to flow to the photocatalytic cracking unit 3 from top to bottom;
the photocatalytic cracking unit 3 comprises a spoiler 3.1, an integrated light source 3.2 and a vacuum reactor 3.3, wherein the spoiler 3.1 is embedded on the inner wall of the vacuum reactor 3.3 in a melting mode in a staggered mode, in the experimental process, the integrated light source 3.2 transfers electrons in a valence band of an exciting photocatalyst to an empty conduction band and leaves a positive hole, when volatile components obtained by pyrolysis of biomass carried by protective gas flow through the spoiler 3.1 from top to bottom, the hole oxidizes water and hydroxyl adsorbed on the surface of the catalyst to generate hydroxyl radicals with stronger oxidability, so that the volatile components and the hydroxyl radicals are subjected to cracking reaction to form light volatile components with average molecular weights smaller than those obtained by pyrolysis;
the control unit 4 can synchronously and accurately regulate and control the carrier gas protection unit 1, the temperature control device 2.4 in the heating unit 2 and the integrated light source 3.2 in the photocatalytic cracking unit 3;
the condensation collection unit 5 comprises a condensation device 5.1 and a gas storage tank 5.2, wherein the obtained biomass light pyrolysis oil is collected by the condensation device 5.1, and the combustible gas obtained by biomass pyrolysis is collected by the gas storage tank 5.2.
Further preferably, the protective gas is an inert gas or nitrogen, the flow rate is in the range of 200mL/min to 400mL/min, the secondary polymerization of the volatile matter is promoted when the flow rate is too low, and the volatile matter cannot be sufficiently contacted with the photocatalyst when the flow rate is too high.
In a further preferred embodiment of the present invention, the biomass is a cellulosic biomass, such as cotton, corn stalks, rice straws, etc., and the cellulosic biomass is pyrolyzed to obtain a large amount of volatile small molecular substances, which are more easily subjected to photocatalytic cracking.
As a further optimization of the invention, the volatile matter obtained by biomass pyrolysis is prepared at a temperature rise rate of not more than 10 ℃/s within a temperature range of 250-400 ℃, the pyrolysis temperature is lower than 250 ℃ and cannot enable the biomass to be fully thermally cracked, the pyrolysis temperature is higher than 400 ℃ and can increase the content of macromolecular substances in the volatile matter, and meanwhile, the content of macromolecular substances in the volatile matter obtained by biomass pyrolysis is further reduced by slow pyrolysis at a temperature rise rate of not more than 10 ℃/s.
As a further preferred aspect of the present invention, the photocatalyst in the spoiler 3.1 is titanium dioxide, and the supporting manner is to mix powdered titanium dioxide and quartz crystal in a mass ratio of not less than 1: 1, the doping proportion is too low, the photocatalytic cracking efficiency is influenced, round rods with the diameter not more than 10mm are prepared, and the round rods are inserted into the inner wall of the vacuum reactor 3.3 in a melting mode in a staggered mode.
As a further optimization of the invention, a vacuum layer with a distance of 2 mm-5 mm is arranged between the inner wall and the outer wall in the vacuum reactor 3.3, the heat preservation effect is reduced when the vacuum layer is too small, and the photocatalytic cracking efficiency is affected when the vacuum layer is too large.
As a further optimization of the invention, the integrated light source 3.2 is formed by surrounding the outer wall of the vacuum reactor 3.3 by a plurality of xenon lamps in a circular manner, the number of the xenon lamps is not more than 10, and the xenon lamps are embedded in the inner wall of the cylindrical sleeve to form the integrated light source sleeve, wherein the control wavelength range of the xenon lamps is within 300 nm-380 nm, because the photocatalyst used in the invention is titanium dioxide, the band gap energy of the titanium dioxide is 3.2eV, which corresponds to photons with the wavelength of 388nm, the titanium dioxide can trigger the photocatalytic reaction only under the irradiation of ultraviolet rays with the wavelength of less than 388nm, and the photocatalytic cracking reaction efficiency is reduced if the wavelength of less than 300 nm.
As a further preferred aspect of the present invention, the thermal reactor 2.1 in the heating unit 2, the integrated light source 3.2 in the photocatalytic cracking unit 3, and the vacuum reactor 3.3 are connected in a ring snap manner, and both can be detached and replaced.
A method for high-value utilization of biomass based on photothermal coupling comprises the following steps:
s1, pyrolyzing the biomass in the heating unit 2 under the protection of inert gas or nitrogen, wherein volatile components carried by the protective gas flow from top to bottom;
s2 volatile matter passes through the spoiler 3.1 under the irradiation of the integrated light source 3.2, so that catalytic cracking reaction occurs;
s3 collects the resultant biomass light pyrolysis oil and combustible gas by the condensation collection unit 5.
The present invention will be further described with reference to specific examples.
Example 1
a, placing 1g of cotton in a loading hanging basket in advance, matching the loading hanging basket with a thermal reactor, placing the loading hanging basket in the center of a heating device, and connecting the thermal reactor, a vacuum reactor and an integrated light source in a circular buckle mode;
b, regulating and controlling the flow rate of carrier gas to be 200mL/min by using a control unit, using nitrogen as protective gas, setting the temperature of a temperature control device to be 300 ℃, the heating rate to be 10 ℃/s and the wavelength of an integrated light source to be 300 nm;
and collecting light volatile components and combustible gas obtained by biomass pyrolysis through a condensation collection unit.
The samples are taken every 5min for measurement, and the graph of the change of the content of the micromolecular substances and the content of the combustible gas in the light tar obtained by condensation in the process is shown in figure 2.
Example 2
Different from the embodiment 1, the raw material in the embodiment is 1g of corn straw, the flow rate of the carrier gas is regulated and controlled to be 300mL/min by using the control unit, the protective gas is nitrogen, the temperature is set to be 350 ℃ by using the temperature control device, the heating rate is 5 ℃/s, and the wavelength of the integrated light source is 320 nm.
Example 3
Different from the embodiment 1, the raw material in the embodiment is 1g of cotton, the flow rate of the carrier gas is controlled to be 400mL/min by using a control unit, argon is used as the protective gas, the temperature is set to be 400 ℃ by using a temperature control device, the heating rate is 5 ℃/s, and the wavelength of the integrated light source is 350 nm.
Example 4
Different from the embodiment 1, the raw material in the embodiment is 1g of straw, the flow rate of the carrier gas is regulated and controlled to be 350mL/min by using a control unit, the protective gas is argon, the temperature is set to be 380 ℃ by using a temperature control device, the heating rate is 8 ℃/s, and the wavelength of the integrated light source is 380 nm.
Example 5
Different from the embodiment 1, the raw material in the embodiment is 1g of straw, the flow rate of the carrier gas is controlled to be 250mL/min by using a control unit, the protective gas is argon, the temperature of a temperature control device is set to be 250 ℃, the heating rate is 0.5 ℃/s, and the wavelength of an integrated light source is 330 nm.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. The device for high-value utilization of biomass based on photothermal coupling is characterized by comprising a carrier gas protection unit (1), a heating unit (2), a photocatalytic cracking unit (3) and a condensation collection unit (5), wherein,
the carrier gas protection unit (1) is connected with the heating unit (2) and the photocatalytic cracking unit (3) to form carrier gas circulation;
the heating unit (2) is arranged above the photocatalytic cracking unit (3), the heating unit (2) comprises a thermal reactor (2.1), a loading basket (2.2) and a heating device (2.3), the loading basket (2.2) is suspended in the thermal reactor (2.1) and is used for loading biomass to be processed, and the heating device (2.3) is arranged outside the thermal reactor and is used for heating the thermal reactor;
the photocatalytic cracking unit (3) comprises a vacuum reactor (3.3), spoilers (3.1) and an integrated light source (3.2), wherein the spoilers (3.1) are arranged on the inner wall of the vacuum reactor (3.3) and are arranged in a staggered mode, the spoilers (3.1) are loaded with photocatalysts, and the integrated light source (3.2) is arranged outside the vacuum reactor and serves as a light source;
the condensation collection unit (5) is arranged below the photocatalytic cracking unit (3), volatile components generated by pyrolysis of biomass to be treated in the heating unit (2) enter the photocatalytic cracking unit (3) to be subjected to photocatalytic cracking under the driving of carrier gas, and biomass light pyrolysis oil and combustible gas generated by cracking are collected by the condensation collection unit (5).
2. The device for high-value utilization of biomass based on photothermal coupling as claimed in claim 1, further comprising a control unit (4) which is connected with the carrier gas protection unit (1), the heating unit (2) and the photocatalytic cracking unit (3) at the same time and controls each unit independently.
3. The device for high-value utilization of biomass based on photothermal coupling according to claim 1, wherein the condensation collection unit (5) comprises a condensation device (5.1) and a gas storage tank (5.2), the condensation device (5.1) is used for collecting biomass light pyrolysis oil, and the gas storage tank (5.2) is used for collecting combustible gas obtained by biomass pyrolysis.
4. A method for photothermal coupling pyrolysis of biomass using the apparatus of any one of claims 1-3, comprising the steps of:
s1, placing the biomass to be treated in the loading hanging basket, preparing the spoiler, and starting the carrier gas protection unit, the heating unit and the photocatalytic cracking unit;
s2, pyrolyzing the biomass to be treated to obtain volatile components, allowing the volatile components to flow from top to bottom in a carrier gas to enter the photocatalytic cracking unit, and performing catalytic cracking reaction under the irradiation of a photocatalyst and a light source;
and the biomass light pyrolysis oil and combustible gas generated by catalytic cracking of S3 enter the condensation collection unit to be collected.
5. The method of photothermal coupling pyrolysis according to claim 4, wherein the biomass to be treated is cellulosic biomass, such as cotton, corn stover or straw.
6. The method of photothermal coupling pyrolysis according to claim 4, wherein the carrier gas is an inert gas or nitrogen, and the flow rate is 200mL/min to 400 mL/min.
7. The method of photothermal coupling pyrolysis according to claim 4, wherein the temperature of biomass pyrolysis is 250 ℃ to 400 ℃ and the rate of temperature rise is no greater than 10 ℃/s.
8. The photothermal coupling pyrolysis method as claimed in claim 4, wherein the spoiler is formed by mixing titanium dioxide and quartz crystal at a mass ratio of not less than 1: 1 to obtain a round rod with the diameter not more than 10mm, wherein the round rod is the required spoiler, and the titanium dioxide is a photocatalyst.
9. The method of photothermal coupling pyrolysis according to claim 4, wherein the wavelength range of the light source is controlled within 300nm to 380 nm.
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