CN112538389A - Method and device for catalytically reforming biomass tar based on photo-thermal synergistic effect - Google Patents
Method and device for catalytically reforming biomass tar based on photo-thermal synergistic effect Download PDFInfo
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- CN112538389A CN112538389A CN202011220904.7A CN202011220904A CN112538389A CN 112538389 A CN112538389 A CN 112538389A CN 202011220904 A CN202011220904 A CN 202011220904A CN 112538389 A CN112538389 A CN 112538389A
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
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Abstract
A method and a device for catalytically reforming biomass tar based on photo-thermal synergistic effect, the method comprises the steps of heating a photo-thermal catalyst to a reaction temperature in a flowing atmosphere, and then providing a light source for irradiation to form a photo-thermal catalytic region; in flowing atmosphere, synthetic gas carrying tar and steam is introduced into the photo-thermal catalysis region, and the tar reacts in the photo-thermal catalysis region, so that the removal is realized. According to the invention, photocatalysis is introduced into the field of thermal catalysis for removing biomass tar for the first time, and a catalyst with excellent photo-thermal catalytic performance is utilized to excite photo-thermal synergistic effect, so that low-temperature and high-efficiency removal of tar is realized; the photo-thermal catalysis effectively promotes the excitation and transfer of electrons in the reaction process, and is beneficial to reducing the average reaction temperature of the reaction, thereby reducing the energy consumption of the traditional thermal catalysis to a certain extent, reducing the time cost in the temperature rise/reduction process, and being expected to reduce the strict requirements on a thermal catalysis device.
Description
Technical Field
The invention belongs to the field of biomass tar removal, and particularly relates to a method and a device for catalytically reforming biomass tar based on a photo-thermal synergistic effect.
Background
Tars are the major organic pollutants produced during biomass gasification and are a complex mixture of various condensable hydrocarbons, including monocyclic to 5-ring aromatics and other oxygenated hydrocarbons and complex Polycyclic Aromatic Hydrocarbons (PAHs). Tar easily condenses at lower temperatures and further polymerizes into more complex structures, causing corrosion and wear of downstream equipment, reducing the overall efficiency of the system, and is one of the great challenges for the application of the biomass gasification industry. At present, the generation of tar in a furnace can be inhibited to a certain extent by optimizing the design of a reactor, adjusting the reaction condition, adopting in-situ catalysts and other means, but the quality of the synthesis gas at the outlet of a gasifier still cannot meet the more severe tar limit of downstream applications such as Fischer-Tropsch synthesis, fuel cells and the like. The need to employ appropriate methods for out-of-furnace decoking is the focus of ongoing research.
The conventional removal method outside the furnace is classified into a physical method and a chemical method. The physical methods based on adsorption and absorption are difficult to realize the fundamental removal of tar, and are often accompanied by energy loss and waste liquid pollution. The chemical method can further improve the quality of the synthesis gas on the basis of tar removal, and is a tar removal method with a good application prospect. The thermal cracking reaction temperature is generally above 1000 ℃, the requirements on equipment are strict, and the energy consumption is high. The steam catalytic reforming method is widely used for tar removal research and has the advantages that: (1) the biomass contains 5-35% of unequal moisture, and the moisture contained in the synthesis gas can be utilized by the tar steam reforming process; (2) compared with tar removal methods such as thermal cracking and dry reforming, steam in the steam reforming process can react with carbon deposition on the catalyst, so that the generation of the carbon deposition can be inhibited to a certain extent. However, even in the steam reforming process, the problem of catalyst deactivation caused by agglomeration, carbon deposition and the like is difficult to eliminate, and meanwhile, the problem of energy consumption caused by higher reaction temperature also limits the large-scale application of the method in the field of tar removal.
Compared with the traditional thermochemical reaction, the photocatalysis utilizes solar energy to drive the chemical reaction, and isA relatively economical, environmentally friendly, sustainable solution. Since 1972 Fujishima et al discovered that TiO was exposed to UV light2Since the phenomenon of water decomposition, semiconductor photocatalytic reactions have been extensively studied in the fields of solar energy utilization, organic synthesis and environmental remediation. Particularly in the indoor environmental management field, many scholars have synthesized various photocatalytic materials for the elimination of typical VOCs such as benzene, toluene and naphthalene, and achieved unusual effects. Considering that the content of monocyclic and bicyclic compounds in tar components is about more than 75 percent and can be used as a treatment object of photocatalysis, introducing a photocatalysis system into the traditional thermal catalysis process is expected to bring new possibility to the field of biomass tar removal.
At present, some photo-thermal catalysis is used for eliminating VOCs and CO2Organic synthesis and related studies in F-T synthesis. The light is introduced into a thermal catalysis system, so that the synergistic photo-thermal effect can be effectively promoted, electrons can be excited and relaxed more, thermal emission is effectively enhanced, the thermal catalysis activity is improved, the defects of low degradation performance and reaction rate of organic matters such as toluene and the like in a single photo-catalysis reaction are hopefully overcome, and the reaction temperature of thermal catalysis can be reduced, so that the energy consumption in the reaction process is reduced.
Aiming at the problems of tar removal, a method for removing the biomass tar based on the photothermal catalytic reaction is provided by combining the characteristics of a thermal catalyst and a photosensitive semiconductor material and introducing a photocatalytic process into a traditional thermal catalytic reaction system.
Disclosure of Invention
In view of the above, one of the main objectives of the present invention is to provide a method and an apparatus for catalytic reforming of biomass tar based on photo-thermal synergistic effect, so as to at least partially solve at least one of the above technical problems.
In order to achieve the above object, as one aspect of the present invention, there is provided a method for catalytic reforming of biomass tar based on photothermal synergistic effect, comprising:
heating the photo-thermal catalyst to a reaction temperature in a flowing atmosphere, and then providing light source irradiation to form a photo-thermal catalytic region;
in flowing atmosphere, synthetic gas carrying tar and steam is introduced into the photo-thermal catalysis region, and the tar reacts in the photo-thermal catalysis region, so that the removal is realized.
As another aspect of the present invention, there is also provided a photo-thermal catalytic device for performing the method as described above, comprising: a photo-thermal catalytic region and a light source that illuminates the photo-thermal catalytic region.
Based on the technical scheme, compared with the prior art, the method and the device for catalytically reforming the biomass tar based on the photothermal synergistic effect have at least one or part of the following advantages:
1. according to the invention, photocatalysis is introduced into the field of thermal catalysis for removing biomass tar for the first time, and a catalyst with excellent photo-thermal catalytic performance is utilized to excite photo-thermal synergistic effect, so that low-temperature and high-efficiency removal of tar is realized;
2. the photo-thermal catalysis effectively promotes the excitation and transfer of electrons in the reaction process, and is beneficial to reducing the average reaction temperature of the reaction, so that the energy consumption of the traditional thermal catalysis is reduced to a certain extent, the time cost of the temperature rise/reduction process is reduced, and the strict requirement on a thermal catalysis device is expected to be reduced;
3. the photo-thermal catalytic reforming process fully utilizes the photo-thermal synergistic effect, improves the tar removal rate and improves the quality of the synthesis gas;
4. the introduction of light reduces the reaction temperature of the traditional thermal catalysis, thereby being beneficial to relieving the problem of catalyst agglomeration caused by overhigh reaction temperature; the photo-thermal synergistic effect improves the reaction efficiency, and is beneficial to relieving carbon deposition on the surface of the catalyst, so that the problem of catalyst inactivation is relieved, and the reaction cost is reduced to a certain extent.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for catalytic reforming of biomass tar based on photothermal synergistic effect in the embodiment of the present invention.
Description of reference numerals:
1-a gas cylinder filled with inert gas;
2-a first gas circuit valve;
3-a hydrogen generator;
4-a second gas circuit valve;
5-a first syringe pump;
6-a second syringe pump;
7-heat preservation belt;
8-a quartz tube;
9-electric heating furnace;
10-a quartz window;
11-xenon lamp;
12-a thermocouple;
13-a condensing unit;
14-gas chromatography;
15-photothermal catalytic device control system.
Detailed Description
Hereinafter, the present invention will be described in detail with reference to the accompanying drawings and examples to assist those skilled in the art in fully understanding the objects, features and effects of the present invention. Exemplary embodiments of the present invention are illustrated in the drawings, but it should be understood that the present invention can be embodied in other various forms and should not be limited to the embodiments set forth herein. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention. In addition, the embodiments of the present invention provided below and the technical features in the embodiments may be combined with each other in an arbitrary manner.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Furthermore, the terms "comprises," "comprising," "includes," "including," "has," "having," and the like, when used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components. All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise defined. It is noted that the terms used herein should be interpreted as having a meaning that is consistent with the context of this specification and should not be interpreted in an idealized or overly formal sense.
In order to solve the defects of the prior art, the invention aims to provideA method for removing biomass tar based on photothermal catalytic reforming. Introducing ultraviolet/visible light by xenon lamp irradiation based on electric heating, and using noble metal with excellent thermal catalysis performance, Ni-based catalyst and photosensitive semiconductor material (such as TiO)2) As a carrier for photothermal effect and a catalyst for tar removal. In the continuous photothermal catalytic reaction process, the biomass gasification tar is removed in different positions in the photothermal catalytic region, and the catalytic reaction activity and stability are promoted by reducing the reaction temperature and prolonging the service life of the catalyst on the basis of the traditional thermal catalytic reforming of the tar.
The invention relates to a method for removing biomass tar based on photo-thermal concerted catalysis effect. The method leads the synthesis gas carrying tar and steam to pass through a photo-thermal catalytic area loaded with a catalyst, so that the tar and the steam are subjected to reforming, cracking and other reactions under the photo-thermal action, thereby efficiently removing the biomass tar at low temperature. The method introduces photocatalysis into the thermal catalysis removal process of tar, excites the photo-thermal catalysis effect, and effectively promotes the excitation and transfer of electrons in the reaction process, thereby reducing the average reaction temperature of the reaction and being beneficial to relieving the catalyst agglomeration problem caused by overhigh reaction temperature; the photo-thermal synergistic effect improves the reaction efficiency, and is beneficial to relieving carbon deposition on the surface of the catalyst, so that the problem of catalyst inactivation is relieved, and the reaction cost is reduced to a certain extent.
The invention discloses a method for catalytically reforming biomass tar based on a photo-thermal synergistic effect, which comprises the following steps:
heating the photo-thermal catalyst to a reaction temperature in a flowing atmosphere, and then providing light source irradiation to form a photo-thermal catalytic region;
in flowing atmosphere, synthetic gas carrying tar and steam is introduced into the photo-thermal catalysis region, and the tar reacts in the photo-thermal catalysis region, so that the removal is realized.
In some embodiments of the invention, the reaction temperature is from 500 to 700 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, and the effect of the photocatalytic tar removal increases with temperature over the temperature range.
In some embodiments of the invention, the ratio of the molar amount of water vapor in the syngas to the molar amount of total carbon in the tar (S/C) is from 2 to 3.
In some embodiments of the invention, the photothermal catalyst comprises at least one of a supported noble metal catalyst, a supported nickel-based catalyst, a metal oxide-type catalyst, and a perovskite-type oxide;
in some embodiments of the invention, the noble metal comprises any of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, platinum;
in some embodiments of the invention, the noble metal loading in the supported noble metal is from 0.1 to 1 wt%, e.g., 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%;
in some embodiments of the invention, the supported nickel-based catalyst has a nickel loading of 1 to 10 wt%, such as 1 wt%, 2 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%.
In some embodiments of the invention, the light source comprises any one of ultraviolet light, visible light, or infrared light.
In some embodiments of the present invention, the output power of the light source is 250 to 350W, such as 250W, 280W, 300W, 320W, 350W, and the photothermal decoking effect increases with the increase of the output power of the light source;
in some embodiments of the invention, the light source has a wavelength of 300 to 780nm, such as 300nm, 350nm, 400nm, 450nm, 500nm, 550nm, 600nm, 650nm, 700nm, 750nm, 800 nm;
in some embodiments of the invention, the light source comprises any one of a xenon lamp, a mercury lamp, a deuterium lamp, and a metal halide lamp.
In some embodiments of the invention, the flowing atmosphere comprises an inert atmosphere.
In some embodiments of the invention, the method further comprises reducing the photothermal catalyst.
In some embodiments of the present invention, the reducing step specifically comprises:
heating the catalyst in hydrogen and inert gas for reduction;
wherein the hydrogen content in the hydrogen and inert gas is 30 to 50%, such as 30%, 35%, 40%, 45%, 50%.
In some embodiments of the invention, the method further comprises incubating the synthesis gas;
in some embodiments of the invention, the incubation temperature is 140 to 150 ℃, e.g., 140 ℃, 145 ℃, 150 ℃.
The invention also discloses a photo-thermal catalytic device for carrying out the method as described above, comprising: a photo-thermal catalytic region and a light source that illuminates the photo-thermal catalytic region.
In an exemplary embodiment, the present invention provides a method for catalytic reforming of biomass tar based on photothermal synergistic effect, comprising the steps of:
1) heating a reaction zone loaded with a photo-thermal catalyst to a reaction temperature by using electric heating in a flowing atmosphere, and then turning on xenon lamps at two sides of a fixed bed to form a photo-thermal catalytic zone;
2) in a flowing atmosphere, synthetic gas carrying tar and steam is introduced into a reaction device, and the tar is subjected to catalytic reforming, cracking and other reactions in a photo-thermal catalytic reaction region, so that effective removal is realized.
In the step 1), the temperature of the reaction zone is raised to 500-700 ℃ by adopting an electric heating method, and the temperature range can effectively relieve the problems of catalyst agglomeration caused by overhigh reaction temperature, high process energy consumption and the like.
In the step 1), the output power of xenon lamps at two sides of the fixed bed is set to be 250-350W, the wavelength range of incident light of the xenon lamps is 300-780nm, the light-heat catalysts with different light response capabilities can be activated by the incident light, and the charge transfer is promoted by exciting the surface plasma effect or strengthening the Mars-van Krevelen redox cycle to realize the photo-thermal concerted catalytic conversion of tar.
In the step 2), the molar ratio (steam-carbon ratio) of the amount of the steam in the synthesis gas entering the reaction zone to the total carbon in the tar is 2-3, so that the generation of hydroxyl radicals on the surface of the photo-thermal catalyst and the progress of the water-gas conversion reaction in the photo-thermal catalytic reforming process of the tar are ensured, and the covering of active sites on the surface of the photo-thermal catalyst due to the overhigh steam content is avoided.
In the step 1), the photothermal catalyst is prepared by an impregnation method, a hydrothermal synthesis method, a precipitation method and the like, and is a supported noble metal catalyst, a supported nickel-based catalyst, a metal oxide catalyst and a perovskite oxide. Wherein, the noble metal mainly refers to gold, silver, platinum group metal (ruthenium, rhodium, palladium, osmium, iridium, platinum) and the like.
The loading capacity of the noble metal in the supported noble metal catalyst can be 0.1-1 wt%, and the loading capacity of the nickel in the supported nickel-based catalyst can be 1-10 wt%, so that the metal can be uniformly loaded on the carrier, the catalyst has sufficient active sites and the ideal response capability of the photosensitive material to ultraviolet/visible light/infrared light, and the photo-thermal synergistic effect is effectively generated, thereby promoting the reactions such as reforming, cracking, water gas conversion and the like.
In another exemplary embodiment, the method for removing biomass gasification tar based on photothermal concerted catalysis effect mainly comprises the following steps:
1) a catalyst having excellent photothermal catalytic activity is prepared by an appropriate method.
2) A proper amount of photo-thermal catalyst is loaded in a photo-thermal reaction zone in a quartz tube, and inert gas is introduced to be used as purge gas to discharge air in a reaction device.
3) Hydrogen and an inert gas are introduced into the apparatus at a suitable ratio and rate, and the catalyst is reduced by heating the catalytic reaction zone to a suitable temperature using an electrically heated furnace.
4) The reaction zone is heated to a proper temperature by using an electric heating furnace, xenon lamps on two sides of the electric heating furnace are turned on, ultraviolet/visible/infrared light irradiates the reaction zone through a quartz window, synthetic gas carrying tar and vapor is introduced into a photo-thermal catalytic reaction device, and the tar and the vapor are subjected to reactions such as reforming and cracking in the photo-thermal catalytic reaction zone to realize effective removal.
Preferably, the inert gas selected in the steps 2) and 3) is nitrogen;
preferably, the content of hydrogen in the reducing atmosphere in the step 3) is 30-50%;
preferably, in the step 4), xenon lamps are adopted to irradiate two sides of the photo-thermal catalytic reaction area, the wavelength can be between 300-780nm, and the power of the xenon lamps is between 250-350W;
preferably, the molar ratio of the amount of the steam to the carbon content of the tar entering the reaction zone in the step 4) is 2-3, so as to ensure that the tar can be fully contacted with the steam and the reforming reaction can be carried out.
Preferably, the temperature of the photo-thermal catalytic reaction in the step 4) can be 500-700 ℃;
preferably, one or more of an impregnation method, a hydrothermal method and a precipitation method can be adopted to prepare the photo-thermal catalyst;
preferably, a supported noble metal/nickel supported catalyst, a metal oxide catalyst, a perovskite oxide catalyst, or the like can be used;
preferably, the loading amount of the supported noble metal catalyst can be 0.1-1 wt%, and the loading amount of the supported nickel-based catalyst can be 1-10 wt%, so that the metal can be uniformly loaded on the carrier, the catalyst has sufficient active sites and the ideal response capability of photosensitive materials to ultraviolet/visible light/infrared light, and the photo-thermal synergistic effect is effectively generated, so that the reactions of reforming, cracking, water gas conversion and the like are promoted;
preferably, the pipeline through which the synthesis gas carrying the tar in the device passes is insulated by a heating zone, and the temperature of the insulation zone is adjusted to be 140-150 ℃ according to specific conditions so as to prevent the tar from being condensed to block and corrode the pipeline.
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
The photothermal catalytic device used in the following embodiment is shown in fig. 1, and includes an inert gas cylinder 1, a first gas path valve 2, a hydrogen generator 3, a second gas path valve 4, a first injection pump 5, a second injection pump 6, a heat preservation belt 7, a quartz tube 8, an electric heating furnace 9, a quartz window 10, a xenon lamp 11, a thermocouple 12, a condensation unit 13, a gas chromatograph 14, and a photothermal catalytic device control system 15, wherein the xenon lamp 11 is disposed on both sides of the quartz window 10 and is used for providing light source irradiation to form a photothermal catalytic region.
Example 1
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube 8 reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and the temperature of the heat preservation zone 7 is set to be 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 500 ℃, xenon lamps 11 on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 288W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS (gas chromatography-mass spectrometry) was used to detect and calculate tar conversion rate, and GC (gas chromatography) was used to detect the permanent gas, and the results are shown in Table 1.
Comparative example 1
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Using the photothermal catalytic device described above, a conventional thermal effect-based tar steam reforming experiment was conducted under xenon lamp off conditions. 0.5g of Ni/TiO was weighed2Catalyst and quartz tubeIn a reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and meanwhile, the temperature of the heat preservation zone is set to be 150 ℃. During the thermal catalytic reaction, an electric heating furnace is adopted to maintain the catalytic area at 500 ℃ (no xenon lamp is turned on); injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS was used to detect and calculate tar conversion rate, and GC was used to detect permanent gas to obtain gas relative amount, the results are shown in Table 1.
Example 2
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube 8 reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and the temperature of the heat preservation zone 7 is set to be 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 600 ℃, xenon lamps 11 on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 288W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of a catalystShould be used. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS was used to detect and calculate tar conversion rate, and GC was used to detect permanent gas to obtain gas relative amount, the results are shown in Table 1.
Comparative example 2
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Using the photothermal catalytic device described above, a conventional thermal effect-based tar steam reforming experiment was conducted under xenon lamp off conditions. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and meanwhile, the temperature of the heat preservation zone is set to be 150 ℃. During the thermal catalytic reaction, an electric heating furnace is adopted to maintain the catalytic area at 600 ℃ (no xenon lamp is turned on); injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS was used to detect and calculate tar conversion rate, and GC was used to detect permanent gas to obtain gas relative amount, the results are shown in Table 1.
Example 3
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. As shown in FIG. 1, 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. Reduction processAfter the end of the process, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and the temperature of the heat preservation zone is set to be 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 700 ℃, xenon lamps on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 288W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS was used to detect and calculate tar conversion rate, and GC was used to detect permanent gas to obtain gas relative amount, the results are shown in Table 1.
Comparative example 3
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Using the photothermal catalytic device described above, a conventional thermal effect-based tar steam reforming experiment was conducted under xenon lamp off conditions. As shown in FIG. 1, 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and meanwhile, the temperature of the heat preservation zone is set to be 150 ℃. During the thermal catalytic reaction, an electric heating furnace is adopted to maintain the catalytic area at 700 ℃ (no xenon lamp is turned on); injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. Obtaining liquid product from reacted gas in an absorption unit, sampling, detecting by adopting GCMS and calculating tar conversion rate, detecting permanent gas by adopting GC to obtain gas relative quantity and gas contentAs shown in table 1.
Example 4
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube 8 reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and the temperature of the heat preservation zone 7 is set to be 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 600 ℃, xenon lamps 11 on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 288W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 2: 1, 100ml/min of nitrogen is taken as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS (gas chromatography-mass spectrometry) was used to detect and calculate tar conversion rate, and GC (gas chromatography) was used to detect the permanent gas, and the results are shown in Table 1.
Comparative example 4
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube 8 reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, and the pipeline is blownSweeping for 15min while setting the temperature of the heat-preserving zone 7 at 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 600 ℃, xenon lamps 11 on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 288W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 1: 1, nitrogen with the concentration of 100ml/min is taken as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS (gas chromatography-mass spectrometry) was used to detect and calculate tar conversion rate, and GC (gas chromatography) was used to detect the permanent gas, and the results are shown in Table 1.
Example 5
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube 8 reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and the temperature of the heat preservation zone 7 is set to be 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 600 ℃, xenon lamps 11 on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 352W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The gas after reaction obtains liquid product in an absorption unit, and GCMS is adopted to detect and calculate tar conversion after samplingThe ratio and the amount of permanent gas were measured by GC to obtain the relative amount of gas, and the results are shown in table 1.
Example 6
By adopting an isometric immersion method, nano TiO is used2Preparing Ni/TiO with Ni content of 5% for carrier2A catalyst. Experiments were conducted according to the present invention on the catalytic reforming method of tar based on photothermal synergistic effect using the above photothermal catalytic device. 0.5g of Ni/TiO was weighed2Catalyst and placed in a quartz tube 8 reactor. Nitrogen is used as a purge gas, and the flow rate is set to be 50ml/min for purging the pipeline and the quartz tube for 15 min. The catalyst is reduced for 1h at 500 ℃ in an atmosphere of hydrogen and nitrogen in a ratio of 1: 1. After the reduction process is finished, the nitrogen flow is set to be 50ml/min, the pipeline is purged for 15min, and the temperature of the heat preservation zone 7 is set to be 150 ℃. In the photo-thermal catalytic reaction stage, an electric heating furnace is adopted to maintain the photo-thermal catalytic region at 600 ℃, xenon lamps 11 on two sides are turned on, the wavelength range of the light absorbed into the reaction region is set to be 300-400nm, and the output power of the lamps is 224W; injecting tar simulation compound toluene and water into the pipeline by using a syringe pump, evaporating in a pipeline heating zone to form water vapor, wherein the concentration of the toluene is about 50g/Nm3The steam-carbon ratio (S/C) is 3: 1, 100ml/min of nitrogen is used as carrier gas, toluene and water vapor are carried to pass through a photo-thermal reaction zone, and thermal cracking and reforming reactions are carried out on the surface of the catalyst. The reacted gas obtained liquid product in the absorption unit, after sampling, GCMS was used to detect and calculate tar conversion rate, and GC was used to detect permanent gas to obtain gas relative amount, the results are shown in Table 1.
TABLE 1 data of examples
Note: gas (H) in all examples2、CO2CO) component is the amount of nitrogen in the air pocket collected each timeThe relative amounts obtained are referenced to compare gas production under different reaction conditions, in units of "1".
From examples 1 to 3 and comparative examples 1 to 3, it was found that photothermal catalysis is more effective than conventional thermocatalytic decoking, and that the decoking effect increases with increasing temperature; from examples 2 and 4 and comparative example 4, it can be seen that the effect of the photothermal catalytic decoking is relatively stable when the steam-carbon ratio (S/C) is 2 to 3; from examples 2, 4, 5 it can be seen that the effect of photo-thermal catalytic removal increases with increasing light output power.
It should be noted that, although the invention has been shown and described with reference to the specific exemplary embodiments thereof, it should be understood by those skilled in the art that the present invention is not limited to the above-mentioned embodiments, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, and it is intended that the invention encompass such changes and modifications as fall within the scope of the claims and the equivalent technical scope of the invention.
In particular, various combinations and/or combinations of features recited in the various embodiments and/or claims of the present invention can be made without departing from the spirit and teachings of the invention, even if such combinations or combinations are not explicitly recited in the present invention. All such combinations and/or associations are within the scope of the present invention. The scope of the invention should, therefore, be determined not with reference to the appended claims, but should instead be determined with reference to the following claims.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for catalytically reforming biomass tar based on photo-thermal synergistic effect comprises the following steps:
heating the photo-thermal catalyst to a reaction temperature in a flowing atmosphere, and then providing light source irradiation to form a photo-thermal catalytic region;
in flowing atmosphere, synthetic gas carrying tar and steam is introduced into the photo-thermal catalysis region, and the tar reacts in the photo-thermal catalysis region, so that the removal is realized.
2. The method of claim 1,
the reaction temperature is from 500 to 700 ℃.
3. The method of claim 1,
the ratio (S/C) of the molar amount of water vapor in the syngas to the molar amount of total carbon in the tar is 2 to 3.
4. The method of claim 1,
the photo-thermal catalyst comprises at least one of a supported noble metal catalyst, a supported nickel-based catalyst, a metal oxide catalyst and a perovskite oxide;
wherein the noble metal comprises any one of gold, silver, ruthenium, rhodium, palladium, osmium, iridium and platinum;
wherein the noble metal loading in the supported noble metal is 0.1 to 1 wt%;
wherein the supported nickel-based catalyst has a nickel loading of 1 to 10 wt%.
5. The method of claim 1,
the light source includes any one of ultraviolet light, visible light, or infrared light.
6. The method of claim 1,
the output power of the light source is 250-350W;
the wavelength of the light source is 300 to 780 nm;
the light source includes any one of a xenon lamp, a mercury lamp, a deuterium lamp, and a metal halide lamp.
7. The method of claim 1,
the flowing atmosphere comprises an inert atmosphere.
8. The method of claim 1,
the method further comprises reducing the photothermal catalyst;
the reduction step specifically comprises:
heating the catalyst in hydrogen and inert gas for reduction;
wherein the hydrogen content in the hydrogen and inert gases is 30 to 50 percent.
9. The method of claim 1,
the method also comprises insulating the synthesis gas;
wherein the heat preservation temperature is 140-150 ℃.
10. A photothermal catalytic device for performing the method of any of claims 1 to 9, comprising: a photo-thermal catalytic region and a light source that illuminates the photo-thermal catalytic region.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0351094A1 (en) * | 1988-04-05 | 1990-01-17 | Imperial Chemical Industries Plc | Gas turbines |
| CN106987284A (en) * | 2017-04-17 | 2017-07-28 | 东南大学 | The device and method for transformation of tar removing conversion in a kind of biomass synthesis gas |
| CN110016365A (en) * | 2019-04-02 | 2019-07-16 | 东南大学 | A kind of device and method of biomass coke tar reforming preparing synthetic gas |
| CN111644176A (en) * | 2020-05-14 | 2020-09-11 | 中国科学院广州能源研究所 | Biomass tar steam reforming catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0351094A1 (en) * | 1988-04-05 | 1990-01-17 | Imperial Chemical Industries Plc | Gas turbines |
| CN106987284A (en) * | 2017-04-17 | 2017-07-28 | 东南大学 | The device and method for transformation of tar removing conversion in a kind of biomass synthesis gas |
| CN110016365A (en) * | 2019-04-02 | 2019-07-16 | 东南大学 | A kind of device and method of biomass coke tar reforming preparing synthetic gas |
| CN111644176A (en) * | 2020-05-14 | 2020-09-11 | 中国科学院广州能源研究所 | Biomass tar steam reforming catalyst and preparation method thereof |
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| CN114570381A (en) * | 2022-03-14 | 2022-06-03 | 天津大学 | Photo-thermal catalyst based on perovskite precursor in-situ reduction and preparation method and application thereof |
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