CN115364840A - Alkaline carbon material catalyst, and preparation method and application thereof - Google Patents

Alkaline carbon material catalyst, and preparation method and application thereof Download PDF

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Publication number
CN115364840A
CN115364840A CN202211079369.7A CN202211079369A CN115364840A CN 115364840 A CN115364840 A CN 115364840A CN 202211079369 A CN202211079369 A CN 202211079369A CN 115364840 A CN115364840 A CN 115364840A
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coal
carbon material
alkaline
tar
caking
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叶泽甫
张帅
徐旭东
朱竹军
王倩
王美君
申岩峰
常丽萍
鲍卫仁
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Shanxi Gemeng Sino Us Clean Energy R & D Center Co ltd
Taiyuan University of Technology
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Shanxi Gemeng Sino Us Clean Energy R & D Center Co ltd
Taiyuan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J35/60—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • C—CHEMISTRY; METALLURGY
    • 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
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment

Abstract

The invention relates to an alkaline carbon material catalyst, which is prepared by mixing and pyrolyzing industrial solid waste containing alkaline metal oxides and caking coal with high caking index, and performing steam activation and ammonia activation on the mixture, wherein the industrial solid waste is one or more of carbide slag, red mud and magnesium slag, the caking coal with high caking index is fat coal and/or coking coal with caking index of 95-110, and the caking coal and/or coking coal is used as a filter material of a particle bed dust remover, so that the synergistic effects of in-situ catalytic upgrading of high-dust-content pyrolysis tar gas and carbon precipitation inhibition are synchronously realized during dust removal.

Description

Alkaline carbon material catalyst, and preparation method and application thereof
Technical Field
The invention relates to a carbon material catalyst, in particular to an alkaline carbon material catalyst based on industrial solid waste. The alkaline carbon material catalyst can be applied to low-rank pulverized coal grading and quality-grading conversion utilization with a pyrolysis technology as a core, and is mainly used for quality control and carbon precipitation inhibition of dust-containing and oil-containing high-temperature pyrolysis tar gas in a granular bed dust removal process.
Background
The clean and efficient development and utilization of coal become important footholds and primary targets for the energy transformation development of China. The pyrolysis technology is an effective way for realizing clean and efficient utilization of coal, solid coal can be converted into valuable liquid tar through the pyrolysis technology, and the tar can be converted into high-quality clean fuel with high added values such as gasoline, kerosene, aviation fuel, diesel oil, naphtha and the like after deep processing.
The low-rank coal reserves are abundant and mainly use the pulverized coal in the global scope, in order to realize the large-scale grading, quality-grading, conversion and utilization of the low-rank pulverized coal and the green low-carbon development of the coal industry, various pyrolysis technologies using the low-rank pulverized coal as a raw material are developed at home and abroad in succession, but the problems of poor tar quality, high dust content and the like exist, so that a plurality of pyrolysis processes are still in a pilot-scale test or industrial demonstration stage.
The main reason is that the dust and heavy tar content in the dust-containing tar gas is high, and the volatile matter reaction is complex, so that the volatile matter re-reaction in the dust separation process and the tar quality are difficult to control.
In a low-temperature environment, heavy tar is easy to condense and agglomerate with dust to form a high-viscosity mixture which is attached to the wall surface of a container or a pipeline, so that process equipment such as a dust remover, the pipeline, a valve and the like is blocked; under the high-temperature environment, the volatile matter can be subjected to cracking, polycondensation, coking and other reactions under the action of the entrained particulate matters, so that the light tar is converted into the heavy tar, the problems of carbon precipitation, coking and the like are caused, the heavy tar and the precipitated carbon are adhered to the surfaces of solid-phase particles and a dust remover, the dust removal efficiency is reduced, and finally the system is blocked.
The problem of dust removal and carbon separation in tar gas leads to the device unable long period stable operation, is the key problem that present low order fine coal pyrolysis technology needs to solve urgently.
The granular bed dust collector is considered to be an effective method for controlling the dust content in tar by a filter material, but the problem of carbon precipitation caused by re-reaction due to high activity of volatile matters cannot be avoided. Heavy components and carbon precipitation in the tar are easily adhered to the surfaces of solid-phase particles, a dust remover and a pipeline, so that the dust removal efficiency is reduced, and finally, a dust removal system is blocked. Therefore, it is necessary to modulate the reaction behavior of the volatile matter to reduce the formation of carbon deposition, thereby alleviating the oil-dust separation pressure of the subsequent high-temperature tar gas.
Wang et al (Fuel, 2021, 285, 119156) used a bed of char particles for catalytic upgrading of volatiles to improve tar quality and significantly increase the yield of light ends and light tars in tar, however, no char formation of tar under the catalytic action of char is given. Wang et al (ACS Omega, 2021, 6, 3800-3808) prepared coke filter material for particulate bed dedusting of coal pyrolysis volatiles, and the results indicated that the coke effectively upgraded tar and inhibited carbon evolution.
The research proves that the carbon-based catalyst is used as the filter material of the granular bed dust remover, and the dust is filtered while the synergistic effect of volatile matter in-situ quality improvement and carbon precipitation inhibition can be realized.
However, the material and physical and chemical properties of the filter material greatly influence the thermal reaction behavior of the dust-containing tar gas in the dust removal process, thereby influencing the yield and quality of the tar and the carbon deposition content. The acid-base property of the catalyst also has an important influence on the quality of the coal pyrolysis tar, and the solid acid catalyst can improve the quality of the tar, but has stronger catalytic cracking activity on tar due to the existence of strong acid sites. On the one hand, the strong acidic sites cause the condensation of macromolecules to produce carbon deposits and the deactivation of catalysts (Fuel, 2022, 321, 124030); on the other hand, strong acid sites promote the conversion of tar to pyrolysis gas and char, resulting in a substantial reduction in tar yield and a reduction in the economics of the pyrolysis process (journal of fuel chemistry, 2021, 49 (03), 257-264). The solid base catalyst has relatively weak cracking effect on tar, can promote the dehydrogenation of hydrocarbon substances in the conversion process of pyrolysis volatile matters, further increases hydrogen-rich micromolecules in a pyrolysis system, reduces the polycondensation reaction among macromolecules, and can effectively inhibit carbon precipitation on the premise of ensuring the yield of the tar.
Therefore, the alkaline carbon-based catalyst with moderate activity is developed to be used as a particle bed filter material, on the premise of ensuring the yield of tar, the in-situ quality improvement and carbon precipitation inhibition of the dust-containing pyrolysis tar gas can be realized, and theoretical and technical support is provided for the development of the dust removal technology of the dust-containing pyrolysis tar gas particle bed.
The carbide slag is solid waste slag discharged when acetylene gas is prepared by hydrolyzing carbide; the red mud is solid waste slag discharged when aluminum oxide is extracted in the aluminum production industry; the magnesium slag is solid waste slag discharged in the magnesium smelting process of a magnesium metal plant. The common characteristics of the solid waste residues are that the solid waste residues are fine in particle size and alkaline, and the alkalinity is a great challenge for resource treatment and utilization of carbide slag, red mud, magnesium slag and the like. However, industrial solid wastes such as carbide slag, red mud and magnesium slag contain CaO and Fe 2 O 3 Basic active components such as MgO, and the like, and metal componentsNot only can adjust the acidity and alkalinity of the carbon-based catalyst, but also can catalyze and crack heavy tar and activate micromolecule hydrogen supply in volatile matters, thereby inhibiting carbon precipitation and effectively improving the quality of the tar.
Based on the current situation, the reaction path of the volatile matter is modulated by developing and developing an alkaline carbon material catalyst based on industrial solid waste, and the synergistic effect of in-situ upgrading of the high-dust-content tar gas and carbon precipitation inhibition can be realized in the dust removal process of the granular bed. In addition, the alkaline carbon material catalyst is prepared by the mixed pyrolysis method, and a novel high-added-value resource treatment approach is provided for alkaline industrial solid wastes such as carbide slag, red mud and magnesium slag.
Disclosure of Invention
The invention aims to provide an alkaline carbon material catalyst, which is used as a granular bed filter material to synchronously realize the synergistic effect of in-situ quality improvement and carbon precipitation inhibition of high-dust-content pyrolysis tar gas in the dedusting process of a granular bed, aiming at the problems that heavy components in the low-rank pulverized coal pyrolysis dust-containing tar gas are more, volatile matter reacts again to precipitate carbon and block pipelines and the like.
The invention firstly provides an economical and feasible preparation method of an alkaline carbon material catalyst, which is used for preparing a molded alkaline carbon material catalyst with moderate activity while realizing the reutilization of industrial solid wastes, so as to be applied to the filtration and dust removal of a granular bed, and simultaneously lightening tar and inhibiting carbon precipitation.
The method for preparing the alkaline carbon material catalyst by utilizing the industrial solid waste is to mix and pyrolyze the industrial solid waste containing the alkaline metal oxide and the caking coal with high caking index, and prepare the alkaline carbon material catalyst by water vapor activation and ammonia activation.
Specifically, the invention provides a detailed preparation method of the alkaline carbon material catalyst.
1) After crushing the industrial solid waste containing the alkaline metal oxide and the caking coal with high caking index, screening the crushed industrial solid waste with the particle size of less than 0.15mm, and fully kneading the crushed industrial solid waste and the caking coal according to the proportion of 1 to 20 weight percent of the industrial solid waste to obtain a mixed material.
2) And wetting the mixed materials with water, and pressing and forming to obtain the molded coal.
3) Under the condition of air isolation, the molded coal is pressurized and heated to 450-950 ℃ for pyrolysis to prepare the molded carbon material with interconnected pore passages.
4) Heating the formed carbon material to 850-950 ℃ under inert atmosphere, introducing steam for activation, further forming holes on the formed carbon material, introducing ammonia for activation, endowing the formed carbon material with alkaline acting groups, and cooling to obtain the alkaline carbon material catalyst simultaneously containing alkaline metal oxides and the acting groups.
In the raw materials for preparing the alkaline carbon material catalyst, the industrial solid waste containing the alkaline metal oxide can include but is not limited to any one or more of carbide slag, red mud, magnesium slag and the like.
The caking coal with a high caking index specifically refers to fat coal and/or coking coal with a caking index of 95-110.
Specifically, the present invention preferably adds water in an amount of 10 to 15wt% of the mass of the mixture to wet the mixture.
Specifically, the wet mixed material is preferably subjected to compression molding at a pressure of 3 to 9 MPa.
Specifically, when the briquette is pyrolyzed, 700-1200N/m is applied to the briquette 2 The pressure of (a).
More specifically, the briquette is preferably heated to 450-950 ℃ at the heating rate of 0.5-2.5 ℃/min and pyrolyzed at the constant temperature for 1.5-2.5 h to prepare the molded carbon material.
Specifically, the molded carbon material is heated to 750-950 ℃ at the heating rate of 5-10 ℃/min under the inert atmosphere, water vapor is introduced for activation for 1-2 h, and ammonia gas is introduced for activation for 1-2 h to prepare the alkaline carbon material catalyst.
More specifically, the ammonia gas in the invention is a mixed gas with nitrogen as a balance gas and 30-70% of ammonia gas by volume.
The mixing manner of the present invention for obtaining the mixed material by kneading the alkaline metal oxide-containing industrial solid waste and the caking coal with a high caking index can be various, for example, it can include but is not limited to mixing 1-20 wt% of industrial solid waste and 80-99 wt% of fat coal or coking coal; 1-20 wt% of industrial solid waste, 30-50 wt% of fat coal and 30-69 wt% of coking coal are mixed, and the like.
The alkaline carbon material catalyst prepared by the method can effectively modulate the physical and chemical characteristics of the carbon material, and effectively regulate the content of metal active components and the acidity and alkalinity by modulating the mass fraction of industrial solid waste; the pore structure of the carbon material catalyst is effectively regulated and controlled by regulating the proportion of the caking coal and the activation time.
Therefore, the alkaline carbon material catalyst can be used as a filter material of a granular bed dust remover and used for filtering, dedusting and catalytic upgrading of low-rank pulverized coal pyrolysis dust-containing tar gas.
In the process of filtering and dedusting the particle bed of the low-rank pulverized coal pyrolysis dust-containing tar gas, the alkaline carbon material catalyst can crack heavy tar in the tar gas and effectively activate CH in volatile matters 4 、CO 2 、H 2 、C 2 H 6 And C 3 H 6 The small molecular gas compounds promote the migration of hydrogen free radicals and the collision with other free radicals, so that the cracking fragments of the large molecular free radicals in the tar gas are stabilized, and the occurrence of polycondensation reaction and the generation of carbon precipitation are avoided.
The alkaline carbon material catalyst is used as a filter material of a particle bed dust remover, the synergistic effect of in-situ quality improvement and carbon precipitation inhibition of the high-dust-content tar gas is synchronously realized in the dust removal process of the particle bed, and the problems that the pyrolysis dust-content tar gas contains a large amount of heavy components, and volatile matters react again to precipitate carbon to block pipelines are solved.
In addition, the alkaline carbon material catalyst prepared by the invention is beneficial to promoting the removal of heterocyclic compounds containing N and S and oxygen-containing compounds in the tar, generating more monocyclic aromatic hydrocarbons and effectively catalyzing and upgrading the tar.
Furthermore, the alkaline carbon material catalyst can also be used for catalyzing the catalytic reforming reaction of tar in the biomass and coal gasification processes, promoting the conversion of high-carbon components to low-carbon components in the tar, effectively eliminating the tar and inhibiting carbon precipitation, and further prolonging the service life of the carbon material.
Drawings
FIG. 1 is an SEM photograph of catalysts of examples 1-3 for preparing basic carbon materials.
FIG. 2 is an XRD pattern of catalysts for preparing basic carbon materials according to examples 1 to 3.
FIG. 3 shows the tar yield after catalytic upgrading of pyrolysis dust-containing tar gas by an alkaline carbon material catalyst.
FIG. 4 is a comparison of relative contents of chemical components of pyrolyzed dust-containing tar gas after catalytic upgrading by an alkaline carbon material catalyst.
FIG. 5 is a comparison of tar yields after catalytic reforming of biomass gasification tar gas over an alkaline carbon material catalyst.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are provided only for more clearly illustrating the technical solution of the present invention so that those skilled in the art can well understand and utilize the present invention, and do not limit the scope of the present invention.
The names and abbreviations of the experimental methods, production processes, instruments and equipment involved in the examples and comparative examples of the present invention are those commonly known in the art and are clearly and clearly understood in the relevant fields of use, and those skilled in the art can understand the conventional process steps and apply the corresponding equipment according to the names and perform the operations according to the conventional conditions or conditions suggested by the manufacturers.
The various starting materials or reagents used in the examples of the present invention and comparative examples are not particularly limited in terms of their sources, and are all conventional products commercially available. They may also be prepared according to conventional methods well known to those skilled in the art.
Example 1.
The method comprises the steps of taking industrial solid waste carbide slag and cohesive willow coking coal as raw materials, respectively crushing and screening until the particle size is smaller than 0.15mm, mixing the carbide slag and the willow coking coal according to the mass ratio of 1: 9, and fully kneading to obtain a mixed sample.
And mixing the mixed sample with deionized water according to the mass ratio of 10: 1, fully and uniformly stirring, placing the mixture into a metal mold, and molding on a pressure molding machine at the pressure of 7MPa to obtain the molded coal.
Placing the molded coal in a corundum crucible, applying 1200N/m on the surface 2 The temperature is raised from the room temperature to 500 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 2 hours, and then the muffle furnace is cooled to the room temperature to prepare the molded carbon material.
Placing the formed carbon material in a tubular furnace, heating the formed carbon material from room temperature to 750 ℃ at the heating rate of 10 ℃/min under the inert atmosphere, introducing 0.042 mL/(min-g) of water vapor for activation for 2h, introducing 50% ammonia mixed gas (nitrogen is used as balance gas) for activation for 1h, and cooling to room temperature to obtain the alkaline carbon material catalyst which is named as CM-1.
Example 2.
The industrial solid waste carbide slag and the willow coking coal with caking property are taken as raw materials, respectively crushed and sieved until the particle size is less than 0.15mm, and then the raw materials are mixed according to the mass ratio of the carbide slag to the willow coking coal of 3: 17, and fully kneaded to obtain a mixed sample.
And mixing the mixed sample with deionized water according to the mass ratio of 10: 1, fully and uniformly stirring, placing the mixture into a metal mold, and forming the mixture on a pressure forming machine under the pressure of 6.5MPa to obtain the molded coal.
Placing the molded coal in a corundum crucible, and applying 1200N/m on the surface 2 The temperature is raised from the room temperature to 850 ℃ at the heating rate of 1 ℃/min, the temperature is kept for 2 hours, and then the muffle furnace is cooled to the room temperature to prepare the formed carbon material.
Placing the formed carbon material in a tubular furnace, heating the formed carbon material to 850 ℃ from room temperature at the heating rate of 10 ℃/min under the inert atmosphere, introducing 0.042 mL/(min-g) of water vapor for activation for 2h, introducing 45% ammonia mixed gas (nitrogen is used as balance gas) for activation for 1h, and cooling to room temperature to obtain the alkaline carbon material catalyst which is named as CM-2.
Example 3.
The method comprises the steps of taking industrial solid waste carbide slag and cohesive willow coking coal as raw materials, respectively crushing and screening until the particle size is smaller than 0.15mm, mixing the carbide slag and the willow coking coal according to the mass ratio of 1: 4, and fully kneading to obtain a mixed sample.
And mixing the mixed sample with deionized water according to the mass ratio of 10: 1, fully and uniformly stirring, placing the mixture into a metal mold, and molding on a pressure molding machine at the pressure of 7MPa to obtain the molded coal.
Placing the molded coal in a corundum crucible, and applying 1200N/m on the surface 2 The temperature is increased from the room temperature to 900 ℃ at the temperature increase rate of 1.5 ℃/min, the temperature is kept for 1.5h, and then the muffle furnace is cooled to the room temperature to prepare the molded carbon material.
Placing the formed carbon material in a tube furnace, heating from room temperature to 900 ℃ at the heating rate of 10 ℃/min under the inert atmosphere, introducing 0.042 mL/(min-g) of water vapor for activation for 1.5h, introducing 60% ammonia gas mixed gas (nitrogen is used as balance gas) for activation for 2h, cooling to room temperature, and obtaining the alkaline carbon material catalyst which is named as CM-3.
Example 4.
The industrial solid waste red mud and the cohesive willow-forest coking coal are taken as raw materials, respectively crushed and sieved until the particle size is less than 0.15mm, and then the red mud and the willow-forest coking coal are mixed according to the mass ratio of 1: 9, and are fully kneaded to obtain a mixed sample.
And mixing the mixed sample with deionized water according to the mass ratio of 10: 1, fully and uniformly stirring, placing the mixture into a metal mold, and molding on a pressure molding machine at the pressure of 7MPa to obtain the molded coal.
Placing the molded coal in a corundum crucible, and applying 800N/m on the surface 2 The temperature is raised from room temperature to 750 ℃ at the temperature raising rate of 1 ℃/min, the temperature is kept for 2 hours, and then the muffle furnace is cooled to room temperature to prepare the formed carbon material.
Placing the formed carbon material in a tube furnace, heating from room temperature to 950 ℃ at a heating rate of 10 ℃/min under an inert atmosphere, introducing 0.042 mL/(min-g) of water vapor for activation for 2 hours, introducing 50% ammonia gas mixed gas (nitrogen is used as balance gas) for activation for 1 hour, and cooling to room temperature to obtain the alkaline carbon material catalyst which is named as CM-4.
Example 5.
The method comprises the steps of taking industrial solid waste magnesium slag and caking kalimeris indica rich coal as raw materials, respectively crushing and screening until the particle size is less than 0.15mm, mixing according to the mass ratio of the magnesium slag to the kalimeris indica rich coal of 1: 4, and fully kneading to obtain a mixed sample.
And mixing the mixed sample with deionized water according to the mass ratio of 10: 1, fully and uniformly stirring, placing the mixture into a metal mold, and molding on a pressure molding machine at the pressure of 7MPa to obtain the molded coal.
Placing the molded coal in a corundum crucible, and applying 1200N/m on the surface 2 The temperature is raised from the room temperature to 950 ℃ at the temperature raising rate of 1.5 ℃/min, the temperature is kept for 1.5h, and then the muffle furnace is cooled to the room temperature to prepare the molded carbon material.
Placing the formed carbon material in a tubular furnace, heating the formed carbon material to 900 ℃ from room temperature at the heating rate of 5 ℃/min under the inert atmosphere, introducing 0.042 mL/(min-g) of water vapor for activation for 1.5h, introducing 50% ammonia mixed gas (nitrogen is used as balance gas) for activation for 1h, and cooling to room temperature to obtain the alkaline carbon material catalyst which is named as CM-5.
FIG. 1 shows SEM images of basic carbon catalysts, represented by CM-1 (a), CM-2 (b), and CM-3 (c), respectively. As can be seen from fig. 1, each basic carbon material catalyst has a rich pore structure and uniformly distributed pores.
The alkaline carbon material catalyst is a material with a network structure formed by mutually communicated or closed holes, so that the diffusion and mass transfer of macromolecular compounds in the dust-containing tar gas are promoted, the polycondensation reaction among the macromolecular compounds is inhibited to a certain extent, and the generation of carbon precipitation is inhibited. In addition, the communicated pore structure can increase the dust holding capacity of the particle bed and reduce the pressure drop of the bed layer, which is beneficial to prolonging the service life of the particle bed.
FIG. 2 further shows XRD patterns of CM-1, CM-2 and CM-3. The alkali metal calcium in the alkaline carbon material catalyst prepared by taking carbide slag as a raw material is mainly Ca (OH) 2 CaO and CaS, and the presence of metal active components can promote the cracking of heavy tar and the generation of small molecular gas compoundsThereby effectively upgrading the tar.
Example 1 is applied.
The basic carbon material catalyst prepared in the above examples 1 to 5 was examined and verified as the filter material of the granular bed dust remover, and the influence on the thermal conversion behavior of the pyrolysis dust-containing tar gas and the catalytic upgrading performance thereof were examined and verified by using the long flame coal in Xinjiang area with the particle size of 0.25 to 0.43mm as the research object and using the fixed bed reaction device as the granular bed dust remover.
The long flame coal and the alkaline carbon material catalyst prepared in the embodiment 1-5 are respectively filled in a two-stage quartz tube reactor according to the mass ratio of 2: 1, wherein the long flame coal is heated to 600 ℃ in a nitrogen atmosphere for fast pyrolysis, and the generated dust-containing pyrolysis tar gas is subjected to in-situ catalytic upgrading through an alkaline carbon material catalyst filtering material heated to 500 ℃.
And collecting the catalytically upgraded tar by a condensing system, calculating the yield of the tar, and detecting and analyzing the chemical composition in the tar by using GC-MS.
Since the residence time of the dust-containing tar gas can affect the reaction behavior of the volatile matters in the particle bed dust remover, the solid acid catalyst gamma-Al 2 O 3 The pyrolysis dust-containing tar gas also has the catalytic upgrading effect, so that the inert substance quartz sand (QB) and the solid acid catalyst gamma-Al are respectively carried out according to the method 2 O 3 Control experiment of (5).
From the tar yield of fig. 3, it can be seen that QB is relatively inert and does not have a catalytic cracking effect on the pyrolysis of the dusty tar gas, so that the tar yield under the effect of QB is the highest. After the pyrolysis dust-containing tar gas is catalyzed and upgraded by granular bed filter materials (CM-1 to CM-5), the tar yield is relatively high and is higher than that of gamma-Al 2 O 3 Tar yield under action. This is mainly gamma-Al 2 O 3 Due to the existence of the strong acid sites, the cracking capability of tar is stronger, which causes the conversion of tar to carbon precipitation and pyrolysis gas, and the yield of tar is greatly reduced.
On the contrary, CM-1 to CM-5 promote the mass transfer of macromolecular compounds based on the interconnected pore channel structures and the alkalinity thereof, promote the dehydrogenation of hydrocarbon substances to generate hydrogen-rich micromolecules, inhibit the polycondensation of the macromolecular substances and obviously reduce the carbon precipitation yield. Therefore, the alkaline carbon material catalyst ensures the tar yield to a certain extent, inhibits the conversion of tar to carbon separation and pyrolysis gas, and improves the economy of the pyrolysis process.
Furthermore, as can be seen from the relative amounts of chemical constituents in the tar in FIG. 4, gamma-Al is observed compared to QB 2 O 3 Under the action of the alkaline carbon material catalyst, the relative contents of oxygen-containing compounds and heterocyclic compounds containing N and S in the tar are reduced, the relative content of monocyclic aromatic hydrocarbon is increased, and the alkaline carbon material catalyst and gamma-Al are added 2 O 3 Effectively improves the tar and changes the chemical composition in the tar. Under the condition that the chemical compositions of the tar and the tar are similar and the relative contents are equivalent, the yield of the tar under the action of the alkaline carbon material catalyst is higher, and the alkaline carbon material catalyst is proved to have more advantages when being used as a granular bed filter material.
Application example 2.
A corncob biomass with a particle size of 0.25-0.43 mm was selected as a research object, and the influence of the alkaline carbon material catalyst prepared in the above examples 1-5 on the catalytic reforming reaction of tar in the biomass gasification process was examined and verified by using a fixed bed reaction apparatus.
Corncob biomass and the alkaline carbon material catalyst prepared in the examples 1 to 5 were filled in a two-stage quartz tube reactor respectively at a mass ratio of 2: 1 with 50% steam (N) 2 As a balance gas) to heat the corn cob biomass to 950 ℃ for gasification, carrying out in-situ catalytic reforming on the generated biomass tar gas by using an alkaline carbon material catalyst heated to 750 ℃, collecting tar and calculating the yield of the tar.
The retention time of the dust-containing tar gas can influence the reaction behavior of volatile matters in the granular bed dust remover, and the solid acid catalyst gamma-Al 2 O 3 The method also has catalytic upgrading effect on the pyrolysis of the dust-containing tar gas, so that the inert substance quartz sand (QB) and the solid acid catalyst gamma-Al are respectively carried out according to the method 2 O 3 Control experiment of (1).
Due to the solid acid catalyst gamma-Al 2 O 3 Also has catalytic reforming effect on biomass tar gas, so that commercial gamma-Al is carried out according to the above method 2 O 3 Control experiment of catalyst.
In addition, for the same gamma-Al 2 O 3 And the alkaline carbon material catalyst, and multiple in-situ catalytic reforming experiments are carried out to measure the cycle service life of the catalyst.
As can be seen from the tar yield of FIG. 5, the alkaline carbon catalyst can promote the catalytic reforming reaction of tar and steam, increase the tar elimination efficiency, and the action effect and the gamma-Al 2 O 3 The catalyst is equivalent.
However, the results of the cycle life test showed that γ -Al 2 O 3 The catalyst is deactivated after being used once, and the alkaline carbon catalyst may be reused and has service life longer than that of gamma-Al 2 O 3 。
Therefore, the alkaline carbon material catalyst has better carbon deposit resistance than a solid acid catalyst, and is more suitable to be used as a catalyst for catalytic reforming of biomass gasification tar.
The above embodiments of the present invention are not intended to be exhaustive or to limit the invention to the precise form disclosed. Various changes, modifications, substitutions and alterations to these embodiments will be apparent to those skilled in the art without departing from the principles and spirit of this invention.

Claims (10)

1. A preparation method of an alkaline carbon material catalyst comprises the steps of mixing and pyrolyzing industrial solid waste containing alkaline metal oxides and caking coal with high caking index, activating with steam and activating with ammonia gas to prepare the alkaline carbon material catalyst, wherein the industrial solid waste containing the alkaline metal oxides is one or more of carbide slag, red mud and magnesium slag, and the caking coal with the high caking index is fat coal and/or coking coal with the caking index of 95-110.
2. The method for preparing an alkaline carbon catalyst according to claim 1, comprising the steps of:
1) Crushing the industrial solid waste containing the alkaline metal oxide and the caking coal with high caking index, screening the crushed industrial solid waste and the caking coal with high caking index, and fully kneading the crushed industrial solid waste and the caking coal with high caking index according to the proportion of 1 to 20 weight percent of the industrial solid waste to obtain a mixed material;
2) Wetting the mixed material with water, and pressing and forming to obtain molded coal;
3) Pressurizing and heating the molded coal to 450-950 ℃ under the condition of air isolation to pyrolyze and prepare a molded carbon material;
4) And heating the formed carbon material to 850-950 ℃ under an inert atmosphere, introducing steam for activation, introducing ammonia for activation, and cooling to obtain the alkaline carbon material catalyst.
3. The method for preparing an alkaline carbon catalyst according to claim 2, wherein water is added to the mixture in an amount of 10 to 15wt% based on the mass of the mixture.
4. The method for preparing an alkaline carbon catalyst according to claim 2, wherein the wet mixture is press-molded at a pressure of 3 to 9 MPa.
5. The method for preparing an alkaline carbon catalyst according to claim 2, wherein 700 to 1200N/m is applied to the molded coal 2 Is subjected to pyrolysis.
6. The preparation method of the alkaline carbon material catalyst according to claim 2, characterized in that the temperature of the molded coal is raised to 450-950 ℃ at a heating rate of 0.5-2.5 ℃/min, and the molded coal is pyrolyzed for 1.5-2.5 h at a constant temperature.
7. The method for preparing the alkaline carbon material catalyst according to claim 2, wherein the temperature of the formed carbon material is raised to 750-950 ℃ at a temperature raising rate of 5-10 ℃/min under an inert atmosphere, water vapor is introduced for activation for 1-2 h, and ammonia gas is introduced for activation for 1-2 h.
8. The basic carbon catalyst prepared by the preparation method according to any one of claims 1 or 2.
9. The use of the basic carbon material catalyst of claim 8 as a filter material for a particle bed dust collector in the filtration, dust removal and catalytic upgrading of low rank pulverized coal pyrolysis dust-laden tar gas.
10. The use of the basic carbon catalyst of claim 8 for catalyzing the catalytic reforming reaction of tar in biomass and coal gasification processes.
CN202211079369.7A 2022-09-05 2022-09-05 Alkaline carbon material catalyst, and preparation method and application thereof Pending CN115364840A (en)

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