CN114100618B - Iron-based porous carbon catalyst and preparation method and application thereof - Google Patents

Iron-based porous carbon catalyst and preparation method and application thereof Download PDF

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CN114100618B
CN114100618B CN202111520229.4A CN202111520229A CN114100618B CN 114100618 B CN114100618 B CN 114100618B CN 202111520229 A CN202111520229 A CN 202111520229A CN 114100618 B CN114100618 B CN 114100618B
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iron
porous carbon
catalyst
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precursor
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CN114100618A (en
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姜海峰
张钰
洪文鹏
刘海鹏
杨尘
董佳欣
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Northeast Electric Power University
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Northeast Dianli University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C10J3/20—Apparatus; Plants
    • 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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • 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
    • C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
    • C10J3/60—Processes
    • C10J3/64—Processes with decomposition of the distillation products
    • C10J3/66—Processes with decomposition of the distillation products by introducing them into the gasification zone
    • 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
    • C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0916—Biomass
    • 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as 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
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0983—Additives
    • C10J2300/0986—Catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides an iron-based porous carbon catalyst, a preparation method and application thereof, and belongs to the technical field of biomass tar catalytic reforming materials. Dehydrating conch meat to obtain a porous carbon precursor; injecting the iron-containing metal active component solution into the porous carbon precursor, soaking the porous carbon precursor in an alkaline environment, and then drying the soaked solid to obtain an iron-based porous carbon precursor; mixing cetyl trimethyl ammonium bromide, ammonium bicarbonate and a pore-forming agent to obtain a mixture; coating the mixture on the surface of the iron-based porous carbon precursor to obtain a catalyst precursor; the catalyst precursor is subjected to solid-phase synthesis to obtain the iron-based porous carbon catalyst, so that migration loss of active metal components on the surface of a carbon carrier is effectively avoided, the catalyst is used for catalyzing the biomass tar steam reforming process, and the catalyst has the characteristics of high tar conversion rate, strong catalytic efficiency, sintering resistance, carbon deposit resistance, multiple recycling times and the like, and has wide application prospects in the fields of organic solid waste conversion and the like.

Description

Iron-based porous carbon catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of biomass tar catalytic reforming materials, in particular to an iron-based porous carbon catalyst, a preparation method and application thereof.
Background
Biomass combustion power generation is one of important ways for relieving the current energy crisis and achieving the aim of carbon neutralization. However, a large amount of tar (30% -50%) is generated in the combustion process of the boiler by biomass, so that the operation efficiency of the boiler is obviously reduced, the biomass is easily condensed on the inner wall of a pipeline, and the operation safety of related equipment is seriously affected. The tar problem has become one of the bottleneck problems that restrict the sustainable utilization of biomass in the power field. The addition of catalysts in biomass pyrolysis/combustion systems is currently one of the most effective ways to inhibit tar formation. Under the action of the catalyst in the reaction system, the energy required by breaking bonds of biomass tar macromolecules is obviously reduced, and the biomass tar macromolecules are promoted to continuously undergo reforming reaction to form CO and CH 4 、H 2 And small molecular components, thereby effectively inhibiting tar formation. Thus, the performance of the catalyst is an important factor in determining tar reforming efficiency.
The iron-based porous carbon catalyst has higher catalytic activity and is widely applied to the field of catalytic reforming of biomass tar. The oxidation-reduction reaction caused by the valence change of Fe element promotes the activation and the reformation of tar molecules and promotes the tar molecules to CH 4 、H 2 And the conversion of small molecules and the like, and the high-value conversion and utilization of tar are realized.
At present, the conventional method for preparing the iron-based catalyst is to load iron particles on carriers/media such as molecular sieves, semicoke, coal, calcium oxide, porous carbon and the like by means of dipping, spraying and the like to form an iron-supported catalyst which is applied to a tar reforming reaction process, for example, chinese patent CN202011412790.6 discloses a method for preparing the iron-based catalyst by taking ferric nitrate as an active component and utilizing various media (semicoke, H-ZSM-5 molecular sieves, USY molecular sieves and the like) as carriers; chinese patent CN201310302954.3 discloses a heavy oil hydrogenation iron-based catalyst and application thereof, wherein a mixed solution of ferric nitrate and an auxiliary agent is slowly dripped into a catalyst carrier to prepare a semi-finished catalyst, and then the catalyst is prepared by high-temperature high-pressure hydrogenation and vulcanization; chinese patent CN201010272981.7 discloses a method for preparing an iron-based catalyst using coal fines as a carrier, wherein an iron-containing solution is loaded on the surface of coal fines by spraying, and then the catalyst is prepared by dehydration and drying.
The preparation method of the iron-based catalyst comprises the steps of firstly preparing a carrier material, then loading active components rich in iron particles on the carrier, drying, roasting and the like to obtain a catalyst finished product, wherein the iron particles and the carrier have low surface crosslinking action strength and poor stability in the process, so that the catalyst has poor activity and is less in recycling times.
Disclosure of Invention
In view of the above, the invention aims to provide an iron-based porous carbon catalyst, and a preparation method and application thereof. The iron-based porous carbon catalyst prepared by the invention has high catalytic activity and multiple recycling times.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an iron-based porous carbon catalyst, which comprises the following steps:
dehydrating conch meat to obtain a porous carbon precursor;
injecting the iron-containing metal active component solution into the porous carbon precursor, soaking the porous carbon precursor in an alkaline environment, and then drying the soaked solid to obtain an iron-based porous carbon precursor;
mixing cetyl trimethyl ammonium bromide, ammonium bicarbonate and a pore-forming agent to obtain a mixture;
coating the mixture on the surface of the iron-based porous carbon precursor to obtain a catalyst precursor;
and (3) carrying out solid phase synthesis on the catalyst precursor to obtain the iron-based porous carbon catalyst.
Preferably, the conch comprises one or more of cat eye snail, flat jade snail, pseudopurple jade snail and green wave dragonfly snail.
Preferably, the iron-containing metal active component solution comprises a soluble iron salt, a soluble magnesium salt and a soluble zirconium salt.
Preferably, the catalyst precursor is loaded with a metal active component, and the metal active component forms a metal component (Fe 2 O 3 ) x (MgO) y (ZrO 2 ) z Wherein x is 0.019 to 0.060, y is 0.012 to 0.046, and z is 0.021 to 0.035.
Preferably, the mass ratio of the cetyl trimethyl ammonium bromide, the ammonium bicarbonate and the pore-forming agent in the mixture is 1.0-2.7: 2.0 to 3.0:2.2 to 4.5.
Preferably, the pore-forming agent comprises one or more of glucose, maltose and fructose.
Preferably, the solid phase synthesis comprises: sequentially presintering and calcining;
the presintering is carried out in a protective atmosphere, the presintering temperature is 300-500 ℃, the heat preservation time is 10min, and the heating rate from the temperature rise to the presintering temperature is 2-5 ℃/min;
the calcination is carried out in a protective atmosphere and CO 2 The calcination is carried out under the mixed atmosphere of 700-900 ℃, the heat preservation time is 1.5-2 h, and the temperature rising rate from the temperature of the calcination to the temperature of 5-10 min/DEG C.
Preferably, the solid phase synthesis further comprises cooling to room temperature, wherein the cooling rate for cooling to room temperature is 5-10 min/DEG C.
The invention also provides the iron-based porous carbon catalyst prepared by the preparation method of the technical scheme, and the iron-based porous carbon catalyst comprises a carbon carrier and an iron-containing active component loaded on the surface of the carbon carrier.
The invention also provides application of the iron-based porous carbon catalyst in biomass tar steam reforming.
The invention provides a preparation method of an iron-based porous carbon catalyst, which comprises the following steps: dehydrating conch meat to obtain a porous carbon precursor; injecting the iron-containing metal active component solution into the porous carbon precursor, soaking the porous carbon precursor in an alkaline environment, and then drying the soaked solid to obtain an iron-based porous carbon precursor; mixing cetyl trimethyl ammonium bromide, ammonium bicarbonate and a pore-forming agent to obtain a mixture; coating the mixture on the surface of the iron-based porous carbon precursor to obtain a catalyst precursor; and (3) carrying out solid phase synthesis on the catalyst precursor to obtain the iron-based porous carbon catalyst.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a mode of preparing a coke carrier and then loading metal is abandoned, and the active components of the target metal are uniformly dispersed in the porous carbon precursor in a penetrating way by utilizing the strong water absorption characteristic of the conch meat, so that the binding force between the active components of the target metal and the carrier is good, the catalytic reforming activity of the metal components is fully exerted, meanwhile, the thermal migration loss of the metal components in the tar reforming process is effectively avoided, and the stability of the iron-based porous carbon catalyst is further improved.
Further, the invention takes Fe as main active component, and MgFe is obtained by introducing Mg and Zr metal components and solid phase synthesis 2 O 4 ，MgZr 7 O 15 ZrO (ZrO) 2 The crystal phase forms an Fe-Mg-Zr-O active center, so that the efficiency and the thermal stability of the catalyst for reforming tar are further improved, the excellent carbon deposition resistance of the catalyst is realized by utilizing the complementary synergistic effect of oxygen supply among different metal components, the catalyst toxicity resistance of the iron-based porous carbon catalyst is improved, and the recycling times of the catalyst are further increased.
Furthermore, the preparation process of the catalyst does not need repeated roasting, only needs presintering and calcining, does not need high-pressure hydrogenation activation treatment, and the prepared catalyst can be directly used as a finished product, has simple process, convenient operation and easy popularization and implementation.
The porous carbon precursor adopted by the invention is prepared from common conch varieties, is low in cost and easy to obtain, does not need tedious pretreatment before use, has low production cost, and is suitable for mass production.
The catalyst prepared by the method is used for biomass tar steam reforming, and the result shows that the catalyst prepared by the method has the characteristics of high activity, strong catalytic efficiency, sintering resistance, carbon deposit resistance, multiple recycling times and the like, and provides possibility for catalyzing biomass tar steam reforming with low cost and high efficiency.
The invention also provides the iron-based porous carbon catalyst prepared by the preparation method, and the catalyst prepared by the preparation method has the advantages of uniform dispersion of active components, excellent thermal stability, high catalytic reforming efficiency, multiple times of recycling and strong carbon deposition resistance.
Drawings
FIG. 1 is a graph of reforming conversion of the iron-based porous carbon catalytic tar prepared in example 5 at various cycle times;
FIG. 2 is an X-ray diffraction pattern of the iron-based porous carbon catalyst prepared in example 5;
fig. 3 is SEM images of the iron-based porous carbon catalyst prepared in example 5 at different magnifications.
Detailed Description
The invention provides a preparation method of an iron-based porous carbon catalyst, which comprises the following steps of;
dehydrating conch meat to obtain a porous carbon precursor;
injecting the iron-containing metal active component solution into the porous carbon precursor, soaking the porous carbon precursor in an alkaline environment, and then drying the soaked solid to obtain an iron-based porous carbon precursor;
mixing cetyl trimethyl ammonium bromide, ammonium bicarbonate and a pore-forming agent to obtain a mixture;
coating the mixture on the surface of the iron-based porous carbon precursor to obtain a catalyst precursor;
and (3) carrying out solid phase synthesis on the catalyst precursor to obtain the iron-based porous carbon catalyst.
In the invention, the conch preferably comprises one or more of cat eye snail, flat jade snail, pseudopurple jade snail and green wave dragonfly snail.
In the present invention, it is preferable that the conch meat is taken out after the conch spit sand is washed.
The invention preferably adopts an extrusion method to extrude the moisture contained in the snail meat clean for standby. The specific manner of extrusion is not particularly limited in the present invention, and methods well known to those skilled in the art may be employed.
The method comprises the steps of injecting an iron-containing metal active component solution into the porous carbon precursor, soaking the porous carbon precursor in an alkaline environment, and drying the soaked solid to obtain the iron-based porous carbon precursor.
In the present invention, the iron-containing metal active ingredient solution preferably includes a soluble iron salt, a soluble magnesium salt and a soluble zirconium salt. The specific kinds of the soluble iron salt, the soluble magnesium salt and the soluble zirconium salt are not particularly limited in the present invention, and may be any kind known to those skilled in the art, and specifically, such as iron nitrate, magnesium nitrate or zirconium nitrate.
In a specific embodiment of the present invention, the mass ratio of the ferric nitrate, the magnesium nitrate and the zirconium nitrate is preferably 9.67:4.44:12.87, 10.88:2.97:15.02, 12.09:4.3:9.02, 13.3:2.97:10.73, 14.51:2.81:9.02.
The specific mode for preparing the iron-containing metal active component solution is not particularly limited, and a mode well known to a person skilled in the art is adopted, specifically, for example, a soluble ferric salt, a soluble magnesium salt and a soluble zirconium salt are dissolved in deionized water, and ethanol and acetic acid are added into the obtained mixed solution, so that the iron-containing metal active component solution is obtained.
In the invention, the volume ratio of deionized water, ethanol and acetic acid is preferably 30-50: 2 to 5: 1-3, in a specific embodiment of the invention, preferably 30:2.5:1.5, 35:3: 2. 40:3.5: 2. 46:3.5:2.3 or 50:5:3. in the present invention, the ethanol and acetic acid mainly play a role in dispersing the metal component solution.
In the invention, the mass ratio of the iron-containing metal active component solution to the porous carbon precursor is preferably 0.1-0.4: 1.
the method preferably adopts a trace multiple injection mode to uniformly convey the iron-containing metal active component solution into the porous carbon precursor in a penetrating way.
In the present invention, the alkaline environment is preferably an aqueous ammonia solution with a mass fraction of 25%. In the present invention, the alkaline environment functions: on the one hand, metal ions are precipitated, and on the other hand, nitrogen elements are provided in the snail meat, so that the metal components are better combined with the snail meat. In the invention, the ammonia water solution does not introduce other metal ions into the snail meat, and further does not influence the tar reforming performance.
In the present invention, the soaking temperature is preferably 70 to 90 ℃, more preferably 75 ℃, and the soaking time is preferably 15 to 30min, more preferably 16min. In the present invention, the soaking is preferably performed under ultrasonic conditions, and specific parameters of the ultrasonic wave are not particularly limited in the present invention, and may be performed in a manner well known to those skilled in the art.
In the present invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 60 to 80 ℃, preferably 70 ℃ and the time is preferably 12 hours.
In the invention, cetyl trimethyl ammonium bromide, ammonium bicarbonate and a pore-forming agent are mixed to obtain a mixture.
In the invention, the mass ratio of the cetyl trimethyl ammonium bromide, the ammonium bicarbonate and the pore-forming agent in the mixture is preferably 1.0-2.7: 2.0 to 3.0:2.2 to 4.5, more preferably 1.2:2.3:3.2, 1.4:2.5:3.5, 2.5:2: 3. 2:2.7:4 or 1.5:2.3:2.5. in the invention, the cetyl trimethyl ammonium bromide is used as a surfactant to enhance the dispersion of the metal solution into the iron-based porous carbon precursor, and the ammonium bicarbonate and the pore-forming agent play roles in pore-forming and pore-expanding.
In the present invention, the pore-forming agent preferably includes one or more of glucose, maltose and fructose.
After the mixture and the iron-based porous carbon precursor are obtained, the mixture is coated on the surface of the iron-based porous carbon precursor to obtain the catalyst precursor.
In the present invention, the coating is preferably spray coating.
In the invention, the mass ratio of the mixture to the iron-based porous carbon precursor is preferably 6.3-8.7: 80 to 150, more preferably 6.3:100.
in the present invention, the post-coating preferably includes a rest for a time of preferably 30 minutes.
After the catalyst precursor is obtained, the solid phase synthesis is carried out on the catalyst precursor to obtain the iron-based porous carbon catalyst.
In the present invention, the solid-phase synthesis preferably includes a pre-firing and a calcination performed sequentially, the pre-firing is preferably performed under a protective atmosphere, the temperature of the pre-firing is preferably 300 to 500 ℃, more preferably 350 to 450 ℃, most preferably 400 ℃, the heat-preserving time is preferably 10min, and the heating rate from the temperature of the pre-firing to the temperature of the pre-firing is preferably 2 to 5 ℃/min, more preferably 3 ℃/min; the calcination is preferably carried out in a protective atmosphere and CO 2 The calcination is preferably carried out under a mixed atmosphere of 700 to 900 ℃, more preferably 750 to 800 ℃, the holding time is preferably 1.5 to 2 hours, and the rate of temperature rise to the calcination temperature is preferably 5 to 10 min/. Degree.C, more preferably 6 to 9 min/. Degree.C.
In the present invention, the protective atmosphere is preferably nitrogen.
In the present invention, the volume percentage of the protective atmosphere in the mixed atmosphere is preferably 1 to 100%.
In the present invention, the solid phase synthesis is preferably followed by cooling to room temperature, and the cooling rate to room temperature is preferably 5 to 10 min/. Degree.C.
In the present invention, the catalyst precursor is supported with a metal active component, which is preferably (Fe) in terms of its molar composition after solid-phase synthesis 2 O 3 ) x (MgO) y (ZrO 2 ) z Wherein x is 0.019 to 0.060, y is 0.012 to 0.046, and z is 0.021 to 0.035.
In the invention, the metal active component preferably comprises the following components in percentage by mass after solid phase synthesis: fe (Fe) 2 O 3 12.46 to 55.12 percent, 4.80 to 40.55 percent of MgO and ZrO 2 29.82% to 76.01%, in particular embodiments of the invention, more preferably include Fe 2 O 3 43.27wt%, mgO 17.87wt% and ZrO 2 38.86wt％。
The invention also provides the iron-based porous carbon catalyst prepared by the preparation method of the technical scheme, and the iron-based porous carbon catalyst comprises a carbon carrier and an iron-containing active component loaded on the surface of the carbon carrier.
In the present invention, the iron-containing active component preferably comprises the following components in percentage by mass: fe (Fe) 2 O 3 12.46 to 55.12 percent, 4.80 to 40.55 percent of MgO and ZrO 2 29.82% to 76.01%, in particular embodiments of the invention, more preferably include Fe 2 O 3 43.27wt%, mgO 17.87wt% and ZrO 2 38.86wt％。
The invention also provides application of the iron-based porous carbon catalyst in biomass tar steam reforming.
The specific mode of the application of the present invention is not particularly limited, and modes well known to those skilled in the art can be adopted.
In the present invention, the temperature of the steam reforming of biomass tar is preferably 550 to 850 ℃.
In the present invention, the steam reforming of biomass tar is preferably performed in a protective atmosphere, the flow rate of which is preferably 0.2L/min, and the protective atmosphere is preferably nitrogen.
In the invention, the raw material for preparing the tar steam by reforming the biomass tar steam is preferably straw.
In the invention, the mass ratio of the straw to the iron-based porous carbon catalyst is preferably 4:1.
For further explanation of the present invention, the iron-based porous carbon catalyst provided by the present invention, and the preparation method and application thereof will be described in detail with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Washing cat-eye snails with net weight of 80g to remove sand, taking out snail meat, and squeezing clean water for later use;
2) At room temperature, 9.67g of ferric nitrate, 4.44g of magnesium nitrate and 12.87g of zirconium nitrate solid powder are weighed to prepare 30mL of aqueous solution, after stirring for 30min, 2.5mL of ethanol and 1.5mL of acetic acid are respectively added into the mixed solution, and stirring is continued for 30min; obtaining a metal active component mixed solution;
3) Injecting the mixed solution into the snail meat for 3 times by using a microinjector, carrying out ultrasonic treatment for 10min after each injection, placing the snail meat into an ammonia water solution with the mass fraction of 25% after the injection is completed, carrying out ultrasonic treatment for 16min at 70 ℃, and drying the snail meat for 12h under the vacuum condition at 70 ℃;
4) 1.2g of cetyltrimethylammonium bromide, 2.3g of ammonium bicarbonate and 3.2g of glucose are weighed to prepare a mixture;
5) Spraying the mixture on the surface of the snail meat, and standing for 30min to obtain a catalyst precursor;
6) Placing a catalyst precursor in N 2 In the atmosphere, the temperature is raised from room temperature to 350 ℃ at a heating rate of 3 ℃/min, the temperature is kept constant for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (3:7), heating to 750 ℃ at a heating rate of 6 ℃/min, keeping the temperature for 1.5 hours, and then cooling to room temperature at a rate of 5 ℃/min; the sample was crushed and ground to obtain an iron-based porous carbon catalyst sample having a particle size of 0.5 mm.
7) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content was 39.43wt%; magnesium oxide (MgO) content 14.96wt%; zirconia (ZrO) 2 ) The content was 45.61wt%.
Example 2
1) Cleaning the flat jade snails with the net weight of 80g to remove sand, taking out the snails, and squeezing clean water for later use;
2) At room temperature, weighing 10.88g of ferric nitrate, 2.97g of magnesium nitrate and 15.02g of zirconium nitrate solid powder to prepare 35mL of aqueous solution, stirring for 30min, respectively adding 3.0mL of ethanol and 2.0mL of acetic acid into the mixed solution, and continuously stirring for 30min; obtaining a metal active component mixed solution;
3) Injecting the mixed solution into the snail meat for 4 times by using a microinjector, carrying out ultrasonic treatment for 10min after each injection, placing the snail meat into an ammonia water solution with the mass fraction of 25% after the injection is completed, carrying out ultrasonic treatment for 16min at 70 ℃, and drying the snail meat for 12h under the vacuum condition at 70 ℃;
4) 1.4g of cetyltrimethylammonium bromide, 2.5g of ammonium bicarbonate and 3.5g of glucose are weighed to prepare a mixture;
5) Spraying the mixture on the surface of the snail meat, and standing for 30min to obtain a catalyst precursor;
6) Placing a catalyst precursor in N 2 In the atmosphere, the temperature is raised from room temperature to 450 ℃ at a heating rate of 5 ℃/min, the temperature is kept constant for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (2:8), heating to 800 ℃ at a heating rate of 9 ℃/min, keeping the temperature for 1.5 hours, and then cooling to room temperature at a rate of 5 ℃/min; and crushing and grinding the sample to obtain an iron-based porous carbon catalyst sample.
7) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content is 41.22wt%; magnesium oxide (MgO) content 9.30wt%; zirconia (ZrO) 2 ) The content was 49.48wt%.
Example 3
1) Cleaning green-wave dragonfly snails with net weight of 150g, removing sand, taking out snail meat, and squeezing clean water for later use;
2) At room temperature, weighing 12.09g of ferric nitrate, 4.30g of magnesium nitrate and 9.02g of zirconium nitrate solid powder to prepare 40mL of aqueous solution, stirring for 30min, respectively adding 3.5mL of ethanol and 2.0mL of acetic acid into the mixed solution, and continuing stirring for 30min; obtaining a metal active component mixed solution;
3) Injecting the mixed solution into the snail meat for 3 times by using a microinjector, carrying out ultrasonic treatment for 10min after each injection, placing the snail meat into an ammonia water solution with the mass fraction of 25% after the injection is completed, carrying out ultrasonic treatment for 16min at 75 ℃, and drying the snail meat for 12h under the vacuum condition at 80 ℃;
4) 2.5g of cetyltrimethylammonium bromide, 2.0g of ammonium bicarbonate and 3.0g of glucose are weighed to prepare a mixture;
5) Spraying the mixture on the surface of the snail meat, and standing for 30min to obtain a catalyst precursor;
6) Placing a catalyst precursor in N 2 In the atmosphere, the temperature is raised from room temperature to 450 ℃ at a heating rate of 5 ℃/min, the temperature is kept constant for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 5:5) at a heating rate of 5 ℃/min to 900 ℃, keeping the temperature for 2.0 hours, and then at a rate of 10 ℃/minCooling to room temperature; and crushing and grinding the sample to obtain an iron-based porous carbon catalyst sample.
7) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content is 51.48wt%; 15.10wt% of magnesium oxide (MgO); zirconia (ZrO) 2 ) The content was 33.42wt%.
Example 4
1) Cleaning the pseudopurple jade snail with the net weight of 80g to remove sand, taking out the snail meat, and squeezing clean water for later use;
2) 13.30g of ferric nitrate, 2.97g of magnesium nitrate and 10.73g of zirconium nitrate solid powder are weighed at room temperature to prepare 46mL of aqueous solution, after stirring for 30min, 3.5mL of ethanol and 2.3mL of acetic acid are respectively added into the mixed solution, and stirring is continued for 30min; obtaining a metal active component mixed solution;
3) Injecting the mixed solution into the snail meat for 4 times by using a microinjector, carrying out ultrasonic treatment for 10min after each injection, placing the snail meat into an ammonia water solution with the mass fraction of 25% after the injection is completed, carrying out ultrasonic treatment for 16min at 75 ℃, and drying the snail meat for 12h under the vacuum condition at 80 ℃;
4) 2.0g of cetyltrimethylammonium bromide, 2.7g of ammonium bicarbonate and 4.0g of glucose are weighed to prepare a mixture;
5) Spraying the mixture on the surface of the snail meat, and standing for 30min to obtain a catalyst precursor;
6) Placing a catalyst precursor in N 2 In the atmosphere, the temperature is raised from room temperature to 450 ℃ at a heating rate of 5 ℃/min, the temperature is kept constant for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (2) is 4:6), the temperature is raised to 800 ℃ at a heating rate of 5 ℃/min, the temperature is kept for 1.5 hours, and then the temperature is lowered to room temperature at a rate of 10 ℃/min; and crushing and grinding the sample to obtain an iron-based porous carbon catalyst sample.
7) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content is 53.02wt%; magnesium oxide (MgO) content 9.80wt%; zirconia (ZrO) 2 ) The content was 37.18% by weight.
Example 5
1) Washing cat-eye snails with net weight of 100g to remove sand, taking out snail meat, and squeezing clean water for later use;
2) 14.51g of ferric nitrate, 2.81g of magnesium nitrate and 9.02g of zirconium nitrate solid powder are weighed at room temperature to prepare 50mL of aqueous solution, after stirring for 30min, 5.0mL of ethanol and 3.0mL of acetic acid are respectively added into the mixed solution, and stirring is continued for 30min; obtaining a metal active component mixed solution;
3) Injecting the mixed solution into the snail meat for 3 times by using a microinjector, carrying out ultrasonic treatment for 10min after each injection, placing the snail meat into an ammonia water solution with the mass fraction of 25% after the injection is completed, carrying out ultrasonic treatment for 16min at 75 ℃, and drying the snail meat for 12h under the vacuum condition at 80 ℃;
4) 1.5g of cetyltrimethylammonium bromide, 2.3g of ammonium bicarbonate and 2.5g of glucose are weighed to prepare a mixture;
5) Spraying the mixture on the surface of the snail meat, and standing for 30min to obtain a catalyst precursor;
6) Placing a catalyst precursor in N 2 In the atmosphere, the temperature is raised from room temperature to 400 ℃ at a heating rate of 2 ℃/min, the temperature is kept constant for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (2) is 8:2), the temperature is increased to 900 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 2.0h, and then the temperature is reduced to the room temperature at the rate of 10 ℃/min; and crushing and grinding the sample to obtain an iron-based porous carbon catalyst sample.
7) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content is 58.85wt%; magnesium oxide (MgO) content 9.34wt%; zirconia (ZrO) 2 ) The content was 31.81wt%.
Comparative example 1
1) Washing cat-eye snails with net weight of 80g to remove sand, taking out snail meat, and squeezing clean water for later use;
2) 1.5g of cetyltrimethylammonium bromide, 2.3g of ammonium bicarbonate and 2.5g of glucose are weighed to prepare a mixture;
3) Spraying the mixture onto the snail meat, standing for 30min, and standing in N 2 In the atmosphere, the temperature is raised from room temperature to 400 ℃ at a heating rate of 2 ℃/min, the temperature is kept for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (2) is 8:2), the temperature is increased to 900 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 2.0h, and then the temperature is reduced to room temperature at the rate of 10 ℃/min, so as to obtain the porous carbon carrier;
4) At room temperature, 9.19g of ferric nitrate, 4.45g of magnesium nitrate and 13.74g of zirconium nitrate solid powder are weighed to prepare 30mL of water solution, after stirring for 30min, 5.0mL of ethanol and 3.0mL of acetic acid are respectively added into the mixed solution, and stirring is continued for 30min; obtaining a metal active component mixed solution;
5) Placing the porous carbon-like carrier in the mixed solution, and performing ultrasonic treatment for 10min; then placing the mixture in an ammonia water solution with the mass fraction of 25%, and carrying out ultrasonic oscillation at 75 ℃ for 16min; and drying the sample for 12 hours under the vacuum condition at 80 ℃ to obtain an iron-based porous carbon catalyst sample.
6) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content was 37.04wt%; magnesium oxide (MgO) content 14.79wt%; zirconia (ZrO) 2 ) The content was 48.17wt%.
Comparative example 2
1) Cleaning the flat jade snails with the net weight of 80g to remove sand, taking out the snails, and squeezing clean water for later use;
2) 1.4g of cetyltrimethylammonium bromide, 2.5g of ammonium bicarbonate and 3.5g of glucose are weighed to prepare a mixture;
3) Spraying the mixture onto the snail meat, standing for 30min, and standing in N 2 In the atmosphere, the temperature is raised from room temperature to 450 ℃ at a heating rate of 5 ℃/min, the temperature is kept for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (3:7), heating to 800 ℃ at the heating rate of 7 ℃/min, keeping the temperature for 1.5 hours, and then cooling to room temperature at the rate of 5 ℃/min to obtain the porous carbon carrier;
4) At room temperature, weighing 10.16g of ferric nitrate, 4.75g of magnesium nitrate and 11.16g of zirconium nitrate solid powder to prepare 35mL of aqueous solution, stirring for 30min, respectively adding 3.0mL of ethanol and 2.0mL of acetic acid into the mixed solution, and continuously stirring for 30min; obtaining a metal active component mixed solution;
5) Placing the porous carbon-like carrier in the mixed solution, and performing ultrasonic treatment for 10min; then placing the mixture in an ammonia water solution with the mass fraction of 25%, carrying out ultrasonic treatment at 70 ℃ for 16min, and drying the snail meat for 12h under the vacuum condition at 70 ℃ to obtain an iron-based porous carbon catalyst sample.
6) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content is 42.73wt%; magnesium oxide (MgO) content 16.45wt%; zirconia (ZrO) 2 ) The content was 40.82wt%.
Comparative example 3
1) Cleaning green-wave dragonfly snails with net weight of 80g, removing sand, taking out snail meat, and squeezing clean water for later use;
2) 2.5g of cetyltrimethylammonium bromide, 2.0g of ammonium bicarbonate and 3.0g of glucose are weighed to prepare a mixture;
3) Spraying the mixture onto the snail meat, standing for 30min, and standing in N 2 In the atmosphere, the temperature is raised from room temperature to 450 ℃ at a heating rate of 5 ℃/min, the temperature is kept constant for 10min, and then the gas is replaced by CO 2 And N 2 Is a mixed gas (CO) 2 And N 2 The volume ratio of (2) is 5:5), the temperature is raised to 900 ℃ at the temperature rising rate of 5 ℃/min, the temperature is kept for 2.0h, and then the temperature is lowered to the room temperature at the rate of 10 ℃/min, so as to obtain the porous carbon carrier;
4) At room temperature, weighing 11.61g of ferric nitrate, 3.26g of magnesium nitrate and 12.88g of zirconium nitrate solid powder to prepare 40mL of aqueous solution, stirring for 30min, respectively adding 3.5mL of ethanol and 2.0mL of acetic acid into the mixed solution, and continuously stirring for 30min; obtaining a metal active component mixed solution;
5) Placing the porous carbon-like carrier in the mixed solution, and performing ultrasonic treatment for 10min; then placing the mixture in an ammonia water solution with the mass fraction of 25%, carrying out ultrasonic treatment at 75 ℃ for 16min, and drying the snail meat for 12h under the vacuum condition at 80 ℃ to obtain an iron-based porous carbon catalyst sample.
6) The catalyst comprises the following metal components in percentage by weight: iron oxide (Fe) 2 O 3 ) The content is 45.49wt%; magnesium oxide (MgO) content 10.57wt%; zirconia (ZrO) 2 ) The content was 43.94% by weight.
Application example 1
The efficiency evaluation of the catalytic reforming reaction of the biomass tar steam is carried out in a two-stage fixed bed reactor, wherein the upper stage is a biomass pyrolysis reaction stage, the reaction temperature is 550 ℃, the lower stage is a tar steam reforming reaction stage, the reaction temperatures are 550, 650, 750 and 850 ℃, the raw material for preparing the tar steam is straw particles, the mass is 20g, and the introducing flow rate of carrier gas nitrogen is 0.2L/min. Tar steam generated by pyrolysis of biomass in the upper section is contacted with a catalyst in the lower section through a sieve plate to carry out reforming reaction, the mass of the catalyst is 5g, and the reaction time is 0.5h. The experimental results are shown in Table 1. As can be seen from Table 1, in the biomass tar steam reforming reaction, the actual tar conversion rate of the catalyst provided by the invention is over 85%, the tar reforming efficiency is obviously higher than that of the comparative example, and the catalyst has the characteristics of high catalytic reforming efficiency, excellent thermal stability and the like.
TABLE 1 catalytic tar conversion of iron-based porous carbon under different conditions
Application example 2
From the above experiments, it is apparent that the catalyst prepared in example 5 has the best tar reforming performance, and thus the catalyst prepared in example 5 is taken as an example in the present invention, and the performance of the catalyst after recycling is evaluated. The performance evaluation of the catalyst is carried out in a two-stage fixed bed reactor, wherein the upper stage is a biomass pyrolysis reaction stage, the reaction temperature is 550 ℃, the lower stage is a tar steam reforming reaction stage, the reaction temperatures are 850 ℃ respectively, and the feeding flow rate of carrier gas nitrogen is 0.2L/min. The raw material for preparing the tar steam is straw particles, 20g of straw particles are placed in the upper end reactor in advance, and the tar steam generated by pyrolysis of the biomass at the upper section is contacted with 5g of catalyst placed at the lower section through a sieve plate to carry out reforming reaction, wherein the reaction time is 0.5h. After 1 reaction of the catalyst, the above procedure was repeated 5 times. The experimental results are shown in FIG. 1. The catalyst provided by the invention has the characteristics of long catalytic action time, multiple times of recycling, strong carbon deposition resistance and the like, and the real tar conversion rate is still more than 90% after 5 times of recycling in the biomass tar steam reforming reaction.
FIG. 2 is an X-ray diffraction pattern of the iron-based porous carbon catalyst prepared in example 5, showing that the iron, magnesium and zirconium metal components of the prepared iron-based porous carbon are respectively represented by MgFe 2 O 4 ，MgZr 7 O 15 ZrO (ZrO) 2 And the Fe particles are formed and can be effectively prevented from being lost due to thermal migration.
FIG. 3 is SEM images of the iron-based porous carbon catalyst prepared in example 5 at various magnifications, showing that MgFe 2 O 4 ，MgZr 7 O 15 ZrO (ZrO) 2 The three components are uniformly distributed on the surface and inside of the porous carbon of the snail meat, are granular and have a crystal structure; porous carbon has loose structure and obvious pore canal structure, and is helpful for improving the heat and mass transfer efficiency in the biological tar reforming process and avoiding carbon deposition inactivation.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.

Claims (9)

1. The preparation method of the iron-based porous carbon catalyst is characterized by comprising the following steps of:
dehydrating conch meat to obtain a porous carbon precursor;
injecting the iron-containing metal active component solution into the porous carbon precursor, soaking the porous carbon precursor in an alkaline environment, and then drying the soaked solid to obtain an iron-based porous carbon precursor; the iron-containing metal active component solution comprises a soluble ferric salt, a soluble magnesium salt and a soluble zirconium salt;
mixing cetyl trimethyl ammonium bromide, ammonium bicarbonate and a pore-forming agent to obtain a mixture;
coating the mixture on the surface of the iron-based porous carbon precursor to obtain a catalyst precursor;
and (3) carrying out solid phase synthesis on the catalyst precursor to obtain the iron-based porous carbon catalyst.
2. The method of claim 1, wherein the conch comprises one or more of cat eye snail, flat jade snail, pseudopurple jade snail, and green wave dragonfly snail.
3. The method according to claim 1, wherein the catalyst precursor has a metal active component supported thereon, and the metal active component is synthesized in a solid phase to form a metal compound having a molar composition (Fe 2 O 3 ) x (MgO) y (ZrO 2 ) z Wherein x is 0.019 to 0.060, y is 0.012 to 0.046, and z is 0.021 to 0.035.
4. The preparation method according to claim 1, wherein the mass ratio of the cetyltrimethylammonium bromide, the ammonium bicarbonate and the pore-forming agent in the mixture is 1.0-2.7: 2.0 to 3.0:2.2 to 4.5.
5. The method of claim 1 or 4, wherein the pore-forming agent comprises one or more of glucose, maltose, and fructose.
6. The method of claim 1, wherein the solid phase synthesis comprises: sequentially presintering and calcining;
the presintering is carried out in a protective atmosphere, the presintering temperature is 300-500 ℃, the heat preservation time is 10min, and the heating rate from the temperature rise to the presintering temperature is 2-5 ℃/min;
the calcination is carried out in a protective atmosphere and CO 2 The calcination is carried out under the mixed atmosphere of 700-900 ℃, the heat preservation time is 1.5-2 h, and the temperature rising rate from the temperature of the calcination to the temperature of 5-10 min/DEG C.
7. The method according to claim 1 or 6, wherein the solid phase synthesis further comprises cooling to room temperature, wherein the cooling rate to room temperature is 5 to 10min/°c.
8. The iron-based porous carbon catalyst produced by the production method according to any one of claims 1 to 7, characterized in that the iron-based porous carbon catalyst comprises a carbon support and an iron-containing active component supported on the surface of the carbon support.
9. Use of the iron-based porous carbon catalyst of claim 8 in biomass tar steam reforming.
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