CN109894133B - Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming - Google Patents

Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming Download PDF

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CN109894133B
CN109894133B CN201910199375.8A CN201910199375A CN109894133B CN 109894133 B CN109894133 B CN 109894133B CN 201910199375 A CN201910199375 A CN 201910199375A CN 109894133 B CN109894133 B CN 109894133B
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石川
张晓�
陈冰冰
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Dalian University of Technology
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    • 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
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    • 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
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    • 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
    • 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
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Abstract

The invention discloses a loaded Ni-MoCxA preparation method of the catalytic material and application thereof in preparing synthesis gas by chemical-looping dry gas reforming. Load type Ni-MoCxThe catalytic material comprises MoCxLarge scale commercial supports and metallic Ni, in which MoCxThe mass percentage of the component (A) is 25-75%; the mass percent of the metal Ni is 2.5-7.5%; the large scale commercial carrier materials mainly comprise: gamma-Al2O3，SiO2，CeO2BN, hydrotalcite and the like in a mass percentage of 22.5-67.5 percent. The invention takes the supported Ni-based catalytic material as a matrix, introduces the auxiliary agent transition metal molybdenum carbide material, regulates and optimizes the microstructure of the oxygen carrier, realizes the high-efficiency preparation of synthesis gas by methane under mild conditions, and has excellent H suitable for the Fischer-Tropsch synthesis process2The ratio of/CO (about 2-2.5) and excellent cycle stability, and improves the energy conversion efficiency.

Description

Preparation method of supported Ni-MoCx catalytic material and application of supported Ni-MoCx catalytic material in preparation of synthesis gas by chemical-looping dry gas reforming
Technical Field
The invention relates to a CH4-CO2A method for preparing synthesis gas by chemical chain reforming and application and preparation of a novel high-efficiency catalyst thereof, belonging to CH4-CO2Reforming synthesis gas technology.
Background
The global petroleum resource is in increasing shortage, the unclean use of energy by human beings causes increasing serious environmental pollution, and the global fossil energy industry revolution has pulled a curtain. The natural gas has rich reserves, wide distribution range and low price, is the third largest world energy next to petroleum and coal, is converted into high-value chemicals and high-energy chemical fuels, and is an effective way for solving the problems of energy shortage and environmental pollution at the same time. In recent years, with the breakthrough of shale gas and combustible ice mining technology, the production of liquid fuels and basic chemicals by replacing petroleum with natural gas has become a hot research spot worldwide. Expert prediction: the "21 st century will be the century for natural gas". The main component of natural gas is methane, and the content is usually 83% -99%, so that the activation conversion of methane has important theoretical and strategic significance.
The conversion of methane can be roughly divided into two conversion routes, direct conversion and indirect conversion. The direct conversion method mainly comprises the following steps: high temperature coupling of methane, aromatization of methane, selectivity of methaneOxidation and homogeneous catalytic oxidation of methane, etc.; so far, the method has no great breakthrough in technology due to the special stability of the molecular structure of methane and the deep oxidation of the target product under the harsh reaction condition, and is far from the industrial aim. The indirect conversion technology of methane mainly comprises three methods: steam Reforming of Methane (SRM), Dry Reforming of Methane (DRM), and Partial Oxidation of Methane (POM). Among them, SRM is the main process for traditionally preparing synthesis gas on a large scale, which has been industrialized. The reaction conditions are harsh (above 800C), the operation of high water-carbon ratio (2.5-3.5) is adopted to prevent the carbon deposition problem of the Ni-based catalyst, the energy consumption is further increased, and H in the produced synthesis gas2the/CO is more than or equal to 3, is not suitable for the F-T synthesis process, and needs further separation treatment, thereby greatly increasing the equipment scale and the production cost. POM is a mild exothermic process with H in the synthesis gas2The ratio of/CO is close to 2, and the catalyst is suitable for being used as raw material gas for methanol synthesis and F-T synthesis, but an expensive air separation oxygen device is needed in the POM process, and a noble metal material is mostly used as a catalytic material, so that the energy consumption and the cost of the process are improved; the reaction rate is fast, the reaction process is difficult to control accurately, and the target product is easy to be deeply oxidized; meanwhile, under the high-temperature condition, the mixing of methane and oxygen can also generate explosion danger, the temperature gradient of a catalyst bed layer is high, the temperature is easy to fly out of control, and great hidden dangers exist in the technical safety.
The methane-carbon dioxide reforming process can simultaneously utilize CH4And CO2The two greenhouse gases have important significance on environmental protection, the hydrogen-carbon ratio of the produced synthesis gas is about 1, and the synthesis gas is suitable for subsequent Fischer-Tropsch synthesis of long-chain hydrocarbon and has a huge application prospect. However, the reaction is also a strong endothermic reaction, and the reaction conditions of the traditional CDR process are harsh, and the energy consumption is high; meanwhile, the reaction activity is low, the single-pass conversion rate of methane is low, and the carbon deposition inactivation of the catalyst is serious under the high-temperature condition. In response to such a problem, in recent years, many researchers have proposed a new process for reacting CH with lattice oxygen provided by an oxide4The partial oxidation is carried out to prepare the synthesis gas, namely chemical looping reforming technology (chemical looping reforming min)g, CLR). The method mainly adopts a chemical chain technology to reform methane-carbon dioxide to prepare synthesis gas.
The methane-carbon dioxide chemical looping reforming technology based on the chemical looping combustion technology is a novel process for methane-carbon dioxide reforming which is developed in recent years. According to the principle of chemical chain reaction, partial oxidation is carried out on methane by using lattice oxygen in an oxygen carrier as an oxygen source to generate synthesis gas; the metal oxide losing lattice oxygen is again coated with CO2And oxidizing to recover lattice oxygen and completing chemical chain circulation reaction. In the whole process, the lattice oxygen partially oxidizes the methane to prepare the synthesis gas, the high conversion rate of the methane can be realized under lower energy consumption, and H in the gas-phase product of the reaction2And the mass ratio of CO is 2: 1, facilitating subsequent Fischer-Tropsch synthesis and other processes. At the same time, CO2In the oxidation stage, the elimination of partial carbon deposition is facilitated while the lattice oxygen is recovered, and the stability of the catalyst is improved. The chemical chain reforming process converts CO compared to the traditional CDR process2And H2Effective isolation, avoids the occurrence of reverse water gas shift reaction, and improves the selectivity of target products in the whole process, thereby having higher energy utilization efficiency and higher economy. The key point of the chemical chain method reforming process is to design and synthesize the oxygen carrier with high activity, selectivity, oxygen storage and release capacity and good stability.
Disclosure of Invention
The invention aims to provide a catalytic material for preparing synthesis gas by methane-carbon dioxide chemical chain reforming, which has high activity, high selectivity and high stability, and is realized by the following technical scheme.
A high efficiency oxygen carrier material for methane-carbon dioxide chemical looping reforming synthesis gas comprises MoCxLarge scale commercial supports and metallic Ni, in which MoCxThe mass percentage of the component (A) is 25-75%; the mass percent of the metal Ni is 2.5-7.5%; the large scale commercial carrier materials mainly comprise: gamma-Al2O3，SiO2，CeO2BN, hydrotalcite and the like in a mass percentage of 22.5-67.5 percent.
The invention takes a supported Ni-based catalytic material as a substrate and introduces the supported Ni-based catalytic materialThe auxiliary agent transition metal molybdenum carbide material regulates and optimizes the microstructure of the oxygen carrier, realizes the high-efficiency preparation of synthesis gas by methane under mild conditions, and has excellent H suitable for the Fischer-Tropsch synthesis process2The ratio of/CO (about 2-2.5) and excellent cycle stability, and improves the energy conversion efficiency.
The invention also aims to provide a preparation method of the catalytic material for preparing the synthesis gas by methane-carbon dioxide chemical chain reforming, which comprises the following steps:
1) preparing a load type metal Ni base material: according to the weight ratio of Ni: the mass percent of (Ni + carrier) is 1-20%, preparing metal nickel salt solution with target amount, mixing the metal nickel salt solution with carrier powder at room temperature, continuously stirring for 1-2 hours, aging for 24 hours at room temperature, drying for 12-24 hours at 100-150 ℃, finally roasting for 4 hours at 400-600 ℃ in the atmosphere of muffle furnace air, and obtaining Ni/carrier matrix material after cooling and grinding; wherein the carrier is selected from gamma-Al2O3，SiO2，CeO2BN, hydrotalcite;
2) preparing a molybdenum carbide auxiliary agent: adding MoO3The powder is prepared and synthesized by a temperature programming carbonization reaction process, and the specific process is a proper amount of MoO3Carbonizing at 590-800 deg.C in the mixed atmosphere of methane and hydrogen, wherein the carbonizing atmosphere is CH of 100-160ml/min4/H2Mixed gas, CH in mixed gas4The volume fraction of the carbon dioxide is 20 percent, the temperature programming carbonization process is that the temperature is increased to 300 ℃ at the rate of 5 ℃/min, then the temperature is increased to 700 ℃ at the rate of 1 ℃/min, the temperature is kept for 2h at 700 ℃, and the temperature is slowly reduced to the room temperature and then is 1 percent O2Passivating for 12 hours in an/Ar atmosphere.
3) Mechanically mixing the Ni/carrier matrix material obtained in the step 1) and the molybdenum carbide auxiliary material obtained in the step 2) at room temperature according to a certain mass percentage, wherein the mass percentage is Ni/carrier: MoCx1: 3-3: 1, fully grinding the mixture in a mortar for 1 to 2 hours, and finally roasting the mixture for 2 to 3 hours at the temperature of 450 to 600 ℃ in a mixed atmosphere of methane and hydrogen to obtain the three-component Ni-MoCxA supported catalyst; wherein the roasting atmosphere is CH of 100-150ml/min4/H2Mixed gas, CH in mixed gas4The percentage by volume of (c) is 15%.
The invention provides application of the catalyst obtained by the method in preparing synthesis gas through methane-carbon dioxide chemical chain reforming reaction.
Further, in the above technical scheme, the methane-carbon dioxide chemical chain reforming reaction is carried out in two steps in a cycle manner, and CH is firstly subjected to4Introducing the mixture into a reactor, and carrying out partial oxidation reaction on the mixture and lattice oxygen species in the catalytic material to prepare synthesis gas; then CO is introduced2Introducing the mixture into a reactor, carrying out oxidation-reduction reaction to prepare CO, and regenerating the catalyst.
Further, in the technical scheme, the reaction temperature is 500-800 ℃.
Further, in the above technical scheme, the reaction pressure is normal pressure.
The obtained catalytic material is tabletted and sieved to prepare powder with the granularity of 40-60 meshes, and the performance of the powder is evaluated through the following processes: the activity evaluation is carried out on a self-made normal-pressure miniature fixed bed reaction device, and the evaluation device mainly comprises a reaction gas simulation system, a reaction system and a detection system. The length of the quartz tube reactor in the reaction system is 40mm, and the inner diameter is 4 mm. The dosage of the activity test sample is 100mg, and the upper end and the lower end of the catalyst bed layer are filled with high-temperature cotton and quartz sand to reduce the dead volume of the reactor. The reactor is heated by a program temperature control tube electric furnace, and the temperature control precision is +/-0.1 ℃. The reaction gas simulation system adopts a miniature mass flow controller to control the atmosphere, and the precision is +/-0.1 ml/min. At the beginning of the experiment, high-purity argon gas is introduced to exhaust air, and then the reaction is switched to 15% CH4/H2Pretreating the mixed gas at 500 ℃ for 1-2 hours, and stabilizing the mixed gas to a target reaction temperature under the protection of high-purity argon, wherein the reaction temperature is 500-800 ℃; then switched to 5% CH by an automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. Wherein the flow rate of Ar in the purging section is 150ml/min and CH4The flow rates of the/Ar mixed gas and the CO2/Ar mixed gas are 100ml/min, and the gas product is monitored on line by a mass spectrometer.
The invention has the advantages and effects that:
1. the invention adopts the loaded Ni-MoCxMethane-carbon dioxide chemical looping reforming technique for catalytic materials4Partial oxidation reaction of (2) and CO2The activation dissociation reaction is carried out in two steps, which is favorable for CH4The realization of high conversion rate improves the conversion rate of reaction materials, the utilization efficiency of the catalyst and the separation efficiency of products; meanwhile, the occurrence of side reactions (such as reverse water gas shift reaction) in the reaction process is effectively reduced, the selectivity of the catalyst is improved, and the service life of the catalyst is prolonged; the carbon dioxide oxidation section can also eliminate carbon deposition on the surface of the catalyst to a certain extent, so that not only CO is obtained after reaction, but also the regeneration of the catalyst can be realized, and the service life is prolonged; the use of separation equipment is reduced, and the synthesis gas H can be effectively regulated and controlled by adding a molybdenum carbide auxiliary agent2The ratio of/CO is favorable for methanol synthesis and F-T process flow, has good industrial application prospect and is CH4-CO2The industrialization of reforming reaction opens up a new way.
2. Ni-MoC prepared by the inventionx/Al2O3Catalytic material of the type applied to methane-carbon dioxide chemical chain reforming reaction has higher CH at lower reaction temperature4The conversion rate, the faster conversion rate and the more excellent cycling stability, and the catalyst preparation process is simple and easy to realize industrialization. The oxygen carrier obtained by the invention is added with an auxiliary agent MoCxSupported Ni-MoC of materialxCompared with the traditional supported Ni-based oxygen carrier without the addition of the auxiliary agent, the material has higher reaction performance, particularly higher methane conversion rate and more excellent cycle stability. Among them, the most active is MoCxOxygen carrier material (MoC) with a doping amount of 50%x50% by mass, Ni/Al2O350% by mass, Ni/Al2O310 percent of medium metal Ni), about 56 percent of initial conversion rate of methane at 500 ℃, about 60 percent of initial conversion rate of carbon dioxide, and H2The ratio of/CO is about 2.35; initial conversion of methane at 600 ℃The rate is about 92 percent, the initial conversion rate of carbon dioxide is about 83 percent, H2The ratio of/CO is about 2.45; the initial conversion rate of methane reaches 100 percent at 700 ℃, the initial conversion rate of carbon dioxide is about 93 percent, and H2The ratio of/CO is about 2.5.
Drawings
The invention is shown in figure 4:
FIG. 1 shows the MoC obtained in example 1x+10％Ni/Al2O3(1/1) catalyst, 5% Ni/CeO obtained in comparative example 12Catalyst and 10% Ni/Al obtained in comparative example 22O3XRD contrast pattern of the catalyst;
FIG. 2 shows the MoC obtained in example 1x+10％Ni/Al2O3(1/1) catalyst and 5% Ni/CeO obtained in comparative example 12A catalytic performance diagram of the catalyst at 500 ℃ in a methane-carbon dioxide chemical chain reforming reaction;
FIG. 3 shows the MoC obtained in example 1x+10％Ni/Al2O3(1/1) catalyst and 10% Ni/Al obtained in comparative example 22O3A catalytic performance diagram of the catalyst under the reaction condition of 600 ℃ in the methane-carbon dioxide chemical chain reforming reaction;
FIG. 4 shows the MoC obtained in example 1x+10％Ni/Al2O3(1/1) catalytic performance diagram of catalyst under the reaction condition of 700 ℃ in methane-carbon dioxide chemical chain reforming reaction.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
Gamma-Al in the following examples2O3From Condya, sasol, but not limited to this source.
Example 1
Preparing a catalyst:
1) first, gamma-Al was measured2O3The water absorption of the powder was 1.4ml H2O/gAl2O3. According to the weight ratio of Ni: (Ni + Al)2O3) Weighing 2g of gamma-Al with the mass percent of 10 percent2O3Powder samples and 0.35g of nickel nitrate, then according to commercial gamma-Al2O3The water absorption of the powder is prepared by dissolving the nickel nitrate in 2.8ml of deionized water by an isometric immersion method to prepare a solution, and mixing the Ni salt solution with commercial gamma-Al2O3Mixing the powders at room temperature, stirring with glass rod for 1-2 hr, aging at room temperature for 24 hr, drying at 100-150 deg.C for 12-24 hr, calcining at 500 deg.C in muffle furnace air atmosphere for 4 hr, cooling, and grinding to obtain Ni/Al2O3A base material.
2) 1.8g of MoO are weighed3At 20% CH4/H2Carbonizing at 700 deg.C in mixed atmosphere with gas flow of 160ml/min, heating to 300 deg.C at 5 deg.C/min, heating to 700 deg.C at 1 deg.C/min, maintaining at 700 deg.C for 2 hr, slowly cooling to room temperature, and adding 1% O2Passivating for 12 hours in an/Ar atmosphere.
3) Weighing 2g of the 10% Ni/Al obtained in the first step2O3And 2g of the matrix material and the molybdenum carbide auxiliary material obtained in the second step are mixed according to the mass percentage of 1: 1 mechanically mixed at room temperature, ground well in a mortar for 1-2 hours, and finally in 15% CH4/H2Roasting for 2 hours at 500 ℃ in mixed atmosphere, wherein the gas flow of the mixed gas is 100ml/min, and obtaining the MoCx+10％Ni/Al2O3(SSI 1/1) catalyst.
Evaluation of catalyst Activity:
the methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, the flow of each path of gas required by the experiment is regulated and controlled by a mass flow meter, and CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly. 100mg of the above catalyst was weighed into a quartz tube reactor, first with 100ml/min 15% CH4/H2Pretreating the mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2The mixed gas of/Ar is used for 1min to realize active oxygen carryingRegenerating the body and carrying out multiple circulating reactions. The reaction temperatures were 500 deg.C, 600 deg.C, and 700 deg.C, respectively. Wherein the reaction temperature is 500 ℃, the initial conversion rate of methane is about 56 percent, the initial conversion rate of carbon dioxide is about 60 percent, and H2The ratio of/CO is about 2.35; initial conversion rate of methane at 600 ℃ is about 92%, initial conversion rate of carbon dioxide is about 83%, and H2The ratio of/CO is about 2.45; the initial conversion rate of methane reaches 100 percent at 700 ℃, the initial conversion rate of carbon dioxide is about 93 percent, and H2The ratio of/CO is about 2.5.
Comparative example 1
Catalyst preparation
First, commercial γ -Al was measured2O3The water absorption of the powder was 1.4mlH2O/gAl2O3. According to the weight ratio of Ni: (Ni + Al)2O3) Weighing 2g of gamma-Al with the mass percent of 10 percent2O3Powder samples and 0.35g of nickel nitrate, then according to commercial gamma-Al2O3The water absorption of the powder is prepared by dissolving the nickel nitrate in 2.8ml of deionized water by an isometric immersion method to prepare a solution, and mixing the Ni salt solution with commercial gamma-Al2O3Mixing the powders at room temperature, stirring with glass rod for 1-2 hr, aging at room temperature for 24 hr, drying at 100-150 deg.C for 12-24 hr, calcining at 500 deg.C in muffle furnace air atmosphere for 4 hr, cooling, and grinding to obtain 10% Ni/Al2O3A catalyst.
Evaluation of catalyst Activity
The methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, the flow of each path of gas required by the experiment is regulated and controlled by a mass flow meter, and CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly. 100mg of the above catalyst was weighed into a quartz tube reactor, first with 15% H at 100ml/min2Pretreating the/Ar mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. The reaction temperatures were 600 ℃ and 800 ℃ respectively. Wherein the initial conversion rate of methane is about 60 percent at 600 ℃, the initial conversion rate of carbon dioxide is about 52 percent, and H is2The ratio of/CO is about 9.5; initial conversion rate of methane at 700 deg.C is about 62%, initial conversion rate of carbon dioxide is about 55%, and H2The ratio of/CO is about 9.2; initial conversion rate of methane at 800 deg.C is about 70%, initial conversion rate of carbon dioxide is about 60%, and H2The ratio of/CO is about 9.0.
Example 1
Preparing a catalyst:
1) first, commercial CeO was measured2The water absorption of the powder was 3.1ml H2O/gAl2O3. According to the weight ratio of Ni: (Ni + CeO)2) Weighing 2g of CeO2Powder samples and 0.35g of nickel nitrate, then according to commercial CeO2The water absorption of the powder is prepared by dissolving the nickel nitrate in 2.8ml of deionized water by an isometric immersion method to prepare a solution, and mixing the Ni salt solution with commercial CeO2Mixing the powders at room temperature, stirring with glass rod for 1-2 hr, aging at room temperature for 24 hr, drying at 100-150 deg.C for 12-24 hr, calcining at 500 deg.C in muffle furnace air atmosphere for 4 hr, cooling, and grinding to obtain Ni/Al2O3A base material.
2) 1.8g of MoO are weighed3At 20% CH4/H2Carbonizing at 700 deg.C in mixed atmosphere with gas flow of 160ml/min, heating to 300 deg.C at 5 deg.C/min, heating to 700 deg.C at 1 deg.C/min, maintaining at 700 deg.C for 2 hr, slowly cooling to room temperature, and adding 1% O2Passivating for 12 hours in an/Ar atmosphere.
3) Weighing 2g of 10 percent Ni/CeO obtained in the first step2And 2g of the matrix material and the molybdenum carbide auxiliary material obtained in the second step are mixed according to the mass percentage of 1: 1 mechanically mixed at room temperature, ground well in a mortar for 1-2 hours, and finally in 15% CH4/H2Roasting for 2 hours at 500 ℃ in mixed atmosphere, wherein the gas flow of the mixed gas is 100ml/min, and obtaining the MoCx+10％Ni/CeO2(SSI 1/1) catalyst.
Evaluation of catalyst Activity:
the methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, the flow of each path of gas required by the experiment is regulated and controlled by a mass flow meter, and CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly. 100mg of the above catalyst was weighed into a quartz tube reactor, first with 100ml/min 15% CH4/H2Pretreating the mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. The reaction temperatures were 500 deg.C, 600 deg.C, and 700 deg.C, respectively. Wherein the reaction temperature is 500 ℃, the initial conversion rate of methane is about 53 percent, the initial conversion rate of carbon dioxide is about 57 percent, and H2The ratio of/CO is about 2.32; initial conversion rate of methane is about 90% at 600 ℃, initial conversion rate of carbon dioxide is about 87%, and H is2The ratio of/CO is about 2.25; the initial conversion rate of methane reaches 100 percent at 700 ℃, the initial conversion rate of carbon dioxide is about 91 percent, and H2the/CO ratio is about 2.34.
Comparative example 2
Catalyst preparation
First, commercial CeO was measured2The water absorption of the powder was 3.1mlH2O/gCeO2. According to the weight ratio of Ni: (Ni + CeO)2) Weighing 2gCeO with the mass percentage of 5 percent2Powder samples and 0.175g of nickel nitrate, then according to commercial CeO2The water absorption of the powder is prepared by dissolving the nickel nitrate in 6.2ml of deionized water by an isometric immersion method to prepare a solution, and mixing the Ni salt solution with commercial CeO2Mixing the powders at room temperature, stirring with glass rod for 1-2 hr, aging at room temperature for 24 hr, drying at 100-150 deg.C for 12-24 hr, calcining at 500 deg.C in muffle furnace for 4 hr, cooling, and grinding to obtain 5% Ni/CeO2A catalyst.
Evaluation of catalyst Activity
The methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, the flow of each path of gas required by the experiment is regulated and controlled by a mass flow meter, and CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly. 100mg of the above catalyst was weighed into a quartz tube reactor, first with 15% H at 100ml/min2Pretreating the/Ar mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. The initial conversion rate of methane is about 40 percent, the initial conversion rate of carbon dioxide is about 28 percent and H is H when the reaction temperature is 500 DEG C2The ratio of/CO is about 7.8; the initial conversion rate of methane at 600 ℃ is about 60 percent, the initial conversion rate of carbon dioxide is about 50 percent, and H2The ratio/CO is about 4.8.
Example 3
the procedure and process conditions of this example were the same as those of example 1 except that 1g of 10% Ni/Al was weighed2O3The matrix material and 3g of molybdenum carbide material are mixed according to the mass percentage of 1: 3 mechanical mixing at room temperature, grinding thoroughly in a mortar for 1-2 hours, and finally in 15% CH4/H2Roasting for 2 hours at 500 ℃ in mixed atmosphere to obtain MoCx+10％Ni/Al2O3(SSI1/3) catalyst, and (II) evaluating the activity of the catalyst, wherein the initial conversion rate of methane is about 82 percent, the initial conversion rate of carbon dioxide is about 75 percent and H is H when the reaction temperature is 600 DEG C2The ratio of/CO is about 3.0.
Example 4
the procedure and process conditions of this example were the same as those of example 1 except that 3g of 10% Ni/Al was weighed2O3The matrix material and 1g of molybdenum carbide material are mixed according to the mass percentage of 1: 1 mechanically mixed at room temperature, ground well in a mortar for 1-2 hours, and finally in 15% CH4/H2Roasting for 2 hours at 500 ℃ in mixed atmosphere to obtain MoCx+10％Ni/Al2O3(SSI3/1) catalyst and (II) evaluating the activity of the catalyst, wherein the initial conversion rate of methane is about 75 percent, the initial conversion rate of carbon dioxide is about 68 percent and H is H when the reaction temperature is 600 DEG C2The ratio of/CO is about 2.35.
Example 5
Preparing a catalyst:
1) first, commercial SiO was measured2The water absorption of the powder was 0.8ml H2O/gAl2O3. According to the weight ratio of Ni: (Ni + SiO)2) Is 10 percent, 2g of SiO is weighed2Powder samples and 0.35g of nickel nitrate, then according to commercial SiO2The water absorption of the powder is prepared by dissolving the nickel nitrate in 2.8ml of deionized water by an isometric immersion method to prepare a solution, and mixing the Ni salt solution with commercial SiO2Mixing the powders at room temperature, stirring with glass rod for 1-2 hr, aging at room temperature for 24 hr, drying at 100-150 deg.C for 12-24 hr, calcining at 500 deg.C in muffle furnace air atmosphere for 4 hr, cooling, and grinding to obtain Ni/SiO2A base material.
2) 1.8g of MoO are weighed3At 20% CH4/H2Carbonizing at 700 deg.C in mixed atmosphere with gas flow of 160ml/min, heating to 300 deg.C at 5 deg.C/min, heating to 700 deg.C at 1 deg.C/min, maintaining at 700 deg.C for 2 hr, slowly cooling to room temperature, and adding 1% O2Passivating for 12 hours in an/Ar atmosphere.
3) Weighing 2g of 10% Ni/SiO obtained in the first step2And 2g of the matrix material and the molybdenum carbide auxiliary material obtained in the second step are mixed according to the mass percentage of 1: 1 mechanically mixed at room temperature, ground well in a mortar for 1-2 hours, and finally in 15% CH4/H2Roasting for 2 hours at 500 ℃ in mixed atmosphere, wherein the gas flow of the mixed gas is 100ml/min, and obtaining the MoCx+10％Ni/SiO2(SSI 1/1) catalyst.
Evaluation of catalyst Activity:
the methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, and each path required by the experimentThe gas flow is regulated and controlled by a mass flow meter, CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly. 100mg of the above catalyst was weighed into a quartz tube reactor, first with 100ml/min 15% CH4/H2Pretreating the mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. The reaction temperatures were 500 ℃ and 600 ℃ respectively. Wherein the reaction temperature is 500 ℃, the initial conversion rate of methane is about 52 percent, the initial conversion rate of carbon dioxide is about 45 percent, and H2The ratio of/CO is about 2.15; initial conversion rate of methane at 600 ℃ is about 93%, initial conversion rate of carbon dioxide is about 80%, and H2The ratio of/CO is about 2.45.
Comparative example 3
Catalyst preparation
First, commercial SiO was measured2The water absorption of the powder was 0.8mlH2O/gSiO2. According to the weight ratio of Ni: (Ni + SiO)2) Is 10 percent, 2g of SiO is weighed2Powder samples and 0.35g of nickel nitrate, then according to commercial SiO2The water absorption of the powder is prepared by dissolving the nickel nitrate in 2.8ml of deionized water by an isometric immersion method to prepare a solution, and mixing the Ni salt solution with commercial SiO2Mixing the powders at room temperature, stirring with glass rod for 1-2 hr, aging at room temperature for 24 hr, drying at 100-150 deg.C for 12-24 hr, calcining at 500 deg.C in muffle furnace air atmosphere for 4 hr, cooling, and grinding to obtain 10% Ni/SiO2A catalyst.
Evaluation of catalyst Activity
The methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, the flow of each path of gas required by the experiment is regulated and controlled by a mass flow meter, and CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly.100mg of the above catalyst was weighed into a quartz tube reactor, first with 15% H at 100ml/min2Pretreating the/Ar mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. The reaction temperatures were 500 ℃ and 600 ℃ respectively. Wherein the initial conversion rate of methane is about 37 percent at 500 ℃, the initial conversion rate of carbon dioxide is about 30 percent, and H is2The ratio of/CO is about 10.5; initial conversion rate of methane at 600 ℃ is about 40%, initial conversion rate of carbon dioxide is about 33%, and H2The ratio/CO was about 9.8.
Example 6
Preparing a catalyst:
1) the water absorption of commercial BN powder was first determined to be 1.7ml H2O/gBN. According to the weight ratio of Ni: weighing 2g of BN powder sample and 0.35g of nickel nitrate according to the mass percent of (Ni + BN) being 10%, then dissolving the nickel nitrate in 2.8ml of deionized water by adopting an isometric immersion method according to the water absorption rate of commercial BN powder to prepare a solution, mixing the Ni salt solution and the commercial BN powder at room temperature, continuously stirring for 1-2 hours by using a glass rod, aging for 24 hours at room temperature, drying for 12-24 hours at 100-150 ℃, finally roasting for 4 hours at 500 ℃ in a muffle furnace air atmosphere, and cooling and grinding to obtain the Ni/BN matrix material.
2) 1.8g of MoO are weighed3At 20% CH4/H2Carbonizing at 700 deg.C in mixed atmosphere with gas flow of 160ml/min, heating to 300 deg.C at 5 deg.C/min, heating to 700 deg.C at 1 deg.C/min, maintaining at 700 deg.C for 2 hr, slowly cooling to room temperature, and adding 1% O2Passivating for 12 hours in an/Ar atmosphere.
3) Weighing 2g of the 10% Ni/BN base material obtained in the step one and 2g of the molybdenum carbide auxiliary material obtained in the step two according to the mass percentage of 1: 1 mechanically mixed at room temperature, ground well in a mortar for 1-2 hours, and finally in 15% CH4/H2Roasting at 500 deg.C for 2 hr in mixed atmosphereThe gas flow is 100ml/min, and the MoC is preparedx+ 10% Ni/BN (SSI 1/1) catalyst.
Evaluation of catalyst Activity:
the methane-carbon dioxide chemical chain reforming reaction is carried out in a self-made miniature fixed bed reactor with the inner diameter of 4mm, the flow of each path of gas required by the experiment is regulated and controlled by a mass flow meter, and CH4Reduction stage and CO2The gas inflow of the oxidation section is automatically controlled by a pneumatic gas switching valve, and the sample introduction is carried out circularly. 100mg of the above catalyst was weighed into a quartz tube reactor, first with 100ml/min 15% CH4/H2Pretreating the mixed gas at 500 ℃ for 2h, and then carrying out circulating sample injection reaction at different reaction temperatures through the following reaction processes: switching to 5% CH by automatic gas switching valve4Reacting for 1min, switching to pure Ar gas for 2min, introducing 5% CO2And the/Ar mixed gas is used for 1min to realize the regeneration of the active oxygen carrier, and multiple cyclic reactions are carried out. The reaction temperatures were 500 ℃ and 600 ℃ respectively. Wherein the reaction temperature is 500 ℃, the initial conversion rate of methane is about 45 percent, the initial conversion rate of carbon dioxide is about 38 percent, and H2The ratio of/CO is about 2.35; initial conversion rate of methane at 600 ℃ is about 83%, initial conversion rate of carbon dioxide is about 76%, and H2The ratio of/CO is about 2.45.

Claims (3)

1. Three-component load type Ni-MoCxThe preparation method of the catalytic material is characterized by comprising the following steps:
1) preparing a load type metal Ni base material: according to the weight ratio of Ni: the mass percent of (Ni + carrier) is 1-20%, preparing metal nickel salt solution with target amount, mixing the metal nickel salt solution with carrier powder at room temperature, continuously stirring for 1-2 hours, aging for 24 hours at room temperature, drying for 12-24 hours at 100-150 ℃, finally roasting for 4 hours at 400-600 ℃ in the atmosphere of muffle furnace air, and obtaining Ni/carrier matrix material after cooling and grinding; wherein the carrier is selected from gamma-Al2O3，SiO2，CeO2BN, hydrotalcite;
2) preparation of molybdenum carbide auxiliary agentPreparing: adding MoO3The powder is prepared and synthesized by a temperature programming carbonization reaction process, and the specific process is a proper amount of MoO3Carbonizing at 590-800 deg.C in the mixed atmosphere of methane and hydrogen, wherein the carbonizing atmosphere is CH of 100-160ml/min4/H2Mixed gas, CH in mixed gas4The volume fraction of the carbon dioxide is 20 percent, the temperature programming carbonization process is that the temperature is increased to 300 ℃ at the rate of 5 ℃/min, then the temperature is increased to 700 ℃ at the rate of 1 ℃/min, the temperature is kept for 2h at 700 ℃, and the temperature is slowly reduced to the room temperature and then is 1 percent O2Passivating for 12 hours in an/Ar atmosphere;
3) mechanically mixing the Ni/carrier matrix material obtained in the step 1) and the molybdenum carbide auxiliary material obtained in the step 2) at room temperature according to a certain mass percentage, wherein the mass percentage is Ni/carrier: MoCx1: 3-3: 1, fully grinding the mixture in a mortar for 1 to 2 hours, and finally roasting the mixture for 2 to 3 hours at the temperature of 450 to 600 ℃ in a mixed atmosphere of methane and hydrogen to obtain the three-component Ni-MoCxA supported catalyst; wherein the roasting atmosphere is CH of 100-150ml/min4/H2Mixed gas, CH in mixed gas4The percentage by volume of (c) is 15%.
2. Use of the catalyst obtained by the preparation method according to claim 1 in the synthesis gas production by methane-carbon dioxide chemical-looping reforming reaction, wherein the methane-carbon dioxide chemical-looping reforming reaction is performed in two cycles, first, CH is added4Introducing the mixture into a reactor, and carrying out partial oxidation reaction on the mixture and lattice oxygen species in the catalytic material to prepare synthesis gas; then CO is introduced2Introducing the mixture into a reactor, carrying out oxidation-reduction reaction to prepare CO, and regenerating a catalyst, wherein the reaction temperature is 500-800 ℃.
3. Use according to claim 2, characterized in that the reaction pressure is atmospheric.
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