CN112827501A - Controllable synthesis of alpha-MoC supported indium and modified catalyst thereof and application of alpha-MoC supported indium in reaction for preparing methanol by carbon dioxide hydrogenation - Google Patents
Controllable synthesis of alpha-MoC supported indium and modified catalyst thereof and application of alpha-MoC supported indium in reaction for preparing methanol by carbon dioxide hydrogenation Download PDFInfo
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- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
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- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
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Abstract
The invention belongs to the field of catalytic conversion and utilization of carbon dioxide, and particularly discloses alpha-MoC supported indium and a modified catalyst thereof, and application of the catalyst in a reaction of synthesizing methanol by hydrogenation of carbon dioxide. The invention loads indium nitrate on alpha-MoC obtained by a temperature programming carbonization method by an isometric impregnation method, and ZrO can be added in the alpha-MoC2And metal additives such as Pt and Co may be added. After in-situ pretreatment, the series of catalysts show excellent performance in the reaction of preparing methanol by pressurized carbon dioxide hydrogenationThe catalytic performance of (2).
Description
Technical Field
The invention belongs to the field of catalytic conversion and utilization of carbon dioxide, and particularly relates to a reaction for catalytically synthesizing methanol by using alpha-MoC loaded indium and a modified catalyst thereof.
Background
Carbon dioxide, a major greenhouse gas, has been increasing in atmospheric concentration year by year, creating a serious environmental problem. At the same time, carbon dioxide is a very abundant and cheap C1 resource. Thus, the catalytic conversion of carbon dioxide has both energy and environmental implications. Meanwhile, methanol is taken as a new generation of energy widely promoted in recent years and can be taken as high-quality automobile fuel and fuel additive; in addition, methanol is also a very important chemical product. Thus, the conversion of carbon dioxide to methanol is of epoch-making significance.
Under the influence of thermodynamics and kinetics, the preparation of methanol by carbon dioxide hydrogenation is generally carried out at 200-300 ℃ and under high pressure (1-10MPa), and a high-activity catalyst is needed. Among them, the catalyst is the key one, and its performance is related to the whole production process, flow and equipment. Therefore, the development of a catalyst having high performance is of great importance.
At present, the most studied carbon dioxide hydrogenation catalysts are copper-based catalysts, which have high activity and methanol selectivity. In addition, the catalytic performance of the catalyst can be further improved by adding an auxiliary agent. Wherein, ZnO and ZrO2The addition of (2) helps to improve the dispersion degree and stability of Cu; ga2O3Then it is advantageous to stabilize Cu+A species; the addition of Pd is beneficial to maintain the catalyst in a highly reduced state, thereby promoting the reaction.
Transition Metal Carbides (TMCs) are interstitial compounds formed by inserting carbon atoms into crystal lattices of transition metals, and due to the insertion of the carbon atoms, the spacing of metal atoms is increased, the crystal lattices are expanded, d-band is shrunk, the fermi level density is increased, and the properties of noble-like metals are further realized. Jose et al combined DFT theory on model catalystCalculate and research CO2Shows the carbide surface to CO2Good dissociation ability. Studies have shown that if the binding energy of the carbide to the oxygen atom is large, CO is present2Dissociation at the carbide surface to produce CO: CO 22→ CO + O, yielding CO (g); if the bonding energy of oxygen and carbide is small, CO2Non-dissociative adsorption, molecular adsorption on catalyst, and direct hydrogenation to generate fuel (CO)2+H2→CH3OH+H2O). In addition, the excellent hydrogenation properties of the transition metal carbide make it show good catalytic performance in HDN, HDS and electrocatalytic HER and HOR reactions.
The alpha-MoC is used as a carrier to load an indium-based catalyst for preparing methanol by carbon dioxide hydrogenation, and the report is not available yet.
Disclosure of Invention
The invention aims to provide an alpha-MoC supported indium and a modified catalyst thereof and a preparation method of the catalyst, and the catalyst is applied to the reaction of preparing methanol by carbon dioxide hydrogenation and has the characteristics of high catalytic activity and good thermal stability.
In order to realize the purpose, the technical scheme of the invention is as follows:
on one hand, the invention discloses a supported catalyst for carbon dioxide hydrogenation, which takes alpha-MoC as a carrier; indium is used as an active component.
Based on the scheme, preferably, the mass fraction of indium in the catalyst is 3-15%; the catalyst further comprises an oxide promoter and/or a metal promoter.
Based on the scheme, preferably, the mass fraction of the metal auxiliary agent is 0.1-5%; the mass fraction of the oxide auxiliary agent is 1-10%; the oxide auxiliary agent is ZrO2(ii) a The metal auxiliary agent is one or two of Pt and Co.
On the other hand, the invention discloses a preparation method of the catalyst, which comprises the following steps:
(1) roasting a metal precursor of molybdenum at 400-700 ℃ for 2-6 h to obtain molybdenum trioxide particles;
(2) carrying out temperature programming nitridation on the molybdenum trioxide at 590-800 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, and then carrying out temperature programming carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain a catalyst carrier;
(3) and (3) soaking the indium nitrate aqueous solution on the catalyst carrier in the same volume to obtain the catalyst.
Based on the scheme, preferably, in the step (2), the nitriding atmosphere is high-purity ammonia gas of 50-200 ml/min; the temperature programming nitridation process comprises the following steps: heating to 590-800 ℃ at a speed of 5-20 ℃/min and preserving heat for 1-5 h; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4The volume fraction of (A) is 5-50%; the temperature programming carbonization process comprises the steps of heating to 590-800 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-5h, cooling to room temperature, and then adding 1% of O2Passivating for 12-36h in/Ar.
Based on the above scheme, preferably, when the catalyst further comprises an oxide promoter, the step (2) comprises the following steps:
isovolumetrically impregnating the metal precursor solution of the oxide auxiliary agent on the molybdenum trioxide by an isovolumetrically impregnating method; and (2) carrying out temperature programming nitridation on molybdenum trioxide impregnated with a peroxide auxiliary agent metal precursor at 590-800 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, and then carrying out temperature programming carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain the oxide auxiliary agent modified alpha-MoC.
Based on the above scheme, preferably, when the catalyst further comprises a metal promoter, the preparation method further comprises step (4), and the step (4) is: and (4) soaking a precursor of the metal auxiliary agent in the catalyst prepared in the step (3) in an equal volume to obtain the metal auxiliary agent modified catalyst.
Specifically, the preparation method of the alpha-MoC supported indium catalyst comprises the following steps:
(1) placing ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting at 400-700 ℃ for 2-6 h to obtain molybdenum trioxide particles;
(2) and (2) performing temperature programmed nitridation on 0.8-1.5 g of molybdenum trioxide at 590-800 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, performing temperature programmed carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC:
nitriding high-purity ammonia gas with the atmosphere of 50-200 ml/min; the temperature programming process is that the temperature is raised to 590-800 ℃ at the speed of 5-20 ℃/min and is kept for 1-5 h; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4The volume fraction of (A) is 5-50%; the temperature programming carbonization process comprises the steps of heating to 590-800 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-5h, cooling to room temperature, and then adding 1% of O2Passivating for 12-36h in/Ar;
(3) indium nitrate was dissolved in water and immersed in the above α -MoC in equal volume.
The invention provides alpha-MoC supported indium obtained by the preparation method, and the mass fraction of indium in the alpha-MoC supported indium catalyst is 3-15%.
Concretely, a ZrO-added alloy2The preparation method of the alpha-MoC supported indium catalyst with the oxide auxiliary agent is characterized by comprising the following steps:
(1) placing ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting at 400-700 ℃ for 2-6 h to obtain molybdenum trioxide particles;
(2) soaking zirconium nitrate in the molybdenum trioxide in an equal volume by an equal volume soaking method; the mass fraction of the zirconia is 1-10%;
(3) and (2) performing temperature programmed nitridation on 0.8-1.5 g of the molybdenum trioxide added with the zirconium peroxynitrate at 590-800 ℃ in a pure ammonia atmosphere, naturally cooling to room temperature, performing temperature programmed carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain the zirconium oxide modified alpha-MoC:
nitriding high-purity ammonia gas with the atmosphere of 50-200 ml/min; the temperature programming process is that the temperature is raised to 590-800 ℃ at the speed of 5-20 ℃/min and is kept for 1-5 h; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4The volume fraction of (A) is 5-50%; the temperature programming carbonization process comprises the steps of heating to 590-800 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-5h, cooling to room temperature, and then adding 1% of O2Passivation in/Ar 12-36h；
(4) Indium nitrate was dissolved in water and immersed in the above ZrO at the same volume2Modified alpha-MoC.
The invention provides alpha-MoC supported indium with an oxide auxiliary agent, which is obtained by the preparation method, wherein the mass fraction of indium in the alpha-MoC supported indium catalyst is 3-15%; the mass fraction of the oxide is 3-50%.
Specifically, the preparation method of the alpha-MoC supported indium catalyst added with metal assistants such as Pt and Co is characterized by comprising the following steps:
(1) placing ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting at 400-700 ℃ for 2-6 h to obtain molybdenum trioxide particles;
(2) and (2) performing temperature programmed nitridation on 0.8-1.5 g of molybdenum trioxide at 590-800 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, performing temperature programmed carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC:
nitriding high-purity ammonia gas with the atmosphere of 50-200 ml/min; the temperature programming process is that the temperature is raised to 590-800 ℃ at the speed of 5-20 ℃/min and is kept for 1-5 h; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4The volume fraction of (A) is 5-50%; the temperature programming carbonization process comprises the steps of heating to 590-800 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-5h, cooling to room temperature, and then adding 1% of O2Passivating for 12-36h in/Ar;
(3) indium nitrate was dissolved in water and immersed in the above α -MoC in equal volume.
(4) Chloroplatinic acid or cobalt nitrate is dipped in the same volume on the alpha-MoC supported indium catalyst.
The invention provides alpha-MoC supported indium added with a metal auxiliary agent, which is obtained by the preparation method, wherein the mass fraction of indium in the alpha-MoC supported indium catalyst is 3-15%; the mass fraction of the metal additive is 0.1-5%.
In another aspect, the invention provides an application of the catalyst in a reaction for preparing methanol by carbon dioxide hydrogenation.
Based on the scheme, preferably, the reaction atmosphere for preparing methanol by hydrogenating carbon dioxide is CO2And H2Mixed gas of H2And CO2The molar ratio of (A) to (B) is 1: 1-1: 4, and the reaction pressure is 1-5 MPa.
The invention has the beneficial effects that:
(1) the alpha-MoC supported indium catalyst and the oxide or metal auxiliary agent modified alpha-MoC supported indium catalyst are firstly used for the reaction of preparing methanol by carbon dioxide hydrogenation;
(2) the alpha-MoC is used as a carrier to disperse indium, so that the performance of preparing methanol by low-temperature carbon dioxide hydrogenation of the indium-based catalyst is improved;
(3) for the In/alpha-MoC catalyst, In the In-situ high-temperature pretreatment process of the reducing atmosphere, the simple substance In is redispersed on the surface of the alpha-MoC, namely the simple substance In and the alpha-MoC show synergistic action;
(4) the oxide or metal auxiliary agent modified In/alpha-MoC further improves the activation capability of reactants and the selectivity of the reactants to product methanol, further improves the catalytic performance of preparing methanol by carbon dioxide hydrogenation, is suitable for the reaction conditions of the reaction, and can be used for CO2The catalytic conversion field has wide utilization prospect.
Drawings
FIG. 1 shows the 9% In/α -MoC prepared In example 1 after impregnation, CH4/H2XRD patterns after pretreatment and after reaction.
FIG. 2 is a 9% In/ZrO prepared In comparative example 129% In/α -MoC prepared In example 1, 9% In/5% ZrO prepared In example 22Comparative plots of space time yields for methanol from carbon dioxide hydrogenation catalyzed by/. alpha. -MoC, 1% Pt/9% In/. alpha. -MoC prepared In example 3, and 1% Co 9% In/. alpha. -MoC prepared In example 4.
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.
Example 1
Preparation of alpha-MoC supported indium catalyst (9% In/alpha-MoC) and evaluation of catalytic activity
(1) Preparation of
Placing ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting at 500 ℃ for 4h to obtainTo molybdenum trioxide particles; and (2) performing programmed heating nitridation on the 1.2g of molybdenum trioxide at 700 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, performing programmed heating carbonization at 700 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC: high-purity ammonia gas with nitriding atmosphere of 150 ml/min; the temperature programming process is that the temperature is raised to 700 ℃ at the speed of 10 ℃/min, and the temperature is kept for 2h at 700 ℃; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4Is 20% by volume; the temperature programming carbonization process comprises heating to 700 deg.C at 10 deg.C/min, maintaining at 700 deg.C for 2h, cooling to room temperature, and adding 1% O2Passivating for 12 hours in/Ar to obtain alpha-MoC. 0.236g of indium nitrate was dissolved In water, immersed In 1g of the above α -MoC In an equal volume, allowed to stand for 12 hours after immersion, and then dried In a forced air drying oven at 60 ℃ to obtain a catalyst 9% In/α -MoC (In this case, In is present as a nitrate, and the active component is present In the following examples and comparative examples In the same manner as In example 1).
(2) Activity evaluation test
The reaction for preparing methanol by carbon dioxide hydrogenation is carried out in a stainless steel reaction tube fixed bed reactor with the inner diameter of 8 mm. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Respectively weighing 200mg of the catalyst (40-60 meshes) and 300mg of quartz sand (40-60 meshes), uniformly mixing, placing in a stainless steel reaction tube, and adding 15% of CH4/H2The catalyst was pretreated with the mixed gas at 500 ℃ for 2 hours (In existed In the form of simple substance after pretreatment, and the active components existed In the following examples and comparative examples In the same manner as In example 1), and then the activity evaluation was performed under the following conditions: the reaction atmosphere adopts N2:CO2:H2The gas space velocity is 18,000mL/g/h, the reaction temperature is 240 ℃, and the reaction pressure is 3.0MPa (during the reaction, due to CO)2By the presence of elemental In which it is oxidized In situ to In2O3The form of the active component in the following examples and comparative examples is the same as in example 1).
Example 2
With addition of ZrO2alpha-MoC indium loaded adjuvant (9% In/5% ZrO)2Preparation of/alpha-MoC) catalyst and evaluation of catalytic activity
(1) Preparation of
And (3) putting ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting at 500 ℃ for 4h to obtain molybdenum trioxide particles. Zirconium nitrate is impregnated in the molybdenum trioxide by an isovolumetric impregnation method; the mass fraction of zirconia is 5%. 1.2g of the zirconium nitrate-impregnated molybdenum trioxide is subjected to temperature programmed nitridation at 700 ℃ under the pure ammonia atmosphere, naturally cooled to room temperature, and then subjected to temperature programmed carbonization at 700 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC: high-purity ammonia gas with nitriding atmosphere of 150 ml/min; the temperature programming process is that the temperature is raised to 700 ℃ at the speed of 10 ℃/min, and the temperature is kept for 2h at 700 ℃; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4Is 20% by volume; the temperature programming carbonization process comprises heating to 700 deg.C at 10 deg.C/min, maintaining at 700 deg.C for 2h, cooling to room temperature, and adding 1% O2Passivating for 12 hours in/Ar to obtain the alpha-MoC loaded zirconia. 0.236g of indium nitrate is dissolved In water, and then dipped In 1g of the alpha-MoC loaded zirconia In the same volume, the dipped solution is kept stand for 12 hours and then dried In a forced air drying oven at 60 ℃ to obtain the catalyst of 9% In/5% ZrO2/α-MoC。
(2) Activity evaluation test
The reaction for preparing methanol by carbon dioxide hydrogenation is carried out in a stainless steel reaction tube fixed bed reactor with the inner diameter of 8 mm. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Respectively weighing 200mg of the catalyst (40-60 meshes) and 300mg of quartz sand (40-60 meshes), uniformly mixing, placing in a stainless steel reaction tube, and adding 15% of CH4/H2The catalyst was pretreated with the mixed gas at 500 ℃ for 2h, and then activity evaluation was performed under the following conditions: the reaction atmosphere adopts N2:CO2:H2The gas space velocity is 18,000mL/g/h, the reaction temperature is 240 ℃, and the reaction pressure is 3.0 MPa.
Example 3
Preparation of metal Pt auxiliary agent-added alpha-MoC supported indium catalyst (1% Pt/9% In/alpha-MoC) and catalytic activity evaluation
(1) Preparation of
Mixing heptamolybdenum tetrahydrateAnd (3) placing the ammonium sulfate in a muffle furnace, and roasting at 500 ℃ for 4h to obtain molybdenum trioxide particles. 1.2g of the molybdenum trioxide is subjected to temperature programming nitridation at 700 ℃ under the pure ammonia atmosphere, naturally cooled to room temperature, and then subjected to temperature programming carbonization at 700 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC: high-purity ammonia gas with nitriding atmosphere of 150 ml/min; the temperature programming process is that the temperature is raised to 700 ℃ at the speed of 10 ℃/min, and the temperature is kept for 2h at 700 ℃; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4Is 20% by volume; the temperature programming carbonization process comprises heating to 700 deg.C at 10 deg.C/min, maintaining at 700 deg.C for 2h, cooling to room temperature, and adding 1% O2Passivating for 12 hours in/Ar to obtain alpha-MoC. 0.236g of indium nitrate was dissolved in water and immersed in the above α -MoC in an equal volume. Then, chloroplatinic acid was impregnated on 1g of the above α -MoC supported indium catalyst by an equivalent volume impregnation method, and after the impregnation, the mixture was left to stand for 12 hours and then dried in a forced air drying oven at 60 ℃. The mass fraction of platinum is 1%, and the catalyst is 1% Pt/9% In/alpha-MoC.
(2) Activity evaluation test
The reaction for preparing methanol by carbon dioxide hydrogenation is carried out in a stainless steel reaction tube fixed bed reactor with the inner diameter of 8 mm. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Respectively weighing 200mg of the catalyst (40-60 meshes) and 300mg of quartz sand (40-60 meshes), uniformly mixing, placing in a stainless steel reaction tube, and adding 15% of CH4/H2The catalyst was pretreated with the mixed gas at 500 ℃ for 2h, and then activity evaluation was performed under the following conditions: the reaction atmosphere adopts N2:CO2:H2The gas space velocity is 18,000mL/g/h, the reaction temperature is 240 ℃, and the reaction pressure is 3.0 MPa.
Example 4
Preparation of alpha-MoC indium-loaded (1% Co/9% In/alpha-MoC) catalyst added with metal Co auxiliary agent and catalytic activity evaluation
(1) Preparation of
And (3) putting ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting at 500 ℃ for 4h to obtain molybdenum trioxide particles. 1.2g of the molybdenum trioxide is nitrided at the temperature of 700 ℃ in the pure ammonia atmosphereNaturally cooling to room temperature, and then carrying out temperature programmed carbonization at 700 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC: high-purity ammonia gas with nitriding atmosphere of 150 ml/min; the temperature programming process is that the temperature is raised to 700 ℃ at the speed of 10 ℃/min, and the temperature is kept for 2h at 700 ℃; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4Is 20% by volume; the temperature programming carbonization process comprises heating to 700 deg.C at 10 deg.C/min, maintaining at 700 deg.C for 2h, cooling to room temperature, and adding 1% O2Passivating for 12 hours in/Ar to obtain alpha-MoC. 0.236g of indium nitrate is dissolved in water, dipped in the alpha-MoC in the same volume, and then is kept stand for 12 to 36 hours after being dipped, and then is dried in an air drying oven at 60 to 110 ℃. Then, cobalt nitrate was impregnated on 1g of the above α -MoC supported indium catalyst by an equal volume impregnation method, and after the impregnation, the catalyst was left to stand for 12 hours and then dried In a forced air drying oven at 60 ℃ with the mass fraction of cobalt being 1%, to obtain a catalyst 1% Co 9% In/α -MoC.
(2) Activity evaluation test
The reaction for preparing methanol by carbon dioxide hydrogenation is carried out in a stainless steel reaction tube fixed bed reactor with the inner diameter of 8 mm. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Respectively weighing 200mg of the catalyst (40-60 meshes) and 300mg of quartz sand (40-60 meshes), uniformly mixing, placing in a stainless steel reaction tube, and adding 15% of CH4/H2The catalyst was pretreated with the mixed gas at 500 ℃ for 2h, and then activity evaluation was performed under the following conditions: the reaction atmosphere adopts N2:CO2:H2The gas space velocity is 18,000mL/g/h, the reaction temperature is 240 ℃, and the reaction pressure is 3.0 MPa.
Comparative example 1
Preparation of zirconium oxide supported indium catalyst and evaluation of catalytic activity
(1) Preparation of
Indium nitrate was impregnated onto commercial zirconia (purchased from Α lfa Α esar) using an equal volume impregnation method with a mass fraction of indium of 9%.
(2) Activity evaluation test
Stainless steel reaction with inner diameter of 8mm in reaction for preparing methanol by carbon dioxide hydrogenationIn a tube fixed bed reactor. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Respectively weighing 200mg of the catalyst (40-60 meshes) and 300mg of quartz sand (40-60 meshes), uniformly mixing, placing in a stainless steel reaction tube, and adding 20% H2The catalyst was pretreated with the mixed gas/Ar at 200 ℃ for 2h, and then activity evaluation was carried out under the following conditions: the reaction atmosphere adopts N2:CO2:H2The gas space velocity is 18,000mL/g/h, the reaction temperature is 240 ℃, and the reaction pressure is 3.0 MPa.
Comparative example 2
Preparation of alpha-MoC supported cobalt catalyst (9% Co/alpha-MoC) and catalytic activity evaluation
(1) Preparation of
Putting ammonium heptamolybdate tetrahydrate in a muffle furnace, and roasting for 4 hours at 500 ℃ to obtain molybdenum trioxide particles; and (2) performing programmed heating nitridation on the 1.2g of molybdenum trioxide at 700 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, performing programmed heating carbonization at 700 ℃ in a mixed gas of methane and hydrogen to obtain alpha-MoC: high-purity ammonia gas with nitriding atmosphere of 150 ml/min; the temperature programming process is that the temperature is raised to 700 ℃ at the speed of 10 ℃/min, and the temperature is kept for 2h at 700 ℃; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4Is 20% by volume; the temperature programming carbonization process comprises heating to 700 deg.C at 10 deg.C/min, maintaining at 700 deg.C for 2h, cooling to room temperature, and adding 1% O2Passivating for 12 hours in/Ar to obtain alpha-MoC. 0.445g of cobalt nitrate hexahydrate is dissolved in water, dipped in 1g of the alpha-MoC in the same volume, and then is kept stand for 12 hours after being dipped, and then is dried in a forced air drying oven at 60 ℃ to obtain the catalyst of 9% Co/alpha-MoC.
(2) Activity evaluation test
The reaction for preparing methanol by carbon dioxide hydrogenation is carried out in a stainless steel reaction tube fixed bed reactor with the inner diameter of 8 mm. All paths of gas flow required by the experiment are regulated and controlled by mass flow meters, and flow into the reactor after being mixed. Respectively weighing 200mg of the catalyst (40-60 meshes) and 300mg of quartz sand (40-60 meshes), uniformly mixing, placing in a stainless steel reaction tube, and adding 15% of CH4/H2The mixed gas enters the catalyst at 500 DEG CPretreatment was carried out for 2h, and then activity evaluation was carried out under the following conditions: the reaction atmosphere adopts N2:CO2:H2The gas space velocity is 18,000mL/g/h, the reaction temperature is 240 ℃, and the reaction pressure is 3.0 MPa.
Table 1 shows 9% In/ZrO prepared In comparative example 129% In/α -MoC prepared In example 1, 9% In/5% ZrO prepared In example 22The results of comparing the space time yield of methanol from the catalytic carbon dioxide hydrogenation of/. alpha. -MoC, 1% Pt/9% In/. alpha. -MoC prepared In example 3, and 1% Co 9% In/. alpha. -MoC prepared In example 4 are reported In the literature.
Claims (9)
1. A supported catalyst for carbon dioxide hydrogenation is characterized in that the catalyst takes alpha-MoC as a carrier; indium is used as an active component.
2. The catalyst according to claim 1, wherein the mass fraction of indium in the catalyst is 3-15%; the catalyst further comprises an oxide promoter and/or a metal promoter.
3. The catalyst according to claim 2, wherein the mass fraction of the metal promoter is 0.1-5%; the mass fraction of the oxide auxiliary agent is 1-10%; the oxide auxiliary agent is ZrO2(ii) a The metal auxiliary agent is one or two of Pt and Co.
4. A method for preparing the catalyst of claim 1, comprising the steps of:
(1) roasting a metal precursor of molybdenum at 400-700 ℃ for 2-6 h to obtain molybdenum trioxide particles;
(2) carrying out temperature programming nitridation on the molybdenum trioxide at 590-800 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, and then carrying out temperature programming carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain a catalyst carrier;
(3) and (3) soaking the indium nitrate solution on the catalyst carrier in the same volume to obtain the catalyst.
5. The preparation method according to claim 4, wherein in the step (2), the nitriding atmosphere is high-purity ammonia gas of 50-200 ml/min; the temperature programming nitridation process comprises the following steps: heating to 590-800 ℃ at a speed of 5-20 ℃/min and preserving heat for 1-5 h; naturally cooling to room temperature, then heating to carbonize in CH atmosphere4/H2Mixed gas, CH in mixed gas4The volume fraction of (A) is 5-50%; the temperature programming carbonization process comprises the steps of heating to 590-800 ℃ at the speed of 5-20 ℃/min, preserving the heat for 1-5h, cooling to room temperature, and then adding 1% of O2Passivating for 12-48h in/Ar.
6. The method according to claim 4, wherein when the catalyst further comprises an oxide promoter, the step (2) comprises the steps of:
isovolumetrically impregnating the metal precursor solution of the oxide auxiliary agent on the molybdenum trioxide by an isovolumetrically impregnating method; and (2) carrying out temperature programming nitridation on molybdenum trioxide impregnated with a peroxide auxiliary agent metal precursor at 590-800 ℃ under the pure ammonia atmosphere, naturally cooling to room temperature, and then carrying out temperature programming carbonization at 590-800 ℃ in a mixed gas of methane and hydrogen to obtain the oxide auxiliary agent modified alpha-MoC.
7. The preparation method according to claim 4, wherein when the catalyst further comprises a metal promoter, the preparation method further comprises a step (4), and the step (4) is: and (4) soaking a precursor of the metal auxiliary agent in the catalyst prepared in the step (3) in an equal volume to obtain the metal auxiliary agent modified catalyst.
8. Use of the catalyst of any one of claims 1 to 3 in a reaction for the hydrogenation of carbon dioxide to methanol.
9. According toThe use of claim 8, wherein the reaction atmosphere for preparing methanol by hydrogenation of carbon dioxide is CO2And H2Mixed gas of H2And CO2The molar ratio of (A) to (B) is 1: 1-1: 4, and the reaction pressure is 1-5 MPa.
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