CN107890870A - A kind of carbon dioxide and water methanation catalyst and its preparation method and application - Google Patents

A kind of carbon dioxide and water methanation catalyst and its preparation method and application Download PDF

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CN107890870A
CN107890870A CN201711009457.9A CN201711009457A CN107890870A CN 107890870 A CN107890870 A CN 107890870A CN 201711009457 A CN201711009457 A CN 201711009457A CN 107890870 A CN107890870 A CN 107890870A
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catalyst
nickel
carbon dioxide
water
substance
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CN107890870B (en
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刘勇军
邓旋
黄伟
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Taiyuan University of Technology
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Abstract

The invention discloses a kind of carbon dioxide and water methanation catalyst and its preparation method and application, belong to chemical technology field.The catalyst is mainly made up of metal simple-substance and loading type nickel-based catalyst.Metal simple-substance includes Zn, Fe, Al, Mn, Ni, Co and Mg, and nickel-base catalyst composition is Ni/C, and wherein C is carrier, includes Al2O3,SiO2,TiO2,ZrO2,CeO2,La2O3.On the basis of total catalyst weight, the mass percent of metal simple-substance is 20 ~ 90%, and the weight/mass percentage composition of nickel-base catalyst is 10 ~ 80%.Then catalyst preparation process is dried, is calcined, being reduced and produce catalyst using dipping, collosol and gel, precipitation or precipitation sedimentation.The reaction raw materials of the present invention are carbon dioxide and water, and wide material sources are cheap, and method for preparing catalyst is simple, easy to operate, and cost is low, have certain application prospect.Catalyst is mainly used in thermocatalytic, is not photocatalysis, nor electro-catalysis.

Description

A kind of carbon dioxide and water methanation catalyst and its preparation method and application
Technical field
The invention belongs to chemical technology field, is related to carbon dioxide conversion methane, is specifically to provide one kind and is used for Catalysis new technology of thermocatalytic carbon dioxide and water methane and its preparation method and application in fixed bed reactors.
Technical background
CO2It is a kind of main greenhouse gases, in recent years, with CO2The increase of discharge, global warming aggravation, causes The great attentions of national governments.In order to reduce CO2Concentration in an atmosphere, how to limit CO2Excessive emissions be on the one hand. On the other hand it is how that its rapid conversion is also particularly important, therefore how to realize CO2It is effective using more and more being ground The concern for the person of studying carefully.
Methane is a kind of high-quality, safe efficient, cleaning hydrocarbon resource.Quickening recently as Development of China's Urbanization and The raising of living standards of the people, domestic natural gas production can not fully meet the market demand, and imbalance between supply and demand increasingly highlights, therefore logical Multipath is crossed, multimode development synthetic natural gas technology not only can effectively alleviate demand of the China to natural gas, and have There are good economic benefit and environmental benefit.By CO2It is catalytically converted into CH4It is CO2One of important channel of recycling, not only may be used To solve CO2Emission problem, and new energy can be synthesized, realize CO2Recycling.
Traditional CO2Methanation refers to CO2Direct hydrogenation methanation, often generating a molecule methane needs to consume Tetramolecular hydrogen, substantial amounts of hydrogen will certainly be so consumed, and Hydrogen Energy is excellent because of its cleaning, efficient, safety, sustainability etc. Point, it is considered as 21 century most potential new energy.Patent CN102091629 A, CN 101773833 A, CN 101757928 A, A of CN 101773833 etc. disclose this kind of CO2Direct hydrogenation methanation catalyst.
Carbon dioxide and water react methane processed and mainly realized by photocatalysis and electro-catalysis reducing process at present.Both Although method achieves certain progress, but still some problems demands be present and solve.Photocatalysis because quantum yield is low, Catalytic efficiency is not high；Electro-catalysis needs to overcome CO under conditions of extra electric field2/CO2 -High redox potential carry out, and This two classes catalyst preparation process is complicated, and cost is high, and industry amplification application is remote.
As can be seen here, develop for thermocatalytic CO2And H2O reacts methane processed, for reducing catalyst preparation cost, improves Catalyst efficiency is extremely necessary.
The content of the invention
The present invention substitutes hydrogen with water, and the reaction of methane is produced for fixed bed thermocatalytic carbon dioxide reduction, it is therefore intended that The of a relatively high carbon dioxide of a kind of technique simple, small investment, catalytic efficiency is provided and water reduction produce methane catalyst and Its preparation method and application.
The present invention is adopted the following technical scheme that to realize：
A kind of carbon dioxide and water methanation catalyst, described catalyst is by metal simple-substance and loading type nickel-based catalyst group Into.
Described metal simple-substance is Zn, Fe, Al, Mn, Ni, one or more of mixing in Co, Mg, can be from Market is directly bought, and with elemental metal, the content of metal simple-substance in the catalyst is 20 ~ 90wt.%.
Loading type nickel-based catalyst composition be Ni/C, the content of loading type nickel-based catalyst in the catalyst for 10 ~ 80wt.%.Wherein active component Ni content is 1 ~ 50 wt.%.Carrier component C is Al2O3, SiO2, TiO2, ZrO2, CeO2, La2O3In one or more of mixtures.
Above-mentioned catalyst preparation process is by dipping, collosol and gel, and the method for precipitation or precipitation deposition is realized, specific step It is rapid as follows：
(1) with Al2O3, SiO2, TiO2, ZrO2, CeO2, La2O3In one or more of mixtures, using dipping legal system Obtain nickeliferous suspending liquid A.
Or with aluminum nitrate, zirconium nitrate, cerous nitrate, lanthanum nitrate, nickel nitrate be raw material, made using sodium carbonate/sodium hydroxide Nickeliferous sediment B is made for precipitating reagent.
Or with tetraethyl orthosilicate and butyl titanate, nickel nitrate is raw material, it is made by sol-gal process and contains nickel sol C。
Or nickel nitrate is deposited on by Al as precipitating reagent using sodium carbonate/sodium hydroxide2O3, SiO2, TiO2, ZrO2, CeO2, La2O3In one or more of mixtures on deposit D is made.
(2) nickeliferous suspending liquid A or sediment B or colloidal sol C or deposit D dryings, roasting, reduction are obtained into Ni-based urge Agent.
(3) one or more in nickel-base catalyst and metal simple-substance Zn, Fe, Al, Mn, Ni, Co, Mg are entered Row mechanical lapping mixes.
Above-mentioned catalyst is mainly used in thermocatalytic, is not photocatalysis, nor electricity is urged.For fixed bed thermocatalytic dioxy Change the reaction of carbon and water, 150 ~ 2400h of reaction velocity-1, 0.01 ~ 0.1mL/min of water, reaction temperature 300 ~ 700oC, reaction 0.5 ~ 5MPa of pressure.
The present invention replaces hydrogen reduction carbon dioxide with water, relative to traditional carbon dioxide direct hydrogenation methanation, raw material Wide material sources and cheap.Compared with existing carbon dioxide by photoelectric catalytic reduction, method for preparing catalyst is simple and is catalyzed Efficiency high, cost is low, easy to spread.Reaction condition is gentle, and integrated artistic meets green chemical concept, there is industrial amplification prospect.
Embodiment
Embodiment provides the present invention a kind of catalyst preparation and the application of carbon dioxide and water methane below It is further described in detail.
Embodiment 1
Weigh 2.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 18g Al2O3, it is small that 12 are impregnated under magnetic stirring When.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2Atmosphere Lower 450oThe h of C reduction treatments 5 produces 2.5 wt. % Ni/Al2O3Catalyst.By this catalyst and metal iron powder in mass ratio 1: 2 ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.
This catalyst granules is placed in fixed bed reactors and in the h of air speed 300-1, water 0.03 mL/min, 300 DEG C, activity rating is carried out under 2 MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 3.5；CH4Selectivity (C-mol It is %) 94.6.
Embodiment 2
Weigh 4.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g TiO2, it is small that 12 are impregnated under magnetic stirring When.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2Atmosphere Lower 450oThe h of C reduction treatments 5 produces 10 wt. % Ni/TiO2Catalyst.By this catalyst and metal Mn powder in mass ratio 1:3 Ratio carry out physical mixed, tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.
This catalyst granules is placed in fixed bed reactors and in the h of air speed 600-1, water 0.05 mL/min, 400 DEG C, activity rating is carried out under 3 MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 7.8；CH4Selectivity (C-mol It is %) 86.4.
Embodiment 3
Weigh 4.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g ZrO2, it is small that 12 are impregnated under magnetic stirring When.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2Atmosphere Lower 450oThe h of C reduction treatments 5 produces 10 wt. % Ni/ZrO2Catalyst.By this catalyst and metal Al powder in mass ratio 1:1 Ratio carry out physical mixed, tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.
This catalyst granules is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.07 mL/min, 500 DEG C, activity rating is carried out under 4 MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 9.3；CH4Selectivity (C-mol It is %) 80.5.
Embodiment 4
Weigh 8.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g SiO2, it is small that 12 are impregnated under magnetic stirring When.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2Atmosphere Lower 450oThe h of C reduction treatments 5 produces 20 wt. % Ni/SiO2Catalyst.By this catalyst and W metal powder in mass ratio 1:5 Ratio carry out physical mixed, tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.
This catalyst granules is placed in fixed bed reactors and in the h of air speed 2400-1, water 0.03 mL/min, 500 DEG C, activity rating is carried out under 0.5 MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 4.2；CH4Selectivity (C- Mol %) it is 76.5.
Embodiment 5
Weigh 4.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g CeO2, it is small that 12 are impregnated under magnetic stirring When.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2Atmosphere Lower 450oThe h of C reduction treatments 5 produces 10 wt. % Ni/SiO2Catalyst.By this catalyst and metal Zn powder in mass ratio 1:3 Ratio carry out physical mixed, tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.
This catalyst granules is placed in fixed bed reactors and in the h of air speed 600-1, water 0.01 mL/min, 400 DEG C, activity rating is carried out under 5 MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 4.7；CH4Selectivity (C-mol It is %) 83.5.
Embodiment 6
Weigh 2.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g La2O3, it is small that 12 are impregnated under magnetic stirring When.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2Atmosphere Lower 450oThe h of C reduction treatments 5 produces 5 wt. % Ni/SiO2Catalyst.By this catalyst and metal Mg powder in mass ratio 1:2 Ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.
This catalyst granules is placed in fixed bed reactors and in the h of air speed 150-1, water 0.03 mL/min, 500 DEG C, activity rating is carried out under 5 MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 4.7；CH4Selectivity (C-mol It is %) 73.5.
Embodiment 7
Weigh 4.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g SiO2And Al2O3In composite oxides, Impregnated 12 hours under magnetic agitation.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC Be calcined 4 h, after in H2450 under atmosphereoThe h of C reduction treatments 5 produces 10 wt. % Ni/SiO2-Al2O3Catalyst.
By this catalyst granules and metal iron powder in mass ratio 1:10 ratio carries out physical mixed, tabletting, broken, screening Obtain the catalyst granules of 40 ~ 60 mesh.This catalyst is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.01 ML/min, activity rating is carried out under 5 MPa reaction condition, as a result by 500 DEG C：CO2Conversion ratio (C-mol %) is 10.4；CH4 Selectivity (C-mol %) is 86.7.
Embodiment 8
Weigh 4.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g SiO2And Al2O3In composite oxides, Impregnated 12 hours under magnetic agitation.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC Be calcined 4 h, after in H2450 under atmosphereoThe h of C reduction treatments 5 produces 10 wt. % Ni/SiO2-Al2O3Catalyst.
By this catalyst granules and metal iron powder in mass ratio 1:10 ratio carries out physical mixed, tabletting, broken, screening Obtain the catalyst granules of 40 ~ 60 mesh.This catalyst is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.05 ML/min, activity rating is carried out under 5 MPa reaction condition, as a result by 600 DEG C：CO2Conversion ratio (C-mol %) is 12.2；CH4 Selectivity (C-mol %) is 84.5.
Embodiment 9
Weigh 4.0 g Ni (NO3)2·6H2O is dissolved in distilled water, rear to add 9 g SiO2And Al2O3In composite oxides, Impregnated 12 hours under magnetic agitation.It is then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC Be calcined 4 h, after in H2450 under atmosphereoThe h of C reduction treatments 5 produces 10 wt. % Ni/SiO2-Al2O3Catalyst.This is catalyzed Agent and metal iron powder in mass ratio 1:10 ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst of 40 ~ 60 mesh Particle.
This catalyst is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.07 mL/min, 700 DEG C, 5 Activity rating is carried out under MPa reaction condition, as a result：CO2Conversion ratio (C-mol %) is 15.8；CH4Selective (C-mol %) is 78.6。
Embodiment 10
Weigh 20.0 g Ni (NO3)2·6H2O and 36.8gAl (NO3)3·6H2O is dissolved in distilled water, then under mechanical agitation with 1mol/L Na2CO3Solution co-precipitation, after aging half an hour, it is washed with deionized water 3 times, is then placed in air dry oven 120 oC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2450 under atmosphereoThe h of C reduction treatments 5 is produced 50 wt. % Ni/Al2O3Catalyst.
By this catalyst granules and metal iron powder in mass ratio 1:5 ratio carries out physical mixed, tabletting, broken, screening Obtain the catalyst granules of 40 ~ 60 mesh.This catalyst is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.03 ML/min, activity rating is carried out under 3 MPa reaction condition, as a result by 500 DEG C：CO2Conversion ratio (C-mol %) is 20.4；CH4 Selectivity (C-mol %) is 86.6.
Embodiment 11
Weigh 20.0 g Ni (NO3)2·6H2O and 17.4 gZr (NO3)4·5H2O is dissolved in distilled water, then under mechanical agitation with 1mol/L NaOH solution co-precipitation, after aging half an hour, it is washed with deionized water 3 times, is then placed in air dry oven 120 oC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2450 under atmosphereoThe h of C reduction treatments 5 is produced 50 wt. % Ni/ZrO2Catalyst.
By this catalyst granules and metal iron powder in mass ratio 1:3 ratio carries out physical mixed, tabletting, broken, screening Obtain the catalyst granules of 40 ~ 60 mesh.This catalyst is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.1 ML/min, activity rating is carried out under 5 MPa reaction condition, as a result by 600 DEG C：CO2Conversion ratio (C-mol %) is 23.4；CH4 Selectivity (C-mol %) is 83.3.
Embodiment 12
Weigh 10.0 g Ni (NO3)2·6H2O is dissolved in distilled water, under mechanical stirring with 1mol/L Na2CO3Solution is simultaneously Stream co-precipitation is deposited on commercialized SiO2And TiO2Complex carrier on, after aging half an hour, be washed with deionized water 3 times, then It is put into 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2450 under atmosphereoThe h of C reduction treatments 5 produces 25 wt. % Ni/TiO2-SiO2Catalyst.By this catalyst and metal iron powder in mass ratio 1:8 Ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.It is anti-that this catalyst is placed in fixed bed Answer in device and in the h of air speed 1200-1, water 0.05 mL/min, 500 DEG C, activity rating is carried out under 4 MPa reaction condition, As a result：CO2Conversion ratio (C-mol %) is 16.3；CH4Selectivity (C-mol %) is 90.3.
Embodiment 13
Weigh 5.0 g Ni (NO3)2·6H2O is dissolved in distilled water, and the NaOH solution cocurrent with 1mol/L is total under mechanical stirring It is deposited on commercialized SiO2And Al2O3Complex carrier on, after aging half an hour, be washed with deionized water 3 times, Ran Houfang Enter 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2450 under atmosphereoC The h of reduction treatment 5 produces 25 wt. % Ni/TiO2-SiO2Catalyst.By this catalyst and metal iron powder in mass ratio 1:12 Ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.This catalyst granules is placed in fixation In bed reactor and in the h of air speed 1200-1, water 0.03 mL/min, activity is carried out under 3 MPa reaction condition and is commented by 500 DEG C Valency, as a result：CO2Conversion ratio (C-mol %) is 21.3；CH4Selectivity (C-mol %) is 93.5.
Embodiment 14
Weigh 5.0 g Ni (NO3)2·6H2O is dissolved in distilled water, and the rear tetraethyl orthosilicate for adding 31.1 g is 70oWater under C 3 h are solved, are then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after in H2 450 under atmosphereoThe h of C reduction treatments 5 produces 10 wt. % Ni/SiO2Catalyst.By this catalyst and metal iron powder in mass ratio 1:6 ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.This catalyst granules is put In fixed bed reactors and in the h of air speed 1200-1, water 0.03 mL/min, 500 DEG C, carry out under 3 MPa reaction condition Activity rating, as a result：CO2Conversion ratio (C-mol %) is 14.3；CH4Selectivity (C-mol %) is 90.5.
Embodiment 15
Weigh 5.0 g Ni (NO3)2·6H2O is dissolved in distilled water, the rear butyl titanate for adding 38.3 g at room temperature under 4 h are hydrolyzed, are then placed in 120 in air dry ovenoC dries 10 h, is put into afterwards 500 in Muffle furnaceoC be calcined 4 h, after H2450 under atmosphereoThe h of C reduction treatments 5 produces 10 wt. % Ni/TiO2Catalyst.This catalyst and metal iron powder are pressed into quality Than 1:12 ratio carries out physical mixed, and tabletting, broken, screening obtain the catalyst granules of 40 ~ 60 mesh.By this catalyst granules It is placed in fixed bed reactors and in the h of air speed 1200-1, water 0.03 mL/min, 500 DEG C, enter under 3 MPa reaction condition Row activity rating, as a result：CO2Conversion ratio (C-mol %) is 18.9；CH4Selectivity (C-mol %) is 83.6.

Claims (8)

1. a kind of carbon dioxide and water methanation catalyst, it is characterised in that the catalyst is by metal simple-substance and loading type nickel-based Catalyst forms；Wherein：
Metal simple-substance is Zn, Fe, Al, Mn, Ni, one or more of mixing in Co, Mg, with elemental metal, gold It is 20 ~ 90wt.% to belong to the content of simple substance in the catalyst；
Loading type nickel-based catalyst composition is Ni/C, and carrier component C is Al2O3, SiO2, TiO2, ZrO2, CeO2, La2O3In One or more of mixtures, the content of loading type nickel-based catalyst in the catalyst is 10 ~ 80wt.%.
2. a kind of carbon dioxide according to claim 1 and water methanation catalyst, it is characterised in that：Its preparation process Comprise the following steps：
(1) with Al2O3, SiO2, TiO2, ZrO2, CeO2, La2O3In one or more of mixtures, using dipping legal system Obtain nickeliferous suspending liquid A；
(2) nickeliferous suspending liquid A drying, roasting, reduction are obtained into nickel-base catalyst；
(3) by one or more of carry out machines in nickel-base catalyst and metal simple-substance Zn, Fe, Al, Mn, Ni, Co, Mg Tool ground and mixed.
3. a kind of carbon dioxide according to claim 1 and water methanation catalyst, it is characterised in that：Its preparation process Comprise the following steps：
(1) it is raw material with aluminum nitrate, zirconium nitrate, cerous nitrate, lanthanum nitrate, nickel nitrate, using sodium carbonate/sodium hydroxide as heavy Nickeliferous sediment B is made in shallow lake agent；
(2) sediment B drying, roasting, reduction are obtained into nickel-base catalyst；
(3) by one or more of carry out machines in nickel-base catalyst and metal simple-substance Zn, Fe, Al, Mn, Ni, Co, Mg Tool ground and mixed.
4. a kind of carbon dioxide according to claim 1 and water methanation catalyst, it is characterised in that：Its preparation process Comprise the following steps：
(1) with tetraethyl orthosilicate and butyl titanate, nickel nitrate is raw material, and nickeliferous colloidal sol C is made by sol-gal process；
(2) colloidal sol C dryings, roasting, reduction are obtained into nickel-base catalyst;
(3) by one or more of carry out machines in nickel-base catalyst and metal simple-substance Zn, Fe, Al, Mn, Ni, Co, Mg Tool ground and mixed.
5. a kind of carbon dioxide according to claim 1 and water methanation catalyst, it is characterised in that：Its preparation process Comprise the following steps：
(1) nickel nitrate is deposited on by Al as precipitating reagent using sodium carbonate/sodium hydroxide2O3, SiO2, TiO2, ZrO2, CeO2, La2O3In one or more of mixtures on deposit D is made；
(2) deposit D dryings, roasting, reduction are obtained into nickel-base catalyst；
(3) by one or more of carry out machines in nickel-base catalyst and metal simple-substance Zn, Fe, Al, Mn, Ni, Co, Mg Tool ground and mixed.
6. according to a kind of carbon dioxide of claim 1 ~ 6 any one and water methanation catalyst, it is characterised in that：Catalysis Agent, it is characterised in that：The content of active component nickel is 1 ~ 50wt.% in nickel-base catalyst.
7. a kind of carbon dioxide according to claim 1 and water methanation catalyst, it is characterised in that：The catalyst should For thermocatalytic.
A kind of 8. carbon dioxide and water methanation catalyst according to claim 1 or 7, it is characterised in that：The catalysis Agent is directly used in the reaction of fixed bed thermocatalytic carbon dioxide and water, and reaction velocity is 150 ~ 2400h-1, water is 0.01 ~ 0.1mL/min, reaction temperature are 300 ~ 700oC, reaction pressure are 0.5 ~ 5MPa.
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CN114367286A (en) * 2022-01-21 2022-04-19 中国科学院地球环境研究所 Metal monatomic catalyst and preparation method thereof
CN114377680A (en) * 2022-01-26 2022-04-22 中国科学院上海高等研究院 Metal-loaded TiO2Base photocatalyst, preparation method and application
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