CN118162194A - Catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation and preparation method and application thereof - Google Patents
Catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 129
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 112
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 53
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 53
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 214
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 67
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 42
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 38
- 230000018044 dehydration Effects 0.000 claims abstract description 33
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 17
- 238000012412 chemical coupling Methods 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 238000013329 compounding Methods 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 83
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- 239000007789 gas Substances 0.000 claims description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000009210 therapy by ultrasound Methods 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
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- 238000000227 grinding Methods 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- -1 methanol dehydrated molecular sieve Chemical class 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000011572 manganese Substances 0.000 description 19
- 239000011777 magnesium Substances 0.000 description 17
- 229910052749 magnesium Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 13
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 5
- 229940044658 gallium nitrate Drugs 0.000 description 5
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 206010024769 Local reaction Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 230000001419 dependent effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation, and a preparation method and application thereof, and belongs to the technical field of dimethyl ether preparation. The catalyst is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 1-4:1, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is at least one of Mn, mg, ce or La, the carrier is a carbon nano tube, and the total mass of Cu, zr, ga, the auxiliary agent M and the carrier is calculated according to 100%, and the content of each component is as follows: 20-40% of Cu, 20-30% of Zr, 5-10% of Ga, 5-10% of auxiliary agent M and the balance of carrier. The catalyst can inhibit reverse water gas shift reaction and improve the selectivity of target products.
Description
Technical Field
The invention belongs to the technical field of dimethyl ether preparation, and particularly relates to a catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation, and a preparation method and application thereof.
Background
The large-scale use of fossil fuels such as coal, petroleum, natural gas and the like brings about rapid economic development and excessive emission of CO 2, so that natural carbon circulation is unbalanced, and carbon neutralization becomes one of the most important targets for environmental management. Not only can the CO 2 be converted into high value-added chemicals reduce the CO 2 concentration in the atmosphere, but also chemicals that meet the needs of industrial development can be provided. Dimethyl ether is known as clean fuel in the 21 st century, has excellent combustion performance and is easy to liquefy and store. Meanwhile, dimethyl ether (DEM for short) is an important organic intermediate and has wide application in the industries of organic synthesis, pharmacy, light industry and the like.
At present, a common dimethyl ether synthesis method is that carbon-containing resources are converted into synthesis gas, the synthesis gas is converted into methanol, and then the methanol is dehydrated to generate dimethyl ether. The process is highly dependent on fossil energy and can lead to significant CO 2 emissions. The method is characterized in that the dimethyl ether is synthesized by hydrogenating carbon dioxide, on one hand, the carbon dioxide is used as a reaction raw material, and on the other hand, the dimethyl ether with high added value is synthesized by the carbon dioxide. From the economic and environmental viewpoints, the hydrogenation synthesis of the dimethyl ether from the carbon dioxide is an effective path for realizing carbon circulation balance and realizing the aim of double carbon.
It is generally believed that the hydrogenation of carbon dioxide to dimethyl ether involves 3 interrelated reaction processes, namely: methanol synthesis, methanol dehydration and water-gas reverse transformation reaction. The one-step synthesis of dimethyl ether by carbon dioxide is completed by coupling the preparation of methanol from carbon dioxide and the preparation of dimethyl ether by dehydration of methanol into one reactor, and has the advantages of short flow, low energy consumption and the like. From the reaction thermodynamic analysis, the low-temperature and high-pressure reaction conditions are more favorable for carbon dioxide conversion, and the equilibrium conversion rate of the preparation of dimethyl ether by carbon dioxide hydrogenation is lower than that of the preparation of dimethyl ether by synthesis gas. Carbon dioxide belongs to linear symmetrical nonpolar molecules, has thermodynamic stability and kinetic inertia, and needs higher temperature for converting carbon dioxide. The side reaction reverse water gas shift reaction and water cause the deactivation of the catalyst, resulting in a decrease in conversion and selectivity of the target product. Therefore, the main task of the invention is to develop a low-temperature high-activity catalyst which can effectively inhibit the reverse water-gas shift reaction so as to improve the conversion rate of carbon dioxide catalytic hydrogenation and the selectivity of target product dimethyl ether.
The catalyst for one-step synthesis of dimethyl ether by carbon dioxide hydrogenation is formed by compounding a methanol synthesis component and a methanol dehydration component. The mixing method of the two types of catalysts directly influences the distance between two types of active centers in the methanol synthesis and dehydration catalysts and the synergistic effect thereof, thereby influencing the performance of the catalysts. The most direct mixing method is mechanical or physical mixing, but the mixing process is poorly reproducible and the active site contact distance is not controllable and directly affects the reaction performance. Thus, chemically coupling methanol synthesis with methanol dehydration catalysts is an effective way to achieve control of the contact between the two types of catalyst activities.
Therefore, in order to realize the sustainable development of the technology for preparing the dimethyl ether by high-efficiency carbon dioxide hydrogenation, the development of the coupling catalyst for synthesizing the dimethyl ether by high-efficiency carbon dioxide hydrogenation in one step has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation, a preparation method and application thereof, wherein the catalyst is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst by a chemical coupling method, can effectively inhibit reverse water gas shift reaction, and has good selectivity.
The catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, wherein the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 1-4:1, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is at least one of Mn, mg, ce or La, the carrier is a carbon nano tube, and the total mass of Cu, zr, ga, the auxiliary agent M and the carrier is calculated according to 100%, and the contents of the components are as follows: 20-40% of Cu, 20-30% of Zr, 5-10% of Ga, 5-10% of auxiliary agent M and the balance of carrier.
Preferably, the methanol dehydration catalyst is one of HZSM5 molecular sieve, MOR molecular sieve or ZSM35 molecular sieve.
Preferably, the SiO 2/Al2O3 ratio in the methanol dehydration catalyst is 15-80; the specific surface area of the carbon nano tube is 200-350 m 2/g.
The preparation method of the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide comprises the following steps:
(1) Preparing an auxiliary agent M modified carrier:
(11) Adding the carrier into nitric acid solution, heating and refluxing at 70-120deg.C for 3-10 hr, filtering, washing with deionized water to neutrality, oven drying, and grinding;
(12) Dissolving metal salt corresponding to the auxiliary agent M in water or ethanol to obtain a mixed solution of the auxiliary agent M;
(13) Adding the carrier obtained in the step (11) into the mixed solution of the auxiliary agent M in the step (12), stirring at room temperature until the mixture is dry, and then drying the mixture to obtain a carrier modified by the auxiliary agent M, namely M-CNTs;
(2) Preparing a catalyst by chemical coupling:
(21) Adding the carrier modified by the auxiliary agent M into alcohol, and carrying out ultrasonic treatment to obtain a solution A;
(22) Adding metal salt corresponding to the active component into alcohol, and performing ultrasonic treatment to obtain a solution B;
(23) Adding a methanol dehydrated molecular sieve into alcohol, and performing ultrasonic treatment to obtain a solution C;
(24) Adding alkali into alcohol, and performing ultrasonic treatment to obtain a solution D;
(25) Mixing the solution A, the solution C and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, then dropwise adding the solution B into the mixed ultrasonic solution at the temperature of 80-140 ℃ for stirring and refluxing for 2-4 hours, filtering, washing with deionized water to be neutral, drying, roasting, tabletting, forming, screening and sieving by a 20-60-mesh sieve to obtain the catalyst.
Preferably, the base is NaOH, KOH or aqueous ammonia; the total molar ratio of the alkali to Cu, zr and Ga is 4-8:1; the alcohol is ethanol or glycol.
Preferably, the metal salt corresponding to the auxiliary agent M and the metal salt corresponding to the active component are nitrate, chloride or acetate; the total concentration of the auxiliary agent M in the mixed solution of the auxiliary agent M is 0.5-1mol/L.
Preferably, the concentration of the nitric acid solution is 2-8moL/L, and the ratio of the carrier to the nitric acid solution is 1g:10-20mL; the ratio of the carrier modified by the auxiliary agent M to the alcohol in the step (21) is 1g:10-30mL; the ratio of the metal salt to the alcohol corresponding to the active component in the step (22) is 1g:20-50mL; the ratio of the methanol-dehydrated molecular sieve to the alcohol in the step (23) is 1g:10-30mL; the ratio of base to alcohol in step (24) is 1g:10-20mL; the ultrasonic treatment time is 0.3-0.8h, and the ultrasonic treatment power is 100-800W.
Preferably, the drying in the step (11) is drying at 80-120 ℃ for 8-12h; the step (13) is drying for 8-12h at 60-100 ℃; and (3) drying in the step (25) for 6-10h at 80-120 ℃ and roasting for 3-5h at 300-450 ℃.
A method for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation comprises the steps of filling a catalyst into a fixed bed reactor, introducing hydrogen-containing gas for reduction and activation, adjusting the reaction temperature to 240-290 ℃, then switching the mixed gas of CO 2 and H 2, and boosting the pressure to 2-5MPa for reaction; wherein the catalyst is the catalyst of the invention.
Preferably, the volume ratio of CO 2 to H 2 in the mixed gas of CO 2 and H 2 is 1:2-6, and the space velocity of the mixed gas of CO 2 and H 2 relative to the catalyst is 2000-8000H -1; the reduction and activation conditions are that the reduction and activation are carried out for 2-8 hours at the temperature of 280-360 ℃ and the normal pressure, wherein the flow rate of the hydrogen-containing gas is 30-100 mL/min, the hydrogen-containing gas is hydrogen or mixed gas of hydrogen and balance gas, the volume ratio of hydrogen in the mixed gas of hydrogen and balance gas is 5% -less than or equal to 100%, and the balance gas is nitrogen, helium or argon.
CNTs are short for carbon nanotubes.
In the invention, the active components CuO, zrO 2 and Ga 2O3 in the methanol synthesis catalyst are compound capable of activating CO 2 and H 2, and inhibiting reverse water gas shift reaction and product CO selectivity; the auxiliary agent plays roles of a structural auxiliary agent and an electronic auxiliary agent, and inhibits aggregation growth of active components and increases activity of electrons; the carrier can enrich reactant gas, increase local reaction pressure and better disperse active components, and the methanol synthesis catalyst further improves the selectivity of the product and the conversion rate of CO 2 after being chemically coupled with a methanol dehydration catalyst.
The invention has the advantages that:
(1) The catalyst provided by the invention, a methanol synthesis catalyst and a methanol dehydration catalyst are formed by chemical coupling and compounding, and can inhibit the reverse water gas shift reaction, so that the selectivity of CO in a reaction product is reduced, the selectivity of a target product is improved, and the one-step synthesis of dimethyl ether by carbon dioxide hydrogenation can be realized;
(2) The catalyst provided by the invention has the advantages of simple preparation method, environment-friendly preparation process and less three wastes.
Detailed Description
Example 1
1. The catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, wherein the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 4:1, the methanol dehydration catalyst is an HZSM5 molecular sieve with the SiO 2/Al2O3 ratio of 25, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is Mn, the carrier is a carbon nano tube with the specific surface area of 280M 2/g, and the weight ratio of Cu, zr, ga, the auxiliary agent Mn and the carrier carbon nano tube CNTs is as follows: cu: zr: ga: mn: cnts=40:30:5:5:20; the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide is expressed as CuO-ZrO 2-Ga2O3/Mn-CNTs/HZSM 5;
2. the preparation method of the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide comprises the following steps:
(1) Preparing an auxiliary agent Mn modified carrier:
(11) Adding the carrier into 8moL/L nitric acid solution according to the ratio of 1g to 10mL, heating and refluxing for 10 hours at 70 ℃, filtering, washing to be neutral by deionized water, drying at 80 ℃ for 12 hours, and grinding;
(12) Dissolving manganese nitrate into ethanol to obtain a manganese nitrate solution with Mn concentration of 1 mol/L;
(13) Adding the carrier obtained in the step (11) into the manganese nitrate solution obtained in the step (12), stirring at room temperature until the mixture is dry, and then drying at 60 ℃ for 12 hours to obtain an auxiliary agent Mn modified carbon nanotube which is marked as Mn-CNTs;
(2) Preparing a catalyst by chemical coupling:
(21) Adding an auxiliary agent Mn modified carbon nano tube into ethylene glycol according to the ratio of 1g to 10mL, and performing ultrasonic treatment for 0.3h under the power of 400W to obtain a solution A;
(22) Adding copper nitrate, zirconium acetate and gallium nitrate into glycol according to the proportion of 1g to 20mL, and performing ultrasonic treatment for 0.3h under the power of 400W to obtain a solution B;
(23) Adding HZSM5 molecular sieve into ethylene glycol according to the proportion of 1g to 10mL, and performing ultrasonic treatment for 0.3h under the power of 400W to obtain solution C;
(24) NaOH is added into glycol according to the proportion of 1g to 10mL, and ultrasonic treatment is carried out for 0.3h under the power of 400W, so as to obtain solution D; wherein, the total mole ratio of NaOH to Cu, zr and Ga is 4:1;
(25) Mixing the solution A, the solution C and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, then dropwise adding the solution B into the mixed ultrasonic solution at 140 ℃ for stirring and refluxing for 2 hours, filtering, washing to be neutral by deionized water, drying for 6 hours at 120 ℃, roasting for 3 hours at 450 ℃ in a muffle furnace, tabletting, forming, and screening by a 20-40-mesh sieve to obtain the catalyst.
Example 2
1. The catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, wherein the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 1:1, the methanol dehydration catalyst is a MOR molecular sieve with the SiO 2/Al2O3 ratio of 15, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is Mg and Ce, the carrier is a carbon nano tube with the specific surface area of 200M 2/g, and the weight ratio of Cu, zr, ga, the auxiliary agent Mg to Ce to the carrier carbon nano tube CNTs is as follows: cu: zr: ga: ce: cnts=20:30:10:4:6:30; the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide is expressed as CuO-ZrO 2-Ga2O3/MgCe-CNTs/MOR;
2. the preparation method of the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide comprises the following steps:
(1) Preparing an auxiliary agent Mg and Ce modified carrier:
(11) Adding the carrier into 2moL/L nitric acid solution according to the ratio of 1g to 20mL, heating and refluxing for 3 hours at 120 ℃, filtering, washing to be neutral by deionized water, drying at 120 ℃ for 8 hours, and grinding;
(12) Dissolving magnesium chloride and cerium nitrate in water to obtain an auxiliary agent mixed solution with the total concentration of Mg and Ce of 0.5 mol/L;
(13) Adding the carrier obtained in the step (11) into the auxiliary agent mixed solution obtained in the step (12), stirring at room temperature until the mixture is dry, and then drying at 100 ℃ for 8 hours to obtain auxiliary agent Mg and Ce modified carbon nanotubes, which are recorded as MgCe-CNTs;
(2) Preparing a catalyst by chemical coupling:
(21) Adding the carbon nano tube MgCe-CNTs modified by the auxiliary agent MgCe into ethanol according to the ratio of 1g to 30mL, and performing ultrasonic treatment for 0.8h under the power of 600W to obtain a solution A;
(22) According to 1g:50mL, adding copper nitrate, zirconium acetate and gallium nitrate into ethanol, and performing ultrasonic treatment for 0.8h under the power of 600W to obtain a solution B;
(23) Adding MOR molecular sieve into ethanol according to the ratio of 1g to 30mL, and performing ultrasonic treatment for 0.8h under the power of 600W to obtain solution C;
(24) KOH was added to ethanol at a ratio of 1g to 10mL and sonicated at 600W for 0.8h to give solution D; wherein the total molar ratio of NaOH to Cu, zr and Ga is 5:1;
(25) Mixing the solution A, the solution C and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, then dropwise adding the solution B into the mixed ultrasonic solution at 80 ℃ for stirring and refluxing for 4 hours, filtering, washing to be neutral by deionized water, drying for 10 hours at 80 ℃, roasting for 3 hours at 300 ℃ in a muffle furnace, tabletting, forming, and screening by a 40-60-mesh sieve to obtain the catalyst.
Example 3
1. The catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, wherein the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 3:1, the methanol dehydration catalyst is a ZSM35 molecular sieve with the SiO 2/Al2O3 ratio of 80, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is La, the carrier is a carbon nano tube with the specific surface area of 350M 2/g, and the weight ratio of Cu, zr, ga, auxiliary agent La and carrier carbon nano tube CNTs is as follows: cu: zr: ga: la: cnts=30:20:10:10:30; the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide is expressed as CuO-ZrO 2-Ga2O3/La-CNTs/ZSM 35;
2. the preparation method of the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide comprises the following steps:
(1) Preparing an auxiliary La modified carrier:
(11) Adding the carrier into 5moL/L nitric acid solution according to the ratio of 1g to 20mL, heating and refluxing for 5 hours at 100 ℃, filtering, washing to be neutral by deionized water, drying at 110 ℃ for 10 hours, and grinding;
(12) Dissolving lanthanum acetate in water to obtain a lanthanum acetate solution with La concentration of 0.6 mol/L;
(13) Adding the carrier obtained in the step (11) into the lanthanum acetate solution obtained in the step (12), stirring to dryness at room temperature, and then drying at 80 ℃ for 8 hours to obtain an auxiliary La modified carbon nanotube which is marked as La-CNTs;
(2) Preparing a catalyst by chemical coupling:
(21) Adding an auxiliary agent La modified carbon nano tube La-CNTs into ethylene glycol according to the ratio of 1g to 20mL, and performing ultrasonic treatment for 0.5h under the power of 100W to obtain a solution A;
(22) Adding copper nitrate, zirconium acetate and gallium nitrate into glycol according to the proportion of 1g to 40mL, and performing ultrasonic treatment for 0.5h under the power of 100W to obtain a solution B;
(23) According to 1g: adding ZSM35 molecular sieve into ethylene glycol according to the proportion of 20mL, and performing ultrasonic treatment for 0.5h under the power of 100W to obtain solution C;
(24) Ammonia water is added into glycol according to the proportion of 1g to 15mL, and ultrasonic treatment is carried out for 0.5h under the power of 100W, so as to obtain solution D; wherein the total molar ratio of ammonia water to Cu, zr and Ga is 8:1;
(25) Mixing the solution A, the solution C and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, dropwise adding the solution B into the mixed ultrasonic solution at 100 ℃ for stirring and refluxing for 3 hours, filtering, washing to be neutral by deionized water, drying for 8 hours at 90 ℃, roasting for 4 hours at 380 ℃ in a muffle furnace, tabletting, forming, and screening by a 20-40-mesh sieve to obtain the catalyst.
Example 4
1. The catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, wherein the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 2:1, the methanol dehydration catalyst is an HZSM5 molecular sieve with the SiO 2/Al2O3 ratio of 40, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is Mn and Mg, the carrier is a carbon nano tube with the specific surface area of 300M 2/g, and the weight ratio of Cu, zr, ga, the auxiliary agent Mn to Mg and the carrier carbon nano tube CNTs is as follows: cu: zr: ga: mn: mg: cnts=40:20:10:3:5:22; the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide is expressed as CuO-ZrO 2-Ga2O3/MnMg-CNTs/HZSM 5;
2. the preparation method of the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide comprises the following steps:
(1) Preparing an auxiliary agent Mn and Mg modified carrier:
(11) Adding the carrier into 6moL/L nitric acid solution according to the ratio of 1g to 15mL, heating and refluxing for 4 hours at 120 ℃, filtering, washing to be neutral by deionized water, drying at 90 ℃ for 10 hours, and grinding;
(12) Dissolving manganese acetate and magnesium chloride in ethanol to obtain an auxiliary agent mixed solution with the total concentration of Mn and Mg of 0.75 mol/L;
(13) Adding the carrier obtained in the step (11) into the auxiliary agent mixed solution obtained in the step (12), stirring at room temperature until the mixture is dry, and then drying at 100 ℃ for 9 hours to obtain auxiliary agent Mn and Mg modified carbon nanotubes, which are recorded as MnMg-CNTs;
(2) Preparing a catalyst by chemical coupling:
(21) Adding auxiliaries Mn and Mg modified carbon nanotubes MnMg-CNTs into ethylene glycol according to the ratio of 1g to 15mL, and performing ultrasonic treatment for 0.5h under the power of 800W to obtain a solution A;
(22) Adding copper nitrate, zirconium acetate and gallium nitrate into glycol according to the proportion of 1g to 30mL, and performing ultrasonic treatment for 0.5h under the power of 800W to obtain a solution B;
(23) Adding HZSM5 molecular sieve into ethylene glycol according to the proportion of 1g to 15mL, and performing ultrasonic treatment for 0.5h under the power of 800W to obtain solution C;
(24) KOH was added to ethylene glycol at a ratio of 1g to 20mL and sonicated at power 800W for 0.5h to give solution D; wherein, the total mole ratio of KOH to Cu, zr and Ga is 5:1;
(25) Mixing the solution A, the solution C and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, then dropwise adding the solution B into the mixed ultrasonic solution at 130 ℃ for stirring and refluxing for 2 hours, filtering, washing to be neutral by deionized water, drying for 7 hours at 100 ℃, roasting for 5 hours at 400 ℃ in a muffle furnace, tabletting, forming, and screening by a 40-60-mesh sieve to obtain the catalyst.
Comparative example 1
The catalyst for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is prepared by physically mixing a methanol synthesis catalyst and a methanol dehydration catalyst in a mass ratio of 2:1, wherein the methanol dehydration catalyst is an HZSM5 molecular sieve with a SiO 2/Al2O3 ratio of 40, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is Mn and Mg, the carrier is a carbon nano tube with a specific surface area of 300M 2/g, and the weight ratio of Cu, zr, ga, the auxiliary agent Mn and Mg to the carrier carbon nano tube CNTs is as follows: cu: zr: ga: mn: mg: cnts=40:20:10:3:5:22; the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide is expressed as CuO-ZrO 2-Ga2O3/MnMg-CNTs+HZSM 5;
The preparation method of the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide comprises the following steps:
(1) Preparing an auxiliary agent Mn and Mg modified carrier:
(11) Adding the carrier into 6moL/L nitric acid solution according to the ratio of 1g to 15mL, heating and refluxing for 4 hours at 120 ℃, filtering, washing to be neutral by deionized water, drying at 90 ℃ for 10 hours, and grinding;
(12) Dissolving manganese acetate and magnesium chloride in ethanol to obtain an auxiliary agent mixed solution with the total concentration of Mn and Mg of 0.75 mol/L;
(13) Adding the carrier obtained in the step (11) into the auxiliary agent mixed solution obtained in the step (12), stirring at room temperature until the mixture is dry, and then drying at 100 ℃ for 9 hours to obtain auxiliary agent Mn and Mg modified carbon nanotubes, which are recorded as MnMg-CNTs;
(2) Preparation of a methanol synthesis catalyst:
(21) Adding auxiliaries Mn and Mg modified carbon nanotubes MnMg-CNTs into ethylene glycol according to the ratio of 1g to 15mL, and performing ultrasonic treatment for 0.5h under the power of 800W to obtain a solution A;
(22) Adding copper nitrate, zirconium acetate and gallium nitrate into glycol according to the proportion of 1g to 30mL, and performing ultrasonic treatment for 0.5h under the power of 800W to obtain a solution B;
(23) KOH was added to ethylene glycol at a ratio of 1g to 20mL and sonicated at power 800W for 0.5h to give solution D; wherein, the total mole ratio of KOH to Cu, zr and Ga is 5:1;
(25) Mixing the solution A and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, then dropwise adding the solution B into the mixed ultrasonic solution at 130 ℃ for stirring and refluxing for 2 hours, filtering, washing to be neutral by deionized water, drying for 7 hours at 100 ℃, roasting for 5 hours at 400 ℃ in a muffle furnace, tabletting, forming, screening, and sieving with a 40-60-mesh sieve to obtain a methanol synthesis catalyst;
(3) Preparing a catalyst for preparing dimethyl ether by catalyzing hydrogenation of carbon dioxide through physical mixing:
Grinding a methanol dehydration catalyst HZSM5 molecular sieve, sieving the ground molecular sieve with a 40-60 mesh sieve, mixing the ground molecular sieve with the methanol synthesis catalyst, and uniformly stirring the mixture to obtain the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide.
Comparative example 2
Based on comparative example 1, step (3) is as follows:
Adding an HZSM5 molecular sieve into ethylene glycol according to the proportion of 1g to 15mL, carrying out ultrasonic treatment for 0.5h under the power of 800W, stirring and refluxing for 2h at 130 ℃, filtering, washing to be neutral by deionized water, drying for 7h at 100 ℃, roasting for 5h at 400 ℃ in a muffle furnace, tabletting, forming, screening, sieving by a 40-60-mesh sieve, mixing with the methanol synthesis catalyst, and uniformly stirring to obtain the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide;
The other is the same as in comparative example 1.
Example 5
A method for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation comprises the steps of filling a catalyst into a fixed bed reactor, introducing hydrogen-containing gas for reduction and activation, adjusting the reaction temperature to 240-290 ℃, then switching the mixed gas of CO 2 and H 2, and boosting the pressure to 2-5MPa for reaction; wherein the volume ratio of CO 2 to H 2 in the mixed gas of CO 2 and H 2 is 1:2-6, and the space velocity of the mixed gas of CO 2 and H 2 relative to the catalyst is 2000-8000H -1; the reduction and activation conditions are that the reduction and activation are carried out for 2-8 hours at the temperature of 280-360 ℃ and the normal pressure, wherein the flow rate of hydrogen-containing gas is 30-100 mL/min, the hydrogen-containing gas is hydrogen or mixed gas of hydrogen and balance gas, the volume ratio of hydrogen in the mixed gas of hydrogen and balance gas is 5% -less than or equal to 100%, the balance gas is nitrogen, helium or argon, and the specific reaction conditions and results are shown in table 1;
TABLE 1 reaction conditions and results
。
Claims (10)
1. A catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide is characterized in that: the catalyst is formed by compounding a methanol synthesis catalyst and a methanol dehydration catalyst through chemical coupling, the mass ratio of the methanol synthesis catalyst to the methanol dehydration catalyst is 1-4:1, the methanol synthesis catalyst consists of an active component, an auxiliary agent M and a carrier, the active component is a compound of CuO, zrO 2 and Ga 2O3, the auxiliary agent M is at least one of Mn, mg, ce or La, the carrier is a carbon nano tube, and the total mass of Cu, zr, ga, the auxiliary agent M and the carrier is calculated according to 100%, and the content of each component is as follows: 20-40% of Cu, 20-30% of Zr, 5-10% of Ga, 5-10% of auxiliary agent M and the balance of carrier.
2. The catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide according to claim 1, wherein: the methanol dehydration catalyst is one of an HZSM5 molecular sieve, a MOR molecular sieve or a ZSM35 molecular sieve.
3. The catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide according to claim 2, wherein: the SiO 2/Al2O3 ratio in the methanol dehydration catalyst is 15-80; the specific surface area of the carbon nano tube is 200-350m 2/g.
4. The method for preparing the catalyst for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide according to claim 1, which is characterized in that: the method comprises the following steps:
(1) Preparing an auxiliary agent M modified carrier:
(11) Adding the carrier into nitric acid solution, heating and refluxing at 70-120deg.C for 3-10 hr, filtering, washing with deionized water to neutrality, oven drying, and grinding;
(12) Dissolving metal salt corresponding to the auxiliary agent M in water or ethanol to obtain a mixed solution of the auxiliary agent M;
(13) Adding the carrier obtained in the step (11) into the mixed solution of the auxiliary agent M in the step (12), stirring at room temperature until the mixture is dry, and then drying the mixture to obtain the carrier modified by the auxiliary agent M;
(2) Preparing a catalyst by chemical coupling:
(21) Adding the carrier modified by the auxiliary agent M into alcohol, and carrying out ultrasonic treatment to obtain a solution A;
(22) Adding metal salt corresponding to the active component into alcohol, and performing ultrasonic treatment to obtain a solution B;
(23) Adding a methanol dehydrated molecular sieve into alcohol, and performing ultrasonic treatment to obtain a solution C;
(24) Adding alkali into alcohol, and performing ultrasonic treatment to obtain a solution D;
(25) Mixing the solution A, the solution C and the solution D, uniformly stirring to obtain a mixed ultrasonic solution, then dropwise adding the solution B into the mixed ultrasonic solution at the temperature of 80-140 ℃ for stirring and refluxing for 2-4 hours, filtering, washing with deionized water to be neutral, drying, roasting, tabletting, forming, screening and sieving by a 20-60-mesh sieve to obtain the catalyst.
5. The method for preparing the catalyst for preparing the dimethyl ether by catalyzing the hydrogenation of the carbon dioxide according to the claim 4, which is characterized in that: the alkali is NaOH, KOH or ammonia water; the total molar ratio of the alkali to Cu, zr and Ga is 4-8:1; the alcohol is ethanol or glycol.
6. The method for preparing the catalyst for preparing the dimethyl ether by catalyzing the hydrogenation of the carbon dioxide according to claim 5, which is characterized in that: the metal salt corresponding to the auxiliary agent M and the metal salt corresponding to the active component are nitrate, chloride or acetate; the total concentration of the auxiliary agent M in the mixed solution of the auxiliary agent M is 0.5-1mol/L.
7. The method for preparing the catalyst for preparing the dimethyl ether by catalyzing the hydrogenation of the carbon dioxide according to claim 6, which is characterized in that: the concentration of the nitric acid solution is 2-8moL/L, and the ratio of the carrier to the nitric acid solution is 1g:10-20mL; the ratio of the carrier modified by the auxiliary agent M to the alcohol in the step (21) is 1g:10-30mL; the ratio of the metal salt to the alcohol corresponding to the active component in the step (22) is 1g:20-50mL; the ratio of the methanol-dehydrated molecular sieve to the alcohol in the step (23) is 1g:10-30mL; the ratio of base to alcohol in step (24) is 1g:10-20mL; the ultrasonic treatment time is 0.3-0.8h, and the ultrasonic treatment power is 100-800W.
8. The method for preparing the catalyst for preparing the dimethyl ether by catalyzing the hydrogenation of the carbon dioxide according to claim 7, which is characterized in that: the step (11) of drying is that the drying is carried out for 8-12 hours at 80-120 ℃; the step (13) is drying for 8-12h at 60-100 ℃; and (3) drying in the step (25) for 6-10h at 80-120 ℃ and roasting for 3-5h at 300-450 ℃.
9. A method for preparing dimethyl ether by catalyzing carbon dioxide hydrogenation is characterized in that: filling a catalyst into a fixed bed reactor, introducing hydrogen-containing gas for reduction and activation, adjusting the reaction temperature to 240-290 ℃, then switching the mixed gas of CO 2 and H 2, and boosting the pressure to 2-5MPa for reaction; wherein the catalyst is the catalyst of claim 1.
10. The method for preparing dimethyl ether by catalyzing the hydrogenation of carbon dioxide according to claim 9, wherein: the volume ratio of CO 2 to H 2 in the mixed gas of CO 2 and H 2 is 1:2-6, and the space velocity of the mixed gas of CO 2 and H 2 relative to the catalyst is 2000-8000H -1; the reduction and activation conditions are that the reduction and activation are carried out for 2-8 hours at the temperature of 280-360 ℃ and the normal pressure, wherein the flow rate of the hydrogen-containing gas is 30-100 mL/min, the hydrogen-containing gas is hydrogen or mixed gas of hydrogen and balance gas, the volume ratio of hydrogen in the mixed gas of hydrogen and balance gas is 5% -less than or equal to 100%, and the balance gas is nitrogen, helium or argon.
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