CN116273131A - Metal-free catalyst for directly converting methane into hydrogen and preparation method thereof - Google Patents
Metal-free catalyst for directly converting methane into hydrogen and preparation method thereof Download PDFInfo
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- CN116273131A CN116273131A CN202310351095.0A CN202310351095A CN116273131A CN 116273131 A CN116273131 A CN 116273131A CN 202310351095 A CN202310351095 A CN 202310351095A CN 116273131 A CN116273131 A CN 116273131A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 title description 2
- 150000004767 nitrides Chemical class 0.000 claims abstract description 57
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 26
- YIDYJOJPIKJUGA-UHFFFAOYSA-N [O-2].[Zr+4].[Na+] Chemical compound [O-2].[Zr+4].[Na+] YIDYJOJPIKJUGA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 16
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000292 calcium oxide Substances 0.000 claims abstract description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 16
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 150000002924 oxiranes Chemical class 0.000 claims description 24
- 229910052582 BN Inorganic materials 0.000 claims description 23
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 23
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910021532 Calcite Inorganic materials 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 8
- -1 polysiloxane Polymers 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 5
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- ZWAJLVLEBYIOTI-OLQVQODUSA-N (1s,6r)-7-oxabicyclo[4.1.0]heptane Chemical compound C1CCC[C@@H]2O[C@@H]21 ZWAJLVLEBYIOTI-OLQVQODUSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 3
- 150000002118 epoxides Chemical class 0.000 abstract 2
- 239000000126 substance Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 235000012239 silicon dioxide Nutrition 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 229910052909 inorganic silicate Inorganic materials 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 6
- 150000004760 silicates Chemical class 0.000 description 6
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 4
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
- C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
- C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
Abstract
The invention relates to a metal-free catalyst for directly converting methane into hydrogen and a preparation method thereof, wherein the metal-free catalyst comprises the following raw materials in parts by weight: 5-10 parts of ammonium borate, 10-20 parts of urea, 20-30 parts of nitrogen, 5-10 parts of aluminum oxide, 1-5 parts of sodium zirconium oxide, 5-10 parts of silicate, 2-6 parts of nitride, 1-9 parts of calcium oxide, 1-3 parts of epoxide and 5-10 parts of polyethylene glycol. The catalyst consists of ammonium borate, urea, nitrogen, aluminum oxide, sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and has high catalytic activity and stability. The catalyst can convert methane into hydrogen at low temperature, and simultaneously generates a small amount of carbon dioxide and carbon monoxide, and the catalytic activity and the stability of the catalyst are superior to those of the traditional noble metal catalyst. The catalyst can directly convert methane into hydrogen, and has the advantages of high reaction rate, high selectivity, good stability, simple preparation method and low cost.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a metal-free catalyst for directly converting methane into hydrogen and a preparation method thereof.
Background
By metal-free catalyst is meant that a catalyst containing metal atoms is not required for the catalytic reaction, but instead a non-metal catalyst is used. The catalyst can be recovered and reused, and has the advantages of high efficiency, environmental protection, low cost and the like. Common metal-free catalysts include acid-base salts, oxides, ionic liquids, and the like. The method has wide application in the fields of organic synthesis, environmental protection industry, chemical industry and the like.
In the prior art, methane is a rich natural gas resource, and the main application of the methane is energy and chemical raw materials. However, efficient use of methane has been a technical problem because of the high strength of the C-H bonds of methane, which are difficult to activate. Traditionally, high temperature and pressure conditions are required to convert methane to hydrogen in order to break the c—h bond. However, this method requires a lot of energy and expensive equipment, and is costly, which is disadvantageous for large-scale application.
To solve this problem, many researchers have tried to convert methane to hydrogen using a catalyst. Traditionally, these catalysts are typically noble metal based, such as platinum, palladium, rhodium, and the like. These catalysts exhibit high catalytic activity but they are costly and disadvantageous for large scale applications. The hydrogen production generally adopts high-temperature steam reforming and other methods, however, the methods have the problems of high energy consumption, slow reaction rate, easy deactivation of the catalyst and the like. Therefore, developing a catalyst for directly converting methane into hydrogen with high efficiency and low cost is of great importance for realizing clean energy conversion.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a metal-free catalyst for directly converting methane into hydrogen and a preparation method thereof.
The above object of the present invention is achieved by the following technical solutions:
the invention provides a metal-free catalyst for directly converting methane into hydrogen, which comprises the following raw materials in parts by weight: 5-10 parts of ammonium borate, 10-20 parts of urea, 20-30 parts of nitrogen, 5-10 parts of aluminum oxide, 1-5 parts of sodium zirconium oxide, 5-10 parts of silicate, 2-6 parts of nitride, 1-9 parts of calcium oxide, 1-3 parts of epoxide and 5-10 parts of polyethylene glycol.
The present invention may be further configured in a preferred example to: the material comprises the following raw materials in parts by weight: 7.5 parts of ammonium borate, 15 parts of urea, 25 parts of nitrogen, 7.5 parts of aluminum oxide, 3 parts of sodium zirconium oxide, 7.5 parts of silicate, 4 parts of nitride, 5 parts of calcium oxide, 2 parts of epoxide and 7.5 parts of polyethylene glycol.
The present invention may be further configured in a preferred example to: the polyethylene glycol has a molecular weight between 300 and 750.
The present invention may be further configured in a preferred example to: the molar ratio of the sodium zirconium oxide to the epoxide to the polyethylene glycol is 3:2:2-3:1:1.
The present invention may be further configured in a preferred example to: the epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide and ethylene oxide.
The present invention may be further configured in a preferred example to: the silicate is one of silicon dioxide, quartz, calcite, silane and polysiloxane.
The present invention may be further configured in a preferred example to: the nitride is one of carbon nitride and boron nitride.
The invention also discloses a preparation method of the metal-free catalyst for directly converting methane into hydrogen, which comprises the following steps:
step 1: preparing raw materials, mixing ammonium borate and urea in a molar ratio of 1:3 to obtain a borazine precursor;
step 2: preparing boron nitride, namely heating a borazine precursor to 1300 ℃ in a nitrogen atmosphere, and keeping the temperature for 2.5 hours to obtain boron nitride;
step 3: preparing a catalyst, uniformly mixing the obtained boron nitride and aluminum oxide according to the weight ratio of 1:1, sequentially adding sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and heating the mixture to 800 ℃ in the atmosphere of hydrogen, and keeping the temperature for 3 hours to obtain the catalyst.
The present invention may be further configured in a preferred example to: the method for using the catalyst comprises the following steps:
methane and a catalyst are mixed in a molar ratio of 5:1, the mixture is reacted at 500-700 ℃, the reaction pressure is 5-10 atm, the reaction time is 6.5 hours, the hydrogen and the graphene are obtained, and the catalyst can be reused.
In summary, the present invention includes at least one of the following beneficial technical effects:
the invention discloses a metal-free catalyst for directly converting methane into hydrogen and a preparation method thereof. The catalyst consists of ammonium borate, urea, nitrogen, aluminum oxide, sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and has high catalytic activity and stability. The catalyst can convert methane into hydrogen at low temperature, and simultaneously generates a small amount of carbon dioxide and carbon monoxide, and the catalytic activity and the stability of the catalyst are superior to those of the traditional noble metal catalyst.
Description of the embodiments
The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application; it is apparent that the described embodiments are only a part of the embodiments of the present application, not all of the embodiments, and all other embodiments obtained by a person having ordinary skill in the art without making creative efforts based on the embodiments in the present application are within the scope of protection of the present application.
Examples
The metal-free catalyst for directly converting methane into hydrogen comprises the following raw materials in parts by weight: 7.5 parts of ammonium borate, 15 parts of urea, 25 parts of nitrogen, 7.5 parts of aluminum oxide, 3 parts of sodium zirconium oxide, 7.5 parts of silicate, 4 parts of nitride, 5 parts of calcium oxide, 2 parts of epoxide and 7.5 parts of polyethylene glycol.
The polyethylene glycol has a molecular weight between 300 and 750. The molar ratio of the sodium zirconium oxide to the epoxide and the polyethylene glycol is 3:2:2-3:1:1. The epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide and ethylene oxide. The silicate is one of silicon dioxide, quartz, calcite, silane and polysiloxane. Silicate refers to a compound having a chemical formula in which silicon element and oxygen element are contained, and oxygen atoms are replaced with one or more metal elements. Silicate is one of the most abundant minerals on earth and also one of the important components in living organisms.
Silicates can be classified into inorganic silicates and organic silicates. Wherein, the inorganic silicate refers to silicate without organic group, such as silicon dioxide, quartz, calcite, etc.; the organic silicate refers to silicate containing organic groups, such as silane, polysiloxane, etc. Silicate has the characteristics of high chemical stability, high temperature resistance, corrosion resistance, good insulating property and the like, so that the silicate is widely applied to the fields of building materials, ceramics, electronic materials, medical appliances and the like.
The nitride is one of carbon nitride and boron nitride. The nitride refers to a compound containing a nitrogen element and a metal element in the chemical formula. The nitride has the characteristics of high hardness, high melting point, high thermal conductivity, high electrical conductivity and the like, so that the nitride has important application in the fields of material science, electronic engineering, chemical industry and the like.
Nitrides can be divided into two categories: metal nitrides and non-metal nitrides. Wherein, the metal nitride refers to a compound formed by metal and nitrogen element, such as silicon nitride, aluminum nitride and the like; nonmetallic nitride refers to a compound formed by nonmetallic elements and nitrogen elements, such as carbon nitride, boron nitride, etc.
Nitrides are widely used in various fields. In material science, nitrides can be used as high temperature materials, high hardness coatings, ceramic materials, cutting tools, etc.; in electronic engineering, nitrides can be used as semiconductor materials, optoelectronic devices, high frequency devices, etc.; in the chemical industry, nitrides can be used as catalysts, adsorbents, etc.
The invention also discloses a preparation method of the metal-free catalyst for directly converting methane into hydrogen, which comprises the following steps:
step 1: preparing raw materials, mixing ammonium borate and urea in a molar ratio of 1:3 to obtain a borazine precursor;
step 2: preparing boron nitride, namely heating a borazine precursor to 1300 ℃ in a nitrogen atmosphere, and keeping the temperature for 2.5 hours to obtain boron nitride;
step 3: preparing a catalyst, uniformly mixing the obtained boron nitride and aluminum oxide according to the weight ratio of 1:1, sequentially adding sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and heating the mixture to 800 ℃ in the atmosphere of hydrogen, and keeping the temperature for 3 hours to obtain the catalyst.
The method for using the catalyst comprises the following steps:
methane and a catalyst are mixed in a molar ratio of 5:1, the mixture is reacted at 500-700 ℃, the reaction pressure is 5-10 atm, the reaction time is 6.5 hours, the hydrogen and the graphene are obtained, and the catalyst can be reused.
Examples
The metal-free catalyst for directly converting methane into hydrogen comprises the following raw materials in parts by weight: 5 parts of ammonium borate, 10 parts of urea, 20 parts of nitrogen, 5 parts of aluminum oxide, 1 part of sodium zirconium oxide, 5 parts of silicate, 2 parts of nitride, 1 part of calcium oxide, 1 part of epoxide and 5 parts of polyethylene glycol.
The polyethylene glycol has a molecular weight between 300 and 750. The molar ratio of the sodium zirconium oxide to the epoxide and the polyethylene glycol is 3:2:2-3:1:1. The epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide and ethylene oxide. The silicate is one of silicon dioxide, quartz, calcite, silane and polysiloxane. Silicate refers to a compound having a chemical formula in which silicon element and oxygen element are contained, and oxygen atoms are replaced with one or more metal elements. Silicate is one of the most abundant minerals on earth and also one of the important components in living organisms.
Silicates can be classified into inorganic silicates and organic silicates. Wherein, the inorganic silicate refers to silicate without organic group, such as silicon dioxide, quartz, calcite, etc.; the organic silicate refers to silicate containing organic groups, such as silane, polysiloxane, etc. Silicate has the characteristics of high chemical stability, high temperature resistance, corrosion resistance, good insulating property and the like, so that the silicate is widely applied to the fields of building materials, ceramics, electronic materials, medical appliances and the like.
The nitride is one of carbon nitride and boron nitride. The nitride refers to a compound containing a nitrogen element and a metal element in the chemical formula. The nitride has the characteristics of high hardness, high melting point, high thermal conductivity, high electrical conductivity and the like, so that the nitride has important application in the fields of material science, electronic engineering, chemical industry and the like.
Nitrides can be divided into two categories: metal nitrides and non-metal nitrides. Wherein, the metal nitride refers to a compound formed by metal and nitrogen element, such as silicon nitride, aluminum nitride and the like; nonmetallic nitride refers to a compound formed by nonmetallic elements and nitrogen elements, such as carbon nitride, boron nitride, etc.
Nitrides are widely used in various fields. In material science, nitrides can be used as high temperature materials, high hardness coatings, ceramic materials, cutting tools, etc.; in electronic engineering, nitrides can be used as semiconductor materials, optoelectronic devices, high frequency devices, etc.; in the chemical industry, nitrides can be used as catalysts, adsorbents, etc.
The invention also discloses a preparation method of the metal-free catalyst for directly converting methane into hydrogen, which comprises the following steps:
step 1: preparing raw materials, mixing ammonium borate and urea in a molar ratio of 1:3 to obtain a borazine precursor;
step 2: preparing boron nitride, namely heating a borazine precursor to 1300 ℃ in a nitrogen atmosphere, and keeping the temperature for 2.5 hours to obtain boron nitride;
step 3: preparing a catalyst, uniformly mixing the obtained boron nitride and aluminum oxide according to the weight ratio of 1:1, sequentially adding sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and heating the mixture to 800 ℃ in the atmosphere of hydrogen, and keeping the temperature for 3 hours to obtain the catalyst.
The method for using the catalyst comprises the following steps:
methane and a catalyst are mixed in a molar ratio of 5:1, the mixture is reacted at 500-700 ℃, the reaction pressure is 5-10 atm, the reaction time is 6.5 hours, the hydrogen and the graphene are obtained, and the catalyst can be reused.
Examples
The metal-free catalyst for directly converting methane into hydrogen comprises the following raw materials in parts by weight: 10 parts of ammonium borate, 20 parts of urea, 30 parts of nitrogen, 10 parts of aluminum oxide, 5 parts of sodium zirconium oxide, 10 parts of silicate, 6 parts of nitride, 9 parts of calcium oxide, 3 parts of epoxide and 10 parts of polyethylene glycol.
The polyethylene glycol has a molecular weight between 300 and 750. The molar ratio of the sodium zirconium oxide to the epoxide and the polyethylene glycol is 3:2:2-3:1:1. The epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, cyclohexene oxide and ethylene oxide. The silicate is one of silicon dioxide, quartz, calcite, silane and polysiloxane. Silicate refers to a compound having a chemical formula in which silicon element and oxygen element are contained, and oxygen atoms are replaced with one or more metal elements. Silicate is one of the most abundant minerals on earth and also one of the important components in living organisms.
Silicates can be classified into inorganic silicates and organic silicates. Wherein, the inorganic silicate refers to silicate without organic group, such as silicon dioxide, quartz, calcite, etc.; the organic silicate refers to silicate containing organic groups, such as silane, polysiloxane, etc. Silicate has the characteristics of high chemical stability, high temperature resistance, corrosion resistance, good insulating property and the like, so that the silicate is widely applied to the fields of building materials, ceramics, electronic materials, medical appliances and the like.
The nitride is one of carbon nitride and boron nitride. The nitride refers to a compound containing a nitrogen element and a metal element in the chemical formula. The nitride has the characteristics of high hardness, high melting point, high thermal conductivity, high electrical conductivity and the like, so that the nitride has important application in the fields of material science, electronic engineering, chemical industry and the like.
Nitrides can be divided into two categories: metal nitrides and non-metal nitrides. Wherein, the metal nitride refers to a compound formed by metal and nitrogen element, such as silicon nitride, aluminum nitride and the like; nonmetallic nitride refers to a compound formed by nonmetallic elements and nitrogen elements, such as carbon nitride, boron nitride, etc.
Nitrides are widely used in various fields. In material science, nitrides can be used as high temperature materials, high hardness coatings, ceramic materials, cutting tools, etc.; in electronic engineering, nitrides can be used as semiconductor materials, optoelectronic devices, high frequency devices, etc.; in the chemical industry, nitrides can be used as catalysts, adsorbents, etc.
The invention also discloses a preparation method of the metal-free catalyst for directly converting methane into hydrogen, which comprises the following steps:
step 1: preparing raw materials, mixing ammonium borate and urea in a molar ratio of 1:3 to obtain a borazine precursor;
step 2: preparing boron nitride, namely heating a borazine precursor to 1300 ℃ in a nitrogen atmosphere, and keeping the temperature for 2.5 hours to obtain boron nitride;
step 3: preparing a catalyst, uniformly mixing the obtained boron nitride and aluminum oxide according to the weight ratio of 1:1, sequentially adding sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and heating the mixture to 800 ℃ in the atmosphere of hydrogen, and keeping the temperature for 3 hours to obtain the catalyst.
The method for using the catalyst comprises the following steps:
methane and a catalyst are mixed in a molar ratio of 5:1, the mixture is reacted at 500-700 ℃, the reaction pressure is 5-10 atm, the reaction time is 6.5 hours, the hydrogen and the graphene are obtained, and the catalyst can be reused.
The implementation principle of the embodiment is as follows: the invention discloses a metal-free catalyst for directly converting methane into hydrogen and a preparation method thereof. The catalyst consists of ammonium borate, urea, nitrogen, aluminum oxide, sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and has high catalytic activity and stability. The catalyst can convert methane into hydrogen at low temperature, and simultaneously generates a small amount of carbon dioxide and carbon monoxide, and the catalytic activity and the stability of the catalyst are superior to those of the traditional noble metal catalyst.
The embodiments of the present invention are all preferred embodiments of the present invention, and are not intended to limit the scope of the present invention in this way, therefore: all equivalent changes in structure, shape and principle of the invention should be covered in the scope of protection of the invention.
Claims (9)
1. The metal-free catalyst for directly converting methane into hydrogen is characterized by comprising the following raw materials in parts by weight: 5-10 parts of ammonium borate, 10-20 parts of urea, 20-30 parts of nitrogen, 5-10 parts of aluminum oxide, 1-5 parts of sodium zirconium oxide, 5-10 parts of silicate, 2-6 parts of nitride, 1-9 parts of calcium oxide, 1-3 parts of epoxide and 5-10 parts of polyethylene glycol.
2. The metal-free catalyst for directly converting methane into hydrogen according to claim 1, comprising the following raw materials in parts by weight: 7.5 parts of ammonium borate, 15 parts of urea, 25 parts of nitrogen, 7.5 parts of aluminum oxide, 3 parts of sodium zirconium oxide, 7.5 parts of silicate, 4 parts of nitride, 5 parts of calcium oxide, 2 parts of epoxide and 7.5 parts of polyethylene glycol.
3. A metal-free catalyst for the direct conversion of methane to hydrogen according to claim 1, wherein said polyethylene glycol has a molecular weight between 300 and 750.
4. A metal-free catalyst for the direct conversion of methane to hydrogen according to claim 1, characterized in that the molar ratio of sodium zirconium oxide to epoxide and polyethylene glycol is 3:2:2-3:1:1.
5. A metal-free catalyst for the direct conversion of methane to hydrogen according to claim 1, wherein said epoxide is one of propylene oxide, epichlorohydrin, styrene oxide, cyclohexane oxide, ethylene oxide.
6. A metal-free catalyst for the direct conversion of methane to hydrogen according to claim 1, wherein said silicate is one of silica, quartz, calcite, silane, polysiloxane.
7. A metal-free catalyst for the direct conversion of methane to hydrogen according to claim 1, wherein said nitride is one of carbon nitride or boron nitride.
8. A method for preparing a metal-free catalyst for the direct conversion of methane to hydrogen according to any one of claims 1 to 7, comprising the steps of:
step 1: preparing raw materials, mixing ammonium borate and urea in a molar ratio of 1:3 to obtain a borazine precursor;
step 2: preparing boron nitride, namely heating a borazine precursor to 1300 ℃ in a nitrogen atmosphere, and keeping the temperature for 2.5 hours to obtain boron nitride;
step 3: preparing a catalyst, uniformly mixing the obtained boron nitride and aluminum oxide according to the weight ratio of 1:1, sequentially adding sodium zirconium oxide, silicate, nitride, calcium oxide, epoxide and polyethylene glycol, and heating the mixture to 800 ℃ in the atmosphere of hydrogen, and keeping the temperature for 3 hours to obtain the catalyst.
9. The method for preparing a metal-free catalyst for direct conversion of methane to hydrogen according to claim 8, wherein the catalyst is used as follows:
methane and a catalyst are mixed in a molar ratio of 5:1, the mixture is reacted at 500-700 ℃, the reaction pressure is 5-10 atm, the reaction time is 6.5 hours, the hydrogen and the graphene are obtained, and the catalyst can be reused.
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