CN111167512B - Photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof - Google Patents
Photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 230000002195 synergetic effect Effects 0.000 claims abstract description 19
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 11
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000011941 photocatalyst Substances 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 150000003624 transition metals Chemical class 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000000084 colloidal system Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 230000003197 catalytic effect Effects 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- -1 p-sulfophenylpropylmethoxysilane Chemical compound 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052724 xenon Inorganic materials 0.000 claims description 8
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 4
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000005431 greenhouse gas Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 2
- VTDPERKJPOAPEQ-UHFFFAOYSA-K bismuth ethanol trichloride Chemical compound C(C)O.[Bi+3].[Cl-].[Cl-].[Cl-] VTDPERKJPOAPEQ-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- DGHWFRFSCWYTQJ-UHFFFAOYSA-N C(C)O.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound C(C)O.[N+](=O)([O-])[O-].[Bi+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] DGHWFRFSCWYTQJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- IPNGSXQUQIUWKO-UHFFFAOYSA-N bismuth;fluoro hypofluorite Chemical compound [Bi].FOF IPNGSXQUQIUWKO-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- B01J35/39—
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane and a preparation method thereof, wherein the catalyst takes a thermal catalyst formed by cheap metal hydrotalcite as a carrier, and a Bi-based photocatalyst is loaded to form the photo-thermal synergistic catalyst; the cheap metals comprise 1 to 3 of transition metals of Cr, mn, fe, co, ni, cu and Zn, 0 to 1 of alkaline earth metals of Ba, ca and Mg and metal Al. The invention has the following beneficial effects: (1) The prepared catalyst shows high activity in the reaction of synthesizing methanol by directly oxidizing methane, the reaction time is 2 to 96 hours under the conditions of low temperature and low pressure, the conversion rate of methane can reach 25 percent at most, and the selectivity of methanol can reach 95 percent at most. (2) The catalyst has simple preparation process, low cost, high activity and unique hydrothermal stability; (3) The obtained catalyst has the advantages of both light and heat catalysts, and can be used for directly oxidizing methane to synthesize methanol under mild conditions.
Description
Technical Field
The invention relates to a photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane and a preparation method thereof, belonging to the field of new materials and technologies.
Background
Methane is a main component of carbon-containing resources such as natural gas, shale gas, methane, combustible ice and the like, has higher hydrogen-carbon ratio compared with coal and petroleum, can be used as fuel and for producing hydrogen, carbon monoxide, acetylene, hydrocyanic acid, formaldehyde and the like, and is considered as a clean energy source with development potential in the 21 st century and a high-quality chemical raw material. However, CH 4 Is also an effective greenhouse gas, and has a greenhouse effect in the earth's atmosphere of more than 20 times as much as carbon dioxide. Thus will be CH 4 Catalytic conversion toThe high value-added product not only can realize the high-efficiency utilization of the product, but also has important academic value and profound environmental protection significance.
CH 4 Can be converted into CH by direct oxidation, non-oxidative coupling and oxidative coupling 3 OH, aromatic compound, C 2+ Products (ethylene, ethane, etc.) and the like. Wherein CH 3 OH is an important platform molecule and can be used for preparing hundreds of chemical products, namely CH 4 Preparation of CH by direct oxidation 3 OH is also considered to be the most economical and promising CH 4 The method is efficiently utilized, but two major problems to be solved are faced in the process: the first is difficult to activate the methane C-H, and the second is the product CH 3 OH is susceptible to further deep oxidation. So that a highly effective activated CH is constructed 4 And inhibit CH 3 Bifunctional catalytic systems for deep OH oxidation have been extremely challenging to date.
For nearly twenty years, CH 4 Preparation of CH by direct oxidation 3 Various catalytic oxidation systems for OH are constantly reported; wherein, homogeneous catalysis system represented by the Periana reaction system obtains unprecedented catalytic effect (CH) 4 Conversion of 81% CH 3 OH selectivity can reach more than 90 percent), but the strong corrosive and expensive catalytic system is not suitable for industrial popularization (Science, 1998, 280 (29): 560 to 564). The Martin and Tang subject group breaks through the traditional research thought, and takes FeO as the raw material under the normal temperature and the normal pressure with the assistance of sunlight (simulation) x /TiO 2 Is a catalyst, H 2 O 2 Is an oxidant, CH within 3 h 4 The conversion rate can reach 15 percent, the total alcohol selectivity can reach 97 percent, wherein CH 3 The selectivity of OH is as high as 90%, and the catalyst has excellent cycle stability (Nature catalysts, 2018, 1: 889 to 896), but H 2 O 2 The commodity price is higher than CH 3 OH inhibits the industrial application prospect, so the problem of direct oxidation of methane to synthesize methanol by developing a cheap and efficient catalyst is urgently needed to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane and a preparation method thereof.
The technical scheme of the invention is as follows:
a photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane takes a thermal catalyst formed by cheap metal hydrotalcite as a carrier, and a Bi-based photocatalyst is loaded to form the photo-thermal synergistic catalyst;
the cheap metal comprises 1 to 3 of transition metals of Cr, mn, fe, co, ni, cu and Zn, 0 to 1 of alkaline earth metals of Ba, ca and Mg and metal Al;
the Bi-based photocatalytic material is BiOX and BiX 3 、BiVO 4 、Bi 2 MoO 6 、Bi 2 WO 6 、Bi(NO 3 ) 3 X is Cl, br, I or F;
the surface of the hydrotalcite-like compound is subjected to hydrophobic organic modification, and the surface modifier is a silane coupling agent;
wherein the supported Bi-based photocatalytic material accounts for 5 to 20 percent of the total mass of the catalyst.
The invention also provides a preparation method of the photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane, which comprises the following steps:
(1) Preparing a mixed colloidal aqueous solution of transition metal oxide, alkaline earth metal hydroxide and aluminum hydroxide, and controlling the molar ratio of divalent metal ions to trivalent metal ions to be 2-5: 1, controlling the total concentration of metal ions to be 2.0-5.0 mol/L, controlling the pH value to be 9-11 by using alkali liquor, stirring for 1-10 hours at room temperature, putting into an autoclave, carrying out hydrothermal treatment at 80-120 ℃ for 12-48 hours, and cooling to room temperature;
(2) Adding a certain amount of Bi salt ethanol solution into the colloid obtained in the step (1), stirring for 1-3 hours at 20-60 ℃, continuously controlling the pH value of the colloid to be 9-11 by using alkali liquor without adding or adding 1-2 of ammonium vanadate, ammonium molybdate or ammonium tungstate, and continuously carrying out hydrothermal treatment for 6-12 hours at 80-120 ℃; then filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at the temperature of between 60 and 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material;
(3) Adding the obtained catalyst into 0.05 to 0.1 mol/L of silane coupling agent toluene solution, carrying out ultrasonic oscillation for 6 to 12 hours, and carrying out refrigerated centrifugal drying to obtain the surface-modified hydrotalcite-like loaded Bi catalytic material, namely the photo-thermal synergistic catalyst.
Further, in the step (1), the transition metal oxide is 1 to 3 kinds of chromium oxide, manganese oxide, ferrous oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide.
Further, in the step (1), the alkaline earth metal hydroxide is 0 to 1 of barium hydroxide, calcium hydroxide and magnesium hydroxide.
Further, in the steps (1) and (2), the alkali solution is any one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea solution.
Further, in the step (2), the Bi salt is any one of bismuth trihalide and bismuth nitrate.
Further, in the step (3), the silane coupling agent is 1 to 2 of mercaptopropyltrimethoxysilane, n-propyltrimethoxysilane, phenyltrimethoxysilane, p-sulfophenyl-propylmethoxysilane and aminopropyltrimethoxysilane.
Compared with the prior art, the invention mainly provides two aspects of technical innovation:
(1) Develops a cheap, efficient and green product and process, thereby synthesizing the photo-thermal synergistic catalyst with a regular structure under the condition of no three-waste emission;
(2) By utilizing the synergistic effect of the photo-thermal active center, a cheap and efficient catalytic system is developed for the direct oxidation synthesis of methanol from methane.
On one hand, the invention provides a new idea for preparing a BiOX/HT cheap catalytic system, strives to realize zero emission of anion waste liquid in the preparation process, improves atom economy and realizes energy conservation and emission reduction; on the other hand, can be an environment-friendly oxidant H 2 O 2 In situ generation of green house gas CH 4 Direct oxidation synthesis of CH 3 An environment-friendly and efficient OH is constructedA catalytic system. The smooth implementation of the two aspects can not only avoid the generation of three wastes in the preparation process of the catalyst from the source, but also inhibit the emission of greenhouse gases; but also can search out a green and high-efficiency energy conversion way. In addition, the method also provides an important reference basis for preparing the Bi-based photocatalytic material with more excellent performance in the field of photocatalytic degradation of pollutants.
As can be seen from the specific implementation mode of the invention, the invention has the following beneficial effects:
(1) The prepared catalyst shows high activity in the reaction of synthesizing methanol by directly oxidizing methane, the reaction time is 2 to 96 hours under the conditions of low temperature and low pressure, the conversion rate of methane can reach 25 percent at most, and the selectivity of methanol can reach 95 percent at most.
(2) The catalyst has simple preparation process, low cost, high activity and unique hydrothermal stability;
(3) The obtained catalyst has the advantages of both light and heat catalysts, and can directly oxidize methane to synthesize methanol under mild conditions.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Reaction and detection conditions: in a 100L photothermal reactor with xenon lamp light source, 30L water is used as solvent, 100 g of the prepared catalyst is added, and reaction mixed gas containing 1.6% of CH is introduced 4 , 6.6% O 2 65% of Ar and 26.8% of He, controlling the temperature of a reactor to be 30-90 ℃, controlling the pressure to be normal pressure-3.0 MPa, connecting the reactor to a gas chromatographic analysis (TCD detector, TDX-1 chromatographic column) on line to form a gas composition, filtering a solid catalyst after the reaction is finished, and analyzing a liquid composition by using a gas chromatographic (FID detector, DV-17 chromatographic column).
Example 1
48 mol MnO and 12 mol Ca (OH) 2 And 30 mol of Al (OH) 3 Preparing 45L colloid with deionized water; and adding NH 4 OH controlling the pH value of the mixed solution to be 9.0; stirring vigorously at room temperature for 1.0 hour, transferringThe mixture was put into an autoclave and hydrothermally treated at 80 ℃ for 12 hours, and then cooled to room temperature. Then adding 45L of 0.4 mol/L bismuth trichloride ethanol solution, stirring for 1 hour at 20 ℃, adding ammonium vanadate with the same mole number as that of bismuth trichloride, and adding NH 4 Controlling the pH value of the mixed solution to be 9.0 by OH, and continuously transferring the mixed solution into an autoclave for hydrothermal treatment for 6 hours at the temperature of 80 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 60 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. 100 g of the obtained material is added into 1L of toluene solution of 0.1 mol/L mercaptopropyl trimethoxy silane, and the mixture is subjected to ultrasonic violent oscillation for 6 hours, frozen centrifugal drying, thus obtaining the mercaptopropyl trimethoxy modified hydrotalcite-like compound loaded bismuth vanadate catalytic material, namely the photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 2 hours under normal pressure at the temperature of 30 ℃, so that the conversion rate of the obtained methane is 1.0 percent, and the selectivity of the methanol is 95 percent.
Example 2
48 mol of CoO, 12 mol of Zn (OH) 2 And 30 mol of Al (OH) 3 Preparing 18L of colloid by using deionized water; adding KOH to control the pH value of the mixed solution to be 11; vigorously stirred at room temperature for 10 hours, transferred into an autoclave for hydrothermal treatment at 120 ℃ for 48 hours, and then cooled to room temperature. Then, 18L of 0.15 mol/L bismuth trifluoride ethanol solution was added thereto, and the mixture was stirred at 20 ℃ for 3 hours, and the pH of the mixture was controlled with KOH to be 11, and then transferred to an autoclave at 120 ℃ for further hydrothermal treatment for 12 hours. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 1L of toluene solution of aminopropyl trimethoxy silane with the concentration of 0.1 mol/L, oscillating the mixture for 12 hours by ultrasonic waves, freezing, centrifuging and drying the mixture to obtain the aminopropyl trimethoxy modified hydrotalcite-like compound loaded bismuth oxyfluoride catalytic material, namely the photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out at 90 ℃ and 3 Mpa for 96 hours, so that the conversion rate of the obtained methane is 25 percent, and the selectivity of the methanol is 55 percent.
Example 3
48 mol of NiO and 12 mol of Ba (OH) 2 And 30 mol of Al (OH) 3 Preparing 30L of colloid by using deionized water; naOH is added to control the pH value of the mixed solution to be 10.0; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 0.8 mol/L bismuth tribromide ethanol solution 30L, stirring for 2 hours at 50 ℃, adding ammonium molybdate with the same mole number as bismuth trichloride, controlling the pH value of the mixed solution to be 10.0 by NaOH, and continuously moving into a high-pressure kettle for hydrothermal treatment for 8 hours at 100 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 1L of toluene solution of n-propyl trimethoxy silane of 0.1 mol/L, oscillating for 10 hours by ultrasonic wave, freezing, centrifuging and drying to obtain the catalytic material of n-propyl trimethoxy modified hydrotalcite-like loaded bismuth vanadate, namely the photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of the obtained methane is 20 percent, and the selectivity of the methanol is 85 percent.
Example 4
Mixing 24 mol of CuO, 24 mol of NiO and 12 mol of Al (OH) 3 And 30 mol of Cr 2 O 3 Preparing 30L of colloid by using deionized water; adding urea to control the pH value of the mixed solution to be 10.0; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave for hydrothermal treatment at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 30L of 0.8 mol/L bismuth triiodide ethanol solution, stirring for 2 hours at 50 ℃, adding ammonium tungstate with the same mole number as that of bismuth triiodide, controlling the pH value of the mixed solution to be 10.0 by using urea, and continuously transferring the mixed solution into an autoclave for hydrothermal treatment for 8 hours at 100 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 1L of toluene solution which is composed of 0.05 mol/L of n-propyl trimethoxy silane and 0.05 mol/L of phenyl trimethoxy silane, oscillating for 10 hours with ultrasonic wave violently, freezing, centrifuging and drying to obtain the hydrotalcite-like loaded bismuth vanadate catalytic material jointly modified by n-propyl trimethoxy and phenyl trimethoxy-a photo-thermal co-catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of methane is 15 percent, and the selectivity of methanol is 83 percent.
Example 5
24 mol of CuO, 24 mol of FeO and 12 mol of Mg (OH) 2 And 30 mol of Al (OH) 3 Preparing 30L of colloid by using deionized water; and adding NH 4 Controlling the pH value of the mixed solution to be 10.0 by OH; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 0.8 mol/L bismuth nitrate ethanol solution 30L, stirring at 50 deg.C for 2 hr, adding ammonium vanadate with equal mole number of bismuth nitrate, and adding NH 4 And (4) controlling the pH value of the mixed solution to be 10.0 by OH, and continuously transferring the mixed solution into an autoclave at 100 ℃ for hydrothermal treatment for 8 hours. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 0.05 mol/L of p-sulfophenyl-methoxy-silane 1L of toluene solution, oscillating the mixture for 10 hours by ultrasonic waves, freezing, centrifuging and drying the mixture to obtain the p-sulfophenyl-methoxy-modified hydrotalcite-like supported bismuth vanadate catalytic material, namely the photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of methane is 18 percent, and the selectivity of methanol is 85 percent.
Example 6
Mixing 45 mol of CuO, 45 mol of NiO and 30 mol of Al (OH) 3 Preparing 50L of colloid by using deionized water; and adding NH 4 OH controlling the pH value of the mixed solution to be 10.0; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 0.8 mol/L bismuth trichloride ethanol solution 50L, stirring at 50 ℃ for 2 hours, and using NH 4 And (4) controlling the pH value of the mixed solution to be 10.0 by OH, and continuously transferring the mixed solution into an autoclave at 100 ℃ for hydrothermal treatment for 8 hours. Then the obtained colloid is centrifugally dewatered, washed to be neutral by water and dried at 100 ℃ to prepare the corresponding hydrotalcite loaded Bi, a composite material. Adding 100 g of the obtained material into 0.1 mol/L of p-sulfophenyl-methoxy-silane 1L of toluene solution, oscillating the mixture for 10 hours by ultrasonic waves, freezing, centrifuging and drying the mixture to obtain the p-sulfophenyl-methoxy-modified hydrotalcite-like compound loaded bismuth oxychloride catalytic material, namely the photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours under normal pressure at 70 ℃, so that the conversion rate of methane is 21 percent, and the selectivity of methanol is 83 percent.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for synthesizing methanol by directly oxidizing methane is characterized by comprising the following steps:
in a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is taken as a solvent, 100 g of catalyst is added, and reaction mixed gas is introduced, wherein the reaction mixed gas contains 1.6 percent of CH 4 , 6.6% O 2 65% of Ar and 26.8% of He, controlling the temperature of a reactor to be 30 to 90 ℃, controlling the pressure to be normal pressure to 3.0 MPa, connecting the reactor with a gas chromatography gas composition on line, filtering out a solid catalyst after the reaction is finished, and analyzing the liquid composition by using the gas chromatography;
the catalyst is a photo-thermal synergistic catalyst, and the catalyst takes a thermal catalyst formed by cheap metal hydrotalcite as a carrier and loads a Bi-based photocatalyst to form the photo-thermal synergistic catalyst;
the cheap metal comprises 1 to 3 of transition metals of Cr, mn, fe, co, ni, cu and Zn, 0 to 1 of alkaline earth metals of Ba, ca and Mg and metal Al;
the Bi-based photocatalyst is BiOX and BiX 3 、BiVO 4 、Bi 2 MoO 6 、Bi 2 WO 6 、Bi(NO 3 ) 3 Any one ofWherein X is Cl, br, I or F;
the surface of the hydrotalcite-like compound is subjected to hydrophobic organic modification, and the surface modifier is a silane coupling agent;
wherein the supported Bi-based photocatalyst accounts for 5 to 20 percent of the total mass of the catalyst;
the preparation method of the photo-thermal synergistic catalyst comprises the following steps:
(1) Preparing a mixed colloidal aqueous solution of transition metal oxide, alkaline earth metal hydroxide and aluminum hydroxide, and controlling the molar ratio of divalent metal ions to trivalent metal ions to be 2-5: 1, controlling the total concentration of metal ions to be 2.0-5.0 mol/L, controlling the pH value of the solution to be 9-11 by using an alkali liquor, stirring the solution at room temperature for 1-10 hours, putting the solution into an autoclave, carrying out hydrothermal treatment at 80-120 ℃ for 12-48 hours, and cooling the solution to the room temperature;
(2) Adding a certain amount of Bi salt ethanol solution into the colloid obtained in the step (1), stirring for 1-3 hours at 20-60 ℃, continuously controlling the pH value of the colloid to be 9-11 by using alkali liquor without adding or adding 1-2 of ammonium vanadate, ammonium molybdate or ammonium tungstate, and continuously carrying out hydrothermal treatment for 6-12 hours at 80-120 ℃; then filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at the temperature of between 60 and 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material;
(3) Adding the obtained catalyst into 0.05 to 0.1 mol/L of silane coupling agent toluene solution, carrying out ultrasonic oscillation for 6 to 12 hours, and carrying out refrigerated centrifugal drying to obtain the surface-modified hydrotalcite-like loaded Bi catalytic material, namely the photo-thermal synergistic catalyst.
2. The method according to claim 1, wherein in the step (1), the transition metal oxide is 1 to 3 kinds of chromium oxide, manganese oxide, ferrous oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide.
3. The method according to claim 1, wherein in the step (1), the alkaline earth metal hydroxide is 0 to 1 of barium hydroxide, calcium hydroxide and magnesium hydroxide.
4. The method of claim 1, wherein in the steps (1) and (2), the alkali solution is any one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea solution.
5. The method according to claim 1, wherein in the step (2), the Bi salt is any one of bismuth trihalide and bismuth nitrate.
6. The method according to claim 1, wherein in the step (3), the silane coupling agent is 1 to 2 selected from mercaptopropyltrimethoxysilane, n-propyltrimethoxysilane, phenyltrimethoxysilane, p-sulfophenylpropylmethoxysilane and aminopropyltrimethoxysilane.
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