CN116139874B - Catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide and preparation method thereof - Google Patents
Catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide and preparation method thereof Download PDFInfo
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- CN116139874B CN116139874B CN202310423900.6A CN202310423900A CN116139874B CN 116139874 B CN116139874 B CN 116139874B CN 202310423900 A CN202310423900 A CN 202310423900A CN 116139874 B CN116139874 B CN 116139874B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 49
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 46
- 230000009467 reduction Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 claims abstract description 64
- 239000010949 copper Substances 0.000 claims abstract description 64
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 27
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical group [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 27
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005751 Copper oxide Substances 0.000 claims abstract description 25
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000004064 recycling Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- 239000006185 dispersion Substances 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims description 15
- 239000004927 clay Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 10
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 3
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 3
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007146 photocatalysis Methods 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 37
- 238000006722 reduction reaction Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003027 oil sand Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- ZUSAAICYKOPBSX-UHFFFAOYSA-N nitric acid;propan-2-one Chemical compound CC(C)=O.O[N+]([O-])=O ZUSAAICYKOPBSX-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
-
- 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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
-
- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
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- 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
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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 belongs to the technical field of photocatalysis and a preparation method thereof, and particularly relates to a catalyst for preparing methanol by circularly using photocatalysis and reduction carbon dioxide and a preparation method thereof. The catalyst for preparing methanol by circularly using the photocatalytic reduction of carbon dioxide comprises the following components: the catalyst comprises a carrier and an active component, wherein the carrier is a copper net, the active component is molybdenum oxide, lanthanum oxide and copper oxide, the total load of the molybdenum oxide, the lanthanum oxide and the copper oxide accounts for 0.54-5.4% of the mass of the copper net, and the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is (1-5) to (1-5). The catalyst for preparing methanol by photocatalytic reduction of carbon dioxide for circulating sleeve improves the photocatalytic conversion of CO 2 The catalyst can be recycled, and the recycling utilization rate is high; the invention also provides a preparation method of the catalyst.
Description
Technical Field
The invention belongs to the technical field of photocatalysts and preparation methods thereof, and particularly relates to a catalyst for preparing methanol by circularly using photocatalytic reduction carbon dioxide and a preparation method thereof.
Background
Currently, noble metal monoatomic (Pt, au, pd, ag) catalysts in CO 2 Light conversion is widely used in high value added products. Although remarkable results have been achieved through research, the wide use of photocatalysts has been limited due to the high price and low reserves of noble metals. Thus, search for non-nobleMetal catalysts become a necessary trend and have very high scientific value.
Currently, research on catalysts mainly focuses on metal materials such as Ni, co, ti and the like, and many excellent results have been achieved after more than ten years of research. In addition, lanthanum and molybdenum materials are considered to be a very potential CO 2 The preparation of photo-conversion catalysts, in particular lanthanum and molybdenum, is highly appreciated by scientists in various countries. However, regarding lanthanum as CO 2 The photo-conversion catalyst has not been studied much. Thus, further explore simple and feasible CO 2 The preparation method of the catalyst which is converted and recycled has high significance and value. At present, CN104190455A discloses a method for applying lanthanum phosphate to photocatalytic reduction of carbon dioxide and water to prepare methane and hydrogen by adopting a hydrothermal method, but lanthanum phosphate wet materials are generally sticky, difficult to solve by the traditional drying technology, uneven drying and high energy consumption. Thus, further explore simple and feasible CO 2 The preparation method of the catalyst which is converted and recycled has high significance and value.
CN104549412a discloses a method for photocatalytic reduction of CO 2 Mesoporous metal oxide catalyst and its preparation, the catalyst is prepared from mesoporous CeO as active component 2 And dopant transition metal ions (iron ions, chromium ions, nickel ions, copper ions and cobalt ions) are formed, and the preparation method comprises the steps of dissolving transition metal nitrate and cerium nitrate in acetone to obtain metal nitrate acetone solution, then adding mesoporous silica materials, stirring and mixing, naturally airing, calcining the obtained first powder in a muffle furnace, continuously etching by using sodium hydroxide aqueous solution, and drying to obtain the catalyst, wherein the powdery catalyst cannot be recovered after being used up, is seriously wasted and pollutes the environment.
CN110327958A discloses a kind of CO 2 Catalyst for synthesizing methanol by hydrogenation and its preparation method and application, which uses high-temperature calcined metal salt (cerium sulfate, cerium carbonate, cerium oxalate, cerium nitrate, copper sulfate, copper carbonate, copper nitrate, zinc sulfate) as precursor, and then introduces non-metal nitrogen by nitrogen doping to obtain composite catalyst, the composite catalyst has no carrier, and active components can not be uniformly distributed in the calcining processAffecting the catalytic efficiency of the catalyst.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides the catalyst for preparing the methanol by circularly using the photocatalytic reduction carbon dioxide, and improves the photocatalytic conversion of CO 2 The catalyst can be recycled, and the recycling utilization rate is high; the invention also provides a preparation method and a recovery method thereof.
The invention relates to a catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide, which comprises the following components: the catalyst comprises a carrier and an active component, wherein the carrier is a copper net, the active component is molybdenum oxide, lanthanum oxide and copper oxide, the total load of the molybdenum oxide, the lanthanum oxide and the copper oxide accounts for 0.54-5.4% of the mass of the copper net, and the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is (1-5) to (1-5).
The thickness of the copper net is 3-10 mu m, the mesh number is 80-200 mesh, and the area is (1-10) × (1-10) cm 2 。
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid;
(2) Mixing a soluble salt of lanthanum and a soluble salt of molybdenum to obtain a solution a;
(3) Mixing the binder and clay to prepare 40-80wt.% slurry, adding the solution a, heating in water bath, and stirring to obtain a solution b;
(4) Mixing the copper mesh dispersion liquid with the solution b, performing hydrothermal treatment at 100-130 ℃ for 10-15h, then washing and drying, placing in a tube furnace, sealing and heating to 700-850 ℃, maintaining at 0.3-0.6MPa for 2-4h, and continuing washing and drying to obtain a catalyst;
(5) Placing the catalyst in the step (4) in argon or N 2 Crystallizing at 500-600deg.C for 5-25min under atmosphere, washing, and drying to obtain catalyst for preparing methanol by photocatalytic reduction of carbon dioxide.
The step of preparing copper mesh dispersion liquid in the step (1) is as follows: placing copper mesh into quartz CO 2 Reactor, addStirring in 12-18deg.C water for 10-30min to obtain copper mesh dispersion; wherein the mass of the copper net and the volume of water are 1g (50-80 mL).
The soluble salt of lanthanum in the step (2) is one of lanthanum acetate, lanthanum nitrate and lanthanum carbonate; the soluble salt of molybdenum is sodium molybdate or molybdenum nitrate, and the concentration of the obtained solution a is 5-10wt.%.
In the step (2), stirring is adopted, wherein the stirring temperature is 12-18 ℃ and the stirring time is 10-30min.
The mass ratio of the binder to the clay in the step (3) is (3:7) - (6:4). The binder is one of oil sand-glycerin, synthetic fat sand-synthetic fat and phenolic resin. The selected binder has good fluidity, is easy to compact, can manufacture the catalyst with complex shape, has good collapsibility, and has low residual strength and little influence on the activity of the catalyst because the binder starts to decompose or burn at 300 ℃.
The concentration of the solution b in the step (3) is 20-30 wt%, the heating temperature of the water bath is 80-100 ℃, and the stirring is carried out at a constant speed for 30-40min.
And (3) in the step (4), the airtight heating rate is 2-10 ℃/min, deionized water and ethanol are adopted for washing for multiple times, the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 2-12h.
The recovery method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: after the reaction of the catalytic methanol is finished, the reactor is opened, oxygen is firstly introduced to fully oxidize lanthanum, lanthanum oxide formed after the oxidation is gradually converted into La in the original solution along with the extension of stirring time 3+ Carbon dioxide is introduced again, and the light deposition and CO of atomic-level copper can be realized 2 The photo-conversion and the catalyst recover the activity and are continuously applied to the photo-catalytic reduction of carbon dioxide reaction.
Specifically, the preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 3-10 mu m, the mesh number is 80-200 mesh, and the area is (1-10) x%1-10）cm 2 Putting quartz CO into the copper mesh of (C) 2 Adding the mixture into water at the temperature of 12-18 ℃ in a reactor, and stirring for 10-30min to obtain copper mesh dispersion liquid; wherein the mass of the copper net and the volume of water are 1g (50-80 mL).
(2) Mixing soluble salt of lanthanum and soluble salt of molybdenum, stirring at 12-18deg.C for 10-30min, and dissolving in water to obtain solution a with concentration of 5-10wt.%.
(3) Mixing the binder and clay according to the mass ratio of (3:7) - (6:4), adding deionized water to prepare 40-80wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 80-100 ℃, adding deionized water, and uniformly stirring for 30-40min to obtain the solution b with the concentration of 20-30 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, performing hydrothermal treatment at 100-130 ℃ for 10-15h, taking out the catalyst after finishing, washing with deionized water and ethanol for multiple times, and then performing vacuum drying at 60-80 ℃ for 2-4h; placing the dried catalyst in a tube furnace, heating to 700-850 ℃ at a speed of 2-10 ℃/min in a closed way, maintaining at 0.3-0.6MPa for 2-4h, continuously washing with deionized water, and vacuum drying at 60-80 ℃ for 10-12h to obtain the catalyst;
the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) Placing the catalyst in the step (4) in argon or N 2 Crystallizing at 500-600deg.C for 5-25min under atmosphere, washing with deionized water, and oven drying at 60deg.C in vacuum oven to obtain catalyst for preparing methanol by photocatalytic reduction of carbon dioxide.
The catalyst prepared by the invention has a unique and stable structure, and the composite material taking the copper oxide nanowire as a core can effectively enhance the light absorption capacity and the photogenerated charge separation degree of the molybdenum oxide and lanthanum oxide shells. The coarse morphology of the catalyst effectively increases the active sites. Thereby enabling the photocatalytic conversion of CO 2 The activity of the catalyst is greatly improved. The catalyst prepared by the invention catalyzes CO 2 During the reduction process, molybdenum oxide and lanthanum oxide are not oxidized by oxygen (oxygen generated by photo-hole oxidation water), therebyThe problems of catalyst performance deactivation and the like are caused, and the catalyst is photocatalytic CO with better stability 2 A catalyst. Under the irradiation of visible light, electrons are excited by light to enter conduction bands of molybdenum oxide and lanthanum oxide, so that CO adsorbed on the surface is reduced 2 Molecular and active substance composite preparation of CO 2 When the catalyst is reduced, the lanthanum oxide nanospheres are arranged on the surface of the composite catalyst, so that CO is effectively enhanced 2 And the specific surface area is increased. Due to the difference in band gap, conduction band and valence band positions, multiple S heterojunctions can be formed between them. Forming an s-type heterojunction, not only can effectively separate photo-generated electron-hole pairs, but also has maximum oxidation-reduction capability, thus CO 2 The conversion rate is high.
The catalyst disclosed by the invention is mainly applied to the field of environmental protection.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst prepared by the invention takes copper oxide, molybdenum oxide and lanthanum oxide as composite active components, takes a copper mesh as a carrier, has wide raw material sources and low cost, and improves CO in the preparation of methanol by photocatalytic reduction of carbon dioxide 2 The photoreduction activity, the conversion rate and the production benefit are high;
(2) The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide has the advantages of simple operation, low preparation cost and no environmental pollution.
(3) The catalyst prepared by the method has the advantages of simple method for recovering the activity, high recycling utilization rate and great improvement in cost and environmental protection.
Drawings
FIG. 1 is a scanning electron microscope image of a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide for a circulation sleeve, which is prepared by the invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
The active components of the catalyst in the embodiment are molybdenum oxide, lanthanum oxide and copper oxide, and the total load amount accounts for 0.95% of the mass of the copper mesh, wherein the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is 1:2:1.
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 3 μm, the mesh number is 100 mesh, and the area is 4×4cm 2 Putting quartz CO into the copper mesh of (C) 2 Adding the reactor into 12 ℃ water, and stirring for 20min to obtain copper mesh dispersion liquid; wherein the mass of the copper mesh and the volumetric feeding ratio of water are 1g to 50mL.
(2) Lanthanum acetate and molybdenum nitrate are mixed, stirred for 10min at 15 ℃, and water is added for dissolution, so that a solution a with the concentration of 5wt.% is obtained.
(3) Mixing the synthetic fat sand-synthetic fat and clay according to the mass ratio of 3:7, adding deionized water to prepare 40wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 80 ℃, adding the deionized water, and uniformly stirring for 30min to obtain the solution b with the concentration of 20 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, carrying out hydrothermal treatment at 100 ℃ for 15 hours, taking out the catalyst after the completion of the hydrothermal treatment, washing the catalyst with deionized water and ethanol for a plurality of times, and then carrying out vacuum drying at 60 ℃ for 4 hours; placing the dried catalyst in a tube furnace, heating to 700 ℃ at a speed of 2 ℃/min in a closed way, maintaining at 0.3Mpa for 4 hours, continuously washing with deionized water, and drying at 60 ℃ in vacuum for 10 hours to obtain the catalyst; the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) And (3) placing the catalyst in the step (4) under argon, crystallizing for 15min at 500 ℃, washing with deionized water, and drying in a vacuum oven at 60 ℃ to obtain the catalyst for preparing methanol by circularly using photocatalytic reduction carbon dioxide.
Example 2
The active components of the catalyst in the embodiment are molybdenum oxide, lanthanum oxide and copper oxide, and the total load amount accounts for 1.4% of the mass of the copper mesh, wherein the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is 2:3:3.
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 8 μm, the mesh number is 90 meshes, and the area is 5×5cm 2 Putting quartz CO into the copper mesh of (C) 2 Adding the reactor into water at 15 ℃ and stirring for 30min to obtain copper mesh dispersion liquid; wherein the mass of the copper mesh and the volume of water are added in a ratio of 1g to 60mL.
(2) Lanthanum nitrate and molybdenum nitrate were mixed and stirred at 12 ℃ for 30min, and dissolved in water to give a solution a with a concentration of 7 wt.%.
(3) Mixing oil sand, glycerin and clay according to a mass ratio of 5:6, adding deionized water to prepare 50wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 100 ℃, adding the deionized water, and uniformly stirring for 35min to obtain a solution b with a concentration of 30 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, carrying out hydrothermal treatment at 120 ℃ for 13 hours, taking out the catalyst after the completion of the hydrothermal treatment, washing the catalyst with deionized water and ethanol for a plurality of times, and then carrying out vacuum drying at 70 ℃ for 3 hours; placing the dried catalyst in a tube furnace, heating to 750 ℃ at a speed of 5 ℃/min in a closed way, maintaining at 0.4Mpa for 3 hours, continuously washing with deionized water, and drying at 70 ℃ in vacuum for 10 hours to obtain the catalyst; the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) And (3) placing the catalyst in the step (4) under argon, crystallizing for 25min at 500 ℃, washing with deionized water, and drying in a vacuum oven at 60 ℃ to obtain the catalyst for preparing methanol by circularly using photocatalytic reduction carbon dioxide.
Example 3
The active components of the catalyst in the embodiment are molybdenum oxide, lanthanum oxide and copper oxide, and the total load amount accounts for 3.5% of the mass of the copper mesh, wherein the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is 4:3:3.
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 5 mu m, the mesh number is 100 mesh, 6X 6cm area 2 Putting quartz CO into the copper mesh of (C) 2 Adding the reactor into water at 18 ℃ and stirring for 10min to obtain copper mesh dispersion liquid; wherein the mass of the copper mesh and the volume of water are fed in a ratio of 1g to 70mL.
(2) Lanthanum carbonate and sodium molybdate are mixed, stirred at 18 ℃ for 10min, and dissolved by adding water to obtain a solution a with the concentration of 8 wt.%.
(3) Mixing oil sand, glycerin and clay according to a mass ratio of 5:5, adding deionized water to prepare 60wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 90 ℃, adding the deionized water, and uniformly stirring for 40min to obtain the solution b with the concentration of 20 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, carrying out hydrothermal treatment at 130 ℃ for 10 hours, taking out the catalyst after the completion of the hydrothermal treatment, washing the catalyst with deionized water and ethanol for a plurality of times, and then carrying out vacuum drying at 70 ℃ for 3 hours; placing the dried catalyst in a tube furnace, heating to 850 ℃ at a speed of 8 ℃/min in a closed way, maintaining at 0.5Mpa for 3 hours, continuously washing with deionized water, and drying at 60 ℃ in vacuum for 12 hours to obtain the catalyst; the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) Placing the catalyst of step (4) in N 2 Crystallizing for 5min at 600 ℃ under the atmosphere, washing with deionized water, and drying in a vacuum oven at 60 ℃ to obtain the catalyst for preparing methanol by circularly using photocatalytic reduction carbon dioxide.
Example 4
The active components of the catalyst in the embodiment are molybdenum oxide, lanthanum oxide and copper oxide, and the total load amount accounts for 5.4% of the mass of the copper mesh, wherein the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is 2:5:1.
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 9 μm, the mesh number is 120 mesh, and the area is 7×7cm 2 Putting quartz CO into the copper mesh of (C) 2 Adding the reactor into 12 ℃ water, and stirring for 30min to obtain copper mesh dispersion liquid; wherein the mass of the copper netAnd the volumetric feeding ratio of water is 1g to 80mL.
(2) Lanthanum nitrate and sodium molybdate were mixed and stirred at 15 ℃ for 20min, and dissolved in water to give a solution a with a concentration of 9 wt.%.
(3) Mixing phenolic resin and clay according to a mass ratio of 6:4, adding deionized water to prepare 70wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 100 ℃, adding the deionized water, and stirring at a constant speed for 30min to obtain a solution b with a concentration of 30 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, carrying out hydrothermal treatment at 100 ℃ for 14 hours, taking out the catalyst after the hydrothermal treatment is finished, washing the catalyst with deionized water and ethanol for multiple times, and then carrying out vacuum drying at 60 ℃ for 4 hours; placing the dried catalyst in a tube furnace, heating to 850 ℃ at a speed of 10 ℃/min in a closed way, maintaining at 0.5Mpa for 3 hours, continuously washing with deionized water, and drying at 60 ℃ in vacuum for 12 hours to obtain the catalyst; the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) Placing the catalyst of step (4) in N 2 Crystallizing for 20min at 550 ℃ under the atmosphere, washing with deionized water, and drying in a vacuum oven at 60 ℃ to obtain the catalyst for preparing methanol by circularly using the photocatalytic reduction carbon dioxide.
Example 5
The active components of the catalyst in the embodiment are molybdenum oxide, lanthanum oxide and copper oxide, and the total load amount accounts for 4.8% of the mass of the copper mesh, wherein the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is 1:3:1.
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 5 μm, the mesh number is 80 mesh, and the area is 4×4cm 2 Putting quartz CO into the copper mesh of (C) 2 Adding the reactor into 12 ℃ water, and stirring for 20min to obtain copper mesh dispersion liquid; wherein the mass of the copper mesh and the volumetric feeding ratio of water are 1g to 50mL.
(2) Lanthanum acetate and molybdenum nitrate are mixed, stirred for 10min at 15 ℃, and water is added for dissolution, so that a solution a with the concentration of 5wt.% is obtained.
(3) Mixing phenolic resin and clay according to a mass ratio of 3:7, adding deionized water to prepare 40wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 80 ℃, adding the deionized water, and uniformly stirring for 30min to obtain a solution b with a concentration of 20 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, carrying out hydrothermal treatment at 100 ℃ for 15 hours, taking out the catalyst after the completion of the hydrothermal treatment, washing the catalyst with deionized water and ethanol for a plurality of times, and then carrying out vacuum drying at 60 ℃ for 4 hours; placing the dried catalyst in a tube furnace, heating to 700 ℃ at a speed of 2 ℃/min in a closed way, maintaining at 0.3Mpa for 4 hours, continuously washing with deionized water, and drying at 60 ℃ in vacuum for 10 hours to obtain the catalyst; the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) Placing the catalyst of step (4) in N 2 Crystallizing for 20min at 500 ℃ under the atmosphere, washing with deionized water, and drying in a vacuum oven at 60 ℃ to obtain the catalyst for preparing methanol by circularly using photocatalytic reduction carbon dioxide.
Example 6
The active components of the catalyst in the embodiment are molybdenum oxide, lanthanum oxide and copper oxide, and the total load amount accounts for 0.54% of the mass of the copper mesh, wherein the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is 5:1:5.
The preparation method of the catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide comprises the following steps: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid: the thickness is 10 μm, the mesh number is 200 mesh, and the area is 10×10cm 2 Putting quartz CO into the copper mesh of (C) 2 Adding the reactor into 12 ℃ water, and stirring for 20min to obtain copper mesh dispersion liquid; wherein the mass of the copper mesh and the volumetric feeding ratio of water are 1g to 50mL.
(2) Lanthanum nitrate and molybdenum nitrate are mixed, stirred at 15 ℃ for 10min, and water is added for dissolution, so that a solution a with the concentration of 10wt.% is obtained.
(3) Mixing phenolic resin and clay according to a mass ratio of 6:4, adding deionized water to prepare 80wt.% slurry, adding the solution a, fully mixing, heating in a water bath at 100 ℃, adding the deionized water, and uniformly stirring for 30min to obtain a solution b with a concentration of 20 wt.%.
(4) Mixing the copper mesh dispersion liquid with the solution b, carrying out hydrothermal treatment at 100 ℃ for 14 hours, taking out the catalyst after the hydrothermal treatment is finished, washing the catalyst with deionized water and ethanol for multiple times, and then carrying out vacuum drying at 60 ℃ for 2 hours; placing the dried catalyst in a tube furnace, heating to 700 ℃ at a speed of 2 ℃/min in a closed way, maintaining at 0.6Mpa for 3 hours, continuously washing with deionized water, and drying at 60 ℃ in vacuum for 10 hours to obtain the catalyst; the sealing is carried out in a sealed container, so that the slurry and the catalyst are fully mixed, and the prepared catalyst has small average particle size and high dispersity.
(5) And (3) placing the catalyst in the step (4) under argon, crystallizing for 25min at 500 ℃, washing with deionized water, and drying in a vacuum oven at 60 ℃ to obtain the catalyst for preparing methanol by circularly using photocatalytic reduction carbon dioxide.
Example 7
The catalyst in example 1 was subjected to the following activation treatments, and then recycled 10 times, namely 7-1 to 7-10, respectively, the steps were: after the reaction of the catalytic methanol is finished, the reactor is opened, oxygen is firstly introduced to fully oxidize lanthanum, lanthanum oxide formed after the oxidation is gradually converted into La in the original solution along with the extension of stirring time 3+ Carbon dioxide is introduced again, and the light deposition and CO of atomic-level copper can be realized 2 The photo-conversion and the catalyst recover the activity and are continuously applied to the photo-catalytic reduction of carbon dioxide reaction.
Comparative example 1
This comparative example was identical to the preparation of example 1, except that the active component was molybdenum oxide, wherein the mass ratio of lanthanum oxide to copper oxide was 2:1.
Comparative example 2
This comparative example was identical to the preparation of example 1, except that lanthanum oxide was removed from the active component, wherein the mass ratio of molybdenum oxide to copper oxide was 1:1.
The catalyst prepared by the method is respectively put into a reactor, and argon is used for blowing before the reaction startsSweeping the reactor to exhaust CO in the reactor 2 Argon gas was introduced for 15min at a gas flow rate of 25ml/min. After the argon is introduced, CO is introduced 2 Reaction gas, CO is introduced into 2 The gas flow rate is 20ml/min, the time is 12h, the reaction temperature is 25 ℃, the reaction pressure is 0.2MPa, and the illumination time of a xenon lamp is 12h.
Among them, the evaluation performance results of the catalysts prepared in the above examples and comparative examples for preparing methanol are shown in table 1.
Table 1 evaluation results
As will be seen from the above table, mn prepared according to the present invention 2 O 3 /MoS 2 The catalyst of CuS/CM effectively realizes the light absorption capacity and the photo-generated charge separation degree of the manganese oxide and molybdenum sulfide shells, and obviously improves CO 2 Photoreductive activity.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (10)
1. A catalyst for preparing methanol by circularly using photocatalytic reduction of carbon dioxide is characterized in that: the catalyst comprises a carrier and an active component, wherein the carrier is a copper net, the active component is molybdenum oxide, lanthanum oxide and copper oxide, the total load of the molybdenum oxide, the lanthanum oxide and the copper oxide accounts for 0.54-5.4% of the mass of the copper net, and the mass ratio of the molybdenum oxide to the lanthanum oxide to the copper oxide is (1-5) to (1-5).
2. The catalyst for preparing methanol by photocatalytic reduction of carbon dioxide for a recycle sleeve according to claim 1, wherein: the thickness of the copper net is 3-10 mu m, the mesh number is 80-200 mesh, and the area is (1-10）×（1-10）cm 2 。
3. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by recycling according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) Preparing copper mesh dispersion liquid;
(2) Mixing a soluble salt of lanthanum and a soluble salt of molybdenum to obtain a solution a;
(3) Mixing the binder and clay to prepare 40-80wt.% slurry, adding the solution a, heating in water bath, and stirring to obtain a solution b;
(4) Mixing the copper mesh dispersion liquid with the solution b, performing hydrothermal treatment at 100-130 ℃ for 10-15h, then washing and drying, placing in a tube furnace, sealing and heating to 700-850 ℃, maintaining at 0.3-0.6MPa for 2-4h, and continuing washing and drying to obtain a catalyst;
(5) Placing the catalyst in the step (4) in argon or N 2 Crystallizing at 500-600deg.C for 5-25min under atmosphere, washing, and drying to obtain catalyst for preparing methanol by photocatalytic reduction of carbon dioxide.
4. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by a circulation sleeve according to claim 3, wherein: the step of preparing copper mesh dispersion liquid in the step (1) is as follows: placing copper mesh into quartz CO 2 Adding the mixture into water at the temperature of 12-18 ℃ in a reactor, and stirring for 10-30min to obtain copper mesh dispersion liquid; wherein the mass of the copper net and the volume of water are 1g (50-80 mL).
5. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by a circulation sleeve according to claim 3, wherein: the soluble salt of lanthanum in the step (2) is one of lanthanum acetate, lanthanum nitrate and lanthanum carbonate; the soluble salt of molybdenum is sodium molybdate or molybdenum nitrate, and the concentration of the obtained solution a is 5-10wt.%.
6. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by a circulation sleeve according to claim 3, wherein: in the step (2), stirring is adopted, wherein the stirring temperature is 12-18 ℃ and the stirring time is 10-30min.
7. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by a circulation sleeve according to claim 3, wherein: the mass ratio of the binder to the clay in the step (3) is (3:7) - (6:4).
8. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by a circulation sleeve according to claim 3, wherein: the concentration of the solution b in the step (3) is 20-30 wt%, the heating temperature of the water bath is 80-100 ℃, and the stirring is carried out at a constant speed for 30-40min.
9. A method for preparing a catalyst for preparing methanol by photocatalytic reduction of carbon dioxide by a circulation sleeve according to claim 3, wherein: and (3) in the step (4), the airtight heating rate is 2-10 ℃/min, deionized water and ethanol are adopted for washing for multiple times, the drying is vacuum drying, the drying temperature is 60-80 ℃, and the drying time is 2-12h.
10. A method for recovering the catalyst for preparing methanol by recycling photocatalytic reduction of carbon dioxide according to claim 1 or 2, characterized in that: the method comprises the following steps: after the reaction of catalyzing the methanol is finished, the reactor is opened, oxygen is firstly introduced, then carbon dioxide is introduced, the activity of the catalyst is recovered, and the catalyst is continuously used in the reaction of photocatalytic reduction of carbon dioxide.
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| CN113751062A (en) * | 2021-10-11 | 2021-12-07 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Porous copper-based catalyst for preparing ethanol by carbon dioxide hydrogenation and preparation method thereof |
| CN114950419A (en) * | 2022-04-20 | 2022-08-30 | 江南大学 | Metal catalyst for preparing methanol by carbon dioxide hydrogenation and application thereof |
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