CN116135306A - High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof - Google Patents
High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof Download PDFInfo
- Publication number
- CN116135306A CN116135306A CN202111390433.9A CN202111390433A CN116135306A CN 116135306 A CN116135306 A CN 116135306A CN 202111390433 A CN202111390433 A CN 202111390433A CN 116135306 A CN116135306 A CN 116135306A
- Authority
- CN
- China
- Prior art keywords
- alkali metal
- contact reaction
- cufezr
- reaction
- catalytic material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 83
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 56
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 42
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000001035 drying Methods 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims abstract description 22
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- -1 alkali metal salt Chemical class 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 7
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 49
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 30
- 239000001099 ammonium carbonate Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 28
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000010949 copper Substances 0.000 claims description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 22
- XTYUEDCPRIMJNG-UHFFFAOYSA-N copper zirconium Chemical compound [Cu].[Zr] XTYUEDCPRIMJNG-UHFFFAOYSA-N 0.000 claims description 16
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 235000011181 potassium carbonates Nutrition 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 8
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 8
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 229910003134 ZrOx Inorganic materials 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000005119 centrifugation Methods 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 14
- 238000009210 therapy by ultrasound Methods 0.000 description 14
- 239000002131 composite material Substances 0.000 description 13
- 239000001569 carbon dioxide Substances 0.000 description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 description 8
- 229910001928 zirconium oxide Inorganic materials 0.000 description 8
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 description 8
- 239000008281 solid sol Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 241000894007 species Species 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910017827 Cu—Fe Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- ZECRJOBMSNYMJL-UHFFFAOYSA-N copper;oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[Cu+2].[Zr+4] ZECRJOBMSNYMJL-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- FUBACIUATZGHAC-UHFFFAOYSA-N oxozirconium;octahydrate;dihydrochloride Chemical compound O.O.O.O.O.O.O.O.Cl.Cl.[Zr]=O FUBACIUATZGHAC-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C29/156—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 iron group metals, platinum group metals or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalytic materials, and particularly relates to a high-performance alkali metal modified CuFeZr catalytic material and a preparation method thereof, wherein the preparation method comprises the following steps: s1, in the presence of a solvent, zirconium salt and propylene oxide undergo a first contact reaction to obtain a solution I; s2, placing the solution I in a high-temperature oven for hydrothermal reaction to obtain an amorphous zirconia material; s3, in the presence of a solvent, carrying out a second contact reaction on zirconia and copper salt to obtain a solution II; s4, carrying out a third contact reaction on the solution II and a precipitator, centrifuging, drying, crushing and calcining the obtained substance after the reaction is finished; s5, carrying out a fourth contact reaction on the obtained solid and ferric salt to obtain a solution III; s6, carrying out a fifth contact reaction on the solution III and a precipitator, centrifuging, drying and crushing the obtained substance after the reaction is finished; s7, carrying out a sixth contact reaction on the obtained material and alkali metal salt to obtain the product. Has the advantages of low cost, high catalytic activity, high thermal stability and the like.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to a high-performance alkali metal modified CuFeZr catalytic material and a preparation method thereof.
Background
Oxide-based porous materials are good carriers in the field of catalysis, but the preparation method of high-performance low-carbon alcohol synthesis catalytic materials still needs to be further explored. Copper-iron based materials are widely used for catalyzing reactions such as hydrogenation of carbon dioxide to synthesize methanol, low-carbon alcohol, fischer-Tropsch reaction and the like due to their unique oxidation-reduction performance and high catalytic activity.
It is generally believed that catalytic reactions proceed primarily at the copper surface and Cu-Fe interface, but copper-based catalysts are subject to rapid decrease or even deactivation of catalytic activity due to their extremely unstable microstructure of active copper species in a reducing atmosphere, susceptibility to metallic copper and susceptibility to sintering at high temperatures.
The metal (such as copper, iron and the like) is highly dispersed in the porous oxide material with high surface area, which is proved to be a good oxidation-reduction reaction catalyst, copper oxide and iron oxide have relatively high thermal stability, and meanwhile, the catalyst is an active component or active auxiliary agent for catalyzing reactions of synthesizing methanol, low-carbon alcohol and the like by hydrogenating synthesis gas and carbon dioxide, the nano-scale copper nanocrystalline can be formed by adding the metal such as copper oxide, iron oxide and the like into the amorphous zirconia with high specific surface, and the alloy/interface species are abundant, so that the stability of the active species and the capability of the catalyst for catalyzing and dissociating hydrogen and activating carbon dioxide are improved, the yield and the selectivity of the low-carbon alcohol are enhanced, the hydrogenation reaction of the carbon dioxide is facilitated, and the high-performance CO is prepared 2 Synthesizing the low-carbon alcohol catalytic material by hydrogenation.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a high-performance alkali metal modified CuFeZr catalytic material, which has the advantages of low preparation cost, simple and safe operation,The reaction period is short, the product repeatability is good, and the like; the high-performance alkali metal modified CuFeZr catalytic material prepared by the method has the advantages of low cost, high catalytic activity, high thermal stability and the like, and can be used for high-selectively catalyzing and reducing CO at a lower temperature 2 The method can be used for synthesizing low-carbon alcohol, and can be applied to the fields of material research and reaction for synthesizing low-carbon alcohol by catalytic hydrogenation of carbon dioxide.
The invention is realized by adopting the following technical scheme:
the preparation method of the high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, adding zirconium salt into an ethanol solvent, ultrasonically dissolving, and then adding propylene oxide for a first contact reaction to obtain a solution I;
s2, carrying out hydrothermal reaction on the solution I, and drying and crushing the obtained substance to obtain amorphous zirconia;
s3, adding amorphous zirconia into water, performing ultrasonic dispersion, adding copper metal salt, and performing a second contact reaction to obtain a solution II;
s4, adding a precipitant aqueous solution into the solution II to carry out a third contact reaction, centrifuging, drying, crushing and calcining the obtained substance after the reaction is finished;
s5, carrying out a fourth contact reaction on the obtained solid and metal ferric salt to obtain a solution III;
s6, carrying out a fifth contact reaction on the solution III and a precipitator, centrifuging, drying and crushing the obtained substance after the reaction is finished;
s7, carrying out a sixth contact reaction on the obtained material and alkali metal salt, and after evaporating the water content by rotation, crushing and calcining the obtained material to obtain the high-performance alkali metal modified CuFeZr catalytic material.
In a preferred embodiment, in step S1, the conditions of ultrasonic dissolution are: ultrasonic dissolving at 40-60KHz for 25-40min; further preferably, the ultrasonic dissolution is carried out for 30min under the condition of 50KHz frequency;
in a preferred embodiment, in step S1, the zirconium salt may be one of zirconium nitrate, zirconyl chloride, zirconium chloride, and zirconium sulfate; the usage amount of the propylene oxide and the zirconium salt calculated as Zr element is (1.5-2.5) in terms of the mole ratio: 1, a step of; in a further preferred embodiment, the propylene oxide, ethanol and zirconium nitrate are used in a molar ratio of (1.5-2.5) as Zr: (60-70): 1.
in a preferred embodiment, in step S1, the conditions of the first contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.05-1h.
In a preferred embodiment, in step S1, the first contact reaction is performed under stirring conditions, and the stirring speed is 50-500rpm; in a further preferred embodiment, the first contact reaction is carried out under stirring at a rate of 350 to 450rpm.
In a preferred scheme, in the step S2, the temperature of the hydrothermal reaction is 100-200 ℃ and the time is 15-25h.
In a preferred embodiment, in step S3, the conditions of the second contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.05-10h.
The copper salt can be any one of copper nitrate, copper sulfate, copper acetate and copper chloride;
the ratio of the metal copper salt in terms of Cu element to the amorphous zirconia in terms of mass ratio is (0.2-0.3): 1, a step of;
in a preferred embodiment, in step S3, the second contact reaction is performed under stirring conditions, and the stirring speed is 50-500rpm; in a further preferred embodiment, the second contact reaction is carried out under stirring at a rate of 350 to 450rpm.
In a preferred embodiment, in step S4, the conditions of the third contact reaction are as follows: the temperature is 70-90 ℃ and the time is 0.1-10h.
The precipitant can be any one of ammonium carbonate, ammonium bicarbonate, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and ammonia water;
the usage ratio of the precipitant to the metal copper salt calculated as Cu element is 1-3:1, a step of;
in a preferred embodiment, in step S5, the conditions of the fourth contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.1-10h.
The ferric salt can be any one of ferric nitrate, ferric acetate, ferric sulfate and ferric chloride;
the mass ratio of the metal ferric salt calculated by Fe element to the copper zirconium material calculated by copper zirconium oxide is (0.1-0.2): 1, a step of;
in a preferred embodiment, in step S6, the fifth contact reaction is performed under stirring conditions, and the stirring speed is 50-500rpm; in a further preferred embodiment, the fifth contact reaction is carried out under stirring at a rate of 350 to 450rpm.
In a preferred embodiment, in step S6, the conditions of the fifth contact reaction are as follows: the temperature is 70-90 ℃ and the time is 0.1-10h.
The precipitant can be any one of ammonium carbonate, ammonium bicarbonate, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and ammonia water;
the dosage ratio of the precipitant to the metallic ferric salt calculated as Fe element is 1-3:1;
in a preferred embodiment, in step S7, the conditions of the sixth contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.1-10h.
The alkali metal salt can be any one of potassium carbonate, sodium carbonate and cesium carbonate;
the molar ratio of the alkali metal salt calculated as alkali metal element to the amorphous zirconia calculated as Zr element is (0.1 to 0.25): 1, a step of;
in a preferred embodiment, in step S7, the sixth contact reaction is performed under stirring conditions, and the stirring speed is 50-500rpm; in a further preferred embodiment, the sixth contact reaction is carried out under stirring at a rate of 350 to 450rpm.
In a preferred embodiment, in steps S2 and S6, the drying conditions are as follows: the temperature is 40-80 ℃ and the time is 2-24 hours;
in a preferred embodiment, in step S4, the drying conditions include: the temperature is 40-80 ℃ and the time is 2-24 hours; the conditions of the calcination include: the temperature is 300-500 ℃ and the time is 0.5-8h.
In a preferred embodiment, in step S7, the conditions of the rotary evaporation include: the temperature is 40-80 ℃, the vacuum degree is-0.08 to-0.1, and the time is 2-6h; the conditions of the calcination include: the temperature is 300-500 ℃ and the time is 3-10h.
The beneficial effects of the invention are as follows:
1. the preparation method has the advantages of low preparation cost, simple and safe operation, short reaction period, good product repeatability and the like.
2. The high-performance alkali metal modified CuFeZr catalytic material prepared by the preparation method can provide nanoscale copper/ferric oxide nanocrystalline or copper-iron alloy/interface species, can increase the stability of active species, the catalytic dissociation hydrogen activity of a catalyst and the capability of activating carbon dioxide, and is favorable for selectively catalyzing the carbon dioxide reduction reaction.
3. The high-performance alkali metal modified CuFeZr catalytic material prepared by the preparation method has the advantages of low cost, high catalytic activity, high thermal stability and the like, and can be used for high-selectively catalyzing and reducing CO at a lower temperature 2 The method can be used for synthesizing low-carbon alcohol, and can be applied to the fields of material research and reaction for synthesizing low-carbon alcohol by catalytic hydrogenation of carbon dioxide.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD spectrum of the CuFeZr catalytic material prepared in example 1 of the present invention and the high performance alkali metal modified CuFeZr catalytic materials prepared in examples 2 to 6.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
A preparation method of a CuFeZr catalytic material comprises the following steps:
s1, dissolving 5.999g of zirconium nitrate pentahydrate in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 30min at 50KHz, and then adding propylene oxide to perform a first contact reaction for 2min to obtain a solution I;
s2, carrying out hydrothermal reaction for 20 hours at 150 ℃, drying the obtained solid sol at 60 ℃ for 24 hours after the reaction is finished, continuously drying at 200 ℃ for 3 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconium nitrate pentahydrate, in molar ratio: ethanol: the propylene oxide was used in an amount of 1:60:1.5;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water under the condition of 25 ℃ and ultrasonic treatment for 15min at the frequency of 50KHz to obtain zirconia water dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving potassium carbonate in water at 25 ℃ to form a potassium carbonate aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.2215g of copper nitrate into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to perform a second contact reaction for 1h; the molar ratio of the potassium carbonate to the copper nitrate calculated by Cu is 1.5:1, a step of;
s6, adding the potassium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 3 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 25Cu/a-ZrOx material;
s7, taking 0.5g of the 25Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; dissolving ammonium bicarbonate in water at 25 ℃ to form an ammonium bicarbonate solution with the mass concentration of 9.6 g/L; the water is deionized water;
s8, taking the zirconium oxide aqueous dispersion, adding 0.537g of ferric sulfate, and stirring at a stirring speed of 400rpm at 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the ammonium bicarbonate to the ferric sulfate calculated by Fe is 2:1, a step of;
s9, adding the ammonium bicarbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed; calcining for 4 hours in the atmosphere of a muffle furnace at 400 ℃ to obtain brown black 15Fe/25Cu/a-ZrO x Catalytic material.
Example 2
A preparation method of a high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, dissolving 4.5036g of zirconyl chloride octahydrate in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 45min at the frequency of 40KHz, and then adding propylene oxide to perform a first contact reaction for 10min to obtain a solution I;
s2, carrying out hydrothermal reaction at 150 ℃ for 24 hours, drying the obtained solid sol at 60 ℃ for 28 hours after the reaction is finished, continuously drying at 200 ℃ for 6 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconyl chloride comprises the following components in mole ratio: ethanol: the propylene oxide was used in an amount of 1:70:2.5;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water at 25 ℃ under the condition of the frequency of 45KHz for 15min by ultrasonic treatment to obtain zirconia aqueous dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving sodium carbonate in water at 25 ℃ to form a sodium carbonate aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.2949g of copper sulfate pentahydrate into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 350rpm at the temperature of 25 ℃ to perform a second contact reaction for 1.5h; the molar ratio of the sodium carbonate to the copper sulfate pentahydrate calculated by Cu is 2.5:1, a step of;
s6, adding the sodium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 5 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 25Cu/a-ZrOx material;
s7, taking 0.5g of the 25Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; dissolving sodium bicarbonate in water at 25 ℃ to form sodium bicarbonate aqueous solution with the mass concentration of 9.6 g/L; the water is deionized water;
s8, adding 0.2086g of ferric acetate into the copper-zirconium composite oxide aqueous dispersion liquid, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the sodium bicarbonate to the iron acetate calculated by Fe is 3:1, a step of;
s9, adding the sodium bicarbonate aqueous solution at 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed;
s10, adding 1mL of aqueous solution of 24.7mg sodium carbonate at 25 ℃, stirring at 400rpm at 25 ℃ to perform a sixth contact reaction for 2h, then drying at 40-70 ℃ for 2-6h in a rotary evaporator with the vacuum degree of minus 0.08 to minus 0.1, and calcining at 400 ℃ in a muffle furnace air atmosphere for 4h to obtain the brownish-black 3Na-10Fe/25Cu/a-ZrOx catalytic material.
Example 3
A preparation method of a high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, dissolving 3.2569g of zirconium chloride in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 45min at the frequency of 30KHz, and then adding propylene oxide to perform a first contact reaction for 8min to obtain a solution I;
s2, carrying out hydrothermal reaction at 150 ℃ for 16 hours, drying the obtained solid sol at 60 ℃ for 24 hours after the reaction is finished, continuously drying at 200 ℃ for 3 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconium chloride comprises the following components in mole ratio: ethanol: the propylene oxide was used in an amount of 1:65:2;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water at 25 ℃ under the condition of the frequency of 45KHz for 15min by ultrasonic treatment to obtain zirconia aqueous dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving sodium bicarbonate in water at 25 ℃ to form sodium bicarbonate aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.1588g of copper chloride into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to perform a second contact reaction for 1h; the molar ratio of the sodium bicarbonate to the copper chloride calculated by Cu is 2:1, a step of;
s6, adding the sodium bicarbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 5 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 25Cu/a-ZrOx material;
s7, taking 0.5g of the 25Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; dissolving potassium hydroxide in water at 25 ℃ to form a potassium hydroxide aqueous solution with the mass concentration of 9.6 g/L; the water is deionized water;
s8, adding 0.2182g of ferric chloride into the copper-zirconium composite oxide aqueous dispersion liquid, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the potassium hydroxide to the ferric chloride calculated as Fe is 2.5:1, a step of;
s9, adding the potassium hydroxide aqueous solution at 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed;
s10, adding 1mL of aqueous solution of 32.2mg of potassium carbonate at 25 ℃, stirring at 400rpm at 25 ℃ to perform a sixth contact reaction for 2h, then drying at 40-70 ℃ for 2-6h in a rotary evaporator with the vacuum degree of minus 0.08 to minus 0.1, and calcining at 400 ℃ in a muffle furnace air atmosphere for 4h to obtain the brownish-black 3K-15Fe/25Cu/a-ZrOx catalytic material.
Example 4
A preparation method of a high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, dissolving 3.96g of zirconium sulfate in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 30min at 50KHz, and then adding propylene oxide to perform a first contact reaction for 6min to obtain a solution I;
s2, carrying out hydrothermal reaction for 20 hours at 150 ℃, drying the obtained solid sol at 60 ℃ for 24 hours after the reaction is finished, continuously drying at 200 ℃ for 3 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconium sulfate comprises the following components in mole ratio: ethanol: the propylene oxide was used in an amount of 1:60:1.5;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water at 25 ℃ under the condition of the frequency of 45KHz for 15min by ultrasonic treatment to obtain zirconia aqueous dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving sodium hydroxide in water at 25 ℃ to form a sodium hydroxide aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.2358g of copper acetate monohydrate into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to perform a second contact reaction for 1h; the molar ratio of the sodium hydroxide to the copper acetate monohydrate calculated by Cu is 3:1, a step of;
s6, adding the sodium hydroxide aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 3 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 25Cu/a-ZrOx material;
s7, taking 0.5g of the 25Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; the water is deionized water;
s8, adding 0.7235g of ferric nitrate nonahydrate into the copper-zirconium composite oxide aqueous dispersion liquid, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the ammonia water to the ferric nitrate nonahydrate calculated by Fe is 1:1, a step of;
s9, adding the ammonia water solution at the temperature of 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed;
s10, adding 75.9mg of cesium carbonate 1mL of aqueous solution at 25 ℃, stirring at 400rpm at 25 ℃ to perform a sixth contact reaction for 2h, then drying at 40-70 ℃ for 2-6h in a rotary evaporator with the vacuum degree of minus 0.08 to minus 0.1, and calcining at 400 ℃ in a muffle furnace air atmosphere for 4h to obtain the brownish-black 3Cs-20Fe/25Cu/a-ZrOx catalytic material.
Example 5
A preparation method of a high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, dissolving 5.999g of zirconium nitrate pentahydrate in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 30min at 50KHz, and then adding propylene oxide to perform a first contact reaction for 4min to obtain a solution I;
s2, carrying out hydrothermal reaction for 20 hours at 150 ℃, drying the obtained solid sol at 60 ℃ for 24 hours after the reaction is finished, continuously drying at 200 ℃ for 3 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconium nitrate pentahydrate, in molar ratio: ethanol: the propylene oxide was used in an amount of 1:60:1.5;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water at 25 ℃ under the condition of the frequency of 45KHz for 15min by ultrasonic treatment to obtain zirconia aqueous dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving ammonium carbonate in water at 25 ℃ to form an ammonium carbonate aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.2358g of copper acetate monohydrate into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to perform a second contact reaction for 1h; the molar ratio of the ammonium carbonate to the copper acetate monohydrate calculated by Cu is 1:1, a step of;
s6, adding the ammonium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 3 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 25Cu/a-ZrOx material;
s7, taking 0.5g of the 25Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; the water is deionized water;
s8, adding 0.5426g of ferric nitrate nonahydrate into the copper-zirconium composite oxide aqueous dispersion liquid, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the ammonium carbonate to the ferric nitrate nonahydrate calculated as Fe is 2:1, a step of;
s9, adding the ammonium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed;
s10, adding 42.9mg of potassium carbonate 1mL of aqueous solution at 25 ℃, stirring at 400rpm at 25 ℃ to perform a sixth contact reaction for 2h, then drying at 40-70 ℃ for 2-6h in a rotary evaporator with the vacuum degree of minus 0.08 to minus 0.1, and calcining at 400 ℃ in a muffle furnace air atmosphere for 4h to obtain the brownish-black 4K-15Fe/25Cu/a-ZrOx catalytic material.
Example 6
A preparation method of a high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, dissolving 5.999g of zirconium nitrate pentahydrate in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 30min at 50KHz, and then adding propylene oxide to perform a first contact reaction for 2min to obtain a solution I;
s2, carrying out hydrothermal reaction for 20 hours at 150 ℃, drying the obtained solid sol at 60 ℃ for 24 hours after the reaction is finished, continuously drying at 200 ℃ for 3 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconium nitrate pentahydrate, in molar ratio: ethanol: the propylene oxide was used in an amount of 1:60:1.5;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water at 25 ℃ under the condition of the frequency of 45KHz for 15min by ultrasonic treatment to obtain zirconia aqueous dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving ammonium carbonate in water at 25 ℃ to form an ammonium carbonate aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.2358g of copper acetate monohydrate into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to perform a second contact reaction for 1h; the molar ratio of ammonium carbonate to copper acetate monohydrate calculated as Cu was 1.5:1, a step of;
s6, adding the ammonium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 3 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 25Cu/a-ZrOx material;
s7, taking 0.5g of the 25Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; the water is deionized water;
s8, adding 0.5426g of ferric nitrate nonahydrate into the copper-zirconium composite oxide aqueous dispersion liquid, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the ammonium carbonate to the ferric nitrate nonahydrate calculated as Fe is 2.5:1, a step of;
s9, adding the ammonium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed;
s10, adding 53.7mg of potassium carbonate 1mL of aqueous solution at 25 ℃, stirring at 400rpm at 25 ℃ to perform a sixth contact reaction for 2h, then drying at 40-70 ℃ for 2-6h in a rotary evaporator with the vacuum degree of minus 0.08 to minus 0.1, and calcining at 400 ℃ in a muffle furnace air atmosphere for 4h to obtain the brownish-black 5K-15Fe/25Cu/a-ZrOx catalytic material.
Example 7
A preparation method of a high-performance alkali metal modified CuFeZr catalytic material comprises the following steps:
s1, dissolving 5.999g of zirconium nitrate pentahydrate in ethanol at 25 ℃ to obtain a mixture, ultrasonically dissolving the mixture for 30min at 50KHz, and then adding propylene oxide to perform a first contact reaction for 2min to obtain a solution I;
s2, carrying out hydrothermal reaction for 20 hours at 150 ℃, drying the obtained solid sol at 60 ℃ for 24 hours after the reaction is finished, continuously drying at 200 ℃ for 3 hours, and crushing to obtain powdery amorphous zirconia solid; the zirconium nitrate pentahydrate, in molar ratio: ethanol: the propylene oxide was used in an amount of 1:60:1.5;
s3, dispersing 0.3g of amorphous zirconia solid in 50mL of water at 25 ℃ under the condition of the frequency of 45KHz for 15min by ultrasonic treatment to obtain zirconia aqueous dispersion with the mass concentration of 6 g/L; the water is deionized water;
s4, dissolving ammonium carbonate in water at 25 ℃ to form an ammonium carbonate aqueous solution with the mass concentration of 9.6 g/L;
s5, adding 0.1886g of copper acetate monohydrate into the zirconium oxide aqueous dispersion, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to perform a second contact reaction for 1h; the molar ratio of the ammonium carbonate to the copper acetate monohydrate calculated as Cu is 1.5:1, a step of;
s6, adding the ammonium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a third contact reaction for 3 hours; after the reaction is finished, the obtained substance is fully washed and centrifuged at 6000-8000rmp, the precipitate obtained after centrifugation is taken, dried at 60 ℃ for 12 hours and crushed, and calcined for 4 hours in a muffle furnace air atmosphere at 400 ℃ to obtain the 20Cu/a-ZrOx material;
s7, taking 0.5g of the 20Cu/a-ZrOx material at 25 ℃, and dispersing the material in 50mL of water by ultrasonic treatment for 15min under the condition of 50KHz frequency to obtain copper-zirconium composite oxide aqueous dispersion with the mass concentration of 10 g/L; the water is deionized water;
s8, adding 0.5426g of ferric nitrate nonahydrate into the copper-zirconium composite oxide aqueous dispersion liquid, and stirring at the stirring speed of 400rpm at the temperature of 25 ℃ to carry out a fourth contact reaction for 1h; the molar ratio of the ammonium carbonate to the ferric nitrate nonahydrate calculated as Fe is 1.5:1, a step of;
s9, adding the ammonium carbonate aqueous solution at the temperature of 80 ℃, and stirring to perform a fifth contact reaction for 3 hours; after the reaction is finished, the obtained substances are fully washed and centrifuged at 6000-8000rmp, and the precipitate obtained after centrifugation is taken and dried at 60 ℃ for 12 hours and then crushed;
s10, adding 1mL of aqueous solution of 32.2mg of potassium carbonate at 25 ℃, stirring at 400rpm at 25 ℃ to perform a sixth contact reaction for 2h, then drying at 40-70 ℃ for 2-6h in a rotary evaporator with the vacuum degree of minus 0.08 to minus 0.1, and calcining at 400 ℃ in a muffle furnace air atmosphere for 4h to obtain the brownish-black 3K-15Fe/20Cu/a-ZrOx catalytic material.
Test example 1
The catalysts of the above examples were tested to obtain specific surface area and pore size.
The specific surface area is obtained by testing Micromeritics ASAP-2010; the pore size was obtained by testing through Micromeritics ASAP-2010.
The results are shown in Table 1.
Table 1 results of specific surface area test of catalytic materials prepared in examples 1 to 6
As can be seen from Table 1, the alkali metal modified CuFeZr catalytic material prepared by the invention has specific surfaceThe product can reach 35-88m 2 And/g, the stability of active metal/interface species can be effectively increased, the capability of catalyzing and dissociating hydrogen and activating carbon dioxide is improved, and the reaction of preparing low-carbon alcohol by hydrogenating the carbon dioxide is facilitated.
Test example 2
The catalyst of the above example was used for CO 2 The performance test experiment of preparing low-carbon alcohol by catalytic hydrogenation of gas is carried out, wherein CO is used for 2 +H 2 The flow rate of the mixed gas was 36.0mL/min (4 vol% N) 2 24% CO by volume 2 72 vol% H 2 ) The airspeed is 3000 mL/(g) cat H) establishing a micro fixed bed simulated reaction system. First, 0.4g of the sample was subjected to 10vol% H before activity test 2 Reducing in Ar gas flow at 320 deg.C for 1 hr, and introducing CO 2 +H 2 +N 2 The reactants were mixed and pressurized to 5MPa. Subsequently, the catalytic performance was evaluated at different target temperatures (280, 300 and 320 ℃). The obtained tail gas component such as CO, CO 2 The data in tables 2, 3 and 4 were obtained by online quantitative analysis of methanol, C2-C5 lower alcohols, C2-C8 olefins and C1-C8 alkanes by gas chromatography with a thermal conductivity detector and a flame ionization detector. In addition, after changing the mass ratio of Cu/Zr, 30.9% of CO is obtained by the 3K-15Fe/20Cu/a-ZrOx catalyst at 320 DEG C 2 Conversion, 21.6% and 46.1mg.g cat -1 h -1 Lower alcohol selectivity and yield.
Table 2: the temperature is 280 DEG C
Table 3: the temperature is 300 DEG C
Table 4: the temperature is 320 DEG C
From the results, the catalytic material provided by the invention has excellent carbon dioxide conversion rate and low-carbon alcohol selectivity/yield, and shows excellent catalytic performance for preparing low-carbon alcohol by hydrogenating carbon dioxide.
Test example 3
The products obtained in examples 1 to 6 above were subjected to X-ray powder diffraction (XRD) experiments using a Miniflex model 600 XRD diffractometer from Rigaku corporation, respectively, and the results are shown in FIG. 1.
As can be seen from FIG. 1, after doping with copper, iron, alkali metal K, the amorphous structure of the catalyst support is maintained, and the crystalline phase peak metals of the metallic copper, iron, potassium and their oxides are not detected, which suggests that the amorphous zirconia with high specific surface area favors the highly dispersed active metals, favors the formation of micro-sized copper, iron, potassium nanocrystals or their abundant alloy interface species, which is CO to the material 2 The performance of preparing low-carbon alcohol by catalytic hydrogenation is obviously improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A preparation method of a high-performance alkali metal modified CuFeZr catalytic material is characterized by comprising the following steps of: the method comprises the following steps:
s1, adding zirconium salt into an ethanol solvent, ultrasonically dissolving, and then adding propylene oxide for a first contact reaction to obtain a solution I;
s2, carrying out hydrothermal reaction on the solution I, and drying and crushing the obtained substance to obtain amorphous zirconia;
s3, adding amorphous zirconia into water, performing ultrasonic dispersion, adding copper salt, and performing a second contact reaction to obtain a solution II;
s4, adding a precipitant aqueous solution into the solution II to carry out a third contact reaction, centrifuging, drying, crushing and calcining the obtained substance after the reaction is finished to obtain a copper-zirconium material;
s5, carrying out a fourth contact reaction on the obtained solid and ferric salt to obtain a solution III;
s6, carrying out a fifth contact reaction on the solution III and a precipitator, centrifuging, drying and crushing the obtained substance after the reaction is finished;
s7, carrying out a sixth contact reaction on the obtained material and alkali metal salt, carrying out rotary evaporation and drying on water, and then crushing and calcining the obtained material to obtain the high-performance alkali metal modified CuFeZr catalytic material.
2. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in the step S1, the zirconium salt may be one of zirconium nitrate, zirconyl chloride, zirconium chloride, and zirconium sulfate;
the usage amount of the propylene oxide and the zirconium salt calculated as Zr element is (1.5-2.5) in terms of the mole ratio: 1.
3. the method of preparing a high surface area amorphous zirconia catalytic material according to claim 1, wherein: the conditions of the first contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.05-1h;
preferably, the first contact reaction is carried out with stirring at a rate of 50-500rpm.
4. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in the step S1, the temperature of the hydrothermal reaction is 100-200 ℃ and the time is 15-25h.
5. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S3, the conditions of the second contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.05-10h;
the copper salt can be any one of copper nitrate, copper sulfate, copper acetate and copper chloride;
the ratio by mass of the metal copper salt in terms of Cu element to the amorphous zirconia in terms of zirconia is (0.2-0.3): 1, a step of;
the second contact reaction is carried out with stirring at a rate of 50-500rpm.
6. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S3, the conditions of the third contact reaction are as follows: the temperature is 70-90 ℃ and the time is 0.1-10h;
the precipitant can be any one of ammonium carbonate, ammonium bicarbonate, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and ammonia water;
the molar ratio of the precipitant to the metal copper salt calculated as Cu element is (1-3).
7. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S2, the drying conditions are as follows: the temperature is 60-100deg.C, and the time is 4-24h.
8. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S4, the drying conditions include: the temperature is 40-80 ℃ and the time is 4-24 hours; the conditions of the calcination include: the temperature is 300-500 ℃ and the time is 3-10h.
9. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S5, the conditions of the fourth contact reaction are as follows: the temperature is 10-40 ℃ and the time is 0.05-10h;
the ferric salt can be any one of ferric nitrate, ferric acetate, ferric sulfate and ferric chloride;
the dosage mass ratio of the metallic ferric salt to the copper zirconium material calculated by Fe element is (0.1-0.2): 1, a step of;
the fourth contact reaction is carried out with stirring at a rate of 50-500rpm.
10. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S6, the conditions of the fifth contact reaction are as follows: the temperature is 70-90 ℃ and the time is 0.1-10h;
the precipitant can be any one of ammonium carbonate, ammonium bicarbonate, potassium carbonate, potassium bicarbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide and ammonia water;
the molar ratio of the precipitant to the metal copper salt calculated as Fe element is (1-3).
11. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S6, the drying conditions include: the temperature is 40-80 ℃ and the time is 4-24h.
12. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S7, the conditions of the sixth contact reaction are: the temperature is 10-50 ℃ and the time is 2-10h;
the alkali metal salt can be any one of potassium carbonate, sodium carbonate and cesium carbonate;
the molar ratio of the alkali metal salt calculated as alkali metal element to the amorphous zirconia calculated as Zr element is (0.10 to 0.25): 1, a step of;
the sixth contact reaction is carried out with stirring at a rate of 50-500rpm.
13. The method for preparing the high-performance alkali metal modified CuFeZr catalytic material according to claim 1, wherein the method comprises the following steps: in step S7, the conditions of the rotary evaporation include: the temperature is 40-80 ℃, the vacuum degree is-0.08 to-0.1, and the time is 2-6h; the conditions of the calcination include: the temperature is 300-500 ℃ and the time is 3-10h.
14. A high-performance alkali metal modified CuFeZr catalytic material is characterized in that: prepared by a process as claimed in any one of claims 1 to 13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111390433.9A CN116135306A (en) | 2021-11-18 | 2021-11-18 | High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111390433.9A CN116135306A (en) | 2021-11-18 | 2021-11-18 | High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116135306A true CN116135306A (en) | 2023-05-19 |
Family
ID=86333307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111390433.9A Pending CN116135306A (en) | 2021-11-18 | 2021-11-18 | High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116135306A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068957A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Zirconium-based arsenic removing material and preparation method and application thereof |
| CN110465302A (en) * | 2019-07-30 | 2019-11-19 | 武汉大学 | A kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation method and application |
| US20210214287A1 (en) * | 2019-07-15 | 2021-07-15 | Battelle Memorial Institute | Integrated capture and conversion of co2 to methane, methanol, or methanol and glycol |
| CN113549662A (en) * | 2020-04-26 | 2021-10-26 | 赤壁市高质量发展研究院有限公司 | Method for efficiently preparing antidepressant prodrug L-4-Cl-kynurenine by using MOF enzyme-carrying technology and application thereof |
-
2021
- 2021-11-18 CN CN202111390433.9A patent/CN116135306A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102068957A (en) * | 2009-11-20 | 2011-05-25 | 中国科学院金属研究所 | Zirconium-based arsenic removing material and preparation method and application thereof |
| US20210214287A1 (en) * | 2019-07-15 | 2021-07-15 | Battelle Memorial Institute | Integrated capture and conversion of co2 to methane, methanol, or methanol and glycol |
| CN110465302A (en) * | 2019-07-30 | 2019-11-19 | 武汉大学 | A kind of CO2Hydrogen is added to prepare low-carbon alcohol catalyst and its preparation method and application |
| CN113549662A (en) * | 2020-04-26 | 2021-10-26 | 赤壁市高质量发展研究院有限公司 | Method for efficiently preparing antidepressant prodrug L-4-Cl-kynurenine by using MOF enzyme-carrying technology and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| SHANGGUI LI等: "Effect of Iron Promoter on Structure and Performance of K/Cu-Zn Catalyst for Higher Alcohols Synthesis from CO2 Hydrogenation", 《CATALYSIS LETTERS》, vol. 143, 2 March 2013 (2013-03-02), pages 345 - 355, XP035372697, DOI: 10.1007/s10562-013-0977-7 * |
| 牛灿等: "载体对Cu-Co基催化剂合成低碳醇的影响", 《纺织高校基础科学学报》, vol. 29, no. 4, 21 December 2016 (2016-12-21), pages 515 - 519 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2019109831A1 (en) | Method for preparing copper-nickel cobaltate nanowires and use thereof in catalyzing hydrolysis of ammonia borane to produce hydrogen | |
| DK1406725T3 (en) | Perovskites comprising noble metals and their use as catalysts | |
| CN101455964B (en) | Preparation method of nickel based metal load type catalyst | |
| CN113209976B (en) | Catalyst for methanol steam reforming hydrogen production, preparation method and application thereof, and methanol steam reforming hydrogen production reaction | |
| CN113231070B (en) | Preparation method and application of composite metal oxide solid solution copper-loaded reverse catalyst | |
| CN100532270C (en) | Nano crystal constructed porous copper oxide aggregate and its preparing method | |
| CN110201680B (en) | Catalyst for selective hydrogenation of alpha, beta-unsaturated aldehyde/ketone, preparation method and catalysis method | |
| CN110773174B (en) | Catalyst for preparing gamma-butyrolactone through dehydrogenation of 1, 4-butanediol and preparation method thereof | |
| CN105727943A (en) | Method for synthesizing nano three-way catalyst | |
| CN105195156A (en) | Preparation method and application of high-dispersity copper-based catalyst | |
| CN104624196A (en) | High-specific-surface-area Fischer-Tropsch synthesis catalyst and preparation method and application of high-specific-surface-area Fischer-Tropsch synthesis catalyst | |
| Huang et al. | Selective synthesis of imines by direct oxidative coupling of amines on Cu-doped CeO2 catalysts | |
| CN113385171A (en) | Metal-based catalyst protected by few-layer carbon and application thereof in ethylene oxide carbonylation | |
| CN114405505A (en) | Platinum modified indium-based oxide catalyst and preparation method and application thereof | |
| CN109847756B (en) | Nickel-based nano catalyst with hollow structure and preparation method and application thereof | |
| CN109926048B (en) | Single-component double-active-site Cu2O-CuO nano mixed phase structure copper oxide catalyst, preparation method and application | |
| CN112316985B (en) | Catalytic material for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN113694929A (en) | Supported monoatomic copper-based metal oxide catalyst, and preparation method and application thereof | |
| Huo et al. | Efficient La–Ba–MgO supported Ru catalysts for ammonia synthesis | |
| CN116135306A (en) | High-performance alkali metal modified CuFeZr catalytic material and preparation method thereof | |
| CN103272611B (en) | Co-M-B amorphous alloy nanotube catalyst, and preparation and application thereof | |
| CN113996303B (en) | Double-active interface supported catalyst, preparation method and application | |
| CN115722222A (en) | High-surface-area amorphous zirconium oxide catalytic material and preparation method thereof | |
| CN110052261A (en) | A kind of catalysis carbon dioxide selectivity prepares solid catalyst and the application of methanol and carbon monoxide | |
| CN115155582A (en) | Active carbon-loaded methanol reforming hydrogen production catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |