CN116422338A - Anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 Catalyst and preparation method thereof - Google Patents
Anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 Catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 230000009467 reduction Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 131
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000013216 MIL-68 Substances 0.000 claims abstract description 72
- 238000000151 deposition Methods 0.000 claims abstract description 19
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- 230000008021 deposition Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 26
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 24
- 238000010926 purge Methods 0.000 claims description 24
- 239000002243 precursor Substances 0.000 claims description 22
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012621 metal-organic framework Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 239000012159 carrier gas Substances 0.000 claims description 10
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 6
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 5
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 5
- SKWCWFYBFZIXHE-UHFFFAOYSA-K indium acetylacetonate Chemical compound CC(=O)C=C(C)O[In](OC(C)=CC(C)=O)OC(C)=CC(C)=O SKWCWFYBFZIXHE-UHFFFAOYSA-K 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000007654 immersion Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 9
- 239000012265 solid product Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J23/825—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 gallium, indium or thallium
-
- 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
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Abstract
The invention belongs to the technical field of catalysis, and in particular relates to an anti-over-reduction xAl 2 O 3 /Ni/In 2 O 3 A catalyst and a method for preparing the same. The invention synthesizes metal organic frame MIL-68 (In) by a hydrothermal method, loads a nickel source by an immersion method and plates Al by an atomic layer deposition technology 2 O 3 The film is baked at high temperature to obtain xAl 2 O 3 /Ni/In 2 O 3 Catalyst (x represents the number of deposition cycles). Will xAl 2 O 3 /Ni/In 2 O 3 For catalysing CO 2 Hydrogenation to methanol, found to be compatible with Ni/In 2 O 3 xAl compared with the catalyst 2 O 3 /Ni/In 2 O 3 After the high-temperature hydrogen reduction treatmentThe structure is not damaged obviously and the excellent methanol generation performance is still maintained, which indicates that the catalyst has good anti-over-reduction capability. The invention has higher practical application value and can be popularized to the anti-reduction protection of different types of catalysts.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to an anti-over-reduction xAl 2 O 3 /Ni/In 2 O 3 A catalyst and a method for preparing the same.
Background
CO 2 The hydrogenation for preparing methanol can not only effectively reduce CO 2 And can also produce methanol with high added value. The catalyst is used for realizing CO 2 The key point of directional hydrogenation to produce methanol.
In recent years, researchers at home and abroad design and develop various kinds of CO 2 Catalyst for preparing methanol by hydrogenation, comprising Cu/ZnO, pd/ZnO and ZnZrO x Solid solution, in 2 O 3 And others. Wherein In 2 O 3 Is considered as a kind of CO 2 Catalyst for preparing methanol by high selective hydrogenation, and its surface oxygen vacancy not only can adsorb and activate CO 2 And the mechanism of periodic generation and annihilation can inhibit side reactions. But In is relatively weak due to the weak self-adsorption capability of dissociating hydrogen 2 O 3 The catalytic activity exhibited is not ideal. To solve the problem, many expert scholars are In 2 O 3 Noble metals such as Pt, pd and the like are introduced into the catalyst to dissociate hydrogen and overflow, so that oxygen vacancy generation and intermediate hydrogenation are effectively assisted, and the catalytic activity is further improved. The replacement of noble metals with inexpensive transition metals is more advantageous for the design cost of the catalyst In view of their price, such as nickel (Ni) base, tianjin university Liu Changjun, etc. for Ni/In prepared by wet chemical reduction 2 O 3 Catalyst for CO 2 Hydrogenation to methanol, the results show highly dispersed Ni sites and In 2 O 3 Effective synergistic action of the carrier enables Ni/In 2 O 3 Has excellent catalytic performance, and CO at 300 ℃ and 5MPa 2 The conversion rate is 18.47%, the selectivity of the methanol exceeds 54%, and the space-time yield of the methanol reaches 0.55g MeOH h -1 g cat -1 (J.energy chem.2020,50, 409-415). However, ni/In 2 O 3 In CO 2 The problem of over-reduction during hydrogenation is of concern. As a reducible oxide, in 2 O 3 At a high temperature H 2 Is easily obtained from In under atmospheric conditions 2 O 3-x Reduction to In 0 Resulting in rapid deactivation of the catalyst. And the presence of Ni enhances H 2 Dissociation and overflow of (C)In-generating 2 O 3 Is easier to reduce and even forms Ni-In alloy, and is extremely unfavorable for methanol generation. In addition, ni/In 2 O 3 The excessive reduction of (a) may cause damage to morphology and structure, so that the catalytic activity is greatly reduced. Therefore, solving the problem of deactivation due to over-reduction is effective for developing Ni/In with stability 2 O 3 The catalyst is of great importance. In summary, the problem of deactivation by over-reduction is to develop highly efficient and stable Ni/In 2 O 3 The difficulty with catalysts is present.
Disclosure of Invention
The invention aims at depositing Ni/In by atomic layer deposition technology 2 O 3 Depositing a permeable layer of Al on the surface of the catalyst 2 O 3 Protecting the film to raise the excessive reduction resistance of the catalyst and develop CO with high efficiency and stability 2 Hydrogenation to prepare methanol xAl 2 O 3 /Ni/In 2 O 3 A method for preparing the catalyst.
Another object of the present invention is to provide an xAl 2 O 3 /Ni/In 2 O 3 Catalyst, deposition of Al by atomic layer deposition technique 2 O 3 The film can promote Ni/In 2 O 3 The catalyst has the capability of resisting over-reduction and has good application value.
In order to achieve the above object, the technical scheme of the present invention is as follows:
anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 The catalyst and the preparation method thereof comprise the following steps:
(1) Taking an indium source and terephthalic acid as raw materials, and taking N, N-dimethylformamide as a solvent, and performing hydro-thermal treatment for a period of time at a certain temperature to obtain a metal-organic framework MIL-68 (In);
(2) Dissolving a certain amount of nickel source In an organic solvent, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuing stirring at room temperature for a period of time, and then evaporating the organic solvent to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) 0.5g of Ni/MIL-68 (In) is put into a reaction chamber of an atomic layer deposition equipmentSetting temperature and pressure in the chamber, using trimethylaluminum and water as precursors, N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure, N 2 Purging, water exposure, N 2 Purging deposited Al 2 O 3 The thickness of (2) is strictly controlled by the deposition cycle times (x), and finally xAl is obtained 2 O 3 Ni/MIL-68 (In) samples;
(4) xAl obtained in step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample for a period of time In an air atmosphere at a certain temperature to obtain xAl 2 O 3 /Ni/In 2 O 3 A catalyst.
As a preferable mode of the invention, the indium source in the step (1) is indium acetate, indium nitrate or indium acetylacetonate, and the dosage is 1-4 g; the dosage of terephthalic acid is 0.5-3 g; the dosage of the N, N-dimethylformamide is 20-80 mL; the hydrothermal temperature is 90-120 ℃, and the hydrothermal time is 12-36 h.
As a preferable mode of the invention, the nickel source in the step (2) is nickel acetylacetonate, nickel nitrate or nickel acetate, and the dosage is 10-50 mg; the organic solvent is methanol or ethanol, and the dosage is 15-40 mL; stirring at room temperature for 6-18 h; the evaporating temperature of the organic solvent is 60-100 ℃.
As a preferred mode of the invention, the temperature and the pressure of the reaction chamber of the atomic layer deposition equipment in the step (3) are respectively 80-150 ℃ and 1-13 Pa; in the atomic layer deposition process, the exposure time of trimethylaluminum is 0.5-2 s, N 2 The purging time is 30-90 s, the water exposure time is 0.3-2 s, N 2 The purging time is 30-90 s.
As a preferable mode of the invention, the roasting temperature in the step (4) is 300-700 ℃ and the roasting time is 1-6 h.
After the technical scheme is adopted, the invention relates to the anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 The catalyst and the preparation method thereof have the beneficial effects that:
1. according to the invention, the metal organic framework MIL-68 (In) is used as a precursor, so that the catalyst with regular morphology and large specific surface area can be obtained;
2. the interaction of organic groups on a metal organic framework MIL-68 (In) and nickel ions is utilized to ensure that nickel active sites are highly dispersed on the catalyst;
3. Ni/In deposition technique 2 O 3 Depositing a permeable layer of Al on the surface of the catalyst 2 O 3 The protective film can effectively avoid the damage of high-temperature hydrogen to the catalyst;
in conclusion, the invention improves the CO 2 Ni/In hydrogenation process for preparing methanol 2 O 3 The catalyst has the performance of anti-over reduction and has good application value.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is 5Al 2 O 3 /Ni/In 2 O 3 EDX element distribution of the catalyst;
FIG. 2 is a diagram of Ni/In after high temperature hydrogen treatment 2 O 3 And 5Al 2 O 3 /Ni/In 2 O 3 Catalyst in CO 2 Performance diagram in hydrogenation methanol preparation reaction;
FIG. 3 is a diagram of Ni/In after high temperature hydrogen treatment 2 O 3 And 5Al 2 O 3 /Ni/In 2 O 3 N of the catalyst 2 Adsorption-desorption drawing;
FIG. 4 is a diagram of Ni/In after high temperature hydrogen treatment 2 O 3 And 5Al 2 O 3 /Ni/In 2 O 3 XRD pattern of the catalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The following is an embodiment of the present invention 2 O 3 /Ni/In 2 O 3 The catalyst and the preparation method thereof are specifically described.
The method comprises the following steps:
(1) Taking an indium source and terephthalic acid as raw materials, and taking N, N-dimethylformamide as a solvent, and performing hydro-thermal treatment for a period of time at a certain temperature to obtain a metal-organic framework MIL-68 (In);
(2) Dissolving a certain amount of nickel source In an organic solvent, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuing stirring at room temperature for a period of time, and then evaporating the organic solvent to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition equipment, setting temperature and pressure, taking trimethylaluminum and water as precursors, and N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure, N 2 Purging, water exposure, N 2 Purging deposited Al 2 O 3 The thickness of (2) is strictly controlled by the deposition cycle times (x), and finally xAl is obtained 2 O 3 Ni/MIL-68 (In) samples;
(4) xAl obtained in step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample for a period of time In an air atmosphere at a certain temperature to obtain xAl 2 O 3 /Ni/In 2 O 3 A catalyst.
As a preferable mode of the invention, the indium source in the step (1) is indium acetate, indium nitrate or indium acetylacetonate, and the dosage is 1-4 g; the dosage of terephthalic acid is 0.5-3 g; the dosage of the N, N-dimethylformamide is 20-80 mL; the hydrothermal temperature is 90-120 ℃, and the hydrothermal time is 12-36 h.
As a preferable mode of the invention, the nickel source in the step (2) is nickel acetylacetonate, nickel nitrate or nickel acetate, and the dosage is 10-50 mg; the organic solvent is methanol or ethanol, and the dosage is 15-40 mL; stirring at room temperature for 6-18 h; the evaporating temperature of the organic solvent is 60-100 ℃.
As a preferred mode of the invention, the temperature and the pressure of the reaction chamber of the atomic layer deposition equipment in the step (3) are respectively 80-150 ℃ and 1-13 Pa; in the atomic layer deposition process, the exposure time of trimethylaluminum is 0.5-2 s, N 2 The purging time is 30-90 s, the water exposure time is 0.3-2 s, N 2 The purging time is 30-90 s.
As a preferable mode of the invention, the roasting temperature in the step (4) is 300-700 ℃ and the roasting time is 1-6 h.
After the technical scheme is adopted, the invention relates to the anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 A catalyst and a method for preparing the same. The beneficial effects of (a) are as follows:
1. according to the invention, the metal organic framework MIL-68 (In) is used as a precursor, so that the catalyst with regular morphology and large specific surface area can be obtained;
2. the interaction of organic groups on a metal organic framework MIL-68 (In) and nickel ions is utilized to ensure that nickel active sites are highly dispersed on the catalyst;
3. Ni/In deposition technique 2 O 3 Depositing a permeable layer of Al on the surface of the catalyst 2 O 3 The protective film can effectively avoid the damage of high-temperature hydrogen to the catalyst;
in conclusion, the invention improves the CO 2 Ni/In hydrogenation process for preparing methanol 2 O 3 The catalyst has the performance of anti-over reduction and has good application value.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
(1) Respectively dissolving 2g of indium nitrate and 1g of terephthalic acid In 25mL of N, N-dimethylformamide, mixing the two solutions, fully stirring for 15min at room temperature, transferring to a hydrothermal synthesis kettle, reacting for 24h at 100 ℃, centrifugally washing a white solid product by ethanol for 3 times, and drying at 60 ℃ for 12h to obtain a metal-organic framework MIL-68 (In);
(2) 34mg of nickel acetylacetonate is dissolved In 25mL of methanol, 0.4g of MIL-68 (In) obtained In the step (1) is added under full stirring, stirring is continued at room temperature for 12h, and then methanol is evaporated to dryness at 100 ℃ to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition device, setting temperature and pressure to 110 ℃ and 10Pa respectively, and using trimethylaluminum and water as precursors, N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure for 1s, N 2 Purging for 50s, water exposure for 0.5s, N 2 Purging for 70s, wherein the deposition cycle time is 5, and finally obtaining 5Al 2 O 3 Ni/MIL-68 (In) samples;
(4) 5Al obtained in the step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample at 500 ℃ under air atmosphere for 2 hours to obtain 5Al 2 O 3 /Ni/In 2 O 3 A catalyst.
As shown in FIG. 1, 5Al prepared in example 1 2 O 3 /Ni/In 2 O 3 The catalyst has a hollow rod-shaped structure, and Ni, in and Al elements are uniformly distributed on the catalyst.
As shown in FIG. 2, 5Al prepared in example 1 2 O 3 /Ni/In 2 O 3 The catalyst was treated under a hydrogen atmosphere at 400℃to give (5 Al 2 O 3 /Ni/In 2 O 3 -R400) after CO 2 The excellent methanol production performance is still maintained In hydrogenation reaction, and Ni/In 2 O 3 R400 essentially lost methanol production, indicating that 5Al was produced 2 O 3 /Ni/In 2 O 3 The catalyst has good over-reduction resistance and higher economic value.
As shown In FIG. 3, compared with Ni/In 2 O 3 R400, 5Al prepared in example 1 2 O 3 /Ni/In 2 O 3 Catalyst at 400 ℃ in hydrogen atmosphereDown treatment (5 Al) 2 O 3 /Ni/In 2 O 3 R400) is still able to maintain a good structure, indicating Al 2 O 3 The thin layer can be used for Ni/In 2 O 3 The structure of the device is protected, and the device has higher application value.
As shown In FIG. 4, compared with Ni/In 2 O 3 R400, 5Al prepared in example 1 2 O 3 /Ni/In 2 O 3 The catalyst was treated under a hydrogen atmosphere at 400℃to give (5 Al 2 O 3 /Ni/In 2 O 3 -R400) then, elemental In and In are formed 3 Ni 2 The alloy is obviously less, indicating that the prepared 5Al 2 O 3 /Ni/In 2 O 3 The catalyst has good over-reduction resistance.
Example 2
(1) Respectively dissolving 1g of indium acetate and 1g of terephthalic acid In 20mL of N, N-dimethylformamide, then mixing the two solutions, fully stirring for 15min at room temperature, transferring to a hydrothermal synthesis kettle, reacting for 12h at 90 ℃, centrifugally washing a white solid product by ethanol for 3 times, and drying at 60 ℃ for 12h to obtain a metal-organic framework MIL-68 (In);
(2) Dissolving 20mg of nickel nitrate In 25mL of ethanol, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuously stirring at room temperature for 6 hours, and then evaporating the ethanol at 80 ℃ to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition device, setting the temperature and pressure to 90 ℃ and 10Pa respectively, taking trimethylaluminum and water as precursors, and N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure for 0.5s, N 2 Purging for 40s, water exposure for 0.5s, N 2 Purging for 40s, wherein the deposition cycle time is 10, and finally obtaining 10Al 2 O 3 Ni/MIL-68 (In) samples;
(4) 10Al obtained in the step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample at 400 ℃ In an air atmosphere for 3 hours to obtain 10Al 2 O 3 /Ni/In 2 O 3 A catalyst.
Example 3
(1) Respectively dissolving 1.5g of indium acetylacetonate and 1.5g of terephthalic acid In 40mL of N, N-dimethylformamide, then mixing the two solutions, fully stirring at room temperature for 15min, transferring to a hydrothermal synthesis kettle, reacting at 110 ℃ for 24h, centrifugally washing a white solid product by ethanol for 3 times, and drying at 60 ℃ for 12h to obtain a metal organic framework MIL-68 (In);
(2) Dissolving 40mg of nickel acetate In 30mL of ethanol, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuing stirring at room temperature for 24 hours, and then evaporating the ethanol at 90 ℃ to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition device, setting the temperature and pressure to be 100 ℃ and 5Pa respectively, taking trimethylaluminum and water as precursors, and N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure for 0.8s, N 2 Purging for 60s, water exposure for 1s, N 2 Purging for 50s, wherein the deposition cycle time is 15, and finally obtaining 15Al 2 O 3 Ni/MIL-68 (In) samples;
(4) 15Al obtained in the step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample at 600 ℃ In an air atmosphere for 1h to obtain 15Al 2 O 3 /Ni/In 2 O 3 A catalyst.
Example 4
(1) Respectively dissolving 1.5g of indium nitrate and 1.5g of terephthalic acid In 30mL of N, N-dimethylformamide, then mixing the two solutions, fully stirring at room temperature for 15min, transferring to a hydrothermal synthesis kettle, reacting for 18h at 120 ℃, centrifugally washing a white solid product by ethanol for 3 times, and drying at 60 ℃ for 12h to obtain a metal organic framework MIL-68 (In);
(2) Dissolving 25mg of nickel nitrate into 30mL of methanol, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuously stirring at room temperature for 15h, and then evaporating ethanol at 80 ℃ to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) 0.5g of Ni/MIL-68 (In) was placed In an atomic layer deposition apparatusSetting the temperature and the pressure in the reaction chamber to be 120 ℃ and 5Pa respectively, taking trimethylaluminum and water as precursors, and N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure for 1.5s, N 2 Purging for 70s, water exposure for 1s, N 2 Purging for 70s, wherein the deposition cycle time is 20, and finally obtaining 20Al 2 O 3 Ni/MIL-68 (In) samples;
(4) 20Al obtained in the step (3) 2 O 3 Calcining the Ni/MIL-68 (In) sample at 700deg.C under air atmosphere for 1 hr to obtain 20Al 2 O 3 /Ni/In 2 O 3 A catalyst.
Example 5
(1) 2.5g of indium acetate and 1.3g of terephthalic acid are respectively dissolved In 50mL of N, N-dimethylformamide, then the two solutions are mixed and fully stirred at room temperature for 15min, the mixture is transferred into a hydrothermal synthesis kettle and reacted for 18h at 100 ℃, and a white solid product is centrifugally washed by ethanol for 3 times and dried at 60 ℃ for 12h to obtain a metal organic framework MIL-68 (In);
(2) Dissolving 25mg of nickel acetylacetonate In 35mL of ethanol, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuing stirring at room temperature for 24 hours, and then evaporating the ethanol at 90 ℃ to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition device, setting the temperature and pressure to 90 ℃ and 13Pa respectively, taking trimethylaluminum and water as precursors, and N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure for 1s, N 2 Purging for 60s, water exposure for 0.8s, N 2 Purging for 50s, and obtaining 25Al finally, wherein the deposition cycle time is 25 2 O 3 Ni/MIL-68 (In) samples;
(4) 25Al obtained in the step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample at 500 ℃ In an air atmosphere for 3 hours to obtain 25Al 2 O 3 /Ni/In 2 O 3 A catalyst.
Example 6
(1) Respectively dissolving 3g of indium acetylacetonate and 2g of terephthalic acid In 50mL of N, N-dimethylformamide, then mixing the two solutions, fully stirring for 15min at room temperature, transferring to a hydrothermal synthesis kettle, reacting for 12h at 110 ℃, centrifugally washing a white solid product by ethanol for 3 times, and drying at 60 ℃ for 12h to obtain a metal organic framework MIL-68 (In);
(2) Dissolving 25mg of nickel acetylacetonate In 40mL of ethanol, adding 0.4g of MIL-68 (In) obtained In the step (1) under full stirring, continuously stirring at room temperature for 12h, and then evaporating ethanol at 100 ℃ to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition equipment, setting temperature and pressure to 110 ℃ and 13Pa respectively, and using trimethylaluminum and water as precursors, N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 The film, the flow of going through includes: trimethylaluminum exposure for 1s, N 2 Purging for 50s, water exposure for 1s, N 2 Purging for 70s, wherein the deposition cycle time is 30, and finally obtaining 30Al 2 O 3 Ni/MIL-68 (In) samples;
(4) 30Al obtained in the step (3) 2 O 3 Roasting a Ni/MIL-68 (In) sample at 600 ℃ In an air atmosphere for 3 hours to obtain 30Al 2 O 3 /Ni/In 2 O 3 A catalyst.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
After the technical scheme is adopted, the invention relates to the anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 The catalyst and the preparation method thereof have the beneficial effects that:
1. according to the invention, the metal organic framework MIL-68 (In) is used as a precursor, so that the catalyst with regular morphology and large specific surface area can be obtained;
2. the interaction of organic groups on a metal organic framework MIL-68 (In) and nickel ions is utilized to ensure that nickel active sites are highly dispersed on the catalyst;
3. Ni/In deposition technique 2 O 3 Depositing a permeable layer of Al on the surface of the catalyst 2 O 3 The protective film can effectively avoid the damage of high-temperature hydrogen to the catalyst;
in conclusion, the invention improves the CO 2 Ni/In hydrogenation process for preparing methanol 2 O 3 The catalyst has the performance of anti-over reduction and has good application value.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected 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 be within the scope of the invention.
Claims (7)
1. Anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 The preparation method of the catalyst is characterized by comprising the following steps:
(1) Taking an indium source and terephthalic acid as raw materials, taking N, N-dimethylformamide as a solvent, and carrying out hydro-thermal treatment for a period of time at a certain temperature to obtain a metal-organic framework MIL-68 (In);
(2) Dissolving a nickel source In an organic solvent, fully stirring, adding 0.4g of MIL-68 (In), stirring at room temperature for a period of time, and then evaporating the organic solvent to dryness to obtain a Ni/MIL-68 (In) precursor;
(3) Placing 0.5g of Ni/MIL-68 (In) into a reaction chamber of an atomic layer deposition equipment, setting temperature and pressure, taking trimethylaluminum and water as precursors, and N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 Obtaining xAl from the film 2 O 3 Ni/MIL-68 (In) samples;
(4) Subjecting the xAl to 2 O 3 Roasting a Ni/MIL-68 (In) sample for a period of time In an air atmosphere at a certain temperature to obtain xAl 2 O 3 /Ni/In 2 O 3 A catalyst.
2. The method of manufacturing according to claim 1, characterized in that: the indium source in the step (1) is indium acetate, indium nitrate or indium acetylacetonate, and the dosage is 1-4 g; the dosage of terephthalic acid is 0.5-3 g; the dosage of the N, N-dimethylformamide is 20-80 mL; the hydrothermal temperature is 90-120 ℃, and the hydrothermal time is 12-36 h.
3. The method of manufacturing according to claim 1, characterized in that: the nickel source in the step (2) is nickel acetylacetonate, nickel nitrate or nickel acetate, and the dosage is 10-50 mg; the organic solvent is methanol or ethanol, and the dosage is 15-40 mL; stirring at room temperature for 6-18 h; the evaporating temperature of the organic solvent is 60-100 ℃.
4. The method of manufacturing according to claim 1, characterized in that: in the step (3), trimethylaluminum and water are used as precursors, N 2 Al is deposited on the surface of Ni/MIL-68 (In) as carrier gas 2 O 3 Obtaining xAl from the film 2 O 3 A sample of/Ni/MIL-68 (In) specifically includes:
trimethylaluminum exposure, N 2 Purging, water exposure, N 2 Purging deposited Al 2 O 3 The thickness of (2) is tightly controlled by the number of deposition cycles (x).
5. The method of manufacturing according to claim 1, characterized in that: the temperature of the reaction chamber of the atomic layer deposition equipment in the step (3) is 80-150 ℃ and the pressure is 1-13 Pa; in the atomic layer deposition process, the exposure time of trimethylaluminum is 0.5-2 s, N 2 The purging time is 30-90 s, the water exposure time is 0.3-2 s, N 2 The purging time is 30-90 s.
6. The method of manufacturing according to claim 1, characterized in that: the roasting temperature in the step (4) is 300-700 ℃ and the roasting time is 1-6 h.
7.Anti-over reduction xAl 2 O 3 /Ni/In 2 O 3 Catalyst, characterized in that it is prepared by a process according to any one of claims 1 to 6.
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