CN116020455A - Catalyst for promoting hydrogenation of carbon dioxide to prepare methanol and application thereof - Google Patents
Catalyst for promoting hydrogenation of carbon dioxide to prepare methanol and application thereof Download PDFInfo
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- CN116020455A CN116020455A CN202310042862.XA CN202310042862A CN116020455A CN 116020455 A CN116020455 A CN 116020455A CN 202310042862 A CN202310042862 A CN 202310042862A CN 116020455 A CN116020455 A CN 116020455A
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- supported catalyst
- carbon dioxide
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- hydrogenation
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 84
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 33
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 230000001737 promoting effect Effects 0.000 title claims abstract description 7
- 239000013216 MIL-68 Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 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 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000004913 activation Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 230000005669 field effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910003437 indium oxide Inorganic materials 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a supported catalyst for promoting hydrogenation of carbon dioxide to prepare methanol, and a preparation method and application thereof, wherein a solvothermal method is firstly utilized to synthesize a metal organic framework material In-MIL-68, then porous finite field effect of the In-MIL-68 is utilized to adsorb Pt as a cocatalyst, and a bottom-up method is utilized to prepare Pt@In 2 O 3 Supported catalysts. The supported catalyst can effectively promote the activation of carbon dioxide and hydrogen, inhibit the high-temperature deactivation of the catalyst, effectively solve the problems of poor stability, low activity, low selectivity and the like of the traditional supported catalyst, and has the advantages of simple synthesis method, considerable yield and lower temperature required by preparing methanol by catalyzing the hydrogenation of carbon dioxideIs beneficial to popularization and application in the existing methanol preparation process by carbon dioxide hydrogenation.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide hydrogenation, and particularly relates to a supported catalyst for preparing methanol by promoting carbon dioxide hydrogenation, and a preparation method and application thereof.
Background
Carbon dioxide is considered to be a major cause of global warming and marine acidification, and thus the continuous rise in atmospheric carbon dioxide concentration caused by human activities has become a serious problem of worldwide concern. To aid the national strategy of "peak carbon and carbon neutralization," researchers have focused on converting carbon dioxide into value-added chemicals, which not only reduce the concentration of carbon dioxide in the atmosphere, but also provide high-energy chemical fuels as alternatives to traditional fossil fuels. At present, the catalytic hydrogenation technology can be utilized to convert carbon dioxide into various fuels such as aromatic hydrocarbon, olefin, formic acid, methanol and the like. Among the numerous carbon dioxide conversion products, methanol is one of the ideal products as a liquid fuel and an important platform molecule for the production of high value-added olefins and aromatics.
The catalyst used for producing methanol by using the thermal catalytic carbon dioxide hydrogenation reduction process in the industry at present is mainly Cu/ZnO/Al 2 O 3 . However, the catalyst has the problems of low activity, low selectivity of methanol, poor stability and the like. Therefore, there is a need to develop a carbon dioxide hydrogenation catalyst having high activity, high selectivity and high stability under mild conditions.
Indium oxide based catalysts have proven useful in catalyzing the hydrogenation of carbon dioxide to methanol. However, most of the traditional indium oxide materials are of bulk phase structures, have small specific surface area and low surface catalytic activity site exposure rate, which is not beneficial to adsorption and activation of carbon dioxide; meanwhile, the traditional indium oxide-based catalyst also has the problems of low selectivity to methanol, poor stability and the like. The addition of a small amount of noble metal on the surface of indium oxide as a cocatalyst is one of effective strategies for improving the performance of catalyzing the hydrogenation of carbon dioxide to prepare methanol. This is because the noble metal can promote activation of carbon dioxide and hydrogen and provide catalytically active sites for reaction, thereby improving reactivity and selectivity. However, noble metal promoters supported by conventional impregnation methods and the like tend to sinter/agglomerate during the reaction, resulting in easy deactivation of the catalyst. Aiming at the problems, the invention utilizes the porous finite field effect of MOF material to effectively inhibit the migration and aggregation of the supported metal cocatalyst, namely, precious metal Pt is embedded into a porous precursor with a finite field effect, and then the supported indium oxide catalyst with high activity, high selectivity and stability is prepared through one-step heat treatment.
Disclosure of Invention
The invention provides a supported catalyst for promoting hydrogenation of carbon dioxide to prepare methanol, and a preparation method and application thereof, aiming at the defects of the existing catalyst. The supported catalyst can effectively activate carbon dioxide and hydrogen, has high activity and high stability, and can inhibit high-temperature deactivation of the catalyst, thereby solving the defects of poor stability, low activity, low selectivity and the like of the traditional catalyst.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a supported catalyst for preparing methanol by promoting hydrogenation of carbon dioxide is prepared by adsorbing Pt precursor with Metal Organic Framework (MOF) material In-MIL-68 and performing one-step heat treatment In air atmosphere 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The preparation method comprises the following steps:
(1) Dissolving indium nitrate and terephthalic acid In N, N-Dimethylformamide (DMF), reacting for 30 min at 120 ℃, washing and drying the obtained precipitate to obtain a metal organic framework material In-MIL-68;
(2) The resulting In-MIL-68 was added at a concentration of 7.4 mg ml -1 The chloroplatinic acid solution is subjected to stirring adsorption, washing and drying, and then calcined in air atmosphere at 500 ℃ for 2 h, thus obtaining the supported catalyst Pt x @In 2 O 3 。
Further, in the step (1), the mass ratio of the indium nitrate to the terephthalic acid is 1:1.
Further, pt In the obtained supported catalyst 2 O 3 The loading amount on the catalyst is 0.5-6wt%.
The supported catalyst obtained by the invention can be used in the reaction of preparing methanol by hydrogenating carbon dioxide.
The invention has the remarkable effects that:
(1) The invention is characterized In that 2 O 3 Pt is loaded on the catalyst, so that Pt In can be effectively inhibited 2 O 3 The aggregation and the deactivation of the catalyst are improved, the activation and the dissociation of carbon dioxide and hydrogen are promoted, and the efficiency of the catalytic reaction can be obviously improved.
(2) The method is simple and easy to implement, has considerable yield, lower temperature required by catalyzing the hydrogenation of the carbon dioxide to prepare the methanol, and higher selectivity of the methanol, and is favorable for popularization and application on the basis of the existing process.
Drawings
FIG. 1 is In 2 O 3 With the supported catalyst Pt prepared in example 2 x @In 2 O 3 XRD contrast pattern of (c).
FIG. 2 is In 2 O 3 (a) With the supported catalyst Pt prepared in example 2 0.5 @In 2 O 3 （b）、Pt 2 @In 2 O 3 (c) And Pt (Pt) 6 @In 2 O 3 (d) SEM images of (a).
FIG. 3 is In 2 O 3 With the supported catalyst Pt prepared in example 2 x @In 2 O 3 And (3) an activity comparison graph for preparing methanol by catalyzing the hydrogenation of carbon dioxide.
FIG. 4 shows the Pt as supported catalyst before and after the catalytic reaction 2 @In 2 O 3 XRD contrast pattern of (c).
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1 preparation of In-MIL-68
60 mg of In (NO) 3 ) 3 ·4.5H 2 O and 60 mg terephthalic acid are fully dissolved In 50 mL DMF and then react for 30 min at 120 ℃, and the obtained white precipitate is washed and dried to obtain In-MIL-68.
Example 2 Pt x @In 2 O 3 Preparation of Supported catalysts
200 of In-MIL-68 prepared In example 1 of mg was dispersed In 50 mL ethanol, and then added with 0.135, 0.54 and 1.62. 1.62 mL concentrations of 7.4 mg. Mu.ml, respectively -1 After fully mixing and stirring 12 h, the obtained precipitate is washed and dried, and then calcined in an air atmosphere at 500 ℃ for 2 h, thus obtaining catalyst Pt with the loading of 0.5wt%, 2wt% and 6wt%, respectively x @In 2 O 3 (x represents Pt In 2 O 3 Load on) the substrate.
FIG. 1 is In 2 O 3 With the catalyst Pt prepared in example 2 x @In 2 O 3 XRD contrast pattern of (c). As shown In FIG. 1, the XRD pattern of the supported catalyst contains In 2 O 3 But does not show characteristic peaks of Pt, mainly due to the small content of Pt and the small particle size.
FIG. 2 is In 2 O 3 (a) With the supported catalyst Pt prepared in example 2 0.5 @In 2 O 3 （b）、Pt 2 @In 2 O 3 (c) And Pt (Pt) 6 @In 2 O 3 (d) SEM images of (a). As can be seen from FIG. 2, pure In 2 O 3 The supported catalyst is hollow hexagonal prism-shaped, and after Pt is supported, the obtained supported catalyst still maintains a hollow hexagonal prism structure.
Example 3 Pt x @In 2 O 3 Evaluation of catalytic carbon dioxide hydrogenation to methanol Activity
Dioxidation of the resulting catalystThe efficiency evaluation experiment of preparing methanol by carbon hydrogenation is carried out in a stainless steel high-pressure reaction kettle device, and the yield of methanol and CO is detected by adopting Agilent 7890B gas chromatography. The experimental process is as follows: placing the catalyst into a stainless steel high-pressure reaction kettle, and filling H into the stainless steel high-pressure reaction kettle 2 /CO 2 Feed gas of =3:1 (v/v) to 3 MPa, reaction 2 h at 260 ℃.
FIG. 3 is In 2 O 3 With the supported catalyst Pt prepared in example 2 x @In 2 O 3 And (3) an activity comparison graph for preparing methanol by catalyzing the hydrogenation of carbon dioxide. As can be seen from the figure, compared to pure In 2 O 3 The supported catalyst can obviously improve the efficiency and selectivity of preparing methanol by hydrogenating carbon dioxide. This is mainly due to the ability of Pt to promote CO 2 Activation and H of (2) 2 And further improves the efficiency of preparing methanol by selectively hydrogenating the carbon dioxide. Wherein, when the Pt load is 2wt%, the catalyst has the most obvious effect of improving the efficiency and selectivity of preparing methanol by hydrogenating carbon dioxide.
FIG. 4 shows the Pt as supported catalyst before and after the catalytic reaction 2 @In 2 O 3 XRD contrast pattern of (c). As can be seen from the XRD patterns before and after the reaction, the supported catalyst has no obvious change after the reaction, and no impurity peak, which indicates porous In 2 O 3 The structure limiting function of the catalyst can effectively inhibit migration and agglomeration of Pt, thereby improving Pt 2 @In 2 O 3 Stability of the catalyst.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. A preparation method of a supported catalyst for promoting hydrogenation of carbon dioxide to prepare methanol is characterized by comprising the following steps: the Pt precursor is adsorbed by utilizing a metal organic framework material In-MIL-68, and the supported catalyst Pt@In is prepared by air atmosphere one-step heat treatment 2 O 3 。
2. Preparation of the Supported catalyst according to claim 1The method is characterized in that: pt In 2 O 3 The loading amount on the catalyst is 0.5-6wt%.
3. The method for preparing a supported catalyst according to claim 1, wherein: the method comprises the following steps:
(1) Dissolving indium nitrate and terephthalic acid In N, N-dimethylformamide, reacting for 30 min at 120 ℃, washing and drying the obtained precipitate to obtain a metal organic framework material In-MIL-68;
(2) 7. mg.ml was added to the obtained In-MIL-68 -1 The chloroplatinic acid solution is subjected to stirring adsorption, washing and drying, and then calcined in air atmosphere at 500 ℃ for 2 h, thus obtaining the supported catalyst Pt x @In 2 O 3 。
4. A method for preparing a supported catalyst according to claim 3, characterized in that: the mass ratio of the indium nitrate to the terephthalic acid in the step (1) is 1:1.
5. A supported catalyst prepared by the method of claim 1.
6. Use of the supported catalyst of claim 5 in a reaction for producing methanol by hydrogenation of carbon dioxide.
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| CN202310042862.XA CN116020455A (en) | 2023-01-28 | 2023-01-28 | Catalyst for promoting hydrogenation of carbon dioxide to prepare methanol and application thereof |
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| CN202310042862.XA CN116020455A (en) | 2023-01-28 | 2023-01-28 | Catalyst for promoting hydrogenation of carbon dioxide to prepare methanol and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
| US20210322957A1 (en) * | 2018-09-06 | 2021-10-21 | Total Se | Noble metal promoted supported indium oxide catalyst for the hydrogenation of co2 to methanol and process using said catalyst |
| CN113663716A (en) * | 2021-09-28 | 2021-11-19 | 南京工业大学 | Indium oxide loaded metal monatomic catalyst and application thereof |
| CN114405505A (en) * | 2022-01-25 | 2022-04-29 | 上海工程技术大学 | Platinum modified indium-based oxide catalyst and preparation method and application thereof |
| CN115155600A (en) * | 2022-06-24 | 2022-10-11 | 盐城工学院 | Catalyst for synthesizing methanol and preparation method and application thereof |
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- 2023-01-28 CN CN202310042862.XA patent/CN116020455A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120149560A1 (en) * | 2010-12-08 | 2012-06-14 | Electronics And Telecommunications Research Institute | Method of manufacturing porous metal oxide |
| US20210322957A1 (en) * | 2018-09-06 | 2021-10-21 | Total Se | Noble metal promoted supported indium oxide catalyst for the hydrogenation of co2 to methanol and process using said catalyst |
| CN113663716A (en) * | 2021-09-28 | 2021-11-19 | 南京工业大学 | Indium oxide loaded metal monatomic catalyst and application thereof |
| CN114405505A (en) * | 2022-01-25 | 2022-04-29 | 上海工程技术大学 | Platinum modified indium-based oxide catalyst and preparation method and application thereof |
| CN115155600A (en) * | 2022-06-24 | 2022-10-11 | 盐城工学院 | Catalyst for synthesizing methanol and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUNSHI LIU等: "《Metal-organic-framework-derived In2O3 microcolumnar structures embedded with Pt nanoparticles for NO2 detection near room temperature》", 《CERAMICS INTERNATIONAL》, vol. 45, no. 8, 31 December 2019 (2019-12-31), pages 9820 - 9828 * |
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