CN117225409A - Cerium oxide loaded platinum catalyst, preparation method and application thereof in catalyzing halogenated nitrobenzene to synthesize halogenated aniline - Google Patents
Cerium oxide loaded platinum catalyst, preparation method and application thereof in catalyzing halogenated nitrobenzene to synthesize halogenated aniline Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 59
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 52
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 150000005181 nitrobenzenes Chemical class 0.000 title claims abstract description 23
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 title claims abstract 5
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 34
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000011068 loading method Methods 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001448 anilines Chemical class 0.000 description 22
- 239000000203 mixture Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 9
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 9
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- -1 Pd/CNTs Chemical compound 0.000 description 5
- 208000012839 conversion disease Diseases 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 230000002194 synthesizing effect Effects 0.000 description 4
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 238000010438 heat treatment Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LPZOCVVDSHQFST-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-ethylpyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)CC LPZOCVVDSHQFST-UHFFFAOYSA-N 0.000 description 1
- 229920002415 Pluronic P-123 Polymers 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001992 poloxamer 407 Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 229920003051 synthetic elastomer Polymers 0.000 description 1
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Classifications
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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
- Y02P20/584—Recycling of catalysts
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Abstract
The application provides a cerium oxide loaded platinum catalyst, a preparation method and application thereof in catalyzing halogenated nitrobenzene to synthesize halogenated aniline, and belongs to the technical field of fine organic chemical industry. The application takes cerium nitrate as raw material and adopts hydrothermal synthesis method to prepare mesoporous CeO 2 The support is then impregnated-reducedBy a method of the mesoporous CeO 2 And loading Pt nano particles on the surface of the carrier to obtain the cerium oxide loaded platinum catalyst, wherein the mass loading of the Pt nano particles in the cerium oxide loaded platinum catalyst is 1% -3%. The cerium oxide loaded platinum catalyst prepared by the application can ensure that the halogenated nitrobenzene has higher conversion rate in the reaction of catalyzing the halogenated nitrobenzene to synthesize the halogenated aniline by selective hydrogenation, the halogenated aniline has good selectivity, can be recovered and reused for 10 times, has stable catalytic activity, is easy to separate the prepared product from the catalyst, and is simple to operate, economical and environment-friendly.
Description
Technical Field
The application belongs to the technical field of fine organic chemical industry, and particularly relates to a cerium oxide loaded platinum catalyst, a preparation method and application thereof in catalyzing halogenated nitrobenzene to synthesize halogenated aniline.
Background
Para-chloroaniline is an important intermediate of organic compounds, and is widely used in industrial production, and is a chemical product such as a chemical reagent, a synthetic rubber, a pigment, a dye and the like, and a main raw material and an intermediate of photographic drugs, pesticides, medicines and the like (Catalysis Today,37 (1997) 121-136). At present, p-chloronitrobenzene is mainly adoptedThe hydrogenation route for the preparation of para-chloroaniline has been of great interest in the prior art in the efficient clean catalytic hydrogenation reduction process (Applied Catalysis A: general,513 (2016) 89-97). From the reported literature, the reaction catalyst comprises non-noble metal catalysts such as Ni-B amorphous alloys, supported Ni (Industrial)&Engineering Chemistry Research,59 (2020) 1422-1435), raney Ni (RSC Advances,5 (2015) 36423-36427), etc., the catalytic effect of these catalysts is not very ideal, dehalogenation side reactions easily occur during catalytic hydrogenation, and the selectivity of halogenated anilines is low. Compared with non-noble metal catalysts, noble metal catalysts have better effect, high reactivity and high selectivity to chloroaniline, such as Pd/CNTs, attapulgite supported Pt, particularly Pt 0.0002 -Au 0.005 /TiO 2 The catalyst (Green Chemistry,14 (2012) 111-116), 0.3% Pt-4% Fe/AC (RSC Advances,7 (2017) 29135-29148) can realize the catalytic conversion of p-chloronitrobenzene into target product p-chloroaniline under milder conditions, but the stability of the catalyst is still not ideal.
The cerium oxide nano material is used as common metal oxide, has good thermal stability, particularly has high specific surface area, can be used as a catalyst carrier, and has important application value in the fields of industrial catalysis and fine chemical industry. The preparation method of the mesoporous cerium oxide catalytic material with high specific surface area mainly comprises the following steps: (1) hard template method: mesoporous SiO is usually selected 2 Or mesoporous carbon is used as a hard template, and cerium oxide precursor salt is filled in pores of a template material by impregnation, and then roasting or dissolving is performed. Common hard template materials such as KIT-6, SBA-15, MCM-41 and the like are adopted to infiltrate rare earth metal salt by a solid-liquid method to prepare mesoporous cerium oxide with high specific surface area; however, solid hard template materials, such as SiO, used in the process 2 The hard template material can generate a large amount of wastewater in the etching process, so as to pollute the environment. (2) Soft template method: the process for preparing mesoporous cerium oxide by using the soft template comprises the steps of pre-consolidation, template roasting, removal and the like, and organic high polymer block polymers such as Pluronic P123, F127 and the like are often used as the soft template to synthesize mesoporous cerium oxide (Journal of applied research and tech)Technology, 16 (2018) 511-523), mesoporous ceria synthesized using soft template techniques may exist in an amorphous state in pore size distribution due to thermal instability of the soft template. (3) sol-gel method: the sol-gel technology can highly control the size, crystal phase, morphology, pore diameter and surface area of the mesoporous cerium oxide, so that the mesoporous cerium oxide nano material can be synthesized by a sol-gel method under proper conditions; for example, kamimura et al do not use a template at room temperature, cerium nitrate hexahydrate and NaOH/H 2 O is used as raw material, and mesoporous cerium oxide (surface area 153-198 m) is simply synthesized in a reaction period of 2 hours by adopting a sol-gel method 2 Per g, pore size 4.3-5.6 nm) (Journal of Colloid and Interface Science,436 (2014) 52-62), the mesoporous cerium oxide material synthesized by the sol-gel method has an irregular mesoporous structure.
Therefore, aiming at the technical bottleneck faced by the selective catalytic hydrogenation synthesis of the high-added-value halogenated aniline and the mesoporous cerium oxide nano catalytic material with high specific surface area, the development of the active site high-dispersion supported mesoporous cerium oxide catalytic material for the high-selective catalytic hydrogenation synthesis of halogenated nitrobenzene to halogenated aniline has great significance.
Disclosure of Invention
In order to solve the technical problems, the application provides a cerium oxide loaded platinum catalyst, a preparation method and application thereof in catalyzing halogenated nitrobenzene to synthesize halogenated aniline.
In order to achieve the above purpose, the present application provides the following technical solutions:
one of the technical schemes of the application is as follows:
cerium oxide loaded platinum catalyst (Pt/CeO) 2 Catalyst), the mass loading of Pt nanoparticles in the ceria-supported platinum catalyst is 1% -3%, i.e. loading = mass of Pt nanoparticles/mass of ceria-supported platinum catalyst.
The second technical scheme of the application is as follows:
the cerium oxide loaded platinum catalyst (Pt/CeO) 2 Catalyst), cerium nitrate is used as a raw material, and a hydrothermal synthesis method is adopted to prepare mesoporous CeO 2 Carrier bodyThen adopting an impregnation-reduction method to prepare the mesoporous CeO 2 Pt nano particles are loaded on the surface of the carrier, and the cerium oxide loaded platinum catalyst (Pt/CeO) is obtained 2 A catalyst).
Further, a hydrothermal synthesis method is used for preparing mesoporous CeO 2 The carrier comprises the following steps: adding cerium nitrate into a mixed solution composed of water and ammonia water, uniformly stirring, reacting at 75 ℃ for 24 hours, and obtaining mesoporous CeO through precipitation and conversion of cerium nitrate 2 And a carrier, wherein ammonia water plays a role in alkaline precipitation.
Further, the method for preparing the cerium oxide supported platinum catalyst by the impregnation-reduction method comprises the following steps:
the mesoporous CeO is subjected to 2 Dispersing a carrier in absolute ethyl alcohol, adding a chloroplatinic acid solution, stirring to obtain a dispersion liquid, evaporating the dispersion liquid to dryness to obtain solid powder, and calcining the solid powder to obtain the cerium oxide-loaded platinum catalyst.
Further, the calcination temperature was 200℃for 3 hours.
Still further, the chloroplatinic acid solution should be added in an amount such that the mass loading of Pt nanoparticles in the cerium oxide-supported platinum catalyst is 1% to 3%.
More specifically, the cerium oxide-supported platinum catalyst (Pt/CeO) 2 Catalyst) comprises the following steps:
adding 92g of distilled water and 10mL of ammonia water into a reaction bottle, sealing the reaction bottle by using a balloon, stirring the mixture at room temperature for 30min, weighing 0.6g of cerium nitrate, adding the cerium nitrate into the reaction bottle, stirring the mixture at room temperature for 1h under a sealed condition, transferring the mixture into a stainless steel water heating kettle with a 250mL polytetrafluoroethylene lining, reacting the mixture for 24h at 75 ℃, cooling the mixture to room temperature, carrying out suction filtration, washing the mixture with distilled water and ethanol for 2-3 times respectively, and drying the mixture in a vacuum drying oven for overnight to obtain mesoporous CeO 2 A carrier having a specific surface area of 179m 2 /g, average pore size of 8.1nm;
1g of the mesoporous CeO is weighed 2 Carrier, dispersing in 15mL absolute ethanol, slowly adding chloroplatinic acid solution under stirring to the above-mentioned dispersed mesoporous CeO 2 Stirring and soaking the carrier in the suspension for 5 hrSlowly evaporating at 40deg.C, transferring the solid powder into porcelain boat, and hydrogen reducing at 200deg.C in tubular furnace for 3 hr to obtain cerium oxide supported platinum catalyst (Pt/CeO) 2 Catalyst) having a specific surface area of 179m 2 And/g, average pore diameter of 6.8nm.
The third technical scheme of the application:
the cerium oxide loaded platinum catalyst is applied to catalyzing selective hydrogenation of halogenated nitrobenzene to synthesize halogenated aniline.
Further, adding the cerium oxide loaded platinum catalyst and halogenated nitrobenzene into absolute ethyl alcohol, and reacting in a normal-pressure hydrogen atmosphere at room temperature to obtain halogenated aniline.
Further, the dosage ratio of the cerium oxide supported platinum catalyst to the halogenated nitrobenzene is 10 mg/1 mmol.
Specifically, the method for synthesizing the halogenated aniline by catalyzing the selective hydrogenation of the halogenated nitrobenzene by using the cerium oxide supported platinum catalyst comprises the following steps: 10mg of cerium oxide supported platinum catalyst and 1mmol of halogenated nitrobenzene are added into a reactor, 5mL of absolute ethyl alcohol is added, the mixture is reacted for 1 to 6 hours in a normal pressure hydrogen atmosphere at room temperature, the halogenated aniline is synthesized by selective catalytic hydrogenation, and the reaction equation is as follows, wherein X represents halogen (F, cl, br, I and the like):
the conversion rate of halogenated nitrobenzene can be up to 99% by using gas chromatograph to analyze the reaction conversion rate and product yield, and the selectivity of product halogenated aniline is >90%.
Compared with the prior art, the application has the following advantages and technical effects:
(1) The application prepares mesoporous CeO through hydrothermal synthesis 2 The carrier is further prepared into the cerium oxide loaded platinum catalyst through the impregnation-reduction method, the preparation method is simple to operate and mild in condition, and the prepared cerium oxide loaded platinum catalyst has good active site dispersibility and larger specific surface area.
(2) The cerium oxide loaded platinum catalyst prepared by the application can ensure that the halogenated nitrobenzene has higher conversion rate and good halogenated aniline selectivity in the reaction of catalyzing the halogenated nitrobenzene to synthesize the halogenated aniline by selective hydrogenation, can be recycled and reused for 10 times, and has stable catalytic activity.
(3) The application adopts cerium oxide loaded platinum catalyst to catalyze halogenated nitrobenzene to synthesize halogenated aniline through selective hydrogenation, the prepared product and the catalyst are easy to separate, the operation is simple, the method is economical and environment-friendly, and the method has good application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 shows mesoporous CeO prepared in example 1 of the present application 2 Scanning electron microscope image (a) of carrier and Pt (3%)/CeO prepared in example 1 of the application 2 TEM images (b) and (c) of the catalyst;
FIG. 2 shows mesoporous CeO prepared in example 1 of the present application 2 Carrier and Pt (3%)/CeO 2 An adsorption and desorption curve and pore size distribution of the catalyst, wherein (a) is the adsorption and desorption curve and (b) is the pore size distribution;
FIG. 3 is Pt (3%)/CeO prepared in example 1 2 Conversion and selectivity results after 10 cycles of catalyst.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The embodiment of the application provides a cerium oxide loaded platinum catalyst (Pt/CeO) 2 Catalyst), cerium nitrate is used as a raw material, and a hydrothermal synthesis method is adopted to prepare mesoporous CeO 2 And (3) a carrier: adding cerium nitrate into a mixed solution composed of water and ammonia water, and uniformly stirring for reaction to obtain mesoporous CeO 2 A carrier;
then adopting a dipping-reduction method to prepare the mesoporous CeO 2 Pt nanoparticles were supported on the carrier surface: the mesoporous CeO is subjected to 2 Dispersing a carrier in absolute ethyl alcohol, adding a chloroplatinic acid solution, stirring to obtain a dispersion liquid, evaporating the dispersion liquid to dryness to obtain solid powder, and calcining the solid powder to obtain the cerium oxide-loaded platinum catalyst.
The embodiment of the application adopts a hydrothermal synthesis method and an impregnation-reduction method to prepare Pt/CeO 2 The catalyst has the advantages that:
in the preferred embodiment of the application, the reaction temperature in the hydrothermal synthesis method is 75 ℃ for 24 hours, the reaction of ammonia water and cerium nitrate is facilitated to be converted into mesoporous cerium oxide with high specific surface area under the temperature condition, and the too high or too low temperature can lead to the too low specific surface area of the prepared cerium oxide and the reduction of the effective void volume.
In a preferred embodiment of the application, the calcination temperature in the impregnation-reduction process is 200℃and the time is 3 hours. The effect of calcination temperature on the cerium oxide-supported platinum catalyst is: the temperature of 200 ℃ is favorable for reducing platinum ions into finer platinum nano particles and uniformly loading the platinum nano particles on the surface of mesoporous cerium oxide, and uneven distribution and loading of the platinum nano particles can be caused by too high and too low temperature, so that the catalytic effect of the cerium oxide loaded platinum catalyst on halogenated nitrobenzene is reduced.
In the preferred embodiment of the application, the addition amount of the chloroplatinic acid solution should enable the mass loading amount of the Pt nano particles in the cerium oxide loaded platinum catalyst to be 1% -3%, and too high loading amount can lead to too high catalyst preparation cost, and too low loading amount can reduce the catalytic effect of the cerium oxide loaded platinum catalyst on halogenated nitrobenzene, so that the hydrogenation activity is lower.
The raw materials used in the examples of the present application are all commercially available.
In the examples of the present application, room temperature refers to 25.+ -. 2 ℃.
The technical scheme of the application is further described by the following examples.
Example 1
Adding 92g of distilled water and 10mL of ammonia water into a reaction bottle, sealing the reaction bottle by using a balloon, stirring the mixture at room temperature for 30min, weighing 0.6g of cerium nitrate, adding the cerium nitrate into the reaction bottle, stirring the mixture at room temperature for 1h under a sealed condition, transferring the mixture into a stainless steel water heating kettle with a 250mL polytetrafluoroethylene lining, reacting the mixture for 24h at 75 ℃, cooling the mixture to room temperature, carrying out suction filtration, washing the mixture with distilled water and ethanol for 2-3 times respectively, and drying the mixture in a vacuum drying oven for overnight to obtain mesoporous CeO 2 A carrier;
1g of the mesoporous CeO is weighed 2 Carrier dispersed in 15mL absolute ethanol under stirringSlowly adding chloroplatinic acid solution (the concentration is 2mg/mL, the addition amount of the chloroplatinic acid solution enables the loading capacity of Pt nano particles in the cerium oxide loaded platinum catalyst to be 3%) into the mesoporous CeO 2 Continuously stirring and impregnating the carrier suspension for 5 hours, slowly evaporating at 40 ℃, transferring the dried solid powder into a porcelain boat, and placing the porcelain boat in a tubular furnace for hydrogen reduction at 200 ℃ for 3 hours to obtain the cerium oxide-loaded platinum catalyst (Pt (3%)/CeO) 2 A catalyst).
Mesoporous CeO prepared in example 1 of the present application 2 The scanning electron microscope of the carrier is shown in FIG. 1 (a), and Pt (3%)/CeO prepared in example 1 of the present application 2 TEM image of the catalyst is shown in FIG. 1 (b) and FIG. 1 (c), and according to FIG. 1, it can be seen that mesoporous CeO prepared according to the present application 2 The carrier is porous and loose.
Mesoporous CeO prepared in example 1 of the present application 2 Carrier and Pt (3%)/CeO 2 The adsorption and desorption curves and pore size distribution of the catalyst are shown in fig. 2, wherein (a) is adsorption and desorption curve, and (b) is pore size distribution, and as can be seen from fig. 2, the mesoporous CeO prepared in embodiment 1 of the present application 2 The specific surface area of the carrier is 179m 2 Per g, average pore size of 8.1nm, pt (3%)/CeO 2 The specific surface area of the catalyst was 179m 2 And/g, average pore diameter of 6.8nm.
Example 2
The difference from example 1 was that the addition amount of the chloroplatinic acid solution was such that the loading amount of Pt nanoparticles in the cerium oxide-supported platinum catalyst was 1%, resulting in Pt (1%)/CeO 2 A catalyst.
Example 3
The difference from example 1 was that the addition amount of the chloroplatinic acid solution was such that the loading amount of Pt nanoparticles in the cerium oxide-supported platinum catalyst was 2%, resulting in Pt (2%)/CeO 2 A catalyst.
Comparative example 1
The difference from example 1 was that the addition amount of the chloroplatinic acid solution was such that the loading amount of Pt nanoparticles in the cerium oxide-supported platinum catalyst was 5%, resulting in Pt (5%)/CeO 2 A catalyst.
Comparative example 2
The difference from example 1 was that the addition amount of the chloroplatinic acid solution was such that the loading amount of Pt nanoparticles in the cerium oxide-supported platinum catalyst was 0.5%, resulting in Pt (0.5%)/CeO 2 A catalyst.
Application example 1
10mg of Pt (3%)/CeO prepared in example 1 was reacted 2 Adding the catalyst and 1mmol of p-chloronitrobenzene into a reactor, adding 5mL of absolute ethyl alcohol, reacting for 2 hours in a normal pressure hydrogen atmosphere at room temperature, synthesizing halogenated aniline by selective catalytic hydrogenation, and analyzing the reaction conversion rate to be 99% by using a gas chromatograph, wherein the selectivity of p-chloroaniline is 100%.
Application examples 2 to 10
10mg of Pt (3%)/CeO prepared in example 1 was reacted 2 The catalyst and 1mmol of halogenated nitrobenzene are respectively added into a reactor, 5mL of absolute ethyl alcohol is added, the reaction is carried out in a hydrogen atmosphere at room temperature and normal pressure, the halogenated aniline is synthesized by selective catalytic hydrogenation, the reaction conversion rate and the selectivity of the halogenated aniline are analyzed by a gas chromatograph, and the results are shown in table 1.
TABLE 1 reaction results of selective hydrogenation of halonitrobenzene to haloaniline using examples 2-10
As can be seen from Table 1, in the selective hydrogenation of various halogenated nitrobenzene, the reaction conversion rate is higher than 99%, almost complete conversion is achieved, and the selectivity of the product halogenated aniline is higher than 90%.
Application example 11
Pt (3%)/CeO in application example 1 was used 2 The catalyst is filtered, separated and recovered, then is added into a reactor containing a mixed solution of 1mmol of p-chloronitrobenzene and 5mL of absolute ethyl alcohol to react for 2 hours in a hydrogen atmosphere at room temperature and normal pressure, halogenated aniline is synthesized by selective catalytic hydrogenation, and the reaction conversion rate and the p-chloronitrobenzene are analyzed by a gas chromatographThe conversion rate is higher than 95%, and the selectivity of the p-chloroaniline is higher than 98%.
The recovery of Pt (3%)/CeO was continued as in application example 11 2 Catalyst and selective catalytic hydrogenation to synthesize halogenated aniline by adding to p-chloronitrobenzene, pt (3%)/CeO prepared in example 1 2 The conversion rate and the selectivity result of the catalyst after 10 cycles are shown in fig. 3, wherein the conversion rate and the selectivity result are sequentially shown as 1-10 times from left to right, and as can be seen from fig. 3, the catalyst prepared by the method can be recovered and reused for 10 times, and the catalytic activity is still stable.
Application example 12
The same as in application example 1, except that 10mg of Pt (3%)/CeO prepared in example 1 was used 2 The catalyst was replaced with 10mg of Pt (1%)/CeO prepared in example 2 2 A catalyst.
Application example 13
The same as in application example 1, except that 10mg of Pt (3%)/CeO prepared in example 1 was used 2 The catalyst was replaced with 10mg of Pt (2%)/CeO prepared in example 3 2 A catalyst.
Application example 14
The same as in application example 1, except that 10mg of Pt (3%)/CeO prepared in example 1 was used 2 The catalyst was replaced with 10mg of Pt (5%)/CeO prepared in comparative example 1 2 A catalyst.
Application example 15
The same as in application example 1, except that 10mg of Pt (3%)/CeO prepared in example 1 was used 2 The catalyst was replaced with 10mg of Pt (0.5%)/CeO prepared in comparative example 2 2 A catalyst.
The results of the selective hydrogenation of p-chloronitrobenzene to synthesize halogenated aniline using examples 12-15 are shown in Table 2 in comparison with example 1.
TABLE 2 reaction results of synthesizing p-chloroaniline by selectively hydrogenating p-chloronitrobenzene under catalysis of application examples 1, 12-15
| Conversion (%) | Selectivity (%) | |
| Application example 1 | 99 | 100 |
| Application example 12 | 78 | 100 |
| Application example 13 | 93 | 100 |
| Application example 14 | 99 | 96 |
| Application example 15 | 28 | 100 |
As can be seen from Table 2, the cerium oxide-supported platinum catalysts prepared in examples 1-3 of the present application all have high reaction selectivity and conversion rate in the reaction of synthesizing halogenated aniline by selective hydrogenation of p-chloronitrobenzene, while application example 14 increases the loading of Pt nanoparticles in the cerium oxide-supported platinum catalyst to 5%, although higher conversion rate and selectivity are achieved, too high loading results in too high catalyst preparation cost, while application example 15 has too low loading of Pt nanoparticles in the cerium oxide-supported platinum catalyst, which reduces the catalytic effect of the cerium oxide-supported platinum catalyst on halogenated nitrobenzene, and thus lower hydrogenation activity.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.
Claims (8)
1. The cerium oxide-supported platinum catalyst is characterized in that the mass loading of Pt nano particles in the cerium oxide-supported platinum catalyst is 1% -3%.
2. The method for preparing the cerium oxide-supported platinum catalyst as claimed in claim 1, wherein cerium nitrate is used as a raw material, and a hydrothermal synthesis method is adopted to prepare mesoporous CeO 2 A carrier, then adopting a dipping-reduction method to prepare the mesoporous CeO 2 And loading Pt nano particles on the surface of the carrier to obtain the cerium oxide loaded platinum catalyst.
3. The method for preparing a cerium oxide supported platinum catalyst according to claim 2, wherein a hydrothermal synthesis method is used for preparing mesoporous CeO 2 The carrier comprises the following steps: adding cerium nitrate into a mixed solution composed of water and ammonia water, uniformly stirring, and reacting at 75 ℃ for 24 hours to obtain mesoporous CeO 2 A carrier.
4. The method for preparing a cerium oxide-supported platinum catalyst according to claim 2, wherein the impregnation-reduction method for preparing the cerium oxide-supported platinum catalyst comprises the steps of:
the mesoporous CeO is subjected to 2 Dispersing a carrier in absolute ethyl alcohol, adding a chloroplatinic acid solution, stirring to obtain a dispersion liquid, evaporating the dispersion liquid to dryness to obtain solid powder, and calcining the solid powder to obtain the cerium oxide-loaded platinum catalyst.
5. The method for preparing a cerium oxide supported platinum catalyst according to claim 4, wherein the calcination temperature is 200 ℃ for 3 hours.
6. The use of the cerium oxide supported platinum catalyst of claim 1 in catalyzing selective hydrogenation of halogenated nitrobenzene to synthesize halogenated aniline.
7. The use according to claim 6, wherein the cerium oxide supported platinum catalyst is reacted with halonitrobenzene in a hydrogen atmosphere at room temperature and normal pressure to obtain haloaniline.
8. The use according to claim 7, wherein the ratio of cerium oxide supported platinum catalyst to halonitrobenzene is 10 mg:1 mmol.
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