CN112973676A - Preparation method of supported porous nano platinum catalyst - Google Patents
Preparation method of supported porous nano platinum catalyst Download PDFInfo
- Publication number
- CN112973676A CN112973676A CN201911295722.3A CN201911295722A CN112973676A CN 112973676 A CN112973676 A CN 112973676A CN 201911295722 A CN201911295722 A CN 201911295722A CN 112973676 A CN112973676 A CN 112973676A
- Authority
- CN
- China
- Prior art keywords
- porous nano
- catalyst
- preparation
- nano platinum
- hydrogenation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 7
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 238000012216 screening Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 12
- 238000002156 mixing Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 235000000069 L-ascorbic acid Nutrition 0.000 description 6
- 239000002211 L-ascorbic acid Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910003322 NiCu Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing a supported porous nano platinum catalyst. The preparation process comprises the following steps: (1) preparing porous nano platinum particles; (2) loading porous nano platinum particles; (3) and (5) carrying out subsequent treatment after loading. The optimized catalyst is obtained by optimizing the preparation conditions of the porous nano platinum particles, screening the carrier and optimizing the operation method of post-treatment. The catalyst prepared by the method can efficiently catalyze the hydrogenation reaction under mild reaction conditions.
Description
Technical Field
The invention belongs to the field of noble metal catalysis, and particularly relates to a preparation method of a supported porous nano platinum catalyst with high activity under a mild condition.
Technical Field
Toluene hydrogenation has received attention because of its broader use and environmental value. The current catalyst for toluene hydrogenation is mainly a supported catalyst with noble metal nano-particles as active components. Supplino et Al (Applied Catalysis a-General,2016,525,41-49) prepared by wet impregnation of Al2O3A supported nano Pt and Pd catalyst which is a carrier. The prepared catalyst has the conversion rates of toluene of 7 percent and 6.2 percent respectively under the conditions that the molar ratio of the active component to the toluene is 1/3038, the reaction temperature is 100 ℃, the reaction pressure is 5MPa and the reaction time is 6 hours. Landers et Al (Reaction Kinetics Mechanisms and Catalysis,2015,114(1),295-309) with Al2O3The supported nanometer Fe and Co catalyst is carrier. The prepared catalyst has the conversion rates of toluene of 3.8% and 3.1% respectively under the conditions that the molar ratio of the active component to the toluene is 1/893, the reaction temperature is 100 ℃, the reaction pressure is 5MPa, and the reaction time is 6 hours. Further literature research can find that the currently commonly used supported nanoparticle catalyst has the problems of relatively harsh reaction pressure and relatively low catalytic activity of the catalyst for toluene hydrogenation.
The hydrogenation of terephthalonitrile, isophthalonitrile and phthalonitrile has very important research value because the obtained hydrogenation product has very wide application. A common catalyst in the current literature is a Ni-based catalyst. Liu et Al (Rsc Advances,2014,4(109),63725-63733) prepared a supported 3KNiCo/Al by K modification2O3The catalyst can obtain 100 percent of m-phthalonitrile conversion rate and 100 percent of m-xylylenediamine selectivity under the conditions of reaction temperature of 80 ℃, reaction pressure of 6MPa and reaction time of 6.5 h. They subsequently (Rsc Advances 2015,5(71),57277-2O3、NiCu/Al2O3A catalyst. NiFe/Al2O3The catalyst obtains 100 percent of m-phthalonitrile conversion rate and 100 percent of m-xylylenediamine selectivity under the reaction temperature of 80 ℃, the reaction pressure of 6MPa and the reaction time of 2.5 h; NiCu-Al2O3The catalyst obtains 100 percent of m-phthalonitrile conversion rate and 96 percent of xylylenediamine selectivity under the conditions of reaction temperature of 80 ℃, reaction pressure of 6MPa and reaction time of 2 hours. Although the activity data obtained are excellent, it is noted that in these reactions, the catalyst is used in a relatively large amount and the molar ratio of active component to isophthalonitrile is less than 1/10, indicating that the activity per unit mass of catalyst is actually low. In addition, the higher reaction pressures also make these catalysts difficult to scale up.
In summary, the hydrogenation of toluene and the hydrogenation of terephthalonitrile, isophthalonitrile and phthalonitrile have several problems: 1. the activity of the catalyst is low; 2. the reaction conditions required are relatively severe.
Disclosure of Invention
Based on the problems of low activity and harsh reaction conditions of the catalyst in the background art, the invention solves the problems by preparing the supported porous nano platinum catalyst. The technical scheme is as follows:
the invention provides a preparation method of a supported porous nano platinum catalyst, which comprises the following steps:
(1) adding a platinum precursor, a template agent and a reducing agent into deionized water, stirring or ultrasonically mixing at 25-50 ℃, reducing for 1-24 h, centrifuging, washing with deionized water at 25-100 ℃, and drying to obtain the porous nano platinum particles. The mole ratio of the platinum precursor, the template agent and the reducing agent is 1: 10-200: 1000-50000;
(2) dispersing the porous nano platinum particles obtained in the step (1) in deionized water, stirring or carrying out ultrasonic treatment for 10-120 min at 25-50 ℃ to disperse the particles, then adding a carrier, continuously stirring for 2-24 h, centrifuging and drying. The mass of the used porous nano platinum particles is 0.1-5.0% of the mass of the carrier;
(3) putting the sample obtained after drying in the step (2) in N2Or H2Or roasting for 1-24 h at 50-1000 ℃ in air atmosphere to obtain the supported porous nano platinum catalyst.
Based on the technical scheme, the template agent in the step (1) is preferably a high molecular surfactant, at least one of PVP, PVA, P-123 and F-127, and is preferably PVP.
Based on the technical scheme, the preferable template agent is PVP, and the molecular weight of the PVP is 8000-1300000, preferably 13000-58000.
Based on the above technical scheme, preferably, the platinum precursor in step (1) is chloroplatinic acid or potassium tetrachloroplatinate, preferably potassium tetrachloroplatinate.
Based on the above technical scheme, preferably, the reducing agent in step (1) is selected from ascorbic acid or sodium borohydride, and is preferably ascorbic acid.
Based on the above technical scheme, preferably, the carrier in the step (2) is a metal oxide or a carbon material.
Based on the above technical solution, preferably, the metal oxide is an acidic, neutral, or basic metal oxide, including but not limited to: al (Al)2O3、TiO2、NiO、CeO2、ZrO2、Fe2O3(ii) a The carbon materials are various carbon materials commonly used as catalyst supports, including but not limited to: activated carbon, carbon nanotubes, graphene.
Based on the technical scheme, preferably, the drying in the step (1) and the step (2) is carried out for 2 to 48 hours in vacuum at the temperature of between 30 and 100 ℃; the washing in the step (1) is washing with deionized water at 25-100 ℃.
The invention also provides the supported porous nano platinum catalyst prepared by the preparation method, wherein the particle size of the porous nano platinum is 30-60 nm, and the pore diameter is 2-5 nm.
The invention also provides application of the supported porous nano platinum catalyst prepared by the preparation method. The catalyst can efficiently catalyze the hydrogenation of toluene to prepare cyclohexane, the hydrogenation of terephthalonitrile to prepare p-xylylenediamine, the hydrogenation of m-phthalonitrile to prepare m-xylylenediamine and the hydrogenation of phthalonitrile to prepare o-xylylenediamine under mild conditions.
Based on the technical scheme, the catalyst is preferably applied to the preparation of cyclohexane by toluene hydrogenation, or the preparation of p-xylylenediamine by the hydrogenation of p-phthalonitrile, or the preparation of m-xylylenediamine by the hydrogenation of m-phthalonitrile, or the preparation of o-xylylenediamine by the hydrogenation of phthalonitrile.
Advantageous effects
(1) In the invention, the active component of the catalyst is nano platinum with a porous structure. The structure can obviously improve the specific surface area of the platinum particles, thereby improving the performance of the catalyst. Besides, the porous mechanism can promote the adsorption of reactants and the desorption of products, so that the relevant reaction can be carried out under relatively mild conditions.
(2) In the invention, the used noble metal is platinum, which is widely used and has lower cost compared with other noble metals with higher hydrogenation activity. The used carriers are common materials, and the preparation process has fewer steps and simpler operation.
(3) The invention can obtain the porous nano platinum with different pore structures by controlling the preparation conditions, such as ultrasound or stirring, and has simple operation conditions and wide application.
(4) The catalyst prepared by the invention has good effects on reactions with certain difficulty and application prospects, such as the preparation of cyclohexane by catalytic hydrogenation of toluene, the preparation of p-xylylenediamine by hydrogenation of p-phthalonitrile, the preparation of m-xylylenediamine by hydrogenation of m-phthalonitrile, the preparation of o-xylylenediamine by hydrogenation of phthalonitrile and the like, and provides a new solution for further industrial application of the reactions.
Drawings
FIG. 1 is a transmission electron microscope image of porous nano platinum prepared in example 1.
FIG. 2 is a transmission electron microscope image of the porous nano platinum prepared in example 2.
FIG. 3 is a transmission electron microscope image of the supported nano platinum catalyst prepared in example 2.
Fig. 4 is a transmission electron micrograph of the catalyst prepared in comparative example 3.
Fig. 5 is a transmission electron micrograph of the catalyst prepared in comparative example 4.
Detailed Description
Example 1
(1) 40mg of potassium tetrachloroplatinate are weighed out, dissolved in 20mL of deionized water and subsequently 0.2g of PVP with a molecular weight of 10000 are added. The above solutions were mixed under magnetic stirring at 25 ℃ and 2mL of 0.4mol/L ascorbic acid was added and stirring was continued for 2.5 h. After stirring, centrifugal separation, washing with deionized water in 30 deg.C water bath for three times, and vacuum drying at 30 deg.C. As shown in FIG. 1 (scale: 100nm), the obtained particles have a size distribution range of 20nm to 150nm, and most particles have a size distribution range of about 100nm, and have fewer pores. (2) 30mg of the resulting granules were weighed, dispersed in 50mL of deionized water, and then 1.0g of activated carbon was added, loaded for 2 hours and dried in vacuo. (3) The obtained catalyst is added into N2Roasting for 3h at 300 ℃ in the atmosphere. The resulting catalyst was labeled catalyst 1.
Example 2
(1) 160mg of potassium tetrachloroplatinate was weighed out, dissolved in 40mL of deionized water, followed by the addition of 0.96g of PVP with a molecular weight of 24000. Mixing the above solutions at 35 deg.C under ultrasonic condition, adding 2mL of 1.0mol/L ascorbic acid, and continuing ultrasonic treatment for 2.5 h. After the ultrasonic treatment, the mixture is centrifugally separated, washed three times by a large amount of deionized water in a water bath at 45 ℃ and dried in vacuum at 30 ℃. As shown in FIG. 2 (scale: 50nm), the obtained particles have a size distribution range of 30-50 nm, most of the particles are about 50nm, and the pores are abundant. (2) 10mg of the resulting particles were weighed, dispersed in 25mL of deionized water, and then 0.5g of CeO was added2And carrying for 4h, and then drying in vacuum. (3) The obtained catalyst is calcined for 2 hours at 400 ℃ in an air atmosphere. The resulting catalyst was labeled catalyst 2. As shown in fig. 3 (scale is 50nm), porous nano platinum is supported on the carrier, and has rich channels.
Example 3
(1) 80mg of potassium tetrachloroplatinate was weighed out, dissolved in 20mL of deionized water, followed by the addition of 1.16g of PVP with a molecular weight of 58000. Mixing the above solutions at 30 deg.C under ultrasonic condition, adding 8mL of 1.0mol/L ascorbic acid, and continuing ultrasonic treatment for 2.5 h. After the ultrasonic treatment, the mixture is centrifugally separated, washed three times by a large amount of deionized water in a water bath at 80 ℃, and dried in vacuum at 30 ℃. (2) 10mg of the resulting particles were weighed, dispersed in 25mL of deionized water, followed by the addition of 0.5g of NiO, loaded for 24h and dried in vacuo. (3) The obtained catalyst is calcined for 4 hours at 300 ℃ in an air atmosphere. The resulting catalyst was labeled catalyst 3.
Example 4
(1) 80mg of potassium tetrachloroplatinate was weighed out, dissolved in 20mL of deionized water, followed by the addition of 0.58g of PVP with a molecular weight of 58000. Mixing the above solutions at 45 deg.C under ultrasonic condition, adding 2mL 0.4mol/L ascorbic acid, and continuing ultrasonic treatment for 2.5 h. After the ultrasonic treatment, the mixture is centrifugally separated, washed three times by a large amount of deionized water in a 60 ℃ water bath, and dried in vacuum at 30 ℃. (2) 30mg of the resulting particles were weighed, dispersed in 50mL of deionized water, and then 1.0g of NiO was added, loaded for 10h and dried in vacuo. (3) The obtained catalyst is calcined for 2 hours at 200 ℃ in an air atmosphere. The resulting catalyst was labeled catalyst 4.
Comparative example 1
160mg of potassium tetrachloroplatinate was weighed out, dissolved in 40mL of deionized water, followed by the addition of 2.32g of PVP with a molecular weight of 58000. Mixing the above solutions under ultrasonic condition, adding 2mL of 1.0mol/L ascorbic acid, and continuing ultrasonic treatment for 2.5 h. After the ultrasonic treatment, the mixture is centrifugally separated, washed three times by a large amount of deionized water in a water bath at 45 ℃ and dried in vacuum at 30 ℃. The resulting catalyst was labeled catalyst 5.
Comparative example 2
(1) 160mg of potassium tetrachloroplatinate was weighed out, dissolved in 40mL of deionized water, followed by the addition of 0.96g of PVP with a molecular weight of 24000. Mixing the above solutions under ultrasonic condition, adding 2mL of 1.0mol/L ascorbic acid, and continuing ultrasonic treatment for 2.5 h. After the ultrasonic treatment, the mixture is centrifugally separated, washed three times by a large amount of deionized water in a water bath at 45 ℃ and dried in vacuum at 30 ℃. (2) 10mg of the resulting particles were weighed, dispersed in 25mL of deionized water, and then 0.5g of CeO was added2And carrying for 4h, and then drying in vacuum. The resulting catalyst was labeled catalyst 6.
Comparative example 3
(1) 22mg of potassium tetrachloroplatinate were weighed out, dissolved in 25mL of deionized water, followed by the addition of 0.5g of CeO2Mixing for 4 hr, centrifuging, and vacuum separatingAnd (5) drying. (2) The obtained catalyst was reduced in a hydrogen atmosphere at 200 ℃ for 2 h. The resulting catalyst was labeled catalyst 7. The TEM characterization of this catalyst is shown in FIG. 4 (scale 50nm), from which it can be seen that platinum is supported on the CeO carrier2The structure is a nano structure, but does not have a pore channel structure.
Comparative example 4
(1) Dissolving 114mg of PVP with molecular weight of 8000 and 62mg of chloroplatinic acid in 100ml of deionized water; dissolving 20m of sodium borohydride in 2ml of ice water, and adding the solution; followed by addition of 2gCeO2Mixing for 1 hr, centrifuging, and vacuum drying. (2) The obtained catalyst is calcined for 2 hours at 400 ℃ in an air atmosphere. The resulting catalyst was labeled catalyst 8. The TEM characterization of this catalyst is shown in FIG. 5 (scale 50 nm).
The performance of the toluene hydrogenation catalyst was evaluated in a high-pressure reactor under the conditions shown in Table 1.
TABLE 1 evaluation conditions for toluene hydrogenation catalytic Activity
| Pt/ |
1/1000 |
| Reaction temperature of | 100 |
| Reaction pressure, MPa | 4.0 |
| Reaction time, h | 3.0 |
The results are shown in Table 2
TABLE 2 catalytic toluene hydrogenation Activity of the catalyst
As can be seen from Table 2, the supported porous nano platinum catalyst prepared by the method has greatly improved toluene catalytic activity compared with the traditional supported nano platinum particle catalyst; compared with the literature report, the method also has obvious advantages. Meanwhile, the catalytic activity of the catalyst can be obviously improved by the load in the preparation process and the subsequent roasting process.
And (3) carrying out the hydrogenation catalytic performance evaluation of the o-, m-and p-phthalonitrile by using the catalyst 2 in a high-pressure reaction kettle. The reaction conditions for the evaluation are shown in Table 3, and the evaluation results are shown in Table 4. Wherein the substrates in tables 3 and 4 refer to ortho-, meta-, or terephthalonitrile; the target products in Table 4 refer to o-, m-, and p-xylylenediamine.
TABLE 3 evaluation conditions for hydrogenation catalytic activity of ortho-, meta-, or para-phthalonitrile
| Pt/ |
1/150 |
| Reaction temperature of | 80 |
| Reaction pressure, MPa | 4.0 |
| Reaction time, h | 3.0 |
TABLE 4 hydrogenation activity of catalyst 2 for o-, m-, p-phthalonitrile
| The substrate used | Substrate conversion rate,% | Target product selectivity,% |
| Phthalonitrile | 90.56 | 45.87 |
| Isophthalonitrile | 89.87 | 54.44 |
| Terephthalonitrile | 92.13 | 65.68 |
As can be seen from Table 4, although the activity data of the catalyst 2 is lower than that of the literature, the ratio of the amount of the catalyst to the amount of the substrate is more than 15 times that of the literature report, which shows that the activity of the catalyst prepared by the invention is obviously better than that of the relevant literature report, and the required reaction pressure and reaction time are both greatly lower than the relevant conditions required in the literature, thus showing the advantages of the method of the invention.
Claims (10)
1. A preparation method of a supported porous nano platinum catalyst is characterized by comprising the following steps:
(1) adding a platinum precursor, a template agent and a reducing agent into deionized water, stirring or ultrasonically treating for 1-24 h at 25-50 ℃, centrifuging, washing and drying to obtain porous nano platinum particles; the mole ratio of the platinum precursor, the template agent and the reducing agent is 1: 10-200: 1000-50000;
(2) dispersing the porous nano platinum particles obtained in the step (1) in deionized water, stirring or carrying out ultrasonic treatment for 10-120 min at 25-50 ℃ to disperse the particles, then adding a carrier, continuously stirring for 2-24 h, centrifuging and drying; the mass ratio of the porous nano platinum particles to the carrier is 0.1-5.0%;
(3) putting the sample obtained after drying in the step (2) in N2Or H2Or roasting for 1-24 h at 50-1000 ℃ in air atmosphere to obtain the supported porous nano platinum catalyst.
2. The method of claim 1, wherein: the template agent in the step (1) is at least one of PVP, PVA, P-123 and F-127.
3. The method of claim 12, wherein: the template agent is PVP, and the molecular weight of the PVP is 8000-1300000, preferably 13000-58000.
4. The method of claim 1, wherein: the platinum precursor in the step (1) is chloroplatinic acid or potassium tetrachloroplatinate, preferably potassium tetrachloroplatinate.
5. The method of claim 1, wherein: the reducing agent in step (1) is selected from ascorbic acid or sodium borohydride, preferably ascorbic acid.
6. The method of claim 2, wherein: the carrier in the step (2) is a metal oxide or a carbon material.
7. The method according to claim 6, wherein the metal oxide is Al2O3、TiO2、NiO、CeO2、ZrO2、Fe2O3(ii) a The carbon material is activated carbon, carbon nanotubes and graphene.
8. The preparation method according to claim 1, wherein the drying in the step (1) and the step (2) is vacuum drying at 30-100 ℃ for 2-48 h; the washing in the step (1) is washing with deionized water at 25-100 ℃.
9. The supported porous nano platinum catalyst prepared by the preparation method of any one of claims 1 to 8, wherein the particle size of the porous nano platinum is 30-60 nm, and the pore diameter is 2-5 nm.
10. The use of the supported porous nano platinum catalyst according to claim 9 in the preparation of cyclohexane by hydrogenation of toluene, or in the preparation of p-xylylenediamine by hydrogenation of p-phthalonitrile, or in the preparation of m-xylylenediamine by hydrogenation of m-phthalonitrile, or in the preparation of o-xylylenediamine by hydrogenation of phthalonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911295722.3A CN112973676A (en) | 2019-12-16 | 2019-12-16 | Preparation method of supported porous nano platinum catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911295722.3A CN112973676A (en) | 2019-12-16 | 2019-12-16 | Preparation method of supported porous nano platinum catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112973676A true CN112973676A (en) | 2021-06-18 |
Family
ID=76343405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911295722.3A Pending CN112973676A (en) | 2019-12-16 | 2019-12-16 | Preparation method of supported porous nano platinum catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112973676A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578316A (en) * | 2021-08-27 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888765A (en) * | 2015-05-04 | 2015-09-09 | 济南大学 | Cage porous platinum-palladium composite nanoparticle having excellent catalysis performance on methanol, and preparation method thereof |
| CN110560065A (en) * | 2019-08-23 | 2019-12-13 | 万华化学集团股份有限公司 | Metal carrier supported catalyst, preparation method and application thereof in preparation of m-xylylenediamine |
-
2019
- 2019-12-16 CN CN201911295722.3A patent/CN112973676A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104888765A (en) * | 2015-05-04 | 2015-09-09 | 济南大学 | Cage porous platinum-palladium composite nanoparticle having excellent catalysis performance on methanol, and preparation method thereof |
| CN110560065A (en) * | 2019-08-23 | 2019-12-13 | 万华化学集团股份有限公司 | Metal carrier supported catalyst, preparation method and application thereof in preparation of m-xylylenediamine |
Non-Patent Citations (1)
| Title |
|---|
| 周敏等: "多壁碳纳米管负载铂的甲苯加氢脱芳催化剂", 《催化学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578316A (en) * | 2021-08-27 | 2021-11-02 | 中国科学院大连化学物理研究所 | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103041826B (en) | Bimetal nanometer catalyst as well as preparation and application method thereof | |
| US11201335B2 (en) | Noble metal nanoparticles on a support | |
| CN110756225B (en) | Metal/MOFs nano catalyst and preparation method and application thereof | |
| CN111135840B (en) | Preparation method of supported monatomic dispersed noble metal catalyst | |
| CN109304476A (en) | Carbon coating transition metal nanocomposite and its preparation method and application | |
| CN106466602B (en) | A kind of carbon-carried palladium catalyst and its preparation method and application | |
| CN107597109A (en) | Load type gold catalyst of nano-metal-oxide doping and preparation method and application | |
| JP2008259993A (en) | Method for dispersing and fixing gold fine particle to carrier, gold fine particle-deposited carrier obtained thereby, catalyst and colorant | |
| CN1970143A (en) | Method for preparing high-activity hydrogenation catalyst nano Ru/C | |
| CN102527377A (en) | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method | |
| CN1903731A (en) | Flower shape structured nano-cerium oxide and its preparation method and use | |
| CN113578316A (en) | Preparation of supported porous nano platinum-ruthenium alloy catalyst and application of supported porous nano platinum-ruthenium alloy catalyst in preparation of chloroaniline by hydrogenation of chloronitrobenzene | |
| CN111266119A (en) | α -unsaturated aldehyde ketone selective hydrogenation platinum-based catalyst, and preparation method and application thereof | |
| CN112371173B (en) | Platinum-carbon catalyst applied to hydrogenation of m-nitrobenzenesulfonic acid and preparation method thereof | |
| CN109317149A (en) | A kind of SiO of nickel-loaded2The preparation method and application of@C core-shell material | |
| CN112138696A (en) | Preparation method of transition metal loaded nitrogen modified ordered mesoporous carbon nanospheres | |
| CN111686721A (en) | Palladium ruthenium alloy catalyst and preparation method and application thereof | |
| CN112495374A (en) | Method for preparing supported noble metal catalyst by adopting low-temperature plasma modified graphene and application | |
| CN105810960A (en) | Composite material taking foam nickel as matrix and preparation method of composite material | |
| CN112973676A (en) | Preparation method of supported porous nano platinum catalyst | |
| US10668460B2 (en) | Composite catalyst, method for manufacturing composite catalyst and application thereof | |
| CN111554944B (en) | Application of hollow mesoporous carbon spheres | |
| CN112774690B (en) | Supported single-atom noble metal catalyst and preparation method and application thereof | |
| CN114457371B (en) | MXene loaded Ni nano-particle composite hydrogen evolution electrocatalyst and preparation method and application thereof | |
| You et al. | Pd/CNT with controllable Pd particle size and hydrophilicity for improved direct synthesis efficiency of H 2 O 2 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210618 |
|
| RJ01 | Rejection of invention patent application after publication |