CN116870906A - Platinum/tungsten trioxide/silicon aluminum oxide compound and preparation method and application thereof - Google Patents

Platinum/tungsten trioxide/silicon aluminum oxide compound and preparation method and application thereof Download PDF

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CN116870906A
CN116870906A CN202110556412.3A CN202110556412A CN116870906A CN 116870906 A CN116870906 A CN 116870906A CN 202110556412 A CN202110556412 A CN 202110556412A CN 116870906 A CN116870906 A CN 116870906A
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platinum
tungsten trioxide
aluminum oxide
silicon
colloid
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施梦晨
梁明会
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Jiangyin Fine Alcohol New Material Technology Co ltd
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Jiangyin Fine Alcohol New Material Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/652—Chromium, molybdenum or tungsten
    • B01J23/6527—Tungsten
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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    • 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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Abstract

The invention relates to a platinum/tungsten trioxide/silicon aluminum oxide compound and a preparation method and application thereof, wherein the platinum colloid and the tungsten trioxide colloid are respectively prepared, and then the platinum colloid and the tungsten trioxide colloid are mixed and added with silicon aluminum oxide to obtain the platinum/tungsten trioxide/silicon aluminum oxide compound, and the preparation method is very simple and easy to repeat and control; the platinum nano particles and the tungsten trioxide nano particles in the platinum/tungsten trioxide/silicon aluminum oxide compound prepared by the method are well combined, and the platinum nano particles and the tungsten trioxide nano particles are used as catalysts in the selective hydrogenolysis reaction of the polyol, so that the platinum/tungsten trioxide/silicon aluminum oxide compound has higher polyol conversion rate and selectivity and good repeatability.

Description

Platinum/tungsten trioxide/silicon aluminum oxide compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite catalysts, and particularly relates to a platinum/tungsten trioxide/silicon aluminum oxide composite and a preparation method and application thereof.
Background
Glycerol (glycerol) is among the simplest polyols, and its selective hydrogenolysis products 1, 3-propanediol and 1, 2-propanediol have important industrial uses. Wherein, 1, 3-propylene glycol is an important monomer for producing polytrimethylene terephthalate (PTT), and the obtained PTT has excellent rebound resilience, easy dyeing property, biodegradability and the like and has wide prospect in industries such as carpets, textile engineering plastics and the like.
The existing industrial production method of 1, 3-propanediol is mainly a biological fermentation method of DuPont company, the production efficiency of the method is low, and the energy consumption required for purifying and separating 1, 3-propanediol is high due to low product concentration. The domestic production method of 1, 3-propanediol is also related to, for example, the acrolein hydration method (China patent CN 93114516.3) adopts gaseous glycerin hydrate to dehydrate under the action of solid acid catalyst to generate acrolein, the generated acrolein is hydrated under the action of acid catalyst to generate 3-hydroxy propanal, the generated 3-hydroxy propanal is hydrogenated under the action of conventional hydrogenation catalyst to prepare 1, 3-propanediol, and meanwhile, the byproduct 1, 2-propanediol is produced.
In addition, there are reports on a method for directly obtaining 1, 3-propanediol from glycerol, which is currently the most ideal and economical method.
Literature (Catal. Commun.2008,9, 1360-1363) reports a process for producing 1, 3-propanediol by hydrogenolysis of glycerol using 1, 3-dimethyl-2-imidazolidinone as a solvent, the yield of 1, 3-propanediol being 24%. Japanese Tomishige task group is in Ir-Re/SiO 2 Adding liquid sulfuric acid (H) under the action of catalyst + Re=1), and reacting in 20% glycerin water solution at the initial pressure of hydrogen of 8MPa and the reaction temperature of 120 ℃ for 36 hours to obtain the 1, 3-propanediol, wherein the yield is as high as 38.0%. Korean Jinhooh reported that Pt was supported on sulfuric acid-acidified ZrO 2 On the contrary, DMI is used as a reaction medium, and the reaction is carried out for 24 hours at the initial pressure of hydrogen of 7.3MPa and the reaction temperature of 170 ℃ to obtain the 1, 3-propanediol, wherein the yield is up to 55.6%. The reaction system for preparing the 1, 3-propanediol adopts an organic solvent as a reaction medium, and the added liquid acid is very unfavorable for the repeated use of the catalyst, and more importantly, the product is difficult to separate from other substances.
The platinum/tungsten trioxide system can be used as a solid catalyst to directly catalyze the glycerol to be converted into 1, 3-propanediol, so that the adoption of an organic solvent as a reaction medium is avoided, and no liquid acid is required to be added.
A simple one is reported in the literature (Chin. J. Catalyst.2012, 33:1257-1261)Pt/mesoporous WO 3 The catalyst is directly used for hydrogenolysis of the glycerol to the 1, 3-propanediol, but the overall yield of the 1, 3-propanediol is still low. According to the results of the mechanism study, the interfacial synergy of platinum and tungsten trioxide is very important for the formation of 1, 3-propanediol. However, the existing preparation method mainly comprises an impregnation method, wherein platinum and tungsten trioxide are respectively or simultaneously loaded on a carrier, and the platinum-tungsten oxide-carrier catalyst is obtained through high-temperature roasting. On the one hand, the high-temperature roasting can lead to the large particle size of the platinum, on the other hand, the combination between the platinum and the tungsten trioxide is random, and the platinum and the tungsten trioxide do not necessarily form good combination, so that the selectivity of the 1, 3-propanediol is not high. In addition, the catalyst structure obtained by the unsuitable preparation method has large randomness and poor repeatability.
In order to solve the problems of low combination probability of platinum and tungsten trioxide and poor repeatability of catalyst performance in a platinum-tungsten trioxide catalyst, a new preparation method needs to be developed to obtain the platinum-tungsten trioxide catalyst.
Disclosure of Invention
The invention aims to provide a preparation method of a platinum/tungsten trioxide/silicon aluminum oxide compound, which enables platinum to be well combined with tungsten trioxide, and the catalyst has high selectivity of 1, 3-propanediol and excellent performance repeatability when being applied to selective hydrogenolysis of glycerol.
The invention solves the problems by adopting the following technical scheme: a method for preparing a platinum/tungsten trioxide/silicon aluminum oxide composite, comprising the steps of:
(1) Preparation of platinum colloid: dissolving platinum salt into ethylene glycol to obtain a solution A, dissolving sodium hydroxide into ethylene glycol to obtain a solution B, uniformly mixing the solution A and the solution B under the condition of stirring, adjusting the pH value of the solution to 7-13, heating to 120-190 ℃ under the protection of inert gas atmosphere, keeping the temperature for 0.5-24h, and cooling to obtain the platinum nano colloid solution.
(2) Preparation of tungsten trioxide colloid: dissolving tungsten hexachloride in an anhydrous solvent C, slowly adding an aqueous solvent D, and obtaining tungsten trioxide colloid when the solution turns from yellow to colorless or bluish.
(3) Mixing the platinum colloid and the tungsten trioxide colloid, stirring for a certain time, adding the silicon-aluminum oxide, and separating solid substances from liquid after the platinum colloid and the tungsten trioxide colloid are loaded on the silicon-aluminum oxide to obtain a solid, namely the platinum/tungsten trioxide/silicon-aluminum oxide compound.
Preferably, the platinum salt in the step (1) is at least one of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate and platinum acetate.
Preferably, the solvent C, D in step (2) is one or more of methanol, ethanol, propanol, butanol, ethylene glycol, and N, N-dimethylformamide.
Preferably, the mass ratio of the platinum colloid to the tungsten trioxide colloid is 1:0.05-1:50; the mass ratio of the platinum colloid to the silicon-aluminum oxide is 0.0005-0.20:1.
More preferably, the mass ratio of the platinum colloid to the tungsten trioxide colloid is 1:0.5-1:10; the mass ratio of the platinum colloid to the silicon aluminum oxide is 0.001-0.10:1.
More preferably, the mass ratio of the platinum colloid to the tungsten trioxide colloid is 1:2-1:5; the mass ratio of the platinum colloid to the silicon aluminum oxide is 0.005-0.05:1.
Preferably, the silicon aluminum oxide is amorphous silicon aluminum oxide or silicon aluminum molecular sieve.
More preferably, the amorphous silica alumina is a compound formed by silica and alumina, wherein the alumina accounts for 3% -30% of the total mass of the compound; the silicon-aluminum molecular sieve is ZSM-5, naX or NaY.
Another object of the present invention is to provide a platinum/tungsten trioxide/silicon aluminum oxide composite, which is prepared by the above-mentioned preparation method of the platinum/tungsten trioxide/silicon aluminum oxide composite.
Preferably, the mass percentage of platinum in the platinum/tungsten trioxide/silicon aluminum oxide composite is 0.1% -5%, and the mass percentage of tungsten trioxide is 2% -40%.
More preferably, the mass percentage of platinum in the platinum/tungsten trioxide/silicon aluminum oxide composite is 0.5% -2%, and the mass percentage of tungsten trioxide is 5% -20%.
It is a further object of the present invention to provide the use of a platinum/tungsten trioxide/silicon aluminum oxide composite in a polyol selective hydrogenolysis reaction.
Preferably, the polyol is glycerol, tetrol, pentitol or hexitol.
Compared with the prior art, the invention has the advantages that:
(1) The platinum colloid and the tungsten trioxide colloid are respectively prepared, then the platinum colloid and the tungsten trioxide colloid are mixed and added with silicon aluminum oxide to obtain a platinum/tungsten trioxide/silicon aluminum oxide compound, and the combination probability of platinum and tungsten trioxide is improved by adopting the assembly of the platinum colloid and the tungsten trioxide colloid; the particle size of the platinum and the particle size of the tungsten trioxide are smaller, and the platinum and the tungsten trioxide are preformed before combination rather than being formed on a carrier randomly, so that the utilization efficiency of the platinum and the tungsten trioxide is improved; the formed platinum/tungsten trioxide complex is assembled on the carrier, so that the high-temperature treatment required by the traditional catalyst preparation technology is avoided, and the growth of platinum particles and tungsten trioxide particles is avoided.
(2) The preparation method of the platinum/tungsten trioxide/silicon aluminum oxide composite is very simple and easy to repeat and control, and the platinum nano particles and the tungsten trioxide nano particles in the prepared platinum/tungsten trioxide/silicon aluminum oxide composite catalyst are well combined, so that the catalyst has good repeatability, and compared with the existing catalyst, the catalyst has higher polyol conversion rate and selectivity.
Drawings
FIG. 1 is a high resolution transmission electron microscopic image of the composite catalyst obtained in example 1, comparative example 2 of the present invention.
Wherein: (a) is a high-resolution transmission electron micrograph of the composite catalyst obtained in example 1, (b) is a high-resolution transmission electron micrograph of the composite catalyst obtained in comparative example 1, and (c) is a high-resolution transmission electron micrograph of the composite catalyst obtained in comparative example 2.
FIG. 2 is a Scanning Transmission Electron Microscope (STEM) of the composite catalyst obtained in example 1 of the present invention.
Wherein: (a) is a Scanning Transmission Electron Microscope (STEM) of the composite catalyst obtained in example 1 of the present invention, (b) is an imaging map of the element Pt in the region A in the figure (a), (c) is an imaging map of the element W in the region A in the figure (a), and (d) is a superimposed map of the figures (a) and (b).
FIG. 3 is a graph of glycerol hydrogenolysis performance of platinum/tungsten trioxide/silica alumina composite catalysts of varying W content.
Fig. 4 is a graph of glycerol hydrogenolysis performance of platinum/tungsten trioxide/silica alumina composite catalysts of varying Pt content.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1
A method for preparing a platinum/tungsten trioxide/silicon aluminum oxide composite, comprising the steps of:
(1) Preparation of platinum colloid: first 1.0. 1.0g H 2 PtCl 6 •6H 2 O (platinum content is more than or equal to 37.0%) is dissolved in 100 mL glycol, stirred at room temperature for 10min, 50mL of NaOH/glycol (0.25 mol/L) solution is added after complete dissolution, stirring is continued at room temperature for 30min, the pH value of the solution is regulated to 10, argon is introduced for protection, an electric heating sleeve is used for heating to 160 ℃, and natural cooling is carried out under the protection of inert gas, so that tan uniform and stable 'non-protection' Pt colloid is obtained.
(2) Preparation of tungsten trioxide colloid: WCl 0.33g 6 Dissolving in 50mL of absolute ethanol, stirring at room temperature for 20min, adding 20mL of 5% water/ethanol mixed solution after complete dissolution, and continuously stirring at room temperature for hydrolysis, wherein when the solution turns from yellow to colorless, the tungsten trioxide colloid is obtained.
(3) Adding Pt colloid (0.04 g of platinum) into tungsten trioxide colloid (0.2 g of tungsten trioxide) obtained in the step (2), continuously stirring for 3h, adding 1.76g of amorphous silicon aluminum oxide (ASA), continuously stirring for 3 hours, sequentially centrifuging, alternately flushing with water and ethanol, and freeze-drying to obtain a platinum/tungsten trioxide/silicon aluminum oxide compound (catalyst 2 Pt/10W/ASA), wherein the mass percentage of platinum in the catalyst 2Pt/10W/ASA is 2%, the mass percentage of tungsten trioxide is 10%, and the name is WO 3 Abbreviated as W).
And carrying out electron microscope characterization and elemental imaging analysis on the prepared composite catalyst 2Pt/10W/ASA, wherein the electron microscope characterization and elemental imaging analysis are respectively shown in FIG. 1a and FIG. 2. As can be seen in fig. 1a, the platinum nanoparticles are tightly bound to the tungsten oxide nanoparticles; as shown in FIG. 2, the platinum element and the tungsten element are well bonded.
Example 2
A method for preparing a platinum/tungsten trioxide/silicon aluminum oxide composite, comprising the steps of:
(1) Preparation of platinum colloid: first 1.0. 1.0g H 2 PtCl 6 •6H 2 O (platinum content is more than or equal to 37.0%) is dissolved in 100 mL glycol, stirred at room temperature for 10min, after complete dissolution, 50 mLNaOH/glycol (0.25 mol/L) solution is added, stirring is continued at room temperature for 30min, the pH value of the solution is regulated to 13, argon is introduced for protection, an electric heating sleeve is used for heating to 160 ℃, reaction is carried out for 3h, natural cooling is carried out under the protection of inert gas, and tan uniform and stable 'non-protection' Pt colloid is obtained.
(2) Preparation of tungsten trioxide colloid: WCl 0.33g 6 Dissolving in 50mL of absolute ethanol, stirring at room temperature for 20min, adding 20mL of 5% water/ethanol mixed solution after complete dissolution, and continuously stirring at room temperature for hydrolysis, wherein when the solution turns from yellow to colorless, the tungsten trioxide colloid is obtained.
(3) Mixing the platinum colloid (0.04 g of platinum) obtained in the step (1) with the tungsten trioxide colloid (0.2 g of tungsten trioxide) obtained in the step (2), continuing stirring for 3 hours, adding 1.76g of molecular sieve ZSM-5, continuing stirring for 3 hours, sequentially centrifuging, alternately flushing with water and ethanol, and freeze-drying to obtain the platinum/tungsten trioxide/silicon aluminum oxide composite (catalyst 2 Pt/10W/ZSM-5).
Example 3
A method for preparing a platinum/tungsten trioxide/silicon aluminum oxide composite, comprising the steps of:
(1) Preparation of platinum colloid: first 1.0. 1.0g H 2 PtCl 6 •6H 2 O (platinum content is more than or equal to 37.0%) is dissolved in 100 mL glycol, stirred at room temperature for 10min, 50mL NaOH/glycol (0.25 mol/L) solution is added after complete dissolution, stirring is continued at room temperature for 30min, and dissolution is regulatedAnd (3) introducing argon for protection, heating to 160 ℃ by using an electric heating sleeve, reacting for 3 hours, and naturally cooling under the protection of inert gas to obtain the brown uniform and stable 'non-protection' Pt colloid.
(2) Preparation of tungsten trioxide colloid: WCl 0.825g 6 Dissolving in 50mL of anhydrous methanol, stirring at room temperature for 20min, adding 20mL of 5% water/propanol mixed solution after complete dissolution, and continuing stirring at room temperature for hydrolysis, wherein the tungsten trioxide colloid is obtained when the solution turns from yellow to colorless.
(3) Adding Pt colloid (containing 0.01g of platinum) into the tungsten trioxide colloid obtained in the step (2), continuously stirring for 3h, continuously stirring for 3 hours after adding 20g of amorphous silicon aluminum oxide (ASA), sequentially centrifuging, alternately flushing with water and ethanol, and freeze-drying to obtain a platinum/tungsten trioxide/silicon aluminum oxide compound, wherein the mass ratio of platinum to tungsten trioxide in the compound is 1:50, ratio of platinum to ASA 0.0005:1.
example 4
A method for preparing a platinum/tungsten trioxide/silicon aluminum oxide composite, comprising the steps of:
(1) Preparation of platinum colloid: first 1.0. 1.0g H 2 PtCl 6 •6H 2 O (platinum content is more than or equal to 37.0%) is dissolved in 100 mL glycol, stirred at room temperature for 10min, 50mL of NaOH/glycol (0.25 mol/L) solution is added after complete dissolution, stirring is continued at room temperature for 30min, the pH value of the solution is regulated to 9, argon is introduced for protection, an electric heating sleeve is used for heating to 160 ℃, reaction is carried out for 3h, natural cooling is carried out under the protection of inert gas, and tan uniform and stable 'non-protection' Pt colloid is obtained.
(2) Preparation of tungsten trioxide colloid: WCl 0.0083g 6 Dissolving into 50mL anhydrous N, N-dimethylformamide, stirring at room temperature for 20min, adding 20mL 5% water/butanol mixed solution after complete dissolution, continuously stirring at room temperature for hydrolysis, and obtaining tungsten trioxide colloid when the solution turns from yellow to colorless.
(3) Adding Pt colloid (containing 0.1g of platinum) into the tungsten trioxide colloid obtained in the step (2), continuously stirring for 3h, continuously stirring for 3 hours after adding 0.5g of amorphous silicon aluminum oxide (ASA), sequentially centrifuging, alternately flushing with water and ethanol, and freeze-drying to obtain a platinum/tungsten trioxide/silicon aluminum oxide compound, wherein the mass ratio of platinum to tungsten trioxide in the compound is 1:0.05, a mass ratio of platinum to ASA of 0.2:1.
example 5
2Pt/10W/ASA catalytic glycerin hydrogenolysis Performance test
In an autoclave, 0.5g of the platinum/tungsten trioxide/silicon aluminum oxide composite (catalyst 2 Pt/10W/ASA) prepared in example 1 was dispersed into 25.0g of a 4% glycerol/water solution, and 3MPa of hydrogen was introduced into the autoclave, and the temperature was raised to 180℃to catalyze the reaction under magnetic stirring (500 rpm) for 12 hours. The product was analyzed by gas chromatography for 77% glycerol conversion and 47% 1, 3-propanediol selectivity.
Example 6
2Pt/10W/ZSM-5 catalytic glycerin hydrogenolysis Performance test
In an autoclave, 0.5g of the platinum/tungsten trioxide/silica alumina composite (catalyst 2 Pt/10W/ZSM-5) prepared in example 2 was dispersed into 25.0g of an 8% glycerol/water solution, and 3MPa of hydrogen gas was introduced into the autoclave, and the temperature was raised to 190℃to catalyze the reaction under magnetic stirring (500 rpm) for 6 hours. The product was analyzed by gas chromatography with a glycerol conversion of 20% and a 1, 3-propanediol selectivity of 42%.
Example 7
Hydrogenolysis Performance test of 2Pt/10W/ASA catalytic polyol
Preparing 5% erythritol/water solution, 5% xylitol/water solution and 5% sorbitol/water solution respectively; 0.5g of the platinum/tungsten trioxide/silicon aluminum oxide composite (2 Pt/10W/ASA catalyst) prepared in example 1 was mixed with 25ml of each of the above three liquids under the following conditions: the autoclave was charged with 6MPa of hydrogen, heated to 220℃and reacted catalytically with magnetic stirring (600 rpm) for 24h. Analyzing the product by liquid chromatography, wherein the conversion rate of erythritol is 45%, and the selectivity of 1, 4-butanediol is 33%; xylitol conversion 22%,1, 5-pentanediol selectivity 25%; sorbitol conversion 18%,1, 6-hexanediol selectivity 28%. The results indicate that the prepared platinum-tungsten catalyst can catalyze other polyol conversions.
Comparative example 1
(1) Pt colloid (0.04 g of platinum) obtained according to the preparation method of example 1, which is 2% of the total mass of the target catalyst, was mixed with 1.76g of amorphous silica-alumina oxide ASA, stirred for 3 hours, centrifuged, washed alternately with water and ethanol, and freeze-dried to obtain Pt/ASA.
(2) WCl 0.33g 6 Dissolving in 50mL of absolute ethanol, stirring at room temperature for 20min, adding 20mL of 5% water/ethanol mixed solution after complete dissolution, and continuing stirring at room temperature for hydrolysis, wherein when the solution turns from yellow to colorless, the tungsten trioxide colloid is obtained.
(3) And (3) adding the Pt/ASA solid obtained in the step (1) into the tungsten trioxide colloid obtained in the step (2) (wherein tungsten trioxide is 0.2 g), continuously stirring for 3 hours, centrifuging, alternately flushing with water and ethanol, and freeze-drying to obtain the catalyst 2Pt/ASA-10W (named according to the assembly sequence). The high resolution electron micrograph is shown in figure 1b, and the platinum nanoparticles and tungsten oxide nanoparticles do not bind effectively.
Comparative example 2
WCl 0.33g 6 Dissolving in 50mL of absolute ethyl alcohol, stirring at room temperature for 20min, after complete dissolution, adding 20mL of 5% water/ethanol mixed solution, continuously stirring at room temperature for hydrolysis, when the solution is changed from yellow to colorless (namely tungsten trioxide colloid), adding 1.76g of amorphous silicon aluminum oxide ASA, stirring for 3h, adding Pt colloid (0.04 g of platinum) which is 2% of the total mass of the target catalyst and is obtained according to the preparation method of the embodiment 1, continuously stirring for 3h, sequentially centrifuging, alternately flushing with water and ethanol, and freeze-drying to obtain a catalyst of 10W/ASA-2Pt (named according to the assembly sequence), wherein high resolution electron microscope pictures of the catalyst are shown in figure 1c, and the platinum nano particles and the tungsten oxide nano particles do not generate effective combination.
Comparative example 3
Hydrogenolysis Performance test of 2Pt/ASA-10W and 10W/ASA-2Pt catalyzed glycerin
According to the same reaction conditions as in example 5, 0.5g of 2Pt/ASA-10W (catalyst obtained in comparative example 1) and 10W/ASA-2Pt (catalyst obtained in comparative example 2) catalysts were dispersed in an autoclave containing 25.0g of 4% glycerin/water solution, respectively, and 3MPa of hydrogen was introduced into the autoclave, and the temperature was raised to 180℃to catalyze the reaction under magnetic stirring (500 rpm) for 12 hours. The product was analyzed by gas chromatography for a glycerol conversion of 32% and a 1, 3-propanediol selectivity of 24% for a 10W/ASA-2Pt catalyst; for the 2Pt/ASA-10W catalyst, the glycerol conversion was 15.6% and the 1, 3-propanediol selectivity was 0%.
From the results of example 5 and comparative example 3, it is apparent that the combination of platinum and tungsten trioxide can improve the conversion of glycerin and the selectivity of 1, 3-propanediol.
In order to achieve the final research effect of the invention, the influence of different tungsten loadings and different platinum loadings on the catalytic performance of the catalyst is examined, and the hydrogenolysis performance of the catalytic glycerin is taken as an example.
Catalytic performance of (one) different tungsten trioxide loadings of platinum/tungsten trioxide/silica alumina composite catalysts
Under the condition of unchanged platinum loading, the loading of tungsten oxide is changed to obtain the catalyst of 2Pt/5W/ASA,2Pt/10W/ASA,2Pt/15W/ASA and 2 Pt/20W/ASA. Performance tests were performed using the same catalytic reaction conditions as in example 5, with the conversion and selectivity shown in fig. 3. From the experimental results, it can be seen that the glycerol conversion and the 1, 3-propanediol selectivity were not greatly different at tungsten loadings exceeding 10%.
(II) catalytic Performance of platinum/tungsten trioxide/silicon aluminum oxide composite catalysts with different platinum loadings
Under the condition of unchanged tungsten loading, the loading of platinum is changed, and 0.5Pt/10W/ASA, 1Pt/10W/ASA, 1.5Pt/10W/ASA, 2Pt/10W/ASA and 3Pt/10W/ASA catalysts are obtained. Performance tests were performed using the same catalytic reaction conditions as in example 5, with the conversion and selectivity shown in fig. 4. From the experimental results, it can be seen that the effect of the amount of platinum on the glycerol conversion and the 1, 3-propanediol selectivity is in volcanic type rule, and that the glycerol conversion and the 1, 3-propanediol selectivity are highest when the platinum content is 2%.
To demonstrate excellent catalyst reproducibility, a parallelism test was performed, specifically as follows:
32 Pt/10W/ASA catalysts were prepared in parallel according to the preparation method described in example 1, and the performance of the parallel samples was evaluated according to the test method described in example 3, and the results of the performance test show that the glycerol conversion range was 75+ -3% and the 1, 3-propanediol selectivity range was 45+ -3%, indicating that the catalyst obtained by the method provided by the invention has better repeatability.
In addition to the above embodiments, the present invention also includes other embodiments, and all technical solutions that are formed by equivalent transformation or equivalent substitution should fall within the protection scope of the claims of the present invention.

Claims (10)

1. A method for preparing a platinum/tungsten trioxide/silicon aluminum oxide composite, which is characterized in that: the method comprises the following steps:
(1) Preparation of platinum colloid: dissolving platinum salt into ethylene glycol to obtain a solution A, dissolving sodium hydroxide into ethylene glycol to obtain a solution B, uniformly mixing the solution A and the solution B under the condition of stirring, adjusting the pH value of the solution to 7-13, heating to 120-190 ℃ under the protection of inert gas atmosphere, keeping the temperature for 0.5-24h, and cooling to obtain a platinum nano colloid solution;
(2) Preparation of tungsten trioxide colloid: dissolving tungsten hexachloride in an anhydrous solvent C, slowly adding an aqueous solvent D, and obtaining tungsten trioxide colloid when the solution is changed from yellow to colorless or bluish;
(3) Mixing platinum colloid and tungsten trioxide colloid, stirring for a certain time, adding silicon-aluminum oxide, and adding water to precipitate the catalyst after the platinum colloid and tungsten trioxide colloid are loaded on the silicon-aluminum oxide to obtain the platinum/tungsten trioxide/silicon-aluminum oxide compound.
2. The method for producing a platinum/tungsten trioxide/silicon aluminum oxide composite according to claim 1, characterized in that: the platinum salt in the step (1) is at least one of chloroplatinic acid, potassium chloroplatinate, sodium chloroplatinate and platinum acetate.
3. The method for producing a platinum/tungsten trioxide/silicon aluminum oxide composite according to claim 1, characterized in that: the solvents C and D in the step (2) are one or more of methanol, ethanol, propanol, butanol, ethylene glycol and N, N-dimethylformamide.
4. The method for producing a platinum/tungsten trioxide/silicon aluminum oxide composite according to claim 1, characterized in that: the mass ratio of the platinum colloid to the tungsten trioxide colloid is 1:0.05-1:50; the mass ratio of the platinum colloid to the silicon-aluminum oxide is 0.0005-0.20:1.
5. The method for producing a platinum/tungsten trioxide/silicon aluminum oxide composite according to claim 1, characterized in that: the silicon aluminum oxide is amorphous silicon aluminum oxide or silicon aluminum molecular sieve.
6. The method for producing a platinum/tungsten trioxide/silicon-aluminum oxide composite according to claim 5, characterized in that: the amorphous silica-alumina is a compound formed by silica and alumina, wherein the alumina accounts for 3% -30% of the total mass of the compound; the silicon-aluminum molecular sieve is ZSM-5, naX or NaY.
7. A platinum/tungsten trioxide/silicon aluminum oxide composite characterized by: a method of preparing a platinum/tungsten trioxide/silicon aluminum oxide composite according to any of claims 1-6.
8. The platinum/tungsten trioxide/silicon-aluminum oxide composite according to claim 7, characterized in that: the mass percentage of platinum in the platinum/tungsten trioxide/silicon aluminum oxide composite is 0.1% -5%, and the mass percentage of tungsten trioxide is 2% -40%.
9. Use of a platinum/tungsten trioxide/silicon-aluminum oxide composite characterized by: use of the platinum/tungsten trioxide/silicon-aluminum oxide composite according to claim 7 in a polyol selective hydrogenolysis reaction.
10. Use of a platinum/tungsten trioxide/silicon-aluminum oxide composite according to claim 9, characterized in that: the polyalcohol is glycerol, tetrol, pentitol or hexaol.
CN202110556412.3A 2021-05-21 2021-05-21 Platinum/tungsten trioxide/silicon aluminum oxide compound and preparation method and application thereof Pending CN116870906A (en)

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