CN111389397A - Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and preparation method thereof - Google Patents

Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and preparation method thereof Download PDF

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CN111389397A
CN111389397A CN202010140281.6A CN202010140281A CN111389397A CN 111389397 A CN111389397 A CN 111389397A CN 202010140281 A CN202010140281 A CN 202010140281A CN 111389397 A CN111389397 A CN 111389397A
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zro
catalyst
glycerol
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CN111389397B (en
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周文斌
关业军
周强
谢海洲
俞先康
夏天昊
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Zhejiang Zhenyang Development Co ltd
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Abstract

The invention relates to a catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and a preparation method thereof, and relates to the technical field of glycerol hydrogenolysis reaction, wherein the catalyst comprises Pt, W, ZrO2, an auxiliary agent and a carrier, wherein the load of the Pt is 1-5% of the mass of the carrier, the load of the W is 6-12% of the mass of the carrier, the load of the ZrO2 is 5-10% of the mass of the carrier, and the load of the auxiliary agent is 0.1-0.5% of the mass of the carrier. The catalyst prepared by the invention can improve the selectivity of 1, 3-propylene glycol in the glycerol hydrogenation product and reduce the generation of 1, 2-propylene glycol.

Description

Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and preparation method thereof
Technical Field
The invention relates to the technical field of glycerol hydrogenolysis reaction, in particular to a catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation and a preparation method thereof.
Background
Glycerol, also known as glycerol, is a nontoxic, biodegradable, multifunctional compound, and is the simplest triol, and its highly functionalized structure makes it possible to convert it into various products with high added values through various conversion processes, and also provides important guidance for constructing more complex polyol and sugar alcohol conversion systems. At present, the main approaches for deep development by using glycerol as a raw material include the following: under certain conditions, the raw materials react with a catalyst to generate dihydroxyacetone through selective oxidation, generate acrolein through dehydration, and generate high value-added chemicals such as propylene glycol through hydrogenolysis.
The glycerol can generate 1, 2-propylene glycol and 1, 3-propylene glycol by hydrogenolysis on a C-O bond, and can generate n-propanol and isopropanol by further hydrogenolysis, and finally generate excessive hydrogenolysis products such as propane and the like; glycerol participates in the hydrogenolysis of C-C bonds to produce degradation products such as ethylene glycol, ethanol, methanol, ethane, and methane. Among the above products, 1, 3-propanediol is the product with the highest added value, can be used as a solvent, an antifreeze, an emulsifier, a plasticizer, a detergent, a preservative and a lubricant, has important applications in medicines, foods, cosmetics and organic synthesis, and is an important chemical raw material. However, the selective formation of 1, 3-propanediol is very difficult, and most catalytic systems use 1, 2-propanediol as the main product. Although 1, 2-propanediol is useful as a monomer of polyester resin, an anti-freezing agent, a component of pigment, etc., and is also an important product, 1, 2-propanediol is not much cheaper than glycerol in the market, and thus there is a need to develop an effective catalyst for the preparation of 1, 3-propanediol by hydrogenolysis of glycerol.
Disclosure of Invention
The invention aims to provide a catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation, which can improve the selectivity of the 1, 3-propylene glycol in a glycerol hydrogenation product and reduce the generation of the 1, 2-propylene glycol; the second purpose of the invention is to provide a preparation method of the catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation; the third purpose of the invention is to provide an application of the catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation.
The technical purpose of the invention is realized by the following technical scheme: a catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation comprises Pt, W and ZrO2The supported amount of Pt is 1-5% of the mass of the carrier, the supported amount of W is 6-12% of the mass of the carrier, and ZrO is added2The loading amount of the auxiliary agent is 5-10% of the mass of the carrier, and the loading amount of the auxiliary agent is 0.1-0.5% of the mass of the carrier.
By adopting the technical scheme, reactants of the hydrogenolysis reaction of the glycerol are hydrogen and the glycerol, Pt can activate hydrogen but can not activate the glycerol, W can react with a hydroxyl group of the glycerol, the auxiliary agent is used for promoting Pt to activate the hydrogen, so that the catalytic activity of the catalyst is improved, the acidic site of the B acid on the surface of the catalyst can be increased by adding the W, and the generation of the 1, 3-propanediol is facilitated by the B acid, so that the selectivity of the 1, 3-propanediol can be improved. Glycerol molecules are adsorbed on the surface of a catalyst, secondary hydroxyl in the glycerol molecules and hydroxyl on a B acid center on the surface of the catalyst are protonated, then dehydration is carried out to remove hydroxyl on secondary carbon to form carbocation, the formed carbocation is adsorbed on the surface of a carrier again through primary hydroxyl in the glycerol molecules to form 3-hydroxy propenol, the 3-hydroxy propenol is easy to form 3-HPA through keto-enol interconversion, and the 3-HPA is quickly hydrogenated with hydrogen species activated on Pt to generate 1, 3-propanediol, so that the catalyst prepared by the method is beneficial to improving the selectivity of the 1, 3-propanediol.
The invention is advancedThe method comprises the following steps: the carrier is Al2O3、SiO2And SBA-15.
By adopting the technical scheme, the abundant specific surface area of the carrier is beneficial to loading the active component on the carrier, and the catalytic effect of the catalyst is improved.
The invention is further provided with: the auxiliary agent is one of Re, Au, Sr and Ba.
By adopting the technical scheme, on one hand, the addition of the auxiliary agent enables H to be generated2Is activated to active hydrogen species at the promoter interface, thereby promoting catalytic activity of the catalyst; on the other hand, the auxiliary particles are in H2The hindered Lewis acid-base pair is easily formed with the assistance of the acid-base pair, so that L acid sites on the surface of the catalyst are reduced, B acid sites on the surface are increased, the B acid is favorable for the generation of an intermediate product 3-HPA, the selectivity of 1, 3-propanediol is further improved, L acid is favorable for the generation of acetol, the acetol is further converted into the 1, 2-propanediol, L acid is reduced, and the generation of the 1, 2-propanediol is favorably reduced.
The invention is further provided with: and the loading amount of the Pt is 2-4% of the mass of the carrier.
The second technical purpose of the invention is realized by the following technical scheme: a preparation method of a catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation comprises the following steps: the method specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate to dissolve in the aqueous solution, then soaking the carrier in the aqueous solution of zirconium nitrate, carrying out ultrasonic treatment for 30-90 min, drying after the ultrasonic treatment is finished, and roasting at 550-750 ℃ to obtain ZrO2A carrier;
step 2, weighing the precursor of W according to the load amount, dissolving the precursor in water, adding the W-containing water solution into a beaker, and adding ZrO2Support for impregnating the surface with ZrO2Carrying out ultrasonic treatment on the surface of the carrier for 30-90 min, and standing for 5-10 h at room temperature; drying after standing, and roasting at 550-750 ℃ to obtain WOx-ZrO2A carrier;
step 3, weighing the WO prepared in step 2x-ZrO2The carrier is spread on the beakerThen, an aqueous solution of chloroplatinic acid at the desired loading of Pt was added dropwise to a beaker and WO was immersedx-ZrO2Carrying out ultrasonic treatment for 30-90 min, standing at room temperature for 5-10 h, drying after standing, and roasting at 550-750 ℃ to obtain Pt-WOx-ZrO2A carrier;
step 4, the Pt-WO prepared in the step 3x-ZrO2Adding the carrier into water, continuously stirring until the carrier is uniformly dispersed, then adding a solution containing the auxiliary metal, and continuously stirring for 0.5-2 hours; continuously stirring and adding a sodium borohydride solution until the pH value is 4-5, aging for 4-6 h, filtering, washing and drying; then reducing for 0.5-1 h at 300-400 ℃ in a hydrogen atmosphere to obtain a material named as an auxiliary agent-Pt-WOx-ZrO2A carrier.
By adopting the technical scheme, the Pt-based catalyst has high activity, good hydrogenation performance when being applied to glycerin hydrogenation reaction, and the adsorbed dissociated hydrogen can be transferred at each adsorption center due to the high-efficiency hydrogen dissociation capability and high dispersity of Pt, so that a hydrogen overflow effect is formed, and ZrO is increased2The support can increase the hydrogen flooding effect of the catalyst. The addition of W can increase the acidic sites of the B acid on the surface of the catalyst, and the B acid is beneficial to the generation of 1, 3-propanediol, so that the selectivity of the 1, 3-propanediol can be improved. The auxiliary is continuously loaded so that the highly dispersed auxiliary can be in H2The hindered Lewis acid-base pair is formed with the assistance of the catalyst, so that the L acid position on the surface of the carrier is reduced, the B acid position on the surface is increased, and the selectivity of the 1, 3-propylene glycol is further improved.
The invention is further provided with: and the precursor of W in the step 2 is ammonium metatungstate.
By adopting the technical scheme, the ammonium metatungstate is dissolved in water and is easily dissolved, and the ZrO 2/carrier is impregnated by the ammonium metatungstate solution, so that the impregnation is more uniform.
The invention is further provided with: the specific reaction conditions are as follows: the reaction pressure is 5MPa, the reaction temperature is 150 ℃, and the reaction raw material is 10wt% of glycerol aqueous solution.
By adopting the technical scheme, the concentration of the glycerol is too low, so that the yield of the 1, 3-propylene glycol in the product is low; the glycerol concentration is too high, the viscosity of the glycerol is high, and the glycerol can not react uniformly when contacting with the catalyst, so that the conversion rate of the glycerol is reduced.
The invention is further provided with: the reaction is carried out in a fixed bed reactor.
By adopting the technical scheme, the catalyst is filled in the fixed bed reactor, and the catalyst is fixed in the reaction process, so that the reaction is favorably and stably carried out, and the catalytic effect of the catalyst is ensured.
In conclusion, the beneficial technical effects of the invention are as follows:
1. the reactants of the hydrogenolysis reaction of the glycerol are hydrogen and glycerol, Pt can activate hydrogen but cannot activate the glycerol, the oxide of W can react with the hydroxyl group of the glycerol, the auxiliary agent is used for promoting Pt to activate the hydrogen so as to improve the catalytic activity of the catalyst, the addition of W can increase the acidic site of B acid on the surface of the catalyst, and the B acid is beneficial to the generation of 1, 3-propanediol, so that the selectivity of the 1, 3-propanediol can be improved. Glycerol molecules are adsorbed on the surface of a catalyst, secondary hydroxyl in the glycerol molecules and hydroxyl on a B acid center on the surface of the catalyst are protonated, then dehydration is carried out to remove hydroxyl on secondary carbon to form carbocation, the formed carbocation is adsorbed on the surface of a carrier again through primary hydroxyl in the glycerol molecules to form 3-hydroxy propenol, the 3-hydroxy propenol is easy to form 3-HPA through keto-enol interconversion, and the 3-HPA is quickly hydrogenated with hydrogen species activated on Pt to generate 1, 3-propanediol, so that the catalyst prepared by the method is beneficial to improving the selectivity of the 1, 3-propanediol;
the Pt-based catalyst has high activity, good hydrogenation performance when being applied to glycerol hydrogenation reaction, and the Pt has high-efficient dissociated hydrogen capacity and high dispersibility, so that the adsorbed dissociated hydrogen can be transferred in each adsorption center to form a hydrogen overflow effect, and the ZrO2 carrier is added to increase the hydrogen overflow effect of the catalyst;
3. the ammonium metatungstate is dissolved in water and is easy to dissolve, and the ZrO 2/carrier is impregnated by the ammonium metatungstate solution, so that the impregnation is more uniform.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The supported amount of Pt is 1 percent of the mass of the carrier, the supported amount of W is 10 percent of the mass of the carrier, the supported amount of ZrO2 is 5 percent of the mass of the carrier, the supported amount of the auxiliary agent is 0.1 percent of the mass of the carrier, the auxiliary agent is Re, and the carrier is Al2O3。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking Al in the zirconium nitrate water solution2O3Performing ultrasonic treatment for 30min, drying after the ultrasonic treatment is finished, and roasting at 550 ℃ to obtain ZrO2/Al2O3；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/Al2O3So that the liquid surface is impregnated with ZrO2/Al2O3Carrying out ultrasonic treatment on the surface for 60min, and standing at room temperature for 5 h; drying after standing, and roasting at 650 ℃ to obtain WOx-ZrO2/Al2O3；
Step 3, weighing the WO prepared in step 2x-ZrO2/Al2O3Spread flat in a beaker and then an aqueous solution of chloroplatinic acid at the desired loading of Pt was added dropwise to the beaker to immerse the WOx-ZrO2/Al2O3Standing for 7h at room temperature after 30min by ultrasonic treatment, drying after standing, and roasting at 750 ℃ to obtain Pt-WOx-ZrO2/Al2O3；
Step 4, the Pt-WOx-ZrO2/Al prepared in the step 32O3Adding the mixture into water, continuously stirring the mixture until the mixture is uniformly dispersed, then adding the perrhenic acid solution with the required load amount of Re, and continuously stirring the mixture for 0.5 hour; continuously stirring and adding a sodium borohydride solution until the pH value is 4, aging for 4 hours, filtering, washing and drying; then reducing for 1h at 300 ℃ in hydrogen atmosphere to obtain the material named Re-Pt-WOx-ZrO2/Al2O3。
Example 2
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The auxiliary agent and the carrier, wherein the load amount of Pt is 3 percent of the mass of the carrier, the load amount of W is 6 percent of the mass of the carrier, and ZrO is added2The loading capacity of the catalyst is 7 percent of the mass of the carrier, the loading capacity of the auxiliary agent is 0.3 percent of the mass of the carrier, the auxiliary agent is Au, and the carrier is SiO2。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking SiO with zirconium nitrate water solution2Performing ultrasonic treatment for 60min, drying after the ultrasonic treatment is finished, and roasting at 650 ℃ to obtain ZrO2/SiO2；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/SiO2So that the liquid surface is impregnated with ZrO2Performing ultrasonic treatment on the surface of SiO2 for 90min, and standing for 7h at room temperature; drying after standing, and roasting at 750 ℃ to obtain WOx-ZrO2/SiO2；
Step 3, weighing the WO prepared in step 2x-ZrO2the/SiO 2 was laid flat in a beaker, and then an aqueous solution of chloroplatinic acid at the desired Pt loading was added dropwise to the beaker and the WO immersedx-ZrO2Performing ultrasonic treatment for 60min, standing at room temperature for 10h, drying after standing, and roasting at 600 ℃ to obtain Pt-WOx-ZrO2/SiO 2;
step 4, adding the Pt-WOx-ZrO2/SiO2 prepared in the step 3 into water, and continuously stirring until the mixture is uniformDispersing, then adding a chloroauric acid solution with the required loading amount of Au, and continuously stirring for 1 h; continuously stirring and adding a sodium borohydride solution until the pH value is 5, aging for 5 hours, filtering, washing and drying; then reducing the mixture for 0.5h at 350 ℃ in hydrogen atmosphere to obtain a material named as Au-Pt-WOx-ZrO2/SiO2。
Example 3
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The supported amount of Pt is 5% of the mass of the carrier, the supported amount of W is 8% of the mass of the carrier, the supported amount of ZrO2 is 10% of the mass of the carrier, the supported amount of the auxiliary agent is 0.4% of the mass of the carrier, the auxiliary agent is Sr, and the carrier is SBA-15.
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate to dissolve in the aqueous solution, soaking SBA-15 in the aqueous solution of zirconium nitrate, performing ultrasonic treatment for 90min, drying after the ultrasonic treatment is finished, and roasting at 750 ℃ to obtain ZrO2/SBA-15；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2SBA-15, impregnating the surface with ZrO2Performing ultrasonic treatment on the surface of SBA-15 for 30min, and standing for 10h at room temperature; drying after standing, and roasting at 550 ℃ to obtain WOx-ZrO2/SBA-15；
Step 3, weighing the WO prepared in step 2x-ZrO2the/SBA-15 was laid flat in a beaker and then an aqueous solution of chloroplatinic acid at the desired loading of Pt was added dropwise to the beaker and WO was immersedx-ZrO2SBA-15, standing for 5 hours at room temperature after ultrasonic treatment for 90min, drying after standing, and roasting at 550 ℃ to obtain Pt-WOx-ZrO 2/SBA-15;
step 4, adding the Pt-WOx-ZrO2/SBA-15 prepared in the step 3 into water, continuously stirring until the Pt-WOx-ZrO2/SBA-15 is uniformly dispersed, then adding a strontium chloride solution with required loading capacity Sr, and continuously stirring for 2 hours; continuously stirring and adding a sodium borohydride solution until the pH value is 4.4, aging for 6 hours, filtering, washing and drying; however, the device is not suitable for use in a kitchenThen reducing for 1h at 400 ℃ in hydrogen atmosphere to obtain the material named as Sr-Pt-WOx-ZrO2/SBA-15。
Example 4
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The auxiliary agent and the carrier, wherein the load amount of Pt is 4 percent of the mass of the carrier, the load amount of W is 7 percent of the mass of the carrier, and ZrO is2The loading capacity of the catalyst is 7 percent of the mass of the carrier, the loading capacity of the auxiliary agent is 0.5 percent of the mass of the carrier, the auxiliary agent is Ba, and the carrier is Al2O3。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking Al in the zirconium nitrate water solution2O3Performing ultrasonic treatment for 30min, drying after the ultrasonic treatment is finished, and roasting at 550 ℃ to obtain ZrO2/Al2O3；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/Al2O3So that the liquid surface is impregnated with ZrO2/Al2O3Carrying out ultrasonic treatment on the surface for 60min, and standing at room temperature for 5 h; drying after standing, and roasting at 650 ℃ to obtain WOx-ZrO2/Al2O3；
Step 3, weighing the WO prepared in step 2x-ZrO2/Al2O3Spread flat in a beaker and then add a drop of an aqueous solution of chloroplatinic acid at the desired loading of Pt to the beaker and immerse the WOx-ZrO2/Al2O3Standing for 7h at room temperature after 30min by ultrasonic treatment, drying after standing, and roasting at 750 ℃ to obtain Pt-WOx-ZrO2/Al2O3；
Step 4, the Pt-WOx-ZrO2/Al prepared in the step 32O3Adding the mixture into water, continuously stirring the mixture until the mixture is uniformly dispersed, then adding a barium nitrate solution with the required loading capacity of Ba, and continuously stirring the mixture for 0.5 hour; continuously stirring, adding sodium borohydride solution until the pH value is 4, aging for 4h, filtering and washingWashing and then drying; then reducing for 1h at 300 ℃ in hydrogen atmosphere to obtain the material named Ba-Pt-WOx-ZrO2/Al2O3。
Example 5
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The auxiliary agent and the carrier, wherein the load amount of Pt is 3 percent of the mass of the carrier, the load amount of W is 9 percent of the mass of the carrier, and ZrO is added2The loading capacity of the catalyst is 8 percent of the mass of the carrier, the loading capacity of the auxiliary agent is 0.1 percent of the mass of the carrier, the auxiliary agent is Au, and the carrier is Al2O3。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking Al in the zirconium nitrate water solution2O3Performing ultrasonic treatment for 50min, drying after the ultrasonic treatment is finished, and roasting at 700 ℃ to obtain ZrO2/Al2O3；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/Al2O3So that the liquid surface is impregnated with ZrO2/Al2O3Carrying out ultrasonic treatment for 45min on the surface, and standing for 9h at room temperature; drying after standing, and roasting at 750 ℃ to obtain WOx-ZrO2/Al2O3；
Step 3, weighing the WO prepared in step 2x-ZrO2/Al2O3Spread flat in a beaker and then add dropwise a loaded amount of an aqueous solution of chloroplatinic acid to the beaker to immerse the WOx-ZrO2/Al2O3Standing for 7h at room temperature after ultrasonic treatment for 50min, drying after standing, and roasting at 700 ℃ to obtain Pt-WOx-ZrO2/Al2O3；
Step 4, the Pt-WOx-ZrO2/Al prepared in the step 32O3Adding the mixture into water, continuously stirring the mixture until the mixture is uniformly dispersed, then adding a chloroauric acid solution with the required loading amount of Au, and continuously stirring the mixture for 0.5 hour; sodium borohydride is added with continuous stirringAging the solution for 5h until the pH value is 4.6, filtering, washing and drying; then reducing for 0.5h at 380 ℃ in hydrogen atmosphere to obtain the material named as Au-Pt-WOx-ZrO2/Al2O3。
Example 6
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The auxiliary agent and the carrier, wherein the load amount of Pt is 1 percent of the mass of the carrier, the load amount of W is 10 percent of the mass of the carrier, and ZrO is2The loading capacity of the catalyst is 6 percent of the mass of the carrier, the loading capacity of the auxiliary agent is 0.4 percent of the mass of the carrier, the auxiliary agent is Au, and the carrier is Al2O3。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking Al in the zirconium nitrate water solution2O3Performing ultrasonic treatment for 80min, drying after the ultrasonic treatment is finished, and roasting at 600 ℃ to obtain ZrO2/Al2O3；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/Al2O3So that the liquid surface is impregnated with ZrO2/Al2O3Carrying out ultrasonic treatment on the surface for 70min, and standing at room temperature for 6 h; drying after standing, and roasting at 600 ℃ to obtain WOx-ZrO2/Al2O3；
Step 3, weighing the WO prepared in step 2x-ZrO2/Al2O3Spread flat in a beaker and then add dropwise a loaded amount of an aqueous solution of chloroplatinic acid to the beaker to immerse the WOx-ZrO2/Al2O3Standing for 6h at room temperature after ultrasonic treatment for 70min, drying after standing, and roasting at 550 ℃ to obtain Pt-WOx-ZrO2/Al2O3；
Step 4, the Pt-WOx-ZrO2/Al prepared in the step 32O3Adding into water, continuously stirring until the mixture is uniformly dispersed, then adding into chloroauric acid solution with the required loading quantity of Au, and thenContinuously stirring for 1.5 h; continuously stirring and adding a sodium borohydride solution until the pH value is 4.8, aging for 4 hours, filtering, washing and drying; then reducing for 1h at 350 ℃ in hydrogen atmosphere to obtain the material named as Au-Pt-WOx-ZrO2/Al2O3。
Example 7
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The auxiliary agent and the carrier, wherein the load amount of Pt is 2 percent of the mass of the carrier, the load amount of W is 11 percent of the mass of the carrier, and ZrO is added2The loading capacity of the catalyst is 9 percent of the mass of the carrier, the loading capacity of the auxiliary agent is 0.3 percent of the mass of the carrier, the auxiliary agent is Re, and the carrier is Al2O3。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking Al in the zirconium nitrate water solution2O3Ultrasonic treatment for 70min, drying after the ultrasonic treatment is finished, and roasting at 750 ℃ to obtain ZrO2/Al2O3；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/Al2O3So that the liquid surface is impregnated with ZrO2/Al2O3Carrying out ultrasonic treatment on the surface for 65min, and standing for 7h at room temperature; drying after standing, and roasting at 700 ℃ to obtain WOx-ZrO2/Al2O3；
Step 3, weighing the WO prepared in step 2x-ZrO2/Al2O3Spread flat in a beaker and then add a drop of an aqueous solution of chloroplatinic acid at the desired loading of Pt to the beaker and immerse the WOx-ZrO2/Al2O3Standing for 9h at room temperature after ultrasonic treatment for 45min, drying after standing, and roasting at 600 ℃ to obtain Pt-WOx-ZrO2/Al2O3；
Step 4, the Pt-WOx-ZrO2/Al prepared in the step 32O3Adding into water, and stirring to disperse uniformlyThen adding perrhenic acid solution with required load capacity Re, and continuously stirring for 1 h; continuously stirring and adding a sodium borohydride solution until the pH value is 4.7, aging for 6 hours, filtering, washing and drying; then reducing for 1h at 300 ℃ in hydrogen atmosphere to obtain the material named Re-Pt-WOx-ZrO2/Al2O3。
Example 8
A catalyst for preparing 1, 3-propanediol by hydrogenating glycerin is prepared from Pt, W and ZrO2The auxiliary agent and the carrier, wherein the load amount of Pt is 3 percent of the mass of the carrier, the load amount of W is 8 percent of the mass of the carrier, and ZrO is added2The loading capacity of the catalyst is 8 percent of the mass of the carrier, the loading capacity of the auxiliary agent is 0.2 percent of the mass of the carrier, the auxiliary agent is Re, and the carrier is Al2O3。
The preparation method of the catalyst specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate, dissolving in water solution, and soaking Al in the zirconium nitrate water solution2O3Performing ultrasonic treatment for 60min, drying after the ultrasonic treatment is finished, and roasting at 650 ℃ to obtain ZrO2/Al2O3；
Step 2, weighing ammonium metatungstate according to the loading capacity, dissolving the ammonium metatungstate in water, adding the ammonium metatungstate aqueous solution into a beaker, and adding ZrO2/Al2O3So that the liquid surface is impregnated with ZrO2/Al2O3Carrying out ultrasonic treatment on the surface for 60min, and standing at room temperature for 8 h; drying after standing, and roasting at 650 ℃ to obtain WOx-ZrO2/Al2O3；
Step 3, weighing the WO prepared in step 2x-ZrO2/Al2O3Spread flat in a beaker and then add a drop of an aqueous solution of chloroplatinic acid at the desired loading of Pt to the beaker and immerse the WOx-ZrO2/Al2O3Standing for 7h at room temperature after ultrasonic treatment for 60min, drying after standing, and roasting at 650 ℃ to obtain Pt-WOx-ZrO2/Al2O3；
Step 4, the Pt-WOx-ZrO2/Al prepared in the step 32O3Adding the mixture into water, continuously stirring the mixture until the mixture is uniformly dispersed, then adding the perrhenic acid solution with the required load amount of Re, and continuously stirring the mixture for 01 h; continuously stirring and adding a sodium borohydride solution until the pH value is 4.6, aging for 5 hours, filtering, washing and drying; then reducing for 1h at 360 ℃ in hydrogen atmosphere to obtain the material named as Re-Pt-WOx-ZrO2/Al2O3。
Comparative example 1
The catalyst for preparing 1, 3-propylene glycol by hydrogenating glycerol is different from the catalyst in the embodiment 8 in that the loading amount of Pt is 0.05 percent of the mass of the carrier, and the catalyst is the same as the catalyst in the embodiment 8.
Comparative example 2
The catalyst for preparing 1, 3-propylene glycol by hydrogenating glycerol is different from the catalyst in example 8 in that the loading amount of Pt is 6 percent of the mass of a carrier, and the catalyst is the same as the catalyst in example 8.
Comparative example 3
The catalyst for preparing 1, 3-propylene glycol by hydrogenating glycerol is different from the catalyst in the embodiment 8 in that the loading amount of the auxiliary agent is 0.05 percent of the mass of the carrier, and the catalyst is the same as the catalyst in the embodiment 8.
Comparative example 4
The catalyst for preparing 1, 3-propylene glycol by hydrogenating glycerol is different from the catalyst in the embodiment 8 in that the loading amount of Pt is 0.6 percent of the mass of the carrier, and the catalyst is the same as the catalyst in the embodiment 8.
The catalysts prepared in examples 1 to 8 and comparative examples 1 to 4 are applied to the reaction for preparing 1, 3-propanediol by hydrogenating glycerol, and the specific reaction conditions are that the pressure of a catalyst bed layer is adjusted to 5MPa, then the reaction temperature is increased to 150 ℃ at the speed of 2.5 ℃/min under the flowing of hydrogen, the raw material is introduced after the temperature is constant, the raw material is 10wt% glycerol aqueous solution with the weight of 50m L, the mass of the catalyst is 2g, and after the reaction is finished, liquid phase products are collected and analyzed by liquid chromatography.
Glycerol conversion (initial moles of glycerol-moles of glycerol remaining)/initial moles of glycerol × 100% product selectivity is × 100% moles of carbon per mole of carbon converted to glycerol.
TABLE 1 reaction evaluation results
Figure BDA0002398851120000091
Note: 1, 3-PD: 1, 3-propanediol; 1, 2-PD: 1,2 propylene glycol; 1-PO: n-propanol; 2-PO: and (3) isopropanol.
The present embodiment is only for explaining the present invention, and not for limiting the present invention, and those skilled in the art can make modifications without inventive contribution to the present embodiment as needed after reading the present specification, but all of which are protected by patent law within the scope of the claims of the present invention.

Claims (8)

1. A catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation is characterized in that: the catalyst comprises Pt, W and ZrO2The supported amount of Pt is 1-5% of the mass of the carrier, the supported amount of W is 6-12% of the mass of the carrier, and ZrO is added2The loading amount of the auxiliary agent is 5-10% of the mass of the carrier, and the loading amount of the auxiliary agent is 0.1-0.5% of the mass of the carrier.
2. The catalyst for preparing 1, 3-propanediol by hydrogenating glycerol according to claim 1, wherein: the carrier is Al2O3、SiO2And SBA-15.
3. The catalyst for preparing 1, 3-propanediol by hydrogenating glycerol according to claim 1, wherein: the auxiliary agent is one of Re, Au, Sr and Ba.
4. The catalyst for preparing 1, 3-propanediol by hydrogenating glycerol according to claim 1, wherein: and the loading amount of the Pt is 2-4% of the mass of the carrier.
5. A method for preparing the catalyst for preparing 1, 3-propanediol by hydrogenating glycerol according to any one of claims 1 to 4, wherein the method comprises the following steps: the method specifically comprises the following steps:
step 1, according to ZrO2Weighing zirconium nitrate to dissolve in the aqueous solution, then soaking the carrier in the aqueous solution of zirconium nitrate, carrying out ultrasonic treatment for 30-90 min, drying after the ultrasonic treatment is finished, and roasting at 550-750 ℃ to obtain ZrO2A carrier;
step 2, weighing the precursor of W according to the load amount, dissolving the precursor in water, adding the W-containing water solution into a beaker, and adding ZrO2Support for impregnating the surface with ZrO2Carrying out ultrasonic treatment on the surface of the carrier for 30-90 min, and standing for 5-10 h at room temperature; drying after standing, and roasting at 550-750 ℃ to obtain WOx-ZrO2A carrier;
step 3, weighing the WO prepared in step 2x-ZrO2The carrier is laid flat in a beaker, and then the required Pt-loaded chloroplatinic acid aqueous solution is dripped into the beaker to immerse the WOx-ZrO2Carrying out ultrasonic treatment for 30-90 min, standing at room temperature for 5-10 h, drying after standing, and roasting at 550-750 ℃ to obtain Pt-WOx-ZrO2A carrier;
step 4, the Pt-WO prepared in the step 3x-ZrO2Adding the carrier into water, continuously stirring until the carrier is uniformly dispersed, then adding a solution containing the auxiliary metal, and continuously stirring for 0.5-2 hours; continuously stirring and adding a sodium borohydride solution until the pH value is 4-5, aging for 4-6 h, filtering, washing and drying; then reducing for 0.5-1 h at 300-400 ℃ in a hydrogen atmosphere to obtain a material named as an auxiliary agent-Pt-WOx-ZrO2A carrier.
6. The method for preparing the catalyst for preparing 1, 3-propanediol by hydrogenating glycerol according to claim 5, wherein: and the precursor of W in the step 2 is ammonium metatungstate.
7. The use of the catalyst of claim 1 in the hydrogenation of glycerol to 1, 3-propanediol, wherein: the specific reaction conditions are as follows: the reaction pressure is 5MPa, the reaction temperature is 150 ℃, and the reaction raw material is 10wt% of glycerol aqueous solution.
8. The use of the catalyst according to claim 7 in the reaction of hydrogenation of glycerol to 1, 3-propanediol, wherein: the reaction is carried out in a fixed bed reactor.
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