CN106944050B - A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol - Google Patents

A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol Download PDF

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CN106944050B
CN106944050B CN201710242714.7A CN201710242714A CN106944050B CN 106944050 B CN106944050 B CN 106944050B CN 201710242714 A CN201710242714 A CN 201710242714A CN 106944050 B CN106944050 B CN 106944050B
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carrier
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CN106944050A (en
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刘雷
冯尚华
董晋湘
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Taiyuan University of Technology
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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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention discloses a kind of catalyst and its preparation method and application for synthesizing 1,3- propylene glycol.Pt nano particle is carried on complex carrier WO by the catalyst3‑Al2O3‑SiO2On, it is denoted as Pt/WAlSi, the mass percent of Pt active component and complex carrier are as follows: Pt active component: 0.2%-10%, complex carrier: 90%-99.8%.The preparation method comprises the following steps: the solution of (1) mixing silica gel, tungsten presoma and aluminium presoma；(2) the above-mentioned mixed system of ammonia precipitation process is used；(3) complex carrier is made in aging, filtering, drying, roasting；(4) it is impregnated above-mentioned carrier with the solution containing Pt presoma and is dried, roasted, restored and be passivated and catalyst is made.Catalyst provided by the present invention and preparation method can convert 1,3-PD for selective glycerol in certain temperature and hydrogen pressure.

Description

A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol
Technical field
The present invention relates to a kind of catalyst and its preparation method and application for synthesizing 1,3-PD, belong to catalyst preparation Technical field.
Background technique
Terephthalic acid-1,3-propylene glycol ester (PTT, similarly hereinafter) is a kind of polyester of function admirable, such as excellent stretching And resilience performance, anti-ultraviolet radiation and anti-chlorine performance and good biodegradability.To which PTT is in clothes, engineering plastics Equal fields have wide practical use.1,3-PD is the primary raw material for producing PTT, industrial 1,3- of existing production the third two The method of alcohol includes the oxirane carbonyl hydrogenation technique of Shell company, the acrolein hydration of DuPont-Degussa company Hydrogenation method.The method for separately having microbe fermentation method and the direct hydrogenolysis of glycerol.
Epoxyethane method (US5,777,182) due to carbonylation process need to carry out under high pressure so that the requirement to equipment very Height, and catalyst is using hypertoxic ligand and at high price, thus the process costs are high and not environmentally；Acryladehyde method (US5,171, 892) raw material propylene aldehyde valence is not high, toxic, inflammable and explosive, easy to operate；Microbe fermentation method (CN1,327,001C) is although item Part is mild, raw material is renewable, but the concentration of target product in fermentation liquor is lower, and contains plurality of inorganic salt and mushroom, and 1,3- third Diol separation purification process is complicated, and low efficiency at high cost limits the extensive use of this method.The direct hydrogenolysis 1,3- third of glycerol The process of glycol is simple, and raw material is cheap and easy to get, great development prospect.
The research for preparing 1,3-PD about the direct hydrogenolysis of glycerol in recent years is more and more, these study multi-purpose Pt, Ru, Rh, Ir, Pd, Cu are as active component, and Au, Re are as addition metal, SiO2、ZrO2、Al2O3Equal acidic oxides or SiO2- TiO2、SiO2-Al2O3、ZrO2-Al2O3Equal composite oxides are in the form of solid acid as carrier, H2SO4、H2WO4、WO3Deng then As crucial addO-on therapy, the preparation method of complex carrier is mainly infusion process, but there is dipping unevenly, is acted on insecure The case where being lost to component.
Document (Chaminand J, Djakovitch L, Gallezot P, Marion P, Pinel C, Rosier C. Glycerol hydrogenolysis on heterogeneous catalysts[J]. Green Chem., 2004, 6 (8): 359-361.) in sulfolane solvent, with addition H2WO4Rh/C be catalyst, in 180 DEG C, initial hydrogen pressure 8.0 To hydrogenolysis of glycerin under conditions of MPa, the molar ratio of 1,3-PD and 1,2-PD can reach 2.0 in product.
Document (Kurasaks T, Maruyama H, Naribayashi I, Sasaki Y. Production of 1,3-propanediol by hydrogenolysis of glycerol catalyzed by Pt/WO3/ZrO2[J]. Catal. Commun., 2008,9 (6): 1360-1363.) in 1,3-Dimethyl-2-imidazolidinone (DMI) solvent, it uses WO3/ZrO2Supporting Pt is catalyst (Pt/WO3/ZrO2), after 443 K, 8.0 MPa of initial hydrogen pressure, 18 h of reaction time, 1, The yield of 3-propanediol is up to 24.2%.
Document (Jinho O, Saswati D, Hyunjoo L. Selective conversion of glycerol to 1,3-propanediol using Pt-sulfated zirconia[J]. Green Chem., 2011, 13, 2004-2007) in DMI solvent, with SO4 2--ZrO2Pt for load is catalyst (Pt/ SO4 2--ZrO2), at 170 DEG C, just It is 55.6% that beginning hydrogen, which presses the 1,3- propylene glycol yield obtained after 7.3 MPa, 24 h of reaction,.
However it is reaction medium that above-mentioned system, which is all made of organic solvent, or uses acid additives, is not met environmentally protective Requirement and severe corrosion to equipment.The complex carrier being related to be unfavorable for being uniformly distributed for component with prepared by infusion process, then When load active component, the interaction between the assembling form of active component and carrier and these two types of components is difficult to ensure, so that The stability of the catalyst prepared in aforementioned manners in the reaction is difficult to ensure.
Summary of the invention
The present invention is intended to provide a kind of catalyst and its preparation method and application for synthesizing 1,3-PD, solves compound The shortcomings that carrier each component is unevenly distributed improves the selection of stability and 1,3-PD of the catalyst in glycerine converting Property.
The present invention provides a kind of catalyst for synthesizing 1,3-PD, and Pt nano particle is carried on complex carrier WO3- Al2O3-SiO2On, it is denoted as Pt/WAlSi, the mass percent of Pt active component and complex carrier are as follows:
Pt active component: 0.2%-10%,
Complex carrier: 90% ~ 99.8%.
Further, the mass percent of Pt active component and complex carrier are as follows:
Pt active component: 0.5% ~ 4%,
Complex carrier: 96% ~ 99.5%.
In above-mentioned catalyst, the complex carrier WO3-Al2O3-SiO2In, the mass percent of three kinds of components is as follows: SiO2 Amount be fixed as 40%, WO3With Al2O3Total amount be fixed as 60%, WO3With Al2O3Mass ratio in 10:1 ~ 1:10.
The present invention provides the preparation methods of the catalyst of above-mentioned synthesis 1,3-PD, comprising the following steps:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
Silica solution is distributed in deionized water；Silica solution and the volume proportion of deionized water are 5.5:10 ~ 50；
ANN aluminium nitrate nonahydrate is weighed, is dissolved in deionized water, the silica solution after being slowly added to dilution continues stirring 30 ~ 60 Min is uniformly mixed it, and wherein the mass ratio of aluminium and silicon is that (aluminium is with Al by 0.01 ~ 1.5:12O3Meter, silicon is with SiO2Meter, similarly hereinafter).? Under the monitoring of pH meter, with the ammonium hydroxide of the speed instillation 15% ~ 25% of 0.5 ~ 3 mL/min to system pH=10.00 in Xiang Shangshu system ± 0.01, stop that ammonium hydroxide is added dropwise, continue 30 ~ 60 min of stirring, the aqueous solution of ammonium metatungstate is added into mixed liquor system, wherein tungsten (with WO3Meter) it with the mass ratio of silicon is 0.01 ~ 1.5:1, tungsten is with WO3Meter, continuing 30 ~ 60 min of stirring is uniformly mixed it, room temperature It is filtered after lower 12 ~ 24 h of aging, washing to wash water is in neutrality, and is dried in vacuo at 60 ~ 100 DEG C after drying 12 ~ 24 h at room temperature 6 ~ 12 h roast 3 h of drying solid at 500 ~ 900 DEG C, obtain WAlSi carrier；
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, being ultrasonically treated 5 ~ 30 Min stirs 4 ~ 12 h, stands 12 ~ 20 h, and 12 ~ 24 h are dried in vacuo at 40 ~ 70 DEG C, spare；
The H for being 1/9 with volume ratio2/N2Gaseous mixture reduction, reduction temperature are 300 ~ 400 DEG C, and the recovery time is 1 ~ 4 h, are turned For N2Protection is cooled to room temperature, then uses O2/N2Gaseous mixture is passivated, and 1% O is contained in gaseous mixture2, passivation time is 1 ~ 6 h；Obtain mesh Mark catalyst Pt/WAlSi.
The present invention provides application of the catalyst of above-mentioned synthesis 1,3- propylene glycol in hydrogenolysis of glycerin 1,3- propylene glycol.
In catalyst using upper, wherein the dosage of catalyst is on the basis of the quality of pure glycerin in reaction solution, catalyst: The mass ratio of glycerol is in 0.01 ~ 0.1:1, preferably 0.05:1；Initial hydrogen pressure is 4 ~ 8 MPa, preferably 6.0 MPa, reaction temperature Degree is 120 ~ 200 DEG C, preferably 160 DEG C；Reaction time is 8 ~ 24 h, preferably 12 h.
Batch tank reactor work can be used by the catalyst provided by the present invention for hydrogenolysis of glycerin 1,3- propylene glycol Skill, continuous fixed bed reactor technique or scale semi-batch reactor technique.Wherein preferred batch tank reactor process, can be with Extend the time of contact of catalyst and reactant, improves glycerol conversion yield.
In this method, the mass fraction of glycerol is all available in 3-90% in material liquid.Since water is needed in last handling process It removes, the content of glycerol in material liquid should be improved as far as possible to reduce energy consumption needed for 1,3-PD purification in product, be relatively suitble to Mass fraction be 40 ~ 70%.Although the glycerine water solution of low concentration can also be used, the energy consumption of post-processing will increase.
The application, specifically includes the following steps: 15 ~ 50 g matter are added in the stainless steel autoclave of 100 mL The glycerine water solution that score is 3 ~ 90% is measured, 0.02 ~ 1.5 g of catalyst in the above way prepared is added, closes autoclave, Successively use N2And H2The H of 4 ~ 8 MPa of initial hydrogen pressure is filled with after displacement gas reactor2, stirring rate is 500 ~ 1200 rpm, heating 8 ~ 24 h are reacted after to 120 ~ 200 DEG C.Gained reaction solution is centrifuged off catalyst, takes supernatant liquid filtering, uses liquid-phase chromatographic analysis Product composition, glycerol conversion yield 17.3 ~ 54.3%, 1,3-PD selectivity 10.3 ~ 55.9%, 1,2-PD selectivity 2.8% ~12.9%。
Beneficial effects of the present invention:
(1) the resulting catalyst of the present invention solves the disadvantage that constituting complex carrier each component is unevenly distributed, to improve The selectivity of stability and 1,3- propylene glycol of the catalyst in glycerine converting.
(2) when gained catalyst is used for hydrogenolysis catalysis of glycerin 1,3-PD, there is simple process, reaction condition temperature The advantages that few with other liquid phase by-products.
Specific embodiment
The present invention is further illustrated below by embodiment, but is not limited to following embodiment.
Embodiment 1:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
5.5 mL of silica solution is distributed in the deionized water of 20 mL；
0.74 g of ANN aluminium nitrate nonahydrate is weighed, is dissolved in 100 mL deionized waters, the silica solution after being slowly added to dilution, after 30 min of continuous stirring are uniformly mixed it；Under the monitoring of pH meter, 15% is instilled with the speed of 0.5 mL/min in Xiang Shangshu system Ammonium hydroxide to system pH=10.00 ± 0.01, stop that ammonium hydroxide is added dropwise, continue to stir 30 min, 0.12 g is added into mixed liquor system Ammonium metatungstate (being denoted as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 30 min of stirring is uniformly mixed it, room temperature It is filtered after lower 12 h of aging, washing is in neutrality to wash water, and it dries be dried in vacuo 6 h after 12 h at 70 DEG C at room temperature, 500 DEG C Lower 3 h of baked solid, obtains WAlSi carrier.
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, the amount load of Pt is 0.5%, 10 min are ultrasonically treated, 6 h are stirred, 18 h is stood, is dried in vacuo 12 h at 40 DEG C, it is spare.Use H2/N2(1/9, volume Than) gaseous mixture reduction, reduction temperature is 300 DEG C, and the recovery time is 4 h, switchs to N2Protection is cooled to room temperature, then uses O2/N2(1% O2Volume ratio) gaseous mixture passivation, passivation time is 2 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, the theoretical negative carrying capacity of Pt is 0.5%, and the dosage of carrier is 99.5%.
(3) evaluation of catalyst
Be added in the stainless steel autoclave of 100 mL 20 g mass fractions be 3% glycerine water solution, add with 0.06 g of catalyst of above method preparation, closes autoclave, successively uses N2And H2Initial hydrogen pressure 4 is filled with after displacement gas reactor The H of MPa2, stirring rate is 500 rpm, and 8 h are reacted after being heated to 120 DEG C.Gained reaction solution is centrifuged off catalyst, takes Clear liquid filtering, is formed, glycerol conversion yield 36.2% with liquid-phase chromatographic analysis product, 1,3-PD selectivity 45.4%, and 1,2- third Glycol selectivity 10.2%.
Embodiment 2:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
5.5 mL of silica solution is distributed in the deionized water of 20 mL；
2.9 g of ANN aluminium nitrate nonahydrate is weighed, is dissolved in 100 mL deionized waters, the silica solution after being slowly added to dilution, after 40 min of continuous stirring are uniformly mixed it；Under the monitoring of pH meter, 20% is instilled with the speed of 1.0 mL/min in Xiang Shangshu system Ammonium hydroxide to system pH=10.00 ± 0.01, stop that ammonium hydroxide is added dropwise, continue to stir 40 min, 0.24 g is added into mixed liquor system Ammonium metatungstate (being denoted as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 40 min of stirring is uniformly mixed it, room temperature It is filtered after lower 16 h of aging, washing is in neutrality to wash water, and it dries be dried in vacuo 6 h after 16 h at 60 DEG C at room temperature, 600 DEG C Lower 3 h of baked solid, obtains WAlSi carrier.
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, the amount load of Pt is 1%, 20 min are ultrasonically treated, 8 h are stirred, 16 h is stood, is dried in vacuo 16 h at 60 DEG C, it is spare.Use H2/N2(1/9) gaseous mixture is also Original, reduction temperature are 350 DEG C, and the recovery time is 3 h, switchs to N2Protection is cooled to room temperature, then uses O2/N2(1% O2) gaseous mixture Passivation, passivation time are 3 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, the theoretical negative carrying capacity of Pt is 1%, and the dosage of carrier is 99%.
(3) evaluation of catalyst
The glycerine water solution that 25 g mass fractions are 10% is added in the stainless steel autoclave of 100 mL, adds 0.25 g of catalyst in the above way prepared closes autoclave, successively uses N2And H2Initial hydrogen pressure is filled with after displacement gas reactor The H of 5 MPa2, stirring rate is 600 rpm, and 12 h are reacted after being heated to 140 DEG C.Gained reaction solution is centrifuged off catalyst, Supernatant liquid filtering is taken, is formed with liquid-phase chromatographic analysis product, glycerol conversion yield 47.7%, 1,3-PD selectivity 55.9%, 1, 2- propylene glycol selectivity 8.1%.
Embodiment 3:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
5.5 mL of silica solution is distributed in the deionized water of 20 mL；
2.2 g of ANN aluminium nitrate nonahydrate is weighed, is dissolved in 100 mL deionized waters, the silica solution after being slowly added to dilution, after 50 min of continuous stirring are uniformly mixed it；Under the monitoring of pH meter, 25% is instilled with the speed of 1.0 mL/min in Xiang Shangshu system Ammonium hydroxide to system pH=10.00 ± 0.01, stop that ammonium hydroxide is added dropwise, continue to stir 40 min, 0.35 g is added into mixed liquor system Ammonium metatungstate (being denoted as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 40 min of stirring is uniformly mixed it, room temperature It is filtered after lower 20 h of aging, washing is in neutrality to wash water, and it dries be dried in vacuo 6 h after 12 h at 80 DEG C at room temperature, 700 DEG C Lower 3 h of baked solid, obtains WAlSi carrier.
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, the amount load of Pt is 2%, 30 min are ultrasonically treated, 12 h are stirred, 12 h is stood, is dried in vacuo 20 h at 70 DEG C, it is spare.Use H2/N2(1/9) gaseous mixture is also Original, reduction temperature are 400 DEG C, and the recovery time is 2 h, switchs to N2Protection is cooled to room temperature, then uses O2/N2(1% O2) gaseous mixture Passivation, passivation time are 1 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, the theoretical negative carrying capacity of Pt is 4%, and the dosage of carrier is 96%.
(3) evaluation of catalyst
The glycerine water solution that 30 g mass fractions are 40% is added in the stainless steel autoclave of 100 mL, adds 0.96 g of catalyst in the above way prepared closes autoclave, successively uses N2And H2Initial hydrogen pressure is filled with after displacement gas reactor The H of 6 MPa2, stirring rate is 800 rpm, and 16 h are reacted after being heated to 180 DEG C.Gained reaction solution is centrifuged off catalyst, Supernatant liquid filtering is taken, is formed with liquid-phase chromatographic analysis product, glycerol conversion yield 32.8%, 1,3-PD selectivity 43.2%, 1, 2- propylene glycol selectivity 11.5%.
Embodiment 4:
(1) complex carrier WO3-Al2O3-SiO2Preparation (with 1 g carrier calculating):
5.5 mL of silica solution is distributed in the deionized water of 20 mL；
1.5 g of ANN aluminium nitrate nonahydrate is weighed, is dissolved in 100 mL deionized waters, the silica solution after being slowly added to dilution, after 60 min of continuous stirring are uniformly mixed it；Under the monitoring of pH meter, 20% is instilled with the speed of 2.0 mL/min in Xiang Shangshu system Ammonium hydroxide to system pH=10.00 ± 0.01, stop that ammonium hydroxide is added dropwise, continue to stir 50 min, 0.47 g is added into mixed liquor system Ammonium metatungstate (being denoted as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 50 min of stirring is uniformly mixed it, room temperature It is filtered after lower 24 h of aging, washing is in neutrality to wash water, and it dries be dried in vacuo 12 h after 20 h at 100 DEG C at room temperature, 800 3 h of baked solid at DEG C, obtains WAlSi carrier.
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, the amount load of Pt is 4%, 30 min are ultrasonically treated, 10 h are stirred, 14 h is stood, is dried in vacuo 20 h at 70 DEG C, it is spare.Use H2/N2(1/9) gaseous mixture is also Original, reduction temperature are 350 DEG C, and the recovery time is 2 h, switchs to N2Protection is cooled to room temperature, then uses O2/N2(1% O2) gaseous mixture Passivation, passivation time are 4 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, the theoretical negative carrying capacity of Pt is 8%, and the dosage of carrier is 92%.
(3) evaluation of catalyst
The glycerine water solution that 40 g mass fractions are 70% is added in the stainless steel autoclave of 100 mL, adds 0.84 g of catalyst in the above way prepared closes autoclave, successively uses N2And H2Initial hydrogen pressure is filled with after displacement gas reactor The H of 7 MPa2, stirring rate is 1000 rpm, and 20 h are reacted after being heated to 180 DEG C.Gained reaction solution is centrifuged off catalyst, Supernatant liquid filtering is taken, is formed with liquid-phase chromatographic analysis product, glycerol conversion yield 28.6%, 1,3-PD selectivity 40.9%, 1, 2- propylene glycol selectivity 10.5%.
Embodiment 5:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
5.5 mL of silica solution is distributed in the deionized water of 20 mL；
0.74 g of ANN aluminium nitrate nonahydrate is weighed, is dissolved in 100 mL deionized waters, the silica solution after being slowly added to dilution, after 30 min of continuous stirring are uniformly mixed it；Under the monitoring of pH meter, 25% is instilled with the speed of 3.0 mL/min in Xiang Shangshu system Ammonium hydroxide to system pH=10.00 ± 0.01, stop that ammonium hydroxide is added dropwise, continue to stir 60 min, 0.59 g is added into mixed liquor system Ammonium metatungstate (being denoted as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 60 min of stirring is uniformly mixed it, room temperature It is filtered after lower 12 h of aging, washing is in neutrality to wash water, and it dries be dried in vacuo 12 h after 24 h at 80 DEG C at room temperature, 900 3 h of baked solid at DEG C, obtains WAlSi carrier.
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, the amount load of Pt is 3%, 5 min are ultrasonically treated, 4 h are stirred, 20 h is stood, is dried in vacuo 16 h at 50 DEG C, it is spare.Use H2/N2(1/9) gaseous mixture is also Original, reduction temperature are 350 DEG C, and the recovery time is 2 h, switchs to N2Protection is cooled to room temperature, then uses O2/N2(1% O2) gaseous mixture Passivation, passivation time are 6 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, the theoretical negative carrying capacity of Pt is 10%, and the dosage of carrier is 90%.
(3) evaluation of catalyst
The glycerine water solution that 50 g mass fractions are 40% is added in the stainless steel autoclave of 100 mL, adds 1.0 g of catalyst in the above way prepared closes autoclave, successively uses N2And H2Initial hydrogen pressure 8 is filled with after displacement gas reactor The H of MPa2, stirring rate is 1200 rpm, and 24 h are reacted after being heated to 200 DEG C.Gained reaction solution is centrifuged off catalyst, takes Supernatant liquid filtering is formed, glycerol conversion yield 28.4% with liquid-phase chromatographic analysis product, 1,3-PD selectivity 39.0%, and 1,2- Propylene glycol selectivity 9.8%.

Claims (9)

1. a kind of catalyst for synthesizing 1,3-PD, it is characterised in that: Pt nano particle is carried on complex carrier WO3- Al2O3-SiO2On, it is denoted as Pt/WAlSi, the mass percent of Pt active component and complex carrier are as follows:
Pt active component: 0.2%-10%,
Complex carrier: 90%-99.8%；
The preparation method of the catalyst of the synthesis 1,3-PD, comprising the following steps:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
Silica solution is distributed in deionized water；Silica solution and the volume proportion of deionized water are 5.5:10 ~ 50；
ANN aluminium nitrate nonahydrate is weighed, is dissolved in deionized water, in the silica solution after being slowly added to dilution, continues stirring 30 ~ 60 Min is uniformly mixed it, and wherein the mass ratio of aluminium and silicon is 0.01 ~ 1.5:1, and aluminium is with Al2O3Meter, silicon is with SiO2Meter, in pH meter 15% ~ 25% ammonium hydroxide is instilled with the speed of 0.5 ~ 3 mL/min under monitoring, in Xiang Shangshu system to system pH=10.00 ± 0.01, Stop that ammonium hydroxide is added dropwise, continue 30 ~ 60 min of stirring, the aqueous solution of ammonium metatungstate is added into mixed liquor system, wherein tungsten and silicon Mass ratio is 0.01 ~ 1.5:1, and tungsten is with WO3Meter, continuing 30 ~ 60 min of stirring is uniformly mixed it, at room temperature 12 ~ 24 h of aging After filter, washing is in neutrality to wash water, dry be dried in vacuo 6 ~ 12 h after 12 ~ 24 h at 60 ~ 100 DEG C at room temperature, 500 ~ 3 h of drying solid is roasted at 900 DEG C, obtains WAlSi carrier；
(2) catalyst Pt/WAlSi preparation
The presoma of Pt/WAlSi is prepared with infusion process: by the aqueous solution of carrier impregnation to Pt, being ultrasonically treated 5 ~ 30 min, is stirred 4 ~ 12 h are mixed, 12 ~ 20 h are stood, 12 ~ 24 h are dried in vacuo at 40 ~ 70 DEG C, it is spare；
The H for being 1:9 with volume ratio2/N2Gaseous mixture reduction, reduction temperature are 300 ~ 400 DEG C, and the recovery time is 1 ~ 4 h, switchs to N2 Protection is cooled to room temperature, then uses O2/N2Gaseous mixture is passivated, the O for being 1% containing volume ratio in gaseous mixture2, passivation time is 1 ~ 6 h；? To final catalyst Pt/WAlSi.
2. the catalyst of synthesis 1,3-PD according to claim 1, it is characterised in that: Pt active component and compound load The mass percent of body are as follows:
Pt active component: 0.5% ~ 4%,
Complex carrier: 96% ~ 99.5%.
3. the catalyst of synthesis 1,3-PD according to claim 1, it is characterised in that: the complex carrier WO3- Al2O3-SiO2In, the mass percent of three kinds of components is as follows: SiO2Amount be 40%, WO3With Al2O3Total amount be 60%, WO3With Al2O3Mass ratio in 10:1 ~ 1:10.
4. the catalyst of synthesis 1,3-PD according to claim 1, it is characterised in that: in step (1), aluminium and silicon Mass ratio is 0.25 ~ 0.8:1；The mass ratio of tungsten and silicon is 0.25 ~ 0.8:1.
5. the catalyst of synthesis 1,3-PD according to claim 1, it is characterised in that: ageing time is 12 ~ 20 h, Drying time is 12 ~ 20 h at room temperature, and vacuum drying time is 8 ~ 10 h, and vacuum drying temperature is 70 ~ 80 DEG C, roasts drying Temperature is 600 ~ 800 DEG C.
6. a kind of catalyst of the described in any item synthesis 1,3- propylene glycol of claim 1 ~ 3 is in hydrogenolysis of glycerin 1,3- propylene glycol In application.
7. application according to claim 6, it is characterised in that: the dosage of catalyst is with the quality of pure glycerin in reaction solution Benchmark, catalyst: the mass fraction of the mass ratio of glycerol glycerol in 0.01 ~ 0.1:1, material liquid is 3% ~ 90%, initial hydrogen pressure For 4 ~ 8 MPa, reaction temperature is 120 ~ 200 DEG C, and the reaction time is 8 ~ 24 h；Using batch tank reactor process, continuous flow Dynamic fixed bed reactors technique or scale semi-batch reactor technique.
8. application according to claim 7, it is characterised in that: the catalyst: the mass ratio of glycerol is 0.05:1, raw material For the mass fraction of pure glycerin in 40-70%, initial hydrogen pressure is 6.0 MPa in liquid, and reaction temperature is 160 DEG C；Reaction time is 12 h；Using batch tank reactor process.
9. application according to claim 6, it is characterised in that: specifically includes the following steps: the stainless steel in 100 mL is high The glycerine water solution for being added that 15 ~ 50 g mass fractions are 3 ~ 90% in reaction kettle is pressed, the catalyst of synthesis 1,3-PD is added 0.02 ~ 1.5 g closes autoclave, successively uses N2And H2The H of 4 ~ 8 MPa of initial hydrogen pressure is filled with after displacement gas reactor2, stirring speed Rate is 500 ~ 1200 rpm, and 8 ~ 24 h are reacted after being heated to 120 ~ 200 DEG C；Gained reaction solution is centrifuged off catalyst, takes supernatant Liquid filtering, is formed, glycerol conversion yield 17.3 ~ 54.3% with liquid-phase chromatographic analysis product, and 1,3-PD selectivity 10.3 ~ 55.9%, 1,2-PD selectivity 2.8% ~ 12.9%.
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