CN106944050A - A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application - Google Patents
A kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application Download PDFInfo
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of catalyst for synthesizing 1,3 propane diols and its preparation method and application.Pt nano particles are carried on complex carrier WO by the catalyst3‑Al2O3‑SiO2On, it is designated as Pt/WAlSi, the mass percent of Pt active components and complex carrier is:Pt active components:0.2% 10%, complex carrier:90%‑99.8%.Preparation method is:(1) solution of 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) impregnated above-mentioned carrier with the solution containing Pt presomas and dried, be calcined, reduced and be passivated and catalyst is made.Catalyst provided by the present invention and preparation method, can be converted into 1,3 propane diols in certain temperature and hydrogen pressure by selective glycerol.
Description
Technical field
The present invention relates to a kind of catalyst for synthesizing 1,3-PD and its preparation method and application, belong to catalyst preparation
Technical field.
Background technology
Terephthalic acid-1,3-propylene glycol ester (PTT, similarly hereinafter) is a kind of polyester of function admirable, such as excellent stretching
And rebound performance, anti-ultraviolet radiation and anti-chlorine performance and good biodegradability.So as to which PTT is in clothes, engineering plastics
Have wide practical use Deng field.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 companies, the acrolein hydration of DuPont-Degussa companies
Hydrogenation method.The another method for having microbe fermentation method and the direct hydrogenolysis of glycerine.
Epoxyethane method (US5,777,182) need to be caused requirement to equipment very under high pressure due to carbonylation process
Height, and catalyst is using hypertoxic part and price is high, thus the process costs are high and not environmentally;Acryladehyde method (US5,171,
892) raw material propylene aldehyde valency is high, poisonous, inflammable and explosive, not easy to operate;Microbe fermentation method (CN1,327,001C) is although bar
Part is gentle, raw material is renewable, but the concentration of target product in fermentation liquor is relatively low, and contains plurality of inorganic salt and mushroom, 1,3- third
Diol separation purification process is complicated, and cost high efficiency is low, limits the extensive use of this method.The direct hydrogenolysis 1,3- third of glycerine
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 on the direct hydrogenolysis of glycerine in recent years is more and more, these study multiplex Pt, Ru,
Rh, Ir, Pd, Cu are used as addition metal, SiO as active component, Au, Re2、ZrO2、Al2O3Deng acidic oxide or SiO2-
TiO2、SiO2-Al2O3、ZrO2-Al2O3Carrier, H are used as using in the form of solid acid Deng composite oxides2SO4、H2WO4、WO3Deng then
As crucial addO-on therapy, the preparation method of complex carrier is mainly infusion process, but uneven in the presence of impregnating, and acts on insecure
Situation about being lost in so as 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 mol 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 DMI (DMI) solvent, use
WO3/ZrO2Supporting Pt is catalyst (Pt/WO3/ZrO2), after 443 K, the MPa of initial hydrogen pressure 8.0, the h of reaction time 18,1,
The yield of ammediol 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 solvents, with SO4 2--ZrO2It is catalyst (Pt/ SO for the Pt of load4 2--ZrO2), at 170 DEG C, just
It is 55.6% that beginning hydrogen, which presses the 1,3- propane diols yield obtained after 7.3 MPa, 24 h of reaction,.
But above-mentioned system uses organic solvent for reaction medium, or acid additives are used, do not meet environmental protection
Requirement and serious to equipment corrosion.The complex carrier being related to is prepared with infusion process, is unfavorable for being uniformly distributed for component, then
During load active component, the interaction between the assembling form of active component and carrier and this two classes component is difficult to ensure that so that
The stability of the catalyst prepared in aforementioned manners in the reaction is difficult to ensure that.
The content of the invention
The present invention is intended to provide a kind of catalyst for synthesizing 1,3-PD and its preparation method and application, is solved compound
Carrier each component shortcoming pockety, improves the selection of stability and 1,3-PD of the catalyst in glycerine converting
Property.
The invention provides a kind of catalyst for synthesizing 1,3-PD, Pt nano particles are carried on complex carrier WO3-
Al2O3-SiO2On, it is designated as Pt/WAlSi, the mass percent of Pt active components and complex carrier is:
Pt active components:0.2%-10%,
Complex carrier:90%~99.8%.
Further, Pt active components and the mass percent of complex carrier are:
Pt active components: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 10:1~1:10.
The invention provides the preparation method of the catalyst of above-mentioned synthesis 1,3-PD, comprise the following steps:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
Ludox is distributed in deionized water;Ludox and the volume proportion of deionized water are 5.5:10~50;
ANN aluminium nitrate nonahydrate is weighed, is dissolved in deionized water, the Ludox after dilution is slowly added to, continues to stir 30 ~ 60 min
It is well mixed it, wherein the mass ratio of aluminium and silicon is 0.01 ~ 1.5:1 (aluminium is with Al2O3Meter, silicon is with SiO2Meter, similarly hereinafter).In pH
Under the monitoring of meter, instilled into above-mentioned system with 0.5 ~ 3 mL/min speed 15% ~ 25% ammoniacal liquor to system pH=10.00 ±
0.01, stop that ammoniacal liquor is added dropwise, continue to stir 30 ~ 60 min, the aqueous solution of ammonium metatungstate, wherein tungsten are added into mixed liquor system
(with WO3Meter) with the mass ratio of silicon it is 0.01 ~ 1.5:1, tungsten is with WO3Meter, continuing 30 ~ 60 min of stirring is well mixed it, room temperature
Filtering after the lower h of aging 12 ~ 24, washing to wash water dries 12 ~ 24 h after vacuum drying at 60 ~ 100 DEG C at room temperature in neutrality
6 ~ 12 h, the h of drying solid 3 is calcined at 500 ~ 900 DEG C, WAlSi carriers are obtained;
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, ultrasonically treated 5 ~ 30 min is stirred
4 ~ 12 h are mixed, stands and 12 ~ 24 h is dried in vacuo at 12 ~ 20 h, 40 ~ 70 DEG C, it is standby;
With the H that volume ratio is 1/92/N2Gaseous mixture is reduced, and reduction temperature is 300 ~ 400 DEG C, and the recovery time is 1 ~ 4 h, switchs to N2
Protection is cooled to normal temperature, then uses O2/N2Gaseous mixture is passivated, and 1% O is contained in gaseous mixture2, passivation time is 1 ~ 6 h;Target is obtained to urge
Agent Pt/WAlSi.
The invention provides application of the catalyst of above-mentioned synthesis 1,3- propane diols in hydrogenolysis of glycerin 1,3- propane diols.
In the application of catalyst, wherein the consumption of catalyst is on the basis of the quality of pure glycerin in reaction solution, catalyst:
The mass ratio of glycerine is 0.01 ~ 0.1:1, preferably 0.05:1;Initial hydrogen pressure is 4 ~ 8 MPa, preferably 6.0 MPa, reaction temperature
Spend for 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- propane diols
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, improve glycerol conversion yield.
In this method, the mass fraction of glycerine all can use in 3-90% in material liquid.Because water is needed in last handling process
Remove, should try one's best and improve the content of glycerine in material liquid to reduce the energy consumption in product needed for 1,3-PD purification, relatively be adapted to
Mass fraction be 40 ~ 70%.Although can also use the glycerine water solution of low concentration, the energy consumption of post processing can be increased.
Described application, specifically includes following steps:15 ~ 50 g matter are added in 100 mL stainless steel autoclave
The glycerine water solution that fraction is 3 ~ 90% is measured, the g of catalyst 0.02 ~ 1.5 of method described above preparation is added, autoclave is closed,
N is used successively2And H2The MPa of initial hydrogen pressure 4 ~ 8 H is filled with after displacement gas reactor2, stir speed (S.S.) 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 is constituted, 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) catalyst obtained by the present invention, solves to constitute complex carrier each component shortcoming pockety, is urged so as to improve
The selectivity of stability and 1,3- propane diols of the agent in glycerine converting.
(2) it is simple with technique when gained catalyst is used for hydrogenolysis catalysis of glycerin 1,3-PD, reaction condition temperature
With, other liquid phase accessory substances it is few the advantages of.
Embodiment
The present invention is further illustrated below by embodiment, but is not limited to following examples.
Embodiment 1:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
The mL of Ludox 5.5 is distributed in 20 mL deionized water;
The g of ANN aluminium nitrate nonahydrate 0.74 is weighed, is dissolved in 100 mL deionized waters, the Ludox after dilution is slowly added to, continues to stir
Mixing 30 min is well mixed it;Under the monitoring of pH meter, into above-mentioned system with the ammonia of 0.5 mL/min speed instillation 15%
Water to system pH=10.00 ± 0.01 stops that ammoniacal liquor is added dropwise, and continues to stir 30 min, the inclined tungsten of 0.12 g is added into mixed liquor system
Sour ammonium (being designated as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 30 min of stirring is well mixed it, at room temperature always
Change after 12 h filter, washing to wash water in neutrality, at room temperature dry 12 h after be dried in vacuo at 70 DEG C at 6 h, 500 DEG C roast
The h of solid 3 is burnt, WAlSi carriers are obtained.
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, Pt amount load is 0.5%, is surpassed
The min of sonication 10, stirs 6 h, to stand and be dried in vacuo 12 h at 18 h, 40 DEG C, standby.Use H2/N2(1/9, volume ratio) is mixed
Gas is reduced, and reduction temperature is 300 DEG C, and the recovery time is 4 h, switchs to N2Protection is cooled to normal temperature, then uses O2/N2(1% O2Body
Product ratio) gaseous mixture passivation, passivation time is 2 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, Pt theoretical negative carrying capacity is 0.5%, and the consumption of carrier is 99.5%.
(3) evaluation of catalyst
The glycerine water solution that 20 g mass fractions are 3% is added in 100 mL stainless steel autoclave, is added with above-mentioned
The g of catalyst 0.06 prepared by method, closes autoclave, N is used successively2And H2The MPa of initial hydrogen pressure 4 is filled with after displacement gas reactor
H2, stir speed (S.S.) is 500 rpm, is heated to after 120 DEG C reacting 8 h.Gained reaction solution is centrifuged off catalyst, takes supernatant
Liquid is filtered, and is constituted with liquid-phase chromatographic analysis product, glycerol conversion yield 36.2%, 1,3-PD selectivity 45.4%, 1,2- the third two
Alcohol selectivity 10.2%.
Embodiment 2:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
The mL of Ludox 5.5 is distributed in 20 mL deionized water;
The g of ANN aluminium nitrate nonahydrate 2.9 is weighed, is dissolved in 100 mL deionized waters, the Ludox after dilution is slowly added to, continues to stir
Mixing 40 min is well mixed it;Under the monitoring of pH meter, into above-mentioned system with the ammonia of 1.0 mL/min speed instillation 20%
Water to system pH=10.00 ± 0.01 stops that ammoniacal liquor is added dropwise, and continues to stir 40 min, the inclined tungsten of 0.24 g is added into mixed liquor system
Sour ammonium (being designated as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 40 min of stirring is well mixed it, at room temperature always
Change after 16 h filter, washing to wash water in neutrality, at room temperature dry 16 h after be dried in vacuo at 60 DEG C at 6 h, 600 DEG C roast
The h of solid 3 is burnt, WAlSi carriers are obtained.
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, Pt amount load is 1%, ultrasound
20 min are handled, 8 h are stirred, to stand and be dried in vacuo 16 h at 16 h, 60 DEG C, it is standby.Use H2/N2(1/9) gaseous mixture is reduced, also
Former temperature is 350 DEG C, and the recovery time is 3 h, switchs to N2Protection is cooled to normal temperature, then uses O2/N2(1% O2) gaseous mixture passivation,
Passivation time is 3 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, Pt theoretical negative carrying capacity is 1%, and the consumption of carrier is 99%.
(3) evaluation of catalyst
The glycerine water solution that 25 g mass fractions are 10% is added in 100 mL stainless steel autoclave, the above is added
The g of catalyst 0.25 of method preparation is stated, autoclave is closed, N is used successively2And H2Initial hydrogen pressure 5 is filled with after displacement gas reactor
MPa H2, stir speed (S.S.) is 600 rpm, is heated to after 140 DEG C reacting 12 h.Gained reaction solution is centrifuged off catalyst, takes
Supernatant liquid filtering, is constituted, glycerol conversion yield 47.7% with liquid-phase chromatographic analysis product, 1,3-PD selectivity 55.9%, 1,2-
Propane diols selectivity 8.1%.
Embodiment 3:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
The mL of Ludox 5.5 is distributed in 20 mL deionized water;
The g of ANN aluminium nitrate nonahydrate 2.2 is weighed, is dissolved in 100 mL deionized waters, the Ludox after dilution is slowly added to, continues to stir
Mixing 50 min is well mixed it;Under the monitoring of pH meter, into above-mentioned system with the ammonia of 1.0 mL/min speed instillation 25%
Water to system pH=10.00 ± 0.01 stops that ammoniacal liquor is added dropwise, and continues to stir 40 min, the inclined tungsten of 0.35 g is added into mixed liquor system
Sour ammonium (being designated as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 40 min of stirring is well mixed it, at room temperature always
Change after 20 h filter, washing to wash water in neutrality, at room temperature dry 12 h after be dried in vacuo at 80 DEG C at 6 h, 700 DEG C roast
The h of solid 3 is burnt, WAlSi carriers are obtained.
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, Pt amount load is 2%, ultrasound
30 min are handled, 12 h are stirred, to stand and be dried in vacuo 20 h at 12 h, 70 DEG C, it is standby.Use H2/N2(1/9) gaseous mixture is reduced,
Reduction temperature is 400 DEG C, and the recovery time is 2 h, switchs to N2Protection is cooled to normal temperature, then uses O2/N2(1% O2) gaseous mixture is blunt
Change, passivation time is 1 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, Pt theoretical negative carrying capacity is 4%, and the consumption of carrier is 96%.
(3) evaluation of catalyst
The glycerine water solution that 30 g mass fractions are 40% is added in 100 mL stainless steel autoclave, the above is added
The g of catalyst 0.96 of method preparation is stated, autoclave is closed, N is used successively2And H2Initial hydrogen pressure 6 is filled with after displacement gas reactor
MPa H2, stir speed (S.S.) is 800 rpm, is heated to after 180 DEG C reacting 16 h.Gained reaction solution is centrifuged off catalyst, takes
Supernatant liquid filtering, is constituted, glycerol conversion yield 32.8% with liquid-phase chromatographic analysis product, 1,3-PD selectivity 43.2%, 1,2-
Propane diols selectivity 11.5%.
Embodiment 4:
(1) complex carrier WO3-Al2O3-SiO2Preparation (with 1 g carriers calculate):
The mL of Ludox 5.5 is distributed in 20 mL deionized water;
The g of ANN aluminium nitrate nonahydrate 1.5 is weighed, is dissolved in 100 mL deionized waters, the Ludox after dilution is slowly added to, continues to stir
Mixing 60 min is well mixed it;Under the monitoring of pH meter, into above-mentioned system with the ammonia of 2.0 mL/min speed instillation 20%
Water to system pH=10.00 ± 0.01 stops that ammoniacal liquor is added dropwise, and continues to stir 50 min, the inclined tungsten of 0.47 g is added into mixed liquor system
Sour ammonium (being designated as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 50 min of stirring is well mixed it, at room temperature always
Change and filtered after 24 h, washing to wash water dries 20 h after being dried in vacuo at 100 DEG C at 12 h, 800 DEG C at room temperature in neutrality
The h of baked solid 3, obtains WAlSi carriers.
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, Pt amount load is 4%, ultrasound
30 min are handled, 10 h are stirred, to stand and be dried in vacuo 20 h at 14 h, 70 DEG C, it is standby.Use H2/N2(1/9) gaseous mixture is reduced,
Reduction temperature is 350 DEG C, and the recovery time is 2 h, switchs to N2Protection is cooled to normal temperature, then uses O2/N2(1% O2) gaseous mixture is blunt
Change, passivation time is 4 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, Pt theoretical negative carrying capacity is 8%, and the consumption of carrier is 92%.
(3) evaluation of catalyst
The glycerine water solution that 40 g mass fractions are 70% is added in 100 mL stainless steel autoclave, the above is added
The g of catalyst 0.84 of method preparation is stated, autoclave is closed, N is used successively2And H2Initial hydrogen pressure 7 is filled with after displacement gas reactor
MPa H2, stir speed (S.S.) is 1000 rpm, is heated to after 180 DEG C reacting 20 h.Gained reaction solution is centrifuged off catalyst, takes
Supernatant liquid filtering, is constituted, glycerol conversion yield 28.6% with liquid-phase chromatographic analysis product, 1,3-PD selectivity 40.9%, 1,2-
Propane diols selectivity 10.5%.
Embodiment 5:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
The mL of Ludox 5.5 is distributed in 20 mL deionized water;
The g of ANN aluminium nitrate nonahydrate 0.74 is weighed, is dissolved in 100 mL deionized waters, the Ludox after dilution is slowly added to, continues to stir
Mixing 30 min is well mixed it;Under the monitoring of pH meter, into above-mentioned system with the ammonia of 3.0 mL/min speed instillation 25%
Water to system pH=10.00 ± 0.01 stops that ammoniacal liquor is added dropwise, and continues to stir 60 min, the inclined tungsten of 0.59 g is added into mixed liquor system
Sour ammonium (being designated as AMT, similarly hereinafter) is dissolved in the solution of 20 mL deionized waters, and continuing 60 min of stirring is well mixed it, at room temperature always
Change and filtered after 12 h, washing to wash water dries 24 h after being dried in vacuo at 80 DEG C at 12 h, 900 DEG C at room temperature in neutrality
The h of baked solid 3, obtains WAlSi carriers.
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, Pt amount load is 3%, ultrasound
5 min are handled, 4 h are stirred, to stand and be dried in vacuo 16 h at 20 h, 50 DEG C, it is standby.Use H2/N2(1/9) gaseous mixture is reduced, also
Former temperature is 350 DEG C, and the recovery time is 2 h, switchs to N2Protection is cooled to normal temperature, then uses O2/N2(1% O2) gaseous mixture passivation,
Passivation time is 6 h.Obtain final catalyst Pt/WAlSi.
In the catalyst of preparation, Pt theoretical negative carrying capacity is 10%, and the consumption of carrier is 90%.
(3) evaluation of catalyst
The glycerine water solution that 50 g mass fractions are 40% is added in 100 mL stainless steel autoclave, the above is added
The g of catalyst 1.0 of method preparation is stated, autoclave is closed, N is used successively2And H2The MPa of initial hydrogen pressure 8 is filled with after displacement gas reactor
H2, stir speed (S.S.) is 1200 rpm, is heated to after 200 DEG C reacting 24 h.Gained reaction solution is centrifuged off catalyst, takes
Clear liquid is filtered, and is constituted with liquid-phase chromatographic analysis product, glycerol conversion yield 28.4%, 1,3-PD selectivity 39.0%, 1,2- third
Glycol selectivity 9.8%.
Claims (10)
1. a kind of catalyst for synthesizing 1,3-PD, it is characterised in that:Pt nano particles are carried on complex carrier WO3-
Al2O3-SiO2On, it is designated as Pt/WAlSi, the mass percent of Pt active components and complex carrier is:
Pt active components:0.2%-10%,
Complex carrier:90%-99.8%.
2. the catalyst of synthesis 1,3-PD according to claim 1, it is characterised in that:Pt active components and compound load
The mass percent of body is:
Pt active components: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 10:1~1:10.
4. a kind of preparation method of the catalyst of the synthesis 1,3-PD described in any one of claim 1 ~ 3, it is characterised in that:
Comprise the following steps:
(1) complex carrier WO3-Al2O3-SiO2Preparation:
Ludox is distributed in deionized water;Ludox and the volume proportion of deionized water are 5.5:10~50;
ANN aluminium nitrate nonahydrate is weighed, is dissolved in deionized water, is slowly added in the Ludox after dilution, continues to stir 30 ~ 60
Min is well mixed it, and wherein the mass ratio of aluminium and silicon is 0.01 ~ 1.5:1, aluminium is with Al2O3Meter, silicon is with SiO2Meter, in pH meter
Under monitoring, into above-mentioned system with the ammoniacal liquor of 0.5 ~ 3 mL/min speed instillation 15% ~ 25% to system pH=10.00 ± 0.01,
Stop that ammoniacal liquor is added dropwise, continue to stir 30 ~ 60 min, the aqueous solution of addition ammonium metatungstate into mixed liquor system, wherein tungsten and silicon
Mass ratio is 0.01 ~ 1.5:1, tungsten is with WO3Meter, continuing 30 ~ 60 min of stirring is well mixed it, at room temperature the h of aging 12 ~ 24
After filter, washing to wash water in neutrality, at room temperature dry 12 ~ 24 h after at 60 ~ 100 DEG C be dried in vacuo 6 ~ 12 h, 500 ~
The h of drying solid 3 is calcined at 900 DEG C, WAlSi carriers are obtained;
(2) catalyst Pt/WAlSi preparation
Pt/WAlSi presoma is prepared with infusion process:By in the aqueous solution of carrier impregnation to Pt, ultrasonically treated 5 ~ 30 min is stirred
4 ~ 12 h are mixed, stands and 12 ~ 24 h is dried in vacuo at 12 ~ 20 h, 40 ~ 70 DEG C, it is standby;
It is 1 with volume ratio:9 H2/N2Gaseous mixture is reduced, and reduction temperature is 300 ~ 400 DEG C, and the recovery time is 1 ~ 4 h, switchs to N2
Protection is cooled to normal temperature, then uses O2/N2Gaseous mixture is passivated, containing the O that volume ratio is 1% in gaseous mixture2, passivation time is 1 ~ 6 h;
To final catalyst Pt/WAlSi.
5. the preparation method of the catalyst of synthesis 1,3-PD according to claim 4, it is characterised in that:Step (1)
In, the mass ratio of aluminium and silicon is 0.25 ~ 0.8:1;The mass ratio of tungsten and silicon is 0.25 ~ 0.8:1.
6. the preparation method of the catalyst of synthesis 1,3-PD according to claim 4, it is characterised in that:Ageing time
For 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, roasting drying temperature is 600 ~ 800 DEG C.
7. a kind of catalyst of the synthesis 1,3- propane diols described in any one of claim 1 ~ 3 is in hydrogenolysis of glycerin 1,3- propane diols
In application.
8. application according to claim 7, it is characterised in that:The quality of the consumption of catalyst pure glycerin using in reaction solution as
Benchmark, catalyst:The mass ratio of glycerine is 0.01 ~ 0.1:1, the mass fraction of glycerine is in 3% ~ 90%, initial hydrogen pressure in material liquid
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 stream
Dynamic fixed bed reactors technique or scale semi-batch reactor technique.
9. application according to claim 8, it is characterised in that:The catalyst:The mass ratio of glycerine is 0.05:1, raw material
The mass fraction of pure glycerin is in 40-70% in liquid, and initial hydrogen pressure is 6.0 MPa, and reaction temperature is 160 DEG C;Reaction time is 12
h;Using batch tank reactor process.
10. application according to claim 7, it is characterised in that:Specifically include following steps:It is high in 100 mL stainless steel
The glycerine water solution for adding that 15 ~ 50 g mass fractions are 3 ~ 90% in reactor is pressed, the catalyst of method described above preparation is added
0.02 ~ 1.5 g, closes autoclave, N is used successively2And H2The MPa of initial hydrogen pressure 4 ~ 8 H is filled with after displacement gas reactor2, stirring speed
Rate is 500 ~ 1200 rpm, is heated to after 120 ~ 200 DEG C reacting 8 ~ 24 h;Gained reaction solution is centrifuged off catalyst, takes supernatant
Liquid is filtered, and is constituted with liquid-phase chromatographic analysis product, glycerol conversion yield 17.3 ~ 54.3%, and 1,3-PD selectivity 10.3 ~
55.9%, 1,2-PD selectivity 2.8% ~ 12.9%.
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CN110102296A (en) * | 2019-05-16 | 2019-08-09 | 广东工业大学 | A kind of catalyst and preparation method thereof for synthesizing 1,5-PD |
CN115041193A (en) * | 2022-07-28 | 2022-09-13 | 山东京博石油化工有限公司 | Catalyst and preparation method and application thereof |
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