CN108144609A - A kind of hydrogenolysis of glycerin prepares the preparation method of the catalyst of 1,3- propylene glycol - Google Patents
A kind of hydrogenolysis of glycerin prepares the preparation method of the catalyst of 1,3- propylene glycol Download PDFInfo
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- CN108144609A CN108144609A CN201611098746.6A CN201611098746A CN108144609A CN 108144609 A CN108144609 A CN 108144609A CN 201611098746 A CN201611098746 A CN 201611098746A CN 108144609 A CN108144609 A CN 108144609A
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- hydrogenolysis
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 26
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 26
- 239000003054 catalyst Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000012279 sodium borohydride Substances 0.000 claims description 9
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000000366 colloid method Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000009790 rate-determining step (RDS) Methods 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A kind of hydrogenolysis of glycerin prepares the preparation method of the catalyst of 1,3 propylene glycol, it is characterised in for preparing the Pt nanoparticle that size is smaller and particle diameter distribution is more uniform using colloid method, the dispersion degree of platinum can be improved significantly.It is supported on WO laterx/γ‑Al2O3On, it is reacted in a hydrogen atmosphere with glycerine water solution after processing.Wherein WOx/γ‑Al2O3It is prepared by equi-volume impregnating;The method of hydrogenolysis of glycerin is:Using glycerine water solution and hydrogen as raw material, by being contacted with a certain amount of catalyst, under high pressure, 180 DEG C of progress liquid phase hydrogenolysis.Extraordinary activity is shown in hydrogenolysis of glycerin reaction using catalyst prepared by this method, there is impetus from the industrialized production of 1,3 propylene glycol of biology base system for catalysis method.
Description
Technical field
1,3-PD body is prepared the present invention relates to a kind of preparation method of catalyst more particularly in glycerine liquid phase hydrogenolysis
The application of system
Background technology
1,3-PD is a kind of important industrial chemicals, is one of six big petrochemical industry new products generally acknowledged in the world at present,
Available for synthesis cosmetics, brake fluid and the excellent new type polyester fiber (PTT) of ink, particularly manufacturing property is printed, is
" omnipotent raw material ".Therefore in following one period 1, the great market prospects of 3-PDO, synthetic method and application study are at home and abroad
It is highly valued.
The Degussa companies of Germany, the Shell companies in the U.S. and E.I.Du Pont Company have monopolized the market of 1,3-PD, state
Interior 1,3-PDO yield is considerably less, and 1, the 3-PDO in China relies primarily on foreign import.At least 300,000 tons/year of 2005 Nian Qi China
The market demand, and the demand of 1,3-PDO will increase substantially.Relation between supply and demand will further deteriorate, and lead to 1,3-PDO
Price always in 50,000/t or so, hinder 1,3-PDO as staple commodities.The 1,3-PDO synthetic routes tool of developing low-cost
There is very important meaning.
Glycerine is the Main By product of oil prodution industry, and in addition the popularization of biodiesel technology is largely cheap by by-product
Glycerine becomes the desirable feedstock of production 1,3-PDO.At present, the industrialized preparing process of 1,3-PDO has chemistry
Synthetic method and microbe fermentation method.However, admittedly be, above-mentioned production 1, the method pattern disadvantage of 3-PDO is closed with chemistry
The production technology for 1, the 3-PDO that Cheng Fawei is represented still will fundamentally rely on the petroleum industry of unsustainable development, biology hair
Ferment method will be often carried out in two steps, and reaction is made slow progress, and the concentration of products obtained therefrom is low.
Invention content
The preparation method of the catalyst of 1,3-PDO is prepared the object of the present invention is to provide a kind of hydrogenolysis of glycerin.
The present invention seeks to what is be accomplished by the following way:
A kind of hydrogenolysis of glycerin prepares the method for preparing catalyst of 1,3-PD, specifically includes following experimental procedure:
(1) with γ-Al2O3It for carrier, places it in beaker, adds in a certain amount of wolframic acid saline solution and carry out in equal volume
Dipping, after drying in the shade, is placed in oven and dried;Be placed in Muffle furnace and roast.Product is denoted as WOx/γ-Al2O3。
(2) with H2PtCl6·4H2O is reaction raw materials, is placed it in the beaker of 200mL, for a certain amount of aqueous solution
In, suitable polyvinylpyrrolidone (PVP) is added in, after stirring the regular hour, adds in the boron hydrogen of a certain amount of new configuration
Change sodium (NaBH4) aqueous solution, after reacting a period of time, add in a certain amount of WOx/γ-Al2O3, will with 1mol/L dilute nitric acid solutions
PH value is transferred to 5, continues stirring after a certain period of time, filters, is washed to neutrality.At room temperature after vacuum drying, it is placed in Muffle furnace and roasts
It burns.
Change the step the loading of tungstates in (1).
The molar ratio 10 of ligand and chloroplatinic acid in rate-determining steps (2):1-100:1.
The molar ratio 4 of reducing agent and chloroplatinic acid in rate-determining steps (2):1.
The molar ratio of sodium borohydride and gold chloride is 1 in rate-determining steps (2):1-3:1.
The WO added in rate-determining steps (2)x/γ-Al2O3Mass ratio with platinum is 100:10-100-2.
Advantageous effect of the present invention is:
(1) the small size Pt nanoparticle prepared by the present invention can improve the dispersion degree of platinum, improve atom utilization, from
And improve its catalytic activity.
(2) the small size platinum cluster synthetic route that prepared by the present invention is simple and convenient.
Description of the drawings
Fig. 1 is the transmission electron microscope figure (TEM) of small size platinum nanometer cluster prepared by embodiment 3.
Fig. 2 is small size Pt/ γ-Al prepared by embodiment 42O3Transmission electron microscope figure (TEM)
Specific embodiment
Below in conjunction with the accompanying drawings and specific implementation case come the present invention is described in further detail.
Embodiment 1:
Rate-determining steps (1) synthetic product is n-WOx/ γ-Al2O3 (the quality loading % that n is WOx) with 2g γ-Al2O3
It for carrier, places it in beaker, is separately added into the metatungstic acid of 0.0536g, 0.1072g, 0.1608g, 0.2144g, 0.2680g
Aqueous ammonium carries out incipient impregnation, after drying in the shade, is placed in oven and dried;Be placed in Muffle furnace 450 DEG C of roasting 5h.Product
It is denoted as nWOx/ γ-Al2O3 (n=2,4,6,8,10).
Embodiment 2:
Rate-determining steps (1) synthetic product is WOx/ γ-Al2O3-T (T is the calcination temperature of WOx) using 2g γ-Al2O3 as load
Body is placed it in beaker, is separately added into the ammonium metatungstate water of 0.0536g, 0.1072g, 0.1608g, 0.2144g, 0.2680g
Solution carries out incipient impregnation, after drying in the shade, is placed in oven and dried;Be placed on Muffle furnace in 300,400,500,600 DEG C
Roast 4h.2 DEG C/min of heating rate from room temperature to calcination temperature;Product is denoted as nWOx/ γ-Al2O3-T, and (n is the quality of WOx
Loading %, n=2,4,6,8,10, calcination temperature T=300,400,500,600).
Embodiment 3:The molar ratio of rate-determining steps (2) chloroplatinic acid and ligand
With 8.3735g 0.0980mol/L H2PtCl6Aqueous solution is reaction raw materials, is placed it in the beaker of 200mL, is used
In the aqueous solution of 92mL, the polyvinylpyrrolidone (PVP) of 4.5689g is added in, after stirring 30min, adds in what is be newly configured
20mL sodium borohydrides containing 0.1541g (NaBH4) aqueous solution, after reacting 30min
Embodiment 4:Rate-determining steps (2) synthetic product is 4Pt/8WOx/γ-Al2O3- T (T=300,400,500,600 DEG C)
With 8.3735g 0.0980mol/L H2PtCl6Aqueous solution is reaction raw materials, is placed it in the beaker of 200mL, is used
In the aqueous solution of 92mL, the polyvinylpyrrolidone (PVP) of 4.5689g is added in, after stirring 30min, adds in what is be newly configured
20mL sodium borohydrides containing 0.1541g (NaBH4) aqueous solution, after reacting 30min, add in the 8WO of 2gx/γ-Al2O3, use 1mol/L
PH value is transferred to 5 by salpeter solution, is continued after stirring 1h, is filtered, be washed to neutrality.At room temperature after vacuum drying, it is placed in Muffle furnace
In 400 DEG C roasting 4h.
Embodiment 5:Rate-determining steps (2) synthetic product is 4Pt/nWOx/γ-Al2O3- 400 (n=2,4,6,8,10)
With 8.3735g 0.0980mol/L H2PtCl6Aqueous solution is reaction raw materials, is placed it in the beaker of 200mL, is used
In the aqueous solution of 92mL, the polyvinylpyrrolidone (PVP) of 4.5689g is added in, after stirring 30min, adds in what is be newly configured
20mL sodium borohydrides containing 0.1541g (NaBH4) aqueous solution, after reacting 30min, add in the nWO of 2gx/γ-Al2O3, use 1mol/L
PH value is transferred to 5 by salpeter solution, is continued after stirring 1h, is filtered, be washed to neutrality.At room temperature after vacuum drying, it is placed in Muffle furnace
In 400 DEG C roasting.
Embodiment 6:Rate-determining steps (2) synthetic product is nPt/10WOx/γ-Al2O3- 400 (n=2,4,6,8)
With 8.3735g 0.0980mol/L H2PtCl6Aqueous solution is reaction raw materials, is placed it in the beaker of 200mL, is used
In the aqueous solution of 92mL, the polyvinylpyrrolidone (PVP) of 4.5689g is added in, after stirring 30min, adds in what is be newly configured
20mL sodium borohydrides containing 0.1541g (NaBH4) aqueous solution, after reacting 30min, it is separately added into the 10WO of 1g, 1.5g, 2g, 4gx/
γ-Al2O3, pH value is transferred to 5 with 1mol/L salpeter solutions, is continued after stirring 1h, is filtered, be washed to neutrality.Vacuum is dried at room temperature
After dry, it is placed in 400 DEG C of roasting 4h in Muffle furnace.
Application examples 1
The calcination temperature that the application example is intended to investigate catalyst prepares 1,3- propylene glycol reacting catalytic performances to hydrogenolysis of glycerin
Influence.
0.8g 4Pt8W-T (T=300,400,500,600) is taken to add in 50mL polytetrafluoros kettle lining, add in 32mL
The glycerine water solution of 10wt%, screws on kettle, after being passed through the hydrogen displacement three times of 4MPa, is passed through the hydrogen of 4MPa, at 180 DEG C into
Row liquid phase hydrogenolysis.
400 DEG C of roastings are more advantageous to the performance of catalyst as can be seen from the table.
Data of the table 1 for the hydrogenolysis of application examples 1
Application examples 2
The loading that the application example is intended to investigate tungsten prepares hydrogenolysis of glycerin the influences of 1,3- propylene glycol reacting catalytic performances.
0.8g 4PtnW-T (n=2,4,6,8,10,12) is taken to add in 50mL polytetrafluoros kettle lining, add in 32mL 10wt%
Glycerine water solution, screw on kettle, be passed through 4MPa hydrogen displacement three times after, be passed through the hydrogen of 4MPa, liquid phase carried out at 180 DEG C
Hydrogenolysis.
The best performance of catalyst when the loading of tungsten is 10wt% as can be seen from Table 2.
Data of the table 2 for the hydrogenolysis of application examples 2
Application examples 3
The loading that the application example is intended to investigate platinum prepares hydrogenolysis of glycerin the influences of 1,3- propylene glycol reacting catalytic performances.
0.8g nPt10W-T (n=2,4,6,8) is taken to add in 50mL polytetrafluoros kettle lining, add in the glycerine of 32mL 10wt%
Aqueous solution screws on kettle, after being passed through the hydrogen displacement three times of 4MPa, is passed through the hydrogen of 4MPa, it is anti-that liquid phase hydrogenolysis is carried out at 180 DEG C
It should.The loading of platinum is very high for the catalytic activity of 4wt% catalyst as can be seen from Table 3, continues to increase loading catalysis
Activity is difficult to have larger promotion.
Data of the table 3 for the hydrogenolysis of application examples 3
Using this method prepare catalyst hydrogenolysis of glycerin reaction in show extraordinary activity, for catalysis method from
The industrialized production of biology base 1,3- propylene glycol has impetus.
Claims (7)
1. a kind of hydrogenolysis of glycerin prepares the method for preparing catalyst of 1,3-PD, following experimental procedure is specifically included:
(1) with γ-Al2O3It for carrier, places it in container, adds in wolframic acid saline solution and carry out incipient impregnation, after drying in the shade,
It is placed in oven and dried;Be placed in Muffle furnace and roast;
Product is denoted as WOx/γ-Al2O3;Wherein X=2.9-3;
(2) with H2PtCl6·4H2O is reaction raw materials, is placed it in container, is dissolved in aqueous solution, adds in polyvinylpyrrolidine
Alkanone (PVP), stirring add in sodium borohydride (NaBH4) aqueous solution, reaction, addition WOx/γ-Al2O3, with 1-5mol/L nitric acid
PH value is transferred to 4-6 by solution, continues to stir, and is filtered, is washed to neutrality;At room temperature after vacuum drying, it is placed in Muffle kiln roasting.
2. hydrogenolysis of glycerin according to claim 1 prepares the preparation method of the catalyst of 1,3-PD, it is characterised in that:
In the step (1) in an oven 120 DEG C overnight.
3. hydrogenolysis of glycerin according to claim 1 prepares the preparation method of the catalyst of 1,3-PD, it is characterised in that:
In the step (1) in Muffle furnace 300-600 DEG C of roasting more than 4h, 2 DEG C of heating rate from room temperature to calcination temperature/
min。
4. hydrogenolysis of glycerin according to claim 1 prepares the preparation method of the catalyst of 1,3-PD, it is characterised in that:
The ratio between amount of substance of chloroplatinic acid and polyvinylpyrrolidone is 1 in the step (2):10-1:100;
The ratio between amount of substance of chloroplatinic acid and sodium borohydride is 1 in the step (2):4-1:1, recovery time 30min;
The WO added in the step (2)x/γ-Al2O3Mass ratio with platinum is 100:8-100:1.
5. hydrogenolysis of glycerin according to claim 1 prepares the preparation method of the catalyst of 1,3-PD, it is characterised in that:
In the step (2) in Muffle furnace 300-600 DEG C of roasting more than 4h, 2 DEG C of heating rate from room temperature to calcination temperature/
min。
6. hydrogenolysis of glycerin according to claim 1 prepares the preparation method of the catalyst of 1,3-PD, it is characterised in that:
Wolframic acid saline solution is the one or two or more kinds of ammonium paratungstate, ammonium metatungstate, sodium tungstate in the step (1);Its quality
Concentration is in 0.05-0.2g/mL.
7. hydrogenolysis of glycerin according to claim 1 prepares the preparation method of the catalyst of 1,3-PD, it is characterised in that:
H in the step (2)2PtCl6·4H2O mass concentrations 0.01-0.02g/mL.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107913722A (en) * | 2017-10-31 | 2018-04-17 | 张家港美景荣化学工业有限公司 | Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation |
CN110026202A (en) * | 2019-05-21 | 2019-07-19 | 北京石油化工学院 | Glycerine hydrogenation catalyst, catalyst precursor and the preparation method and application thereof |
CN112121791A (en) * | 2020-09-15 | 2020-12-25 | 青岛亿恩方能源环保科技有限公司 | Photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atom cluster and preparation method and application thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101069850A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院大连化学物理研究所 | Loaded and non-loaded catalyst and preparing method |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101069850A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院大连化学物理研究所 | Loaded and non-loaded catalyst and preparing method |
Non-Patent Citations (1)
Title |
---|
SHANHUI ZHU ET AL.: "Promoting effect of WOx on selective hydrogenolysis of glycerol to 1,3-propanediol over bifunctional Pt–WOx/Al2O3 catalysts", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN107913722A (en) * | 2017-10-31 | 2018-04-17 | 张家港美景荣化学工业有限公司 | Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation |
CN107913722B (en) * | 2017-10-31 | 2020-03-27 | 张家港美景荣化学工业有限公司 | Metal/solid acid catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenation |
CN110026202A (en) * | 2019-05-21 | 2019-07-19 | 北京石油化工学院 | Glycerine hydrogenation catalyst, catalyst precursor and the preparation method and application thereof |
CN112121791A (en) * | 2020-09-15 | 2020-12-25 | 青岛亿恩方能源环保科技有限公司 | Photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atom cluster and preparation method and application thereof |
CN112121791B (en) * | 2020-09-15 | 2023-06-06 | 青岛亿恩方能源环保科技有限公司 | Photocatalyst formaldehyde removal catalyst based on titanium dioxide/platinum atomic clusters, and preparation method and application thereof |
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