CN108654609A - A kind of platiniferous and or supported palladium catalyst preparation method and catalyst and hydrogenolysis of glycerin method - Google Patents
A kind of platiniferous and or supported palladium catalyst preparation method and catalyst and hydrogenolysis of glycerin method Download PDFInfo
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- CN108654609A CN108654609A CN201710190679.9A CN201710190679A CN108654609A CN 108654609 A CN108654609 A CN 108654609A CN 201710190679 A CN201710190679 A CN 201710190679A CN 108654609 A CN108654609 A CN 108654609A
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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
- B01J23/38—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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- 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
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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- 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
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Abstract
The invention discloses a kind of platiniferous and or supported palladium catalyst preparation method, the catalyst that is obtained by this method and hydrogenolysis catalysis of glycerin reaction method, the method includes following step：(1) prepare containing platiniferous and or the first component of palladium compound, alkali metal containing and or alkaline-earth metal component the second component and B containing Section VI and/or VIIB races metallic element compound third component mixed solution, it reacts under certain condition, obtains colloidal solution；(2) by support dispersion in solvent, the suspension containing carrier is obtained；(3) colloidal solution of step (1) is mixed with the suspension of step (2), then through dry and optional roasting, obtain the platiniferous and or supported palladium catalyst.Compared with the catalyst of the identical bullion content of prior art preparation, platiniferous of the invention and or supported palladium catalyst for hydrogenolysis catalysis of glycerin react when, have higher hydrogenolysis catalysis of glycerin reactivity and 1,3 propylene glycol selectivity.
Description
Technical field
The present invention relates to a kind of preparation method of noble metal carrier catalyst, be more specifically related to a kind of platiniferous and
Or the method for the preparation method and the catalyst and hydrogenolysis catalysis of glycerin reaction that are obtained by this method of supported palladium catalyst.
Background technology
1,3-PD is the important source material for producing degradable polyester propylene glycol ester terephthalate (PTT) etc., demand
Constantly increase；Moreover, as a kind of important industrial chemicals, it may also be used for solvent, emulsifier, medicine, cosmetics and organic conjunction
Cheng Zhong.Currently, industrial production 1,3-PD mainly uses oxirane carbonyl method and acrolein hydration hydrogenization method, both
The raw material of process route both is from oil.With the continuous exhaustion of petroleum resources, the non-petroleum road of production 1,3-PD is found
Line is of great significance.Glycerine is metering during production of biodiesel than by-product (about 10%), with biodiesel
The yield of wilderness demand and large-scale production, by-product glycerin is also significantly increased.This makes glycerine become production 1,3- the third two
The desirable feedstock of alcohol, and the production cost of biodiesel can be reduced.
CN102372602B discloses a kind of method of preparing 1,3-propylene glycol by hydrogenation of glycerin, that is, uses continuous flow fixed bed
Reactor and Pt/WO3/TiO2-SiO2Catalyst, glycerine are continuously introduced into reactor after being mixed with solvent, in the hydrogen atmosphere of flowing
It is lower to contact and reacted with the catalyst of filling in the reactor.Unreacted glycerine, the hydrogen come out from reactor outlet
And solvent recycles after being detached with product.Compared with prior art, the method provided by the invention, can have higher
1,3- propylene glycol yields.
CN102728380A discloses the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3-PD, specifically a kind of Jie
The preparation and application for the platinum based catalyst that hole tungsten oxide supports.Using mesoporous tungsten oxide as carrier, activity component metal platinum or other
Noble metal high dispersive is the 0.1-40% of carrier quality in carrier surface, the wherein theoretical content of active component.Catalyst has
Selectivity is good, the high feature of activity, it can realize glycerine under 120-300 DEG C, the hydrothermal conditions of 0.1-15MPa Hydrogen Vapor Pressures
Hydrogenolysis high selection prepares 1,3- propylene glycol.
CN101747150A discloses one kind using glycerine as raw material, and 1,3-PD is prepared by the phase hydrogenolysis of glycerine
Method, this method make glycerine phase hydrogenolysis prepare 1,3-PD in the presence of being included in metal-acid bifunctional catalyst.Described
Metal-acid bifunctional catalyst includes the following components being carried on carrier：(a) a kind of solid acid active constituent and (b) have
Metal component (one kind in copper, nickel or cobalt) with hydrogenation efficiency, and optional addition (c) metal promoter component (iron,
It is one or more in zinc, tin, manganese and chromium).
Alcohothermal method process is reducing agent and solvent using alcohol (generally polyalcohol), and does not use and stablize mostly
Agent, catalyst granules dispersion degree height, the particle diameter distribution uniform, controllable of preparation, and it is of low cost, easy to operate.Wang reports one
Kind prepares the monometallics nanometer such as stable Pt, Rh, Ru using alcohothermal method without using in the case of stabilizer in organic media
Method (Chemistry ofMaterials, 2000,12 (6) of particle:1622-1627).
The comprehensive progress for being disclosed document, the selectivity that hydrogenolysis of glycerin generates 1,3-PD depend primarily on two
Aspect, when the intrinsic properties of metal and auxiliary agent selected by catalyst, second is that the acid-base property and solvent of reaction condition especially solution
Effect.Although having more document report, the catalyst hydrogenolysis of glycerin activity and selectivity of the reaction is still greatly improved
With the leeway of raising.It is disclosed above for hydrogenolysis of glycerin generate 1,3- propylene glycol platiniferous and or supported palladium catalyst base
This be all obtained by conventional impregnation method, co-impregnation or step impregnation method, however, alcohothermal method this sent out in recent years
The novel important method for preparing high-dispersion nano metallic catalyst of exhibition is fresh in the catalyst field reacted suitable for hydrogenolysis of glycerin
It appears in the newspapers.
Invention content
The purpose of the present invention is to provide it is a kind of have compared with high glycerine hydrogenolysis activity and selectivity platiniferous and or palladium load
Type catalyst and preparation method and application and the method reacted using the catalyst hydrogenolysis of glycerin.
The present invention provides a kind of platiniferous and or supported palladium catalyst preparation method, include the following steps：
(1) prepare containing platiniferous and or the first component of palladium compound, alkali metal containing and or alkali earth metal chemical combination
The mixed solution of second component of object and B containing Section VI and/or VIIB races metallic element compound third component, at 50~200 DEG C
Under the conditions of react 0.5~24 hour, obtain colloidal solution；
(2) by support dispersion in solvent, the suspension containing carrier is obtained；
(3) colloidal solution of step (1) is mixed with the suspension of step (2), then through dry and optional roasting, is obtained
To the platiniferous and or supported palladium catalyst.
The present invention also provides the platiniferous made from the above method and or supported palladium catalyst.
The present invention also provides application of the above-mentioned loaded catalyst in hydrogenolysis catalysis of glycerin reaction.
Invention further provides a kind of hydrogenolysis of glycerin reaction method, this method is included in hydrogenolysis catalysis of glycerin reaction item
Under part, the raw material containing glycerine, hydrogen are contacted with catalyst, wherein the catalyst is above-mentioned platiniferous loaded catalyst.
With the identical platinum of prior art preparation and or the catalyst of palladium content compared with, platiniferous of the invention and or palladium load
Type catalyst has considerably higher hydrogenolysis catalysis of glycerin activity and selectivity.Other features and advantages of the present invention will be subsequent
Specific embodiment part be described in detail.
Description of the drawings
Attached drawing is to be used to provide further understanding of the present invention, an and part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the X of the Pt 4f of comparative catalyst D1 made from catalyst R1 made from the embodiment of the present invention 1 and comparative example 1
X-ray photoelectron spectroscopy X figure；
Fig. 2 is the X of the W 4f of comparative catalyst D1 made from catalyst R1 made from the embodiment of the present invention 1 and comparative example 1
X-ray photoelectron spectroscopy X figure.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of platiniferous and or supported palladium catalyst preparation method, this method includes the following steps：
(1) prepare containing platiniferous and or the first component of palladium compound, alkali metal containing and or alkali earth metal chemical combination
The mixed solution of second component of object and B containing Section VI and/or VIIB races metallic element compound third component, at 50~200 DEG C
Under the conditions of react 0.5~24 hour, preferably reacted 2-10 hours under the conditions of 100-180 DEG C and obtain colloidal solution；
(2) by support dispersion in solvent, the suspension containing carrier is obtained；
(3) colloidal solution of step (1) is mixed with the suspension of step (2), then through dry and optional roasting, is obtained
To the noble metal carrier catalyst.
Wherein, three kinds of components of the step (1) can be separately formulated molten according to properties such as respective solubility, intermiscibilities
It remixes after liquid, or is directly prepared in same a solution；For example, preparing the solution containing the first component respectively and containing simultaneously
The solution of second component and third component, then mixes the two；Either, it prepares respectively while containing the first component and third group
The solution divided and the solution containing the second component, then mix the two.
After the solution mixing containing three kinds of components of the step (1), preferably carried out under inert atmosphere and/or reducing atmosphere
Reaction, the inert atmosphere and/or reducing atmosphere can be nitrogen, argon gas, helium, hydrogen and their gaseous mixture.
Preferably, in step (1), the platiniferous and or palladium the first component composition be Pt (NH3)4(NO3)2、Pt
(NH3)4Cl2、H2PtCl6、H2PtCl4、Pd(NH3)4(NO3)2、Pd(NH3)4Cl2、H2PdCl4At least one of；It is further excellent
Selection of land, first component composition are selected from Pt (NH3)4(NO3)2、Pt(NH3)4Cl2、H2PtCl6、H2PtCl4In at least one
Kind.
Alkali or alkaline earth metal element preferably is selected from least one of Li, Na, K, Rb, Ba described in step (1), described
Alkali metal containing and or the compound of alkali earth metal be preferably hydroxide, the Section VI B and/or VIIB races metallic element
Preferably at least one of Mo, W, Re, Mn.
Preferably, the solvent that the solution use of three kinds of components is prepared described in step (1) can with solvent described in step (2)
To be same solvent, it can also be different solvent, the two can be independently selected from the mixture of alcohol or alcohol and water, institute
It is at least one of monohydric alcohol selected from 1-6 carbon atom, dihydric alcohol, trihydroxylic alcohol to state alcohol, and the content of alcohol is in the solvent
40-100 weight %；It is further preferred that the alcohol is in ethyl alcohol, ethylene glycol, 1,2-PD, 1,3-PD, glycerine
At least one, the content of alcohol is 70-100 weight % in the solvent.
In order to which final catalyst performance is more preferable, when preparing colloidal solution, it is preferable that the dosage of each component in step (1)
So that on the basis of the colloidal solution weight, by platinum and or palladium element in terms of the first constituent content for 1-200 grams per liters, with alkali
Metal and or alkali earth metal meter the second constituent content be 1-500 grams per liters, with Section VI B and/or VIIB races metallic element
The third component content of meter is 1-500 grams per liters.The carrier of the step (2) is not particularly limited, it is preferable that can be selected from
One kind in aluminium oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, activated carbon or
It is a variety of.
The method by support dispersion in solvent of the step (2) is not particularly limited, and can be those skilled in the art
Well known various methods；For example, can be electromagnetic agitation dispersion, ultrasonic disperse.
In finally obtained catalyst, it is preferable that step (1) and the dosage of step (2) each component make in catalyst
Each component content based on the element is as follows：Precious metal element content is 0.2-15 weight %, Section VI B and/or VIIB races metal member
Cellulose content be 0.2-15 weight %, alkali metal and or alkaline earth metal content be 0-2%, remaining is carrier, meet total amount be 100
Weight %.It is further preferred that precious metal element content is 0.5-10 weight %, Section VI B and/or VIIB races metal element content
For 0.5-10 weight %, alkali metal and or alkaline earth metal content be 0-2%, remaining is carrier.
After the colloidal solution of step (1) and the suspension mixing of step (2), re-dry after can first being detached,
It can be with convection drying.In general, when solid content is relatively low, when such as 50% or less, preferentially take re-dry after separation, solid content compared with
Gao Shi, when such as 50% or more, convection drying.The separation method and drying mode of the step (3) are not particularly limited, Ke Yiwei
Well known to a person skilled in the art various methods；Separation method may be used natural filtration washing, be filtered under diminished pressure washing, centrifugation point
From washing, drying mode can be oven drying in air atmosphere, vacuum drying.Drying condition is also not particularly limited, it is excellent
The drying condition of choosing includes：40-200 DEG C of temperature, time 0.1-24 hour.After can also be according to different require to above-mentioned drying
Product carry out roast or do not roast, the condition of roasting is not particularly limited, it is preferable that can be roasted at 200-600 DEG C
0.1-24 hours.
The present invention also provides the platiniferous made from the above method and or supported palladium catalyst.Under optimum condition, with member
Element meter and on the basis of catalyst total amount, platinum and or palladium content be 0.2-15 weight %, Section VI B and/or VIIB races constituent content
For 0.2-15 weight %, alkali metal and/or alkaline earth metal content are 0-2 weight %, remaining is carrier；It is further preferred that platinum
With or palladium content be 0.5-10 weight %, Section VI B and/or VIIB races constituent content be 0.5-10 weight %, alkali metal and/or
Alkaline earth metal content is 0-1 weight %, remaining is carrier.
The catalyst metal content that inventor obtains the present invention is tested, the results showed that, the method for the invention
Obtained noble metal carrier catalyst meets (M2/M1)XPS/(M2/M1)XRF=2-20, preferably 2.5-10, more preferable 3-5,
In, M1Platinum and or palladium, M2Section VI B and/or VIIB races metallic element, (M2/M1)XPSIt is to be urged with what x-ray photoelectron spectroscopy characterized
M in agent2With M1With the weight ratio of elemental metal, (M2/M1)XRFIt is M in the catalyst characterized with X-ray fluorescence spectra2With M1
With the weight ratio of elemental metal.The x-ray photoelectron spectroscopy uses excitation light source for the monochromator AlK α X-rays of 150kW
It measures, the measuring condition of the X-ray fluorescence spectra includes rhodium target, laser voltage is 50kV and laser current is 50mA.
The present invention also provides above-mentioned platiniferous and or supported palladium catalyst hydrogenolysis catalysis of glycerin reaction in application.
In addition, the present invention also provides a kind of hydrogenolysis catalysis of glycerin reaction method, this method is included in hydrogenolysis catalysis of glycerin
Under the conditions of, the raw material containing glycerine, hydrogen are contacted with catalyst, wherein the catalyst be above-mentioned platiniferous and or palladium load
Type catalyst.
The condition of reaction is referred to prior art progress, and by taking the evaluation of autoclave reactor as an example, qualities of glycerin is dense
Degree is 5-95%, and solvent is water, methanol, ethyl alcohol, at least one of propyl alcohol, Hydrogen Vapor Pressure 2-15MPa, preferably 4-10MPa,
Reaction temperature is 90-300 DEG C, and preferably 100-220 DEG C, glycerine and 0.5 hour catalyst reaction time or more, preferably 4-36 is small
When.
The device of the reaction can it is any be enough to make the glycerinated raw material under hydrogenation conditions with it is described
Platiniferous and or the catalytic reactor of supported palladium catalyst in carry out, such as fixed bed reactors or autoclave reactor.
With the identical platinum of prior art preparation and or the catalyst of palladium content compared with, made from method using the present invention
Platiniferous and or supported palladium catalyst there is considerably higher hydrogenolysis of glycerin activity, and to the 1,3-PD of high added value
Selective increase rate bigger.It traces it to its cause, it may be possible to because the preparation method of catalyst provided by the invention increases substantially
Platinum and or palladium and B containing Section VI and/or the species of VIIB races elements interaction interface, to be conducive to glycerol molecule
The Selective activation of secondary hydroxyl.
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.It is described in following embodiments
Percentage composition is unless otherwise instructed mass percentage；Catalyst composition is the institute on the basis of the total weight of catalyst
The mass percentage of hydrogenation active metals element is stated, and the composition is calculated according to inventory；X-ray photoelectron spectroscopy
Measuring instrument is the ESCALab250 type instruments of Thermo Scientific companies, and measuring condition is：Excitation light source is 150kW
Monochromator Al K α X-rays, in conjunction with can use the peaks C 1s (284.8eV) correct；The measuring instrument of X-ray fluorescence spectra is day
3271 type instrument of this Liue electrical machinery Industrial Co., Ltd, measuring condition are：Pressed powder pellet is molded, rhodium target, laser voltage
50kV, laser current 50mA.
Embodiment 1
The embodiment is for illustrating catalyst provided by the invention and preparation method thereof.
The ethylene glycol solution for preparing the chloroplatinic acid of 100 milliliters of 4.1 grams per liters of platiniferous, adds it to 100 milliliters under stiring
In the ethylene glycol solution of the ammonium metatungstate of 10.0 grams per liter of sodium hydroxide and tungstenic of 5.6 grams per liter containing sodium, continue to stir at room temperature
It mixes 1 hour, gained reactant is flowed back 4 hours at 160 DEG C under nitrogen protection, about 200 milliliters of Pt colloids solution is made,
It is cooled to room temperature spare.
Take 20 grams of SiO2Carrier (Haiyang Chemical Plant, Qingdao, same as below) electromagnetic agitation is scattered in 50 milliliters of ethyl alcohol.
Above-mentioned 200 milliliters of Pt colloids solution above-mentioned 50 milliliters are added drop-wise under quick electromagnetic stirring to be dispersed in the ethyl alcohol of carrier, after
Continuous electromagnetic agitation 2 hours.Solid is depressurized and is filtered, washed several times with water is dried in vacuo 12 hours in 120 DEG C, obtains platiniferous load
Type catalyst, it is spare to be stored in drier.Obtained catalyst is denoted as R1, and composition, XPS and XRF characterization results are shown in Table 1, wherein X
X-ray photoelectron spectroscopy X figure is as shown in Figure 1 and Figure 2.Table is obtained according to the corresponding peak area conversion of the electron binding energy of Pt 4f and W 4f
Layer atomic ratio (M2/M1)XPS.Wherein composition is the platinum based on the element, third, the on the basis of the total weight of catalyst
The mass percentage (similarly hereinafter) of two component metals elements.
Comparative example 1
The comparative example is for illustrating comparative catalyst and preparation method thereof.
Platiniferous loaded catalyst is prepared using co-impregnation.Prepare the chloroplatinic acid and tungstenic of 44 milliliters of 7.8 grams per liters of platiniferous
The aqueous solution of the ammonium metatungstate of 15.9 grams per liters, incipient impregnation to 20 grams of SiO2Carrier stirs evenly at 20 DEG C, stands 4 hours
Afterwards, it is dried through 120 DEG C, roast 4 hours at 400 DEG C, 400 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 megapascal.It is dropped after reduction
To room temperature, it is spare to be stored in drier.Obtained catalyst is denoted as D1, and composition, XPS and XRF characterization results are shown in Table 1.Wherein X is penetrated
Photoelectron spectra figure is as shown in Figure 1 and Figure 2.
Comparative example 2
The comparative example is for illustrating comparative catalyst and preparation method thereof.
Catalyst is prepared according to the method for embodiment 1, unlike, it prepares in the ethylene glycol solution used in Pt colloids solution
Without ammonium metatungstate.Obtained catalyst is denoted as D2, and composition, XPS and XRF characterization results are shown in Table 1.
Embodiment 2
The embodiment is for illustrating catalyst provided by the invention and preparation method thereof.
The ethylene glycol solution for preparing the chloroplatinic acid of 100 milliliters of 4.1 grams per liters of platiniferous, adds it to 100 milliliters under stiring
In the ethylene glycol solution of the ammonium metatungstate of 17.4 grams per liter of sodium hydroxide and tungstenic of 5.6 grams per liter containing sodium, continue to stir at room temperature
It mixes 1 hour, gained reactant is flowed back 4 hours at 160 DEG C under nitrogen protection, about 200 milliliters of Pt colloids solution is made,
It is cooled to room temperature spare.
Take 20 grams of γ-Al2O3Carrier (Chang Ling catalyst plant product, granularity 20-40 mesh are same as below) electromagnetic agitation is disperseed
In 50 milliliters of ethyl alcohol.Above-mentioned 200 milliliters of Pt colloids solution is added drop-wise to above-mentioned 50 milliliters of dispersions under quick electromagnetic stirring
Have in the ethyl alcohol of carrier, continues electromagnetic agitation 4 hours.Solid is depressurized and is filtered, washed several times with water is small in 120 DEG C of vacuum drying 24
When, platiniferous loaded catalyst is obtained, it is spare to be stored in drier.Obtained catalyst is denoted as R2, composition, XPS and XRF tables
Sign the results are shown in Table 1.
Embodiment 3
The embodiment is for illustrating catalyst provided by the invention and preparation method thereof.
The ethylene glycol solution for preparing the chloroplatinic acid of 100 milliliters of 8.2 grams per liters of platiniferous, adds it to 100 milliliters under stiring
In the ethylene glycol solution of the sodium tungstate of 17.4 grams per liter of sodium hydroxide and tungstenic of 11.2 grams per liter containing sodium, continue to stir at room temperature
1 hour, gained reactant is flowed back 5 hours at 160 DEG C under nitrogen protection, about 200 milliliters of Pt colloids solution is made, it is cold
But spare to room temperature.
Take 20 grams of γ-Al2O3Carrier electromagnetic agitation is scattered in 50 milliliters of ethyl alcohol.By above-mentioned 200 under quick electromagnetic stirring
The Pt colloids solution of milliliter is added drop-wise to above-mentioned 50 milliliters and is dispersed in the ethyl alcohol of carrier, continues electromagnetic agitation 4 hours.Solid is subtracted
Pressure filters, washed several times with water, is dried in vacuo 24 hours in 120 DEG C, obtains platiniferous loaded catalyst, it is spare to be stored in drier.
Obtained catalyst is denoted as R3, and composition, XPS and XRF characterization results are shown in Table 1.
Embodiment 4
The embodiment is for illustrating catalyst provided by the invention and preparation method thereof.
The 1,2- propylene glycol for preparing the perrhenic acid of 10.0 grams per liter of chlorine palladium acid and rhenium-containing of 100 milliliters of 4.1 grams per liters containing palladium is molten
Liquid adds it in the 1,2-PD solution of the potassium hydroxide of 100 milliliters of 19.0 grams per liters containing potassium, under stiring in room temperature
Under continue stirring 1 hour, gained reactant flow back 6 hours at 180 DEG C under nitrogen protection, obtained about 200 milliliters of palladium
Colloidal solution is cooled to room temperature spare.
Take 20 grams of SiO2Carrier electromagnetic agitation is scattered in 50 milliliters of propyl alcohol.By above-mentioned 200 milli under quick electromagnetic stirring
The palladium colloidal solution risen is added drop-wise to above-mentioned 50 milliliters and is dispersed in the propyl alcohol of carrier, continues electromagnetic agitation 2 hours.Solid is depressurized
It filters, washed several times with water, is dried in vacuo 12 hours in 140 DEG C, obtains containing supported palladium catalyst, it is spare to be stored in drier.
To catalyst be denoted as R4, composition, XPS and XRF characterization results are shown in Table 1.
Embodiment 5-8
These embodiments are for illustrating the performance that catalyst provided by the invention reacts hydrogenolysis of glycerin.
Evaluate catalyst R1, R2, R3 and R4 respectively as steps described below.
Hydrogenolysis of glycerin reaction carries out in 500 milliliters of Parr stainless steel autoclaves, weighs 2.5 grams of catalyst, and 300
The aqueous solution of milliliter qualities of glycerin a concentration of 20%.Using 1 megapascal hydrogen purge, five air driven away in autoclave, in room temperature
Lower be passed through into kettle after hydrogen makes pressure reach 4 megapascal is warming up to 180 DEG C, opens under stirring (1000rpm) and reacts 15 hours, waits for
Temperature in the kettle drops to pressure release after certain room temperature, and product is after filtering or centrifugation, using the liquid before GC analysis reactions and after reaction
Composition.Reaction result is listed in table 2.
Comparative example 3-4
These comparative examples are used to illustrate the hydrogenolysis of glycerin activity of comparative catalyst.
According to method and condition evaluation comparative catalyst D1 and D2 same as Example 5.Reaction result is listed in table 2.
Table 1
Table 2
The same metal content of these embodiment results explanation, catalyst provided by the present invention and prior art preparation
Catalyst is compared, and has better hydrogenolysis of glycerin activity, and more to the selective increase rate of the 1,3-PD of high added value
Greatly.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
Claims (12)
1. a kind of platinum and or supported palladium catalyst preparation method, include the following steps：
(1) prepare containing platiniferous and or the first component of palladium compound, alkali metal containing and or alkaline-earth metal component
The mixed solution of second component and B containing Section VI and/or VIIB races metallic element compound third component, in 50~200 DEG C of conditions
Lower reaction 0.5~24 hour, obtains colloidal solution；
(2) by support dispersion in solvent, the suspension containing carrier is obtained；
(3) colloidal solution of step (1) is mixed with the suspension of step (2), then through dry and optional roasting, obtains institute
State platiniferous and or supported palladium catalyst.
2. preparation method according to claim 1, wherein the platiniferous and or palladium compound be selected from Pt (NH3)4
(NO3)2、Pt(NH3)4Cl2、H2PtCl6、H2PtCl4、Pd(NH3)4(NO3)2、Pd(NH3)4Cl2、H2PdCl4At least one of,
The alkali or alkaline earth metal element be selected from least one of Li, Na, K, Rb, Ba, the alkali metal containing and or alkaline earth
The compound of metallic element is hydroxide, the Section VI B and/or VIIB races metallic element be in Mo, W, Re, Mn extremely
Few one kind.
3. preparation method according to claim 1 or 2, wherein in the solvent of solution and step (2) described in step (1)
The solvent is identical or different, is independently selected from the mixture of alcohol or alcohol and water, and the alcohol is selected from 1-6 carbon atom
At least one of monohydric alcohol, dihydric alcohol, trihydroxylic alcohol, the content of alcohol is 40-100 weight % in the solvent.
4. preparation method according to claim 3, wherein the alcohol is ethyl alcohol, ethylene glycol, 1,2-PD, 1,3- third
At least one of glycol, glycerine, the content of alcohol is 70-100 weight % in the solvent.
5. preparation method according to claim 1, wherein the dosage of each component makes molten with the colloid in step (1)
On the basis of liquid weight, by platinum and or palladium element in terms of the first constituent content be 1-200 grams per liters, with alkali metal and or alkaline earth gold
The second constituent content for belonging to element meter is 1-500 grams per liters, with the third component content of Section VI B and/or VIIB races elemental metal
For 1-500 grams per liters.
6. preparation method according to claim 1, wherein step (1) and the dosage of step (2) each component finally to urge
Each component content in agent based on the element is as follows：Platinum and or palladium content be 0.2-15 weight %, Section VI B and/or VIIB races gold
Category constituent content be 0.2-15 weight %, alkali metal and or alkaline earth metal content be 0-2%, remaining is carrier.
7. preparation method according to claim 6, wherein step (1) and the dosage of step (2) each component finally to urge
Each component content in agent based on the element is as follows：Platiniferous and or palladium content be 0.5-10 weight %, Section VI B and or VIIB
Race's metal element content be 0.5-10 weight %, alkali metal and or alkaline earth metal content be 0-1%, remaining is carrier.
8. preparation method according to claim 1, wherein dry operating condition described in step (3) includes：Temperature is
40-200 DEG C, the time is 0.1-24 hours；The operating condition roasted described in step (3) includes：Temperature is 200-600 DEG C, when
Between be 0.1-24 hours.
9. according to the preparation method described in any one of claim 1-8, wherein the carrier is aluminium oxide, silica, oxygen
Change one or more in titanium, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, activated carbon.
10. the platinum made from the method described in any one of claim 1-9 and or supported palladium catalyst.
11. platinum described in claim 10 and or application of the supported palladium catalyst in hydrogenolysis catalysis of glycerin reaction.
12. a kind of hydrogenolysis of glycerin reaction method, this method are included under the conditions of hydrogenolysis catalysis of glycerin, by the raw material containing glycerine,
Hydrogen is contacted with catalyst, wherein the catalyst be claim 10 described in platinum and or supported palladium catalyst, institute
State hydrogenolysis catalysis of glycerin condition include Hydrogen Vapor Pressure be 2-15MPa, temperature be 90-300 DEG C, reaction time 0.5-72 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112570039A (en) * | 2019-09-29 | 2021-03-30 | 中国科学院大连化学物理研究所 | Reduction method of polyhydric alcohol hydrogenolysis catalyst, catalyst and application |
| CN114073985A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and application thereof |
| CN114471542A (en) * | 2022-01-07 | 2022-05-13 | 北京工业大学 | Preparation method of supported Pd cluster catalyst activated by alkali metal and alkaline earth metal |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009045606A1 (en) * | 2007-09-28 | 2009-04-09 | Battelle Memorial Institute | Multi-metal hydrogenation catalysts |
| CN101547882A (en) * | 2006-12-05 | 2009-09-30 | 花王株式会社 | Process for producing product of hydrogenolysis of polyhydric alcohol |
| CN101670286A (en) * | 2008-09-12 | 2010-03-17 | 北京大学 | Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof |
| CN101767018A (en) * | 2009-01-06 | 2010-07-07 | 北京大学 | Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof |
| CN104275181A (en) * | 2013-07-10 | 2015-01-14 | 清华大学 | Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and preparation method thereof |
-
2017
- 2017-03-28 CN CN201710190679.9A patent/CN108654609A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101547882A (en) * | 2006-12-05 | 2009-09-30 | 花王株式会社 | Process for producing product of hydrogenolysis of polyhydric alcohol |
| WO2009045606A1 (en) * | 2007-09-28 | 2009-04-09 | Battelle Memorial Institute | Multi-metal hydrogenation catalysts |
| CN101670286A (en) * | 2008-09-12 | 2010-03-17 | 北京大学 | Supported transition metal or transition metal alloy nanocluster catalyst and preparation method and application thereof |
| CN101767018A (en) * | 2009-01-06 | 2010-07-07 | 北京大学 | Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof |
| CN104275181A (en) * | 2013-07-10 | 2015-01-14 | 清华大学 | Pd-Re catalyst for propylene glycol preparation by glycerol hydrogenolysis and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112570039A (en) * | 2019-09-29 | 2021-03-30 | 中国科学院大连化学物理研究所 | Reduction method of polyhydric alcohol hydrogenolysis catalyst, catalyst and application |
| CN112570039B (en) * | 2019-09-29 | 2022-08-09 | 中国科学院大连化学物理研究所 | Reduction method of polyhydric alcohol hydrogenolysis catalyst, catalyst and application |
| CN114073985A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and application thereof |
| CN114073985B (en) * | 2020-08-19 | 2024-03-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst, preparation method and application thereof |
| CN114471542A (en) * | 2022-01-07 | 2022-05-13 | 北京工业大学 | Preparation method of supported Pd cluster catalyst activated by alkali metal and alkaline earth metal |
| CN114471542B (en) * | 2022-01-07 | 2023-12-08 | 北京工业大学 | Preparation method of alkali metal and alkaline earth metal activated supported Pd cluster catalyst |
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