CN104248970B - A kind of carried phospho-tungstic acid catalyst and its preparation method and application and the preparation method of Ketohexamethylene glycerol ketal - Google Patents
A kind of carried phospho-tungstic acid catalyst and its preparation method and application and the preparation method of Ketohexamethylene glycerol ketal Download PDFInfo
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Abstract
The invention discloses a kind of carried phospho-tungstic acid catalyst and its preparation method and application and the preparation method of Ketohexamethylene glycerol ketal, wherein, this catalyst contains preparing spherical SiO 2 and silica gel complex carrier and is supported on the phosphotungstic acid on described preparing spherical SiO 2 and silica gel complex carrier, and on the basis of the gross weight of this catalyst, the content of described phosphotungstic acid is 1 50 weight %, and the content of described complex carrier is 50 99 weight %；The mean particle diameter of described complex carrier is 5 30 microns, and specific surface area is 300 390 meters squared per gram, and pore volume is 0.5 1.5 mls/g, and most probable pore size is 0.5 4 nanometers；When applying the ketal reaction that this catalyst comes catalysis of pimelinketone and glycerol, side reaction does not produces corrosion to equipment, and conversion ratio improves simultaneously, and the carried phospho-tungstic acid catalyst of the present invention can be through reclaiming and Reusability, and aftertreatment technology is simple.
Description
Technical field
The present invention relates to a kind of carried phospho-tungstic acid catalyst and preparation method thereof, further relate to use this load
The application in ketal synthesis reacts of the type phosphotungstic acid catalyst, and the preparation side of Ketohexamethylene glycerol ketal
Method.
Background technology
Within 1992, Mobile company synthesizes mesoporous material (Beck J S, Vartuli J C, Roth W J, et
Al.J.Am.Chem.Soc., 1992,114 (27): 10834-10843), this mesoporous material has high ratio
Surface, regular pore passage structure and narrow pore-size distribution so that mesoporous material is being catalyzed, separates, is curing
The application in the fields such as medicine has obtained the biggest concern；Zhao east in 1998 unit et al. synthesizes a kind of material-Jie
Porous materials SBA-15 (D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science 279 (1998)
548-550), this material has cube single-crystal meso-pore material aperture (6-30nm), the hole body of high-sequential
Long-pending big (1.0cm3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) and good catalysis
Absorption property；Zhao Dongyuan, Yu Chengzhong, the preparation side of the remaining a kind of mesonic pore molecular sieve carrier material of invention of person of outstanding talent forever
Method (CN1341553A), this mesoporous material, as heterogeneous reaction catalyst carrier, easily realizes catalyst
(Wight, A.P. is separated with product；Davis,M.E.Chem.Rev.2002,102,3589；De Vos,
D.E.；Dams,M.；Sels,B.F.；Jacobs,P.A.Chem.Rev.2002,102,3615.).
Conventional ordered mesoporous material SBA-15 microscopic appearance is bar-shaped, is spherical material with microscopic appearance
It is poor that itself mobility compared by material, and its big specific surface area and the cause of high pore volume make it have stronger
Water suction, moisture absorption ability, this will be further exacerbated by the reunion of bar-shaped ordered mesopore material, to bar-shaped ordered Jie
The storage of Porous materials, transport, post-treatment and application are made troubles.And the geometric shape of microsphere is reducing powder
The reunion of body, improving the aspects such as its mobility has obvious advantage.Therefore, if microsphere, being situated between in order
The advantage of Porous materials and silicon dioxide and silica gel combines, and can retain the Gao Bibiao of ordered mesoporous material
Area, big pore volume, aperture be big and the feature of narrowly distributing, can reduce again the reunion of ordered mesoporous material, increase
Add its mobility, simultaneously because the introducing of cheap natural clay mineral material, reduce the cost of material,
Application for ordered mesoporous material is provided more preferable platform by this, and expands the application neck of ordered mesoporous material
Territory.
Along with developing rapidly of chemical industry, ketal kind and demand are continuously increased.Ketal is a class
Can be used for the carbonyl-protection of organic compound or the intermediate of pharmaceuticals industry, molten even serving as specific response
Agent.The synthesis of ketal is usually under strong acid catalyst, and by ketone and alcohols synthesis, catalyst used has
Sulphuric acid, phosphoric acid, hydrogen chloride gas, p-methyl benzenesulfonic acid, its advantage is that catalyst is cheap and easy to get.But,
Reaction terminates rear catalyst and separates with product and need to be neutralized and the process such as washing, and not only complex process is also
Produce contaminated wastewater environment, along with the raising of living standards of the people, environmental conservation is proposed more and more higher
Ground requirement；And Bronsted acid has stronger corrosiveness to equipment.
Therefore, develop a kind of for synthesizing the problem that the catalyst of ketal becomes in the urgent need to address.
Summary of the invention
It is an object of the invention to overcome that the catalyst being currently used for Synthesis of Ketal exists to equipment
The shortcomings such as seriously corroded, many, the complex process of side reaction, it is provided that a kind of catalyst for synthesizing ketal
And the preparation method of Ketohexamethylene glycerol ketal.
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst contains spherical dioxy
SiClx and silica gel complex carrier and be supported on the phosphorus on described preparing spherical SiO 2 and silica gel complex carrier
Wolframic acid, and on the basis of the gross weight of this catalyst, the content of described phosphotungstic acid is 1-50 weight %, institute
The content stating preparing spherical SiO 2 and silica gel complex carrier is 50-99 weight %；Described preparing spherical SiO 2
And the mean particle diameter of silica gel complex carrier is 5-30 micron, specific surface area is 300-390 square metre/
Gram, pore volume is 0.5-1.5 ml/g, and most probable pore size is 0.5-4 nanometer.
Present invention also offers the preparation method of a kind of carried phospho-tungstic acid catalyst, wherein, the method bag
Include: described preparing spherical SiO 2 and silica gel complex carrier are configured in the presence of deionized water with phosphotungstic acid
It is spray-dried after slurry, makes phosphotungstic acid be supported on described preparing spherical SiO 2 and silica gel complex carrier
On, by described preparing spherical SiO 2 and silica gel complex carrier on the basis of the gross weight with phosphotungstic acid, described phosphorus
The consumption of wolframic acid is 1-50 weight %, and the consumption of described preparing spherical SiO 2 and silica gel complex carrier is
50-99 weight %；The mean particle diameter of described preparing spherical SiO 2 and silica gel complex carrier is that 5-30 is micro-
Rice, specific surface area is 300-390 meters squared per gram, and pore volume is 0.5-1.5 ml/g, most probable pore size
For 0.5-4 nanometer.
Additionally, present invention also offers the application in ketal reaction of the described catalyst.
Further, present invention also offers the preparation method of a kind of Ketohexamethylene glycerol ketal, wherein, the party
Method includes: in the presence of a catalyst, under conditions of ketal reaction, makes Ketohexamethylene contact with glycerol,
To obtain ketal, wherein, the carried phospho-tungstic acid catalyst that described catalyst provides for the present invention.
In the present invention, by spray drying method, phosphotungstic acid is carried on specific preparing spherical SiO 2 and silica gel
On complex carrier, and when using reaction that this catalyst comes catalysis of pimelinketone and glycerol, catalyst can
With through reclaiming and Reusability, and the carried phospho-tungstic acid catalyst that the present invention provides can have and subtracts
Few side reaction, to improve conversion ratio, not etching apparatus, aftertreatment technology simply and beneficially environmental protection etc. excellent
Point.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, and wherein, a is preparing spherical SiO 2 and silica gel complex carrier
(MCMGJ) XRD spectra, b are the preparing spherical SiO 2 by spray drying method load phosphotungstic acid
And the XRD spectra of silica gel complex carrier (MCMGJ-HPA-1), abscissa is 2 θ, and vertical coordinate is
Intensity；
Fig. 2 A is the SEM of the microscopic appearance of preparing spherical SiO 2 and silica gel complex carrier (MCMGJ)
Scanning electron microscope (SEM) photograph；
Fig. 2 B is the microcosmic shape of the amplification of preparing spherical SiO 2 and silica gel complex carrier (MCMGJ)
The SEM scanning electron microscope (SEM) photograph of looks；
Fig. 3 A is the preparing spherical SiO 2 by spray drying method load phosphotungstic acid and silica gel complex carrier
(MCMGJ-HPA-1) the SEM scanning electron microscope (SEM) photograph of microscopic appearance；
Fig. 3 B is the preparing spherical SiO 2 by spray drying method load phosphotungstic acid and silica gel complex carrier
(MCMGJ-HPA-1) the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of amplification.
Detailed description of the invention
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst contains spherical dioxy
SiClx and silica gel complex carrier and be supported on the phosphorus on described preparing spherical SiO 2 and silica gel complex carrier
Wolframic acid, and on the basis of the gross weight of this catalyst, the content of described phosphotungstic acid is 1-50 weight %, institute
The content stating preparing spherical SiO 2 and silica gel complex carrier is 50-99 weight %；In the case of more preferably, with
On the basis of the gross weight of described catalyst, the content of described phosphotungstic acid is 5-45 weight %, described spherical two
The content of silicon oxide and silica gel complex carrier is 55-95 weight %；Described preparing spherical SiO 2 and silica gel are multiple
The mean particle diameter closing carrier is 5-30 micron, preferably 10-30 micron；Specific surface area is 300-390
Meters squared per gram, preferably 330-370 meters squared per gram, more preferably 350 meters squared per gram；Pore volume is
0.5-1.5 ml/g, preferably 0.8-1.2 ml/g, more preferably 1 ml/g；Most probable pore size is
0.5-4 nanometer, preferably 1-3 nanometer, more preferably 2 nanometers；In this case, it is possible not only to obtain
Obtain gratifying catalytic effect, but also cost can be reduced.
According to the present invention, the mean particle diameter of described carried phospho-tungstic acid catalyst is 5-30 micron,
Specific surface area is 180-220 meters squared per gram, preferably 190-210 meters squared per gram, more preferably 200
Meters squared per gram；Most probable pore size is 1-3 nanometer, preferably 1.2-1.8 nanometer, more preferably 1.5 nanometers；
Pore volume is 0.1-1 ml/g, preferably 0.1-0.5 ml/g, more preferably 0.2 ml/g.
According to the present invention, described carrier is preparing spherical SiO 2 and silica gel complex carrier, described spherical dioxy
SiClx and silica gel complex carrier can be prepared by the method comprised the following steps:
(1) template and ammonia mixing are fully dissolved to solids；
(2) step (1) gained solution and esters of silicon acis are 25-60 DEG C in temperature, mechanical agitation speed
For sucking filtration after mixing contacts 1-100 hour under 100-400r/min；
(3) waterglass is contacted with mineral acid, and by the washing of gained mixture, sucking filtration after contact；
(4) by the mesoporous silicon oxide filter cake prepared by (1) and (2) and the silica gel prepared by (3)
Filter cake and silicon dioxide and silica gel complex carrier ball milling together；
(5) spray after the pressed powder obtained by (4) being configured to slurry in the presence of deionized water
Mist is dried；
(6) afterproduct heating, removed template method will be spray-dried by (5) gained.
According to the present invention, described template can be cetyl trimethyl bromination commonly used in the art
Ammonium, described esters of silicon acis is tetraethyl orthosilicate.
In the case of according to the invention it is preferred to, the temperature of described contact is 10-60 DEG C, and the time is that 1-5 is little
Time；Waterglass and mineral acid are the most specifically particularly limited to, and described waterglass is the solution of sodium silicate, described
Mineral acid is one or more in sulphuric acid, nitric acid and hydrochloric acid, and usual described mineral acid is solution, and institute
The pH value stating waterglass and described mineral acid mixed solution is 2-4；Described waterglass: described mineral acid
Weight ratio is 3-6:1.
It is a kind of separation liquid well-known to those skilled in the art and solid particle that described sucking filtration separates
Mode, for utilizing air pressure, separates the mixture of liquid and solid particle or liquid and liquid；Institute
State the mode of washing that is well known to those skilled in the art of washing, be preferably washing, pure wash in one or
Multiple.
According to the present invention, to the condition ground and concrete operation method, there is no particular limitation, not destroy
Or the most do not destroy carrier structure and make silica gel, silicon dioxide and silica gel be as the criterion in entering carrier duct.This
Skilled person can select various suitable conditions to implement the present invention according to mentioned above principle.
According to one embodiment of the present invention, described silicon dioxide and the preparation method of silica gel complex carrier
Including: mesoporous silicon oxide filter cake and silica gel filter cake are joined in the ball grinder of ball mill, in ball grinder
Wall is polytetrafluoroethyllining lining, a diameter of 2-3mm of abrading-ball, and rotating speed is 300-500r/min.At ball milling
Continuously grinding 0.1-100 hour at temperature is 15-100 DEG C in tank, takes out pressed powder afterwards.Abrading-ball
Quantity depends on the size of ball grinder, is the ball grinder of 50-150ml for size, it is possible to use 1
Abrading-ball.The material of described abrading-ball can be Achates, politef, preferably Achates；After ball milling
Pressed powder is configured to slurry in the presence of deionized water at temperature is 25-60 DEG C, then by this slurry
Joining high speed rotating in nebulizer, rotating speed is 10000-15000r/min, preferably 12000r/min.
According to the present invention, there is no particular limitation for the condition of described removed template method, and such as, temperature is permissible
For 300-600 DEG C, the time can be 10-80 hour.
According to the present invention, during preparing mesoporous silicon oxide filter cake, cetyl trimethyl bromination
The mol ratio of ammonium, silicate, ammonia and deionized water can change within the specific limits, cetyl three
The mol ratio of methyl bromide ammonium, silicate, ammonia and deionized water can be 1:0.1-1:0.1-5:
100-200, preferably 1:0.2-0.8:0.5-4:110-180, more preferably 1:0.37:2.8:142.
Wherein, the molal quantity of cetyl trimethylammonium bromide is according to the average mark of cetyl trimethylammonium bromide
Son amount is calculated.
Present invention also offers the preparation method of a kind of carried phospho-tungstic acid catalyst, wherein, the method bag
Include: described preparing spherical SiO 2 and silica gel complex carrier are configured in the presence of deionized water with phosphotungstic acid
It is spray-dried after slurry, makes phosphotungstic acid be supported on described preparing spherical SiO 2 and silica gel complex carrier
On；By described preparing spherical SiO 2 and silica gel complex carrier on the basis of the gross weight with phosphotungstic acid, described phosphorus
The consumption of wolframic acid is 1-50 weight %, and the consumption of described preparing spherical SiO 2 and silica gel complex carrier is
50-99 weight %；The mean particle diameter of described preparing spherical SiO 2 and silica gel complex carrier is that 5-30 is micro-
Rice, specific surface area is 300-390 meters squared per gram, and pore volume is 0.5-1.5 ml/g, most probable pore size
For 0.5-4 nanometer.
According to one embodiment of the present invention, the preparation method bag of described carried phospho-tungstic acid catalyst
Include: by described preparing spherical SiO 2 and silica gel complex carrier and described phosphotungstic acid in the presence of deionized water
Stir 1-24 hour at a temperature of 25-60 DEG C, be configured to slurry, in molar ratio, preparing spherical SiO 2 and silicon
Glue complex carrier: deionized water: phosphotungstic acid can be 1:15-35:0.5-1.5；Preparing spherical SiO 2 and
Silica gel complex carrier: deionized water: phosphotungstic acid can be preferably 1:20-25:0.8-1.2；Spherical dioxy
SiClx and silica gel complex carrier: deionized water: phosphotungstic acid can be more preferably 1:25:1, then should
Slurry joins high speed rotating in nebulizer, and rotating speed is 10000-15000r/min, and preferably 12000
R/min, obtains preparing spherical SiO 2 and the catalyst of silica gel complex carrier of load phosphotungstic acid.
According to the present invention, the size of described preparing spherical SiO 2 and silica gel complex carrier can be in very wide range
Interior change, it is preferable that the mean particle diameter of described preparing spherical SiO 2 and silica gel complex carrier is 5-30
Micron, preferably 10-30 micron；Specific surface area is 300-390 meters squared per gram, preferably 330-370
Meters squared per gram, more preferably 350 meters squared per gram；Pore volume is 0.5-1.5 ml/g, preferably 0.8-1.2
Ml/g, more preferably 1 ml/g；Most probable pore size is 0.5-4 nanometer, preferably 1-3 nanometer,
More preferably 2 nanometers.
According to the present invention, described preparing spherical SiO 2 and silica gel complex carrier can be by comprising the following steps
Method prepare:
(1) template and ammonia mixing are fully dissolved to solids；
(2) step (1) gained solution and esters of silicon acis are 25-60 DEG C in temperature, mechanical agitation speed
For sucking filtration after mixing contacts 1-100 hour under 100-400r/min；
(3) waterglass is contacted with mineral acid, and by the washing of gained mixture, sucking filtration after contact；
(4) by the mesoporous silicon oxide filter cake prepared by (1) and (2) and the silica gel prepared by (3)
Filter cake and silicon dioxide and silica gel complex carrier ball milling together；
(5) spray after the pressed powder obtained by (4) being configured to slurry in the presence of deionized water
Mist is dried；
(6) afterproduct heating, removed template method will be spray-dried by (5) gained.
According to the present invention, described template can be cetyl trimethyl bromination commonly used in the art
Ammonium, described esters of silicon acis is tetraethyl orthosilicate.
In the case of according to the invention it is preferred to, the temperature of described contact is 10-60 DEG C, and time of contact is 1-5
Hour；Waterglass and mineral acid are the most specifically particularly limited to, it is preferable that described waterglass is sodium silicate
Solution, described mineral acid is the solution of one or more in sulphuric acid, nitric acid and hydrochloric acid, usual described nothing
Machine acid is solution, and the pH value of the solution of described waterglass and described mineral acid is 2-4；Described water glass
Glass: described mineral acid weight ratio is 3-6:1.
It is a kind of separation liquid well-known to those skilled in the art and solid particle that described sucking filtration separates
Mode, for utilizing air pressure, separates the mixture of liquid and solid particle or liquid and liquid；Institute
State the mode of washing that is well known to those skilled in the art of washing, be preferably washing, pure wash in one or
Multiple.
According to the present invention, to the condition ground and concrete operation method, there is no particular limitation, not destroy
Or the most do not destroy carrier structure and make silica gel, silicon dioxide and silica gel be as the criterion in entering carrier duct.This
Skilled person can select various suitable conditions to implement the present invention according to mentioned above principle.
According to the present invention, to the condition being spray-dried and concrete operation method, there is no particular limitation, ability
Field technique personnel can select various suitable condition to implement the present invention.
According to one embodiment of the present invention, described silicon dioxide and the preparation method of silica gel complex carrier
Including: mesoporous silicon oxide filter cake and silica gel filter cake are joined in the ball grinder of ball mill, in ball grinder
Wall is polytetrafluoroethyllining lining, a diameter of 2-3mm of abrading-ball, and rotating speed is 300-500r/min.At ball milling
Continuously grinding 0.1-100 hour at temperature is 15-100 DEG C in tank, takes out pressed powder afterwards.Abrading-ball
Quantity depends on the size of ball grinder, is the ball grinder of 50-150ml for size, it is possible to use 1
Abrading-ball.The material of described abrading-ball can be Achates, politef, preferably Achates；After ball milling
Pressed powder is configured to mixture slurry in the presence of deionized water at temperature is 25-60 DEG C, then will
This slurry joins high speed rotating in nebulizer, and rotating speed is 10000-15000r/min, and preferably 12000
r/min。
According to the present invention, there is no particular limitation for the condition of described removed template method, and such as, temperature is permissible
For 300-600 DEG C, the time can be 10-80 hour.
According to the present invention, during preparing mesoporous silicon oxide filter cake, cetyl trimethyl bromination
The mol ratio of ammonium, silicate, ammonia and deionized water can change within the specific limits, cetyl three
The mol ratio of methyl bromide ammonium, silicate, ammonia and deionized water can be 1:0.1-1:0.1-5:
100-200, preferably 1:0.2-0.8:0.5-4:110-180, more preferably 1:0.37:2.8:142.
Wherein, the molal quantity of cetyl trimethylammonium bromide is according to the average mark of cetyl trimethylammonium bromide
Son amount is calculated.
According to one embodiment of the present invention, the preparation method bag of described carried phospho-tungstic acid catalyst
Include: by preparing spherical SiO 2 and silica gel complex carrier and described phosphotungstic acid in the presence of deionized water 25
At a temperature of DEG C-60 DEG C, stirring is to dissolving, and is configured to mixture slurry, preparing spherical SiO 2 and silica gel compound
Carrier: deionized water: the mol ratio of phosphotungstic acid can be 1:15-35:0.5-1.5, preparing spherical SiO 2
And silica gel complex carrier: deionized water: the mol ratio of phosphotungstic acid can be preferably 1:20-25:0.8-1.2,
Preparing spherical SiO 2 and silica gel complex carrier: deionized water: the mol ratio of phosphotungstic acid can be more preferably 1:
25:1；And be spray-dried at a temperature of 100 DEG C-300 DEG C, preferably spray at a temperature of 200 DEG C
Mist is dried, and obtains carried phospho-tungstic acid catalyst.
Additionally, present invention also offers the application in ketal reaction of the described catalyst.
Further, present invention also offers the preparation method of a kind of ketal, wherein, the method includes: urging
In the presence of agent, under conditions of ketal reaction, Ketohexamethylene is made to contact with glycerol, to obtain ketal,
Wherein, the carried phospho-tungstic acid catalyst that described catalyst provides for the present invention.
According to the present invention, in ketal reaction, the mol ratio of Ketohexamethylene and glycerol can be in very wide range
Interior change, such as, the mol ratio of Ketohexamethylene and glycerol can be 1:0.5-10, described support type phosphorus
The consumption of tungstic acid catalyst has no particular limits, and those skilled in the art can enter according to the needs of reaction
The adjustment that row is suitable, but under preferable case, relative to the Ketohexamethylene of 100 weight portions, described catalyst
Consumption can be 1-15 weight portion, more preferably 2-14 weight portion.
In the present invention, the condition of described ketal reaction is known to those skilled in the art, such as, described
Under the conditions of the condition of ketal reaction may include that back flow reaction, the time of reaction is 1-10 hour, excellent
Selection of land, the time of reaction can be 2-8 hour.
According to the present invention, after ketal reaction terminates, final reactant mixture can be centrifuged point
From, the centrifugal solid formation obtained is vacuum dried 1-24 hour, preferably at 50-120 at 25-200 DEG C
It is vacuum dried 6-10 hour at DEG C, the catalyst that can be recycled.
Below in conjunction with embodiment, the present invention is described in detail.
In following example, cetyl trimethylammonium bromide (CTAB) is purchased from lark prestige (J&K),
Mean molecule quantity 364, CAS:57-09-0.
In following example, X-ray diffraction analysis purchased from the model of Bruker AXS company of Germany is being
Carry out on the X-ray diffractometer of D8 Advance；Scanning electron microscope analysis is purchased from FEI Co. of the U.S.
Model is to carry out in the scanning electron microscope of XL-30；Elementary analysis is purchased from An Jielun company type of the U.S.
Number for carrying out on 7500CX instrument；Pore structure study is at U.S. Autosorb-1 type nitrogen adsorption desorption instrument
Test；Reaction product liquid phase composition analysis is purchased from Agilent company of Britain 7890A/5973N makings connection
Carry out with on instrument.
Embodiment 1
Preparing spherical SiO 2 and the preparation of silica gel complex carrier:
Cetyl trimethylammonium bromide and tetraethyl orthosilicate are joined in ammonia spirit, feeds intake by mole
Ratio, cetyl trimethylammonium bromide: tetraethyl orthosilicate: ammonia (25%): deionized water=1:0.37:
2.8:142, at a temperature of 80 DEG C, stirring is to dissolving, by solution sucking filtration and obtain mesoporous silicon oxide filter cake.
By waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight %, and press water glass
Glass: sulphuric acid weight ratio=5:1 fully reacts 1.5 hours, adjusts with the sulphuric acid that concentration is 98 weight %
Whole pH is 3, and through sucking filtration, distilled water wash, reaction mass is washed till sodium ions content is 0.02 weight
Amount %, obtains silica gel filter cake.
10 grams of mesoporous silicon oxide filter cakes and 10 grams of silica gel filter cakes of above-mentioned preparation are put into together
In 100ml ball grinder, wherein, ball grinder material is politef, and Material quality of grinding balls is Achates, abrading-ball
A diameter of 3mm, quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, temperature in ball grinder
Degree is ball milling 1 hour at 60 DEG C, obtains 20 grams of pressed powders；This pressed powder is dissolved at 25 DEG C
In 100 grams of deionized waters, it is spray-dried under rotating speed is 12000r/min；After being spray-dried
To product in Muffle furnace 500 DEG C calcine 24 hours, removed template method, obtain 20 grams removing templates
The target product preparing spherical SiO 2 of agent and silica gel complex carrier, named MCMGJ.
By above-mentioned 20 grams of preparing spherical SiO 2s and silica gel complex carrier at a temperature of 25 DEG C together with phosphotungstic acid
Putting in deionized water, stirring is to dissolving, and preparing spherical SiO 2 and silica gel complex carrier: deionized water:
The mol ratio of phosphotungstic acid is 1:25:1, and is spray-dried at a temperature of 200 DEG C, obtains loading phosphorus
The preparing spherical SiO 2 of wolframic acid and silica gel complex carrier, named MCMGJ-HPA-1.
With XRD, scanning electron microscope and xrf analysis instrument, this carried phospho-tungstic acid catalyst is carried out table
Levy.
Fig. 1 is X-ray diffracting spectrum, and wherein, a is preparing spherical SiO 2 and silica gel complex carrier
(MCMGJ) XRD spectra, b are the preparing spherical SiO 2 by spray drying method load phosphotungstic acid
And the XRD spectra of silica gel complex carrier (MCMGJ-HPA-1), abscissa is 2 θ, and vertical coordinate is
Intensity.The low-angle spectral peak occurred from XRD spectra, preparing spherical SiO 2 and silica gel complex carrier
(MCMGJ) XRD spectra a, by the preparing spherical SiO 2 of spray drying method load phosphotungstic acid and
XRD spectra b of silica gel complex carrier (MCMGJ-HPA-1) is respectively provided with specific to mesoporous material
The hexagonal hole road structure of 2D.
Fig. 2 A and Fig. 2 B is SEM scanning electron microscope (SEM) photograph, and wherein, Fig. 2 A is preparing spherical SiO 2 and silicon
The SEM scanning electron microscope (SEM) photograph of the microscopic appearance of glue complex carrier (MCMGJ)；Fig. 2 B is spherical dioxy
The SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the amplification of SiClx and silica gel complex carrier (MCMGJ).
As seen from the figure, the microscopic appearance of preparing spherical SiO 2 and silica gel complex carrier (MCMGJ) is average
Granularity is the Mesoporous Spheres of 5-30 μm.
Fig. 3 A and Fig. 3 B is SEM scanning electron microscope (SEM) photograph, and wherein, Fig. 3 A is loaded by spray drying method
The preparing spherical SiO 2 of phosphotungstic acid and the microscopic appearance of silica gel complex carrier (MCMGJ-HPA-1)
SEM scanning electron microscope (SEM) photograph；Fig. 3 B passes through preparing spherical SiO 2 and the silica gel of spray drying method load phosphotungstic acid
The SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the amplification of complex carrier (MCMGJ-HPA-1).By
Figure understands, by preparing spherical SiO 2 and the silica gel complex carrier of spray drying method load phosphotungstic acid
(MCMGJ-HPA-1) microscopic appearance is the most basic keeps spherical, and average particle size is 5-30 μm.
What table 1 was preparing spherical SiO 2 and silica gel complex carrier (MCMGJ) with load phosphotungstic acid is spherical
Silicon dioxide and the pore structure parameter of silica gel complex carrier (MCMGJ-HPA-1).
Table 1
By the data of upper table 1 it can be seen that sphericity mesoporous silicon dioxide is after load phosphotungstic acid, pore volume
The most significantly reduce with specific surface area, and, the sample of load phosphotungstic acid is drawn by elemental analyser analysis
Middle phosphorus content is 0.1 weight %, and W content is 2.4 weight %, this explanation phosphorus tungsten during load-reaction
Acid enters into sphericity mesoporous silicon dioxide composite inner.
Embodiment 2
Preparing mesoporous silicon oxide filter cake by method same as in Example 1, difference is that silica gel is filtered
Cake is by by waterglass that concentration is 15 weight % and hydrochloric acid solution that concentration is 12 weight %, and presses
Waterglass: hydrochloric acid weight ratio=3:1 fully reacts 1.5 hours, with the salt that concentration is 37 weight %
It is 2 that acid adjusts pH, and through sucking filtration, distilled water wash, reaction mass is washed till sodium ions content is 0.2
Weight %, prepares.
10 grams of mesoporous silicon oxide filter cakes and 10 grams of silica gel filter cakes of above-mentioned preparation are put into together
In 100ml ball grinder, wherein, ball grinder material is politef, and Material quality of grinding balls is Achates, abrading-ball
A diameter of 3mm, quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, temperature in ball grinder
Degree is ball milling 1 hour at 60 DEG C, obtains 20 grams of pressed powders；This pressed powder is dissolved at 60 DEG C
In 100 grams of deionized waters, it is spray-dried under rotating speed is 12000r/min；After being spray-dried
To product in Muffle furnace 500 DEG C calcine 24 hours, removed template method, obtain 20 grams removing templates
The target product preparing spherical SiO 2 of agent and silica gel complex carrier, named MCMGJ-2.
By above-mentioned 20 grams of preparing spherical SiO 2s and silica gel complex carrier at a temperature of 25 DEG C together with phosphotungstic acid
Putting in deionized water, stirring is to dissolving, and preparing spherical SiO 2 and silica gel complex carrier: deionized water:
The mol ratio of phosphotungstic acid is 1:15:0.5, and is spray-dried at a temperature of 200 DEG C, is loaded
The preparing spherical SiO 2 of phosphotungstic acid and silica gel complex carrier, named MCMGJ-HPA-2.
Table 2 is the ball of preparing spherical SiO 2 and silica gel complex carrier (MCMGJ-2) and load phosphotungstic acid
Shape silicon dioxide and the pore structure parameter of silica gel complex carrier (MCMGJ-HPA-2).
Table 2
By the data of upper table 2 it can be seen that sphericity mesoporous silicon dioxide is after load phosphotungstic acid, pore volume
The most significantly reduce with specific surface area, and, the sample of load phosphotungstic acid is drawn by elemental analyser analysis
Middle phosphorus content is 0.1 weight %, and W content is 11 weight %, this explanation phosphorus tungsten during load-reaction
Acid enters into sphericity mesoporous silicon dioxide composite inner.
Comparative example 1
Identical with the method that embodiment 1 prepares carried phospho-tungstic acid catalyst, institute's difference is this system
Preparation Method does not has silica gel filter cake, and this meso-porous titanium dioxide silicon carrier does not has ball milling, does not the most spray
Be dried, but by by this mesoporous silicon oxide carrier impregnation in Salkowski's solution, make phosphotungstic acid load
On meso-porous titanium dioxide silicon carrier, named MCM-HPA-3.
Comparative example 2
Identical with the method that embodiment 1 prepares carried phospho-tungstic acid catalyst, institute's difference is this system
Preparation Method does not carry out the method step being spray-dried, obtains carried phospho-tungstic acid catalyst, named
MCMGJ-HPA-QM-4。
Comparative example 3
Identical with the method that embodiment 1 prepares carried phospho-tungstic acid catalyst, institute's difference is this system
Preparation Method does not carry out the method step of ball milling, obtains carried phospho-tungstic acid catalyst, named
MCMGJ-HPA-PW-5。
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for illustrating the catalysis activity of the carried phospho-tungstic acid catalyst according to the present invention.
By the carried phospho-tungstic acid catalyst (MCMGJ-HPA-1) in embodiment 1 at 150 DEG C true
Empty dry 6 hours, after being cooled to room temperature, weigh 0.5 gram, then weigh 11.3 grams of Ketohexamethylene and 9.2
Gram glycerol is sequentially placed in 100ml there-necked flask, stirs 2 little under conditions of being heated to reflux at 100 DEG C
Time, after being cooled to room temperature, centrifugation, in course of reaction, side reaction is few and equipment is not produced corrosion,
Employing gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: the conversion ratio of Ketohexamethylene is 80.5%,
The selectivity of Ketohexamethylene-glycerol ketal is 99%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for urging after the carried phospho-tungstic acid catalyst recovery according to the present invention is described
Change activity.
Carried phospho-tungstic acid catalyst (MCMGJ-HPA-1) in EXPERIMENTAL EXAMPLE 1 is reclaimed, and
It is vacuum dried 6 hours at 150 DEG C, after being cooled to room temperature, weighs 0.5 gram, then weigh 11.3 grams of rings
Hexanone and 9.2 grams of glycerol are sequentially placed in 100ml there-necked flask, at 100 DEG C of bars being heated to reflux
Stirring 2 hours under part, after being cooled to room temperature, centrifugation, in course of reaction, side reaction is few and the most right
Equipment produces corrosion, uses gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: turning of Ketohexamethylene
Rate is 79%, and the selectivity of Ketohexamethylene-glycerol ketal is 99%.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for illustrating the catalysis activity of the carried phospho-tungstic acid catalyst according to the present invention.
By the carried phospho-tungstic acid catalyst (MCMGJ-HPA-2) in embodiment 2 at 150 DEG C true
Empty dry 6 hours, after being cooled to room temperature, weigh 1 gram, then weigh 22.6 grams of Ketohexamethylene and 18.4
Gram glycerol is sequentially placed in 100ml there-necked flask, stirs 2 little under conditions of being heated to reflux at 100 DEG C
Time, after being cooled to room temperature, centrifugation, in course of reaction, side reaction is few and equipment is not produced corrosion,
Use gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: the conversion ratio of Ketohexamethylene is 80%, ring
The selectivity of hexanone-glycerol ketal is 99%.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for urging after the carried phospho-tungstic acid catalyst recovery according to the present invention is described
Change activity.
Carried phospho-tungstic acid catalyst (MCMGJ-HPA-2) in EXPERIMENTAL EXAMPLE 3 is reclaimed, and
It is vacuum dried 6 hours at 150 DEG C, after being cooled to room temperature, weighs 1 gram, then weigh 22.6 grams of hexamethylenes
Ketone and 18.4 grams of glycerol are sequentially placed in 100ml there-necked flask, 100 DEG C of conditions being heated to reflux
Lower stirring 2 hours, after being cooled to room temperature, centrifugation, in course of reaction, side reaction is few and does not has setting
Standby generation is corroded, and uses gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, and result is: turning of Ketohexamethylene
Rate is 78%, and the selectivity of Ketohexamethylene-glycerol ketal is 99%.
Experimental comparison's example 1
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, except for the difference that, carried phospho-tungstic acid catalyst
(MCMGJ-HPA-1) the carried phospho-tungstic acid catalyst prepared by the comparative example 1 of identical weight
(MCM-HPA-3) replace, result: in course of reaction, side reaction is many and equipment is produced corrosion, ring
The conversion ratio of hexanone is 74%, and Ketohexamethylene-glycerol ketal selectivity is 99%.
Experimental comparison's example 2
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, except for the difference that, the EXPERIMENTAL EXAMPLE 1 of recovery
Carried phospho-tungstic acid catalyst (MCMGJ-HPA-1) is by Experimental comparison's example 1 of the recovery of identical weight
Load phosphotungstic acid catalyst (MCM-HPA-3) replace, result: in course of reaction side reaction many and
Equipment is produced corrosion, and the conversion ratio of Ketohexamethylene is 70%, and Ketohexamethylene-glycerol ketal selectivity is 99
%
Experimental comparison's example 3
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, except for the difference that, carried phospho-tungstic acid catalyst
(MCMGJ-HPA-1) the carried phospho-tungstic acid catalyst prepared by the comparative example 2 of identical weight
(MCMGJ-HPA-QM-4) replace, result: in course of reaction, side reaction is many and equipment is produced corruption
Erosion, the conversion ratio of Ketohexamethylene is 72%, and Ketohexamethylene-glycerol ketal selectivity is 99%.
Experimental comparison's example 4
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, except for the difference that, the EXPERIMENTAL EXAMPLE 1 of recovery
Carried phospho-tungstic acid catalyst (MCMGJ-HPA-1) is by Experimental comparison's example 2 of the recovery of identical weight
Load phosphotungstic acid catalyst (MCMGJ-HPA-QM-4) replace, result: secondary anti-in course of reaction
How and equipment should be produced corrosion, the conversion ratio of Ketohexamethylene is 69%, and Ketohexamethylene-glycerol ketal selects
Property is 99%.
Experimental comparison's example 5
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, except for the difference that, carried phospho-tungstic acid catalyst
(MCMGJ-HPA-1) the carried phospho-tungstic acid catalyst prepared by the comparative example 3 of identical weight
(MCMGJ-HPA-PW-5) replace, result: in course of reaction, side reaction is many and equipment is produced corruption
Erosion, the conversion ratio of Ketohexamethylene is 71%, and Ketohexamethylene-glycerol ketal selectivity is 99%.
Experimental comparison's example 6
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, except for the difference that, the EXPERIMENTAL EXAMPLE 1 of recovery
Carried phospho-tungstic acid catalyst (MCMGJ-HPA-1) is by Experimental comparison's example 3 of the recovery of identical weight
Load phosphotungstic acid catalyst (MCMGJ-HPA-PW-5) replace, result: secondary anti-in course of reaction
How and equipment should be produced corrosion, the conversion ratio of Ketohexamethylene is 65%, and Ketohexamethylene-glycerol ketal selects
Property is 99%.
By above example 1-2 and comparative example 1-3 and EXPERIMENTAL EXAMPLE 1-4, Experimental comparison's example 1-6
Data it can be seen that EXPERIMENTAL EXAMPLE 1-4 substantially effective than Experimental comparison's example 1-6, explanation is adopted
With spray drying method, phosphotungstic acid is carried on preparing spherical SiO 2 and silica gel complex carrier, it is thus achieved that load
The catalytic performance of type phosphotungstic acid catalyst is preferable so that apply this catalyst to carry out catalysis of pimelinketone and the third three
During the ketal reaction of alcohol, side reaction does not produces corrosion to equipment, and conversion ratio improves simultaneously, and this
The carried phospho-tungstic acid catalyst of invention can be through reclaiming and Reusability, and aftertreatment technology is simple.
Claims (18)
1. a carried phospho-tungstic acid catalyst, it is characterised in that this catalyst contains spherical titanium dioxide
Silicon and silica gel complex carrier and be supported on the phosphorus tungsten on described preparing spherical SiO 2 and silica gel complex carrier
Acid, and on the basis of the gross weight of this catalyst, the content of described phosphotungstic acid is 1-50 weight %, described
The content of preparing spherical SiO 2 and silica gel complex carrier is 50-99 weight %；Described preparing spherical SiO 2 and
The mean particle diameter of silica gel complex carrier is 5-30 micron, and specific surface area is 300-390 meters squared per gram,
Pore volume is 0.5-1.5 ml/g, and most probable pore size is 0.5-4 nanometer；
The preparation of described preparing spherical SiO 2 and silica gel complex carrier comprises the steps: that (1) is by template
Fully dissolve to solids with ammonia mixing；(2) by step (1) gained solution and esters of silicon acis in temperature
For 25-60 DEG C, mechanical agitation speed be under 100-400r/min mixing contact 1-100 hour after sucking filtration；(3)
Waterglass is contacted with mineral acid, and by the washing of gained mixture, sucking filtration after contact；(4) will be by
And (2) mesoporous silicon oxide filter cake ball milling together with the silica gel filter cake prepared by (3) of preparing (1)；
(5) spray dried is carried out after the pressed powder obtained by (4) being configured to slurry in the presence of deionized water
Dry；(6) afterproduct heating, removed template method will be spray-dried by (5) gained.
Carried phospho-tungstic acid catalyst the most according to claim 1, wherein, with this catalyst
On the basis of gross weight, the content of described phosphotungstic acid is 5-45 weight %, described preparing spherical SiO 2 and silica gel
The content of complex carrier is 55-95 weight %；Described preparing spherical SiO 2 and silica gel complex carrier average
Particle diameter is 10-30 micron, and specific surface area is 330-370 meters squared per gram, and pore volume is 0.8-1.2
Ml/g, most probable pore size is 1-3 nanometer.
Carried phospho-tungstic acid catalyst the most according to claim 1, wherein, described support type phosphorus
The mean particle diameter of tungstic acid catalyst is 5-30 micron, and specific surface area is 180-220 meters squared per gram,
Pore volume is 0.1-1 ml/g, and most probable pore size is 1-3 nanometer.
Carried phospho-tungstic acid catalyst the most according to claim 1, wherein, described template is
Cetyl trimethylammonium bromide, described esters of silicon acis is tetraethyl orthosilicate.
Carried phospho-tungstic acid catalyst the most according to claim 1, wherein, in step (3),
The temperature of described contact is 10-60 DEG C, and the time is 1-5 hour；Described mineral acid be sulphuric acid, nitric acid and
One or more in hydrochloric acid, and the pH value of described mineral acid is 2-4.
Carried phospho-tungstic acid catalyst the most according to claim 1, wherein, the bar of described ball milling
Part includes: a diameter of 2-3mm of abrading-ball, and rotating speed is 300-500r/min, and in ball grinder, temperature is 15-100
DEG C, the time is 0.1-100 hour；The condition of described spray drying includes: temperature is 25-60 DEG C, rotating speed
For 10000-15000r/min；Described removed template method temperature is 300-600 DEG C, and the time is 10-80 hour.
Carried phospho-tungstic acid catalyst the most according to claim 1, wherein, ratio,
Cetyl trimethylammonium bromide: esters of silicon acis: ammonia: deionized water=1:0.1-1:0.1-5:100-200；
Waterglass: the weight ratio of mineral acid is 3-6:1.
8. a preparation method for carried phospho-tungstic acid catalyst, wherein, the method includes: by described
It is laggard that preparing spherical SiO 2 and silica gel complex carrier and phosphotungstic acid are configured to slurry in the presence of deionized water
Row is spray-dried, and makes phosphotungstic acid be supported on described preparing spherical SiO 2 and silica gel complex carrier；With described
On the basis of the gross weight of preparing spherical SiO 2 and silica gel complex carrier and phosphotungstic acid, the consumption of described phosphotungstic acid
For 1-50 weight %, the consumption of described preparing spherical SiO 2 and silica gel complex carrier is 50-99 weight %；
The mean particle diameter of described preparing spherical SiO 2 and silica gel complex carrier is 5-30 micron, specific surface area
For 300-390 meters squared per gram, pore volume is 0.5-1.5 ml/g, and most probable pore size is 0.5-4 nanometer；
The preparation of described preparing spherical SiO 2 and silica gel complex carrier comprises the steps: that (1) is by template
Fully dissolve to solids with ammonia mixing；(2) by step (1) gained solution and esters of silicon acis in temperature
For 25-60 DEG C, mechanical agitation speed be under 100-400r/min mixing contact 1-100 hour after sucking filtration；(3)
Waterglass is contacted with mineral acid, and by the washing of gained mixture, sucking filtration after contact；(4) will be by
And (2) mesoporous silicon oxide filter cake ball milling together with the silica gel filter cake prepared by (3) of preparing (1)；
(5) spray dried is carried out after the pressed powder obtained by (4) being configured to slurry in the presence of deionized water
Dry；(6) afterproduct heating, removed template method will be spray-dried by (5) gained.
Preparation method the most according to claim 8, wherein, with described preparing spherical SiO 2 and silicon
On the basis of the gross weight of glue complex carrier and phosphotungstic acid, the consumption of described phosphotungstic acid is 5-45 weight %, institute
The consumption stating preparing spherical SiO 2 and silica gel complex carrier is 55-95 weight %；And described spherical titanium dioxide
The mean particle diameter of silicon and silica gel complex carrier is 10-30 micron, and specific surface area is 330-370 square
Rice/gram, pore volume is 0.8-1.2 ml/g, and most probable pore size is 1-3 nanometer.
Preparation method the most according to claim 8 or claim 9, wherein, preparing spherical SiO 2 and silica gel
Complex carrier: deionized water: the mol ratio of phosphotungstic acid is 1:15-35:0.5-1.5.
11. preparation methoies according to claim 8, wherein, described template is cetyl three
Methyl bromide ammonium, described esters of silicon acis is tetraethyl orthosilicate.
12. preparation methoies according to claim 8, wherein, the temperature of described contact is 10-60
DEG C, the time is 1-5 hour；Described mineral acid is one or more in sulphuric acid, nitric acid and hydrochloric acid, and
Described waterglass is 2-4 with the pH value of the mixed solution of described mineral acid.
13. preparation methoies according to claim 8, wherein, the condition of described ball milling includes: mill
A diameter of 2-3mm of ball, rotating speed is 300-500r/min, and in ball grinder, temperature is 15-100 DEG C, the time
For 0.1-100 hour；The condition of described spray drying includes: temperature 25-60 DEG C, and rotating speed is
10000-15000r/min；Described removed template method temperature is 300-600 DEG C, and the time is 10-80 hour.
14. preparation methoies according to claim 8, wherein, ratio, cetyl three
Methyl bromide ammonium: esters of silicon acis: ammonia: deionized water=1:0.1-0.6:5-50:100-500；Waterglass:
Mineral acid weight ratio is 3-6:1.
The catalyst that in 15. claim 8-14, preparation method described in any one prepares.
Catalyst described in any one application in ketal reaction in 16. claim 1-7 and 15.
The preparation method of 17. 1 kinds of Ketohexamethylene glycerol ketal, wherein, the method includes: at catalyst
In the presence of, under conditions of ketal reaction, make Ketohexamethylene contact with glycerol, to obtain ketal, its
Being characterised by, described catalyst is the catalyst in claim 1-7 and 15 described in any one.
18. preparation methoies according to claim 17, wherein, Ketohexamethylene and glycerol mole
Ratio is 1:0.5-10, and in terms of the phosphotungstic acid of load in described catalyst, relative to 100 weight portions
Ketohexamethylene, the consumption of described catalyst is 1-15 weight portion.
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| CN110496617B (en) * | 2018-05-17 | 2021-12-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN110496637B (en) * | 2018-05-17 | 2021-10-19 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN110075920B (en) * | 2019-03-26 | 2022-07-12 | 万华化学集团股份有限公司 | Preparation method and application of hierarchical porous silicon sphere loaded phosphomolybdic tungstic heteropoly acid catalyst |
| CN114345412A (en) * | 2020-10-13 | 2022-04-15 | 中石化南京化工研究院有限公司 | Supported polyoxometallate catalyst and preparation method and application thereof |
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