CN104248981B - The spherical complex carrier in three-dimensional cubic duct and catalyst and its preparation method and application and the preparation method of ethyl acetate - Google Patents
The spherical complex carrier in three-dimensional cubic duct and catalyst and its preparation method and application and the preparation method of ethyl acetate Download PDFInfo
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- CN104248981B CN104248981B CN201310264429.7A CN201310264429A CN104248981B CN 104248981 B CN104248981 B CN 104248981B CN 201310264429 A CN201310264429 A CN 201310264429A CN 104248981 B CN104248981 B CN 104248981B
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Abstract
The application in the esterification reaction of the preparation method that the invention provides the spherical complex carrier in the spherical complex carrier in a kind of three-dimensional cubic duct, a kind of three-dimensional cubic duct, the method spherical complex carrier in three-dimensional cubic duct prepared, a kind of phosphoric acid loaded catalyst, the preparation method of a kind of phosphoric acid loaded catalyst, described phosphoric acid loaded catalyst and the preparation method of a kind of ethyl acetate.The average particulate diameter of the spherical complex carrier in described three-dimensional cubic duct is 10 50 microns, specific surface area is 200 600 meters squared per gram, pore volume is 0.5 2 mls/g, and pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 48 nanometers and 20 30 nanometers.The phosphoric acid loaded catalyst that the present invention provides not only has higher catalysis activity, but also can be with Reusability.
Description
Technical field
The present invention relates to the spherical complex carrier in a kind of three-dimensional cubic duct, the ball in a kind of three-dimensional cubic duct
The preparation method of shape complex carrier, the spherical compound load in the three-dimensional cubic duct prepared by the method
Body, a kind of phosphoric acid loaded catalyst, the preparation method of a kind of phosphoric acid loaded catalyst, described phosphoric acid
Loaded catalyst application in the esterification reaction and the preparation method of a kind of ethyl acetate.
Background technology
Meso-porous molecular sieve material has that duct is orderly, aperture is adjustable, specific surface area and the advantage such as pore volume is bigger,
It is good catalyst and carrier material.In recent years, prepare with meso-porous molecular sieve material for template
It is active that the heterogeneous catalyst such as solid acid, heteropoly acid not only has higher catalysis, and side reaction is less,
Post processing is relatively simple.
At present, industrial usual concentrated sulphuric acid is as catalyst with synthesizing ethyl acetate, and it has equipment and throws
Money is big, side reaction is many, product separates the defects such as complicated and liquid waste processing difficulty, therefore, in order to overcome
Drawbacks described above, the catalyst for esterification reaction that exploitation makes new advances is to replace concentrated sulphuric acid, and people have carried out substantial amounts of grinding
Study carefully.Wherein, solid acid, solid super-strong acid and cation exchange resin etc. as the catalyst of esterification,
Being all more successfully to explore, these catalyst are respectively provided with higher catalysis activity, but there is also some not
Foot, as more in by-product etc..
Summary of the invention
It is an object of the invention to provide the spherical complex carrier in a kind of new three-dimensional cubic duct, a kind of three-dimensional
The preparation method of the spherical complex carrier in cube duct, the three-dimensional cubic duct that prepared by the method
Spherical complex carrier, a kind of phosphoric acid loaded catalyst, the preparation method of a kind of phosphoric acid loaded catalyst,
The application in the esterification reaction of described phosphoric acid loaded catalyst and the preparation method of a kind of ethyl acetate.
The invention provides the spherical complex carrier in a kind of three-dimensional cubic duct, wherein, described three-dimensional cubic
The average particulate diameter of the spherical complex carrier in duct is 10-50 micron, and specific surface area is that 200-600 puts down
Side's rice/gram, pore volume is 0.5-2 ml/g, and pore-size distribution is bimodal distribution, and described bimodal correspondence
Most probable pore size is respectively 4-8 nanometer and 20-30 nanometer.
Present invention also offers the preparation method of the spherical complex carrier in a kind of three-dimensional cubic duct, the method
Comprise the following steps:
(1) in the presence of template and butanol, tetraethyl orthosilicate is carried out first with acid agent and contacts, and
The product crystallization that obtains filtering after contacting first, obtains mesoporous silicon oxide filter cake；
(2) with mineral acid, waterglass is carried out second to contact, and the product obtained after the second contact is filtered,
Obtain silica gel filter cake；
(3) described mesoporous silicon oxide filter cake is mixed homogeneously and ball milling with silica gel filter cake, and by after ball milling
It is spray-dried after the pressed powder water slurrying obtained, the more described template in the product that will obtain
Removing.
Present invention also offers the spherical complex carrier in the three-dimensional cubic duct prepared by said method.
Present invention also offers a kind of phosphoric acid loaded catalyst, wherein, this phosphoric acid loaded catalyst bag
Include the spherical complex carrier in described three-dimensional cubic duct and be supported on the spherical of described three-dimensional cubic duct
Phosphoric acid on complex carrier.
Present invention also offers the preparation method of a kind of phosphoric acid loaded catalyst, the method includes described
The spherical complex carrier in three-dimensional cubic duct, phosphoric acid and water mix homogeneously, and the mixture obtained is carried out
It is spray-dried.
Present invention also offers the application in the esterification reaction of described phosphoric acid loaded catalyst.
Additionally, present invention also offers the preparation method of a kind of ethyl acetate, the method includes: in catalysis
In the presence of agent and under conditions of esterification, acetic acid is contacted with ethanol, obtain ethyl acetate, its
In, described catalyst is described phosphoric acid loaded catalyst.
It was found by the inventors of the present invention that include having the catalyst of the spherical complex carrier of above-mentioned pore structure
Catalysis activity higher, it is possible to catalysis acetic acid and the esterification of ethanol and obtain higher acetic acid conversion and
Ethyl acetate selectivity.Speculate its reason, it may be possible to due to: on the one hand, as a rule, although three-dimensional
The bigger serface of cube duct material and high pore volume can make it have higher catalysis activity, but simultaneously
Also stronger water suction, moisture absorption ability can be made it have, therefore, when three-dimensional cubic duct material is bar-shaped,
Agglomeration traits will be aggravated, stored, transport, post-treatment and application are made troubles.And what the present invention provided
The carrier in three-dimensional cubic duct is spherical, it is possible to reduces the agglomeration traits of powder body, improve its mobility.Separately
On the one hand, described carrier not only remains the high-specific surface area of ordered mesoporous material, big pore volume, large aperture
And the feature of narrow ditribution, and its pore-size distribution presents the bimodal distribution of uniqueness, more conducively active component
Load.That is, the present invention provide three-dimensional cubic duct spherical complex carrier dexterously by micro-sphere structure with
The advantage of the ordered mesoporous material that aperture has bimodal distribution combines, thus is described three-dimensional cubic duct
The application of spherical complex carrier more preferable platform is provided, and widened its application.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is X-ray diffracting spectrum (XRD figure spectrum), and wherein, a is the spherical of three-dimensional cubic duct
The XRD spectra of complex carrier (C1)；B is the three-dimensional of the load phosphoric acid obtained by spray drying method
The XRD spectra of the spherical complex carrier (Cat-1) in cube duct, abscissa is 2 θ, and vertical coordinate is strong
Degree；
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical complex carrier (C1) in three-dimensional cubic duct
(SEM figure)；
Fig. 3 A and 3B is three-dimensional cubic duct spherical of the load phosphoric acid obtained by spray drying method
The scanning electron microscope (SEM) photograph of complex carrier (Cat-1).
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The average particulate diameter of the spherical complex carrier in the three-dimensional cubic duct that the present invention provides is that 10-50 is micro-
Rice, specific surface area is 200-600 meters squared per gram, and pore volume is 0.5-2 ml/g, and pore-size distribution is double
Peak is distributed, and the most probable pore size of described bimodal correspondence is respectively 4-8 nanometer and 20-30 nanometer.Preferably
In the case of, the average particulate diameter of the spherical complex carrier in described three-dimensional cubic duct is 10-50 micron,
Specific surface area is 210-600 meters squared per gram, and pore volume is 0.8-1.8 ml/g, and pore-size distribution is bimodal
It is distributed, and the most probable pore size of described bimodal correspondence is respectively 5-8 nanometer and 22-28 nanometer.
The spherical complex carrier in described three-dimensional cubic duct has the meso-hole structure that three-dimensional cubic is orderly, its
In, duct interconnects, and this directly load being active substance such as phosphoric acid provides one well
Template, can make the active substance of load dispersed and be formed without the bulky grain of reunion in whole duct.
In the present invention, described average particulate diameter uses laser fineness gage to record, specific surface area,
Pore volume and most probable pore size record according to nitrogen adsorption methods.
The spherical complex carrier in the three-dimensional cubic duct according to the present invention, by by spherical complex carrier
Particle size controls within the scope of above-mentioned, it can be ensured that described spherical complex carrier is not susceptible to reunite, and
And be used as the loaded catalyst that carrier makes and can improve the reaction raw materials in esterification reaction process
Conversion ratio.When described spherical mesoporous meerschaum complex carrier specific surface area less than 200 meters squared per gram and/
Or pore volume less than 0.5 ml/g time, be used as the loaded catalyst that carrier is made catalysis activity
Can significantly reduce；When the specific surface area of described spherical complex carrier is more than 600 meters squared per gram and/or hole body
Long-pending more than 2 mls/g time, be used as the loaded catalyst that carrier makes and hold in esterification reaction process
Easily reunite, thus affect the reaction raw materials conversion ratio in esterification reaction process.
The preparation method of the spherical complex carrier in the three-dimensional cubic duct that the present invention provides comprises the following steps:
(1) in the presence of template and butanol, tetraethyl orthosilicate is carried out first with acid agent and contacts, and
The product crystallization that obtains filtering after contacting first, obtains mesoporous silicon oxide filter cake；
(2) with mineral acid, waterglass is carried out second to contact, and the product obtained after the second contact is filtered,
Obtain silica gel filter cake；
(3) described mesoporous silicon oxide filter cake is mixed homogeneously and ball milling with silica gel filter cake, and by after ball milling
It is spray-dried after the pressed powder water slurrying obtained, the more described template in the product that will obtain
Removing.
In the preparation process of the spherical complex carrier in above-mentioned three-dimensional cubic duct, mainly mesoporous by controlling
The pore-size distribution of the spherical complex carrier in described three-dimensional cubic duct is controlled by the composition of silica filter cake
For bimodal distribution, and mainly by control forming method (i.e., first by described mesoporous silicon oxide filter cake with
Silica gel filter cake mix homogeneously ball milling, spray dried after the pressed powder water slurrying that then will obtain after ball milling
Dry) microscopic appearance of the spherical complex carrier in described three-dimensional cubic duct is controlled as spherical.
The kind of described template is not particularly limited by the present invention, as long as the three-dimensional enabled to is stood
The spherical complex carrier of square duct has an above-mentioned pore structure, and such as, described template can be three embedding
Section copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene.Wherein, this template can be commercially available
(for example, it is possible to purchased from Aldrich, trade name P123, molecular formula is EO20PO70EO20),
Can also be prepared by existing various methods.When described template be PULLRONIC F68-
During polyoxyethylene, the molal quantity of described template is equal according to the number of polyoxyethylene-poly-oxypropylene polyoxyethylene
Molecular weight is calculated.
According to the present invention, the kind of described acid agent can be the conventional selection of this area, can be existing
Various acid or the mixture of acid.Wherein, the mixture of described acid or acid can use with pure state, it is also possible to
Use with the form of its aqueous solution, use the most in form of an aqueous solutions.Such as, described acid agent can be
One or more in aqueous hydrochloric acid solution, aqueous sulfuric acid, phosphate aqueous solution and aqueous solution of nitric acid, preferably
For aqueous hydrochloric acid solution.The pH value of described aqueous hydrochloric acid solution can be such as 1-6, preferably 3-5.
The condition of described first contact is not particularly limited by the present invention, such as, and described first contact
Condition generally includes temperature can be 10-60 DEG C, and the time can be 10-72 hour, and pH value can be 1-7；
Under preferable case, the condition of described first contact includes that temperature is 30-45 DEG C, and the time is 20-40 hour,
PH value is 3-6.For the uniform mixing being more beneficial between each material, described first contact is preferably in stirring
Under the conditions of carry out.The consumption of described acid agent is preferably so that the pH value of described first haptoreaction system is
1-7, more preferably 3-6.
The condition of described crystallization is also not particularly limited by the present invention, and such as, the condition of described crystallization is led to
Often including that temperature can be 30-150 DEG C, the time can be 10-72 hour；Under preferable case, described crystalline substance
The condition changed includes that temperature is 60-120 DEG C, and the time is 20-40 hour.Described crystallization passes through hydrothermal crystallizing
Method is implemented.
According to the present invention, during preparing mesoporous silicon oxide filter cake, the consumption of each material can be
Select in wider scope and adjust.Such as, described template, butanol rub with tetraethyl orthosilicate
Your ratio can be 1:10-100:10-90, preferably 1:30-80:40-80.Wherein, when described mould
When plate agent is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of described template according to polyoxyethylene-
The number-average molecular weight of polyoxypropylene polyoxyethylene is calculated.
Additionally, the present invention is to the way of contact between described template, butanol, tetraethyl orthosilicate and acid agent
It is not particularly limited, for example, it is possible to above-mentioned four kinds of materials are mixed contact simultaneously, it is also possible to will wherein
Several materials first mix contact, remaining material is added the mixture that obtains continues mixing connect again
Touch.Under preferable case, the described way of contact is first described template, butanol to be mixed homogeneously with acid agent,
And the mixture obtained is placed in 10-60 DEG C, in the water-bath of preferred 30-45 DEG C, then keeps temperature-resistant,
Again tetraethyl orthosilicate is slowly dropped in said mixture, and stirs reaction 10-72 hour, preferably
20-40 hour.On the basis of the template of 1g, the drop rate of described tetraethyl orthosilicate can be
0.1-1g/min。
The condition of described second contact is not particularly limited by the present invention, such as, and described second contact
Condition generally includes temperature can be 10-60 DEG C, preferably 20-40 DEG C；Time can be 1-5 hour,
It is preferably 1.5-3 hour；PH value is 2-4.For the uniform mixing being more beneficial between each material, described
Second contact is carried out the most under agitation.
As well known to those skilled in the art, described waterglass is the aqueous solution of sodium silicate, and its concentration can be
10-50 weight %, preferably 12-30 weight %.
The kind of described mineral acid can be the conventional selection of this area, for example, it is possible to be sulphuric acid, nitric acid
With one or more in hydrochloric acid.Described mineral acid can use in pure form, it is also possible to Yi Qishui
The form of solution uses.The consumption of described mineral acid is preferably so that the haptoreaction body of waterglass and mineral acid
The pH value of system is 2-4.
According to the present invention, in the preparation process of the spherical complex carrier in described three-dimensional cubic duct, step
(1) to use, the mode and filtered described in (2) can well known to a person skilled in the art that various mode is entered
OK, preferably sucking filtration separates.It is well-known to those skilled in the art to utilize air pressure that described sucking filtration separates
Power realizes a kind of mode that liquid separates with solid particle.
Additionally, during preparing described mesoporous silicon oxide filter cake and silica gel filter cake, by filter with
The process obtaining filter cake may include that after filtration, and with distilled water cyclic washing, (washing times is permissible
2-10), sucking filtration is then carried out.
According to the present invention, in step (3), described mesoporous silicon oxide filter cake and the consumption of silica gel filter cake
Can select according to the component of the spherical complex carrier in the three-dimensional cubic duct that expection obtains, such as,
Relative to the described mesoporous silicon oxide filter cake of 100 weight portions, the consumption of described silica gel filter cake can be
100-300 weight portion.
There is no particular limitation to the concrete operation method of ball milling and condition for the present invention, not destroy or substantially
Do not destroy carrier structure and make silica gel be as the criterion in entering carrier duct.Those skilled in the art can be according to upper
Stating principle selects various suitable conditions to implement the present invention.Specifically, described ball milling enters in ball mill
OK, wherein, in ball mill, the diameter of abrading-ball can be 2-3mm；The quantity of abrading-ball can be according to ball grinder
Size reasonably select, be the ball grinder of 50-150mL for size, generally can use 1
Individual abrading-ball；The material of described abrading-ball can be Achates, politef etc., preferably Achates.Described ball
The condition of mill includes: the rotating speed of abrading-ball can be 300-500r/min, and the temperature in ball grinder can be
15-100 DEG C, the time of ball milling can be 0.1-100 hour.
Additionally, during by pressed powder use water slurrying, described pressed powder does not has with the consumption of water
Limit especially, if the slurry that can be beneficially spray-dried, such as, described solid powder
End can be 1:0.5-5, preferably 1:1-2 with the weight ratio of water.
It is that those skilled in the art are public according to the present invention, the concrete operation method of described spray drying and condition
Know.Specifically, described pressed powder and water the slurry being made into is joined in nebulizer high speed rotating with
Realize being spray-dried.Wherein, the condition of spray drying includes that temperature can be 100-300 DEG C, rotation
Rotating speed can be 10000-15000r/min；In the case of Te Bieyouxuan, the condition of described spray drying includes
Temperature is 200 DEG C, and the rotating speed of rotation is 12000r/min.
According to the present invention, the method for removed template method is usually calcination method.Wherein, the bar of described calcination method
Part includes that temperature can be 300-600 DEG C, preferably 350-550 DEG C, most preferably 500 DEG C；Time can
Think 10-80 hour, preferably 20-30 hour, most preferably 24 hours.
Present invention also offers the spherical mesoporous meerschaum complex carrier prepared by said method.
Present invention also offers a kind of phosphoric acid loaded catalyst, wherein, this phosphoric acid loaded catalyst bag
Include the spherical complex carrier in above-mentioned three-dimensional cubic duct and be supported on the spherical of described three-dimensional cubic duct
Phosphoric acid on complex carrier.
Wherein, the spherical complex carrier in described three-dimensional cubic duct and the content of phosphoric acid can be this area
Conventional selection, such as, on the basis of the gross weight of described catalyst, the content of described phosphoric acid can be 1-50
Weight %, preferably 5-50 weight %；The content of the spherical complex carrier in described three-dimensional cubic duct is permissible
For 50-99 weight %, preferably 50-95 weight %.
In the present invention, described phosphoric acid loaded catalyst can be according to various sides commonly used in the art
Prepared by method, it is only necessary to loaded on the carrier by phosphoric acid.
In a preferred embodiment, in order to make the phosphoric acid loaded catalyst of preparation may be repeated
Utilizing, and still can obtain higher reaction raw materials conversion ratio during recycling, preparation is negative
The method of supported catalyst includes: spherical complex carrier, phosphoric acid and the water in above-mentioned three-dimensional cubic duct are mixed
Close uniformly, and the mixture obtained is spray-dried.
Wherein, the consumption of spherical complex carrier, phosphoric acid and the water in described three-dimensional cubic duct can be according in advance
The catalyst that phase obtains reasonably selects, such as, with the spherical compound load in described three-dimensional cubic duct
On the basis of total consumption of body and phosphoric acid, the consumption of described phosphoric acid can be 1-50 weight %, preferably 5-50
Weight %；The consumption of the spherical complex carrier in described three-dimensional cubic duct can be 50-99 weight %, excellent
Elect 50-95 weight % as.Additionally, the spherical complex carrier in described three-dimensional cubic duct and the weight ratio of water
Can be 1:15-35, preferably 1:20-25.
The method of described spray drying is known to the skilled person, as it has been described above, usually by described
The mixture of the spherical complex carrier in three-dimensional cubic duct, water and phosphoric acid joins high speed rotating in nebulizer
To realize being spray-dried, wherein, the condition of spray drying includes that temperature can be 100-300 DEG C, rotates
Rotating speed can be 10000-15000r/min；In the case of Te Bieyouxuan, the condition bag of described spray drying
Including temperature is 200 DEG C, and the rotating speed of rotation is 12000r/min.
Present invention also offers the application in the esterification reaction of above-mentioned phosphoric acid loaded catalyst.
Additionally, present invention also offers the preparation method of a kind of ethyl acetate, the method includes: in catalysis
In the presence of agent and under conditions of esterification, acetic acid is contacted with ethanol, obtain ethyl acetate, its
In, described catalyst is above-mentioned phosphoric acid loaded catalyst.
The consumption of described acetic acid and ethanol is not particularly limited by the present invention, obtains second as long as can react
Acetoacetic ester, but in order to improve the utilization rate of raw material, under preferable case, rubbing of described acetic acid and ethanol
That ratio is 1:0.5-10.
Additionally, the consumption of described phosphoric acid loaded catalyst is also not particularly limited by the present invention, permissible
Addition according to acetic acid in course of reaction and/or ethanol suitably selects, as a rule, relative to
The acetic acid of 100 weight portions, the consumption of described phosphoric acid loaded catalyst can be 1-15 weight portion, preferably
For 2-14 weight portion.
According to the present invention, the condition of described esterification is known to those skilled in the art, generally includes
Reaction temperature and response time.Wherein, in order to be more beneficial for the carrying out of esterification, described reaction is preferred
Under reflux conditions carry out, i.e. described reaction temperature is reflux temperature.The prolongation in response time can be
Improve conversion ratio and the yield of product of reactant in certain limit, but the response time is long to reaction
Amplitude that thing conversion ratio and product yield improve is the most inconspicuous, therefore, considers effect and efficiency,
Under preferable case, the described response time is 1-10 hour, more preferably 2-8 hour.
According to the present invention, the preparation method of described ethyl acetate is further preferably included in after esterification terminates,
It is centrifuged final reactant mixture separating, and by the centrifugal solid product obtained at 25-200 DEG C
It is vacuum dried 1-24 hour, is preferably vacuum dried 6-10 hour at 50-120 DEG C, negative to reclaim phosphoric acid
Supported catalyst.
Below in conjunction with embodiment, the present invention is described in detail.
In following example and comparative example, polyoxyethylene-poly-oxypropylene polyoxyethylene is public purchased from Aldrich
Department, is abbreviated as P123, and molecular formula is EO20PO70EO20, the registration number at U.S. chemical abstract is
The material of 9003-11-6, number-average molecular weight Mn is 5800.
In following example and comparative example, X-ray diffraction analysis is purchased from Bruker AXS company of Germany
The X-ray diffractometer that model is D8Advance on carry out；Scanning electron microscope analysis is purchased from U.S. FEI
The model of company is to carry out in the scanning electron microscope of XL-30；Pore structure parameter is analyzed purchased from the U.S.
The model of Kang Ta company is to carry out on the nitrogen adsorption desorption instrument of Autosorb-1, wherein, before testing,
Sample is deaerated 4 hours at 200 DEG C；The analysis of product liquid phase ingredient is purchased from Britain Agilent
Carry out on company's 7890A/5973N gas chromatograph-mass spectrometer.
In following example and comparative example, the conversion ratio (%) of acetic acid=(consumption-product of acetic acid
The content of middle acetic acid) consumption × 100% of ÷ acetic acid；Selectivity (the %)=ethyl acetate of ethyl acetate
Theoretical yield × 100% of actual production ÷ ethyl acetate.
Embodiment 1
The spherical complex carrier in the three-dimensional cubic duct that this embodiment provides for the present invention is described and catalysis
Agent and preparation method thereof.
(1) preparation of the spherical complex carrier in three-dimensional cubic duct:
By 6g(0.001mol) triblock copolymer template P123 be dissolved in 10mL concentrated hydrochloric acid and
In the mixed solution of 220mL deionized water, at 15 DEG C, stir 4h by P123 dissolving, to be formed thoroughly
Bright solution, then in this solution, add 6g(0.081mol) n-butyl alcohol stir 1h, then that this is molten
Liquid is placed in the water-bath of 30 DEG C, and is slowly added dropwise 12.9g(0.062mol with the speed of 1g/min) positive silicon
Acetoacetic ester, then at 30 DEG C, pH value be to stir 24h under conditions of 4.5, the most again 100 DEG C of conditions
Lower hydrothermal treatment consists 24h, is washed with deionized four times after finally filtering, obtains meso-porous titanium dioxide after sucking filtration
Silicon filter cake.
By waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight % by waterglass with
Sulphuric acid weight ratio is 5:1 mix homogeneously, then stirring reaction 1.5 hours at 15 DEG C, and will obtain
The sulfuric acid solution that product concentration is 98 weight % adjust pH value be 3, then by reaction mass
It is 0.02 weight % that sucking filtration, distilled water wash are washed till sodium ions content, obtains silica gel filter cake.
20 grams of mesoporous silicon oxide filter cakes are put in 100mL ball grinder together with 20 grams of silica gel filter cakes
(wherein, ball grinder material is politef, and Material quality of grinding balls is Achates, a diameter of 3mm of abrading-ball,
Quantity is 1, and rotating speed is 400r/min), closure ball grinding jar, ball at temperature is 60 DEG C in ball grinder
Grind 1 hour, obtain 40 grams of pressed powders.This pressed powder is dissolved in 30 grams of deionized waters, and
It is spray-dried at 200 DEG C, under rotating speed is 12000r/min, the product obtained after being then spray-dried
Thing calcine in the Muffle furnace of 500 DEG C 24 hours with removed template method, obtain 30 grams of removed template methods
The spherical complex carrier in target product three-dimensional cubic duct, named C1.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, the spherical complex carrier in above-mentioned 30 grams of three-dimensional cubic ducts is put into together with phosphoric acid
In deionized water, stirring to dissolve, control the spherical complex carrier in three-dimensional cubic duct, deionized water with
The weight ratio of phosphoric acid is 1:25:1, then by the mixture obtained at 200 DEG C, at rotating speed be
It is spray-dried under 12000r/min, obtains loading the spherical complex carrier in the three-dimensional cubic duct of phosphoric acid
(that is, phosphoric acid loaded catalyst), named Cat-1.
With X-ray diffractometer, scanning electron microscope and nitrogen adsorption desorption instrument to this three-dimensional cubic duct
The spherical complex carrier in the three-dimensional cubic duct of spherical complex carrier and load phosphoric acid characterizes.
Fig. 1 is X-ray diffracting spectrum (XRD figure spectrum), and wherein, a is the spherical of three-dimensional cubic duct
The XRD spectra of complex carrier (C1)；B is the three-dimensional of the load phosphoric acid obtained by spray drying method
The XRD spectra of the spherical complex carrier (Cat-1) in cube duct, abscissa is 2 θ, and vertical coordinate is strong
Degree.From the result of Fig. 1 it can be seen that by spray drying method obtain load phosphoric acid three-dimensional cubic pore
(211), (220) and (311) crystal face in XRD spectra b of the spherical complex carrier (Cat-1) in road
Diffraction maximum remains the most well, shows to have loaded the spherical complex carrier in the three-dimensional cubic duct of phosphoric acid
(Cat-1) pore passage structure still can keep the cubic structure of C1 and have good order.
Fig. 2 is the scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical complex carrier (C1) in three-dimensional cubic duct
(SEM figure), as seen from the figure, the microscopic appearance of the spherical complex carrier (C1) in three-dimensional cubic duct is
The Mesoporous Spheres of a diameter of 10-50 μm.
Fig. 3 A and Fig. 3 B is the spherical complex carrier in the three-dimensional cubic duct obtained by spray drying method
(Cat-1) scanning electron microscope (SEM) photograph of microscopic appearance.Wherein, Fig. 3 A is obtained by spray drying method
The scanning electron microscope (SEM) photograph of the microscopic appearance of the spherical complex carrier (Cat-1) in the three-dimensional cubic duct of load phosphoric acid；
Fig. 3 B is the spherical complex carrier in the three-dimensional cubic duct loading phosphoric acid obtained by spray drying method
(Cat-1) scanning electron microscope (SEM) photograph of high-amplification-factor.As seen from the figure, by bearing that spray drying method obtains
The microscopic appearance of the spherical complex carrier (Cat-1) carrying the three-dimensional cubic duct of phosphoric acid still keeps ball substantially
Shape, and particle diameter is 10-50 μm.
Table 1 be three-dimensional cubic duct spherical complex carrier (C1) and by spray drying method obtain negative
Carry the pore structure parameter of the spherical complex carrier (Cat-1) in the three-dimensional cubic duct of phosphoric acid.
Table 1
By the data of upper table 1 it can be seen that the spherical complex carrier in three-dimensional cubic duct is after load phosphoric acid,
Pore volume and aperture the most significantly reduce, and it can be said that bright, and during load-reaction, phosphoric acid enters into
The spherical complex carrier in three-dimensional cubic duct.
Comparative example 1
This comparative example for illustrate the spherical complex carrier in three-dimensional cubic duct of reference and catalyst and
Preparation method.
Prepare the spherical complex carrier in three-dimensional cubic duct according to the method for embodiment 1 and phosphoric acid support type is urged
Agent, except for the difference that, in the preparation process of the spherical complex carrier in three-dimensional cubic duct, do not include by
This pressed powder is dissolved in 30 grams of deionized waters, and is 12000r/min at 200 DEG C, at rotating speed
The step of lower spray drying, but directly described pressed powder is calcined in the Muffle furnace of 500 DEG C 24
Hour with removed template method, obtain the spherical complex carrier C1 and the three of load phosphoric acid in three-dimensional cubic duct
The spherical complex carrier DC1 in dimension cube duct.
Comparative example 2
This comparative example for illustrate the spherical complex carrier in three-dimensional cubic duct of reference and catalyst and
Preparation method.
Prepare the spherical complex carrier in three-dimensional cubic duct according to the method for embodiment 1 and phosphoric acid support type is urged
Agent, except for the difference that, in the preparation process of the spherical complex carrier in three-dimensional cubic duct, described mesoporous
The bar-shaped mesoporous silicon oxide SBA-15 filter cake of silica filter cake identical weight part is (commercially available from Changchun
High-tech limited company of Jilin University) substitute, obtain the spherical complex carrier in three-dimensional cubic duct
The spherical complex carrier DC2 in the three-dimensional cubic duct of C2 and load phosphoric acid.
Embodiment 2
The spherical complex carrier in the three-dimensional cubic duct that this embodiment provides for the present invention is described and catalysis
Agent and preparation method thereof.
(1) preparation of the spherical complex carrier in three-dimensional cubic duct:
By 6g(0.001mol) triblock copolymer template P123 be dissolved in 12mL concentrated hydrochloric acid and
In the mixed solution of 220mL deionized water, at 60 DEG C, stir 4h by P123 dissolving, to be formed thoroughly
Bright solution, then in this solution, add 2.2g(0.03mol) n-butyl alcohol stir 1h, then that this is molten
Liquid is placed in the water-bath of 30 DEG C, and is slowly added dropwise 16.7g(0.08mol with the speed of 1g/min) positive silicon
Acetoacetic ester, then at 60 DEG C, pH value be to stir 24h under conditions of 5.5, the most again 60 DEG C of conditions
Lower hydrothermal treatment consists 24h, is washed with deionized four times after finally filtering, obtains meso-porous titanium dioxide after sucking filtration
Silicon filter cake.
By waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight % by waterglass with
Sulphuric acid weight ratio is 5:1 mix homogeneously, then stirring reaction 1 hour at 60 DEG C, and will obtain
Product concentration be 98 weight % sulfuric acid solution adjust pH value be 2, then reaction mass is taken out
It is 0.02 weight % that filter, distilled water wash are washed till sodium ions content, obtains silica gel filter cake.
20 grams of mesoporous silicon oxide filter cakes are put in 100mL ball grinder together with 40 grams of silica gel filter cakes
(wherein, ball grinder material is politef, and Material quality of grinding balls is Achates, a diameter of 3mm of abrading-ball,
Quantity is 1, and rotating speed is 400r/min), closure ball grinding jar, ball at temperature is 60 DEG C in ball grinder
Grind 1 hour, obtain 60 grams of pressed powders.This pressed powder is dissolved in 30 grams of deionized waters, and
It is spray-dried at 200 DEG C, under rotating speed is 12000r/min, the product obtained after being then spray-dried
Thing calcine in the Muffle furnace of 500 DEG C 24 hours with removed template method, obtain 50 grams of removed template methods
The spherical complex carrier in target product three-dimensional cubic duct, named C2.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, the spherical complex carrier in above-mentioned 50 grams of three-dimensional cubic ducts is put into together with phosphoric acid
In deionized water, stirring to dissolve, control the spherical complex carrier in three-dimensional cubic duct, deionized water with
The weight ratio of phosphoric acid is 1:25:1, then by the mixture obtained at 200 DEG C, at rotating speed be
It is spray-dried under 12000r/min, obtains loading the spherical complex carrier in the three-dimensional cubic duct of phosphoric acid
(that is, phosphoric acid loaded catalyst), named Cat-2.
Table 2 be three-dimensional cubic duct spherical complex carrier (C2) and by spray drying method obtain negative
Carry the pore structure parameter of the spherical complex carrier (Cat-2) in the three-dimensional cubic duct of phosphoric acid.
Table 2
By the data of upper table 2 it can be seen that the spherical complex carrier in three-dimensional cubic duct is after load phosphoric acid,
Pore volume and aperture the most significantly reduce, and it can be said that bright, and during load-reaction, phosphoric acid enters into
The spherical complex carrier in three-dimensional cubic duct.
Embodiment 3
The spherical complex carrier in the three-dimensional cubic duct that this embodiment provides for the present invention is described and catalysis
Agent and preparation method thereof.
(1) preparation of the spherical complex carrier in three-dimensional cubic duct:
By 6g(0.001mol) triblock copolymer template P123 is dissolved in 9mL concentrated hydrochloric acid and 220mL
In the mixed solution of deionized water, at 40 DEG C, stirring 4h is to dissolve P123, forms clear solution,
4.5g(0.06mol is added again in this solution) n-butyl alcohol stir 1h, then this solution is placed in 40
DEG C water-bath in, and be slowly added dropwise 8.3g(0.04mol with the speed of 1g/min) tetraethyl orthosilicate, then
At 40 DEG C, pH value be to stir 24h under conditions of 3.5, the most again at 150 DEG C of Water Under heat treatments
10h, is washed with deionized four times after finally filtering, obtains mesoporous silicon oxide filter cake after sucking filtration.
By waterglass that concentration is 15 weight % and sulfuric acid solution that concentration is 12 weight % by waterglass with
Sulphuric acid weight ratio is 5:1 mix homogeneously, then stirring reaction 5 hours at 30 DEG C, and will obtain
Product concentration be 98 weight % sulfuric acid solution adjust pH value be 4, then reaction mass is taken out
It is 0.02 weight % that filter, distilled water wash are washed till sodium ions content, obtains silica gel filter cake.
20 grams of mesoporous silicon oxide filter cakes are put in 100mL ball grinder together with 60 grams of silica gel filter cakes
(wherein, ball grinder material is politef, and Material quality of grinding balls is Achates, a diameter of 3mm of abrading-ball,
Quantity is 1, and rotating speed is 400r/min), closure ball grinding jar, ball at temperature is 60 DEG C in ball grinder
Grind 1 hour, obtain 80 grams of pressed powders.This pressed powder is dissolved in 30 grams of deionized waters, and
It is spray-dried at 200 DEG C, under rotating speed is 12000r/min, the product obtained after being then spray-dried
Thing calcine in the Muffle furnace of 500 DEG C 24 hours with removed template method, obtain 70 grams of removed template methods
The spherical complex carrier in target product three-dimensional cubic duct, named C3.
(2) preparation of phosphoric acid loaded catalyst:
At 25 DEG C, the spherical complex carrier in above-mentioned 70 grams of three-dimensional cubic ducts is put into together with phosphoric acid
In deionized water, stirring to dissolve, control the spherical complex carrier in three-dimensional cubic duct, deionized water with
The weight ratio of phosphoric acid is 1:25:1, then by the mixture obtained at 200 DEG C, at rotating speed be
It is spray-dried under 12000r/min, obtains loading the spherical complex carrier in the three-dimensional cubic duct of phosphoric acid
(that is, phosphoric acid loaded catalyst), named Cat-3.
Table 3 be three-dimensional cubic duct spherical complex carrier (C3) and by spray drying method obtain negative
Carry the pore structure parameter of the spherical complex carrier (Cat-3) in the three-dimensional cubic duct of phosphoric acid.
Table 3
By the data of upper table 3 it can be seen that the spherical complex carrier in three-dimensional cubic duct is after load phosphoric acid,
Pore volume and aperture the most significantly reduce, and it can be said that bright, and during load-reaction, phosphoric acid enters into
The spherical complex carrier in three-dimensional cubic duct.
Embodiment 4
The spherical complex carrier in the three-dimensional cubic duct that this embodiment provides for the present invention is described and catalysis
Agent and preparation method thereof.
Prepare the spherical complex carrier in three-dimensional cubic duct according to the method for embodiment 1 and phosphoric acid support type is urged
Agent, except for the difference that, does not has the step being spray-dried during preparing phosphoric acid loaded catalyst,
And only by the method for dipping, phosphoric acid is supported on spherical complex carrier, thus prepares phosphoric acid support type and urge
Agent Cat-4.
Embodiment 5
The preparation method of the ethyl acetate that this embodiment provides for the present invention is described.
Phosphoric acid loaded catalyst Cat-1 in embodiment 1 is vacuum dried 6 hours at 150 DEG C,
Weigh 0.5 gram after being cooled to room temperature 25 DEG C, add successively with 11.5 grams of ethanol and 15 grams of acetic acid and put into 100mL
In there-necked flask, under heated reflux condition, stirring reaction 3 hours, are then cooled to room temperature 25 DEG C and take out
Filter separates, and utilizes the liquid phase ingredient of gas chromatograph-mass spectrometer analytical reactions product, and by calculating acetic acid
Conversion ratio and the selectivity of ethyl acetate, result is as shown in table 4.
Embodiment 6-8
The preparation method of the ethyl acetate that embodiment 6-8 provides for the present invention is described.
Prepare ethyl acetate according to the method for embodiment 5, except for the difference that, prepare by embodiment 2-4 respectively
Loaded catalyst replace described loaded catalyst Cat-1.As a result, acetic acid is each calculated
Conversion ratio and the selectivity of ethyl acetate, result is as shown in table 4.
Comparative example 3-4
Comparative example 3-4 is used for illustrating the reference preparation method of ethyl acetate.
Prepare ethyl acetate according to the method for embodiment 5, except for the difference that, prepare by comparative example 1-2 respectively
Loaded catalyst replace described loaded catalyst Cat-1.As a result, acetic acid is each calculated
Conversion ratio and the selectivity of ethyl acetate, result is as shown in table 4.
Table 4
| Numbering | Catalyst | The conversion ratio of acetic acid | The selectivity of ethyl acetate |
| Embodiment 5 | Cat-1 | 99.5% | 99% |
| Embodiment 6 | Cat-2 | 99.6% | 99% |
| Embodiment 7 | Cat-3 | 99.4% | 99% |
| Embodiment 8 | Cat-4 | 99.2% | 98% |
| Comparative example 3 | DCat-1 | 92% | 98% |
| Comparative example 4 | DCat-2 | 90% | 98% |
Embodiment 9-12 and comparative example 5-6
Prepare ethyl acetate according to the method for embodiment 5, except for the difference that, respectively with from embodiment 5-8 and
The catalyst that comparative example 3-4 reclaims replaces described loaded catalyst Cat-1.As a result, each calculate
The conversion ratio of acetic acid and the selectivity of ethyl acetate, result is as shown in table 5.
Table 5
| Numbering | Catalyst | The conversion ratio of acetic acid | The selectivity of ethyl acetate |
| Embodiment 9 | The Cat-1 reclaimed | 99.4% | 99% |
| Embodiment 10 | The Cat-2 reclaimed | 99.5% | 99% |
| Embodiment 11 | The Cat-3 reclaimed | 99.3% | 99% |
| Embodiment 12 | The Cat-4 reclaimed | 97.5% | 98% |
| Comparative example 5 | The DCat-1 reclaimed | 89% | 98% |
| Comparative example 6 | The DCat-2 reclaimed | 87% | 97% |
As can be seen from the above results, the support preparation method using the present invention to provide can obtain average
Grain a diameter of 10-50 micron, specific surface area is 200-600 meters squared per gram, pore volume be 0.5-2 milliliter/
Gram, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence be respectively 4-8 nanometer and
The spherical complex carrier in the three-dimensional cubic duct of 20-30 nanometer.Additionally, the phosphoric acid that the present invention provides is born
Supported catalyst, when the preparation of ethyl acetate, not only has higher acetic acid conversion and ethyl acetate
Selectivity, and also can be by reclaiming and Reusability, aftertreatment technology is simple.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
Execute the detail in mode, in the technology concept of the present invention, can be to the technical side of the present invention
Case carries out multiple simple variant, and these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technology described in above-mentioned detailed description of the invention is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, various possible compound modes are illustrated by the present invention the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as its
Without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (14)
1. the spherical complex carrier in a three-dimensional cubic duct, it is characterized in that, the average particulate diameter of the spherical complex carrier in described three-dimensional cubic duct is 10-50 micron, specific surface area is 200-600 meters squared per gram, pore volume is 0.5-2 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 4-8 nanometer and 20-30 nanometer；
Wherein, the spherical complex carrier in described three-dimensional cubic duct is obtained by following preparation method, and this preparation method comprises the following steps:
(1) in the presence of template and butanol, tetraethyl orthosilicate is carried out first contacts with acid agent, and the product crystallization that obtains after contacting first filtering, obtain mesoporous silicon oxide filter cake；
(2) with mineral acid, waterglass is carried out second to contact, and the product obtained after the second contact is filtered, obtain silica gel filter cake；
(3) described mesoporous silicon oxide filter cake is mixed homogeneously and ball milling with silica gel filter cake, and be spray-dried after the pressed powder water slurrying that will obtain after ball milling, the more described template removal in the product that will obtain.
Carrier the most according to claim 1, wherein, the average particulate diameter of the spherical complex carrier in described three-dimensional cubic duct is 10-50 micron, specific surface area is 210-600 meters squared per gram, pore volume is 0.8-1.8 ml/g, pore-size distribution is bimodal distribution, and the most probable pore size of described bimodal correspondence is respectively 5-8 nanometer and 22-28 nanometer.
3. a preparation method for the spherical complex carrier in three-dimensional cubic duct, the method comprises the following steps:
(1) in the presence of template and butanol, tetraethyl orthosilicate is carried out first contacts with acid agent, and the product crystallization that obtains after contacting first filtering, obtain mesoporous silicon oxide filter cake；
(2) with mineral acid, waterglass is carried out second to contact, and the product obtained after the second contact is filtered, obtain silica gel filter cake；
(3) described mesoporous silicon oxide filter cake is mixed homogeneously and ball milling with silica gel filter cake, and be spray-dried after the pressed powder water slurrying that will obtain after ball milling, the more described template removal in the product that will obtain.
Preparation method the most according to claim 3, wherein, in step (3), relative to the described mesoporous silicon oxide filter cake of 100 weight portions, the consumption of described silica gel filter cake is 100-300 weight portion.
Preparation method the most according to claim 3, wherein, in step (1), described template, butanol are 1:10-100:10-90 with the mol ratio of tetraethyl orthosilicate.
6., according to the preparation method described in claim 3 or 5, wherein, in step (1), described template is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；Described acid agent be pH value be the aqueous hydrochloric acid solution of 1-6.
7. according to the preparation method described in claim 3 or 5, wherein, the condition of described first contact includes that temperature is 10-60 DEG C, and the time is 10-72 hour, and pH value is 1-7；The condition of described crystallization includes that temperature is 30-150 DEG C, and the time is 10-72 hour.
Preparation method the most according to claim 3, wherein, in step (2), the condition of described second contact includes that temperature is 10-60 DEG C, and the time is 1-5 hour, and pH value is 2-4；Described mineral acid is one or more in sulphuric acid, nitric acid and hydrochloric acid.
Preparation method the most according to claim 3, wherein, in step (3), the condition of described ball milling includes: the rotating speed of abrading-ball is 300-500r/min, and the temperature in ball grinder is 15-100 DEG C, and the time of ball milling is 0.1-100 hour；Preferably, the condition of described spray drying includes: temperature is 100-300 DEG C, and rotating speed is 10000-15000r/min；Preferably, the condition of removed template method includes: temperature is 300-600 DEG C, and the time is 10-80 hour.
10. the spherical complex carrier in the three-dimensional cubic duct prepared by the method described in any one in claim 3-9.
11. 1 kinds of phosphoric acid loaded catalysts, it is characterised in that this phosphoric acid loaded catalyst includes the spherical complex carrier in the three-dimensional cubic duct described in claim 1,2 or 10 and is supported on the phosphoric acid on the spherical complex carrier in described three-dimensional cubic duct.
The preparation method of 12. 1 kinds of phosphoric acid loaded catalysts, the method includes the spherical complex carrier in three-dimensional cubic duct, phosphoric acid and the water mix homogeneously described in claim 1,2 or 10, and is spray-dried by the mixture obtained.
The application in the esterification reaction of phosphoric acid loaded catalyst described in 13. claim 11.
The preparation method of 14. 1 kinds of ethyl acetate, the method includes: in the presence of a catalyst and under conditions of esterification, is contacted with ethanol by acetic acid, obtains ethyl acetate, it is characterized in that, described catalyst is the phosphoric acid loaded catalyst described in claim 11.
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| CN108855068B (en) * | 2017-05-10 | 2019-08-20 | 中国石油化工股份有限公司 | The method of loaded catalyst and its preparation method and application and preparing propylene by dehydrogenating propane |
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| CN110496634B (en) * | 2018-05-17 | 2021-09-21 | 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 |
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