CN104415795B - Spherical zeolite mesoporous composite material and loaded catalyst and its preparation method and application and the preparation method of ethyl acetate - Google Patents
Spherical zeolite mesoporous composite material and loaded catalyst and its preparation method and application and the preparation method of ethyl acetate Download PDFInfo
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Abstract
The present invention relates to a kind of spherical zeolite mesoporous composite material, the preparation method of this spherical zeolite mesoporous composite material, the spherical zeolite mesoporous composite material prepared by the method, loaded catalyst containing this spherical zeolite mesoporous composite material, the preparation method of this loaded catalyst, the loaded catalyst prepared by the method, the application in the esterification reaction of this loaded catalyst, and use the method preparing ethyl acetate of this loaded catalyst, wherein, described spherical zeolite mesoporous composite material contains zeolite and has the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture.The described spherical zeolite mesoporous composite material using the present invention can significantly improve the conversion ratio of reaction raw materials in esterification reaction process as the loaded catalyst that carrier is made.
Description
Technical field
The present invention relates to a kind of spherical zeolite mesoporous composite material, the system of this spherical zeolite mesoporous composite material
Preparation Method, the method the spherical zeolite mesoporous composite material prepared, composite mesoporous containing this spherical zeolite
The loaded catalyst of material, the preparation method of this loaded catalyst, the method the support type prepared
Catalyst, the application in the esterification reaction of this loaded catalyst, and use this loaded catalyst
The method preparing ethyl acetate.
Background technology
Ethyl acetate is also known as ethyl acetate.Pure ethyl acetate is the liquid that water white transparency has aromatic odor
Body, is a kind of broad-spectrum fine chemical product, has the dissolubility of excellence, quick-drying, and purposes is wide
General, it is a kind of very important Organic Chemicals and fabulous industrial solvent, is widely used in acetic acid fine
Dimension, ethyl cellulose, vinyl, acetate fiber resin, chlorinated rubber, synthetic rubber, coating and oil
In the production process of paint etc..Its main application has: as industrial solvent, for coating, adhesive, second
In the products such as base cellulose, artificial leather, malthoid colouring agent, staple fibre；As adhesive, it is used for printing
Brush ink, the production of olivet；As extractant, for the production of the products such as medicine, organic acid.
In the traditional synthesis of ethyl acetate, generally using the concentrated sulfuric acid as catalyst, its shortcoming is
Equipment corrosion is serious, side reaction is many, product separates complicated and liquid waste processing difficulty etc..Dense in order to replace
Sulfuric acid has carried out substantial amounts of research as the catalyst of esterification, people.Employing loaded catalyst is made
Catalyst for esterification is one of more successful probing direction.
In existing loaded catalyst, use conventional meso-porous molecular sieve material as carrier.Typical case
Meso-porous molecular sieve material have bar-shaped mesoporous silicon oxide SBA-15.Although the mesoporous molecular of these routines
Sieve material has that duct is orderly, aperture is adjustable, specific surface area and the advantage such as pore volume is bigger so that use this
The loaded catalyst that a little meso-porous molecular sieve materials are made as carrier is in the preparation technology of ethyl acetate
Showing lot of advantages, such as, catalysis activity is high, side reaction is few, post processing is simple, but, greatly
Specific surface area and high pore volume make these meso-porous molecular sieve materials have stronger water suction, moisture absorption energy
Power, thus these loaded catalysts can be caused to reunite in esterification reaction process, and then can be serious
Reduce the conversion ratio of acetic acid in ethyl acetate preparation technology.
Summary of the invention
The invention aims to overcome the support type using existing meso-porous molecular sieve material to make to urge
The agent defect that reaction raw materials conversion ratio is relatively low in esterification reaction process, it is provided that one is suitable as carrier
Spherical zeolite mesoporous composite material, and the preparation method of this spherical zeolite mesoporous composite material, by this
Spherical zeolite mesoporous composite material prepared by method, containing the support type of this spherical zeolite mesoporous composite material
Catalyst, the preparation method of this loaded catalyst, the method the loaded catalyst prepared, this is born
Supported catalyst application in the esterification reaction, and use the ethyl acetate of preparing of this loaded catalyst
Method.
In order to achieve the above object, the present inventor, by finding after research, has one-dimensional channels
The meso-porous molecular sieve material of diplopore distributed architecture introduces zeolite, makes zeolite enter meso-porous molecular sieve material
In duct, and this mesoporous composite material is made be not susceptible to reunite spherical, so can retain Jie
The high-specific surface area of porous molecular sieve material, big pore volume, large aperture and have one-dimensional channels diplopore distribution knot
The features such as structure, can reduce again the reunion of meso-porous molecular sieve material, increase its mobility so that use this Jie
The loaded catalyst that hole composite material is made can obtain significantly improve anti-when for esterification
Answer feed stock conversion, thus complete the present invention.
To this end, the invention provides a kind of spherical zeolite mesoporous composite material, wherein, this spherical zeolite is situated between
Hole composite material contains zeolite and has the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, and
The average grain diameter of this spherical zeolite mesoporous composite material is 30-60 micron, and specific surface area is that 150-600 puts down
Side's rice/gram, pore volume is 0.5-1.5 ml/g, and aperture is bimodal distribution, and bimodal the most corresponding first
Most probable pore size and the second most probable pore size, described first most probable pore size is less than described second most probable hole
Footpath, and described first most probable pore size is 5-15 nanometer, described second most probable pore size is 10-40 nanometer.
Present invention also offers a kind of method preparing spherical zeolite mesoporous composite material, the method include with
Lower step:
(1) provide and there is the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, as component a；
(2) silica gel is provided or prepares the filter cake of silica gel, as component b；
(3) carry out mixing and ball milling by described component a, described component b and zeolite, and will obtain after ball milling
The pressed powder water slurrying arrived, is then spray-dried the slurry obtained；
Wherein, described component a makes the average grain diameter of described spherical zeolite mesoporous composite material be 30-60
Micron, specific surface area is 150-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and aperture is double
Peak is distributed, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, and described first may be used
Several apertures are less than described second most probable pore size, and described first most probable pore size is 5-15 nanometer, institute
Stating the second most probable pore size is 10-40 nanometer.
Present invention also offers the spherical zeolite mesoporous composite material prepared by said method.
Present invention also offers a kind of loaded catalyst, this catalyst contains carrier and is supported on described load
Benzene sulfonic acid on body, wherein, described carrier is the described spherical zeolite mesoporous composite material according to the present invention.
Present invention also offers a kind of method preparing loaded catalyst, the method includes: by carrier,
Benzene sulfonic acid and water mix, and are spray-dried by the mixture obtained, and wherein, described carrier is
Spherical zeolite mesoporous composite material according to the present invention.
Present invention also offers the loaded catalyst prepared by said method.
Present invention also offers the application in the esterification reaction of above-mentioned loaded catalyst.
Present invention also offers the preparation method of a kind of ethyl acetate, the method includes: depositing at catalyst
Under, under conditions of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, wherein,
Described catalyst is the described loaded catalyst according to the present invention.
Spherical zeolite mesoporous composite material according to the present invention, combines and has one-dimensional channels diplopore and divide
The advantage of the meso-porous molecular sieve material of cloth structure, zeolite and ball type carrier so that this spherical zeolite is mesoporous
Composite is suitable as the carrier of loaded catalyst, is particularly suitable as using in the esterification reaction
The carrier of loaded catalyst.
In the described loaded catalyst of the present invention, the spherical zeolite mesoporous composite material as carrier has
There is the feature of the loose structure of meso-porous molecular sieve material, but also be loaded with benzene sulfonic acid so that this support type
Catalyst had both had the advantage such as catalysis activity height of loaded catalyst, side reaction is few, post processing is simple,
Have again acid catalytic performance so that this loaded catalyst in esterification reaction process time the most not
Equipment corrosion can be caused, but also the conversion ratio of reaction raw materials can be significantly improved.
It addition, when the method by being spray-dried prepares described loaded catalyst, described support type is urged
Agent may be repeated utilization, and it is former still can to obtain higher reaction during recycling
Material conversion ratio.
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 specification, 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 spherical zeolite mesoporous composite material according to the present invention and described loaded catalyst
X-ray diffraction spectrogram；
Fig. 2 is the X-ray diffraction spectrogram of support type benzene sulfonic acid catalyst according to the present invention；
Fig. 3 is that the SEM of the microscopic appearance of spherical zeolite mesoporous composite material according to the present invention sweeps
Retouch Electronic Speculum figure；
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of loaded catalyst according to the present invention.
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.It should be appreciated that
Detailed description of the invention described herein is merely to illustrate and explains the present invention, is not limited to this
Bright.
The invention provides a kind of spherical zeolite mesoporous composite material, wherein, this spherical zeolite is composite mesoporous
Material contains zeolite and has the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, and this is spherical
The average grain diameter of zeolite mesoporous composite material is 30-60 micron, specific surface area is 150-600 square metre/
Gram, pore volume is 0.5-1.5 ml/g, and aperture is bimodal distribution, and bimodal the most corresponding first may be used
Several apertures and the second most probable pore size, described first most probable pore size is less than described second most probable pore size,
And described first most probable pore size is 5-15 nanometer, described second most probable pore size is 10-40 nanometer.
Spherical zeolite mesoporous composite material according to the present invention has one-dimensional channels diplopore distributed architecture,
The average grain diameter of its particle uses laser fineness gage to record, specific surface area, pore volume and most probable hole
Footpath records according to nitrogen adsorption methods.
Spherical zeolite mesoporous composite material according to the present invention, by by composite mesoporous for spherical zeolite material
The particle size of material controls within the scope of above-mentioned, it can be ensured that described spherical zeolite mesoporous composite material is not
Easily reunite, and be used as the loaded catalyst that carrier makes and can improve esterification reaction process
In reaction raw materials conversion ratio.When the specific surface area of described spherical zeolite mesoporous composite material is flat less than 150
Side rice/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 zeolite mesoporous composite material is more than 600
When meters squared per gram and/or pore volume are more than 1.5 mls/g, it is used as the supported catalyst that carrier is made
Agent is susceptible to reunite in esterification reaction process, thus the reaction raw materials affected in esterification reaction process turns
Rate.
In the preferred case, the average grain diameter of described spherical zeolite mesoporous composite material is 35-55 micron,
Specific surface area is 180-600 meters squared per gram, and pore volume is 0.8-1.2 ml/g, described first most probable
Aperture is 6-12 nanometer, and described second most probable pore size is 25-35 nanometer.
In described spherical zeolite mesoporous composite material, relative to described in 100 weight portions, there is one-dimensional hole
The meso-porous molecular sieve material of road diplopore distributed architecture, the content of described zeolite can be 1-50 weight portion,
It is preferably 20-50 weight portion.
In the present invention, described spherical zeolite mesoporous composite material can also be containing two introduced by silica gel
Silica." silica introduced by silica gel " is referred at described spherical zeolite mesoporous composite material
In preparation process, bring in the final spherical zeolite mesoporous composite material prepared as preparing raw material silica gel
Silica component.In described spherical zeolite mesoporous composite material, relative to the institute of 100 weight portions
State the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, the described dioxy introduced by silica gel
The content of SiClx can be 1-200 weight portion, preferably 50-150 weight portion.
In the present invention, the meso-porous molecular sieve material described in one-dimensional channels diplopore distributed architecture can be
Meso-porous molecular sieve material commonly used in the art, and can prepare according to the conventional method.
Present invention also offers a kind of method preparing spherical zeolite mesoporous composite material, the method include with
Lower step:
(1) provide and there is the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, as component a；
(2) silica gel is provided or prepares the filter cake of silica gel, as component b；
(3) carry out mixing and ball milling by described component a, described component b and zeolite, and will obtain after ball milling
The pressed powder water slurrying arrived, is then spray-dried the slurry obtained；
Wherein, described component a makes the average grain diameter of described spherical zeolite mesoporous composite material be 30-60
Micron, specific surface area is 150-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and aperture is double
Peak is distributed, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, and described first may be used
Several apertures are less than described second most probable pore size, and described first most probable pore size is 5-15 nanometer, institute
Stating the second most probable pore size is 10-40 nanometer.
In step (1), preparation has the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture
The process of filter cake may include that in the presence of template, trimethylpentane and ethanol, by tetramethoxy
Silane contacts with acid agent, and the mixture obtained after contact is carried out crystallization and filtration.
The mol ratio of described template, ethanol, trimethylpentane and tetramethoxy-silicane can be 1:
100-500:200-500:50-200, preferably 1:200-400:250-400:70-150.
Described template can be various templates commonly used in the art.Most preferably, described template
Agent is triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene, and this template can be by being purchased
To (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, average according to polyoxyethylene-poly-oxypropylene polyoxyethylene of the molal quantity of described template
Molecular weight is calculated.
Described acid agent can be that various routine may be used for the regulation material of pH value or mixture (as molten
Liquid).Described acid agent uses the most in form of an aqueous solutions, and its pH value can be 1-6, preferably 3-5.
It is highly preferred that described acid agent be pH value be 1-6(more preferably 3-5) acetic acid and sodium acetate buffer solution.
With the acid condition that contacts of agent, tetramethoxy-silicane may include that temperature is 10-60 DEG C, the time is
10-72 hour, pH value was 1-7.For the uniform mixing being more beneficial between each material, described four methoxies
Base silane contacts with acid agent and carries out the most under agitation.The consumption of described acid agent is preferably so that four methoxies
Base silane is 1-7 with the pH value of the haptoreaction system of acid agent.
The condition of described crystallization may include that temperature is 30-150 DEG C, and the time is 10-72 hour.Preferably
In the case of, the condition of described crystallization includes: temperature is 40-100 DEG C, and the time is 20-40 hour.Described
Crystallization is implemented by hydrothermal crystallization method.
There is the mistake of the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture in above-mentioned preparation
Cheng Zhong, may include that after filtration, by deionized water repeatedly by filtering with the process obtaining filter cake
Washing (washing times can be 2-10), then carries out suction filtration.
In step (1), the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture " offer have "
It can be the product directly weighing or choosing the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture
Product, it is also possible to be the meso-porous molecular sieve material prepared and there is one-dimensional channels diplopore distributed architecture.Described have
The preparation method of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture can be according to the conventional method
Implementing, such as, its preparation method may include that having one-dimensional channels diplopore according to said method preparation divides
The filter cake of the meso-porous molecular sieve material of cloth structure, then by gained filtration cakes torrefaction, and will obtain after drying
Template removal in product.The condition of described removed template method may include that temperature is 300-600 DEG C,
Time is 10-80 hour.
In step (2), the process of the filter cake preparing silica gel may include that waterglass and inorganic acid
Contact, and the mixture obtained after contact is filtered.
There is no particular limitation for the condition that waterglass contacts with inorganic acid, can be according to the routine preparing silica gel
Technique suitably determines.Under preferable case, the condition that waterglass contacts with inorganic acid may include that temperature
Degree is 10-60 DEG C, preferably 20-40 DEG C；Time is 1-5 hour, preferably 1.5-3 hour；PH value
For 2-4.
For the uniform mixing being more beneficial between each material, waterglass process catalytic with inorganic acid is excellent
Choosing is carried out under agitation.
Described waterglass is the aqueous solution of sodium metasilicate, and its concentration can be 10-50 weight %, is preferably
12-30 weight %.
Described inorganic acid can be various inorganic acids commonly used in the art, for example, it is possible to be sulfuric acid,
At least one in nitric acid and hydrochloric acid.Described inorganic acid can use in pure form, it is also possible to it
The form of the aqueous solution uses.The consumption of described inorganic acid is preferably so that the haptoreaction of waterglass and inorganic acid
The pH value of system is 2-4.
In step (2), " offer silica gel " can be directly to weigh or choose silica gel product, it is also possible to
It is to prepare silica gel.The method preparing silica gel can be implemented according to the conventional method, such as, may include that root
The filter cake of silica gel is prepared, then by gained filtration cakes torrefaction according to said method.
In step (3), relative to the consumption of described component a of 100 weight portions, described component b
Consumption can be 1-200 weight portion, preferably 50-150 weight portion；The consumption of described zeolite can be
1-50 weight portion, preferably 20-50 weight portion.
In step (3), described ball milling can be carried out in ball mill, ball grinder in described ball mill
Inwall be preferably polytetrafluoroethyllining lining, the diameter of the abrading-ball in ball mill can be 2-3mm；Abrading-ball
Quantity reasonably can select according to the size of ball grinder, be the ball of 50-150ml for size
Grinding jar, generally can use 1 abrading-ball；The material of described abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc.,
It is preferably agate.The condition of described ball milling may include that the rotating speed of abrading-ball can be 300-500r/min,
Temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100 hour.
In step (3), the process by the pressed powder water slurrying obtained after ball milling can be at 25-60
Carry out at DEG C.In pulping process, pressed powder can be 1:0.1-2 with the weight ratio of the consumption of water,
It is preferably 1:0.3-0.9.
In step (3), described spray drying can be implemented according to conventional mode, such as can be
Atomizer is carried out.The condition of described spray drying may include that temperature is 100-300 DEG C, rotation
Rotating speed can be 10000-15000r/min；Under preferable case, the condition of described spray drying includes: temperature
Degree is for 150-250 DEG C, and the rotating speed of rotation is 11000-13000r/min.
In step (3), it is mesoporous point with one-dimensional channels diplopore distributed architecture when described component a
The filter cake of son sieve material, when described component b is the filter cake of silica gel, namely when step (1) is preparation tool
Having the process of the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, step (2) is system
During for the process of the filter cake of silica gel, the preparation method of described spherical zeolite mesoporous composite material can also be wrapped
Include: after the spray drying of step (3), from being spray-dried removed template method the product obtained.
The condition of described removed template method may include that temperature is 300-600 DEG C, and the time is 10-80 hour.
Present invention also offers the spherical zeolite mesoporous composite material prepared by said method.
Present invention also offers a kind of loaded catalyst, this catalyst contains carrier and is supported on described load
Benzene sulfonic acid on body, wherein, the above-mentioned spherical zeolite mesoporous composite material that described carrier provides for the present invention.
In described loaded catalyst, there is no particular limitation for the content of described carrier and benzene sulfonic acid, can
Suitably determine with the loaded catalyst conventional according to this area, such as, urge with described support type
On the basis of the gross weight of agent, the content of benzene sulfonic acid can be 1-50 weight %, preferably 5-50 weight
%；The content of described carrier is 50-99 weight %, preferably 50-95 weight %.
In the present invention, described loaded catalyst can be according to various method systems commonly used in the art
Standby, it is only necessary to benzene sulfonic acid is loaded on the carrier.
In a preferred embodiment, in order to make the loaded catalyst of preparation may be repeated profit
With, and during recycling, still can obtain higher reaction raw materials conversion ratio, preparation load
The method of type catalyst includes: carrier, benzene sulfonic acid and water are mixed, and is entered by the mixture obtained
Row is spray-dried, wherein, and the above-mentioned spherical zeolite mesoporous composite material that described carrier provides for the present invention.
Above-mentioned prepare loaded catalyst during, with total consumption of described carrier and benzene sulfonic acid as base
Standard, the consumption of benzene sulfonic acid can be 1-50 weight %, preferably 5-50 weight %；The use of described carrier
Amount can be 50-99 weight %, preferably 50-95 weight %.
Described spray drying can be implemented according to conventional mode, such as, can carry out in atomizer.Institute
The condition stating spray drying may include that temperature is 100-300 DEG C, and the rotating speed of rotation can be
10000-15000r/min；Under preferable case, the condition of described spray drying includes: temperature is 150-250
DEG C, the rotating speed of rotation is 11000-13000r/min.
Present invention also offers the loaded catalyst prepared by above-mentioned spray drying process.
Present invention also offers the application in the esterification reaction of above-mentioned 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, under conditions of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate,
It is characterized in that, the above-mentioned loaded catalyst that described catalyst provides for the present invention.
In the preparation method of described ethyl acetate, there is no particular limitation for the consumption of acetic acid and ethanol, only
Want to react to obtain ethyl acetate, but in order to improve the utilization rate of raw material, under preferable case, second
The mol ratio of acid and ethanol is 1:0.5-10.
Also there is no particular limitation for the consumption of described catalyst, can prepare work according to conventional ethyl acetate
Skill suitably determines.Under preferable case, relative to the acetic acid of 100 weight portions, described catalyst
Consumption is 1-15 weight portion, more preferably 2-14 weight portion.
In described esterification reaction process, 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.Reaction time can be 1-10
Hour, preferably 2-8 hour.
The preparation method of described ethyl acetate is additionally may included in after esterification terminates, to final reaction
Mixture carries out suction filtration separation, and is vacuum dried at 25-200 DEG C by the solid product of suction filtration isolated
1-24 hour, preferably it is vacuum dried 6-10 hour at 50-120 DEG C, to reclaim catalyst.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples, 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, average molecular mass Mn is 5800.
In following example and comparative example, X-ray diffraction analysis is purchased from Bruker AXS company of Germany
Model is to carry out on the X-ray diffractometer of D8Advance；Scanning electron microscope analysis is purchased from FEI Co. of the U.S.
The SEM that model is XL-30 on carry out；Pore structure parameter is analyzed purchased from U.S. Kang Ta
The model of company is to carry out on the nitrogen adsorption desorption instrument of Autosorb-1, wherein, before testing, and will
Sample deaerates 4 hours at 200 DEG C；The analysis of product liquid phase ingredient is purchased from Agilent company of Britain
Carry out on 7890A/5973N gas chromatograph-mass spectrometer；Described zeolite is purchased from Tianjin good fortune chemical reagent factory in morning, point
Minor is Na2O.Al2O3.xSiO2.yH2O。
In following EXPERIMENTAL EXAMPLE and Experimental comparison's example, the conversion ratio of acetic acid and the selectivity root of ethyl acetate
It is calculated according to below equation.
The consumption of the conversion ratio (%) of acetic acid=(content of acetic acid in the consumption-product of acetic acid) ÷ acetic acid
×100%
Theoretical yield × 100% of the actual production ÷ ethyl acetate of selectivity (the %)=ethyl acetate of ethyl acetate
Embodiment 1
The present embodiment for illustrate the spherical zeolite mesoporous composite material of the present invention and loaded catalyst with
And their preparation method.
(1) spherical zeolite mesoporous composite material is prepared
By 1.0g(0.0002mol) triblock copolymer surfactant P123 and 1.69g(0.037mol)
Ethanol joins 28ml, pH value be 4 acetic acid and sodium acetate buffer in, stir at 15 DEG C to
P123 is completely dissolved, the backward solution obtained in add 6g(0.053mol) trimethylpentane,
At 15 DEG C stir 8h, then be added thereto to 2.13g(0.014mol) tetramethoxy-silicane, 15 DEG C,
PH value is stirring 20h under conditions of 4.5, then the solution obtained is transferred to teflon-lined
In reactor, crystallization 24h at 60 DEG C, then carry out filtering and and being washed with deionized 4 times, so
Rear suction filtration obtains the filter cake A1 with the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture.
By waterglass and the sulfuric acid solution that concentration is 12 weight % that concentration is 15 weight % with weight ratio it is
5:1 carries out mixed being incorporated in haptoreaction 2 hours at 30 DEG C, then adjusts with the sulfuric acid that concentration is 98 weight %
Whole pH value, to 3, then carries out suction filtration to the reaction mass obtained, and is washed with distilled water to sodium ion
Content is 0.02 weight %, obtains the filter cake B1 of silica gel.
100ml ball is put into together with 10g filter cake A1,10g filter cake B1 and 10g zeolite of above-mentioned preparation
In grinding jar, wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, the diameter of abrading-ball
For 3mm, quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is
Ball milling 1 hour at 60 DEG C, obtains 30g pressed powder；This pressed powder is dissolved in 30 grams of deionizations
In water, it is spray-dried under rotating speed is 12000r/min at 200 DEG C；The product obtained after being spray-dried
Thing is calcined 24 hours in Muffle furnace at 500 DEG C, and removed template method obtains 30 grams and has one-dimensional hole
The spherical zeolite mesoporous composite material C1 of road diplopore distributed architecture.
(2) loaded catalyst is prepared
At 25 DEG C, by the 30g spherical zeolite mesoporous composite material C1 of preparation in above-mentioned steps (1)
Putting into together with benzene sulfonic acid in deionized water, stirring is to dissolving, and spherical zeolite mesoporous composite material C1
Being 50:50 with the weight ratio of benzene sulfonic acid, deionized water is 25:1 with the mol ratio of benzene sulfonic acid, at 200 DEG C
Under under rotating speed is 12000r/min be spray-dried, obtain loaded catalyst Cat-1.
Come this support type benzene sulphur with XRD, ESEM and U.S.'s Kang Ta company Atsorb-1 type instrument
Acid catalyst characterizes.
Fig. 1 is X-ray diffracting spectrum, and wherein, a is the XRD spectrum of spherical zeolite mesoporous composite material C1
Figure, b is the XRD spectra of loaded catalyst Cat-1.Can by the low-angle spectral peak occurred in XRD spectra
Knowing, it is peculiar that spherical zeolite mesoporous composite material C1 and loaded catalyst Cat-1 is respectively provided with mesoporous material institute
One-dimensional channels diplopore distributed architecture.
Fig. 2 is X-ray diffracting spectrum, for the XRD spectra of support type benzene sulfonic acid catalyst Cat-1.By
The low-angle spectral peak occurred in XRD spectra understands, and support type benzene sulfonic acid catalyst Cat-1 has mesoporous material
The specific one-dimensional channels diplopore distributed architecture of material.
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical zeolite mesoporous composite material C1.By scheming
Understand, the microscopic appearance of spherical zeolite mesoporous composite material C1 be particle diameter be the mesoporous of 30-60 μm
Ball.
Fig. 4 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of loaded catalyst Cat-1.As seen from the figure,
The microscopic appearance of loaded catalyst Cat-1 keeps spherical substantially, and its particle diameter is 30-60 μm.
The pore structure parameter such as table 1 below of spherical zeolite mesoporous composite material C1 and loaded catalyst Cat-1
Shown in.
Table 1
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C1 | 290 | 1.1 | 8,40 | 30-60 |
| Catalyst Cat-1 | 160 | 0.9 | 7,28 | 30-60 |
By the data of upper table 1 it can be seen that spherical zeolite mesoporous composite material is after load benzene sulfonic acid,
Specific surface area and pore volume have reduced, and this explanation benzene sulfonic acid during load-reaction enters into spherical
The inside of zeolite mesoporous composite material.
Comparative example 1
Method according to embodiment 1 prepares spherical zeolite mesoporous composite material and loaded catalyst, and institute is not
With, during preparation is used as the mesoporous composite material of carrier, it is added without zeolite, thus prepares respectively
Mesoporous composite material D1 and loaded catalyst Cat-D-1.
Comparative example 2
Method according to embodiment 1 prepares spherical zeolite mesoporous composite material and loaded catalyst, and institute is not
With, during preparing loaded catalyst, with the bar-shaped mesoporous silicon oxide of identical weight
SBA-15(is purchased from high-tech limited company of Jilin University) replace that there is one-dimensional channels diplopore distribution knot
The filter cake A1 of the meso-porous molecular sieve material of structure, thus prepare mesoporous composite material D2 respectively and support type is urged
Agent Cat-D-2.
Embodiment 2
The present embodiment for illustrate the spherical zeolite mesoporous composite material of the present invention and loaded catalyst with
And their preparation method.
Method according to embodiment 1 prepares spherical zeolite mesoporous composite material and loaded catalyst, and institute is not
With, during preparing loaded catalyst, there is no the step being spray-dried, and only by dipping
Benzene sulfonic acid is supported on spherical zeolite mesoporous composite material by method, thus prepares loaded catalyst
Cat-2。
Embodiment 3
The present embodiment for illustrate the spherical zeolite mesoporous composite material of the present invention and loaded catalyst with
And their preparation method.
(1) spherical zeolite mesoporous composite material is prepared
By 1.0g(0.0002mol) triblock copolymer surfactant P123 and 1.84g(0.04mol)
Ethanol joins 28ml, pH value be 5 acetic acid and sodium acetate buffer in, stir at 15 DEG C to
P123 is completely dissolved, the backward solution obtained in add 9.12g(0.08mol) trimethylpentane,
At 15 DEG C stir 8h, then be added thereto to 3.04g(0.02mol) tetramethoxy-silicane, 25 DEG C,
PH value is stirring 15h under conditions of 5.5, then the solution obtained is transferred to teflon-lined
In reactor, crystallization 10h at 100 DEG C, then carry out filter and and be washed with deionized 4 times,
Then suction filtration obtains the filter cake A3 with the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture.
By waterglass and the sulfuric acid solution that concentration is 12 weight % that concentration is 15 weight % with weight ratio it is
4:1 carries out mixed being incorporated in haptoreaction 1.5 hours at 40 DEG C, then with the sulfuric acid that concentration is 98 weight %
Adjust pH value to 2, then the reaction mass obtained carried out suction filtration, and be washed with distilled water to sodium from
Sub-content is 0.02 weight %, obtains the filter cake B3 of silica gel.
100ml ball is put into together with 20g filter cake A3,15g filter cake B3 and 15g zeolite of above-mentioned preparation
In grinding jar, wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, the diameter of abrading-ball
For 3mm, quantity is 1, and rotating speed is 300r/min.Closure ball grinding jar, in ball grinder, temperature is
Ball milling 0.5 hour at 80 DEG C, obtains 50g pressed powder；This pressed powder is dissolved in 36 grams of deionizations
In water, it is spray-dried under rotating speed is 11000r/min at 250 DEG C；The product obtained after being spray-dried
Thing is calcined 15 hours in Muffle furnace at 550 DEG C, removed template method, obtains 30 grams of spherical zeolite and is situated between
Hole composite material C3.
(2) loaded catalyst is prepared
At 25 DEG C, by the 20g spherical zeolite mesoporous composite material C3 of preparation in above-mentioned steps (1)
Putting into together with benzene sulfonic acid in deionized water, stirring is to dissolving, and spherical zeolite mesoporous composite material C3
Being 95:5 with the weight ratio of benzene sulfonic acid, deionized water is 25:1 with the mol ratio of benzene sulfonic acid, at 150 DEG C
It is spray-dried under rotating speed is 13000r/min, obtains loaded catalyst Cat-3.
The pore structure parameter such as table 2 below of spherical zeolite mesoporous composite material C3 and loaded catalyst Cat-3
Shown in.
Table 2
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C3 | 300 | 1.3 | 6,25 | 30-60 |
| Catalyst Cat-3 | 220 | 1.2 | 5,22 | 30-60 |
Embodiment 4
The present embodiment for illustrate the spherical zeolite mesoporous composite material of the present invention and loaded catalyst with
And their preparation method.
(1) spherical zeolite mesoporous composite material is prepared
By 1.0g(0.0002mol) triblock copolymer surfactant P123 and 3.68g(0.08mol)
Ethanol joins 28ml, pH value be 3 acetic acid and sodium acetate buffer in, stir at 15 DEG C to
P123 is completely dissolved, the backward solution obtained in add 5.7g(0.05mol) trimethylpentane,
At 15 DEG C stir 8h, then be added thereto to 4.56g(0.03mol) tetramethoxy-silicane, 40 DEG C,
PH value is stirring 10h under conditions of 3.5, then the solution obtained is transferred to teflon-lined
In reactor, crystallization 48h at 40 DEG C, then carry out filtering and and being washed with deionized 4 times, so
Rear suction filtration obtains the filter cake A4 with the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture.
By waterglass and the sulfuric acid solution that concentration is 12 weight % that concentration is 15 weight % with weight ratio it is
6:1 carries out mixed being incorporated in haptoreaction 3 hours at 20 DEG C, then adjusts with the sulfuric acid that concentration is 98 weight %
Whole pH value, to 4, then carries out suction filtration to the reaction mass obtained, and is washed with distilled water to sodium ion
Content is 0.02 weight %, obtains the filter cake B4 of silica gel.
100ml ball is put into together with 20g filter cake A4,30g filter cake B4 and 5g zeolite of above-mentioned preparation
In grinding jar, wherein, the material of ball grinder is polytetrafluoroethylene (PTFE), and Material quality of grinding balls is agate, the diameter of abrading-ball
For 3mm, quantity is 1, and rotating speed is 500r/min.Closure ball grinding jar, in ball grinder, temperature is
Ball milling 10 hours at 40 DEG C, obtain 55g pressed powder；This pressed powder is dissolved in 30 grams of deionizations
In water, it is spray-dried under rotating speed is 13000r/min at 150 DEG C；The product obtained after being spray-dried
Thing is calcined 70 hours in Muffle furnace at 450 DEG C, removed template method, obtains 33 grams of spherical zeolite and is situated between
Hole composite material C4.
(2) loaded catalyst is prepared
At 25 DEG C, by the 20g spherical zeolite mesoporous composite material C4 of preparation in above-mentioned steps (1)
Putting into together with benzene sulfonic acid in deionized water, stirring is to dissolving, and spherical zeolite mesoporous composite material C4
Being 85:15 with the weight ratio of benzene sulfonic acid, deionized water is 25:1 with the mol ratio of benzene sulfonic acid, at 250 DEG C
Under under rotating speed is 11000r/min be spray-dried, obtain loaded catalyst Cat-4.
The pore structure parameter such as table 3 below of spherical zeolite mesoporous composite material C4 and loaded catalyst Cat-4
Shown in.
Table 3
| Sample | Specific surface area (m2/g) | Pore volume (ml/g) | Most probable pore size (nm) | Particle diameter (μm) |
| Composite C4 | 270 | 0.8 | 9,33 | 30-60 |
| Catalyst Cat-4 | 150 | 0.7 | 8,30 | 30-60 |
Embodiment 5
The application of the described loaded catalyst that the present embodiment provides for the present invention is described and acetic acid second
The preparation method of ester.
Loaded catalyst Cat-1 embodiment 1 prepared is vacuum dried 6 hours at 150 DEG C, cold
But to after room temperature, weigh 0.5 gram, be sequentially placed into 100ml tri-with 11.5 grams of ethanol and 15 grams of acetic acid
In mouth flask, stir 3 hours under heated reflux condition, be then cooled to room temperature and suction filtration separates, profit
With the liquid phase ingredient of gas chromatograph-mass spectrometer analytical reactions product, and by calculating, the conversion ratio of acetic acid is
99.5%, ethyl acetate selectivity is 100%.
Embodiment 6-8 and comparative example 3-4
Method according to embodiment 5 prepares ethyl acetate, except that, respectively by embodiment 2-4 and
Loaded catalyst prepared by comparative example 1-2 replaces described loaded catalyst Cat-1.As a result, each
Conversion ratio and the ethyl acetate selective data of calculated acetic acid are as shown in table 4 below.
Table 4
| Catalyst | The conversion ratio of acetic acid | Ethyl acetate selectivity | |
| Embodiment 5 | Cat-1 | 99.9% | 100% |
| Embodiment 6 | Cat-2 | 97.0% | 100% |
| Embodiment 7 | Cat-3 | 99.8% | 100% |
| Embodiment 8 | Cat-4 | 99.7% | 100% |
| Comparative example 3 | Cat-D-1 | 84.5% | 99% |
| Comparative example 4 | Cat-D-2 | 85.5% | 99% |
Embodiment 9-12 and comparative example 5-6
Method according to embodiment 5 prepares ethyl acetate, except that, respectively with from embodiment 5-8
The catalyst reclaimed with comparative example 3-4 replaces described loaded catalyst Cat-1.As a result, each calculate
Conversion ratio and the ethyl acetate selective data of the acetic acid obtained are as shown in table 5 below.
Table 5
| Catalyst | The conversion ratio of acetic acid | Ethyl acetate selectivity | |
| Embodiment 9 | The Cat-1 reclaimed | 99.0% | 100% |
| Embodiment 10 | The Cat-2 reclaimed | 85.0% | 99% |
| Embodiment 11 | The Cat-3 reclaimed | 96.9% | 100% |
| Embodiment 12 | The Cat-4 reclaimed | 98.5% | 100% |
| Comparative example 5 | The Cat-D-1 reclaimed | 83.1% | 99% |
| Comparative example 6 | The Cat-D-2 reclaimed | 82.0% | 99% |
By the data of above-mentioned table 4 and 5 it can be seen that the described spherical zeolite of the employing present invention is composite mesoporous
It is former that material can significantly improve reaction as the loaded catalyst that carrier is made in esterification reaction process
The conversion ratio of material.And, when the method by being spray-dried prepares described loaded catalyst, described
Loaded catalyst may be repeated utilization, and still can obtain higher during recycling
Reaction raw materials conversion ratio.
Claims (25)
1. a spherical zeolite mesoporous composite material, it is characterised in that the composite mesoporous material of this spherical zeolite
Material is containing zeolite and the meso-porous molecular sieve material with one-dimensional channels diplopore distributed architecture, and this spherical boiling
The average grain diameter of stone mesoporous composite material is 30-60 micron, and specific surface area is 150-600 meters squared per gram,
Pore volume is 0.5-1.5 ml/g, and aperture is bimodal distribution, and the corresponding first most probable hole of bimodal difference
Footpath and the second most probable pore size, described first most probable pore size is less than described second most probable pore size, and institute
Stating the first most probable pore size is 5-15 nanometer, and described second most probable pore size is 10-40 nanometer；
Wherein, the method preparing described spherical zeolite mesoporous composite material comprises the following steps:
(1) provide and there is the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, as component a；
(2) silica gel is provided or prepares the filter cake of silica gel, as component b；
(3) carry out mixing and ball milling by described component a, described component b and zeolite, and will obtain after ball milling
The pressed powder water slurrying arrived, is then spray-dried the slurry obtained.
Composite the most according to claim 1, wherein, described in 100 weight portions
Having the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, the content of described zeolite is 1-50 weight
Amount part.
Composite the most according to claim 2, wherein, described in 100 weight portions
Having the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, the content of described zeolite is 20-50 weight
Amount part.
4. the method preparing spherical zeolite mesoporous composite material, the method comprises the following steps:
(1) provide and there is the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture or preparation has
The filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, as component a；
(2) silica gel is provided or prepares the filter cake of silica gel, as component b；
(3) carry out mixing and ball milling by described component a, described component b and zeolite, and will obtain after ball milling
The pressed powder water slurrying arrived, is then spray-dried the slurry obtained；
Wherein, described component a makes the average grain diameter of described spherical zeolite mesoporous composite material be 30-60
Micron, specific surface area is 150-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and aperture is double
Peak is distributed, and corresponding first most probable pore size of bimodal difference and the second most probable pore size, and described first may be used
Several apertures are less than described second most probable pore size, and described first most probable pore size is 5-15 nanometer, institute
Stating the second most probable pore size is 10-40 nanometer.
Method the most according to claim 4, wherein, in step (3), relative to 100 weights
The consumption of described component a of amount part, the consumption of described component b is 1-200 weight portion；Described zeolite
Consumption is 1-50 weight portion.
Method the most according to claim 5, wherein, in step (3), relative to 100 weights
The consumption of described component a of amount part, the consumption of described component b is 50-150 weight portion；Described zeolite
Consumption is 20-50 weight portion.
Method the most according to claim 4, wherein, in step (1), preparation has one-dimensional
The process of the filter cake of the meso-porous molecular sieve material of duct diplopore distributed architecture includes: at template, trimethyl
In the presence of pentane and ethanol, tetramethoxy-silicane is contacted with sour agent, and will obtain after contacting
Mixture carries out crystallization and filtration.
Method the most according to claim 7, wherein, template, ethanol, trimethylpentane and
The mol ratio of tetramethoxy-silicane is 1:100-500:200-500:50-200.
Method the most according to claim 8, wherein, template, ethanol, trimethylpentane and
The mol ratio of tetramethoxy-silicane is 1:200-400:250-400:70-150.
10. according to the method described in any one in claim 7-9, wherein, described template is three
Block copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene；Described acid agent be pH value be 1-6 acetic acid and
Sodium acetate buffer solution；The condition that tetramethoxy-silicane contacts with acid agent includes: temperature is 10-60 DEG C,
Time is 10-72 hour, and pH value is 1-7；The condition of described crystallization includes: temperature is 30-150 DEG C,
Time is 10-72 hour.
11. methods according to claim 4, wherein, in step (2), prepare silica gel
The process of filter cake includes: contacted with inorganic acid by waterglass, and is entered by the mixture obtained after contact
Row filters.
12. methods according to claim 11, wherein, the condition that waterglass contacts with inorganic acid
Including: temperature is 10-60 DEG C, and the time is 1-5 hour, and pH value is 2-4；Described inorganic acid be sulfuric acid,
One or more in nitric acid and hydrochloric acid.
13. according to the method described in any one in claim 4-7 and 11, wherein, in step (3)
In, 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, the time of ball milling is 0.1-100 hour；The condition of described spray drying includes: temperature
100-300 DEG C, rotating speed is 10000-15000r/min.
14. according to the method described in any one in claim 4-6, and wherein, described component a is tool
Having the filter cake of the meso-porous molecular sieve material of one-dimensional channels diplopore distributed architecture, described component b is the filter of silica gel
Cake, described method also includes: after the spray-drying process of step (3), obtain from spray drying
Product in removed template method.
15. methods according to claim 14, wherein, the condition of described removed template method includes:
Temperature is 300-600 DEG C, and the time is 10-80 hour.
16. spherical zeolite prepared by the method described in any one in claim 4-15 are composite mesoporous
Material.
17. 1 kinds of loaded catalysts, this catalyst contains carrier and load benzene sulphur on the carrier
Acid, it is characterised in that described carrier is the spherical boiling in claim 1-3 and 16 described in any one
Stone mesoporous composite material.
18. catalyst according to claim 17, wherein, total with described loaded catalyst
On the basis of weight, the content of benzene sulfonic acid is 1-50 weight %；The content of described carrier is 50-99 weight %.
19. catalyst according to claim 18, wherein, total with described loaded catalyst
On the basis of weight, the content of benzene sulfonic acid is 5-50 weight %；The content of described carrier is 50-95 weight %.
20. the method preparing loaded catalyst, the method includes: by carrier, benzene sulfonic acid and water
Mixing, and be spray-dried by the mixture obtained, wherein, described carrier is claim 1-3
With 16 in spherical zeolite mesoporous composite material described in any one.
21. methods according to claim 20, wherein, with described carrier and total use of benzene sulfonic acid
On the basis of amount, the consumption of benzene sulfonic acid is 1-50 weight %；The consumption of described carrier is 50-99 weight %.
22. methods according to claim 21, wherein, with described carrier and total use of benzene sulfonic acid
On the basis of amount, the consumption of benzene sulfonic acid is 5-50 weight %；The consumption of described carrier is 50-95 weight %.
23. loaded catalysts prepared by the method described in any one in claim 20-22.
In 24. claims 17-19 and 23, the loaded catalyst described in any one is in esterification
In application.
The preparation method of 25. 1 kinds of ethyl acetate, the method includes: in the presence of a catalyst, at ester
Under conditions of changing reaction, acetic acid is contacted with ethanol, to obtain ethyl acetate, it is characterised in that described
Catalyst is the loaded catalyst in claim 17-19 and 23 described in any one.
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| CN105195212B (en) * | 2015-10-13 | 2017-11-03 | 延边大学 | The preparation method of spherical full skeleton monolithic construction zeolite molecular sieve catalyst |
| CN107262158B (en) * | 2016-04-07 | 2019-07-19 | 中国石油化工股份有限公司 | The spherical mesoporous composite material of attapulgite containing aluminium and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
| CN107262159B (en) * | 2016-04-07 | 2019-07-19 | 中国石油化工股份有限公司 | The preparation method of spherical shape mesoporous composite material containing mackensite and loaded catalyst and its preparation method and application and acid isopropyl |
| CN107262136B (en) * | 2016-04-07 | 2019-07-19 | 中国石油化工股份有限公司 | The preparation method of spherical shape illite containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl |
| CN107262135B (en) * | 2016-04-07 | 2019-07-19 | 中国石油化工股份有限公司 | The preparation method of spherical shape kaolin containing aluminium mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl |
| CN107262157B (en) * | 2016-04-07 | 2019-07-19 | 中国石油化工股份有限公司 | The preparation method of spherical shape mesoporous composite material containing meerschalminite and loaded catalyst and its preparation method and application and acid isopropyl |
| CN107456992B (en) * | 2016-06-06 | 2019-07-19 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
| CN107457005B (en) * | 2016-06-06 | 2019-07-19 | 中国石油化工股份有限公司 | Spherical diatomite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
| CN107457004B (en) * | 2016-06-06 | 2019-07-19 | 中国石油化工股份有限公司 | Spherical montmorillonite mesoporous composite material and loaded catalyst and its preparation method and application and acid isopropyl preparation method |
| CN107999115B (en) * | 2016-11-02 | 2020-04-07 | 中国石油化工股份有限公司 | Supported metallocene catalyst, preparation method and application thereof, and preparation method of methyl acrylate |
| CN108855201B (en) * | 2017-05-10 | 2019-09-27 | 中国石油化工股份有限公司 | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane |
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