CN107999115A - The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate - Google Patents
The preparation method of carried metallocene catalyst and its preparation method and application and methyl acrylate Download PDFInfo
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- CN107999115A CN107999115A CN201610944182.7A CN201610944182A CN107999115A CN 107999115 A CN107999115 A CN 107999115A CN 201610944182 A CN201610944182 A CN 201610944182A CN 107999115 A CN107999115 A CN 107999115A
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- metallocene catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0225—Complexes comprising pentahapto-cyclopentadienyl analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
The present invention relates to carried metallocene catalyst field, disclose the preparation method of a kind of carried metallocene catalyst and its preparation method and application and methyl acrylate, the catalyst includes the metallocene compound of carrier and load on the carrier, and the carrier is hollow ball-shape mesoporous composite material.Wherein, the metallocene compound has the structure shown in Formulas I.Using the carried metallocene catalyst, catalytic activity it is good it is efficient, can reuse.Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or C1‑C5Alkyl, and R1、R2、R3、R4And R5In it is at least one be C1‑C5Alkyl, R1’、R2’、R3’、R4' and R5' in it is at least one be C1‑C5Alkyl, M be titanium, zirconium and hafnium in one kind, X is halogen.
Description
Technical field
The present invention relates to carried metallocene catalyst field, and in particular, to a kind of carried metallocene catalyst, one
The application of the preparation method, the metallocene catalyst, metallocene catalyst that are obtained by this method of kind carried metallocene catalyst
With a kind of preparation method of methyl acrylate.
Background technology
Since the regular mesoporous material of Mobile companies synthesis duct high-sequential in 1992, since it is with high ratio table
Face, regular pore passage structure and narrow pore-size distribution so that mesoporous material is applied in catalysis, separation, medicine and other fields
Very big concern is arrived.Zhao east member in 1998 et al. synthesizes a kind of new material-mesoporous material SBA-15, which has height
Spend orderly aperture（6-30nm）, big pore volume（1.0cm3/g）, thicker hole wall（4-6nm）, keep high mechanical properties
And good catalytic adsorption performance（See D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science 279 (1998)
548-550）.CN1341553A discloses a kind of preparation method of mesonic pore molecular sieve carrier material, mesoporous material made from this method
Material is used as heterogeneous reaction catalyst carrier, the separation of catalyst and product easy to implement.
But conventional ordered mesoporous material SBA-15 microscopic appearances are bar-shaped, itself mobility is poor, its big ratio
Surface area and high pore volume cause to make it have stronger water suction, moisture absorption ability, this has been further exacerbated by the group of ordered mesoporous material
It is poly-, limit the storage of ordered mesoporous material, transport, post-processing and application.
Methyl acrylate is a kind of important raw material of industry, and traditional handicraft is during methyl acrylate is prepared using dense
Sulphur acid as catalyst, which pollutes environment again, and catalyst can not reuse.
Therefore, a kind of catalyst of the methyl acrylate of high-efficiency environment friendly is developed to be very important.
The content of the invention
It is an object of the invention to overcome, the catalyst that existing methyl acrylate synthesis uses is not environmentally friendly enough, can not repeat
The shortcomings of utilization, there is provided a kind of carried metallocene catalyst, using the carried metallocene catalyst, catalytic activity is imitated well
Rate is high, can reuse.
Specifically, in a first aspect, the present invention provides a kind of carried metallocene catalyst, the catalyst include carrier and
The metallocene compound of load on the carrier, the carrier is hollow ball-shape mesoporous composite material, and the hollow ball-shape is situated between
Hole composite material contains the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure, the composite mesoporous material of hollow ball-shape
The average grain diameter of material is 21-29 microns, and specific surface area is 100-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, hole
Footpath is in tri-modal distribution, and three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size, and institute respectively
The first most probable pore size is stated as 1-10 nanometers, second most probable pore size is 20-50 nanometers, and the 3rd most probable pore size is
55-65 nanometers；
Wherein, the metallocene compound has the structure shown in Formulas I,
Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or C1-C5Alkyl, and R1、
R2、R3、R4And R5In it is at least one be C1-C5Alkyl, R1’、R2’、R3’、R4' and R5' in it is at least one be C1-C5Alkane
Base, M are one kind in titanium, zirconium and hafnium, and X is halogen.
Second aspect, invention provides a kind of preparation method of carried metallocene catalyst, the support type cyclopentadienyl
Metallic catalyst is the metallocene catalyst that the invention described above provides, and this method includes, in the presence of an inert gas, on carrier
Load metallocene compound.
The third aspect, the present invention provides the carried metallocene catalyst being prepared by the above method.
Fourth aspect, the present invention provides the application of above-mentioned carried metallocene catalyst in the esterification reaction.
5th aspect, the present invention provides a kind of preparation method of methyl acrylate, this method includes：In esterification
Under the conditions of, in the presence of a catalyst, acrylic acid and methanol are contacted, the catalyst is support type provided by the invention cyclopentadienyl
Metallic catalyst.
Present invention employs the Cyclone Separation Technology in secondary ball milling technology and spray drying technology, secondary ball milling technology makes
Obtained slurry is finer and smoother, the spheroidal particle stable structure obtained after being spray-dried, can be with as catalyst carrier
Recycle, intensity height is non-breakable, and the preparation of the hollow ball-shape mesoporous composite material of the present invention need not be used and bonded
Agent, can thus be destroyed to avoid the structure of the sample during high temperature removal binding agent.Using Cyclone Separation Technology,
The particle diameter of obtained hollow ball-shape mesoporous composite material is small, particle diameter distribution is uniform and grading curve is narrow, can be to avoid making
The reunion of ordered mesoporous material during, improves its mobility, storage to ordered mesoporous material, transport, post-processing and
Using bringing convenience.
Metallocene is supported on specific hollow ball-shape mesoporous composite material carrier by load method in the catalyst of the present invention
On, process is simple and easy to do, and gained catalyst also keeps spherical after load, on the one hand, not only so that the loaded metallocene is catalyzed
Agent catalytic esterification activity it is higher, and reuse when the carried metallocene catalyst catalytic esterification activity
Still higher, this, which allows for the carried metallocene catalyst, can be recovered and recycled recycling.On the other hand due also to will
Metallocene is loaded on specific hollow ball-shape mesoporous composite material carrier and used as catalyst, is avoided using in the prior art
The concentrated sulfuric acid, can prevent equipment corrosion, reduce side reaction, improve product purity, therefore the carried metallocene catalyst is
A kind of environmentally protective catalyst.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the x-ray diffraction pattern of the hollow ball-shape mesoporous composite material in embodiment 1（XRD spectra）, abscissa 2
θ, ordinate are intensity；
Fig. 2 is the scanning electron microscope (SEM) photograph of the hollow ball-shape mesoporous composite material microscopic appearance in embodiment 1（SEM）；
Fig. 3 is the size distribution curve of the hollow ball-shape mesoporous composite material in embodiment 1；
Fig. 4 is the graph of pore diameter distribution of the hollow ball-shape mesoporous composite material in embodiment 1.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of carried metallocene catalyst, which includes carrier and load on the carrier
Metallocene compound, the carrier is hollow ball-shape mesoporous composite material, and the hollow ball-shape mesoporous composite material contains tool
There is the meso-porous molecular sieve material of one-dimensional hollow ball-shape pore passage structure, the average grain diameter of the hollow ball-shape mesoporous composite material is
21-29 microns, specific surface area is 100-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size, and the first most probable hole respectively
Footpath is 1-10 nanometers, and second most probable pore size is 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers；
Wherein, the metallocene compound has the structure shown in Formulas I,
Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or C1-C5Alkyl, and R1、
R2、R3、R4And R5In it is at least one be C1-C5Alkyl, R1’、R2’、R3’、R4' and R5' in it is at least one be C1-C5Alkane
Base, M are one kind in titanium, zirconium and hafnium, and X is halogen.
Carried metallocene catalyst according to the present invention, the M in Formulas I can be one kind in titanium, zirconium and hafnium.Different cyclopentadienyls
M in metallic compound molecule can be identical or different.Preferably, M is zirconium.
Carried metallocene catalyst according to the present invention, the X in Formulas I is halogen.Specifically, the X in Formulas I can be
One kind in fluorine, chlorine, bromine and iodine.X in different metallocene compound molecules can be identical or different.Preferably, in Formulas I
X is chlorine or bromine.It is highly preferred that the X in Formulas I is chlorine.
According to the present invention, in Formulas I, cyclopentadienyl group is that can form η with central metal5Key and with alkyl substituent
The derivative of cyclopentadienyl.Preferably, the R on the cyclopentadienyl group in Formulas I1、R2、R3、R4、R5、R1’、R2’、R3’、
R4' and R5' it is each independently hydrogen or C1-C5Alkyl, and R1、R2、R3、R4And R5In it is at least one be C1-C5Alkyl,
R1’、R2’、R3’、R4' and R5' in it is at least one be C1-C5Alkyl.
In the present invention, the C1-C5Alkyl can be methyl, it is ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, different
One or more in butyl, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
Meeting the instantiation of the cyclopentadienyl group of above-mentioned requirements includes：Methyl cyclopentadienyl, 1,2- dimethyl-ring penta
Dialkylene, 1,3- dimethyl-cyclopentadienyl group, 1,2,3- trimethyls-cyclopentadienyl group, 1,2,4- trimethyls-cyclopentadienyl group,
1,2,3,4- tetramethyls-cyclopentadienyl group, pentamethylcyclopentadiene base, ethyicydopentadi etanyf group, 1,2- diethyl-cyclopentadiene
Base, 1,3- diethyl-cyclopentadienyl group, 1,2,4- triethyl groups-cyclopentadienyl group, 1,3,5- triethyl groups-cyclopentadienyl group, 1- first
Base -2- ethyls-cyclopentadienyl group, 1- methyl -3- ethyls-cyclopentadienyl group, n-propyl cyclopentadienyl group, isopropylcyclopentadiene
Base, 1,3- diη-propyls-cyclopentadienyl group, 1- methyl -3- n-propyls-cyclopentadienyl group, 1,3- diisopropyls-cyclopentadiene
Base, 1- methyl -3- isopropyl-cyclopentadienyls, n-butyl cyclopentadienyl, sec-butylcycSopentadienyl group, isobutyl basic ring penta 2
Alkenyl, t-butyl cyclopentadienyl, 1,3- di-n-butyls-cyclopentadienyl group, 1- methyl -3- normal-butyls-cyclopentadienyl group, 1,3-
Di-sec-butyl-cyclopentadienyl group, 1- methyl -3- sec-butyls-cyclopentadienyl group, 1,3- diisobutyls-cyclopentadienyl group, 1- methyl
3- isobutyl groups-cyclopentadienyl group, 1,3- di-t-butyls-cyclopentadienyl group, 1- methyl 3- t-butylcyclopentadienyls, n-pentyl
Cyclopentadienyl group, isoamyl cyclopentadienyl group, tertiary pentyl cyclopentadienyl group, neopentyl cyclopentadienyl group, bis- n-pentyls of 1,3--ring
Pentadienyl, 1- methyl -3- n-pentyls-cyclopentadienyl group, 1,3- diisoamyl-cyclopentadienyl group, 1- methyl -3- isopentyl -
Cyclopentadienyl group, bis- tertiary pentyls of 1,3--cyclopentadienyl group, 1- methyl -3- tertiary pentyls-cyclopentadienyl group, 1,3- di neo-pentyls-ring
Pentadienyl, 1- methyl -3- neopentyls-cyclopentadienyl group.
Preferably, the R in Formulas I1And R1' it is each independently C1-C5Alkyl, R2、R3、R4、R5、R2’、R3’、R4' and R5’
It is hydrogen.Meeting the instantiation of the cyclopentadienyl group of above-mentioned requirements includes：Methyl cyclopentadienyl, ethyicydopentadi etanyf group,
N-propyl cyclopentadienyl group, isopropylcyclopentadienyl, n-butyl cyclopentadienyl, sec-butylcycSopentadienyl group, isobutyl basic ring
Pentadienyl, t-butyl cyclopentadienyl, n-pentyl cyclopentadienyl group, isoamyl cyclopentadienyl group, tertiary pentyl cyclopentadienyl group,
Neopentyl cyclopentadienyl group.
It is highly preferred that R1And R1' it is each independently normal-butyl or the tert-butyl group, most preferably, R1And R1' it is normal-butyl.
The present inventor has found in the course of the research, the R in formula 11And R1' it is normal-butyl, M is zirconium, and X is chlorine, i.e.,
When the metallocene compound is double (n-butyl cyclopentadienyl) zirconium dichlorides, the carried metallocene catalyst is used to urge
During the esterification of change acrylic acid and methanol, excellent catalytic activity is shown.
According to the present invention, in the carried metallocene catalyst, the content of the metallocene compound and carrier can
With in interior variation in a big way.For example, on the basis of the gross weight of the carried metallocene catalyst, the metallocene chemical combination
The content of thing can be 0.1-2 weight %, be preferably 0.15-1.5 weight %；The content of the carrier can be 98-99.9 weights
% is measured, is preferably 98.5-99.85 weight %.
A kind of preferred embodiment according to the present invention, the average grain diameter of the hollow ball-shape mesoporous composite material are
22-28 microns, specific surface area is 250-350 meters squared per grams, and pore volume is 1-1.5 mls/g, and aperture is in tri-modal distribution, and three
Peak corresponds to 2-9 nanometers of the first most probable pore size, 30-50 nanometers of the second most probable pore size and the 3rd most probable pore size 56-64 respectively
Nanometer.
A kind of preferred embodiment according to the present invention, the average grain diameter of the hollow ball-shape mesoporous composite material are
23-27 microns, specific surface area is 275-300 meters squared per grams, and pore volume is 1.1-1.4 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to 3-7 nanometers of the first most probable pore size, 35-45 nanometers of the second most probable pore size and the 3rd most probable pore size 57- respectively
63 nanometers.
In the present invention, the average grain diameter of the carrier is measured using laser fineness gage, specific surface area, pore volume and
Most probable pore size is measured according to nitrogen adsorption methods, and the surface topography of the carrier passes through scanning electron microscope instrument（SEM）Measure.In this hair
In bright, the average grain diameter is average particulate diameter.
In the present invention, the hollow ball-shape mesoporous composite material does not contain binding agent such as polyvinyl alcohol or polyethylene glycol
Deng.
In the present invention, the hollow ball-shape mesoporous composite material can also contain the silica introduced by silica gel.
" silica being introduced into by silica gel " refers in the preparation process of the hollow ball-shape mesoporous composite material, by silica gel conduct
Preparing raw material brings the silica component in the hollow shape mesoporous composite material finally prepared into.It is mesoporous multiple in the hollow ball-shape
It is described logical relative to the meso-porous molecular sieve material described in 100 parts by weight with one-dimensional hollow ball-shape pore passage structure in condensation material
The content for crossing the silica of silica gel introducing can be 1-200 parts by weight, be preferably 20-180 parts by weight, more preferably 50-150
Parts by weight.
In the present invention, the carrier is prepared by method comprising the following steps：
（1）Meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure is provided or is prepared with one-dimensional hollow ball
The filter cake of the meso-porous molecular sieve material of shape pore passage structure, as component a；
（2）Silica gel is provided or prepares the filter cake of silica gel, as component b；
（3）The component a and the component b are subjected to mixing and the first ball milling, the first ball milling slurry and water that will be obtained
Mixed pulp, then carries out the second ball milling and obtains the second ball milling slurry, used after the second ball milling slurry is spray-dried
Cyclone Separation Technology is screened；
Wherein, above-mentioned steps make it that the average grain diameter of the hollow ball-shape mesoporous composite material is 21-29 microns, compare surface
Product is 100-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to first respectively
Most probable pore size, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, it is described
Second most probable pore size is 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers.
A kind of preferred embodiment according to the present invention, the average grain diameter of the hollow ball-shape mesoporous composite material are
22-28 microns, specific surface area is 250-350 meters squared per grams, and pore volume is 1-1.5 mls/g, and aperture is in tri-modal distribution, and three
Peak corresponds to 2-9 nanometers of the first most probable pore size, 30-50 nanometers of the second most probable pore size and the 3rd most probable pore size 56-64 respectively
Nanometer.
A kind of preferred embodiment according to the present invention, the average grain diameter of the hollow ball-shape mesoporous composite material are
23-27 microns, specific surface area is 275-300 meters squared per grams, and pore volume is 1.1-1.4 mls/g, and aperture is in tri-modal distribution, and
Three peaks correspond to 3-7 nanometers of the first most probable pore size, 35-45 nanometers of the second most probable pore size and the 3rd most probable pore size 57- respectively
63 nanometers.
In the present invention, by by the control of the particle size of hollow ball-shape mesoporous composite material within the above range, can be with
Ensure that the carrier is not susceptible to reunite, and be used as carried metallocene catalyst made of carrier to improve esterification
Reaction raw materials conversion ratio in reaction process.
In the preparation process of above-mentioned carrier, mainly by controlling mesoporous material filter cake（Component a）Composition, by the ball
The pore-size distribution control of shape mesoporous composite material is tri-modal distribution, and mainly by controlling forming method（That is, first by the component
The a and component b carries out mixing and the first ball milling, by the first obtained ball milling slurry and water mixed pulp, then carries out second
Ball milling simultaneously obtains the second ball milling slurry, and the second ball milling slurry is spray-dried）By the micro- of the spherical mesoporous composite material
It is spherical to see pattern control.
According to the present invention, in step（1）In, prepare the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
The process of filter cake can include：Template, silicon source, ethanol, trimethylpentane and sour agent are carried out first to be mixed, and will
The mixture arrived carries out crystallization and filtering.There is no particular limitation for first order being mixed, can first by template,
Silicon source, ethanol, trimethylpentane and sour agent are carried out at the same time mixing, can also be mixed any two or three, add other
Component is uniformly mixed.Template, ethanol and sour agent, are first uniformly mixed, so by a kind of preferred embodiment according to the present invention
Trimethylpentane is added afterwards to be uniformly mixed, and then adds silicon source（It is preferred that tetramethoxy-silicane）It is uniformly mixed.
In the present invention, the dosage of the template, ethanol, trimethylpentane and silicon source can be in interior change in a big way
It is dynamic, for example, template, ethanol, the molar ratio of trimethylpentane and silicon source can be 1：100-500：200-500：50-200, more
Preferably 1：180-400：250-400：70-150.
In the present invention, the template can be the various templates of this area routine, as long as the ball enabled to
The pore structure of shape mesoporous composite material meets the requirements.For example, the template can be triblock copolymer polyoxyethylene-
Polyoxypropylene polyoxyethylene.Wherein, which can be commercially available（For example, Aldrich, commodity can be purchased from
Entitled P123, molecular formula EO20PO70EO20, molecular weight Mn is 5800）, can also be prepared by existing various methods.
When the template is polyoxyethylene-poly-oxypropylene polyoxyethylene, the molal quantity of the template is according to polyoxyethylene-poly-
Oxypropylene-polyoxyethylated number-average molecular weight is calculated.
In the present invention, the silicon source can be various silicon sources commonly used in the art.For example, the silicon source can be
Ethyl orthosilicate, methyl orthosilicate（Also known as tetramethoxy-silicane）, positive silicic acid propyl ester, at least one in sodium metasilicate and Ludox
Kind, it is preferably tetramethoxy-silicane.
In the present invention, the sour agent can be various acidic aqueous solutions commonly used in the art, it is preferable that the acid
Agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6.There is no particular limitation for the dosage of the acid agent, can be in larger model
Enclose interior variation, it is preferable that the first pH value being mixed is 1-7.
To first condition being mixed there is no particular limitation by the present invention, for example, described first is mixed
Condition generally includes：Temperature can be 10-60 DEG C, be preferably 10-20 DEG C；It is preferably 10-30 when time can be 10-72 small
Hour；PH value can be 1-7, be preferably 3-6.It is a kind of excellent according to the present invention in order to be more advantageous to the uniform mixing between each material
The embodiment of choosing, described first is mixed and carries out under agitation.
In the present invention, the condition of the crystallization includes：Temperature can be 30-150 DEG C, be preferably 40-80 DEG C；Time can
When thinking that 10-72 is small, when being preferably 20-30 small.According to a kind of preferred embodiment, the crystallization by hydrothermal crystallization method come
Implement.
In step（1）In, in the filter cake of meso-porous molecular sieve material of the above-mentioned preparation with one-dimensional hollow ball-shape pore passage structure
During, it can be included with the process for obtaining filter cake by filtering：After filtration, washed repeatedly with deionized water（Washing
Number can be 2-10）, then filtered.
In step（1）In, " providing the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure " can be direct
Weigh or choose the product of the meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure or prepare with one-dimensional
The meso-porous molecular sieve material of hollow ball-shape pore passage structure.The meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure
Preparation method can implement according to the conventional method, for example, its preparation method can include：Being prepared according to the above method has
The filter cake of the meso-porous molecular sieve material of one-dimensional hollow ball-shape pore passage structure, then by gained filtration cakes torrefaction.
According to the present invention, in step（2）In, preparing the process of the filter cake of silica gel can include：By waterglass, polyalcohol and
Inorganic acid carries out second and is mixed, and obtained mixture is filtered.
In the present invention, there is no particular limitation for second condition being mixed, can be according to preparing the normal of silica gel
Rule technique suitably determines.For example, second condition being mixed includes：Temperature can be 10-60 DEG C, be preferably 20-
40℃；When time can be 1-5 small, when being preferably 1-3 small；PH value is 2-4.It is uniformly mixed between each material in order to be more advantageous to
Close, second process being mixed preferably carries out under agitation.
In the present invention, the dosage of the waterglass, inorganic acid and polyalcohol can be in interior variation in a big way.For example,
The weight ratio of the waterglass, inorganic acid and polyalcohol can be 1-8：0.1-5：1, it is preferably 3-6：0.5-4：1, more preferably
3-6：1-3：1.
In the present invention, the waterglass is the aqueous solution of sodium metasilicate, its concentration can be 3-20 weight %, is preferably 10-
20 weight %.The inorganic acid can be various inorganic acids commonly used in the art, such as can be sulfuric acid, nitric acid and hydrochloric acid
In one or more.The inorganic acid can use in pure form, can also be used in the form of its aqueous solution, preferably
Used in the form of the aqueous solution of 3-20 weight %.The dosage of the inorganic acid is preferably so that the haptoreaction of waterglass and inorganic acid
The pH value of system is 2-4.
In the present invention, there is no particular limitation for the species of the polyalcohol, such as can be glycerine and/or second two
Alcohol, is preferably glycerine.
According to the present invention, in step（2）In, " offer silica gel " can directly weigh or choose silica gel product, can also
It is to prepare silica gel.Preparing the method for silica gel can implement according to the conventional method, such as can include：Prepared according to the above method
The filter cake of silica gel, then by gained filtration cakes torrefaction.
It is above-mentioned prepare the filter cake of silica gel during, can be included with the process for obtaining filter cake by filtering：Filtering
Afterwards, it is below 0.2 weight % to wash to the content of sodium ion, is preferably 0.01-0.03 weight %, is then filtered.Washing
Mode be this area conventional selection, can be washing and/or alcohol wash, actual conditions is well known to those skilled in the art,
Details are not described herein.
According to the present invention, in step（3）In, the dosage of the component a and component b can be in interior variations in a big way.Example
Such as, relative to 100 parts by weight the component a dosage, the dosage of the component b can be 1-200 parts by weight, be preferably
20-180 parts by weight, more preferably 50-150 parts by weight.
The present invention is realized using to the secondary ball milling method of slurry in order to improve the intensity of the carrier.
According to the present invention, in step（3）In, first ball milling and the second ball milling can carry out in the ball mill, described
The inner wall of ball grinder is preferably agate liner in ball mill, and the diameter of the abrading-ball in ball mill can be 2-3mm；The quantity of abrading-ball
It can reasonably be selected according to the size of ball grinder, for the ball grinder that size is 50-150mL, can usually use 1
Abrading-ball；The material of the abrading-ball can be agate, polytetrafluoroethylene (PTFE) etc., be preferably agate.First ball milling and the second ball milling
Condition can be identical or different, the condition of first ball milling and the second ball milling includes independently of one another：The rotating speed of abrading-ball can
Think 200-800r/min, the temperature in ball grinder can be 15-100 DEG C, and the time of ball milling can be 0.1-100h；It is preferred that
Ground, the rotating speed of abrading-ball are 300-500r/min, and the temperature in ball grinder is 25-50 DEG C, and the time of ball milling is 5-20h.
According to the present invention, in step（3）In, the temperature by obtained the first ball milling slurry and water mixed pulp can be
25-60 DEG C, be preferably 25-50 DEG C；The weight ratio of the dosage of the first ball milling slurry and water can be 1：0.1-5, is preferably
1：0.5-3.5.
According to the present invention, in step（3）In, the spray drying can be implemented according to conventional mode, can be selected from pressure
At least one of gentle flow type spray seasoning of power spray drying process, centrifugal spray drying method.It is a kind of preferred according to the present invention
Embodiment, the spray drying uses centrifugal spray drying method.The spray drying can carry out in atomizer.It is described
The condition of spray drying can include：Temperature is 150-600 DEG C, rotating speed 10000-15000r/min；It is described under preferable case
The condition of spray drying includes：Temperature is 150-250 DEG C, and rotating rotating speed is 11000-13000r/min.
According to the present invention, the step of being screened after the second ball milling slurry is spray-dried using Cyclone Separation Technology
It can include：The second ball milling slurry is spray-dried, by gas of the discharge containing powder carry out cyclonic separation with
Collect the powder.Specifically, powder contained in discharge gas is separated using Cyclone Separation Technology, the powder of recycling falls into collection
Powder drum, for exhaust gas by separator outlet to centrifugal blower, cyclone separator lower part is provided with butterfly valve, and when work opens butterfly valve, obtains
Sample there is the particle diameter that is evenly distributed.
According to the present invention, in step（3）In, when the component a is with a cube mesopore molecular sieve for caged pore passage structure
The filter cake of material, when the component b is the filter cake of silica gel, namely works as step（1）To prepare with cube caged pore passage structure
The process of the filter cake of meso-porous molecular sieve material, step（2）During to prepare the process of the filter cake of silica gel, the preparation method of the carrier
It can also include：In step（3）Spray-drying process after, the removed template method from the powder collected by cyclonic separation.
The condition of the removed template method includes：Temperature can be 90-600 DEG C, be preferably 300-600 DEG C；Time can be that 10-80 is small
When, it is preferably 10-24h.
Present invention also offers a kind of method for preparing carried metallocene catalyst, wherein, this method includes：In inertia
In the presence of gas, in supported on carriers metallocene compound.
The carrier and metallocene compound hereinbefore have been carried out describing, and details are not described herein.
According to the present invention it is possible to using well known to a person skilled in the art method in the presence of an inert gas by metallocene
Compound loads on the carrier.Preferably, include in the method for supported on carriers metallocene compound：By the carrier and cyclopentadienyl
Metallic compound is loaded in closed inert gas environment together so that metallocene compound is loaded on the carrier.
There is no particular limitation for condition of the present invention to load, for example, the condition of the load includes：Temperature can be
15-100 DEG C, be preferably 40-80 DEG C；When time can be 0.1-20 small, when being preferably 1-5 small.The load is preferably being stirred
Lower progress.
The dosage of metallocene compound and the carrier can be in interior variation in a big way in the present invention.For example, the cyclopentadienyl
The dosage of metallic compound and the carrier causes in the carried metallocene catalyst that is prepared, with support type cyclopentadienyl gold
On the basis of the gross weight of metal catalyst, the content of the metallocene compound is 0.1-2 weight %, is preferably 0.15-1.5 weights
Measure %；The content of the carrier is 98-99.9 weight %, is preferably 98.5-99.85 weight %.In the loaded metallocene of the present invention
In catalyst, the content of the carrier is calculated in the following manner：Weight/load of the carrier of content=addition of carrier
Weight × 100% of type metallocene catalyst.
The method according to the invention is additionally may included in before the load metallocene compound, is existed in inert gas
Under, by the carrier when heating 7-10 is small at a temperature of 300-900 DEG C, contained with removing in the hydroxyl of carrier surface and carrier
Some volatile materials（Such as：Water）.
In the present invention, the inert gas is the gas not reacted with raw material and product, such as can be ability
At least one of group 0 element gas in the nitrogen or the periodic table of elements of domain routine, is preferably nitrogen.
Present invention also offers the carried metallocene catalyst prepared by the above method.
Present invention also offers the application of carried metallocene catalyst in the esterification reaction, wherein, the support type cyclopentadienyl
Metallic catalyst is carried metallocene catalyst provided by the invention.
Present invention also offers a kind of preparation method of methyl acrylate, this method includes：Under conditions of esterification,
In the presence of a catalyst, acrylic acid and methanol are contacted, wherein, the catalyst is support type provided by the invention cyclopentadienyl gold
Metal catalyst.
There is no particular limitation for dosage of the present invention to the acrylic acid and methanol, as long as can react to obtain acrylic acid first
Ester, but in order to improve raw material availability, under preferable case, the weight ratio of the dosage of the acrylic acid and methanol is 1:
0.1-10。
In addition, also there is no particular limitation for dosage of the present invention to the carried metallocene catalyst, can be according to anti-
The addition of acrylic acid and/or methanol is suitably selected during answering.For example, relative to the acrylic acid of 100 parts by weight, it is described
The dosage of carried metallocene catalyst is 1-30 parts by weight, is preferably 3-20 parts by weight.
According to the present invention, the condition of the esterification is known to those skilled in the art, generally includes reaction temperature
And the reaction time.Wherein, in order to be more advantageous to the progress of esterification, the esterification carries out under reflux conditions, i.e. anti-
It is reflux temperature to answer temperature.The extension of reaction response time can improve the conversion ratio of reactant within the specific limits and reaction is produced
The yield of thing, but the reaction time long amplitude improved to reaction-ure conversion-age and reaction product yield and unobvious, it is therefore, comprehensive
Close and consider effect and efficiency, under preferable case, when the reaction time is 1-10 small, when more preferably 2-8 is small.
According to the present invention, after the preparation method of the methyl acrylate is further preferably included in esterification, to final
Reaction mixture be centrifuged, and will centrifuge obtained solid product be dried in vacuo at 25-200 DEG C 1-24 it is small when,
It is preferred that when vacuum drying 6-10 is small at 50-120 DEG C, to recycle carried metallocene catalyst.
The present invention is described in detail with reference to embodiments.
In the following Examples and Comparative Examples, polyoxyethylene-poly-oxypropylene polyoxyethylene is purchased from Aldrich, writes a Chinese character in simplified form
For P123, molecular formula EO20PO70EO20, the material for being 9003-11-6 in the registration number of U.S. chemical abstract, number-average molecular weight
Mn is 5800.
In following embodiments and comparative example, X-ray diffraction analysis are in the model purchased from German Bruker AXS companies
Carried out on the X-ray diffractometer of D8Advance；Scanning of the scanning electron microscope analysis in the model XL-30 purchased from FEI Co. of the U.S.
Carried out on electron microscope；Pore structure parameter analysis is inhaled de- in the nitrogen of the model Autosorb-1 purchased from Kang Ta companies of the U.S.
Carried out on attached instrument, wherein, before being tested, by sample when 200 DEG C of degassings 4 are small；X-ray fluorescence analysis is in dutch company
Carried out on the x-ray fluorescence analyzer of model Axios-Advanced；Size distribution curve is surveyed by Malvern laser particle analyzer
.
Weight × 100% of weight/carried metallocene catalyst of the carrier of content=addition of carrier.
Analytic approach analysis reaction is used in conjunction by gaschromatographic mass spectrometry in the conversion ratio of acrylic acid and the selectivity of methyl acrylate
The constituent content of product is simultaneously calculated, the conversion ratio of acrylic acid（%）=（Acrylic acid contains in dosage-reaction product of acrylic acid
Amount）Dosage × 100% of ÷ acrylic acid；The selectivity of methyl acrylate（%）The actual production ÷ acrylic acid first of=methyl acrylate
Theoretical yield × 100% of ester.
Embodiment 1
The present embodiment is used to illustrate carried metallocene catalyst of the present invention and preparation method thereof
（1）Prepare hollow ball-shape mesoporous composite material
By 1g（0.00017mol）Template P123 and 1.69g（0.037mol）Ethanol is added to the second of pH=4.4 of 28mL
In acid and sodium acetate buffer solution, stirring to template is completely dissolved at 15 DEG C, by 6g（0.05mol）Trimethylpentane is added to
In above-mentioned solution, after stirring 8h at 15 DEG C, then by 2.13g（0.014mol）Tetramethoxy-silicane is added in above-mentioned solution, and 15
After stirring 20h at DEG C, transfer the solution into the reaction kettle of agate liner, after 60 DEG C of baking oven crystallization 24h, then filtered simultaneously
It is washed with deionized 4 times, then filters the filter cake for the meso-porous molecular sieve material for obtaining having one-dimensional hollow ball-shape pore passage structure
A1。
By the waterglass that concentration is 15 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as 4：
1：1 is mixed and when haptoreaction 1 is small at 40 DEG C, then adjusts pH value to 3 with the sulfuric acid that concentration is 98 weight %, then
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter cake of silica gel
B1。
The 20g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein, ball grinder
Material is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 400r/min.Close ball milling
Tank, carries out the first ball milling in ball grinder, and temperature is 25 DEG C, when the time is 5 small.By the first obtained ball milling slurry and 15g water
The mixed pulp at 25 DEG C, then carries out the second ball milling, and temperature is 25 DEG C, when the time is 5 small.The the second ball milling slurry that will be obtained
Then screened using Cyclone Separation Technology to be spray-dried under 12000r/min in rotating speed at 200 DEG C, screening is obtained
Product calcine 10h at 600 DEG C in Muffle furnace, remove P123（Template）, obtain hollow ball-shape mesoporous composite material C1.
（2）The preparation of carried metallocene catalyst
In the presence of nitrogen, hollow ball-shape mesoporous composite material C1 is calcined at 400 DEG C 10 it is small when to carry out thermal activation,
Eliminating hydroxide and Residual water, obtain the hollow ball-shape mesoporous composite material C1 of thermal activation.
In the presence of nitrogen, by double (normal-butyl rings of hollow ball-shape the mesoporous composite material C1 and 4.9mg of 3.5g thermal activations
Pentadienyl) zirconium dichloride（Purchased from Alfa Aesar companies, article No. H27576 is same as below）100ml tri- is added at 25 DEG C
In mouthful bottle, there-necked flask is closed, when keeping that stirring 1 is small at a temperature of temperature is 60 DEG C in there-necked flask, loaded metallocene is obtained and urges
Agent（It is named as Cat-1）.In the carried metallocene catalyst Cat-1, the content of metallocene is 0.1 weight %, carrier
Content be 99.9 weight %.
Hollow ball-shape mesoporous composite material C1 and loaded metallocene are catalyzed with XRD, scanning electron microscope and nitrogen adsorption instrument
Agent Cat-1 is characterized.
Fig. 1 is X-ray diffracting spectrum, and as seen from the figure, hollow ball-shape mesoporous composite material C1 is peculiar with mesoporous material institute
One-dimensional hollow ball-shape pore passage structure.
Fig. 2 is the microscopic appearance SEM figures of hollow ball-shape mesoporous composite material C1, it can be seen from the figure that hollow ball-shape is situated between
The microscopic appearance of hole composite material C1 is the microballoon that particle diameter is 21-29 μm, and its good dispersion property.
Fig. 3 is the size distribution curve of hollow ball-shape mesoporous composite material C1, it can be seen from the figure that hollow ball-shape is mesoporous
Composite material C1 has uniform size distribution.
Fig. 4 is the graph of pore diameter distribution of hollow ball-shape mesoporous composite material C1, it can be seen from the figure that hollow ball-shape is mesoporous multiple
Condensation material C1 has three pore size distribution$s, and duct is uniform.
The pore structure parameter of hollow ball-shape mesoporous composite material C1 and carried metallocene catalyst Cat-1 such as table 1 below institute
Show.
Table 1
*：First most probable pore size, the second most probable pore size and the 3rd most probable pore size are separated with comma：According to by it is left extremely
Right order is the first most probable pore size, the second most probable pore size and the 3rd most probable pore size successively.
Hollow ball-shape mesoporous composite material carrier is after load metallocene it can be seen from the data of table 1, pore volume and
Aperture reduces, it is possible thereby to illustrate, metallocene is entered in mesoporous material duct.
Embodiment 2
The present embodiment is used to illustrate carried metallocene catalyst of the present invention and preparation method thereof
（1）Prepare hollow ball-shape mesoporous composite material
By 1g（0.00017mol）Template P123 and 1.4g（0.03mol）Ethanol is added to the acetic acid of pH=4.4 of 28mL
In sodium acetate buffer solution, stirring to template is completely dissolved at 10 DEG C, by 4.56g（0.04mol）Trimethylpentane adds
Into above-mentioned solution, after stirring 8h at 10 DEG C, then by 1.83g（0.012mol）Tetramethoxy-silicane is added in above-mentioned solution,
After stirring 30h at 10 DEG C, transfer the solution into the reaction kettle of agate liner, after 80 DEG C of baking oven crystallization 20h, then filtered
And be washed with deionized 6 times, then filter the filter for the meso-porous molecular sieve material for obtaining having one-dimensional hollow ball-shape pore passage structure
Cake A2.
By the waterglass that concentration is 20 weight % and the sulfuric acid solution that concentration is 12 weight % and glycerine using weight ratio as 3：
2：1 is mixed and the haptoreaction 3h at 20 DEG C, then adjusts pH value to 4 with the sulfuric acid that concentration is 98 weight %, then to
To reaction mass filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter cake B2 of silica gel.
The 10g filter cake A2 and 15g filter cakes B2 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein, ball grinder
Material is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 500r/min.Close ball milling
Tank, carries out the first ball milling in ball grinder, and temperature is 35 DEG C, when the time is 20 small.The the first ball milling slurry and 87.5g that will be obtained
Water mixed pulp at 35 DEG C, then carries out the second ball milling, and temperature is 25 DEG C, when the time is 10 small.The second ball milling that will be obtained
Slurry is to be spray-dried under 13000r/min in rotating speed at 150 DEG C, is then screened, will screened using Cyclone Separation Technology
Obtained product calcines 15h in Muffle furnace at 500 DEG C, removes P123（Template）, obtain the composite mesoporous material of hollow ball-shape
Expect C2.
（2）The preparation of carried metallocene catalyst
In the presence of nitrogen, hollow ball-shape mesoporous composite material C2 is calcined at 400 DEG C 10 it is small when to carry out thermal activation,
Eliminating hydroxide and Residual water, obtain the hollow ball-shape mesoporous composite material C2 of thermal activation.
In the presence of nitrogen, by double (normal-butyls of hollow ball-shape the mesoporous composite material C2 and 5.25mg of 3.5g thermal activations
Cyclopentadienyl group) zirconium dichloride（Added at 25 DEG C in 100ml there-necked flasks, close there-necked flask, it is 40 to keep temperature in there-necked flask
When stirring 5 is small at a temperature of DEG C, carried metallocene catalyst is obtained（It is named as Cat-2）.Urged in the loaded metallocene
In agent Cat-2, the content of metallocene is 0.15 weight %, and the content of carrier is 98.5 weight %.
The pore structure parameter of hollow ball-shape mesoporous composite material C2 and carried metallocene catalyst Cat-2 such as table 2 below institute
Show.
Table 2
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Hollow ball-shape mesoporous composite material carrier is after load metallocene it can be seen from the data of table 2, pore volume and
Aperture reduces, it is possible thereby to illustrate, metallocene is entered in mesoporous material duct.
Embodiment 3
The present embodiment is used to illustrate carried metallocene catalyst of the present invention and preparation method thereof
（1）Prepare hollow ball-shape mesoporous composite material
By 1g（0.00017mol）Template P123 and 3.13g（0.068mol）Ethanol is added to the second of pH=4.4 of 28mL
In acid and sodium acetate buffer solution, stirring to template is completely dissolved at 20 DEG C, by 7.75g（0.068mol）Trimethylpentane adds
Enter into above-mentioned solution, after stirring 8h at 20 DEG C, then by 3.8g（0.025mol）Tetramethoxy-silicane is added in above-mentioned solution,
After stirring 10h at 20 DEG C, transfer the solution into the reaction kettle of agate liner, after 40 DEG C of baking oven crystallization 30h, then filtered
And be washed with deionized 6 times, then filter the filter for the meso-porous molecular sieve material for obtaining having one-dimensional hollow ball-shape pore passage structure
Cake A3.
By the waterglass that concentration is 10 weight % and the sulfuric acid solution that concentration is 12 weight % and ethylene glycol using weight ratio as 6：
3：1 is mixed and the haptoreaction 1.5h at 30 DEG C, then adjusts pH value to 2 with the sulfuric acid that concentration is 98 weight %, then right
Obtained reaction mass is filtered, and it is 0.02 weight % to be washed with distilled water to sodium ions content, obtains the filter cake of silica gel
B3。
The 10g filter cake A3 and 10g filter cakes B3 of above-mentioned preparation is put into togerther in the ball grinder of 100mL, wherein, ball grinder
Material is agate, and Material quality of grinding balls is agate, and a diameter of 3mm of abrading-ball, quantity is 1, rotating speed 300r/min.Close ball milling
Tank, carries out the first ball milling in ball grinder, and temperature is 50 DEG C, when the time is 10 small.By the first obtained ball milling slurry and 40g water
The mixed pulp at 50 DEG C, then carries out the second ball milling, and temperature is 40 DEG C, when the time is 5 small.The the second ball milling slurry that will be obtained
Then screened using Cyclone Separation Technology to be spray-dried under 11000r/min in rotating speed at 250 DEG C, screening is obtained
Product calcine 24h at 300 DEG C in Muffle furnace, remove P123（Template）, obtain hollow ball-shape mesoporous composite material C3.
（2）The preparation of carried metallocene catalyst
In the presence of nitrogen, hollow ball-shape mesoporous composite material C3 is calcined at 400 DEG C 10 it is small when to carry out thermal activation,
Eliminating hydroxide and Residual water, obtain the hollow ball-shape mesoporous composite material C3 of thermal activation.
In the presence of nitrogen, by double (normal-butyls of hollow ball-shape the mesoporous composite material C3 and 52.5mg of 3.5g thermal activations
Cyclopentadienyl group) zirconium dichloride added in 100ml there-necked flasks at 25 DEG C, closes there-necked flask, and it is 80 to keep temperature in there-necked flask
When stirring 2 is small at a temperature of DEG C, carried metallocene catalyst is obtained（It is named as Cat-3）.Urged in the loaded metallocene
In agent Cat-3, the content of metallocene is 1.5 weight %, and the content of carrier is 98.5 weight %.
The pore structure parameter of hollow ball-shape mesoporous composite material C3 and carried metallocene catalyst Cat-3 such as table 3 below institute
Show.
Table 3
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Hollow ball-shape mesoporous composite material carrier is after load metallocene it can be seen from the data of table 3, pore volume and
Aperture reduces, it is possible thereby to illustrate, metallocene is entered in mesoporous material duct.
Comparative example 1
This comparative example is used to illustrate carried metallocene catalyst of reference and preparation method thereof
By rod-like mesoporous material SBA-15（Purchased from high-tech limited company of Jilin University）400 DEG C under nitrogen protection
Calcine 10 it is small when（Thermal activation）, alkyl and Residual water are removed, obtains the rod-like mesoporous material DC1 after thermal activation.
Method according to embodiment 1 prepares metallocene catalyst, unlike, after the above-mentioned thermal activation of identical weight
Rod-like mesoporous material DC1 replace thermal activation hollow ball-shape mesoporous composite material C1, obtain carried metallocene catalyst
DCat-1.In the carried metallocene catalyst DCat-1, the content of metallocene is 0.1 weight %, carrier（It is bar-shaped mesoporous
Material）Content be 99.9 weight %.
Rod-like mesoporous material DC1 and carried metallocene catalyst DCat-1 are characterized using nitrogen adsorption instrument, hole
Structural parameters are listed in Table 4 below.
Table 4
Comparative example 2
When by industrial 955 silica gel, 400 DEG C of calcinings 10 are small under nitrogen protection（Thermal activation）, remove alkyl and remaining water
Point, obtain the industrial 955 silica gel DC2 after thermal activation.
Method according to embodiment 1 prepares metallocene catalyst, unlike, after the above-mentioned thermal activation of identical weight
Industrial 955 silica gel DC2 replace thermal activation hollow ball-shape mesoporous composite material C1, obtain carried metallocene catalyst
DCat-2.In the carried metallocene catalyst DCat-2, the content of metallocene is 0.1 weight %, carrier（Silica gel）Contain
Measure as 99.9 weight %.
Comparative example 3
This comparative example is used to illustrate carried metallocene catalyst of reference and preparation method thereof
Method according to embodiment 1 prepares hollow ball-shape mesoporous composite material and loaded catalyst.Unlike, only into
The first ball milling of row, without the second ball milling.Specifically, the 20g filter cake A1 and 10g filter cakes B1 of above-mentioned preparation is put into togerther
In the ball grinder of 100mL.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is 25 DEG C, when the time is 5 small.Will
The the first ball milling slurry arrived and 87.5g water mixed pulp at 25 DEG C, are in rotating speed at 200 DEG C by obtained slurry
It is spray-dried under 12000r/min.Hollow ball-shape mesoporous composite material DC3 and carried metallocene catalyst DCat-3 is made.
The pore structure parameter of hollow ball-shape mesoporous composite material DC3 and carried metallocene catalyst DCat-3 such as table 5 below
It is shown.
Table 5
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Comparative example 4
This comparative example is used to illustrate carried metallocene catalyst of reference and preparation method thereof
Method according to embodiment 1 prepares hollow ball-shape mesoporous composite material and loaded catalyst.Unlike, do not adopt
Screened with Cyclone Separation Technology, specifically, by the second obtained ball milling slurry at 200 DEG C in rotating speed be 12000r/min
Lower spray drying, then calcines 10h in Muffle furnace by the product obtained after spray drying at 600 DEG C, removes P123（Template
Agent）, hollow ball-shape mesoporous composite material DC4 and carried metallocene catalyst DCat-4 is made.
The pore structure parameter of hollow ball-shape mesoporous composite material DC4 and carried metallocene catalyst DCat-4 such as table 6 below
It is shown.
Table 6
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
Comparative example 5
This comparative example is used to illustrate carried metallocene catalyst of reference and preparation method thereof
Method according to embodiment 1 prepares spherical mesoporous composite material and loaded catalyst.Unlike, only carry out the
One ball milling, without the second ball milling, does not also use Cyclone Separation Technology to be screened.Specifically, by the 20g filter cakes of above-mentioned preparation
A1 and 10g filter cakes B1 is put into togerther in the ball grinder of 100mL.Ball grinder is closed, the first ball milling is carried out in ball grinder, temperature is
25 DEG C, when the time is 5 small.By the first obtained ball milling slurry and 87.5g water mixed pulp at 25 DEG C, obtained slurry is existed
At 200 DEG C in rotating speed be 12000r/min under be spray-dried, then by the product obtained after spray drying in Muffle furnace in 600
10h is calcined at DEG C, removes P123（Template）, obtain hollow ball-shape mesoporous composite material DC5 and carried metallocene catalyst
DD5。
The pore structure parameter of hollow ball-shape mesoporous composite material DC5 and carried metallocene catalyst DD5 such as table 7 below institute
Show.
Table 7
*：Separated between first most probable pore size, the second most probable pore size and the 3rd most probable pore size with comma.
EXPERIMENTAL EXAMPLE 1
The present embodiment is used for the preparation method for illustrating methyl acrylate provided by the invention
By the carried metallocene catalyst in embodiment 1（Cat-1）0.5 gram, 6 grams of acrylic acid and methanol（Analyze pure, make
With it is preceding after re-distillation）7.4 grams are added sequentially in the round-bottomed flask of the drying equipped with water knockout drum, under conditions of being heated to reflux
Stir 3 it is small when, after being cooled to room temperature, centrifuge, reaction product liquid component analyzed using gas chromatography combined with mass spectrometry, and is led to
Cross the selectivity of conversion ratio and methyl acrylate that acrylic acid is calculated.The results are shown in Table 8.
EXPERIMENTAL EXAMPLE 2-3
Method according to EXPERIMENTAL EXAMPLE 1 prepares methyl acrylate, unlike, embodiment 2-3 preparations are respectively adopted
Carried metallocene catalyst replaces the carried metallocene catalyst Cat-1, and the conversion ratio and third of acrylic acid is calculated
The selectivity of e pioic acid methyl ester.The results are shown in Table 8.
EXPERIMENTAL EXAMPLE 4
Method according to EXPERIMENTAL EXAMPLE 1 prepares methyl acrylate, unlike, with what is recycled from EXPERIMENTAL EXAMPLE 1
Catalyst replaces the carried metallocene catalyst Cat-1.The choosing of the conversion ratio and methyl acrylate of acrylic acid is calculated
Selecting property.The results are shown in Table 5.
EXPERIMENTAL EXAMPLE 5
Method according to EXPERIMENTAL EXAMPLE 1 prepares methyl acrylate, unlike, with what is recycled from EXPERIMENTAL EXAMPLE 4
Catalyst replaces the carried metallocene catalyst Cat-1.The choosing of the conversion ratio and methyl acrylate of acrylic acid is calculated
Selecting property.The results are shown in Table 5.
EXPERIMENTAL EXAMPLE 6
Method according to EXPERIMENTAL EXAMPLE 1 prepares methyl acrylate, unlike, with what is recycled from EXPERIMENTAL EXAMPLE 5
Catalyst replaces the carried metallocene catalyst Cat-1.The choosing of the conversion ratio and methyl acrylate of acrylic acid is calculated
Selecting property.The results are shown in Table 5.
Experimental comparison's example 1-5
Method according to EXPERIMENTAL EXAMPLE 1 prepares methyl acrylate, unlike, comparative example 1-5 preparations are respectively adopted
Carried metallocene catalyst replaces the carried metallocene catalyst Cat-1, and the conversion ratio and third of acrylic acid is calculated
The selectivity of e pioic acid methyl ester.The results are shown in Table 8.
Experimental comparison's example 6-8
Method according to EXPERIMENTAL EXAMPLE 1 prepares methyl acrylate, unlike, respectively with from Experimental comparison's example 1-3
The catalyst of recycling replaces the carried metallocene catalyst Cat-1.The conversion ratio and acrylic acid first of acrylic acid is calculated
The selectivity of ester.The results are shown in Table 8.
Table 8
| Numbering | Catalyst | The conversion ratio of acrylic acid | The selectivity of methyl acrylate |
| EXPERIMENTAL EXAMPLE 1 | Cat-1 | 93% | 99% |
| EXPERIMENTAL EXAMPLE 2 | Cat-2 | 91% | 99% |
| EXPERIMENTAL EXAMPLE 3 | Cat-3 | 90% | 99% |
| EXPERIMENTAL EXAMPLE 4 | The Cat-1 of recycling | 91% | 99% |
| EXPERIMENTAL EXAMPLE 5 | The Cat-1 of secondary recovery | 88% | 99% |
| EXPERIMENTAL EXAMPLE 6 | The Cat-1 recycled three times | 87% | 99% |
| Experimental comparison's example 1 | DCat-1 | 75% | 99% |
| Experimental comparison's example 2 | DCat-2 | 70% | 99% |
| Experimental comparison's example 3 | DCat-3 | 72% | 99% |
| Experimental comparison's example 4 | DCat-4 | 66% | 99% |
| Experimental comparison's example 5 | DCat-5 | 71% | 99% |
| Experimental comparison's example 6 | The DCat-1 of recycling | 69% | 99% |
| Experimental comparison's example 7 | The DCat-2 of recycling | 65% | 90% |
| Experimental comparison's example 8 | The DCat-3 of recycling | 62% | 90% |
It can be seen that from the result of EXPERIMENTAL EXAMPLE 1-6 and Experimental comparison's example 1-4 and loaded to metallocene using load method
On hollow ball-shape mesoporous composite material carrier, the carried metallocene catalyst of acquisition is good for the catalytic performance of esterification,
And the carried metallocene catalyst can be reused by recycling, and recovery process is simple, while the catalysis recycled
Agent reactivity is still higher.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (14)
1. a kind of carried metallocene catalyst, which includes the metallocene chemical combination of carrier and load on the carrier
Thing, it is characterised in that the carrier is hollow ball-shape mesoporous composite material, and the hollow ball-shape mesoporous composite material, which contains, to be had
The meso-porous molecular sieve material of one-dimensional hollow ball-shape pore passage structure, the average grain diameter of the hollow ball-shape mesoporous composite material is 21-
29 microns, specific surface area is 100-650 meters squared per grams, and pore volume is 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three
Peak corresponds to the first most probable pore size, the second most probable pore size and the 3rd most probable pore size, and first most probable pore size respectively
For 1-10 nanometers, second most probable pore size is 20-50 nanometers, and the 3rd most probable pore size is 55-65 nanometers；
Wherein, the metallocene compound has the structure shown in Formulas I,
Wherein, R1、R2、R3、R4、R5、R1’、R2’、R3’、R4' and R5' it is each independently hydrogen or C1-C5Alkyl, and R1、R2、
R3、R4And R5In it is at least one be C1-C5Alkyl, R1’、R2’、R3’、R4' and R5' in it is at least one be C1-C5Alkyl,
M is one kind in titanium, zirconium and hafnium, and X is halogen.
2. carried metallocene catalyst according to claim 1, wherein, with the total of the carried metallocene catalyst
On the basis of weight, the content of the metallocene compound is 0.1-2 weight %, and the content of the carrier is 98-99.9 weight %；
Preferably, the average grain diameter of the hollow ball-shape mesoporous composite material is 22-28 microns, and specific surface area is put down for 250-350
Square rice/gram, pore volume is 1-1.5 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size 2-9 and receive respectively
56-64 nanometers of rice, 30-50 nanometers of the second most probable pore size and the 3rd most probable pore size.
3. carried metallocene catalyst according to claim 1 or 2, wherein, M is zirconium, and X is chlorine.
4. the carried metallocene catalyst according to claim 1 or 3, wherein, R1And R1' it is each independently C1-C5's
Alkyl, preferably normal-butyl, and R2、R3、R4、R5、R2’、R3’、R4' and R5' it is hydrogen.
5. the carried metallocene catalyst according to claim 1 or 4, wherein, the metallocene compound is double (positive fourths
Cyclopentadienyl group) zirconium dichloride.
6. carried metallocene catalyst according to claim 1 or 5, wherein, the carrier is by comprising the following steps
Method be prepared：
(1) meso-porous molecular sieve material with one-dimensional hollow ball-shape pore passage structure is provided or is prepared with one-dimensional hollow ball-shape hole
The filter cake of the meso-porous molecular sieve material of road structure, as component a；
(2) provide silica gel or prepare the filter cake of silica gel, as component b；
(3) the component a and the component b are subjected to mixing and the first ball milling, the first obtained ball milling slurry is mixed with water
Slurrying, then carries out the second ball milling and obtains the second ball milling slurry, whirlwind is used after the second ball milling slurry is spray-dried
Isolation technics is screened；
Wherein, above-mentioned steps cause the carrier average grain diameter be 21-29 micron, specific surface area be 100-650 square metres/
Gram, pore volume is 0.5-1.8 mls/g, and aperture is in tri-modal distribution, and three peaks correspond to the first most probable pore size, second most respectively
Can several apertures and the 3rd most probable pore size, and first most probable pore size is 1-10 nanometers, and second most probable pore size is
20-50 nanometers, the 3rd most probable pore size is 55-65 nanometers.
7. carried metallocene catalyst according to claim 6, wherein, in step (3), relative to 100 parts by weight
The component a dosage, the dosage of the component b is 1-200 parts by weight, be preferably 20-180 parts by weight, more preferably 50-
150 parts by weight.
8. carried metallocene catalyst according to claim 6, in step (1), preparation has one-dimensional hollow ball-shape
The process of the filter cake of the meso-porous molecular sieve material of pore passage structure includes：By template, silicon source, ethanol, trimethylpentane and sour agent
Carry out first to be mixed, and obtained mixture is subjected to crystallization and filtering；
Preferably, the template is triblock copolymer polyethylene glycol glycerine-polyethylene glycol；The silicon source is tetramethyl
Oxysilane；The acid agent is the acetic acid and sodium acetate buffer solution that pH value is 1-6；
Preferably, the molar ratio of template, ethanol, trimethylpentane and silicon source is 1：100-500：200-500：50-200, more
Preferably 1：180-400：250-400：70-150；
Preferably, first condition being mixed includes：Temperature is 10-60 DEG C, when the time is 10-72 small, pH value 1-
7；The condition of the crystallization includes：Temperature is 30-150 DEG C, when the time is 10-72 small；
Preferably, in step (2), preparing the process of the filter cake of silica gel includes：Waterglass, polyalcohol and inorganic acid are carried out the
Two are mixed, and obtained mixture is filtered；
Preferably, second condition being mixed includes：Temperature is 10-60 DEG C, when the time is 1-5 small, pH value 2-4；
It is highly preferred that the weight ratio of the waterglass, inorganic acid and polyalcohol is 1-8：0.1-5：1；The inorganic acid for sulfuric acid,
One or more in nitric acid and hydrochloric acid；The polyalcohol is glycerine and/or ethylene glycol.
9. according to the carried metallocene catalyst described in any one in claim 6-8, wherein, it is described in step (3)
The condition of first ball milling and the second ball milling is identical or different, and the condition of first ball milling and the second ball milling is wrapped independently of one another
Include：The rotating speed of abrading-ball is 200-800r/min, and the temperature in ball grinder is 15-100 DEG C, time of ball milling for 0.1-100 it is small when；
Preferably, the weight ratio of the dosage of the first ball milling slurry and water is 1：0.1-5, the first ball milling slurry and water mixed pulp
Temperature is 25-60 DEG C；
Preferably, the condition of the spray drying includes：Temperature is 150-600 DEG C, rotating speed 10000-15000r/min；
Preferably, the step of being screened after the second ball milling slurry is spray-dried using Cyclone Separation Technology is included institute
State the second ball milling slurry to be spray-dried, the gas containing powder of discharge is subjected to cyclonic separation to collect the powder；
Preferably, the component a is to be with a cube filter cake for the meso-porous molecular sieve material of caged pore passage structure, the component b
The filter cake of silica gel；The method further includes：After the spray-drying process of step (3), from the powder collected by cyclonic separation
Removed template method in grain；
Preferably, the condition of the removed template method includes：Temperature is 90-600 DEG C, when the time is 10-80 small.
10. a kind of method for preparing the carried metallocene catalyst in claim 1-9 described in any one, its feature exist
In this method includes：In the presence of an inert gas, in supported on carriers metallocene compound.
11. according to the method described in claim 10, wherein, this method is additionally included in before load metallocene compound, lazy
Property gas in the presence of, by the carrier at a temperature of 300-900 DEG C heat 7-10 it is small when；
Preferably, the condition of the load includes：Temperature is 15-100 DEG C, when the time is 0.1-100 small.
12. the carried metallocene catalyst prepared as the method described in claim 10 or 11.
13. the application of carried metallocene catalyst in the esterification reaction in claim 1-9 and 12 described in any one.
14. a kind of preparation method of methyl acrylate, this method include：Under conditions of esterification, in the presence of a catalyst,
Acrylic acid and methanol are contacted, it is characterised in that the catalyst is described in any one in claim 1-9 and 12
Carried metallocene catalyst.
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| CN113354761A (en) * | 2021-06-10 | 2021-09-07 | 上海廷锦技术有限公司 | Method for preparing polar polymer by using metallocene catalyst |
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