CN103586078A - Supported metallocene catalyst, preparation method and application thereof, and n-butyl acetate preparation method - Google Patents
Supported metallocene catalyst, preparation method and application thereof, and n-butyl acetate preparation method Download PDFInfo
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- CN103586078A CN103586078A CN201210289004.7A CN201210289004A CN103586078A CN 103586078 A CN103586078 A CN 103586078A CN 201210289004 A CN201210289004 A CN 201210289004A CN 103586078 A CN103586078 A CN 103586078A
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Abstract
The invention discloses a supported metallocene catalyst, a preparation method thereof, and an n-butyl acetate preparation method. The catalyst is composed of 98-99.9wt% of a support and 0.1-2wt% of a metallocene supported on the support, and the support is rod-shaped meso-porous silica; and the rod length, the specific surface area, the most probable aperture and the average aspect ratio of the support are 0.5-3mum, 200-500m<2>/g, 10-15nm and 1-3 respectively; and the structure of the metallocene is represented by formula 1. In the catalyst, the metallocene is supported on the specific rod-shaped meso-porous silica support, so the esterifying catalysis activity of the catalyst is high, and is still high after repeated use, thereby the catalyst can be recovered and recycled. The formula 1 is shown in the specification.
Description
Technical field
The present invention relates to a kind of carried metallocene catalyst and preparation method thereof, also relate to and use the application of this catalyst in esterification, and a kind of preparation method of n-butyl acetate.
Background technology
Within 1992, Mobile company synthesizes mesoporous material (Beck J S, Vartuli J C, Roth W J, et al.J.Am.Chem.Soc., 1992,114 (27): 10834-10843), this mesoporous material has high specific surface, regular pore passage structure and narrow pore-size distribution, make mesoporous material obtain very large concern in the application of catalysis, separation, medicine and other fields; Within 1998, Zhao east unit waits people to synthesize a kind of new material-mesoporous material SBA-15 (D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science 279 (1998) 548-550), this material has the large (1.0cm of cube single-crystal meso-pore material aperture (6-30nm), pore volume of high-sequential
3/ g), the high mechanical properties that thicker hole wall (4-6nm) keeps and good catalytic adsorption performance; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao invent a kind of preparation method (CN1341553A) of mesonic pore molecular sieve carrier material, and this mesoporous material is as heterogeneous reaction catalyst carrier, easily realize separated (Wight, the A.P. of catalyst and product; Davis, M.E.Chem.Rev.2002,102,3589; De Vos, D.E.; Dams, M.; Sels, B.F.; Jacobs, P.A.Chem.Rev.2002,102,3615.).Yet conventional ordered mesoporous material SBA-15 has stronger water suction, moisture absorption ability at present, rod length approaches 5 μ m, and there is adhesion between rod and rod, in catalytic reaction process, be unfavorable for that material transmits in mesopore orbit, this will further aggravate the reunion of ordered mesoporous material, give ordered mesoporous material storage, transport, rear processing and application make troubles.
Load again after traditional handicraft needs toluene as solvent, metallocene to be dissolved when utilizing mesoporous material to carry out metallocene load; after load, also to utilize n-hexane to carry out cyclic washing to head product; not only technique is loaded down with trivial details, also causes environmental pollution, is unfavorable for environmental protection.
About utilize magnesium chloride as patent (a kind of magnesium chloride load non-metallocene schiff base catalyst component and method for making thereof and application, the patent No. 200610137778.2 of carrier loaded metallocene by ball-milling method; A kind of magnesium chloride loaded metallocene catalyst component and method for making and application, the patent No. 200610137778.8) have been reported, yet above-mentioned patent utilization magnesium chloride carries out metallocene load as carrier, except needs solvent carries out metallocene load again as toluene dissolves metallocene, also need the solvent that utilizes n-hexane to wash to remove on carrier to cause secondary pollution, and magnesium chloride itself is very easy to the moisture absorption, in air, be difficult to preserve, in detesting the metallocene loading process of water anaerobism, easily make metallocene lose catalytic effect.
Therefore, develop a kind of novel catalyst for the synthesis of n-butyl acetate and become problem in the urgent need to address.
Summary of the invention
The object of the invention is to overcome that the existing catalyst for Catalytic Synthesis exists is serious to equipment corrosion, complex process, easily lose the shortcomings such as catalytic effect, the preparation method of a kind of novel Catalysts and its preparation method for the synthesis of n-butyl acetate and application and n-butyl acetate is provided.
The invention provides a kind of carried metallocene catalyst, this catalyst is comprised of carrier and the metallocene compound that loads on described carrier, it is characterized in that, described carrier is bar-shaped mesoporous silicon oxide, and the gross weight of described catalyst of take is benchmark, the content of described metallocene compound is 0.1-2 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier is long is 0.5-3 micron, and specific area is 200-500 meters squared per gram, and most probable aperture is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and average aspect ratio value is 1-3; Described metallocene compound has the structure shown in formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
The present invention also provides a kind of preparation method of carried metallocene catalyst, wherein, the method comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with metallocene, metallocene is loaded on described bar-shaped meso-porous titanium dioxide silicon carrier, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and metallocene compound of take is benchmark, the consumption of described metallocene is 0.1-2 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier is long is 0.5-3 micron, and specific area is 200-500 meters squared per gram, and most probable aperture is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and average aspect ratio value is 1-3; Described metallocene compound has the structure shown in formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
In addition, the present invention also provides the application of described catalyst in esterification.
Also have, the present invention also provides a kind of preparation method of n-butyl acetate, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain n-butyl acetate with n-butanol, wherein, described catalyst is carried metallocene catalyst provided by the invention.
In catalyst of the present invention, metallocene loads on specific bar-shaped meso-porous titanium dioxide silicon carrier, on the one hand, not only the activity of this carried metallocene catalyst catalytic esterification is higher, and the activity of this carried metallocene catalyst catalytic esterification is still higher while reusing, and this carried metallocene catalyst is recovered and cycling and reutilization.Also owing to metallocene being loaded on specific bar-shaped meso-porous titanium dioxide silicon carrier, prevented equipment corrosion, so this carried metallocene catalyst is a kind of catalyst of environmental protection on the other hand.
In the present invention, by ball-milling method, metallocene is carried on specific bar-shaped meso-porous titanium dioxide silicon carrier, in whole mechanical milling process, do not introduce solvent, process is simple and easy to do, and after mechanical milling process, gained catalyst also keeps bar-shaped, and while carrying out the esterification of catalysis acetic acid and n-butanol with this catalyst, catalyst can pass through and reclaim and Reusability, and carried metallocene catalyst provided by the invention can reduce side reaction, raising product purity, etching apparatus, is not conducive to environmental protection.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, and wherein, a is the XRD spectra of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), the XRD spectra that b is the bar-shaped mesoporous silicon oxide (DBK-BU) by ball-milling method load metallocene compound, and abscissa is 2 θ, and ordinate is intensity.
Fig. 2 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), b for by ball-milling method load the microscopic appearance figure of bar-shaped mesoporous silicon oxide (DBK-BU) of metallocene compound.
Fig. 3 is TEM scanning electron microscope (SEM) photograph, and wherein, a is the transmission plot of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), the transmission plot of the bar-shaped mesoporous silicon oxide (DBK-BU) that b is the load metallocene compound prepared by ball-milling method.
Fig. 4 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of rod-like mesoporous material SBA-15, the microscopic appearance figure of the rod-like mesoporous material SBA-15 that b is the load metallocene prepared by ball-milling method.
Fig. 5 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of industrial 955 silica gel, the microscopic appearance figure of industrial 955 silica gel (GJ-BU-2) that b is the load metallocene prepared by ball-milling method.
Fig. 6 is TEM transmission electron microscope picture, and wherein, a is the micro-structure diagram of industrial 955 silica gel (GJ), the micro-structure diagram that b is industrial 955 silica gel (GJ-BU-2) by ball-milling method load metallocene.
The specific embodiment
The invention provides a kind of carried metallocene catalyst, it is characterized in that, this catalyst is comprised of carrier and the metallocene compound that loads on described carrier, wherein, described carrier is bar-shaped mesoporous silicon oxide, and the gross weight of described catalyst of take is benchmark, the content of described metallocene compound is 0.1-2 % by weight, the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight, more preferably in situation, the gross weight of described catalyst of take is benchmark, the content of described metallocene is 0.15-1.5 % by weight, the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 98.5-99.85 % by weight, and the rod of described bar-shaped meso-porous titanium dioxide silicon carrier is long is 0.5-3 micron, and specific area is 200-500 meters squared per gram, is preferably 300-400 meters squared per gram, more elect 350 meters squared per gram as, pore volume is 1.0-2.0 ml/g, is preferably 1.2-1.8 ml/g, more preferably 1.5 mls/g, most probable aperture is 10-15 nanometer, is preferably 11-14 nanometer, 12 nanometers more preferably, and pore wall thickness is 1.5-2 nanometer, is preferably 1.6-1.8 nanometer, 1.7 nanometers more preferably, average aspect ratio value is 1-3, described metallocene compound has the structure shown in formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen; In this case, not only can obtain gratifying catalytic effect, but also can reduce costs.
According to carried metallocene catalyst of the present invention, what the M in formula 1 can be in titanium, zirconium and hafnium is a kind of.M in different metallocene compound molecules can be identical or different, and preferably, M is zirconium.
According to carried metallocene catalyst of the present invention, the X in formula 1 is halogen.What particularly, the X in formula 1 can be in fluorine, chlorine, bromine and iodine is a kind of.Preferably, the X in formula 1 is chlorine or bromine.X in different metallocene compound molecules can be identical or different, and more preferably, the X in formula 1 is chlorine.
According to the present invention, in formula 1, cyclopentadienyl group is for forming η with central metal
5key and with the derivative of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl group in formula 1
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl.
In the present invention, described C
1-C
5alkyl can be one or more in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
The instantiation that meets the cyclopentadienyl group of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl group, n-pro-pyl cyclopentadienyl group, isopropyl cyclopentadienyl group, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl group, isobutyl group cyclopentadienyl group, tert-butyl group cyclopentadienyl group, n-pentyl cyclopentadienyl group, isopentyl cyclopentadienyl group, tertiary pentyl cyclopentadienyl group, neopentyl cyclopentadienyl group, 1,2-dimethyl cyclopentadienyl group, 1,3-dimethyl cyclopentadienyl group, 1,2,3-trimethyl cyclopentadienyl group, 1,2,4-trimethyl cyclopentadienyl group, 1,2,3,4-tetramethyl-ring pentadienyl, pentamethyl cyclopentadienyl group, 1,2-diethyl cyclopentadienyl group, 1,3-diethyl cyclopentadienyl group, 1,2,4-triethyl group cyclopentadienyl group, 1-methyl-2-ethyl cyclopentadienyl group, 1-methyl-3-ethyl cyclopentadienyl group, 1,3-diη-propyl cyclopentadienyl group, 1-methyl-3-n-pro-pyl cyclopentadienyl group, 1,3-diisopropyl cyclopentadienyl group, 1-methyl-3-isopropyl cyclopentadienyl group, 1,3-di-n-butyl cyclopentadienyl group, 1-methyl-3-n-butyl cyclopentadienyl, 1,3-di-sec-butyl cyclopentadienyl group, 1-methyl-3-sec-butyl cyclopentadienyl group, 1,3-diisobutyl cyclopentadienyl group, 1-methyl-3-isobutyl group cyclopentadienyl group, 1,3-di-t-butyl cyclopentadienyl group, 1-methyl-3-tert-butyl group cyclopentadienyl group, 1,3-, bis-n-pentyl cyclopentadienyl groups, 1-methyl-3-n-pentyl cyclopentadienyl group, 1,3-diisoamyl cyclopentadienyl group, 1-methyl-3-isopentyl cyclopentadienyl group, 1,3-, bis-tertiary pentyl cyclopentadienyl groups, 1-methyl-3-tertiary pentyl cyclopentadienyl group, 1,3-di neo-pentyl cyclopentadienyl group and 1-methyl-3-neopentyl cyclopentadienyl group.
Preferably, the R in formula 1
1, R
1' and be C independently of one another
1-C
5alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
The instantiation that meets the cyclopentadienyl group of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl group, propyl group cyclopentadienyl group, isopropyl cyclopentadienyl group, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl group, isobutyl group cyclopentadienyl group, tert-butyl group cyclopentadienyl group, n-pentyl cyclopentadienyl group, isopentyl cyclopentadienyl group, tertiary pentyl cyclopentadienyl group and neopentyl cyclopentadienyl group.
More preferably, R
1and R
1' be C
4alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.Particularly, described cyclopentadienyl group is n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl group, isobutyl group cyclopentadienyl group, tert-butyl group cyclopentadienyl group.
Most preferably, described cyclopentadienyl group is n-butyl cyclopentadienyl.
The present inventor finds in research process, the R in formula 1
1and R
1' be normal-butyl, M is zirconium, X is chlorine, when described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichloride, when described carried metallocene catalyst is used for the polymerisation of catalyzed alkene, demonstrates excellent catalytic activity.
According to the present invention, the specific area of described carried metallocene catalyst can be 270-295 meters squared per gram, is preferably 280-295 meters squared per gram, more preferably 290 meters squared per gram; Pore volume can be 0.5-0.9 ml/g, is preferably 0.8-0.9 ml/g, more preferably 0.9 ml/g; Most probable aperture can be 5-15 nanometer, is preferably 6-10 nanometer, more preferably 8.6 nanometers; Pore wall thickness is 1.8-2 nanometer, more preferably 2 nanometers; Average aspect ratio value is 1-3.
According to the present invention, described carrier is bar-shaped mesoporous silicon oxide, and described bar-shaped mesoporous silicon oxide can prepare by the method comprising the following steps:
(1) template, ammonium fluoride and mixed in hydrochloric acid to solids is fully dissolved;
(2) by step (1) gained solution and esters of silicon acis and heptane standing 2-5 hour after 25-60 ℃ of temperature, mechanical agitation speed are to stir 1-10 hour under 200-500r/min;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and will filter deionized water washing for gained solid, dry;
(5) by the dry products therefrom heating of step (4), removed template method;
Described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
Under preferable case, described esters of silicon acis is preferably ethyl orthosilicate.
Under preferable case, described crystallization condition comprises that temperature is 90-180 ℃, is preferably 95-150 ℃, and the time is 10-40 hour, is preferably 15-30 hour.
According to the present invention, the method for described removed template method can be calcination method, and the condition of described calcination method comprises that temperature is 300-600 ℃, is preferably 400-550 ℃, and the time is 8-20 hour, is preferably 10-18 hour.
Under preferable case, count in molar ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: ammonium fluoride: water: hydrogen chloride: esters of silicon acis: heptane=1:1-3:1000-30000:100-2000:20-500:20-500, be preferably 1:1.2-2.8:1200-28000:120-1800:25-100:280-400, be particularly preferably 1:1.8:5225:1306:64:279.Wherein, the molal quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene.
According to the present invention, described template can be the conventional various triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene templates that use in this area, for example, can be the commodity P123 by name that Aldrich company produces, and molecular formula is EO
20pO
70eO
20template.
The present invention also provides a kind of preparation method of catalyst, wherein, the method comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with metallocene, metallocene is loaded on described bar-shaped meso-porous titanium dioxide silicon carrier, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and metallocene compound of take is benchmark, the consumption of described metallocene is 0.1-2 % by weight, the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight, more preferably in situation, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and metallocene compound of take is benchmark, the consumption of described metallocene is 0.15-1.5 % by weight, the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 98.5-99.85 % by weight.
According to the present invention, the rod length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-3 micron, specific area is 200-500 meters squared per gram, be preferably 300-400 meters squared per gram, 350 meters squared per gram more preferably, pore volume is 1.0-2.0 ml/g, is preferably 1.2-1.8 ml/g, more preferably 1.5 mls/g; Most probable aperture is 10-15 nanometer, is preferably 11-14 nanometer, 12 nanometers more preferably, and pore wall thickness is 1.5-2 nanometer, is preferably 1.6-1.8 nanometer, 1.7 nanometers more preferably, average aspect ratio value is 1-3.
According to the present invention, described metallocene compound has the structure shown in formula 1:
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen; In this case, not only can obtain gratifying catalytic effect, but also can reduce costs.
According to carried metallocene catalyst of the present invention, what the M in formula 1 can be in titanium, zirconium and hafnium is a kind of.M in different metallocene compound molecules can be identical or different, and preferably, M is zirconium.
According to carried metallocene catalyst of the present invention, the X in formula 1 is halogen.What particularly, the X in formula 1 can be in fluorine, chlorine, bromine and iodine is a kind of.Preferably, the X in formula 1 is chlorine or bromine.X in different metallocene compound molecules can be identical or different, and more preferably, the X in formula 1 is chlorine.
According to the present invention, in formula 1, cyclopentadienyl group is for forming η with central metal
5key and with the derivative of the cyclopentadienyl of alkyl substituent.Preferably, the R on the cyclopentadienyl group in formula 1
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl.
In the present invention, described C
1-C
5alkyl can be one or more in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl, tertiary pentyl and neopentyl.
The instantiation that meets the cyclopentadienyl group of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl group, n-pro-pyl cyclopentadienyl group, isopropyl cyclopentadienyl group, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl group, isobutyl group cyclopentadienyl group, tert-butyl group cyclopentadienyl group, n-pentyl cyclopentadienyl group, isopentyl cyclopentadienyl group, tertiary pentyl cyclopentadienyl group, neopentyl cyclopentadienyl group, 1,2-dimethyl cyclopentadienyl group, 1,3-dimethyl cyclopentadienyl group, 1,2,3-trimethyl cyclopentadienyl group, 1,2,4-trimethyl cyclopentadienyl group, 1,2,3,4-tetramethyl-ring pentadienyl, pentamethyl cyclopentadienyl group, 1,2-diethyl cyclopentadienyl group, 1,3-diethyl cyclopentadienyl group, 1,2,4-triethyl group cyclopentadienyl group, 1-methyl-2-ethyl cyclopentadienyl group, 1-methyl-3-ethyl cyclopentadienyl group, 1,3-diη-propyl cyclopentadienyl group, 1-methyl-3-n-pro-pyl cyclopentadienyl group, 1,3-diisopropyl cyclopentadienyl group, 1-methyl-3-isopropyl cyclopentadienyl group, 1,3-di-n-butyl cyclopentadienyl group, 1-methyl-3-n-butyl cyclopentadienyl, 1,3-di-sec-butyl cyclopentadienyl group, 1-methyl-3-sec-butyl cyclopentadienyl group, 1,3-diisobutyl cyclopentadienyl group, 1-methyl-3-isobutyl group cyclopentadienyl group, 1,3-di-t-butyl cyclopentadienyl group, 1-methyl-3-tert-butyl group cyclopentadienyl group, 1,3-, bis-n-pentyl cyclopentadienyl groups, 1-methyl-3-n-pentyl cyclopentadienyl group, 1,3-diisoamyl cyclopentadienyl group, 1-methyl-3-isopentyl cyclopentadienyl group, 1,3-, bis-tertiary pentyl cyclopentadienyl groups, 1-methyl-3-tertiary pentyl cyclopentadienyl group, 1,3-di neo-pentyl cyclopentadienyl group and 1-methyl-3-neopentyl cyclopentadienyl group.
Preferably, the R in formula 1
1, R
1' and be C independently of one another
1-C
5alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
The instantiation that meets the cyclopentadienyl group of above-mentioned requirements comprises: methyl cyclopentadienyl, ethyl cyclopentadienyl group, propyl group cyclopentadienyl group, isopropyl cyclopentadienyl group, n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl group, isobutyl group cyclopentadienyl group, tert-butyl group cyclopentadienyl group, n-pentyl cyclopentadienyl group, isopentyl cyclopentadienyl group, tertiary pentyl cyclopentadienyl group and neopentyl cyclopentadienyl group.
More preferably, R
1and R
1' be C
4alkyl, R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.Particularly, described cyclopentadienyl group is n-butyl cyclopentadienyl, sec-butyl cyclopentadienyl group, isobutyl group cyclopentadienyl group, tert-butyl group cyclopentadienyl group.
Most preferably, described cyclopentadienyl group is n-butyl cyclopentadienyl.
The present inventor finds in research process, the R in formula 1
1and R
1' be normal-butyl, M is zirconium, X is chlorine, when described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichloride, when described carried metallocene catalyst is used for the polymerisation of catalyzed alkene, demonstrates excellent catalytic activity.
To the condition of grinding and concrete operation method, there is no particular limitation, not destroy or substantially not destroy carrier structure and metallocene is entered in carrier duct, is as the criterion.Those skilled in the art can select various suitable conditions to implement the present invention according to mentioned above principle.
According to one embodiment of the present invention, the preparation method of described carried metallocene catalyst comprises: bar-shaped mesoporous silicon oxide and metallocene are joined in the ball grinder of ball mill, ball grinder inwall is polytetrafluoroethyllining lining, and the diameter of abrading-ball is 2-3mm, and rotating speed is 400r/min.In ball grinder, temperature is continuously grinding 0.1-100 hour at 15-100 ℃, takes out afterwards pressed powder, obtains the bar-shaped mesoporous silicon oxide of load metallocene.The quantity of abrading-ball depends on the size of ball grinder, and the ball grinder that is 50-150ml for size can be used 1 abrading-ball.The material of described abrading-ball can be agate, polytetrafluoroethylene (PTFE), is preferably polytetrafluoroethylene (PTFE).
According to a kind of specific embodiment of the present invention, the preparation method of described carried metallocene catalyst comprises the following steps:
The 1st step, by triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (EO
20pO
70eO
20, be abbreviated as P123) and ammonium fluoride, join in hydrochloric acid, by molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ammonium fluoride: water: hydrogen chloride=1:1-3:1000-30000:100-2000, be preferably 1:1.2-2.8:1200-28000:120-1800, be particularly preferably 1:1:1.8:5225:1306, wherein, the molal quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene
Being mixed to solids fully dissolves;
The 2nd step adds ethyl orthosilicate and heptane in previous step gained solution, at 25 ℃ of-60 ℃ of temperature mechanical agitation speed be to stir 1-10 hour under 200-500r/min after standing 2-5 hour; Press molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ethyl orthosilicate: heptane=1:20-200:20-500; Be preferably 1:25-100:280-400; More elect 1:64:279 as;
The 3rd step, is placed in closed reaction vessel by upper step gained solution, and at 90 ℃ of-180 ℃ of temperature, crystallization is 10 hours-40 hours;
The 4th step, filters crystallization afterproduct (preferably with after deionized water dilution), will filter deionized water washing for gained solid, dry, obtains the former powder of rod-like mesoporous material;
The 5th step, by the former powder of gained rod-like mesoporous material, at 300-600 ℃ of calcining 8-20 hour, removed template method, obtains the bar-shaped mesoporous silicon oxide of removed template method;
The 6th step, in the ball grinder that the bar-shaped mesoporous silicon oxide of upper step gained removed template method and metallocene are joined to ball mill, rotating speed be under 300-500r/min in ball grinder temperature be continuously grinding 0.1-100 hour at 15-100 ℃, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and metallocene of take is benchmark, the consumption of described metallocene is 0.1-2 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight; The consumption that is preferably described metallocene is 0.15-1.5 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 98.5-99.85 % by weight; Take out afterwards pressed powder, obtain the bar-shaped mesoporous silicon oxide of load metallocene.
According to the present invention, described template can be the conventional various triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene templates that use in this area, for example, can be the commodity P123 by name that Aldrich company produces, and molecular formula is EO
20pO
70eO
20template.
Method and the condition of described crystallization and removed template method are known to the skilled person, and for example, the temperature of crystallization can be 90-180 ℃, the time of crystallization can be 10-40 hour, preferably, the temperature of crystallization can be 95-150 ℃, and the time of crystallization can be 15-30 hour.The temperature of removed template method is 300-600 ℃, is preferably 400-550 ℃, and the time is 8-20 hour, is preferably 10-18 hour.
In addition, the present invention also provides the application of described catalyst in esterification.
Also have, the present invention also provides a kind of preparation method of n-butyl acetate, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain n-butyl acetate with n-butanol, wherein, described catalyst is carried metallocene catalyst provided by the invention.
According to the present invention, the application of two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of described carried metallocene catalyst in esterification and a kind of preparation method of n-butyl acetate comprise the steps:
The 1st step, in reactor, add acetic acid and n-butanol, and add the rod-like mesoporous material that contains two (n-butyl cyclopentadienyl) zirconium dichloride BUCP of the present invention as catalyst, in esterification, the consumption of described carried metallocene catalyst has no particular limits, those skilled in the art can carry out suitable adjustment according to the needs of reaction, the ratio of acetic acid and n-butanol also can in very large range change, under preferable case, by quality rate of charge, acetic acid: n-butanol: described catalyst=1:0.1-10:0.01-0.3;
The 2nd step, is adding under the condition of hot reflux, and the temperature of reaction is 10-150 ℃, and stirring reaction 0.1 hour-72 hours, is cooled to after room temperature, and centrifugal solid-liquid is separated;
The 3rd step, the liquid product rectifying obtaining is separated, obtain product n-butyl acetate.
In the present invention, the condition of described esterification is conventionally known to one of skill in the art, and for example, the condition of described esterification can comprise: under back flow reaction condition, the reaction time is 1-10 hour, and preferably, the reaction time can be 2-8 hour.
According to the present invention, after esterification finishes, can carry out centrifugation to final reactant mixture, by the centrifugal solid formation obtaining vacuum drying 1-24 hour at 25-200 ℃, preferred vacuum drying 6-10 hour at 50-120 ℃, the catalyst that can be recycled.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, polyethylene glycol oxide-PPOX-polyethylene glycol oxide, is abbreviated as P123, and molecular formula is EO
20pO
70eO
20, the material that is 9003-11-6 in the registration number of U.S. chemical abstract, its average molecular mass Mn=5800.
In following examples, X-ray diffraction analysis is to carry out on the X-ray diffractometer of D8 Advance in the model purchased from German Bruker AXS company; In the SEM that scanning electron microscope analysis is XL-30 in the model purchased from U.S. FEI Co., carry out; On the nitrogen adsorption desorption instrument that nitrogen adsorption desorption instrument is Autosorb-1 purchased from the model of U.S. Kang Ta company, carry out.
The present embodiment is for illustrating according to carried metallocene catalyst of the present invention and preparation method thereof.
In the hydrochloric acid that the concentration that 2.4 grams of P123 and 0.028 gram of ammonium fluoride are joined to 80ml is 1.75mlo/l, at 20 ℃, be stirred to P123 and ammonium fluoride is molten completely altogether; Again 17ml normal heptane and 5.5ml ethyl orthosilicate are joined in above-mentioned solution, at 25 ℃ of temperature, after mechanical agitation speed is to stir 4 hours under 200r/min standing 2 hours; Gained solution is transferred in teflon-lined reactor, 100 ℃ of crystallization, after 24 hours, after filtering, wash, being dried, obtained the former powder of rod-like mesoporous material; By the 500 ℃ of calcinings 20 hours in Muffle furnace of the former powder of rod-like mesoporous material, removed template method, obtains the bar-shaped mesoporous silicon oxide (called after DBK) of removed template method.
The bar-shaped mesoporous silicon oxide of removed template method, under nitrogen protection, in 400 ℃ of calcinings 10 hours, is obtained to the bar-shaped mesoporous silicon oxide after thermal activation.
Under anhydrous and oxygen-free condition, 3.5 grams after above-mentioned thermal activation bar-shaped mesoporous silicon oxide DBK are put into 100ml ball grinder at room temperature state together with 4.9 milligrams of metallocene compounds, wherein, the material of ball grinder and abrading-ball is polytetrafluoroethylene (PTFE), the diameter of abrading-ball is 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 ℃, obtain 3.5049 grams of carried metallocene catalysts with fine mobility, and by the loaded catalyst called after DBK-BU obtaining, wherein, the total amount of carried metallocene catalyst of take is benchmark, and the content of metallocene is 0.1 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 99.9 % by weight.
With XRD, ESEM, gas chromatography combined with mass spectrometry analyzer, this carried metallocene catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, and wherein, a is the XRD spectra of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), the XRD spectra that b is the bar-shaped mesoporous silicon oxide (DBK-BU) by ball-milling method load metallocene, and abscissa is 2 θ, and ordinate is intensity.The low-angle spectrum peak being occurred from XRD spectra, the XRD spectra b of the bar-shaped mesoporous silicon oxide (DBK-BU) of the XRD spectra a of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), load metallocene all has the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material.
Fig. 2 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), b for by ball-milling method load the microscopic appearance figure of bar-shaped mesoporous silicon oxide (DBK-BU) of metallocene.As shown in Figure 2, the excellent length of bar-shaped mesoporous silicon oxide DBK microscopic appearance is 0.5-3 μ m, and DBK-BU microscopic appearance prepared by ball-milling method is still basic keeps bar-shaped, and excellent length is 0.5-3 μ m.
Fig. 3 is TEM transmission plot, and wherein, a is the transmission plot of rod-like mesoporous material SBA-15, the transmission plot of the rod-like mesoporous material SBA-15 that b is the load metallocene prepared by ball-milling method.As shown in Figure 3, DBK and DBK-BU have the duct cloth of the peculiar high-sequential of mesoporous material, and this result is consistent with the result of XRD.
Fig. 4 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of rod-like mesoporous material SBA-15, the microscopic appearance figure of the rod-like mesoporous material SBA-15 that b is the load metallocene prepared by ball-milling method.The microscopic appearance of the rod-like mesoporous material SBA-15 of the load metallocene of preparing by ball-milling method as shown in Figure 4, is completely destroyed.
Fig. 5 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of industrial 955 silica gel, the microscopic appearance figure of industrial 955 silica gel (GJ-BU-2) that b is the load metallocene catalyst prepared by ball-milling method.The industrial 955 silica G J-BU-2 microscopic appearances of the load metallocene catalyst of preparing by ball-milling method as shown in Figure 5, are completely destroyed.
Fig. 6 is TEM transmission electron microscope picture, and wherein, a is the micro-structure diagram of micro-structure diagram, the b of industrial 955 silica gel (GJ) industrial 955 silica gel (GJ-BU-2) that are load metallocene.As shown in Figure 6, the pore passage structure of GJ and GJ-BU is completely unordered.
Table 1 is the pore structure parameter of the bar-shaped mesoporous silicon oxide (DBK-BU) of bar-shaped meso-porous titanium dioxide silicon carrier (DBK) and load metallocene of the present invention.
Table 1
Note: average pore wall thickness=(a
0* 3
1/2)/2-average pore size;
Cell parameter a
0=d
100* 2
1/2;
D
100be 100 interplanar distances.
Data by upper table 1 can find out, bar-shaped mesoporous silicon oxide is after load metallocene, and pore volume and specific area all significantly reduce, and this explanation metallocene in load-reaction process enters into bar-shaped mesoporous silicon oxide composite inner.
The present embodiment is for illustrating the preparation with the bar-shaped silica of dipping method load metallocene
By 1 gram of bar-shaped mesoporous silicon oxide DBK of embodiment 1 preparation, 400 ℃ of calcinings 10 hours under nitrogen protection, to remove hydroxyl and remaining moisture, thereby obtain the bar-shaped mesoporous silicon oxide through thermal activation.
By above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DBK through thermal activation vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, again 30ml methyl alcohol and 4mg metallocene are put into 100ml teflon-lined reactor together, capping still, under 35 ℃ of conditions, stir 24 hours, obtain 1.003 grams of target product carried metallocene catalysts, called after DBK-BU-JZ, wherein, the total amount of carried metallocene catalyst of take is benchmark, the content of metallocene is 0.3 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 99.7 % by weight.
With gas chromatography combined with mass spectrometry analyzer, this carried metallocene catalyst is characterized.
Comparative example 1
This comparative example is for illustrating the bar-shaped mesoporous silicon oxide of preparing loaded metallocene
By bar-shaped mesoporous silicon oxide SBA-15(purchased from high-tech share Co., Ltd of Jilin University) under nitrogen protection 400 ℃ calcining 10 hours (thermal activation), remove alkyl and remaining moisture, obtain the rod-like mesoporous material after thermal activation.
Under anhydrous and oxygen-free condition, bar-shaped mesoporous silicon oxide SBA-15 after 3.5 grams of thermal activations is put into 100ml ball grinder under room temperature state together with 4.9 milligrams of metallocene compounds, wherein, the material of ball grinder and abrading-ball is polytetrafluoroethylene (PTFE), the diameter of abrading-ball is 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 ℃, obtains the rod-like mesoporous material (called after SBA-15-BU) of 3.5049 grams of load metallocenes.Wherein, the total amount of carried metallocene catalyst of take is benchmark, and the content of metallocene is 0.1 % by weight, and the content of rod-like mesoporous material is 99.9 % by weight.
With ESEM, gas chromatography combined with mass spectrometry analyzer, this carried metallocene catalyst is characterized.
Table 2
Comparative example 2
The 400 ℃ of calcinings under nitrogen protection of industrial 955 silica gel are carried out to thermal activation for 10 hours; remove hydroxyl and remaining moisture; obtain industrial 955 silica gel materials after thermal activation; under anhydrous and oxygen-free condition, industrial 955 silica gel after 3.5 grams of thermal activations are put into 100ml ball grinder under room temperature state together with 4.9 milligrams of metallocene compounds, wherein; the material of ball grinder and abrading-ball is polytetrafluoroethylene (PTFE); the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 ℃, obtains 3.5049 grams of industrial 955 silica gel materials/metallocene catalysts with good mobility, and by the catalyst called after GJ-BU-2 obtaining.Wherein, the total amount of carried metallocene catalyst of take is benchmark, and the content of metallocene is 0.1 % by weight, and the content of industrial 955 silica gel is 99.9 % by weight.
With ESEM, transmission electron microscope and gas chromatography combined with mass spectrometry analyzer, this carried metallocene catalyst is characterized.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of carried metallocene catalyst of the present invention.
0.5 gram of carried metallocene catalyst in embodiment 1 (DBK-BU), 6 grams of acetic acid and n-butanol (are analyzed pure, before use after re-distillation) 7.4 grams join successively in the dry round-bottomed flask that water knockout drum is housed, stir 3 hours adding under the condition of hot reflux, be cooled to after room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analytic approach analytical reactions product liquid component, result is: the conversion ratio of acetic acid is 92.2%, n-butyl acetate be selectively 99%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after carried metallocene catalyst recovery of the present invention.
Carried metallocene catalyst in EXPERIMENTAL EXAMPLE 1 (DBK-BU) is reclaimed, 12 grams of 1 gram of carried metallocene catalyst (DBK-BU), the acetic acid and the n-butanol that reclaim (are analyzed pure, before use after re-distillation) 14.8 grams join successively in the dry round-bottomed flask that water knockout drum is housed, stir 3 hours adding under the condition of hot reflux, be cooled to after room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analytic approach analytical reactions product liquid component, result is: the conversion ratio of acetic acid is 93%, n-butyl acetate be selectively 99%.
EXPERIMENTAL EXAMPLE 3
Method according to EXPERIMENTAL EXAMPLE 1 is prepared n-butyl acetate, different is, the rod-like mesoporous material DBK(called after DBK-BU-JZ of the loaded metallocene that carried metallocene catalyst (DBK-BU) is made by dipping method by the embodiment 2 of identical weight) replace, result is: the conversion ratio of acetic acid is 90%, n-butyl acetate be selectively 99%.
EXPERIMENTAL EXAMPLE 4
Method according to EXPERIMENTAL EXAMPLE 2 is prepared n-butyl acetate, different is, the carried metallocene catalyst (DBK-BU) of the EXPERIMENTAL EXAMPLE 1 reclaiming is by the rod-like mesoporous material DBK(called after DBK-BU-JZ of EXPERIMENTAL EXAMPLE 3 loaded metallocenes of the recovery of identical weight) replace, result is: the conversion ratio of acetic acid is 89%, n-butyl acetate be selectively 99%.
Experiment comparative example 1
Method according to EXPERIMENTAL EXAMPLE 1 is prepared n-butyl acetate, different is, the rod-like mesoporous material SBA-15(called after SBA-15-BU of the load metallocene that carried metallocene catalyst (DBK-BU) is made by the comparative example 1 of identical weight) replace, result is: the conversion ratio of acetic acid is 85%, n-butyl acetate be selectively 99%.
Experiment comparative example 2
Method according to EXPERIMENTAL EXAMPLE 2 is prepared n-butyl acetate, different is, the carried metallocene catalyst (DBK-BU) of the EXPERIMENTAL EXAMPLE 1 reclaiming is by the rod-like mesoporous material SBA-15(called after SBA-15-BU of the load metallocene of the experiment comparative example 1 of the recovery of identical weight) replace, result is: the conversion ratio of acetic acid is 82%, n-butyl acetate be selectively 99%.
Experiment comparative example 3
Method according to EXPERIMENTAL EXAMPLE 1 is prepared n-butyl acetate, different is, industrial 955 silica gel (called after GJ-BU-2) of the load metallocene that carried metallocene catalyst (DBK-BU) is made by the comparative example 2 of identical weight replace, result is: the conversion ratio of acetic acid is 76%, n-butyl acetate be selectively 99%.
Experiment comparative example 4
Method according to EXPERIMENTAL EXAMPLE 2 is prepared n-butyl acetate, different is, the carried metallocene catalyst (DBK-BU) of the EXPERIMENTAL EXAMPLE 1 reclaiming is replaced by industrial 955 silica gel (called after GJ-BU-2) of the load metallocene of the experiment comparative example 3 of the recovery of identical weight, result is: the conversion ratio of acetic acid is 70%, n-butyl acetate be selectively 99%.
Experiment comparative example 5
Method according to EXPERIMENTAL EXAMPLE 1 is prepared n-butyl acetate, different, does not add carried metallocene catalyst (DBK-BU), and result is: the conversion ratio of acetic acid is 50%, n-butyl acetate be selectively 99%.
By above embodiment 1-2, comparative example 1-2 and EXPERIMENTAL EXAMPLE 1-4, the data of experiment comparative example 1-5 can be found out, EXPERIMENTAL EXAMPLE 1-4 is obviously than testing the effective of comparative example 1-5, and EXPERIMENTAL EXAMPLE 1-2 is more effective than EXPERIMENTAL EXAMPLE 3-4's, illustrate and adopt ball-milling method that metallocene is carried on bar-shaped meso-porous titanium dioxide silicon carrier, the catalytic performance of the carried metallocene catalyst obtaining is better, when making to apply this catalyst and carrying out the esterification of catalysis acetic acid and n-butanol, side reaction does not produce corrosion to equipment less simultaneously yet, and loaded catalyst of the present invention can pass through and reclaim and Reusability, aftertreatment technology is simple.
Claims (21)
1. a carried metallocene catalyst, it is characterized in that, this catalyst is comprised of carrier and the metallocene compound that loads on described carrier, wherein, described carrier is bar-shaped mesoporous silicon oxide, and the gross weight of described catalyst of take is benchmark, and the content of described metallocene compound is 0.1-2 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier is long is 0.5-3 micron, and specific area is 200-500 meters squared per gram, and most probable aperture is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and average aspect ratio value is 1-3; Described metallocene compound has the structure shown in formula 1:
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
2. carried metallocene catalyst according to claim 1, wherein, the gross weight of described catalyst of take is benchmark, and the content of described metallocene is 0.15-1.5 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 98.5-99.85 % by weight; And the specific area of described bar-shaped meso-porous titanium dioxide silicon carrier is 300-400 meters squared per gram, most probable aperture is 11-14 nanometer, and pore wall thickness is 1.6-1.8 nanometer.
3. carried metallocene catalyst according to claim 1 and 2, wherein, the specific area of described carried metallocene catalyst is 270-295 meters squared per gram, and most probable aperture is 5-15 nanometer, and pore wall thickness is 1.8-2 nanometer, and average aspect ratio value is 1-3.
4. according to the carried metallocene catalyst described in claim 1 or 3, wherein, M is zirconium, and X is chlorine.
5. according to the carried metallocene catalyst described in claim 1 or 4, wherein, R
1and R
1' be C independently of one another
1-C
5alkyl, be preferably normal-butyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
6. carried metallocene catalyst according to claim 1 or 5, wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
7. according to the carried metallocene catalyst described in claim 1 or 6, wherein, described bar-shaped meso-porous titanium dioxide silicon carrier is made by the method comprising the following steps:
(1) template, ammonium fluoride and mixed in hydrochloric acid to solids is fully dissolved;
(2) by step (1) gained solution and esters of silicon acis and heptane standing 2-5 hour after 25-60 ℃ of temperature, mechanical agitation speed are to stir 1-10 hour under 200-500r/min;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and will filter deionized water washing for gained solid, dry;
(5) by the dry products therefrom heating of step (4), removed template method;
Described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
8. carried metallocene catalyst according to claim 7, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 90-180 ℃, and the time is 10-40 hour; The condition of described removed template method comprises that temperature is 300-600 ℃, and the time is 8-20 hour.
9. according to the carried metallocene catalyst described in claim 7 or 8, wherein, count in molar ratio polyethylene glycol oxide-PPOX-polyethylene glycol oxide: ammonium fluoride: water: hydrogen chloride: esters of silicon acis: heptane=1:1-3:1000-30000:100-2000:20-500:20-500.
10. the preparation method of a carried metallocene catalyst, wherein, the method comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with metallocene, metallocene is loaded on described bar-shaped meso-porous titanium dioxide silicon carrier, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and metallocene compound of take is benchmark, the consumption of described metallocene is 0.1-2 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 98-99.9 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier is long is 0.5-3 micron, and specific area is 200-500 meters squared per gram, and most probable aperture is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and average aspect ratio value is 1-3; Described metallocene compound has the structure shown in formula 1:
Formula 1
Wherein, R
1, R
2, R
3, R
4, R
5, R
1', R
2', R
3', R
4' and R
5' be hydrogen or C independently of one another
1-C
5alkyl in a kind of, and R
1, R
2, R
3, R
4and R
5in at least one be C
1-C
5alkyl, R
1', R
2', R
3', R
4' and R
5' at least one be C
1-C
5alkyl; M is a kind of in titanium, zirconium and hafnium; X is halogen.
11. preparation methods according to claim 10, wherein, M is zirconium, X is chlorine.
12. according to the preparation method described in claim 10 or 11, wherein, and R
1and R
1' be C independently of one another
1-C
5alkyl, be preferably normal-butyl, and R
2, R
3, R
4, R
5, R
2', R
3', R
4' and R
5' be hydrogen.
13. according to the preparation method described in claim 10 or 12, and wherein, described metallocene compound is two (n-butyl cyclopentadienyl) zirconium dichlorides.
14. preparation methods according to claim 10, wherein, the condition of described ball milling comprises: ball radius is 2-3mm, and rotating speed is 300-500r/min, and in ball grinder, temperature is 15-100 ℃, and the time is 0.1-100 hour.
15. preparation methods according to claim 10, wherein, described bar-shaped meso-porous titanium dioxide silicon carrier is made by the method comprising the following steps:
(1) template, ammonium fluoride and mixed in hydrochloric acid to solids is fully dissolved;
(2) by step (1) gained solution and esters of silicon acis and heptane standing 2-5 hour after 25-60 ℃ of temperature, mechanical agitation speed are to stir 1-10 hour under 200-500r/min;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and will filter deionized water washing for gained solid, dry;
(5) by the dry products therefrom heating of step (4), removed template method;
Described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
16. preparation methods according to claim 15, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 90-180 ℃, and the time is 10-40 hour; The condition of described removed template method comprises that temperature is 300-600 ℃, and the time is 8-20 hour.
17. according to the preparation method described in claim 15 or 16, wherein, count in molar ratio polyethylene glycol oxide-PPOX-polyethylene glycol oxide: ammonium fluoride: water: hydrogen chloride: esters of silicon acis: heptane=1:1-3:1000-30000:100-2000:20-500:20-500.
The catalyst that preparation method in 18. claim 10-17 described in any one makes.
The application of catalyst in esterification described in any one in 19. claim 1-9 and 18.
The preparation method of 20. 1 kinds of n-butyl acetates, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain n-butyl acetate with n-butanol, it is characterized in that, described catalyst is the catalyst described in any one in claim 1-9 and 18.
21. preparation methods according to claim 20, wherein, in mass ratio, acetic acid: n-butanol: described catalyst=1:0.1-10:0.01-0.3.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089912A (en) * | 2017-05-16 | 2017-08-25 | 湖南大学 | A kind of method that metallocene complex selective catalysis synthesizes mandelic acid ester type compound |
| CN113754798A (en) * | 2020-06-05 | 2021-12-07 | 中国石油化工股份有限公司 | Spheroidal ultra-macroporous mesoporous material, polyolefin catalyst, preparation method of polyolefin catalyst and olefin polymerization method |
| WO2021243936A1 (en) * | 2020-06-05 | 2021-12-09 | 中国石油化工股份有限公司 | Sphere-like super-macroporous mesoporous material and polyolefin catalyst containing same |
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| Publication number | Publication date |
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| CN103586078B (en) | 2015-08-19 |
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