CN103586070A - Supported copper (II) trifluoromethanesulfonate catalyst, preparation method and application thereof, and cyclohexanone ethylene ketal preparation method - Google Patents
Supported copper (II) trifluoromethanesulfonate catalyst, preparation method and application thereof, and cyclohexanone ethylene ketal preparation method Download PDFInfo
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Abstract
The invention discloses a supported copper (II) trifluoromethanesulfonate catalyst, a preparation method thereof, and a cyclohexanone ethylene ketal preparation method. The catalyst is composed of 10-90wt% of a support and 10-90wt% of copper (II) trifluoromethanesulfonate 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, the pore wall thickness and the average aspect ratio of the support are 0.5-2mum, 600-800m<2>/g, 6-9nm, 1-3nm and 1-3 respectively In the catalyst, the copper (II) trifluoromethanesulfonate is supported on the specific rod-shaped meso-porous silica support, so the ketalation catalysis activity of the catalyst is high, and is still high after repeated use, thereby the catalyst can be recovered and recycled.
Description
Technical field
The present invention relates to a kind of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method, also relate to and use the application of this support type TFMS copper catalyst in ketal synthesis reaction, and the preparation method of cyclohexanone ethylene ketal.
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.Along with developing rapidly of chemical industry, ketal kind and demand are constantly increased.Ketal is that a class can be used for the carbonyl-protection of organic compound or the intermediate of pharmaceuticals industry, even as special reaction solvent.The synthetic of ketal is generally under strong acid catalysis, by ketone and alcohols, synthesized, and catalyst used has sulfuric acid, phosphoric acid, hydrogen chloride gas, p-methyl benzenesulfonic acid, and its advantage is that catalyst is cheap and easy to get.But reaction finishes that rear catalyst neutralizes with the separated need of product and the process such as washing, not only complex process also produces contaminated wastewater environment, along with the raising of living standards of the people, environmental protection has been proposed to more and more highland requirement; And Bronsted acid has stronger corrosion to equipment and does.
Therefore, develop a kind of novel catalyst for the synthesis of ketal and become problem in the urgent need to address.
Summary of the invention
The object of the invention is to overcome the shortcomings such as that the existing catalyst for Synthesis of Ketal exists is serious to equipment corrosion, complex process, a kind of preparation method of novel catalyst and cyclohexanone ethylene ketal for the synthesis of ketal is provided.
The invention provides a kind of support type TFMS copper catalyst, wherein, this catalyst is comprised of bar-shaped meso-porous titanium dioxide silicon carrier and the copper trifluoromethanesulfcomposite that loads on described bar-shaped meso-porous titanium dioxide silicon carrier, and the gross weight of described catalyst of take is benchmark, the content of described copper trifluoromethanesulfcomposite is 10-90 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; The excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-2 micron, and specific area is 600-800 meters squared per gram, and most probable aperture is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and average aspect ratio value is 1-3.
The present invention also provides a kind of preparation method of support type TFMS copper catalyst, wherein, the method comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with copper trifluoromethanesulfcomposite, copper trifluoromethanesulfcomposite 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 copper trifluoromethanesulfcomposite of take is benchmark, the consumption of described copper trifluoromethanesulfcomposite is 10-90 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; The excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-2 micron, and specific area is 600-800 meters squared per gram, and most probable aperture is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and average aspect ratio value is 1-3.
In addition, the present invention also provides the application of described catalyst in ketal reaction.
Also have, the present invention also provides the preparation method of a kind of cyclohexanone and ethylene ketal, wherein, the method comprises: under the existence of catalyst, under the condition of ketal reaction, cyclohexanone is contacted, to obtain ketal with ethylene glycol, wherein, described catalyst is support type TFMS copper catalyst provided by the invention.
In catalyst of the present invention, copper trifluoromethanesulfcomposite loads on specific bar-shaped meso-porous titanium dioxide silicon carrier, on the one hand, the activity of this support type copper trifluoromethanesulfcomposite catalyst ketal reaction is higher, and the activity of this support type copper trifluoromethanesulfcomposite catalyst ketal reaction is still higher while reusing, and this support type TFMS copper catalyst is recovered and cycling and reutilization.Also owing to thering is corrosive copper trifluoromethanesulfcomposite, load on specific bar-shaped meso-porous titanium dioxide silicon carrier on the other hand, prevented equipment corrosion, so this support type TFMS copper catalyst is a kind of catalyst of environmental protection.
In the present invention, by ball-milling method, copper trifluoromethanesulfcomposite 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, after mechanical milling process, gained catalyst also keeps bar-shaped, and while carrying out the ketal reaction of catalysis of pimelinketone and ethylene glycol with this catalyst, catalyst can pass through and reclaim and Reusability, and support type TFMS copper catalyst provided by the invention can reduce side reaction, improve 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 (DB), the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) that b is load copper trifluoromethanesulfcomposite
2) XRD spectra, abscissa is 2 θ, ordinate is intensity.
Fig. 2 is TEM transmission electron microscope picture, wherein, and a
1and a
2for the pore structure schematic diagram of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b
1and b
2for load the bar-shaped mesoporous silicon oxide of copper trifluoromethanesulfcomposite (DB-Cu (OTf)
2) pore structure schematic diagram.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b the has been load bar-shaped mesoporous silicon oxide of copper trifluoromethanesulfcomposite (DB-Cu (OTf)
2) microscopic appearance figure.
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 copper trifluoromethanesulfcomposite prepared by ball-milling method.
The specific embodiment
The invention provides a kind of support type TFMS copper catalyst, wherein, this catalyst is comprised of bar-shaped meso-porous titanium dioxide silicon carrier and the copper trifluoromethanesulfcomposite that loads on described bar-shaped meso-porous titanium dioxide silicon carrier, and the gross weight of described catalyst of take is benchmark, the content of described copper trifluoromethanesulfcomposite is 10-90 % by weight, the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight, more preferably in situation, the total amount of described catalyst of take is benchmark, the content of described copper trifluoromethanesulfcomposite is 30-60 % by weight, the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight, the excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-2 micron, is preferably 0.5-1 micron, specific area is 600-800 meters squared per gram, is preferably 650-750 meters squared per gram, more preferably 700 meters squared per gram, pore volume is 0.5-1.7 ml/g, is preferably 0.6-1.5 ml/g, more preferably 1.1 mls/g, most probable aperture is 6-9 nanometer, is preferably 6-8 nanometer, more preferably 7.5 nanometers, pore wall thickness is 1-3 nanometer, is preferably 2-3 nanometer, more preferably 2.3 nanometers, average aspect ratio value is 1-3, is preferably 1.5-2.5.
According to the present invention, the specific area of described support type TFMS copper catalyst can be 200-300 meters squared per gram, is preferably 220-280 meters squared per gram, more preferably 249 meters squared per gram; Pore volume can be 0.2-0.6 ml/g, is preferably 0.3-0.5 ml/g, more preferably 0.4 ml/g; Most probable aperture can be 3-6 nanometer, is preferably 3-5 nanometer, more preferably 3.8 nanometers; Pore wall thickness is 5.0-10.0 nanometer, is preferably 6-8 nanometer, more preferably 7.5 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, glycerine and mixed in hydrochloric acid to solids is fully dissolved;
(2) the standing 5-100 hour after 25-60 ℃ of temperature, mechanical agitation speed are to stir 1-10 hour under 100-200r/min by step (1) gained solution and esters of silicon acis;
(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 ethyl orthosilicate.
Under preferable case, described crystallization condition comprises: temperature is 90-180 ℃, and the time is 10-40 hour.
Under preferable case, the condition of described removed template method comprises that temperature is 300-600 ℃, and the time is 8-20 hour.
Under preferable case, count in molar ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: glycerine: water: hydrogen chloride: esters of silicon acis=1:10-800:10000-30000:100-9000:20-200, be preferably 1:50-700:12000-25000:500-8500:30-100, be particularly preferably 1:63:14320:1846:60.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 together with copper trifluoromethanesulfcomposite in ball sealer grinding jar ball milling, copper trifluoromethanesulfcomposite 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 copper trifluoromethanesulfcomposite of take is benchmark, the consumption of described copper trifluoromethanesulfcomposite is 10-90 % by weight, the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight, more preferably, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite of take is benchmark, the consumption of described copper trifluoromethanesulfcomposite is 30-60 % by weight, the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight.
According to the present invention, the excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-2 micron, is preferably 0.5-1 micron; Specific area is 600-800 meters squared per gram, is preferably 650-750 meters squared per gram, more preferably 700 meters squared per gram; Pore volume is 0.5-1.7 ml/g, is preferably 0.6-1.5 ml/g, more preferably 1.1 mls/g; Most probable aperture is 6-9 nanometer, is preferably 6-8 nanometer, more preferably 7.5 nanometers; Pore wall thickness is 1-3 nanometer, is preferably 2-3 nanometer, more preferably 2.3 nanometers; Average aspect ratio value is 1-3, is preferably 1.5-2.5.
To the condition of grinding and concrete operation method, there is no particular limitation, not destroy or substantially not destroy carrier structure and copper trifluoromethanesulfcomposite 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 support type TFMS copper catalyst comprises: bar-shaped mesoporous silicon oxide and copper trifluoromethanesulfcomposite are joined in the ball grinder of ball mill, ball grinder inwall is polytetrafluoroethyllining lining, the diameter of abrading-ball is 2-3mm, and rotating speed is 300-500r/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 copper trifluoromethanesulfcomposite.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 support type TFMS copper catalyst comprises the following steps:
The 1st step, by triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (EO
20pO
70eO
20, be abbreviated as P123) and glycerine, join in hydrochloric acid, by molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: glycerine: water: hydrogen chloride=1:10-800:10000-30000:100-9000, be preferably 1:50-700:12000-25000:500-8500, be particularly preferably 1:63:14320:1846, 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 in previous step gained solution, at 25 ℃ of-60 ℃ of temperature after mechanical agitation speed is slowly to stir 1-10 hour under 100-200r/min standing 5-100 hour; Press molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ethyl orthosilicate=1:20-200; Be preferably 1:30-100, more preferably 1:60;
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 copper trifluoromethanesulfcomposite 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 copper trifluoromethanesulfcomposite of take is benchmark, the consumption of described copper trifluoromethanesulfcomposite is 10-90 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; The consumption that is preferably described copper trifluoromethanesulfcomposite is 30-60 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight; Take out afterwards pressed powder, obtain the bar-shaped mesoporous silicon oxide of load copper trifluoromethanesulfcomposite.
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 ℃, and the time of crystallization can be 10-40 hour.
In addition, the present invention also provides the application of described catalyst in ketal reaction.
Also have, the present invention also provides a kind of preparation method of ketal, wherein, the method comprises: under the existence of catalyst, under the condition of ketal reaction, cyclohexanone is contacted with ethylene glycol, to obtain ketal, wherein, described catalyst is support type TFMS copper catalyst provided by the invention.
According to the present invention, in ketal reaction, the mol ratio of cyclohexanone and ethylene glycol can in very large range change, and for example, the mol ratio of cyclohexanone and ethylene glycol can be 1:0.1-0.2, the consumption of described support type TFMS copper catalyst has no particular limits, those skilled in the art can carry out suitable adjustment according to the needs of reaction, but under preferable case, with respect to the cyclohexanone of 100 weight portions, the consumption of described catalyst can be 1-15 weight portion, more preferably 2-14 weight portion.
In the present invention, the condition of described ketal reaction is conventionally known to one of skill in the art, and for example, the condition of described ketal reaction can comprise: under back flow reaction condition, the time of reaction is 1-10 hour, and preferably, the time of reaction can be 2-8 hour.
According to the present invention, after ketal reaction 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, copper trifluoromethanesulfcomposite is purchased from ACROS, CAS:34946982-2.
In following examples, P123, 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; Transmission electron microscope analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model purchased from Dutch FEI Co.; 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 the experiment of nitrogen adsorption-desorption is Autosorb-1 in the model purchased from U.S. Kang Ta company, carry out.
The present embodiment is for illustrating according to support type copper trifluoromethanesulfcomposite Catalysts and its preparation method of the present invention.
1.8 grams of P123 and 1.8 grams of glycerine are joined in the hydrochloric acid that the concentration of 69 grams is 2mlo/l, mix to P123 and glycerine molten completely altogether; Again 3.87 grams of ethyl orthosilicates are joined in above-mentioned solution, at 35 ℃ of temperature, after stir speed (S.S.) is to stir 8 hours under 120r/min standing 24 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 24 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 DB) of removed template method.
Above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DB is put into 100ml ball grinder at room temperature state together with 1 gram of copper trifluoromethanesulfcomposite, and wherein, the material of ball grinder and abrading-ball is polytetrafluoroethylene (PTFE), and 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 2 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2, wherein, the total amount of support type TFMS copper catalyst of take is benchmark, and the content of copper trifluoromethanesulfcomposite is 50 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 50 % by weight.
With XRD, ESEM, nitrogen adsorption desorption instrument, transmission electron microscope and gas chromatographicanalyzer, this support type TFMS copper 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 (DB), the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) that b is load copper trifluoromethanesulfcomposite
2) XRD spectra, abscissa is 2 θ, ordinate is intensity.The low-angle spectrum peak being occurred from XRD spectra, the XRD spectra b of the XRD spectra a of bar-shaped meso-porous titanium dioxide silicon carrier (DB), the bar-shaped mesoporous silicon oxide of load copper trifluoromethanesulfcomposite (DB-Cu (OTf) 2) all has the hexagonal hole road structure of the peculiar sequential 2 D of mesoporous material.
Fig. 2 is TEM transmission electron microscope picture, wherein, and a
1, a
2be the pore structure schematic diagram of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b
1and b
2for load the bar-shaped mesoporous silicon oxide of copper trifluoromethanesulfcomposite (DB-Cu (OTf)
2) pore structure schematic diagram.From TEM transmission electron microscope picture, bar-shaped meso-porous titanium dioxide silicon carrier (DB) is in the forward and backward peculiar two-dimentional hexagonal hole of the mesoporous material road structure that all shows of load copper trifluoromethanesulfcomposite, the pore passage structure that shows sample substantially remains unchanged after supported catalyst, and the conclusion that this conclusion and XRD spectra obtain is consistent.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b the has been load bar-shaped mesoporous silicon oxide of copper trifluoromethanesulfcomposite (DB-Cu (OTf)
2) microscopic appearance figure.As seen from the figure, the excellent length of bar-shaped mesoporous silicon oxide DB microscopic appearance is 0.5-2 μ m, DB-Cu prepared by ball-milling method (OTf)
2microscopic appearance is still basic keeps bar-shaped, and excellent length is still 0.5-2 μ m.
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 copper trifluoromethanesulfcomposite prepared by ball-milling method.The microscopic appearance of the rod-like mesoporous material SBA-15 of the load copper trifluoromethanesulfcomposite of preparing by ball-milling method as shown in Figure 4, is completely destroyed.
Table 1 is the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) of bar-shaped meso-porous titanium dioxide silicon carrier DB and load copper trifluoromethanesulfcomposite of the present invention
2) pore structure parameter.
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 copper trifluoromethanesulfcomposite, and pore volume and specific area all significantly reduce, and this explanation copper trifluoromethanesulfcomposite in load-reaction process enters into bar-shaped mesoporous silicon oxide composite inner.
The present embodiment is for illustrating according to support type copper trifluoromethanesulfcomposite Catalysts and its preparation method of the present invention.
According to the method for embodiment 1, prepare bar-shaped mesoporous silicon oxide (called after DB).
Above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DB is put into 100ml ball grinder at room temperature state together with 2 grams of copper trifluoromethanesulfcomposites, and wherein, the material of ball grinder and abrading-ball is polytetrafluoroethylene (PTFE), and 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 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2-2, wherein, the total amount of support type TFMS copper catalyst of take is benchmark, and the content of copper trifluoromethanesulfcomposite is 67 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 33 % by weight.
With the analysis of nitrogen adsorption desorption and gas chromatography combined with mass spectrometry analyzer, this support type TFMS copper catalyst is characterized.
Table 2
The present embodiment is for illustrating according to support type copper trifluoromethanesulfcomposite Catalysts and its preparation method of the present invention.
According to the method for embodiment 1, prepare bar-shaped mesoporous silicon oxide (called after DB).
Above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DB is put into 100ml ball grinder at room temperature state together with 0.5 gram of copper trifluoromethanesulfcomposite, and wherein, the material of ball grinder and abrading-ball is polytetrafluoroethylene (PTFE), and 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 1.5 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2-3, wherein, the total amount of support type TFMS copper catalyst of take is benchmark, and the content of copper trifluoromethanesulfcomposite is 33 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 67 % by weight.
With nitrogen adsorption desorption instrument and gas chromatography-mass spectrography analyzer, this support type TFMS copper catalyst is characterized.
Table 3
The present embodiment is for illustrating the preparation with the bar-shaped silica of dipping method load copper trifluoromethanesulfcomposite
By 1 gram of bar-shaped mesoporous silicon oxide DB 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 DB through thermal activation vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, again 30ml methyl alcohol and 1g copper trifluoromethanesulfcomposite are put into 100ml teflon-lined reactor together, capping still, under 35 ℃ of conditions, stir 24 hours, obtain 1.25 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2-JZ, wherein, the total amount of support type TFMS copper catalyst of take is benchmark, and the content of copper trifluoromethanesulfcomposite is 20 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 80 % by weight.
With nitrogen adsorption desorption instrument and gas chromatography-mass spectrography analyzer, this support type TFMS copper catalyst is characterized.
Table 4
Comparative example 1
This comparative example is for illustrating the bar-shaped mesoporous silicon oxide of preparing support type copper trifluoromethanesulfcomposite
By 1 gram of bar-shaped mesoporous silicon oxide SBA-15(purchased from high-tech share Co., Ltd of Jilin University) under room temperature state, put into 100ml ball grinder together with 1 gram of copper trifluoromethanesulfcomposite, 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 rod-like mesoporous material (the called after SBA-15-Cu (OTf) of 2 grams of load copper trifluoromethanesulfcomposites
2).Wherein, the total amount of support type TFMS copper catalyst of take is benchmark, and the content of copper trifluoromethanesulfcomposite is 50 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 50 % by weight.
With ESEM and gas chromatography combined with mass spectrometry analyzer, this support type TFMS copper catalyst is characterized.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of support type TFMS copper catalyst of the present invention.
By the support type TFMS copper catalyst (DB-Cu (OTf) in embodiment 1
2) vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 1.2 grams, then take 7.44 grams of ethylene glycol, 60 grams of cyclohexanone are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 1 hour, be cooled to after room temperature, centrifugation, adopts gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid component, result is: the conversion ratio of cyclohexanone is 95%, cyclohexanone-ethylene ketal be selectively 99%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after support type copper trifluoromethanesulfcomposite catalyst recovery of the present invention.
By the support type TFMS copper catalyst (DB-Cu (OTf) in EXPERIMENTAL EXAMPLE 1
2) reclaim, and vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 2.4 grams, take again 14.88 grams of ethylene glycol, 120 grams of cyclohexanone are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 1 hour, be cooled to after room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid component, result is: the conversion ratio of cyclohexanone is 96%, cyclohexanone-ethylene ketal be selectively 99%.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of support type TFMS copper catalyst of the present invention.
By the support type TFMS copper catalyst (DB-Cu (OTf) in embodiment 2
2-2) vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 3.6 grams, then take 22.32 grams of ethylene glycol, 180 grams of cyclohexanone are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 1 hour, be cooled to after room temperature, centrifugation, adopts gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid component, result is: the conversion ratio of cyclohexanone is 92%, cyclohexanone-ethylene ketal be selectively 99%.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after support type copper trifluoromethanesulfcomposite catalyst recovery of the present invention.
By the support type TFMS copper catalyst (DB-Cu (OTf) in EXPERIMENTAL EXAMPLE 3
2-2) reclaim, and vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 4.8 grams, take again 29.76 grams of ethylene glycol, 240 grams of cyclohexanone are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 1 hour, be cooled to after room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid component, result is: the conversion ratio of cyclohexanone is 90%, cyclohexanone-ethylene ketal be selectively 99%.
EXPERIMENTAL EXAMPLE 5
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of support type TFMS copper catalyst of the present invention.
By the support type TFMS copper catalyst (DB-Cu (OTf) in embodiment 3
2-3) vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 1.2 grams, take again 7.44 grams of ethylene glycol, 60 grams of cyclohexanone are put into 100ml there-necked flask together, under 100 ℃ of conditions that add hot reflux, stir 1 hour, be cooled to after room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid component, result is: the conversion ratio of cyclohexanone is 88%, and cyclohexanone-ethylene ketal is selectively 99%.
EXPERIMENTAL EXAMPLE 6
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after support type copper trifluoromethanesulfcomposite catalyst recovery of the present invention.
By the support type TFMS copper catalyst (DB-Cu (OTf) in EXPERIMENTAL EXAMPLE 5
2-3) reclaim, and vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 2.4 grams, take again 14.88 grams of ethylene glycol, 120 grams of cyclohexanone are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 1 hour, be cooled to after room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid component, result is: the conversion ratio of cyclohexanone is 90%, and cyclohexanone-ethylene ketal is selectively 99%.
EXPERIMENTAL EXAMPLE 7
Method according to EXPERIMENTAL EXAMPLE 1 is prepared ketal, different, support type TFMS copper catalyst (DB-Cu (OTf)
2) the rod-like mesoporous material DB(called after DB-Cu (OTf) of the support type copper trifluoromethanesulfcomposite that made by dipping method by the embodiment 4 of identical weight
2-JZ) replace, result is: the conversion ratio of cyclohexanone is 88%, and cyclohexanone-ethylene ketal is selectively 99%.
EXPERIMENTAL EXAMPLE 8
Method according to EXPERIMENTAL EXAMPLE 2 is prepared ketal, different, the support type TFMS copper catalyst (DB-Cu (OTf) of the EXPERIMENTAL EXAMPLE 1 of recovery
2) by the rod-like mesoporous material DB(called after DB-Cu (OTf) of the EXPERIMENTAL EXAMPLE 7 support type copper trifluoromethanesulfcomposites of the recovery of identical weight
2-JZ) replace, result is: the conversion ratio of cyclohexanone is 85%, and cyclohexanone-ethylene ketal is selectively 99%.
Experiment comparative example 1
Method according to EXPERIMENTAL EXAMPLE 1 is prepared ketal, different, support type TFMS copper catalyst (DB-Cu (OTf)
2) the rod-like mesoporous material SBA-15(called after SBA-15-Cu (OTf) of the load copper trifluoromethanesulfcomposite that made by the comparative example 1 of identical weight
2) replace, result is: the conversion ratio of cyclohexanone is 75%, cyclohexanone-ethylene ketal is selectively 99%.
Experiment comparative example 2
Method according to EXPERIMENTAL EXAMPLE 2 is prepared ketal, different, the support type TFMS copper catalyst (DB-Cu (OTf) of the EXPERIMENTAL EXAMPLE 1 of recovery
2) by the rod-like mesoporous material SBA-15(called after SBA-15-Cu (OTf) of the load copper trifluoromethanesulfcomposite of the experiment comparative example 1 of the recovery of identical weight
2) replace, the conversion ratio that result is cyclohexanone is 76%, cyclohexanone-ethylene ketal is selectively 99%.
Experiment comparative example 3
Method according to EXPERIMENTAL EXAMPLE 1 is prepared ketal, different, does not add support type TFMS copper catalyst (DB-Cu (OTf)
2), result is: the conversion ratio of cyclohexanone is 56%, cyclohexanone-ethylene ketal be selectively 99%.
By above embodiment 1-4 and comparative example 1 and EXPERIMENTAL EXAMPLE 1-8, the data of experiment comparative example 1-3 can be found out, EXPERIMENTAL EXAMPLE 1-8 is obviously than testing the effective of comparative example 1-3, and EXPERIMENTAL EXAMPLE 1-6's is effective, illustrate and adopt ball-milling method that copper trifluoromethanesulfcomposite is carried on bar-shaped meso-porous titanium dioxide silicon carrier, the catalytic performance of the support type TFMS copper catalyst obtaining is better, when making to apply this catalyst and carrying out the ketal reaction of catalysis of pimelinketone and ethylene glycol, 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 (16)
1. a support type TFMS copper catalyst, it is characterized in that, this catalyst is comprised of bar-shaped meso-porous titanium dioxide silicon carrier and the copper trifluoromethanesulfcomposite that loads on described bar-shaped meso-porous titanium dioxide silicon carrier, and the gross weight of described catalyst of take is benchmark, the content of described copper trifluoromethanesulfcomposite is 10-90 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; The excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-2 micron, and specific area is 600-800 meters squared per gram, and most probable aperture is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and average aspect ratio value is 1-3.
2. support type TFMS copper catalyst according to claim 1, wherein, the gross weight of described catalyst of take is benchmark, and the content of described copper trifluoromethanesulfcomposite is 30-60 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight; The excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-1 micron, and specific area is 650-750 meters squared per gram, and most probable aperture is 6-8 nanometer, and pore wall thickness is 2-3 nanometer, and average aspect ratio value is 1.5-2.5.
3. support type TFMS copper catalyst according to claim 1 and 2, wherein, the specific area of described support type TFMS copper catalyst is 200-300 meters squared per gram, and most probable aperture is 3-6 nanometer, pore wall thickness is 5-10 nanometer, and average aspect ratio value is 1-3.
4. according to the support type TFMS copper catalyst described in claim 1 or 3, wherein, described bar-shaped meso-porous titanium dioxide silicon carrier is made by the method comprising the following steps:
(1) template, glycerine and mixed in hydrochloric acid to solids is fully dissolved;
(2) the standing 5-100 hour after 25-60 ℃ of temperature, mechanical agitation speed are to stir 1-10 hour under 100-200r/min by step (1) gained solution and esters of silicon acis;
(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.
5. support type TFMS copper catalyst according to claim 4, 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.
6. according to the support type TFMS copper catalyst described in claim 4 or 5, wherein, count in molar ratio polyethylene glycol oxide-PPOX-polyethylene glycol oxide: glycerine: water: hydrogen chloride: esters of silicon acis=1:10-800:10000-30000:100-9000:20-200.
7. the preparation method of a support type TFMS copper catalyst, wherein, the method comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with copper trifluoromethanesulfcomposite, copper trifluoromethanesulfcomposite 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 copper trifluoromethanesulfcomposite of take is benchmark, the consumption of described copper trifluoromethanesulfcomposite is 10-90 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; The excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-2 micron, and specific area is 600-800 meters squared per gram, and most probable aperture is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and average aspect ratio value is 1-3.
8. preparation method according to claim 7, wherein, the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite of take is benchmark, and the consumption of described copper trifluoromethanesulfcomposite is 30-60 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight; The excellent length of described bar-shaped meso-porous titanium dioxide silicon carrier is 0.5-1 micron, and specific area is 650-750 meters squared per gram, and most probable aperture is 6-8 nanometer, and pore wall thickness is 2-3 nanometer, and average aspect ratio value is 1.5-2.5.
9. preparation method according to claim 7, 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.
10. preparation method according to claim 7, wherein, described bar-shaped meso-porous titanium dioxide silicon carrier is made by the method comprising the following steps:
(1) template, glycerine and mixed in hydrochloric acid to solids is fully dissolved;
(2) the standing 5-100 hour after 25-60 ℃ of temperature, mechanical agitation speed are to stir 1-10 hour under 100-200r/min by step (1) gained solution and esters of silicon acis;
(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.
11. preparation methods according to claim 10, 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.
12. according to the preparation method described in claim 10 or 11, wherein, counts in molar ratio polyethylene glycol oxide-PPOX-polyethylene glycol oxide: glycerine: water: hydrogen chloride: esters of silicon acis=1:10-800:10000-30000:100-9000:20-200.
The catalyst that preparation method in 13. claim 7-12 described in any one makes.
The application of catalyst in 14. claim 1-6 and 13 described in any one in ketal reaction.
The preparation method of 15. 1 kinds of cyclohexanone ethylene ketals, wherein, the method comprises: under the existence of catalyst, under the condition of ketal reaction, cyclohexanone is contacted with ethylene glycol, to obtain ketal, it is characterized in that, described catalyst is the catalyst described in any one in claim 1-6 and 13.
16. preparation methods according to claim 15, wherein, the mol ratio of cyclohexanone and ethylene glycol can be 1:0.1-0.2, and in the copper trifluoromethanesulfcomposite of load in described catalyst, with respect to the cyclohexanone of 100 weight portions, the consumption of described catalyst can be 1-15 weight portion.
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| CN105126926A (en) * | 2014-06-09 | 2015-12-09 | 中国石油化工股份有限公司 | Chlorite mesoporous composite, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105214734A (en) * | 2014-06-09 | 2016-01-06 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
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| CN105126926A (en) * | 2014-06-09 | 2015-12-09 | 中国石油化工股份有限公司 | Chlorite mesoporous composite, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
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| CN105435853A (en) * | 2014-06-09 | 2016-03-30 | 中国石油化工股份有限公司 | Illite mesoporous composite material, supported catalyst and preparation method and application thereof and preparation method of cyclohexanone glyceryl ketal |
| CN105435853B (en) * | 2014-06-09 | 2017-09-29 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105435850B (en) * | 2014-06-09 | 2017-09-29 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105214734B (en) * | 2014-06-09 | 2017-11-07 | 中国石油化工股份有限公司 | The preparation method of illite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN105126926B (en) * | 2014-06-09 | 2018-04-13 | 中国石油化工股份有限公司 | The preparation method of chlorite mesoporous composite material and loaded catalyst and its preparation method and application and cyclohexanone glycerol ketals |
| CN106854196A (en) * | 2016-12-15 | 2017-06-16 | 徐州诺克非医药科技有限公司 | A kind of synthesis technique of organic synthesis intermediate cyclohexanone ethylene ketal |
| CN106854196B (en) * | 2016-12-15 | 2019-06-04 | 深圳深创生物技术有限公司 | A kind of synthesis technology of organic synthesis intermediate cyclohexanone ethylene ketal |
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