CN103586070B - The preparation method of a kind of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method and application and cyclohexanone ethylene ketal - Google Patents
The preparation method of a kind of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method and application and cyclohexanone ethylene ketal Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method and cyclohexanone ethylene ketal, wherein, this catalyst is made up of carrier and load copper trifluoromethanesulfcomposite on the carrier, described carrier is bar-shaped mesoporous silicon oxide, and with the gross weight of described catalyst for benchmark, the content of described copper trifluoromethanesulfcomposite is 10-90 % by weight, and the content of described carrier is 10-90 % by weight; The excellent length of described carrier is 0.5-2 micron, and specific area is 600-800 meters squared per gram, and most probable pore size is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and Mean aspect ratio is 1-3.In catalyst of the present invention, copper trifluoromethanesulfcomposite load is on specific bar-shaped meso-porous titanium dioxide silicon carrier, the activity of this catalyst ketal reaction is higher, and the activity of this catalyst ketal reaction is still higher when reusing, this catalyst is recovered and cycling and reutilization.
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 (BeckJS, VartuliJC, RothWJ, etal.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, etalScience279 (1998) 548-550), this material has cube single-crystal meso-pore material aperture (6-30nm), the large (1.0cm of pore volume of high-sequential
3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) 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, and what easily realize catalyst and product is separated (Wight, A.P.; Davis, M.E.Chem.Rev.2002,102,3589; DeVos, D.E.; Dams, M.; Sels, B.F.; Jacobs, P.A.Chem.Rev.2002,102,3615.).But ordered mesoporous material SBA-15 conventional at present has stronger water suction, moisture absorption ability, rod length is close to 5 μm, and there is adhesion between rod and rod, in catalytic reaction process, be unfavorable for that material transmits in mesopore orbit, this will aggravate the reunion of ordered mesoporous material further, to the storage of ordered mesoporous material, transport, aft-loaded airfoil 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, is even used as special reaction solvent.The synthesis of ketal is generally under strong acid catalyst, and synthesized by ketone and alcohols, 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 terminates being separated of rear catalyst and product and need carry out neutralizing and the process such as washing, and not only complex process also produces contaminated wastewater environment, along with the raising of living standards of the people, proposes more and more highland requirement to environmental protection; And Bronsted acid has stronger corrosion to equipment to be done.
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, provide a kind of novel for the synthesis of the catalyst of ketal and the preparation method of cyclohexanone ethylene ketal.
The invention provides a kind of support type TFMS copper catalyst, wherein, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the copper trifluoromethanesulfcomposite on described bar-shaped meso-porous titanium dioxide silicon carrier forms this catalyst, and with the gross weight of described catalyst for 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 pore size is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and Mean aspect ratio is 1-3.
Present invention also offers 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, make copper trifluoromethanesulfcomposite load on described bar-shaped meso-porous titanium dioxide silicon carrier, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite for 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 pore size is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and Mean aspect ratio is 1-3.
In addition, present invention also offers the application of described catalyst in ketal reaction.
Also have, present invention also offers the preparation method of a kind of cyclohexanone and ethylene ketal, wherein, the method comprises: in the presence of a 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.
In catalyst of the present invention, copper trifluoromethanesulfcomposite load is 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 when reusing, this support type TFMS copper catalyst is recovered and cycling and reutilization.Also load on specific bar-shaped meso-porous titanium dioxide silicon carrier owing to will have corrosive copper trifluoromethanesulfcomposite on the other hand, prevent equipment corrosion, therefore 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, solvent is not introduced in whole mechanical milling process, process is simple and easy to do, after mechanical milling process, gained catalyst also keeps bar-shaped, and when using this catalyst to carry out the ketal reaction of catalysis of pimelinketone and ethylene glycol, 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, not etching apparatus, is conducive to environmental protection.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, wherein, and the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) that the XRD spectra that a is bar-shaped meso-porous titanium dioxide silicon carrier (DB), b are load copper trifluoromethanesulfcomposite
2) XRD spectra, abscissa is 2 θ, and 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
2the bar-shaped mesoporous silicon oxide of the copper trifluoromethanesulfcomposite (DB-Cu (OTf) for load
2) pore structure schematic diagram.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) of a to be the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b be load copper trifluoromethanesulfcomposite
2) microscopic appearance figure.
Fig. 4 is SEM scanning electron microscope (SEM) photograph, wherein, and the microscopic appearance figure of the rod-like mesoporous material SBA-15 of a load copper trifluoromethanesulfcomposite that to be the microscopic appearance figure of rod-like mesoporous material SBA-15, b be is prepared by ball-milling method.
Detailed description of the invention
The invention provides a kind of support type TFMS copper catalyst, wherein, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the copper trifluoromethanesulfcomposite on described bar-shaped meso-porous titanium dioxide silicon carrier forms this catalyst, and with the gross weight of described catalyst for 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, with the total amount of described catalyst for 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, is more preferably 700 meters squared per gram, pore volume is 0.5-1.7 ml/g, is preferably 0.6-1.5 ml/g, is more preferably 1.1 mls/g, most probable pore size is 6-9 nanometer, is preferably 6-8 nanometer, is more preferably 7.5 nanometers, pore wall thickness is 1-3 nanometer, is preferably 2-3 nanometer, is more preferably 2.3 nanometers, Mean aspect ratio 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, is 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, is more preferably 0.4 ml/g; Most probable pore size can be 3-6 nanometer, is preferably 3-5 nanometer, is more preferably 3.8 nanometers; Pore wall thickness is 5.0-10.0 nanometer, is preferably 6-8 nanometer, is more preferably 7.5 nanometers; Mean aspect ratio is 1-3.
According to the present invention, described carrier is bar-shaped mesoporous silicon oxide, and described bar-shaped mesoporous silicon oxide can be prepared by the method comprised the following steps:
(1) template, glycerine and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis are left standstill 5-100 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 1-10 hour under being 100-200r/min;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and filtration gained solid is spent deionized water, drying;
(5) by dry for step (4) products therefrom heating, 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 DEG C, and the time is 10-40 hour.
Under preferable case, it is 300-600 DEG C that the condition of described removed template method comprises temperature, and the time is 8-20 hour.
Under preferable case, 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 and obtains.
According to the present invention, described template can be the various triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene templates that this area routine uses, and can be such as that the commodity that Aldrich company produces are called P123, molecular formula be EO
20pO
70eO
20template.
Present invention also offers 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, make copper trifluoromethanesulfcomposite load on described bar-shaped meso-porous titanium dioxide silicon carrier, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite for 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, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite for 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, is more preferably 700 meters squared per gram; Pore volume is 0.5-1.7 ml/g, is preferably 0.6-1.5 ml/g, is more preferably 1.1 mls/g; Most probable pore size is 6-9 nanometer, is preferably 6-8 nanometer, is more preferably 7.5 nanometers; Pore wall thickness is 1-3 nanometer, is preferably 2-3 nanometer, is more preferably 2.3 nanometers; Mean aspect ratio is 1-3, is preferably 1.5-2.5.
To grinding condition and concrete operation method there is no particular limitation, be as the criterion not destroy or substantially not destroy carrier structure and make copper trifluoromethanesulfcomposite enter in carrier duct.Those skilled in the art can select various suitable condition 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: join in the ball grinder of ball mill by bar-shaped mesoporous silicon oxide and copper trifluoromethanesulfcomposite, 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 DEG C, takes out pressed powder afterwards, namely obtains the bar-shaped mesoporous silicon oxide of load copper trifluoromethanesulfcomposite.The quantity of abrading-ball depends on the size of ball grinder, is the ball grinder of 50-150ml for size, can use 1 abrading-ball.The material of described abrading-ball can be agate, polytetrafluoroethylene (PTFE), is preferably polytetrafluoroethylene (PTFE).
According to a kind of detailed description of the invention of the present invention, the preparation method of described support type TFMS copper catalyst comprises the following steps:
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 and obtains
Be mixed to solids fully to dissolve;
2nd step, adds ethyl orthosilicate in previous step gained solution, slowly stirs after 1-10 hour and leave standstill 5-100 hour at 25 DEG C of-60 DEG C of temperature under mechanical agitation speed is 100-200r/min; By molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ethyl orthosilicate=1:20-200; Be preferably 1:30-100, be more preferably 1:60;
3rd step, is placed in closed reaction vessel by upper step gained solution, crystallization 10 hours-40 hours at 90 DEG C of-180 DEG C of temperature;
4th step, filters (preferably with after deionized water dilution), filtration gained solid is spent deionized water, drying, obtain the former powder of rod-like mesoporous material by crystallization afterproduct;
5th step, by former for gained rod-like mesoporous material powder at 300-600 DEG C of calcining 8-20 hour, removed template method, obtains the bar-shaped mesoporous silicon oxide of removed template method;
6th step, the bar-shaped mesoporous silicon oxide of upper step gained removed template method and copper trifluoromethanesulfcomposite are joined in the ball grinder of ball mill, under rotating speed is 300-500r/min, in ball grinder, temperature is continuously grinding 0.1-100 hour at 15-100 DEG C, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite for 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 being 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 pressed powder afterwards, namely obtain the bar-shaped mesoporous silicon oxide of load copper trifluoromethanesulfcomposite.
According to the present invention, described template can be the various triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene templates that this area routine uses, and can be such as that the commodity that Aldrich company produces are called P123, molecular formula be EO
20pO
70eO
20template.
Method and the condition of described crystallization and removed template method are known to the skilled person, and such as, the temperature of crystallization can be 90-180 DEG C, and the time of crystallization can be 10-40 hour.
In addition, present invention also offers the application of described catalyst in ketal reaction.
Further, present invention also offers a kind of preparation method of ketal, wherein, the method comprises: in the presence of a 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 such as, 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, relative to the cyclohexanone of 100 weight portions, the consumption of described catalyst can be 1-15 weight portion, is 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 such as, the condition of described ketal reaction can comprise: under back flow reaction condition, and 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 terminates, centrifugation can be carried out to final reactant mixture, by the centrifugal solid formation obtained vacuum drying 1-24 hour at 25-200 DEG C, preferably vacuum drying 6-10 hour at 50-120 DEG C, 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, be the material of 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 that the X-ray diffractometer of D8Advance carries out in the model purchased from German BrukerAXS company; Transmission electron microscope analysis is that the transmission electron microscope of Tecnai20 carries out in the model purchased from Dutch FEI Co.; Scanning electron microscope analysis is that the SEM of XL-30 is carried out in the model of purchased from American FEI Co.; Nitrogen adsorption-detachment assays is that the nitrogen adsorption desorption instrument of Autosorb-1 carries out in the model of purchased from American Kang Ta company.
Embodiment 1
The present embodiment is for illustration of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method according to the present invention.
Be in the hydrochloric acid of 2mlo/l by the concentration that 1.8 grams of P123 and 1.8 gram glycerine join 69 grams, mix to P123 and glycerine is molten completely altogether; Again 3.87 grams of ethyl orthosilicates are joined in above-mentioned solution, at 35 DEG C of temperature, stir under stir speed (S.S.) is 120r/min after 8 hours and leave standstill 24 hours, gained solution is transferred in teflon-lined reactor, after filtration, washing, drying, obtain the former powder of rod-like mesoporous material 100 DEG C of crystallization after 24 hours; By former for rod-like mesoporous material powder in Muffle furnace 500 DEG C calcining 24 hours, 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 DEG C, obtains 2 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2, wherein, with the total amount of support type TFMS copper catalyst for benchmark, 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, wherein, and the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) that the XRD spectra that a is bar-shaped meso-porous titanium dioxide silicon carrier (DB), b are load copper trifluoromethanesulfcomposite
2) XRD spectra, abscissa is 2 θ, and ordinate is intensity.The low-angle spectrum peak 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 (DB-Cu (OTf) 2) of load copper trifluoromethanesulfcomposite all has the hexagonal hole road structure of sequential 2 D specific to 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
2the bar-shaped mesoporous silicon oxide of the copper trifluoromethanesulfcomposite (DB-Cu (OTf) for load
2) pore structure schematic diagram.From TEM transmission electron microscope picture, bar-shaped meso-porous titanium dioxide silicon carrier (DB) all shows two-dimentional hexagonal hole road structure specific to mesoporous material load copper trifluoromethanesulfcomposite is forward and backward, show that the pore passage structure of sample substantially remains unchanged after supported catalyst, the conclusion that this conclusion and XRD spectra obtain is consistent.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and the bar-shaped mesoporous silicon oxide (DB-Cu (OTf) of a to be the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b be load copper trifluoromethanesulfcomposite
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 μm, DB-Cu (OTf) prepared by ball-milling method
2microscopic appearance is still basic keeps bar-shaped, and excellent length is still 0.5-2 μm.
Fig. 4 is SEM scanning electron microscope (SEM) photograph, wherein, and the microscopic appearance figure of the rod-like mesoporous material SBA-15 of a load copper trifluoromethanesulfcomposite that to be the microscopic appearance figure of rod-like mesoporous material SBA-15, b be is prepared by ball-milling method.As shown in Figure 4, the microscopic appearance of the rod-like mesoporous material SBA-15 of the load copper trifluoromethanesulfcomposite prepared by ball-milling method is then 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.
As can be seen from the data of upper table 1, bar-shaped mesoporous silicon oxide is after load copper trifluoromethanesulfcomposite, and pore volume and specific area all significantly reduce, and this illustrates that copper trifluoromethanesulfcomposite enters into bar-shaped mesoporous silicon oxide composite inner in load-reaction process.
Embodiment 2
The present embodiment is for illustration of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method according to the present invention.
Bar-shaped mesoporous silicon oxide (called after DB) is prepared according to the method for embodiment 1.
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 DEG C, obtains 3 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2-2, wherein, with the total amount of support type TFMS copper catalyst for benchmark, 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
Embodiment 3
The present embodiment is for illustration of support type copper trifluoromethanesulfcomposite Catalysts and its preparation method according to the present invention.
Bar-shaped mesoporous silicon oxide (called after DB) is prepared according to the method for embodiment 1.
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 DEG C, obtains 1.5 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2-3, wherein, with the total amount of support type TFMS copper catalyst for benchmark, 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
Embodiment 4
The present embodiment is for illustration of the preparation of the bar-shaped silica with dipping method load copper trifluoromethanesulfcomposite
1 gram that embodiment 1 is prepared bar-shaped mesoporous silicon oxide DB, 400 DEG C of calcinings 10 hours under nitrogen protection, with eliminating hydroxide and Residual water, thus 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 DEG C, after being cooled to room temperature, again 30ml methyl alcohol and 1g copper trifluoromethanesulfcomposite are put into 100ml teflon-lined reactor together, capping still, stir 24 hours under 35 DEG C of conditions, obtain 1.25 grams of target product support type TFMS copper catalysts, called after DB-Cu (OTf)
2-JZ, wherein, with the total amount of support type TFMS copper catalyst for benchmark, 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 illustration of the bar-shaped mesoporous silicon oxide preparing support type copper trifluoromethanesulfcomposite
By 1 gram of bar-shaped mesoporous silicon oxide SBA-15(purchased from high-tech limited company 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 DEG C, obtains rod-like mesoporous material (the called after SBA-15-Cu (OTf) of 2 grams of load copper trifluoromethanesulfcomposites
2).Wherein, with the total amount of support type TFMS copper catalyst for benchmark, 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 the catalytic activity according to support type TFMS copper catalyst of the present invention is described.
By the support type TFMS copper catalyst (DB-Cu (OTf) in embodiment 1
2) vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 1.2 grams, then take 7.44 grams of ethylene glycol, 100ml there-necked flask put into together by 60 grams of cyclohexanone, adds condenser pipe, stir 1 hour under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopts gas chromatography combined with mass spectrometry analyzer analytical reactions Product liquid composition, result is: the conversion ratio of cyclohexanone is 95%, and the selective of cyclohexanone-ethylene ketal is 99%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating 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 DEG C, after being cooled to room temperature, take 2.4 grams, take 14.88 grams of ethylene glycol again, 100ml there-necked flask put into together by 120 grams of cyclohexanone, add condenser pipe, stir 1 hour under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions Product liquid composition, result is: the conversion ratio of cyclohexanone is 96%, and the selective of cyclohexanone-ethylene ketal is 99%.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to support type TFMS copper catalyst of the present invention is described.
By the support type TFMS copper catalyst (DB-Cu (OTf) in embodiment 2
2-2) vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 3.6 grams, then take 22.32 grams of ethylene glycol, 100ml there-necked flask put into together by 180 grams of cyclohexanone, adds condenser pipe, stir 1 hour under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopts gas chromatography combined with mass spectrometry analyzer analytical reactions Product liquid composition, result is: the conversion ratio of cyclohexanone is 92%, and the selective of cyclohexanone-ethylene ketal is 99%.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for illustrating 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 DEG C, after being cooled to room temperature, take 4.8 grams, take 29.76 grams of ethylene glycol again, 100ml there-necked flask put into together by 240 grams of cyclohexanone, add condenser pipe, stir 1 hour under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions Product liquid composition, result is: the conversion ratio of cyclohexanone is 90%, and the selective of cyclohexanone-ethylene ketal is 99%.
EXPERIMENTAL EXAMPLE 5
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to support type TFMS copper catalyst of the present invention is described.
By the support type TFMS copper catalyst (DB-Cu (OTf) in embodiment 3
2-3) vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 1.2 grams, take 7.44 grams of ethylene glycol again, 100ml there-necked flask put into together by 60 grams of cyclohexanone, stir 1 hour under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions Product liquid composition, result is: the conversion ratio of cyclohexanone is 88%, and cyclohexanone-ethylene ketal is selective is 99%.
EXPERIMENTAL EXAMPLE 6
This EXPERIMENTAL EXAMPLE is used for illustrating 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 DEG C, after being cooled to room temperature, take 2.4 grams, take 14.88 grams of ethylene glycol again, 100ml there-necked flask put into together by 120 grams of cyclohexanone, add condenser pipe, stir 1 hour under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions Product liquid composition, result is: the conversion ratio of cyclohexanone is 90%, and cyclohexanone-ethylene ketal is selective is 99%.
EXPERIMENTAL EXAMPLE 7
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, support type TFMS copper catalyst (DB-Cu (OTf)
2) rod-like mesoporous material DB(called after DB-Cu (OTf) of support type copper trifluoromethanesulfcomposite that obtained 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 selective is 99%.
EXPERIMENTAL EXAMPLE 8
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the support type TFMS copper catalyst (DB-Cu (OTf) of the EXPERIMENTAL EXAMPLE 1 of recovery
2) by rod-like mesoporous material DB(called after DB-Cu (OTf) of the EXPERIMENTAL EXAMPLE 7 support type copper trifluoromethanesulfcomposite of the recovery of identical weight
2-JZ) replace, result is: the conversion ratio of cyclohexanone is 85%, and cyclohexanone-ethylene ketal is selective is 99%.
Experimental comparison's example 1
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, support type TFMS copper catalyst (DB-Cu (OTf)
2) by rod-like mesoporous material SBA-15(called after SBA-15-Cu (OTf) of the obtained load copper trifluoromethanesulfcomposite of the comparative example 1 of identical weight
2) replace, result is: the conversion ratio of cyclohexanone is 75%, and cyclohexanone-ethylene ketal is selective is 99%.
Experimental comparison's example 2
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the support type TFMS copper catalyst (DB-Cu (OTf) of the EXPERIMENTAL EXAMPLE 1 of recovery
2) by rod-like mesoporous material SBA-15(called after SBA-15-Cu (OTf) of the load copper trifluoromethanesulfcomposite of Experimental comparison's example 1 of the recovery of identical weight
2) replace, result is the conversion ratio of cyclohexanone is 76%, and cyclohexanone-ethylene ketal is selective is 99%.
Experimental comparison's example 3
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, do not add support type TFMS copper catalyst (DB-Cu (OTf)
2), result is: the conversion ratio of cyclohexanone is 56%, and the selective of cyclohexanone-ethylene ketal is 99%.
By above embodiment 1-4 and comparative example 1 and EXPERIMENTAL EXAMPLE 1-8, the data of Experimental comparison's example 1-3 can be found out, EXPERIMENTAL EXAMPLE 1-8 obviously than Experimental comparison example 1-3 effective, and EXPERIMENTAL EXAMPLE 1-6's is effective, illustrate and adopt ball-milling method to be carried on by copper trifluoromethanesulfcomposite on bar-shaped meso-porous titanium dioxide silicon carrier, the catalytic performance of the support type TFMS copper catalyst obtained is better, make to apply this catalyst when carrying out the ketal reaction of catalysis of pimelinketone and ethylene glycol, side reaction does not also produce corrosion to equipment less simultaneously, and loaded catalyst of the present invention can through and recovery and Reusability, aftertreatment technology is simple.
Claims (12)
1. the preparation method of a cyclohexanone ethylene ketal, wherein, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with ethylene glycol, to obtain ketal, it is characterized in that, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the copper trifluoromethanesulfcomposite on described bar-shaped meso-porous titanium dioxide silicon carrier forms described catalyst, and with the gross weight of described catalyst for 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 pore size is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and Mean aspect ratio is 1-3;
Wherein, the condition of described ketal reaction comprises: the mol ratio of cyclohexanone and ethylene glycol is 1:0.1-0.2.
2. method according to claim 1, wherein, with the gross weight of described catalyst for benchmark, 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 pore size is 6-8 nanometer, and pore wall thickness is 2-3 nanometer, and Mean aspect ratio is 1.5-2.5.
3. method according to claim 1, wherein, described bar-shaped meso-porous titanium dioxide silicon carrier is obtained by the method comprised the following steps:
(1) template, glycerine and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis are left standstill 5-100 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 1-10 hour under being 100-200r/min;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and filtration gained solid is spent deionized water, drying;
(5) by dry for step (4) products therefrom heating, removed template method;
Described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
4. method according to claim 3, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 90-180 DEG C, and the time is 10-40 hour; It is 300-600 DEG C that the condition of described removed template method comprises temperature, and the time is 8-20 hour.
5. the method according to claim 3 or 4, wherein, 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.
6. method according to claim 1, wherein, the preparation method of described catalyst comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with copper trifluoromethanesulfcomposite, make copper trifluoromethanesulfcomposite load on described bar-shaped meso-porous titanium dioxide silicon carrier, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite for 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 pore size is 6-9 nanometer, and pore wall thickness is 1-3 nanometer, and Mean aspect ratio is 1-3.
7. method according to claim 6, wherein, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and copper trifluoromethanesulfcomposite for benchmark, 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 pore size is 6-8 nanometer, and pore wall thickness is 2-3 nanometer, and Mean aspect ratio is 1.5-2.5.
8. method according to claim 6, 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 DEG C, and the time is 0.1-100 hour.
9. method according to claim 6, wherein, described bar-shaped meso-porous titanium dioxide silicon carrier is obtained by the method comprised the following steps:
(1) template, glycerine and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis are left standstill 5-100 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 1-10 hour under being 100-200r/min;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and filtration gained solid is spent deionized water, drying;
(5) by dry for step (4) products therefrom heating, removed template method;
Described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
10. method according to claim 9, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 90-180 DEG C, and the time is 10-40 hour; It is 300-600 DEG C that the condition of described removed template method comprises temperature, and the time is 8-20 hour.
11. methods according to claim 9 or 10, wherein, 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.
12. methods according to claim 1, wherein, in the copper trifluoromethanesulfcomposite of load in described catalyst, relative to the cyclohexanone of 100 weight portions, the consumption of described catalyst is 1-15 weight portion.
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| 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 |
| 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 |
| 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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| CN1933904A (en) * | 2004-03-23 | 2007-03-21 | 沙特基础工业公司 | Catalyst composition for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
| CN101850984A (en) * | 2010-06-12 | 2010-10-06 | 上海应用技术学院 | Elliptic mesoporous silicon dioxide molecular sieve and preparation method thereof |
| CN102451756A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded zinc trifluoromethanesulfonate catalyst, its preparation method, and preparation method of butanone-glycol ketal |
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| CN1933904A (en) * | 2004-03-23 | 2007-03-21 | 沙特基础工业公司 | Catalyst composition for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof |
| CN101850984A (en) * | 2010-06-12 | 2010-10-06 | 上海应用技术学院 | Elliptic mesoporous silicon dioxide molecular sieve and preparation method thereof |
| CN102451756A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded zinc trifluoromethanesulfonate catalyst, its preparation method, and preparation method of butanone-glycol ketal |
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