CN103586065B - The preparation method of a kind of support type silver nitrate catalyst and its preparation method and application and cyclohexanone ethylene ketal - Google Patents
The preparation method of a kind of support type silver nitrate catalyst 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 silver nitrate catalyst and preparation method thereof and cyclohexanone ethylene ketal, wherein, this catalyst is made up of carrier and load silver nitrate 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 silver nitrate is 10-90 % by weight, and the content of described carrier is 10-90 % by weight; The rod of described carrier is long is 0.5-3 micron, and specific area is 200-500 meters squared per gram, and most probable pore size is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and Mean aspect ratio is 1-3.In catalyst of the present invention, silver nitrate 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 silver nitrate catalyst and preparation method thereof, also relate to and use the application of this support type silver nitrate 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 corrosiveness to equipment.
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 silver nitrate catalyst, wherein, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the silver nitrate 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 silver nitrate is 10-90 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier length is 0.5-3 micron, specific area is 200-500 meters squared per gram, and most probable pore size is 10.0-15.0 nanometer, and pore wall thickness is 1.5-2.0 nanometer, and Mean aspect ratio is 1-3.
Present invention also offers a kind of preparation method of support type silver nitrate catalyst, wherein, the method comprises: by described bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with silver nitrate, make silver nitrate 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 silver nitrate for benchmark, the consumption of described silver nitrate is 10-90 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier length is 0.5-3 micron, specific area is 200-500 meters squared per gram, and most probable pore size is 10-15 nanometer, and pore wall thickness is 1.5-2 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 silver nitrate catalyst provided by the invention.
In catalyst of the present invention, silver nitrate load is on specific bar-shaped meso-porous titanium dioxide silicon carrier, on the one hand, the activity of this support type silver nitrate catalyst catalysis ketal reaction is higher, and the activity of this support type silver nitrate catalyst catalysis ketal reaction is still higher when reusing, this support type silver nitrate catalyst is recovered and cycling and reutilization.Also load on specific bar-shaped meso-porous titanium dioxide silicon carrier owing to will have corrosive silver nitrate on the other hand, prevent equipment corrosion, therefore this support type silver nitrate catalyst is a kind of catalyst of environmental protection.
In the present invention, by ball-milling method, silver nitrate is carried on specific bar-shaped meso-porous titanium dioxide silicon carrier, do not introduce solvent in whole mechanical milling process, process is simple and easy to do, and 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 silver nitrate catalyst provided by the invention can reduce side reaction, improves product purity, not etching apparatus, is conducive to environmental protection.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, and wherein, the XRD spectra that the XRD spectra that a is bar-shaped meso-porous titanium dioxide silicon carrier (DBK), b are the bar-shaped mesoporous silicon oxide (DBK-Ag) by ball-milling method load silver nitrate, abscissa is 2 θ, and ordinate is intensity.
Fig. 2 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), b
1and b
2for passing through the microscopic appearance figure of the bar-shaped mesoporous silicon oxide (DBK-Ag) of ball-milling method load silver nitrate.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and the microscopic appearance figure of the rod-like mesoporous material SBA-15 of a load silver nitrate 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 silver nitrate catalyst, wherein, this catalyst comprises bar-shaped meso-porous titanium dioxide silicon carrier and the silver nitrate of load on described bar-shaped meso-porous titanium dioxide silicon carrier, and with the gross weight of described catalyst for benchmark, the content of described silver nitrate 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 gross weight of described catalyst for benchmark, the content of described silver nitrate is 30-60 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier length is 0.5-3 micron, specific area is 200-500 meters squared per gram, is preferably 300-400 meters squared per gram, be more preferably 350 meters squared per gram, pore volume is 1.0-2.0 ml/g, is preferably 1.2-1.8 ml/g, is more preferably 1.5 mls/g; Most probable pore size is 10-15 nanometer, is preferably 11-14 nanometer, is more preferably 12 nanometers; Pore wall thickness is 1.5-2 nanometer, and be preferably 1.6-1.8 nanometer, be more preferably 1.7 nanometers, Mean aspect ratio is 1-3; In this case, not only can obtain gratifying catalytic effect, but also can reduce costs.
According to the present invention, the specific area of described support type silver nitrate catalyst can be 50-150 meters squared per gram, is preferably 80-120 meters squared per gram, is more preferably 100 meters squared per gram; Pore volume can be 0.9-1.5 ml/g, is preferably 1.1-1.3 ml/g, is more preferably 1.2 mls/g; Most probable pore size can be 2-10 nanometer, is preferably 4-8 nanometer, is more preferably 6 nanometers; Pore wall thickness is 2-10 nanometer, is preferably 4-8 nanometer, is more preferably 6.2 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, ammonium fluoride and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis and heptane are left standstill 2-5 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 1-10 hour under being 200-500r/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 preferably ethyl orthosilicate.
Under preferable case, described crystallization condition comprises: temperature is 90-180 DEG C, and be preferably 95-150 DEG C, the time is 10-40 hour, is preferably 15-30 hour.
According to the present invention, the method for described removed template method can be calcination method, and it is 300-600 DEG C that the condition of described calcination method comprises temperature, and be preferably 400-550 DEG C, the time is 8-20 hour, is preferably 10-18 hour.
Under preferable case, ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: ammonium fluoride: water: hydrogen chloride: esters of silicon acis: heptane=1:1-3:1000-30000:100-2000:20-500:20-500, be preferably 1:1.2-2.8:1200-28000:120-1800:25-100:280-400, be particularly preferably 1:1.8:5225:1306:64:279.Wherein, the molal quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene 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 silver nitrate in ball sealer grinding jar ball milling, make silver nitrate 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 silver nitrate for benchmark, the consumption of described silver nitrate 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 silver nitrate for benchmark, the consumption of described silver nitrate 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 rod of described bar-shaped meso-porous titanium dioxide silicon carrier is long is 0.5-3 micron, specific area is 200-500 meters squared per gram, be preferably 300-400 meters squared per gram, be more preferably 350 meters squared per gram, pore volume is 1.0-2.0 ml/g, is preferably 1.2-1.8 ml/g, is more preferably 1.5 mls/g; Most probable pore size is 10-15 nanometer, is preferably 11-14 nanometer, is more preferably 12 nanometers; Pore wall thickness is 1.5-2 nanometer, and be preferably 1.6-1.8 nanometer, be more preferably 1.7 nanometers, Mean aspect ratio is 1-3.
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 silver nitrate 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 silver nitrate catalyst comprises: join in the ball grinder of ball mill by bar-shaped mesoporous silicon oxide and silver nitrate, ball grinder inwall is polytetrafluoroethyllining lining, and 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 silver nitrate.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 silver nitrate catalyst comprises the following steps:
1st step, by triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene (EO
20pO
70eO
20, be abbreviated as P123) and ammonium fluoride, join in hydrochloric acid, by molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ammonium fluoride: water: hydrogen chloride=1:1-3:1000-30000:100-2000, be preferably 1:1.2-2.8:1200-28000:120-1800, be particularly preferably 1:1:1.8:5225:1306, wherein, the molal quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene calculates according to the mean molecule quantity of polyoxyethylene-poly-oxypropylene polyoxyethylene and obtains
Be mixed to solids fully to dissolve;
2nd step, adds ethyl orthosilicate and heptane in previous step gained solution, and at 25 DEG C of-60 DEG C of temperature, mechanical agitation speed is stir under 200-500r/min after 1-10 hour to leave standstill 2-5 hour; By molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ethyl orthosilicate: heptane=1:20-200:20-500; Be preferably 1:25-100:280-400; More elect 1:64:279 as.
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 silver nitrate 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 silver nitrate for benchmark, the consumption of described silver nitrate 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 silver nitrate 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 silver nitrate.
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, the time of crystallization can be 10-40 hour, preferably, the temperature of crystallization can be 95-150 DEG C, and the time of crystallization can be 15-30 hour.The temperature of removed template method is 300-600 DEG C, and be preferably 400-550 DEG C, the time is 8-20 hour, is preferably 10-18 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 silver nitrate 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 silver nitrate 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, polyethylene glycol oxide-PPOX-polyethylene glycol oxide, is abbreviated as P123, and 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; 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 silver nitrate catalyst according to the present invention and preparation method thereof.
Be in the hydrochloric acid of 1.75mol/l by the concentration that 2.4 grams of P123 and 0.028 gram ammonium fluorides join 80ml, be stirred to P123 and ammonium fluoride is molten completely altogether at 20 DEG C; Again 17ml normal heptane and 5.5ml ethyl orthosilicate are joined in above-mentioned solution, at 25 DEG C of temperature, stir under mechanical agitation speed is 200r/min after 4 hours and leave standstill 2 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 20 hours, removed template method, obtains the bar-shaped mesoporous silicon oxide (called after DBK) of removed template method.
Above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DBK is put into 100ml ball grinder at room temperature state together with 1 gram of silver nitrate, 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, obtain 2 grams of target product support type silver nitrate catalyst, called after DBK-Ag, wherein, with the total amount of support type silver nitrate catalyst for benchmark, the content of silver nitrate is 50 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 50 % by weight.
With XRD, ESEM, gas chromatography combined with mass spectrometry analyzer, this support type silver nitrate catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, and wherein, the XRD spectra that the XRD spectra that a is bar-shaped meso-porous titanium dioxide silicon carrier (DBK), b are the bar-shaped mesoporous silicon oxide (DBK-Ag) by ball-milling method load silver nitrate, 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 (DBK), the bar-shaped mesoporous silicon oxide (DBK-Ag) of load silver nitrate all has the hexagonal hole road structure of sequential 2 D specific to mesoporous material.
Fig. 2 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DBK), b
1and b
2for passing through the microscopic appearance figure of the bar-shaped mesoporous silicon oxide (DBK-Ag) of ball-milling method load silver nitrate.As seen from the figure, the excellent length of bar-shaped mesoporous silicon oxide DBK microscopic appearance is 0.5-3 μm, and DBK-Ag microscopic appearance still basic maintenance prepared by ball-milling method is bar-shaped, and excellent length is 0.5-3 μm, and Mean aspect ratio is 1-3.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and the microscopic appearance figure of the rod-like mesoporous material SBA-15 of a load silver nitrate 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 3, the microscopic appearance of the rod-like mesoporous material SBA-15 of the load silver nitrate prepared by ball-milling method is then completely destroyed.
Table 1 is the pore structure parameter of the bar-shaped mesoporous silicon oxide (DBK-Ag) of bar-shaped meso-porous titanium dioxide silicon carrier DBK and load silver nitrate of the present invention.
Table 1
Note: average pore wall thickness=(a
0* 3
1/2)/2-average pore size;
Cell parameter a
0=d
100* 2
1/2;
D
100be 100 interplanar distances.
As can be seen from the data of upper table 1, bar-shaped mesoporous silicon oxide is after load silver nitrate, and pore volume and specific area all significantly reduce, and this illustrates that silver nitrate enters into bar-shaped mesoporous silicon oxide composite inner in load-reaction process.
Embodiment 2
The present embodiment is for illustration of support type silver nitrate catalyst according to the present invention and preparation method thereof.
Bar-shaped mesoporous silicon oxide (called after DBK) is prepared according to the method for embodiment 1.
Above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DBK is put into 100ml ball grinder at room temperature state together with 2 grams of silver nitrates, 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, obtain 3 grams of target product support type silver nitrate catalyst, called after DBK-Ag-2, wherein, with the total amount of support type silver nitrate catalyst for benchmark, the content of silver nitrate is 67 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 33 % by weight.
With nitrogen adsorption desorption instrument, gas chromatography combined with mass spectrometry analyzer, analytical test and sign are carried out to this support type silver nitrate catalyst.
Table 2
Embodiment 3
The present embodiment is for illustration of support type silver nitrate catalyst according to the present invention and preparation method thereof.
Bar-shaped mesoporous silicon oxide (called after DBK) is prepared according to the method for embodiment 1.
Above-mentioned 1 gram of bar-shaped mesoporous silicon oxide DBK is put into 100ml ball grinder at room temperature state together with 0.2 gram of silver nitrate, 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, obtain 1.5 grams of target product support type silver nitrate catalyst, called after DBK-Ag-3, wherein, with the total amount of support type silver nitrate catalyst for benchmark, the content of silver nitrate 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, gas chromatography combined with mass spectrometry analyzer, analytical test and sign are carried out to this support type silver nitrate catalyst.
Table 3
Embodiment 4
The present embodiment is for illustration of the preparation of the bar-shaped silica with dipping method load silver nitrate
1 gram that embodiment 1 is prepared bar-shaped mesoporous silicon oxide DBK, 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 DBK through thermal activation vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, again 30ml methyl alcohol and 1g silver nitrate 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 silver nitrate catalyst, called after DBK-Ag-JZ, wherein, with the total amount of support type silver nitrate catalyst for benchmark, the content of silver nitrate is 20 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 80 % by weight.
With gas chromatography combined with mass spectrometry analyzer, this support type silver nitrate catalyst is characterized.
Comparative example 1
This comparative example is for illustration of the bar-shaped mesoporous silicon oxide preparing support type silver nitrate
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 silver nitrate, 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 the rod-like mesoporous material (called after SBA-15-Ag) of load silver nitrate.Wherein, with the total amount of support type silver nitrate catalyst for benchmark, the content of silver nitrate 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 silver nitrate catalyst is characterized.
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to support type silver nitrate catalyst of the present invention is described.
By the vacuum drying 6 hours at 150 DEG C of the support type silver nitrate catalyst (DBK-Ag) in embodiment 1, after being cooled to room temperature, take 1.2 grams, take 7.44 grams of ethylene glycol again, 100ml teflon-lined reactor put into together by 60 grams of cyclohexanone, stir 3 hours under the condition adding hot reflux, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid phase ingredient, result is: the conversion ratio of cyclohexanone is 85%, and the selective of cyclohexanone-ethylene ketal is 99%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity after according to support type silver nitrate catalyst recovery of the present invention.
Support type silver nitrate catalyst (DBK-Ag) in EXPERIMENTAL EXAMPLE 1 is reclaimed, 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 teflon-lined reactor put into together by 120 grams of cyclohexanone, stir 3 hours under the condition adding hot reflux, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid phase ingredient, result is: the conversion ratio of cyclohexanone is 92%, 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 silver nitrate catalyst of the present invention is described.
By the vacuum drying 6 hours at 150 DEG C of the support type silver nitrate catalyst (DBK-Ag-2) in embodiment 2, after being cooled to room temperature, take 3.6 grams, take 22.32 grams of ethylene glycol again, 100ml teflon-lined reactor put into together by 180 grams of cyclohexanone, stir 3 hours under the condition adding hot reflux, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid phase ingredient, result is: the conversion ratio of cyclohexanone is 85%, and cyclohexanone-ethylene ketal is selective is 99%.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity after according to support type silver nitrate catalyst recovery of the present invention.
Support type silver nitrate catalyst (DBK-Ag-2) in EXPERIMENTAL EXAMPLE 3 is reclaimed, and vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 4.8 grams, claim 29.76 grams of ethylene glycol again, 240 grams of cyclohexanone put into 100ml teflon-lined reactor together, stir 3 hours under the condition adding hot reflux, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid phase ingredient, result is: the conversion ratio of cyclohexanone is 88%, and cyclohexanone-ethylene ketal is selective is 99%.
EXPERIMENTAL EXAMPLE 5
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to support type silver nitrate catalyst of the present invention is described.
By the vacuum drying 6 hours at 150 DEG C of the support type silver nitrate catalyst (DBK-Ag-3) in embodiment 3, after being cooled to room temperature, take 1.2 grams, take 7.44 grams of ethylene glycol again, 100ml teflon-lined reactor put into together by 60 grams of cyclohexanone, add condenser pipe, stir 3 hours under the condition adding hot reflux, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid phase ingredient, result is: the conversion ratio of cyclohexanone is 82%, and cyclohexanone-ethylene ketal is selective is 99%.
EXPERIMENTAL EXAMPLE 6
This EXPERIMENTAL EXAMPLE is used for illustrating the catalytic activity after according to support type silver nitrate catalyst recovery of the present invention.
Support type silver nitrate catalyst (DBK-Ag-3) in EXPERIMENTAL EXAMPLE 5 is reclaimed, 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 teflon-lined reactor put into together by 120 grams of cyclohexanone, add condenser pipe, stir 3 hours under the condition adding hot reflux, after being cooled to room temperature, centrifugation, adopt gas chromatography combined with mass spectrometry analyzer analytical reactions product liquid phase ingredient, result is: the conversion ratio of cyclohexanone is 84%, cyclohexanone-ethylene ketal is selective is 99%.
EXPERIMENTAL EXAMPLE 7
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the rod-like mesoporous material DBK(called after DBK-Ag-JZ of the support type silver nitrate that support type silver nitrate catalyst (DBK-Ag) is obtained by dipping method by the embodiment 4 of identical weight) replace, result is: the conversion ratio of cyclohexanone is 80%, 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 silver nitrate catalyst (DBK-Ag) of the EXPERIMENTAL EXAMPLE 1 reclaimed is by the rod-like mesoporous material DBK(called after DBK-Ag-JZ of the EXPERIMENTAL EXAMPLE 7 support type silver nitrate of the recovery of identical weight) replace, result is: the conversion ratio of cyclohexanone is 81%, 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, the rod-like mesoporous material SBA-15(called after SBA-15-Ag of the load silver nitrate that support type silver nitrate catalyst (DBK-Ag) is obtained by the comparative example 1 of identical weight) replace, result is: the conversion ratio of cyclohexanone is 70%, 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 silver nitrate catalyst (DBK-Ag) of the EXPERIMENTAL EXAMPLE 1 reclaimed is by the rod-like mesoporous material SBA-15(called after SBA-15-Ag of the load silver nitrate of Experimental comparison's example 1 of the recovery of identical weight) replace, result is: the conversion ratio of cyclohexanone is 71%, 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 silver nitrate catalyst (DBK-Ag), 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 silver nitrate on bar-shaped meso-porous titanium dioxide silicon carrier, the catalytic performance of the support type silver nitrate 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 (16)
1. a support type silver nitrate catalyst, it is characterized in that, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the silver nitrate 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 silver nitrate is 10-90 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier length is 0.5-3 micron, specific area is 200-500 meters squared per gram, and most probable pore size is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and Mean aspect ratio is 1-3.
2. support type silver nitrate catalyst according to claim 1, wherein, with the gross weight of described catalyst for benchmark, the content of described silver nitrate is 30-60 % by weight, and the content of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight; And the specific area of described bar-shaped meso-porous titanium dioxide silicon carrier is 300-400 meters squared per gram, most probable pore size is 11-14 nanometer, and pore wall thickness is 1.6-1.8 nanometer.
3. support type silver nitrate catalyst according to claim 1 and 2, wherein, the specific area of described support type silver nitrate catalyst is 50-150 meters squared per gram, and most probable pore size is 2-10 nanometer, and pore wall thickness is 2-10 nanometer, and Mean aspect ratio is 1-3.
4. support type silver nitrate catalyst 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, ammonium fluoride and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis and heptane are left standstill 2-5 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 1-10 hour under being 200-500r/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.
5. support type silver nitrate catalyst according to claim 4, 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.
6. the support type silver nitrate catalyst according to claim 4 or 5, wherein, ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: ammonium fluoride: water: hydrogen chloride: esters of silicon acis: heptane=1:1-3:1000-30000:100-2000:20-500:20-500.
7. the preparation method of a support type silver nitrate catalyst, wherein, the method comprises: by bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with silver nitrate, make silver nitrate 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 silver nitrate for benchmark, the consumption of described silver nitrate is 10-90 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 10-90 % by weight; And the rod of described bar-shaped meso-porous titanium dioxide silicon carrier length is 0.5-3 micron, specific area is 200-500 meters squared per gram, and most probable pore size is 10-15 nanometer, and pore wall thickness is 1.5-2 nanometer, and Mean aspect ratio is 1-3.
8. preparation method according to claim 7, wherein, with the gross weight of described bar-shaped meso-porous titanium dioxide silicon carrier and silver nitrate for benchmark, the consumption of described silver nitrate is 30-60 % by weight, and the consumption of described bar-shaped meso-porous titanium dioxide silicon carrier is 40-70 % by weight; And the specific area of described bar-shaped meso-porous titanium dioxide silicon carrier is 300-400 meters squared per gram, most probable pore size is 11-14 nanometer, and pore wall thickness is 1.6-1.8 nanometer.
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 DEG C, 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 obtained by the method comprised the following steps:
(1) template, ammonium fluoride and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis and heptane are left standstill 2-5 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 1-10 hour under being 200-500r/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.
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 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.
12. preparation methods according to claim 10 or 11, wherein, ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: ammonium fluoride: water: hydrogen chloride: esters of silicon acis: heptane=1:1-3:1000-30000:100-2000:20-500:20-500.
The catalyst that preparation method in 13. claim 7-12 described in any one obtains.
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: 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, described catalyst is the catalyst in claim 1-6 and 13 described in any one.
16. preparation methods according to claim 15, wherein, the mol ratio of cyclohexanone and ethylene glycol is 1:0.1-0.2, and in the silver nitrate 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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| SU753459A1 (en) * | 1978-04-12 | 1980-08-07 | Ленинградский Ордена Трудового Красного Знамени Технологический Институт Им. Ленсовета | Method of preparing argentum catalyst for ethanol oxidation |
| JP2000167403A (en) * | 1998-12-08 | 2000-06-20 | Tokyo Gas Co Ltd | Silver carrying alumina catalyst for purification of exhaust gas of lean burning gas engine and its production |
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| JP2000167403A (en) * | 1998-12-08 | 2000-06-20 | Tokyo Gas Co Ltd | Silver carrying alumina catalyst for purification of exhaust gas of lean burning gas engine and its production |
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