CN103586056B - The preparation method of a kind of carried phospho-tungstic acid Catalysts and its preparation method and application and ethyl acetate - Google Patents
The preparation method of a kind of carried phospho-tungstic acid Catalysts and its preparation method and application and ethyl acetate Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of carried phospho-tungstic acid Catalysts and its preparation method and ethyl acetate, wherein, this catalyst is made up of carrier and load phosphotungstic acid 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 phosphotungstic acid 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, phosphotungstic acid load is on specific bar-shaped meso-porous titanium dioxide silicon carrier, not only the activity of this catalyst esterification is higher, and the activity of this catalyst esterification when reusing is still higher, this catalyst is recovered and cycling and reutilization.
Description
Technical field
The present invention relates to a kind of carried phospho-tungstic acid Catalysts and its preparation method, also relate to and use this catalyst in application in the esterification reaction, and the preparation method of ethyl acetate.
Background technology
Within 1992, Mobile company synthesizes mesoporous material (Beck J S, Vartuli J C, Roth W J, 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, et al Science 279 (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; De Vos, 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.
Esterification catalytic reaction common acid, as catalyst, except traditional inorganic acid, is solid super-strong acid (Van Rhijn, the W.M. of carrier with mesoporous material in addition; De Vos, D.E.; Sels, B.F.; Et al.Chem.Commun.1998, No.3,317.; Du, C.H.; Qin, Y.N.; He, Y. F.; Et al.Chin.J.Chem.Phys.2003,16,504. [Du Changhai, Qin Yongning, He Yan stitch, Ma Zhi, Wu Shuxin, Chinese Journal of Chemical Physics, 2003,16,504.]) and ionic liquid (Chiappe, C.; Pieraccini, D.J. Phys.Org.Chem.2005,18,275.; Qiao, K.; Hagiwara, H.; Yokoyama, C.J.Mole.Catal.A:Chem.2006,246,65.; Chen Weiyi, ground force, Zhang Yong, organic chemistry, 2006,26,87.) etc.Inorganic acid catalyst is to instrument seriously corroded, and homogeneous catalysis product is not easily separated, easily produces the pollutants such as spent acid waste liquid; Solid acid has the shortcoming to instrument seriously corroded equally, and catalytic activity reduces fast, and cost is higher.As using mesoporous material as carrier loaded homogeneous catalyst, then instrument can be avoided to corrode, and catalyst easily realizes being separated of catalyst and product, can recycling repeatedly.Carrying method conventional is at present solvent method supported catalyst, and also must remove added solvent in process catalyst process, technique is more complicated, and cost is increased.
Therefore, develop a kind of novel catalyst for the synthesis of ethyl acetate 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 catalyzing and synthesizing ethyl acetate exists is serious to equipment corrosion, complex process, providing a kind of novel for the synthesis of the catalyst of ethyl acetate and the preparation method of ethyl acetate.
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the phosphotungstic acid 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 phosphotungstic acid 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 carried phospho-tungstic acid catalyst, wherein, the method comprises: by bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with phosphotungstic acid, make phosphotungstic acid 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 phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid 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 in the esterification reaction of described catalyst.
Further, present invention also offers a kind of preparation method of ethyl acetate, wherein, the method comprises: in the presence of a catalyst, under the condition of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, wherein, described catalyst is carried phospho-tungstic acid catalyst provided by the invention.
In catalyst of the present invention, phosphotungstic acid load is on specific bar-shaped meso-porous titanium dioxide silicon carrier, on the one hand, not only the activity of this carried phospho-tungstic acid catalyst esterification is higher, and the activity of this carried phospho-tungstic acid catalyst esterification is still higher when reusing, this carried phospho-tungstic acid catalyst is recovered and cycling and reutilization.Also load on specific bar-shaped meso-porous titanium dioxide silicon carrier owing to will have corrosive phosphotungstic acid on the other hand, prevent equipment corrosion, therefore this carried phospho-tungstic acid catalyst is a kind of catalyst of environmental protection.
In the present invention, by ball-milling method, phosphotungstic acid 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 esterification of catalysis acetic acid and ethanol, catalyst can pass through and reclaim and Reusability, and carried phospho-tungstic acid 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, wherein, a is the XRD spectra of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b is be the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA) of the reacted load phosphotungstic acid of quadric catalysis by the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA) of ball-milling method load phosphotungstic acid and c, abscissa is 2 θ, and ordinate is intensity.
Fig. 2 is TEM transmission electron microscope picture, wherein, and a
1and a
2be the pore structure schematic diagram of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b is the pore structure schematic diagram of the bar-shaped mesoporous silicon oxide (DB-HPA) by ball-milling method load.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and the microscopic appearance figure of the bar-shaped mesoporous silicon oxide (DB-HPA) of a to be the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b be by ball-milling method load phosphotungstic acid.
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 phosphotungstic acid that to be the microscopic appearance figure of rod-like mesoporous material SBA-15, b be is prepared by ball-milling method.
Fig. 5 is X-ray diffracting spectrum, and wherein, a is the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA-JZ) of infusion process load phosphotungstic acid, and abscissa is 2 θ, and ordinate is intensity.
Fig. 6 is TEM transmission electron microscope picture, and wherein, a is the pore structure schematic diagram of the bar-shaped meso-porous titanium dioxide silicon carrier (DB-HPA-JZ) of infusion process load phosphotungstic acid.
Fig. 7 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of the bar-shaped meso-porous titanium dioxide silicon carrier (DB-HPA-JZ) of infusion process load phosphotungstic acid.
Detailed description of the invention
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst comprises bar-shaped meso-porous titanium dioxide silicon carrier and the phosphotungstic acid 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 phosphotungstic acid 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 phosphotungstic acid is 30-60 % by weight, and the content 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, more elects 2.3 nanometers as; Mean aspect ratio is 1-3, is preferably 1.5-2.5.
According to the present invention, the specific area of described carried phospho-tungstic acid catalyst can be 500-800 meters squared per gram, is preferably 600-700 meters squared per gram, is more preferably 671 meters squared per gram; Pore volume can be 0.5-1.5 ml/g, is preferably 0.8-1.3 ml/g, is more preferably 0.9 ml/g; Most probable pore size can be 3-10 nanometer, is preferably 5-8 nanometer, is more preferably 6.5 nanometers; Pore wall thickness is 2-7 nanometer, is preferably 3-6 nanometer, is more preferably 4.6 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.
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 the template of P123, molecular formula be EO
20pO
70eO
20.
Present invention also offers a kind of preparation method of catalyst, wherein, the method comprises: by bar-shaped meso-porous titanium dioxide silicon carrier together with phosphotungstic acid in ball sealer grinding jar ball milling, make phosphotungstic acid 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 phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid 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 phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid 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 phosphotungstic acid 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 carried phospho-tungstic acid catalyst comprises: join in the ball grinder of ball mill by bar-shaped mesoporous silicon oxide and phosphotungstic acid, 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 phosphotungstic acid.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 carried phospho-tungstic acid 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 stir speed (S.S.) 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 phosphotungstic acid 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 phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid 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 phosphotungstic acid 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 phosphotungstic acid.
Described template can be the various triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene templates that this area routine uses, such as, can be that the commodity that Aldrich company produces are called the template of P123.
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 a kind of preparation method of ethyl acetate, wherein, the method comprises: in the presence of a catalyst, under the condition of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, wherein, described catalyst is carried phospho-tungstic acid catalyst provided by the invention.
According to the present invention, in the esterification reaction, the mol ratio of acetic acid and ethanol can in very large range change, such as, the mol ratio of acetic acid and ethanol can be 1:0.5-10, and the consumption of described carried phospho-tungstic acid 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 acetic acid of 100 weight portions, the consumption of described catalyst can be 0.5-50 weight portion.
In the present invention, the condition of described esterification is conventionally known to one of skill in the art, such as, the condition of described esterification can comprise: the temperature of reaction is 100-150 DEG C, the time of reaction is 0.5-72 hour, preferably, the temperature of reaction can be 120-140 DEG C, and the time of reaction can be 20-30 hour.
According to the present invention, after esterification 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, 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, phosphotungstic acid (CAS12501-2-4) is a kind of heteropoly acid, buys from ACROS, and mean molecule quantity is 2880.
In following examples, X-ray diffraction analysis is that the X-ray diffractometer of D8 Advance carries out in the model purchased from German Bruker AXS company; Transmission electron microscope analysis is that the transmission electron microscope of Tecnai 20 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 carried phospho-tungstic acid Catalysts and its preparation method according to the present invention.
Be in the hydrochloric acid of 2mol/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 phosphotungstic acid, 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 carried phospho-tungstic acid catalyst, called after DB-HPA, wherein, calculate, with the total amount of carried phospho-tungstic acid catalyst for benchmark according to weight × 100% of the weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, the content of phosphotungstic acid is 50 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 50 % by weight.
With XRD, ESEM, transmission electron microscope and nitrogen adsorption desorption instrument, this carried phospho-tungstic acid catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, wherein, a is the XRD spectra of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b is be the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA) of the reacted load phosphotungstic acid of quadric catalysis by the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA) of ball-milling method load phosphotungstic acid and c, abscissa is 2 θ, and ordinate is intensity.The low-angle spectrum peak occurred from XRD spectra, the XRD spectra c of the XRD spectra a of bar-shaped meso-porous titanium dioxide silicon carrier (DB), the XRD spectra b of the bar-shaped mesoporous silicon oxide (DB-HPA) of load phosphotungstic acid and the bar-shaped mesoporous silicon oxide (DB-HPA) of the reacted load phosphotungstic acid of quadric catalysis 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 is the pore structure schematic diagram of the bar-shaped mesoporous silicon oxide (DB-HPA) by ball-milling method load.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 phosphotungstic acid is forward and backward, shows 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 microscopic appearance figure of the bar-shaped mesoporous silicon oxide (DB-HPA) of a to be the microscopic appearance figure of bar-shaped meso-porous titanium dioxide silicon carrier (DB), b be by ball-milling method load phosphotungstic acid.As seen from the figure, the excellent length of bar-shaped mesoporous silicon oxide DB microscopic appearance is 0.5-2 μm, and DB-HPA microscopic appearance still basic maintenance prepared by ball-milling method is bar-shaped, and excellent length is 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 phosphotungstic acid 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 bar-shaped mesoporous silicon oxide SBA-15 microscopic appearance of the load phosphotungstic acid prepared by ball-milling method is then completely destroyed.
Fig. 5 is X-ray diffracting spectrum, and wherein, a is the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA-JZ) of infusion process load phosphotungstic acid, and abscissa is 2 θ, and ordinate is intensity.The low-angle spectrum peak occurred from XRD spectra, the XRD spectra of the bar-shaped mesoporous silicon oxide (DB-HPA-JZ) of infusion process load phosphotungstic acid has the hexagonal hole road structure of sequential 2 D specific to mesoporous material.
Fig. 6 is TEM transmission electron microscope picture, and wherein, a is the bar-shaped mesoporous silicon oxide (DB-HPA-JZ) of infusion process load phosphotungstic acid.From TEM transmission electron microscope picture, bar-shaped meso-porous titanium dioxide silicon carrier (DB) shows two-dimentional hexagonal hole road structure specific to mesoporous material after load phosphotungstic acid.
Fig. 7 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of the bar-shaped mesoporous silicon oxide (DB-HPA-JZ) of infusion process load phosphotungstic acid.As seen from the figure, DB-HPA microscopic appearance still basic maintenance prepared by infusion process is bar-shaped, and excellent length is 0.5-2 μm.
Table 1 is the pore structure parameter of the bar-shaped mesoporous silicon oxide (DB-HPA) of bar-shaped meso-porous titanium dioxide silicon carrier DB and load phosphotungstic acid 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 phosphotungstic acid, and pore volume and specific area all significantly reduce, and this illustrates that phosphotungstic acid enters into bar-shaped mesoporous silicon oxide composite inner in load-reaction process.
Embodiment 2
The present embodiment is for illustration of carried phospho-tungstic acid 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 phosphotungstic acids, 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 carried phospho-tungstic acid catalyst, called after DB-HPA-2, wherein, calculate, with the total amount of carried phospho-tungstic acid catalyst for benchmark according to weight × 100% of the weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, the content of phosphotungstic acid 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, this carried phospho-tungstic acid catalyst is characterized.
Table 2
Embodiment 3
The present embodiment is for illustration of carried phospho-tungstic acid 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 phosphotungstic acid, 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 carried phospho-tungstic acid catalyst, called after DB-HPA-3, wherein, calculate, with the total amount of carried phospho-tungstic acid catalyst for benchmark according to weight × 100% of the weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, the content of phosphotungstic acid is 33 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 67 % by weight.
With the analysis of nitrogen adsorption desorption, this carried phospho-tungstic acid 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 phosphotungstic acid
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 4g phosphotungstic acid 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 carried phospho-tungstic acid catalyst, called after DB-HPA-JZ, wherein calculate according to weight × 100% of the weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, with the total amount of carried phospho-tungstic acid catalyst for benchmark, the content of phosphotungstic acid is 20 % by weight, the content of bar-shaped meso-porous titanium dioxide silicon carrier is 80 % by weight.
With XRD, nitrogen adsorption desorption instrument, ESEM, transmission electron microscope, X-ray energy spectrometer and ICP elementary analysis, this carried phospho-tungstic acid catalyst is characterized.
Table 4
Comparative example 1
Prepare the bar-shaped mesoporous silicon oxide of carried phospho-tungstic acid
The bar-shaped mesoporous silicon oxide of carried phospho-tungstic acid is prepared according to the method for embodiment 1, unlike embodiment 1 prepare 1 gram of bar-shaped mesoporous silicon oxide DB by 1 gram of bar-shaped mesoporous silicon oxide SBA-15(purchased from high-tech limited company of Jilin University) replace, obtain the rod-like mesoporous material (called after SBA-15-HPA) of 2 grams of load phosphotungstic acids.Wherein, weight × 100% according to the weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add calculates, with the total amount of carried phospho-tungstic acid catalyst for benchmark, the content of phosphotungstic acid is 50 % by weight, and the content of bar-shaped meso-porous titanium dioxide silicon carrier is 50 % by weight.
With nitrogen adsorption desorption instrument, ESEM, this carried phospho-tungstic acid catalyst is characterized.
Table 5
EXPERIMENTAL EXAMPLE 1
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to carried phospho-tungstic acid catalyst of the present invention is described.
By the vacuum drying 6 hours at 150 DEG C of the carried phospho-tungstic acid catalyst (DB-HPA) in embodiment 1, after being cooled to room temperature, take 4 grams, then take 46 grams of ethanol, 100ml there-necked flask put into together by 60 grams of acetic acid, adds condenser pipe, stir 4 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopts gas chromatography analytical reactions Product liquid composition, result is: ethyl acetate is selective is 99%, and acetic acid conversion is 90%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for illustrating according to the catalytic activity after carried phospho-tungstic acid catalyst recovery of the present invention.
Carried phospho-tungstic acid catalyst (DB-HPA) in EXPERIMENTAL EXAMPLE 1 is reclaimed, and vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 3 grams, take 34.5 grams of ethanol again, 100ml there-necked flask put into together by 45 grams of acetic acid, add condenser pipe, stir 4 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography analytical reactions Product liquid composition, result is: ethyl acetate is selective is 99%, and acetic acid conversion is 88%.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to carried phospho-tungstic acid catalyst of the present invention is described.
By the vacuum drying 6 hours at 150 DEG C of the carried phospho-tungstic acid catalyst (DB-HPA-2) in embodiment 2, after being cooled to room temperature, take 2 grams, then take 23 grams of ethanol, 100ml there-necked flask put into together by 30 grams of acetic acid, adds condenser pipe, stir 4 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopts gas chromatography analytical reactions Product liquid composition, result is: ethyl acetate is selective is 99%, and acetic acid conversion is 83%.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for illustrating according to the catalytic activity after carried phospho-tungstic acid catalyst recovery of the present invention.
Carried phospho-tungstic acid catalyst (DB-HPA-2) in EXPERIMENTAL EXAMPLE 3 is reclaimed, and vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 1 gram, take 11.5 grams of ethanol again, 100ml there-necked flask put into together by 15 grams of acetic acid, add condenser pipe, stir 4 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography analytical reactions Product liquid composition, result is: ethyl acetate is selective is 99%, and acetic acid conversion is 80%.
EXPERIMENTAL EXAMPLE 5
This EXPERIMENTAL EXAMPLE is used for the catalytic activity according to carried phospho-tungstic acid catalyst of the present invention is described.
By the vacuum drying 6 hours at 150 DEG C of the carried phospho-tungstic acid catalyst (DB-HPA-3) in embodiment 3, after being cooled to room temperature, take 2 grams, then take 23 grams of ethanol, 100ml there-necked flask put into together by 30 grams of acetic acid, adds condenser pipe, stir 4 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopts gas chromatography analytical reactions Product liquid composition, result is: ethyl acetate is selective is 99%, and acetic acid conversion is 79%.
EXPERIMENTAL EXAMPLE 6
This EXPERIMENTAL EXAMPLE is used for illustrating according to the catalytic activity after carried phospho-tungstic acid catalyst recovery of the present invention.
Carried phospho-tungstic acid catalyst (DB-HPA-3) in EXPERIMENTAL EXAMPLE 5 is reclaimed, and vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 1 gram, take 11.5 grams of ethanol again, 100ml there-necked flask put into together by 15 grams of acetic acid, add condenser pipe, stir 4 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, adopt gas chromatography analytical reactions Product liquid composition, result is: ethyl acetate is selective is 99%, and acetic acid conversion is 77%.
EXPERIMENTAL EXAMPLE 7
Ethyl acetate is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the rod-like mesoporous material DB(called after DB-HPA-JZ of the carried phospho-tungstic acid that carried phospho-tungstic acid catalyst (DB-HPA) is obtained by dipping method by the embodiment 4 of identical weight) replace, result is: acetic acid conversion is 82%, and the selective of ethyl acetate is 80%.
EXPERIMENTAL EXAMPLE 8
Ethyl acetate is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the carried phospho-tungstic acid catalyst (DB-HPA) of the EXPERIMENTAL EXAMPLE 1 reclaimed is by the rod-like mesoporous material DB(called after DB-HPA-JZ of EXPERIMENTAL EXAMPLE 7 carried phospho-tungstic acid of the recovery of identical weight) replace, result is: acetic acid conversion is 80%, and the selective of ethyl acetate is 90%.
Experimental comparison's example 1
Ethyl acetate is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the rod-like mesoporous material SBA-15(called after SBA-15-HPA of the load phosphotungstic acid that carried phospho-tungstic acid catalyst (DB-HPA) is obtained by the comparative example 1 of identical weight) replace, result is: acetic acid conversion is 76%, and the selective of ethyl acetate is 81%.
Experimental comparison's example 2
Ethyl acetate is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the carried phospho-tungstic acid catalyst (DB-HPA) of the EXPERIMENTAL EXAMPLE 1 reclaimed is by the rod-like mesoporous material SBA-15(called after SBA-15-HPA of the load phosphotungstic acid of Experimental comparison's example 1 of the recovery of identical weight) replace, result is: acetic acid conversion is 70%, and the selective of ethyl acetate is 80%.
By above embodiment 1-4 and comparative example 1 and EXPERIMENTAL EXAMPLE 1-8, the data of Experimental comparison's example 1-2 can be found out, EXPERIMENTAL EXAMPLE 1-8 obviously than Experimental comparison example 1-2 effective, and preferred EXPERIMENTAL EXAMPLE 1, EXPERIMENTAL EXAMPLE 2 is than EXPERIMENTAL EXAMPLE 3, EXPERIMENTAL EXAMPLE 4, EXPERIMENTAL EXAMPLE 5, EXPERIMENTAL EXAMPLE 6 effective, illustrate and adopt ball-milling method to be carried on by phosphotungstic acid on bar-shaped meso-porous titanium dioxide silicon carrier, the catalytic performance of the carried phospho-tungstic acid catalyst obtained is better, make to apply this catalyst when carrying out the esterification of catalysis acetic acid and ethanol, 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 (11)
1. a carried phospho-tungstic acid catalyst, it is characterized in that, by bar-shaped meso-porous titanium dioxide silicon carrier and load, the phosphotungstic acid 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 phosphotungstic acid 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;
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.
2. carried phospho-tungstic acid catalyst according to claim 1, wherein, the specific area of described carried phospho-tungstic acid catalyst is 500-800 meters squared per gram, and most probable pore size is 3-10 nanometer, and pore wall thickness is 2-7 nanometer, and Mean aspect ratio is 1-3.
3. carried phospho-tungstic acid catalyst according to claim 1, 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.
4. carried phospho-tungstic acid catalyst according to claim 1, 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.
5. the preparation method of a carried phospho-tungstic acid catalyst, wherein, the method comprises: by bar-shaped meso-porous titanium dioxide silicon carrier ball milling together with phosphotungstic acid, make phosphotungstic acid 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 phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid 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;
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;
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, stir speed (S.S.) 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) gained crystallization product heating, removed template method;
Described template is polyethylene glycol oxide-PPOX-polyethylene glycol oxide.
6. preparation method according to claim 5, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 10-150 DEG C, and the time is 0.1-72 hour; It is 300-600 DEG C that the condition of described removed template method comprises temperature, and the time is 8-20 hour.
7. preparation method according to claim 5, 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.
8. the catalyst that the preparation method in claim 5-7 described in any one obtains.
9. catalyst application in the esterification reaction described in any one in claim 1-4 and 8.
10. a preparation method for ethyl acetate, wherein, the method comprises: in the presence of a catalyst, under the condition of esterification, acetic acid is contacted with ethanol, to obtain ethyl acetate, it is characterized in that, described catalyst is the catalyst in claim 1-4 and 8 described in any one.
11. preparation methods according to claim 10, wherein, the mol ratio of acetic acid and ethanol is 1:0.5-10, and in the phosphotungstic acid of load in described catalyst, relative to the acetic acid of 100 weight portions, the consumption of described catalyst is 0.5-50 weight portion.
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| CN102049275A (en) * | 2009-11-06 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst loading phosphoric acid on macro/mesoporous material, preparation method and application thereof |
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| CN1635929A (en) * | 2000-09-07 | 2005-07-06 | 昭和电工株式会社 | Heteropolyacid catalyst for producing lower aliphatic carboxylic acid ester |
| CN102049275A (en) * | 2009-11-06 | 2011-05-11 | 中国石油化工股份有限公司 | Catalyst loading phosphoric acid on macro/mesoporous material, preparation method and application thereof |
| CN102453141A (en) * | 2010-10-19 | 2012-05-16 | 中国石油化工股份有限公司 | Loaded metallocene catalyst and preparation method thereof |
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