CN103586058B - 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 the block mesoporous silicon oxide of hexahedron, and with the gross weight of described catalyst for benchmark, the content 10-90 % by weight of described phosphotungstic acid, the content 10-90 % by weight of described carrier; The bottom surface length of side 2.5-5.0 micron of described carrier, high 1-10 micron, specific area 500-700 meters squared per gram, pore volume 0.4-1.0 ml/g, most probable pore size 3.0-7.0 nanometer, pore wall thickness 6-7 nanometer.In catalyst of the present invention, phosphotungstic acid load is on the block meso-porous titanium dioxide silicon carrier of specific hexahedron, 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 the application in the esterification reaction of this catalyst, 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 the block mesoporous material aperture (6-30nm) of hexahedron, 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.
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 the block meso-porous titanium dioxide silicon carrier of hexahedron and load, the phosphotungstic acid on the block meso-porous titanium dioxide silicon carrier of described hexahedron 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 the block meso-porous titanium dioxide silicon carrier of described hexahedron is 10-90 % by weight; The bottom surface length of side of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 2.5-5.0 micron, and height is 1-10 micron, and specific area is 500-700 meters squared per gram, and most probable pore size is 3.0-7.0 nanometer, and pore wall thickness is 6-7 nanometer.
Present invention also offers a kind of preparation method of carried phospho-tungstic acid catalyst, wherein, the method comprises: by the block meso-porous titanium dioxide silicon carrier of hexahedron ball milling together with phosphotungstic acid, make phosphotungstic acid load on the block meso-porous titanium dioxide silicon carrier of described hexahedron, with the gross weight of the block meso-porous titanium dioxide silicon carrier of described hexahedron and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, and the consumption of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 10-90 % by weight; The bottom surface length of side of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 2.5-5.0 micron, and height is 1-10 micron, and specific area is 500-700 meters squared per gram, and most probable pore size is 3.0-7.0 nanometer, and pore wall thickness is 6-7 nanometer.
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 the block meso-porous titanium dioxide silicon carrier of specific hexahedron, 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 the block meso-porous titanium dioxide silicon carrier of specific hexahedron 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 the block meso-porous titanium dioxide silicon carrier of specific hexahedron, solvent is not introduced in whole mechanical milling process, process is simple and easy to do, after mechanical milling process, gained catalyst also keeps hexahedron block, 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, improve 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 block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron, b is be the XRD spectra of the block mesoporous silicon oxide (FDU-HPA) of hexahedron of the reacted load phosphotungstic acid of quadric catalysis by the XRD spectra of the block mesoporous silicon oxide (FDU-HPA) of the hexahedron 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
2for the pore structure schematic diagram of block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron, b is the pore structure schematic diagram of the hexahedron block mesoporous silicon oxide (FDU-HPA) of the phosphotungstic acid by ball-milling method load.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron, b
1for the microscopic appearance figure of the block mesoporous silicon oxide (FDU-HPA) of the hexahedron passing through 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.
Detailed description of the invention
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst comprises the block meso-porous titanium dioxide silicon carrier of hexahedron and the phosphotungstic acid of load on the block meso-porous titanium dioxide silicon carrier of described hexahedron, and with the gross weight of described catalyst for benchmark, the content of described phosphotungstic acid is 10-90 % by weight, the content of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 10-90 % by weight, more preferably in situation, with the gross weight of described catalyst for benchmark, the content of described phosphotungstic acid is 30-60 % by weight, the content of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 40-70 % by weight.
The bottom surface length of side of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 2.5-5.0 micron, is preferably 2.5-4.5 micron, is more preferably 4 microns; Height is 1-10 micron, is preferably 2-8 micron, is more preferably 5 microns; Specific area is 500-700 meters squared per gram, is preferably 550-650 meters squared per gram, is more preferably 598 meters squared per gram; Pore volume is 0.4-1.0 ml/g, is preferably 0.5-0.9 ml/g, is more preferably 0.7 ml/g; Most probable pore size is 3.0-7.0 nanometer, is preferably 4-6 nanometer, is more preferably 4.8 nanometers; Pore wall thickness is 6-7 nanometer, is preferably 6.4 nanometers.
The various hexahedron structures that hexahedron bulk described in the present invention can it has been generally acknowledged that for this area; 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 carried phospho-tungstic acid catalyst can be 20-50 meters squared per gram, is preferably 25-40 meters squared per gram, is more preferably 32 meters squared per gram; Pore volume can be 0.1-0.5 ml/g, is preferably 0.1-0.3 ml/g, is more preferably 0.1 ml/g; Most probable pore size can be 1-7 nanometer, is preferably 3-5 nanometer, is more preferably 3.8 nanometers; Pore wall thickness is 4-10.0 nanometer, is preferably 6-8 nanometer, is more preferably 7.5 nanometers.
According to the present invention, described carrier is the block mesoporous silicon oxide of hexahedron, and the block mesoporous silicon oxide of described hexahedron can be prepared by the method comprised the following steps:
(1) template, potassium sulfate and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis are left standstill 1-20 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 5-60 minute under being 100-400r/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, it is 90-180 DEG C that described crystallization condition comprises temperature, and be preferably 95-110 DEG C, the time is 10-40 hour, is preferably 12-30 hour.
Under preferable case, it is 300-600 DEG C that the condition of described removed template method comprises temperature, and be preferably 350-550 DEG C, the time is 8-20 hour, is preferably 10-19 hour.
Under preferable case, ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: potassium sulfate: water: hydrogen chloride: esters of silicon acis=1:100-800:10000-30000:10-9000:20-200, 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, such as, can be that the commodity that Fuka company produces are called
the template of F108, molecular formula is EO
132pO
60eO
132.
Present invention also offers a kind of preparation method of catalyst, wherein, the method comprises: by block for hexahedron meso-porous titanium dioxide silicon carrier together with phosphotungstic acid in ball sealer grinding jar ball milling, make phosphotungstic acid load on the block meso-porous titanium dioxide silicon carrier of described hexahedron, with the gross weight of the block meso-porous titanium dioxide silicon carrier of described hexahedron and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, the consumption of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 10-90 % by weight, more preferably, with the gross weight of the block meso-porous titanium dioxide silicon carrier of described hexahedron and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 30-60 % by weight, the consumption of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 40-70 % by weight.
According to the present invention, the bottom surface length of side of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 2.5-5.0 micron, is preferably 2.5-4.5 micron, is more preferably 4 microns; Height is 1-10 micron, is preferably 2-8 micron, is more preferably 5 microns; Specific area is 500-700 meters squared per gram, is preferably 550-650 meters squared per gram, is more preferably 598 meters squared per gram; Pore volume is 0.4-1.0 ml/g, is preferably 0.5-0.9 ml/g, is more preferably 0.7 ml/g; Most probable pore size is 3.0-7.0 nanometer, is preferably 4-6 nanometer, is more preferably 4.8 nanometers; Pore wall thickness is 6-7 nanometer, is preferably 6.4 nanometers.The various hexahedrons that hexahedron bulk described in the present invention can it has been generally acknowledged that for this area.
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 block for hexahedron mesoporous silicon oxide and phosphotungstic acid, ball grinder inwall is polytetrafluoroethyllining lining, the diameter of abrading-ball is 2-3mm, 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 block mesoporous silicon oxide of hexahedron 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 polyethylene glycol oxide-PPOX-polyethylene glycol oxide (EO
132pO
60eO
132, be abbreviated as F108) and potassium sulfate, join in hydrochloric acid, by molar feed ratio,
Ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: potassium sulfate: water: hydrogen chloride=1:100-800:10000-30000:10-9000,
Be mixed to solids fully to dissolve;
2nd step, adds ethyl orthosilicate in previous step gained solution, and at 25 DEG C of-60 DEG C of temperature, mechanical agitation speed is stir under 100-400r/min after 5-60 minute to leave standstill 1-20 hour; By molar feed ratio,
Triblock copolymer polyoxyethylene-poly-oxypropylene polyoxyethylene: ethyl orthosilicate=1:20-200; Elect 1:30-100 as, be more preferably 1:63;
3rd step, is placed in closed reaction vessel, crystallization 10-40 hour at 90-180 DEG C of temperature by upper step gained solution;
4th step, filters (preferably with after deionized water dilution), filtration gained solid is spent deionized water, drying, obtain the block mesoporous material raw powder of hexahedron by crystallization afterproduct;
5th step, by block for gained hexahedron mesoporous material raw powder in Muffle furnace at 250-800 DEG C of temperature lower calcination 10-40 hour, removed template method, obtains the block mesoporous material of hexahedron of removed template method;
6th step, block for the hexahedron of upper step gained removed template method mesoporous silicon oxide 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 the block meso-porous titanium dioxide silicon carrier of described hexahedron and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, and the consumption of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 10-90 % by weight; The consumption being preferably described phosphotungstic acid is 30-60 % by weight, and the consumption of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 40-70 % by weight, takes out pressed powder afterwards, namely obtains the block mesoporous silicon oxide of hexahedron 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 F108.
Method and the condition of described crystallization and removed template method are known to the skilled person, and such as, crystallization temperature is 90-180 DEG C, and be preferably 95-110 DEG C, the time is 10-40 hour, are preferably 12-30 hour; It is 300-600 DEG C that the condition of described removed template method comprises temperature, and be preferably 350-550 DEG C, the time is 8-20 hour, is preferably 10-19 hour.
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.
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, polyethylene glycol oxide-PPOX-polyethylene glycol oxide, is abbreviated as F108, and molecular formula is EO
132pO
60eO
132, commodity are called
the material of F108.
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 D8Advance 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.
By 2.0 grams of F108 and 5.24 gram potassium sulfate K
2sO
4join in the hydrochloric acid of 60 gram of 2 mol/L, mix to F108 and dissolve completely; Again 4.2 grams of ethyl orthosilicates are joined in above-mentioned solution at 38 DEG C of temperature, stir under stir speed (S.S.) is 200r/min after 1 hour and leave standstill 20 hours; Gained solution is transferred in teflon-lined reactor, after filtration, washing, drying, obtain the block mesoporous material raw powder of hexahedron 100 DEG C of crystallization after 24 hours; By the 400 DEG C of calcinings 10 hours in Muffle furnace of block for hexahedron mesoporous material raw powder, removed template method, obtains the block mesoporous silicon oxide (FDU) of hexahedron of removed template method.
Block for above-mentioned 1 gram of hexahedron mesoporous silicon oxide FDU is put into 100ml ball grinder at room temperature state together with 1 gram of phosphotungstic acid, and 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 FDU-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 the block meso-porous titanium dioxide silicon carrier of hexahedron 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 block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron, b is the XRD spectra by the block mesoporous silicon oxide (FDU-HPA) of the hexahedron of ball-milling method load phosphotungstic acid, and c is the XRD spectra of the block mesoporous silicon oxide (FDU-HPA) of hexahedron of the reacted load phosphotungstic acid of quadric catalysis, abscissa is 2 θ, and ordinate is intensity.By finding out in XRD spectra that sample F DU and FDU-HPA occurs 1 diffraction maximum in little angular region significantly.The XRD spectra of block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron and the block mesoporous silicon oxide (FDU-HPA) of hexahedron by the block mesoporous silicon oxide (FDU-HPA) of the hexahedron of ball-milling method load phosphotungstic acid and the reacted load phosphotungstic acid of quadric catalysis is described, there is good mesoporous phase structure, and there is two-dimentional hexagonal structure, consistent (the Sun Jinyu of mesoporous material XRD spectra of this and bibliographical information, Zhao Dongyuan, the synthesis of " six squares " shape high-sequential big-pore mesoporous molecular sieve SBA-15, SCI, 2000, 1 (21): 21 ~ 23).
Fig. 2 is TEM transmission electron microscope picture, wherein, and a
1and a
2be the pore structure schematic diagram of block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron, b is the pore structure schematic diagram of the hexahedron block mesoporous silicon oxide (FDU-HPA) of the phosphotungstic acid by ball-milling method load.From TEM transmission electron microscope picture, block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron all shows two-dimentional hexagonal hole road structure specific to mesoporous material load phosphotungstic acid is forward and backward, show that the pore passage structure of sample substantially remains unchanged after supported catalyst, the conclusion that this conclusion and XRD spectra obtain is consistent.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of block meso-porous titanium dioxide silicon carrier (FDU) of hexahedron, b
1for the microscopic appearance figure of the block mesoporous silicon oxide (FDU-HPA) of the hexahedron passing through ball-milling method load phosphotungstic acid.As seen from the figure, hexahedron block mesoporous silicon oxide FDU microscopic appearance is the bottom surface length of side is 2.5-5 micron, and height is that the hexahedron of 1-10 micron is block, and FDU-HPA microscopic appearance prepared by ball-milling method still keeps hexahedron block substantially, the bottom surface length of side is 2.5-5 micron, and height is 1-10 micron.
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.
Table 1 is the pore structure parameter of the block mesoporous silicon oxide (FDU-HPA) of hexahedron of the block meso-porous titanium dioxide silicon carrier FDU of hexahedron 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, the block mesoporous silicon oxide of hexahedron is after load phosphotungstic acid, and pore volume and specific area all significantly reduce, and this illustrates that phosphotungstic acid enters into the block mesoporous silicon oxide composite inner of hexahedron 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.
The block mesoporous silicon oxide (FDU) of hexahedron is prepared according to the method for embodiment 1.
Block for above-mentioned 1 gram of hexahedron mesoporous silicon oxide FDU is put into 100ml ball grinder at room temperature state together with 2 grams of phosphotungstic acids, and 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 FDU-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 the block meso-porous titanium dioxide silicon carrier of hexahedron 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.
The block mesoporous silicon oxide (FDU) of hexahedron is prepared according to the method for embodiment 1.
Block for above-mentioned 1 gram of hexahedron mesoporous silicon oxide FDU is put into 100ml ball grinder at room temperature state together with 0.5 gram of phosphotungstic acid, and 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 FDU-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 the block meso-porous titanium dioxide silicon carrier of hexahedron is 67 % by weight.
With nitrogen adsorption desorption instrument, this carried phospho-tungstic acid catalyst is characterized.
Table 3
Embodiment 4
The present embodiment is for illustration of the preparation of the hexahedron bulk silicon dioxide with dipping method load phosphotungstic acid
The block mesoporous silicon oxide FDU of 1 gram of hexahedron embodiment 1 prepared 400 DEG C of calcinings 10 hours under nitrogen protection, with eliminating hydroxide and Residual water, thus obtain the block mesoporous silicon oxide of hexahedron through thermal activation.
By block for above-mentioned 1 gram of hexahedron through thermal activation mesoporous silicon oxide FDU 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 FDU-HPA-JZ, 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 20 % by weight, the content of the block meso-porous titanium dioxide silicon carrier of hexahedron is 80 % by weight.
With nitrogen adsorption desorption instrument, 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
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 phosphotungstic acid, 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-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, 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 (FDU-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 95%.
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 (FDU-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 90%.
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 (FDU-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 84%.
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 (FDU-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 85%.
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 (FDU-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 85%.
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 (FDU-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 85%.
EXPERIMENTAL EXAMPLE 7
Ethyl acetate is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, the hexahedron block mesoporous material FDU(called after FDU-HPA-JZ of the carried phospho-tungstic acid that carried phospho-tungstic acid catalyst (FDU-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 99%.
EXPERIMENTAL EXAMPLE 8
Ethyl acetate is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the carried phospho-tungstic acid catalyst (FDU-HPA) of the EXPERIMENTAL EXAMPLE 1 reclaimed is by the hexahedron of EXPERIMENTAL EXAMPLE 7 carried phospho-tungstic acid of the recovery of identical weight block mesoporous material FDU(called after FDU-HPA-JZ) replace, result is: the conversion ratio of acetic acid is 83%, and the selective of ethyl acetate is 99%.
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 (FDU-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 (FDU-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 the block meso-porous titanium dioxide silicon carrier of hexahedron, 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 (12)
1. a carried phospho-tungstic acid catalyst, it is characterized in that, by the block meso-porous titanium dioxide silicon carrier of hexahedron and load, the phosphotungstic acid on the block meso-porous titanium dioxide silicon carrier of described hexahedron 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 the block meso-porous titanium dioxide silicon carrier of described hexahedron is 40-70 % by weight; The bottom surface length of side of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 2.5-5 micron, and height is 1-10 micron, and specific area is 500-700 meters squared per gram, and most probable pore size is 4-6 nanometer, and pore wall thickness is 6-7 nanometer;
Wherein, the block meso-porous titanium dioxide silicon carrier of described hexahedron is obtained by the method comprised the following steps:
(1) template, potassium sulfate and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis are left standstill 1-20 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 5-60 minute under being 100-400r/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 20-50 meters squared per gram, and most probable pore size is 1-7 nanometer, and pore wall thickness is 4-10 nanometer.
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: potassium sulfate: water: hydrogen chloride: esters of silicon acis=1:100-800:10000-30000:10-9000:20-200.
5. the preparation method of a carried phospho-tungstic acid catalyst, wherein, the method comprises: by the block meso-porous titanium dioxide silicon carrier of hexahedron ball milling together with phosphotungstic acid, make phosphotungstic acid load on the block meso-porous titanium dioxide silicon carrier of described hexahedron, with the gross weight of the block meso-porous titanium dioxide silicon carrier of described hexahedron and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 30-60 % by weight, and the consumption of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 40-70 % by weight; The bottom surface length of side of the block meso-porous titanium dioxide silicon carrier of described hexahedron is 2.5-5 micron, and height is 1-10 micron, and specific area is 500-700 meters squared per gram, and most probable pore size is 4-6 nanometer, and pore wall thickness is 6-7 nanometer;
Wherein, the block meso-porous titanium dioxide silicon carrier of described hexahedron is obtained by the method comprised the following steps:
(1) template, potassium sulfate and mixed in hydrochloric acid are fully dissolved to solids;
(2) step (1) gained solution and esters of silicon acis are left standstill 1-20 hour after 25-60 DEG C of temperature, mechanical agitation speed stir 5-60 minute under being 100-400r/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, 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.
7. described preparation method according to claim 5, 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.
8. preparation method according to claim 5, wherein, ratio, polyethylene glycol oxide-PPOX-polyethylene glycol oxide: potassium sulfate: water: hydrogen chloride: esters of silicon acis=1:100-800:10000-30000:10-9000:20-200.
9. the catalyst that the preparation method in claim 5-8 described in any one obtains.
10. the catalyst application in the esterification reaction in claim 1-4 and 9 described in any one.
The preparation method of 11. 1 kinds 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, it is characterized in that, described catalyst is the catalyst in claim 1-4 and 9 described in any one.
12. preparation methods according to claim 11, 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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