CN103586059A - Supported phospho-tungstic acid catalyst, preparation method thereof, applications thereof and preparation method of ethyl acetate - Google Patents
Supported phospho-tungstic acid catalyst, preparation method thereof, applications thereof and preparation method of ethyl acetate Download PDFInfo
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Abstract
The invention discloses a supported phospho-tungstic acid catalyst, a preparation method thereof, applications thereof and a preparation method of ethyl acetate. The catalyst comprises a carrier, and phospho-tungstic acid carried on the carrier. The carrier is spherical mesoporous silica. Based on the total weight of the catalyst, the weight content of the phospho-tungstic acid is 10-90%, and the weight content of the carrier is 10-90%. The particle diameter of the carrier is 3-20 [mu]m. The specific surface area is 1000-2000 m<2>/g. The most probable pore diameter is 1-3 nm. The thickness of a pore wall is 1.5-2.3 nm. According to the catalyst, the phospho-tungstic acid is carried on the specific spherical mesoporous silica carrier, the activity of the catalyst for catalyzing esterification is high, and the activity of the catalyst when being used repetitively for catalyzing the esterification is also high, and therefore the catalyst is recycled and reutilized.
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 of this catalyst in esterification, 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, et al.J.Am.Chem.Soc., 1992,114 (27): 10834-10843), this mesoporous material has high specific surface, regular pore passage structure and narrow pore-size distribution, make mesoporous material obtain very large concern in the application of catalysis, separation, medicine and other fields; Within 1998, Zhao east unit waits people to synthesize a kind of new material-mesoporous material SBA-15 (D.Y.Zhao, J.L.Feng, Q.S.Huo, et al Science 279 (1998) 548-550), this material has the large (1.0cm of cube single-crystal meso-pore material aperture (6-30nm), pore volume of high-sequential
3/ g), the high mechanical properties that thicker hole wall (4-6nm) keeps and good catalytic adsorption performance; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao invent a kind of preparation method (CN1341553A) of mesonic pore molecular sieve carrier material, and this mesoporous material is as heterogeneous reaction catalyst carrier, easily realize separated (Wight, the A.P. of catalyst and product; Davis, M.E.Chem.Rev.2002,102,3589; De Vos, D.E.; Dams, M.; Sels, B.F.; Jacobs, P.A.Chem.Rev.2002,102,3615.).Yet conventional ordered mesoporous material SBA-15 has stronger water suction, moisture absorption ability at present, rod length approaches 5 μ m, and there is adhesion between rod and rod, in catalytic reaction process, be unfavorable for that material transmits in mesopore orbit, this will further aggravate the reunion of ordered mesoporous material, give ordered mesoporous material storage, transport, rear processing and application make troubles.
Esterification catalytic reaction common acid is as catalyst, except traditional inorganic acid, and solid super-strong acid (Van Rhijn, W.M. that the mesoporous material of take is in addition carrier; 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.[，Qin Yongning, Changhai of shutting out, He Yan seam, 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 pair shortcoming of instrument seriously corroded equally, and catalytic activity reduction is fast, and cost is higher.As using mesoporous material as carrier loaded homogeneous catalyst, can avoid instrument corrosion, catalyst is easily realized the separated of catalyst and product, recycling repeatedly.Conventional carrying method is solvent method supported catalyst at present, processes in catalyst process and also must remove added solvent, and 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 existing shortcomings such as, complex process serious to equipment corrosion for catalyzing and synthesizing that the catalyst of ethyl acetate exists, a kind of preparation method of novel catalyst and ethyl acetate for the synthesis of ethyl acetate is provided.
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst is comprised of sphericity mesoporous silicon dioxide carrier and the phosphotungstic acid that loads on described sphericity mesoporous silicon dioxide carrier, the gross weight of described catalyst of take is benchmark, the content of described phosphotungstic acid is 10-90 % by weight, the content of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight, and the particle diameter of described sphericity mesoporous silicon dioxide carrier is 3-20 micron, specific area is 1000-2000 meters squared per gram, most probable aperture is 1.0-3.0 nanometer, pore wall thickness is 1.5-2.3 nanometer.
The present invention also provides a kind of preparation method of carried phospho-tungstic acid catalyst, wherein, the method comprises: by sphericity mesoporous silicon dioxide carrier ball milling together with phosphotungstic acid, phosphotungstic acid is loaded on described sphericity mesoporous silicon dioxide carrier, the gross weight of described sphericity mesoporous silicon dioxide carrier and phosphotungstic acid of take is benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, and the consumption of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight; And the particle diameter of described sphericity mesoporous silicon dioxide carrier is 3-20 micron, specific area is 1000-2000 meters squared per gram, and most probable aperture is 1-3 nanometer, and pore wall thickness is 1.5-2.3 nanometer.
In addition, the present invention also provides the application of described catalyst in esterification.
Also have, the present invention also provides a kind of preparation method of ethyl acetate, wherein, the method comprises: under the existence of 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 loads on specific sphericity mesoporous silicon dioxide 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 catalytic esterification of catalyst is still higher while reusing, and this this carried phospho-tungstic acid catalyst is recovered and cycling and reutilization.Also owing to thering is corrosive phosphotungstic acid, load on sphericity mesoporous silicon dioxide carrier on the other hand, prevented equipment corrosion, so this this carried phospho-tungstic acid catalyst catalyst that is a kind of environmental protection.
In the present invention, by ball-milling method, phosphotungstic acid is carried on specific sphericity mesoporous silicon dioxide carrier, in whole mechanical milling process, do not introduce solvent, process is simple and easy to do, and after mechanical milling process, gained catalyst also keeps spherical, and while carrying out the esterification of catalysis acetic acid and ethanol with this catalyst, catalyst can pass through and reclaim and Reusability, and carried phospho-tungstic acid catalyst provided by the invention can reduce side reaction, raising product purity, etching apparatus, is not conducive to environmental protection.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, and wherein, a is the XRD spectra of sphericity mesoporous silicon dioxide carrier (JKQ), the XRD spectra that b is the sphericity mesoporous silicon dioxide (JKQ-HPA) by ball-milling method load phosphotungstic acid, and abscissa is 2 θ, and ordinate is intensity.
Fig. 2 is TEM transmission electron microscope picture, and wherein, a is the pore structure schematic diagram of sphericity mesoporous silicon dioxide carrier (JKQ), the pore structure schematic diagram that b is the sphericity mesoporous silicon dioxide (JKQ-HPA) by ball-milling method load phosphotungstic acid.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of sphericity mesoporous silicon dioxide carrier (JKQ), b
1and b
2for by ball-milling method load the microscopic appearance figure of the sphericity mesoporous silicon dioxide of phosphotungstic acid (JKQ-HPA).
Fig. 4 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of rod-like mesoporous material SBA-15, the microscopic appearance figure of the rod-like mesoporous material SBA-15 that b is the load phosphotungstic acid prepared by ball-milling method.
Fig. 5 is X-ray diffracting spectrum, wherein, the XRD spectra of the sphericity mesoporous silicon dioxide (JKQ-HPA-JZ) of a infusion process load phosphotungstic acid, abscissa is 2 θ, ordinate is intensity.
Fig. 6 is SEM scanning electron microscope (SEM) photograph, wherein, and a the has been infusion process load microscopic appearance figure of the sphericity mesoporous silicon dioxide of phosphotungstic acid (JKQ-HPA-JZ).
Fig. 7 is TEM transmission electron microscope picture, and wherein, a is the pore structure schematic diagram of the sphericity mesoporous silicon dioxide (JKQ-HPA-JZ) of infusion process load phosphotungstic acid.
The specific embodiment
The invention provides a kind of phosphotungstic acid loading on described sphericity mesoporous silicon dioxide carrier, wherein, this catalyst is comprised of preparing spherical SiO 2 carrier and the phosphotungstic acid that loads on described sphericity mesoporous silicon dioxide carrier, the gross weight of described catalyst of take is benchmark, the content of described phosphotungstic acid is 10-90 % by weight, the content of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight, more preferably in situation, the gross weight of described catalyst of take is benchmark, the content of described phosphotungstic acid is 30-60 % by weight, the content of described sphericity mesoporous silicon dioxide carrier is 40-70 % by weight, and the particle diameter of described sphericity mesoporous silicon dioxide carrier is 3-20 micron, be preferably 10-20 micron, specific area is 1000-2000 meters squared per gram, is preferably 1100-1500 meters squared per gram, more preferably 1200 meters squared per gram, pore volume can be 0.5-1.5 ml/g, is preferably 0.6-1.0 ml/g, most preferably is 0.7 ml/g, most probable aperture is 1.0-3.0 nanometer, is preferably 1.5-2.5 nanometer, more preferably 1.9 nanometers, pore wall thickness is 1.5-2.3 nanometer, is preferably 1.7-2.1 nanometer, and more preferably 1.9 nanometers, 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 650-950 meters squared per gram, is preferably 700-900 meters squared per gram, more preferably 800 meters squared per gram; Pore volume can be 0.1-1.0 ml/g, is preferably 0.3-0.7 ml/g, more preferably 0.5 ml/g; Most probable aperture can be 1.0-3.0 nanometer, is preferably 1.5-2.0 nanometer, more preferably 1.8 nanometers; Pore wall thickness is 1.0-3.0 nanometer, is preferably 1.5-2.5 nanometer, more preferably 2.0 nanometers.
According to the present invention, described carrier is sphericity mesoporous silicon dioxide, and described sphericity mesoporous silicon dioxide carrier is made by the method comprising the following steps:
(1) template and mixed in hydrochloric acid to solids are fully dissolved;
(2) by step (1) gained solution and esters of silicon acis, in temperature, be 25-60 ℃, mechanical agitation speed is under 100-400r/min, to stir standing 5-100 hour after 1-100 hour;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and will filter deionized water washing for gained solid, dry;
(5) by the dry gained crystallization product heating of step (4), removed template method;
Described template is softex kw and Triton X-100 (having another name called triton x-100).
According to the present invention, described esters of silicon acis, Triton X-100, softex kw, acid in acidic aqueous solution and the mol ratio of the water in acidic aqueous solution can change within the specific limits, preferably, described esters of silicon acis, Triton X-100 (triton x-100), softex kw, acid in acidic aqueous solution and the mol ratio of water are 1:0.1-0.5:0.1-0.6:5-50:100-500, more preferably, described esters of silicon acis, Triton X-100 (triton x-100), softex kw, acid in acidic aqueous solution and the mol ratio of water are 1:0.2-0.5:0.2-0.4:10-20:200-300, most preferably, described esters of silicon acis, Triton X-100 (triton x-100), softex kw, acid in acidic aqueous solution and the mol ratio of water are 1:0.4:0.217:13:244.Wherein, the molal quantity of softex kw and Triton X-100 calculates according to the mean molecule quantity of softex kw and Triton X-100.
Under preferable case, described esters of silicon acis can be ethyl orthosilicate.
According to the present invention, described acidic aqueous solution can be any acidic aqueous solution, is preferably the mineral acid aqueous solution, more preferably hydrochloride aqueous solution.
Under preferable case, the condition of described contact comprises that temperature can be 25-60 ℃, is preferably 30-50 ℃, most preferably is 40 ℃.Time can be 10-60 minute, most preferably is 15 minutes.Described contact is preferably under agitation carried out.
Under preferable case, the condition of described crystallization comprises that temperature can be 25-60 ℃, is preferably 30-50 ℃, most preferably is 40 ℃.Time can be 10-40 hour, is preferably 20-30 hour, most preferably is 24 hours.The temperature of described contact and crystallization can be identical or different, as long as in above-mentioned scope.
According to the present invention, the method for described removed template method can be calcination method, and the condition of described calcination method comprises, temperature can be 500-700 ℃, is preferably 600 ℃.Time can be 10-40 hour, is preferably 20-30 hour, most preferably is 24 hours.
Described template can be conventional for example softex kw and the Triton X-100 template using in this area.
The present invention also provides a kind of preparation method of catalyst, wherein, the method comprises: by sphericity mesoporous silicon dioxide carrier ball milling together with phosphotungstic acid, phosphotungstic acid is loaded on described sphericity mesoporous silicon dioxide carrier, the gross weight of described sphericity mesoporous silicon dioxide carrier and phosphotungstic acid of take is benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, the consumption of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight, more preferably, the gross weight of described sphericity mesoporous silicon dioxide carrier and phosphotungstic acid of take is benchmark, the consumption of described phosphotungstic acid is 30-60 % by weight, the consumption of described sphericity mesoporous silicon dioxide carrier is 40-70 % by weight, and the particle diameter of described sphericity mesoporous silicon dioxide carrier is 3-20 micron, be preferably 10-20 micron, specific area is 1000-2000 meters squared per gram, is preferably 1100-1500 meters squared per gram, more preferably 1200 meters squared per gram, pore volume is 0.5-1.5 ml/g, is preferably 0.6-1.0 ml/g, more preferably 0.7 ml/g, most probable aperture is 1.0-3.0 nanometer, is preferably 1.5-2.5 nanometer, more preferably 1.9 nanometers, pore wall thickness is 1.5-2.3 nanometer, is preferably 1.7-2.1 nanometer, more preferably 1.9 nanometers.
To the condition of grinding and concrete operation method, there is no particular limitation, not destroy or substantially not destroy carrier structure and phosphotungstic acid is entered in carrier duct, is as the criterion.Those skilled in the art can select various suitable conditions to implement the present invention according to mentioned above principle.
According to one embodiment of the present invention, the preparation method of described carried phospho-tungstic acid catalyst comprises: sphericity mesoporous silicon dioxide and phosphotungstic acid are joined in the ball grinder of ball mill, 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 ℃, takes out afterwards pressed powder, obtains the sphericity mesoporous silicon dioxide of load phosphotungstic acid.The quantity of abrading-ball depends on the size of ball grinder, and the ball grinder that is 50-150ml for size can be used 1 abrading-ball.The material of described abrading-ball can be agate, polytetrafluoroethylene (PTFE), is preferably polytetrafluoroethylene (PTFE).
According to a kind of specific embodiment of the present invention, the preparation method of described carried phospho-tungstic acid catalyst comprises the following steps:
The 1st step, by softex kw (CTAB) and Triton X-100 (triton x-100), join in hydrochloric acid, being mixed to solids fully dissolves, at 25 ℃ of-60 ℃ of temperature, in previous step gained solution, add esters of silicon acis, the time is 10-60 minute, by molar feed ratio
Esters of silicon acis: Triton X-100 (triton x-100): softex kw: hydrogen chloride: water=1:0.1-0.5:0.1-0.6:5-50:100-500, be preferably 1:0.2-0.5:0.2-0.4:10-20:200-300, be particularly preferably 1:0.4:0.217:13:244.Wherein, the molal quantity of softex kw and Triton X-100 calculates according to the mean molecule quantity of softex kw and Triton X-100,
Being mixed to solids fully dissolves;
The 2nd step, is placed in closed reaction vessel by upper step gained solution, and at 25-60 ℃ of temperature, crystallization is 10 hours-40 hours;
The 3rd step, filters crystallization afterproduct (preferably with after deionized water dilution), will filter deionized water washing for gained solid, dry, obtains the former powder of spherical mesoporous material;
The 4th step, by the former powder of gained spherical mesoporous material, at 500-700 ℃ of calcining 10-40 hour, removed template method, obtains the sphericity mesoporous silicon dioxide of removed template method;
The 6th step, in the ball grinder that the sphericity mesoporous silicon dioxide of upper step gained removed template method and phosphotungstic acid are joined to ball mill, rotating speed be under 300-500r/min in ball grinder temperature be continuously grinding 0.1-100 hour at 15-100 ℃, the gross weight of described sphericity mesoporous silicon dioxide carrier and phosphotungstic acid of take is benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, and the consumption of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight; The consumption that is preferably described phosphotungstic acid is 30-60 % by weight, and the consumption of described sphericity mesoporous silicon dioxide carrier is 40-70 % by weight; Take out afterwards pressed powder, obtain the sphericity mesoporous silicon dioxide of load phosphotungstic acid.
Described template can be conventional for example softex kw and the Triton X-100 template using in this area.
Method and the condition of described crystallization and removed template method are known to the skilled person, and for example, described crystallization condition comprises: temperature can be 25-60 ℃, is preferably 30-50 ℃, most preferably are 40 ℃.Time can be 10-40 hour, is preferably 20-30 hour, most preferably is 24 hours; The temperature of template agent removing can be 500-700 ℃, is preferably 600 ℃.Time can be 10-40 hour, is preferably 20-30 hour, most preferably is 24 hours.
In addition, the present invention also provides the application of described catalyst in esterification.
Also have, the present invention also provides a kind of preparation method of ethyl acetate, wherein, the method comprises: under the existence of 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 esterification, the mol ratio of acetic acid and ethanol can in very large range change, for example, 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, with respect 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, for example, the condition of described esterification can comprise: the temperature of reaction is 100-150 ℃, the time of reaction is 0.5-72 hour, preferably, the temperature of reaction can be 120-140 ℃, and the time of reaction can be 20-30 hour.
According to the present invention, after esterification finishes, can carry out centrifugation to final reactant mixture, by the centrifugal solid formation obtaining vacuum drying 1-24 hour at 25-200 ℃, preferred vacuum drying 6-10 hour at 50-120 ℃, the catalyst that can be recycled.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, phosphotungstic acid (CAS12501-23-4) is a kind of heteropoly acid, buys from ACROS, and mean molecule quantity is 2880.
In following examples, on the X-ray diffractometer that X-ray diffraction analysis is D8Advance in the model purchased from German Bruker AXS company, carry out; Transmission electron microscope analysis is to carry out on the transmission electron microscope of Tecnai 20 in the model purchased from Dutch FEI Co.; In the SEM that scanning electron microscope analysis is XL-30 in the model purchased from U.S. FEI Co., carry out; On the nitrogen adsorption desorption instrument that the experiment of nitrogen adsorption-desorption is Autosorb-1 in the model purchased from U.S. Kang Ta company, carry out.
Softex kw (CTAB) is purchased from lark prestige (J & K), mean molecule quantity 364, CAS:57-09-0; Triton X-100 (triton x-100) is purchased from Shanghai Sheng Gong bioengineering Co., Ltd, article No. TB0198.
The present embodiment is for illustrating according to carried phospho-tungstic acid Catalysts and its preparation method of the present invention.
By 1.5 grams of CTAB(softex kws) join in the hydrochloric acid of 37% the concentrated hydrochloric acid of 29.6 grams and 75 grams of water with the Triton X-100 (Bio-Rad-Laboratories) of 1.5ml, at 40 ℃, mix to CTAB and dissolve completely; 4.35 grams of ethyl orthosilicates being joined in above-mentioned solution, at 40 ℃ of temperature, is under 340r/min, to stir 15 minutes in mechanical agitation speed again, standing 24 hours at 40 ℃; Gained solution is transferred in teflon-lined reactor, 50 ℃ of crystallization, after 24 hours, after filtering, wash, being dried, obtained the former powder of spherical mesoporous material; By the 600 ℃ of calcinings 24 hours in Muffle furnace of the former powder of spherical mesoporous material, removed template method, obtains the sphericity mesoporous silicon dioxide (called after JKQ) of removed template method.
Above-mentioned 1 gram of sphericity mesoporous silicon dioxide JKQ is put into 100ml ball grinder at room temperature state together with 1 gram of phosphotungstic acid, and wherein, the material of ball grinder 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 ℃, obtain 2 grams of target product carried phospho-tungstic acid catalyst, called after JKQ-HPA, wherein, according to weight * 100% of weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, calculate, the total amount of carried phospho-tungstic acid catalyst of take is benchmark, the content of phosphotungstic acid is 50 % by weight, and the content of sphericity mesoporous silicon dioxide 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, and wherein, a is the XRD spectra of sphericity mesoporous silicon dioxide carrier JKQ, and b is the XRD spectra of the sphericity mesoporous silicon dioxide (JKQ-HPA) by ball-milling method load phosphotungstic acid, and abscissa is 2 θ, and ordinate is intensity.From above-mentioned two XRD spectras, sphericity mesoporous silicon dioxide carrier JKQ and JKQ-HPA all have good mesoporous phase structure, consistent (the Xuelei Pang of mesoporous material XRD spectra of this and bibliographical information, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1 ~ 6).
Fig. 2 is TEM transmission electron microscope picture, and wherein, a is the pore structure schematic diagram of sphericity mesoporous silicon dioxide carrier (JKQ), and b is the pore structure schematic diagram of the sphericity mesoporous silicon dioxide (JKQ-HPA) by ball-milling method load phosphotungstic acid.From TEM transmission electron microscope picture, sphericity mesoporous silicon dioxide carrier (JKQ) is in the forward and backward peculiar two-dimentional hexagonal hole of the mesoporous material road structure that all shows of load phosphotungstic acid, the pore passage structure that shows sample substantially remains unchanged after supported catalyst, and the conclusion that this conclusion and XRD spectra obtain is consistent.
Fig. 3 is SEM scanning electron microscope (SEM) photograph, wherein, and a
1and a
2for the microscopic appearance figure of sphericity mesoporous silicon dioxide carrier (JKQ), b
1and b
2for load the microscopic appearance figure of the sphericity mesoporous silicon dioxide of phosphotungstic acid (JKQ-HPA).As seen from the figure, sphericity mesoporous silicon dioxide JKQ microscopic appearance is the Mesoporous Spheres of granularity 3-20 μ m, and JKQ-HPA microscopic appearance prepared by ball-milling method is still basic keeps spherical, granularity 3-20 μ m.
Fig. 4 is SEM scanning electron microscope (SEM) photograph, and wherein, a is the microscopic appearance figure of rod-like mesoporous material SBA-15, the microscopic appearance figure of the rod-like mesoporous material SBA-15 that b is the load phosphotungstic acid prepared by ball-milling method.The bar-shaped mesoporous silicon oxide SBA-15 microscopic appearance of the load phosphotungstic acid of preparing by ball-milling method as shown in Figure 4, is completely destroyed.
The a of Fig. 5 is the XRD spectra of the sphericity mesoporous silicon dioxide (JKQ-HPA-JZ) by infusion process load phosphotungstic acid, and abscissa is 2 θ, and ordinate is intensity.From XRD spectra, sphericity mesoporous silicon dioxide (JKQ-HPA-JZ) by infusion process load phosphotungstic acid has good mesoporous phase structure, consistent (the Xuelei Pang of mesoporous material XRD spectra of this and bibliographical information, Fangqiong Tang, Microporous and mesoporous Materials, 2005 (85): 1 ~ 6).
Fig. 6 is SEM scanning electron microscope (SEM) photograph, wherein, and a the has been infusion process load microscopic appearance figure of the sphericity mesoporous silicon dioxide of phosphotungstic acid (JKQ-HPA-JZ).As seen from the figure, infusion process load the sphericity mesoporous silicon dioxide of phosphotungstic acid (JKQ-HPA-JZ) microscopic appearance is still basic keeps spherical, granularity 3-20 μ m.
Fig. 7 is TEM transmission electron microscope picture, and wherein, a is the pore structure schematic diagram of the sphericity mesoporous silicon dioxide (JKQ-HPA-JZ) of infusion process load phosphotungstic acid.From TEM transmission electron microscope picture, sphericity mesoporous silicon dioxide carrier (JKQ) shows the peculiar two-dimentional hexagonal hole of mesoporous material road structure after load phosphotungstic acid, the pore passage structure that shows sample substantially remains unchanged after supported catalyst, and the conclusion that this conclusion and XRD spectra obtain is consistent.
Table 1 is the pore structure parameter of the sphericity mesoporous silicon dioxide (JKQ-HPA) of sphericity mesoporous silicon dioxide carrier JKQ 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.
Data by upper table 1 can find out, sphericity mesoporous silicon dioxide is after load phosphotungstic acid, and pore volume and specific area all significantly reduce, and this explanation phosphotungstic acid in load-reaction process enters into sphericity mesoporous silicon dioxide composite inner.
The present embodiment is for illustrating according to carried phospho-tungstic acid Catalysts and its preparation method of the present invention.
According to the method for embodiment 1, prepare sphericity mesoporous silicon dioxide (called after JKQ).
Above-mentioned 1 gram of sphericity mesoporous silicon dioxide JKQ 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 ℃, obtain 3 grams of target product carried phospho-tungstic acid catalyst, called after JKQ-HPA-2, wherein, according to weight * 100% of weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, calculate, the total amount of carried phospho-tungstic acid catalyst of take is benchmark, the content of phosphotungstic acid is 67 % by weight, and the content of sphericity mesoporous silicon dioxide carrier is 33 % by weight.
With XRD, ESEM, transmission electron microscope and nitrogen adsorption desorption instrument, this carried phospho-tungstic acid catalyst is characterized.
Table 2
The present embodiment is for illustrating according to carried phospho-tungstic acid Catalysts and its preparation method of the present invention.
According to the method for embodiment 1, prepare sphericity mesoporous silicon dioxide (called after JKQ).
Above-mentioned 1 gram of sphericity mesoporous silicon dioxide JKQ 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 3cm, 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 ℃, obtain 1.5 grams of target product carried phospho-tungstic acid catalyst, called after JKQ-HPA-3, wherein, according to weight * 100% of weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, calculate, the total amount of carried phospho-tungstic acid catalyst of take is benchmark, the content of phosphotungstic acid is 67 % by weight, and the content of sphericity mesoporous silicon dioxide carrier is 33 % by weight.
With XRD, ESEM, transmission electron microscope and nitrogen adsorption desorption instrument, this carried phospho-tungstic acid catalyst is characterized.
Table 3
The present embodiment is for illustrating the preparation with the preparing spherical SiO 2 of dipping method load phosphotungstic acid
By 1 gram of sphericity mesoporous silicon dioxide JKQ of embodiment 1 preparation, 400 ℃ of calcinings 10 hours under nitrogen protection, to remove hydroxyl and remaining moisture, thereby obtain the sphericity mesoporous silicon dioxide through thermal activation.
By above-mentioned 1 gram of sphericity mesoporous silicon dioxide JKQ through thermal activation vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, again 30ml methyl alcohol and 4g phosphotungstic acid are put into 100ml teflon-lined reactor together, capping still, under 35 ℃ of conditions, stir 24 hours, obtain 1.25 grams of target product carried phospho-tungstic acid catalyst, called after JKQ-HPA-4, wherein according to weight * 100% of weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, calculate, the total amount of carried phospho-tungstic acid catalyst of take is benchmark, the content of phosphotungstic acid is 20 % by weight, the content of sphericity mesoporous silicon dioxide carrier is 80 % by weight.
With XRD, the experiment of nitrogen adsorption-desorption, ESEM, transmission electron microscope, X-ray energy spectrometer and nitrogen adsorption desorption instrument, this carried phospho-tungstic acid catalyst is characterized.
Table 4
Comparative example 1
The bar-shaped mesoporous silicon oxide of preparing carried phospho-tungstic acid
By 1 gram of bar-shaped mesoporous silicon oxide SBA-15(purchased from high-tech share Co., Ltd of Jilin University) under room temperature state, put into 100ml ball grinder together with 1 gram of phosphotungstic acid, wherein, the material of ball grinder and ball milling is polytetrafluoroethylene (PTFE), the diameter of abrading-ball is 3mm, quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 ℃, obtains the rod-like mesoporous material (called after SBA-15-HPA) of 2 grams of load phosphotungstic acids.Wherein, according to weight * 100% of weight/carried phospho-tungstic acid catalyst of the carrier of the content of carrier=add, calculate, the total amount of carried phospho-tungstic acid catalyst of take is benchmark, and the content of phosphotungstic acid is 50 % by weight, and the content of sphericity mesoporous silicon dioxide 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 explanation according to the catalytic activity of carried phospho-tungstic acid catalyst of the present invention.
By the vacuum drying 6 hours at 150 ℃ of the carried phospho-tungstic acid catalyst (JKQ-HPA) in embodiment 1, be cooled to after room temperature, take 4 grams, then take 46 grams of ethanol, 60 grams of acetic acid are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 4 hours, be cooled to after room temperature, centrifugation, adopts gc analysis reaction product liquid composition, result is: ethyl acetate is selectively 100%, and acetic acid conversion ratio is 87%.
EXPERIMENTAL EXAMPLE 2
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after carried phospho-tungstic acid catalyst recovery of the present invention.
Carried phospho-tungstic acid catalyst (JKQ-HPA) in EXPERIMENTAL EXAMPLE 1 is reclaimed, and vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 3 grams, take again 34.5 grams of ethanol, 45 grams of acetic acid are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 4 hours, be cooled to after room temperature, centrifugation, adopt gc analysis reaction product liquid composition, result is: ethyl acetate is selectively 100%, and acetic acid conversion ratio is 88%.
EXPERIMENTAL EXAMPLE 3
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of carried phospho-tungstic acid catalyst of the present invention.
By the vacuum drying 6 hours at 150 ℃ of the carried phospho-tungstic acid catalyst (JKQ-HPA-2) in embodiment 2, be cooled to after room temperature, take 2 grams, then take 23 grams of ethanol, 30 grams of acetic acid are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 4 hours, be cooled to after room temperature, centrifugation, adopts gc analysis reaction product liquid composition, result is: ethyl acetate is selectively 98%, and acetic acid conversion ratio is 81.5%.
EXPERIMENTAL EXAMPLE 4
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after carried phospho-tungstic acid catalyst recovery of the present invention.
Carried phospho-tungstic acid catalyst (JKQ-HPA-2) in EXPERIMENTAL EXAMPLE 3 is reclaimed, and vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 1 gram, take again 11.5 grams of ethanol, 15 grams of acetic acid are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 4 hours, be cooled to after room temperature, centrifugation, adopt gc analysis reaction product liquid composition, result is: ethyl acetate is selectively 99%, and acetic acid conversion ratio is 85%.
EXPERIMENTAL EXAMPLE 5
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity of carried phospho-tungstic acid catalyst of the present invention.
By the vacuum drying 6 hours at 150 ℃ of the carried phospho-tungstic acid catalyst (JKQ-HPA-3) in embodiment 3, be cooled to after room temperature, take 2 grams, then take 23 grams of ethanol, 30 grams of acetic acid are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 4 hours, be cooled to after room temperature, centrifugation, adopts gc analysis reaction product liquid composition, result is: ethyl acetate is selectively 99%, and acetic acid conversion ratio is 81%.
EXPERIMENTAL EXAMPLE 6
This EXPERIMENTAL EXAMPLE is used for explanation according to the catalytic activity after carried phospho-tungstic acid catalyst recovery of the present invention.
Carried phospho-tungstic acid catalyst (JKQ-HPA-3) in EXPERIMENTAL EXAMPLE 5 is reclaimed, and vacuum drying 6 hours at 150 ℃, be cooled to after room temperature, take 1 gram, take again 11.5 grams of ethanol, 15 grams of acetic acid are put into 100ml there-necked flask together, add condenser pipe, under 100 ℃ of conditions that add hot reflux, stir 4 hours, be cooled to after room temperature, centrifugation, adopt gc analysis reaction product liquid composition, result is: ethyl acetate is selectively 99%, and acetic acid conversion ratio is 85%.
EXPERIMENTAL EXAMPLE 7
Method according to EXPERIMENTAL EXAMPLE 1 is prepared ethyl acetate, different is, the spherical mesoporous material JKQ(called after JKQ-HPA-4 of the carried phospho-tungstic acid that carried phospho-tungstic acid catalyst (JKQ-HPA) is made by dipping by the embodiment 4 of identical weight) replace, result is: acetic acid conversion ratio is 80%, ethyl acetate be selectively 99%.
EXPERIMENTAL EXAMPLE 8
Method according to EXPERIMENTAL EXAMPLE 2 is prepared ethyl acetate, different is, the carried phospho-tungstic acid catalyst (JKQ-HPA) of the EXPERIMENTAL EXAMPLE 1 reclaiming is by the spherical mesoporous material JKQ(called after JKQ-HPA-4 of EXPERIMENTAL EXAMPLE 7 carried phospho-tungstic acids of the recovery of identical weight) replace, result is: acetic acid conversion ratio is 80.5%, ethyl acetate be selectively 99%.
Experiment comparative example 1
Method according to EXPERIMENTAL EXAMPLE 1 is prepared ethyl acetate, different is, the rod-like mesoporous material SBA-15(called after SBA-15-HPA of the load phosphotungstic acid that carried phospho-tungstic acid catalyst (JKQ-HPA) is made by the comparative example 1 of identical weight) replace, result is: acetic acid conversion ratio is 76%, ethyl acetate be selectively 81%.
Experiment comparative example 2
Method according to EXPERIMENTAL EXAMPLE 2 is prepared ethyl acetate, different is, the carried phospho-tungstic acid catalyst (JKQ-HPA) of the EXPERIMENTAL EXAMPLE 1 reclaiming is by the rod-like mesoporous material SBA-15(called after SBA-15-HPA of the load phosphotungstic acid of the experiment comparative example 1 of the recovery of identical weight) replace, result is: acetic acid conversion ratio is 70%, ethyl acetate be selectively 80%.
By above embodiment 1-4 and comparative example 1 and EXPERIMENTAL EXAMPLE 1-8, experiment comparative example 1, the data of experiment comparative example 2 can be found out, EXPERIMENTAL EXAMPLE 1-8 is obviously than testing the effective of comparative example 1-2, 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 that phosphotungstic acid is carried on sphericity mesoporous silicon dioxide carrier, the catalytic performance of the carried phospho-tungstic acid catalyst obtaining is better, when making to apply this catalyst and carrying out the esterification of catalysis acetic acid and ethanol, side reaction does not produce corrosion to equipment less simultaneously yet, and loaded catalyst of the present invention can pass through and reclaim and Reusability, aftertreatment technology is simple.
Claims (16)
1. a carried phospho-tungstic acid catalyst, it is characterized in that, this catalyst is comprised of sphericity mesoporous silicon dioxide carrier and the phosphotungstic acid that loads on described sphericity mesoporous silicon dioxide carrier, the gross weight of described catalyst of take is benchmark, the content of described phosphotungstic acid is 10-90 % by weight, and the content of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight; And the particle diameter of described sphericity mesoporous silicon dioxide carrier is 3-20 micron, specific area is 1000-2000 meters squared per gram, and most probable aperture is 1-3 nanometer, and pore wall thickness is 1.5-2.3 nanometer.
2. carried phospho-tungstic acid catalyst according to claim 1, wherein, the gross weight of described catalyst of take is benchmark, and the content of described phosphotungstic acid is 30-60 % by weight, and the content of described sphericity mesoporous silicon dioxide carrier is 40-70 % by weight; And the particle diameter of described sphericity mesoporous silicon dioxide carrier is 10-20 micron, specific area is 1100-1500 meters squared per gram, and most probable aperture is 1.5-2.5 nanometer, and pore wall thickness is 1.7-2.1 nanometer.
3. carried phospho-tungstic acid catalyst according to claim 1 and 2, wherein, the specific area of described carried phospho-tungstic acid catalyst is 650-950 meters squared per gram, and most probable aperture is 1-3 nanometer, and pore wall thickness is 1.5-3 nanometer.
4. according to the carried phospho-tungstic acid catalyst described in claim 1 or 3, wherein, described sphericity mesoporous silicon dioxide carrier is made by the method comprising the following steps:
(1) template and mixed in hydrochloric acid to solids are fully dissolved;
(2) by step (1) gained solution and esters of silicon acis, in temperature, be 25-60 ℃, mechanical agitation speed is under 100-400r/min, to stir standing 5-100 hour after 1-100 hour;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and will filter deionized water washing for gained solid, dry;
(5) by the dry products therefrom heating of step (4), removed template method;
Described template is softex kw and Triton X-100.
5. carried phospho-tungstic acid catalyst according to claim 4, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 25-60 ℃, and the time is 10-40 hour; The condition of described removed template method comprises that temperature is 500-700 ℃, and the time is 10-40 hour.
6. according to the carried phospho-tungstic acid catalyst described in claim 4 or 5, wherein, count in molar ratio esters of silicon acis: Triton X-100: softex kw: hydrogen chloride: water=1:0.1-0.5:0.1-0.6:5-50:100-500.
7. the preparation method of a carried phospho-tungstic acid catalyst, wherein, the method comprises: by sphericity mesoporous silicon dioxide carrier ball milling together with phosphotungstic acid, phosphotungstic acid is loaded on described sphericity mesoporous silicon dioxide carrier, the gross weight of described sphericity mesoporous silicon dioxide carrier and phosphotungstic acid of take is benchmark, the consumption of described phosphotungstic acid is 10-90 % by weight, and the consumption of described sphericity mesoporous silicon dioxide carrier is 10-90 % by weight; And the particle diameter of described sphericity mesoporous silicon dioxide carrier is 3-20 micron, specific area is 1000-2000 meters squared per gram, and most probable aperture is 1-3 nanometer, and pore wall thickness is 1.5-2.3 nanometer.
8. preparation method according to claim 7, wherein, the gross weight of described sphericity mesoporous silicon dioxide carrier and phosphotungstic acid of take is benchmark, and the consumption of described phosphotungstic acid is 30-60 % by weight, and the consumption of described sphericity mesoporous silicon dioxide carrier is 40-70 % by weight; The particle diameter of described sphericity mesoporous silicon dioxide carrier is 10-20 micron, and specific area is 1100-1500 meters squared per gram, and most probable aperture is 1.5-2.5 nanometer, and pore wall thickness is 1.7-2.1 nanometer.
9. preparation method according to claim 7, wherein, the condition of described ball milling comprises: ball radius is 2-3mm, and rotating speed is 300-500r/min, and in ball grinder, temperature is 15-100 ℃, and the time is 0.1-100 hour.
10. preparation method according to claim 7, wherein, described sphericity mesoporous silicon dioxide carrier is made by the method comprising the following steps:
(1) template and mixed in hydrochloric acid to solids are fully dissolved;
(2) by step (1) gained solution and esters of silicon acis, in temperature, be 25-60 ℃, mechanical agitation speed is under 100-400r/min, to stir standing 5-100 hour after 1-100 hour;
(3) by step (2) products therefrom crystallization under crystallization condition;
(4) step (3) gained crystallization product is filtered, and will filter deionized water washing for gained solid, dry;
(5) by the dry gained crystallization product heating of step (4), removed template method;
Described template is softex kw and Triton X-100.
11. preparation methods according to claim 10, wherein, described esters of silicon acis is ethyl orthosilicate, and described crystallization condition comprises: temperature is 25-60 ℃, and the time is 10-40 hour; The condition of described removed template method comprises that temperature is 500-700 ℃, and the time is 10-40 hour.
12. according to the preparation method described in claim 10 or 11, wherein, counts in molar ratio esters of silicon acis: Triton X-100: softex kw: hydrogen chloride: water=1:0.1-0.5:0.1-0.6:5-50:100-500.
The catalyst that preparation method in 13. claim 7-12 described in any one makes.
The application of catalyst in esterification described in any one in 14. claim 1-6 and 13.
The preparation method of 15. 1 kinds of ethyl acetate, wherein, the method comprises: under the existence of catalyst, under the condition of esterification, acetic acid is contacted, to obtain ethyl acetate with ethanol, it is characterized in that, described catalyst is the catalyst described in any one in claim 1-6 and 13.
16. preparation methods according to claim 15, wherein, the mol ratio of acetic acid and ethanol is 1:0.5-10, and in the phosphotungstic acid of load in described catalyst, with respect to the acetic acid of 100 weight portions, the consumption of described catalyst is 0.5-50 weight portion.
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| CN113546669B (en) * | 2020-04-24 | 2023-11-14 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent containing phosphotungstic acid modified mesoporous material with high specific surface area, and preparation method and application thereof |
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