CN104248976A - Supported phosphotungstic acid catalyst, preparation method and application thereof, and cyclohexanone glyceryl ketal preparation method - Google Patents
Supported phosphotungstic acid catalyst, preparation method and application thereof, and cyclohexanone glyceryl ketal preparation method Download PDFInfo
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- CN104248976A CN104248976A CN201310267845.2A CN201310267845A CN104248976A CN 104248976 A CN104248976 A CN 104248976A CN 201310267845 A CN201310267845 A CN 201310267845A CN 104248976 A CN104248976 A CN 104248976A
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Abstract
The present invention discloses a supported phosphotungstic acid catalyst, a preparation method and an application thereof, and a cyclohexanone glyceryl ketal preparation method. The catalyst contains, by weight, 50-99 wt% of a spherical attapulgite clay mineral composite carrier and 1-50 wt% of phosphotungstic acid supported on the spherical attapulgite clay mineral composite carrier, wherein the average particle diameter of the composite carrier is 20-50 [mu]m, the specific surface area is 560-600 m<2>/g, the pore volume is 0.5-1.5 ml/g, and the most probable pore size is 9-15 nm. With application of the catalyst to catalyze the ketal reaction of cyclohexanone and glycerol, the side reaction is less, no corrosion is produced on the equipment, the conversion rate is improved, the supported phosphotungstic acid catalyst of the present invention can be recovered so as to be re-used, and the post-treatment process is simple.
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 carried phospho-tungstic acid catalyst in ketal synthesis reaction, and the preparation method of cyclohexanone glycerol ketal.
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 Science279 (1998) 548-550), this material has cube single-crystal meso-pore material aperture (6-30nm), the large (1.0cm of pore volume of high-sequential
3/ g), the high mechanical properties that keeps of thicker hole wall (4-6nm) and good catalytic adsorption performance; Zhao Dongyuan, Yu Chengzhong, Yu Yonghao invent a kind of preparation method (CN1341553A) of mesonic pore molecular sieve carrier material, and this mesoporous material is as heterogeneous reaction catalyst carrier, and what easily realize catalyst and product is separated (Wight, A.P.; Davis, M.E.Chem.Rev.2002,102,3589; De Vos, D.E.; Dams, M.; Sels, B.F.; Jacobs, P.A.Chem.Rev.2002,102,3615.).
Concave-convex clay rod (being called for short recessed soil) is a kind of moisture zeopan crystalline mineral, its basic structural unit is the elementary layer that two-layer silicon-oxy tetrahedron presss from both sides one deck magnesia octahedron composition, in each 2:1 layer, tetrahedral sheet angle is pushed up direction at a certain distance and is put upside down and form a layer chain structure, form the duct parallel with c-axis direction at tetrahedron bar interband, there is unique layer chain crystal structure and the crystal habit of porous.Recessed soil has very high specific area, absorption property, catalytic action, rheological characteristic and heat resistance, can be applied to the fields such as dyeing wastewater process, deodorant, filter aid, cleanser, decolorizer, dytory, thixotropic agent and binding agent.Because recessed native surface area is long-pending large, in crystal structure, there is specific channel, there is a large amount of active centre, there is the shape selective catalysis splitting action that carbonium ion in organic reaction turns use, concerted acid-base catalysis and molecular sieve into.
Conventional ordered mesoporous material SBA-15 microscopic appearance is bar-shaped, compared with being spherical material with microscopic appearance, itself mobility is poor, and its large specific area and high pore volume cause and make it have stronger water suction, moisture absorption ability, this will aggravate the reunion of bar-shaped ordered mesopore material further, to the storage of bar-shaped ordered mesopore material, transport, aft-loaded airfoil and application make troubles.And the geometric shape of microballoon is in the reunion reducing powder, improving the aspects such as its mobility has obvious advantage.Therefore, if the advantages of microballoon, ordered mesoporous material and attapulgite clay mineral is got up, large and the feature of narrowly distributing in the high-specific surface area of ordered mesoporous material, large pore volume, aperture can be retained, the reunion of ordered mesoporous material can be reduced again, increase its mobility, simultaneously due to the introducing of the natural clay mineral material of cheapness, reduce the cost of material, application for ordered mesoporous material is provided better platform by this, and expands the application of ordered mesoporous material.
Along with developing rapidly of chemical industry, ketal kind and demand are constantly increased.Ketal is that a class can be used for the carbonyl-protection of organic compound or the intermediate of pharmaceuticals industry, is even used as special reaction solvent.The synthesis of ketal is generally under strong acid catalyst, and synthesized by ketone and alcohols, catalyst used has sulfuric acid, phosphoric acid, hydrogen chloride gas, p-methyl benzenesulfonic acid, and its advantage is that catalyst is cheap and easy to get.But reaction terminates being separated of rear catalyst and product and need carry out neutralizing and the process such as washing, and not only complex process also produces contaminated wastewater environment, along with the raising of living standards of the people, proposes more and more highland requirement to environmental protection; And Bronsted acid has stronger corrosiveness to equipment.
Therefore, develop a kind of novel catalyst for the synthesis of ketal and become problem in the urgent need to address.
Summary of the invention
The object of the invention is to overcome, the shortcoming such as side reaction many, complex process serious to equipment corrosion that the existing catalyst for Synthesis of Ketal exists, the preparation method of a kind of novel catalyst for the synthesis of ketal and cyclohexanone glycerol ketal is provided.
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst contains spherical attapulgite clay mineral complex carrier and the phosphotungstic acid of load on described spherical attapulgite clay mineral complex carrier, and with the gross weight of this catalyst for benchmark, the content of described phosphotungstic acid is 1-50 % by weight, and the content of described spherical attapulgite clay mineral complex carrier is 50-99 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, and specific area is 560-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable pore size is 9-15 nanometer.
Present invention also offers a kind of preparation method of carried phospho-tungstic acid catalyst, wherein, the method comprises: carry out spraying dry after described spherical attapulgite clay mineral complex carrier and phosphotungstic acid are mixed with slurry under deionized water exists, make phosphotungstic acid load on described spherical attapulgite clay mineral complex carrier, with the gross weight of described spherical attapulgite clay mineral complex carrier and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 1-50 % by weight, and the consumption of described spherical attapulgite clay mineral complex carrier is 50-99 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, and specific area is 560-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable pore size is 9-15 nanometer.
In addition, present invention also offers the application of described catalyst in ketal reaction.
Also have, present invention also offers a kind of preparation method of cyclohexanone glycerol ketal, wherein, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with glycerine, to obtain ketal, wherein, described catalyst is carried phospho-tungstic acid catalyst provided by the invention.
In the present invention, by spray drying process, phosphotungstic acid is carried on specific spherical attapulgite clay mineral complex carrier, and when using this catalyst to carry out the reaction of catalysis of pimelinketone and glycerine, catalyst can through reclaiming Reusability, and carried phospho-tungstic acid catalyst provided by the invention have can reduce side reaction, improve conversion ratio, not etching apparatus, aftertreatment technology is simple and be conducive to the advantages such as environmental protection.
Accompanying drawing explanation
Fig. 1 is X-ray diffracting spectrum, wherein, the XRD spectra that the XRD spectra that a is spherical attapulgite clay mineral complex carrier (MBQGJAT), b are the spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) by spray drying process load phosphotungstic acid, abscissa is 2 θ, and ordinate is intensity;
Fig. 2 A is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical attapulgite clay mineral complex carrier (MBQGJAT);
Fig. 2 B is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the multiplication factor of spherical attapulgite clay mineral complex carrier (MBQGJAT);
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) by spray drying process load phosphotungstic acid.
Detailed description of the invention
The invention provides a kind of carried phospho-tungstic acid catalyst, wherein, this catalyst contains spherical attapulgite clay mineral complex carrier and the phosphotungstic acid of load on described spherical attapulgite clay mineral complex carrier, and with the gross weight of this catalyst for benchmark, the content of described phosphotungstic acid is 1-50 % by weight, and the content of described spherical attapulgite clay mineral complex carrier is 50-99 % by weight; More preferably in situation, with the gross weight of described catalyst for benchmark, the content of described phosphotungstic acid is 5-45 % by weight, and the content of described spherical attapulgite clay mineral complex carrier is 55-95 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, is preferably 20-40 micron; Specific area is 560-600 meters squared per gram, is preferably 580-600 meters squared per gram, is more preferably 590 meters squared per gram; Pore volume is 0.5-1.5 ml/g, is preferably 0.8-1.3 ml/g, is more preferably 1.2 mls/g; Most probable pore size is 9-15 nanometer, is preferably 9-12 nanometer, is more preferably 9.6 nanometers; In this case, not only can obtain gratifying catalytic effect, but also can reduce costs.
According to the present invention, the mean particle diameter of described carried phospho-tungstic acid catalyst is 20-50 micron, and specific area is 350-440 meters squared per gram, is preferably 360-400 meters squared per gram, is more preferably 380 meters squared per gram; Pore volume is 0.1-1 ml/g, is preferably 0.2-0.8 ml/g, is more preferably 0.5 ml/g; Most probable pore size is 9-15 nanometer, is preferably 9-12 nanometer, is more preferably 9.9 nanometers.
According to the present invention, described carrier is spherical attapulgite clay mineral complex carrier, and described spherical attapulgite clay mineral complex carrier can be prepared by the method comprised the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and acidic aqueous solution being carried out first time contacts, and will gained mixture crystallization, washing, suction filtration after first time contact;
(2) waterglass and inorganic acid are carried out second time to contact, and by the washing of gained mixture, suction filtration after second time contact;
(3) by the mesoporous silicon oxide filter cake prepared by (1) and the silica gel filter cake ball milling together with attapulgite clay mineral prepared by (2);
(4) spraying dry is carried out after the pressed powder obtained by (3) being mixed with slurry under deionized water exists;
(5) will be heated by (4) gained spraying dry afterproduct, removed template method.
According to the present invention, described template can be various triblock copolymer polyglycerols-polyethylene glycol-glycerine template that this area routine uses, and can be such as that the commodity that Aldrich company produces are called P123, molecular formula be EO
20pO
70eO
20template.
According to the present invention, the kind of described acidic aqueous solution has no particular limits, and its pH value can be 1-6, and more preferably pH is 3-5; Preferably, described acidic aqueous solution is the acetic acid of 1-5mol/L and the cushioning liquid of sodium acetate.
According to the present invention, under preferable case, the described temperature that the condition that tetramethoxy-silicane contacted with the described first time of acidic aqueous solution comprised can be 10-60 DEG C, and the time can be 10-72 hour, and described first time contact is preferably carried out under agitation; Method and the condition of described crystallization are known to the skilled person, and such as, crystallization temperature can be 30-150 DEG C, and crystallization time can be 10-72 hour.
According to the present invention, under preferable case, the temperature of described second time contact is 10-60 DEG C, and the time is 1-5 hour; Waterglass and inorganic acid are not specifically particularly limited to, described waterglass is the solution of sodium metasilicate, described inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid, and usual described inorganic acid is solution, and the pH value of described waterglass and described inorganic acid mixed solution is 2-4; Described waterglass: described inorganic acid weight ratio is 3-6:1.
Described suction filtration separation is the mode of a kind of separating liquid well-known to those skilled in the art and solid particle, for utilizing air pressure, and the mixture of separating liquid and solid particle or liquid and liquid; The mode of washing that described washing is well known to those skilled in the art, be preferably washing, pure wash in one or more.
According to the present invention, to the condition of grinding and concrete operation method, there is no particular limitation, with do not destroy or substantially do not destroy carrier structure and make silica gel, attapulgite clay mineral enters in carrier duct and is as the criterion.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 attapulgite clay mineral complex carrier comprises: join in the ball grinder of ball mill by mesoporous silicon oxide filter cake, silica gel filter cake and attapulgite clay mineral, ball grinder inwall is polytetrafluoroethyllining lining, the diameter of abrading-ball is 2-3mm, and rotating speed is 300-500r/min.In ball grinder, temperature is continuously grinding 0.1-100 hour at 15-100 DEG C, takes out pressed powder afterwards.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 agate; Pressed powder after ball milling is mixed with slurry under deionized water exists at temperature is 25 ~ 60 DEG C, and then this slurry is joined High Rotation Speed in atomizer, rotating speed is 10000-15000r/min, is preferably 12000r/min.
According to the present invention, there is no particular limitation for the condition of described removed template method, and such as, temperature can be 300-600 DEG C, and the time can be 10-80 hour.
According to the present invention, in the process preparing mesoporous silicon oxide filter cake, triblock copolymer polyglycerol-polyethylene glycol-glycerine, ethanol, acidic aqueous solution, the weight ratio of trimethylpentane and tetramethoxy-silicane can change within the specific limits, triblock copolymer polyglycerol-polyethylene glycol-glycerine, ethanol, acidic aqueous solution, the mol ratio of trimethylpentane and tetramethoxy-silicane can be 1:100-500:150-900:200-500:50-200, be preferably 1:200-400:300-600:250-400:70-150, be more preferably 1:212.76:487.2:304.73:81.16.Wherein, the molal quantity of polyglycerol-polyethylene glycol-glycerine calculates according to the mean molecule quantity of polyglycerol-polyethylene glycol-glycerine and obtains.
Present invention also offers a kind of preparation method of carried phospho-tungstic acid catalyst, wherein, the method comprises: carry out spraying dry after described spherical attapulgite clay mineral complex carrier and phosphotungstic acid are mixed with slurry under deionized water exists, and makes phosphotungstic acid load on described spherical attapulgite clay mineral complex carrier; With the gross weight of described spherical attapulgite clay mineral complex carrier and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 1-50 % by weight, and the consumption of described spherical attapulgite clay mineral complex carrier is 50-99 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, and specific area is 560-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable pore size is 9-15 nanometer.
According to one embodiment of the present invention, the preparation method of described carried phospho-tungstic acid catalyst comprises: described spherical attapulgite clay mineral complex carrier and described phosphotungstic acid are stirred 1-24 hour under deionized water exists at 25-60 DEG C of temperature, be mixed with slurry, in molar ratio, spherical attapulgite clay mineral complex carrier: deionized water: phosphotungstic acid can be 1:15-35:0.5-1.5; Spherical attapulgite clay mineral complex carrier: deionized water: phosphotungstic acid can be preferably 1:20-25:0.8-1.2; Spherical attapulgite clay mineral complex carrier: deionized water: phosphotungstic acid can be more preferably 1:25:1, then this slurry is joined High Rotation Speed in atomizer, rotating speed is 10000-15000r/min, be preferably 12000r/min, obtain the catalyst of the spherical attapulgite clay mineral complex carrier of load phosphotungstic acid.
According to the present invention, the size of described spherical attapulgite clay mineral complex carrier can in very large range change, and preferably, the mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, is preferably 20-40 micron; Specific area is 560-600 meters squared per gram, is preferably 580-600 meters squared per gram, is more preferably 590 meters squared per gram; Pore volume is 0.5-1.5 ml/g, is preferably 0.8-1.3 ml/g, is more preferably 1.2 mls/g; Most probable pore size is 9-15 nanometer, is preferably 9-12 nanometer, is more preferably 9.6 nanometers.
According to the present invention, described spherical attapulgite clay mineral complex carrier can be prepared by the method comprised the following steps:
(1) under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and acidic aqueous solution being carried out first time contacts, and will gained mixture crystallization, washing, suction filtration after first time contact;
(2) waterglass and inorganic acid are carried out second time to contact, and by the washing of gained mixture, suction filtration after second time contact;
(3) by the mesoporous silicon oxide filter cake prepared by (1) and the silica gel filter cake ball milling together with attapulgite clay mineral prepared by (2);
(4) spraying dry is carried out after the pressed powder obtained by (3) being mixed with slurry under deionized water exists;
(5) will be heated by (4) gained spraying dry afterproduct, removed template method.
According to the present invention, described template can be various triblock copolymer polyglycerols-polyethylene glycol-glycerine template that this area routine uses, and can be such as that the commodity that Aldrich company produces are called P123, molecular formula be EO
20pO
70eO
20template.
According to the present invention, the kind of described acidic aqueous solution has no particular limits, and its pH value can be 1-6, and more preferably pH is 3-5; Preferably, described acidic aqueous solution is the acetic acid of 1-5mol/L and the cushioning liquid of sodium acetate.
According to the present invention, under preferable case, the described temperature that the condition that tetramethoxy-silicane contacted with the described first time of acidic aqueous solution comprised can be 10-60 DEG C, and the time can be 10-72 hour, and described first time contact is preferably carried out under agitation; Method and the condition of described crystallization are known to the skilled person, and such as, crystallization temperature can be 30-150 DEG C, and crystallization time can be 10-72 hour.
According to the present invention, under preferable case, the temperature of described second time contact is 10-60 DEG C, and the time is 1-5 hour; Described waterglass and inorganic acid are not specifically particularly limited to, preferably, described waterglass is sodium metasilicate, and described inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid, usual described inorganic acid is solution, and the pH value of the solution of described waterglass and described inorganic acid is 2-4; Described waterglass: described inorganic acid weight ratio is 3-6:1.
Described suction filtration separation is the mode of a kind of separating liquid well-known to those skilled in the art and solid particle, for utilizing air pressure, and the mixture of separating liquid and solid particle or liquid and liquid; The mode of washing that described washing is well known to those skilled in the art, be preferably washing, pure wash in one or more.
According to the present invention, to the condition of grinding and concrete operation method, there is no particular limitation, with do not destroy or substantially do not destroy carrier structure and make silica gel, attapulgite clay mineral enters in carrier duct and is as the criterion.Those skilled in the art can select various suitable condition to implement the present invention according to mentioned above principle.
According to the present invention, to spray-dired condition and concrete operation method, there is no particular limitation, and those skilled in the art can select various suitable condition to implement the present invention.
According to one embodiment of the present invention, the preparation method of described attapulgite clay mineral complex carrier comprises: join in the ball grinder of ball mill by mesoporous silicon oxide filter cake, silica gel filter cake and attapulgite clay mineral, ball grinder inwall is polytetrafluoroethyllining lining, the diameter of abrading-ball is 2-3mm, and rotating speed is 300-500r/min.In ball grinder, temperature is continuously grinding 0.1-100 hour at 15-100 DEG C, takes out pressed powder afterwards.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 agate; Pressed powder after ball milling is mixed with mixture slurry under deionized water exists at temperature is 25 ~ 60 DEG C, and then this slurry is joined High Rotation Speed in atomizer, rotating speed is 10000-15000r/min, is preferably 12000r/min.
According to the present invention, there is no particular limitation for the condition of described removed template method, and such as, temperature can be 300-600 DEG C, and the time can be 10-80 hour.
According to the present invention, in the process preparing mesoporous silicon oxide filter cake, triblock copolymer polyglycerol-polyethylene glycol-glycerine, ethanol, acidic aqueous solution, the mol ratio of trimethylpentane and tetramethoxy-silicane can change within the specific limits, triblock copolymer polyglycerol-polyethylene glycol-glycerine, ethanol, acidic aqueous solution, the mol ratio of trimethylpentane and tetramethoxy-silicane is 1:100-500:150-900:200-500:50-200, be preferably 1:200-400:300-600:250-400:70-150, be more preferably 1:212.76:487.2:304.73:81.16.Wherein, the molal quantity of polyglycerol-polyethylene glycol-glycerine calculates according to the mean molecule quantity of polyglycerol-polyethylene glycol-glycerine and obtains.
According to one embodiment of the present invention, the preparation method of described carried phospho-tungstic acid catalyst comprises: spherical attapulgite clay mineral complex carrier and phosphotungstic acid are stirred to dissolving under deionized water exists at 25 DEG C of-60 DEG C of temperature, be mixed with mixture slurry, spherical attapulgite clay mineral complex carrier: deionized water: the mol ratio of phosphotungstic acid can be 1:15-35:0.5-1.5, spherical attapulgite clay mineral complex carrier: deionized water: the mol ratio of phosphotungstic acid can be preferably 1:20-25:0.8-1.2, spherical attapulgite clay mineral complex carrier: deionized water: the mol ratio of phosphotungstic acid can be more preferably 1:25:1, and spraying dry is carried out at 100 DEG C of-300 DEG C of temperature, preferably at 200 DEG C of temperature, carry out spraying dry, obtain carried phospho-tungstic acid catalyst.
In addition, present invention also offers the application of described catalyst in ketal reaction.
Further, present invention also offers a kind of preparation method of ketal, wherein, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with glycerine, to obtain ketal, wherein, described catalyst is carried phospho-tungstic acid catalyst provided by the invention.
According to the present invention, in ketal reaction, the mol ratio of cyclohexanone and glycerine can in very large range change, and such as, the mol ratio of cyclohexanone and glycerine can be 1:0.5-10, 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 cyclohexanone of 100 weight portions, the consumption of described catalyst can be 1-15 weight portion, is more preferably 2-14 weight portion.
In the present invention, the condition of described ketal reaction is conventionally known to one of skill in the art, and such as, the condition of described ketal reaction can comprise: under back flow reaction condition, and the time of reaction is 1-10 hour, and preferably, the time of reaction can be 2-8 hour.
According to the present invention, after ketal reaction terminates, centrifugation can be carried out to final reactant mixture, by the centrifugal solid formation obtained vacuum drying 1-24 hour at 25-200 DEG C, preferably vacuum drying 6-10 hour at 50-120 DEG C, the catalyst that can be recycled.
Below in conjunction with embodiment, the present invention is described in detail.
In following examples, polyglycerol-polyethylene glycol-glycerine, is abbreviated as P123, and molecular formula is EO
20pO
70eO
20, be the material of 9003-11-6 in the registration number of U.S. chemical abstract, its average molecular mass Mn=5800.
In following examples, X-ray diffraction analysis is that the X-ray diffractometer of D8Advance carries out in the model purchased from German Bruker AXS company; Scanning electron microscope analysis is that the SEM of XL-30 is carried out in the model of purchased from American FEI Co.; Elementary analysis is that 7500CX instrument carries out in purchased from American An Jielun company model, and pore structure study tests at U.S. Autosorb-1 type nitrogen adsorption desorption instrument; Reaction product liquid phase composition analysis is carrying out purchased from Britain Agilent company 7890A/5973N gas chromatograph-mass spectrometer.
Embodiment 1
The preparation of spherical attapulgite clay mineral complex carrier:
1.0 grams of triblock copolymer polyglycerol-polyethylene glycol-glycerine and 1.69 grams of ethanol are joined in the acetic acid of 28ml and the cushioning liquid (pH=4.4) of sodium acetate, at 15 DEG C, be stirred to polyglycerol-polyethylene glycol-glycerine dissolve completely, afterwards the trimethylpentane of 6g is joined in above-mentioned solution, 15 DEG C are stirred after 10 hours, again 2.13 grams of tetramethoxy-silicanes are joined in above-mentioned solution, 15 DEG C are stirred after 20 hours, solution is transferred in teflon-lined reactor, at 60 DEG C baking oven crystallization after 24 hours through suction filtration, mesoporous silicon oxide filter cake is obtained after distilled water washing.
By concentration be 15 % by weight waterglass and concentration be 12 % by weight sulfuric acid solution, and by waterglass: sulfuric acid weight ratio=5:1 carries out fully reaction 1.5 hours, adjusting pH with the sulfuric acid that concentration is 98 % by weight is 3, and reaction mass is washed till sodium ions content through suction filtration, distilled water is 0.02 % by weight, obtain silica gel filter cake.
10 of above-mentioned preparation grams of mesoporous silicon oxide filter cakes, 10 grams of silica gel filter cakes and 10 grams of attapulgite clay minerals are put into 100ml ball grinder together, and wherein, ball grinder material is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 DEG C, obtains 30 grams of pressed powders; This pressed powder is dissolved at 25 DEG C in 100 grams of deionized waters, spraying dry under rotating speed is 12000r/min; By the 500 DEG C of calcinings 24 hours in Muffle furnace of the product that obtains after spraying dry, removed template method, obtains the spherical attapulgite clay mineral complex carrier of target product of 30 grams of removed template methods, called after MBQGJAT.
Above-mentioned 30 grams of spherical attapulgite clay mineral complex carriers are put into deionized water at 25 DEG C of temperature together with phosphotungstic acid, be stirred to dissolving, and spherical attapulgite clay mineral complex carrier: deionized water: the mol ratio of phosphotungstic acid is 1:25:1, and spraying dry is carried out at 200 DEG C of temperature, obtain the spherical attapulgite clay mineral complex carrier of load phosphotungstic acid, called after MBQGJAT-HPA-1.
With XRD, ESEM and xrf analysis instrument, this carried phospho-tungstic acid catalyst is characterized.
Fig. 1 is X-ray diffracting spectrum, wherein, the XRD spectra that the XRD spectra that a is spherical attapulgite clay mineral complex carrier (MBQGJAT), b are the spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) by spray drying process load phosphotungstic acid, abscissa is 2 θ, and ordinate is intensity.The low-angle spectrum peak occurred from XRD spectra, the XRD spectra a of spherical attapulgite clay mineral complex carrier (MBQGJAT), all has the hexagonal hole road structure of 2D specific to mesoporous material by the XRD spectra b of the spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) of spray drying process load phosphotungstic acid.
Fig. 2 A and Fig. 2 B is SEM scanning electron microscope (SEM) photograph, and wherein, Fig. 2 A is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical attapulgite clay mineral complex carrier (MBQGJAT); Fig. 2 B is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of the multiplication factor of spherical attapulgite clay mineral complex carrier (MBQGJAT).As seen from the figure, the microscopic appearance of spherical attapulgite clay mineral complex carrier (MBQGJAT) to be average particle size the be Mesoporous Spheres of 20-50 μm.
Fig. 3 is the SEM scanning electron microscope (SEM) photograph of the microscopic appearance of spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) by spray drying process load phosphotungstic acid.As seen from the figure, keep spherical by the microscopic appearance of the spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) of spray drying process load phosphotungstic acid is still basic, average particle size is 20-50 μm.
Table 1 is the pore structure parameter of the spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-1) of spherical attapulgite clay mineral complex carrier (MBQGJAT) and load phosphotungstic acid.
Table 1
As can be seen from the data of upper table 1, sphericity mesoporous silicon dioxide is after load phosphotungstic acid, pore volume and specific area all significantly reduce, and, shown that by elemental analyser analysis in the sample of load phosphotungstic acid, phosphorus content is 0.3 % by weight, W content is 15 % by weight, and this illustrates that phosphotungstic acid enters into sphericity mesoporous silicon dioxide composite inner in load-reaction process.But sphericity mesoporous silicon dioxide is after load phosphotungstic acid, and most probable pore size slightly increases, this be due in the process of load phosphotungstic acid ball clay mineral complex carrier hole wall to some extent fragmentation cause its most probable pore size to increase.
Embodiment 2
Mesoporous silicon oxide filter cake is prepared by the method identical with embodiment 1, difference be silica gel filter cake make the waterglass by by concentration being 15 % by weight and concentration be 12 % by weight hydrochloric acid solution, and by waterglass: hydrochloric acid weight ratio=3:1 carries out fully reaction 1.5 hours, adjusting pH with the hydrochloric acid that concentration is 37 % by weight is 2, and reaction mass is washed till sodium ions content through suction filtration, distilled water is 0.2 % by weight, prepare.
10 of above-mentioned preparation grams of mesoporous silicon oxide filter cakes, 10 grams of silica gel filter cakes and 10 grams of attapulgite clay minerals are put into 100ml ball grinder together, and wherein, ball grinder material is polytetrafluoroethylene (PTFE), Material quality of grinding balls is agate, the diameter of abrading-ball is 3mm, and quantity is 1, and rotating speed is 400r/min.Closure ball grinding jar, in ball grinder, temperature is ball milling 1 hour at 60 DEG C, obtains 30 grams of pressed powders; This pressed powder is dissolved at 60 DEG C in 100 grams of deionized waters, spraying dry under rotating speed is 12000r/min; By the 500 DEG C of calcinings 24 hours in Muffle furnace of the product that obtains after spraying dry, removed template method, obtains the spherical attapulgite clay mineral complex carrier of target product of gram removed template method, called after MBQGJAT-2.
Above-mentioned 30 grams of spherical attapulgite clay mineral complex carriers are put into deionized water at 25 DEG C of temperature together with phosphotungstic acid, be stirred to dissolving, and spherical attapulgite clay mineral complex carrier: deionized water: the mol ratio of phosphotungstic acid is 1:15:0.5, and spraying dry is carried out at 200 DEG C of temperature, obtain the spherical attapulgite clay mineral complex carrier of load phosphotungstic acid, called after MBQGJAT-HPA-2.
Table 2 is the pore structure parameter of the spherical attapulgite clay mineral complex carrier (MBQGJAT-HPA-2) of spherical attapulgite clay mineral complex carrier (MBQGJAT-2) and load phosphotungstic acid.
Table 2
As can be seen from the data of upper table 2, sphericity mesoporous silicon dioxide is after load phosphotungstic acid, pore volume and specific area all significantly reduce, and, shown that by elemental analyser analysis in the sample of load phosphotungstic acid, phosphorus content is 0.2 % by weight, W content is 14 % by weight, and this illustrates that phosphotungstic acid enters into sphericity mesoporous silicon dioxide composite inner in load-reaction process.
Comparative example 1
Identical with the method that embodiment 1 prepares carried phospho-tungstic acid catalyst, institute's difference is not add attapulgite clay mineral in this preparation method, obtains carried phospho-tungstic acid catalyst, called after MBQGJ-HPA-3.
Comparative example 2
Identical with the method that embodiment 1 prepares carried phospho-tungstic acid catalyst, institute's difference is not carry out spray-dired method step in this preparation method, obtains carried phospho-tungstic acid catalyst, called after MBQGJAT-HPA-QM-4.
Comparative example 3
Identical with the method that embodiment 1 prepares carried phospho-tungstic acid catalyst, institute's difference is the method step not carrying out ball milling in this preparation method, obtains carried phospho-tungstic acid catalyst, called after MBQGJAT-HPA-PW-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 (MBQGJAT-HPA-1) in embodiment 1, after being cooled to room temperature, take 0.5 gram, take 11.3 grams of cyclohexanone again and 100ml there-necked flask put into successively by 9.2 grams of glycerine, stir 2 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, in course of reaction side reaction few and to equipment produce corrosion, adopt gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: the conversion ratio of cyclohexanone is 83%, the selective of cyclohexanone-glycerol ketal is 99%.
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 (MBQGJAT-HPA-1) in EXPERIMENTAL EXAMPLE 1 is reclaimed, and vacuum drying 6 hours at 150 DEG C, after being cooled to room temperature, take 0.5 gram, take 11.3 grams of cyclohexanone again and 100ml there-necked flask put into successively by 9.2 grams of glycerine, stir 2 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, in course of reaction side reaction few and to equipment produce corrosion, adopt gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: the conversion ratio of cyclohexanone is 82%, the selective of cyclohexanone-glycerol ketal is 99%.
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 (MBQGJAT-HPA-2) in embodiment 2, after being cooled to room temperature, take 1 gram, take 22.6 grams of cyclohexanone again and 100ml there-necked flask put into successively by 18.4 grams of glycerine, stir 2 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, in course of reaction side reaction few and to equipment produce corrosion, adopt gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: the conversion ratio of cyclohexanone is 81.5%, the selective of cyclohexanone-glycerol ketal is 99%.
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 (MBQGJAT-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 22.6 grams of cyclohexanone again and 100ml there-necked flask put into successively by 18.4 grams of glycerine, stir 2 hours under adding the condition of hot reflux at 100 DEG C, after being cooled to room temperature, centrifugation, in course of reaction side reaction few and to equipment produce corrosion, adopt gas chromatograph-mass spectrometer analytical reactions product liquid phase ingredient, result: the conversion ratio of cyclohexanone is 81%, the selective of cyclohexanone-glycerol ketal is 99%.
Experimental comparison's example 1
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, carried phospho-tungstic acid catalyst (MBQGJAT-HPA-1) is replaced by the carried phospho-tungstic acid catalyst (MBQGJ-HPA-3) that the comparative example 1 of identical weight is obtained, result: in course of reaction side reaction many and to equipment produce corrosion, the conversion ratio of cyclohexanone is 80%, and cyclohexanone-glycerol ketal is selective is 99%.
Experimental comparison's example 2
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the carried phospho-tungstic acid catalyst (MBQGJAT-HPA-1) of the EXPERIMENTAL EXAMPLE 1 reclaimed is replaced by the load phosphotungstic acid catalyst (MBQGJ-HPA-3) of Experimental comparison's example 1 of the recovery of identical weight, result: in course of reaction side reaction many and to equipment produce corrosion, the conversion ratio of cyclohexanone is 71%, and cyclohexanone-glycerol ketal is selective is 99%
Experimental comparison's example 3
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, carried phospho-tungstic acid catalyst (MBQGJAT-HPA-1) is replaced by the carried phospho-tungstic acid catalyst (MBQGJAT-HPA-QM-4) that the comparative example 2 of identical weight is obtained, result: in course of reaction side reaction many and to equipment produce corrosion, the conversion ratio of cyclohexanone is 79%, and cyclohexanone-glycerol ketal is selective is 99%.
Experimental comparison's example 4
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the carried phospho-tungstic acid catalyst (MBQGJAT-HPA-1) of the EXPERIMENTAL EXAMPLE 1 reclaimed is replaced by the load phosphotungstic acid catalyst (MBQGJAT-HPA-QM-4) of Experimental comparison's example 2 of the recovery of identical weight, result: in course of reaction side reaction many and to equipment produce corrosion, the conversion ratio of cyclohexanone is 68%, and cyclohexanone-glycerol ketal is selective is 99%.
Experimental comparison's example 5
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 1, unlike, carried phospho-tungstic acid catalyst (MBQGJAT-HPA-1) is replaced by the carried phospho-tungstic acid catalyst (MBQGJAT-HPA-PW-5) that the comparative example 3 of identical weight is obtained, result: in course of reaction side reaction many and to equipment produce corrosion, the conversion ratio of cyclohexanone is 73%, and cyclohexanone-glycerol ketal is selective is 99%.
Experimental comparison's example 6
Ketal is prepared according to the method for EXPERIMENTAL EXAMPLE 2, unlike, the carried phospho-tungstic acid catalyst (MBQGJAT-HPA-1) of the EXPERIMENTAL EXAMPLE 1 reclaimed is replaced by the load phosphotungstic acid catalyst (MBQGJAT-HPA-PW-5) of Experimental comparison's example 3 of the recovery of identical weight, result: in course of reaction side reaction many and to equipment produce corrosion, the conversion ratio of cyclohexanone is 63%, and cyclohexanone-glycerol ketal is selective is 99%.
By above embodiment 1-2 and comparative example 1-3 and EXPERIMENTAL EXAMPLE 1-4, the data of Experimental comparison's example 1-6 can be found out, EXPERIMENTAL EXAMPLE 1-4 obviously than Experimental comparison example 1-6 effective, illustrate and adopt spray drying process to be carried on by phosphotungstic acid on spherical attapulgite clay mineral complex carrier, the catalytic performance of the carried phospho-tungstic acid catalyst obtained is better, make to apply this catalyst when carrying out the ketal reaction of catalysis of pimelinketone and glycerine, side reaction does not also produce corrosion to equipment less, conversion ratio improves simultaneously, and carried phospho-tungstic acid catalyst of the present invention can through and recovery and Reusability, aftertreatment technology is simple.
Claims (20)
1. a carried phospho-tungstic acid catalyst, it is characterized in that, this catalyst contains spherical attapulgite clay mineral complex carrier and the phosphotungstic acid of load on described spherical attapulgite clay mineral complex carrier, and with the gross weight of this catalyst for benchmark, the content of described phosphotungstic acid is 1-50 % by weight, and the content of described spherical attapulgite clay mineral complex carrier is 50-99 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, and specific area is 560-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable pore size is 9-15 nanometer.
2. carried phospho-tungstic acid catalyst according to claim 1, wherein, with the gross weight of this catalyst for benchmark, the content of described phosphotungstic acid is 5-45 % by weight, and the content of described spherical attapulgite clay mineral complex carrier is 55-95 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-40 micron, and specific area is 580-600 meters squared per gram, and pore volume is 0.8-1.3 ml/g, and most probable pore size is 9-12 nanometer.
3. carried phospho-tungstic acid catalyst according to claim 1, wherein, the mean particle diameter of described carried phospho-tungstic acid catalyst is 20-50 micron, and specific area is 350-440 meters squared per gram, pore volume is 0.1-1 ml/g, and most probable pore size is 9-15 nanometer.
4. the carried phospho-tungstic acid catalyst according to claim 1 or 3, wherein, the preparation of described spherical attapulgite clay mineral complex carrier comprises the steps: that (1) is under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and acidic aqueous solution being carried out first time contacts, and will gained mixture crystallization, washing, suction filtration after first time contact; (2) waterglass and inorganic acid are carried out second time to contact, and by the washing of gained mixture, suction filtration after second time contact; (3) by the mesoporous silicon oxide filter cake prepared by (1) ball milling together with the silica gel filter cake prepared by (2) and attapulgite clay mineral; (4) spraying dry is carried out after the pressed powder obtained by (3) being mixed with slurry under deionized water exists; (5) will be heated by (4) gained spraying dry afterproduct, removed template method.
5. carried phospho-tungstic acid catalyst according to claim 4, wherein, described template is polyglycerol-polyethylene glycol-glycerine; Described acidic aqueous solution is the cushioning liquid of acetic acid and sodium acetate, and the pH value of described cushioning liquid is 1-6; The temperature of described first time contact is 10-60 DEG C, and the time is 10-72 hour; Crystallization temperature is 30-150 DEG C, and crystallization time is 10-72 hour.
6. carried phospho-tungstic acid catalyst according to claim 4, wherein, the temperature of described second time contact is 10-60 DEG C, and the time is 1-5 hour; Described inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid, and the pH value of described inorganic acid is 2-4.
7. carried phospho-tungstic acid catalyst according to claim 4, wherein, the condition of described ball milling comprises: the diameter of abrading-ball 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; Described spray-dired condition comprises: temperature is 25-60 DEG C, and rotating speed is 10000-15000r/min; The temperature of described removed template method is 300-600 DEG C, and the time is 10-80 hour.
8. carried phospho-tungstic acid catalyst according to claim 4, wherein, polyglycerol-polyethylene glycol-glycerine: ethanol: acidic aqueous solution: trimethylpentane: the mol ratio of tetramethoxy-silicane is 1:100-500:150-900:200-500:50-200; Waterglass: the weight ratio of inorganic acid is 3-6:1.
9. the preparation method of a carried phospho-tungstic acid catalyst, wherein, the method comprises: carry out spraying dry after described spherical attapulgite clay mineral complex carrier and phosphotungstic acid are mixed with slurry under deionized water exists, and makes phosphotungstic acid load on described spherical attapulgite clay mineral complex carrier; With the gross weight of described spherical attapulgite clay mineral complex carrier and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 1-50 % by weight, and the consumption of described spherical attapulgite clay mineral complex carrier is 50-99 % by weight; The mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-50 micron, and specific area is 560-600 meters squared per gram, and pore volume is 0.5-1.5 ml/g, and most probable pore size is 9-15 nanometer.
10. preparation method according to claim 9, wherein, with the gross weight of described spherical attapulgite clay mineral complex carrier and phosphotungstic acid for benchmark, the consumption of described phosphotungstic acid is 5-45 % by weight, and the consumption of described spherical attapulgite clay mineral complex carrier is 55-95 % by weight; And the mean particle diameter of described spherical attapulgite clay mineral complex carrier is 20-40 micron, specific area is 580-600 meters squared per gram, and pore volume is 0.8-1.3 ml/g, and most probable pore size is 9-12 nanometer.
11. preparation methods according to claim 9 or 10, wherein, spherical attapulgite clay mineral complex carrier: deionized water: the mol ratio of phosphotungstic acid is 1:15-35:0.5-1.5.
12. preparation methods according to claim 9 or 11, wherein, the preparation of described spherical attapulgite clay mineral complex carrier comprises the steps: that (1) is under the existence of template, trimethylpentane and ethanol, tetramethoxy-silicane and acidic aqueous solution being carried out first time contacts, and will gained mixture crystallization, washing, suction filtration after first time contact; (2) waterglass and inorganic acid are carried out second time to contact, and by the washing of gained mixture, suction filtration after second time contact; (3) by the mesoporous silicon oxide filter cake prepared by (1) and the silica gel filter cake ball milling together with attapulgite clay mineral prepared by (2); (4) spraying dry is carried out after the pressed powder obtained by (3) being mixed with slurry under deionized water exists; (5) will be heated by (4) gained spraying dry afterproduct, removed template method.
13. preparation methods according to claim 12, wherein, described template is polyglycerol-polyethylene glycol-glycerine; Described acidic aqueous solution is the cushioning liquid of acetic acid and sodium acetate, and the pH value of described cushioning liquid is 1-6; The temperature of described first time contact is 10-60 DEG C, and time of contact is 10-72 hour; Described crystallization temperature is 30-150 DEG C, and crystallization time is 10-72 hour.
14. preparation methods according to claim 12, wherein, the temperature of described second time contact is 10-60 DEG C, and the time is 1-5 hour; Described inorganic acid is one or more in sulfuric acid, nitric acid and hydrochloric acid, and the pH value of the solution of described waterglass and described inorganic acid is 2-4.
15. preparation methods according to claim 12, wherein, the condition of described ball milling comprises: the diameter of abrading-ball 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; Described spray-dired condition comprises: temperature is 25-60 DEG C, and rotating speed is 10000-15000r/min; The temperature of described removed template method is 300-600 DEG C, and the time is 10-80 hour.
16. preparation methods according to claim 12, wherein, polyglycerol-polyethylene glycol-glycerine: ethanol: acidic aqueous solution: trimethylpentane: the mol ratio of tetramethoxy-silicane is 1:100-500:150-900:200-500:50-200; Waterglass: inorganic acid weight ratio is 3-6:1.
The catalyst that preparation method in 17. claim 9-16 described in any one obtains.
The application of catalyst in 18. claim 1-8 and 17 described in any one in ketal reaction.
The preparation method of 19. 1 kinds of cyclohexanone glycerol ketal, wherein, the method comprises: in the presence of a catalyst, under the condition of ketal reaction, cyclohexanone is contacted with glycerine, to obtain ketal, it is characterized in that, described catalyst is the catalyst in claim 1-8 and 17 described in any one.
20. preparation methods according to claim 19, wherein, the mol ratio of cyclohexanone and glycerine is 1:0.5-10, and in the phosphotungstic acid of load in described catalyst, relative to the cyclohexanone of 100 weight portions, the consumption of described catalyst is 1-15 weight portion.
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