WO1999008960A1 - Corps spherique poreux - Google Patents

Corps spherique poreux Download PDF

Info

Publication number
WO1999008960A1
WO1999008960A1 PCT/JP1998/003681 JP9803681W WO9908960A1 WO 1999008960 A1 WO1999008960 A1 WO 1999008960A1 JP 9803681 W JP9803681 W JP 9803681W WO 9908960 A1 WO9908960 A1 WO 9908960A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic
particles
porous
inorganic porous
fluorine
Prior art date
Application number
PCT/JP1998/003681
Other languages
English (en)
Japanese (ja)
Inventor
Kazuo Okuyama
Original Assignee
Asahi Kasei Kogyo Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kogyo Kabushiki Kaisha filed Critical Asahi Kasei Kogyo Kabushiki Kaisha
Publication of WO1999008960A1 publication Critical patent/WO1999008960A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties

Definitions

  • the present invention relates to a spherical inorganic porous material and a method for producing the same.
  • the spherical inorganic porous material of the present invention is useful as various carriers and molecular sieves.
  • the present invention relates to a porous composite and a method for producing the same, and more specifically, to a novel porous composite obtained by immobilizing a fluorine-containing organic substance in inorganic porous particles and immobilizing the same, and a method for producing the same.
  • the porous composite of the present invention is suitable for ion exchange, peroxidation, various kinds of chromatography, etc., or a catalyst, particularly an acid catalyst.
  • Inorganic porous materials have been conventionally used for applications such as catalyst carriers, adsorbents, and filter media. It is considered that the reason why the inorganic porous material is used in such a field is that the inorganic substance has excellent rigidity, heat resistance and chemical resistance. On the other hand, the requirements for the properties of the pores of the inorganic porous material are becoming diverse and precise depending on the application.
  • uniform macropores in the present invention, macropores have a pore diameter of 100 or more persons
  • An inorganic porous body having the following is considered to be advantageous, and a material having a large porosity is strongly desired.
  • the inorganic porous material is used for the above purpose, it is very advantageous that it is spherical. In the case of crushed or deformed particles, the particle angle is likely to collapse during handling, which not only tends to cause clogging of the generated fine powder and increases pressure loss, but also makes the packing state unstable. From such a viewpoint, a spherical inorganic large pore porous support is desired.
  • silica gel and porous glass have been known as inorganic porous materials.
  • Silica gel is usually produced by reacting sodium silicate with sulfuric acid or hydrochloric acid to obtain a silica hydrate gel, which is washed with water, dried and, if necessary, calcined.
  • the silica gel thus obtained has the property that it is often spherical, has a wide pore size distribution, or has a small pore size (several hundred A). Furthermore, its skeleton The strength is relatively low because the silica fine particles have a particulate structure in which the fine particles are maintained while maintaining the shape.
  • the silica composition is about 98% by weight. Examples of the method for producing silica gel include JP-A-58-1040417 and JP-A-47-51817.
  • Porous glass is made by melting and molding borage acid glass with a specific composition, heat-treating it within a certain temperature range to cause phase separation, and then perform acid treatment to remove the eluted phase and wash the remaining solid phase with water. It is manufactured by drying.
  • the porous glass obtained in this way has a structure in which the skeleton is columnar and intertwined (columnar structure).
  • boric anhydride and sodium oxide are used. Since it contains as a constituent component, not only is the chemical resistance of acids and the like limited, but also the pore volume is generally small.
  • porous glass is melted at a high temperature, it must be crushed in order to turn it into powder, resulting in broken frame-shaped particles.
  • the production method of porous glass is described in, for example, US—A—2, 106, 744 (1934) and US—A—4, 657, 875 (1968) Have been.
  • Ion exchange resins, chelate resins, and inorganic ion exchangers are widely used in separation processes such as adsorption chromatography, ion exchange chromatography, and distribution chromatography, and in adsorption processes.
  • the ion exchange resin and the chelate resin have physical strength, particle dimensional stability, etc., and the inorganic ion exchanger has the particle shape and effective absorption capacity. Height, particle packing density, deployment pressure, etc. are severely restricted and are not satisfactory.
  • non-porous ala is a complex obtained by introducing a functional group into the outer surface of a porous inorganic material by a silylation reaction. 2—4 8 5 18
  • the amount of exchange groups that can be introduced in this complex is extremely small, and it is insufficient to obtain a large amount of adsorption and separation per unit complex.
  • the polymerizable monomer enters the pores of the porous inorganic carrier by capillary action, but enters the pores so as to close the pores, so that the substance to be adsorbed moves toward the functional groups in the pores
  • the space to be absorbed is greatly limited, and as a result, the problem of low absorption speed ⁇ occurs.
  • fluorine-containing compounds form a dense structure due to the high electronegativity and small atomic radius of fluorine atoms, and exhibit high heat resistance and chemical resistance.
  • the compound containing fluorine has a cation exchange group such as sulfonic acid-sulfonic acid, the carboxylic acid-sulfonic acid exhibits high acidity.
  • naphion manufactured by EI duPont de Nemours and Comany
  • EI duPont de Nemours and Comany which is one of three perfluorocarbon sulfonic acid.
  • a composite porous body in which a naphthion is entangled with a silica skeleton has been proposed by adding a solution of a naphthion to an alkoxysilane and hydrolyzing the solution (sol-gel method) (J. Am. Chem. Soc.). , (1996) 1 1 8,7708).
  • naphthion is temporarily fixed to a silica skeleton, and it is said that naphthion is difficult to escape during use.
  • naphth ions escape.
  • the acid catalyst examples include mineral acids such as sulfuric acid and strong organic acids such as trifluoromethanesulfonic acid, which are currently used as acid catalysts for various organic reactions.
  • these acid catalysts have drawbacks such as being corrosive, difficult to separate the product or reactant from the catalyst, and incapable of regenerating and reusing the catalyst.
  • the complex of the nafion and silica by the sol-gel method has a problem in that the nafion component is eluted in a polar organic solvent, and the reaction speed is low due to too small pores, resulting in poor reaction efficiency. There is a problem that becomes.
  • phosphotungstic acid can be compounded only at 1 O wt% or less, so that the number of active sites as an acid catalyst is small, the shape of particles is crushed,
  • it has disadvantages such as that it is small and takes a long time to diffuse, and that the acidity is lower than that of perfluorocarbonsulfonic acid.
  • An object of the present invention is to provide a spherical inorganic large-pore porous body having a large average pore diameter and a high porosity, and having excellent rigidity and chemical resistance, and a method for producing the same.
  • a fluorine-containing organic substance exhibits chemical resistance and heat resistance, and exhibits excellent ion exchange ability, catalytic ability, and metal ion adsorption ability by having appropriate functional groups.
  • the inventor of the present invention has made intensive studies to solve the above problems, and as a result, has accomplished the present invention.
  • the present invention is as follows.
  • Silica sol and inorganic salts having a melting point in the range of 400 to 800 ° C are formed by heterogeneizing a homogeneous aqueous solution of a mixture of inorganic salts, followed by granulation. A method for producing a porous body.
  • the inorganic salt is molybdate, molybdenum oxide, molybdate or a mixture of molybdenum oxide and phosphate, phosphate, aluminum chloride, aluminum sulfate, and the like. 4. The method for producing a spherical inorganic porous material according to the above item 3, wherein the spherical inorganic porous material is at least one selected from the group consisting of a mixture of any one of the above and an alkaline earth metal salt. 5. Inorganic porous particles having a particle size of 1 ⁇ m to 5 mm, a porosity of 0.20 to 0.90, and an average pore size of 5 to 500 nm, A porous composite containing a supported fluorine-containing organic substance.
  • FIG. 1 is a scanning electron micrograph showing a skeleton of a columnar entangled structure of the first spherical inorganic porous particles of the present invention.
  • FIG. 2 is a scanning electron micrograph showing an example in which the skeleton of the inorganic porous particles has a particulate structure (commercially available silica gel, trade name: MB-100, manufactured by Fuji Silica Chemical Co., Ltd.).
  • Examples of the constituent components of the first spherical inorganic porous material of the present invention include silica, alumina, silica-alumina, titania, zirconia, and a mixture of two or more of these. Among them, silica is preferred because of its high acid resistance.
  • the present invention will be described with reference to the die force as an example.
  • the first spherical inorganic porous material of the present invention is a spherical particle, and has a spheroidization ratio A of 75 to 100 (defined below).
  • A spheroidization ratio
  • the shape of the particles spherical, an inorganic porous body having high rigidity can be obtained. If the spheroidization ratio is larger than 75, the strength of the particles is large and the particles are hard to break, and this may be due to the loss of particles in practical use or the fine powder generated by crushing clogging the filter of the power ram. Pressure loss is less likely to occur.
  • the spheroidization ratio A is defined by the following equation (1):
  • A B X 100 / C (1)
  • B the area of the particle
  • C the area of the smallest circumcircle of the particle surface.
  • the inorganic porous material of the present invention has a skeleton having a columnar entangled structure.
  • the columnar entangled structure mentioned here refers to a structure in which columnar sili- cle forces of approximately the same thickness have developed three-dimensionally, for example, the structure shown in Fig. 1. In such a structure, it is considered that the strength inherent in silica is exhibited because a weak portion where stress is concentrated is not specified or is small.
  • the skeletal structure of porous particles has a columnar entangled structure and a particulate structure.
  • the fine particles of silicon force contact each other while maintaining the An original structure is formed, and the diameter of the contact portion between the fine particles is smaller than the diameter of the fine particles themselves. Therefore, when a force such as compression is applied, stress concentration occurs at the weakest contact point of the silica fine particles, and the overall strength is thought to decrease.
  • the skeleton of the particulate structure is shown, for example, in FIG.
  • the fracture strength when a compressive load is applied to a single porous silica particle is measured using a micro-compression tester MC TM-500 type (manufactured by Shimadzu Corporation), which is an example of a porous silica material having a particulate structure. porosity 0 compressive fracture strength. 6 8 silica gel MB 5 0 0 0 (manufactured by Fuji Shirishia chemical) whereas a 9 1 kg / cm 2, the porous silica of the columnar entanglement structure used in the present invention For example, the porosity was 0.74, and the compressive fracture strength was 128 kg / cm 2 . It is experimentally clear that the strength of the porous porous body of ordinary granular structure is lower than that of porous silica of columnar entangled structure.
  • the first spherical inorganic porous material of the present invention has a large average pore diameter and a large pore volume (porosity). This was achieved because the strength of the porous body was large because it had a columnar entangled structure and was spherical. It is a feature of the spherical inorganic porous material of the present invention that it is a spherical particle having such an internal structure.
  • the average pore diameter of the spherical inorganic porous material is 100 to 200 nm, preferably 300 to 150 nm, more preferably 500 to 150 nm, and still more preferably 500 nm. 1100 nm. Within this range, the spherical inorganic porous material tends to have a columnar entangled structure.
  • the porosity is defined as the ratio of the volume of pores to the total volume of the inorganic porous material particles, and is 0.5 to 0.9, preferably 0.6 to 0.9, more preferably 0.65 to 0.9. .8.
  • the porosity is in a range larger than 0.5, the amount of various kinds of supported materials can be increased. Further, when the porosity is in a range smaller than 0.9, the strength of the porous particles becomes large and the porous particles become suitable for practical use.
  • the spherical inorganic porous body of the present invention has a solid interior.
  • solid as used herein means that the interior is not hollow, that is, one or a few large pores do not occupy the majority of the particle volume, but rather countless pores having a small diameter compared to the particle size. It means that a porous body is formed. Preferably, it means that there are no or few holes having a hole diameter larger by one digit or more than the average pore diameter inside the particles. Solid or hollow Whether it is present can be easily determined by observing the cross section with a scanning electron microscope.
  • the particle diameter of the first spherical inorganic porous material of the present invention is 1 m to 5 mm, preferably 1 m to 3 mm, more preferably 10 ⁇ to 1 ⁇ , and still more preferably 10 m to 200 m. It is. If the particle diameter is larger than 1 m, a columnar entangled structure tends to be formed due to the balance between the pore diameter and the particle diameter. Further, when the particle diameter is smaller than 5 mm, when the particles are used as various carriers, for example, diffusion of reactive molecules and ions in the particles becomes sufficient. Further, when the constituent material of the porous body is silica, it is preferable that the spherical inorganic porous body substantially contains a silicic anhydride as a constituent unit.
  • a substantial part of the skeleton of the porous silica is a three-dimensional polymer containing 99% or more by weight of gay acid as a constituent unit. If the content of gay anhydride is 99% or more, high chemical resistance, especially acid resistance can be obtained because there are few impurities (inorganic salts and inorganic oxides) in the mixture. There is little adverse effect as impurities in the atmosphere.
  • the first method for producing a spherical inorganic porous material starts with preparing an aqueous solution of silica sol and an inorganic salt.
  • water is used as a solvent, but water is selected from the viewpoint of environmental safety, and other solvents such as alcohols and polar solvents such as dimethylformamide that dissolve inorganic salts are also used.
  • the solid content of the solution is not particularly limited, but is preferably from 10 to 80% by weight, more preferably from 20 to 50% by weight. The higher the water content of the solution, the greater the amount of heat required for drying. On the other hand, if the solids content is too high, the dispersibility of the solids tends to deteriorate, and the physical properties of the porous material tend to be uneven.
  • Inorganic salts are (1) compounds that exhibit a melting point between 400 and 800 ° C during sintering, and (2) compounds that have a high affinity with the silicic power of inorganic porous materials and are easily compatible. preferable.
  • the sintering operation is performed at a temperature higher than the sintering temperature of the sintering force.
  • the conditions (1) and (2) above are closely related to the sintering temperature. This is because at the sintering temperature, the added inorganic salt is molten and becomes liquid, This is because it is considered that the interaction at the interface between the liquid phase and the solid of the Siri force acts to form the structure of the first porous body of the present invention. Any inorganic salt that satisfies the conditions (1) and (2) can be used.
  • molybdate molybdenum oxide
  • molybdenum oxide or a mixture of molybdate and phosphate.
  • Phosphates alkali metal chlorides such as sodium chloride and potassium chloride; alkali metal sulfates such as potassium sulfate; and mixtures of these with alkaline earth metal salts such as calcium chloride.
  • molybdenum oxide has low solubility in water and is difficult to use as it is, it is preferably used in the form of an ammonium molybdate salt which is oxidized during sintering and changes into molybdenum oxide, and has high solubility in water.
  • inorganic salts can be used alone or in a mixture of two or more.
  • conditions such as the type of salt used a porous silicon material having a desired pore size / narrow pore size distribution can be obtained.
  • the method disclosed in JP-B-3-39730 or JP-B-6-154427 is exemplified.
  • Anmoniumu and monosodium phosphate molybdate as an inorganic salt N a / / M with o molar ratio 6 Z 4 ⁇ 0. 5/ 9. 5 Composition of
  • volume ratio of the use ,, inorganic salt / silica force It is preferable to use an aqueous solution having a charge composition of 2/1 (porosity 0.60) to 12Z1 (porosity 0.90).
  • the hot air temperature under the spray drying conditions ⁇ the amount of the feed liquid, and the amount of hot air can be varied, However, particles having a low spheroidization ratio can be obtained even if the viscosity of the mixture, the solid content, and the drying conditions, which are considered to be other factors, are changed. On the other hand, particles having a high spheroidization ratio can be obtained only when the mixture is brought into a state in which precipitation occurs or in a non-uniform state in which gelation occurs.
  • the non-uniformity referred to in the invention of the present application is a microscopic phenomenon in which the solution is gelled or precipitated and the solution becomes cloudy. Refers to unevenness. It is presumed that the uniformity of the composition inside the particles after granulation and drying has been improved by making the liquid mixture once uniform and then making it non-uniform.
  • the method of making the mixture non-uniform is not particularly limited. One of them is the acidity of the mixture.
  • the acid and acid added to the mixed solution to control the pH can be exemplified.
  • the acid is preferably a mineral acid, particularly nitric acid, and the acid is particularly preferably aqueous ammonia. This is because both nitric acid and ammonia vaporize as nitrogen oxides during the baking process and are removed from the particles.
  • the pH at which the mixed solution becomes uneven depends on the type and amount of the inorganic salt used and the temperature of the solution. For example, when ammonium molybdate and sodium phosphate are used as the inorganic salt, the mixture becomes non-uniform at either pH 1 or lower or 7 or higher and 10 or lower.
  • the value of pH here is, of course, a value measured in a state where the aqueous solution is stirred to some extent. If the aqueous solution is not sufficiently stirred or if the aqueous solution is not stirred, a phenomenon in which only local opacity and gelation occur is observed, and the apparent pH is 1 or less or 7 or more and 10 or less. However, it may not be within the range of deviation. If granulation is carried out with a spray dryer using this insufficiently stirred liquid, a part of the force to obtain spherical particles will be partly mixed with irregularly shaped particles. Therefore, the liquid is preferably stirred.
  • the acidity (pH) of the solution of silica gel, ammonium molybdate, and monosodium phosphate is preferable to adjust the acidity (pH) of the solution of silica gel, ammonium molybdate, and monosodium phosphate. Spray-drying is carried out in a state where gelation has been advanced.
  • Granulation means removing mixed water by producing mixed droplets having a predetermined diameter and then drying. There is no particular limitation on the granulation method.
  • the shape of the porous silica particles also depends on the granulation conditions.
  • the granulation method include a spray drying method and a method in which uniform droplets are formed using ultrasonic waves and then dried (JP-B-3-39730).
  • the particle shape becomes Decided.
  • Factors that determine the particle shape include non-uniformity of the mixture, physical properties such as solid content and viscosity, and drying conditions such as temperature and humidity.
  • the drying conditions are also factors directly related to the productivity and price of the product.
  • the temperature of the hot air at the entrance of the drying tower is preferably around 200 ° C.
  • a spray drying method capable of mass production was selected in consideration of economy, but the present invention is not limited thereto.
  • the change in the shape of the obtained particles is relatively small even if the granulation conditions such as the hot air temperature, the amount of hot air, and the amount of the mixed liquid introduced are variously changed.
  • the firing temperature is usually from 400 to 100 ° C.
  • the inorganic salt used must be melted, that is, at a temperature not lower than the melting point of the inorganic salt and not higher than 200 ° C higher than the melting point of the inorganic salt.
  • baking is performed. If the temperature is higher than the melting point of the inorganic salt, the average pore size is likely to be large. If the temperature is 200 ° C. or lower than the melting point, the average pore size is unlikely to be too large. For example, baking is performed at 675 for 1 hour (average pore diameter of 500 nm) to 75 ° C for 4 hours (average pore diameter of 2000 nm). The melting point is 10
  • the desired product may be obtained even at temperatures as low as ⁇ 20 ° C.
  • the firing time is set in relation to the firing temperature.
  • the baking is performed in a short time at a high temperature and for a long time at a low temperature. Considering workability, etc.
  • calcination is performed at around 300 to 400 ° C. to remove ammonia, and then calcination is performed at the above temperature.
  • the inorganic salt is removed from the obtained calcined product by washing.
  • Any washing solution can be used as long as it does not dissolve silica but dissolves inorganic salts.
  • water is preferably used in terms of cost and environment.
  • an existing spherical inorganic porous material is used as a starting material. Used as In this method, the spherical inorganic porous body having a large pore diameter of the present invention can be produced while maintaining the spherical shape of the existing spherical inorganic porous body. Therefore, it is necessary that the existing spherical inorganic porous material itself has an appropriate spheroidizing ratio.
  • the existing spherical inorganic porous material is not particularly limited as long as it has an appropriate spheroidizing ratio. Examples thereof include silica, alumina, silica-alumina, titania, zirconium, and a mixture of two or more of these. And a spherical inorganic porous material. Among these, spherical porous silica is most commonly used as typified by silica gel, and is preferably used because of the high acid resistance of silica.
  • the second method will be described using a spherical porous body as an example of the existing spherical inorganic porous body.
  • the first step of the second method is to prepare an aqueous solution of an inorganic salt.
  • water is used as the solvent, it is not limited to water as in the first production method of the present invention.
  • the concentration of the solution is between 0.1% and 80% by weight, preferably between 5% and 80% by weight.
  • the concentration is 0.1% by weight or more, the inorganic salt easily enters the porous silica and the phase separation easily proceeds by only one impregnation and drying step. Therefore, the number of times of repeating the impregnation / drying process is reduced, which is efficient.
  • the inorganic salt used here is the same as the inorganic salt that can be used in the first method.
  • an aqueous solution of an inorganic salt is impregnated into the porous silica.
  • the amount (volume) of the aqueous inorganic salt solution is 50% to 100%, preferably 60% to 90%, of the pore volume (volume) of the used porous silica material. If it is 50% or more, the inorganic salt aqueous solution easily enters the pores of the porous silica material as a whole, and spots hardly occur. On the other hand, if the content is less than 100%, it becomes difficult for the aqueous solution of the inorganic salt to exist outside the porous silica, and the dissolved inorganic salt is effectively used, which causes coalescence of the porous silica particles. Hateful.
  • the porous silicon body is brought into contact with and mixed with an aqueous solution of an inorganic salt under atmospheric pressure or reduced pressure.
  • the mixing method is not limited, but an evaporator or various mixers can be used.
  • the mixing time is until the aqueous solution of the inorganic salt enters the porous porous body, and is, for example, 0.5 to 1 hour.
  • the porous silicon body containing the inorganic salt aqueous solution is dried.
  • the drying method is not particularly limited, and drying is performed under normal pressure or reduced pressure, at normal temperature, or while heating.
  • the rate is between 10 and 100%, preferably between 30 and 100%, more preferably between 50 and 100%. If it is lower than 100%, the pores are unlikely to be enlarged by sintering, and if it is higher than 100%, the coalescence of particles may be caused.
  • residual moisture there is no limitation on the residual moisture during drying, but it is preferably 0.1 to 10% by weight. Residual water is removed in the next baking step, but if more than 10% by weight of water remains, there is a possibility of rapid evaporation of water during baking and destroying the structure of porous silica. .
  • This firing step is the same as the above-mentioned first manufacturing method.
  • the inorganic salt is removed from the obtained fired product by washing. This step is also the same as the first production method of the present invention.
  • the inorganic porous material obtained by these methods and the like is classified, for example, by a sieve so as to have a predetermined particle size, and if necessary, washed with water and dried before being used. There is no particular limitation on the drying method.
  • the first spherical inorganic porous material of the present invention is extremely excellent in that despite its high porosity, it has excellent mechanical strength, is hard to crack during use, and can have a relatively uniform particle size. It has characteristics.
  • porosity and strength are higher than those using commercially available silica gel or porous glass, stationary phases for gas chromatography and liquid chromatography, stationary phases for preparative chromatography, and cell culture carriers It is useful as an adsorbent, a catalyst, or a carrier thereof.
  • the porous composite of the present invention is obtained by incorporating a fluorine-containing organic substance into inorganic porous particles and substantially preventing elution of the fluorine-containing organic substance from the pores of the inorganic porous particles serving as a carrier. Fluorine-containing organic substances are substantially fixed to inorganic porous particles.
  • the particle diameter of the inorganic porous material particles used as the carrier of the porous composite is 1 zm to 5 mm, preferably 1 zm to 3 mm, and more preferably 10 ⁇ m to 1 mm. If the particle size of the inorganic porous particles is 1 / m or more, handling is relatively easy, and for example, when used by filling in a power ram, the pressure loss before and after the power ram can be relatively low. : When the particle diameter is 5 mm or less, it is necessary for diffusion inside the pores of the porous composite Since the time is short, the functions of organic substances, such as ion exchange, catalyst, and adsorption of metal elements, can be sufficiently exhibited.
  • the porosity of the inorganic porous material particles is from 0.2 to 0.9, preferably from 0.6 to 0.9, more preferably from 0.65 to 0.8, from the viewpoint of compatibility between mechanical strength and catalytic efficiency. It is. The higher the porosity, the more organic substances can be supported, and the capacity as a porous composite, for example, the amount of catalytic active sites, can be increased.
  • polytrifluorostyrene sulfonic acid is supported on the porous silicon bodies (i) and (ii) having a porosity of 0.50 and 0.80, respectively. It is assumed that the amount of vacancy is 0.25 ml with 1 ml of the inorganic-organic composite.
  • the silica becomes 0.50 m
  • the polytrifluorostyrene sulfonic acid becomes 0.25 m1
  • the porosity becomes 0.25 m1
  • the volume of the porous composite becomes 1.47 meq / m1 and 1.01 meq Zg, respectively (the specific gravity of silica is 2.2, the specific gravity of polytrifluorofluorstyrenesulfonic acid is 1.40).
  • porous silica (ii) has only 1.6 times greater porosity than porous silica (i), but has an exchange capacity per volume and weight of 2.2 times, respectively. 2. You can see that it is 6 times. It is preferable to increase the porosity as much as the mechanical strength allows, since the diffusion rate of the substance in the porous composite particles can be increased.
  • the average pore size of the inorganic porous particles is 5 to 200 nm, preferably 100 to 2000 nm, and more preferably 800 to 200 nm.
  • the average pore diameter is equal to or larger than the lower limit, it is easy to secure a route for the reactant to enter the organic substance in the pores of the inorganic porous material particles.As a result, for example, a catalytic reaction occurs efficiently c
  • the average pore diameter is equal to or smaller than the upper limit. Then, the mechanical strength of the inorganic porous material particles is maintained.
  • porous ceramic particles are preferably used as the inorganic porous particles.
  • inorganic porous particles made of silica, alumina, silica-alumina, titania, zirconia, or a mixture of two or more thereof are exemplified.
  • porous silica particles are preferably used because they can easily produce substantially spherical particles, have a narrow particle size distribution, and have high acid resistance of silica.
  • the pore state of the porous silica particle surface is the same as that of the inside, and there are no shells with a low pore state on the surface, for example, when the adsorbed species moves into the particles when used as an adsorbent. It is preferable from the viewpoint of easiness.
  • the porous composite of the present invention it is particularly preferable to use the first or second spherical inorganic porous material of the present invention from the viewpoint of particle strength and utilization efficiency of the fluorine-containing organic substance.
  • the content of the fluorine-containing organic substance per unit volume can be increased, and the apparatus can be made more compact.
  • the column pressure since the amount of space (porosity) after the fluorine-containing organic substance is included in the inorganic porous material can be increased, the column pressure must be kept low, for example, when the column is filled and used. Can be.
  • an ion exchanger is used as the fluorine-containing organic substance, the resistance to changes in the type and concentration of the eluent during adsorption and desorption increases, and the particles are crushed when packed into a large column. Atomization can be prevented, and the separation operation can be repeated stably.
  • the porous composite of the present invention is obtained by supporting a fluorine-containing organic substance on the inorganic porous particles as described above and substantially fixing the same.
  • the fluorinated organic substance referred to here is not limited in chemical properties such as its composition and molecular structure, and can be selected from various organic compounds having fluorine molecules. Fluoride is preferred because of its excellent heat resistance and solvent resistance due to the large electronegativity and small atomic diameter of fluorine. In particular, perfluorocarbon is preferable because of its excellent heat resistance and solvent resistance. Further, not limited to the fluorine-containing organic substance, a halogen-containing organic substance having a halogen atom other than fluorine may be used.
  • the fluorine-containing organic substance has functional groups corresponding to various uses.
  • the term “functional group” refers to a functional group having functionality and a reactive group that is an atom or atomic group having high chemical reactivity. Specific examples of the functionality of the functional group include: , Chelating ability, redox ability, catalytic coordination ability, etc. Examples of functional groups having these functions include sulfonic acid groups, carboxylic acid groups, phosphonic acid groups, primary to tertiary amine-derived amino groups, hydroquinone groups, and thiol groups. There are groups.
  • the reactive group having high chemical reactivity includes, for example, an isocyanate group, a diazonium group, a chloromethyl group, an aldehyde group, an epoxy group, a halogen group, a carboxyl group, and an amino group.
  • the fluorine-containing organic substances having these functional groups include ion-exchange fluorine-containing resins, chelate fluorine-containing resins containing chelating ligands, and redox fluorine-containing resins having hydroquinone and thiol.
  • the ion-exchange fluororesin may be a fluororesin having both cation and anion exchange groups in addition to a fluororesin having a cation or anion exchange group.
  • cation exchange groups include sulfonic, carboxyl or phosphate groups.
  • the fluorine-containing organic material before being contained in the inorganic porous material particles may have a functional group, or the organic material may be reacted with the functional group-introducing agent after being carried on the inorganic porous material particles.
  • a functional group may be introduced.
  • examples of useful fluorine-containing organic substances when the porous composite of the present invention is used as an acid catalyst or the like include one or more polymerizable monomers represented by the following formula (2) and a polymerizable monomer described below. And copolymers obtained by combining one or more polymerizable monomers selected from the group of hydrophilic monomers.
  • _Y are, - S0 3 H, -SO, F, -SO 3 Na, - S0 3 K, one S0 2 NH 2, One S0 2 NH 4, One CO_ ⁇ _H one CN, one COF, One COOR
  • R is an alkyl group having 1 to 1 0 carbon
  • _PO alkyl group having 1 to 1 0 carbon
  • _PO alkyl group having 1 to 1 0 carbon
  • _PO alkyl group having 1 to 1 0 carbon
  • _PO alkyl group having 1 to 1 0 carbon
  • a is an integer of 0 to 6
  • b is an integer of 0 to 6
  • c is 0 or 1
  • n is an integer from 0 to 6.
  • X is any one of ⁇ 1, Br or F when 11 ⁇ 1, or a combination of plural kinds.
  • R t and R t ′ independently comprise F, Cl, a perfluoroalkyl group having 1 to 10 carbon atoms and a fluorochloroalkyl group having 1 to 10 carbon atoms. It is selected from a group.
  • the polymerizable monomers to be copolymerized with these are tetrafluoroethylene, trifluoromonoethylene, trifluoroethylene, vinylidene fluoride, 1,1-difluoro-2,2- Dichloroethylene, 1,1-difluoro-2-chloroethylene, hexafluoropropylene, 1,1,1,3,3_pentafluorofluoropropylene, octafluoroisobutylene, ethylene, vinyl chloride and alkyl vinyl Esters and the like.
  • the copolymerization may be performed before or after the polymerizable monomer is contained in the inorganic porous particles as a carrier. After the copolymerization, if necessary, the functional group is converted to an ion-exchange group by a post-treatment such as hydrolysis.
  • the exchange capacity of the ion-exchange group of such a fluorine-containing organic substance is defined by the number of moles of the ion-exchange group per gram, and is usually measured by a titration method. Desirable exchange capacity of the fluorine-containing organic substance used in the porous composite of the present invention is 0.70 to 2.00 meq / g, preferably 0.90 to 1.40 meq / g. And more preferably from 1.0 to 1.40 meq Zg. If it is smaller than 0.90 milliequivalent Zg, the exchange capacity of the composite becomes small and the performance is reduced. On the other hand, if it is more than 2.0 meq / g, it becomes difficult to maintain the shape in the composite, and the fluorine-containing organic substance tends to elute from the inorganic porous material.
  • the exchange capacity of the composite of the fluorine-containing organic substance and the inorganic porous particles is not limited, but is preferably 0.10 meq / g or more. If it is smaller than this, the adsorptivity and the efficiency as a catalyst are low, which is practically disadvantageous.
  • the fluorinated organic substance contained in the inorganic porous particles does not elute from the inorganic porous particles as a carrier under various use conditions and is substantially fixed. Is important.
  • porous composite of the present invention is not limited by the elution prevention method exemplified below. Absent.
  • One method is to include a fluorine-containing organic substance in the inorganic porous material particles, heat the same for a certain time in a certain temperature range, and then cool it.
  • the fluorine-containing organic substance can be substantially immobilized on the inorganic porous material particles by performing the heat treatment under appropriate conditions. For example, when silica and a fluorine-containing organic substance are mixed and dried by the sol-gel method, or when a solution of the fluorine-containing organic substance is impregnated into inorganic porous material particles and dried, the polymer chains of the fluorine-containing organic substance are sufficient. No entanglement, no crystallization.
  • the heating temperature is preferably at least 50 ° C. lower than the melting point of the fluorinated organic substance and not higher than the decomposition temperature of the fluorinated organic substance. It is more preferable that the temperature is lower than the decomposition temperature.
  • the fluorine-containing organic substance is perfluorocarbon sulfonic acid, if it is a Na salt or a K salt, the melting point clearly appears in the measurement with a differential scanning calorimeter. It is preferable to heat around the melting point.
  • the heating time is related to the heating temperature. Heating at a relatively high temperature for a relatively short time and at a relatively low temperature for a relatively long time are effective in preventing elution. Preferably, the heating time is between 30 minutes and 2 hours.
  • the cooling temperature may be around room temperature.
  • a wide-angle X-ray diffraction method (Rigakusha Co., Ltd.) was used for a porous composite made through impregnation, heating, and cooling steps using Amplex (manufactured by Asahi Chemical Industry Co., Ltd.), which is one of perfluorocarbon sulfonic acids.
  • the crystallinity of perfluorocarbon sulfonic acid was measured by Rigaku Rotaf 1 ex RU-200), and the exchange capacity was 1.11 meq Zg and the crystallinity was 10% and 1%. It was 16% at 0.00 meq / 8 and 18% at 0.91 meq Zg.
  • Another method for preventing the elution of the fluorinated organic substance is to allow the fluorinated organic substance to be contained in the inorganic porous material particles and then to crosslink the fluorinated organic substance.
  • Divinylbenzene, divinyltoluene, divinylxylene, divinylethylbenze Divinylbenzene, divinyldiphenyl, divinyldiphenylmethane, divinyldibenzyl, divinylphenylether, divinyldiphenylsulfide, divinyldiphenylamine, divinylsulfone, divinylketone, divinylpyri Gin, diaryl phthalate, diaryl maleate, diaryl fumarate, diaryl succinate, diaryl oxalate, diaryl adipate, diaryl sebacate, diarylamine, triarylamine, N, N'-ethylenediacrylamide, N , N'-Methylenediacrylamide, N, N'-
  • Yet another method for preventing elution is to bond a fluorine-containing organic substance to the inorganic porous particles by a covalent bond.
  • a functional group is introduced into the surface of the porous silicon body by a silylating agent having a functional group such as vinylsilanediarylsilane, and a radical polymerization reaction is performed between the functional group and a fluorine-containing organic substance having a vinyl group.
  • a functional group is introduced into the surface of the porous silicon body by a silylating agent having a functional group such as vinylsilanediarylsilane, and a radical polymerization reaction is performed between the functional group and a fluorine-containing organic substance having a vinyl group.
  • the first method is the simplest and preferred because it has less restrictions on conditions.
  • the composites obtained by the above-mentioned elution prevention methods are obtained by attaching a fluoropolymer in a layered or granular form to the surface of the skeleton inside the inorganic porous particles.
  • the reactant and the adsorbed material move in the remaining space of the pores of the inorganic porous material not occupied by the fluoropolymer.
  • the inorganic porous particles have a relatively large pore size and porosity, even if a large amount of fluoropolymer is supported, a space (pore) through which the reactant and the adsorbent move is left. As a result, large utilization efficiency and reaction efficiency can be expected.
  • Whether or not the fluorinated organic substance is substantially immobilized on the inorganic porous material can be evaluated by heating the complex carrying the fluorinated organic substance having an ion-exchange group in dimethyl sulfoxide. .
  • 1 g of the complex was added to 100 g of dimethyl sulfoxide (special grade manufactured by Wako Pure Chemical Industries, Ltd.), heated at 90 ° C for 3 hours, filtered, and washed with dimethyl sulfoxide (hereinafter, referred to as dimethyl sulfoxide). This is referred to as dimethyl sulfoxide treatment.) Then, measure the exchange capacity.
  • the dissolution rate (%) is defined by the following equation (3), where D is the exchange capacity of the complex before dimethyl sulfoxide treatment and E is the exchange capacity after treatment.
  • the dissolution rate of the complex of the present invention is preferably from 0 to 70%, more preferably from 0 to 50%.
  • the remaining portion after the easily eluted portion is not eluted. Therefore, the exchange capacity after the eluted portion elutes is also important.
  • the preferred exchange capacity after the dimethyl sulfoxide heat treatment is 0.10 meq Z g or more. With an exchange capacity smaller than 0.10 meq Zg, there is little part that acts as an ion-exchange group, and this is likely to be practically disadvantageous. Next, a method for producing the composite of the present invention will be described.
  • One of the methods for producing the composite of the present invention is to include a homogeneous mixed solution containing a fluorine-containing organic substance and a diluent in the pores of the inorganic porous material particles, and then remove the diluent.
  • This is a method of performing a heating treatment and a cooling treatment, which are one of the above-described fixing treatments.
  • the composition of the homogeneous mixture containing the fluorine-containing organic substance and the diluent is not particularly limited, but preferably contains 1 to 70 wt%, more preferably 2 to 50 ⁇ % of the fluorine-containing organic substance. .
  • the amount of the fluorinated organic substance is too small, it is not efficient because a large number of the steps of including and drying the mixed solution are repeated in order to include a predetermined amount of the fluorinated organic substance in the pores of the inorganic porous material. On the other hand, if the amount is too large, the viscosity of the homogeneous mixed solution becomes too large, and the containing treatment becomes substantially difficult.
  • the homogeneous mixture is brought into contact with the inorganic porous particles in order to introduce the homogeneous mixture containing the fluoropolymer substance and the diluent into the pores of the inorganic porous particles.
  • Various methods can be used for introducing the mixed solution. For example, a method in which the particles and the homogeneous mixed solution are simply brought into contact with each other under atmospheric pressure, preferably with low-speed stirring, a method in which the particles and the homogeneous mixed solution are brought into contact under vacuum, and a method in which the particles are treated by a silyl reaction or the like.
  • a method of contacting with a homogeneous mixed solution may, for example, be mentioned.
  • the mixed liquid adheres and remains on the outer surface to some extent.
  • adjust the amount of The amount of pores should be equal to or less than the pore size, and then brought into contact under low-speed stirring. In this way, the mixture remaining on the outer surface of the particles can be made very small.
  • the inorganic porous particles can be placed on a glass filter, etc., and then washed with an inert liquid insoluble in the mixture. Good.
  • the type of inert liquid used is selected according to the type of homogeneous mixture. For example, water is used as an inert liquid when the mixture is fat-soluble.
  • the diluent is removed.
  • the method of removal but for example, evaporative drying by heating (in this case, the pressure may be reduced if necessary), a solvent that does not dissolve the fluoropolymer substance but dissolves the diluent
  • the method include washing.
  • a heating step is performed.
  • the purpose of this step is to fix the fluorine-containing polymer substance by melting and crystallization as described above, and the heating temperature for that purpose is not less than 50 ° C lower than the melting point of the fluorine-containing polymer substance.
  • the temperature is not higher than the decomposition temperature of the fluorine-containing polymer substance, preferably from the melting point of the fluorine-containing polymer substance to the decomposition temperature of the fluorine-containing polymer substance. According to the measurement by the differential scanning calorimeter, the polymer substance shows a relatively broad endothermic curve.
  • the melting phenomenon occurs even at a lower temperature.Therefore, even if the temperature is 50 ° C lower than the melting point, the melting time may be prolonged by prolonging the heating time. Can be.
  • the heating time depends on the heating temperature, but it is 30 minutes to 2 hours to perform it efficiently.
  • cooling is performed.
  • the purpose of cooling is to maintain the entanglement of the molecular chains of the molten polymer and to crystallize the polymer. It is considered that the fluorine-containing organic substance contained in the carrier is thereby immobilized on the carrier.
  • the cooling method is not particularly limited as long as it achieves this purpose. For example, there are a method in which the furnace is taken out of the heating furnace to room temperature and allowed to cool, and a method in which the power of the heating furnace is turned off and allowed to cool as is.
  • Another method for producing a composite is a sol-gel method in which a porous silicon force is produced by hydrolysis of an alkoxysilane.
  • the fluorine-containing organic substance and the inorganic porous material can be mixed.
  • a gel solution is formed by adding a mixed solution of naphion, which is one of the fluorine-containing organic substances, and sodium hydroxide to this mixed solution, and then dried and washed with hydrochloric acid.
  • W0 9 5/1 9 2 2 2 Contact Ri is disclosed in, actually SAC - 1 3 R marketed in (US D u P 0 nt Co.) the trade name I have.
  • the fluorinated organic substance is simply included in the skeleton of the inorganic porous material, and since the above-mentioned immobilization treatment has not been performed, methanol, acetone, When heated in a raw solvent such as dimethyl sulfoxide, naphth ions in the mixed solid elute.
  • a raw solvent such as dimethyl sulfoxide
  • naphth ions in the mixed solid elute.
  • Another method for producing the composite of the present invention is a method for producing a composite including a polymerizable monomer or a polymerizable oligomer which can be a fluorine-containing polymer in pores of an inorganic porous material, a crosslinking agent, a radical initiator and a diluent.
  • a mixed liquid or a homogeneous mixed liquid containing a fluorine-containing organic substance, a cross-linking agent and a diluent polymerization or Z or cross-linking reaction is carried out by heating or light irradiation, and then the resulting resin This is a method of removing diluent from the inside.
  • This production method is started by introducing the mixed liquid into the pores by contacting the inorganic porous material with the homogeneous mixed liquid as described above.
  • the polymerizable monomer that can be a fluorine-containing polymer substance used in the homogeneous mixed solution, one having a vinyl group is preferable.
  • the diluent may be any as long as it can form a uniform mixture with the monomer, oligomer or polymer compound and the crosslinking agent.
  • the monomer, oligomer or polymer compound is lipophilic, an organic liquid is preferable, and when these raw materials are hydrophilic, water or an aqueous solution is preferable.
  • the diluent may be used not only alone but also as a mixture.
  • preferred types of diluents include not only compatibility but also various conditions for producing the complex, such as the configuration of the reaction system, temperature and pressure, or the spatial characteristics to be imparted to the resin in the produced complex. Etc.
  • a method of forming a resin by polymerization or cross-linking reaction after allowing the homogeneous mixed solution to be contained in the pores of the inorganic porous material is performed by directly heating or irradiating light, or by mixing the homogeneous mixed solution in the dispersion.
  • the method is broadly divided into methods in which the inorganic porous material particles are dispersed and then heated or irradiated with light.
  • the compatibility between the dispersion and the diluent must be considered. That is, when the dispersion is hydrophilic, a lipophilic organic liquid is preferable as the diluent. On the other hand, when the dispersion is lipophilic, a hydrophilic liquid is preferable.
  • diluents include water and chlorobenzene, toluene, xylene, octane, decane, methanol, butanol, octanol, getyl phthalate, dioctyl phthalate, ethyl benzoate, methyl isobutyl ketone, ethyl acetate, Organic liquids such as getyl oxalate, ethyl carbonate, nitroethane, and cyclohexanone are exemplified.
  • the amount of the homogeneous mixture adhering may be reduced as much as possible before starting the polymerization reaction or the crosslinking reaction. Two methods can be exemplified as this method.
  • the first method is a filtration method. That is, by filtering the particles containing the mixed liquid, the mixed liquid remaining on the outer surface thereof can be reduced. In this case, it is preferable to use a filtration method such as pressure filtration or centrifugal filtration because the filtration time is reduced.
  • the second method is to incorporate the mixed solution into the particles and then disperse the particles in the liquid while forcibly agitating them without reacting with the mixed solution or dissolving the mixed solution.
  • a dispersion containing a dispersant it is preferable to use a dispersion containing a dispersant. The dispersion stably holds the mixed liquid shaken off from the outer surface of the particles by forced stirring in the dispersed liquid, and prevents the mixed liquid from re-adhering to the particle surface.
  • dispersing agents such as gum arabic, rosin, pectin, alginate, tragacanth, agar, methylcellulose, starch, carboxymethylcellulose, karaya gum, gelatin, etc., and sodium polyacrylate , Polyvinyl alcohol, polyvinylpyrrolidone, carbopol, synthetic polymers such as diacetolein, magnesium, aluminum silicate, velmagel, hydrated magnesium silicate, titanium oxide, zinc oxide, calcium carbonate, tanolek, barium sulfate, Inorganic substances such as calcium phosphate, aluminum hydroxide, and anhydrous sulfuric acid can be used. If necessary, salts such as salt, pH adjusters, and surfactants Etc. may be added.
  • the inorganic porous particles after the treatment for containing the homogeneous mixed solution are subjected to a heat treatment or a light irradiation treatment.
  • the homogeneous mixture is composed of a monomer or oligomer, a cross-linking agent and a diluent
  • polymerization or cross-linking reaction occurs by heating or light irradiation.
  • a monomer containing a vinyl group is used, the polymerization reaction generates a force that can be used in any polymerization reaction that proceeds according to the radical polymerization or ion polymerization mechanism depending on the added chemicals and the configuration of the reaction system. Radical polymerization is preferred because the properties of the resin can be easily controlled.
  • suitable polymerization initiators for radical polymerization include benzoyl peroxide, lauroyl peroxide, and other acyl peroxides, azobisdisoptyronitrile, 2,2, -azobis (2,4-dimethylmalelonitrile).
  • Azonitrile compounds such as tolyl), peroxides such as dibutyl peroxide, dicumyl peroxide, methylethyl ketone peroxide, hydroperoxides such as cumene hydroperoxide and tertiary hydroperoxide. Oxides can be exemplified.
  • the amount of the polymerization initiator required depends on the polymerization reaction temperature and the amount and type of the monomer, but is usually 0.01 to 12% by weight based on the weight of the monomer.
  • the temperature and time of the heat treatment for causing the polymerization reaction and the crosslinking reaction are 40 to 150 ° C. and 2 to 100 hours, respectively.
  • the particles including the mixed solution may be heated as it is, or may be heated while being dispersed in the dispersion.
  • the porous composite manufactured under the above conditions contains a diluent inside. Therefore, the complex is immersed in a solvent that dissolves them and left for a while to be filtered off, or the complex is put into a column, and the washing solvent is allowed to flow down, so that the diluent is effective from inside the complex. Can be removed.
  • a solvent that dissolves them and left for a while to be filtered off, or the complex is put into a column, and the washing solvent is allowed to flow down, so that the diluent is effective from inside the complex. Can be removed.
  • a water-soluble solvent such as methanol or acetone is used as a washing solvent, and the diluent can be easily removed by further washing the washing solvent with water.
  • the composite obtained in this manner may be used as it is for a filler for ion-exchange resin chromatography or as an adsorbent, or may be subjected to a post-reaction to be used as it is.
  • a functional group may be introduced into the resin for use.
  • the reaction for introducing a functional group is not limited, and a normal organic reaction can be performed.
  • the composite particles of perfluorocarbon sulfonic acid and porous silica which is one of the porous composites of the present invention, can be used as a solid acid catalyst by utilizing its large acidity.
  • the use form of the porous composite of the present invention as a reaction catalyst is not particularly limited, and examples thereof include a fluidized bed type, a fixed bed type, and a reactive distillation type.
  • the reaction solution and the solid catalyst can be easily separated by, for example, a filtration method.
  • the reaction product precipitates as a solid from the reaction solution for example, the reaction solution is separated from the catalyst and the product by a filtration method, then dissolved in a solvent that dissolves the product, and the product is dissolved. Can be separated from catalyst. If necessary, the complex of the present invention separated from the reaction system can be easily regenerated and purified by contact with a mineral acid.
  • the organic reaction using the porous composite of the present invention as a solid acid catalyst is not particularly limited.
  • alkylation of aromatic compounds such as benzene and toluene with olefins, alcohols, alkyl halides, alkyl esters, etc .
  • Isomerization, disproportionation and transalkylation dimerization of ⁇ -methylstyrene; di-tolization, sulphonation, sulfonylation and phosphorylation of aromatic compounds
  • isomerization of brominated aromatic compounds Cationic polymerization of olefins; synthesis reaction of ether and ester; synthesis reaction of acetal, thioacetal and gem-diacetate; hydrolysis reaction of epoxy group and ester group; transfer reaction such as pinacol / pinacolone; And condensation reactions such as dioxane synthesis.
  • the porous composite of the present invention has, for example, an ion-exchange group, its substantial ion exchange capacity is extremely high, and its mechanical strength is relatively small while the amount of ion exchanger is small. It has extremely excellent properties such as excellent resistance to cracking during use, and a relatively uniform particle size. Further, the ion exchanger using the porous composite of the present invention has a larger porosity and a skeleton having a columnar entangled structure as compared with a case where commercially available silica gel or porous glass is used as a carrier. Therefore, it has great strength.
  • the porous composite can be used as a stationary phase for gas chromatography and liquid chromatography, a stationary phase for preparative chromatography, a cell culture carrier, an adsorbent, a catalyst or its carrier, particularly an acid catalyst.
  • an esterification reaction applied acid catalyst such as an esterification reaction applied acid catalyst, an ester hydrolysis acid catalyst, a nitration reaction acid catalyst, an olefin hydration reaction acid catalyst, a trioxane synthesis acid catalyst, or cooling water of a nuclear power plant.
  • An ion exchange treatment agent of hot water can be used.
  • B is the area of the particle in the photograph
  • C is the area of the minimum circumscribed circle of the particle surface in the photograph.
  • the measurement pressure range was 0.1 to 20 OMPa, and the measurement hole radius was 3.7 to 750 nm.
  • a densitometer (trade name: Multi-Volume Densitometer 1305, manufactured by Micromeritex Corporation) using helium gas as the substance that enters the pores, the inorganic porous particles and And the specific gravity d (g / ml) of the complex.
  • the amount of pores per unit weight of 0 (mlg) was measured using a mercury porosimeter (trade name: PAS CAL — 240, manufactured by CE-Instrument).
  • the volume average particle diameter was measured using Microtrack X-100 manufactured by Honeywell.
  • ICP inductively coupled plasma
  • the measurement was performed with a differential scanning calorimeter (trade name: DSC 210, manufactured by Seiko Instruments Inc.).
  • the measurement conditions are as follows: in air, at a heating rate of 5 ° CZ, and in a measuring temperature range of 25 to 800 ° C.
  • micro compression tester (trade name: MCTM-500 type, manufactured by Shimadzu Corporation), measured at room temperature at a load speed of 0.79 g / sec, the load at the break point was calculated, and the following formula (5) was used. Was used to calculate the strength.
  • the porous composite was placed in a special column with a glass filter of 3 G attached to the bottom of a glass ring with a diameter of 100 mm and a length of 100 mm, and 1N hydrochloric acid was passed through the column to make a sulfonic acid type. Subsequently, the hydrochloric acid in the void was removed by flowing methanol. At this time, it was confirmed with litmus paper that the eluted methanol was neutral.
  • the temperature of hot air entering the drying tower is 230 ° C, the amount of hot air is 310 Nm 3 Z hours, and the amount of mixed liquid introduced is 90 LZ hours.
  • the obtained granulated powder (1 OmL) was calcined in an electric furnace at 350 ° C for 2 hours, and then at 690 ° C for 2 hours. This is added to 10OmL of hot water at 70 ° C, kept while stirring for 30 minutes, then filtered with a filter paper, washed with excess water, and then meshed with 400 mesh (opening of 32 ⁇ m). ) And a sieve having a mesh size of 200 (mesh size: 75 jm), and dried under reduced pressure at 70 ° C.
  • the average spheroidization ratio of the obtained porous silica having a large pore diameter was 86.5, and the columnar entangled skeleton structure having an average pore diameter of 675 nm, a porosity of 0.74, and a silica composition of 99.5% by weight was used. It was built. The strength was 1.3 kgf / mm 2 .
  • the average spheroidization ratio of the obtained porous silica having a large pore diameter was 87.0, and the average pore diameter was 87.0.
  • Example 2 Using this mixture, granulation was performed by spray drying in the same manner as in Example 1.
  • the obtained granulated powder (10 mL) was calcined in an electric furnace at 350 ° C. for 2 hours and then at 69 ° C. for 2 hours. This was added to 10OmL of hot water at 70 ° C, kept while stirring for 30 minutes, then filtered with filter paper, washed with excess water, and then meshed with 400 mesh (opening of 32 ⁇ m). ) And a sieve having a mesh size of 200 (mesh size: 75 ⁇ m), and then dried under reduced pressure at 70 ° C.
  • the average spheroidization ratio of the obtained porous silica having a large pore diameter was 84.5, and the average pore diameter was 84.5.
  • Example 1 The firing conditions were changed using the granulated particles prepared in Example 1. A porous material with a large pore diameter and a different average pore diameter having a spheroidization ratio of 86.5 and a porosity of 0.74 was obtained. Table 1 shows the firing conditions and the average pore size of the obtained porous body. Table 1 Firing temperature (° C) Firing time (hour) Average pore size obtained (nm) Example 4 700 1 820
  • silica gel 5D Take 20 g of silica gel 5D into a 50 OmL eggplant-shaped flask, add 14.8 mL of the above aqueous solution of the inorganic salt (98.6% based on the pore volume of silica gel) to this, and add a rotary evaporator. The mixture was rotated and mixed for 30 minutes. Then, it was dried in a vacuum dryer at 70 ° C under reduced pressure for 5 hours. 1 l mL of the above inorganic salt solution was added to the silica gel, and the mixture was rotated under the same conditions and dried. Further, 9 mL of an inorganic salt solution was added, and the third rotation mixing and drying were performed. The pore volume of the obtained inorganic salt-impregnated silica gel was 0.332 mL / g.
  • the average spheroidization ratio of the obtained porous silica having a large pore diameter was 69.6, and a columnar entangled skeleton having an average pore diameter of 81.4 nm, a porosity of 0.71, and a sily force composition of 99.6% by weight. It was a structure.
  • the strength was 0.7 kg fZmm 2 .
  • the solid content of this solution was 26% by weight.
  • granulation was carried out by spray drying in the same manner as in Example 1.
  • the obtained granulated powder (1 OmL) was calcined in an electric furnace at 350 ° C. for 2 hours and then at 69 ° C. for 2 hours. This was added to 10OmL of hot water at 70 ° C, kept while stirring for 30 minutes, then filtered off with filter paper, washed with excess water, and then meshed with 400 mesh (32 urn and 2 mesh). After classifying through a sieve of 00 mesh (opening of 75 ⁇ m), the mixture was dried under reduced pressure at 70 ° C.
  • the average spheroidization ratio of the obtained porous silica having a large pore diameter was 72.9.
  • the obtained granulated powder (1 OmL) was calcined in an electric furnace at 350 ° C for 2 hours and then at 700 ° C for 2 hours. This was added to 10OmL of hot water at 70 ° C, kept while stirring for 30 minutes, then filtered off with filter paper, washed with excess water, and reduced to 400 mesh (mesh size 32rn). After classification with a sieve of 200 mesh (opening of 75 ⁇ m), drying was performed at 70 ° C. under reduced pressure.
  • the average spheroidization ratio of the obtained spherical silica large pore porous material was 72.2. It had a columnar entangled skeletal structure with an average pore size of 3666 nm, a porosity of 0.69, and a silica composition of 99.0% by weight. The strength was 0.8 kgf / mm 2 .
  • the mixed aqueous solution was introduced into a spray dryer (trade name: OC-16, manufactured by Okawara Kakoki Co., Ltd.) while stirring, and granulated.
  • the rotating dish for generating droplets used had a diameter of 8 cm, and had a rotation speed of 2100 rpm.
  • the temperature at the inlet of the drying tower was 230 ° C, the amount of hot air was 310 Nm 3 / hour, and the introduced amount of the mixed liquid was 90 LZ hours.
  • the obtained granulated product was heated in an electric furnace at 350 ° C.
  • the obtained spherical inorganic porous body had a columnar entangled structure with an average pore diameter of 705 nm and a porosity of 0.70.
  • the pressure was reduced while heating in a water bath, and water-methanol as a solvent was removed by evaporation. This operation was repeated for a total of 5 times to obtain an inorganic porous material containing an acylplex.
  • the aqueous methanol solution of the acylplex fed in each operation was 14.8 g for the second time, 14.1 g for the third time, 13.6 g for the fourth time, and 13.2 g for the fifth time.
  • Part of the obtained inorganic porous material containing a complex is immersed in an excess of 5 wt% aqueous sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade) aqueous solution, kept at room temperature for 2 hours, and then filtered and dried. And heat-treated in air at 250 ° C. for 1 hour. After the heat treatment was completed, the mixture was taken out to room temperature and allowed to cool to obtain a porous inorganic-organic composite.
  • aqueous sodium chloride manufactured by Wako Pure Chemical Industries, Ltd., special grade
  • the exchange capacity of the composite was 0.20 meq / g per dry composite weight.
  • Example 11 A portion of the inorganic porous body containing a complex obtained by liquid impregnation and drying in 1 was immersed in an excess 5 wt% aqueous solution of sodium chloride (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and kept at room temperature for 2 hours. Then, the mixture was filtered, dried, and then heat-treated in an air at 250 ° C. for 30 minutes using an electric furnace. After the completion of the heat treatment, it was taken out to room temperature and allowed to cool.
  • sodium chloride special grade, manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 11 A portion of the inorganic porous body containing a complex obtained by liquid impregnation and drying in 1 was immersed in an excess 5 wt% aqueous solution of sodium chloride (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and kept at room temperature for 2 hours. Then, the resultant was filtered, dried, and then heat-treated in an air at 250 ° C. for 10 minutes using an electric furnace. After the completion of the heat treatment, it was taken out to room temperature and allowed to cool.
  • sodium chloride special grade, manufactured by Wako Pure Chemical Industries, Ltd.
  • the exchange capacity of the obtained composite was measured. However, when trying to flow methanol, the flow force became very slow. The methanol flow was completed overnight, and the measured value was 0.0 meq Zg. The elution rate was 100%.
  • the aqueous methanol solution of the aciplex fed in each operation was 14.8 g for the second run, 14.1 g for the third run, 13.6 g for the fourth run, 13.2 g for the fifth run, and 12.8 for the sixth run. g, 72.5 times, 12.5 g.
  • Part of the obtained inorganic porous material containing a complex is immersed in an excess of 5 wt% aqueous sodium chloride (manufactured by Wako Pure Chemical Industries, Ltd., special grade) aqueous solution, kept at room temperature for 2 hours, and then filtered and dried. And heat-treated in air at 250 ° C. for 1 hour. After the heat treatment, the sample was taken out into room temperature and allowed to cool.
  • aqueous sodium chloride manufactured by Wako Pure Chemical Industries, Ltd., special grade
  • This liquid was added to the above tetramethoxysilane mixed liquid and stirred.
  • the liquid immediately gelled and further solidified.
  • This solid was dried at 95 ° C for 24 hours. This was crushed in a mortar and then placed in a 3.5 M aqueous hydrochloric acid solution and left overnight. Thereafter, it was filtered off, washed with water, and it was confirmed that the washing solution became neutral, and dried at 95 ° C.
  • the exchange capacity of the obtained powder was 0.19 meq /.
  • Example 14 The powder before heat treatment obtained in Example 14 was subjected to a dimethyl sulfoxide heat treatment.
  • the subsequent exchange capacity was 0.05 meq Zg (74% elution).
  • SAC-13 manufactured by DuPont, USA, a mixture of naphion and silicide by a sol-gel method
  • the exchange capacity was 0.04 meq / g (elution rate 75%).
  • Example 11 Using the porous composite synthesized in Example 11 as a solid acid catalyst, a hydrolysis reaction of ethyl acetate was performed.
  • ethyl acetate (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) was added to 475 g of water to prepare a 5 wt% aqueous solution of ethyl acetate. Initially, the ethyl acetate and water were separated. When the mixture was stirred at room temperature, it became a homogeneous liquid in about 10 minutes. 200 g of this aqueous solution of ethinole acetate was taken, 0.50 g of the porous composite synthesized in Example 1 was added thereto, and the mixture was stirred and reacted at 57 ° C. After starting the reaction, 10 ml of the reaction solution was sampled at 30 minutes, 1 hour, 2 hours, and 3 hours.
  • the sampling liquid was diluted to 150 ml with water, and titrated with a 0.1 N aqueous sodium hydroxide solution (manufactured by Wako Pure Chemical Industries, Ltd., for titration). From the value, the concentration of acetic acid generated in the reaction solution was determined. The results were 2.2 mmol / L at 30 minutes, 4.0 mmol ZL at 1 hour, 7.6 mmol / L at 2 hours, and 11.2 mmo1Z at 3 hours.
  • This hydrolysis reaction can be analyzed by a primary reaction.
  • the reaction rate constant: k (1 / m i ⁇ ) can be calculated by the following equation (7).
  • C A is the concentration of acetic acid produced (mmo 1ZL)
  • C A is the initial ethyl acetate concentration (mmolZL)
  • t is the time (min).
  • reaction rate constant per functional group k 1 (1 / minZ equivalent) was calculated by the following equation (8) and used for comparison of solid acid catalyst performance.
  • k av is the reaction rate constant (lZmin)
  • F is the amount of catalyst used (g)
  • EC is the exchange capacity (equivalent Zg).
  • the reaction rate constant per functional group in the hydrolysis reaction of ethyl acetate of the porous composite obtained in Example 1 was 1.18 ZminZ equivalent.
  • Example 14 The same reaction as in Example 14 was performed, except that 0.55 g of Amberlyst 15 (manufactured by Rohm and House, USA) was used instead of the porous composite.
  • the concentration of acetic acid generated in the reaction was 7.8 mmoLZL in 30 minutes, 16.6 mmoL / L in 65 minutes, 32.OmmoLZL in 2 hours, and the reaction rate constant per functional group was 0. 2 / minZ equivalent, which was 6 times higher than the result of Example 14 by 1 Z.
  • a spherical inorganic large-pore porous body having a large average pore diameter and a high porosity, and having excellent mechanical rigidity and chemical resistance. It is easy to obtain a porous body with a relatively uniform particle shape, and despite its relatively large pores, it has excellent mechanical strength, so particles are not easily broken during use, handling is easy, and columns The column pressure can be prevented from increasing even when used after filling.
  • the porous composite of the present invention has a fluorine-containing organic substance substantially immobilized on a carrier, and can be used with stable performance. For example, it can be used relatively stably even in an environment where it comes into contact with a polar organic solvent.
  • the use efficiency of the fluorinated organic substance is excellent, and the effective use rate of the properties of the fluorinated organic substance, for example, the reaction in the functional group, is high for the supported amount of the fluorinated organic substance.
  • the use efficiency of separation, adsorption, etc. is excellent, the pore volume can be increased, so that the operating pressure of the separation column can be kept low.
  • a porous inorganic composite containing, for example, perfluorocarbon sulfonic acid as a fluorine-containing organic substance is useful as a solid acid catalyst because of its super-strong acidity, excellent heat resistance and solvent resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Corps inorganique sphérique poreux possédant un diamètre de 1 νm à 5 mm, une vitesse moyenne de globulisation égale ou supérieure à 75, un squelette présentant une structure entremêlée en forme de colonne, un diamètre moyen de pore de 100 à 2.000 nm et une porosité de 0,50 à 0,90.
PCT/JP1998/003681 1997-08-20 1998-08-20 Corps spherique poreux WO1999008960A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9/223795 1997-08-20
JP22379597 1997-08-20
JP29820597 1997-10-30
JP9/298205 1997-10-30

Publications (1)

Publication Number Publication Date
WO1999008960A1 true WO1999008960A1 (fr) 1999-02-25

Family

ID=26525692

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1998/003681 WO1999008960A1 (fr) 1997-08-20 1998-08-20 Corps spherique poreux

Country Status (1)

Country Link
WO (1) WO1999008960A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015211665A (ja) * 2014-01-29 2015-11-26 ダイキン工業株式会社 温度応答性基材、その製造方法及びその評価方法
JP2016044148A (ja) * 2014-08-25 2016-04-04 国立研究開発法人物質・材料研究機構 粒子形成方法及び粒子

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0615427B2 (ja) * 1984-11-15 1994-03-02 旭化成工業株式会社 無機多孔体とその製造方法
JPH07165414A (ja) * 1993-08-06 1995-06-27 Eniricerche Spa シリカ基材物質

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0615427B2 (ja) * 1984-11-15 1994-03-02 旭化成工業株式会社 無機多孔体とその製造方法
JPH07165414A (ja) * 1993-08-06 1995-06-27 Eniricerche Spa シリカ基材物質

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015211665A (ja) * 2014-01-29 2015-11-26 ダイキン工業株式会社 温度応答性基材、その製造方法及びその評価方法
US10689615B2 (en) 2014-01-29 2020-06-23 Daikin Industries, Ltd. Temperature-responsive base material, method for producing same, and method for evaluating same
JP2016044148A (ja) * 2014-08-25 2016-04-04 国立研究開発法人物質・材料研究機構 粒子形成方法及び粒子

Similar Documents

Publication Publication Date Title
US4732887A (en) Composite porous material, process for production and separation of metallic element
Yeskendir et al. From metal–organic framework powders to shaped solids: recent developments and challenges
US7128884B2 (en) Porous silica microsphere scavengers
JP3200623B2 (ja) 中空球状ケイ酸塩クラスターの製造方法
US6867275B2 (en) Solid media
JP2875824B2 (ja) 多孔性硬質樹脂およびその製造方法
US6054111A (en) Lyotropic liquid-crystal phases of amphiphilic block copolymers as template for the preparation of mesoporous solids
CN103933911B (zh) 一种聚合物基分级孔结构互锁微囊的制备方法
JP2006290680A (ja) ナノ球状粒子多孔体及びその合成方法
KR100449372B1 (ko) 조절된 티타늄 분포를 갖는 실리카 촉매
JPH11199351A (ja) 多孔性無機有機複合体およびその製造方法
JP4574215B2 (ja) 重合体被覆粒子粉末の製造方法及び、重合体被覆無機粒子
JP4712223B2 (ja) 固体酸触媒
WO1999008960A1 (fr) Corps spherique poreux
JPH11171947A (ja) 多孔性無機有機複合体
KR102257560B1 (ko) Mof-비즈 하이브리드 구형 입자 및 그 제조방법
JP2008264732A (ja) 多孔性イオン交換体およびその製造方法
Liu et al. Facile synthesis of hollow mesoporous silica microspheres via surface sol–gel process on functional polymeric microsphere template
JP4146536B2 (ja) 低滲出性（ｌｏｗ−ｂｌｅｅｄｉｎｇ）カチオン交換体の調製方法
WO1998016467A1 (fr) Composite mineral poreux et procede de separation d'elements metalliques a l'aide de celui-ci
JPH11319574A (ja) エステル化用触媒
JPH11216363A (ja) オレフィンの水和反応用触媒
JP3680342B2 (ja) 遷移アルミナ成形体の製造方法
JP4522105B2 (ja) 物質の液体からの分離方法
JPH11267499A (ja) 熱水処理用吸着剤

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA CN JP KR SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: KR

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA