WO2020054134A1 - 有機無機複合材料 - Google Patents
有機無機複合材料 Download PDFInfo
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- WO2020054134A1 WO2020054134A1 PCT/JP2019/020643 JP2019020643W WO2020054134A1 WO 2020054134 A1 WO2020054134 A1 WO 2020054134A1 JP 2019020643 W JP2019020643 W JP 2019020643W WO 2020054134 A1 WO2020054134 A1 WO 2020054134A1
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- organic
- composite material
- inorganic composite
- organosilicon compound
- silica carrier
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
Definitions
- the present invention relates to an organic-inorganic composite material in which the surface of a silica carrier is modified with an organosilicon compound having a functional group.
- Silica can change its chemical and physical properties as an inorganic oxide material by modifying its surface with an organosilicon compound, and silica with such a modification can be used in various adsorption and catalytic applications. It was known as an inorganic composite material. (Patent Documents 1 to 4, Non-Patent Document 1)
- Scavenger which is an application of adsorbent, separates transition metal ions from the solvent by adsorbing the transition metal ions dissolved in the solvent with the functional group of the organosilicon compound and filtering it together with the inorganic oxide material. It is.
- Such a scavenger adsorbs transition metal ions through chemical bonding, it is possible to separate low concentrations of transition metal ions. Therefore, it is particularly useful for separating expensive components such as noble metals from a solution.
- Examples of the solution containing the noble metal component include a solution used for a reaction using a homogeneous catalyst.
- a homogeneous catalyst uses a solution of a noble metal salt or noble metal complex as a catalyst.
- a noble metal salt includes a noble metal complex.
- concentration of such a noble metal salt is high, precipitating the noble metal salt in the solution by means such as neutralization and filtering the solution is one of the efficient methods for separating the noble metal component.
- Scavengers are particularly effective in separating noble metal components from such low concentration noble metal salt solutions.
- the solution containing the low-concentration noble metal component is not limited to the solution used for the homogeneous catalyst, but also includes a washing solution generated in the process of manufacturing a heterogeneous catalyst and a waste solution generated in the process of manufacturing the noble metal compound itself. . Scavengers are also widely used to separate noble metal components from such low concentration noble metal solutions.
- the composite material of an inorganic carrier and an organosilicon compound as in the present invention is also known as a catalyst.
- a catalyst is obtained by chemically bonding a metal component serving as an active species to a reactive group of an organosilicon compound modifying a silica carrier, and using an organic-inorganic composite material bonded with the metal component as a catalyst.
- organosilicon compound on the support must be tightly bound to the silica support. If the bond is weak or there is an unbonded organosilicon compound, the organosilicon compound is released into the solution in a state of being bound to the transition metal component or the like.For example, when the scavenger is used, the separation efficiency by filtration is low. It will be something.
- the organic silicon compound needs to be firmly bonded to the silica carrier, but the organic silicon compound used for modifying the organic-inorganic composite material is modified.
- the structure is not significantly changed before and after, and it is difficult to specify the strength of the bond, that is, the quality of the performance before use.
- silica is known to have high physical adsorption capacity as a carrier.
- the organic silicon compound forms a chemical bond on the surface of the silica carrier, so that the bond becomes strong.
- a considerably strong supported state is maintained. For this reason, there may be no difference in the elution of the organosilicon compound into the filtrate or the washing liquid in the degree of filtration or washing in the loading process.
- an organic-inorganic composite material in which an organosilicon compound is firmly bonded to a silica carrier is expected to have excellent industrial effects, but it is not actually manufactured and its physical properties are not measured. I wouldn't decide whether it would be industrially useful.
- An object of the present invention is to obtain an organic-inorganic composite material that can be confirmed to be industrially useful only by absorbance measurement without performing analysis or measurement using an expensive analyzer or complicated means.
- a silica carrier is an organic-inorganic composite material modified with an organosilicon compound containing a functional group that binds to a transition metal element and an alkoxysilane,
- an ultraviolet-visible spectrophotometer When the absorbance of the solution containing the organic-inorganic composite material measured by an ultraviolet-visible spectrophotometer is within a specific range, it is industrially useful as a scavenger, a catalyst, etc., without measuring physical properties. Heading, the present invention has been completed. Further, the present inventors have found that the organic-inorganic composite material can be produced when the water content of the silica carrier before the modification is in a specific range, and completed the present invention.
- the present invention is an organic-inorganic composite material obtained by modifying a silica carrier with an organosilicon compound containing a functional group that binds to a transition metal element and an alkoxysilane,
- An organic-inorganic composite material characterized in that the absorbance at a wavelength of 400 [nm] measured by an ultraviolet-visible spectrophotometer of 0.5 or less is obtained by removing a solid content from the mixed solution prepared under the following measurement conditions. is there.
- the present invention relates to the production of an organic-inorganic composite material by modifying a silica carrier with an organosilicon compound containing a functional group that binds to a transition metal element and an alkoxysilane.
- the present invention is a scavenger containing the above-mentioned organic-inorganic composite material.
- the present invention also relates to the organic-inorganic composite material containing a transition metal element and a catalyst containing the same.
- the organic-inorganic composite material of the present invention is characterized in that the organosilicon compound is firmly bonded to the silica carrier, and can be firmly bonded to the transition metal element. They are also industrially useful.
- the organic-inorganic composite material of the present invention can efficiently separate the transition metal element adsorbed as a scavenger by filtration.
- the organic-inorganic composite material of the present invention can be easily reused as a catalyst such as a heterogeneous catalyst or separated from a reaction system.
- the organic-inorganic composite material of the present invention can strongly bind not only a metal as a metal but also a metal ion that can be expected to have higher activity as the transition metal element. Can also be expected.
- FIG. 1 is a schematic view of an organic-inorganic composite material obtained in Example 1 of the present invention.
- an organic silicide and a palladium component are firmly bonded to a silica carrier in a bonded state.
- 2 shows an organic-inorganic composite material showing the appearance of the above.
- FIG. 2 is a schematic diagram of the organic-inorganic composite material obtained in Comparative Example 1 of the present invention, and shows a state in which the bonding between the silica carrier and the organic silicide is incomplete in a THF solution to which palladium acetate is added.
- the organic-inorganic composite material of the present invention is an organic-inorganic composite material obtained by modifying a silica carrier with an organosilicon compound containing a functional group capable of binding to a transition metal element and alkoxysilane.
- silica carrier used in the organic-inorganic composite material of the present invention examples include the following.
- the shape of the organic-inorganic composite material of the present invention is not particularly limited since the organosilicon compound modifies the silanol group on the silica surface as a carrier, and the organic-inorganic composite material is formed into a spherical shape, a cylindrical shape, a cylindrical shape, or the like. It may have a given geometrical shape, and in the case of a cylindrical shape, its space may be partitioned by walls of any shape. Further, not only such a molded carrier but also powdered or gel-like silica may be used.
- the shape of the silica carrier is not limited as described above, but when the organic-inorganic composite material of the present invention is used as a scavenger, the shape is preferably spherical. Due to the spherical shape, clogging hardly occurs at the time of filtration from the reaction system, rapid separation becomes possible, and the working time is shortened, which is an industrially advantageous shape.
- a spherical silica carrier When a spherical silica carrier is used, its size is not particularly limited and may be appropriately selected according to the intended use, but when the organic-inorganic composite material of the present invention is used as a scavenger, its particle size Has a volume-based cumulative 10% particle diameter (D10 diameter) of preferably from 30 to 100 ⁇ m, more preferably from 50 to 100 ⁇ m. Filtering can be performed efficiently because the particle size is as large as possible, and the geometric surface area per unit volume and weight in the bulk state increases when the particle size is not too large. And the amount of the adsorbable component per unit weight and unit volume of the component to be adsorbed increases.
- the diameter of the spherical silica is a value measured by a laser diffraction type particle size distribution analyzer.
- the physical properties of the silica used in the present invention are also not particularly limited because they are appropriately selected according to the environment in which the organic-inorganic composite material of the present invention is used, and are generally used as a carrier for a heterogeneous catalyst. May be the physical properties to be performed. Specific surface area value, pore volume, pore diameter and the like can be mentioned.
- the specific surface area of the silica carrier is preferably from 200 to 1,500 m 2 / g, more preferably from 500 to 1,000 m 2 / g.
- the specific surface area is high, the area per weight of the carrier capable of modifying the organosilicon compound is large, and the ability to adsorb the transition metal is increased.
- the specific surface area value is not too large, the stability as a carrier is excellent, and the density of the organosilicon compound modified on the carrier surface can be easily optimized.
- the silica carrier specific surface area is a value measured by a nitrogen gas adsorption method.
- the pore volume is preferably from 0.3 to 5 mL / g, more preferably from 0.8 to 2 mL / g.
- the average pore diameter is preferably from 2 to 20 nm, more preferably from 3 to 10 nm.
- the pore volume and the average pore diameter are values measured by a nitrogen gas adsorption method.
- silica carriers that are commercially available include water. There are various reasons why water is contained in the silica carrier, and there is a capillary condensation effect derived from pores of the silica carrier. By having the capillary condensation, moisture in the atmosphere during the manufacturing process or during storage is absorbed. In other words, when humidity is high during the manufacturing process or during storage, the amount of water vapor adsorbed by the pores increases, and the amount of water vapor adsorbed by the pores during drying decreases. In particular, during drying, moisture adsorbed in the pores is also released, and the water content of the silica carrier is reduced.
- the water content of the silica carrier used in the present invention is important in producing the organic-inorganic composite material of the present invention, and is preferably 0.15% by weight or more in terms of mass of the silica carrier before modification. ⁇ 3 wt% is more preferable, and 0.2-2 wt% is most preferable.
- the water content of the silica can be adjusted according to a conventional method such as drying and immersion in water. Although the reason why such a suitable water content is present is not clear, it is thought that there is an effect on silanol groups formed in the surface modification of the silica carrier with the organosilicon compound, especially at a low water content. It is presumed that such an effect is large.
- the silica carrier surface may be covered with water molecules and it may be difficult to modify the surface with the organosilicon compound, or the silica carrier itself may aggregate to form a silica carrier due to the organosilicon compound.
- the modification to the surface may be uneven.
- the water content can be measured according to a conventional method.
- the silica carrier can be dried by heating, and the water content can be determined by the weight difference before and after the drying.
- the water content specified by the mass difference between the silica carrier before and after the drying treatment at 110 ° C. for 16 hours is defined as the water content of the silica carrier.
- organosilicon compound used for the organic-inorganic composite material of the present invention which modifies the silica carrier and contains a functional group capable of binding to a transition metal element and alkoxysilane.
- Organic silicon compound is not particularly limited as long as it is an organic silicon compound that can be chemically bonded to the surface of the silica carrier and contains a functional group and an alkoxysilane bonded to a transition metal element, and may be a known compound available on the market. .
- the functional group bonded to the transition metal element is not particularly limited, and examples thereof include a vinyl group, an epoxy group, a styryl group, a methacryl group, an acryl group, an amino group, an ureido group, an isocyanate group, and a thiol group.
- the thiol group is also known as a functional group that forms a self-assembled monolayer on various metal surfaces such as gold, silver, copper, platinum, palladium, and mercury, and is also used in scavenger applications of transition metal elements. It can be said that it is preferable.
- the alkoxysilane is not particularly limited as long as it can form a siloxane bond (Si—O—Si) with the Si element on the silica carrier.
- a methoxy group, an ethoxy group, a dialkoxy group, Trialkoxy groups and the like are commercially available at a low price, and are excellent in price competitiveness for the use of the present invention, but may be poor in binding to a silica carrier. .
- an organic-inorganic composite material modified with an organosilicon compound that is not firmly bonded to a silica carrier can be sorted out by an easy method, and an organic-inorganic composite material suitable for applications such as scavengers Can be provided.
- Preferred organosilicon compounds include, for example, thiol compounds selected from the following formulas (III) and (IV).
- Y is 2X + 1, X is preferably 0 to 5, and C X H Y O is more preferably -OCH 3 or -OC 2 H 5 in consideration of reactivity, easiness of handling, cost, and the like.
- b is 2a, and a is preferably 1 to 5, more preferably 2 to 3.
- b is 2a, and a is preferably 1 to 5, more preferably 2 to 3.
- 3-mercaptopropyltrimethoxysilane represented by the following formula (I) is preferable.
- an organic-inorganic composite material having the structure of the following formula (II) is obtained.
- Si 3+ forms a siloxane bond (Si—O—Si) with three Si elements on the silica carrier and is firmly supported on the silica carrier.
- Method of modifying silica carrier The method of modifying a silica carrier with an organosilicon compound containing a functional group capable of binding to a transition metal element and an alkoxysilane is not particularly limited as long as the method is a method of binding the organosilicon compound and a silanol group on the surface of the silica carrier through a siloxane bond. Although not mentioned, for example, a method of mixing a silica carrier and an organosilicon compound in a solvent may be mentioned.
- the solvent examples include organic solvents such as aromatic hydrocarbons such as toluene and xylene, aliphatic saturated hydrocarbons such as pentane and hexane, and alcohols such as methanol and ethanol. These solvents may be used alone or in combination of two or more.
- organic solvents such as aromatic hydrocarbons such as toluene and xylene, aliphatic saturated hydrocarbons such as pentane and hexane, and alcohols such as methanol and ethanol. These solvents may be used alone or in combination of two or more.
- the ratio of the solvent and the silica carrier can be arbitrarily selected, but if the solvent is too small, the silica carrier and the organosilicon compound are difficult to be mixed. Since the concentration becomes low, a long time is required for bonding. Therefore, the ratio of the solvent to the silica carrier is preferably 1:10 to 100: 1 by volume.
- the ratio between the organosilicon compound and the silica carrier can be arbitrarily selected, but if the organosilicon compound is too small, the concentration of the organosilicon compound on the organic-inorganic composite material becomes dilute, and conversely, if it is too large. Since the amount of organosilicon compounds that cannot be bonded to the surface of the silica carrier increases, the volume ratio is preferably from 1: 1000 to 100: 1.
- the mixture may be kept at room temperature, but may be heated. When heating here, the temperature is not particularly limited, but is preferably 90 to 150 ° C., and more preferably 110 to 130 ° C. By heating, the time required for modifying the silica carrier can be reduced, and the energy cost required for production can be reduced.
- the structure of the organosilicon compound can be maintained, and the metal-adsorbing performance corresponding to the amount of the organosilicon compound modified on the silica carrier can be exhibited.
- the organosilicon compound is mixed with the silica carrier in the solvent as described above to form an organic-inorganic composite material in which the silica carrier is modified with the organosilicon compound.
- the organic-inorganic composite material mixed with the solvent may be subjected to separation from the mixed solution from the solvent, washing, and drying as necessary in a later step.
- the technique applied in such a post-process is not particularly limited, and may be selected from techniques widely practiced by those skilled in the art. For example, in the case of separation, physical filtration such as centrifugation, natural filtration, or suction filtration may be used, or a combination thereof may be used. If washing, it may be washed by mixing the precipitate or the filtrate after separation with the solvent used for mixing the organosilicon compound and the silica carrier, or may be washed by supplying a solvent for filtration. May be combined.
- the organic-inorganic composite material may be solidified through the separation and drying steps, but may be subjected to crushing and pulverizing treatment as necessary.
- the thus obtained organic-inorganic composite material of the present invention has a high bonding strength between the silica carrier and the organosilicon compound.
- the conditions for this measurement are as follows. This measurement condition can be said to be a harsh stirring condition based on the use of the catalyst reaction or as a scavenger, and the degree of elimination of the organosilicon compound under such conditions is an industrially significant index.
- THF solution tetrahydrofuran
- This THF is a solvent that is frequently used in a synthesis reaction using a complex, is easily available, has excellent solubility of palladium acetate, is an aprotic solvent, has a small effect on siloxane bonds, and is a solvent suitable for measurement purposes. You can say that.
- the temperature at the time of mixing is not particularly limited, and may be, for example, about 15 to 25 ° C.
- an organic-inorganic composite material containing 0.147 [mmol] of an organosilicon compound is mixed in a THF solution under the above conditions to prepare a mixed solution.
- the amount of the silica carrier is not particularly limited, but the amount [mmol / g] of the organosilicon compound in the organic-inorganic composite material is preferably 0.5 or more, and more preferably 0.8 or more. More preferably, there is.
- the amount of the organosilicon compound is dominant in the bond with a transition metal such as a noble metal, there is no theoretical problem if the amount is less than 0.5, but the amount of the organosilicon compound in the organic-inorganic composite material (ratio ) Is too low, the total amount of the organic-inorganic composite material required for bonding with a transition metal such as a noble metal becomes too large, which may not be industrially preferable.
- a large amount (high ratio) of the organosilicon compound in the organic-inorganic composite material indicates that the organic silicon compound per unit weight of the organic-inorganic composite material is large, which is high as an adsorbent material. It can also be said that performance is an index that can be expected.
- the fact that the amount (ratio) of the organosilicon compound in the organic-inorganic composite material is large (high) means that the density of the organosilicon compound on the surface of the silica carrier is high, and although it depends on the surface state of the silica carrier, excessive If the density is too high, it may be difficult to maintain the bonding stability of the organosilicon compound.
- the amount (ratio) of the organosilicon compound in the organic-inorganic composite material is preferably 2 or less, and more preferably 1.5 or less.
- the mixed solution obtained by mixing the THF solution and the organic-inorganic composite material as described above is further subjected to removal of silica as a solid to form a solution, and the absorbance of the solution is measured.
- the method for removing solids is not particularly limited, and any method may be used, such as filtration, centrifugation, precipitation of solids, and separation of supernatant. Can be measured.
- ⁇ ⁇ Of these, it is preferable that the removal operation in an open system be performed promptly in consideration of the possibility of concentrating the solution by volatilization of THF as a solvent.
- An example of such a filtering means is suction filtration.
- suction filtration When the solid is precipitated and the supernatant is collected, it is necessary to allow the solid to sufficiently precipitate. Therefore, it is preferable to allow the solid to stand for 12 hours or more in a sealed state. Thus, a mixed solution is prepared.
- the solution prepared above is measured for absorbance at a wavelength of 400 [nm] measured with an ultraviolet-visible spectrophotometer.
- the solution containing the organic-inorganic composite material of the present invention has an absorbance of 0.5 or less, preferably 0.3 or less.
- the absorbance of the solution obtained by simply mixing only palladium acetate and THF under the above conditions was 2.6. This can be said to be the coloring of THF with palladium acetate.
- the palladium component in the THF solution is adsorbed by the organic-inorganic composite material.
- the color of the THF solution on which the palladium component has been adsorbed fades.
- the organosilicon compound bound to palladium is detached from the surface of the silica carrier due to stress caused by stirring or the like for promoting adsorption. It is difficult to remove the separated organosilicon compound from the solution by simple filtration.
- Such a drawback is the elimination of the active species from the support in the case of a catalyst, and in the reuse of the catalyst by filtration from the reaction system, the amount of the active species carried decreases with each filtration. Not only does the activity as a catalyst decrease, but also the problem of mixing of active species into the reaction product arises.
- the transition metal element such as a noble metal to which the organosilicon compound desorbed from the silica carrier is adsorbed cannot be removed by filtration, leading to a decrease in the recovery rate of the transition metal element.
- the performance of the organic-inorganic composite material of the present invention is not only measured by absorbance, but also determined by actually measuring the amount of a transition metal element such as a noble metal represented by palladium adsorbed on the organic-inorganic composite material.
- the transition metal element may be quantified by any method effective for metal quantification such as ICP emission spectroscopy, but may be derived from Lambert-Beer's law based on absorbance.
- the transition metal element to which the organic-inorganic composite material of the present invention can bind is not particularly limited, and includes, for example, palladium, platinum, copper, mercury, silver, lead, and the like.
- organic-inorganic composite material of the present invention can be used, for example, as a scavenger of a transition metal element as long as the transition metal element is not bound thereto.
- the organic-inorganic composite material of the present invention is used as a catalyst for hydrogenation or the like as long as a transition metal element such as palladium, platinum, or copper having a catalytic action is bonded to the transition metal element. be able to.
- the method for bonding the transition metal element to the organic-inorganic composite material of the present invention is not particularly limited, and may be mixed with a carrier in a solvent, stirred, appropriately heated, or the like.
- Example 1 Preparation of organic-inorganic composite material: In a reaction vessel filled with nitrogen gas, n-paraffin: 120 L, silica carrier (specific surface area: 750 m 2 / g, pore volume: 1.24 ml / g, average pore diameter: 6.6 nm, average particle diameter (D10): 62 ⁇ m, water content: 0.31 wt%): 40 kg and 3-mercaptopropyltrimethoxysilane (organosilicon compound of formula (I)): 12 kg were stirred for 8 hours while heating to 120 ° C. Thereafter, the heating was stopped and the reaction vessel was allowed to stand for 16 hours. The reaction vessel was cooled with water and cooled to room temperature, and the solid content was filtered using a filter. Vacuum drying was performed on the filtered solids while heating to 60 ° C. to obtain a powdered organic-inorganic composite material.
- silica carrier specific surface area: 750 m 2 / g, pore volume: 1.24
- the particle size of the silica carrier was measured using a laser diffraction type particle size distribution analyzer HRA manufactured by Microtrac Bell Co., Ltd. The specific surface area and average pore diameter were measured by Shimadzu Corporation. A pore distribution measuring device ASAP2420 was used, and TriStar II II 3020 manufactured by Micromeritics was used for measurement of the pore volume and the average pore diameter.
- Comparative example 1 Preparation of organic-inorganic composite material: An organic-inorganic composite material was prepared in the same apparatus and in the same procedure, except that the silica carrier of Example 1 was subjected to a drying treatment so as to have a water content of 0.1 wt%.
- Test example 1 The performance of the organic-inorganic composite material obtained in Example 1 and Comparative Example 1 as a scavenger was evaluated.
- the amount of the organosilicon compound supported on the silica carrier was substantially the same.
- UV-visible spectrophotometer U-3310 manufactured by Hitachi High-Tech Science Corporation
- Spectrophotometer measurement cell quartz, optical path length 10 [mm]
- Example 1 a remarkable difference was observed in coloring behavior and palladium adsorption performance due to a slight difference in water content of the silica carrier before modification. It was also found that the performance could be predicted by measuring the absorbance.
- the organic-inorganic composite material of the present invention can be used for scavengers, catalysts, and the like. That's all
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Abstract
Description
下記測定条件により調製された混合液から固形分を除去した溶液の紫外可視分光光度計で測定された波長400[nm]における吸光度が0.5以下であることを特徴とする有機無機複合材料である。
[測定条件]
<発色試薬>
金属換算パラジウム濃度が1[g/l]である酢酸パラジウムのテトラヒドロフラン溶液15[ml]
<粉体としての有機無機複合材料>
有機ケイ素化合物換算で0.147[mmol]
<混合条件>
攪拌子:長さ1[cm]、直径4[mm]
回転数:300[rpm]
混合容器:内径25[mm]円筒形密閉容器
攪拌時間:1[時間]
<分光光度計測定セル>
光路長:10[mm]
修飾前のシリカ担体の含水量が、シリカ担体の質量換算で、0.15wt%以上であることを特徴とする上記有機無機複合材料の製造方法である。
本発明の有機無機複合材料は、有機ケイ素化合物が担体としてのシリカ表面のシラノール基を修飾するものであることから、その形状は特に限定されるものでは無く、球状、円柱状、円筒状など成型された幾何学的な形状を有するものであっても良く、円筒状についてはその空間が任意の形状の壁により仕切られていても良い。また、このような成型担体のみならず粉体やゲル状のシリカであっても良い。
本発明に使用されるシリカの物性も、本発明の有機無機複合材料を使用する環境に応じて適宜選択するもので特に限定されるものではなく、不均一系触媒用の担体として一般的に使用される物性であっても良い。比表面積値、細孔容積、細孔径等が挙げられる。
通常工業的に入手可能なシリカ担体には水分が含まれる。シリカ担体に水分が含まれる理由は様々であるが、シリカ担体が有する細孔に由来した毛細管凝縮作用が挙げられる。毛細管凝縮を有することで、製造工程や保管中の雰囲気中の水分を吸収してしまう。言い換えると、製造工程や保管中の湿度が高いときは細孔が吸着する水蒸気の量が増え、乾燥時には細孔に吸着される水蒸気の量は少なくなる。特に乾燥時には細孔に吸着されている水分も放出されシリカ担体が含有する含水量が減少する。
有機ケイ素化合物としては、シリカ担体表面に化学結合可能で、遷移金属元素と結合する官能基とアルコキシシランとを含む有機ケイ素化合物であれば特に限定されず、市場から入手可能な公知の化合物で良い。
シリカ担体を、遷移金属元素と結合する官能基とアルコキシシランとを含む有機ケイ素化合物で修飾する方法は、有機ケイ素化合物とシリカ担体表面のシラノール基とをシロキサン結合をもって結合させる方法であれば特に限定されないが、例えば、溶媒中でシリカ担体と有機ケイ素化合物を混合する方法等が挙げられる。
<発色試薬>
金属換算パラジウム濃度が1[g/l]である酢酸パラジウムのテトラヒドロフラン溶液15[ml]
<粉体としての有機無機複合材料>
有機ケイ素化合物換算で0.147[mmol]
<混合条件>
攪拌子:長さ1[cm]、直径4[mm]
回転数:300[rpm]
混合容器:内径25[mm]円筒形密閉容器
攪拌時間:1[時間]
<分光光度計測定セル>
光路長:10[mm]
上記測定において、発色試薬として、金属換算パラジウム濃度が1[g/l]である酢酸パラジウムのテトラヒドロフラン(THF)溶液(以下、「THF溶液」という)15[ml]を使用した。
上記で調製された溶液は、紫外可視分光光度計で測定された波長400[nm]における吸光度を測定する。本発明の有機無機複合材料を含む溶液は、吸光度が0.5以下であり、好ましくは0.3以下である。
本発明の有機無機複合材料が結合可能な遷移金属元素としては、特に限定されず、例えば、パラジウム、白金、銅、水銀、銀、鉛等が挙げられる。
本発明の有機無機複合材料は、遷移金属元素を結合させていない状態であれば、例えば、遷移金属元素のスカベンジャーに使用することができる。
有機無機複合材料の調製:
窒素ガスで満たされた反応容器中で、n-パラフィン:120L、シリカ担体(比表面積値:750m2/g、細孔容積:1.24ml/g、平均細孔径:6.6nm、平均粒子径(D10):62μm、含水量:0.31wt%):40kgと3-メルカプトプロピルトリメトキシシラン(式(I)の有機ケイ素化合物):12kgを120℃まで昇温しながら8時間攪拌した。その後、加熱を止め16時間放置し、反応容器を水冷して室温まで冷却し、フィルターを使用して固形分を濾過した。濾別された固形分について60℃に加熱しながら真空乾燥を施し、粉体の有機無機複合材料を得た。
有機無機複合材料の調製:
実施例1のシリカ担体に乾燥処理を施し、含水量が0.1wt%としたものを用いる以外は、同じ装置、同じ手順で有機無機複合材料を調製した。
実施例1および比較例1で得られた有機無機複合材料のスカベンジャーとしての性能を評価した。
上記の様にして得られた有機無機複合材料について、ICP発光分光分析法を用いて硫黄元素の量を測定し、シリカ担体に担持された有機ケイ酸化合物の量を測定した。ICP発光分光分析法に使用する試料としては、800℃で有機無機複合材料を苛性ソーダと過酸化ナトリウムでアルカリ溶融したものを水で抽出した後に定容したものを使用した。その結果を表1に示した。
実施例1および比較例1の有機無機複合材料について、3-メルカプトプロピルトリメトキシシランの仕込み量換算で0.147[mmol]を、金属換算パラジウム濃度が1[g/L]である酢酸パラジウムのテトラヒドロフラン溶液15[ml]と、下記条件で混合した。
<混合条件>
攪拌子:長さ1[cm]、直径4[mm]
回転数:300[rpm]
混合容器:内径25[mm]円筒形密閉容器(キャップ付きスクリュー管
)
温度:23℃
攪拌時間:1[時間]
紫外可視分光光度計:株式会社日立ハイテクサイエンス社製U-3310
分光光度計測定セル:石英製、光路長10[mm]
実施例1および比較例1の吸光度測定のために調製した濾液について、そのパラジウム含有量をICP発光分光分析法で測定し、酢酸パラジウムとしての仕込み量との差からパラジウム吸着率を求め、スカベンジャーとしての性能を比較した。結果を表3に示した。
以 上
Claims (10)
- シリカ担体を、遷移金属元素と結合する官能基とアルコキシシランとを含む有機ケイ素化合物で修飾した有機無機複合材料であって、
下記測定条件により調製された混合液から固形分を除去した溶液の紫外可視分光光度計で測定された波長400[nm]における吸光度が0.5以下であることを特徴とする有機無機複合材料。
[測定条件]
<発色試薬>
金属換算パラジウム濃度が1[g/l]である酢酸パラジウムのテトラヒドロフラン溶液15[ml]
<粉体としての有機無機複合材料>
有機ケイ素化合物換算で0.147[mmol]
<混合条件>
攪拌子:長さ1[cm]、直径4[mm]
回転数:300[rpm]
混合容器:内径25[mm]円筒形密閉容器
攪拌時間:1[時間]
<分光光度計測定セル>
光路長:10[mm] - 有機無機複合材料中の有機ケイ素化合物の量[mmol/g]が、0.5以上である請求項1記載の有機無機複合材料。
- 更に、遷移金属元素を含むものである請求項1~4の何れかに記載の有機無機複合材料。
- 遷移金属元素がパラジウムである請求項5記載の有機無機複合材料。
- シリカ担体を、シリカ担体上の遷移金属元素と結合する官能基とアルコキシシランとを含む有機ケイ素化合物で修飾して有機無機複合材料を製造するにあたり、
修飾前のシリカ担体の含水量が、シリカ担体の質量換算で、0.15wt%以上であることを特徴とする請求項1~4の何れかに記載の有機無機複合材料の製造方法。 - 請求項5または6記載の有機無機複合材料を含むことを特徴とする触媒。
- 請求項1~4の何れかに記載の有機無機複合材料を含むことを特徴とするスカベンジャー。
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Citations (6)
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JP2004175793A (ja) * | 2002-11-15 | 2004-06-24 | Toyota Central Res & Dev Lab Inc | 有機修飾基の無機系固体への結合方法 |
JP2006052357A (ja) * | 2004-08-16 | 2006-02-23 | Denki Kagaku Kogyo Kk | 充填材及びその製造方法 |
WO2009110531A1 (ja) * | 2008-03-07 | 2009-09-11 | 独立行政法人産業技術総合研究所 | 有機無機複合材料およびその利用 |
JP4964772B2 (ja) * | 2004-08-04 | 2012-07-04 | フォスフォニックス リミテッド | 置換有機ポリシロキサン類及びそれらの使用 |
JP2013043791A (ja) * | 2011-08-23 | 2013-03-04 | Nof Corp | 変性中空シリカ微粒子 |
JP2016022465A (ja) * | 2014-07-24 | 2016-02-08 | 株式会社東芝 | ヨウ素吸着剤、水処理用タンク、及びヨウ素吸着システム |
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DE19540497A1 (de) | 1995-10-31 | 1997-05-07 | Degussa | Sulfonat- und mercaptogruppenhaltige anorganische Trägermaterialien, Verfahren zu ihrer Herstellung und Verwendung als Katalysatoren |
CA2499782A1 (en) * | 2005-03-07 | 2006-09-07 | Queen's University At Kingston | Sol gel functionalized silicate catalyst and scavenger |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2004175793A (ja) * | 2002-11-15 | 2004-06-24 | Toyota Central Res & Dev Lab Inc | 有機修飾基の無機系固体への結合方法 |
JP4964772B2 (ja) * | 2004-08-04 | 2012-07-04 | フォスフォニックス リミテッド | 置換有機ポリシロキサン類及びそれらの使用 |
JP2006052357A (ja) * | 2004-08-16 | 2006-02-23 | Denki Kagaku Kogyo Kk | 充填材及びその製造方法 |
WO2009110531A1 (ja) * | 2008-03-07 | 2009-09-11 | 独立行政法人産業技術総合研究所 | 有機無機複合材料およびその利用 |
JP2013043791A (ja) * | 2011-08-23 | 2013-03-04 | Nof Corp | 変性中空シリカ微粒子 |
JP2016022465A (ja) * | 2014-07-24 | 2016-02-08 | 株式会社東芝 | ヨウ素吸着剤、水処理用タンク、及びヨウ素吸着システム |
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