JP5276777B2 - Method for producing porous body - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims description 161
- 238000009826 distribution Methods 0.000 claims description 39
- 238000002441 X-ray diffraction Methods 0.000 claims description 37
- 239000004094 surface-active agent Substances 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 8
- 208000019901 Anxiety disease Diseases 0.000 abstract 1
- 125000004429 atom Chemical group 0.000 description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 16
- -1 silicon alkoxide Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000000470 constituent Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000223 polyglycerol Polymers 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229930182558 Sterol Natural products 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- OKSFAFCZNADJOC-UHFFFAOYSA-N propane-1,2,3-triol tetradecanoic acid Chemical compound OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.OCC(O)CO.CCCCCCCCCCCCCC(O)=O OKSFAFCZNADJOC-UHFFFAOYSA-N 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003432 sterols Chemical class 0.000 description 1
- 235000003702 sterols Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
本発明は、耐熱性及び耐水熱性に優れた新規多孔体に関する。 The present invention relates to a novel porous body excellent in heat resistance and hydrothermal resistance.
従来、触媒や吸着剤等として利用可能な無機系多孔質材料として、ゼオライト等が知られている。また、均一なメソ細孔を有する無機系多孔質材料として、界面活性剤のミセルを鋳型として合成されるシリカが知られ（例えば、非特許文献１参照）、ゼオライトの細孔では小さすぎて入れることが困難であった分子径の大きな化合物が関与する触媒や吸着剤としての利用が検討されている。しかしながら、このような多孔質材料はシラノール基が多く残存しており、触媒や吸着剤として利用する場合、耐熱性や耐水熱性の観点からその効果は必ずしも満足されるものではなかった。 Conventionally, zeolite or the like is known as an inorganic porous material that can be used as a catalyst, an adsorbent, or the like. As an inorganic porous material having uniform mesopores, silica synthesized using surfactant micelles as a template is known (see, for example, Non-Patent Document 1), and the zeolite pores are too small. The use as a catalyst or adsorbent involving a compound having a large molecular diameter, which has been difficult, has been studied. However, such a porous material has many silanol groups remaining, and when used as a catalyst or an adsorbent, its effect is not always satisfactory from the viewpoint of heat resistance and hydrothermal resistance.
本発明の目的は、耐熱性及び耐水熱性に優れた、新規な構造を持つ多孔体を提供することにある。 An object of the present invention is to provide a porous body having a novel structure which is excellent in heat resistance and hydrothermal resistance.
すなわち、本発明は、
〔１〕 珪素含有物質と、界面活性剤とを反応させて、珪素含有物質と界面活性剤とからなる複合体を形成させた後、該複合体から有機物を除去することを特徴とする、Ｑ４Ｓｉ原子の量がＳｉ原子全体の量の９０％より多いＳｉ含有物質からなり、ｄ間隔が４０Åから８０Åの位置に少なくとも１つのピークが存在するＸ線回折パターンを有する多孔体の製造方法、
〔２〕 多孔体のｄ間隔が４０Åから８０Åの位置に半価幅が０．４〜１．０の少なくとも１つのピークを有し、４０Åから８０Åの位置にある最強のピークの５０％より大きい相対強度でｄ間隔が４０Åより小さい位置にピークが存在しないＸ線回折パターンを有してなる前記〔１〕記載の製造方法、
〔３〕 多孔体の細孔分布曲線において細孔直径が１０Åより小さい範囲と１０Å以上の範囲とに各々ピークを少なくとも１つ有する前記〔１〕または〔２〕記載の製造方法、
〔４〕 多孔体の全細孔容積が０．４〜１．５ｃｍ３／ｇであり、細孔分布曲線における細孔直径が１０Å〜１００Åの細孔の容積が０．２〜１．２ｃｍ３／ｇであり、細孔分布曲線における細孔直径が１０Åより小さい細孔の容積が０．１〜０．４５ｃｍ３／ｇである前記〔１〕〜〔３〕いずれか記載の製造方法、
〔５〕 多孔体の細孔分布曲線における細孔直径が１０Å〜１００Åの細孔の容積が全細孔容積の５０〜８０％を占める前記〔１〕〜〔４〕いずれか記載の製造方法、
〔６〕 多孔体の（細孔分布曲線における細孔直径が１０Åより小さい細孔の容積）／［（細孔分布曲線における細孔直径が１０Åより小さい細孔の容積）＋（細孔分布曲線における細孔直径が１００Åより大きい細孔の容積）］×１００の値が６０〜９５である前記〔１〕〜〔５〕いずれか記載の製造方法、
〔７〕 多孔体の細孔壁の厚さが２０〜５０Åである前記〔１〕〜〔６〕いずれか記載の製造方法、
〔８〕 多孔体の細孔のチャネルが非直線である前記〔１〕〜〔７〕いずれか記載の製造方法、並びに
〔９〕 反応時間により、１０Å〜１００Åの範囲で多孔体の平均細孔直径を制御する前記〔１〕〜〔８〕いずれか記載の製造方法
に関する。
That is, the present invention
[1] A method comprising: reacting a silicon-containing substance with a surfactant to form a complex composed of the silicon-containing substance and the surfactant, and then removing an organic substance from the complex. 4 A method for producing a porous body having an X-ray diffraction pattern comprising an Si-containing material in which the amount of Si atoms is more than 90% of the total amount of Si atoms, and wherein at least one peak is present at a position where d interval is 40 to 80 inches,
[2] At least one peak having a half width of 0.4 to 1.0 at a position where the d interval of the porous body is 40 to 80 inches and greater than 50% of the strongest peak at a position of 40 to 80 inches The production method according to the above [1], which has an X-ray diffraction pattern having no peak at a position where the d interval is less than 40 mm in relative intensity.
[3] The production method according to the above [1] or [2], wherein the pore distribution curve of the porous body has at least one peak each in a range in which the pore diameter is less than 10 mm and in a range of 10 mm or more,
[4] The total pore volume of the porous body is 0.4 to 1.5 cm 3 / g, and the volume of pores having a pore diameter of 10 to 100 cm in the pore distribution curve is 0.2 to 1.2 cm 3. The production method according to any one of [1] to [3], wherein the pore volume in the pore distribution curve is 0.1 to 0.45 cm 3 / g.
[5] The production method according to any one of [1] to [4], wherein the volume of the pores having a pore diameter of 10 to 100 mm in the pore distribution curve of the porous body accounts for 50 to 80% of the total pore volume,
[6] Porous volume ( volume of pores whose pore diameter in pore distribution curve is smaller than 10 mm) / [ ( volume of pores whose pore diameter in pore distribution curve is smaller than 10 mm ) + (pore distribution curve The pore volume in which the pore diameter is greater than 100 mm)] × 100 is 60 to 95, the production method according to any one of [1] to [5] above,
[7] The method according to any one of [1] to [6], wherein the thickness of the pore wall of the porous body is 20 to 50 mm,
[8] The production method according to any one of [1] to [7] above, wherein the pore channels of the porous body are non-linear, and [9] the average pores of the porous body in the range of 10 to 100% depending on the reaction time It is related with the manufacturing method in any one of said [1]-[8] which controls a diameter.
本発明により、耐熱性、耐水熱性に優れた新規多孔体が得られるため、優れた触媒、吸着剤等としての利用が可能である。 According to the present invention, since a novel porous body excellent in heat resistance and hydrothermal resistance is obtained, it can be used as an excellent catalyst, adsorbent and the like.
本発明の多孔体は、Ｑ４Ｓｉ原子の量がＳｉ原子全体の量の９０％より多いＳｉ含有物質からなり、ｄ間隔が４０Åから８０Åの位置に半価幅が０．４〜１．０の少なくとも１つのピークを有することを一つの大きな特徴とする。かかる特徴を有することにより、本発明の多孔体は、耐熱性、耐水熱性等の特性が従来の無機多孔質材料と比較して格段に向上している。ここで、％は２９Ｓｉ ＭＡＳ ＮＭＲ測定により得られた化学シフト−９８ｐｐｍ〜−１１１ｐｐｍ間のＮＭＲスペクトルに対する−１０２ｐｐｍ〜−１１１ｐｐｍ間に最大ピークを有するＱ４Ｓｉ原子を示すＮＭＲスペクトルの面積比を示す。またｄ間隔とは、格子面間隔でありＸ線回折により得られる。 The porous body of the present invention is made of a Si-containing material in which the amount of Q 4 Si atoms is more than 90% of the total amount of Si atoms, and the half-value width is 0.4 to 1.0 at a position where d interval is 40 to 80 inches. One major characteristic is that it has at least one peak. By having such characteristics, the porous body of the present invention is remarkably improved in properties such as heat resistance and hydrothermal resistance as compared with conventional inorganic porous materials. Here,% indicates the area ratio of the NMR spectrum showing the Q 4 Si atom having the maximum peak between −102 ppm and −111 ppm with respect to the NMR spectrum between −98 ppm and −111 ppm obtained by 29 Si MAS NMR measurement. . The d interval is a lattice plane interval and is obtained by X-ray diffraction.
本発明におけるＱ４Ｓｉ原子は珪素の周囲に存在する４つのシラノール基が全てシロキサン結合（Ｓｉ−Ｏ）している珪素原子を示す。 The Q 4 Si atom in the present invention is a silicon atom in which all four silanol groups present around silicon are siloxane bonds (Si—O).
本発明の多孔体はまた、耐熱性及び耐水熱性等の特性の観点から、Ｑ４Ｓｉ原子の量がＳｉ原子全体の量の９５％以上のＳｉ含有物質からなることがより好ましく、Ｑ４Ｓｉ原子の量がＳｉ原子全体の量の９９％以上のＳｉ含有物質からなることがさらに好ましい。 Porous body of the present invention also in view of properties such as heat resistance and hydrothermal resistance, it is more preferable that the amount of Q 4 Si atoms is 95% or more Si-containing material in the amount of the total Si atoms, Q 4 Si More preferably, the amount of atoms is 99% or more of the total amount of Si atoms.
本発明の多孔体の細孔はまた、触媒活性の観点から、細孔分布曲線において、細孔直径が１０Åより小さい範囲と１０Å以上の範囲とに各々ピークを少なくとも１つ有することが好ましく、各々のピークの数は好ましくは１つである。さらに、１０Åより小さい範囲と１０Å以上の範囲とに各々ピークを１つ有することがより好ましく、各々のピークの数は好ましくは1つである。本発明において細孔分布曲線とは、窒素吸着等温線からｔ-プロット法等により算出して得られる。また、細孔直径は、細孔分布曲線のピーク位置より算出される。なお、本発明において特に断りなく細孔の長さに言及する場合には細孔直径を意味するものとする。 From the viewpoint of catalytic activity, the pores of the porous body of the present invention preferably have at least one peak in the pore distribution curve in the range where the pore diameter is less than 10 mm and in the range of 10 mm or more. The number of peaks is preferably one. Furthermore, it is more preferable to have one peak each in a range smaller than 10 mm and in a range larger than 10 mm, and the number of each peak is preferably one. In the present invention, the pore distribution curve is obtained by calculating from a nitrogen adsorption isotherm by a t-plot method or the like. The pore diameter is calculated from the peak position of the pore distribution curve. In the present invention, when referring to the length of the pore without particular notice, it means the pore diameter.
本発明の多孔体は細孔直径が１０Å以上の細孔が存在することにより、主に細孔壁に存在する細孔直径が１０Åより小さい細孔での基質の選択的吸着性、触媒活性を向上させることが出来る。 Since the porous body of the present invention has pores having a pore diameter of 10 mm or more, the substrate has selective adsorption and catalytic activity mainly on pores having a pore diameter of less than 10 mm. Can be improved.
本発明の多孔体はまた、選択的吸着性及び触媒活性の観点から、ｄ間隔が４０Åから８０Åの位置に少なくとも１つのピークを有するＸ線回折パターンを有していることが好ましく、ｄ間隔が４０Åから８０Åの位置に１つのピークを有するＸ線回折パターンを有していることがより好ましく、かつｄ間隔が４０Åから８０Åの位置にある最強のピークの５０％より大きい相対強度でｄ間隔が４０Åより小さい位置にピークが存在しないＸ線回折パターンを有していることが好ましく、ｄ間隔が４０Åから８０Åの位置にある最強のピークの３０％より大きい相対強度でｄ間隔が４０Åより小さい位置にピークが存在しないＸ線回折パターンを有していることがより好ましく、ｄ間隔が４０Åから８０Åの位置にある最強のピークの２０％より大きい相対強度でｄ間隔が４０Åより小さい位置にピークが存在しないＸ線回折パターンを有していることがさらに好ましい。 The porous body of the present invention preferably also has an X-ray diffraction pattern having at least one peak at a position where the d interval is 40 to 80 mm from the viewpoint of selective adsorption and catalytic activity. It is more preferable to have an X-ray diffraction pattern having one peak at a position of 40 to 80 inches, and the d interval is at a relative intensity greater than 50% of the strongest peak at a position of 40 to 80 inches. It is preferable to have an X-ray diffraction pattern in which no peak exists at a position smaller than 40 mm, and a position where the d interval is smaller than 40 mm with a relative intensity greater than 30% of the strongest peak at a position of 40 mm to 80 mm. It is more preferable to have an X-ray diffraction pattern in which no peak exists at 20% of the strongest peak at a position where the d interval is 40 to 80 mm. It is further preferred that the d-spacing has a X-ray diffraction pattern having no peak at 40Å positions less than a large relative intensity.
本発明の多孔体はまた、選択的吸着性及び触媒活性の観点から、ｄ間隔が４０Åから８０Åの位置に有するピークの半価幅が０．４〜１．０のピークを少なくとも１つ有するＸ線回折パターンを有することが好ましく、ｄ間隔が４０Åから８０Åの位置に有するピークの半価幅が０．５〜１．０のピークを少なくとも１つ有するＸ線回折パターンを有することがさらに好ましい。本発明の多孔体はまた、選択的吸着性及び触媒活性の観点から、ｄ間隔が４０Åから８０Åの位置に有するピークの半価幅が好ましくは０．４〜１．０のピーク、さらに好ましくは０．５〜１．０のピークを1つ有するＸ線回折パターンを有することが好ましい。本発明において半価幅とは、回折ピークの１／２の高さにおけるピーク幅であり、Ｘ線回折パターンにより得られる。また、Ｘ線回折パターンは全自動Ｘ線回折装置（ＲＩＮＴ ＵＬＴＩＭＡ II、理学電機株式会社製）により測定する。 The porous body of the present invention also has an X having at least one peak having a half-value width of 0.4 to 1.0 at a position where the d interval is in the range of 40 to 80 mm from the viewpoint of selective adsorption and catalytic activity. It preferably has a line diffraction pattern, and more preferably has an X-ray diffraction pattern having at least one peak having a half-value width of 0.5 to 1.0 at a position where the distance d is 40 to 80 mm. The porous body of the present invention also preferably has a peak half-value width of 0.4 to 1.0, more preferably from the viewpoint of selective adsorptivity and catalytic activity. It is preferable to have an X-ray diffraction pattern having one peak of 0.5 to 1.0. In the present invention, the half width is a peak width at half the height of a diffraction peak, and is obtained by an X-ray diffraction pattern. The X-ray diffraction pattern is measured by a fully automatic X-ray diffractometer (RINT ULTIMA II, manufactured by Rigaku Corporation).
本発明の多孔体の全細孔容積は、触媒活性の観点から、０．４〜１．５ｃｍ３／ｇが好ましく、０．８〜１．５ｃｍ３／ｇがより好ましく、０．９９〜１．５ｃｍ３／ｇがさらに好ましい。本発明おいて全細孔容積とは、公知の窒素吸着により算出される全細孔容積を指す。 Total pore volume of the porous material of the present invention, from the viewpoint of catalytic activity, preferably 0.4~1.5cm 3 / g, more preferably 0.8~1.5cm 3 / g, 0.99~1 More preferably, it is 0.5 cm 3 / g. In the present invention, the total pore volume refers to the total pore volume calculated by known nitrogen adsorption.
本発明の多孔体の細孔直径が１０Å〜１００Åの細孔の容積は、触媒活性の観点から、０．２〜１．２ｃｍ３／ｇが好ましく、０．４〜１．２ｃｍ３／ｇがより好ましく、０．６〜１．２ｃｍ３／ｇが最も好ましい。本発明における細孔分布曲線における細孔直径が１０Åより小さい細孔の容積は、触媒活性の観点から、０．１〜０．４５ｃｍ３／ｇが好ましく、０．２〜０．４５ｃｍ３／ｇがより好ましく、０．２４〜０．４５ｃｍ３／ｇがさらに好ましい。 Porous volume of pores having a pore diameter of the pores of 10Å~100Å of the present invention, from the viewpoint of catalytic activity, preferably 0.2~1.2cm 3 / g, 0.4~1.2cm 3 / g is More preferred is 0.6 to 1.2 cm 3 / g. Volume of pore diameter of 10Å pores smaller than the pore distribution curve according to the present invention, from the viewpoint of catalytic activity, 0.1~0.45cm 3 / g are preferred, 0.2~0.45cm 3 / g Is more preferable, and 0.24-0.45 cm < 3 > / g is still more preferable.
本発明の多孔体の細孔分布曲線における細孔直径が１０Å〜１００Åの細孔の容積は、触媒活性の観点から、全細孔容積の５０〜８０％を占めることが好ましく、５９％〜８０％を占めることがより好ましい。 From the viewpoint of catalytic activity, the volume of pores having a pore diameter of 10 to 100 in the pore distribution curve of the porous body of the present invention preferably occupies 50 to 80% of the total pore volume, and 59 to 80%. % Is more preferable.
本発明の多孔体は、触媒活性の観点から、（細孔分布曲線における細孔直径が１０Åより小さい細孔の容積）／［（細孔分布曲線における細孔直径が１０Åより小さい細孔の容積）＋（細孔分布曲線における細孔直径が１００Åより大きい細孔の容積）］×１００の値が、６０〜９５であることが好ましく、６９〜９５であることがより好ましい。 From the viewpoint of catalytic activity, the porous body of the present invention has a volume of pores having a pore diameter smaller than 10 mm in the pore distribution curve / [volume of pores having a pore diameter smaller than 10 mm in the pore distribution curve. ) + (Pore volume in pore distribution curve having pore diameter larger than 100 mm)] × 100 is preferably 60 to 95, and more preferably 69 to 95.
本発明の多孔体の細孔壁の厚さは、耐熱性及び耐水熱の観点から、２０〜５０Åが好ましく、２５〜５０Åがより好ましい。 From the viewpoint of heat resistance and hydrothermal resistance, the thickness of the pore wall of the porous body of the present invention is preferably 20 to 50 mm, and more preferably 25 to 50 mm.
本発明の多孔体の細孔壁の厚さは
式：（２×ｄ１００値／√３）−（平均細孔直径１０〜１００Åの範囲の細孔径）
により算出することができる。本発明の平均細孔直径は公知の窒素吸脱着により算出した。すなわち、平均細孔直径は公知のＢＪＨ法により算出した。ここで、ｄ１００は六方晶系における（１００）面の面間隔を示しＸ線回折パターンより算出する。
The thickness of the pore wall of the porous body of the present invention is expressed by the formula: (2 × d 100 value / √3) − (pore diameter in the range of average pore diameter of 10 to 100 mm)
Can be calculated. The average pore diameter of the present invention was calculated by known nitrogen adsorption / desorption. That is, the average pore diameter was calculated by a known BJH method. Here, d 100 is calculated from the X-ray diffraction pattern indicates the spacing of (100) plane in the hexagonal system.
本発明の多孔体の比表面積は、選択的吸着性及び触媒活性の観点から、４５０〜１２００ｍ２／ｇが好ましく、６００〜１２００ｍ２／ｇがより好ましく、６５０〜１２００ｍ２／ｇがさらに好ましい。 The specific surface area of the porous body of the present invention, from the viewpoint of selective adsorption and catalytic activity, preferably 450~1200m 2 / g, more preferably 600~1200m 2 / g, more preferably 650~1200m 2 / g.
本発明の多孔体の細孔容積及び比表面積は公知の窒素脱吸着により算出することができる。 The pore volume and specific surface area of the porous body of the present invention can be calculated by known nitrogen desorption.
本発明の多孔体の１次粒子径は特に限定されるものではないが、選択的吸着性及び触媒活性の観点から、１００ｎｍ〜８００ｎｍが好ましく、３００〜４００ｎｍがより好ましい。 The primary particle diameter of the porous body of the present invention is not particularly limited, but is preferably 100 nm to 800 nm, more preferably 300 to 400 nm, from the viewpoint of selective adsorptivity and catalytic activity.
本発明の多孔体の細孔のチャネルは、触媒活性の観点から、非直線が好ましい。 The channel of the pores of the porous body of the present invention is preferably non-linear from the viewpoint of catalytic activity.
本発明の多孔体の１次粒子径及び細孔のチャネルは透過型電子顕微鏡により観察することができる。 The primary particle diameter and pore channels of the porous body of the present invention can be observed with a transmission electron microscope.
本発明の多孔体はＳｉを含有すれば特に限定されるものではないが、例えば、下記式：
ＭｘＡｌｙＳｉｚＯ２
（式中、ＭはＡｌ以外の金属元素であり、ｘは０以上１以下であり、ｙは０以上１以下であり、ｚは０より大きく１以下である）
で表される。ここで、Ｍは、Ａｌ以外の金属架橋に用いられる１種以上の金属元素であり、例えば、Ｍｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｍｇ、Ｃｒ、Ｇａ、Ｇｅ、Ｔｉ等が挙げられる。Ｍが２種以上のカチオンである場合、その２種以上の金属元素を合計したものがｘであればよい。
The porous body of the present invention is not particularly limited as long as it contains Si. For example, the following formula:
MxAlySizO 2
(Wherein M is a metal element other than Al, x is 0 or more and 1 or less, y is 0 or more and 1 or less, and z is greater than 0 and 1 or less)
It is represented by Here, M is one or more metal elements used for metal crosslinking other than Al, and examples thereof include Mn, Co, Ni, Fe, Mg, Cr, Ga, Ge, and Ti. When M is two or more kinds of cations, the sum of the two or more kinds of metal elements may be x.
本発明の多孔体の製造方法としては、特に限定されるものではないが、例えば、珪素含有物質を界面活性剤と混合し、反応させることにより、界面活性剤を鋳型としてそのまわりに珪素含有物質の骨格が形成された界面活性剤と珪素含有物質の複合体を形成させた後、得られた複合体から、有機物を除去する方法が挙げられる。 The method for producing the porous body of the present invention is not particularly limited. For example, a silicon-containing substance is mixed with a surfactant and reacted to cause a silicon-containing substance around the surfactant as a template. There is a method in which a complex of a surfactant having a skeleton of 5 and a silicon-containing substance is formed, and then organic substances are removed from the obtained complex.
珪素含有物質は、特に限定されるものではないが、例えば、シリコンアルコキシド等の有機シリカ、層状珪酸塩、非層状珪酸塩等の珪酸塩を含む物質及び珪酸塩以外の珪素を含有する物質が挙げられる。有機シリカとしては、、テトラエトキシシラン（ＴＥＯＳ）、テトラメトキシシラン（ＴＭＯＳ）、テトラメチルアンモニウム（ＴＭＡ）シリケート、テトラエチルオルトシリケート等のシリコンアルコキシド等が挙げられ、層状珪酸塩としては、カネマイト（ＮａＨＳｉ２Ｏ５・３Ｈ２Ｏ）、ジ珪酸ナトリウム結晶（Ｎａ２Ｓｉ２Ｏ５）、マカタイト（ＮａＨＳｉ４Ｏ９・５Ｈ２Ｏ）、アイラアイト（ＮａＨＳｉ８Ｏ１７・ＸＨ２Ｏ）、マガディアイト（Ｎａ２ＨＳｉ１４Ｏ２９・ＸＨ２Ｏ）、ケニヤアイト（Ｎａ２ＨＳｉ２０Ｏ４１・ＸＨ２Ｏ）等が挙げられ、非層状珪酸塩としては、水ガラス（珪酸ソーダ）、ガラス、無定形珪酸ナトリウムまた、珪酸塩以外の珪素を含有する物質としては、シリカ、シリカ酸化物、シリカ−金属複合酸化物などが挙げられる。これらは、単独で又は２種以上を混合して用いて良い。 The silicon-containing material is not particularly limited, and examples thereof include organic silica such as silicon alkoxide, materials containing silicates such as layered silicates and non-layered silicates, and materials containing silicon other than silicates. It is done. Examples of the organic silica include silicon alkoxides such as tetraethoxysilane (TEOS), tetramethoxysilane (TMOS), tetramethylammonium (TMA) silicate, and tetraethylorthosilicate. Examples of the layered silicate include kanemite (NaHSi 2). O 5 · 3H 2 O), sodium disilicate crystal (Na 2 Si 2 O 5 ), macatite (NaHSi 4 O 9 · 5H 2 O), eyeraite (NaHSi 8 O 17 · XH 2 O), magadiite (Na 2 HSi 14 O 29 · XH 2 O), Kenyaite (Na 2 HSi 20 O 41 · XH 2 O) and the like, and non-layered silicates include water glass (sodium silicate), glass, amorphous sodium silicate, Examples of substances containing silicon other than silicate include silica and silica Product, silica - and metal composite oxides. These may be used alone or in admixture of two or more.
鋳型となる界面活性剤は単独で又は２種以上を混合して用いることができる。 Surfactants that serve as templates can be used alone or in admixture of two or more.
界面活性剤としては特に限定されるものではないが、耐熱性及び耐水熱の観点から、非イオン型界面活性剤が好ましい。 The surfactant is not particularly limited, but a nonionic surfactant is preferable from the viewpoint of heat resistance and hydrothermal resistance.
非イオン型界面活性剤としては、特に限定される物ではないが、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン２級アルコールエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンステロールエーテル、ポリオキシエチレンラノリン酸誘導体、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリプロピレングリコール、ポリエチレングリコール等のエーテル型のものや、ポリオキシエチレンアルキルアミン等の含窒素型のものを使用することができるが、触媒活性、選択的吸着性の観点から、ポリグリセリンに脂肪酸をエステル化したポリグリセリン脂肪酸エステルが好ましい。これらは単独で又は２種以上を混合して用いてもよい。 The nonionic surfactant is not particularly limited, but examples thereof include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene. Lanolinic acid derivatives, polyoxyethylene polyoxypropylene alkyl ethers, ether-types such as polypropylene glycol and polyethylene glycol, and nitrogen-containing types such as polyoxyethylene alkylamine can be used. From the viewpoint of static adsorptivity, polyglycerol fatty acid ester obtained by esterifying a fatty acid with polyglycerol is preferable. You may use these individually or in mixture of 2 or more types.
ポリグリセリン脂肪酸エステルは触媒活性、選択的吸着性の観点から、ＨＬＢが１４．０〜１８．０であることが好ましく、１５．０〜１８．０であることがさらに好ましく、１５．０〜１６．０であることが最も好ましい。ここで、ＨＬＢは分子中の親水基と親油基のバランスを表し、分子中の親水基が０％の時を０、１００％の時を２０として等分したもので、計算又は実験的に求められる。 From the viewpoint of catalytic activity and selective adsorptivity, the polyglycerol fatty acid ester preferably has an HLB of 14.0 to 18.0, more preferably 15.0 to 18.0, and more preferably 15.0 to 16 0.0 is most preferred. Here, HLB represents the balance between the hydrophilic group and the lipophilic group in the molecule and is equally divided into 0 when the hydrophilic group in the molecule is 0% and 20 when the hydrophilic group is 100%. Desired.
ポリグリセリン脂肪酸エステルは触媒活性、選択的吸着性の観点から、ポリグリセリン組成中、グリセリン３量体〜１０量体の中から選ばれる１種のポリグリセリンの含量が３５％以上であることが好ましい。この組成分布はガスクロマトグラフィーや液体クロマトグラフィーにより分析でき、特にポリグリセリンをトリメチルシリル化誘導体とした後、ガスクロマトグラフィーに付すことにより簡便に分析することができる。 From the viewpoint of catalytic activity and selective adsorptivity, the polyglycerin fatty acid ester preferably has a content of one kind of polyglycerin selected from glycerin trimer to demer in the polyglycerin composition is 35% or more. . This composition distribution can be analyzed by gas chromatography or liquid chromatography, and in particular, it can be easily analyzed by subjecting polyglycerin to a trimethylsilylated derivative followed by gas chromatography.
ポリグリセリン脂肪酸エステルは、触媒活性及び選択的吸着性の観点から、ポリグリセリン脂肪酸エステルの構成脂肪酸の炭素数は１０〜１４が好ましく、１２〜１４がさらに好ましい。 In the polyglycerol fatty acid ester, the number of carbon atoms of the constituent fatty acid of the polyglycerol fatty acid ester is preferably 10 to 14, and more preferably 12 to 14 from the viewpoint of catalytic activity and selective adsorptivity.
珪素含有物質と界面活性剤を混合する場合、適当な溶媒を用いても良い。溶媒としては、特に限定されるものではないが、水、アルコール等が挙げられる。 When the silicon-containing substance and the surfactant are mixed, an appropriate solvent may be used. Although it does not specifically limit as a solvent, Water, alcohol, etc. are mentioned.
珪素含有物質と界面活性剤の混合方法は、特に限定されるものではないが、界面活性剤を酸性溶液に溶解させた後、この溶液に珪素含有物質を添加し、２２℃〜２６℃で３時間〜１４日間混合することが好ましい。珪素含有物質と界面活性剤の混合比（重量比）は特に限定されるものではないが、珪素含有物質：界面活性剤＝１：０．５〜１：２が好ましく、１：１〜１：１．５がより好ましい。 The method for mixing the silicon-containing substance and the surfactant is not particularly limited. After the surfactant is dissolved in the acidic solution, the silicon-containing substance is added to the solution, and the mixture is added at 22 ° C. to 26 ° C. for 3 hours. It is preferable to mix for a time to 14 days. The mixing ratio (weight ratio) of the silicon-containing substance and the surfactant is not particularly limited, but silicon-containing substance: surfactant = 1: 0.5 to 1: 2 is preferable, and 1: 1 to 1: 1.5 is more preferable.
酸性溶液を調製するための酸性物質は特に限定されるものではないが、塩酸、臭化水素、ヨウ化水素、蟻酸、酢酸、硝酸、硫酸、燐酸等が挙げられる。 The acidic substance for preparing the acidic solution is not particularly limited, and examples thereof include hydrochloric acid, hydrogen bromide, hydrogen iodide, formic acid, acetic acid, nitric acid, sulfuric acid, phosphoric acid and the like.
珪素含有物質と界面活性剤とを攪拌し反応させる際のｐＨ条件は、耐熱性及び耐水熱性の観点から、酸性条件であれば特に限定されるものではないが、ｐＨ３〜ｐＨ−３が好ましく、ｐＨ１〜ｐＨ−３がより好ましく、ｐＨ０〜ｐＨ−３がさらに好ましい。 The pH condition when the silicon-containing substance and the surfactant are stirred and reacted is not particularly limited as long as it is acidic from the viewpoint of heat resistance and hydrothermal resistance, but preferably pH 3 to pH-3. pH 1 to pH-3 is more preferable, and pH 0 to pH-3 is more preferable.
界面活性剤と珪素含有物質の複合体から有機物を除去する方法としては、複合体を濾取し、水等により洗浄、乾燥した後、４００℃〜６００℃で焼成する方法や、有機溶媒等により抽出する方法が挙げられる。 As a method of removing the organic substance from the complex of the surfactant and the silicon-containing substance, the complex is collected by filtration, washed with water or the like, dried and then fired at 400 ° C. to 600 ° C., or by an organic solvent. The method of extracting is mentioned.
本発明の多孔体は、珪素含有物質と界面活性剤の反応時間により１０Å〜１００Åの範囲で多孔体の平均細孔直径を制御することができる。具体的には、例えば珪素含有物質としてテトラエトキシシラン（ＴＥＯＳ）、界面活性剤としてペンタグリセリンモノミリステート（構成ポリグリセリン中グリセリン５量体の含量が４２％・ＨＬＢ１５．０）を使用し、２５℃で３時間〜１４日間の範囲で反応時間を制御することにより、１０Åより大きい範囲における平均細孔直径を３０Å〜５０Åの範囲で制御することができる。すなわち、反応時間が長いほど１０Åより大きい範囲における平均細孔直径を３０Å〜５０Åの範囲で増大させることができる。 In the porous body of the present invention, the average pore diameter of the porous body can be controlled in the range of 10 to 100 に よ り depending on the reaction time of the silicon-containing substance and the surfactant. Specifically, for example, tetraethoxysilane (TEOS) is used as the silicon-containing substance, and pentaglycerin monomyristate (content of glycerin pentamer in the constituent polyglycerin is 42% · HLB15.0) is used as the surfactant. By controlling the reaction time in the range of 3 hours to 14 days at ° C, the average pore diameter in the range larger than 10 mm can be controlled in the range of 30 mm to 50 mm. That is, as the reaction time is longer, the average pore diameter in the range larger than 10 mm can be increased in the range of 30 mm to 50 mm.
本発明はまた、本発明の多孔体を含有してなる触媒に関する。本発明の触媒は、例えばクネーベナーゲル縮合反応を触媒する。 The present invention also relates to a catalyst comprising the porous body of the present invention. The catalyst of the present invention catalyzes, for example, the Kunebener gel condensation reaction.
本発明はまた、本発明の多孔体を含有してなる吸着剤に関する。本発明の吸着剤は、例えば、ホルムアルデヒド、アセトアルデヒド、酢酸、蟻酸、アンモニア、トルエン、ベンゼン、ｎ-アルカン等を吸着することが出来る。 The present invention also relates to an adsorbent comprising the porous body of the present invention. The adsorbent of the present invention can adsorb, for example, formaldehyde, acetaldehyde, acetic acid, formic acid, ammonia, toluene, benzene, n-alkane and the like.
以下、実施例を挙げて本発明をさらに具体的に説明するが、本発明は、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example.
製造例１
６０ｍｌの６Ｎ塩酸に１ｇの界面活性剤｛ペンタグリセリンモノミリステート／商品名：サンソフトＡ−１４Ｅ（構成ポリグリセリン中グリセリン５量体の含量が４２％・HLB１５．０）太陽化学株式会社製｝を添加混合し、界面活性剤を完全に溶解させた。この溶液に１．２５ｇのテトラエトキシシラン（ＴＥＯＳ）を添加した。この溶液（ｐＨ０以下）を密封系にて２５℃で２４時間攪拌した。生じた沈殿物を濾過にて回収後、イオン交換水にて水洗・濾過を３回繰り返した。エタノールにて洗浄・濾過後、この固形物を６０℃で３時間乾燥させ、その後５４０℃で６時間焼成を行い、多孔体Ａ０．２７ｇを得た。
Production Example 1
1 ml of surfactant in 60 ml of 6N hydrochloric acid {pentaglycerin monomyristate / trade name: Sunsoft A-14E (content of glycerin pentamer in constituent polyglycerin is 42%, HLB 15.0) manufactured by Taiyo Chemical Co., Ltd.} Were added and mixed to completely dissolve the surfactant. To this solution was added 1.25 g of tetraethoxysilane (TEOS). This solution (pH 0 or lower) was stirred in a sealed system at 25 ° C. for 24 hours. The resulting precipitate was collected by filtration, and then washed with ion-exchanged water and filtered three times. After washing with ethanol and filtration, the solid was dried at 60 ° C. for 3 hours, and then calcined at 540 ° C. for 6 hours to obtain 0.27 g of porous material A.
製造例２〜６
６０ｍｌの６Ｎ塩酸に１ｇの界面活性剤｛ペンタグリセリンモノミリステート／商品名：サンソフトＡ−１４Ｅ（構成ポリグリセリン中グリセリン５量体の含量が４２％・HLB１５．０）太陽化学株式会社製｝を添加混合し、界面活性剤を完全に溶解させた。この溶液（ｐＨ０以下）に１．２５ｇのＴＥＯＳを添加した。この溶液を密封系にて２５℃で３時間、３日間、７日間、１０日間、及び１４日間攪拌する以外は製造例１と同様にして、それぞれ多孔体Ｂ、Ｃ、Ｄ、Ｅ、Ｆを得た。
Production Examples 2-6
1 ml of surfactant in 60 ml of 6N hydrochloric acid {pentaglycerin monomyristate / trade name: Sunsoft A-14E (content of glycerin pentamer in constituent polyglycerin is 42%, HLB 15.0) manufactured by Taiyo Chemical Co., Ltd.} Were added and mixed to completely dissolve the surfactant. To this solution (pH 0 or lower), 1.25 g of TEOS was added. Porous bodies B, C, D, E, and F were respectively obtained in the same manner as in Production Example 1 except that this solution was stirred in a sealed system at 25 ° C. for 3 hours, 3 days, 7 days, 10 days, and 14 days. Obtained.
製造例７
界面活性剤として｛ペンタグリセリンモノラウレート／商品名：サンソフトＡ-１２Ｅ（構成ポリグリセリン中グリセリン５量体の含量が４２％・ＨＬＢ１５．６）を使用した以外は製造例１と同様にして、多孔体Ｇを得た。
Production Example 7
The same as in Production Example 1 except that {pentaglycerin monolaurate / trade name: Sunsoft A-12E (content of glycerin pentamer in constituent polyglycerin is 42% · HLB 15.6) was used as the surfactant. A porous body G was obtained.
得られた多孔体Ａの２９Ｓｉ ＭＡＳ ＮＭＲを測定し、Ｑ４Ｓｉ原子のＳｉ原子全体に対する割合を求めた。すなわち、得られた化学シフト−９８ｐｐｍ〜−１１１ｐｐｍ間のＮＭＲスペクトルを逆重畳積分（ｄｅｃｏｎｖｏｌｕｔｅ）し、−１０２ｐｐｍ〜−１１１ｐｐｍ間に最大ピークを有するＱ４Ｓｉ原子を示すＮＭＲスペクトルの面積比を求めた。結果を図１に示す。なお、ＮＭＲは、４-ｍｍ ＺｒＯ２中マジック角回転プローブを含むＢｒｕｋｅｒ ＤＲＸ-４００検出器にて測定した。 29 Si MAS NMR of the obtained porous body A was measured, and the ratio of Q 4 Si atoms to the entire Si atoms was determined. That is, the obtained NMR spectrum between -98 ppm and -111 ppm was deconvolved, and the area ratio of the NMR spectrum showing the Q 4 Si atom having the maximum peak between -102 ppm and -111 ppm was determined. . The results are shown in FIG. NMR was measured with a Bruker DRX-400 detector including a magic angle rotating probe in 4-mm ZrO 2 .
図１に示したように多孔体Ａ前駆体物質の２９Ｓｉ ＭＡＳ ＮＭＲはＱ４ユニットに起因するピークとＱ３ユニットに起因するピークとＱ２ユニットに起因するピークを有したが、多孔体Ａの２９Ｓｉ ＭＡＳ ＮＭＲはＱ４ユニットに起因するピークのみを有し、Ｑ４Ｓｉ原子の量はＳｉ原子全体の量は９８％であった。 As shown in FIG. 1, 29 Si MAS NMR of the porous body A precursor material had a peak due to the Q 4 unit, a peak due to the Q 3 unit, and a peak due to the Q 2 unit. 29 Si MAS NMR had only a peak due to the Q 4 unit, and the amount of Q 4 Si atoms was 98% of the total Si atoms.
多孔体Ｂ〜Ｆについても同様にＱ４Ｓｉ原子はＳｉ原子全体の９０％より大きかった。 Similarly, in the porous bodies B to F, Q 4 Si atoms were larger than 90% of the entire Si atoms.
得られた多孔体Ａ〜Ｆの細孔分布を測定した。多孔体Ａ〜Ｆの細孔分布曲線を図２に示す。 The pore distribution of the obtained porous bodies A to F was measured. The pore distribution curves of the porous bodies A to F are shown in FIG.
図２に示したように得られた多孔体Ａ〜Ｆの細孔は、細孔分布曲線において細孔直径が１０Åより小さい範囲と１０Å以上の範囲にそれぞれピークを１つ有した。 The pores of the porous bodies A to F obtained as shown in FIG. 2 each had one peak in the pore distribution curve in the range where the pore diameter was smaller than 10 mm and in the range larger than 10 mm.
得られた多孔体Ａ〜ＦのＸ線回折パターンを測定した。多孔体Ａ〜Ｃの結果を図３に、多孔体Ｄ〜Ｆの結果を図４に示す。 X-ray diffraction patterns of the obtained porous bodies A to F were measured. The results of porous bodies A to C are shown in FIG. 3, and the results of porous bodies D to F are shown in FIG.
図３及び図４に示すように得られた多孔体Ａ〜ＦのＸ線回折パターンはｄ間隔が４０Åから８０Åの位置にピークを１つ有し、このピークの２０％より大きい相対強度でｄ間隔が４０Åより小さい位置にピークを有さなかった。また、この半価幅は０．４〜１．０の範囲であった。 The X-ray diffraction patterns of the porous bodies A to F obtained as shown in FIGS. 3 and 4 have one peak at a position where the d interval is 40 to 80 mm, and the relative intensity is greater than 20% of this peak. There was no peak at a position where the interval was less than 40 mm. Further, the half width was in the range of 0.4 to 1.0.
得られた多孔体Ａ〜Ｆの半価幅、Ｓｉ原子全体に対するＱ４Ｓｉ原子の量、及び細孔容積を求めた。結果を表１に示す。 The half width of the obtained porous bodies A to F, the amount of Q 4 Si atoms relative to the entire Si atoms, and the pore volume were determined. The results are shown in Table 1.
表１中、Ｉは全細孔容積（ｃｍ３／ｇ）であり、IIは細孔分布曲線における細孔直径が１０Åより小さい細孔の容積（ｃｍ３／ｇ）であり、IIIは細孔分布曲線における細孔直径が１０Å〜１００Åの容積（ｃｍ３／ｇ）であり、IVは細孔分布曲線における細孔直径が１００Åより大きい細孔の容積（ｃｍ３／ｇ）であり、Ｖは細孔分布曲線における細孔直径が１０Åより小さい細孔の容積＋細孔直径が１００Åより大きい細孔の容積（ｃｍ３／ｇ）［II＋IV］である。 In Table 1, I is the total pore volume (cm 3 / g), II is the pore diameter of 10Å pores smaller than the volume in the pore distribution curve (cm 3 / g), III pore The pore diameter in the distribution curve is a volume of 10 to 100 cm (cm 3 / g), IV is the volume of pores with a pore diameter in the pore distribution curve of more than 100 mm (cm 3 / g), and V is The pore volume in the pore distribution curve is the volume of pores smaller than 10 mm + the volume of pores having a pore diameter larger than 100 mm (cm 3 / g) [II + IV].
表１に示したように得られた多孔体Ａ〜Ｆの全細孔容積は０．４〜１．５ｃｍ３／ｇの範囲にあり、細孔分布曲線における細孔直径が１０Å〜１００Åの細孔の容積は０．２〜１．２ｃｍ３／ｇの範囲にあり、細孔分布曲線における細孔直径が１０Åより小さい細孔の容積は０．１〜０．４５ｃｍ３／ｇの範囲にあった。また、多孔体Ａ〜Ｆの細孔分布曲線における細孔直径が１０Å〜１００Åの容積は全細孔容積の５０〜８０％の範囲にあった。また、式：（細孔分布曲線における細孔直径が１０Åより小さい細孔の容積）／［（細孔分布曲線における細孔直径が１０Åより小さい細孔の容積）＋（細孔分布曲線における細孔直径が１００Åより大きい細孔の容積）］×１００の値は６０〜９５の範囲であった。 The total pore volume of the porous bodies A to F obtained as shown in Table 1 is in the range of 0.4 to 1.5 cm 3 / g, and the pore diameter in the pore distribution curve is as small as 10 to 100 cm. The pore volume is in the range of 0.2 to 1.2 cm 3 / g, and the pore diameter in the pore distribution curve is less than 10 mm, and the pore volume is in the range of 0.1 to 0.45 cm 3 / g. It was. Further, the volume of the pore diameters in the pore distribution curves of the porous bodies A to F was 10 to 100% was in the range of 50 to 80% of the total pore volume. Also, the formula: (volume of pores whose pore diameter is smaller than 10 mm in pore distribution curve) / [(volume of pores whose pore diameter is smaller than 10 mm in pore distribution curve) + (fine volume in pore distribution curve) The value of the pore volume with a pore diameter greater than 100 mm)] × 100 ranged from 60 to 95.
得られた多孔体Ａ〜Ｆの細孔壁の厚さ、ｄ１００値及び比表面積を求めた。結果を表２に示す。 The thickness of the pore walls of the resulting porous body to F, were determined d 100 value and the specific surface area. The results are shown in Table 2.
表２に示したように得られた多孔体Ａ〜Ｆの細孔壁は２０〜５０Åの範囲にあり、ｄ１００値は４０〜８０Åの範囲にあり、比表面積は４５０〜１２００ｍ２／ｇの範囲にあった。 The pore walls of the porous bodies A to F obtained as shown in Table 2 are in the range of 20 to 50 mm, the d 100 value is in the range of 40 to 80 mm, and the specific surface area is 450 to 1200 m 2 / g. Was in range.
２９Ｓｉ ＭＡＳ ＮＭＲは、４-ｍｍ ＺｒＯ２中マジック角回転プローブを含むＢｒｕｋｅｒ ＤＲＸ-４００検出器にて測定した。細孔分布曲線、平均細孔直径、細孔容量、比表面積及び細孔壁は公知の窒素吸脱着により算出した。すなわち、平均細孔直径は公知のＢＪＨ法により算出し、細孔容量は公知のＢＪＨ法により算出し、比表面積は公知のＢＥＴ法により算出し、細孔壁は、
式：（２×ｄ１００値／√３）−（細孔直径１０〜１００Åの範囲の細孔径）
により算出した。ｄ１００値及びＸ線回折パターンは、全自動Ｘ線回折装置（商品名：ＲＩＮＴ ＵＬＴＩＭＡ II、理学電機株式会社製）により測定した。Ｘ線回折は、ＣｕＫα線（４０ｋｖ、３０ｍＡ）をＸ線源として１°〜１０°まで、1°２θ／秒でスキャンした。
29 Si MAS NMR was measured with a Bruker DRX-400 detector containing a magic angle rotating probe in 4-mm ZrO 2 . The pore distribution curve, average pore diameter, pore volume, specific surface area and pore wall were calculated by known nitrogen adsorption / desorption. That is, the average pore diameter is calculated by a known BJH method, the pore volume is calculated by a known BJH method, the specific surface area is calculated by a known BET method,
Formula: (2 × d 100 value / √3) − (pore diameter in the range of pore diameter 10 to 100 mm)
Calculated by d 100 value and X-ray diffraction pattern were measured by a fully automatic X-ray diffraction apparatus (trade name: RINT ULTIMA II, manufactured by Rigaku Corporation). X-ray diffraction was scanned at 1 ° 2θ / second from 1 ° to 10 ° using CuKα rays (40 kv, 30 mA) as an X-ray source.
多孔体Ａを透過型電子顕微鏡により観察した。透過型電子顕微鏡写真のイメージ図を図５、図６及び図７に示す。透過型電子顕微鏡はＪＥＯＬ ＪＥＭ-２０１０にて加速電圧１００kＶで測定した。 The porous body A was observed with a transmission electron microscope. Image diagrams of transmission electron micrographs are shown in FIGS. The transmission electron microscope was measured with JEOL JEM-2010 at an acceleration voltage of 100 kV.
図５に示すように多孔体Ａの１次粒子は３００ｎｍ〜４００ｎｍであった。図６に示すように多孔体Ａの細孔の規則性は高くなかった。図７に示すように多孔体Ａの細孔のチャネルは非直線であった。 As shown in FIG. 5, the primary particles of the porous body A were 300 nm to 400 nm. As shown in FIG. 6, the regularity of the pores of the porous body A was not high. As shown in FIG. 7, the channel of the pores of the porous body A was non-linear.
比較品の製造例１
Ｂｅｃｋらの方法（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．１９９２，１１４，１０８３４−１０８４３）にて論文に記載の多孔質材料、ＭＣＭ−４１を得た。ＭＣＭ-４１のＸ線回折パターンを測定した。結果を図８に示す。
Comparative product production example 1
The porous material described in the paper, MCM-41, was obtained by the method of Beck et al. (J. Am. Chem. Soc. 1992, 114, 10834-10843). The X-ray diffraction pattern of MCM-41 was measured. The results are shown in FIG.
図８に示したように多孔質材料ＭＣＭ−４１は半価幅が０．２７のピークを有するＸ線回折パターンを示した。Ｑ４Ｓｉ原子の量がＳｉ原子全体の量の７０％であった。 As shown in FIG. 8, the porous material MCM-41 showed an X-ray diffraction pattern having a peak with a half width of 0.27. The amount of Q 4 Si atoms was 70% of the total amount of Si atoms.
比較品の製造例２
界面活性剤として｛デカグリセリンモノミリステート／商品名：サンソフトＱ−１４Ｓ（構成ポリグリセリン中、グリセリン１５％、グリセリン２量体１８％、グリセリン３量体２３％、グリセリン４量体１６％、グリセリン５量体以上２０％、環状ポリグリセリンが８％・HLB１４．５）太陽化学株式会社製｝を使用した以外は製造例１と同様にして、多孔体Ｈを得た。
Comparative product production example 2
As a surfactant {decaglycerin monomyristate / trade name: Sunsoft Q-14S (in constituent polyglycerin, glycerin 15%, glycerin dimer 18%, glycerin trimer 23%, glycerin tetramer 16%, Porous material H was obtained in the same manner as in Production Example 1 except that 20% of glycerin pentamer, 8% of cyclic polyglycerin and HLB 14.5) manufactured by Taiyo Kagaku Co., Ltd. were used.
比較品の製造例３
界面活性剤として｛トリグリセリンモノミリステート／商品名：サンソフト Ａ−１４１E
（構成ポリグリセリン中、グリセリン３量体の含量が４２％・ＨＬＢ１３．０）太陽化学株式会社製｝を使用した以外は製造例１と同様にして、多孔体Ｉを得た。
Comparative product production example 3
As a surfactant {triglycerin monomyristate / trade name: Sunsoft A-141E
Porous material I was obtained in the same manner as in Production Example 1 except that the content of glycerin trimer in the constituent polyglycerin was 42% · HLB13.0, manufactured by Taiyo Kagaku Co., Ltd.}.
比較品の製造例２及び３で得られた多孔体Ｈ、ＩのＸ線回折パターンを測定した。多孔体Ｈの結果を図９に、多孔体Ｉの結果を図１０に示す。 The X-ray diffraction patterns of the porous bodies H and I obtained in Comparative Production Examples 2 and 3 were measured. The result of porous body H is shown in FIG. 9, and the result of porous body I is shown in FIG.
図９、図１０に示したように得られた多孔体Ｈ、Ｉは、ｄ間隔が４０Åから８０Åの位置に半価幅が０．４〜１．０のピークを有さなかった。 The porous bodies H and I obtained as shown in FIGS. 9 and 10 did not have a peak with a half-value width of 0.4 to 1.0 at a position where the d interval was 40 to 80 mm.
耐熱性試験
（１）製造例１にて得た多孔体Ａを８５０℃で２４時間加熱した。この時のＸ線回折パターンを図１１に示す。また、このときの２９Ｓｉ ＭＡＳ ＮＭＲの結果を図１２に示す。
Heat resistance test (1) The porous body A obtained in Production Example 1 was heated at 850 ° C. for 24 hours. The X-ray diffraction pattern at this time is shown in FIG. Moreover, the result of 29 Si MAS NMR at this time is shown in FIG.
図１１に示すように多孔体Ａを８５０℃で２４時間加熱後のＸ線回折パターンのｄ１００のピーク強度を求めたところ加熱前の５３．０％であった。 The porous body A was 53.0% before heating was determined peak intensities of d 100 of X-ray diffraction pattern after heating for 24 hours at 850 ° C. As shown in FIG. 11.
図１２に示すようにＱ４Ｓｉ原子の量はＳｉ原子全体の量の少なくとも９０％より多かった。 As shown in FIG. 12, the amount of Q 4 Si atoms was at least 90% of the total amount of Si atoms.
（２）比較品の製造例1で得られたＭＣＭ-４１を８５０℃で２４時間加熱した。この時のＸ線回折パターンを図１３に示す。 (2) MCM-41 obtained in Comparative Production Example 1 was heated at 850 ° C. for 24 hours. The X-ray diffraction pattern at this time is shown in FIG.
また、８５０℃で２４時間加熱後のＸ線回折パターンのｄ１００のピーク強度を求めたところ加熱前の４４．１％であった。 Moreover, it was 44.1% before heating was determined peak intensities of d 100 of X-ray diffraction pattern after heating at 850 ° C. 24 hours.
耐水熱性試験
製造例１にて得た多孔体Ａを５０℃、６０℃、及び７０℃のイオン交換水中で２日間加熱した。この時のＸ線回折パターンを図１４に示す。
Hydrothermal resistance test The porous body A obtained in Production Example 1 was heated in ion-exchanged water at 50 ° C, 60 ° C, and 70 ° C for 2 days. The X-ray diffraction pattern at this time is shown in FIG.
図１４に示すように多孔体Ａを５０℃、６０℃、及び７０℃のイオン交換水中で２日間加熱後のＸ線回折パターンのｄ１００のピーク強度を求めたところ、それぞれ加熱前の１００％、８９．３％、及び７９．２％であった。 As shown in FIG. 14, the peak intensity of d 100 of the X-ray diffraction pattern after heating the porous body A in ion exchange water at 50 ° C., 60 ° C., and 70 ° C. for 2 days was determined. , 89.3%, and 79.2%.
本発明により耐熱性及び耐水熱性に優れた、新規な構造を持つ多孔体を提供することができ、触媒や吸着剤用途等に好適に用いられるものであり、その産業上の利用価値は大である。 According to the present invention, it is possible to provide a porous body having a novel structure excellent in heat resistance and hydrothermal resistance, and is suitably used for a catalyst or an adsorbent, and its industrial utility value is great. is there.
１ 多孔体Ｃ
２ 多孔体Ａ
３ 多孔体Ｂ
４ 多孔体Ｄ
５ 多孔体Ｅ
６ 多孔体Ｆ
７ 加熱前
８ ５０℃
９ ６０℃
１０ ７０℃
1 Porous material C
2 Porous material A
3 Porous body B
4 Porous body D
5 Porous body E
6 Porous body F
7 Before heating 8 50 ℃
9 60 ℃
10 70 ° C
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