JP3530926B2 - Method for producing crystalline layered metallosilicate - Google Patents
Method for producing crystalline layered metallosilicateInfo
- Publication number
- JP3530926B2 JP3530926B2 JP2000202249A JP2000202249A JP3530926B2 JP 3530926 B2 JP3530926 B2 JP 3530926B2 JP 2000202249 A JP2000202249 A JP 2000202249A JP 2000202249 A JP2000202249 A JP 2000202249A JP 3530926 B2 JP3530926 B2 JP 3530926B2
- Authority
- JP
- Japan
- Prior art keywords
- metallosilicate
- crystalline layered
- layered
- producing
- crystalline
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims description 19
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 14
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 150000001768 cations Chemical class 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 11
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- -1 alkali metal cation Chemical class 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004115 Sodium Silicate Substances 0.000 description 5
- PIOLJLKNDPUWIR-UHFFFAOYSA-N [Na+].C[N+](C)(C)C Chemical compound [Na+].C[N+](C)(C)C PIOLJLKNDPUWIR-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910052665 sodalite Inorganic materials 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 125000005372 silanol group Chemical group 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 208000005156 Dehydration Diseases 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 241000282376 Panthera tigris Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical class CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- JOIVCDIWUSKTHY-UHFFFAOYSA-N potassium tetramethylazanium Chemical compound [K+].C[N+](C)(C)C JOIVCDIWUSKTHY-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- APSPVJKFJYTCTN-UHFFFAOYSA-N tetramethylazanium;silicate Chemical compound C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.C[N+](C)(C)C.[O-][Si]([O-])([O-])[O-] APSPVJKFJYTCTN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は分離・吸着剤、形状
選択性固体触媒、イオン交換剤、クロマトグラフィー充
填剤等に用いることのできる結晶性層状メタロシリケー
トに関するものである。TECHNICAL FIELD The present invention relates to a crystalline layered metallosilicate which can be used as a separating / adsorbing agent, a shape-selective solid catalyst, an ion-exchange agent, a chromatographic packing material and the like.
【０００２】[0002]
【従来の技術】メタロシリケート多孔質材料はシリケー
ト（ケイ酸塩）骨格の一部が金属陽イオンで置換された
骨格構造を有し、一般に耐熱性が高く化学的にも安定な
ものが数多く得られることから様々な分野で利用されて
いる。特に多孔質メタロシリケートとして代表的な材料
であるゼオライトはシリケート骨格が３次元的に発達
し、通常はＳｉの一部がＡｌに置換したアルミノシリケ
ートとして知られる。分子オーダーの細孔を有し、立体
選択的な吸着作用を持つことによりモレキュラーシーブ
（分子ふるい）としての機能を有する。数十種類の天然
に産出するゼオライトの他に、これまでに多種のゼオラ
イトが合成されており、触媒、分離吸着剤、イオン交換
剤等の分野で幅広く用いられている。また、アルミニウ
ムを含まない純粋なシリケート骨格を有するシリカライ
トは高い疎水性を有し分離吸着剤として用いられる。ま
たＢ、Ｃａ、Ｔｉ、Ｆｅ、Ｖ、Ｃｏ、Ｓｎ、Ｚｎ、Ｍ
ｎ、Ｃｒ等の元素でアルミニウムを置換したメタロシリ
ケートも多種知られており、骨格置換元素の種類及び置
換量により固体酸性や触媒活性等が発現し、主に固体触
媒として広く利用されている。しかしながら、チャンネ
ル構造であるが故に細孔径や細孔容量が小さく、吸着分
子の拡散速度が遅いことが触媒や分離・吸着剤としての
性能向上の妨げとなっている。一方、ゼオライトのよう
な３次元シリケート骨格とは異なり、２次元層状シリケ
ート骨格を有し、その層間にアルカリ金属等の陽イオン
や水を含む層状シリケートも天然、合成を問わず数多く
知られている。ゼオライトと異なり一般にチャンネル構
造を有しておらずそのままでは多孔質でないものがほと
んどであるが、酸化物クラスター等を用いた層間架橋
（山中昭司、服部信、表面、１９８９年、２７巻、２９
０頁）により層面間隔を拡大したり、界面活性剤を用い
たシート折畳み（ＦＳＭ）（稲垣ら、Ｊ．Ｃｈｅｍ．Ｓ
ｏｃ．，Ｃｈｅｍ．Ｃｏｍｍｕｍ．，１９９３年、６８
０頁）やデラミネーション（Ｃｏｒｍａら、Ｎａｔｕｒ
ｅ，１９９９年、３９６巻、３５３頁）等により多孔化
する方法が知られている。多孔性層状シリケートはゼオ
ライトとは異なり２次元空間を利用して吸着分子が移動
することができるため拡散速度が早いものの、ほとんど
の多孔性層状シリケートは結晶性が悪く細孔の形状やサ
イズが一定でないため、形状選択性はゼオライト類に比
べ著しく劣る。2. Description of the Related Art A metallosilicate porous material has a skeleton structure in which a part of a silicate (silicate) skeleton is replaced with a metal cation, and in general, many heat resistant and chemically stable materials can be obtained. Therefore, it is used in various fields. In particular, zeolite, which is a typical material as a porous metallosilicate, has a silicate skeleton developed three-dimensionally, and is generally known as an aluminosilicate in which a part of Si is replaced by Al. It has a pore of molecular order and has a function as a molecular sieve by having a stereoselective adsorption action. In addition to dozens of naturally occurring zeolites, various zeolites have been synthesized so far and are widely used in the fields of catalysts, separation / adsorbents, ion exchange agents, and the like. Further, silicalite having a pure silicate skeleton containing no aluminum has high hydrophobicity and is used as a separation / adsorption agent. In addition, B, Ca, Ti, Fe, V, Co, Sn, Zn, M
A variety of metallosilicates in which aluminum is substituted with elements such as n and Cr are also known, and solid acidity and catalytic activity are exhibited depending on the type and substitution amount of the skeleton-replacement element, and are widely used mainly as solid catalysts. However, due to the channel structure, the pore size and pore volume are small, and the diffusion speed of adsorbed molecules is slow, which hinders the improvement of performance as a catalyst or a separation / adsorbent. On the other hand, unlike a three-dimensional silicate skeleton such as zeolite, a large number of layered silicates having a two-dimensional layered silicate skeleton and containing a cation such as an alkali metal or water between the layers are known regardless of whether they are natural or synthetic. . Unlike zeolites, most of them do not generally have a channel structure and are not porous as they are, but inter-layer cross-linking using oxide clusters etc. (Akira Yamanaka, Shin Hattori, Surface, 1989, 27, 29)
(Page 0) to increase the inter-layer spacing and sheet folding (FSM) using a surfactant (Inagaki et al., J. Chem. S.
oc. Chem. Commum. , 1993, 68
Page 0) and delamination (Corma et al., Nature)
e, 1999, vol. 396, p. 353) and the like are known. Unlike zeolite, porous layered silicates have a fast diffusion rate because adsorbed molecules can move using a two-dimensional space, but most porous layered silicates have poor crystallinity and the shape and size of pores are constant. Therefore, the shape selectivity is significantly inferior to that of zeolites.
【０００３】[0003]
【発明が解決しようとする課題】したがって本発明の目
的は、ゼオライトの欠点である吸着分子の低拡散速度、
並びに多孔性層状シリケートの低形状選択性という両材
料の欠点を克服しうる新しいタイプの材料を提供するこ
とである。The object of the present invention is therefore the disadvantage of zeolites, namely the low diffusion rate of adsorbed molecules,
Another object is to provide a new type of material which can overcome the disadvantages of both materials, namely the low shape selectivity of porous layered silicates.
【０００４】[0004]
【課題を解決するための手段】本発明者は、上記の目的
に適合するメタロシリケートの合成について鋭意検討し
た結果、シリカ原料、アルカリ金属源、テトラメチルア
ンモニウム塩のようなテトラ低級アルキルアンモニウム
塩を水及び有機溶媒と混合し、圧力容器中で自然圧下加
熱することにより、テトラ低級アルキルアンモニウム陽
イオンとアルカリ金属陽イオンを共に構造中に含む結晶
性層状メタロシリケートが得られることを見い出し、こ
の知見に基づき本発明を完成するに至った。すなわち本
発明は、
（１）シリカ原料、アルカリ金属源、及びテトラ低級ア
ルキルアンモニウム塩を水及び有機溶媒と混合して、圧
力容器中で自然圧下加熱し、化学組成が下記一般式
（Ｉ）
［(ＳｉＯ２）１−ｘ・（Ｔ２／ｎＯ）ｘ・（ＴＲＡ２
Ｏ）ｙ・（Ｍ２Ｏ）ｚ・（Ｈ２Ｏ)ｗ］
（式中、ＴＲＡはテトラ低級アルキルアンモニウム陽イ
オン、ＴはＢまたは価数が２以上５以下の金属陽イオ
ン、ｎはＴで表されるＢまたは金属陽イオンの価数、Ｍ
はＮａ、Ｋ、Ｌｉ等のアルカリ金属陽イオンを表し、ｘ
は０≦ｘ≦０．１、ｙは０．０５≦ｙ≦０．２、ｚは
０．０２≦ｚ≦０．２５、ｗは０≦ｗ≦２．０の数であ
る。）で表され、シリケート及びＴからなる層状骨格構
造及び一定間隔の２次元層間を有する結晶性層状メタロ
シリケートの製造方法、
（２）前記層状骨格構造がケイ素１０員環以上の大きさ
の開口部を有する細孔を層内に有することを特徴とする
（１）項記載の結晶性層状メタロシリケートの製造方
法、
（３）前記一般式中のＴがＡｌ、Ｇａ、Ｔｉ、Ｆｅ、
Ｖ、Ｃｏ、Ｓｎ、Ｚｎ、ＭｎまたはＣｒの金属陽イオン
である（１）項記載の結晶性層状メタロシリケートの製
造方法、
（４）前記一般式中のＴがＢである（１）項記載の結晶
性層状メタロシリケートの製造方法、
（５）前記一般式中のｘが０である（３）または（４）
項記載の結晶性層状メタロシリケートの製造方法、
（６）前記一般式中のＭがＮａである（３）または
（４）項記載の結晶性層状メタロシリケートの製造方
法、
（７）前記一般式中のＭがＫである（３）または（４）
項記載の結晶性層状メタロシリケートの製造方法、
（８）結晶性層状メタロシリケートが下記表１
（表中、ｄは面間隔を表す。また、相対強度をｍ＝中
位、ｓ＝強い、ｖｓ＝極めて強い、として表記した。）
に記載されたｄの回折面間隔を少なくとも含む粉末Ｘ線
回折パターンを示す（３）または（４）項記載の結晶性
層状メタロシリケートの製造方法、
（９）結晶性層状メタロシリケートが下記表２
（表中、ｄは面間隔を表す。また、相対強度をｍ＝中
位、ｓ＝強い、ｖｓ＝極めて強い、として表記した。）
に記載されたｄの回折面間隔を少なくとも含む粉末Ｘ線
回折パターンを示す（３）または（４）項記載の結晶性
層状メタロシリケートの製造方法、 （１０）結晶性層状メタロシリケートが結晶性層状テト
ラ低級アルカリ金属メタロシリケートである（１）〜
（９）のいずれか１項に記載の結晶性層状メタロシリケ
ートの製造方法、および、 （１１）シリカ原料：アルカリ金属源のモル比が１０
０：１〜１：１であり、テトラ低級アルキルアンモニウ
ム塩がシリカ原料に対して２〜４０モル％である構成比
で混合することを特徴とする（１）〜（１０）のいずれ
か１項に記載の結晶性層状メタロシリケートの製造方
法
。
を提供するものである。Means for Solving the Problems As a result of earnest studies on the synthesis of metallosilicates which meet the above-mentioned objects, the present inventors have found that silica raw materials, alkali metal sources, and tetra-lower alkylammonium salts such as tetramethylammonium salts are used. It was found that a crystalline layered metallosilicate containing both a tetra-lower alkylammonium cation and an alkali metal cation in the structure can be obtained by mixing with water and an organic solvent and heating under a natural pressure in a pressure vessel. Based on this, the present invention has been completed. That is, the present invention provides (1) a silica raw material, an alkali metal source, and a tetra-lower alkyl
Ruquillammonium salt is mixed with water and organic solvent and
It is heated under natural pressure in a pressure vessel and has a chemical composition represented by the following general formula (I) [(SiO 2 ) 1-x · (T 2 / n O) x · (TRA 2
O) y · (M 2 O) z · (H 2 O) w ] (wherein, TRA is a tetra-lower alkyl ammonium cation, T is B or a metal cation having a valence of 2 or more and 5 or less, and n is T. The valence of B or a metal cation represented by
Represents an alkali metal cation such as Na, K or Li, x
Is 0 ≦ x ≦ 0.1, y is 0.05 ≦ y ≦ 0.2, z is 0.02 ≦ z ≦ 0.25, and w is 0 ≦ w ≦ 2.0. ), A crystalline layered metallo having a layered skeleton structure composed of silicate and T and having two-dimensional layers at regular intervals.
(2) A method for producing a silicate , (2) The crystalline layered metallosilicate according to item (1), wherein the layered skeleton structure has pores having openings having a size of 10-membered ring of silicon or more in the layer. Manufacturing method
Method , (3) T in the general formula is Al 2 , Ga, Ti, Fe,
The crystalline layered metallosilicate according to item (1), which is a metal cation of V, Co, Sn, Zn, Mn or Cr .
Manufacturing method , (4) The crystal according to item (1), wherein T in the general formula is B.
Of the organic layered metallosilicate , (5) wherein x in the general formula is 0 (3) or (4)
Item 6. A method for producing a crystalline layered metallosilicate according to item (6), wherein M in the general formula is Na (3) or
Method for producing crystalline layered metallosilicate according to item (4)
Law, (7) M in the formula is K (3) or (4)
The method for producing a crystalline layered metallosilicate according to the item (8), the crystalline layered metallosilicate is shown in Table 1 below. (In the table, d represents the interplanar spacing, and the relative intensities are expressed as m = medium, s = strong, vs = extremely strong.)
(3) or (4), which shows a powder X-ray diffraction pattern containing at least the d-spacing of d described in 1 .
Method for producing layered metallosilicate , (9) Crystalline layered metallosilicate is shown in Table 2 below. (In the table, d represents the interplanar spacing, and the relative intensities are expressed as m = medium, s = strong, vs = extremely strong.)
(3) or (4), which shows a powder X-ray diffraction pattern containing at least the d-spacing of d described in 1 .
Method for producing layered metallosilicate, (10) Crystalline layered metallosilicate is crystalline layered tet
La lower alkali metal metallosilicate (1) ~
(9) The crystalline layered metallo-silikee according to any one of (9).
And a silica raw material: alkali metal source molar ratio of 10
0: 1 to 1: 1 and tetra-lower alkylammonium
The composition ratio in which the salt content is 2 to 40 mol% with respect to the silica raw material
Any of (1) to (10), characterized in that
The method for producing the crystalline layered metallosilicate according to Item 1.
Law . Is provided.
【０００５】[0005]
【発明の実施の形態】図１は本発明の一般式（Ｉ）で表
わされるメタロシリケートの構造の概念図を示す斜視図
であり、図中１は層状骨格構造部、２は２次元層間部で
あり、３が層状骨格構造部の表裏面に形成されたケイ素
１０員環（Ｓｉ−Ｏ−Ｓｉ結合のＯを算入しない）以上
の大きさの開口部を有する細孔（くぼみ）である。本発
明の結晶性層状メタロシリケートの一例としてアルカリ
金属としてナトリウムを用いたテトラメチルアンモニウ
ムシリケートの結晶構造を図２に示す。図２は図１の一
対の層状骨格構造部１，１と、その間の層間部２におけ
る結晶構造を示し、大きな薄灰色のボール２１はＮａ、
中位の薄灰色のボール２２はＴＲＡ、及び小さな薄灰色
のボール２３は末端シラノール基のＯの存在位置を示
す。太線はシリケート骨格構造を示し、Ｓｉ−Ｏ−Ｓｉ
結合をＯを省略して表示したものである。この太線のシ
リケート骨格構造がＳｉ１〜Ｓｉ１２の１２員環からな
る開口部を形成し、これが上記図１の３に相当する開口
部を形成することになる。また、点線は結晶の単位格子
を示し、ａ、ｂ及びｃは０（零）を基準とする結晶軸の
方向を示したものである。なお、図２のＳｉ１〜Ｓｉ
１２により形成されるケイ素１２員環の開口部の平面図
を後述する図３に示した。図２に示すようにシリケート
骨格は２次元層状構造をなし、層間に末端シラノール基
が突き出ている。ナトリウム陽イオンは層間に存在し、
シラノール基と結合しているが、図中に示された全ての
位置を必ずしも占めているわけではなく、製造方法や溶
媒洗浄等によりナトリウムの含有量を調節することが可
能である。この他のアルカリ金属陽イオン（Ｍ）を用い
た場合には、ナトリウムの場合と若干異なるメタロシリ
ケート骨格構造を取るが、２次元層状構造の層間にアル
カリ金属陽イオンが存在し、層内に細孔を有する点にお
いて同様である。Ｍの量は、通常Ｍ／Ｓｉ原子比で０．
０２ないし０．２５であり、好ましくは０．０５ないし
０．２である。また層内には、図３について述べるよう
なケイ素１２員環（酸素を含めると２４員環）開口部を
持つ半球状の細孔が層間をはさんで向かい合って存在し
ており、細孔内にテトラメチルアンモニウム陽イオンが
位置している。テトラメチルアンモニウムのようなＴＲ
Ａの存在量は酸洗浄等により制御できる。ＴＲＡ量は、
通常ＴＲＡ／Ｓｉモル比で０．０５ないし０．２であ
り、好ましくは０．０５ないし０．１２である。1 is a perspective view showing a conceptual diagram of the structure of a metallosilicate represented by the general formula (I) of the present invention, in which 1 is a layered skeleton structure part and 2 is a two-dimensional interlayer part. And 3 is a pore (recess) formed on the front and back surfaces of the layered skeleton structure portion and having an opening having a size of at least a silicon 10-membered ring (does not include O of Si—O—Si bond). As an example of the crystalline layered metallosilicate of the present invention, FIG. 2 shows the crystal structure of tetramethylammonium silicate using sodium as an alkali metal. FIG. 2 shows a crystal structure in the pair of layered skeleton structure parts 1 and 1 and the interlayer part 2 between them in FIG. 1. The large light gray ball 21 is Na,
The medium light gray ball 22 indicates the position of TRA, and the small light gray ball 23 indicates the position of O of the terminal silanol group. The thick line shows the silicate skeleton structure, Si-O-Si
The bond is displayed with O omitted. The thick silicate skeleton structure forms an opening formed of a 12-membered ring of Si 1 to Si 12 , which forms an opening corresponding to 3 in FIG. The dotted line indicates the unit cell of the crystal, and a, b, and c indicate the directions of the crystal axes with 0 (zero) as a reference. Note that Si 1 to Si in FIG.
Shows a plan view of the opening of the silicon 12-membered ring formed in FIG. 3 to be described later by 12. As shown in FIG. 2, the silicate skeleton has a two-dimensional layered structure with terminal silanol groups protruding between the layers. Sodium cations exist between the layers,
Although it is bonded to the silanol group, it does not necessarily occupy all the positions shown in the figure, and the sodium content can be adjusted by the production method, solvent washing or the like. When the other alkali metal cation (M) is used, it has a metallosilicate skeleton structure slightly different from that of sodium, but the alkali metal cation is present between the layers of the two-dimensional layered structure, and the metal silicate skeleton exists in the layer. It is similar in that it has holes. The amount of M is usually 0.
It is from 02 to 0.25, preferably from 0.05 to 0.2. Further, in the layer, hemispherical pores having a silicon 12-membered ring (24-membered ring when oxygen is included) opening as described with reference to FIG. The tetramethylammonium cation is located at. TR such as tetramethylammonium
The existing amount of A can be controlled by acid washing or the like. The amount of TRA is
Usually, the TRA / Si molar ratio is 0.05 to 0.2, preferably 0.05 to 0.12.
【０００６】図３は図２のＳｉ１〜Ｓｉ１２を有して形
成されるケイ素１２員環を模式的に示した平面図であ
り、本発明のテトラメチルアンモニウムナトリウムシリ
ケートのケイ素１２員環開口部を表す（図中、大きな灰
色のボール３１はＳｉ、小さな灰色のボール３２はＯの
存在位置を示したものである）。本発明の一般式（Ｉ）
で表されるメタロシリケートにおいて、図１、２に示す
層間部にはナトリウムの他に結晶水も存在するが、水の
存在量は合成条件や加熱脱水等の処理により骨格構造を
本質的に損なうことなく制御できる。含水量は、通常Ｈ
２Ｏ／Ｓｉモル比で０ないし２である。また、Ｂ、ある
いは、Ａｌ、Ｇａ、Ｔｉ、Ｆｅ、Ｖ、Ｃｏ、Ｓｎ、Ｚ
ｎ、ＭｎまたはＣｒをはじめとする数多くの多価金属陽
イオン（Ｔ）がシリケート骨格の一部を骨格構造を本質
的に損なうことなく置換することができる。Ｔの量は、
通常Ｔ／Ｓｉ原子比で０ないし０．１、好ましくは０な
いし０．０４である。本発明において合成時に役割の異
なる２種類の陽イオンを導入することにより上記の構造
構築を行うことが可能となったものと思われる。すなわ
ち、テトラ低級アルキルアンモニウム陽イオンがケージ
構造やチャンネル構造を構築することのできる構造誘導
剤としての役割を果たし、アルカリ金属陽イオンがシリ
ケート骨格の３次元成長を防ぎシリケート層間構造の構
築を司ることにより、シリケート層内に細孔構造を有す
る層状メタロシリケートが得られると考えられる。本発
明の結晶性層状メタロシリケートの製造方法を一般的に
説明すると、シリカ原料、アルカリ金属源、テトラ低級
アルキルアンモニウム塩を水及び有機溶媒と混合し、圧
力容器中で自然圧下加熱することより行うことができ
る。この製造における反応成分とその反応モル比は上記
の目的とする一般式（Ｉ）で表わされる、メタロシリケ
ートの組成によって定まるが、これについて具体的に述
べると、用いるシリカ原料としてはシリカゲル、シリカ
ゾル、四塩化ケイ素などが用いられる。アルカリ金属源
としては、水酸化ナトリウム、水酸化カリウム、水酸化
リチウムなどが用いられ、多価金属源としては塩化物、
硝酸塩等が用いられるが、ゾルゲル法等の手法により調
製された金属酸化物シリカ複合体を用いることもでき
る。テトラ低級アルキルアンモニウム塩としては、テト
ラメチルアンモニウム塩、テトラエチルアンモニウム
塩、テトラブチルアンモニウム塩などが挙げられるが、
好ましくはテトラメチルアンモニウム塩である。反応は
シリカ原料：アルカリ金属源を１００：１〜１：１の反
応モル比で反応させるのが好ましい。テトラ低級アルキ
ルアンモニウム塩は、前記のシリカ源に対し、好ましく
は２〜４０モル％、より好ましくは１０〜３０モル％用
いる。反応は水及び有機溶媒中で行われ、反応温度は、
好ましくは８０〜２５０℃、より好ましくは１００〜１
８０℃、反応時間は、好ましくは１０時間〜３６０日、
より好ましくは１日〜１００日であり、反応圧力は、自
然圧が望ましい。反応に用いる水の量は、シリカ原料、
アルカリ金属源、テトラ低級アルキルアンモニウム塩の
合計モルに対し、好ましくは１００〜２０００モル％で
ある。また用いる有機溶媒の量はテトラ低級アルキルア
ンモニウム塩に対し、質量比で、好ましくは５〜３０倍
である。FIG. 3 is a plan view schematically showing the silicon 12-membered ring formed with Si 1 to Si 12 of FIG. 2, and the silicon 12-membered ring opening of tetramethylammonium sodium silicate of the present invention is shown. (In the figure, a large gray ball 31 indicates the position of Si and a small gray ball 32 indicates the position of O). General formula (I) of the present invention
In the metallosilicate represented by, crystal water is present in addition to sodium in the interlayer portion shown in FIGS. 1 and 2, but the amount of water essentially impairs the skeletal structure due to synthesis conditions and heat dehydration treatment. Can be controlled without Water content is usually H
The 2 O / Si molar ratio is 0 to 2. Also, there is B
There is, Al, Ga, Ti, Fe , V, Co, Sn, Z
Numerous polyvalent metal cations (T), including n, Mn or Cr, can replace part of the silicate skeleton without essentially compromising the skeleton structure. The amount of T is
Usually, the T / Si atomic ratio is 0 to 0.1, preferably 0 to 0.04. In the present invention, it is considered possible to construct the above structure by introducing two kinds of cations having different roles during synthesis. That is, the tetra-lower alkyl ammonium cation plays a role as a structure inducer capable of constructing a cage structure or a channel structure, and the alkali metal cation prevents the three-dimensional growth of the silicate skeleton and controls the construction of the silicate interlayer structure. It is considered that this gives a layered metallosilicate having a pore structure in the silicate layer. The method for producing the crystalline layered metallosilicate of the present invention will be described generally. It is performed by mixing a silica raw material, an alkali metal source, and a tetra-lower alkylammonium salt with water and an organic solvent, and heating the mixture in a pressure vessel under a natural pressure. be able to. The reaction components and the reaction molar ratio thereof in this production are determined by the composition of the metallosilicate represented by the above-mentioned general formula (I), and specifically, the silica raw material used is silica gel, silica sol, Silicon tetrachloride or the like is used. Sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are used as the alkali metal source, and chloride is used as the polyvalent metal source.
A nitrate or the like is used, but a metal oxide-silica composite prepared by a method such as a sol-gel method can also be used. The tetra-lower-alkyl ammonium salt, tetramethylammonium salt, tetraethylammonium salt, although such Te tiger butyl ammonium salts,
Preferred is a tetramethylammonium salt. In the reaction, it is preferable to react silica raw material: alkali metal source at a reaction molar ratio of 100: 1 to 1: 1. The tetra-lower alkyl ammonium salt is used in an amount of preferably 2 to 40 mol%, more preferably 10 to 30 mol%, based on the silica source. The reaction is carried out in water and an organic solvent, and the reaction temperature is
Preferably 80 to 250 ° C, more preferably 100 to 1
80 ° C., the reaction time is preferably 10 hours to 360 days,
It is more preferably 1 to 100 days, and the reaction pressure is preferably natural pressure. The amount of water used for the reaction is the silica raw material,
It is preferably 100 to 2000 mol% with respect to the total mol of the alkali metal source and the tetra-lower alkyl ammonium salt. The amount of the organic solvent used is preferably 5 to 30 times by mass ratio with respect to the tetra-lower alkyl ammonium salt.
【０００７】[0007]
【発明の効果】本発明の層状メタロシリケートにおいて
は層間の２次元空間を利用できるのみならず、層そのも
のに均一なサイズのミクロ細孔構造を有しておりＴＲＡ
を除去することにより吸着場として使用できるので、多
孔質材料として分離・吸着用途に優れた特性を有するこ
とが期待される。また、イオン交換やインターカレーシ
ョンにより層間に種々の酸化物クラスターや有機物架橋
剤を導入することにより層間架橋させることができるの
で、さらに空間容量を増やすことも自在である。すなわ
ち、ゼオライトで実現される高い形状選択性と多孔性層
状シリケートによって得られる大細孔容量という両材料
の長所を併せ持った新しい多孔質材料であり、分離・吸
着剤やクロマトグラフィー充填剤等として優れた特性を
示すことが期待される。また、シリケート骨格中に骨格
置換された金属陽イオンによって固体酸点や触媒活性点
を導入することができ、形状選択性固体触媒やイオン交
換剤としても利用できる。また例えば図２の場合を例に
説明すると、本発明の層状テトラメチルアンモニウムナ
トリウムシリケートはアルカリ金属を挟んで向かい合っ
ている末端シラノール基同士を縮合させることにより容
易にソーダライトに変換することができる。層内のミク
ロ細孔は層面間隔を拡大することでアクセスが容易とな
るので、ゲストとなる原子や分子をミクロ細孔中に導入
した後、ソーダライト変換することによりこれらをソー
ダライトのカプセル中に安定に閉じこめることができ
る。従って有害有機分子や放射性元素の封じ込めに使用
できる。さらに、本層状メタロシリケートを原料とする
ことにより新規なゼオライトやメソポーラスシリカ等の
高機能多孔質材料が得られることが期待される。In the layered metallosilicate of the present invention, not only the two-dimensional space between layers can be utilized but also the layer itself has a micropore structure of uniform size.
Since it can be used as an adsorption field by removing, it is expected to have excellent properties as a porous material for separation / adsorption applications. Further, since inter-layer cross-linking can be achieved by introducing various oxide clusters or organic cross-linking agents between the layers by ion exchange or intercalation, it is possible to further increase the space capacity. In other words, it is a new porous material that has the advantages of both the high shape selectivity realized by zeolite and the large pore volume obtained by porous layered silicate, and is excellent as a separation / adsorbent or chromatography packing material. It is expected to exhibit excellent characteristics. In addition, a solid acid site or a catalytically active site can be introduced into the silicate skeleton by skeleton-substituted metal cations, and the silicate skeleton can also be used as a shape-selective solid catalyst or an ion exchange agent. For example, taking the case of FIG. 2 as an example, the layered tetramethylammonium sodium silicate of the present invention can be easily converted to sodalite by condensing terminal silanol groups facing each other with an alkali metal sandwiched therebetween. The micropores in a layer can be easily accessed by expanding the layer spacing.Therefore, after introducing the guest atoms and molecules into the micropores, they are converted into sodalite in the sodalite capsule. Can be stably locked in. Therefore, it can be used to contain harmful organic molecules and radioactive elements. Furthermore, it is expected that novel functional materials such as zeolite and mesoporous silica can be obtained by using the present layered metallosilicate as a raw material.
【０００８】[0008]
【実施例】次に本発明を実施例に基づきさらに詳細に説
明する。以下、粉末Ｘ線回折パターンはマックサイエン
ス社ＭＸＰ１８を使用し、ＣｕＫα線を用いて、０．０
２°間隔のステップスキャンにより得た。化学分析は
Ｃ、Ｈ及びＮは燃焼法により、また、Ｓｉ及びＮａは固
体試料の化学分解によって得られた溶液を用いてＩＣＰ
発光分光分析により行った。熱重量分析はマックサイエ
ンス社製ＴＧＤＴＡ２０００（商品名）を使用した。
実施例１
結晶性層状テトラメチルアンモニウムナトリウムシリケ
ートの製造
（ａ）シリカゲル（Ｃａｂｏｔ社製、商品名：Ｃａｂ−
Ｏ−Ｓｉｌ Ｍ５）１０ｇ、及び１５％水酸化テトラメ
チルアンモニウム溶液２２ｇに１Ｎ水酸化ナトリウム水
溶液６０ｇ、水５３ｇ及び１，４−ジオキサン５０ｇを
加え、ステンレス製耐圧容器内で自然圧下、１５０℃、
５日間恒温槽中で加熱した後、室温まで冷却した。固形
物を濾過、空気中で乾燥した。これにより図１、図２及
び図３に示される層状構造を有し、層状部そのものに均
一なサイズ（径６Å）のミクロ細孔構造を有する結晶性
層状メタロシリケートを得た。層面間隔は１１Åであっ
た。この生成物は表５に示すような強度データに特徴づ
けられる粉末Ｘ線回折パターンを与えた。また、本生成
物は化学分析により９．１質量％のＣ、２．５質量％の
Ｎ、３．７質量％のＨ、２９．１質量％のＳｉ及び４．
５質量％のＮａを含んでいた。
（ｂ）上で得られた結晶性生成物を２２０℃で加熱する
ことにより、層面間隔がｄ＝１１．２Åからｄ＝９．５
４Åまで縮小し層内の脱水が起こった。しかし、室温ま
で冷却すると（ａ）で得られた生成物とほぼ同じ回折パ
ターンに戻ることから、骨格構造は本質的には変化して
いない。The present invention will be described in more detail based on the following examples. Hereinafter, for the powder X-ray diffraction pattern, using MXP18 manufactured by Mac Science Co., Ltd.
Obtained by step scanning at 2 ° intervals. For chemical analysis, C, H, and N were analyzed by a combustion method, and Si and Na were analyzed by ICP using a solution obtained by chemical decomposition of a solid sample.
It was performed by optical emission spectroscopy. For thermogravimetric analysis, TGDTA2000 (trade name) manufactured by Mac Science Co. was used. Example 1 Production of crystalline layered tetramethylammonium sodium silicate (a) Silica gel (manufactured by Cabot, trade name: Cab-
O-Sil M5) 10 g, and 15% tetramethylammonium hydroxide solution 22 g, 1N aqueous sodium hydroxide solution 60 g, water 53 g and 1,4-dioxane 50 g were added, and natural pressure was applied in a stainless steel pressure vessel at 150 ° C.
After heating in a constant temperature bath for 5 days, it was cooled to room temperature. The solid was filtered and dried in air. Thus, a crystalline layered metallosilicate having the layered structure shown in FIGS. 1, 2 and 3 and having a micropore structure of uniform size (diameter 6Å) in the layered portion itself was obtained. The layer-to-layer spacing was 11Å. The product gave a powder X-ray diffraction pattern characterized by intensity data as shown in Table 5. In addition, the product was analyzed by chemical analysis to have 9.1 mass% C, 2.5 mass% N, 3.7 mass% H, 29.1 mass% Si and 4.
It contained 5 mass% Na. (B) By heating the crystalline product obtained above at 220 ° C., the interplanar spacing is d = 11.2Å to d = 9.5.
It was reduced to 4Å and dehydration within the layer occurred. However, the framework structure is essentially unchanged, as it returns to a diffraction pattern that is almost the same as the product obtained in (a) when cooled to room temperature.
【０００９】実施例２
結晶性層状テトラメチルアンモニウムナトリウムシリケ
ートの製造
（ａ）シリカゲル（Ｃａｂｏｔ社製、商品名：Ｃａｂ−
Ｏ−Ｓｉｌ Ｍ５）１０ｇ、及び１５％水酸化テトラメ
チルアンモニウム溶液２２ｇに０．５Ｎ水酸化ナトリウ
ム水溶液２５ｇ、水５ｇ及び１，４−ジオキサン５０ｇ
を加え、ステンレス製耐圧容器内で自然圧下、１５０
℃、１０日間恒温槽中で加熱した後、室温まで冷却し
た。固形物を濾過、空気中で乾燥した。これにより実施
例１の図１〜３に示すと同様のミクロ細孔構造（６Å）
を有する結晶性層状メタロシリケートを得た。層面間隔
は１１Åであった。この生成物は表６に示すような強度
データに特徴づけられる粉末Ｘ線回折パターンを与え
た。また、本生成物は化学分析により９．３質量％の
Ｃ、２．７質量％のＮ、３．４質量％のＨを含んでい
た。
（ｂ）上で得られた結晶性生成物の５ｇをとり０．２Ｍ
塩酸２００ｍｌ中に分散させ一夜放置することにより陽
イオン交換を行った。濾過後、空気中で乾燥した生成物
は表７に示すような強度データに特徴づけられ、上記
（ａ）の生成物とよく似た粉末Ｘ線回折パターンを与え
た。ＴＲＡ含量は熱重量分析より上記（ａ）の生成物の
およそ５０％と見積もられた。
Example 2 Production of crystalline layered tetramethylammonium sodium silicate (a) Silica gel (trade name: Cab-, manufactured by Cabot)
10 g of O-Sil M5) and 22 g of 15% tetramethylammonium hydroxide solution, 25 g of 0.5N sodium hydroxide aqueous solution, 5 g of water and 50 g of 1,4-dioxane.
, And under natural pressure in a stainless pressure vessel, 150
After heating at 0 ° C for 10 days in a constant temperature bath, it was cooled to room temperature. The solid was filtered and dried in air. Thereby, the micropore structure (6Å) similar to that shown in FIGS.
A crystalline layered metallosilicate having The layer-to-layer spacing was 11Å. The product gave a powder X-ray diffraction pattern characterized by intensity data as shown in Table 6. Moreover, this product contained 9.3 mass% C, 2.7 mass% N, and 3.4 mass% H by the chemical analysis. (B) Taking 5 g of the crystalline product obtained above, 0.2M
Cation exchange was performed by dispersing in 200 ml of hydrochloric acid and leaving it to stand overnight. After filtration, the product dried in air was characterized by intensity data as shown in Table 7, giving a powder X-ray diffraction pattern very similar to the product of (a) above. The TRA content was estimated by thermogravimetric analysis to be approximately 50% of the product of (a) above.
【００１０】実施例３
結晶性層状テトラメチルアンモニウムナトリウムシリケ
ートの製造
シリカゲル（Ｃａｂｏｔ社、Ｃａｂ−Ｏ−Ｓｉｌ Ｍ
５）１０ｇ、及び１５％水酸化テトラメチルアンモニウ
ム溶液２２ｇに０．５Ｎ水酸化ナトリウム水溶液１５
ｇ、水５ｇ及び１，４−ジオキサン５０ｇを加え、ステ
ンレス製耐圧容器内で自然圧下、１５０℃、８０日間恒
温槽中で加熱した後、室温まで冷却した。固形物を濾
過、空気中で乾燥した。これにより実施例１の図１〜３
に示すと同様のミクロ細孔構造を有する結晶性層状メタ
ロシリケートを得た。層面間隔は１１Åであった。この
生成物は表８に示すような強度データに特徴づけられる
粉末Ｘ線回折パターンを与えた。熱重量分析から水含量
３．０質量％、ＴＲＡ含量１１．８質量％と見積もられ
た。
実施例４
結晶性層状テトラメチルアンモニウムカリウムアルミノ
シリケートの製造
ゾル・ゲル法により調製したＳｉ／Ａｌ＝５０のシリカ
アルミナ１０ｇに１５％水酸化テトラメチルアンモニウ
ム溶液２２ｇ、１Ｎ水酸化カリウム水溶液２０ｍｌ及び
１，４−ジオキサン５０ｇを加え、ステンレス製耐圧容
器内で自然圧下、１５０℃、５日間恒温槽中で加熱した
後、室温まで冷却した。固形物を濾過、空気中で乾燥し
た。これにより実施例１の図１〜３に示すと同様のミク
ロ細孔構造を有する結晶性層状メタロシリケートを得
た。層面間隔は１５Åであった。この生成物は表９に示
すような強度データに特徴づけられる粉末Ｘ線回折パタ
ーンを与えた。
Example 3 Preparation of Crystalline Layered Tetramethylammonium Sodium Silicate Silica Gel (Cabot, Cab-O-Sil M)
5) 0.5 g sodium hydroxide aqueous solution 15 in 10 g and 15% tetramethylammonium hydroxide solution 22 g
g, 5 g of water and 50 g of 1,4-dioxane were added, and the mixture was heated in a stainless steel pressure vessel under natural pressure at 150 ° C. for 80 days in a constant temperature bath and then cooled to room temperature. The solid was filtered and dried in air. As a result, FIGS.
A crystalline layered metallosilicate having a micropore structure similar to that shown in was obtained. The layer-to-layer spacing was 11Å. The product gave a powder X-ray diffraction pattern characterized by intensity data as shown in Table 8. It was estimated from thermogravimetric analysis that the water content was 3.0% by mass and the TRA content was 11.8% by mass. Example 4 Production of Crystalline Layered Tetramethylammonium Potassium Aluminosilicate 10 g of Si / Al = 50 silica alumina prepared by the sol-gel method was added to 22 g of 15% tetramethylammonium hydroxide solution, 20 ml of 1N aqueous potassium hydroxide solution, and 1, After adding 50 g of 4-dioxane, the mixture was heated in a pressure vessel made of stainless steel under natural pressure at 150 ° C. for 5 days in a constant temperature bath, and then cooled to room temperature. The solid was filtered and dried in air. As a result, a crystalline layered metallosilicate having a micropore structure similar to that shown in FIGS. The layer surface spacing was 15Å. The product gave a powder X-ray diffraction pattern characterized by intensity data as shown in Table 9.
【００１１】比較例１
ゾル・ゲル法により調製したＳｉ／Ａｌ＝１０のシリカ
アルミナ１０ｇに１５％水酸化テトラメチルアンモニウ
ム溶液２２ｇ、０．５Ｎ水酸化ナトリウム水溶液１５ｇ
及び１，４−ジオキサン５０ｇを加え、ステンレス製耐
圧容器内で自然圧下、１５０℃、５日間恒温槽中で加熱
した後、室温まで冷却した。得られた固形物を濾過、空
気中で乾燥した。粉末Ｘ線回折パターンより、この生成
物はソーダライト構造であると同定された。ソーダライ
トはケイ素６員環を有するゼオライトであり、層状構造
ではない。
比較例２
実施例２（ａ）で得られたシリケートを２４時間水中に
浸した後、乾燥させた。得られた生成物の組成は３０．
１質量％のＳｉ、及び０．４質量％のＮａで、Ｎａが減
少していた。Ｘ線回折パターンは明確なピークを示さ
ず、結晶性ではなかった。Comparative Example 1 22 g of 15% tetramethylammonium hydroxide solution and 15 g of 0.5N sodium hydroxide aqueous solution were added to 10 g of silica / alumina of Si / Al = 10 prepared by the sol-gel method.
And 1,4-dioxane (50 g) were added, and the mixture was heated in a stainless steel pressure vessel under natural pressure at 150 ° C. for 5 days in a constant temperature bath, and then cooled to room temperature. The solid obtained was filtered and dried in air. The product was identified as having a sodalite structure by a powder X-ray diffraction pattern. Sodalite is a zeolite having a silicon 6-membered ring and does not have a layered structure. Comparative Example 2 The silicate obtained in Example 2 (a) was immersed in water for 24 hours and then dried. The composition of the product obtained is 30.
With 1 mass% of Si and 0.4 mass% of Na, Na was reduced. The X-ray diffraction pattern showed no clear peaks and was not crystalline.
【図１】本発明の一般式（Ｉ）で表されるメタロシリケ
ートの一例の概念図を示す斜視図である。FIG. 1 is a perspective view showing a conceptual view of an example of a metallosilicate represented by the general formula (I) of the present invention.
【図２】本発明のメタロシリケートの一実施例の結晶構
造図である。FIG. 2 is a crystal structure diagram of an example of the metallosilicate of the present invention.
【図３】本発明のメタロシリケートの一実施例における
ケイ素１２員環開口部の説明図である。FIG. 3 is an explanatory diagram of a silicon 12-membered ring opening in one example of the metallosilicate of the present invention.
１ 層状骨格構造部
２ ２次元層間部
３ 層状骨格構造部の表裏面に形成されたケイ素１０員
環（Ｓｉ−Ｏ−Ｓｉ結合のＯを算入しない）以上の大き
さの開口部を有する細孔（くぼみ）1 Layered skeleton structure part 2 Two-dimensional interlayer part 3 Pore having an opening of a size equal to or larger than a silicon 10-membered ring (not including O of Si-O-Si bond) formed on the front and back surfaces of the layered skeleton structure part (Dent)
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平10−330110（ＪＰ，Ａ) 特開 昭62−297210（ＪＰ，Ａ) 特開 平６−263427（ＪＰ，Ａ) 特開2000−176277（ＪＰ，Ａ) 特開2000−154018（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 33/12 - 33/20 ＪＳＴＰｌｕｓ（ＪＯＩＳ)─────────────────────────────────────────────────── --Continued from the front page (56) Reference JP-A-10-330110 (JP, A) JP-A-62-297210 (JP, A) JP-A-6-263427 (JP, A) JP-A-2000-176277 (JP, A) JP 2000-154018 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C01B 33/12-33/20 JSTPlus (JOIS)
Claims (11)
ラ低級アルキルアンモニウム塩を水及び有機溶媒と混合
して、圧力容器中で自然圧下加熱し、化学組成が下記一
般式（Ｉ） ［(ＳｉＯ２）１−ｘ・（Ｔ２／ｎＯ）ｘ・（ＴＲＡ２
Ｏ）ｙ・（Ｍ２Ｏ）ｚ・（Ｈ２Ｏ)ｗ］ （式中、ＴＲＡはテトラ低級アルキルアンモニウム陽イ
オン、ＴはＢまたは価数が２以上５以下の金属陽イオ
ン、ｎはＴで表されるＢまたは金属陽イオンの価数、Ｍ
はＮａ、Ｋ、Ｌｉ等のアルカリ金属陽イオンを表し、ｘ
は０≦ｘ≦０．１、ｙは０．０５≦ｙ≦０．２、ｚは
０．０２≦ｚ≦０．２５、ｗは０≦ｗ≦２．０の数であ
る。）で表され、シリケート及びＴからなる層状骨格構
造及び一定間隔の２次元層間を有する結晶性層状メタロ
シリケートの製造方法。1. A silica raw material, an alkali metal source, and tet.
La lower alkyl ammonium salt mixed with water and organic solvent
Then, it is heated under a natural pressure in a pressure vessel to have a chemical composition represented by the following general formula (I) [(SiO 2 ) 1-x. (T2 / nO) x. (TRA 2
O) y · (M 2 O) z · (H 2 O) w ] (wherein, TRA is a tetra-lower alkyl ammonium cation, T is B or a metal cation having a valence of 2 or more and 5 or less, and n is T. The valence of B or a metal cation represented by
Represents an alkali metal cation such as Na, K or Li, x
Is 0 ≦ x ≦ 0.1, y is 0.05 ≦ y ≦ 0.2, z is 0.02 ≦ z ≦ 0.25, and w is 0 ≦ w ≦ 2.0. ), A crystalline layered metallo having a layered skeleton structure composed of silicate and T and having two-dimensional layers at regular intervals.
Method for producing silicate .
の大きさの開口部を有する細孔を層内に有することを特
徴とする請求項１記載の結晶性層状メタロシリケートの
製造方法。2. The crystalline layered metallosilicate according to claim 1, wherein the layered skeleton structure has pores having openings each having a size of 10-membered ring of silicon or more in the layer.
Manufacturing method .
Ｆｅ、Ｖ、Ｃｏ、Ｓｎ、Ｚｎ、ＭｎまたはＣｒの金属陽
イオンである請求項１記載の結晶性層状メタロシリケー
トの製造方法。3. T in the general formula is Al 2 , Ga, Ti,
The crystalline layered metallosilicate according to claim 1, which is a metal cation of Fe, V, Co, Sn, Zn, Mn, or Cr.
Manufacturing method .
載の結晶性層状メタロシリケートの製造方法。 4. T in the general formula is B.
A method for producing a crystalline layered metallosilicate according to claim 1 .
たは４記載の結晶性層状メタロシリケートの製造方法。5. The x in the general formula is 0 claim 3 or
Or the method for producing a crystalline layered metallosilicate according to Item 4 .
または４記載の結晶性層状メタロシリケートの製造方
法。6. The M in the general formula is Na.
Or a method for producing a crystalline layered metallosilicate according to item 4.
Law .
たは４記載の結晶性層状メタロシリケートの製造方法。7. The method of claim 3 M in formula is K or
Or the method for producing a crystalline layered metallosilicate according to Item 4 .
位、ｓ＝強い、ｖｓ＝極めて強い、として表記した。）
に記載されたｄの回折面間隔を少なくとも含む粉末Ｘ線
回折パターンを示す請求項３または４記載の結晶性層状
メタロシリケートの製造方法。8. A crystalline layered metallosilicate is shown in Table 1 below. (In the table, d represents the interplanar spacing, and the relative intensities are expressed as m = medium, s = strong, vs = extremely strong.)
5. The crystalline layered structure according to claim 3 or 4, which shows a powder X-ray diffraction pattern including at least the d-plane spacing described in d.
Method for producing metallosilicate .
位、ｓ＝強い、ｖｓ＝極めて強い、として表記した。）
に記載されたｄの回折面間隔を少なくとも含む粉末Ｘ線
回折パターンを示す請求項３または４記載の結晶性層状
メタロシリケートの製造方法。 9. A crystalline layered metallosilicate is shown in Table 2 below. (In the table, d represents the interplanar spacing, and the relative intensities are expressed as m = medium, s = strong, vs = extremely strong.)
5. The crystalline layered structure according to claim 3 or 4, which shows a powder X-ray diffraction pattern including at least the d-plane spacing described in d.
Method for producing metallosilicate.
層状テトラ低級アルカリ金属メタロシリケートである請
求項１〜９のいずれか１項に記載の結晶性層状メタロシ
リケートの製造方法。10. A crystalline layered metallosilicate is crystalline.
A contract that is a layered tetra-lower alkali metallosilicate.
The crystalline layered metallosi according to any one of claims 1 to 9.
Method of manufacturing replicates .
が１００：１〜１：１であり、テトラ低級アルキルアン
モニウム塩がシリカ原料に対して２〜４０モル％である
構成比で混合することを特徴とする請求項１〜１０のい
ずれか１項に記載の結晶性層状メタロシリケートの製造
方法。11. A silica raw material: alkali metal source molar ratio.
Is 100: 1 to 1: 1 and is tetra-lower alkyl
Monium salt is 2 to 40 mol% with respect to the silica raw material
It mixes by a composition ratio, It is characterized by the above-mentioned.
Production of crystalline layered metallosilicate according to item 1
Way .
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