JPH10182144A - Mesoporous molecular sieve material - Google Patents
Mesoporous molecular sieve materialInfo
- Publication number
- JPH10182144A JPH10182144A JP9291303A JP29130397A JPH10182144A JP H10182144 A JPH10182144 A JP H10182144A JP 9291303 A JP9291303 A JP 9291303A JP 29130397 A JP29130397 A JP 29130397A JP H10182144 A JPH10182144 A JP H10182144A
- Authority
- JP
- Japan
- Prior art keywords
- molecular sieve
- alkylamine
- pore size
- sieve material
- product
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000011148 porous material Substances 0.000 claims abstract description 55
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003141 primary amines Chemical class 0.000 claims abstract description 5
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 229940100684 pentylamine Drugs 0.000 claims abstract description 4
- 238000000926 separation method Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 10
- -1 triethoxymethoxysilane Chemical compound 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- ITAHRPSKCCPKOK-UHFFFAOYSA-N ethyl trimethyl silicate Chemical compound CCO[Si](OC)(OC)OC ITAHRPSKCCPKOK-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005262 alkoxyamine group Chemical group 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract 4
- 239000000047 product Substances 0.000 description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 239000002994 raw material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000002336 sorption--desorption measurement Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- JZRYQZJSTWVBBD-UHFFFAOYSA-N pentaporphyrin i Chemical compound N1C(C=C2NC(=CC3=NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JZRYQZJSTWVBBD-UHFFFAOYSA-N 0.000 description 8
- UUXJVUOOLAOWRM-UHFFFAOYSA-N C(CC)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)CCC)N=4)CCC)N3)CCC)=N2 Chemical compound C(CC)C1=C2C=CC(C(=C3C=CC(=C(C=4C=CC(=C(C5=CC=C1N5)CCC)N=4)CCC)N3)CCC)=N2 UUXJVUOOLAOWRM-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- GPAAEXYTRXIWHR-UHFFFAOYSA-N (1-methylpiperidin-1-ium-1-yl)methanesulfonate Chemical compound [O-]S(=O)(=O)C[N+]1(C)CCCCC1 GPAAEXYTRXIWHR-UHFFFAOYSA-N 0.000 description 6
- GWESVXSMPKAFAS-UHFFFAOYSA-N Isopropylcyclohexane Chemical compound CC(C)C1CCCCC1 GWESVXSMPKAFAS-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- CUAJPFGLNDCFAH-UHFFFAOYSA-N 1,1-di(propan-2-yl)cyclohexane Chemical compound CC(C)C1(C(C)C)CCCCC1 CUAJPFGLNDCFAH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- MEYJFPSSUOZNOL-UHFFFAOYSA-N 1,1,2-tri(propan-2-yl)cyclohexane Chemical compound CC(C)C1CCCCC1(C(C)C)C(C)C MEYJFPSSUOZNOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 101100456282 Caenorhabditis elegans mcm-4 gene Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- QFKMMXYLAPZKIB-UHFFFAOYSA-N undecan-1-amine Chemical compound CCCCCCCCCCCN QFKMMXYLAPZKIB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、各種流体の成分分
離、反応触媒もしくは触媒担体として用いることのでき
る分子ふるい材料に関する。The present invention relates to a molecular sieve material which can be used as a component separation of various fluids, a reaction catalyst or a catalyst carrier.
【０００２】[0002]
【従来の技術】孔径１．５〜１０ｎｍの「メソポーラス
な分子ふるい材料」（以後ＭＰＭＳと略称）が合成さ
れ、触媒材料、吸着剤として利用されている。これら
は、規則的なシリンダー状の細孔配列、大きな比表面
積、高耐熱性などが特徴とされる。また、これらのメソ
孔を有するシリカは、秩序構造を持った非晶質で高い耐
熱性と、各々固有の吸着特性、触媒特性を示す。代表的
なものにＭＣＭ−４１、ＦＳＭ−１６、ＨＭＳの三種類
の物質が知られている。2. Description of the Related Art A "mesoporous molecular sieve material" (hereinafter abbreviated as MPMS) having a pore size of 1.5 to 10 nm has been synthesized and used as a catalyst material and an adsorbent. These are characterized by a regular cylindrical pore arrangement, a large specific surface area, and high heat resistance. Further, silica having these mesopores is amorphous having an ordered structure, exhibits high heat resistance, and exhibits specific adsorption characteristics and catalytic characteristics. Representatively, three types of substances, MCM-41, FSM-16, and HMS, are known.
【０００３】ＭＣＭ−４１は、シリカゾルとアルキルト
リメチルアンモニウムを原料にし、１００℃以上の水熱
条件下で合成される。アルキル基の炭素数を１０〜１６
程度まで変化させることによって、細孔径を１．５〜１
０ｎｍ間で制御することができる［Ｊ．Ｓ．ＢＥＣＫ，
Ｊ．Ｃ．ＶＡＲＴＵＬＩ，Ｊ．ＲＯＴＨ，Ｍ．Ｅ．ＬＥ
ＯＮＯＷＩＣＺ，Ｃ．Ｔ．ＫＲＥＳＧＥ，Ｋ．Ｄ．ＳＣ
ＨＭＩＴＴ，Ｃ．Ｔ−Ｗ．ＣＨＵ，Ｄ．Ｈ．ＯＬＳＯ
Ｎ，Ｅ．Ｗ．ＳＨＥＰＰＡＲＤ，Ｓ．Ｂ．ＭＣＣＵＬＬ
ＥＮ，Ｊ．Ｂ．ＨＩＧＧＩＮＳ，ａｎｄ Ｊ．Ｌ．ＳＣ
ＨＬＥＮＫＥＲ，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１１
４，１０８３４（１９９２）］。[0003] MCM-41 is synthesized from silica sol and alkyltrimethylammonium as raw materials under hydrothermal conditions at 100 ° C or higher. 10 to 16 carbon atoms of the alkyl group
By changing the pore size to 1.5 to 1
0 nm [J. S. BECK,
J. C. VARTULI, J .; ROTH, M .; E. FIG. LE
ONOWICZ, C.I. T. KRESGE, K .; D. SC
HMITT, C.I. T-W. CHU, D.A. H. OLSO
N, E .; W. SHEPPARD, S.M. B. MCCULL
EN, J.A. B. HIGINS, and J.M. L. SC
HLENKER, J.A. Am. Chem. Soc. , 11
4, 10834 (1992)].
【０００４】ＦＳＭ−１６は、層状ケイ酸塩カネマイト
（ＨＳｉ2 Ｏ5 ・３Ｈ2 Ｏ）へアルキルトリメチルアン
モニウムを約50℃の水溶液中でイオン交換によって導入
し、その後、約700 ℃で焼成して得られる。ＭＣＭ−４
１と同様に、アルキル基の炭素数を１０〜１６程度まで
変化させることによって、細孔径を１．５〜１０ｎｍの
間で制御し得る［Ｓ．ＩＮＡＧＡＫＩ，Ａ．ＫＯＩＷＡ
Ｉ，Ｎ．ＳＵＺＵＫＩ，Ｙ．ＦＵＫＵＳＨＩＭＡ，ａｎ
ｄ Ｋ．ＫＵＲＯＤＡ，Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．
Ｊｐｎ．，６９，１４４９（１９９６）］。In FSM-16, alkyltrimethylammonium is introduced into layered silicate kanemite (HSi 2 O 5 .3H 2 O) by ion exchange in an aqueous solution at about 50 ° C., and then calcined at about 700 ° C. can get. MCM-4
1, the pore diameter can be controlled between 1.5 and 10 nm by changing the carbon number of the alkyl group to about 10 to 16 [S. INAGAKI, A .; KOIWA
I, N .; SUZUKI, Y .; FUKUSHIMA, an
dK. KURODA, Bull. Chem. Soc.
Jpn. , 69, 1449 (1996)].
【０００５】一方、ＨＭＳは、テトラエトキシシランと
アルキルアミンを原料にして、室温下で合成する事がで
きる。アルキル基の炭素数を１０〜１２程度まで変化さ
せることによって、細孔径を２．５〜３ｎｍの間で制御
し得る［Ｐ．Ｔ．ＴＡＮＥＶ，Ｍ．ＣＨＩＢＷＥ，ａｎ
ｄ Ｔ．Ｊ．ＰＩＮＮＡＶＡＩＡ，Ｎａｔｕｒｅ，３６
８，３２１（１９９４）］。On the other hand, HMS can be synthesized at room temperature using tetraethoxysilane and alkylamine as raw materials. By changing the carbon number of the alkyl group to about 10 to 12, the pore diameter can be controlled between 2.5 and 3 nm [P. T. TANEV, M .; CHIBWE, an
d T. J. PINNAVAIA, Nature, 36
8, 321 (1994)].
【０００６】[0006]
【発明が解決しようとする課題】上述のＭＰＭＳのう
ち、ＭＣＭ−４１とＦＳＭ−１６には、以下に示すよう
に経済性の点で改善されるべき部分がある。Among the above-mentioned MPMSs, the MCM-41 and the FSM-16 have parts to be improved in terms of economy as described below.
【０００７】ＭＣＭ−４１の合成には、原料に高価なア
ルキルトリメチルアンモニウムを用いなければならず、
さらに、合成設備に耐圧容器を必要とするなど、製造コ
ストがかさむ。[0007] In the synthesis of MCM-41, expensive alkyltrimethylammonium must be used as a raw material.
Further, the production cost is increased, for example, a pressure vessel is required for the synthesis equipment.
【０００８】ＦＳＭ−１６の合成には、層状ケイ酸塩カ
ネマイトとアルキルトリメチルアンモニウムが用いられ
る。層状ケイ酸塩カネマイトは、空気との接触で炭酸ガ
スを吸収するので、その取り扱いは空気遮断のもとで行
わねばならない。さらに前述のごとく、もう一つの原料
であるアルキルトリメチルアンモニウムが高価であり、
さらにイオン交換工程を要すなど、原料コストおよび設
備コストがかさむ事が容易に推定される。For the synthesis of FSM-16, phyllosilicate kanemite and alkyltrimethylammonium are used. Since the sheet silicate kanemite absorbs carbon dioxide on contact with air, its handling must be carried out with air blocking. Further, as described above, another material, alkyltrimethylammonium, is expensive,
Further, it is easily estimated that the raw material cost and the equipment cost are increased, for example, the ion exchange step is required.
【０００９】これに対しＨＭＳは、室温で、テトラエト
キシシランと安価なアルキルアミンを原料にして水ーエ
タノール混合溶媒中で調製できる。しかし、その細孔径
は２．５〜３ｎｍという限られた範囲でしか制御する事
ができず、触媒反応、あるいは分離プロセス用吸着剤と
しての利用範囲は限定される。On the other hand, HMS can be prepared at room temperature in a mixed solvent of water and ethanol using tetraethoxysilane and inexpensive alkylamine as raw materials. However, the pore diameter can be controlled only within a limited range of 2.5 to 3 nm, and the range of use as an adsorbent for a catalytic reaction or a separation process is limited.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、ＨＭＳ製
造のように比較的低廉な原料を用いつつ、製造工程を不
均一溶媒系反応とすることにより、細孔径制御範囲の広
いＭＰＭＳを経済的に製造する方法を見出した。すなわ
ち、本発明は、アルキルアミンの水懸濁液中にアルコキ
シシランを加え攪拌し、生成する沈殿物を固―液分離し
た後、生成沈殿物からアルキルアミンを除去することを
特徴とする１〜２．２ｎｍの細孔径を有する分子篩材料
の製造方法を提供するものである。また、本発明は、中
心細孔径が０．８５〜１．２ｎｍの直管状細孔を有する
実質的にシリカからなる分子ふるい及び分子ふるいの製
造方法を提供するものである。Means for Solving the Problems The present inventors have developed an MPMS having a wide pore diameter control range by using a relatively inexpensive raw material such as HMS production and making the production process a heterogeneous solvent-based reaction. An economical manufacturing method was found. That is, the present invention is characterized in that alkoxysilane is added to an aqueous suspension of an alkylamine, the mixture is stirred, and a precipitate formed is subjected to solid-liquid separation, and then the alkylamine is removed from the formed precipitate. It is intended to provide a method for producing a molecular sieve material having a pore size of 2.2 nm. The present invention also provides a molecular sieve substantially composed of silica having straight tubular pores having a central pore diameter of 0.85 to 1.2 nm, and a method for producing the molecular sieve.
【００１１】[0011]
【発明の実施形態】以下、本発明の実施の形態について
詳細に説明する。 （合成に用いる出発原料）合成には、二種類の原料が用
いられる。第一の原料はＭＰＭＳの骨核を形成するシリ
コンと酸素の源であり、テトラエトキシシラン、テトラ
ブトキシシラン、テトラプロポキシシラン、トリエトキ
シメトキシシラン、トリメトキシエトキシシラン、ジエ
トキシジメトキシシラン、ジメトキジエトキシシランな
どのアルコキシシラン類の中の一種もしくは複数が用い
られる。Embodiments of the present invention will be described below in detail. (Starting Materials Used for Synthesis) Two types of starting materials are used for the synthesis. The first material is a source of silicon and oxygen that form the bone nucleus of MPMS, and includes tetraethoxysilane, tetrabutoxysilane, tetrapropoxysilane, triethoxymethoxysilane, trimethoxyethoxysilane, diethoxydimethoxysilane, and dimethoxydiethoxysilane. One or more of alkoxysilanes such as silane are used.
【００１２】第二の原料はＭＰＭＳの細孔径を定めるた
めの鋳型の役割を果たす、いわゆるテンプレート剤であ
り、エチルアミン、プロピルアミン、ブチルアミン、ペ
ンチルアミン、ヘキシルアミン、ヘプチルアミン、オク
チルアミン、ノニルアミン、デシルアミン、ウンデシル
アミン、ドデシルアミンなどのアルキルアミン類の中の
一種もしくは複数が用いられる。The second raw material is a so-called template agent which plays a role of a template for determining the pore diameter of MPMS, and includes ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine and decylamine. , One or more of alkylamines such as undecylamine and dodecylamine.
【００１３】（メソポーラスな分子ふるい材料の合成方
法）第一原料であるアルコキシシラン類との反応に先立
ち、第二の原料であるアルキルアミン類の水懸濁液を調
製する。水懸濁液には、エタノール等のアルコールを含
んでいてもよい。エタノール等のアルコールを添加する
ことによって、アルキルアミンの溶解度を向上させるこ
とができる。水懸濁液の調製割合は水とアルキルアミン
類のモル混合比で10000 ：1 〜1 ：1 であることが好ま
しい。より好ましい混合比は300 ：1 〜10：1 であり、
さらに好ましい混合比は100 ：1 〜20：1 である。水懸
濁液の調製の温度は懸濁させるアルキルアミン類が液化
する温度以上に設定される。細孔径１．８ｎｍ以下のＭ
ＰＭＳの合成には昇温は不要で、常温で懸濁処理を行う
ことができる。(Method for synthesizing mesoporous molecular sieve material) Prior to the reaction with the alkoxysilanes as the first raw material, an aqueous suspension of alkylamines as the second raw material is prepared. The aqueous suspension may contain an alcohol such as ethanol. By adding an alcohol such as ethanol, the solubility of the alkylamine can be improved. The water suspension is preferably prepared in a molar mixing ratio of water and alkylamine of 10,000: 1 to 1: 1. A more preferred mixing ratio is from 300: 1 to 10: 1,
A more preferred mixing ratio is from 100: 1 to 20: 1. The temperature at which the aqueous suspension is prepared is set to a temperature equal to or higher than the temperature at which the alkylamines to be suspended are liquefied. M having a pore size of 1.8 nm or less
No temperature rise is required for the synthesis of PMS, and suspension treatment can be performed at room temperature.
【００１４】アルキルアミン類の水懸濁液に、第一原料
であるアルコキシシラン類を加え、十分撹拌する。第一
原料であるアルコキシシラン類と第二の原料であるアル
キルアミン類の水懸濁液との混合割合は、アルコキシシ
ラン類とアルキルアミン類のモル混合比で10000 ：1 〜
1 ：100 であることが好ましい。この混合比より大きい
場合、反応のための撹拌工程および反応生成物の濾過・
分離工程で過大な設備と動力を要する。この混合比より
も小さい場合、第一原料であるアルコキシシラン類と第
二の原料であるアルキルアミン類の水懸濁液中での接触
が不十分になり、反応の進行が阻害される。従って、よ
り好ましい混合比は100 ：1 〜1 ：10であり、さらに好
ましい混合比は50：1 〜1 ：1 である。例えば、第一原
料にテトラエトキシシランと第二原料にヘキシルアミン
を用いた場合の最適な混合比は4：1 である。[0014] To the aqueous suspension of the alkylamines, the alkoxysilanes as the first raw material are added and sufficiently stirred. The mixing ratio of the alkoxysilanes as the first raw material and the aqueous suspension of the alkylamines as the second raw material is 10,000: 1 to 1 in terms of the molar mixing ratio of the alkoxysilanes and the alkylamines.
1: 100 is preferred. If the mixing ratio is larger than this, the stirring step for the reaction and the filtration of the reaction product
Excessive equipment and power are required in the separation process. If the mixing ratio is smaller than this, the contact between the alkoxysilanes as the first raw material and the alkylamines as the second raw material in the aqueous suspension becomes insufficient, and the progress of the reaction is hindered. Therefore, a more preferable mixing ratio is 100: 1 to 1:10, and a still more preferable mixing ratio is 50: 1 to 1: 1. For example, when tetraethoxysilane is used as the first raw material and hexylamine is used as the second raw material, the optimal mixing ratio is 4: 1.
【００１５】反応の進行に伴い、沈殿物が生成する。得
られた沈殿物を濾過法などで固−液分離する。その後、
沈殿物から第二の原料であるアルキルアミン類を分離す
る。その分離方法としては、昇温して減圧脱離させる方
法、有機溶媒によって抽出・洗浄する方法、昇温して酸
素導入により燃焼除去する方法などがある。前二法で
は、第二原料の回収が可能であるが、燃焼除去法も含
め、いずれの方法をとるかは主として経済性評価にゆだ
ねられる。As the reaction proceeds, a precipitate is formed. The obtained precipitate is subjected to solid-liquid separation by a filtration method or the like. afterwards,
The second raw material, alkylamines, is separated from the precipitate. Examples of the separation method include a method of desorption under reduced pressure by increasing the temperature, a method of extraction and washing with an organic solvent, and a method of burning and removing by heating and introducing oxygen. The former two methods allow the recovery of the second raw material, but the choice of method, including the combustion removal method, is mainly left to economic evaluation.
【００１６】燃焼除去法の場合は、酸素を含む気流中
で、適切な昇温速度で500 ℃以上に加熱する。昇温途中
から第１級アミンの分解が開始される。さらに、昇温す
る過程において、燃焼が開始される。気流中、酸素濃度
及び昇温速度が過大な場合、燃焼熱による材料の局部昇
温を引き起こし、材料の構造破壊をもたらす危険性があ
る。このため、十分に昇温速度及び加熱温度を制御する
ことが好ましい。５００℃以上に保持することにより、
第１級アミンとその分解残留物であるカーボンが沈殿物
が除去され、白色の粉末状のＭＰＭＳを得ることができ
る。In the case of the combustion removal method, the material is heated to a temperature of 500 ° C. or more at an appropriate heating rate in a stream of oxygen. Decomposition of the primary amine is started during the temperature rise. Further, in the process of increasing the temperature, combustion is started. If the oxygen concentration and the heating rate are too high in the airflow, there is a risk that the heating of the material causes a local heating of the material, resulting in structural destruction of the material. For this reason, it is preferable to sufficiently control the heating rate and the heating temperature. By holding at 500 ° C or higher,
The precipitate is removed from the primary amine and carbon which is a decomposition residue thereof, and a white powdery MPMS can be obtained.
【００１７】燃焼除去法を行わない場合、第二原料成分
を除かれた反応生成物はさらに減圧あるいは昇温加熱、
もしくはその組み合わせによって、残留する溶媒を反応
生成物より除去し、さらに酸素を含む気流中で500 ℃以
上に加熱する事によってＭＰＭＳを得る事ができる。昇
温減圧法、溶媒抽出法とも、アミンの回収が可能である
が、微量の残留アミンを除去するのに、燃焼除去法との
組み合わせは有効である。When the combustion removal method is not performed, the reaction product from which the second raw material component has been removed is further heated under reduced pressure or elevated temperature,
Alternatively, depending on the combination, MPMS can be obtained by removing the remaining solvent from the reaction product and heating the mixture to 500 ° C. or more in a stream of oxygen. The amine can be recovered by both the temperature-increasing decompression method and the solvent extraction method, but the combination with the combustion removal method is effective for removing a trace amount of residual amine.
【００１８】（分子ふるい材料の細孔径制御）分子ふる
い材料合成に用いるアルキルアミンの炭素鎖の炭素の数
を変化させることで、分子ふるい材料の細孔径を制御す
ることができる。第１級アミンとして、ペンチルアミ
ン、ヘキシルアミン、ヘプチルアミン、を用いることに
より、細孔径が０．８５〜１．２ｎｍの直管状細孔を有
する実質的にシリカからなる分子ふるい材料を得ること
ができる。本発明によって得られた分子ふるい材料は、
全く新規な分子ふるい材料であり、新しい触媒反応、あ
るいは吸着分離プロセスを提供することが可能である。
また、本発明によって得られた分子ふるい材料は、特定
成分に対する親和性に基づく選択性の合わせ有するた
め、吸着材料や透過膜材料としての様々な分離プロセス
に適用可能である。さらに、細孔径０．８５〜１．２ｎ
ｍの直管状細孔を有する分子ふるい材料によって、これ
らの細孔寸法を利用した吸着分離プロセス、膜分離プロ
セス、選択反応触媒、あるいはメンブレンリアクタ−等
を新たに提供できることとなった。特に、二酸化炭素な
ど、特定の成分に対して選択的親和性を利用した新規な
分離プロセスをも提供することができる。(Control of Pore Diameter of Molecular Sieve Material) The pore diameter of the molecular sieve material can be controlled by changing the number of carbon atoms in the carbon chain of the alkylamine used in the synthesis of the molecular sieve material. By using pentylamine, hexylamine, and heptylamine as the primary amine, it is possible to obtain a molecular sieve material substantially composed of silica having straight tubular pores having a pore diameter of 0.85 to 1.2 nm. it can. The molecular sieve material obtained according to the present invention is:
It is a completely new molecular sieve material and can provide a new catalytic reaction or adsorption separation process.
Further, the molecular sieve material obtained by the present invention has selectivity based on affinity for a specific component, and thus can be applied to various separation processes as an adsorbent material or a permeable membrane material. Furthermore, a pore diameter of 0.85 to 1.2 n
With a molecular sieve material having straight tubular pores of m, it has become possible to newly provide an adsorption separation process, a membrane separation process, a selective reaction catalyst, a membrane reactor or the like utilizing these pore sizes. In particular, a novel separation process utilizing selective affinity for a specific component such as carbon dioxide can be provided.
【００１９】（実施例１）２５℃において、２６．６ｍ
ｌの脱イオン水と１３．５ｍｍｏｌ相当のアルキルアミ
ンを加え、懸濁液を調製した。アルキルアミンとして
（ａ）ドデシルアミン（２．５６ｇ）、（ｂ）ノニルア
ミン（１．９３ｇ）、（ｃ）ヘキシルアミン（１．３４
ｇ）の三種を用いた。それぞれの懸濁液に１０．４ｇ
（５０ｍｍｏｌ相当）のテトラエトキシシランを加え
た。１時間撹拌を続けた後、２５℃で１８時間静置し
た。次に沈澱生成物をブフナロートで濾過し、３００ｍ
ｌのエタノールで洗浄した。その後、５００℃で空気雰
囲気中で加熱し、それぞれ白色の微粉末（Ａ）、
（Ｂ）、（Ｃ）を得た。(Example 1) At 25 ° C., 26.6 m
1 deionized water and 13.5 mmol of alkylamine were added to prepare a suspension. As alkylamines, (a) dodecylamine (2.56 g), (b) nonylamine (1.93 g), (c) hexylamine (1.34)
g) were used. 10.4g for each suspension
(Equivalent to 50 mmol) of tetraethoxysilane was added. After continuing stirring for 1 hour, it was left still at 25 ° C. for 18 hours. Next, the precipitated product was filtered through a Buchner funnel,
Washed with 1 liter of ethanol. Thereafter, the mixture is heated at 500 ° C. in an air atmosphere, and each of the fine white powders (A) and
(B) and (C) were obtained.
【００２０】実施例１において得られた白色の微粉末の
７７Ｋにおける窒素吸脱着等温線を図１に示す。図１よ
り、実施例１における生成物（Ａ）、（Ｂ）、（Ｃ）の
吸着等温線と脱離等温線はほぼ一致し、ヒステリシスは
観測され無いことから、直管状の細孔構造の存在が示唆
される。さらに（Ａ）で窒素の相対圧 Ｐ/ Ｐ0 = ０．
２５ に顕著に見られ、また（Ｂ）では窒素の相対圧
Ｐ/ Ｐ0 = ０．１に見られる急峻な立ち上がりは、この
示唆を明瞭に裏づけるものである。これらは、前述のＭ
ＣＭ−４１、ＦＳＭ−１６、ＨＭＳにおいても観察され
る特徴である。FIG. 1 shows a nitrogen adsorption / desorption isotherm at 77 K of the white fine powder obtained in Example 1. From FIG. 1, the adsorption isotherms and desorption isotherms of the products (A), (B), and (C) in Example 1 almost coincide with each other, and no hysteresis is observed. Suggested presence. Further, in (A), the relative pressure of nitrogen P / P0 = 0.
25, and (B) shows the relative pressure of nitrogen.
The sharp rise seen at P / P0 = 0.1 clearly supports this suggestion. These are the M
This feature is also observed in CM-41, FSM-16, and HMS.
【００２１】図１に示される吸脱着等温線の解析により
得られる、細孔分布曲線を図２に示す。図２において、
（Ａ）では直径２．２ｎｍ、（Ｂ）では直径１．７ｎ
ｍ、（Ｃ）では直径１．０ｎｍを中心とする比較的シャ
ープな細孔径分布を有することがわかった。FIG. 2 shows a pore distribution curve obtained by analyzing the adsorption / desorption isotherm shown in FIG. In FIG.
(A) has a diameter of 2.2 nm and (B) has a diameter of 1.7 n.
m and (C) were found to have a relatively sharp pore size distribution centered on a diameter of 1.0 nm.
【００２２】（Ａ）のＣｕＫα線による粉末Ｘ線回折チ
ャートを図３に示す。図３において、２θ＝２．７゜に
観測される回折パターン、また２θ＝２０゜の部分に観
測される幅広い回折パターンは、ＭＣＭ−４１、ＦＳＭ
−１６、ＨＭＳなどにも共通の特徴である。FIG. 3 shows an X-ray powder diffraction chart of (A) using CuKα radiation. In FIG. 3, the diffraction pattern observed at 2θ = 2.7 ° and the wide diffraction pattern observed at 2θ = 20 ° are MCM-41, FSM
-16, HMS, etc. are common features.
【００２３】図１に示される吸脱着等温線の解析により
得られる（Ａ）、（Ｂ）、（Ｃ）の比表面積、細孔容積
について、表１に細孔直径とともに示す。The specific surface area and pore volume of (A), (B) and (C) obtained by analyzing the adsorption / desorption isotherm shown in FIG. 1 are shown together with the pore diameter in Table 1.
【表１】 試料 細孔直径 比表面積 細孔容積 （ｎｍ） （ｍ2 ／ｇ） （ｃｃ／ｇ） （Ａ） ２．２ ２４００ １．７ （Ｂ） １．７ ２２００ １．５ （Ｃ） １．０ １５００ １．１Table 1 Sample Pore diameter Specific surface area Pore volume (nm) (m 2 / g) (cc / g) (A) 2.2 2400 1.7 (B) 1.7 2200 1.5 (C) 1.0 1500 1.1
【００２４】（実施例２）生成物（A ）の５０ｇを、芳
香族の一種であるジクロロピリジルポルフィリン５％を
含有するベンゼン１０００ｍｌの溶液中に投入し、２４
時間撹拌し、溶液をガス- クロマトグラフによって分析
したところ、ジクロロピリジルポルフィリンは全て
（Ａ）に吸着され、検出されなかった。従って（Ａ）は
ジクロロピリジルポルフィリンの分子サイズ （約２０
Å）より大きい孔径を有していることが確認された。Example 2 50 g of the product (A) was put into a solution of 5 ml of benzene containing 1000% of dichloropyridyl porphyrin, which is a kind of aromatic compound.
After stirring for an hour and analyzing the solution by gas-chromatography, all dichloropyridyl porphyrin was adsorbed on (A) and was not detected. Therefore, (A) shows the molecular size of dichloropyridyl porphyrin (approximately 20
Ii) It was confirmed that it had a larger pore size.
【００２５】（実施例３）生成物（A ）の５０ｇを、実
施例２で用いたジクロロピリジルポルフィリンと同じ芳
香族のテトラクロロピリジルポルフィリン５％を含有す
るベンゼン１０００ｍｌの溶液中に投入し、２４時間撹
拌し、溶液をガス- クロマトグラフによって分析したと
ころ、テトラクロロピリジルポルフィリンは全く（Ａ）
に吸着されなかった。従って（Ａ）はテトラクロロピリ
ジルポルフィリンの分子サイズ （約２５Å）より小さ
い孔径を有していることが確認された。(Example 3) 50 g of the product (A) was put into a solution of 1,000 ml of benzene containing 5% of the same aromatic tetrachloropyridyl porphyrin as the dichloropyridyl porphyrin used in Example 2, and 24 g of the product (A) was added. After stirring for an hour and analyzing the solution by gas-chromatography, tetrachloropyridylporphyrin was completely (A)
Was not adsorbed. Therefore, it was confirmed that (A) has a pore size smaller than the molecular size of tetrachloropyridyl porphyrin (about 25 °).
【００２６】（実施例４）生成物（Ａ）の５０ｇを、飽
和脂肪酸の一種であるトリイソプロピルシクロヘキサン
５００ｐｐｍを含有する水溶液に投入し、１０時間撹拌
し、水溶液の分析を行ったところ、トリイソプロピルシ
クロヘキサンは検出されず、全て（Ａ）に吸着されたも
のと考えられる。従って（Ａ）は大過剰に存在する水に
比べて、トリイソプロピルシクロヘキサンをより選択的
に吸着し得るといえる。Example 4 50 g of the product (A) was put into an aqueous solution containing 500 ppm of triisopropylcyclohexane, which is a kind of saturated fatty acid, and stirred for 10 hours. No cyclohexane was detected, and it is considered that all were adsorbed to (A). Therefore, it can be said that (A) can adsorb triisopropylcyclohexane more selectively than water which is present in a large excess.
【００２７】（実施例５）生成物（Ｂ）の５０ｇを、芳
香族の一種であるポルフィン５％を含有するベンゼン１
０００ｍｌの溶液中に投入し、２４時間撹拌し、溶液を
ガス- クロマトグラフによって分析したところ、ポルフ
ィンは全て（Ｂ）に吸着され、検出されなかった。従っ
て（Ｂ）はポルフィンの分子サイズ（約１０Å）より大
きい孔径を有していることが確認された。Example 5 50 g of the product (B) was mixed with benzene 1 containing 5% of porphine, one of aromatics.
After pouring into 000 ml of the solution and stirring for 24 hours, the solution was analyzed by gas-chromatography. As a result, porphine was completely adsorbed on (B) and was not detected. Therefore, it was confirmed that (B) has a pore size larger than the molecular size of porphine (about 10 °).
【００２８】（実施例６）生成物（Ｂ）の５０ｇを、実
施例５で用いたポルフィンと同族のテトラプロピルポル
フィリン５％を含有するベンゼン１０００ｍｌの溶液中
に投入し、２４時間撹拌し、溶液をガス- クロマトグラ
フによって分析したところ、テトラプロピルポルフィリ
ン濃度は全く変化なく、それ故テトラプロピルポルフィ
リンは（Ｂ）に吸着されないことがわかった。従って
（Ｂ）はテトラプロピルポルフィリンの分子サイズ（約
１９Å）より小さい孔径を有していることが確認され
た。(Example 6) 50 g of the product (B) was put into a solution of benzene containing 1000% of benzene containing 5% of tetrapropylporphyrin homologous to porphine used in Example 5, and stirred for 24 hours. Was analyzed by gas-chromatography, and it was found that the tetrapropylporphyrin concentration did not change at all and therefore tetrapropylporphyrin was not adsorbed on (B). Therefore, it was confirmed that (B) has a pore size smaller than the molecular size of tetrapropylporphyrin (about 19 °).
【００２９】（実施例７）生成物（Ｂ）の５０ｇを、飽
和脂肪酸の一種であるジイソプロピルシクロヘキサン５
００ｐｐｍを含有する水溶液に投入し、１０時間撹拌
し、水溶液の分析を行ったところ、ジイソプロピルシク
ロヘキサンは検出されず、全て（Ｂ）に吸着された。従
って（Ｂ）は水に比べてジイソプロピルシクロヘキサン
を選択的に吸着し得る。Example 7 50 g of the product (B) was mixed with diisopropylcyclohexane 5 which is a kind of saturated fatty acid.
The solution was added to an aqueous solution containing 00 ppm, stirred for 10 hours, and the aqueous solution was analyzed. As a result, no diisopropylcyclohexane was detected and all were adsorbed to (B). Therefore, (B) can selectively adsorb diisopropylcyclohexane as compared with water.
【００３０】（実施例８）生成物（Ｃ）の５０ｇを、芳
香族の一種であるポルフィン５％を含有するベンゼン１
０００ｍｌの溶液中に投入し、２４時間撹拌し、溶液を
ガス- クロマトグラフによって分析したところ、ポルフ
ィンは全て（Ｃ）に吸着され、検出されなかった。従っ
て（Ｃ）はポルフィンの分子サイズ（約１０Å）より大
きい孔径を有していることが確認された。(Example 8) 50 g of the product (C) was mixed with benzene 1 containing 5% of porphine, a kind of aromatic compound.
After pouring into 000 ml of the solution and stirring for 24 hours, the solution was analyzed by gas-chromatography. As a result, porphine was completely adsorbed on (C) and was not detected. Therefore, it was confirmed that (C) had a pore size larger than the molecular size of porphine (about 10 °).
【００３１】（実施例９）生成物（Ｃ）の５０ｇを、実
施例５で用いたポルフィンと同族のテトラプロピルポル
フィン５％を含有するベンゼン１０００ｍｌの溶液中に
投入し、２４時間撹拌し、溶液をガス- クロマトグラフ
によって分析したところ、テトラプロピルポルフィンは
全く（Ｃ）に吸着されなかった。従って（Ｃ）はテトラ
プロピルポルフィンの分子サイズ（約１５Å）より小さ
い孔径を有していることが確認された。Example 9 50 g of the product (C) was put into a solution of 5 ml of benzene containing 1,000% of tetrapropylporphine, which is the same as the porphine used in Example 5, and stirred for 24 hours. Was analyzed by gas-chromatography. As a result, no tetrapropylporphine was adsorbed on (C). Therefore, it was confirmed that (C) had a pore size smaller than the molecular size of tetrapropylporphine (about 15 °).
【００３２】（実施例１０）生成物（Ｃ）の５０ｇを、
飽和脂肪酸の一種であるイソプロピルシクロヘキサン５
００ｐｐｍを含有する水溶液に投入し、１０時間撹拌
し、水溶液の分析を行ったところ、イソプロピルシクロ
ヘキサンは検出されず、全て（Ｃ）に吸着された。従っ
て（Ｃ）は水に比べてイソプロピルシクロヘキサンを選
択的に吸着し得ることがわかった。Example 10 50 g of the product (C) was
Isopropylcyclohexane 5 which is a kind of saturated fatty acid
The solution was added to an aqueous solution containing 00 ppm, stirred for 10 hours, and the aqueous solution was analyzed. As a result, no isopropylcyclohexane was detected, and all were adsorbed to (C). Therefore, it was found that (C) can selectively adsorb isopropylcyclohexane as compared with water.
【００３３】（実施例１１）２５℃において、２６．６
ｍｌの脱イオン水と、１．５３ｇ（１３．２ｍｍｏｌ）
のn-ヘプチルアミンを混合し、得られた懸濁液に１０．
４ｇ（５０．０ｍｍｏｌ相当）のテトラエトキシシラン
を加えた。この混合液を１時間攪拌した後、２５℃で１
８時間静置した。次に、沈殿生成物をブフナロートでろ
過し、３００ｍｌのエタノールで洗浄した。その後、５
００℃で空気雰囲気中で加熱し、白色の微粉末（生成物
Ｄ）を得た。Example 11 26.6 at 25 ° C.
ml of deionized water and 1.53 g (13.2 mmol)
9. n-Heptylamine was mixed and 10.
4 g (equivalent to 50.0 mmol) of tetraethoxysilane was added. After stirring this mixture for 1 hour,
It was left for 8 hours. Next, the precipitated product was filtered through a Buchner funnel and washed with 300 ml of ethanol. Then 5
The mixture was heated at 00 ° C. in an air atmosphere to obtain a white fine powder (product D).
【００３４】２５℃において、２６．６ｍｌの脱イオン
水と、１．３４ｇ（１３．５ｍｍｏｌ）のn-ヘキシルア
ミンを混合して懸濁液を得た。以下、生成物Ｄを得たと
きと同様の操作によって、白色の微粉末（生成物Ｅ）を
得た。At 25 ° C., 26.6 ml of deionized water and 1.34 g (13.5 mmol) of n-hexylamine were mixed to obtain a suspension. Hereinafter, a white fine powder (product E) was obtained by the same operation as that for obtaining product D.
【００３５】２５℃において、２６．６ｍｌの脱イオン
水と、１．１５ｇ（１３．５ｍｍｏｌ）のn-ペンチルア
ミンを混合して懸濁液を得た。以下、生成物Ｄを得たと
きと同様の操作によって、白色の微粉末（生成物Ｆ）を
得た。At 25 ° C., 26.6 ml of deionized water and 1.15 g (13.5 mmol) of n-pentylamine were mixed to obtain a suspension. Thereafter, a white fine powder (product F) was obtained by the same operation as that for obtaining product D.
【００３６】（実施例１２）実施例１１によって得られ
た生成物Ｄ，Ｅ，Ｆの７７Ｋにおける窒素吸脱着等温線
をカンタクロム社（米国製）オートソーブワンを用いて
観測した。その吸脱着等温線を図４、図５及び図６に示
す。図４〜図６に示すように、これらの生成物Ｄ，Ｅ，
Ｆにおいて、吸着等温線と脱離等温線はほぼ一致し、ヒ
ステリシスは観測されないことから、直管状の細孔構造
の存在が推測された。さらに、窒素の相対圧Ｐ／Ｐ０＝
０．２５に顕著にみられる急峻な立ち上がりは、ＭＣＭ
―４１、ＦＳＭ―１６、ＨＭＳにおいても観察される特
徴である。すなわち、この急峻な立ち上がりは、直管状
細孔構造の存在の推測が妥当性をもっていることを裏付
けるものであった。Example 12 Nitrogen adsorption / desorption isotherms at 77 K of the products D, E, and F obtained in Example 11 were observed by using an autosorb one (manufactured by Qantachrome, USA). The adsorption and desorption isotherms are shown in FIGS. 4, 5 and 6. As shown in FIGS. 4 to 6, these products D, E,
In F, the adsorption isotherm and the desorption isotherm almost coincide with each other, and no hysteresis was observed, suggesting the existence of a straight tubular pore structure. Further, the relative pressure of nitrogen P / P0 =
The steep rise remarkably observed in 0.25 is due to the MCM
-41, FSM-16, and HMS. In other words, this steep rise supported that the estimation of the existence of the straight tubular pore structure was valid.
【００３７】図４〜図６に示される吸脱着等温線の解析
から得られる生成物Ｄ，Ｅ，Ｆのそれぞれの比表面積、
比細孔容積を以下の表に示す。The specific surface area of each of the products D, E, and F obtained from the analysis of the adsorption-desorption isotherm shown in FIGS.
The specific pore volume is shown in the table below.
【表２】 生成物 Ｄ Ｅ Ｆ 比表面積（m 2 /g） 1000 1000 700 細孔容積（cc/g） 0.5 0.5 0.3 TABLE 2 product D E F specific surface area (m 2 / g) 1000 1000 700 pore volume (cc / g) 0.5 0.5 0.3
【００３８】また、図４〜図６の窒素吸脱着等温線の解
析により得られる、生成物Ｄ，Ｅ，Ｆの細孔分布曲線を
図７に示す。図７から、生成物Ｄ，Ｅ，Ｆが、それぞ
れ、中心細孔直径１．２ｎｍ，１．０ｎｍ及び０．８５
ｎｍを中心とする細孔径分布を有することがわかった。FIG. 7 shows the pore distribution curves of the products D, E, and F obtained by analyzing the nitrogen adsorption / desorption isotherms in FIGS. From FIG. 7, it can be seen that the products D, E, and F have central pore diameters of 1.2 nm, 1.0 nm and 0.85, respectively.
It was found to have a pore size distribution centered at nm.
【００３９】（実施例１３）生成物Ｆ５０ｇを分子サイ
ズ約１．０ｎｍのペルフルオロトリノルマルブチルアミ
ン（（Ｃ4 Ｆ9 ）3 Ｎ）５％を含有するベンゼン１００
０ｍｌ中に投入した。２４時間攪拌後、このベンゼン溶
液をガスクロマトグラフによって分析した。接触後のペ
ルフルオロトリノルマルブチルアミン濃度は接触前と全
く変化がなく、生成物Ｆに吸着されていなかった。した
がって、生成物Ｆの細孔径は、１．０ｎｍよりも小さ
く、分子ふるい作用を有することが確認できた。Example 13 50 g of the product F was treated with 100% of benzene containing 5% of perfluorotrinormal butylamine ((C 4 F 9 ) 3 N) having a molecular size of about 1.0 nm.
Poured into 0 ml. After stirring for 24 hours, the benzene solution was analyzed by gas chromatography. The concentration of perfluorotrinormal butylamine after the contact was not changed at all from that before the contact, and was not adsorbed on the product F. Therefore, the pore size of the product F was smaller than 1.0 nm, and it was confirmed that the product F had a molecular sieve action.
【００４０】（実施例１４）生成物Ｅを分子径約０．７
ｎｍのベンジルアルコ−ルの５％水溶液と接触させ、接
触前後のベンジルアルコ−ルの濃度の変化を観測したと
ころ、接触後のベンジルアルコ−ル濃度は検出限界以下
であった。したがって、生成物Ｅは、その孔径より小さ
い分子寸法のベンジルアルコ−ルを吸着した。(Example 14) The product E was treated with a molecular diameter of about 0.7
The sample was brought into contact with a 5% aqueous solution of benzyl alcohol having a thickness of 10 nm, and the change in the concentration of the benzyl alcohol before and after the contact was observed. The concentration of the benzyl alcohol after the contact was below the detection limit. Thus, product E adsorbed benzyl alcohol with a molecular size smaller than its pore size.
【００４１】（実施例１５）生成物Ｅ，Ｆのそれぞれ
に、無機系結合剤を添加して混練後、押し出し成形によ
り直径約１．５ｍｍ、平均長さ３．５ｍｍの柱状成形体
を得た。これらの成形体を粉砕分級後、６０−１００メ
ッシュ部分を採取し、それぞれを内径１ｍｍ、長さ１．
５ｍのカラムに充填した。これら２種のカラムをガスク
ロマトグラフ装置に装着し、二酸化炭素と窒素の混合ガ
スを注入し、それぞれのカラムにおける両成分の保持時
間を測定した。ガスクロマトグラフのカラムオーブン温
度は１５０℃、キャリアガスはヘリウムを用い、入り口
圧は１．２キロであった。生成物Ｅ由来のカラムにおけ
る窒素と二酸化炭素の保持時間は、それぞれ、５２秒、
７３秒であった。また、生成物Ｆ由来のカラムでは、そ
れぞれ７７秒、１０８秒であった。(Example 15) An inorganic binder was added to each of the products E and F, kneaded, and extruded to obtain a columnar molded body having a diameter of about 1.5 mm and an average length of 3.5 mm. . After pulverizing and classifying these compacts, 60-100 mesh portions were collected, each having an inner diameter of 1 mm and a length of 1.100.
Packed in a 5 m column. These two types of columns were mounted on a gas chromatograph, a mixed gas of carbon dioxide and nitrogen was injected, and the retention time of both components in each column was measured. The column oven temperature of the gas chromatograph was 150 ° C., helium was used as the carrier gas, and the inlet pressure was 1.2 kg. The retention time of nitrogen and carbon dioxide in the column from product E was 52 seconds, respectively.
73 seconds. In the column derived from the product F, the time was 77 seconds and 108 seconds, respectively.
【００４２】以上の結果から、生成物Ｅ，Ｆが、窒素よ
りも二酸化炭素に対する選択性が高いことがわかった。
したがって、生成物Ｅ，Ｆは、その孔径に基づく選択性
のみならず、特定成分に対する親和性に基づく選択性も
合わせ有していた。このことから、生成物Ｅ，Ｆは、吸
着材料や透過膜材料として様々な分離プロセスに応用で
きることが明らかとなった。From the above results, it was found that the products E and F had higher selectivity for carbon dioxide than nitrogen.
Therefore, the products E and F had not only the selectivity based on the pore size but also the selectivity based on the affinity for a specific component. From this, it became clear that the products E and F can be applied to various separation processes as an adsorbent material or a permeable membrane material.
【００４３】[0043]
【発明の効果】請求項１ないし３記載の発明によると、
簡易にメソポーラスな分子ふるい材料が得られる。請求
項４及び５記載の発明によると、従来より小さい細孔径
の直管状細孔を有する分子ふるい材料を得ることができ
る。According to the first to third aspects of the present invention,
A mesoporous molecular sieve material can be easily obtained. According to the fourth and fifth aspects of the present invention, it is possible to obtain a molecular sieve material having straight tubular pores having a smaller pore diameter than conventional ones.
【図１】実施例１によって合成された分子ふるい材料
（Ａ）、（Ｂ）、（Ｃ）の窒素吸脱着等温線。FIG. 1 is a nitrogen adsorption / desorption isotherm of molecular sieve materials (A), (B), and (C) synthesized according to Example 1.
【図２】実施例１によって合成された分子ふるい材料
（Ａ）、（Ｂ）、（Ｃ）の細孔分布。FIG. 2 shows pore distributions of molecular sieve materials (A), (B), and (C) synthesized according to Example 1.
【図３】実施例１によって合成された分子ふるい材料
（Ａ）の粉末Ｘ線回折チャート。FIG. 3 is a powder X-ray diffraction chart of the molecular sieve material (A) synthesized in Example 1.
【図４】実施例１１によって合成された分子ふるい材料
（Ｄ）の窒素吸脱着等温線。FIG. 4 is a nitrogen adsorption / desorption isotherm of the molecular sieve material (D) synthesized according to Example 11.
【図５】実施例１１によって合成された分子ふるい材料
（Ｅ）の窒素吸脱着等温線。FIG. 5 is a nitrogen adsorption / desorption isotherm of the molecular sieve material (E) synthesized according to Example 11.
【図６】実施例１１によって合成された分子ふるい材料
（Ｆ）の窒素吸脱着等温線。FIG. 6 is a nitrogen adsorption / desorption isotherm of the molecular sieve material (F) synthesized according to Example 11.
【図７】実施例１１によって合成された分子ふるい材料
（Ｄ）、（Ｅ）、（Ｆ）の細孔分布。FIG. 7 is a pore distribution of molecular sieve materials (D), (E), and (F) synthesized according to Example 11.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 福井 武久 名古屋市熱田区六野二丁目４番１号 財団 法人ファインセラミックスセンター内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takehisa Fukui 2-4-1 Rokuno, Atsuta-ku, Nagoya-shi Inside the Fine Ceramics Center
Claims (5)
シシランを加え撹拌し、生成する沈殿物を固−液分離し
た後、生成沈殿物からアルキルアミンを除去することを
特徴とする１〜２．２ｎｍの細孔径を有する分子ふるい
材料の製造方法。An alkoxyamine is added to an aqueous suspension of an alkylamine, and the mixture is stirred. The resulting precipitate is subjected to solid-liquid separation, and then the alkylamine is removed from the resulting precipitate. 2.2 A method for producing a molecular sieve material having a pore size of 2.2 nm.
請求項１に記載の分子ふるい材料の製造方法。2. The method for producing a molecular sieve material according to claim 1, wherein the alkylamine has 6 to 11 carbon atoms.
シラン、テトラブトキシシラン、テトラプロポキシシラ
ン、トリエトキシメトキシシラン、トリメトキシエトキ
シシラン、ジエトキシジメトキシシラン、ジメトキジエ
トキシシランなどよりなる群の中の一種もしくは複数を
用いる請求項１に記載の分子ふるい材料の製造方法。3. The alkoxysilane may be one or more of the group consisting of tetraethoxysilane, tetrabutoxysilane, tetrapropoxysilane, triethoxymethoxysilane, trimethoxyethoxysilane, diethoxydimethoxysilane, dimethoxydiethoxysilane, and the like. The method for producing a molecular sieve material according to claim 1, wherein
孔を有する実質的にシリカからなる分子ふるい材料。4. A molecular sieve material comprising silica substantially having straight tubular pores having a pore diameter of 0.85 to 1.2 nm.
キシルアミン及びペンチルアミンのうちから選択される
１種類あるいは２種類以上の第１級アミンとの水懸濁液
中に生成する沈殿物を固−液分離した後、生成沈殿物か
らアルキルアミンを除去することを特徴とする分子ふる
い材料の製造方法。5. A solid-liquid precipitate formed in an aqueous suspension of an alkoxysilane and one or more primary amines selected from heptylamine, hexylamine and pentylamine. A method for producing a molecular sieve material, comprising removing an alkylamine from a formed precipitate after separation.
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|---|---|---|---|
| JP8-323288 | 1996-10-28 | ||
| JP32328896 | 1996-10-28 | ||
| JP29130397A JP4036937B2 (en) | 1996-10-28 | 1997-10-23 | Method for producing mesoporous molecular sieve material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001096242A1 (en) * | 2000-06-12 | 2001-12-20 | Japan Science And Technology Corporation | Meso-porous transition metal oxide having crystallized pore wall and method for preparing the same |
| WO2003002458A1 (en) * | 2001-06-29 | 2003-01-09 | Japan Science And Technology Corporation | Method for preparing inorganic porous material |
| KR100392194B1 (en) * | 2000-07-19 | 2003-07-22 | 이종협 | Preparation of Ceramic Hollow Sphere |
| KR100455333B1 (en) * | 2002-05-29 | 2004-11-06 | 우제완 | Method for preparing silica hollow microspheres |
| WO2008004687A1 (en) * | 2006-07-03 | 2008-01-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
-
1997
- 1997-10-23 JP JP29130397A patent/JP4036937B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001096242A1 (en) * | 2000-06-12 | 2001-12-20 | Japan Science And Technology Corporation | Meso-porous transition metal oxide having crystallized pore wall and method for preparing the same |
| KR100392194B1 (en) * | 2000-07-19 | 2003-07-22 | 이종협 | Preparation of Ceramic Hollow Sphere |
| WO2003002458A1 (en) * | 2001-06-29 | 2003-01-09 | Japan Science And Technology Corporation | Method for preparing inorganic porous material |
| KR100455333B1 (en) * | 2002-05-29 | 2004-11-06 | 우제완 | Method for preparing silica hollow microspheres |
| WO2008004687A1 (en) * | 2006-07-03 | 2008-01-10 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
| JP2008012382A (en) * | 2006-07-03 | 2008-01-24 | Toyota Motor Corp | Catalyst for purifying exhaust gas |
| US8999878B2 (en) | 2006-07-03 | 2015-04-07 | Toyota Jidosha Kabushiki Kaisha | Exhaust gas purifying catalyst |
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| Publication number | Publication date |
|---|---|
| JP4036937B2 (en) | 2008-01-23 |
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