JPH0551530B2 - - Google Patents
Info
- Publication number
- JPH0551530B2 JPH0551530B2 JP58059159A JP5915983A JPH0551530B2 JP H0551530 B2 JPH0551530 B2 JP H0551530B2 JP 58059159 A JP58059159 A JP 58059159A JP 5915983 A JP5915983 A JP 5915983A JP H0551530 B2 JPH0551530 B2 JP H0551530B2
- Authority
- JP
- Japan
- Prior art keywords
- strong
- group
- methanol
- molar ratio
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000010304 firing Methods 0.000 description 8
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 6
- 229910052810 boron oxide Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 241000511343 Chondrostoma nasus Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 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
- 239000007864 aqueous solution Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
- C01B35/10—Compounds containing boron and oxygen
- C01B35/1009—Compounds containing boron and oxygen having molecular-sieve properties
Description
本発明は結晶性メタロシリケートの新規な製造
方法に関する。
各種の結晶性メタロシリケートはその分子篩作
用、固体酸機能を有効に利用することによつて吸
着剤、触媒、触媒担体などの用途分野で多用され
ている。
このような結晶性メタロシリケートは天然産の
もの若しくは合成されたものなど多数のものが知
られている。
合成品は一般に、シリカ（SiO2）源とアルミ
ナ（Al2O3）を主とする各種の金属（メタル）源
とを所定の量比で水溶液中において反応させるこ
とにより製造されている。最近では、この水溶液
中に所定量のアルコールを添加して反応させる方
法も開発されている（米国特許第4199556号明細
書、特開昭52−43800号公報参照）。
これらの方法で得られた結晶性メタロシリケー
トはいずれも、結晶性アルミノシリケートとして
著名なZSM−５ゼオライト、ゼーター３（いずれ
も商品名）と同じ結晶構造を有するものである。
また、比較的多量のメタノールの存在下で、シ
リカ源、アルミナ源、アルカリ金属源若しくはア
ルカリ土類金属源及び水とを反応させて新規な結
晶性アルミノシリケートを製造する方法をわれわ
れは提案した（特願昭57−16395号参照）。
本発明は、上記した特願昭57−16395号で提案
した結晶性アルミノシリケートとその結晶構造及
び分子篩作用は同一であるが、しかし骨格成分と
してアルミニウム（Al）を含むことのない新規
な結晶性メタロシリケートの製造方法の提供を目
的とするものである。
すなわち、本発明方法は、
次式：pM2/nＯ・XOo/2・qSiO2
（式中、Ｍはアルカリ金属及び／又はアルカリ
土類金属を表わし；Ｘは周期律表B族、B族、
族、族、族、B族、B族又は族に属す
る少なくとも１種の金属（ただし、ケイ素とアル
ミニウムは除く。）を表わし；ｐ，ｑはそれぞれ
0.3〜3.0、10以上の数を表わし；ｍ，ｎはそれぞ
れＭ，Ｘの原子価表わす。）
で示され、かつ下記Ｘ線回折パターンを示す結晶
性メタロシリケートの製造方法であつて、シリカ
源、Ｍ源、水及びメタノールを、M2/nＯ／SiO2
のモル比が0.1〜３、SiO2／XOo/2のモル比が５以
上、メタノール／SiO2のモル比が１〜100、メタ
ノール／水のモル比が0.1〜10となるように混合
し、得られた混合物を加熱しながら反応させるこ
とを特徴とする結晶性メタロシリケートの製造方
法である。
Ｘ線回折パターン
The present invention relates to a novel method for producing crystalline metallosilicates. Various crystalline metallosilicates are widely used in fields such as adsorbents, catalysts, and catalyst supports by effectively utilizing their molecular sieving and solid acid functions. A large number of such crystalline metallosilicates are known, including naturally occurring ones and synthetic ones. Synthetic products are generally produced by reacting a silica (SiO 2 ) source and various metal sources, mainly alumina (Al 2 O 3 ), in a predetermined quantitative ratio in an aqueous solution. Recently, a method has also been developed in which a predetermined amount of alcohol is added to this aqueous solution for reaction (see U.S. Pat. No. 4,199,556 and Japanese Patent Application Laid-open No. 52-43800). All of the crystalline metallosilicates obtained by these methods have the same crystal structure as ZSM-5 zeolite and Zeta 3 (both trade names), which are well-known as crystalline aluminosilicate. We also proposed a method for producing a new crystalline aluminosilicate by reacting a silica source, an alumina source, an alkali metal source or an alkaline earth metal source, and water in the presence of a relatively large amount of methanol ( (See Japanese Patent Application No. 16395/1983). The present invention is a novel crystalline aluminosilicate that has the same crystal structure and molecular sieving action as the crystalline aluminosilicate proposed in Japanese Patent Application No. 16395/1982, but does not contain aluminum (Al) as a skeleton component. The object of the present invention is to provide a method for producing metallosilicate. That is, the method of the present invention has the following formula: pM 2/n O・XO o/2・qSiO 2 (wherein M represents an alkali metal and / or an alkaline earth metal; family,
Represents at least one metal belonging to Group, Group, Group B , Group B , or Group (excluding silicon and aluminum); p and q are each
Represents a number from 0.3 to 3.0 and 10 or more; m and n represent the valences of M and X, respectively. ) and exhibiting the following X-ray diffraction pattern, the method comprises: silica source, M source, water and methanol, M 2/n O/SiO 2
The molar ratio of SiO 2 /XO o/2 is 5 or more, the molar ratio of methanol/SiO 2 is 1-100, and the molar ratio of methanol/water is 0.1-10. , is a method for producing a crystalline metallosilicate, characterized in that the resulting mixture is reacted while being heated. X-ray diffraction pattern
【表】【table】
【表】
（ただし、表中、非常に強い、強い、中程度、
弱いの表示はそれぞれ70〜100，40〜50，15〜40，
０〜15の相対強度を表わす。）
本発明方法にあつては、まず、上記したシリカ
源、Ｍ源、Ｘ源、水及びメタノールをそれぞれが
後述するモル比を満足するような関係の量比で混
合して水性混合物を調製する。
これら５種の成分のうち、シリカ源、Ｍ源、Ｘ
源はいずれも目的とする結晶性メタロシリケート
の骨格成分となるものである。
本発明で用いるシリカ源は、特に限定されるも
のではなく、シリカ粉末、ケイ酸、コロイド状シ
リカ、溶解シリカなどをあげることができる。こ
れらのうち溶解シリカは好適である。溶解シリカ
としては例えば、Na2Ｏ又はK2O1モルに対し
SiO2１〜５モルを含有して成る水ガラス、アル
カリ金属のケイ酸塩をあげることができる。
Ｍ源としては、水酸化ナトリウム、水酸化カリ
ウム、ケイ酸ナトリウム、アルミン酸ナトリウ
ム、ケイ酸カリウム、水酸化リチウム、水酸化セ
シウム、水酸化ルビジウムなどのアルカリ金属の
化合物；硝酸カルシウム、塩化カルシウム、臭化
バリウム、塩化ストロンチウムなどのアルカリ土
類金属の化合物のそれぞれいずれか又は適宜に選
定した２種以上のものをあげることができる。本
発明方法におけるＭ源のＭとしてはナトリウムが
とくに好ましい。
水性混合物におけるシリカ源とＭ源の量比は、
それぞれをSiO2、M2/nＯ（ｍはＭの原子価）の形
で表わした場合、M2/nＯ／SiO2のモル比が0.1〜
３の関係を満足する範囲内に設定される。好まし
くは0.2〜１の範囲である。これらＭ源は、製造
する目的組成の結晶性メタロシリケートに含有さ
れるＭの種類との関係で適宜に選定すればよい。
本発明方法にあつては、とくに酸化物の形で用い
ることが好ましい。
Ｘ源は、周期律表B族、B族、族、族、
族、B族、B族又は族に属する少なくとも
１種の金属（ただし、Si及びAlは除く。）の酸化
物、水酸化物、塩化物、硝酸塩、硫酸塩のいずれ
か又はこれらのうち２種以上を適宜に組合せたも
のをあげることができる。これらＸ源は、製造す
べき目的組成の結晶性メタロシリケートに含有さ
れるＸの種類との関係で適宜に選定すればよい。
本発明方法にあつてはとくに酸化物の形で用いる
ことが好ましい。
水性混合物におけるシリカ源とＸ源との量比
は、それぞれをSiO2、XOo/2（ｎはＸの原子価）
の形で表わした場合、SiO2／XOo/2のモル比が５
以上となるように設定される。好ましくは、20〜
1000の範囲内がよい。
本発明にかかる水性混合物において、メタノー
ルは目的とする結晶性メタロシリケートの構成成
分として含有されるものではないが、全体の製造
過程において結晶性メタロシリケートの結晶構造
の形成に重要な機能を果す成分である。本発明方
法にあつては、このメタノールの使用量は、モル
比で表わして、メタノール／SiO2が１〜100、メ
タノール／水が0.1〜10の関係を満足することが
必要である。好ましくは、メタノール／SiO2は
３〜60、メタノール／水は0.2〜５の範囲におけ
るメタノール量である。
本発明にかかる水性混合物は後述する反応条件
下で反応せしめられて本発明の結晶性メタロシリ
ケートを形成するが、その際、水性混合物中の水
酸イオンの量は、モル比表示で水酸イオン〜
SiO2が0.01〜0.5、好ましくは0.01〜0.3の関係を
満足するように調整される。この場合、水酸イオ
ンの量は原料混合物中の酸と塩基の量から計算に
よりもとめたものである。
このような水性混合物において、各成分の量比
がそれぞれ上記した関係を満足する範囲を外れた
場合、又はいずれかの関係が１つでも満足してい
なかつた場合には、本発明方法では目的とする組
成及び結晶構造の結晶性メタロシリケートを形成
することはできない。
水性混合物の調製は、各成分の溶液をそれぞれ
別個に調製し、又は適宜に組合せて成る各成分の
混合溶液を調製し、これらを最後には全体として
混合することによつて行なえばよい。
本発明方法では、つぎに、以上のようにして調
製された水性混合物を加熱しながら各成分を反応
させる。
反応は、例えばオートクレーブ中で進められ、
その反応条件としては、温度100〜300℃、好まし
くは120〜200℃、反応時間５時間〜10日間、好ま
しくは10時間〜５日間、圧力は特に限定されず通
常は自己圧力である。反応は通常攪拌下で進めら
れる。
反応終了後、反応混合物を水洗し所定温度（通
常120℃程度）で乾燥すれば目的とする結晶性メ
タロシリケートが得られる。
本発明の結晶性メタロシリケートは、Alは骨
格成分として含有されていないが特願昭57−
16395号に提案したものと同じ結晶構造を有し、
かつ固体酸であつて、化学工業一般、とりわけ、
石油精製、石油化学工業の分野における触媒、触
媒担体、吸着剤として有用である。
以下に、本発明を実施例に基づいて更に詳細に
説明する。
実施例 １
酸化ホウ素1.4ｇ（0.02モル）を硫酸（97％濃
度）17.6ｇ（0.17モル）及び水150ml（8.33モル）
に溶解した溶液Ａを調製した。二酸化ケイ素29.0
重量％、酸化ナトリウム9.4重量％、水61.1重量
％から成る水ガラス211ｇ（二酸化ケイ素：1.02
モル、酸化ナトリウム：3.2モル、水：7.16モル）
を水96ml（5.33モル）に溶解した溶液Ｂを調製し
た。
反応容器中に溶液Ａ及び溶液Ｂを徐々に滴下し
両者を攪拌混合した。ついで、50％硫酸14.8ｇを
加えて全体のPHを8.5に調整した後、ここにメタ
ノール376ml（9.3モル）を添加して混合し、全体
を内容積１のオートクレーブに入れて攪拌しな
がら170℃、自己圧力下で20時間反応させた。
得られた反応混合物を過して固形分を取
し、これを120℃で６時間乾燥して53.0ｇの結晶
性シリケートを得た。
この生成物を550℃で６時間焼成した後の組成
は、1.3Na2Ｏ・B2O3・125SiO2であつた。
また、このもののＸ線回折パターンを図及び第
１表に示した。[Table] (However, in the table, very strong, strong, moderate,
Weak indications are 70-100, 40-50, 15-40, respectively.
Represents relative intensity from 0 to 15. ) In the method of the present invention, first, an aqueous mixture is prepared by mixing the above-mentioned silica source, M source, . Among these five components, silica source, M source,
All of the sources serve as skeleton components of the target crystalline metallosilicate. The silica source used in the present invention is not particularly limited, and examples include silica powder, silicic acid, colloidal silica, and dissolved silica. Among these, fused silica is preferred. As dissolved silica, for example, per mole of Na 2 O or K 2 O
Examples include water glass containing 1 to 5 moles of SiO 2 and silicates of alkali metals. M sources include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium silicate, sodium aluminate, potassium silicate, lithium hydroxide, cesium hydroxide, and rubidium hydroxide; calcium nitrate, calcium chloride, and odor. Examples include compounds of alkaline earth metals such as barium chloride and strontium chloride, or two or more appropriately selected compounds. Sodium is particularly preferred as the M source in the method of the present invention. The quantitative ratio of silica source and M source in the aqueous mixture is:
When expressed in the form of SiO 2 and M 2/n O (m is the valence of M), the molar ratio of M 2/n O/SiO 2 is from 0.1 to
It is set within a range that satisfies the relationship 3. Preferably it is in the range of 0.2-1. These M sources may be appropriately selected in relation to the type of M contained in the crystalline metallosilicate having the intended composition to be produced.
In the method of the present invention, it is particularly preferable to use it in the form of an oxide. The X source is Group B of the periodic table, Group B , Group, Group,
oxides, hydroxides, chlorides, nitrates, and sulfates of Group B , Group B , or at least one metal belonging to Group B (excluding Si and Al), or two of these. An appropriate combination of the above may be used. These X sources may be appropriately selected in relation to the type of X contained in the crystalline metallosilicate having the desired composition to be produced.
In the method of the present invention, it is particularly preferable to use it in the form of an oxide. The quantitative ratio of the silica source and the X source in the aqueous mixture is SiO 2 and XO o/2 (n is the valence of X), respectively.
When expressed in the form, the molar ratio of SiO 2 /XO o/2 is 5
The settings are as follows. Preferably 20~
A value within the range of 1000 is good. In the aqueous mixture according to the present invention, methanol is not contained as a component of the target crystalline metallosilicate, but it is a component that plays an important function in forming the crystal structure of the crystalline metallosilicate in the entire manufacturing process. It is. In the method of the present invention, the amount of methanol used needs to satisfy the relationship of methanol/SiO 2 of 1 to 100 and methanol/water of 0.1 to 10, expressed in molar ratio. Preferably, the amount of methanol is in the range of 3 to 60 for methanol/ SiO2 and 0.2 to 5 for methanol/water. The aqueous mixture according to the present invention is reacted under the reaction conditions described below to form the crystalline metallosilicate of the present invention. ~
SiO2 is adjusted to satisfy the relationship of 0.01 to 0.5, preferably 0.01 to 0.3. In this case, the amount of hydroxide ions is calculated from the amounts of acid and base in the raw material mixture. In such an aqueous mixture, if the quantitative ratio of each component is out of the range that satisfies the above-mentioned relationships, or if even one of the relationships is not satisfied, the method of the present invention does not meet the objectives. It is not possible to form crystalline metallosilicates with a composition and crystal structure that The aqueous mixture may be prepared by separately preparing solutions of each component, or by preparing a mixed solution of each component by appropriately combining them, and finally mixing them as a whole. In the method of the present invention, the components are then reacted while heating the aqueous mixture prepared as described above. The reaction is carried out in an autoclave, for example,
The reaction conditions include a temperature of 100 DEG to 300 DEG C., preferably 120 DEG to 200 DEG C., a reaction time of 5 hours to 10 days, preferably 10 hours to 5 days, and a pressure which is not particularly limited and is usually autogenous pressure. The reaction is usually carried out under stirring. After the reaction is completed, the reaction mixture is washed with water and dried at a predetermined temperature (usually about 120°C) to obtain the desired crystalline metallosilicate. Although the crystalline metallosilicate of the present invention does not contain Al as a skeleton component,
It has the same crystal structure as the one proposed in No. 16395,
and is a solid acid, which is used in the chemical industry in general, especially,
It is useful as a catalyst, catalyst carrier, and adsorbent in the fields of petroleum refining and petrochemical industry. The present invention will be explained in more detail below based on examples. Example 1 1.4 g (0.02 mol) of boron oxide was mixed with 17.6 g (0.17 mol) of sulfuric acid (97% concentration) and 150 ml (8.33 mol) of water.
Solution A was prepared by dissolving . silicon dioxide 29.0
211 g of water glass (silicon dioxide: 1.02
mol, sodium oxide: 3.2 mol, water: 7.16 mol)
Solution B was prepared by dissolving the following in 96 ml (5.33 mol) of water. Solution A and solution B were gradually dropped into the reaction container and mixed by stirring. Next, 14.8 g of 50% sulfuric acid was added to adjust the overall pH to 8.5, and then 376 ml (9.3 mol) of methanol was added and mixed, and the whole was placed in an autoclave with an internal volume of 1 and heated at 170°C while stirring. , reacted for 20 hours under autogenous pressure. The resulting reaction mixture was filtered to remove solid matter, which was dried at 120° C. for 6 hours to obtain 53.0 g of crystalline silicate. After calcining this product at 550° C. for 6 hours, the composition was 1.3Na 2 O.B 2 O 3.125SiO 2 . Further, the X-ray diffraction pattern of this product is shown in the figure and Table 1.
【表】
実施例 ２
溶液Ａにおける酸化ホウ素量が0.7ｇ（0.01モ
ル）であつたことを除いては実施例１と同様にし
て結晶性シリケートを製造した。焼成後の組成は
1.5Na2Ｏ・B2O3・162SiO2であつた。このものの
Ｘ線回折パターンを第２表に示した。[Table] Example 2 A crystalline silicate was produced in the same manner as in Example 1, except that the amount of boron oxide in solution A was 0.7 g (0.01 mol). The composition after firing is
It was 1.5Na 2 O.B 2 O 3.162SiO 2 . The X-ray diffraction pattern of this product is shown in Table 2.
【表】【table】
【表】
実施例 ３
酸化ホウ素の代りに硝酸第２鉄（９水塩）8.08
ｇ（0.02モル）を用いたことを除いては実施例１
と同様の方法で結晶性シリケートを製造した。焼
成後の組成は1.2Na2Ｏ・Fe2O3・81.7SiO2であつ
た。このもののＸ線回折パターンを第３表に示し
た。[Table] Example 3 Ferric nitrate (nase hydrate) instead of boron oxide 8.08
Example 1 except that g (0.02 mol) was used.
Crystalline silicate was produced in a similar manner. The composition after firing was 1.2Na 2 O.Fe 2 O 3.81.7SiO 2 . The X-ray diffraction pattern of this product is shown in Table 3.
【表】
実施例 ４
酸化ホウ素の代りに硝酸クロム（９水塩）8.00
ｇ（0.02モル）を用いたことを除いては実施例１
と同様の方法で結晶性シリケートを製造した。焼
成後の組成は、2.8Na2Ｏ・Cr2O3・75.8SiO2であ
つた。このもののＸ線回折パターンを第４表に示
した。[Table] Example 4 Chromium nitrate (nase hydrate) 8.00 instead of boron oxide
Example 1 except that g (0.02 mol) was used.
Crystalline silicate was produced in a similar manner. The composition after firing was 2.8Na2O.Cr2O3.75.8SiO2 . The X-ray diffraction pattern of this product is shown in Table 4.
【表】
実施例 ５
実施例１で溶液Ａと溶液Ｂの混合液のPHを10.5
に調整（50％硫酸0.3ｇを加えた）したことを除
いては実施例１と同様の方法で結晶性シリケート
を製造した。焼成後の組成は、1.3Na2Ｏ・B2
O3・88SiO2であつた。このもののＸ線回折パタ
ーンを第５表に示した。[Table] Example 5 In Example 1, the pH of the mixture of solution A and solution B was set to 10.5.
A crystalline silicate was produced in the same manner as in Example 1, except that 0.3 g of 50% sulfuric acid was added. The composition after firing is 1.3Na 2 O・B 2
It was O3.88SiO2 . The X-ray diffraction pattern of this product is shown in Table 5.
【表】【table】
【表】
実施例 ６
実施例１で溶液Ａと溶液Ｂの混合液のPHを7.5
に調整（50％硫酸21.0ｇを加えた）したことを除
いては実施例１と同様の方法で結晶性シリケート
を製造した。焼成後の組成は、2.1Na2Ｏ・B2
O3・128SiO2であつた。このもののＸ線回折パタ
ーンを第６表に示した。[Table] Example 6 In Example 1, the pH of the mixture of solution A and solution B was set to 7.5.
A crystalline silicate was produced in the same manner as in Example 1, except that 21.0 g of 50% sulfuric acid was added. The composition after firing is 2.1Na 2 O・B 2
It was O3.128SiO2 . The X-ray diffraction pattern of this product is shown in Table 6.
【表】【table】
【表】
実施例 ７
実施例１で反応温度170℃、反応時間20時間に
代えて、それぞれを140℃、４日としたことを除
いては実施例１と同様の方法で結晶性シリケート
を製造した。焼成後の組成は、1.3Na2Ｏ・B2
O3・102SiO2であつた。このもののＸ線回折パタ
ーンを第７表に示した。[Table] Example 7 Crystalline silicate was produced in the same manner as in Example 1, except that instead of the reaction temperature of 170°C and reaction time of 20 hours in Example 1, the reaction time was 140°C and 4 days. did. The composition after firing is 1.3Na 2 O・B 2
It was O3・102SiO2 . The X-ray diffraction pattern of this product is shown in Table 7.
【表】
実施例 ８
溶液Ａが、酸化ホウ素0.7ｇ（0.01モル）、硫酸
（97％濃度）8.8ｇ（0.09モル）及び水75ml（4.17
モル）で構成されていること、溶液Ｂが、二酸化
ケイ素29.0重量％、酸化ナトリウム9.4重量％、
水61.1重量％から成る水ガラス105ｇ（二酸化ケ
イ素：0.51モル、酸化ナトリウム：0.16モル、
水：3.56モル）で構成されていること、及びメタ
ノール使用量が560ml（13.9モル）であつたこと
を除いては実施例１と同様の方法で結晶性シリケ
ートを製造した。焼成後の組成は、1.0Na2Ｏ・
B2O3・109SiO2であつた。このもののＸ線回折パ
ターンを第８表に示した。[Table] Example 8 Solution A contains 0.7 g (0.01 mol) of boron oxide, 8.8 g (0.09 mol) of sulfuric acid (97% concentration) and 75 ml (4.17 mol) of water.
29.0% by weight of silicon dioxide, 9.4% by weight of sodium oxide,
105 g of water glass consisting of 61.1% by weight of water (silicon dioxide: 0.51 mol, sodium oxide: 0.16 mol,
A crystalline silicate was produced in the same manner as in Example 1, except that the amount of methanol used was 560 ml (13.9 mol). The composition after firing is 1.0Na 2 O.
It was B2O3 ・ 109SiO2 . The X-ray diffraction pattern of this product is shown in Table 8.
【表】
酸化ホウ素の代りに、オルトリン酸（濃度85
％）2.6ｇ（0.02モル）を用いたことを除いては
実施例１と同様の方法で結晶性シリケートを製造
した。焼成後の組成は、1.5Na2Ｏ・P2O5・
85SiO2であつた。このもののＸ線回折パターン
を第９表に示した。[Table] Orthophosphoric acid (concentration 85
A crystalline silicate was produced in the same manner as in Example 1, except that 2.6 g (0.02 mol) of %) was used. The composition after firing is 1.5Na 2 O・P 2 O 5・
It was 85SiO2 . The X-ray diffraction pattern of this product is shown in Table 9.
【表】【table】
【表】【table】
図は、実施例１で製造した結晶性シリケートの
Ｘ線回折パターンを示す。
The figure shows the X-ray diffraction pattern of the crystalline silicate produced in Example 1.
Claims (1)
土類金属を表わし；Ｘは周期律表B族、B族、
族、族、族、B族、B族又は族に属す
る少なくとも１種の金属（ただし、ケイ素、アル
ミニウムは除く。）を表わし；ｐ，ｑはそれぞれ
0.3〜3.0、10以上の数を表わし；ｍ，ｎはそれぞ
れＭ，Ｘの原子価を表わす。）で示され、かつ下
記Ｘ線回折パターンを示す結晶性メタロシリケー
トの製造方法であつて、シリカ源、Ｍ源、水及び
メタノールを、M2/nＯ／SiO2のモル比が0.1〜３、
SiO2／XOo/2のモル比が５以上、メタノール／
SiO2のモル比が１〜100、メタノール／水のモル
比が0.1〜10となるように混合し、得られた混合
物を加熱しながら反応させることを特徴とする結
晶性メタロシリケートの製造方法。 格子面間隔（ｄ：Å） 相対強度 10.89±0.2 強い〜非常に強い 8.74±0.2 中程度 6.94±0.15 中程度 5.43±0.15 弱い〜中程度 4.58±0.15 弱い 4.37±0.1 非常に強い 3.68±0.1 非常に強い 3.62±0.07 強い〜非常に強い 3.46±0.07 強い 3.34±0.07 弱い 3.30±0.07 弱い 2.52±0.05 中程度[Claims] Primary formula: pM 2/n O・XO o/2・qSiO 2 (wherein, M represents an alkali metal and / or an alkaline earth metal; family,
Represents at least one metal belonging to Group, Group, Group B , Group B , or Group (excluding silicon and aluminum); p and q are each
Represents a number from 0.3 to 3.0 and 10 or more; m and n represent the valences of M and X, respectively. ) and exhibiting the following X-ray diffraction pattern, the silica source, M source, water and methanol are mixed in a molar ratio of M 2/n O/SiO 2 of 0.1 to 3. ,
The molar ratio of SiO 2 /XO o/2 is 5 or more, methanol/
A method for producing a crystalline metallosilicate, which comprises mixing SiO2 at a molar ratio of 1 to 100 and methanol/water at a molar ratio of 0.1 to 10, and reacting the resulting mixture while heating. Lattice spacing (d: Å) Relative strength 10.89±0.2 Strong to very strong 8.74±0.2 Moderate 6.94±0.15 Moderate 5.43±0.15 Weak to moderate 4.58±0.15 Weak 4.37±0.1 Very strong 3.68±0.1 Very Strong 3.62±0.07 Strong to very strong 3.46±0.07 Strong 3.34±0.07 Weak 3.30±0.07 Weak 2.52±0.05 Moderate
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5915983A JPS59184722A (en) | 1983-04-06 | 1983-04-06 | Manufacture of crystalline metallosilicate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5915983A JPS59184722A (en) | 1983-04-06 | 1983-04-06 | Manufacture of crystalline metallosilicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59184722A JPS59184722A (en) | 1984-10-20 |
| JPH0551530B2 true JPH0551530B2 (en) | 1993-08-02 |
Family
ID=13105303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5915983A Granted JPS59184722A (en) | 1983-04-06 | 1983-04-06 | Manufacture of crystalline metallosilicate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59184722A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5243800A (en) * | 1975-09-29 | 1977-04-06 | Ici Ltd | Process for preparing zeolite |
| JPS54151600A (en) * | 1978-04-06 | 1979-11-28 | Shell Int Research | Manufacture of zeolite |
-
1983
- 1983-04-06 JP JP5915983A patent/JPS59184722A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5243800A (en) * | 1975-09-29 | 1977-04-06 | Ici Ltd | Process for preparing zeolite |
| JPS54151600A (en) * | 1978-04-06 | 1979-11-28 | Shell Int Research | Manufacture of zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59184722A (en) | 1984-10-20 |
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