JPH0343207B2 - - Google Patents
Info
- Publication number
- JPH0343207B2 JPH0343207B2 JP2103983A JP2103983A JPH0343207B2 JP H0343207 B2 JPH0343207 B2 JP H0343207B2 JP 2103983 A JP2103983 A JP 2103983A JP 2103983 A JP2103983 A JP 2103983A JP H0343207 B2 JPH0343207 B2 JP H0343207B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction mixture
- water
- hours
- sio
- aluminosilicate zeolite
- 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
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 239000010457 zeolite Substances 0.000 claims description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 150000007530 organic bases Chemical class 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- -1 sodium cations Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
【発明の詳細な説明】
本発明はケイバン比（シリカ対アルミナのモル
比を言う。以下同じ）の高い合成結晶性アルミノ
シリケートゼオライトの製造法に関するものであ
つて、さらに詳しくはゼオライト合成のアルカリ
源として有機塩基を使用することなく、古典的な
水酸化ナトリウム又はナトリウム塩を用いてケイ
バン比が40以上の合成結晶性アルミノシリケート
ゼオライトを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a synthetic crystalline aluminosilicate zeolite with a high Cylban ratio (meaning the molar ratio of silica to alumina; the same applies hereinafter), and more specifically to an alkali source for zeolite synthesis. The present invention relates to a method for producing synthetic crystalline aluminosilicate zeolites with a Cavan ratio of 40 or more using classical sodium hydroxide or sodium salts without using organic bases.
一般に合成ゼオライトはアルカリ、シリカ、ア
ルミナ及び水からなる４成分系の反応混合物を所
定の条件下に保持して、結晶を生成させる方法で
調製することができる。そしてこの方法で得られ
る各種の合成結晶性ゼオライトは、吸着剤、触
媒、触媒用担体として工業的に広く利用されてい
る。 Generally, synthetic zeolite can be prepared by a method in which a four-component reaction mixture consisting of alkali, silica, alumina, and water is maintained under predetermined conditions to generate crystals. Various synthetic crystalline zeolites obtained by this method are widely used industrially as adsorbents, catalysts, and catalyst carriers.
ところで、合成結晶性ゼオライトのなかにあつ
て、ケイバン比が高いものは低いものに比較し
て、炭化水素のクラツキンク反応、アルキル化反
応、異性化反応に対して高活性の触媒能を有し、
しかも耐熱性、耐酸性に優れているため、合成結
晶性ゼオライトを工業的に利用する場合には、ケ
イバン比の高いものが好ましいとされている。こ
うした事情から、当業界ではケイバン比の高い合
成結晶性ゼオライトの開発を目指して研究が続け
られ、その研究の成果としてゼオライト合成のア
ルカリ源に、テトラプロピルアンモニウムハイド
ロキサイドのような有機塩基を用いる方法が提案
されている。しかし、この合成法は原料に使用す
る有機塩基が比較的高価である点で、必ずしも賞
用できない。 By the way, among synthetic crystalline zeolites, those with a high Cayban ratio have a higher catalytic ability for the Klutzkink reaction, alkylation reaction, and isomerization reaction of hydrocarbons than those with a low Cavan ratio.
Moreover, since it has excellent heat resistance and acid resistance, when synthetic crystalline zeolite is used industrially, it is said that one with a high C-Ban ratio is preferable. Under these circumstances, research continues in the industry with the aim of developing synthetic crystalline zeolites with a high C-ban ratio, and as a result of this research, organic bases such as tetrapropylammonium hydroxide are used as alkali sources for zeolite synthesis. A method is proposed. However, this synthetic method is not always practical because the organic base used as a raw material is relatively expensive.
本発明者らは、有機塩基を用いずに高ケイバン
比の合成結晶性アルミノシリケートゼオライトを
製造する方法について検討を重ねた結果、反応混
合物の組成を厳密に特定するとともに、その反応
混合物を極めて狭隘な一定温度に保持することに
よつて、有機塩基を使用しなくても、高ケイバン
比の合成結晶性アルミノシリケートゼオライトが
製造できることを見出した。 As a result of repeated studies on a method for producing synthetic crystalline aluminosilicate zeolite with a high Cylban ratio without using an organic base, the present inventors have determined that the composition of the reaction mixture is strictly specified and that the reaction mixture is extremely narrow. It has been found that by maintaining the temperature at a constant temperature, a synthetic crystalline aluminosilicate zeolite with a high Cylvan ratio can be produced without using an organic base.
而して本発明に係る合成結晶性アルミノシリケ
ートゼオライトの製造法は、ナトリウム源（アル
カリ源）、シリカ源、アルミナ源及び水の４成分
からなり、酸化物のモル比で、
Na2O／SiO2＝0.13
H2O／SiO2＝45.90
SiO2／Al2O3＝40.0〜100.0
なる組成の反応混合物を調製し、この反応混合物
をアルミノシリケートゼオライトの結晶が生成さ
れるまでの時間、190℃の温度に保持し、生成し
た結晶を分離回収することを特徴とする。 Therefore, the method for producing synthetic crystalline aluminosilicate zeolite according to the present invention consists of four components: a sodium source (alkali source), a silica source, an alumina source, and water, and the molar ratio of oxides is Na 2 O / SiO 2 = 0.13 H 2 O / SiO 2 = 45.90 SiO 2 /Al 2 O 3 = 40.0 to 100.0 A reaction mixture was prepared, and the reaction mixture was heated at 190°C for a period of time until crystals of aluminosilicate zeolite were generated. It is characterized by maintaining the temperature at a temperature of , and separating and collecting the generated crystals.
本発明の合成結晶性アルミノシリケートゼオラ
イトを製造するに当つて、シリカ源には普通よく
用いられているシリカゾル、シリカゲル、水硝子
などを用いることができ、アルミナ源にはアルミ
ナゲル、アルミナゾル、アルミン酸ソーダ、アル
ミニウム塩などの通常のものを用いることができ
る。そしてアルカリ源には水溶性のナトリウム塩
又は水酸化ナトリウムが使用される。 In producing the synthetic crystalline aluminosilicate zeolite of the present invention, commonly used silica sol, silica gel, water glass, etc. can be used as the silica source, and alumina gel, alumina sol, aluminic acid, etc. can be used as the alumina source. Common substances such as soda and aluminum salts can be used. A water-soluble sodium salt or sodium hydroxide is used as the alkali source.
本発明によれば、上記したシリカ源、アルミナ
源、アルカリ源及び水を使用して反応混合物がま
ず調製されるが、その反応混合物の組成は既述の
酸化物モル比を保持していることが必要であつ
て、これを逸脱した場合には所期の合成結晶性ア
ルミノシリケートゼオライトを得ることができな
い。 According to the present invention, a reaction mixture is first prepared using the above-mentioned silica source, alumina source, alkali source, and water, and the composition of the reaction mixture maintains the above-mentioned oxide molar ratio. is necessary, and if this is deviated from, the desired synthetic crystalline aluminosilicate zeolite cannot be obtained.
前記反応混合物は合成結晶性アルミノシリケー
トゼオライトが生成するに充分な温度および時間
で反応せしめられるが、反応温度は190℃であり、
反応時間は24時間〜48時間の範囲であるのが一般
的である。この反応は加圧下で行なうことが好ま
しいが、自生圧で充分である。かくして得られた
結晶性生成物は濾別し、水洗し、反応媒体から分
離する。さらに結晶は必要に応じ乾燥及び焼成す
ることができる。例えば、乾燥は110℃で３時間
〜24時間の範囲で、また焼成は200℃〜1000℃、
好ましくは400℃〜800℃の範囲で行なうことがで
きる。 The reaction mixture is allowed to react at a temperature and time sufficient to form a synthetic crystalline aluminosilicate zeolite, the reaction temperature being 190°C;
Reaction times generally range from 24 hours to 48 hours. This reaction is preferably carried out under pressure, but autogenous pressure is sufficient. The crystalline product thus obtained is filtered off, washed with water and separated from the reaction medium. Furthermore, the crystals can be dried and calcined if necessary. For example, drying at 110℃ for 3 to 24 hours, baking at 200℃ to 1000℃,
Preferably, it can be carried out at a temperature in the range of 400°C to 800°C.
本発明の合成結晶性アルミノシリケートゼオラ
イトは合成形態のナトリウムカチオンの少なくと
も一部を、従来公知の方法によつて、水素、水素
先駆体及び元素周期表第族ないし第族までの
金属から成る群から選択されるカチオンまたはカ
チオン混合物でイオン交換することができる。 The synthetic crystalline aluminosilicate zeolite of the present invention is prepared by converting at least a portion of the sodium cations in synthetic form into hydrogen, hydrogen precursors and metals from Groups 1 to 3 of the Periodic Table of the Elements. Ion exchange can be carried out with selected cations or cation mixtures.
以下実施例を掲げて本発明方法を詳述する。 The method of the present invention will be described in detail below with reference to Examples.
実施例 １
1.3742ｇのアルミン酸ソーダを、21.75ｇの水
酸化ナトリウム溶液（10.45wt％NaOH）と84.26
ｇの水とからなる溶液に溶解し、そして64.94ｇ
の水中の85.18ｇのシリカゾル（20wt％SiO2）溶
液に撹拌しながら添加して反応混合物を調製し
た。この反応混合物はモル比で次の組成を有す
る。Example 1 1.3742g of sodium aluminate was mixed with 21.75g of sodium hydroxide solution (10.45wt% NaOH) and 84.26g of sodium hydroxide solution (10.45wt% NaOH).
g of water and 64.94 g of
A reaction mixture was prepared by adding 85.18 g of silica sol (20 wt% SiO2 ) in water with stirring. The reaction mixture has the following composition in molar ratios:
5.33Na2O・Al2O3・40.0SiO2・1836H2O
この反応混合物を１時間室温で撹拌しながら熟
成し、オートクレーブに仕込んで190℃、自生圧
にて15時間保持した後、得られた生成物を濾別
し、水洗し、110℃で16時間乾燥した。 5.33Na 2 O・Al 2 O 3・40.0SiO 2・1836H 2 O This reaction mixture was aged for 1 hour with stirring at room temperature, charged into an autoclave, and kept at 190°C and autogenous pressure for 15 hours. The resulting product was filtered off, washed with water, and dried at 110°C for 16 hours.
得られた生成物はこれの粉末Ｘ線回析図から結
晶性であつた。 The obtained product was crystalline based on its powder X-ray diffraction pattern.
実施例 ２〜４
1.0895ｇのアルミン酸ソーダを、23.21ｇの水
酸化ナトリウム溶液（10.45wt％NaOH）と79.41
ｇの水とからなる溶液に溶解し、そして70.50ｇ
の水中の85.18ｇのシリカゾル（20wt％SiO2）溶
液に撹拌しながら添加して反応混合物を調製し
た。この反応混合物はモル比で次の組成を有す
る。Examples 2-4 1.0895g of sodium aluminate was mixed with 23.21g of sodium hydroxide solution (10.45wt% NaOH) and 79.41g of sodium hydroxide solution (10.45wt% NaOH)
g of water and 70.50 g of
A reaction mixture was prepared by adding 85.18 g of silica sol (20 wt% SiO2 ) in water with stirring. The reaction mixture has the following composition in molar ratios:
6.67Na2O・Al2O3・50.0SiO2・2295H2O
この反応混合物を１時間室温で撹拌しながら熟
成し、オートクレーブに仕込んで190℃、自生圧
にて15時間（実施例２）、24時間（実施例３）お
よび48時間（実施例４）それぞれ保持した後、得
られた生成物を濾別し、水洗し、110℃で16時間
乾燥した。 6.67Na 2 O・Al 2 O 3・50.0SiO 2・2295H 2 O This reaction mixture was aged for 1 hour with stirring at room temperature, charged into an autoclave, and heated at 190° C. and autogenous pressure for 15 hours (Example 2). After holding for 24 hours (Example 3) and 48 hours (Example 4), respectively, the resulting products were filtered off, washed with water and dried at 110° C. for 16 hours.
得られた生成物はこれの粉末Ｘ線回析図からい
ずれも結晶性であつた。ただし、実施例４で生成
した生成物には極微量の石英が存在した。 The obtained products were all crystalline based on their powder X-ray diffraction patterns. However, a trace amount of quartz was present in the product produced in Example 4.
実施例 ５〜６
0.7640ｇのアルミン酸ソーダを24.89ｇの水酸
化ナトリウム溶液（10.45wt％NaOH）と77.94ｇ
の水とからなる溶液に溶解し、そして68.49ｇの
水中の85.18ｇのシリカゾル（20wt％SiO2）溶液
に撹拌しながら添加して反応混合物を調製した。
この反応混合物はモル比で次の組成を有する。Examples 5-6 0.7640g of sodium aluminate was mixed with 24.89g of sodium hydroxide solution (10.45wt% NaOH) and 77.94g
of water and added with stirring to a solution of 85.18 g of silica sol (20 wt% SiO 2 ) in 68.49 g of water.
The reaction mixture has the following composition in molar ratios:
9.33Na2O・Al2O3・70.0SiO2・3213H2O
この反応混合物を１時間室温で撹拌しながら熟
成し、オートクレーブに仕込んで190℃、自生圧
にて15時間（実施例５）および24時間（実施例
６）それぞれ保持した後、得られた生成物を濾別
し、水洗し、110℃で16時間乾燥した。 9.33Na 2 O・Al 2 O 3・70.0SiO 2・3213H 2 O This reaction mixture was aged for 1 hour at room temperature with stirring, then charged into an autoclave and aged at 190°C and autogenous pressure for 15 hours (Example 5) and After each holding for 24 hours (Example 6), the product obtained was filtered off, washed with water and dried at 110° C. for 16 hours.
得られた生成物はこれの粉末Ｘ線回析図からい
ずれも結晶性であつた。 The obtained products were all crystalline based on their powder X-ray diffraction patterns.
実施例 ７
0.5198ｇのアルミン酸ソーダを26.15ｇの水酸
化ナトリウム溶液（10.45wt％NaOH）と78.62ｇ
の水とからなる溶液に溶解し、そして67.70ｇの
水中の85.18ｇのシリカゾル（20wt％SiO2）溶液
に撹拌しながら添加して反応混合物を調製した。
この反応混合物はモル比で次の組成を有する。Example 7 0.5198g of sodium aluminate was mixed with 26.15g of sodium hydroxide solution (10.45wt% NaOH) and 78.62g
of water and added to a solution of 85.18 g of silica sol (20 wt% SiO 2 ) in 67.70 g of water with stirring to prepare a reaction mixture.
The reaction mixture has the following composition in molar ratios:
13.33Na2O・Al2O3・100.0SiO2・4590H2O
この反応混合物を１時間室温で撹拌しながら熟
成し、オートクレーブに仕込んで190℃、自生圧
にて15時間保持した後、得られた生成物を濾別
し、水洗し、110℃で16時間乾燥した。13.33Na 2 O・Al 2 O 3・100.0SiO 2・4590H 2 O This reaction mixture was aged with stirring at room temperature for 1 hour, then charged into an autoclave and kept at 190°C and autogenous pressure for 15 hours. The resulting product was filtered off, washed with water, and dried at 110°C for 16 hours.
得られた生成物はこれの粉末Ｘ線回析図から結
晶性であつた。 The obtained product was crystalline based on its powder X-ray diffraction pattern.
Claims (1)
イトの結晶が生成されるまでの時間、190℃の温
度に保持し、生成した結晶を分離回収することを
特徴とする合成結晶性アルミノシリケートゼオラ
イトの製法。[Claims] 1. A reaction mixture whose composition expressed in molar ratio of oxides is Na 2 O / SiO 2 = 0.13 H 2 O / SiO 2 = 45.90 SiO 2 /Al 2 O 3 = 40.0 to 100.0. A method for producing synthetic crystalline aluminosilicate zeolite, which comprises maintaining the temperature at 190°C until crystals of aluminosilicate zeolite are formed, and separating and collecting the formed crystals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2103983A JPS59146924A (en) | 1983-02-10 | 1983-02-10 | Production of synthetic crystalline aluminosilicate zeolite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2103983A JPS59146924A (en) | 1983-02-10 | 1983-02-10 | Production of synthetic crystalline aluminosilicate zeolite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59146924A JPS59146924A (en) | 1984-08-23 |
| JPH0343207B2 true JPH0343207B2 (en) | 1991-07-01 |
Family
ID=12043802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2103983A Granted JPS59146924A (en) | 1983-02-10 | 1983-02-10 | Production of synthetic crystalline aluminosilicate zeolite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59146924A (en) |
-
1983
- 1983-02-10 JP JP2103983A patent/JPS59146924A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59146924A (en) | 1984-08-23 |
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