JPH0568410B2 - - Google Patents
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- Publication number
- JPH0568410B2 JPH0568410B2 JP9419985A JP9419985A JPH0568410B2 JP H0568410 B2 JPH0568410 B2 JP H0568410B2 JP 9419985 A JP9419985 A JP 9419985A JP 9419985 A JP9419985 A JP 9419985A JP H0568410 B2 JPH0568410 B2 JP H0568410B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction mixture
- silica sol
- type zeolite
- silica
- ratio
- 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 - Fee Related
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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 69
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 68
- 239000010457 zeolite Substances 0.000 claims description 67
- 229910021536 Zeolite Inorganic materials 0.000 claims description 65
- 239000011541 reaction mixture Substances 0.000 claims description 60
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 36
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000008119 colloidal silica Substances 0.000 claims description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 27
- 229910004298 SiO 2 Inorganic materials 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910008828 WSiO Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 229910001683 gmelinite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 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
- 238000009776 industrial production Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明はシリカ対アルミナのモル比（以下ケイ
バン比と称す）が高く、しかも高純度なＹ型結晶
性アルミノシリケートゼオライト（以下Ｙ型ゼオ
ライトと称す）の構造方法に関する。さらに詳し
くはシリカ源としてシリカゾルを用いてＹ型ゼオ
ライトを製造するに際し、シリカゾルを２段階で
添加して特定な組成範囲にある反応混合物を調製
し、これから結晶を析出させることにより、高ケ
イバン比で高純度のＹ型ゼオライトを成形する方
法に係る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for constructing a Y-type crystalline aluminosilicate zeolite (hereinafter referred to as Y-type zeolite) which has a high silica to alumina molar ratio (hereinafter referred to as Cavan ratio) and is highly pure. More specifically, when producing Y-type zeolite using silica sol as a silica source, silica sol is added in two steps to prepare a reaction mixture with a specific composition range, and crystals are precipitated from this to produce a high C-ban ratio. The present invention relates to a method for molding high-purity Y-type zeolite.
Ｙ型ゼオライトは米国特許第313007号に記載さ
れているように、次の一般式
0.9±0.2Na2O：Al2O3：Ｗ SiO：Ｘ H2O
（ここでＷは３〜６、Ｘは９までの数である。）
で表示される。Ｙ型ゼオライトは炭化水素をクラ
ツキングや異性化する場合の触媒として、あるい
はｐ−キシレンを吸着分離する場合の吸着材とし
て今日工業的に広く使用されている。 Y-type zeolite has the following general formula 0.9±0.2Na2O: Al2O3 : WSiO : XH2O (where W is 3 to 6, is a number up to 9). Y-type zeolite is widely used industrially today as a catalyst for cracking or isomerizing hydrocarbons, or as an adsorbent for adsorbing and separating p-xylene.
一般に触媒ないしは吸着材として用いられるＹ
型ゼオライトには、耐熱性、耐水熱性、耐酸性が
要求される。しかしてこれらの性質は、ゼオライ
トのケイバン比に強く依存し、普通この比が高い
程これらの性質は優れていることが知られてい
る。こうしたことから、ケイバン比の高いＹ型ゼ
オライトの製造方法の研究に力が注がれ、これま
でにも高ケイバン比の、換言すれば高ケイ酸質で
あるＹ型ゼオライトの製造法がいくつか提案され
ている。 Y is generally used as a catalyst or adsorbent
Type zeolite is required to have heat resistance, hydrothermal resistance, and acid resistance. However, these properties strongly depend on the Cavan ratio of the zeolite, and it is known that the higher this ratio, the better these properties are. For this reason, efforts have been focused on research into methods for producing Y-type zeolite with a high C-ban ratio, and there have been several methods for producing Y-type zeolite with a high C-ban ratio, in other words, a high silicic acid content. Proposed.
シリカゾルをシリカ源にして、高ケイ酸質Ｙ型
ゼオライトを製造する先行技術としては、特公昭
38−124号公報に提案されている方法がある。 As a prior art for producing high-silicate Y-type zeolite using silica sol as a silica source,
There is a method proposed in Publication No. 38-124.
Na2O／SiO2＝0.28〜0.30
SiO2／Al2O3＝８〜10
H2O／Na2O＝30〜50またはNa2O／SiO2＝0.4
SiO2／Al2O3＝10〜27
H2O／Na2O＝30〜50
この方法は酸化物モル比で表わした組成が上記
のような反応混合物を調製し、この反応混合物を
周囲温度で保持した後、これを昇温して結晶を析
出させることにより、ケイバン比が５〜６である
Ｙ型ゼオライトを製造するものであつて、この方
法によれば、ケイバン比が5.2〜６の高ケイ酸質
Ｙ型ゼオライトを３〜８日間で製造することがで
きる。 Na2O / SiO2 =0.28~0.30 SiO2 / Al2O3 = 8 ~10 H2O / Na2O =30~50 or Na2O / SiO2 =0.4 SiO2 / Al2O3 = 10 ~27 H 2 O / Na 2 O = 30 ~ 50 This method involves preparing a reaction mixture having the above composition expressed in terms of oxide molar ratio, maintaining the reaction mixture at ambient temperature, and then raising the temperature. This method produces Y-type zeolite with a C-ban ratio of 5 to 6 by precipitating crystals. According to this method, high-silicate Y-type zeolite with a C-Ban ratio of 5.2 to 6 is It can be manufactured in ~8 days.
しかしながら、一般的には製造せんとするＹ型
ゼオライトのケイバン比を高くするためには、生
成ゼオライトのそれに比較して、かなり高いケイ
バン比の反応混合物を用意しなければならないの
が通例である。高ケイ酸質Ｙ型ゼオライトを製造
するにあたり反応混合物のケイバン比を低くする
ことは、特に工業的生産に於いては経済的効果が
大きいため、重要な問題であつた。 However, in general, in order to increase the Cylban ratio of the Y-type zeolite to be produced, it is usually necessary to prepare a reaction mixture with a considerably higher Cylban ratio compared to that of the produced zeolite. In producing high-silicic acid Y-type zeolite, lowering the C-ban ratio of the reaction mixture has been an important problem, especially in industrial production, since it has a large economic effect.
本発明者らは上記の問題点を克服すべく鋭意検
討した結果、シリカ源にシリカゾルを用いて高ケ
イ酸質Ｙ型ゼオライトを製造するに当り、シリカ
源たるシリカゾルを分割使用して所望のゼオライ
トを析出させるのに必要な反応混合物を２段階で
調製することにより、前記の従来法と同じケイバ
ン比の反応混合物から従来法よりも高ケイ酸質Ｙ
型ゼオライトを製造できることを見い出し、本発
明を完成した。 As a result of intensive studies to overcome the above-mentioned problems, the present inventors found that when producing high-silicate Y-type zeolite using silica sol as a silica source, the silica sol as a silica source is used in portions to produce the desired zeolite. By preparing the reaction mixture necessary to precipitate Y in two steps, a higher silicate Y
They discovered that it is possible to produce type zeolite, and completed the present invention.
本発明に係る高ケイ酸質Ｙ型ゼオライトの製造
法はシリカ源としてシリカゾルを用いるＹ型ゼオ
ライトの製造法において、
(a) シリカゾル、アルミナ源、アルカリ金属源及
び水を用いて次の酸化物モル比が下記の範囲に
ある第１反応混合物を調製し、
M2O／SiO2＝0.31〜0.35
SiO2／Al2O3＝7.75〜8.25
H2O／M2O＝35〜45
（ここでＭはアルカリ金属を示す）
(b) 前記第１反応混合物を室温で少なくとも10時
間保持し、
(c) 工程(b)からの第１反応混合物にシリカゾルを
新たに添加して、酸化物モル比が下記の範囲に
ある第２反応混合物を調製し、
M2O／SiO2＝0.27〜0.31
SiO2／Al2O3＝8.75〜10
H2O／M2O＝40〜50
（ここでＭはアルカリ金属を示す）
(d) 工程(c)で得られた第２反応混合物をＹ型ゼオ
ライト析出するのに十分な温度及び時間保持
し、
(e) 析出したＹ型ゼオライトを第２反応混合物か
ら回収する
ことを特徴とする。 The method for producing a high-silicate Y-type zeolite according to the present invention is a method for producing a Y-type zeolite using silica sol as a silica source. (a) Using silica sol, an alumina source, an alkali metal source, and water, A first reaction mixture having a ratio in the following range is prepared, M2O / SiO2 = 0.31-0.35 SiO2 / Al2O3 = 7.75-8.25 H2O / M2O = 35-45 (where M represents an alkali metal) (b) maintaining said first reaction mixture at room temperature for at least 10 hours; (c) adding fresh silica sol to the first reaction mixture from step (b) to increase the oxide molar ratio; Prepare a second reaction mixture in which M 2 O/SiO 2 =0.27-0.31 SiO 2 /Al 2 O 3 = 8.75-10 H 2 O/M 2 O = 40-50 (where M (indicates an alkali metal) (d) The second reaction mixture obtained in step (c) is maintained at a temperature and time sufficient to precipitate Y-type zeolite, (e) The precipitated Y-type zeolite is added to the second reaction mixture. It is characterized by being collected from.
本発明で使用されるシリカゾルは、コロイダル
シリカ粒子が水に分散した所謂ヒドロゾルであつ
て、そのシリカ濃度及び粒子径は下記の範囲１、
好ましくは範囲２で規定される。 The silica sol used in the present invention is a so-called hydrosol in which colloidal silica particles are dispersed in water, and the silica concentration and particle size are within the following ranges 1, 1,
Preferably, it is defined in range 2.
範囲１ 範囲２
シリカ濃度 20wt％以上 30wt％以上
平均粒子径 ３〜50ｍμ ３〜50ｍμ
一般にシリカゾルがシリカ粒子径３〜400ｍμ、
シリカ濃度10〜50wt％程度であるが、上記の範
囲１を逸脱したシリカゾルは、本発明ではこれを
使用しない。ちなみに、濃度が20wt％以下であ
るシリカゾルは、本発明の特定反応混合物を調製
する際の水分量の制約から使用できない。平均粒
子径が50ｍμより大きいシリカゾルは、これに分
散するコロイダルシリカの反応性が乏しいためＹ
型ゼオライトが析出しないので、他のゼオライト
種が析出しやすいので好ましくない。 Range 1 Range 2 Silica concentration 20wt% or more 30wt% or more Average particle size 3-50mμ 3-50mμ Generally, silica sol has a silica particle size of 3-400mμ,
Silica sol with a silica concentration of about 10 to 50 wt%, but outside of the above range 1, is not used in the present invention. Incidentally, silica sol having a concentration of 20 wt% or less cannot be used due to restrictions on water content when preparing the specific reaction mixture of the present invention. Y
Since zeolite type zeolite does not precipitate, other zeolite types tend to precipitate, which is not preferable.
本発明におけるシリカ源はすべてシリカゾルで
あるが、アルミナ源には、ゼオライト合成に通常
用いられるアルミン酸ナトリウム、硫酸アルミニ
ウムなどのアルミニウム塩、水酸化アルミニウ
ム、アルミナゲルなどが使用され、アルカリ金属
源には、普通よく用いられているアルカリ金属が
使用可能であるが、特に水酸化ナトリウムが好ま
しい。 All the silica sources in the present invention are silica sol, but the alumina sources include sodium aluminate, aluminum salts such as aluminum sulfate, aluminum hydroxide, alumina gel, etc., which are commonly used in zeolite synthesis, and the alkali metal sources include Although commonly used alkali metals can be used, sodium hydroxide is particularly preferred.
本発明によれば、上記のシリカ源、アルミナ
源、アルカリ金属源及び水を用いてまず第１反応
混合物が工程(a)で調製される。第１反応混合物の
組成、特にM2O／SiO2モル比およびSiO2／Al2O3
モル比は厳密なものであつて、これらのモル比が
規定した範囲を逸脱した場合には、たとえ工程(c)
でのシリカゾルの添加によつて第２反応混合物の
酸化物モル比が所定の範囲に維持されても、所望
のＹ型ゼオライトを得ることができない。すなわ
ちM2O／SiO2モル比が0.35より高い反応混合物か
ら本発明の第２反応混合物を調製すると、析出す
るＹ型ゼオライトのケイバン比は低下し、前記の
比が0.31よりも低い反応混合物から出発すると、
Ｙ型ゼオライトが析出しにくくなり、グメリナイ
トあるいはＰ型ゼオライトなどの有用でないゼオ
ライトが析出しやすい。同様にしてSiO／Al2O3
モル比に関して云えば、この比が7.75より低い反
応混合物から本発明の第２反応混合物を調製した
場合には、生成Ｙ型ゼオライトのケイバン比が低
下するとか、Ｙ型ゼオライト以外のゼオライトが
析出するとかという不都合があり、また前記の比
が8.25よりも高い場合には、生成ゼオライトのケ
イバン比に再現性が得られにくい。 According to the present invention, a first reaction mixture is first prepared in step (a) using the silica source, alumina source, alkali metal source and water described above. The composition of the first reaction mixture, in particular the M 2 O/SiO 2 molar ratio and the SiO 2 /Al 2 O 3
The molar ratios are strict, and if these molar ratios deviate from the specified range, even if step (c)
Even if the oxide molar ratio of the second reaction mixture is maintained within a predetermined range by the addition of silica sol, the desired Y-type zeolite cannot be obtained. That is, when the second reaction mixture of the present invention is prepared from a reaction mixture with a molar ratio of M 2 O / SiO 2 higher than 0.35, the Cavan ratio of the Y-type zeolite precipitated decreases, and when the second reaction mixture of the present invention is prepared from a reaction mixture with a molar ratio of M 2 O / SiO 2 lower than 0.31, Upon departure,
Y-type zeolite becomes difficult to precipitate, and unuseful zeolites such as gmelinite or P-type zeolite tend to precipitate. Similarly, SiO/Al 2 O 3
Regarding the molar ratio, if the second reaction mixture of the present invention is prepared from a reaction mixture with a lower molar ratio than 7.75, the Cavan ratio of the Y-type zeolite produced may decrease, or zeolites other than the Y-type zeolite may precipitate. Moreover, if the ratio is higher than 8.25, it is difficult to obtain reproducibility in the Cavan ratio of the produced zeolite.
工程(a)での所定の酸化物モル比に調製された第
１反応混合は、工程(b)で定温熟成されるが、この
低温熟成はＹ型ゼオライトを生成させるために極
めて重要である。本発明の低温熟成は室温で、好
ましくは25〜35℃で２〜150時間、好ましくは16
〜30時間で行われる。低温熟成された第１反応混
合物には、次の工程(c)で新たにシリカゾルが添加
され、下記のような酸化物モル比を有する第２反
応混合物が調製される。 The first reaction mixture prepared to have a predetermined oxide molar ratio in step (a) is aged at a constant temperature in step (b), and this low temperature aging is extremely important for producing Y-type zeolite. The low temperature aging of the present invention is carried out at room temperature, preferably at 25-35°C for 2-150 hours, preferably for 16
Done in ~30 hours. In the next step (c), silica sol is newly added to the first reaction mixture that has been aged at low temperature to prepare a second reaction mixture having the following oxide molar ratio.
M2O／SiO2＝0.27〜0.31
SiO2／Al2O3＝8.75〜10
H2O／M2O＝40〜50
（ここでＭはアルカリ金属を示す）
工程(c)で使用されるシリカゾルとしては、工程
(a)の場合と同様、コロイダルシリカの平均粒子径
３〜50ｍμ、シリカ濃度20wt％以上のシリカゾ
ルが選ばれる。 M 2 O/SiO 2 = 0.27 to 0.31 SiO 2 /Al 2 O 3 = 8.75 to 10 H 2 O/M 2 O = 40 to 50 (here M represents an alkali metal) used in step (c) As silica sol, process
As in the case of (a), a silica sol with an average particle size of colloidal silica of 3 to 50 mμ and a silica concentration of 20 wt% or more is selected.
所望の酸化物モル比に調製された第２反応混合
物は工程(d)において結晶生成物が析出するに十分
な温度及び時間が保持される。結晶生成物は通常
第２反応混合物を60〜105℃、好ましくは95〜100
℃で、２〜10日間、好ましくは３〜８日間保持す
ることによつて析出させることができる。結晶化
したＹ型ゼオライトは工程(e)において反応媒体か
ら濾別され、水洗されて乾燥される。 The second reaction mixture prepared to have the desired oxide molar ratio is maintained at a temperature and time sufficient to precipitate a crystalline product in step (d). The crystalline product is usually obtained by heating the second reaction mixture at 60-105°C, preferably at 95-105°C.
C. for 2 to 10 days, preferably 3 to 8 days. The crystallized Y-type zeolite is filtered from the reaction medium in step (e), washed with water and dried.
本発明の寸法によれば、第２反応混合物の
SiO2／Al2O3モル比ゼオライト合成に従来使用さ
れた反応混合物のSiO2／Al2O3モル比と同じ場合
には、従来より高ケイバン比で高純度なＹ型ゼオ
ライトを製造することができる。一般にシリカ源
にシリカゾルを使用して反応混合物を調製した場
合、多くのコロイダルシリカは反応混合物中の固
相ゲルに取り込まれ、固相のSiO2／Al2O3モル比
は液相のSiO2／Al2O3モル比に比べて著しく高
く、固相ゲルのシリカは主に結晶化に際しての高
温熟成過程で溶解し、ゼオライトの結晶化に強く
関与するとみられる。従つて固相ゲルのシリカの
溶解性が生成ゼオライトのケイバン比に影響する
ものと推定される。 According to the dimensions of the invention, the second reaction mixture
SiO 2 /Al 2 O 3 molar ratio When the SiO 2 /Al 2 O 3 molar ratio is the same as the SiO 2 /Al 2 O 3 molar ratio of the reaction mixture conventionally used for zeolite synthesis, it is possible to produce high-purity Y-type zeolite with a higher C-Van ratio than before. I can do it. Generally, when a reaction mixture is prepared using silica sol as a silica source, most of the colloidal silica is incorporated into the solid phase gel in the reaction mixture, and the solid phase SiO 2 /Al 2 O 3 molar ratio is lower than that of the liquid phase SiO 2 /Al 2 O 3 molar ratio, and the silica in the solid phase gel is mainly dissolved during the high temperature aging process during crystallization, and it seems to be strongly involved in the crystallization of zeolite. Therefore, it is presumed that the solubility of silica in the solid-phase gel influences the Cavan ratio of the produced zeolite.
本発明で高ケイバン比のゼオライトが得られる
理由は明らかではないが、前記した如く、工程(a)
及び(b)を経て得られる低温熟成された第１反応混
合物へ、新たにシリカゾルを添加して第２反応混
合物を調製するときは、液相中のシリカ濃度が高
められる結果、高温熟成過程におけるゼオライト
の成長が、高いSiO2／Al2O3モル比の液相のもと
で進行するのでケイバン比の高いゼオライトが得
られるものと推定される。 Although it is not clear why zeolite with a high Cavan ratio can be obtained in the present invention, as described above, step (a)
When preparing a second reaction mixture by newly adding silica sol to the first reaction mixture aged at low temperature obtained through (b), the silica concentration in the liquid phase is increased, and as a result, the silica concentration in the high temperature aging process is increased. It is presumed that since the growth of zeolite proceeds in a liquid phase with a high SiO 2 /Al 2 O 3 molar ratio, a zeolite with a high C-Van ratio can be obtained.
本発明の方法で得られるＹ型ゼオライトは、そ
のカチオンの少なくとも一部を、常法に従つて、
水素、水素前駆体及び周期表第族ないし第族
から選ばれるカチオン又はカチオン混合物でイオ
ン交換することがでる。本発明で得たＹ型ゼオラ
イトはケイバン比が高いため、吸着分離材、イオ
ン交換材、クラツキングや異性化などの触媒さら
には触媒担体として特に有用で工業的に広く利用
することができる。 In the Y-type zeolite obtained by the method of the present invention, at least a part of its cations are converted into
Ion exchange can be carried out with hydrogen, a hydrogen precursor, and a cation or cation mixture selected from Groups 1 to 3 of the Periodic Table. Since the Y-type zeolite obtained in the present invention has a high C-ban ratio, it is particularly useful as an adsorption/separation material, an ion exchange material, a catalyst for cracking or isomerization, and a catalyst support, and can be widely used industrially.
実施例 １
3909ｇの水酸化ナトリウム溶液（49.5wt％
NaOH）及び3549ｇの水を9252ｇのアルミ酸ソ
ーダ溶液（17.0wt％Na2O、22.0wt％Al2O3）に
撹拌しながら添加し、混合液のNa2O／Al2O3モ
ル比を約2.5とした。この溶液への分散粒子径10
〜20ｍμのシリカゾル（触媒化成工業(株)製
Cataloid Ｓ−30L、30wt％SiO2）32000ｇを撹拌
しながら添加して、下記のモル組成の第１反応混
合物を調製した。Example 1 3909g of sodium hydroxide solution (49.5wt%
NaOH) and 3549 g of water were added to 9252 g of sodium aluminate solution (17.0 wt% Na 2 O, 22.0 wt% Al 2 O 3 ) with stirring, and the Na 2 O / Al 2 O 3 molar ratio of the mixture was adjusted. It was set to about 2.5. Particle size dispersed in this solution: 10
~20mμ silica sol (manufactured by Catalysts & Chemicals Co., Ltd.)
32000 g of Cataloid S-30L, 30 wt% SiO 2 ) was added with stirring to prepare a first reaction mixture having the following molar composition.
2.6Na2：Al2O3：8SiO2：106H2O
この第１反応混合物3000ｇを30℃で106時間放
置し、次いでこれに上述したと同じシリカゾル
170ｇを撹拌しながら添加して、下記のモル組成
の第２反応混合物を調製した。2.6Na 2 :Al 2 O 3 :8SiO 2 :106H 2 O 3000 g of this first reaction mixture was left at 30° C. for 106 hours and then added with the same silica sol as described above.
170 g was added with stirring to prepare a second reaction mixture with the following molar composition.
2.63Na2：Al2O3：8.75SiO2：116H2O
この混合物を常圧95℃で87時間保持して結晶生
成物を析出させ、これを別後水洗し、110℃で
16時間乾燥した。得られた結晶生成物はＸ線回析
法及び化学分析から、ケイバン比2.9、結晶化度
108％のＹ型ゼオライトであることを確認した。2.63Na 2 :Al 2 O 3 :8.75SiO 2 :116H 2 O This mixture was kept at normal pressure at 95°C for 87 hours to precipitate a crystal product, which was separated, washed with water, and heated at 110°C.
Dry for 16 hours. X-ray diffraction and chemical analysis revealed that the obtained crystalline product had a Cavan ratio of 2.9 and a degree of crystallinity.
It was confirmed that it was 108% Y-type zeolite.
なお、Ｙ型ゼオライトの結晶化度は、（533）及
び（642）面の総ピーク面積Ｓを求め、市販のＹ
型ゼオライト（ユニオカ−バイド製 SK−40）
の場合の総ピーク面積S0を結晶化度100％として
次式から求めた。 The crystallinity of Y-type zeolite is determined by determining the total peak area S of the (533) and (642) planes, and using commercially available Y-type zeolite.
Type zeolite (Uniocarbide SK-40)
The total peak area S 0 in the case of 100% crystallinity was calculated from the following formula.
結晶化度＝100S／S0
実施例 ２
実施例１で調製した第１反応混合物3000ｇを30
℃で16時間放置し、次いでこれに実施例１で使用
したと同じシリカゾル226ｇを撹拌しながら添加
して下記のモル組成の第２反応混合物を調製し
た。 Crystallinity = 100S/S 0 Example 2 3000g of the first reaction mixture prepared in Example 1 was
C. for 16 hours, and then 226 g of the same silica sol used in Example 1 was added with stirring to prepare a second reaction mixture having the following molar composition.
2.63Na2：Al2O3：9.0SiO2：110H2O
この混合物を常圧95℃で113時間保持して結晶
生成物を析出させ、これを別後水洗し、110℃
で16時間乾燥した。得られた結晶生成物はＸ線回
折法及び化学分析から、ケイバン比6.2、結晶化
度106％のＹ型ゼオライトであることを確認した。 2.63Na 2 :Al 2 O 3 :9.0SiO 2 :110H 2 O This mixture was kept at normal pressure at 95°C for 113 hours to precipitate a crystal product, which was separated, washed with water, and heated at 110°C.
and dried for 16 hours. The obtained crystalline product was confirmed by X-ray diffraction and chemical analysis to be a Y-type zeolite with a Cavan ratio of 6.2 and a crystallinity of 106%.
実施例 ３
実施例１で調製した第１反応混合物3000ｇを30
時間で16時間放置し、次いでこれに実施例１で使
用したと同じシリカゾル283ｇを撹拌しながら添
加して、下記のモル組成の第２反応混合物を調製
した。Example 3 3000 g of the first reaction mixture prepared in Example 1 was
The mixture was allowed to stand for 16 hours, and then 283 g of the same silica sol used in Example 1 was added with stirring to prepare a second reaction mixture having the following molar composition.
2.65Na2：Al2O3：9.25SiO2：123H2O
この混合物を常圧95℃で140時間保持して結晶
生成物を析出させ、これを別後水洗し、110℃
で16時間乾燥した。得られた結晶生成物はＸ線回
折法及び化学分析から、ケイバン比6.4、結晶化
度105％のＹ型ゼオライトであることを確認した。2.65Na 2 :Al 2 O 3 :9.25SiO 2 :123H 2 O This mixture was kept at normal pressure at 95°C for 140 hours to precipitate a crystal product, which was separated, washed with water, and heated at 110°C.
and dried for 16 hours. The obtained crystalline product was confirmed by X-ray diffraction and chemical analysis to be a Y-type zeolite with a Cavan ratio of 6.4 and a crystallinity of 105%.
実施例 ４
実施例１で調製した第１反応混合物3000ｇを30
時間で16時間放置し、次いでこれに実施例１で使
用したと同じシリカゾル339ｇを撹拌しながら添
加して下記のモル組成の第２反応混合物を調製し
た。Example 4 3000 g of the first reaction mixture prepared in Example 1 was
The mixture was left to stand for 16 hours, and then 339 g of the same silica sol used in Example 1 was added with stirring to prepare a second reaction mixture having the following molar composition.
2.67Na2：Al2O3：9.5SiO2：126H2O
この混合物を常圧95℃で216時間保持して結晶
生成物を析出させ、これを別後水洗し、110℃
で16時間乾燥した。得られた結晶生成物はＸ線回
折法及び化学分析から、ケイバン比6.8、結晶化
度105％のＹ型ゼオライトであることを確認した。2.67Na 2 :Al 2 O 3 :9.5SiO 2 :126H 2 O This mixture was kept at normal pressure at 95°C for 216 hours to precipitate a crystal product, which was separated, washed with water, and heated at 110°C.
and dried for 16 hours. The obtained crystalline product was confirmed by X-ray diffraction and chemical analysis to be a Y-type zeolite with a Cavan ratio of 6.8 and a crystallinity of 105%.
比較例 １
この比較例は本発明の方法におけるシリカゾル
に関する規定が厳密なものであることを示すもの
である。Comparative Example 1 This comparative example shows that the regulations regarding silica sol in the method of the present invention are strict.
第１反応混合物の調製に際して分散粒子径80ｍ
μのシリカゾル（触媒化成工業(株)製Cataloid SI
−80P、40wt％ SiO2）を使用した以外は実施例
１と全く同様にして同一モル組成の第１及び第２
反応混合物を調製し（第２反応混合物の調製に関
しては、実施例１と同じシリカゾルを使用）、得
られた第２反応混合物を実施例１と同様に処理し
て結晶精製物を得た。この結晶生成物はＸ線回析
法によりＡ型ゼオライトであることを確認した。 When preparing the first reaction mixture, the dispersed particle size was 80 m.
μ silica sol (Catalyst Chemical Industry Co., Ltd. Cataloid SI)
-80P, 40wt% SiO 2 ) was used in the same manner as in Example 1, and the first and second
A reaction mixture was prepared (for the preparation of the second reaction mixture, the same silica sol as in Example 1 was used), and the obtained second reaction mixture was treated in the same manner as in Example 1 to obtain a crystalline purified product. This crystalline product was confirmed to be type A zeolite by X-ray diffraction.
以下の比較例２、３は、従来技術を使用した場
合、析出するＹ型ゼオライトのケイバン比が本発
明の方法に比較して低くなることを示す
比較例 ２
240.8ｇの水酸化ナトリウム溶液（49.5wt％
NaOH）及び218.6ｇの水を569.8ｇのアルミン酸
ソーダ溶液（17.0wt％Na2O、22.0wt％Al2O3）
に撹拌しながら添加し、Na2O／Al2O3モル比が
約2.5の溶液を調製した。 Comparative Examples 2 and 3 below show that when the conventional technique is used, the Cayban ratio of the precipitated Y-type zeolite is lower compared to the method of the present invention. wt%
NaOH) and 218.6 g of water to 569.8 g of sodium aluminate solution (17.0 wt% Na 2 O, 22.0 wt % Al 2 O 3 )
was added to the solution with stirring to prepare a solution with a Na 2 O/Al 2 O 3 molar ratio of about 2.5.
この溶液に実施例１で使用したシリカゾル
2140.9ｇを撹拌しながら添加して実施例１の第２
反応混合物と同一モル組成の下記の反応混合物を
調製した。 Add the silica sol used in Example 1 to this solution.
2140.9g was added with stirring to prepare the second sample of Example 1.
The following reaction mixture having the same molar composition as the reaction mixture was prepared.
2.63Na2：Al2O3：8.75SiO2：110H2O
この反応混合物を30℃で16時間放置後、95℃で
87時間保持して結晶生成物を析出させ、これを
別後水洗し、110℃で16時間乾燥した。得られた
結晶生成物はＸ線回折方法及び化学分析から、ケ
イバン比5.6、結晶化度106％のＹ型ゼオライトで
あることを確認した。2.63Na 2 :Al 2 O 3 :8.75SiO 2 :110H 2 O The reaction mixture was left at 30°C for 16 hours and then heated at 95°C.
The mixture was maintained for 87 hours to precipitate a crystalline product, which was separated, washed with water, and dried at 110°C for 16 hours. The obtained crystalline product was confirmed by X-ray diffraction method and chemical analysis to be a Y-type zeolite with a Cavan ratio of 5.6 and a crystallinity of 106%.
比較例 ３
240.8ｇの水酸化ナトリウム溶液（49.5wt％
NaOH）及び218.6ｇの水を569.8ｇのアルミン酸
ソーダ溶液（17.0wt％Na2O、22.0wt％Al2O3）
に撹拌しながら添加し、Na2O／Al2O3モル比が
約2.5の溶液を調製した。Comparative Example 3 240.8g of sodium hydroxide solution (49.5wt%
NaOH) and 218.6 g of water to 569.8 g of sodium aluminate solution (17.0 wt% Na 2 O, 22.0 wt % Al 2 O 3 )
was added to the solution with stirring to prepare a solution with a Na 2 O/Al 2 O 3 molar ratio of about 2.5.
この溶液に実施例１で使用したシリカゾル
2253.8ｇを撹拌しながら添加して実施例３の第２
反応混合物と同一モル組成の下記の反応混合物を
調製した。 Add the silica sol used in Example 1 to this solution.
2253.8g was added with stirring to prepare the second sample of Example 3.
The following reaction mixture having the same molar composition as the reaction mixture was prepared.
2.65Na2O：Al2O3：9.25SiO2：123H2O
この反応混合物を30℃で16時間放置後、95℃で
140時間保持して結晶生成物を析出させ、これを
別後水洗し、110℃で16時間乾燥した。得られ
た結晶生成物はＸ線回折方法及び化学分析から、
ケイバン比6.2、結晶化度105％のＹ型ゼオライト
であることを確認した。2.65Na 2 O: Al 2 O 3 : 9.25 SiO 2 : 123H 2 O The reaction mixture was left at 30°C for 16 hours and then at 95°C.
The mixture was held for 140 hours to precipitate a crystalline product, which was separated, washed with water, and dried at 110°C for 16 hours. The obtained crystalline product was determined by X-ray diffraction method and chemical analysis.
It was confirmed that it was a Y-type zeolite with a Cavan ratio of 6.2 and a crystallinity of 105%.
本発明の方法によれば、ゼオライトが結晶化せ
しめられる反応混合物のSiO2／Al2O3モル比が同
一であつても、高ケイバン比のＹ型ゼオライトが
得られることを明確にするため、実施例１〜４及
び比較例２、３に於ける各生成物Ｙ型ゼオライト
のケイバン比と、そのゼオライトが生成せしめら
れる反応混合物SiO2／Al2O3モル比との関係を図
面に示す。 In order to clarify that according to the method of the present invention, a Y-type zeolite with a high Cavan ratio is obtained even if the SiO 2 /Al 2 O 3 molar ratio of the reaction mixture in which the zeolite is crystallized is the same: The relationship between the Kayban ratio of each Y-type zeolite product in Examples 1 to 4 and Comparative Examples 2 and 3 and the SiO 2 /Al 2 O 3 molar ratio of the reaction mixture in which the zeolite is produced is shown in the drawing.
図面からより容易に理解できるように、本発明
の方法は、従来技術と対比して、反応混合物の
SiO2／Al2O3モル比をより低く設定してもケイバ
ン比の高いＹ型ゼオライトを製造することがで
き、従つて同じケイバン比のＹ型ゼオライトを製
造する場合、従来よりもシリカ源であるシリカゾ
ルの使用量を節減できる点で極めて大きい経済的
効果をもたらす。 As can be more easily understood from the drawings, the method of the invention, in contrast to the prior art,
Even if the SiO 2 /Al 2 O 3 molar ratio is set lower, it is possible to produce Y-type zeolite with a high C-ban ratio. Therefore, when producing Y-type zeolite with the same C-Ban ratio, it is necessary to use a silica source more than before. This has an extremely large economic effect in that the amount of silica sol used can be reduced.
図面は生成Ｙ型ゼオライトのケイバン比と、そ
のゼオライトが生成せしめられる反応混合物の
SiO2／Al2O3モル比との関係を示すグラフであ
る。
The drawing shows the Cavan ratio of the Y-type zeolite produced and the reaction mixture in which the zeolite is produced.
It is a graph showing the relationship with the SiO 2 /Al 2 O 3 molar ratio.
Claims (1)
性アルミノシリケートゼオライトの製造法におい
て、 (a) シリカゾル、アルミナ源、アルカリ金属源及
び水を用いて次の酸化物モル比を有する第１反
応混合物を調製する工程、 M2O／SiO2＝0.31〜0.35 SiO2／Al2O3＝7.75〜8.25 H2O／M2O＝35〜45 （ここでＭはアルカリ金属を示す） (b) 前記第１反応混合物を室温で少なくとも10時
間保持する工程、 (c) 工程(b)からの反応混合物にシリカゾルを追加
して次の酸化物モル比を有する第２反応混合物
を調製する工程、 M2O／SiO2＝0.27〜0.31 SiO2／Al2O3＝8.75〜10 H2O／M2O＝40〜50 （ここでＭはアルカリ金属を示す） (d) 前記第２反応混合物を結晶生成物が析出する
のに十分な温度及び時間保持する工程、 (e) 工程(d)からの反応混合物から結晶生成物を回
収する工程、 からなるＹ型結晶性アルミノシリケートゼオライ
トの製造法。 ２ 前記のシリカゾルに分散するコロイダルシリ
カの粒子径が３〜50μｍの範囲にあり、シリカゾ
ルのシリカ濃度が20wt％以上であることを特徴
とする特許請求の範囲第１項記載の方法。[Claims] 1. A method for producing a Y-type crystalline aluminosilicate zeolite using silica sol as a silica source, (a) a method for producing a Y-type crystalline aluminosilicate zeolite using silica sol, an alumina source, an alkali metal source, and water having the following oxide molar ratio: 1 Step of preparing a reaction mixture, M2O / SiO2 = 0.31 to 0.35 SiO2 / Al2O3 = 7.75 to 8.25 H2O / M2O = 35 to 45 (where M represents an alkali metal) (b) maintaining said first reaction mixture at room temperature for at least 10 hours; (c) adding silica sol to the reaction mixture from step (b) to prepare a second reaction mixture having an oxide molar ratio of Step, M2O / SiO2 = 0.27 to 0.31 SiO2 / Al2O3 = 8.75 to 10 H2O / M2O = 40 to 50 (here, M represents an alkali metal) (d) the second (e) recovering the crystalline product from the reaction mixture from step (d); Manufacturing method. 2. The method according to claim 1, wherein the particle size of the colloidal silica dispersed in the silica sol is in the range of 3 to 50 μm, and the silica concentration of the silica sol is 20 wt% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9419985A JPS61256914A (en) | 1985-05-01 | 1985-05-01 | Preparation of y type crystalline alumino-silicate zeolite having high silica content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9419985A JPS61256914A (en) | 1985-05-01 | 1985-05-01 | Preparation of y type crystalline alumino-silicate zeolite having high silica content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61256914A JPS61256914A (en) | 1986-11-14 |
| JPH0568410B2 true JPH0568410B2 (en) | 1993-09-28 |
Family
ID=14103625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9419985A Granted JPS61256914A (en) | 1985-05-01 | 1985-05-01 | Preparation of y type crystalline alumino-silicate zeolite having high silica content |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61256914A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5716593A (en) * | 1996-07-31 | 1998-02-10 | Chevron U.S.A. Inc. | Preparation of Y-type faujasite using an organic template |
-
1985
- 1985-05-01 JP JP9419985A patent/JPS61256914A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61256914A (en) | 1986-11-14 |
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