JPH0471845B2 - - Google Patents
Info
- Publication number
- JPH0471845B2 JPH0471845B2 JP58085129A JP8512983A JPH0471845B2 JP H0471845 B2 JPH0471845 B2 JP H0471845B2 JP 58085129 A JP58085129 A JP 58085129A JP 8512983 A JP8512983 A JP 8512983A JP H0471845 B2 JPH0471845 B2 JP H0471845B2
- Authority
- JP
- Japan
- Prior art keywords
- borosilicate
- catalyst
- solution
- hours
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 12
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- -1 phosphorus compound Chemical class 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Description
本発明は新規な焼成結晶性硼珪酸の製造法に関
する。
結晶性硼珪酸は特有の結晶構造を有しており、
触媒あるいは吸着材としての用途が知られてい
る。結晶性硼珪酸の触媒としての利用の１つにト
ルエンとメタノールからｐ−キシレンを製造する
方法が知られている。しかし、この反応は選択性
が十分でないため、結晶性硼珪酸に燐化合物，周
期律表第族金属などで修飾することにより改良
することが提案されている。ところが、このよう
にして改良された触媒を用いても十分に満足しう
る結果が得られていない。
このような実情に鑑み、本発明者は転化反応に
よるエチレン，ｐ−キシレンなどの有機化合物の
製造方法に有用な触媒を開発すべく検討を重ねた
結果、特定の結晶性硼珪酸をアルミナ水和ゲルま
たはその前駆体からなる結合剤と混合し、成形し
た後、700〜1000℃の温度で焼成したものが該触
媒として極めて有効であることを見出し、本発明
を完成するに至つた。
すなわち本発明は、一般式pR2/oＯ・xB2O3・
SiO2（ただし、ｐは０＜ｐ≦0.08，Ｒは水素、ア
ンモニウムイオンまたは有機アンモニウムカチオ
ンであり、ｎはＲの原子価を示し、ｘは０＜ｘ≦
0.08である。）で表わされる結晶性硼珪酸をアル
ミナ水和ゲルまたはその前駆体からなる結合材と
混合し、成形した後、700〜1000℃の温度で焼成
することを特徴とする焼成結晶性硼珪酸の製造法
を提供するものである。
本発明の方法により得られる焼成結晶性硼珪酸
は新規なものであり、有機化合物の転化反応、特
にエチレンとｐ−キシレンを同時に効率よく製造
する方法の触媒として極めて有用である。
本発明において原料として用いる結晶性硼珪酸
は一般式pR2/oＯ・xB2O3・SiO2（ただし、ｐは０
＜ｐ≦0.08，Ｒは水素、アンモニウムイオンまた
は有機アンモニウムカチオンであり、ｎはＲの原
子価を示し、ｘは０＜ｘ≦0.08である。）で表わ
されるものであり、具体的には特開昭53−55500
号公報，同55−7598号公報，同56−84313号公報，
同57−123817号公報，同57−129820号公報などに
記載されている結晶性硼珪酸を挙げることができ
る。これらの硼珪酸は各種の方法で調製すること
が可能であるが、一般的には次のような方法によ
り調製される。まずはじめに、硼酸，濃硫酸およ
びテトラプロピルアンモニウムプロマイドを含む
水溶液（溶液Ａ）、酸化珪素，酸化ナトリウムお
よび水からなる水溶液（溶液Ｂ）および塩化ナト
リウム水溶液（溶液Ｃ）をそれぞれ調製し、次い
で溶液Ａと溶液Ｂを溶液Ｃに滴下し、必要に応じ
て混合液のPHを８〜11に調製したのち、オートク
レープ中で加熱する。その後、冷却，洗浄，乾燥
および必要に応じて焼成することにより結晶性硼
珪酸ナトリウムが得られる。この結晶性硼珪酸ナ
トリウムを硝酸アンモニウム水溶液と処理するこ
とによりアンモニウム型の硼珪酸が得られる。こ
のようにして得られる結晶性硼珪酸は粉末状であ
る。
本発明では上記結晶性硼珪酸を700〜1000℃の
温度で焼成することが必要である。その場合、焼
成前に該硼珪酸をアルミナ水和ゲルまたはその前
駆体からなる結合剤と混合し、成形する。焼成は
上記温度で10分〜1000時間、好ましくは２〜100
時間行なうが、不活性ガス，水蒸気，酸素含有ガ
ス等の存在下で行なうことが望ましい。なお、こ
の焼成については、後記実施例に示したように、
予め350〜550℃、好適には450〜550℃の温度で予
備的に焼成しておくことにより一層すぐれた焼成
結晶性硼珪酸を得ることができる。
このようにて得られた焼成結晶性硼珪酸は有機
化合物の転化反応を行なうときの触媒として極め
て有用であり、代表的な反応はメタノールおよ
び／またはジメチルエーテルとトルエンを反応さ
せてエチレンを主成分とするオレフイン混合物お
よびｐ−キシレンを主成分とする芳香族炭化水素
を製造する方法である。この反応は流通式、バツ
チ式のいずれの方式によつても行なうことがで
き、エチレンを高濃度に、かつｐ−キシレンを高
い選択率で製造することができる。上記焼成結晶
性硼珪酸の存在下、メタノールおよび／またはジ
メチルエーテルとトルエンを転化反応せしめると
きの条件については適宜定めればよいが、通常は
反応温度400〜700℃、好ましくは450〜650℃、圧
力常圧〜10気圧、好ましくは常圧〜５気圧にて重
量空間速度（WHSV）は0.5〜20hr-1、好ましく
は１〜10hr-1とする。また、メタノールおよび／
またはジメチルエーテルとトルエンの使用割合に
ついては前者／後者（モル比）＝10/1〜1/10、好
ましくは2/1〜1/4が適当である。
上記の転化方法では、エチレンを主成分とする
オレフイン混合物がガス状物として得られ、ｐ−
キシレンを主成分とする芳香族炭化水素は液状物
として得られる。なお、本発明の焼成結晶性硼珪
酸は、上記の如き触媒としての用途のほか各種触
媒の担体や吸着剤等としても有用である。
次に、本発明を実施例により詳しく説明する。
製造例（結晶性硼珪酸の製造）
硼酸1.34ｇ，濃硫酸17.68ｇおよびテトラプロ
ピルアンモニウムプロマイド26.32ｇを水250mlに
加えた溶液Ａと、水ガラス（組成酸化珪素28.95
重量％，酸化ナトリウム9.40重量％，水61.65重
量％）211.1ｇを水250mlに加えた溶液Ｂをそれぞ
れ調製した。次いで、溶液ＡおよびＢを、塩化ナ
トリウム79.0ｇを水122mlに加えてなる溶液に室
温にて10分間にわたつて同時に滴下した。得られ
た混合液は硫酸を用いてPH9.5に調製した。さら
に、この溶液をオートクレープに入れて反応温度
170℃で20時間加熱処理した。冷却下、オートク
レープ内容物を濾過し、得られた固形物を洗浄し
た後、120℃で６時間乾燥した。さらに、550℃で
８時間焼成することにより結晶性硼珪酸ナトリウ
ム50ｇが得られた。
次に、この結晶性硼珪酸ナトリウム30ｇを５倍
重量の１規定硝酸アンモニウム水溶液に加え８時
間還流した。その後、冷却，静置して上澄み液を
デカンテーシヨンにより除いた。還流，デカンテ
ーシヨンの操作を３回繰り返した後、内容物を濾
過，洗浄し、120℃で10時間乾燥してアンモニウ
ム型硼珪酸29.5ｇを得た。
実施例１および比較例
製造例により得た結晶性硼珪酸にアルミナ含量
が20重量％（乾燥した成形品として）となるよう
にアルミナゾルを加え、成形したのち120℃で14
時間乾燥処理を行ない触媒成形物を得た。
この成形物を550℃で６時間空気焼成した（こ
の焼成物を触媒Ｅと称する。）。しかる後、焼成温
度をさらに上げ900℃，1000℃または1200℃で４
時間焼成して３種類の触媒Ａ，ＢおよびＣを得
た。
実施例 ２
実施例１で得た触媒Ｅをさらに水蒸気気流中に
て900℃で４時間処理し、触媒Ｄを得た。
参考例 １
常圧固定床流通式反応管に触媒Ａまたは触媒Ｅ
を２ｇ充填し、反応温度600℃に保ち
WHSV9.2hr-1，トルエンとメタノールを２：１
（モル比）の割合で導入して転化反応を行なつた。
反応開始後３時間の結果を第１表に示す。
The present invention relates to a novel method for producing calcined crystalline borosilicate. Crystalline borosilicate has a unique crystal structure,
It is known to be used as a catalyst or adsorbent. One known method of using crystalline borosilicate as a catalyst is to produce p-xylene from toluene and methanol. However, since this reaction does not have sufficient selectivity, it has been proposed to improve the reaction by modifying crystalline borosilicate with a phosphorus compound, a group metal of the periodic table, etc. However, even with the use of catalysts improved in this way, fully satisfactory results have not been obtained. In view of these circumstances, the present inventor conducted repeated studies to develop a catalyst useful for the production method of organic compounds such as ethylene and p-xylene through a conversion reaction. The present inventors have discovered that a mixture of a gel or a binder made of a gel or its precursor, molded, and then calcined at a temperature of 700 to 1000°C is extremely effective as the catalyst, leading to the completion of the present invention. That is, the present invention provides the general formula pR 2/o O・xB 2 O 3・
SiO 2 (where p is 0<p≦0.08, R is hydrogen, ammonium ion, or organic ammonium cation, n is the valence of R, and x is 0<x≦
It is 0.08. ) is mixed with a binder consisting of hydrated alumina gel or its precursor, molded, and then fired at a temperature of 700 to 1000°C. It provides law. The calcined crystalline borosilicate obtained by the method of the present invention is novel and extremely useful as a catalyst for conversion reactions of organic compounds, particularly for methods for efficiently producing ethylene and p-xylene simultaneously. The crystalline borosilicate used as a raw material in the present invention has the general formula pR 2/o O・xB 2 O 3・SiO 2 (where p is 0
<p≦0.08, R is hydrogen, ammonium ion or organic ammonium cation, n indicates the valence of R, and x satisfies 0<x≦0.08. ), specifically, JP-A-53-55500.
Publication No. 55-7598, Publication No. 56-84313,
Examples include crystalline borosilicate described in Publications No. 57-123817 and No. 57-129820. Although these borosilicate acids can be prepared by various methods, they are generally prepared by the following method. First, an aqueous solution containing boric acid, concentrated sulfuric acid, and tetrapropylammonium bromide (solution A), an aqueous solution containing silicon oxide, sodium oxide, and water (solution B), and an aqueous sodium chloride solution (solution C) were prepared, and then solution A and solution B are added dropwise to solution C, and the pH of the mixture is adjusted to 8 to 11 as required, and then heated in an autoclave. Thereafter, crystalline sodium borosilicate is obtained by cooling, washing, drying and, if necessary, baking. By treating this crystalline sodium borosilicate with an aqueous ammonium nitrate solution, ammonium-type borosilicate is obtained. The crystalline borosilicate thus obtained is in powder form. In the present invention, it is necessary to sinter the crystalline borosilicate at a temperature of 700 to 1000°C. In that case, before firing, the borosilicate is mixed with a binder consisting of alumina hydrate gel or its precursor and shaped. Firing is performed at the above temperature for 10 minutes to 1000 hours, preferably 2 to 100 hours.
It is preferably carried out in the presence of an inert gas, water vapor, oxygen-containing gas, etc. Regarding this firing, as shown in the examples below,
By preliminarily calcining at a temperature of 350 to 550°C, preferably 450 to 550°C, even better calcined crystalline borosilicate can be obtained. The calcined crystalline borosilicate obtained in this way is extremely useful as a catalyst for conversion reactions of organic compounds, and a typical reaction is to react methanol and/or dimethyl ether with toluene to produce ethylene as the main component. This is a method for producing an olefin mixture containing p-xylene and an aromatic hydrocarbon containing p-xylene as a main component. This reaction can be carried out either by a flow system or a batch system, and can produce ethylene at a high concentration and p-xylene at a high selectivity. The conditions for the conversion reaction of methanol and/or dimethyl ether with toluene in the presence of the calcined crystalline borosilicate may be determined as appropriate, but usually the reaction temperature is 400 to 700°C, preferably 450 to 650°C, and the pressure is The weight hourly space velocity (WHSV) is 0.5 to 20 hr -1 , preferably 1 to 10 hr -1 at normal pressure to 10 atm, preferably normal pressure to 5 atm. Also, methanol and/or
As for the ratio of dimethyl ether and toluene used, the former/latter (molar ratio) is suitably 10/1 to 1/10, preferably 2/1 to 1/4. In the above conversion process, an olefin mixture based on ethylene is obtained as a gaseous product, p-
Aromatic hydrocarbons containing xylene as a main component are obtained as a liquid. The calcined crystalline borosilicate of the present invention is useful not only as a catalyst as described above but also as a carrier for various catalysts, an adsorbent, and the like. Next, the present invention will be explained in detail with reference to examples. Production example (production of crystalline borosilicate) Solution A in which 1.34 g of boric acid, 17.68 g of concentrated sulfuric acid, and 26.32 g of tetrapropylammonium bromide were added to 250 ml of water, and water glass (composition: silicon oxide 28.95
Solution B was prepared by adding 211.1 g of sodium oxide (9.40 wt.%, water 61.65 wt.%) to 250 ml of water. Solutions A and B were then simultaneously added dropwise to a solution of 79.0 g of sodium chloride in 122 ml of water at room temperature over 10 minutes. The resulting mixed solution was adjusted to pH 9.5 using sulfuric acid. Furthermore, this solution was placed in an autoclave and the reaction temperature was
Heat treatment was performed at 170°C for 20 hours. While cooling, the contents of the autoclave were filtered, and the resulting solid was washed and dried at 120° C. for 6 hours. Further, 50 g of crystalline sodium borosilicate was obtained by firing at 550° C. for 8 hours. Next, 30 g of this crystalline sodium borosilicate was added to 5 times the weight of a 1N aqueous ammonium nitrate solution and refluxed for 8 hours. Thereafter, the mixture was cooled and allowed to stand, and the supernatant liquid was removed by decantation. After repeating the reflux and decantation operations three times, the contents were filtered, washed, and dried at 120° C. for 10 hours to obtain 29.5 g of ammonium-type borosilicate. Example 1 and Comparative Example Alumina sol was added to the crystalline borosilicate obtained in the production example so that the alumina content was 20% by weight (as a dry molded product), and after molding, it was heated at 120°C for 14 hours.
A catalyst molded article was obtained by performing a drying treatment for a period of time. This molded product was air fired at 550°C for 6 hours (this fired product is referred to as catalyst E). After that, the firing temperature was further increased to 900℃, 1000℃ or 1200℃ for 4 hours.
Three types of catalysts A, B and C were obtained by firing for a period of time. Example 2 Catalyst E obtained in Example 1 was further treated at 900° C. for 4 hours in a steam stream to obtain catalyst D. Reference example 1 Catalyst A or catalyst E in a normal pressure fixed bed flow reaction tube
Filled with 2g of and kept the reaction temperature at 600℃.
WHSV9.2hr -1 , toluene and methanol 2:1
(molar ratio) to carry out the conversion reaction.
Table 1 shows the results 3 hours after the start of the reaction.
【表】
＊ 比較例
参考例 ２
常圧固定床流通式反応管に所定の触媒を２ｇ充
填し、反応温度を600℃に保ちWHSV9.2hr-1，ト
ルエンとメタノールを４：１（モル比）の割合で
導入して転化反応を行なつた。反応開始後３時間
の結果を第２表に示す。[Table] * Comparative Example Reference Example 2 A normal pressure fixed bed flow reaction tube was filled with 2g of the specified catalyst, the reaction temperature was maintained at 600℃, WHSV9.2hr -1 , and toluene and methanol were mixed at 4:1 (molar ratio). The conversion reaction was carried out by introducing at a ratio of . Table 2 shows the results 3 hours after the start of the reaction.
【表】
＊ 比較例
[Table] * Comparative example
Claims (1)
０＜ｐ≦0.08，Ｒは水素、アンモニウムイオンま
たは有機アンモニウムカチオンであり、ｎはＲの
原子価を示し、ｘは０＜ｘ≦0.08である。）で表
わされる結晶性硼珪酸をアルミナ水和ゲルまたは
その前駆体からなる結合剤と混合し、成形した
後、700〜1000℃の温度で焼成することを特徴と
する焼成結晶性硼珪酸の製造法。1 General formula pR 2/o O・xB 2 O 3・SiO 2 (where p is 0<p≦0.08, R is hydrogen, ammonium ion or organic ammonium cation, n indicates the valence of R, is 0 < A method for producing calcined crystalline borosilicate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58085129A JPS59213441A (en) | 1983-05-17 | 1983-05-17 | Conversion catalyst for organic compound, its preparation and process for preparing organic compound using said catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58085129A JPS59213441A (en) | 1983-05-17 | 1983-05-17 | Conversion catalyst for organic compound, its preparation and process for preparing organic compound using said catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59213441A JPS59213441A (en) | 1984-12-03 |
| JPH0471845B2 true JPH0471845B2 (en) | 1992-11-16 |
Family
ID=13850037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58085129A Granted JPS59213441A (en) | 1983-05-17 | 1983-05-17 | Conversion catalyst for organic compound, its preparation and process for preparing organic compound using said catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59213441A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2746790A1 (en) * | 1976-10-18 | 1978-04-20 | Standard Oil Co | CRYSTALLINE BORSILICATE (AMS-1B) AND THE METHOD OF USING THEREOF |
| JPS557598A (en) * | 1978-06-22 | 1980-01-19 | Snam Progetti | Silicon based synthetic substance and method |
| JPS5576825A (en) * | 1978-11-30 | 1980-06-10 | Stamicarbon | Conversion of dimethylether |
| US4292457A (en) * | 1978-04-18 | 1981-09-29 | Standard Oil Company (Indiana) | Alkylation of aromatic hydrocarbons |
-
1983
- 1983-05-17 JP JP58085129A patent/JPS59213441A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2746790A1 (en) * | 1976-10-18 | 1978-04-20 | Standard Oil Co | CRYSTALLINE BORSILICATE (AMS-1B) AND THE METHOD OF USING THEREOF |
| US4292457A (en) * | 1978-04-18 | 1981-09-29 | Standard Oil Company (Indiana) | Alkylation of aromatic hydrocarbons |
| JPS557598A (en) * | 1978-06-22 | 1980-01-19 | Snam Progetti | Silicon based synthetic substance and method |
| JPS5576825A (en) * | 1978-11-30 | 1980-06-10 | Stamicarbon | Conversion of dimethylether |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59213441A (en) | 1984-12-03 |
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