JPH0672904A - Production of tertiary olefin - Google Patents
Production of tertiary olefinInfo
- Publication number
- JPH0672904A JPH0672904A JP4252186A JP25218692A JPH0672904A JP H0672904 A JPH0672904 A JP H0672904A JP 4252186 A JP4252186 A JP 4252186A JP 25218692 A JP25218692 A JP 25218692A JP H0672904 A JPH0672904 A JP H0672904A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- tertiary
- isobutylene
- tertiary olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、第３級オレフィンの製
造法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a tertiary olefin.
【０００２】[0002]
【従来の技術】アルキル第３級アルキルエーテルを酸触
媒の存在下で分解すると、主として相当する第３級オレ
フィンを生じることは特開昭５５−２６９５号、同５７
−１３４４２１号、同５９−１０５２８号、同５９−１
５７０３７号及び特開平２−５３７３９号各公報等に数
多く報告されている。例えば、メチル第３級ブチルエー
テル（以下、ＭＴＢＥという。）は分解すると主生成物
としての第３級オレフィンであるイソブチレン及びアル
キルアルコールであるメタノールを生じるが、また、副
生成物として、イソブチレンの二量体、三量体やジメチ
ルエーテル等を生じる場合が多い。このため得られたイ
ソブチレンを工業原料として使用する場合、副生成物を
除去するため、高純度に分離精製する必要がある。2. Description of the Related Art When an alkyl tertiary alkyl ether is decomposed in the presence of an acid catalyst, a corresponding tertiary olefin is mainly produced, as disclosed in JP-A-55-2695 and 57-57.
-134421, 59-10528, 59-1
Many reports have been made in Japanese Patent Laid-Open No. 57037 and Japanese Unexamined Patent Publication No. 2-53739. For example, methyl tertiary butyl ether (hereinafter referred to as MTBE) decomposes to produce isobutylene which is a tertiary olefin as a main product and methanol which is an alkyl alcohol, but dimer of isobutylene as a by-product. It often produces the body, trimer and dimethyl ether. Therefore, when the obtained isobutylene is used as an industrial raw material, it is necessary to separate and purify it in high purity in order to remove by-products.
【０００３】従って、アルキル第３級アルキルエーテル
の分解反応を高い変化率（供給した原料に対する反応し
た原料の割合）で行い、且つ、第３級オレフィンを高い
選択率（反応した原料に対する生成した生成物の割合）
で得る方法の出現が望まれている。Therefore, the decomposition reaction of the alkyl tertiary alkyl ether is carried out at a high rate of change (the ratio of the reacted raw material to the fed raw material), and the tertiary olefin is produced at a high selectivity (generated to the reacted raw material). Ratio of things)
The emergence of a method of obtaining in.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的とすると
ころは、アルキル第３級アルキルエーテルの分解反応を
高い変化率で行い、且つ、第３級オレフィンを高い選択
率で得ることにある。An object of the present invention is to carry out a decomposition reaction of an alkyl tertiary alkyl ether at a high conversion rate and to obtain a tertiary olefin at a high selectivity.
【０００５】[0005]
【課題を解決するための手段】本発明は、アルキル第３
級アルキルエーテルを分解して相当する第３級オレフィ
ンを製造する方法に於て、該分解反応を組成式 Ｓｉa Ａｌb Ｚｒc Ｘd Ｏe （ここで、Ｓｉ、Ａｌ、Ｚｒ及びＯはそれぞれケイ素、
アルミニウム、ジルコニウム及び酸素を表し、Ｘはナト
リウム、カリウム、セシウム、セリウム、亜鉛、マグネ
シウム及びカルシウムからなる群より選ばれた少なくと
も１種の元素を示す。ただし、ａ、ｂ、ｃ、ｄ及びｅは
各元素の原子比率を表し、ａ＝１のとき、ｂ＝０．０１
〜１、ｃ＝０．００１〜１、ｄ＝０．００１〜１であ
り、ｅは前記各成分の原子価を満足するのに必要な酸素
原子数である。）で示される組成を有し、かつ、該組成
物を５００〜１１００℃で熱処理して得られた触媒の存
在下で反応を行うことを特徴とする第３級オレフィンの
製造法にある。SUMMARY OF THE INVENTION The present invention provides an alkyl tertiary
In the method for producing a corresponding tertiary olefin by decomposing a primary alkyl ether, the decomposition reaction is carried out by the compositional formula Si a Al b Zr c X d O e (wherein Si, Al, Zr and O are respectively Silicon,
It represents aluminum, zirconium and oxygen, and X represents at least one element selected from the group consisting of sodium, potassium, cesium, cerium, zinc, magnesium and calcium. However, a, b, c, d and e represent the atomic ratio of each element, and when a = 1, b = 0.01
˜1, c = 0.001 to 1, d = 0.001 to 1, and e is the number of oxygen atoms required to satisfy the valence of each component. ), And carrying out the reaction in the presence of a catalyst obtained by heat-treating the composition at 500 to 1100 ° C., a process for producing a tertiary olefin.
【０００６】更に本発明は、上記の熱処理後の触媒に、
硫酸アルミニウムを触媒重量に対し３０重量％以下添加
し、更に５００〜１１００℃で熱処理して得られた触媒
の存在下でアルキル第３級アルキルエーテルの分解反応
を行う方法を包含する。The present invention further provides a catalyst after the above heat treatment,
A method of decomposing an alkyl tertiary alkyl ether in the presence of a catalyst obtained by adding 30% by weight or less of aluminum sulfate to the weight of the catalyst and further heat-treating at 500 to 1100 ° C is included.
【０００７】本発明に用いられるアルキル第３級アルキ
ルエーテルの具体例としては、例えばＭＴＢＥ、メチル
第３級アミルエーテル（以下、ＭＴＡＥという。）、エ
チル第３級ブチルエーテル（以下、ＥＴＢＥとい
う。）、エチル第３級アルミエーテル（以下、ＥＴＡＥ
という。）等が挙げられる。Specific examples of the alkyl tertiary alkyl ether used in the present invention include MTBE, methyl tertiary amyl ether (hereinafter referred to as MTAE), ethyl tertiary butyl ether (hereinafter referred to as ETBE), and the like. Ethyl tertiary aluminum ether (hereinafter ETAE
Say. ) And the like.
【０００８】本発明で得られる第３級オレフィンとして
は、原料としてＭＴＢＥを用いた場合にはイソブチレン
及びメタノール、ＭＴＡＥの場合にはイソプレン及びメ
タノール、ＥＴＢＥの場合にはイソブチレン及びエタノ
ール、ＥＴＡＥの場合にはイソプレン及びエタノールで
ある。The tertiary olefins obtained in the present invention include isobutylene and methanol when MTBE is used as a raw material, isoprene and methanol when MTBE, isobutylene and ethanol when ETBE, and isobutylene and ethanol in the case of ETAE. Is isoprene and ethanol.
【０００９】本発明に於て使用される触媒は、前記で示
される組成式を有する触媒であり、該触媒の原料および
調製方法は特に限定はなく、公知の方法が利用できる。
調製法の具体例としては沈澱法、共沈法、混練法、担持
法等が挙げられる。The catalyst used in the present invention is a catalyst having the composition formula shown above, and the starting material and preparation method of the catalyst are not particularly limited, and known methods can be used.
Specific examples of the preparation method include a precipitation method, a coprecipitation method, a kneading method, and a supporting method.
【００１０】本発明に於ては、ケイ素、アルミニウム、
ジルコニウム及びＸ成分を含む熱処理後の触媒に、硫酸
アルミニウムを該熱処理触媒に対し３０重量％以下、好
ましくは２〜２５重量％添加したものを用いると反応成
績が一層向上する。この場合、硫酸アルミニウムの添加
量が２重量％未満では添加効果は小さく、また、３０重
量％を超えると反応成績が悪くなる。In the present invention, silicon, aluminum,
When a catalyst containing zirconium and a component X after heat treatment and containing aluminum sulfate in an amount of 30% by weight or less, preferably 2 to 25% by weight, is used, the reaction result is further improved. In this case, if the amount of aluminum sulfate added is less than 2% by weight, the effect of addition is small, and if it exceeds 30% by weight, the reaction results deteriorate.
【００１１】触媒の形状は、円柱状成型品、円筒状成型
品、破砕品、粉体、担持品等いずれでも利用可能であ
り、目的により任意に選択することができる。The shape of the catalyst may be any of a cylindrical molded product, a cylindrical molded product, a crushed product, a powdered product, a supported product, etc., and can be arbitrarily selected according to the purpose.
【００１２】触媒の熱処理温度は、硫酸アルミニウム未
添加触媒、硫酸アルミニウム添加触媒、何れも５００〜
１１００℃、特に５５０〜１０５０℃の温度範囲が好ま
しい。熱処理温度が５００℃未満では十分に触媒を焼成
できないため、選択率が悪くなる。また、１１００℃を
超えると触媒の比表面積が減少し、触媒の活性低下を引
き起こす。The heat treatment temperature of the catalyst is 500 to 500 for both aluminum sulfate-free catalyst and aluminum sulfate-added catalyst.
A temperature range of 1100 ° C, especially 550 to 1050 ° C, is preferred. If the heat treatment temperature is lower than 500 ° C., the catalyst cannot be sufficiently calcined, and the selectivity becomes poor. On the other hand, if the temperature exceeds 1100 ° C, the specific surface area of the catalyst decreases, causing a decrease in catalyst activity.
【００１３】本発明を実施する場合の反応方法には特に
限定はなく、公知の手段が利用される。具体例として固
定床方式、移動床方式、流動床方式などが挙げられる
が、操作上の点からは固定床方式が好ましい。反応条件
としては特に限定はなく、従来公知の条件が採用され
る。通常、反応温度１４０〜４００℃、ＬＨＳＶ（触媒
体積に対し１時間当りに供給される液体原料の体積割
合）０．１〜１００ｈ-1、反応圧力は常圧〜２０ｋｇ／
ｃｍ2 の範囲で実施される。また、原料気体中には窒
素、ヘリウム等の不活性ガス、水蒸気等を同伴してもよ
い。特に、水蒸気を同伴させると触媒寿命が長くなる利
点を有する。The reaction method for carrying out the present invention is not particularly limited, and known means can be used. Specific examples include a fixed bed system, a moving bed system, a fluidized bed system, and the like, but the fixed bed system is preferable from the viewpoint of operation. The reaction conditions are not particularly limited, and conventionally known conditions are adopted. Usually, the reaction temperature is 140 to 400 ° C., LHSV (volume ratio of liquid raw material supplied per hour to catalyst volume) 0.1 to 100 h −1 , reaction pressure is normal pressure to 20 kg /
It is performed in the range of cm 2 . Further, the raw material gas may be accompanied by an inert gas such as nitrogen or helium, water vapor or the like. In particular, entrainment of water vapor has the advantage of prolonging the catalyst life.
【００１４】本発明において使用される触媒は、反応分
解物による炭素析出の割合が少ないため、長期に亘って
安定に反応を維持することができる。しかしながら、触
媒の持つ寿命には限度がある。そこで、失活した触媒に
は公知の再生法を適用して再び使用することができる。
このような再生方法としては、例えば、空気や空気及び
水蒸気等の流通下３００〜１０００℃で熱処理する方法
が挙げられる。Since the catalyst used in the present invention has a small carbon deposition rate due to the reaction decomposition product, the reaction can be stably maintained over a long period of time. However, the life of the catalyst is limited. Therefore, the deactivated catalyst can be reused by applying a known regeneration method.
Examples of such a regeneration method include a method of heat treatment at 300 to 1000 ° C. under the flow of air or air and water vapor.
【００１５】[0015]
【実施例】以下、本発明を実施例、比較例により説明す
る。説明中「部」とあるのは重量部を意味する。なお、
分析はガスクロマトグラフィーにより行った。 実施例１ 日揮化学（株）製シリカアルミナ（商品名Ｎ−６３１
Ｌ）１００部を、酸化塩化ジルコニウム・８水和物５
１．３部及び炭酸ナトリウム５．４部に水１５０部を加
えて調製した水溶液に含浸後、蒸発乾固し、９００℃で
熱処理することにより触媒を調製した。EXAMPLES The present invention will be described below with reference to examples and comparative examples. In the description, “part” means part by weight. In addition,
The analysis was performed by gas chromatography. Example 1 Silica-Alumina (trade name N-631, manufactured by JGC Chemical Co., Ltd.)
L) 100 parts of zirconium oxide chloride octahydrate 5
A catalyst was prepared by impregnating an aqueous solution prepared by adding 150 parts of water to 1.3 parts and 5.4 parts of sodium carbonate, evaporating to dryness, and heat-treating at 900 ° C.
【００１６】こうして得られた触媒の組成は式 Ｓｉ1 Ａｌ0.18Ｚｒ0.11Ｎａ0.07Ｏe で表される。式中、酸素の原子比率ｅは他の元素の原子
価により自然に決まる値であるので以下記載を省略す
る。この触媒を２３０℃に保持したステンレス製の反応
管に充填し、原料となるＭＴＢＥをＬＨＳＶ３ｈ-1で気
化器に供給し、気化したＭＴＢＥを反応器に導入するこ
とにより分解反応を行った。その結果、ＭＴＢＥの変化
率は９９．３％、イソブチレンの選択率は９９．８％
で、メタノールは定量的に得られた。又、イソブチレン
二量体の選択率は０．２％、ジメチルエーテルの副生は
認められなかった。The composition of the catalyst thus obtained is represented by the formula Si 1 Al 0.18 Zr 0.11 Na 0.07 O e . In the formula, the atomic ratio e of oxygen is a value that is naturally determined by the valences of other elements, and therefore the description thereof is omitted below. This catalyst was filled in a stainless steel reaction tube kept at 230 ° C., MTBE as a raw material was supplied to a vaporizer with LHSV3h −1 , and vaporized MTBE was introduced into the reactor to carry out a decomposition reaction. As a result, the MTBE change rate was 99.3% and the isobutylene selectivity was 99.8%.
Thus, methanol was obtained quantitatively. Further, the selectivity of isobutylene dimer was 0.2%, and no by-product of dimethyl ether was observed.
【００１７】実施例２ 実施例１で、触媒熱処理温度を７００℃に変えた外は同
様にして、実施例１と同一組成の触媒を得た。この触媒
を用いて、実施例１と同様にして反応を行った。その結
果、ＭＴＢＥの変化率は９９．３％、イソブチレンの選
択率は９９．８％で、メタノールは定量的に得られた。Example 2 A catalyst having the same composition as in Example 1 was obtained in the same manner as in Example 1, except that the catalyst heat treatment temperature was changed to 700 ° C. Using this catalyst, a reaction was performed in the same manner as in Example 1. As a result, the change rate of MTBE was 99.3%, the selectivity of isobutylene was 99.8%, and methanol was obtained quantitatively.
【００１８】実施例３ 実施例１で、触媒熱処理温度を８００℃に変えた外は同
様にして、実施例１と同一組成の触媒を得た。この触媒
を用いて、実施例１と同様にして反応を行った。その結
果、ＭＴＢＥの変化率は９９．３％、イソブチレンの選
択率は９９．９％で、メタノールは定量的に得られた。Example 3 A catalyst having the same composition as in Example 1 was obtained in the same manner as in Example 1, except that the catalyst heat treatment temperature was changed to 800 ° C. Using this catalyst, a reaction was performed in the same manner as in Example 1. As a result, the MTBE change rate was 99.3%, the isobutylene selectivity was 99.9%, and methanol was obtained quantitatively.
【００１９】実施例４〜８ 実施例１に準じて下記の触媒を調製した。 実施例４ Ｓｉ1 Ａｌ0.18Ｚｒ0.11Ｋ0.07 実施例５ Ｓｉ1 Ａｌ0.18Ｚｒ0.11Ｃｓ0.04Ｃａ0.04 実施例６ Ｓｉ1 Ａｌ0.18Ｚｒ0.05Ｃｅ0.04 実施例７ Ｓｉ1 Ａｌ0.18Ｚｒ0.21Ｚｎ0.07 実施例８ Ｓｉ1 Ａｌ0.18Ｚｒ0.21Ｍｇ0.07 これらの触媒を用いて、実施例１と同様にして反応を行
った。その結果を表１に示す。いずれの場合も、メタノ
ールは定量的に得られた。Examples 4 to 8 The following catalysts were prepared according to Example 1. Example 4 Si 1 Al 0.18 Zr 0.11 K 0.07 Example 5 Si 1 Al 0.18 Zr 0.11 Cs 0.04 Ca 0.04 Example 6 Si 1 Al 0.18 Zr 0.05 Ce 0.04 Example 7 Si 1 Al 0.18 Zr 0.21 Zn 0.07 Example 8 Si 1 Al 0.18 Zr 0.21 Mg 0.07 A reaction was carried out in the same manner as in Example 1 using these catalysts. The results are shown in Table 1. In each case, methanol was obtained quantitatively.
【００２０】[0020]
【表１】 [Table 1]
【００２１】実施例９ 実施例１により調製した触媒に硫酸アルミニウムを２０
重量％添加し、更に９００℃で熱処理することにより触
媒を調製した。この触媒を用いて、実施例１と同様にし
て反応を行った。その結果、ＭＴＢＥの変化率は９９．
６％、イソブチレンの選択率は９９．８％で、メタノー
ルは定量的に得られた。Example 9 20% aluminum sulfate was added to the catalyst prepared in Example 1.
A catalyst was prepared by adding wt% and heat-treating at 900 ° C. Using this catalyst, a reaction was performed in the same manner as in Example 1. As a result, the rate of change in MTBE is 99.
6%, isobutylene selectivity 99.8%, methanol was obtained quantitatively.
【００２２】実施例１０ 実施例１により調製した触媒に硫酸アルミニウムを１０
重量％添加し、更に９００℃で熱処理することにより触
媒を調製した。この触媒を用いて、実施例１と同様にし
て反応を行った。その結果、ＭＴＢＥの変化率は９９．
５％、イソブチレンの選択率は９９．９％で、メタノー
ルは定量的に得られた。Example 10 The catalyst prepared according to Example 1 was mixed with 10 parts of aluminum sulfate.
A catalyst was prepared by adding wt% and heat-treating at 900 ° C. Using this catalyst, a reaction was performed in the same manner as in Example 1. As a result, the rate of change in MTBE is 99.
5%, the selectivity of isobutylene was 99.9%, and methanol was obtained quantitatively.
【００２３】実施例１１ 実施例１により調製した触媒に硫酸アルミニウムを１５
重量％添加し、更に７００℃で熱処理することにより触
媒を調製した。この触媒を用いて、実施例１と同様にし
て反応を行った。その結果、ＭＴＢＥの変化率は９９．
６％、イソブチレンの選択率は９９．８％で、メタノー
ルは定量的に得られた。Example 11 Aluminum sulfate was added to the catalyst prepared according to Example 1
A catalyst was prepared by adding it in a weight percentage and further heat treating at 700 ° C. Using this catalyst, a reaction was performed in the same manner as in Example 1. As a result, the rate of change in MTBE is 99.
6%, isobutylene selectivity 99.8%, methanol was obtained quantitatively.
【００２４】実施例１２ 実施例２により調製した触媒に硫酸アルミニウムを１５
重量％添加し、更に６００℃で熱処理することにより触
媒を調製した。この触媒を用いて、実施例１と同様にし
て反応を行った。その結果、ＭＴＢＥの変化率は９９．
６％、イソブチレンの選択率は９９．９％で、メタノー
ルは定量的に得られた。Example 12 15% aluminum sulfate was added to the catalyst prepared in Example 2.
A catalyst was prepared by adding it in an amount of wt% and further heat treating it at 600 ° C. Using this catalyst, a reaction was performed in the same manner as in Example 1. As a result, the rate of change in MTBE is 99.
6%, isobutylene selectivity 99.9%, methanol was obtained quantitatively.
【００２５】比較例１ 炭酸ナトリウム５．４部を除き、その外は実施例１と同
様にして式 Ｓｉ1 Ａｌ0.18Ｚｒ0.11 で表される組成の触媒を得た。この触媒を用い、実施例
１と同様にして反応を行ったところ、ＭＴＢＥの変化率
は９９．７％、イソブチレンの選択率は９８．６％、イ
ソブチレン二重体の選択率１．４％、ジメチルエーテル
の選択率０．４％であった。Comparative Example 1 A catalyst having a composition represented by the formula Si 1 Al 0.18 Zr 0.11 . Was obtained in the same manner as in Example 1 except that 5.4 parts of sodium carbonate was removed . Using this catalyst, a reaction was carried out in the same manner as in Example 1. As a result, the rate of change in MTBE was 99.7%, the selectivity in isobutylene was 98.6%, the selectivity in the isobutylene duplex was 1.4%, dimethyl ether. Was 0.4%.
【００２６】比較例２ 市販のシリカ担体１００部を、酸化塩化ジルコニウム・
８水和物５９．０部に、水１５０部を加えて調製した水
溶液に含浸後、蒸発乾固し、９００℃で熱処理すること
により式 Ｓｉ1 Ｚｒ0.11 で表される組成の触媒を得た。この触媒を用い、実施例
１と同様にして反応を行ったところ、ＭＴＢＥの変化率
は９６．４％、イソブチレンの選択率は９９．８％であ
った。Comparative Example 2 100 parts of a commercially available silica carrier was mixed with zirconium oxide chloride.
After impregnating an aqueous solution prepared by adding 150 parts of water to 59.0 parts of octahydrate, evaporating to dryness and heat treatment at 900 ° C., a catalyst having a composition represented by the formula Si 1 Zr 0.11 was obtained. . When a reaction was carried out in the same manner as in Example 1 using this catalyst, the MTBE change rate was 96.4% and the isobutylene selectivity was 99.8%.
【００２７】比較例３ 実施例１の熱処理温度を４５０℃に変更して調製した触
媒を用い、実施例１と同様にして反応を行ったところ、
ＭＴＢＥの変化率は９９．１％、イソブチレンの選択率
は９８．４％であった。Comparative Example 3 A reaction was carried out in the same manner as in Example 1 using the catalyst prepared by changing the heat treatment temperature in Example 1 to 450 ° C.
The change rate of MTBE was 99.1%, and the selectivity rate of isobutylene was 98.4%.
【００２８】比較例４ 実施例１の熱処理温度を１２００℃に変更して調製した
触媒を用い、実施例１と同様にして反応を行ったとこ
ろ、ＭＴＢＥの変化率は９７．２％、イソブチレンの選
択率は９９．８％であった。Comparative Example 4 When a catalyst prepared by changing the heat treatment temperature of Example 1 to 1200 ° C. was used and a reaction was carried out in the same manner as in Example 1, the MTBE change rate was 97.2%, and isobutylene The selectivity was 99.8%.
【００２９】比較例５ 実施例１により調製した触媒に硫酸アルミニウムを３５
重量％添加し、更に９００℃で熱処理することにより触
媒を得た。この触媒を用い、実施例１と同様にして反応
を行ったところ、ＭＴＢＥの変化率は９８．７％、イソ
ブチレンの選択率は９９．８％であった。Comparative Example 5 The catalyst prepared according to Example 1 was mixed with 35% aluminum sulfate.
A catalyst was obtained by adding wt% and heat-treating at 900 ° C. When a reaction was carried out in the same manner as in Example 1 using this catalyst, the MTBE change rate was 98.7% and the isobutylene selectivity was 99.8%.
【００３０】[0030]
【発明の効果】本発明の方法によれば、アルキル第３級
アルキルエーテルの分解反応を高い変化率で行い、且つ
工業原料として重要な第３級オレフィンを高い選択率で
得ることができ、その工業的意義は極めて大きいもので
ある。According to the method of the present invention, the decomposition reaction of an alkyl tertiary alkyl ether can be carried out at a high rate of change, and a tertiary olefin important as an industrial raw material can be obtained with a high selectivity. The industrial significance is extremely great.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 1/20 // Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C07C 1/20 // C07B 61/00 300
Claims (2)
して相当する第３級オレフィンを製造する方法に於て、
該分解反応を組成式 Ｓｉa Ａｌb Ｚｒc Ｘd Ｏe （ここで、Ｓｉ、Ａｌ、Ｚｒ及びＯはそれぞれケイ素、
アルミニウム、ジルコニウム及び酸素を表し、Ｘはナト
リウム、カリウム、セシウム、セリウム、亜鉛、マグネ
シウム及びカルシウムからなる群より選ばれた少なくと
も１種の元素を示す。ただし、ａ、ｂ、ｃ、ｄ及びｅは
各元素の原子比率を表し、ａ＝１のとき、ｂ＝０．０１
〜１、ｃ＝０．００１〜１、ｄ＝０．００１〜１であ
り、ｅは前記各成分の原子価を満足するのに必要な酸素
原子数である。）で示される組成を有し、かつ、該組成
物を５００〜１１００℃で熱処理して得られた触媒の存
在下で反応を行うことを特徴とする第３級オレフィンの
製造法。1. A method for producing a corresponding tertiary olefin by decomposing an alkyl tertiary alkyl ether,
The decomposition reaction is represented by the compositional formula Si a Al b Zr c X d O e (where Si, Al, Zr and O are each silicon,
It represents aluminum, zirconium and oxygen, and X represents at least one element selected from the group consisting of sodium, potassium, cesium, cerium, zinc, magnesium and calcium. However, a, b, c, d and e represent the atomic ratio of each element, and when a = 1, b = 0.01
˜1, c = 0.001 to 1, d = 0.001 to 1, and e is the number of oxygen atoms required to satisfy the valence of each component. ), And carrying out the reaction in the presence of a catalyst obtained by heat-treating the composition at 500 to 1100 ° C., a process for producing a tertiary olefin.
の触媒に、硫酸アルミニウムを触媒重量に対し３０重量
％以下添加し、更に５００〜１１００℃で熱処理して得
られた触媒の存在下で反応を行うことを特徴とする請求
項１の第３級オレフィンの製造法。2. In the presence of a catalyst obtained by adding 30% by weight or less of aluminum sulfate to the catalyst having the compositional formula of claim 1 after heat treatment and further heat treating at 500 to 1100 ° C. The method for producing a tertiary olefin according to claim 1, wherein the reaction is carried out at.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4252186A JP2939065B2 (en) | 1992-08-27 | 1992-08-27 | Method for producing tertiary olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4252186A JP2939065B2 (en) | 1992-08-27 | 1992-08-27 | Method for producing tertiary olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0672904A true JPH0672904A (en) | 1994-03-15 |
| JP2939065B2 JP2939065B2 (en) | 1999-08-25 |
Family
ID=17233697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4252186A Expired - Fee Related JP2939065B2 (en) | 1992-08-27 | 1992-08-27 | Method for producing tertiary olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2939065B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005066101A1 (en) * | 2003-12-23 | 2005-07-21 | Exxonmobil Chemical Patents Inc. | Selective decomposition of ethers |
| WO2006135475A1 (en) | 2005-06-08 | 2006-12-21 | Exxonmobil Chemical Patents Inc. | Process for alcohol production by selective ether decomposition |
| US7173158B2 (en) | 2005-05-31 | 2007-02-06 | Exxonmobil Chemical Patents Inc. | Mixed metal oxide containing sulfur |
| EP1894621A1 (en) * | 2006-08-29 | 2008-03-05 | Oxeno Olefinchemie GmbH | Catalyst and method for producing iso-olefins |
| US7468465B2 (en) | 2005-05-31 | 2008-12-23 | Exxonmobil Chemical Patents Inc. | Method of making mixed metal oxide containing sulfur |
| CN114380658A (en) * | 2020-10-22 | 2022-04-22 | 中国科学院大连化学物理研究所 | Method for preparing isoprene by catalyzing isobutene-methanol with Pr-doped cerium oxide |
-
1992
- 1992-08-27 JP JP4252186A patent/JP2939065B2/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7102037B2 (en) | 2003-12-23 | 2006-09-05 | Exxonmobil Chemical Patents Inc. | Selective decomposition of ethers |
| WO2005066101A1 (en) * | 2003-12-23 | 2005-07-21 | Exxonmobil Chemical Patents Inc. | Selective decomposition of ethers |
| US7173158B2 (en) | 2005-05-31 | 2007-02-06 | Exxonmobil Chemical Patents Inc. | Mixed metal oxide containing sulfur |
| US7282192B2 (en) | 2005-05-31 | 2007-10-16 | Exxonmobil Chemical Patents Inc. | Mixed metal oxide containing sulfur |
| US7468465B2 (en) | 2005-05-31 | 2008-12-23 | Exxonmobil Chemical Patents Inc. | Method of making mixed metal oxide containing sulfur |
| US7399891B2 (en) | 2005-06-08 | 2008-07-15 | Exxonmobil Chemical Patents Inc. | Process for alcohol production by selective ether decomposition |
| WO2006135475A1 (en) | 2005-06-08 | 2006-12-21 | Exxonmobil Chemical Patents Inc. | Process for alcohol production by selective ether decomposition |
| JP2008055420A (en) * | 2006-08-29 | 2008-03-13 | Evonik Oxeno Gmbh | Production method of catalyst formally comprising alkali metal oxide and/or alkaline earth metal oxide, aluminum oxide, and silicon dioxide, this kind of catalyst, and production method of isoolefin having 4-6 carbon atoms |
| EP1894621A1 (en) * | 2006-08-29 | 2008-03-05 | Oxeno Olefinchemie GmbH | Catalyst and method for producing iso-olefins |
| US20110152596A1 (en) * | 2006-08-29 | 2011-06-23 | Oxeno Olefinchemie Gmbh | Catalyst and process for preparing isoolefins |
| US7977523B2 (en) | 2006-08-29 | 2011-07-12 | Evonik Oxeno Gmbh | Catalyst and process for preparing isoolefins |
| EP2620214A3 (en) * | 2006-08-29 | 2014-01-01 | Evonik Degussa GmbH | Method for manufacturing a catalyst, catalyst thereby obtained and method for manufacturing iso-olefines |
| US8680356B2 (en) | 2006-08-29 | 2014-03-25 | Evonik Oxeno Gmbh | Catalyst and process for preparing isoolefins |
| CN114380658A (en) * | 2020-10-22 | 2022-04-22 | 中国科学院大连化学物理研究所 | Method for preparing isoprene by catalyzing isobutene-methanol with Pr-doped cerium oxide |
| CN114380658B (en) * | 2020-10-22 | 2023-04-11 | 中国科学院大连化学物理研究所 | Method for preparing isoprene by catalyzing isobutene-methanol with Pr-doped cerium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2939065B2 (en) | 1999-08-25 |
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