JPH058054B2 - - Google Patents
Info
- Publication number
- JPH058054B2 JPH058054B2 JP60222468A JP22246885A JPH058054B2 JP H058054 B2 JPH058054 B2 JP H058054B2 JP 60222468 A JP60222468 A JP 60222468A JP 22246885 A JP22246885 A JP 22246885A JP H058054 B2 JPH058054 B2 JP H058054B2
- Authority
- JP
- Japan
- Prior art keywords
- moo
- catalyst
- tetramethyltin
- sio
- activity
- 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
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000005649 metathesis reaction Methods 0.000 claims description 12
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 30
- 230000000694 effects Effects 0.000 description 18
- 230000004913 activation Effects 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000005078 molybdenum compound Substances 0.000 description 2
- 150000002752 molybdenum compounds Chemical class 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- QQONPFPTGQHPMA-QNYGJALNSA-N 1,1,2,3,3,3-hexadeuterioprop-1-ene Chemical compound [2H]C([2H])=C([2H])C([2H])([2H])[2H] QQONPFPTGQHPMA-QNYGJALNSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 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
イ 産業上の利用分野
この発明は、メタセシス反応用触媒に関し、更
に詳しくはオレフインのメタセシス反応に使用さ
れる触媒に関する。
ロ 従来技術
1964年にバンクス（Banks）及びベイリー
（Bailey）がアルミナ担体に担持した酸化モリブ
デン又はモリブデンヘキサカルボニルを触媒に用
いてオレフインのメタセシス（Metathesis）反
応に成功して以来、この反応が工業的な展開を見
るまでに検討され、発展してきている。
モリブデン化合物触媒に限定しても、上記の酸
化物系（三酸化モリブデン、及びその担持物、モ
リブデン酸コバルト等のオキシ酸塩又は複合酸化
物）、カルボニル化合物系の他に、ハロゲン化物、
硫化物、更には、種々の有機モリブデン錯体がメ
タセシス反応の活性を有するものと各種の特許明
細書、文献等において報告されている。
しかしながら、従来提案されているこの種のモ
リブデン化合物触媒は、メタセシス反応以外の反
応、例えば異性化反応が起るため、構造保持選択
性（以下、単に選択性と称する。）が充分ではな
く、また、選択性の高いものはメタセシス反応に
対する活性が低いため、高活性でかつ高選択性を
示す触媒が望まれている。
ハ 発明の目的
本発明は、上記の事情に鑑みてなされたもので
あつて、高活性でかつ高選択性を有するオレフイ
ンのメタセシス反応用触媒を提供することを目的
としている。
ニ 発明の構成
本発明は、γ−Al2O3又はSiO2を担体とし、こ
の担体に担持され、テトラメチル錫によつて活性
化されたMoO3及びMoO3−ｘ（但し、0.1＜ｘ＜
0.7）で表わされる酸化モリブデンのいずれか一
方又は双方によつて構成されている、メタセシス
反応用触媒に係る。
ホ 実施例
以下、本発明の実施例について説明する。
γ−Al2O3及びSiO2の所定量をモルブデン酸ア
ンモニウム水溶液中に浸漬した後、蒸発固化さ
せ、空気中で焼成して酸化させ、約６重量％の
MoO3を担持したMoO3／γ−Al2O3及びMoO3／
SiO2触媒とした。
また、上記の方法で得られたMoO3を担持した
各触媒を500℃にて一酸化炭素は水素によつて還
元した後、200℃でN2Ｏ＋H2ガスによつて調整
酸化して種々の還元度のMoO3−ｘ／γ−Al2O3
及びMoO3−ｘ／SiO2触媒とした。
上記の如くして得られたγ−Al2O3又はSiO2担
体にMoO3又はMoO3−ｘ（この例ではｘが約0.6）
を担持した触媒について、室温で30分間1Torrの
テトラメチル錫（Sn（CH3）4）蒸気を含む60Torr
のヘリウムガスに曝した後、30分間排気する処理
により、これら触媒のテトラメチル錫による活性
化処理を施した。
比較のために、テトラメチル錫による活性化処
理を施さず、その他は上記と同様にして作製した
触媒、並びにβ−TiO2を担体とし、その他は上
記と同様（テトラメチル錫による活性化処理を施
したもの及びこの処理を施さぬものの双方）にし
て作成した触媒を用意した。
これらの触媒を使用して〔2H0〕−プロペン及
び〔2H6〕−プロペンの１：１混合物（25Torr）
でメタセシス反応をさせ、エチレン生成量（１モ
リブデン原子について１秒間当たりの生成分子
数）で表されるターンオーバー数（絶対活性）及
び生成する２−ブテンのシス異性体とトランス異
性体との比（平衡定数は0.3である。）を測定し
た。
その結果の一例を下記表に示す。
B. Industrial Application Field The present invention relates to a catalyst for metathesis reaction, and more particularly to a catalyst used for metathesis reaction of olefin. B. Prior art Since Banks and Bailey succeeded in the metathesis reaction of olefins using molybdenum oxide or molybdenum hexacarbonyl supported on an alumina support as a catalyst in 1964, this reaction has become industrially popular. It has been considered and developed to the point where it has been fully developed. Even if it is limited to molybdenum compound catalysts, in addition to the above-mentioned oxides (molybdenum trioxide and its supports, oxyacid salts or composite oxides such as cobalt molybdate), carbonyl compounds, halides,
It has been reported in various patent specifications, literature, etc. that sulfides and furthermore, various organic molybdenum complexes have metathesis reaction activity. However, this kind of molybdenum compound catalysts that have been proposed so far do not have sufficient structure retention selectivity (hereinafter simply referred to as selectivity) because reactions other than metathesis reactions, such as isomerization reactions, occur. Since catalysts with high selectivity have low activity for metathesis reactions, catalysts with high activity and high selectivity are desired. C. Purpose of the Invention The present invention was made in view of the above circumstances, and an object of the present invention is to provide a catalyst for metathesis reaction of olefins having high activity and high selectivity. D. Structure of the Invention The present invention uses γ-Al 2 O 3 or SiO 2 as a carrier, and MoO 3 and MoO 3 −x supported on this carrier and activated by tetramethyltin (where 0.1<x <
The present invention relates to a metathesis reaction catalyst composed of one or both of molybdenum oxides represented by 0.7). E. Examples Examples of the present invention will be described below. A predetermined amount of γ-Al 2 O 3 and SiO 2 is immersed in an aqueous ammonium molybdate solution, evaporated and solidified, and oxidized by firing in air to form a solution of about 6% by weight.
MoO 3 supporting MoO 3 / γ-Al 2 O 3 and MoO 3 /
It was used as a SiO 2 catalyst. In addition, each catalyst supporting MoO 3 obtained by the above method was heated to 500°C to reduce carbon monoxide with hydrogen, and then adjusted to oxidation with N 2 O + H 2 gas at 200°C to produce various Degree of reduction MoO 3 −x/γ-Al 2 O 3
and MoO 3 -x/SiO 2 catalyst. MoO 3 or MoO 3 -x (in this example, x is about 0.6) is added to the γ-Al 2 O 3 or SiO 2 support obtained as described above.
For the supported catalyst, 60 Torr containing 1 Torr of tetramethyltin (Sn( CH3 ) 4 ) vapor for 30 min at room temperature.
These catalysts were activated with tetramethyltin by exposing them to helium gas and then evacuating for 30 minutes. For comparison, we used a catalyst prepared in the same manner as above without activation treatment with tetramethyltin, and a catalyst prepared with β-TiO 2 as a carrier, but in the same manner as above (without activation treatment with tetramethyltin). Catalysts prepared both with and without this treatment were prepared. Using these catalysts, a 1:1 mixture of [2H 0 ]-propene and [2H 6 ]-propene (25 Torr)
The turnover number (absolute activity) expressed as the amount of ethylene produced (the number of molecules produced per second per molybdenum atom) and the ratio of the cis and trans isomers of the 2-butene produced (The equilibrium constant is 0.3). An example of the results is shown in the table below.
【表】
上記の表より、テトラメチル錫（Sn（CH3）4）
処理を施した各触媒は、同処理を施さない触媒に
較べていずれの場合もメタセシス反応の活性が顕
著に増加している。特に担体にγ−Al2O3を使用
した場合は高活性を示し、担体にβ−TiO2を使
用した場合に比して活性はMoO3担持で10倍以
上、MoO3−ｘ担持で20倍以上になる。また、
SiO2担体触媒はβ−TiO2担体触媒と同等以上の
活性を示している。
なお、テトラメチル錫による活性化処理を施し
たMoO3／γ−Al2O3触媒の活性と同様の処理を
施したMoO3−ｘ／γ−Al2O3触媒の活性とを比
較すると、後者は前者に較べてメタセシス反応の
ターンオーバー数で約10倍高い。また、テトラメ
チル錫処理したMoO3／SiO2とMoO3−ｘ／SiO2
の活性の比較でも、部分的に還元した触媒の方が
高活性を示している。
更に特筆すべきことは、テトラメチル錫処理に
より活性化した触媒は、同処理を施さない触媒に
較べてシス異性体とトランス異性体との比は実質
的に変化していない。このことは、テトラメチル
錫による活性化処理は、オレフインのメタセシス
反応を著しく活性化させるにも拘わらず、オレフ
インの異性化反応を活性化させることがなく、従
つて、オレフインのメタセシス反応に於ける高い
選択性が保持されることを示している。
上記の例では、各MoO3−ｘ担持触媒に於ける
ｘを約0.6としているが、ｘは0.1＜ｘ＜0.7の範囲
内で活性化効果が顕著に認められる。即ち、上記
の例はγ−Al2O3及びSiO2にMoO3又はMoO3−
ｘ（ｘ＝0.6）を担持し、テトラメチル錫で活性化
した触媒の例であるが、酸化モリブデンの還元度
を上記ｘを0.1〜0.7の範囲内とする任意の還元度
としても、上記の例と同様の活性化効果が奏せら
れる。
なお、担体としては、上記のγ−Al2O3、SiO2
以外にもZrO2やSnO2等が使用可能である。
ヘ 発明の効果
以上説明したように、本発明に基づく触媒は、
MoO3及び／又はMoO3−ｘ（但し、0.1＜ｘ＜0.7）
をγ−Al2O3又はSiO2に担持させ、更にテトラメ
チル錫によつて活性化しているので、オレフイン
のメタセシス反応用触媒として使用する場合に、
高活性でかつ高選択性を示し、産業上の利用価値
は大である。[Table] From the table above, tetramethyltin (Sn(CH 3 ) 4 )
The metathesis reaction activity of each of the treated catalysts was significantly increased compared to the untreated catalyst. In particular, when γ-Al 2 O 3 is used as a carrier, high activity is shown. Compared to when β-TiO 2 is used as a carrier, the activity is more than 10 times when MoO 3 is supported, and 20 times when MoO 3 −x is supported. It will more than double. Also,
The SiO 2 carrier catalyst shows an activity equal to or higher than that of the β-TiO 2 carrier catalyst. In addition, when comparing the activity of MoO 3 / γ-Al 2 O 3 catalyst subjected to activation treatment with tetramethyltin and the activity of MoO 3 -x / γ-Al 2 O 3 catalyst subjected to similar treatment, The latter has a metathesis reaction turnover rate about 10 times higher than the former. In addition, tetramethyltin-treated MoO 3 /SiO 2 and MoO 3 -x/SiO 2
Comparing the activities of , the partially reduced catalyst shows higher activity. It is also noteworthy that the ratio of cis to trans isomers in the catalyst activated by the tetramethyltin treatment is not substantially changed compared to the catalyst without the same treatment. This means that although the activation treatment with tetramethyltin significantly activates the metathesis reaction of olefin, it does not activate the isomerization reaction of olefin, and therefore, the activation treatment with tetramethyltin does not activate the isomerization reaction of olefin. This shows that high selectivity is maintained. In the above example, x in each MoO 3 -x supported catalyst is set to approximately 0.6, but a significant activation effect is observed when x falls within the range of 0.1<x<0.7. That is, in the above example, γ-Al 2 O 3 and SiO 2 are combined with MoO 3 or MoO 3 −
This is an example of a catalyst supporting x (x = 0.6) and activated with tetramethyltin, but even if the reduction degree of molybdenum oxide is set to an arbitrary reduction degree where x is within the range of 0.1 to 0.7, the above The same activation effect as in the example can be achieved. In addition, as a carrier, the above-mentioned γ-Al 2 O 3 and SiO 2
In addition, ZrO 2 , SnO 2 , etc. can also be used. F. Effects of the Invention As explained above, the catalyst based on the present invention has the following effects:
MoO 3 and/or MoO 3 −x (0.1<x<0.7)
is supported on γ-Al 2 O 3 or SiO 2 and further activated with tetramethyltin, so when used as a catalyst for olefin metathesis reaction,
It exhibits high activity and high selectivity, and has great industrial utility value.
Claims (1)
担持され、テトラメチル錫によつて活性化された
MoO3及びMoO3−ｘ（但し、0.1＜ｘ＜0.7）で表
わされる酸化モリブデンのいずれか一方又は双方
によつて構成されている、メタセシス反応用触
媒。1 γ-Al 2 O 3 or SiO 2 as a carrier, supported on this carrier and activated by tetramethyltin
A metathesis reaction catalyst comprising either or both of MoO 3 and MoO 3 −x (0.1<x<0.7).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60222468A JPS6283043A (en) | 1985-10-04 | 1985-10-04 | Catalyst for metathesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60222468A JPS6283043A (en) | 1985-10-04 | 1985-10-04 | Catalyst for metathesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6283043A JPS6283043A (en) | 1987-04-16 |
| JPH058054B2 true JPH058054B2 (en) | 1993-02-01 |
Family
ID=16782889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60222468A Granted JPS6283043A (en) | 1985-10-04 | 1985-10-04 | Catalyst for metathesis |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6283043A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8726925D0 (en) * | 1987-11-18 | 1987-12-23 | Shell Int Research | Catalyst systems |
| US5114899A (en) * | 1990-08-27 | 1992-05-19 | Shell Oil Company | Olefin disproportionation catalyst and process |
| US5098876A (en) * | 1990-08-27 | 1992-03-24 | Shell Oil Company | Olefin disproportionation catalyst and process |
| CN102872921B (en) * | 2011-07-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for activating olefin disproportionation catalyst |
| CN107233892B (en) * | 2017-06-12 | 2019-09-24 | 山西大学 | For low-temperature catalyzed decomposition N2The composite oxide catalysts of O and its preparation |
| CN111704167A (en) * | 2020-06-28 | 2020-09-25 | 山东大学 | MoO regulated and controlled by one-dimensional plasma resonance absorption3-xNanobelt material and application thereof |
-
1985
- 1985-10-04 JP JP60222468A patent/JPS6283043A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6283043A (en) | 1987-04-16 |
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