JPH0371175B2 - - Google Patents
Info
- Publication number
- JPH0371175B2 JPH0371175B2 JP59247433A JP24743384A JPH0371175B2 JP H0371175 B2 JPH0371175 B2 JP H0371175B2 JP 59247433 A JP59247433 A JP 59247433A JP 24743384 A JP24743384 A JP 24743384A JP H0371175 B2 JPH0371175 B2 JP H0371175B2
- Authority
- JP
- Japan
- Prior art keywords
- moo
- catalyst
- butene
- tio
- tetramethyltin
- 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 23
- 238000005649 metathesis reaction Methods 0.000 claims description 16
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 46
- 229910010413 TiO 2 Inorganic materials 0.000 description 30
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- IAQRGUVFOMOMEM-BDYLZKADSA-N (e)-1,1,1,2,3,4,4,4-octadeuteriobut-2-ene Chemical compound [2H]C([2H])([2H])C(/[2H])=C(\[2H])C([2H])([2H])[2H] IAQRGUVFOMOMEM-BDYLZKADSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000007306 turnover Effects 0.000 description 3
- IAQRGUVFOMOMEM-VYMTUXDUSA-N 1,1,1,2-tetradeuteriobut-2-ene Chemical compound [2H]C(C(=CC)[2H])([2H])[2H] IAQRGUVFOMOMEM-VYMTUXDUSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005865 alkene metathesis reaction Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- -1 chlorine ions Chemical class 0.000 description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical group C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-OXUPVTBTSA-N (E)-1,1,1,2-tetradeuteriobut-2-ene Chemical compound [2H]\C(=C/C)C([2H])([2H])[2H] IAQRGUVFOMOMEM-OXUPVTBTSA-N 0.000 description 1
- IAQRGUVFOMOMEM-PIODKIDGSA-N 1,1,1,2,3,4,4,4-octadeuteriobut-2-ene Chemical compound [2H]C(=C([2H])C([2H])([2H])[2H])C([2H])([2H])[2H] IAQRGUVFOMOMEM-PIODKIDGSA-N 0.000 description 1
- 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
- QQONPFPTGQHPMA-DICFDUPASA-N 1,1-dideuterioprop-1-ene Chemical compound C(=CC)([2H])[2H] QQONPFPTGQHPMA-DICFDUPASA-N 0.000 description 1
- QQONPFPTGQHPMA-YODZYWACSA-N C(=C(C[2H])[2H])([2H])[2H] Chemical compound C(=C(C[2H])[2H])([2H])[2H] QQONPFPTGQHPMA-YODZYWACSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 125000004431 deuterium atom Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000010412 oxide-supported catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 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。
当初触媒として研究された三酸化モリブデン担
持触媒は活性が充分でなく、100〜300℃の高温で
実施された。また、モリブデンヘキサカルボニル
担持触媒も活性は著しく低く、高温脱気してカル
ボニルのCOを除去してから活性の増大の起こる
ことが分かつた。
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
タシセ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、メタセシス反応において
活性の高いものは選択性が充分でなく、また選択
性の高いものは活性が低いため、高活性でかつ高
選択性を示す触媒が望まれていた。
本願明細書で「選択性が高い」とは、構造保持
選択性が高いことと水素原子のスクランブリング
のないこととの双方を満足することを意味する。
ハ 発明の目的
この発明は、上記に鑑み、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する。
ニ 発明の構成
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
先ず、β―TiO2に担持された酸化モリブデン
（MoO3又はMoO3-x）触媒の製法について述べ
る。
四塩化チタン水溶液を中和してから得られる沈
澱物を蒸留水中で約10時間煮沸後、塩素イオンが
検出されなくなるまで充分に水洗し、更に120℃
で一昼夜乾燥してβ―TiO2担体を得た。次に、
この担体をモリブデン酸アンモニウム水溶液中に
浸漬し、蒸発固化させ空気中焼成により酸化させ
て約６重量％のMoO3を担持したMoO3／β―
TiO2触媒を得た。
また、上記の方法で得られたMoO3／β―TiO2
触媒を一酸化炭素または水素によつて還元した
後、N2O＋H2ガスに調整酸化して種々の還元度
のMoO3Ax／β―TiO2触媒を得た。特にＸは0.1
＜Ｘ＜0.7が望ましい。
上記のようにして得られたMoO3／β―TiO2触
媒またはMoO3-x／β―TiO2触媒を、室温で30
分間1Torrのテトラメチル錫（Su（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行つた。
テトラメチル錫を用いた上記の酸化モリブデン
表面処理では、気相中に少量のメタが生じた。こ
の事実は、その表面上にCH2種を含むいくらかの
水素原子不足種の生成を示している。
オレフイン炭化水素中の水素（2H）原子（重
水素）の濃度は、予め吸着されたテトラメチル錫
からの水素（1H）原子によつて希釈されなかつ
たので、テトラメチル錫によつて処理されたこの
触媒上でのオレフインのメタセシス反応は接触反
応的に進み、かつ、100℃での排気によつてメタ
セシスのための初期活性が復活した。
以下、MoO3／β―TiO2触媒及びMoO3-x／β
―TiO2触媒のＸを0.6とした例を挙げて説明す
る。
上記の如くして得られた酸化モリブデン担持触
媒及びテトラメチル錫で活性化処理を施した触媒
をそれぞれ0.5ｇ使用して、〔2Ho〕―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た。ここで、〔2Ho〕は、
ｎ個の水素がｎ個の重水素で置換されていること
を意味する（以下、同様）。例えば、上記〔2H0〕
は、重水素で全く置換されていないことを意味
し、また上記〔2H6〕は、６個の重水素で置換さ
れていることを意味している。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、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。）、及びデジエネレイトメ
タセシス（Degenerate Metathesise）反応で生
成する〔2H2〕―プロペン又は〔2H4〕―プロペ
ンの量VDとプロダクテイブメタセシス
（Productive Metathesise）反応で生成するエチ
レン（（2H0）、（2H2）、（2H4））又は２―ブテン
（（2H0）、（2H4）、（2H8））の量VPとの比VD／VP
を測定した。
その結果を下記表に示す。
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. The molybdenum trioxide-supported catalysts that were initially investigated as catalysts did not have sufficient activity and were carried out at high temperatures of 100-300°C. It was also found that the activity of the molybdenum hexacarbonyl-supported catalyst was extremely low, and that the activity increased after high-temperature degassing to remove CO from the carbonyl. 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 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 selectivity in metathesis reactions, and those with high selectivity have low activity. A catalyst that shows this is desired. As used herein, "high selectivity" means that both high structure retention selectivity and no scrambling of hydrogen atoms are satisfied. C. Purpose of the Invention In view of the above, an object of the present invention is to provide a catalyst for metathesis reaction of olefins which has high activity and high selectivity. D. Structure of the invention MoO 3 and MoO 3- x supported on a carrier and activated by tetramethyltin (however, 0.1<X<
The present invention relates to a metathesis reaction catalyst composed of one or both of molybdenum oxides represented by 0.7). Example First, a method for producing a molybdenum oxide (MoO 3 or MoO 3- x) catalyst supported on β-TiO 2 will be described. The precipitate obtained by neutralizing the titanium tetrachloride aqueous solution was boiled in distilled water for about 10 hours, washed thoroughly with water until no chlorine ions were detected, and further boiled at 120°C.
After drying for a day and a night, a β-TiO 2 carrier was obtained. next,
This carrier was immersed in an aqueous ammonium molybdate solution, evaporated and solidified, and then oxidized by firing in air to form MoO 3 /β-, which supported about 6% by weight of MoO 3 .
A TiO2 catalyst was obtained. In addition, MoO 3 /β-TiO 2 obtained by the above method
The catalysts were reduced with carbon monoxide or hydrogen and then oxidized to N 2 O + H 2 gas to obtain MoO 3 Ax/β-TiO 2 catalysts with various degrees of reduction. Especially X is 0.1
<X<0.7 is desirable. The MoO 3 /β-TiO 2 catalyst or MoO 3- x /β-TiO 2 catalyst obtained as above was heated at room temperature for 30 minutes.
These catalysts were activated with tetramethyltin by exposing them to 60 Torr of helium gas containing 1 Torr of tetramethyltin (Su(CH 3 ) 4 ) vapor per minute, followed by evacuating for 30 minutes. The above molybdenum oxide surface treatment using tetramethyltin produced a small amount of meth in the gas phase. This fact indicates the formation of some hydrogen atom-deficient species, including CH 2 species, on its surface. The concentration of hydrogen ( 2 H) atoms (deuterium) in the olefin hydrocarbon was not diluted by the hydrogen ( 1 H) atoms from the preadsorbed tetramethyltin, so it was The metathesis reaction of olefins on this catalyst proceeded in a catalytic manner, and the initial activity for metathesis was restored by evacuation at 100°C. Hereinafter, MoO 3 /β-TiO 2 catalyst and MoO 3- x /β
-Explain using an example where X of the TiO 2 catalyst is 0.6. Using 0.5 g each of the molybdenum oxide supported catalyst obtained as above and the catalyst activated with tetramethyltin, [ 2 Ho]-propene and [ 2 H 6 ]-propene were mixed in a ratio of 1:1. Mixture (25Torr)
A metathesis reaction was carried out. Here, [ 2 H o ] is
This means that n hydrogens are replaced with n deuteriums (the same applies hereinafter). For example, the above [ 2 H 0 ]
means that it is not substituted with deuterium at all, and [ 2 H 6 ] above means that it is substituted with six deuterium atoms. The turnover number expressed as the amount of ethylene produced (the number of molecules produced per second per molybdenum atom), the ratio of the cis and trans isomers of the 2-butene produced (the equilibrium constant is 0.3), and the amount of [ 2 H 2 ]-propene or [ 2 H 4 ]-propene produced in the Degenerate Metathesise reaction and the amount of ethylene (( 2 H 0 ), ( 2 H 2 ), ( 2 H 4 )) or the ratio to the amount V P of 2-butene (( 2 H 0 ), ( 2 H 4 ), ( 2 H 8 )) V D /V P
was measured. The results are shown in the table below.
【表】
上記の表より、テトラメチル錫（Su（CH3）4）
処理を施すことにより、MoO3及びMoO3-x／β
―TiO2触媒の活性が顕著になり、また、
MoO3-x／β―TiO2触媒のVD／VP比は同処理を
施すことによつて約４倍に増大することが解る。
また、上記の表から明らかなように、プロダク
テイブメタセシス反応で生成するエチレン分子の
数で表したターンオーバー数（T.F.）は、テト
ラメチル錫処理をしたMoO3-x／β―TiO2触媒
のではテトラメチル錫処理を施さないMoO3-x／
β―TiO2触媒の103倍であり、これからもテトラ
メチル錫処理による活性化効果の顕著であること
が理解される。
なお、テトラメチル錫による活性化処理を施し
たMoO3／β―TiO2触媒とMoO3-x／β―TiO2
触媒の活性を比較すると、後者は前者に対して、
メタセシス反応のターンオーバー数は約５倍、ま
たは選択性についてはシス―ブテン／トランス―
ブテンの値は2.5分の１以下、VD／VPの値は約３
倍であり、活性、選択性共に後者は前者に較べて
一層良好な成績を示している。
また、シス―〔2H0〕―２―ブテン、シス―
〔2H8〕―２―ブテンの混合物をテトラメチル錫
で活性化した本発明の触媒と接触させたところ、
トランス―〔2H4〕―２―ブテン、トランス―
〔2H0〕―２―ブテン、シス―〔2H4〕―２―ブテ
ン、トランス―〔2H8〕―２―ブテンが生成され
た。２―ブテンの全量を圧力16.0Torr、触媒量
を10〜15mg、反応温度を室温とする条件下で、テ
トラメチル錫処理で活性化したMoO3／β―TiO2
又はMoO3-x／β―TiO2触媒でのシス―〔2H0〕
―２―ブテン及びシス―〔2H8〕―２―ブテンの
等モル混合物の反応における転化率と〔2H4〕―
２―ブテン（シス及びトランス）中のシス―異性
体の量との関係は、図面に示す通りであつた。
なお、同図には、トランス―〔2H0〕―２―ブ
テン及びトランス―〔2H8〕―２―ブテンの等モ
ル混合物を上記と同様の条件で反応させたときの
結果を併記した。
図中、○印（曲線１）および●印（曲線２）は
それぞれ、シス―〔2H0〕―２―ブテンとシス―
〔2H8〕―ブテンとの混合物をテトラメチル錫処
理したMoO3／β―TiO2触媒とMoO3-x／β―
TiO2触媒を使用してメタセシス反応させたとき
に生成してくる〔2H4〕―２―ブテン中のシス異
性体の割合を示す。
また、△印（曲線３）および▲印（曲線３に同
じ）はそれぞれ、トランス―〔2H0〕―２―ブテ
ンとトランス―〔2H8〕―２―ブテンとの混合物
をテトラメチル錫処理したMoO3／β―TiO2触媒
とMoO3-x／β―TiO2触媒を使用してメタセシ
ス反応させたときに生成してくる〔2H4〕―２―
ブテン中のシス異性体の割合を示す。
シス―２―ブテンを原料とした場合は、転化率
０％において、選択性を表すシス―〔2H4〕―２
―ブテンの量は、テトラメチル錫処理した
MoO3／β―TiO2触媒を使用したとき85％、テト
ラメチル錫処理をしたMoO3-x／β―TiO2触媒
を使用したとき75％であつた。これに対してテト
ラメチル錫処理を施さないMoO3-x／β―TiO2
触媒は活性が低いだけでなく、選択性においても
60％であり可成り低い値を示していた。
また、図面は、上記の本発明の活性触媒を使用
し、トランス―２―ブテンを原料とした場合は、
シス―異性対が０％、即ち、トランス―〔2H4〕
―２―ブテンが100％選択的に生成されることを
示している。
これらの結果から、テトラメチル錫により活性
化処理した酸化モリブデン触媒は、活性度が増大
されているばかりでなく、オレフインのメタセシ
ス反応において原料オレフインの異性化や原料オ
レフインの水素原子のスクランブルが生ぜずかつ
原料オレフインの立体構造を保持する高選択性を
示すことが理解できる。
即ち、水素原子のスクランブリングは、オレフ
インの異性化と同様、テトラメチル錫処理によつ
て影響を受けなかつた。
上記の例では、MoO3-x／β―TiO2における
Ｘを約0.6とした触媒の例を示したが、本発明で
は0.1＜Ｘ＜0.7の範囲で本発明の効果が顕著に認
められる。
また、上記の例では、MoO3又はMoO3-x／β
―TiO2をテトラメチル錫で活性化処理した触媒
の例を示したが、MoO3及びMoO3-x／β―TiO2
をテトラメチル錫で活性化処理した触媒としても
同様な効果が奏せられることは言うまでもない。
また、担体は、β―TiO2に限られるものではな
い。
ヘ 発明の効果
以上説明したように、本発明による活性触媒
は、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 (Su(CH 3 ) 4 )
By treatment, MoO 3 and MoO 3- x/β
-The activity of TiO 2 catalyst becomes remarkable, and
It can be seen that the V D /V P ratio of the MoO 3- x /β-TiO 2 catalyst increases approximately four times by applying the same treatment. Furthermore, as is clear from the table above, the turnover number (TF), expressed as the number of ethylene molecules generated in the productive metathesis reaction, is higher than that of the tetramethyltin-treated MoO 3- MoO 3- x/ without tetramethyltin treatment
This is 10 3 times that of the β-TiO 2 catalyst, which indicates that the activation effect of the tetramethyltin treatment is significant. In addition, MoO 3 /β-TiO 2 catalyst activated with tetramethyltin and MoO 3- x /β-TiO 2
Comparing the activity of the catalyst, the latter has a higher activity than the former.
The turnover number of the metathesis reaction is about 5 times, or the selectivity is cis-butene/trans-
The value of butene is less than 1/2.5, and the value of V D /V P is approximately 3
The latter shows better results in both activity and selectivity than the former. Also, cis-[ 2 H 0 ]-2-butene, cis-
When a mixture of [ 2 H 8 ]-2-butene was contacted with the catalyst of the invention activated with tetramethyltin,
Trans-[ 2 H 4 ]-2-butene, trans-
[ 2 H 0 ]-2-butene, cis-[ 2 H 4 ]-2-butene, and trans-[ 2 H 8 ]-2-butene were produced. MoO 3 /β-TiO 2 activated by tetramethyltin treatment under the conditions that the total amount of 2-butene is at a pressure of 16.0 Torr, the amount of catalyst is 10 to 15 mg, and the reaction temperature is room temperature.
or MoO 3- x/β-cis with TiO 2 catalyst [ 2 H 0 ]
-Conversion rate in reaction of equimolar mixture of 2-butene and cis-[ 2 H 8 ]-2-butene and [ 2 H 4 ]-
The relationship with the amount of cis-isomer in 2-butene (cis and trans) was as shown in the drawing. In addition, the same figure also shows the results when an equimolar mixture of trans-[ 2 H 0 ]-2-butene and trans-[ 2 H 8 ]-2-butene was reacted under the same conditions as above. . In the figure, ○ (curve 1) and ● (curve 2) indicate cis-[ 2 H 0 ]-2-butene and cis-
[ 2 H 8 ]-MoO 3 /β-TiO 2 catalyst obtained by treating the mixture with butene with tetramethyltin and MoO 3- x /β-
It shows the proportion of cis isomer in [ 2 H 4 ]-2-butene produced when a metathesis reaction is carried out using a TiO 2 catalyst. Moreover, the △ mark (curve 3) and the ▲ mark (same as curve 3) indicate that the mixture of trans-[ 2 H 0 ]-2-butene and trans-[ 2 H 8 ]-2-butene was mixed with tetramethyltin. [ 2 H 4 ]-2- is produced when a metathesis reaction is carried out using the treated MoO 3 /β-TiO 2 catalyst and MoO 3- x /β-TiO 2 catalyst.
Shows the percentage of cis isomer in butene. When cis-2-butene is used as a raw material, cis-[ 2 H 4 ]-2, which represents selectivity, at a conversion rate of 0%
-The amount of butene is determined by the tetramethyltin treatment.
It was 85% when the MoO 3 /β-TiO 2 catalyst was used and 75% when the tetramethyltin-treated MoO 3- x /β-TiO 2 catalyst was used. On the other hand, MoO 3- x/β-TiO 2 without tetramethyltin treatment
Catalysts not only have low activity but also low selectivity.
It was 60%, which is a fairly low value. In addition, the drawing shows that when the active catalyst of the present invention described above is used and trans-2-butene is used as the raw material,
cis-isomer pair is 0%, i.e. trans-[ 2 H 4 ]
This shows that -2-butene is produced 100% selectively. These results show that the molybdenum oxide catalyst activated with tetramethyltin not only has increased activity, but also does not cause isomerization of the raw olefin or scrambling of hydrogen atoms in the raw olefin in the olefin metathesis reaction. Moreover, it can be understood that it exhibits high selectivity in maintaining the steric structure of the raw material olefin. That is, hydrogen atom scrambling, as well as olefin isomerization, was unaffected by the tetramethyltin treatment. In the above example, a catalyst was shown in which X in MoO 3- x /β-TiO 2 was about 0.6, but in the present invention, the effect of the present invention is noticeable in the range of 0.1<X<0.7. Moreover, in the above example, MoO 3 or MoO 3- x/β
-Although we have shown examples of catalysts in which TiO 2 is activated with tetramethyltin, MoO 3 and MoO 3- x/β-TiO 2
It goes without saying that a similar effect can be obtained using a catalyst activated with tetramethyltin.
Furthermore, the carrier is not limited to β-TiO 2 . F. Effects of the Invention As explained above, the active catalyst of the present invention exhibits high activity and high selectivity when used as a catalyst for olefin metathesis reaction, and has great industrial utility value.
図面は、シス―〔2H0〕―２―ブテンとシス―
〔2H8〕―２―ブテンとの等モル混合物、又はト
ランス−〔2H0〕−２−ブテンとトランス―〔2H8〕
―２―ブテンとの等モル混合物とのメタセシス反
応のおける転化率と〔2H4〕―２―ブテン中のシ
ス―異性体の量との関係を示すグラフである。
なお、図に示された符号に於いて、１……混合
物：シス―〔2H0〕―２―ブテン及びシス―
〔2H8〕―２―ブテン、触媒：活性化MoO3／β―
TiO2、２……混合物：１に同じ、触媒：活性化
MoO3-x／β―TiO2、３……混合物：トランス
―〔2H0〕―２―ブテン及びトランス〔2H8〕―
２―ブテン、触媒：活性化MoO3／β―TiO2又は
活性化MoO3-x／β―TiO2である。
The drawing shows cis-[ 2 H 0 ]-2-butene and cis-
[ 2 H 8 ] - Equimolar mixture with 2-butene, or trans - [ 2 H 0 ] - 2-butene and trans - [ 2 H 8 ]
2 is a graph showing the relationship between the conversion rate in a metathesis reaction with an equimolar mixture of -2-butene and the amount of cis-isomer in [ 2 H 4 ]-2-butene. In addition, in the symbols shown in the figure, 1... mixture: cis-[ 2 H 0 ]-2-butene and cis-
[ 2 H 8 ]-2-butene, catalyst: activated MoO 3 /β-
TiO 2 , 2...Mixture: Same as 1, Catalyst: Activated
MoO 3- x/β-TiO 2 , 3...Mixture: trans-[ 2 H 0 ]-2-butene and trans [ 2 H 8 ]-
2-Butene, catalyst: activated MoO 3 /β-TiO 2 or activated MoO 3- x /β-TiO 2 .
Claims (1)
性化されたMoO3及びMoO3-x（但し、0.1＜Ｘ＜
0.7）で表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 MoO 3 and MoO 3- x supported on a carrier and activated by tetramethyltin (where 0.1<X<
A metathesis reaction catalyst composed of one or both of molybdenum oxides represented by 0.7).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59247433A JPS61125438A (en) | 1984-11-22 | 1984-11-22 | Catalyst for metathesis reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59247433A JPS61125438A (en) | 1984-11-22 | 1984-11-22 | Catalyst for metathesis reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61125438A JPS61125438A (en) | 1986-06-13 |
| JPH0371175B2 true JPH0371175B2 (en) | 1991-11-12 |
Family
ID=17163365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59247433A Granted JPS61125438A (en) | 1984-11-22 | 1984-11-22 | Catalyst for metathesis reaction |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61125438A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5098876A (en) * | 1990-08-27 | 1992-03-24 | Shell Oil Company | Olefin disproportionation catalyst and process |
| US5114899A (en) * | 1990-08-27 | 1992-05-19 | Shell Oil Company | Olefin disproportionation catalyst and process |
-
1984
- 1984-11-22 JP JP59247433A patent/JPS61125438A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61125438A (en) | 1986-06-13 |
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