JPH0243538B2 - - Google Patents
Info
- Publication number
- JPH0243538B2 JPH0243538B2 JP56046018A JP4601881A JPH0243538B2 JP H0243538 B2 JPH0243538 B2 JP H0243538B2 JP 56046018 A JP56046018 A JP 56046018A JP 4601881 A JP4601881 A JP 4601881A JP H0243538 B2 JPH0243538 B2 JP H0243538B2
- Authority
- JP
- Japan
- Prior art keywords
- toluene
- xylene
- catalyst
- oxide
- present
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 90
- 239000003054 catalyst Substances 0.000 claims description 28
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 25
- 239000008096 xylene Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 13
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910003438 thallium oxide Inorganic materials 0.000 claims description 9
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 3
- 238000006025 oxidative dimerization reaction Methods 0.000 claims 1
- 229910052716 thallium Inorganic materials 0.000 claims 1
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000006471 dimerization reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000447 dimerizing effect Effects 0.000 description 7
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000539 dimer Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical class C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- 150000005481 1,2-diphenylethanes Chemical class 0.000 description 2
- QFEPNMCDSBNJDB-UHFFFAOYSA-N 1-methyl-2-[2-(2-methylphenyl)ethyl]benzene Chemical class CC1=CC=CC=C1CCC1=CC=CC=C1C QFEPNMCDSBNJDB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- ARZIVALJTPLLHF-UHFFFAOYSA-N 1-methyl-2-[2-(2-methylphenyl)ethenyl]benzene Chemical class CC1=CC=CC=C1C=CC1=CC=CC=C1C ARZIVALJTPLLHF-UHFFFAOYSA-N 0.000 description 1
- BSZXAFXFTLXUFV-UHFFFAOYSA-N 1-phenylethylbenzene Chemical compound C=1C=CC=CC=1C(C)C1=CC=CC=C1 BSZXAFXFTLXUFV-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens 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
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- -1 silica Chemical compound 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- LPHBARMWKLYWRA-UHFFFAOYSA-N thallium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tl+3].[Tl+3] LPHBARMWKLYWRA-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N trans-stilbene Chemical group C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はトルエン又はキシレンを酸化的脱水素
による二量化反応により二量化するための触媒に
関する。
従来、トルエン又はキシレンを脱水素により
１，２−ジフエニルエタン類又は１，２−ジフエ
ニルエチレン類等を製造する方法は多く知られて
いる。例えば、この脱水素反応における水素受容
体としてハロゲン、イオウ、二硫化炭素などを用
いる方法が古くより知られているが、この方法で
は水素受容体が高価であり、腐蝕性物質を生成す
ること、又、目的生成物中にハロゲン化物や硫化
物が混入してくるなどの不都合がみられる。
上記脱水素反応による欠点を解消する方法とし
て酸素を水素受容体とする方法が提案されてお
り、この水素受容体となる酸素として酸化鉛のよ
うな金属酸化物が反応中の酸素源となることは、
特開昭50−105602号に開示されている。即ち、こ
の方法はプロペン、トルエンおよび酢酸その他の
化合物を酸素含有の再生しうる試剤の存在下に遊
離の分子酸素を存在させることなく酸化的カツプ
リングによつて夫々の脱水素二量化生成物に転換
せしめうる方法である。ここで“酸素含有の再生
しうる試剤”とは特定の金属酸化物であり、上記
特開昭50−105602号には三酸化ビスマスの他に三
酸化タリウムがあげられている。このような金属
酸化物を触媒とする二量化方法については多数の
提案がなされており、種々の金属酸化物が二量化
触媒として効果のあることが知られている。
また、上記金属酸化物としては酸化鉛、酸化タ
リウム及び酸化ビスマス等が知られているが、こ
れら金属酸化物はそれ自体では二量化用触媒とし
ての効果は格別なものではなく、したがつて特開
昭50−105602号では酸化タリウム、酸化ビスマス
を表面積が20m2／ｇ以上である塩基性担体材料上
に担持させることによりその触媒活性を増大させ
ることを提案している。
本発明者等はトルエン又はキシレンを二量化し
て１，２−ジフエニルエタン類、１，２−ジフエ
ニルエチレン類又は１，２−ジトリルエタン類、
１，２−ジトリルエチレン類の製造についてその
収率を向上させるべく研究した結果、酸化タリウ
ムを酸化イツトリウムで活性化したとき、トルエ
ン又はキシレンの転化率を著しく向上させ得るこ
とを見出し、本発明に至つた。すなわち、本発明
はトルエン又はキシレンを有利に二量化するため
の触媒を提供すること、及び該触媒を用いてトル
エン又はキシレンを有利に二量化する方法を提供
することを目的とする。
以下本発明を詳しく説明する。
本発明に係る触媒は酸化イツトリウムで活性化
された酸化タリウムであつて、その組成比が式
TlaYbOc
（式中、ａは0.2〜4.0、ｂは１を表わし、ｃは上
記組成物中の酸化状態におけるTl及びＹの平均
原子価をみたすために必要な数を表わす）
の関係にあることにより特徴付けられるトルエン
又はキシレンを酸化的脱水素反応により二量化す
るための触媒である。
又本発明に係る二量化方法はトルエン又はキシ
レンを含む気体を上記触媒の存在下で加熱するこ
とを特徴とする。
本発明の触媒は酸化タリウムに酸化イツトリウ
ムを所望の組成比になるごとく混合し、この混合
物を成型、乾燥後600乃至800℃の温度で焼成する
ことにより調製し得る。
すなわち、上記混合物の焼成により酸化タリウ
ムは酸化イツトリウムにより活性化される。この
ようにして得られる金属酸化物は下記式の組成比
を有する。
TlaYbOc
（式中、ａ、ｂ及びｃは前記と同じ意味を表わ
す）ここで使用する酸化イツトリウムはそれ自体
触媒活性の低いものであることを考慮すると、酸
化タリウムが酸化イツトリウムにより活性化され
てトルエン又はキシレンの高い転化率を示す触媒
活性を呈するようになることは驚くべきことと言
えよう。
本発明の触媒はトルエン並びにキシレンに対し
て不活性な担体、例えばシリカ、アルミナ、シリ
カ−アルミナ等に担持させてもよい。
なお、本発明の触媒は上記一般式においてａが
0.4〜2.0及びｂが１である組成比を有するものが
トルエン又はキシレンの転化率を著しく高めるの
で特に好ましい。
次に、上記触媒を用いてのトルエン又はキシレ
ンの二量化方法にいて説明する。
本発明においてはトルエン又はキシレンは気相
で用いられるが、それらは単独でもよく、又窒素
やヘリウムのごとき反応上不活性な気体と混合し
て用いてもよい。又トルエン又はキシレンを水蒸
気と混合して用いることもでき、この場合には水
蒸気は反応に際しトルエン又はキシレンの完全酸
化（完全酸化によりCO2を生成する）を抑制する
ので本発明の方法の実施上好ましい。水蒸気の混
合割合は水とトルエン又はキシレンとのモル比が
0.5〜３である範囲が適当である。
トルエン又はキシレンの二量化反応は、本発明
に係る触媒の層を設けた反応器へトルエン又はキ
シレンを気相で供給し加熱することによつて行な
われる。この際の加熱温度は500〜650℃、好まし
くは550〜630℃である。反応は大気圧下、減圧下
又は加圧下でも行ない得る。
上記反応に際してのトルエン又はキシレンと触
媒との接触時間は0.1〜２秒、好ましくは0.3〜１
秒である。また、トルエン又はキシレンは通常予
め加熱して気相として反応器へ供給されるが、液
相で反応器へ供給し、反応器内へ加熱して気相に
してもよい。
本発明の方法では、触媒を流動床又は移動床と
して用いて触媒の還元−酸化を連続的に繰返し行
なつてトルエン又はキシレンを連続的に脱水素二
量化することができ、又触媒を固定床として用い
て上記二量化を断続的に行なうことも可能であ
る。又反応後の触媒の再生は粒径及び還元度に応
じて空気或は酸素中で400〜600℃の温度で10分〜
１時間処理することにより行ない得る。
本発明の方法によるトルエン又はキシレンの転
化率の向上は後記実施例から明らかになるであろ
う。
以下に実施例を示す。
実施例 １
本例は本発明の触媒の調整を例示したものであ
る。
Tl2O3274ｇとY2O3135ｇとを秤量、混合した。
この混合物に水110ｇを加え十分混合した後、加
熱して水を蒸発させた。さらに、この混合物を
150℃で10時間乾燥した後700℃で３時間焼成し、
得られた酸化物を10〜30メツシユに粉砕した。こ
のようにして得られた触媒は組成比がTl／Ｙ＝
１／１の原子比を有する。
実施例 ２
本例は実施例１で得られた各触媒を用いてトル
エンを二量化する方法を例示したものである。
直径25mm、長さ100mmのステンレス鋼管を反応
器として用い、この反応器に実施例１で得られた
触媒50mlを充填し、次いで反応器をその内壁に取
付けたヒーターで所定温度（後記第１表参照）に
加熱した後、これにトルエン及び水を気体状態で
トルエン150ml／hr、水53ml／hrの割合で導入し、
10分間加熱下で反応を行なつた。得られた反応生
成物を反応器出口に取付けた捕集器に通し、ガス
クロマトグフに導入して分析した。
反応したトルエンの割合を表わした転化率と生
成物における二量体、ベンゼン及び炭酸ガスの割
合を表わした選択率とを第１表に示す。
ここに二量体とは反応により生成した１，２−
ジフエニルエタンと１，２−ジフエニルエチレン
の和を表わす。
比較例
本例は酸化イツトリウムで活性化されていない
酸化タリウム自体及び酸化ジルコニウム自体をそ
れぞれ触媒として用いて実施例２と同様の手順で
トルエンの二量化を行なつた結果を示したもので
ある。結果は第１表に示すとおりである。
The present invention relates to a catalyst for dimerizing toluene or xylene by a dimerization reaction by oxidative dehydrogenation. Conventionally, many methods are known for producing 1,2-diphenylethanes or 1,2-diphenylethylenes by dehydrogenating toluene or xylene. For example, a method using halogen, sulfur, carbon disulfide, etc. as a hydrogen acceptor in this dehydrogenation reaction has been known for a long time, but in this method, the hydrogen acceptor is expensive and corrosive substances are generated. Further, there are disadvantages such as halides and sulfides being mixed into the target product. As a method to eliminate the drawbacks caused by the above dehydrogenation reaction, a method has been proposed in which oxygen is used as a hydrogen acceptor, and a metal oxide such as lead oxide serves as the oxygen source during the reaction. teeth,
It is disclosed in Japanese Patent Application Laid-Open No. 50-105602. That is, the process converts propene, toluene, and acetic acid, and other compounds, into their respective dehydrodimerized products by oxidative coupling in the presence of an oxygen-containing regenerable agent and in the absence of free molecular oxygen. This is a method that can be used. Here, the "oxygen-containing regenerable agent" is a specific metal oxide, and thallium trioxide is mentioned in addition to bismuth trioxide in the above-mentioned Japanese Patent Application Laid-Open No. 105602/1983. Many proposals have been made regarding such dimerization methods using metal oxides as catalysts, and it is known that various metal oxides are effective as dimerization catalysts. In addition, lead oxide, thallium oxide, bismuth oxide, etc. are known as the above-mentioned metal oxides, but these metal oxides are not particularly effective as dimerization catalysts by themselves, and therefore are not particularly effective as dimerization catalysts. Japanese Patent Publication No. 105602/1983 proposes increasing the catalytic activity of thallium oxide and bismuth oxide by supporting them on a basic carrier material having a surface area of 20 m 2 /g or more. The present inventors dimerized toluene or xylene to produce 1,2-diphenylethanes, 1,2-diphenylethylenes, or 1,2-ditolylethanes.
As a result of research to improve the yield of 1,2-ditolylethylenes, it was discovered that when thallium oxide was activated with yttrium oxide, the conversion rate of toluene or xylene could be significantly improved, and the present invention It came to this. That is, an object of the present invention is to provide a catalyst for advantageously dimerizing toluene or xylene, and to provide a method for advantageously dimerizing toluene or xylene using the catalyst. The present invention will be explained in detail below. The catalyst according to the present invention is thallium oxide activated with yttrium oxide, and its composition ratio is expressed by the formula Tl a Y b O c (wherein a represents 0.2 to 4.0, b represents 1, and c represents the above composition. It is a catalyst for dimerizing toluene or xylene by an oxidative dehydrogenation reaction, which is characterized by the following relationship: . Further, the dimerization method according to the present invention is characterized in that a gas containing toluene or xylene is heated in the presence of the above catalyst. The catalyst of the present invention can be prepared by mixing thallium oxide and yttrium oxide in a desired composition ratio, molding the mixture, drying it, and then calcining it at a temperature of 600 to 800°C. That is, by firing the mixture, thallium oxide is activated by yttrium oxide. The metal oxide thus obtained has a composition ratio of the following formula. Tl a Y b O c (In the formula, a, b and c represent the same meanings as above) Considering that the yttrium oxide used here itself has low catalytic activity, thallium oxide is It is surprising that the catalyst can be activated to exhibit catalytic activity that exhibits a high conversion rate of toluene or xylene. The catalyst of the present invention may be supported on a carrier inert to toluene and xylene, such as silica, alumina, silica-alumina, and the like. In addition, in the above general formula, a of the catalyst of the present invention is
Particularly preferred is one having a composition ratio of 0.4 to 2.0 and b of 1 because it significantly increases the conversion rate of toluene or xylene. Next, a method for dimerizing toluene or xylene using the above catalyst will be explained. In the present invention, toluene or xylene is used in a gas phase, but they may be used alone or in a mixture with a reaction-inert gas such as nitrogen or helium. It is also possible to use toluene or xylene mixed with water vapor. In this case, the water vapor suppresses the complete oxidation of toluene or xylene (to produce CO 2 due to complete oxidation) during the reaction, so it is difficult to carry out the method of the present invention. preferable. The mixing ratio of water vapor is determined by the molar ratio of water and toluene or xylene.
A range of 0.5 to 3 is suitable. The dimerization reaction of toluene or xylene is carried out by supplying toluene or xylene in a gas phase to a reactor provided with a layer of the catalyst according to the present invention and heating the reactor. The heating temperature at this time is 500 to 650°C, preferably 550 to 630°C. The reaction may also be carried out under atmospheric pressure, reduced pressure or increased pressure. The contact time of toluene or xylene with the catalyst during the above reaction is 0.1 to 2 seconds, preferably 0.3 to 1 second.
Seconds. Further, toluene or xylene is usually heated in advance and supplied to the reactor in a gaseous phase, but it may also be supplied to the reactor in a liquid phase and heated into the reactor to be converted into a gaseous phase. In the method of the present invention, toluene or xylene can be continuously dehydrogenated and dimerized by continuously repeating reduction and oxidation of the catalyst using a catalyst as a fluidized bed or a moving bed. It is also possible to perform the above dimerization intermittently by using it as a compound. In addition, the catalyst is regenerated after the reaction at a temperature of 400 to 600℃ in air or oxygen for 10 minutes or more depending on the particle size and degree of reduction.
This can be done by treating for 1 hour. The improvement in the conversion rate of toluene or xylene by the method of the present invention will become clear from the examples below. Examples are shown below. Example 1 This example illustrates the preparation of the catalyst of the present invention. 274 g of Tl 2 O 3 and 135 g of Y 2 O 3 were weighed and mixed.
110 g of water was added to this mixture, thoroughly mixed, and then heated to evaporate the water. Furthermore, this mixture
After drying at 150℃ for 10 hours, baking at 700℃ for 3 hours,
The resulting oxide was ground into 10-30 meshes. The catalyst thus obtained has a composition ratio of Tl/Y=
It has an atomic ratio of 1/1. Example 2 This example illustrates a method for dimerizing toluene using each catalyst obtained in Example 1. A stainless steel tube with a diameter of 25 mm and a length of 100 mm was used as a reactor. This reactor was filled with 50 ml of the catalyst obtained in Example 1, and then the reactor was heated to a predetermined temperature (see Table 1 below) using a heater attached to the inner wall of the reactor. ), then toluene and water were introduced in the gaseous state at a rate of 150 ml/hr of toluene and 53 ml/hr of water.
The reaction was carried out under heating for 10 minutes. The obtained reaction product was passed through a collector attached to the outlet of the reactor and introduced into a gas chromatograph for analysis. The conversion, expressed as the proportion of toluene reacted, and the selectivity, expressed as the proportion of dimer, benzene and carbon dioxide in the product, are shown in Table 1. Here, dimer refers to 1,2-
Represents the sum of diphenylethane and 1,2-diphenylethylene. Comparative Example This example shows the results of dimerizing toluene in the same manner as in Example 2 using thallium oxide itself and zirconium oxide itself, which have not been activated with yttrium oxide, as catalysts. The results are shown in Table 1.
【表】
上表にみられるように、酸化イツトリウムで活
性化した本発明の触媒を用いるとトルエンの転化
率が著しく向上する。
実施例 ３
実施例１で調製した触媒を用い、実施例２と同
様の手順により、反応温度600℃でキシレンを二
量化した。
反応したキシレンの割合を表わした転化率は
21.1％であり、二量体の選択率は73.2％、炭酸ガ
スの選択率は8.8％であつた。
なお、二量体は１，２−ジトリルエタンと１，
２−ジトリルエチレンの和である。[Table] As seen in the above table, the conversion of toluene is significantly improved using the catalyst of the present invention activated with yttrium oxide. Example 3 Using the catalyst prepared in Example 1, xylene was dimerized at a reaction temperature of 600° C. in the same manner as in Example 2. The conversion rate, which represents the proportion of xylene reacted, is
The selectivity for dimer was 73.2%, and the selectivity for carbon dioxide was 8.8%. In addition, the dimer is 1,2-ditolylethane and 1,
It is the sum of 2-ditolylethylene.
Claims (1)
ムであつて、その組成比が式 TlaYbOc （式中、ａは0.2〜4.0、ｂは１を表し、ｃは上記
組成物中の酸化状態におけるTl及びＹの平均原
子価をみたすために必要な数を表す）の関係にあ
ることを特徴とするトルエン又はキシレンの酸化
的脱水素二量化用触媒。[Claims] 1. Thallium oxide activated with yttrium oxide, whose composition ratio is expressed by the formula Tl a Y b O c (wherein a represents 0.2 to 4.0, b represents 1, and c represents the above-mentioned A catalyst for oxidative dehydrogenation and dimerization of toluene or xylene, characterized by having the following relationship (representing the number necessary to satisfy the average valence of Tl and Y in the oxidation state in the composition)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56046018A JPS57159543A (en) | 1981-03-27 | 1981-03-27 | Catalyst for oxidative dehydrogenation dimerization |
| US06/358,214 US4438021A (en) | 1981-03-27 | 1982-03-15 | Catalyst for dehydrocoupling of toluene or xylene |
| DE3210709A DE3210709C2 (en) | 1981-03-27 | 1982-03-24 | Thallium oxide-containing catalyst and its use |
| GB8208995A GB2097278B (en) | 1981-03-27 | 1982-03-26 | Catalyst for dehydrocoupling toluene or xylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56046018A JPS57159543A (en) | 1981-03-27 | 1981-03-27 | Catalyst for oxidative dehydrogenation dimerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57159543A JPS57159543A (en) | 1982-10-01 |
| JPH0243538B2 true JPH0243538B2 (en) | 1990-09-28 |
Family
ID=12735302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56046018A Granted JPS57159543A (en) | 1981-03-27 | 1981-03-27 | Catalyst for oxidative dehydrogenation dimerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57159543A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60161747A (en) * | 1984-01-28 | 1985-08-23 | エクソン リサ−チ アンド エンヂニアリング コムパニ− | Manufacture of inorganic metallic oxygen composition which can dehydrogenation-couple toluene |
-
1981
- 1981-03-27 JP JP56046018A patent/JPS57159543A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57159543A (en) | 1982-10-01 |
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