JPH089481B2 - Process for producing a mixture of isobutylene and synthesis gas - Google Patents
Process for producing a mixture of isobutylene and synthesis gasInfo
- Publication number
- JPH089481B2 JPH089481B2 JP62086594A JP8659487A JPH089481B2 JP H089481 B2 JPH089481 B2 JP H089481B2 JP 62086594 A JP62086594 A JP 62086594A JP 8659487 A JP8659487 A JP 8659487A JP H089481 B2 JPH089481 B2 JP H089481B2
- Authority
- JP
- Japan
- Prior art keywords
- isobutylene
- mixture
- synthesis gas
- catalyst
- producing
- 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
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
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明はイソブチレンと合成ガスとの混合物の製造方
法に関し、詳しくはイソブチレンとメタノールの混合物
を200〜400℃の温度下、銅系触媒に接触させることを特
徴とするイソブチレンと合成ガスとの混合物の製造方法
に関する。DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to a method for producing a mixture of isobutylene and synthesis gas, more specifically, a mixture of isobutylene and methanol is contacted with a copper-based catalyst at a temperature of 200 to 400 ° C. And a method for producing a mixture of isobutylene and synthesis gas.
＜従来の技術＞ オレフィン類と合成ガス（一酸化炭素と水素の混合
物）は、例えばオキソ反応によるアルデヒド類の製造原
料として有用であり、両者は通常混合して使用される
（例えば特開昭58−206537号公報）。<Prior Art> Olefins and synthesis gas (a mixture of carbon monoxide and hydrogen) are useful as raw materials for producing aldehydes by, for example, an oxo reaction, and both are usually mixed and used (for example, JP-A-58). -206537).
また合成ガスはメタノールの分解により得られ、触媒
としてVIII族金属触媒、銅または亜鉛系の触媒等が使用
され、中でも白金、パラジウム触媒が高い分解活性を示
すことも知られている（例えば、特開昭57−68140号公
報、石油化学誌24，（５）,322（1981））。It is also known that the synthesis gas is obtained by decomposing methanol, and a Group VIII metal catalyst, a copper- or zinc-based catalyst, or the like is used as a catalyst, and among them, platinum and palladium catalysts show high decomposition activity (for example, KAISHO 57-68140, Petrochemical magazine 24 , (5), 322 (1981)).
＜発明が解決しようとする問題点＞ しかしながら、イソブチレンの共存下にイソブチレン
の水添等の副反応を殆ど惹起することなしに、メタノー
ルを選択的に合成ガスに変換する技術は全く知られてい
ない。<Problems to be Solved by the Invention> However, there is no known technique for selectively converting methanol into synthesis gas without causing side reactions such as hydrogenation of isobutylene in the presence of isobutylene. .
＜問題を解決するための手段＞ 本発明者らはイソブチレンとメタノールの混合物から
イソブチレンと合成ガスとの混合物を工業的に有利に製
造する方法を開発すべく、鋭意検討を重ねた結果、触媒
および反応条件の選定が重要であり、特定の触媒を特定
条件下で使用すれば共存するイソブチレンの水添等の副
反応を殆ど伴うことなしに、メタノールが選択的に合成
ガスに変換することを見い出し、更に種々の検討を加え
本発明に至った。<Means for Solving the Problem> The present inventors have earnestly studied to develop a method for industrially advantageously producing a mixture of isobutylene and synthesis gas from a mixture of isobutylene and methanol, and as a result, catalyst and It has been found that the selection of reaction conditions is important, and that when a specific catalyst is used under specific conditions, methanol is selectively converted into syngas with almost no side reaction such as hydrogenation of coexisting isobutylene. Further, various studies have been conducted to arrive at the present invention.
すなわち本発明はイソブチレンとメタノールの混合物
を200〜400℃の温度下、銅系触媒に接触させることを特
徴とするイソブチレンと合成ガスとの混合物の工業的に
優れた製造方法を提供するものである。That is, the present invention provides an industrially excellent method for producing a mixture of isobutylene and synthesis gas, which comprises contacting a mixture of isobutylene and methanol at a temperature of 200 to 400 ° C. with a copper-based catalyst. .
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明において使用される原料はイソブチレンとメタ
ノールの混合物であるが、そのモル比は特に制限はな
く、通常1/10〜10/1の範囲である。またブテン類、ブタ
ン類が混入していても良い。The raw material used in the present invention is a mixture of isobutylene and methanol, but the molar ratio thereof is not particularly limited and is usually in the range of 1/10 to 10/1. Also, butenes and butanes may be mixed.
かかる原料はイソブチレンとメタノールを混合したも
のでも良いが、工業的にはメチル−ｔ−ブチルエーテル
（MTBE）の分解により得られたものが、両者を分離する
ことなしにそのまま使用できるので有利である。例えば
MTBEをシリカ−アルミナ、シリカ−チタニア、硫酸ニッ
ケル、硫酸アルミニウム、リン酸ジルコニウム、リン酸
ホウ素、モンモリロナイト、モレキュラーシーブ13X、1
3Y、ZSM−５等の各種固体酸触媒に70〜500℃、常圧〜10
0気圧で接触せしめることにより容易にイソブチレンと
合成ガスとの混合物が得られるが、該混合物を使用する
こともできる。この場合、同一の反応器に上記したよう
な固体酸触媒と、後述の本発明に使用する銅系触媒とを
充填するか、もしくは直列につながった二つの反応器に
それぞれの触媒を充填することにより、一挙にMTBEから
イソブチレンと合成ガスを製造することもできる。Such a raw material may be a mixture of isobutylene and methanol, but industrially, a raw material obtained by decomposing methyl-t-butyl ether (MTBE) can be used as it is without separating the two, and is advantageous. For example
MTBE silica-alumina, silica-titania, nickel sulfate, aluminum sulfate, zirconium phosphate, boron phosphate, montmorillonite, molecular sieve 13X, 1
Various solid acid catalysts such as 3Y, ZSM-5, 70-500 ℃, normal pressure-10
A mixture of isobutylene and synthesis gas can be easily obtained by contacting at 0 atm, but the mixture can also be used. In this case, the same reactor is charged with the solid acid catalyst as described above and the copper-based catalyst used in the present invention described below, or two reactors connected in series are charged with the respective catalysts. Thus, isobutylene and synthesis gas can be produced from MTBE all at once.
本発明で使用される触媒は銅系の触媒であり、該触媒
を用いることにより、イソブチレンの水添等の副反応を
防止でき、しかもメタノールを選択的に一酸化炭素と水
素に変換させることができる。The catalyst used in the present invention is a copper-based catalyst, and by using the catalyst, a side reaction such as hydrogenation of isobutylene can be prevented, and further, methanol can be selectively converted into carbon monoxide and hydrogen. it can.
かかる触媒としては、例えば銅もしくは銅と亜鉛およ
び／またはクロムを含む触媒が挙げられ、好ましくは銅
を含む上記二元系、三元系触媒である。これ等は酸化物
の形で表わすと、CuO系、CuO−ZnO系、CuO−Cr2O3系、C
uO−ZnO−Cr2O3系触媒等が例示でき、単味で用いてもシ
リカやアルミナ等の担体で希釈して用いても良く、また
担体に担持されたものを用いても良い。Examples of such a catalyst include a catalyst containing copper or copper and zinc and / or chromium, and preferably the above binary or ternary catalyst containing copper. When expressed in the form of oxides, these are CuO-based, CuO-ZnO-based, CuO-Cr 2 O 3 -based, C
Examples include uO—ZnO—Cr 2 O 3 based catalysts, which may be used alone or diluted with a carrier such as silica or alumina, or may be supported on a carrier.
ここで、触媒中の銅の含有率は通常CuOとして、約５
〜80重量％の範囲であり、亜鉛および／またはクロムを
含む場合のそれらの含有率は通常は、それぞれZnOとし
て約５〜80重量％、Cr2O3として約５〜80重量％の範囲
である。また本発明で使用される触媒は常法に従い沈澱
法、含浸法、イオン交換法、熱分解法等によって製造す
ることができ、通常H2/N2気流下等で還元処理を行った
後に反応に供される。Here, the content of copper in the catalyst is usually about 5 as CuO.
The content of zinc and / or chromium is usually in the range of about 5 to 80% by weight as ZnO and about 5 to 80% by weight as Cr 2 O 3 , respectively. is there. Further, the catalyst used in the present invention can be produced by a precipitation method, an impregnation method, an ion exchange method, a thermal decomposition method, etc. according to a conventional method, and the reaction is usually carried out after a reduction treatment under an H 2 / N 2 stream or the like. Be used for.
反応温度は200〜400℃の範囲が好ましく、この範囲以
外では目的物の選択性あるいは触媒活性の維持等の点で
良好な結果が得られない。より好ましくは240〜380℃で
ある。The reaction temperature is preferably in the range of 200 to 400 ° C. Outside of this range, good results cannot be obtained in terms of selectivity of the target product or maintenance of catalyst activity. More preferably, it is 240 to 380 ° C.
また原料供給速度は反応温度、反応圧力等にもよる
が、空塔速度（SV）は通常１×103〜１×105hr-1の範囲
である。Although the raw material supply rate depends on the reaction temperature, the reaction pressure, etc., the superficial velocity (SV) is usually in the range of 1 × 10 3 to 1 × 10 5 hr −1 .
反応圧力は特に制限されないが、通常、常圧〜100気
圧であり、好ましくは常圧〜40気圧である。The reaction pressure is not particularly limited, but is usually atmospheric pressure to 100 atm, preferably atmospheric pressure to 40 atm.
かくしてイソブチレンと一酸化炭素と水素との混合物
が得られるが、これ等は高純度であるので、そのままで
もオキソ反応の原料ともなり得る。また各成分を分離し
た後、種々の用途に使用することもできる。Thus, a mixture of isobutylene, carbon monoxide and hydrogen is obtained. Since these are highly pure, they can be used as they are as a raw material for the oxo reaction. Moreover, after separating each component, it can be used for various purposes.
＜発明の効果＞ 本発明によれば、メタノールを選択的に合成ガスに変
更させることができ、しかもイソブチレンの水添等の副
反応を防止できるので、イソブチレンと合成ガスとの混
合物が高収率でしかも高純度で得られる。<Effects of the Invention> According to the present invention, since methanol can be selectively changed to synthesis gas and side reactions such as hydrogenation of isobutylene can be prevented, a high yield of a mixture of isobutylene and synthesis gas can be obtained. Moreover, it can be obtained with high purity.
また本発明は、原料としてメチル−ｔ−ブチルエーテ
ル（MTBE）の分解により得られるイソブチレンとメタノ
ールの混合物を、そのまま使用し得る。すなわちMTBEの
分解工程と本発明を結合することによりMTBEからイソブ
チレンと合成ガスとの混合物を一挙に効率良く製造し得
るという利点も有す。Further, in the present invention, a mixture of isobutylene and methanol obtained by decomposing methyl-t-butyl ether (MTBE) as a raw material can be used as it is. That is, there is also an advantage that a mixture of isobutylene and synthesis gas can be efficiently produced from MTBE all at once by combining the MTBE decomposition step and the present invention.
＜実施例＞ 以下、本発明を実施例によりさらに詳細に説明する
が、本発明は実施例のみに限定されるものではない。<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.
実施例１〜６、および比較例1,2 原料供給ポンプ、予熱器、反応器および生成物補集器
を備えた常圧気相流通反応装置を用いて反応を行った。Examples 1 to 6 and Comparative Examples 1 and 2 The reaction was carried out using an atmospheric pressure gas phase flow reactor equipped with a raw material supply pump, a preheater, a reactor and a product collector.
反応器に表１に示した触媒（24〜28メッシュに粉砕）
3.0gを充填し、H2/N2気流下200〜230℃で７時間還元処
理した後、イソブチレンとメタノールの等モル混合物を
8.3g/hrで供給し、所定の温度で反応させた。Catalyst shown in Table 1 in reactor (crushed to 24-28 mesh)
After filling with 3.0 g and reducing treatment at 200 to 230 ° C. for 7 hours under H 2 / N 2 gas flow, an equimolar mixture of isobutylene and methanol was added.
It was supplied at 8.3 g / hr and reacted at a predetermined temperature.
定常状態になった時点（反応後約２〜６時間後）の結
果を表１に示した。Table 1 shows the results when the steady state was reached (about 2 to 6 hours after the reaction).
尚、表中の転化率、収率は下式により算出した。 The conversion rate and yield in the table were calculated by the following formulas.
＜触媒＞ ＜参考例＞ 原料のフィードポンプ、予熱器、直列につながった２
個の反応器および生成物の捕集器を備えた気相流通反応
装置を使用して反応を行った。 <Catalyst> <Reference example> Feed pump of raw material, preheater, 2 connected in series
The reaction was carried out using a gas phase flow reactor equipped with a single reactor and a product collector.
一段目の反応器には空気中、550℃で焼成したシリカ
−アルミナ触媒を2.0g、二段目の反応器にはCuOを45wt
％、ZnOを45wt％、Cr2O3を10wt％含有する複合酸化物触
媒を3.0gを充填し、一段目、二段目の反応温度がそれぞ
れ147℃および285℃になるように設定した。2.0g of silica-alumina catalyst calcined at 550 ℃ in air was used for the first reactor, and 45wt of CuO was used for the second reactor.
%, ZnO of 45 wt% and Cr 2 O 3 of 10 wt% were charged in an amount of 3.0 g, and the reaction temperatures of the first and second stages were set to 147 ° C. and 285 ° C., respectively.
メチル−ｔ−ブチルエーテルを10g/hrでフィードして
反応を行った。得られた結果を以下に示す。収率、転化
率はメチル−ｔ−ブチルエーテルのフィードモル数基準
で示した。The reaction was carried out by feeding methyl-t-butyl ether at 10 g / hr. The results obtained are shown below. The yield and conversion rate are shown on the basis of the number of feed moles of methyl-t-butyl ether.
メチル−ｔ−ブチルエーテルの転化率は98.9％、一酸
化炭素の収率は93.7％、水素の収率は187.1％、メタノ
ールの収率は2.5％、メタンの収率は0.6％、炭酸ガスの
収率は1.5％であり、イソブチレンの収率は98.7％であ
った。Conversion rate of methyl-t-butyl ether is 98.9%, carbon monoxide yield is 93.7%, hydrogen yield is 187.1%, methanol yield is 2.5%, methane yield is 0.6%, carbon dioxide gas yield is The ratio was 1.5% and the yield of isobutylene was 98.7%.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｃ 45/50 9049−4Ｈ 47/22 Ｇ 9049−4Ｈ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical indication C07C 45/50 9049-4H 47/22 G 9049-4H
Claims (1)
で該混合物を200〜400℃の温度下、銅系触媒に接触させ
ることを特徴とするイソブチレンと合成ガスとの混合物
の製造方法。1. A method for producing a mixture of isobutylene and synthesis gas, which comprises mixing isobutylene and methanol and then contacting the mixture with a copper-based catalyst at a temperature of 200 to 400 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62086594A JPH089481B2 (en) | 1987-04-07 | 1987-04-07 | Process for producing a mixture of isobutylene and synthesis gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62086594A JPH089481B2 (en) | 1987-04-07 | 1987-04-07 | Process for producing a mixture of isobutylene and synthesis gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63252902A JPS63252902A (en) | 1988-10-20 |
| JPH089481B2 true JPH089481B2 (en) | 1996-01-31 |
Family
ID=13891327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62086594A Expired - Lifetime JPH089481B2 (en) | 1987-04-07 | 1987-04-07 | Process for producing a mixture of isobutylene and synthesis gas |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH089481B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110342712A (en) * | 2019-06-28 | 2019-10-18 | 金澳科技（湖北）化工有限公司 | A kind of processing system and method applied to MTBE extraction water |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335532A (en) * | 1986-07-31 | 1988-02-16 | Sumitomo Chem Co Ltd | Production of isovaleraldehyde and/or isoamyl alcohol |
-
1987
- 1987-04-07 JP JP62086594A patent/JPH089481B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6335532A (en) * | 1986-07-31 | 1988-02-16 | Sumitomo Chem Co Ltd | Production of isovaleraldehyde and/or isoamyl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63252902A (en) | 1988-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5559275A (en) | Process for the conversion of lower alcohols to higher branched oxygenates | |
| US5573990A (en) | Process for the conversion of methanol to light olefins and catalyst for such process | |
| US6376562B1 (en) | Hybrid catalyst for hydrocarbon synthesis via hydrogenation of carbon dioxide | |
| KR100192527B1 (en) | Process for preparation of hydrogen rich gas | |
| EP2796197A1 (en) | Catalyst for preparing ethylene and propylene by using methyl alcohol and/or dimethyl ether, and preparation method and application of ethylene and propylene | |
| AU602438B2 (en) | One-step process for dimethyl ether synthesis utilizing a liquid phase reactor system | |
| US5216034A (en) | Process for the production of methanol | |
| EP0050992A1 (en) | Production of tertiary olefins | |
| EP0009976A1 (en) | Process for the production of amorphous aluminosilicates and their use as catalysts | |
| Gredig et al. | Comparative study of synthesis of methylamines from carbon oxides and ammonia over Cu/A12O3 | |
| EP0393895B1 (en) | Silicometallate molecular sieves and their use as catalysts in oxidation of alkanes | |
| US4433174A (en) | Process for preparation of alpha, beta-unsaturated aldehydes using AMS-1B borosilicate crystalline molecular sieve | |
| JPH1036311A (en) | Production of alpha, beta-unsaturated carboxylic acid | |
| EP0409517B1 (en) | Process for decomposition of methanol | |
| JPH089481B2 (en) | Process for producing a mixture of isobutylene and synthesis gas | |
| JP2813770B2 (en) | Ethanol production method | |
| JPH0637401B2 (en) | Method for producing hydrocarbon by hydrogenation of carbon dioxide | |
| JP2841500B2 (en) | Method for producing propane by hydrogenation of carbon dioxide | |
| JPH08176034A (en) | Synthesis of methanol | |
| CN112661620A (en) | Preparation method of cyclopentanone | |
| US20190262821A1 (en) | Catalyst composition for conversion of alkanes to alkenes and method of preparation thereof | |
| JPH0660113B2 (en) | Method for producing isovaleraldehyde and / or isoamyl alcohol | |
| JPH04273829A (en) | Transformation of formaldehyde to hydrocarbon | |
| EP0080759B1 (en) | Process for the preparation of 3,5-dimethylphenol | |
| JP2005246261A (en) | Catalyst for synthesizing formate and methanol and method for producing formate and methanol |