JPH0150278B2 - - Google Patents
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- Publication number
- JPH0150278B2 JPH0150278B2 JP56194125A JP19412581A JPH0150278B2 JP H0150278 B2 JPH0150278 B2 JP H0150278B2 JP 56194125 A JP56194125 A JP 56194125A JP 19412581 A JP19412581 A JP 19412581A JP H0150278 B2 JPH0150278 B2 JP H0150278B2
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated hydrocarbons
- water
- highly unsaturated
- hydrocarbons
- reaction
- 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
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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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
本発明はジエン類、アセチレン類のモノエン類
への選択的水素添加法に関するものである。さら
に詳しくは分子内に２以上の二重結合および／ま
たは１以上の三重結合を有する不飽和炭化水素
（以下、高度に不飽和な炭化水素と称す）を含む
炭素数４以上の不飽和炭化水素混合物を触媒の存
在下に水素と接触させて二重結合の異性化を伴わ
ずに高度に不飽和な炭化水素のみを対応する低不
飽和度の炭化水素に転化する方法に関するもので
ある。
高度に不飽和な炭化水素を含む炭素数４以上の
不飽和炭化水素混合物と水素を水素化触媒の存在
下に反応させて高度に不飽和な炭化水素を対応す
る低不飽和度の炭化水素に選択的に水素添加する
方法は一般に公知であり、たとえばブタジエン、
メチルアレン等のジエン類、ジメチルアセチレ
ン、エチルアセチレン、ビニルアセチレン等のア
セチレン類および１−ブテン、２−ブテン、イソ
ブテン等のモノオレフイン類を含有する炭素数４
の不飽和炭化水素混合物を水素とともにパラジウ
ム、白金、ニツケルなどの水素化触媒の存在下に
反応させてジエン類、アセチレン類のみを選択的
に水添する方法は工業的にも採用されている。
しかしながらこれら公知の選択的水素添加方法
においては、２以上の二重結合および１以上の三
重結合など高度に不飽和な結合への選択的水素添
加と同時に二重結合の分子内移動が容易に起こり
反応生成物の組成が大きく変つてしまう欠点があ
つた。たとえばブタジエン類、ブチン類を含む炭
素数４の不飽和炭化水素の選択的水添反応を行な
つた場合、ブタジエン類、ブチン類からブテンへ
の選択的水素添加と同時に１−ブテンから２−ブ
テンへの異性化が容易に進みこのため反応生成物
中の１−ブテン濃度が大きく減少してしまう。
１−ブテンはポリオレフイン製造用モノマーと
して重要であり、炭素数４の炭化水素混合物中の
１−ブテンの有効利用をはかる上からも異性化を
伴わないで高度に不飽和な炭化水素のみを選択的
に水添できる方法の出現が強く望まれていた。
本発明者らはこのようなオレフイン類の異性化
を伴わない高度に不飽和な炭化水素の選択的水添
方法について鋭意研究を行ない本発明に到達した
ものである。
すなわち高度に不飽和な炭化水素を含む炭素数
４以上の低不飽和度の炭化水素をパラジウム触媒
の存在下に水素と接触させ前記の高度に不飽和な
炭化水素を選択的に水素添加する方法において、
高度に不飽和な炭化水素を含む炭素数４以上の低
不飽和度の炭化水素混合物に対して0.005〜５重
量％の水および０〜0.5重量％のアンモニアの存
在下に水添反応を行なうことにより、オレフイン
類の異性化をほとんど伴うことなく高度に不飽和
な炭化水素の選択的水添反応のみが進行すること
を見出したものである。
本発明方法には水を存在させることが必要であ
るが、水は液体の状態で系に添加してもよいし、
また水蒸気の形で系に添加してもよい。
水のみを系に存在させても十分その効果が発揮
されるが、アンモニアを水と共に存在させるとよ
り望ましい結果が得られる。
水は原料炭化水素混合物に対して0.005〜５重
量％存在させることが必要であり、好ましくは
0.01〜1.0重量％存在させるのがよい。水を原料
炭化水素混合物に対して0.005重量％未満存在さ
せても水の添加効果はほとんどなく、また５重量
％を越えて存在させても特に効果の増加は期待で
きない。またアンモニアは原料炭化水素に対して
０〜0.5重量％存在させることが必要であり、好
ましくは0.005〜0.1重量％存在させるのがよい。
オレフイン類の異性化を伴わずに高度に不飽和な
炭化水素を選択的に水添する方法として大量の
COガスを含んだH2ガスを用いて選択的水添反応
を行なう方法（特公昭46−30808号）一段目に気
液混相で水添し、二段目は液相で水添する方法
（特公昭52−16082号）あるいは特殊な触媒を用い
る方法（特公昭50−28922号、ドイツ特許2108276
号）等が提案されている。しかしながらこれらの
方法はそれぞれ高価なCOガスを用いる必要があ
るとか、特殊な触媒を用いる必要があるとか、ま
たプロセスが煩雑になるとかの欠点を有してい
た。
本発明方法は安価な水もしくは水およびアンモ
ニアを少量存在させるだけでオレフイン類の異性
化を伴なうことなく高度に不飽和な炭化水素の選
択的水素添加反応のみが進行する方法を提供する
ものでありその工業的意義は大きい。
本発明方法に用いられる高度に不飽和な炭化水
素を含む炭素数４以上の低不飽和度の炭化水素混
合物としてはナフサ等のスチームクラツキングに
よつて得られるいわゆるC4留分と呼ばれるブタ
ジエン、ブテン、ブタン等からなるC4炭化水素
混合物、そしてこのC4留分からブタジエンの大
部分を抽出によつて取り除いたいわゆるスペント
BB留分と呼ばれるC4炭化水素混合物、このスペ
ントBB留分からさらにイソブチレンを取り除い
た１−ブテンおよび２−ブテンを主成分とする
C4炭化水素混合物、それにイソプレン等のC5炭
化水素類を主成分とする炭化水素混合物などが挙
げられる。これらの炭化水素混合物中に含まれる
高度に不飽和な炭化水素としてはプロパジエン、
メチルアセチレン、１，２−ブタジエン、１，３
−ブタジエン、エチルアセチレン、ビニルアセチ
レン、１，３−ペンタジエン等がある。
本発明方法には水添触媒としてパラジウム触媒
が用いられる。パラジウム触媒としてはパラジウ
ムブラツク、パラジウム担持カーボン、パラジウ
ム担持アルミナ等があるが、通常、アルミナ等の
担体にパラジウムを0.02〜２重量％担持した触媒
が用いられる。
本発明方法における反応形態は特に限定される
ものではなく、液相、気相あるいはトリクル相の
ような気液混相のいずれの方法で行なつてもよい
が、気相反応において水または水およびアンモニ
アの共存効果が最も発揮され好ましくは気相反応
で行なわれる。また反応条件としては通常反応温
度は−20〜150℃、反応圧力は常圧〜50気圧の条
件下で行なわれる。以下に実施例を用いて本発明
方法の説明を行なうが、本発明の範囲はこれらに
よつて制限を受けるものではない。
実施例 １
0.1重量％のパラジウムをアルミナに担持した
触媒100mlを内径20mmの垂直に配置した反応管内
に充填し温度60℃、圧力４気圧の条件下で第１表
の原料欄に記載した組成を持つ炭化水素混合物を
500ｇ／hrの供給速度でまた水を２ｇ／hrの供給
速度で反応器に導入し、また水素ガスを８
（N.T.P.換算）／hrの供給速度で反応器に導入し
選択的水素添加反応を行なつた。得られた炭化水
素生成物の組成は第１表の生成物欄に示すとおり
であつた。
The present invention relates to a method for selectively hydrogenating dienes and acetylenes to monoenes. More specifically, unsaturated hydrocarbons having 4 or more carbon atoms, including unsaturated hydrocarbons having 2 or more double bonds and/or 1 or more triple bonds in the molecule (hereinafter referred to as highly unsaturated hydrocarbons) The present invention relates to a method of contacting a mixture with hydrogen in the presence of a catalyst to convert only highly unsaturated hydrocarbons into corresponding hydrocarbons with a lower degree of unsaturation without isomerization of double bonds. A mixture of unsaturated hydrocarbons with a carbon number of 4 or more, including highly unsaturated hydrocarbons, is reacted with hydrogen in the presence of a hydrogenation catalyst to convert the highly unsaturated hydrocarbons into corresponding hydrocarbons with a low degree of unsaturation. Methods of selective hydrogenation are generally known; for example, butadiene,
Carbon number 4 containing dienes such as methylalene, acetylenes such as dimethylacetylene, ethylacetylene, vinyl acetylene, and monoolefins such as 1-butene, 2-butene, isobutene, etc.
A method of selectively hydrogenating only dienes and acetylenes by reacting a mixture of unsaturated hydrocarbons with hydrogen in the presence of a hydrogenation catalyst such as palladium, platinum, or nickel has also been adopted industrially. However, in these known selective hydrogenation methods, intramolecular movement of double bonds easily occurs at the same time as selective hydrogenation of highly unsaturated bonds such as two or more double bonds and one or more triple bonds. The drawback was that the composition of the reaction product changed significantly. For example, when carrying out a selective hydrogenation reaction of unsaturated hydrocarbons having 4 carbon atoms including butadienes and butynes, it is possible to selectively hydrogenate from butadienes and butynes to butenes and simultaneously convert 1-butene to 2-butene. The isomerization to 1-butene easily proceeds, resulting in a large decrease in the concentration of 1-butene in the reaction product. 1-Butene is important as a monomer for producing polyolefins, and in order to effectively utilize 1-butene in a mixture of hydrocarbons with 4 carbon atoms, highly unsaturated hydrocarbons can be selectively extracted without isomerization. There was a strong desire for a method that could hydrogenate The present inventors have conducted intensive research on a method for selective hydrogenation of highly unsaturated hydrocarbons that does not involve isomerization of such olefins, and have arrived at the present invention. That is, a method of selectively hydrogenating the highly unsaturated hydrocarbons by contacting hydrocarbons with a low degree of unsaturation with carbon atoms of 4 or more, including highly unsaturated hydrocarbons, with hydrogen in the presence of a palladium catalyst. In,
Performing a hydrogenation reaction on a hydrocarbon mixture having a carbon number of 4 or more and having a low degree of unsaturation, including highly unsaturated hydrocarbons, in the presence of 0.005 to 5% by weight of water and 0 to 0.5% by weight of ammonia. It was discovered that only the selective hydrogenation reaction of highly unsaturated hydrocarbons proceeds with almost no isomerization of olefins. Although the method of the invention requires the presence of water, water may be added to the system in liquid form or
It may also be added to the system in the form of water vapor. Although the effect is sufficiently exhibited even when water alone is present in the system, more desirable results are obtained when ammonia is present together with water. Water needs to be present in an amount of 0.005 to 5% by weight based on the raw material hydrocarbon mixture, preferably
Preferably, it is present in an amount of 0.01 to 1.0% by weight. Even if water is present in an amount less than 0.005% by weight based on the raw material hydrocarbon mixture, there is almost no effect of adding water, and even if it is present in an amount exceeding 5% by weight, no particular increase in the effect can be expected. Further, ammonia needs to be present in an amount of 0 to 0.5% by weight, preferably 0.005 to 0.1% by weight, based on the raw material hydrocarbon.
A method for selectively hydrogenating highly unsaturated hydrocarbons without isomerizing olefins.
A method in which selective hydrogenation is carried out using H2 gas containing CO gas (Special Publication No. 30808/1983) A method in which hydrogenation is carried out in a gas-liquid mixed phase in the first step, and a method in which hydrogenation is carried out in a liquid phase in the second step ( (Special Publication No. 52-16082) or method using a special catalyst (Special Publication No. 50-28922, German Patent No. 2108276)
No.) etc. have been proposed. However, each of these methods has drawbacks such as the need to use expensive CO gas, the need to use a special catalyst, and the complicated process. The method of the present invention provides a method in which only the selective hydrogenation reaction of highly unsaturated hydrocarbons proceeds without isomerization of olefins in the presence of a small amount of inexpensive water or water and ammonia. Therefore, its industrial significance is great. The hydrocarbon mixture containing highly unsaturated hydrocarbons and having a carbon number of 4 or more and having a low degree of unsaturation used in the method of the present invention is butadiene, a so-called C 4 fraction obtained by steam cracking of naphtha, etc. , a C 4 hydrocarbon mixture consisting of butene, butane, etc., and a so-called spent product from which most of the butadiene has been removed by extraction from this C 4 fraction.
A C4 hydrocarbon mixture called the BB fraction, whose main components are 1-butene and 2-butene, which are obtained by further removing isobutylene from this spent BB fraction.
Examples include C 4 hydrocarbon mixtures and hydrocarbon mixtures containing C 5 hydrocarbons such as isoprene as a main component. Highly unsaturated hydrocarbons contained in these hydrocarbon mixtures include propadiene,
Methylacetylene, 1,2-butadiene, 1,3
-butadiene, ethylacetylene, vinylacetylene, 1,3-pentadiene, etc. A palladium catalyst is used as a hydrogenation catalyst in the method of the present invention. Palladium catalysts include palladium black, palladium-supported carbon, palladium-supported alumina, etc., but catalysts in which 0.02 to 2% by weight of palladium is supported on a carrier such as alumina are usually used. The reaction form in the method of the present invention is not particularly limited, and may be carried out in any of the liquid phase, gas phase, or gas-liquid mixed phase such as trickle phase, but in the gas phase reaction, water or water and ammonia Since the coexistence effect of the two is best exhibited, the reaction is preferably carried out in a gas phase. As for the reaction conditions, the reaction temperature is usually -20 to 150°C and the reaction pressure is normal pressure to 50 atmospheres. The method of the present invention will be explained below using Examples, but the scope of the present invention is not limited by these. Example 1 100 ml of a catalyst containing 0.1% by weight of palladium supported on alumina was filled into a vertically arranged reaction tube with an inner diameter of 20 mm, and the composition listed in the raw material column of Table 1 was prepared under conditions of a temperature of 60°C and a pressure of 4 atm. hydrocarbon mixture with
Water was introduced into the reactor at a feed rate of 500 g/hr, water was introduced at a feed rate of 2 g/hr, and hydrogen gas was introduced at a rate of 8 g/hr.
It was introduced into the reactor at a feed rate of (in terms of NTP)/hr to perform a selective hydrogenation reaction. The composition of the obtained hydrocarbon product was as shown in the product column of Table 1.
【表】
このようにブタジエン類、プロパジエン、ビニ
ルアセチレンのような高度に不飽和な炭化水素は
ほとんど水添されかつ１−ブテンの異性化率（転
化率）は３％程度であつた。
比較例 １
水を添加しないこと以外は実施例１に記載した
のと同じ方法、同じ反応条件下で水添反応を行な
い下記の結果を得た。
生成物中のブタジエン濃度 …128ppm
１−ブテン転化率 …10.2％
実施例 ２、３
炭化水素混合物に対して水を第２表に示す供給
速度で反応器に供給して反応を行なつた。なお他
の反応条件については実施例１に記載したのと同
じ方法で行なつた。また用いた炭化水素混合物も
実施例１で用いたものと同じであつた。
結果は第２表に示すとおりであつた。[Table] As can be seen, most of the highly unsaturated hydrocarbons such as butadienes, propadiene, and vinyl acetylene were hydrogenated, and the isomerization rate (conversion rate) of 1-butene was about 3%. Comparative Example 1 A hydrogenation reaction was carried out in the same manner and under the same reaction conditions as described in Example 1, except that water was not added, and the following results were obtained. Butadiene concentration in the product: 128 ppm 1-butene conversion: 10.2% Examples 2 and 3 A reaction was carried out by supplying water to the hydrocarbon mixture to the reactor at the rate shown in Table 2. The other reaction conditions were the same as those described in Example 1. The hydrocarbon mixture used was also the same as that used in Example 1. The results were as shown in Table 2.
【表】
実施例 ４、５
水のかわりに10重量％のアンモニア水を第３表
に示す供給速度で反応器に供給して反応を行なつ
た。なお他の反応条件については実施例１に記載
したのと同じ方法で行なつた。[Table] Examples 4 and 5 A reaction was carried out by supplying 10% by weight aqueous ammonia to the reactor at the supply rate shown in Table 3 instead of water. The other reaction conditions were the same as those described in Example 1.
Claims (1)
の低不飽和の炭化水素をパラジウム触媒の存在下
に水素と接触させ前記の高度に不飽和な炭化水素
を選択的に水素添加する方法において高度に不飽
和な炭化水素を含む炭素数４以上の低不飽和度の
炭化水素に対して0.005〜５重量％の水および０
〜0.5重量％のアンモニアを存在させることを特
徴とする炭化水素類の選択的水素添加法。1. In a method of selectively hydrogenating the highly unsaturated hydrocarbons by contacting low unsaturated hydrocarbons having 4 or more carbon atoms, including highly unsaturated hydrocarbons, with hydrogen in the presence of a palladium catalyst. 0.005 to 5% by weight of water and 0.005% to 5% by weight of hydrocarbons with a low degree of unsaturation having 4 or more carbon atoms, including highly unsaturated hydrocarbons.
A method for selective hydrogenation of hydrocarbons, characterized by the presence of ~0.5% by weight of ammonia.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56194125A JPS5896684A (en) | 1981-12-02 | 1981-12-02 | Selective hydrogenation of hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56194125A JPS5896684A (en) | 1981-12-02 | 1981-12-02 | Selective hydrogenation of hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5896684A JPS5896684A (en) | 1983-06-08 |
| JPH0150278B2 true JPH0150278B2 (en) | 1989-10-27 |
Family
ID=16319319
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56194125A Granted JPS5896684A (en) | 1981-12-02 | 1981-12-02 | Selective hydrogenation of hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5896684A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0696709B2 (en) * | 1987-10-23 | 1994-11-30 | 日本石油株式会社 | Method for selective hydrogenation of hydrocarbons |
-
1981
- 1981-12-02 JP JP56194125A patent/JPS5896684A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5896684A (en) | 1983-06-08 |
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