JPH0720891B2 - Method for producing cyclopentene - Google Patents
Method for producing cyclopenteneInfo
- Publication number
- JPH0720891B2 JPH0720891B2 JP62052682A JP5268287A JPH0720891B2 JP H0720891 B2 JPH0720891 B2 JP H0720891B2 JP 62052682 A JP62052682 A JP 62052682A JP 5268287 A JP5268287 A JP 5268287A JP H0720891 B2 JPH0720891 B2 JP H0720891B2
- Authority
- JP
- Japan
- Prior art keywords
- cyclopentene
- cyclopentadiene
- modifier
- reaction
- cyclopentane
- 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 - Fee Related
Links
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 title claims description 44
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 17
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 cyclic aldehydes Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003152 propanolamines Chemical class 0.000 description 1
- 238000003756 stirring Methods 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
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明はシクロペンタジエンをシクロペンテンに選択的
に転換することに関する方法である。更に詳しくはパラ
ジウムを含有する触媒と修飾剤の存在下シクロペンタジ
エンを水素添加してほぼ完全にシクロペンテンへ転換
し、且つシクロペンタンの生成を抑制することによっ
て、高収率、高選択率でシクロペンテンを製造せんとす
るものである。DETAILED DESCRIPTION OF THE INVENTION INDUSTRIAL FIELD OF APPLICATION The present invention is a method relating to the selective conversion of cyclopentadiene to cyclopentene. More specifically, by hydrogenating cyclopentadiene in the presence of a catalyst containing palladium and a modifier to almost completely convert it to cyclopentene, and suppressing the formation of cyclopentane, cyclopentene can be produced with high yield and high selectivity. It is to be manufactured.
この様にして得られたシクロペンテンはシクロペンテン
ポリマーあるいはグルタル酸、グルタルアルデヒド、環
状アルデヒド類、アルコール類及び燃料として有用であ
る。The cyclopentene thus obtained is useful as a cyclopentene polymer, glutaric acid, glutaraldehyde, cyclic aldehydes, alcohols and fuel.
＜従来の技術＞ シクロペンタジエンの水素添加反応によシクロペンテン
の生成に関しては、従来種々の研究がなされているが、
いずれも選択率、転化率が低く問題があった。即ち、シ
クロペンタジエン→シクロペンテン→シクロペンタンと
反応が進行するため、シクロペンタジエンを完全に転換
しようとすれば、シクロペンタンの生成を伴いシクロペ
ンタンの生成を抑制しようとすれば、シクロペンタジエ
ンを完全に反応せしめ、かつシクロペンテンの収率を高
くすることは困難であった。<Prior Art> Various studies have been made on the production of cyclopentene by the hydrogenation reaction of cyclopentadiene.
All had problems with low selectivity and conversion. That is, the reaction proceeds in the order of cyclopentadiene → cyclopentene → cyclopentane, so if cyclopentadiene is completely converted, cyclopentadiene is accompanied by the formation of cyclopentane. It was difficult to increase the yield of cyclopentene.
又シクロペンタジエン（BP38〜39℃）とシクロペンテン
（BP44〜44.2℃）の沸点が近似しているため、両者の分
離は困難であるとともにシクロペンタジエンは容易に二
量体を作る性質があり、その取り扱いは複雑となる。従
ってシクロペンタジエンの水素添加反応においてシクロ
ペンタジエンを完全に転換すると共にシクロペンタンの
生成を抑制する製造方法の開発が望まれていた。In addition, since the boiling points of cyclopentadiene (BP38-39 ℃) and cyclopentene (BP44-44.2 ℃) are similar, it is difficult to separate the two and cyclopentadiene has the property of easily forming a dimer. Becomes complicated. Therefore, it has been desired to develop a production method for completely converting cyclopentadiene in the hydrogenation reaction of cyclopentadiene and suppressing the formation of cyclopentane.
＜発明が解決しようとする問題点＞ かかる従来技術の欠点に鑑み、本発明はシクロペンタジ
エンの水素添加に際し、シクロペンタジエンからのシク
ロペンテンへの水添活性を低下させることなく、シクロ
ペンテンからシクロペンタンへの水添活性を低下せしめ
て、高転化率、高選択率でシクロペンテンを製造する方
法を提供することを目的とする。<Problems to be Solved by the Invention> In view of the above-mentioned drawbacks of the prior art, the present invention, when hydrogenating cyclopentadiene, converts cyclopentene to cyclopentane without lowering the hydrogenation activity of cyclopentadiene to cyclopentene. It is an object of the present invention to provide a method for producing cyclopentene with reduced hydrogenation activity and high conversion and high selectivity.
＜問題点を解決するための手段＞ 本発明は、かかる目的を達成するものであって、以下の
要件を備えることを特徴とするものである。即ち、パラ
ジウムを含有する触媒と修飾剤の存在下にシクロペンタ
ジエンをシクロペンテンに選択的に水素添加することを
特徴とするシクロペンテンの製造方法である。<Means for Solving Problems> The present invention achieves this object, and is characterized by having the following requirements. That is, the method for producing cyclopentene is characterized in that cyclopentadiene is selectively hydrogenated to cyclopentene in the presence of a catalyst containing palladium and a modifier.
本発明において修飾剤とは、シクロペンタジエンの水素
添加反応において生成したシクロペンテンからシクロペ
ンタンへの水素添加反応を抑制するものを云う。修飾剤
としては下記に示す一般式 （R1およびR2は同一または互いに異なる水素または炭素
数10以下のアルキル基、R3は水酸を持ったアルキル基）
で表わされるものが用いられる。例えばモノエタノール
アミン、３−アミノ−１−プロパノール、２−アミノ−
１−プロパノール、１−アミノ−２−プロパノールなど
のプロパノールアミン類、ブタノールアミン類、Ｎ−メ
チルエタノールアミンなどが例示される。In the present invention, the modifier means an agent that suppresses the hydrogenation reaction of cyclopentene produced in the hydrogenation reaction of cyclopentadiene to cyclopentane. The modifier has the general formula shown below. (R 1 and R 2 are the same or different hydrogen or an alkyl group having 10 or less carbon atoms, and R 3 is an alkyl group having hydroxy)
The one represented by is used. For example, monoethanolamine, 3-amino-1-propanol, 2-amino-
Examples thereof include propanolamines such as 1-propanol and 1-amino-2-propanol, butanolamines, N-methylethanolamine and the like.
パラジウムを含有する触媒としては、パラジウムを担体
重量に対して0.01〜5wt％含有するものであり好ましく
は0.01〜2.0wt％のものが用いられる。通常の浸漬法な
どで製造されるものである。As the catalyst containing palladium, one containing 0.01 to 5 wt% of palladium relative to the weight of the carrier, and preferably one containing 0.01 to 2.0 wt% is used. It is manufactured by an ordinary dipping method or the like.
担体としてはAl2O3、CaCO3、BaSO4、カーボン等があげ
られ、ペレット状または顆粒状、粉末状のものなどを使
用することができる。反応時の触媒の濃度には特に制限
はなく反応速度、除熱、触媒コストなど考慮して定めら
れるが、シクロペンタジエンに対して出来る限り少量で
あることが好ましい。修飾剤はパラジウムに対して１〜
100モル当量好ましくは10〜50モル当量添加することが
望ましい。Examples of the carrier include Al 2 O 3 , CaCO 3 , BaSO 4 , carbon and the like, and pellets, granules, powders and the like can be used. The concentration of the catalyst during the reaction is not particularly limited and may be determined in consideration of the reaction rate, heat removal, catalyst cost, etc., but it is preferably as small as possible with respect to cyclopentadiene. Modifier is 1 to palladium
It is desirable to add 100 molar equivalents, preferably 10 to 50 molar equivalents.
本反応は無溶媒でも、また溶媒を使用しても行うことが
できるが溶媒を使用する場合は通常シクロヘキサン、ヘ
プタン等の炭化水素類を用いることができる。反応条件
は使用する修飾剤、溶媒の種類などにより若干異なる
が、一般に反応温度−10〜60℃、好ましくは０〜30℃、
反応圧力は１〜50kg/cm2で行われる。This reaction can be carried out without solvent or using a solvent, but when a solvent is used, hydrocarbons such as cyclohexane and heptane can be usually used. The reaction conditions are slightly different depending on the modifier used, the type of solvent, etc., but generally the reaction temperature is -10 to 60 ° C, preferably 0 to 30 ° C,
The reaction pressure is 1 to 50 kg / cm 2 .
本発明方法によれば穏和な反応条件でしかも短い滞留時
間でシクロペンタジエン及びシクロペンタン含有率の少
ないシクロペンテンを選択的に製造することができる。According to the method of the present invention, cyclopentene having a low cyclopentadiene and cyclopentane content can be selectively produced under mild reaction conditions and with a short residence time.
本発明を一層明瞭にするため、次に実施例を示すが、本
発明がこれによって限定されるものではない。The following examples are provided to further clarify the present invention, but the present invention is not limited thereto.
＜実施例＞ 実施例−１〜４ 200mlのオートクレーブに、1wt％Pd-Al2O3触媒1.06g、
シクロペンタジエン6.6g、ｎ−ヘプタン50mlを入れ、表
−１に示す各種の修飾剤、モノエタノールアミン、１−
アミン−２−プロパノール、３−アミノ−１−プロパノ
ールアミン、Ｎ−メチルモノエタノールアミンをそれぞ
れPd1モルに対し50モル当量になるように添加した後、
オートクレーブの空間をN2で置換し、撹拌下、水素圧10
kg/cm2かけて反応を行った。反応開始後30分の結果を表
−１に示す。Autoclave <Example> Example -1~4 200ml, 1wt% Pd-Al 2 O 3 catalyst 1.06 g,
6.6 g of cyclopentadiene and 50 ml of n-heptane were added, and various modifiers shown in Table 1, monoethanolamine, 1-
Amine-2-propanol, 3-amino-1-propanolamine, and N-methylmonoethanolamine were added so as to each have a molar equivalent of 50 relative to 1 mol of Pd.
The autoclave space was replaced with N 2 , and the hydrogen pressure was adjusted to 10 with stirring.
The reaction was carried out at kg / cm 2 . The results obtained 30 minutes after the start of the reaction are shown in Table 1.
比較例−１ 実施例−１と同一条件で、ただし修飾剤を加えない条件
で反応を行った。その結果を表−１に示す。Comparative Example-1 The reaction was carried out under the same conditions as in Example-1, except that no modifier was added. The results are shown in Table-1.
比較例−２ 実施例−１と同一条件で、ただし修飾剤としてノルマル
ブチルアミン 100モル当量を添加し反応を行った。そ
の結果を表−１に示す。 Comparative Example-2 The reaction was carried out under the same conditions as in Example-1, but adding 100 molar equivalents of normal butylamine as a modifier. The results are shown in Table-1.
比較例−１に比べて多少改善されているもののシクロペ
ンテンからシクロペンタンの反応は抑制されていないこ
とがわかる。It can be seen that the reaction of cyclopentane from cyclopentane is not suppressed, although it is slightly improved as compared with Comparative Example-1.
＜発明の効果＞ 本発明の修飾剤を用いることによって、本発明はシクロ
ペンタジエンの水素添加に際し、シクロペンタジエンか
らのシクロペンテンへの水添活性を低下させることな
く、シクロペンテンからのシクロペンタンへの水添活性
を低下せしめて、高転化率、高選択率でシクロペンテン
を製造することができた。<Effects of the Invention> By using the modifying agent of the present invention, the present invention allows hydrogenation of cyclopentadiene to cyclopentane without reducing hydrogenation activity of cyclopentadiene to cyclopentene. It was possible to produce cyclopentene with reduced activity and high conversion and high selectivity.
Claims (2)
下にシクロペンタジエンをシクロペンテンに選択的に水
素添加するシクロペンテンの製造方法であって、該修飾
剤が一般式 （R1およびR2は同一または互いに異なる水素または炭素
数10以下のアルキル基、R3は水酸基を持ったアルキル
基）で表されるシクロペンテンの製造方法。1. A method for producing cyclopentene, which comprises selectively hydrogenating cyclopentadiene to cyclopentene in the presence of a catalyst containing palladium and a modifier, wherein the modifier is represented by the general formula: (R 1 and R 2 are the same or different from each other, hydrogen or an alkyl group having 10 or less carbon atoms, and R 3 is an alkyl group having a hydroxyl group).
ノ−２−プロパノールあるいは３−アミノ−１−プロパ
ノールである特許請求の範囲第１項記載のシクロペンテ
ンの製造方法。2. The method for producing cyclopentene according to claim 1, wherein the modifier is monoethanolamine, 1-amino-2-propanol or 3-amino-1-propanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62052682A JPH0720891B2 (en) | 1987-03-06 | 1987-03-06 | Method for producing cyclopentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62052682A JPH0720891B2 (en) | 1987-03-06 | 1987-03-06 | Method for producing cyclopentene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63218634A JPS63218634A (en) | 1988-09-12 |
| JPH0720891B2 true JPH0720891B2 (en) | 1995-03-08 |
Family
ID=12921656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62052682A Expired - Fee Related JPH0720891B2 (en) | 1987-03-06 | 1987-03-06 | Method for producing cyclopentene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0720891B2 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1038403B (en) * | 1975-05-23 | 1979-11-20 | Snam Progetti | PROCEDURE OF SELECTIVE HYDROGENATION IN THE GASEOUS PHASE OF MULTI-UNSATURATED COMPOUNDS |
-
1987
- 1987-03-06 JP JP62052682A patent/JPH0720891B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63218634A (en) | 1988-09-12 |
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