JPS59164739A - Process for continuous hydrogenation - Google Patents
Process for continuous hydrogenationInfo
- Publication number
- JPS59164739A JPS59164739A JP58038978A JP3897883A JPS59164739A JP S59164739 A JPS59164739 A JP S59164739A JP 58038978 A JP58038978 A JP 58038978A JP 3897883 A JP3897883 A JP 3897883A JP S59164739 A JPS59164739 A JP S59164739A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- reaction
- aldehyde
- aqueous solution
- alcohol
- 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.)
- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 5
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000011437 continuous method Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 230000007423 decrease Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract 1
- 229910052748 manganese Inorganic materials 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 150000001299 aldehydes Chemical class 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- JTMCAHGCWBGWRV-UHFFFAOYSA-N 3-hydroxy-2-methylpropanal Chemical compound OCC(C)C=O JTMCAHGCWBGWRV-UHFFFAOYSA-N 0.000 description 3
- 239000007868 Raney catalyst Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007037 hydroformylation reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229940035429 isobutyl alcohol Drugs 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 description 2
- UIKQNMXWCYQNCS-UHFFFAOYSA-N 2-hydroxybutanal Chemical compound CCC(O)C=O UIKQNMXWCYQNCS-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical class OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はラネーニッケル触妹を用いた連続水素化法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a continuous hydrogenation process using a Raney nickel catalyst.
ラネーニッケル触媒はアルデヒド類の水素化触媒として
高い活性？示すので、従来がら広（用いられているが、
（り返し、あるいは連続して使用することにより、短時
間で活性が低下してしまうという欠点がある。再生を行
なう為に失活触媒をアルカリ液で洗い、新しいラネー合
金を加えてアルカリ液中で加熱する方法（＠開明５ｌ−
８４７９２）なども考案されているが、触媒の分離回収
、強アルカリ液処理、水洗などの煩雑な操作が必要とさ
れ、特に連続反応で使用される触媒の再生法としては十
分渦電できるものでない。Is Raney nickel catalyst highly active as a hydrogenation catalyst for aldehydes? Because it shows, it is traditionally wide (used, but
(The disadvantage is that the activity decreases in a short period of time if used repeatedly or continuously. To regenerate, wash the deactivated catalyst with alkaline solution, add new Raney alloy, and add it to the alkaline solution.) Method of heating with (@Kaimei 5l-
84792) have been devised, but they require complicated operations such as separation and recovery of the catalyst, treatment with a strong alkaline solution, and washing with water, and are not suitable for regenerating catalysts used in continuous reactions. .
本発明者は、アリルアルコールのヒドロホルミル化物か
ら得られる４−ヒドロキシブチルアルデヒドと２−メチ
ル−３−ヒドロキシプロピオンアルデヒドとを含む水溶
液を連続的に水素化してブタンジオール類を製造する方
法につき検討をおこなったが、このような連続反応に用
いたラネーニッケル触媒の活性保持時間が比較的短かく
、問題があることを知った。新触媒の仕込量を増せば活
性保持時間も延びるが、はｙ仕込量に比例した延長なの
で連続反応の中析を避ける利点はあるものの、触媒コス
トの改善にはならない。The present inventor investigated a method for producing butanediols by continuously hydrogenating an aqueous solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxypropionaldehyde obtained from a hydroformylated product of allyl alcohol. However, it was discovered that the Raney nickel catalyst used in such continuous reactions had a relatively short activation retention time, which caused a problem. If the amount of new catalyst charged is increased, the activity retention time will be extended, but since y is extended in proportion to the amount charged, although there is an advantage of avoiding interruption of the continuous reaction, it does not improve the catalyst cost.
そこで更に検討を進めたところ、使用する新触媒（ラネ
ーニッケルの展開品）の一部分を反応途中で添加すれば
、低下しかけた触媒活性が初期活性とほとんど同程度に
まで回復し、しかも途中添加触媒量に比して著るしく長
時間高活性を保持することを見出し、この発明を完成し
た。Further investigation showed that by adding a portion of the new catalyst (a developed product of Raney Nickel) during the reaction, the catalytic activity, which had begun to decline, could be restored to almost the same level as the initial activity. The present invention was completed based on the discovery that the compound retains high activity for a significantly longer period of time than the conventional method.
新触媒の添加量は初めに仕込んだ触媒に対して１１５０
〜１／２、好ましくは１／１０〜１／３で十分であり、
アルカリ処理など添加以外の操作を何ら必要としない極
めて簡便な方法である。従って、連続運転中であっても
スラリーポンプ圧入法、同圧法などにより反応器内に新
触媒を添加することにより、活性の回復を計ることが可
能なので、運転を停止する必要がす（、非常に効率的で
あり、工業的に有利である。新触媒を反応途中で添加す
る時期は、転化率が低下し始め活性保持手段をとるべき
時期を知った段階が好ましい。活性低下が進んで、はと
んど失活してから行なうのは水素化生成物の品質管理上
好ましくない。The amount of new catalyst added is 1150 compared to the initially charged catalyst.
~1/2, preferably 1/10 to 1/3 is sufficient,
This is an extremely simple method that does not require any operations other than addition, such as alkali treatment. Therefore, even during continuous operation, it is possible to recover activity by adding new catalyst into the reactor using the slurry pump injection method, isopressure method, etc. It is efficient and industrially advantageous.It is preferable to add the new catalyst in the middle of the reaction when the conversion rate starts to decrease and you know when to take measures to maintain the activity.As the activity decreases, It is undesirable to carry out the process after the hydrogenation process has been mostly deactivated in terms of quality control of the hydrogenated product.
ラネーニッケル触媒を用℃・たアルテヒド類の水素化反
応は、通常１〜１１０気圧、常Ｙ晶〜１２５℃の条件下
に行なわれる。The hydrogenation reaction of altehydes using a Raney nickel catalyst is usually carried out under the conditions of 1 to 110 atm and normal Yc to 125°C.
アリルアルコールのヒドロホルミル化と水抽出で得たア
ルデヒド水溶液の水素化の場合についても、公知の反応
条件を用いろことができる。この場合、副生成物の生成
を抑制するためにも水素圧２０〜８０気圧、温間７０〜
１２０°Ｃが好ましい。Known reaction conditions can also be used for hydroformylation of allyl alcohol and hydrogenation of an aqueous aldehyde solution obtained by water extraction. In this case, in order to suppress the formation of by-products, the hydrogen pressure is 20 to 80 atm, and the warm temperature is 70 to 80 atm.
120°C is preferred.
水素圧は８０気圧以上でも反応上は問題ないが、装置コ
ストの而よりみて、あまり有利でない。Although a hydrogen pressure of 80 atm or higher does not cause any problem in terms of reaction, it is not very advantageous in terms of equipment cost.
触媒としては通常のラネーニッケルの他に微量の他種金
属（Ｔ １１ Ｃｒ Ｉ Ｍｏ ＋ Ｍｎなど）を含む
ものであってもよ（（１１触媒調製１白崎高保、藤堂尚
之編ｐ８０〜８３、講談社、５４９）、通常カセイソー
ダ水溶液で展開したものを用いる。触媒の初めの仕込量
は液中濃度として０．５〜１０％、好ましくは２〜７％
量使用した方がよい。The catalyst may contain trace amounts of other metals (T 11 Cr I Mo + Mn, etc.) in addition to ordinary Raney nickel ((11 Catalyst Preparation 1 edited by Takayasu Shirasaki and Naoyuki Todo p80-83, Kodansha, 549), which is usually developed with an aqueous solution of caustic soda.The initial amount of catalyst charged is 0.5 to 10% as a concentration in the liquid, preferably 2 to 7%.
It is better to use the amount.
アルデヒドを多量（たとえば、５０％以上）の水を含む
水溶液中で水素化する場合、液は酸性側になりやすい。When an aldehyde is hydrogenated in an aqueous solution containing a large amount (for example, 50% or more) of water, the solution tends to be acidic.
ソルビトールの製造にみもれるようにアルカリを加える
ことのできる例もあるが、アルカリを加えるとアルデヒ
ドの縮合反応が起って不都合な場合も多い。本発明はこ
のようなアルデヒドの水溶液を連続的に水素化する場合
、例えば７１Ｊルアルコールのヒドロホルミル化で得た
４−ヒドロキシブチルアルデヒドと２−メチル−３−ヒ
ドロキシプロピオンアルデヒドとを含む反応液の水抽出
で得られるアルデヒド水溶液をラネーニッケル触媒を用
いて連続的に水素化し、１．４−− ブタンジオール類
を得る方法において特に有用である。以下具体例により
本発明を説明する。In some cases, as in the production of sorbitol, it is possible to add alkali, but in many cases, adding alkali causes a condensation reaction of aldehydes, which is disadvantageous. In the case of continuous hydrogenation of such an aqueous solution of aldehyde, the present invention is effective in hydrogenating a reaction solution containing 4-hydroxybutyraldehyde and 2-methyl-3-hydroxypropionaldehyde obtained by hydroformylation of 71J alcohol, for example. It is particularly useful in a method in which an aqueous aldehyde solution obtained by extraction is continuously hydrogenated using a Raney nickel catalyst to obtain 1,4-butanediols. The present invention will be explained below using specific examples.
参考例１
水素ガス及び液仕込み口、フィルター付液抜取口、電磁
攪拌機を備えた内容積５００罰のオートクレーブにカセ
イソーダ水溶液により９０℃で展開したラネーニッケル
触媒４７ｇを加えプロピオンアルデヒド１％、３−ヒド
ロキシ−２−メチルプロピオンアルデヒド１．５％、４
−ヒドロキシブチルアルデヒド１２％を含む水溶液を３
１５ ｍｅ／ Ｈｒ の速度で仕込み、１００℃ ５−
で反応を行なわせた。水素ガスは全圧が５０ ｋｇ／ｃ
４を保つように供給した。第１図に示すように３４時間
まではアルデヒド転化率が９９９％以上であったが、以
後活性が急激に低下した。Reference Example 1 47 g of Raney nickel catalyst developed at 90°C with aqueous caustic soda solution was added to an autoclave with an internal volume of 500 mm equipped with a hydrogen gas and liquid inlet, a liquid outlet with a filter, and an electromagnetic stirrer, and 1% propionaldehyde and 3-hydroxy- 2-methylpropionaldehyde 1.5%, 4
- 3 ml of an aqueous solution containing 12% hydroxybutyraldehyde
The mixture was charged at a rate of 15 me/Hr, and the reaction was carried out at 100°C. The total pressure of hydrogen gas is 50 kg/c
4 was maintained. As shown in FIG. 1, the aldehyde conversion rate was 999% or more until 34 hours, but the activity rapidly decreased after that.
触媒１ｇあたりの活性持続時間は７２３時間である。The duration of activity per gram of catalyst is 723 hours.
実施例１゜
ラネーニッケル量を９４５ｇとした以外は参考例１と同
じ条件で反応を行なわせたところ、活性は７４時間（７
８３時間／ｇ）持続したが、以後急激に低下した（第２
図Ａ点）。この反応液に新触媒を２ｇ添加したところ、
活性は回復しくＢ点）、さらに０点まで９２時間持続し
た（４６時間／ｇ途中添加量）。再び２ｇの新触媒を添
加すると、活性が回復しくＤ点）９４時間持続した。（
４７時間／ｇ）
第３図、第４図は第１図、第２図と時間軸を共通にする
イソブチルアルコール副生率（モル％）の変化を示し、
この図から新触媒の添加による触媒活性回復は副生成物
の生成抑制の点で ６−
も効果あることがわかる。Example 1 A reaction was carried out under the same conditions as Reference Example 1 except that the amount of Raney nickel was 945 g.
83 hours/g), but after that it rapidly decreased (second
Figure point A). When 2g of new catalyst was added to this reaction solution,
The activity recovered (point B) and continued for 92 hours until it reached point 0 (46 hours/g intermediate addition amount). When 2 g of new catalyst was added again, the activity recovered and continued for 94 hours (point D). (
47 hours/g) Figures 3 and 4 show changes in the isobutyl alcohol by-product rate (mol%), which share the same time axis as Figures 1 and 2,
From this figure, it can be seen that the recovery of catalytic activity by the addition of a new catalyst is as effective as 6- in terms of suppressing the production of by-products.
第１図、第２図はアルデヒドの水素化反応の転化率を経
時的に示した図であり、第３図、第４図はイソブチルア
ルコール副生率を経時的に示した図である。
特許出願人
ダイセル化学工業株式会社
−７ユｈFIGS. 1 and 2 are diagrams showing the conversion rate of aldehyde hydrogenation reaction over time, and FIGS. 3 and 4 are diagrams showing the isobutyl alcohol by-product rate over time. Patent applicant: Daicel Chemical Industries, Ltd.
Claims (2)
の存在下に連続的に水素化してアルコールを製造する方
法において使用する新触媒（展開品）の一部分を反応途
中に添刃口することを特徴とする連続水素化法。(1) A continuous method characterized by adding a part of the new catalyst (developed product) used in the method for producing alcohol by continuously hydrogenating aldehyde in an aqueous solution in the presence of a Raney nickel catalyst during the reaction. Hydrogenation method.
のヒドロホルミル化物から得たアルデヒド水浴液からブ
タンジオール類への水素化反応である特許請求の範囲第
１項記載の方法ｄ（３）新触媒の途中添加量が初めに仕
込んだ触媒の量に対してユ〜ユ量である特許請求の範囲
０ ２ 第１項又は第２項記載の方法。(2) Method d according to claim 1, wherein the aldehyde hydrogenation reaction is a hydrogenation reaction of an aldehyde water bath solution obtained from a hydroformylated allyl alcohol to butanediols (3) Midway addition of a new catalyst 2. The method according to claim 02, wherein the amount is between 1 and 20 ml with respect to the amount of catalyst initially charged.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58038978A JPS59164739A (en) | 1983-03-11 | 1983-03-11 | Process for continuous hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58038978A JPS59164739A (en) | 1983-03-11 | 1983-03-11 | Process for continuous hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59164739A true JPS59164739A (en) | 1984-09-17 |
| JPH0457654B2 JPH0457654B2 (en) | 1992-09-14 |
Family
ID=12540236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58038978A Granted JPS59164739A (en) | 1983-03-11 | 1983-03-11 | Process for continuous hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59164739A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010551A1 (en) * | 1994-09-30 | 1996-04-11 | Shell Internationale Research Maatschappij B.V. | Process for preparing 1,3-alkanediols and 3-hydroxyaldehydes |
| JP2008524326A (en) * | 2004-12-20 | 2008-07-10 | ライオンデル ケミカル テクノロジー、 エル．ピー． | Production of butanediol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000246109A (en) * | 1999-02-26 | 2000-09-12 | Japan Energy Corp | Hydrorefining catalyst, hydrorefining method and production of catalyst |
-
1983
- 1983-03-11 JP JP58038978A patent/JPS59164739A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010551A1 (en) * | 1994-09-30 | 1996-04-11 | Shell Internationale Research Maatschappij B.V. | Process for preparing 1,3-alkanediols and 3-hydroxyaldehydes |
| JP2008524326A (en) * | 2004-12-20 | 2008-07-10 | ライオンデル ケミカル テクノロジー、 エル．ピー． | Production of butanediol |
| JP4913752B2 (en) * | 2004-12-20 | 2012-04-11 | ライオンデル ケミカル テクノロジー、 エル．ピー． | Production of butanediol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0457654B2 (en) | 1992-09-14 |
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