JPH07121887B2 - Method for producing high-grade alcohol - Google Patents
Method for producing high-grade alcoholInfo
- Publication number
- JPH07121887B2 JPH07121887B2 JP62058560A JP5856087A JPH07121887B2 JP H07121887 B2 JPH07121887 B2 JP H07121887B2 JP 62058560 A JP62058560 A JP 62058560A JP 5856087 A JP5856087 A JP 5856087A JP H07121887 B2 JPH07121887 B2 JP H07121887B2
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- alcohol
- hue
- sulfated
- oxo
- 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
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、オキソ法によつて製造される高級アルコール
（以下オキソアルコールと呼ぶ）の製造方法に関する。
更に詳しくは、オキソ法によつて得られる高級アルコー
ルから、通常の蒸留等の方法では、除去する事が困難
な、着色等の原因となる不純物を除去し、品質を改良
し、工業的用途、特に洗浄剤用途に好適なオキソアルコ
ールを得る方法に関する。オキソアルコールは、洗浄
剤、潤滑油添加剤、その他多くの工業製品用として用い
られる。TECHNICAL FIELD The present invention relates to a method for producing a higher alcohol (hereinafter referred to as oxo alcohol) produced by the oxo method.
More specifically, from the higher alcohol obtained by the oxo method, impurities that are difficult to remove, such as coloration, are removed by a method such as ordinary distillation, quality is improved, and industrial applications, Particularly, it relates to a method for obtaining an oxoalcohol suitable for use as a detergent. Oxo alcohols are used in detergents, lubricant additives, and many other industrial products.
〈従来の技術〉 オレフィンに水素、一酸化炭素をCo、Rh等の触媒の存在
下反応させるいわゆるオキソ法は、高級アルコール類の
最も一般的な方法であるが、その製造工程中で種々の副
生物、例えばアルデヒド類、エステル類、パラフイン類
等が含まれるので、通常、これら不純物を除去するため
酸やアルカリ水溶液による洗浄、蒸留水素化等種々の処
理が行われる。<Prior Art> The so-called oxo method in which hydrogen and carbon monoxide are reacted with an olefin in the presence of a catalyst such as Co or Rh is the most common method for higher alcohols, but various sub-methods are used during the production process. Since organisms such as aldehydes, esters, and paraffins are contained, various treatments such as washing with an acid or alkaline aqueous solution and distillation hydrogenation are usually performed to remove these impurities.
しかしながら、これらの方法だけでは完全に除去する事
の困難な着色、におい等の原因となる不純物が尚も存在
する場合が少なくない。However, in many cases, impurities that cause coloring, odor, etc., which are difficult to completely remove by these methods, are still present.
特に洗浄剤用オキソアルコールの場合、それ自体の着色
のみでなく、硫酸エステル化やエトキシ化等により種々
の誘導体に転換する際の着色を抑える事が品質上に非常
に重要であり、しかもその原因となるアルコール中の微
量の不純物が何であるかは必ずしも明確になつていない
のが実状である。Especially in the case of oxoalcohol for detergents, it is very important not only to color itself but also to suppress the coloration when it is converted into various derivatives by sulfate esterification, ethoxylation, etc. In reality, it is not always clear what the trace amount of impurities in the alcohol is.
オキソ化によつて得られるアルコール中の微量のカルボ
ニル化合物を除去する為、通常Ni、Cuクロマイト等の触
媒により水素化処理される。たとえば、英国特許第1149
281号明細書ではC12〜C14アルコール中に含まれる微量
カルボニル化合物を減少させるためにNi触媒を用いて11
0〜140℃、20〜50kg/cm2の条件で水素化処理している。In order to remove a small amount of carbonyl compound in alcohol obtained by oxo oxidation, it is usually hydrotreated with a catalyst such as Ni or Cu chromite. For example, British Patent No. 1149
No. 281 uses a Ni catalyst to reduce trace carbonyl compounds contained in C 12 -C 14 alcohols.
It is hydrotreated under conditions of 0 to 140 ° C and 20 to 50 kg / cm 2 .
又、米国特許第1302337号明細書には、可塑剤アルコー
ル自体の色相改良方法としてNi触媒を用い二段に分けて
115〜155℃、20〜55kg/cm2の条件で水添処理する方法が
開示されている。Also, U.S. Pat.No. 1302337 describes that a Ni catalyst is used in two steps as a method for improving the hue of a plasticizer alcohol itself.
A method of hydrogenating at 115 to 155 ° C. and 20 to 55 kg / cm 2 is disclosed.
〈考案が解決しようとする問題点〉 しかしながら、オキソ法製造工程で最も普通に行われ
る、蒸留分離と前記のような従来の精製水添処理とを併
せ行う方法では、高級アルコールの硫酸エステル化時の
色相（以下硫酸化色相と略称）をある程度まで改良可能
ではあるが、未だ不十分である。<Problems to be Solved by the Invention> However, in the method of performing both the distillation separation and the conventional purified hydrogenation treatment as described above, which is most commonly performed in the oxo process production step, when the higher alcohol is sulfated, The hue (hereinafter abbreviated as sulfated hue) can be improved to some extent, but it is still insufficient.
本発明の目的は、オレフィンからオキソ化によつて得ら
れる高級アルコールから、可塑剤、洗浄剤、或いは、そ
の他の誘導体の合成に適した高級アルコール、特に洗浄
剤等の誘導体へ転換する際に着色しにくい、種々の着色
の原因となる物質を実質的に含まない、高品質の高級ア
ルコールを製造する方法を提供する事にある。The object of the present invention is to color the conversion of a higher alcohol obtained from an olefin by oxo oxidation into a higher alcohol suitable for the synthesis of a plasticizer, a detergent or other derivative, particularly a derivative such as a detergent. Another object of the present invention is to provide a method for producing a high-quality higher alcohol that is difficult to produce and does not substantially contain various coloring-causing substances.
〈問題点を解決するための手段〉 本発明者らはオキソ法によつて得られる高級アルコール
の精製水添を種々の触媒を用いて検討した所、Ni又はCu
−クロマイト触媒で水添処理した高級アルコールをPd触
媒を使用して更に水添処理する事により、先述の問題点
となつていた硫酸化色相が大巾に改良される事を見い出
し本発明を完成した。<Means for Solving Problems> The present inventors have investigated purified hydrogenation of higher alcohols obtained by the oxo method using various catalysts and found that Ni or Cu
-By further hydrogenating a higher alcohol hydrogenated with a chromite catalyst using a Pd catalyst, it was found that the sulfated hue, which had been a problem described above, was greatly improved, and the present invention was completed. did.
即ち本発明は、オキソ法により製造されNi又は、Cu−ク
ロマイト等の触媒で水添処理をし、微量カルボニル化合
物の除去処理をした高級アルコールをPd系触媒で50〜20
0℃、10〜100kg/cm2の条件下で水添処理する事により、
硫酸化色相の改良された、洗浄剤原料として好適な高級
アルコールの製造方法を提供するものである。That is, the present invention, Ni or produced by the oxo method, or hydrogenated with a catalyst such as Cu-chromite, a higher alcohol treated to remove trace carbonyl compounds with a Pd-based catalyst 50 to 20
0 ° C., by the hydrogenation treatment under the conditions of 10 to 100 kg / cm 2,
It is intended to provide a method for producing a higher alcohol, which has an improved sulfated hue and is suitable as a detergent raw material.
本発明でPd触媒の存在下水添処理されるオキソ法によつ
て製造される高級アルコールは、オレフインと水素、一
酸化炭素によるヒドロホルミル化及び水素化（いわゆる
オキソ化）によつて得られる炭素数９ないし15の直鎖率
40〜85％程度のアルコールの混合物であり、カルボニル
化合物の水添処理されたものである。カルボニル化合物
の水添処理は通常、温度50〜200℃、圧力20〜100kg/cm2
でNi又はCuクロマイト触媒の存在下に行なわれる。In the present invention, the higher alcohol produced by the oxo method, which is hydrogenated in the presence of a Pd catalyst, has a carbon number of 9 obtained by hydroformylation with olefin and hydrogen, carbon monoxide and hydrogenation (so-called oxo). Linear rate of 15 to 15
It is a mixture of about 40 to 85% alcohol, which is a hydrogenated carbonyl compound. Hydrogenation of carbonyl compounds is usually performed at a temperature of 50 to 200 ° C and a pressure of 20 to 100 kg / cm 2.
In the presence of Ni or Cu chromite catalyst.
本発明において触媒として用いられるPdは、アルミナ、
活性炭等に担持された担持触媒として使用される。担持
触媒中のPd濃度は0.1〜1.0wt％の範囲のものが好まし
い。Pd used as a catalyst in the present invention is alumina,
It is used as a supported catalyst supported on activated carbon. The Pd concentration in the supported catalyst is preferably in the range of 0.1 to 1.0 wt%.
本発明の方法は、温度50〜200℃、圧力10〜100kg/cm2の
反応条件下で行なわれる。この範囲をはずれた場合に
は、有効な処理効果が得られず、又は、触媒寿命の低下
を招く等好ましくない。特に好ましい範囲は100〜150
℃、50〜80kg/cm2である。The method of the present invention is carried out under reaction conditions of a temperature of 50 to 200 ° C. and a pressure of 10 to 100 kg / cm 2 . When it is out of this range, it is not preferable because effective treatment effect cannot be obtained or the catalyst life is shortened. Particularly preferred range is 100 to 150
C, 50 to 80 kg / cm 2 .
本発明の実施方法としては、１）槽型反応器を用いて、
前記Pd担持触媒をスラリー状にして回分式で反応する方
法や、２）管型流通反応器を用いて、Pd担持触媒を固定
床触媒として連続的に反応する方法がある。As a method for carrying out the present invention, 1) using a tank reactor,
There is a method in which the Pd-supported catalyst is made into a slurry and reacted in a batch system, or 2) a method in which the Pd-supported catalyst is continuously reacted as a fixed bed catalyst using a tubular flow reactor.
後者の方法の場合、特にNi或いは、Cu−クロマイト触媒
を充填させた反応器にPd触媒を充填させた反応器を直列
で結合する事により、効率よくアルコールの水素処理が
できる。In the case of the latter method, the hydrogen treatment of alcohol can be efficiently carried out by connecting the reactor filled with the Pd catalyst to the reactor filled with the Ni or Cu-chromite catalyst in series.
更にNi又は、Cu−クロマイト触媒を反応器の前半部に充
填し、本発明で用いるPd担持触媒を反応器の後半部に充
填する事により、一つの管型流通反応器のみで通常のオ
キソアルコール中の微量カルボニル化合物を除去すると
同時に着色の少ない高品質な高級アルコールを得る事も
可能である。Ni or Cu-chromite catalyst is charged in the first half of the reactor, and the Pd-supported catalyst used in the present invention is charged in the second half of the reactor, so that only one tubular flow reactor is used for ordinary oxo alcohol. It is possible to obtain a high-quality higher alcohol with little coloring while removing a trace amount of carbonyl compounds.
〈実施例〉 次に本発明を実施例を挙げて更に具体的に説明する。
尚、下記実施例では、直鎖状オレフィンをコバルト触媒
の存在下、オキソ化する事により得られた炭素数14、15
のアルコールを更にNi触媒、或いは、Cu−クロマイト触
媒で水添して微量カルボニル化合物の除去処理したもの
を原料アルコールとして用いた。又、硫酸エステル化時
の色相は、アルコールをクロルスルホン酸で硫酸化し反
応液を苛性ソーダ水溶液で中和後、中和物をエタノール
と水の混合溶媒で10wt％に希釈し420mμで測定した吸光
度をもつて硫酸化色相とした。<Examples> Next, the present invention will be described more specifically with reference to Examples.
In the following examples, the linear olefins were oxo-oxidized in the presence of a cobalt catalyst to obtain 14, 15 carbon atoms.
The above alcohol was hydrogenated with a Ni catalyst or a Cu-chromite catalyst to remove a trace amount of carbonyl compound, and used as a raw material alcohol. In addition, the hue at the time of sulfate esterification is to sulphate alcohol with chlorosulfonic acid, neutralize the reaction solution with an aqueous solution of caustic soda, dilute the neutralized product to 10 wt% with a mixed solvent of ethanol and water, and measure the absorbance measured at 420 mμ. It was a sulfated hue.
〈実施例−１〉 200mlステンレス製電磁誘導攪拌機付オートクレープに
炭素数14、15混合アルコール（硫酸化色相0.215）70g、
0.3wt％Pd/アルミナ触媒粒状5gを入れ、温度150℃、H2
加圧50kg/cm2にて1.0時間処理した。<Example-1> 70 ml of a 200 ml stainless steel autoclave equipped with an electromagnetic induction stirrer, having 14 and 15 carbon atoms, mixed alcohol (sulfated hue 0.215),
Put 0.3g% Pd / alumina catalyst granular 5g, temperature 150 ℃, H 2
It was treated at a pressure of 50 kg / cm 2 for 1.0 hour.
その後、室温まで冷却し、内容物を取り出し触媒を別
した。アルコールの着色度を確認したところ硫酸化色相
0.089を示した。Then, it cooled to room temperature, took out the content, and separated the catalyst. When the coloring degree of alcohol was confirmed, the sulfated hue
It showed 0.089.
〈実施例−２〉 触媒として0.3wt％Pd/アルミナの代りに、0.5wt％Pd/カ
ーボン粒を使用した事以外全て実施例−１と同様に反応
を実施した。反応液の硫酸化色相は0.097を示した。<Example-2> The reaction was performed in the same manner as in Example-1 except that 0.5 wt% Pd / carbon particles were used as the catalyst instead of 0.3 wt% Pd / alumina. The sulfated hue of the reaction solution was 0.097.
〈比較例−１〉 触媒として0.5wt％Ptカーボン粒を使用した事以外全て
実施例−１と同様に反応を実施した。硫酸化色相0.142
であつた。<Comparative Example-1> The reaction was performed in the same manner as in Example-1 except that 0.5 wt% Pt carbon particles were used as a catalyst. Sulfated hue 0.142
It was.
〈比較例−２〉 触媒として70wt％Ni/アルミナペレツトを使用した事以
外全て実施例−１と同様に反応を実施した。硫酸化色相
0.134を示した。<Comparative Example-2> The reaction was carried out in the same manner as in Example-1 except that 70 wt% Ni / alumina pellets were used as the catalyst. Sulfated hue
It showed 0.134.
〈比較例−３〉 反応温度40℃、H2圧力5kg/cm2にて反応を実施する他
は、全て実施例−１と同様に反応した。反応液は、硫酸
化色相0.165を示した。<Comparative Example -3> reaction temperature 40 ° C., another to carry out the reaction at a H 2 pressure of 5 kg / cm 2 was reacted in the same manner as in Example -1. The reaction solution showed a sulfated hue of 0.165.
〈実施例−３〉 内径52mm、長さ1000mmのステンレス製管型流通反応器に
0.3wt％Pd/アルミナ触媒粒状を200ml充填し、反応温度1
00℃、H2圧力50kg/cm2の条件で、炭素数14、15混合アル
コール（硫酸化色相0.092）を200〜1200ml/Hrで、反応
管に流通した。処理後のアルコール中に浮遊している触
媒を除去して各々硫酸化色相を確認したところ下記の値
を示した。<Example-3> In a stainless steel tubular flow reactor having an inner diameter of 52 mm and a length of 1000 mm.
200ml of 0.3wt% Pd / alumina catalyst granules were filled and the reaction temperature was 1
Under the conditions of 00 ° C. and H 2 pressure of 50 kg / cm 2 , mixed alcohol having 14 and 15 carbon atoms (sulfated hue 0.092) was passed through the reaction tube at 200 to 1200 ml / Hr. The catalyst floating in the treated alcohol was removed and the sulfated hue was confirmed.
アルコール流量（ml/Hr） 硫酸化色相 200 0.042 300 0.045 500 0.052 1200 0.057 Alcohol flow rate (ml / Hr) Sulfated hue 200 0.042 300 0.045 500 0.052 1200 0.057
Claims (1)
マト触媒を用いて水添処理された高級アルコールを、Pd
触媒の存在下、50〜200℃、10〜100kg/cm2で水素添加処
理する事を特徴とする高級アルコールの製造方法。1. A higher alcohol produced by the oxo method and hydrogenated using a Ni or Cu chromatographic catalyst is treated with Pd.
A method for producing a higher alcohol, which comprises hydrogenating at 50 to 200 ° C and 10 to 100 kg / cm 2 in the presence of a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62058560A JPH07121887B2 (en) | 1987-03-13 | 1987-03-13 | Method for producing high-grade alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62058560A JPH07121887B2 (en) | 1987-03-13 | 1987-03-13 | Method for producing high-grade alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63227534A JPS63227534A (en) | 1988-09-21 |
| JPH07121887B2 true JPH07121887B2 (en) | 1995-12-25 |
Family
ID=13087838
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62058560A Expired - Fee Related JPH07121887B2 (en) | 1987-03-13 | 1987-03-13 | Method for producing high-grade alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07121887B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7538060B2 (en) | 2007-02-14 | 2009-05-26 | Eastman Chemical Company | Palladium-copper chromite hydrogenation catalysts |
-
1987
- 1987-03-13 JP JP62058560A patent/JPH07121887B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63227534A (en) | 1988-09-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |