JPS6052139B2 - Separation method of ethylene glycol - Google Patents
Separation method of ethylene glycolInfo
- Publication number
- JPS6052139B2 JPS6052139B2 JP17867082A JP17867082A JPS6052139B2 JP S6052139 B2 JPS6052139 B2 JP S6052139B2 JP 17867082 A JP17867082 A JP 17867082A JP 17867082 A JP17867082 A JP 17867082A JP S6052139 B2 JPS6052139 B2 JP S6052139B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene glycol
- present
- separation method
- dioxolane
- produced
- 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
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims description 75
- 238000000926 separation method Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims description 9
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- SIJBDWPVNAYVGY-UHFFFAOYSA-N 2,2-dimethyl-1,3-dioxolane Chemical compound CC1(C)OCCO1 SIJBDWPVNAYVGY-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- -1 attraglyme Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はエチレングリコールを効率よく分離する新規
な方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for efficiently separating ethylene glycol.
エチレングリコールは、ポリエステルの原料、有機溶
媒、不揮発性不凍剤又は冷却剤として工業的に重要な基
幹化合物である。Ethylene glycol is an industrially important basic compound as a raw material for polyester, an organic solvent, a nonvolatile antifreeze agent, or a coolant.
従来、エチレングリコールはエチレンを原料とする石油
化学法で製造されているが、それ以外には、一酸化炭素
、ホルムアルデヒドなどの炭素数１（Ｃｌ）化合物を原
料として製造する方法が知られている。 例えばロジウ
ム触媒の存在下に合成ガスから直接エチレングリコール
を製造する方法（特開昭５３−１２１、７１４）、ある
いはルテニウム触媒の存在下に、同様にしてエチレング
リコールを製造する方法（特開昭５５−１１５、８３４
）が知られており、また本発明者らはコバルトカルボニ
ルを触媒として用いても、合成ガス、あるいは合成ガス
とホルムアルデヒドからエチレングリコールが製造され
ることをすでに見出している（特開昭５８−９０５２訝
）。Traditionally, ethylene glycol has been produced by a petrochemical method using ethylene as a raw material, but other methods are also known in which it is produced using one-carbon (Cl) compounds such as carbon monoxide and formaldehyde as raw materials. . For example, a method for producing ethylene glycol directly from synthesis gas in the presence of a rhodium catalyst (Japanese Patent Application Laid-open No. 53-121, 714), or a method for producing ethylene glycol in the same manner in the presence of a ruthenium catalyst (Japanese Patent Application Laid-Open No. 55-1989) -115, 834
), and the present inventors have already discovered that ethylene glycol can be produced from synthesis gas or synthesis gas and formaldehyde even when cobalt carbonyl is used as a catalyst (Japanese Patent Laid-Open No. 58-9052). (Suspicious)
しかし、これらの方法は、ロジウム、ルテニウム、コ
バルト等の重金属を触媒として用いるだけでなく、溶媒
としてアトラグライム、スルホラン、フェノール等の高
沸点化合物を用いており、製造されるエチレングリコー
ル自身も高沸点（１９８゜Ｃ）化合物であるため、反応
混合物からのエチレングリコールの分離は容易でなかつ
た。 本発明者らはコバルトカルボニル触媒を用いて種
々の溶媒中でエチレングリコールの合成を行つた後、反
応混合物中にアセトン、あるいはメチルエチルケトン等
の低級ケトンを加えたところ、エチレングリコールがア
セトンあるいはメチルエチルケトンと反応して環状ケタ
ールである２、２−ジメチルー１、３−ジオキソラン、
あるいは２ーメチルー２−エチルー１、３−ジオキソラ
ンが生成することを見出し、本発明をなすに至つた。す
なわち、本発明はエチレングリコールを含む混合物に、
アセトン、あるいはメチルエチルケトン等の低級ケトン
を添加することにより、エチレングリコールを２、２−
ジメチルー１、３−ジオキソラン（常圧下の沸点９５゜
Ｃ）、あるいは２−メチルー２−エチルー１、３−ジオ
キソラン（常圧下の沸点７１ＴＣ）等の低沸点化合物に
変え、ついでこれらの環状ケタールを蒸留することを特
徴とするエチレングリコールの分離方法を提供するもの
である。なお分離された環状ケタールに過剰の水を加え
て再び蒸留を行うと、まず低級ケトンが蒸留され、つい
で過剰の水が蒸留され、エチレングリコールが蒸留残と
して得られる。However, these methods not only use heavy metals such as rhodium, ruthenium, and cobalt as catalysts, but also high-boiling compounds such as attraglyme, sulfolane, and phenol as solvents, and the ethylene glycol itself produced has a high boiling point. (198°C) compound, it was not easy to separate ethylene glycol from the reaction mixture. The present inventors synthesized ethylene glycol in various solvents using a cobalt carbonyl catalyst, and then added acetone or a lower ketone such as methyl ethyl ketone to the reaction mixture, and ethylene glycol reacted with acetone or methyl ethyl ketone. 2,2-dimethyl-1,3-dioxolane, which is a cyclic ketal,
Alternatively, it was discovered that 2-methyl-2-ethyl-1,3-dioxolane is produced, and the present invention was completed. That is, the present invention provides a mixture containing ethylene glycol,
By adding acetone or a lower ketone such as methyl ethyl ketone, ethylene glycol can be converted to 2,2-
Dimethyl-1,3-dioxolane (boiling point at normal pressure 95°C) or 2-methyl-2-ethyl-1,3-dioxolane (boiling point at normal pressure 71TC) is converted to a lower boiling point compound, and then these cyclic ketals are distilled. The present invention provides a method for separating ethylene glycol. Note that when excess water is added to the separated cyclic ketal and distillation is performed again, lower ketones are first distilled, then excess water is distilled off, and ethylene glycol is obtained as a distillation residue.
本発明の原理は次式で表わされる。The principle of the present invention is expressed by the following equation.
Ｒ及びＲ″はそれぞれ、メチル基、エチル基等のアルキ
ル基を表わし、ＲとＲ″は同一であつてもあるいは異つ
たものであつてもよい。R and R'' each represent an alkyl group such as a methyl group or an ethyl group, and R and R'' may be the same or different.
本発明の方法は合成ガスからＣ１化学法により製造され
たエチレングリコールの触媒及び溶媒からの分離に限定
されるものではなく、エチレングリコールを含む廃溶媒
、あるいはエチレングリコールを含む各種プロセスの蒸
留残渣等のどのような混合物中からのエチレングリコー
ルの分離にも適用可能てあり、本発明の産業上の意義は
大きい。The method of the present invention is not limited to the separation of ethylene glycol produced from synthesis gas by the C1 chemical method from catalysts and solvents, but also waste solvents containing ethylene glycol, distillation residues of various processes containing ethylene glycol, etc. The present invention is applicable to the separation of ethylene glycol from any kind of mixture, and the present invention has great industrial significance.
次に本発明を実施例によりさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
フェノール２０ｙ１トルエン１０ｙからなる混合溶媒に
コバルトカルボニル０．８５５ｙ（ＣＯとして５ｍ９ａ
ｔ０ｍ）を溶かし、合成ガス（ＣＯ：Ｈ２＝１１）の加
圧下９８０〜９３０ｋｇ／Ｃｌｔｌ２２Ｏ℃で２時間反
応を行つたところ、エチレングリコールが２．９ｎ１ｍ
０１生成した。Example 1 0.855y of cobalt carbonyl (5m9a as CO) was added to a mixed solvent consisting of 20y of phenol and 10y of toluene.
t0m) was dissolved and reacted for 2 hours at 980-930kg/Cltl22O℃ under pressure of synthesis gas (CO:H2=11), resulting in 2.9n1m of ethylene glycol.
01 was generated.
反応管から抜出した直後の反応混合物にアセトン１０ｙ
を加え、一昼夜室温に放置すると″エチレングリコール
の１００％が２，２−ジメチルー１，３−ジオキソラン
に転化した。ついでロータリーエバポレーターを用いて
１０Ｔ！ｒ！ＮＨｇの減圧下で蒸留を行つたところ、２
，２−ジメチルー１，３−ジオキソランの９６％が蒸留
された。実施例２
フェノール２０ｙ．．ｍ−クレゾール１０ｙからなる混
合溶媒にコバルトカルボニル０．８５５ｙ（ＣＯとして
５ＴｒＬｇａｔ０ｍ）を溶かし、実施例１と同様にして
９７５〜９１０ｋ９／Ｃｆｌｌ２２Ｏ℃で２時間反応を
行つたところ、エチレングリコールが５．８ｍｍ０１生
成した。10 y of acetone was added to the reaction mixture immediately after it was extracted from the reaction tube.
was added and left at room temperature for a day and night, and 100% of the ethylene glycol was converted to 2,2-dimethyl-1,3-dioxolane. Distillation was then carried out using a rotary evaporator under reduced pressure of 10 T!r!NHg. 2
, 96% of the 2-dimethyl-1,3-dioxolane was distilled. Example 2 Phenol 20y. ．． 0.855y of cobalt carbonyl (5TrLgat0m as CO) was dissolved in a mixed solvent consisting of 10y of m-cresol, and the reaction was carried out in the same manner as in Example 1 at 975-910k9/Cfl220°C for 2 hours, resulting in 5.8mm01 of ethylene glycol. generated.
Claims (1)
加することによりエチレングリコールを環状ケタールに
変え、ついで環状ケタールを蒸留することを特徴とする
エチレングリコールの分離方法。1. A method for separating ethylene glycol, which comprises converting ethylene glycol into a cyclic ketal by adding a lower ketone to a mixture containing ethylene glycol, and then distilling the cyclic ketal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17867082A JPS6052139B2 (en) | 1982-10-12 | 1982-10-12 | Separation method of ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17867082A JPS6052139B2 (en) | 1982-10-12 | 1982-10-12 | Separation method of ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5967233A JPS5967233A (en) | 1984-04-16 |
| JPS6052139B2 true JPS6052139B2 (en) | 1985-11-18 |
Family
ID=16052510
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17867082A Expired JPS6052139B2 (en) | 1982-10-12 | 1982-10-12 | Separation method of ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6052139B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622348A (en) * | 2014-11-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Separation method for mixture of polyhydric alcohols with approximate boiling points |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62238732A (en) * | 1986-04-10 | 1987-10-19 | Gunze Ltd | Film for printed laminate and its hot press bonding method |
| CN102451756B (en) * | 2010-10-19 | 2013-11-06 | 中国石油化工股份有限公司 | Loaded zinc trifluoromethanesulfonate catalyst, its preparation method, and preparation method of butanone-glycol ketal |
| CN103435482B (en) * | 2013-08-06 | 2015-06-17 | 陕西煤业化工技术研究院有限责任公司 | Separation method and separation device of synthesis gas ethylene glycol product |
-
1982
- 1982-10-12 JP JP17867082A patent/JPS6052139B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622348A (en) * | 2014-11-28 | 2016-06-01 | 中国科学院大连化学物理研究所 | Separation method for mixture of polyhydric alcohols with approximate boiling points |
| CN105622348B (en) * | 2014-11-28 | 2018-06-08 | 中国科学院大连化学物理研究所 | A kind of separation method of the close polyol blends of boiling point |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5967233A (en) | 1984-04-16 |
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