JPH0145458B2 - - Google Patents
Info
- Publication number
- JPH0145458B2 JPH0145458B2 JP56111796A JP11179681A JPH0145458B2 JP H0145458 B2 JPH0145458 B2 JP H0145458B2 JP 56111796 A JP56111796 A JP 56111796A JP 11179681 A JP11179681 A JP 11179681A JP H0145458 B2 JPH0145458 B2 JP H0145458B2
- Authority
- JP
- Japan
- Prior art keywords
- ruthenium
- reaction
- glycolic acid
- ethylene glycol
- present
- 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 class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 24
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 23
- 239000012327 Ruthenium complex Substances 0.000 claims description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- MLXDUYUQINCFFV-UHFFFAOYSA-N 2-acetyloxyacetic acid Chemical compound CC(=O)OCC(O)=O MLXDUYUQINCFFV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- -1 ester derivatives of glycolic acid Chemical class 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 3
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 150000003303 ruthenium Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- HJYGWLFMHCJRJG-UHFFFAOYSA-N 2-propanoyloxyacetic acid Chemical compound CCC(=O)OCC(O)=O HJYGWLFMHCJRJG-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000008096 xylene Substances 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)
Description
本発明は、ルテニウム錯体の存在下にグリコー
ル酸およびアセトキシ酢酸、グリコール酸メチル
などのグリコール酸のエステル型誘導体を水素添
加してエチレングリコール、エチレングリコール
モノアセテートなどのエチレングリコール類を製
造する方法に関するものである。
担体付ルテニウム触媒の存在下にグリコール酸
を水添してエチレングリコールを製造する方法は
古くから知られている（USP 2607805）。しかし
ながら、この方法はエチレングリコールの収率が
不十分であることもさることながら、石油化学の
勃興により、安価なエチレンを原料として銀触媒
による気相酸化反応で得られるエチレンオキサイ
ドを水和して製造する方法に完全に駆逐されてい
る。
一方、昨今の原油価格の高騰が石油化学製品の
コストを上昇させ、安定した原油供給に対する不
安と相俟つて、化学工業原料の脱石油の機運が高
まつており、エチレングリコールの製造法につい
てもホルムアルデヒド→グリコール酸→エチレン
グリコールという製造ルートが見直されつつあ
る。
本発明者らはホルムアルデヒドを一酸化炭素お
よび水もしくはアルコールと反応させて得られる
グリコール酸およびアセトキシ酢酸、グリコール
酸メチルなどのアルコール酸のエステル型誘導体
を水素添加して高収率でエチレングリコール類を
製造する方法について種々検討した結果、第三級
ホスフインを配位子として含有するルテニウム錯
体を触媒として用いることにより、グリコール酸
のみならずグリコール酸メチルなどのグリコール
酸エステルのカルボキシル基も還元されることを
見い出し、また、反応系内にルテニウムに配位し
うる一酸化炭素がルテニウムに対して一定の比率
以上に存在すると触媒が不活性になることを見い
出し本発明を完成したものである。
ルテニウム錯体を触媒とするカルボン酸の均一
系水素添加についてはジヤーナル・オブ・オーガ
ノメタリツク・ケミストリー（Jounal of
Organometallic Chemistry），188（1980）109〜
119に報告されているが、上記文献では飽和モノ
カルボン酸またはジカルボン酸および対応する酸
無水物の水素添加について紹介されているがグリ
コール酸およびその誘導体の水素添加については
記載がなく、また、その触媒がH4Ru4（CO）8
（PBU3）4などのカルボニル含有ルテニウム錯体
である点が本発明と異なつている。
以下に本発明について詳細に説明する。
本発明方法において使用される原料はグリコー
ル酸またはそのエステル型誘導体である。グリコ
ール酸のエステル型誘導体としては、グリコール
酸メチル、グリコール酸エチル等のグリコール酸
エステル、アセトキシ酢酸、プロピオニルオキシ
酢酸等のアシルオキシ酢酸が挙げられる。これら
のグリコール酸またはそのエステル型誘導体は酸
触媒の存在下にホルムアルデヒドを一酸化炭素お
よび水またはアルコールと反応させることにより
製造することができる。（特開昭49−55617、同51
−13719、特願昭55−103365等）
本発明の反応はルテニウム錯体触媒の存在下に
行なわれる。ルテニウム錯体は少くとも第三級ホ
スフインと錯結合していることが必須であり、こ
のほかにハロゲン、ヒドリド、カルボキシレー
ト、アルコラートなどの陰イオン性配位子を含ん
でいてもよいが、カルボニル配位子はルテニウム
錯体を本反応に対して不活性化するので、カルボ
ニル含有ルテニウム錯体の使用を避け、且つ一酸
化炭素含有率の小さな水素ガスを使用し、反応系
内の全CO存在量をルテニウムに対して等モル以
下に抑制することが要求される。
上記の条件を満たす限り、反応系へのルテニウ
ム錯体の供給形態は限定されることはなく、予め
ルテニウム錯体を形成して反応系に供給してもま
たルテニウムをハロゲン化物、カルボン酸塩など
の形態で反応系に供給し、別途反応系に供給され
る第三級ホスフインと反応系内で錯体を形成させ
てもよい。
ルテニウムの使用量は単体に換算して、反応基
質1molに対して0.001〜0.5mol、好ましくは0.001
〜0.1molである。
第三級ホスフインとしては、トリ（ｎ―ブチ
ル）ホスフインなどのトリアルキルホスフイン、
トリフエニルホスフインなどのトリアリールホス
フインがルテニウムに対して過剰量、好ましくは
ルテニウム1molに対して１〜100mol使用され
る。
反応を行なうにあたつて、溶媒の使用は必ずし
も必要ではないが、液相を均一に保持するのを助
けるために、反応に不活性な溶媒を使用すること
ができる。このような溶媒の一例としては、ベン
ゼン、トルエン、キシレン等の芳香族炭化水素、
ジオキサン、セロソルブ等のエーテル類、ブタノ
ール、エチレングリコール等のアルコールなどが
挙げられる。
本発明の反応は水またはアルコールを副生する
反応であるので、化学平衡の見地から反応系に水
あるいはアルコールを多量に存在させないことが
好ましいが、反応基質１モルに対して0.5〜５モ
ル程度の少量の水を反応系に添加することにより
反応速度あるいはエチレングリコール類の収率を
向上させることができる。
本発明方法は、水素圧力５〜200Kg／cm3Ｇ、反
応温度100〜300℃の条件下において回分法、連続
法のいずれの方法においても実施することができ
る。
次に本発明を実施例により更に具体的に説明す
る。
実施例１〜５、比較例１〜４
チタンで内張りされた50ml容の誘導回転撹拌型
オートクレーブにグリコール酸50.0mmol、三塩
化ルテニウム1.0mmol、配位子10mmol（比較例
１では使用しなかつた）、溶媒20ｇおよび場合に
より水100mmolを仕込み、205℃に加熱して、蓄
圧器から圧力調節器を通じて水素ガスを圧入し、
30Kg／cm2Ｇの圧力を維持しつつ３時間反応を行な
つた。３時間後にオートクレーブを水で急冷し、
オートクレーブを放圧したのち反応生成液をガス
クロマトグラフイーにより分析し、生成したエチ
レングリコールを定量した。
使用した配位子の種類、水の添加量、溶媒の種
類およびエチレングリコールの収率を表―１に示
す。
The present invention relates to a method for producing ethylene glycols such as ethylene glycol and ethylene glycol monoacetate by hydrogenating glycolic acid and ester derivatives of glycolic acid such as acetoxyacetic acid and methyl glycolate in the presence of a ruthenium complex. It is. A method for producing ethylene glycol by hydrogenating glycolic acid in the presence of a supported ruthenium catalyst has been known for a long time (USP 2607805). However, this method has an insufficient yield of ethylene glycol, and with the rise of petrochemistry, ethylene oxide, which is obtained by a silver-catalyzed gas phase oxidation reaction using cheap ethylene as a raw material, is hydrated. The manufacturing method has been completely eliminated. On the other hand, the recent rise in crude oil prices has increased the cost of petrochemical products, and together with concerns about a stable crude oil supply, there is a growing momentum to move away from petroleum as a raw material for the chemical industry, and there are also concerns about the production method of ethylene glycol. The production route of formaldehyde → glycolic acid → ethylene glycol is being reconsidered. The present inventors have hydrogenated ester derivatives of glycolic acid and alcoholic acids such as acetoxyacetic acid and methyl glycolate, which are obtained by reacting formaldehyde with carbon monoxide and water or alcohol, to produce ethylene glycols in high yield. As a result of various studies on production methods, we found that by using a ruthenium complex containing tertiary phosphine as a ligand as a catalyst, not only glycolic acid but also the carboxyl group of glycolic acid esters such as methyl glycolate can be reduced. They also discovered that the catalyst becomes inactive when carbon monoxide, which can coordinate with ruthenium, is present in the reaction system above a certain ratio to ruthenium, thereby completing the present invention. Homogeneous hydrogenation of carboxylic acids catalyzed by ruthenium complexes is described in the Journal of Organometallic Chemistry.
Organometallic Chemistry), 188 (1980) 109~
119, the above literature introduces the hydrogenation of saturated monocarboxylic acids or dicarboxylic acids and the corresponding acid anhydrides, but does not mention the hydrogenation of glycolic acid and its derivatives. The catalyst is H 4 Ru 4 (CO) 8
It differs from the present invention in that it is a carbonyl-containing ruthenium complex such as (PBU 3 ) 4 . The present invention will be explained in detail below. The raw material used in the method of the present invention is glycolic acid or its ester derivative. Examples of ester derivatives of glycolic acid include glycolic acid esters such as methyl glycolate and ethyl glycolate, and acyloxyacetic acids such as acetoxyacetic acid and propionyloxyacetic acid. These glycolic acids or their ester derivatives can be produced by reacting formaldehyde with carbon monoxide and water or alcohol in the presence of an acid catalyst. (Unexamined Japanese Patent Publication No. 49-55617, 51
-13719, Japanese Patent Application No. 55-103365, etc.) The reaction of the present invention is carried out in the presence of a ruthenium complex catalyst. It is essential that the ruthenium complex has a complex bond with at least a tertiary phosphine, and may also contain anionic ligands such as halogens, hydrides, carboxylates, and alcoholates, but may contain carbonyl ligands. Since the ions inactivate the ruthenium complex for this reaction, avoid using carbonyl-containing ruthenium complexes, and use hydrogen gas with a low carbon monoxide content to reduce the total amount of CO present in the reaction system to ruthenium. It is required to suppress the amount to less than equimolar. As long as the above conditions are met, the form in which the ruthenium complex is supplied to the reaction system is not limited, and even if a ruthenium complex is formed in advance and supplied to the reaction system, ruthenium can also be supplied in the form of a halide, carboxylate, etc. may be supplied to the reaction system to form a complex within the reaction system with a tertiary phosphine that is separately supplied to the reaction system. The amount of ruthenium to be used is 0.001 to 0.5 mol, preferably 0.001 mol, per 1 mol of the reaction substrate.
~0.1mol. Examples of tertiary phosphine include trialkylphosphines such as tri(n-butyl)phosphine;
Triarylphosphine such as triphenylphosphine is used in excess of ruthenium, preferably from 1 to 100 mol per mol of ruthenium. Although the use of a solvent is not necessary in carrying out the reaction, a solvent inert to the reaction can be used to help maintain a homogeneous liquid phase. Examples of such solvents include aromatic hydrocarbons such as benzene, toluene, and xylene;
Examples include ethers such as dioxane and cellosolve, and alcohols such as butanol and ethylene glycol. Since the reaction of the present invention is a reaction that produces water or alcohol as a by-product, from the viewpoint of chemical equilibrium, it is preferable not to allow a large amount of water or alcohol to exist in the reaction system, but about 0.5 to 5 moles per mole of reaction substrate. By adding a small amount of water to the reaction system, the reaction rate or the yield of ethylene glycols can be improved. The method of the present invention can be carried out either batchwise or continuously under conditions of a hydrogen pressure of 5 to 200 kg/cm 3 G and a reaction temperature of 100 to 300°C. Next, the present invention will be explained in more detail with reference to Examples. Examples 1 to 5, Comparative Examples 1 to 4 50.0 mmol of glycolic acid, 1.0 mmol of ruthenium trichloride, and 10 mmol of ligand (not used in Comparative Example 1) were placed in a 50 ml titanium-lined induction rotation stirring autoclave. , 20 g of solvent and optionally 100 mmol of water are charged, heated to 205°C, and hydrogen gas is injected from a pressure accumulator through a pressure regulator.
The reaction was carried out for 3 hours while maintaining a pressure of 30 kg/cm 2 G. After 3 hours, quench the autoclave with water and
After the autoclave was depressurized, the reaction product liquid was analyzed by gas chromatography to quantify the amount of ethylene glycol produced. Table 1 shows the type of ligand used, the amount of water added, the type of solvent, and the yield of ethylene glycol.
【表】
実施例 ６
グリコール酸のかわりにアセトキシ酢酸
30mmolを使用し、三塩化ルテニウムおよびトリ
（ｎ―ブチル）ホスフインの使用量をそれぞれ
0.6mmolおよび6.0mmolに変更したこと以外は実
施例２と同様に実験を行なつた。反応生成液をガ
スクロマトグラフイーにより分析し、エチレング
リコール、エチレングリコールモノアセテートお
よびエチレングリコールジアセテートの定量を行
なつた。結果は表―２に示す。
実施例 ７
水60mmolを添加したこと以外は実施例６と同
様に反応を行なつた。結果は表―２に示す。[Table] Example 6 Acetoxyacetic acid instead of glycolic acid
Using 30 mmol, the amounts of ruthenium trichloride and tri(n-butyl)phosphine were determined respectively.
The experiment was conducted in the same manner as in Example 2 except that the amounts were changed to 0.6 mmol and 6.0 mmol. The reaction product liquid was analyzed by gas chromatography to quantify ethylene glycol, ethylene glycol monoacetate, and ethylene glycol diacetate. The results are shown in Table-2. Example 7 The reaction was carried out in the same manner as in Example 6 except that 60 mmol of water was added. The results are shown in Table-2.
【表】
実施例 ８，９
グリコール酸のかわりにグリコール酸メチル
30mmolを使用し、三塩化ルテニウムおよびトリ
（ｎ―ブチル）ホスフインの使用量ならびに水素
圧力を表―３に記載した値として実施例２と同様
に実験を行なつた。結果を表―３に示す。[Table] Examples 8 and 9 Methyl glycolate instead of glycolic acid
An experiment was conducted in the same manner as in Example 2 using 30 mmol and using the amounts of ruthenium trichloride and tri(n-butyl)phosphine and the hydrogen pressure as shown in Table 3. The results are shown in Table-3.
【表】
比較例 ５〜７
ルテニウム錯体の活性に対するCOの影響を確
認するために水素ガスに一酸化炭素ガスを混合し
て使用したこと以外は実施例１と同様に実験を行
なつた。結果は表―４に示す。[Table] Comparative Examples 5 to 7 In order to confirm the influence of CO on the activity of the ruthenium complex, an experiment was conducted in the same manner as in Example 1, except that hydrogen gas and carbon monoxide gas were mixed and used. The results are shown in Table 4.
【表】
比較例７においてはガス吸収が認められず、反
応は全く進行しなかつたが、比較例５および６に
おいてはガス吸収が途中で停止し、その後反応は
進行せず、触媒が失活したことが明らかである。[Table] In Comparative Example 7, no gas absorption was observed and the reaction did not proceed at all, but in Comparative Examples 5 and 6, gas absorption stopped midway and the reaction did not proceed thereafter, indicating that the catalyst was deactivated. It is clear that he did.
Claims (1)
ルテニウム錯体の存在下、反応系内の全CO存在
量がルテニウムに対して等モル以下の条件下で、
グリコール酸またはそのエステル型誘導体を水素
ガスと接触させることを特徴とするエチレングリ
コール類の製造法。1. In the presence of a ruthenium complex complexed with at least tertiary phosphine, under conditions where the total amount of CO present in the reaction system is equal mole or less to ruthenium,
A method for producing ethylene glycols, which comprises contacting glycolic acid or an ester derivative thereof with hydrogen gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56111796A JPS5813527A (en) | 1981-07-17 | 1981-07-17 | Manufacturing method of ethylene glycols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56111796A JPS5813527A (en) | 1981-07-17 | 1981-07-17 | Manufacturing method of ethylene glycols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5813527A JPS5813527A (en) | 1983-01-26 |
| JPH0145458B2 true JPH0145458B2 (en) | 1989-10-03 |
Family
ID=14570365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56111796A Granted JPS5813527A (en) | 1981-07-17 | 1981-07-17 | Manufacturing method of ethylene glycols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5813527A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5077442A (en) * | 1990-04-26 | 1991-12-31 | Mitsubishi Kasei Corporation | Method for producing 1,4-butanediol |
| US5258058A (en) * | 1992-10-05 | 1993-11-02 | Air Products And Chemicals, Inc. | Nitrogen adsorption with a divalent cation exchanged lithium X-zeolite |
| US7615671B2 (en) | 2007-11-30 | 2009-11-10 | Eastman Chemical Company | Hydrogenation process for the preparation of 1,2-diols |
| GB202201979D0 (en) * | 2022-02-15 | 2022-03-30 | Johnson Matthey Plc | Process |
-
1981
- 1981-07-17 JP JP56111796A patent/JPS5813527A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5813527A (en) | 1983-01-26 |
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