JPS6139294B2 - - Google Patents
Info
- Publication number
- JPS6139294B2 JPS6139294B2 JP59176321A JP17632184A JPS6139294B2 JP S6139294 B2 JPS6139294 B2 JP S6139294B2 JP 59176321 A JP59176321 A JP 59176321A JP 17632184 A JP17632184 A JP 17632184A JP S6139294 B2 JPS6139294 B2 JP S6139294B2
- Authority
- JP
- Japan
- Prior art keywords
- formaldehyde
- ethylene glycol
- present
- mixed gas
- phenol
- 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 claims description 72
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 65
- 239000007789 gas Substances 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000047 product 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- -1 glycolic acid ester Chemical class 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance 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
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製造す
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 producing 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
業的に重要な基礎化学品である。 Ethylene glycol is a raw material for polyester,
It is an industrially important basic chemical as an organic solvent, non-volatile antifreeze, or 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、石油価格の
高騰、石油の重質化傾向などにより、石炭、天然
ガス、重質油などから容易に得られる一酸化炭
素、水素、あるいは一酸化炭素、水素を原料とし
て製造されるメタノール、ホルムアルデヒドなど
の炭素数１（C1）化合物からの製造法が重要な課
題になつている。 Traditionally, ethylene glycol has been produced using a petrochemical method using ethylene as a raw material, but due to the soaring oil prices and the tendency for petroleum to become heavier, ethylene glycol has been produced using monoxide, which is easily obtained from coal, natural gas, heavy oil, etc. An important issue is the production method from carbon, hydrogen, or carbon monoxide (C 1 ) compounds such as methanol and formaldehyde, which are produced using carbon monoxide and hydrogen as raw materials.
その一つの方法として、ロジウム触媒の存在下
に合成ガスからエチレングリコールを製造する方
法（特開昭52―42809号公報）があるが、この方
法は高価なロジウムを触媒として使用するという
欠点を有する。また、ホルムアルデヒドを一酸化
炭素と反応させてグリコール酸を製造し、グリコ
ール酸ををエステル化してグリコール酸エステル
に変え、次いでグリコール酸をエステルを水素化
してエチレングリコールを得る方法（特開昭54―
106408号公報）が提案されているが、この方法の
根本的問題点は多くの複雑な工程を必要とするこ
とである。 One method is to produce ethylene glycol from synthesis gas in the presence of a rhodium catalyst (Japanese Unexamined Patent Publication No. 1983-42809), but this method has the disadvantage of using expensive rhodium as a catalyst. . In addition, a method of producing glycolic acid by reacting formaldehyde with carbon monoxide, esterifying the glycolic acid to convert it into a glycolic acid ester, and then hydrogenating the ester of glycolic acid to obtain ethylene glycol (Japanese Unexamined Patent Publication No. 1983-1999)
106408) has been proposed, but the fundamental problem with this method is that it requires many complicated steps.
更に、ホルムアルデヒドを合成ガスと反応させ
て１段でエチレングリコールを得る方法（特開昭
51―128903号公報、同53―53607号公報）が知ら
れているが、この方法はエチレングリコールの選
択性が低い欠点を有し、エチレングリコールのホ
ルムアルデヒドからの収率は40％以下にすぎなか
つた。 Furthermore, a method for obtaining ethylene glycol in one step by reacting formaldehyde with synthesis gas (Japanese Patent Application Laid-open No.
51-128903 and 53-53607), but this method has the drawback of low selectivity for ethylene glycol, and the yield of ethylene glycol from formaldehyde is only 40% or less. Ta.
本発明者らはすでに、ホルムアルデヒドと合成
ガスをコバルトカルボニル触媒及びフエノールの
存在下に合成ガスと反応させることにより、従来
法に比べて高成績でエチレングリコールが得られ
ることを見出している（特開昭58―90522号公
報）。しかしこの方法の問題点はエチレングリコ
ールのホルムアルデヒドからの収率を高く保つた
めには反応液中のホルムアルデヒド濃度を１重量
パーセント以下に保つ必要があり、ホルムアルデ
ヒドの濃度を１〜10重量パーセントに増加すると
エチレングリコールの収率が50％以下に低下する
ことであつた。 The present inventors have already discovered that by reacting formaldehyde and synthesis gas with synthesis gas in the presence of a cobalt carbonyl catalyst and phenol, ethylene glycol can be obtained with higher performance than conventional methods (JP Publication No. 58-90522). However, the problem with this method is that in order to maintain a high yield of ethylene glycol from formaldehyde, the formaldehyde concentration in the reaction solution must be kept below 1% by weight; The yield of ethylene glycol decreased to less than 50%.
本発明者らは、このようなこれまで知られてい
るエチレングリコール製造法の欠点、問題点を克
服するために鋭意検討を重ねた結果、触媒として
コバルトカルボニルの他に少量のルテニウムカル
ボニルを用いることにより従来法に比べて著しく
高成績でエチレングリコールが得られることを見
出し、本発明をなすに至つた。 The present inventors have conducted extensive studies to overcome the drawbacks and problems of the previously known ethylene glycol production methods, and as a result, have discovered that a small amount of ruthenium carbonyl can be used in addition to cobalt carbonyl as a catalyst. The inventors have discovered that ethylene glycol can be obtained with significantly better results than conventional methods, leading to the present invention.
即ち、本発明は一酸化炭素と水素の混合ガスを
コバルトカルボニル及びフエノールおよび／また
はアルキルフエノールの存在下にホルムアルデヒ
ドと反応させる際に、少量のルテニウムカルボニ
ルを共存させることを特徴とするエチレングリコ
ールの製造方法を提供するものである。 That is, the present invention relates to the production of ethylene glycol, which is characterized in that a small amount of ruthenium carbonyl is allowed to coexist when reacting a mixed gas of carbon monoxide and hydrogen with formaldehyde in the presence of cobalt carbonyl and phenol and/or alkylphenol. The present invention provides a method.
本発明に係る反応は次式で表わすことができ
る。 The reaction according to the present invention can be represented by the following formula.
CH2O＋CO＋2H2→HOCH2CH2OH
またエチレングリコールの生成に伴う主な副生
成物はメタノールであり、次式により生成する。 CH 2 O+CO+2H 2 →HOCH 2 CH 2 OH Furthermore, the main by-product accompanying the production of ethylene glycol is methanol, which is produced according to the following formula.
CH2O＋H2→CH3OH
本発明によれば合成ガスとホルムアルデヒドか
ら選択性よく、かつ容易にエチレングリコールを
製造することができるので本発明の意義は大き
い。 CH 2 O+H 2 →CH 3 OH According to the present invention, ethylene glycol can be easily produced from synthesis gas and formaldehyde with good selectivity, so the present invention has great significance.
本発明に用いられる混合ガスの一酸化炭素と水
素のモル比は通常CO：H2＝１：１〜１：20であ
るが好ましくは１：２〜１：10の範囲である。圧
力は200〜1000Kg／cm2が好ましい。本発明に用い
るフエノール及び／またはアルキルフエノールの
中ではフエノール及びクレゾールが最も好まし
い。本発明のフエノールおよび／またはアルキル
フエノールは適当な溶媒、好ましくはトルエン、
ジフエニルメタン等の芳香族炭化水素溶媒でうす
めて用いることができ、全溶媒中に占めるフエノ
ールおよび／またはアルキルフエノールの割合
は、10〜100重量パーセントの範囲が好ましい。 The molar ratio of carbon monoxide and hydrogen in the mixed gas used in the present invention is usually CO:H 2 =1:1 to 1:20, but preferably in the range of 1:2 to 1:10. The pressure is preferably 200 to 1000 Kg/cm 2 . Among the phenols and/or alkylphenols used in the present invention, phenols and cresols are most preferred. The phenol and/or alkylphenol of the present invention can be prepared in a suitable solvent, preferably toluene,
It can be used diluted with an aromatic hydrocarbon solvent such as diphenylmethane, and the proportion of phenol and/or alkylphenol in the total solvent is preferably in the range of 10 to 100 weight percent.
本発明で使用するホルムアルデヒドはホルムア
ルデヒド水溶液またはパラホルムアルデヒドを用
いることができるが、工業的見地からはホルムア
ルデヒド水溶液が望ましい。 As the formaldehyde used in the present invention, an aqueous formaldehyde solution or paraformaldehyde can be used, but an aqueous formaldehyde solution is desirable from an industrial standpoint.
反応液中のホルムアルデヒドの濃度は１〜20重
量パーセントの範囲であるが、エチレングリコー
ルの選択性を高く保つためには１〜10重量パーセ
ントの範囲が好ましい。 The concentration of formaldehyde in the reaction solution is in the range of 1 to 20 percent by weight, but is preferably in the range of 1 to 10 percent by weight in order to maintain high selectivity to ethylene glycol.
本発明で使用するルテニウムカルボニルのコバ
ルトカルボニルに対するモル比はRu／Co比で1/1
００〜1/1の範囲であり、工業的には高価なルテニ
ウムの使用量は少ない方が有利であるが、エチレ
ングリコールの収率を高めるためには1/20〜1/5
の範囲が好ましい。コバルトカルボニルのホルム
アルデヒドに対する使用モル比はCoとして２〜
20モル％の範囲が好ましい。 The molar ratio of ruthenium carbonyl to cobalt carbonyl used in the present invention is 1/1 in Ru/Co ratio.
The range is from 1/20 to 1/1, and from an industrial perspective, it is advantageous to use a small amount of expensive ruthenium, but in order to increase the yield of ethylene glycol, it is from 1/20 to 1/5.
A range of is preferred. The molar ratio of cobalt carbonyl to formaldehyde used is 2 to 2 as Co.
A range of 20 mol% is preferred.
本発明の方法は回分式、連続式のいずれかの反
応様式によつても実施可能であり、また反応液か
ら生成物及び触媒の分離は蒸留、抽出等公知の方
法により容易に行いうる。 The method of the present invention can be carried out either batchwise or continuously, and the product and catalyst can be easily separated from the reaction solution by known methods such as distillation and extraction.
次に、本発明を実施例及び比較例により更に詳
細に説明する。 Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
実施例 １
ハステロイＣ―276製、内容積100mlの電磁上下
かきまぜ式オートクレーブにフエノール10ｇ、ト
ルエン10ｇ、ホルムアルデヒド37％水溶液3.24ｇ
（CH2Oとして40ｍmol）及びジコバルトオクタカ
ルボニルCo2（CO）8、0.855ｇ（Coとして５mg―
atom）及びトリルテニウムドデカカルボニルRu3
（CO）120.107ｇ（Ruとして0.5mg―atom）を仕込
み、CO：H2＝１：４の混合ガスで反応器内の空
気を置換した後、同組成の混合ガスを圧入して
500Kg／cm2とし、昇温して210℃で２時間反応させ
た。この間最高圧力は620Kg／cm2に達した。反応
後オートクレーブを冷却し、生成物をガスクロマ
ト分析した結果、ホルムアルデヒドの反応率は
95.2％、反応したホルムアルデヒドからのエチレ
ングリコール及びメタノールの収率（選択率）は
それぞれ68.6％、11.5％であつた。Example 1 10 g of phenol, 10 g of toluene, and 3.24 g of a 37% formaldehyde aqueous solution were placed in an electromagnetic vertical stirring autoclave made of Hastelloy C-276 and having an internal volume of 100 ml.
(40 mmol as CH 2 O) and dicobalt octacarbonyl Co 2 (CO) 8 , 0.855 g (5 mg as Co)
atom) and triruthenium dodecacarbonyl Ru 3
(CO) 12 0.107g (0.5mg-atom as Ru) was charged, and after replacing the air in the reactor with a mixed gas of CO:H 2 = 1:4, a mixed gas of the same composition was injected under pressure.
The pressure was adjusted to 500 Kg/cm 2 , and the temperature was raised to 210° C. for 2 hours. During this period, the maximum pressure reached 620Kg/cm 2 . After the reaction, the autoclave was cooled and the product was analyzed by gas chromatography. As a result, the reaction rate of formaldehyde was
The yields (selectivity) of ethylene glycol and methanol from the reacted formaldehyde were 68.6% and 11.5%, respectively.
比較例 １
Ru3（CO）12を用いなかつたほかは実施例１と
同様の条件で反応を行つた結果、ホルムアルデヒ
ドの反応率は99.1％、反応したホルムアルデヒド
からのエチレングリコール及びメタノールの収率
（選択率）はそれぞれ41.4％、4.6％であつた。Comparative Example 1 A reaction was carried out under the same conditions as in Example 1 except that Ru 3 (CO) 12 was not used. As a result, the reaction rate of formaldehyde was 99.1%, and the yield of ethylene glycol and methanol from the reacted formaldehyde ( The selection rate) was 41.4% and 4.6%, respectively.
実施例 ２
実施例１に記載したと同様なオートクレーブに
フエノール10ｇ、トルエン10ｇ、ホルムアルデヒ
ド37％水溶液3.24ｇ（CH2Oとして40ｍmol）及
びジコバルトオクタカルボニル0.855ｇ（Coとし
て５mg―atom）、及びトリルテニウムデドカカル
ボニル0.107ｇ（Ruとして0.5mg―atom）を仕込
み、CO：H2＝１：４の混合ガスで反応器内の空
気を置換した後、同組成の混合ガスを圧入して
400Kg／cm2とし、昇温して180℃で２時間反応させ
た。この間器内の最高圧力は500Kg／cm2に達し
た。Example 2 In an autoclave similar to that described in Example 1, 10 g of phenol, 10 g of toluene, 3.24 g of a 37% formaldehyde aqueous solution (40 mmol as CH 2 O), and 0.855 g of dicobalt octacarbonyl (5 mg-atom as Co), After charging 0.107g of ruthenium dedocacarbonyl (0.5mg-atom as Ru) and replacing the air in the reactor with a mixed gas of CO:H 2 = 1:4, a mixed gas of the same composition was injected under pressure.
The pressure was adjusted to 400 Kg/cm 2 , and the temperature was raised to 180° C. for 2 hours. During this period, the maximum pressure within the vessel reached 500Kg/cm 2 .
実施例１と同様にして分析を行つた結果、ホル
ムアルデヒドの反応率は97.3％、反応したホルム
アルデヒドからのエチレングリコール及びメタノ
ールの収率（選択率）はそれぞれ65.3％、9.6％
であつた。 As a result of analysis conducted in the same manner as in Example 1, the reaction rate of formaldehyde was 97.3%, and the yields (selectivity) of ethylene glycol and methanol from the reacted formaldehyde were 65.3% and 9.6%, respectively.
It was hot.
実施例 ３
CO：H2＝１：5.25の混合ガスを用い、500Kg／
cm2に圧入した以外は、実施例２と同様の条件で反
応を行つた結果、器内の最高圧力は620Kg／cm2に
達した。分析の結果、ホルムアルデヒドの反応率
は96.8％、反応したホルムアルデヒドからのエチ
レングリコール及びメタノールの収率（選択率）
はそれぞれ69.5％、4.3％であつた。Example 3 Using a mixed gas of CO:H 2 = 1:5.25, 500Kg/
The reaction was carried out under the same conditions as in Example 2 , except that the pressure was injected into the vessel at a pressure of 620 kg/cm 2 . As a result of the analysis, the reaction rate of formaldehyde was 96.8%, and the yield (selectivity) of ethylene glycol and methanol from the reacted formaldehyde.
were 69.5% and 4.3%, respectively.
Claims (1)
ボニル及びフエノールおよび／またはアルキルフ
エノールの存在下にホルムアルデヒドと反応させ
る際に、ルテニウムカルボニルを共存させること
を特徴とするエチレングリコールの製造方法。1. A method for producing ethylene glycol, which comprises allowing ruthenium carbonyl to coexist when reacting a mixed gas of carbon monoxide and hydrogen with formaldehyde in the presence of cobalt carbonyl and phenol and/or alkylphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59176321A JPS6153235A (en) | 1984-08-24 | 1984-08-24 | Production of ethylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59176321A JPS6153235A (en) | 1984-08-24 | 1984-08-24 | Production of ethylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6153235A JPS6153235A (en) | 1986-03-17 |
| JPS6139294B2 true JPS6139294B2 (en) | 1986-09-03 |
Family
ID=16011536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59176321A Granted JPS6153235A (en) | 1984-08-24 | 1984-08-24 | Production of ethylene glycol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6153235A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61192173U (en) * | 1985-05-17 | 1986-11-29 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5731472A (en) * | 1995-12-06 | 1998-03-24 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
| EP2915584A1 (en) * | 2014-03-05 | 2015-09-09 | Basf Se | Ruthenium-phenol catalysts for transfer hydrogenation reactions |
-
1984
- 1984-08-24 JP JP59176321A patent/JPS6153235A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61192173U (en) * | 1985-05-17 | 1986-11-29 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6153235A (en) | 1986-03-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |