JPS62210056A - Catalyst for reducing carboxylic acid - Google Patents
Catalyst for reducing carboxylic acidInfo
- Publication number
- JPS62210056A JPS62210056A JP61050192A JP5019286A JPS62210056A JP S62210056 A JPS62210056 A JP S62210056A JP 61050192 A JP61050192 A JP 61050192A JP 5019286 A JP5019286 A JP 5019286A JP S62210056 A JPS62210056 A JP S62210056A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- carboxylic acid
- acid
- rhenium
- osmium
- 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.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims 2
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 10
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 8
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001257 hydrogen Substances 0.000 abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 235000019260 propionic acid Nutrition 0.000 abstract description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 20
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- PGZSVAXKRVWAHV-UHFFFAOYSA-N [Re].[Os] Chemical compound [Re].[Os] PGZSVAXKRVWAHV-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000489 osmium tetroxide Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- -1 aromatic carboxylic acids Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000012285 osmium tetroxide Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMTKGALBDOEZCA-UHFFFAOYSA-N 2-tetradecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCC(C(O)=O)C(O)=O SMTKGALBDOEZCA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920006051 Capron® Polymers 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- GRLYPOPFNDQSKV-UHFFFAOYSA-N rhenium ruthenium Chemical compound [Ru].[Re] GRLYPOPFNDQSKV-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はカルボン酸を水素によって接触還元してアルコ
ールを製造する際に用いる触媒に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a catalyst used in the production of alcohol by catalytic reduction of carboxylic acid with hydrogen.
カルボン酸からアルコールを得る方法としては、カルボ
ン酸を予め低級アルコールでエステルにし、Ａｄｋｉ、
ｎｓ触媒で接触還元することが知られているＣＬ、１１
．八ｄｋｉｎｓ、ｏｒｇ、Ｒｅａｃｔｉｏｎ、 ８ 、
１ （１９５４）） （、しかし、この接触還元は一般
に２００℃以上の高温かつ２００気圧以上の水素圧下で
行われるので１、エネルギー的にも、設備的にも、また
エステル転換工程を含む点でも、極めて不経済な方法で
ある。As a method for obtaining alcohol from carboxylic acid, carboxylic acid is esterified with a lower alcohol in advance, Adki,
CL, 11, which is known to be catalytically reduced with ns catalyst
．． 8dkins, org, Reaction, 8,
1 (1954)) (However, this catalytic reduction is generally carried out at a high temperature of 200°C or higher and under a hydrogen pressure of 200 atmospheres or higher1, so it is difficult in terms of energy, equipment, and the inclusion of an ester conversion step. , which is an extremely uneconomical method.
一方、カルボン酸を直接接触還元する触媒として、レニ
ウム触媒が知られているが、レニウムを用いてカルボン
酸を接触還元しようとすると、１５０℃以上の高温、１
５０気圧以上の水素圧が必要である。また、α位がアル
キル置換されて立体障害の非常に大きいカルボン酸（例
えば、ピバリン酸）はレニウム触媒を用いても還元され
ないという問題点がある（Ｈ，Ｓ、Ｂｒｏａｄｂｅｎｔ
ｅｔ ａｌ、、 Ｊ、八ｍ、Ｃｈｅｍ。On the other hand, rhenium catalysts are known as catalysts for direct catalytic reduction of carboxylic acids.
A hydrogen pressure of 50 atmospheres or more is required. In addition, there is a problem that carboxylic acids that are highly sterically hindered due to alkyl substitution at the α-position (e.g., pivalic acid) cannot be reduced even using a rhenium catalyst (H, S, Broadbent).
et al., J. H., Chem.
Ｓｏｃ、＋ ２４．１８４７ （１９５９） ）。Soc, +24.1847 (1959)).
更に、（／ニウム触媒の耐酸性を向上させるために、レ
ニウム−パラジウム触媒（特開昭５２−９７９０１号公
報）が、また、活性を向上させるために、レニウム−ル
テニウムまたはロジウムまたは白金触媒ＣＵＳＰ ４１
０４４７８号明細書）が開示されているが、満足される
ものではない。Furthermore, to improve the acid resistance of the (/nium catalyst), a rhenium-palladium catalyst (JP-A-52-97901) is used, and a rhenium-ruthenium or rhodium or platinum catalyst, CUSP 41, is used to improve the activity.
04478), but it is not satisfactory.
本発明者らは、さらに活性の晶いカルボン酸還元用触媒
について鋭意検討した結果、貴金属の中で検討されてい
なかったオスミウムとレニウムとを併せて用いることに
よって最大限の活性が示されるごとを見出し本発明に至
った。The inventors of the present invention further conducted extensive studies on highly active crystalline carboxylic acid reduction catalysts, and found that maximum activity could be achieved by using osmium and rhenium together, which had not been studied among noble metals. Heading This invention has been achieved.
即ち、本発明は、オスミウムとレニウムとを必須成分と
するカルボン酸還元用触媒を提供するものである。That is, the present invention provides a carboxylic acid reduction catalyst containing osmium and rhenium as essential components.
レニウムとオスミウムによる相乗効果は、先に知られて
いる他の貴金属（ルテニウム、ロジウム、白金、パラジ
ウムなど）の相乗効果に比較して優れており、触媒活性
のみならず、耐酸性の効果をも有しており、本発明の触
媒を用いることにより、従来よりも温和な条件でカルボ
ン酸を高効率に接触還元してアルコールを製造すること
ができる。The synergistic effect of rhenium and osmium is superior to that of other previously known noble metals (ruthenium, rhodium, platinum, palladium, etc.), and it not only improves catalytic activity but also improves acid resistance. By using the catalyst of the present invention, alcohol can be produced by catalytically reducing carboxylic acids with high efficiency under milder conditions than conventional ones.
本発明の触媒を用いて接触還元することができる原料カ
ルボン酸としては、カルボン酸であればいずれのもので
もよく、例えば、酢酸、プロピオン酸、カプロン酸、高
級脂肪酸、コハク酸、グルタル酸、アジピン酸、デカン
ジカルボン酸、ペンタデカンジカルボン酸、マレイン酸
、フマル酸、安息香酸等が挙げられ、さらに、ヒドロキ
シル基を持つ脂肪族カルボン酸、ポリカルボン酸、芳香
族カルボン酸等も対象となり、また、立体障害のため接
触還元されにくい、即ち、α位がアルキル基で３置換さ
れたカルボン酸（例えば、ピバリン酸、多環式カルボン
酸等）も対象となる。The starting carboxylic acid that can be catalytically reduced using the catalyst of the present invention may be any carboxylic acid, such as acetic acid, propionic acid, caproic acid, higher fatty acids, succinic acid, glutaric acid, and adipine. acid, decanedicarboxylic acid, pentadecanedicarboxylic acid, maleic acid, fumaric acid, benzoic acid, etc., and also aliphatic carboxylic acids, polycarboxylic acids, aromatic carboxylic acids, etc. having hydroxyl groups, and steric Also targeted are carboxylic acids that are difficult to undergo catalytic reduction due to hindrance, that is, trisubstituted α-positions with alkyl groups (eg, pivalic acid, polycyclic carboxylic acids, etc.).
本発明の触媒は、前記のＩｔ、 Ｓ、 Ｂｒｏａｄｂｅ
ｎ ｔらの方法に従い、７酸化２レニウム及び４酸化オ
スミウｌ、を溶媒に溶かし、オートクレーブ中で水素加
圧下（１〜１００気圧）、５０〜１５０°Ｃの温度で還
元処理したものを濾過することによって容易に製造する
ことができる。The catalyst of the present invention has the above-mentioned It, S, Broadbe
According to the method of n t et al., dirhenium heptaoxide and osmiurium tetraoxide are dissolved in a solvent, and the resultant is subjected to reduction treatment in an autoclave under hydrogen pressure (1 to 100 atm) at a temperature of 50 to 150°C, and then filtered. It can be easily manufactured by
この時、一般の担体（シリカ、アルミナ、活性炭等）を
加えておくことにより、レニウム−オスミウム触媒を担
持させ、これをカルボン酸の接触還元に用いることもで
きる。At this time, by adding a general carrier (silica, alumina, activated carbon, etc.), a rhenium-osmium catalyst can be supported, and this can be used for the catalytic reduction of carboxylic acid.
触媒中のレニウムとオスミウムの割合は重量比で１：０
．０１〜１：５の範囲が好ましく、特に１：０．１〜１
：ｌの範囲が好ましい。The ratio of rhenium and osmium in the catalyst is 1:0 by weight.
．． The range is preferably from 01 to 1:5, particularly from 1:0.1 to 1.
:l range is preferred.
本発明の触媒を製造する際に用いることのできる溶媒と
しては、エーテル系溶媒、例えばエーテル、テトラヒド
ロフラン、ジオキサンなどが挙げられる。本発明の触媒
を製造する際には生成するレニウム−オスミウム微粒子
の凝集による活性低下を防くために、酢酸、プロピオン
酸、高級脂肪酸などの活性剤を溶媒に対し１〜２０ ｍ
ｏ１％加えると良い。Examples of solvents that can be used in producing the catalyst of the present invention include ether solvents such as ether, tetrahydrofuran, and dioxane. When producing the catalyst of the present invention, an activator such as acetic acid, propionic acid, higher fatty acid, etc. is added to the solvent at a concentration of 1 to 20 m
It is good to add o1%.
本発明の触媒を用いてカルボン酸を還元する際には、５
０〜２５０℃、特に８０〜１５０℃の温度、水素圧５０
〜２５０気圧、特に５０〜１００気圧の温和な条件で実
施することができる。また、この際に、未反応カルボン
酸とアルコールとから起こり得るエステル形成を阻止す
るために、水あるいはアルコール系あるいはエーテル系
溶剤あるいは炭化水素溶剤をカルボン酸に対して１〜１
０倍モル加えることが有利である。When reducing carboxylic acid using the catalyst of the present invention, 5
Temperature of 0 to 250℃, especially 80 to 150℃, hydrogen pressure of 50℃
It can be carried out under mild conditions of ~250 atm, especially 50-100 atm. In addition, at this time, in order to prevent ester formation that may occur from unreacted carboxylic acid and alcohol, water, alcohol, ether solvent, or hydrocarbon solvent is added to the carboxylic acid at a ratio of 1 to 1.
It is advantageous to add 0 times the molar amount.
使用する触媒の量はカルボン酸に対して０．１〜５０重
量％の範囲が適当であり、経済性及び反応時間を考慮す
ると、１〜５重量％の範囲が特に好ましい。The amount of catalyst used is suitably in the range of 0.1 to 50% by weight based on the carboxylic acid, and in consideration of economy and reaction time, the range of 1 to 5% by weight is particularly preferred.
本発明の触媒を使用する際の反応形式は、流動床法によ
ってでも、液層法によってでも良く、連続的に実施でき
る。The reaction method when using the catalyst of the present invention may be a fluidized bed method or a liquid bed method, and can be carried out continuously.
反応生成物の精製は、副生成物が少量の沸点の低い炭化
水素のみであるので、蒸留によってでも、カラムクロマ
トによってでも、簡単に行える。Purification of the reaction product can be easily carried out either by distillation or by column chromatography, since the only by-product is a small amount of low-boiling hydrocarbon.
以下、実施例を示して本発明を具体的に説明するが、本
発明はこれらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
尚、以下の実施例及び比較例における生成物の同定及び
定量は、ＩＲ，ＮＭＲ，及びガスクロマトグラフ分析法
によった。The products in the following examples and comparative examples were identified and quantified by IR, NMR, and gas chromatography analysis methods.
なお、５％Ｒｕ／Ｃは日本エンケルハルト社製のものを
用いた。Note that the 5% Ru/C manufactured by Nippon Enkelhard Co., Ltd. was used.
実施例ル
ニウムーオスミマシム角媒によるカフプロン酸ＱＭ元
７酸化２レニウム（１，００ｇ、 ４．１３ ｍｇ原子
）と４酸化オスミウム（１，ｏＯｇ、 ３．９３ ｍｇ
原子）を酢酸（１，８０ｇ、 ３０ ｍｍｏｌ）とジオ
キサン（２６，４３ｇ、 ３００ｍｍｏ＋）の混合溶液
に溶かし、次に１００ｍ ｌのオートクレーブ中で、水
素圧１００気圧、温度１４０℃の条件下、４時間攪拌す
る。その後、室温まで冷却し、常圧に戻し、生成してい
る黒色微粉末（１，４９８）を口取する。Example: Cafproic acid QM with rhenium-osmimaxim square medium
Atom) was dissolved in a mixed solution of acetic acid (1,80 g, 30 mmol) and dioxane (26,43 g, 300 mmol), and then in a 100 ml autoclave under the conditions of hydrogen pressure of 100 atm and temperature of 140°C for 4 hours. Stir. Thereafter, it is cooled to room temperature, returned to normal pressure, and the produced black fine powder (1,498) is taken out.
このようにして得られた本発明の触媒（１，４９ｇ）を
カプロン６Ｍ （１１，６２ｇ、 ］ＯＯｍｍｏｌ）の
ジオキサン（２６，４３ｇ、 ３００ｍｍｏｌ）溶液に
加え、１００ｍ ｌオートクレーブ中で、水素圧１００
気圧、温度９０℃の条件下、４時間撹拌する。反応終了
後、反応生成物のガスクロマトグラフ分析により、
カプロン酸の転化率；７５．８％
ヘキサノール収率、 ７１．４％
ヘキサノール選択率； ９４．２％
であることが判った。The catalyst of the present invention (1,49 g) thus obtained was added to a solution of Capron 6M (11,62 g, ]OO mmol) in dioxane (26,43 g, 300 mmol), and the mixture was heated at a hydrogen pressure of 100 in a 100 ml autoclave.
Stir for 4 hours under conditions of atmospheric pressure and temperature of 90°C. After the reaction was completed, gas chromatography analysis of the reaction product revealed that the conversion rate of caproic acid was 75.8%, the hexanol yield was 71.4%, and the hexanol selectivity was 94.2%.
比較例１
単独触媒によるカプロン酸の還元
実施例１において、７酸化２レニウムまたは４酸化オス
ミウムのみで調製した他は同様の操作を行い、反応生成
物を分析すると
Ｒｅ触媒
カプロン酸転化率； ２０．５％
ヘキサノール収率、 １９．１％
ヘキサノール選択率； ９３．０％
凭と腑−蝶
カブロン酸転化率；５．６％
ヘキサノール収率；５．２％
ヘキサノール選択率、 ９３．３％
であり、加成性以上の相乗効果をレニウム−オスミウム
触媒は有していることが判った。Comparative Example 1 Reduction of Caproic Acid Using a Single Catalyst The same operation as in Example 1 was carried out except that the preparation was made using only dirhenium heptoxide or osmium tetraoxide, and the reaction product was analyzed and found that the Re catalyst caproic acid conversion rate; 5% hexanol yield, 19.1% hexanol selectivity; 93.0% conversion rate of cabronic acid; 5.6% hexanol yield; 5.2% hexanol selectivity, 93.3%. It was found that the rhenium-osmium catalyst has a synergistic effect that is more than additive.
比較例２
↓ヒ較触媒によるカプロン酸の７ｘ
実施例１において、４酸化オスミウムの代わりに５％Ｒ
ｕ／Ｃ（８，３５ｇ、 Ｒｕ＝４．１３ｍｇ原子）を用
いる他は、全く同様の操作を行い、反応生成物を分析す
ると、
カプロン酸転化率、 ３１．７％
ヘキサノール収率； ２９．５％
ヘキサノール選択率、９３．１％
であった。Comparative Example 2 ↓ 7x of caproic acid with comparison catalyst In Example 1, 5%R was used instead of osmium tetroxide.
Exactly the same operation was performed except that u/C (8.35 g, Ru = 4.13 mg atom) was used, and the reaction product was analyzed. Caproic acid conversion rate, 31.7% Hexanol yield; 29.5 % hexanol selectivity was 93.1%.
実施例２
レニウム−オスミウム触媒によるカプロン隨色這実施例
１において、反応時間を６時間とした他は全く同様の操
作を行い、反応生成物の分析を行ったところ、
カプロン酸の転化率；１００％
ヘキサノール収率； ９２．７％
ヘキサノール選択率； ９２．７％
であり、副生成物として炭化水素が生成していた。Example 2 Caproic acid conversion using rhenium-osmium catalyst The same procedure as in Example 1 was carried out except that the reaction time was changed to 6 hours, and the reaction product was analyzed. The conversion rate of caproic acid was 100. % hexanol yield: 92.7% Hexanol selectivity: 92.7%, and hydrocarbons were produced as by-products.
この触媒を口取し、５回リサイクル使用したが、活性の
低下は認められなかった。This catalyst was collected and recycled and used five times, but no decrease in activity was observed.
実施例３
レニウム−オスミウム触媒によるピバリン酸の還元
７酸化２レニウム（１，００ｇ、 ４．１３ｍｇ原子）
と４酸化オスミウム（１，００ｇ、 ３．９３ｍｇ原子
）をパルミチン酸（７，６９ｇ、 ３０ｍｍｏｌ）とジ
オキサン（２６，４３ｇ。Example 3 Reduction of pivalic acid with a rhenium-osmium catalyst 7 Rhenium oxide (1,00 g, 4.13 mg atoms)
and osmium tetroxide (1,00 g, 3.93 mg atoms) with palmitic acid (7,69 g, 30 mmol) and dioxane (26,43 g.
３００ｍｍｏｌ）のｌ昆合？容液に？容かし、次に１０
０ｍ１のオートクレーブ中で、水素圧１００気圧、温度
１００℃の条件下、４時間撹拌する。その後、室温まで
冷却し、常圧に戻し、生成している黒色微粉末（１，４
７ｇ）を口取する。300 mmol) of 1? In the liquid? Enter, then 10
Stir in a 0 ml autoclave under conditions of hydrogen pressure of 100 atm and temperature of 100° C. for 4 hours. After that, it is cooled to room temperature, returned to normal pressure, and the black fine powder (1,4
Take 7g).
このようにして得られた触媒（１，４７ｇ）をピバリン
酸（１０，２１ｇ、 Ｉｏｏｍｍｏｌ）のジオキサン（
２６，４３ｇ。The catalyst thus obtained (1.47 g) was mixed with pivalic acid (10.21 g, Ioommol) in dioxane (
26.43g.
３００ ｍｍｏｌ）溶液に加え、１００ｍ１オートクレ
ーブ中で、水素圧１００気圧、温度９０℃の条件下、４
時間攪拌する。300 mmol) solution in a 100 ml autoclave under conditions of a hydrogen pressure of 100 atm and a temperature of 90°C.
Stir for an hour.
反応生成物の分析により、
ピバリン酸転化率；１００％
ネオペンチルアルコール収率 ；９４．３％ネオペンチ
ルアルコールＭｊＲ率； ９４．３％であることが判っ
た。Analysis of the reaction product revealed that the conversion rate of pivalic acid was 100%, the yield of neopentyl alcohol was 94.3%, and the MjR rate of neopentyl alcohol was 94.3%.
実施例４
レニウム−オスミウム触媒によるバルミチン１］Ｌ但
実施例３と同様にして調製したレニウム−オスミウム触
媒を用いてミパルミチン酸（２５，６ｇ、１００ｍｍｏ
Ｉ ）のジオキサン（２６，４３ｇ、 ３００ｍｍｏ
ｌ ）ン容液を１００ｍ１のオートクレーブ中で、水素
圧１００気圧、温度９０℃の条件下、４時間能７１する
。Example 4 Valmitin 1] L using a rhenium-osmium catalyst However, using a rhenium-osmium catalyst prepared in the same manner as in Example 3, mipalmitic acid (25.6 g, 100 mmol
I) dioxane (26.43g, 300mmo
l) The liquid was heated in a 100 ml autoclave under the conditions of hydrogen pressure of 100 atm and temperature of 90° C. for 4 hours.
反応生成物の分析により
バルミチン酸転化率；１００％
ヘキザデカノール収率； ９１．４％ヘキサデカノー
ル選択率； ９１．４％であることが判った。Analysis of the reaction product revealed that the conversion rate of barmitic acid was 100%, the hexadecanol yield was 91.4%, and the hexadecanol selectivity was 91.4%.
実施例５
実施例３と同様にして調製したレニウム−オスミウム触
媒を用いて、トリシクロ（５，２，１，Ｑ２＝ ６）デ
カン−２−カルボン酸（１８，０３ｇ、 １００ｍｍｏ
ｌ）のジオキサン（２６，４３ｇ、 ３００ｍｍｏｌ
）溶液をｌｏＯｍｌのオートクレーブ中で、水素圧１０
０気圧、温度１１０℃で４時間撹拌する。Example 5 Using a rhenium-osmium catalyst prepared in the same manner as in Example 3, tricyclo(5,2,1,Q2=6)decane-2-carboxylic acid (18,03 g, 100 mmo
l) dioxane (26.43g, 300mmol
) solution in a loOml autoclave under a hydrogen pressure of 10
Stir for 4 hours at 0 atm and 110°C.
反応生成物の分析により
トリシクロ（５，２，１，Ｏ”′”ｌデカン−２−カル
ボン酸転化率、 １００％
トリシクロＣ５，２，１，０２°６〕デカン−２−メチ
ロール収率 ； ９２．０％
トリシクロ（５，２，１，０２＝ ６）デカン−２−メ
チロール選択率；９２．０％
であることが判った。Analysis of the reaction products revealed that tricyclo(5,2,1,O"'"ldecane-2-carboxylic acid conversion rate, 100% tricycloC5,2,1,02°6]decane-2-methylol yield; 92 It was found that the selectivity for tricyclo(5,2,1,02=6)decane-2-methylol was 92.0%.
本発明のカルホン酸還元用；独媒は、１５０°Ｃ以下の
温度、水素圧１００気圧以下という極めて温和な条件下
でカルボン酸を還元してアルコールを製造することを可
能にするものであり、工業的な設備及びエネルギーコス
トの面での大きな利点をもたらすことができるものであ
る。The solvent for reducing carboxylic acid of the present invention makes it possible to produce alcohol by reducing carboxylic acid under extremely mild conditions of a temperature of 150°C or less and a hydrogen pressure of 100 atmospheres or less, This can offer significant advantages in terms of industrial equipment and energy costs.
Claims (1)
酸還元用触媒。1. A carboxylic acid reduction catalyst containing osmium and rhenium as essential components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61050192A JPS62210056A (en) | 1986-03-07 | 1986-03-07 | Catalyst for reducing carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61050192A JPS62210056A (en) | 1986-03-07 | 1986-03-07 | Catalyst for reducing carboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62210056A true JPS62210056A (en) | 1987-09-16 |
Family
ID=12852291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61050192A Pending JPS62210056A (en) | 1986-03-07 | 1986-03-07 | Catalyst for reducing carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62210056A (en) |
-
1986
- 1986-03-07 JP JP61050192A patent/JPS62210056A/en active Pending
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