JPS62265243A - Production of 1,4-cyclohexadione - Google Patents
Production of 1,4-cyclohexadioneInfo
- Publication number
- JPS62265243A JPS62265243A JP61107729A JP10772986A JPS62265243A JP S62265243 A JPS62265243 A JP S62265243A JP 61107729 A JP61107729 A JP 61107729A JP 10772986 A JP10772986 A JP 10772986A JP S62265243 A JPS62265243 A JP S62265243A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- water
- give
- bismuth
- carrier
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 10
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 229940049676 bismuth hydroxide Drugs 0.000 abstract description 2
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- -1 bismuth hydroxide Chemical class 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000003021 water soluble solvent Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BXBJZYXQHHPVGO-UHFFFAOYSA-N 4-hydroxycyclohexan-1-one Chemical compound OC1CCC(=O)CC1 BXBJZYXQHHPVGO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 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)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は各種合成用中間体として有用な１，４−シクロ
ヘキサンジオンの合成法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for synthesizing 1,4-cyclohexanedione, which is useful as an intermediate for various syntheses.
（従来技術と問題点）
１．４−シクロヘキサンジオンの製造に際しては従来は
例えば、次亜塩素酸ソーダを酸化剤として用い、三塩化
ルテニウムの存在下にて行う方法が知られていた。しか
し、Ｎａ０Ｃ１−ＲｕＣＬｓの反応系では（１）触媒の
ＲｕＣ１３が非常に高価であること、（２）酸化反応が
均一系で行われるため、触媒Ｒｕ Ｃ１０の回収再利用
が困難であること等の問題があった。(Prior Art and Problems) In the production of 1.4-cyclohexanedione, a method has been known that uses, for example, sodium hypochlorite as an oxidizing agent in the presence of ruthenium trichloride. However, in the Na0C1-RuCLs reaction system, (1) the RuC13 catalyst is very expensive, and (2) the oxidation reaction is carried out in a homogeneous system, making it difficult to recover and reuse the RuC10 catalyst. There was a problem.
（発明が解決せんとする課題）
本発明は、１．４−シクロヘキサンジオールの酸化によ
る１、４−シクロヘキサンジオンの製造を経済的有利に
実施し得る方法を開発せんとして種々研究の結果なされ
たものである。(Problems to be Solved by the Invention) The present invention was made as a result of various studies aimed at developing an economically advantageous method for producing 1,4-cyclohexanedione by oxidizing 1,4-cyclohexanediol. It is.
（解決手段）
本発明によれば、金属状の白金とビスマス化合物を担持
した触媒の存在下に１，４−シクロヘキサンジオールを
含酸素ガスで酸化することを特徴とする１、４−シクロ
ヘキサンジオンの製造法が提供される。(Solution Means) According to the present invention, 1,4-cyclohexanediol is oxidized with an oxygen-containing gas in the presence of a catalyst supporting metallic platinum and a bismuth compound. A manufacturing method is provided.
以下に本発明の方法について更に詳細に説明する。The method of the present invention will be explained in more detail below.
本発明の方法において用いられる触媒は、金属の白金と
ビスマス化合物を含有する触媒であって、担体上に担持
して反応に供する。担体としては、アルミナ、シリカ、
活性炭のいずれかを用いることが望ましい。担持の方法
については必ずしも兆Ｊ限はなく触媒調製法として慣用
の方法、例え：ば、塩化白金酸を水に溶解せしめてこれ
に上記の如き担体を浸し、塩化白金酸を担体に吸着させ
る。次に塩化白金酸を吸着した担体を乾燥させ、水素等
の適当な還元剤にて還元することにより金属の白金を担
持した触媒が得られる。次にビスマス化合物を水に溶解
せしめ、これに金属の白金を担持した担体を浸し、ビス
マス化合物を吸着後、乾燥し、反応に供する。ここに使
用すべきビスマス化合物としては、水酸化物、塩化物、
酸化物、硫酸塩。The catalyst used in the method of the present invention is a catalyst containing metal platinum and a bismuth compound, and is supported on a carrier and subjected to the reaction. As a carrier, alumina, silica,
It is desirable to use either activated carbon. The method of supporting the catalyst is not necessarily limited to any particular method, and may be any conventional catalyst preparation method, for example, by dissolving chloroplatinic acid in water and immersing the above-mentioned carrier in the solution, thereby adsorbing the chloroplatinic acid onto the carrier. Next, the carrier adsorbing chloroplatinic acid is dried and reduced with a suitable reducing agent such as hydrogen to obtain a catalyst supporting platinum metal. Next, a bismuth compound is dissolved in water, and a carrier supporting metal platinum is immersed in the solution to adsorb the bismuth compound, dried, and subjected to a reaction. Bismuth compounds to be used here include hydroxide, chloride,
Oxides, sulfates.
硝酸塩の中から任意に選択することができる。触媒成分
の担体上への担持量は、白金０．５〜１０ｗｔ％、好ま
しくは１〜５ｗｔ１ビスマス化合物１〜１５ｗｔ％好ま
しくは２〜ｌＱｗｔチの範囲である。It can be arbitrarily selected from nitrates. The amount of the catalyst component supported on the carrier is in the range of 0.5 to 10 wt % platinum, preferably 1 to 5 wt %, 1 to 15 wt % bismuth compound, preferably 2 to 1 Qwt.
反応は通常適当な溶媒中で行われるが、溶媒としては原
料、目的物および触媒等反応に関与する物質に対して安
定であり、原料を溶解するものであれば特に制限はない
が、一般的に経済的な観点から水ヲ啓媒として用いるの
が有利である。The reaction is usually carried out in an appropriate solvent, and there are no particular restrictions on the solvent as long as it is stable to the materials involved in the reaction, such as the raw materials, the target product, and the catalyst, and dissolves the raw materials. From an economic point of view, it is advantageous to use water as a medium.
反応を実施する際の１，４−シクロヘキサンノオールの
濃度は、必ずしも厳密な制限はないが、通常は３〜２０
ｗｔ％好ましくは５〜ｌＱｗｔチの範囲である。The concentration of 1,4-cyclohexaneol when carrying out the reaction is not necessarily strictly limited, but is usually between 3 and 20
The wt% is preferably in the range of 5 to 1Qwt.
本発明の方法に用いる酸化剤は酸素または空気その他の
含酸素ガスであり一般に空気を用いることが有利である
。The oxidizing agent used in the method of the invention is oxygen, air or other oxygen-containing gas, and it is generally advantageous to use air.
本発明の方法における反応温度は、室温〜１００℃、好
ましくは５０〜８５℃反応圧力は常圧〜８５ｋｇ／ｃｒ
ｎ２の範囲である。反応に要する時間は、触媒の使用量
９反応源度２反応圧力１反応装置の型および、かくはん
の方法において、かなりの変更が許される。通常は２〜
８時間の範囲である。The reaction temperature in the method of the present invention is room temperature to 100°C, preferably 50 to 85°C, and the reaction pressure is normal pressure to 85 kg/cr.
The range is n2. The time required for the reaction can vary considerably depending on the amount of catalyst used, the source level, the reaction pressure, the type of reactor, and the method of agitation. Usually 2~
The range is 8 hours.
以下に本発明の方法についての代表的な例を示し更に具
体的に説明するがこれは例示の為のものであり、従って
本発明はこれのみに限定されるものではなく、また、こ
れによって伺ら制限されないことは言うまでもない。Typical examples of the method of the present invention will be described below in more detail; however, these are for illustrative purposes only, and the present invention is not limited thereto. Needless to say, there are no restrictions.
〈実施例〉
内容１１の機械的かくはん機、温度計、および圧力計を
備えたステンレス製のオートクレーブ中に、１，４−シ
クロヘキサンノオール３０９を蒸留水に爵かした水溶液
３３０Ｊおよび５ｗｔ％白金、１０ｗｔ％水酸化ビスマ
スを担持した活性炭粉末触媒１５９全仕込み、空気を導
入して圧力を４５ｋｇ／ｃｍ２、温度を８０℃に保ち、
５００ｒｐｍでかくはんしながら反応させた。<Example> In a stainless steel autoclave equipped with a mechanical stirrer, a thermometer, and a pressure gauge as described in Content 11, 330 J of an aqueous solution of 1,4-cyclohexaneol 309 in distilled water and 5 wt% platinum, The activated carbon powder catalyst 159 supporting 10 wt% bismuth hydroxide was fully charged, air was introduced, the pressure was maintained at 45 kg/cm2, and the temperature was maintained at 80°C.
The reaction was carried out while stirring at 500 rpm.
反応開始後、４時間後に反応を中止し、反応液から触媒
を戸別した。The reaction was stopped 4 hours after the start of the reaction, and the catalyst was separated from the reaction solution.
高速液クロマトグラフイーおよび、ガスクロマトグラフ
ィーで反応液の定量分析を行ったところ１．４−７クロ
ヘキサンソオン８．９、シクロヘキサン−４−オン−１
−オール１６１１未反応１，４−シクロヘキサンノオー
ル６ｇの組成であった。Quantitative analysis of the reaction solution by high performance liquid chromatography and gas chromatography revealed 1.4-7 chlorohexanesonone 8.9, cyclohexane-4-one-1
-ol 1611 The composition was 6 g of unreacted 1,4-cyclohexaneol.
Claims (1)
に１，４−シクロヘキサンジオールを含酸素ガスで酸化
することを特徴とする１，４−シクロヘキサンジオンの
製造法。A method for producing 1,4-cyclohexanedione, which comprises oxidizing 1,4-cyclohexanediol with an oxygen-containing gas in the presence of a catalyst supporting metallic platinum and a bismuth compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61107729A JPS62265243A (en) | 1986-05-13 | 1986-05-13 | Production of 1,4-cyclohexadione |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61107729A JPS62265243A (en) | 1986-05-13 | 1986-05-13 | Production of 1,4-cyclohexadione |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62265243A true JPS62265243A (en) | 1987-11-18 |
Family
ID=14466468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61107729A Pending JPS62265243A (en) | 1986-05-13 | 1986-05-13 | Production of 1,4-cyclohexadione |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62265243A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999018058A1 (en) * | 1997-10-02 | 1999-04-15 | RWE-DEA Aktiengesellschaft für Mineraloel und Chemie | Method for producing aldehydes and carboxylic acids by oxidizing primary alcohols |
-
1986
- 1986-05-13 JP JP61107729A patent/JPS62265243A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999018058A1 (en) * | 1997-10-02 | 1999-04-15 | RWE-DEA Aktiengesellschaft für Mineraloel und Chemie | Method for producing aldehydes and carboxylic acids by oxidizing primary alcohols |
| US6476260B1 (en) | 1997-10-02 | 2002-11-05 | Rwe-Dea Aktiengesellschraft Fur Mineraloel Und Chemie | Method of producing aldehydes and carboxylic acids by oxidizing primary alcohols |
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