JPS6054338A - Preparation of 2-keto-l-gulonic acid - Google Patents
Preparation of 2-keto-l-gulonic acidInfo
- Publication number
- JPS6054338A JPS6054338A JP58161888A JP16188883A JPS6054338A JP S6054338 A JPS6054338 A JP S6054338A JP 58161888 A JP58161888 A JP 58161888A JP 16188883 A JP16188883 A JP 16188883A JP S6054338 A JPS6054338 A JP S6054338A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- gulonic acid
- catalyst
- keto
- lead
- 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.)
- Granted
Links
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
- Saccharide Compounds (AREA)
- 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】
本発明は、２−ケ）−Ｌ−グロン酸をＬ−ソルボースの
酸化により製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 2-ke)-L-gulonic acid by oxidation of L-sorbose.
従来、２−ケ）−Ｌ−グロン酸をＬ−ソルボースの酸化
で製造するには、ソルボースとアセトンとを反応させて
、ジアセトン−Ｌ−ソルボースとし、これを次亜塩素酸
塩または過マンガン酸塩を用いて酸化し、ジアセトン−
２−ケ）−Ｌ−グロン酸を製造し、これを脱アセトンす
る多段階の工程を経て、製造している。Conventionally, in order to produce 2-ke)-L-gulonic acid by oxidizing L-sorbose, sorbose and acetone are reacted to form diacetone-L-sorbose, which is then treated with hypochlorite or permanganate. Oxidize with salt to form diacetone-
It is produced through a multi-step process of producing 2-ke)-L-gulonic acid and deacetonizing it.
費する等の欠点がある。これらの欠点を克服するために
、Ｌ−ソルボースをそのままの状態でアセトン化せずに
、貴金属触媒の存在下に空気酸化する試みは古くからな
されているが（ＵＳＰ２，１９０，３７７（１９４０）
）、目的物の収率も低く、反応に６０時間も要する等で
充分な結果は得られていない。これらの欠点を改良する
目的で、本発明者は先に貴金属に鉛またはビスマスを添
加した触媒を用いると、従来既知の貴金属触媒に比較し
て反応時間が大巾に短縮され、収率も向上することを見
出し、この触媒を用いる方法を既に提案した（特開昭５
７−１６３３４０ ）。There are disadvantages such as spending a lot of money. In order to overcome these drawbacks, attempts have been made for a long time to air oxidize L-sorbose in the presence of a noble metal catalyst without acetonizing it as it is (USP 2, 190, 377 (1940)).
), the yield of the target product was low, and the reaction required 60 hours, so satisfactory results were not obtained. In order to improve these drawbacks, the present inventor found that by using a catalyst in which lead or bismuth was added to a noble metal, the reaction time was significantly shortened and the yield was improved compared to conventionally known noble metal catalysts. We have already proposed a method using this catalyst (Japanese Unexamined Patent Publication No.
7-163340).
本発明の目的とするところは、先に本発明者の提案した
触媒系よりもより高活性を持った触媒系を用いる２−ケ
）−Ｌ−グロン酸の製造法を提供することにある。An object of the present invention is to provide a method for producing 2-ke)-L-gulonic acid using a catalyst system having higher activity than the catalyst system previously proposed by the present inventors.
本発明者は、先に提案した、貴金属−鉛またはビスマス
系」：りもより活性の優れた触媒を得ることを目的とし
て種々研究した結果、貴金属−鉛系に更にカドミウムを
添加した貴金属−鉛一カドミウム系触媒がより高活性を
示めすことを見出して、本発明を完成するに至った。As a result of various researches aimed at obtaining a catalyst with better activity than the previously proposed noble metal-lead or bismuth system, the inventors discovered that the noble metal-lead system, in which cadmium is further added to the noble metal-lead system, has been developed. The present invention was completed by discovering that monocadmium-based catalysts exhibit higher activity.
即ち、本発明は、■、−ソルボースを水溶液中で白金お
よび／またはパラジウムに鉛およびカドミウムを含有ず
２）触媒の存在下に反応液のＰＨを６〜１０に保って、
含酸素ガスで酸化して２−ケトグ。That is, in the present invention, (1) -sorbose is mixed with platinum and/or palladium in an aqueous solution without containing lead and cadmium; (2) the pH of the reaction solution is maintained at 6 to 10 in the presence of a catalyst;
Oxidized with oxygen-containing gas to form 2-ketog.
−１、−グロン酸を製造する方法である。This is a method for producing -1,-gulonic acid.
本発明の方法によれば、ｌ、−ソルボースをアセトンと
反応させて、ジアセトン−■、−ソルボースに誘ｉ、Ｉ
ｌ〜てから酸化する必要が無（、また、次亜塩素酸塩
または、過マンガン酸塩のような高価な酸化剤も必要と
せずに工業的に有利に２−ケトーグ
ｒ、−グロン酸を製造することが出来る。According to the method of the present invention, l,-sorbose is reacted with acetone to form diacetone-■,-sorbose.
It is industrially advantageous to produce 2-ketogulonic acid without the need for subsequent oxidation (and without the need for expensive oxidizing agents such as hypochlorite or permanganate). It can be manufactured.
本発明の方法で用いる触媒は、白金または／′およびパ
ラジウムに鉛およびカドミウムを添加したものであって
、通常は適当な担体、例えば活性炭、アルミナ等に担持
して使用する。白金およびパラジウムは金属状または酸
化物であり、鉛およびカドミウムは金属状、水酸化物、
酸化物、塩化物、炭酸塩または硝酸塩等の無機酸塩ある
いは有機酸塩等である。The catalyst used in the method of the present invention is platinum or palladium to which lead and cadmium are added, and is usually supported on a suitable carrier such as activated carbon or alumina. Platinum and palladium are metallic or oxides; lead and cadmium are metallic, hydroxide,
These include inorganic acid salts and organic acid salts such as oxides, chlorides, carbonates, and nitrates.
担体上への担持量は、白金またはパラジウムが０．１〜
１０ｗｔ％、鉛が０．１〜１０ｗｔ％、カドミウムが０
．０１〜５ｗｔ％の範囲が多用される。The amount of platinum or palladium supported on the carrier is 0.1~
10wt%, lead 0.1-10wt%, cadmium 0
．． A range of 0.01 to 5 wt% is often used.
触媒の調製方法は、常法、例えば、塩化白金酸と硝酸鉛
および硝酸カドミウムの混合水溶液を活性炭粉末に浸漬
し、ホルマリン水溶液で還元処理する等の方法による。The catalyst can be prepared by a conventional method, for example, by immersing activated carbon powder in a mixed aqueous solution of chloroplatinic acid, lead nitrate, and cadmium nitrate, followed by reduction treatment with an aqueous formalin solution.
あるいは、市販の貴金属を担持した炭素粉末触媒を鉛お
よびカドミウム塩を溶解せしめた水溶液に浸漬する等の
方法で触媒を調製するのが最も簡便である。または、Ｌ
−ソルボースの酸化反応を実施する際に、反応溶媒であ
る水の中に、貴金属を担持した触媒と共に鉛およびカド
ミウムの水可溶性塩を添加し、反応と触媒調製とを同時
に行う方法でもよい。Alternatively, it is most convenient to prepare a catalyst by immersing a commercially available carbon powder catalyst supporting a noble metal in an aqueous solution in which lead and cadmium salts are dissolved. Or L
- When carrying out the oxidation reaction of sorbose, a method may be adopted in which water-soluble salts of lead and cadmium are added together with a catalyst carrying a noble metal into water, which is a reaction solvent, and the reaction and catalyst preparation are carried out simultaneously.
本発明の方法は、溶媒中で実施するが、溶媒としては水
を用いる。水溶媒中に仕込む原料Ｉ７−ソルボースの濃
度は、１〜２０ｗｔ％、特に２〜１０ｗｔ％の範囲が多
用される。The method of the invention is carried out in a solvent, and water is used as the solvent. The concentration of raw material I7-sorbose charged into the water solvent is often in the range of 1 to 20 wt%, particularly 2 to 10 wt%.
触媒の使用用［は、例えば、反応をバッチで実施する場
合では、反応液１１に対して、前述の相持触媒１０〜１
００ｇを用いる。For example, when the reaction is carried out in batches, the above-mentioned supported catalysts 10 to 1 are added to the reaction solution 11.
Use 00g.
反応の進行により、酸化により生じた目的物、２−ケ）
−１、−グロン酸のために、反応液のＰＨは中性近傍か
ら、酸性側に移行する。酸化反応の速１０−は反応液の
円ｌが酸性側では急激に低下するため、反応液のＩ）Ｉ
Ｉは中性近傍乃至弱アルカリ性に保つことが、好ま１．
い。この目的のために、反応の進行に同期させて、アル
カリ物質を逐時、反応液中に添加し反応液のＰＩ−１を
６〜１０に保つ。使用するアルカリ物質は、苛性アルカ
リ、アルカリ金属の炭酸塩・重炭酸塩・有機酸塩または
燐酸塩等である。ｊｆｌ常はこ」１．らの塩の水溶液を
ＰＨコントローラーに同期させた定量ポンプで反応液中
に添加する３２反応液のｐＨを逆に１０より塩基性にす
ると、酸化反応の速度は増大するが、重合物やタール状
の副生物が増加するので好ましくない。As the reaction progresses, the target product produced by oxidation, 2-ke)
Due to the -1,-gulonic acid, the pH of the reaction solution shifts from near neutral to acidic. The rate of oxidation reaction 10- is rapidly decreased when the circle l of the reaction solution is acidic, so the I)I of the reaction solution
It is preferable to keep I near neutrality or slightly alkaline.1.
stomach. For this purpose, an alkaline substance is added to the reaction solution from time to time in synchronization with the progress of the reaction to maintain the PI-1 of the reaction solution at 6 to 10. The alkaline substances used include caustic alkali, alkali metal carbonates, bicarbonates, organic acid salts, or phosphates. jfl Tsunehako” 1. An aqueous solution of these salts is added to the reaction solution using a metering pump synchronized with a pH controller.32 If the pH of the reaction solution is made more basic than 10, the rate of the oxidation reaction increases, but polymers and tar-like substances This is undesirable because it increases the amount of by-products.
以上の理由で、反応液のＰＨは６〜１０．更に好ましく
は、７〜９の範囲に保って、反応を実施する。For the above reasons, the pH of the reaction solution is 6-10. More preferably, the reaction is carried out while keeping the number in the range of 7 to 9.
本発明の方法で用いられる酸化剤は含酸素ガスであって
、酸素または空気が多用される。通常は、空気を用いる
のが好ましい。含酸素ガスの圧力は常圧乃至５Ｉｃ９／
Ｃ１１！の範囲が多用される。含酸素ガスと反応液およ
び触媒との混合状態は、ガスを効率良く反応液中に分散
吹込み充分に攪拌する等の手段で、良好に保つことが必
要である。The oxidizing agent used in the method of the present invention is an oxygen-containing gas, and oxygen or air is often used. It is usually preferable to use air. The pressure of the oxygen-containing gas is normal pressure to 5Ic9/
C11! range is often used. It is necessary to maintain a good mixing state of the oxygen-containing gas, the reaction liquid, and the catalyst by means such as efficiently dispersing and blowing the gas into the reaction liquid and thoroughly stirring the mixture.
反応の温度は室温乃至１００℃、特に３０°Ｃ〜６０℃
の範囲が好ましい。反応に要する時間は、バッチで反応
させる場合を例で示せば０．５〜２０時間、通常は１〜
１０時間の範囲である。The reaction temperature is room temperature to 100°C, especially 30°C to 60°C.
A range of is preferred. The time required for the reaction is 0.5 to 20 hours in the case of batch reaction, and usually 1 to 20 hours.
The range is 10 hours.
反応器の型式は、完全混合型の懸濁床で攪拌槽式あるい
は、気泡格式の反応器が多用される。粒状の触媒を用い
る固定床式の反応器でもよい。反応槽は一段でも多段で
も同様に使用できる。As for the type of reactor, a completely mixed suspended bed type, stirred tank type, or a bubble cell type reactor is often used. A fixed bed reactor using a granular catalyst may also be used. The reaction tank can be used in a single stage or in multiple stages.
反応終了後、触媒を抑制した反応液を減圧下に濃縮し、
これにイソプロピルアルコール等の水可溶性有機溶媒を
添加しよく攪拌すると、目的物のアルカリ金属塩の結晶
が析出する。After the reaction is complete, the reaction solution with the catalyst suppressed is concentrated under reduced pressure.
When a water-soluble organic solvent such as isopropyl alcohol is added to this and thoroughly stirred, crystals of the target alkali metal salt are precipitated.
本発明の方法でイｎられる、２−ヶ）−Ｌ−グロン酸ハ
アスコルビン酸（ビタミンＣ）の前駆体として、極めて
有用な化合物である。2-L-gulonic acid is an extremely useful compound as a precursor of ascorbic acid (vitamin C), which is incorporated in the method of the present invention.
以下、実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
実施例−１
内径５ｃＩｎのガラス製円筒の底部に焼結ガラスフィル
ターを付け、その下部に空気吹込管を付けたものを反応
器とｔ７て用いた。Example 1 A sintered glass filter was attached to the bottom of a glass cylinder having an inner diameter of 5 cIn, and an air blowing pipe was attached to the bottom of the cylinder, and a reactor was used at t7.
との反応器に４ｗｔ％のＬ−ソルボース水溶液４００ｔ
ｎ１１５ ｗ １％ｐｉ、４ｗｔ％Ｉ）ｌ）（ＮＯ３）
２ ＋ １ｗｔ％ｃｄ（Ｎ０３）２を、Ｊｊｊ持ｌ−だ
活性炭粉末触媒）１ ｃｐを仕込み、外部６１：り加熱
１〜温度を４８℃に昇温した。常圧空気を反応管下部の
空気吹込口から５００ｉ／＠分で吹込み反応させた。反
応の進行に伴ない、反応液のＰｌ＋を７〜８に保つ様に
苛性曹達水溶液を逐時注入した。400 tons of 4wt% L-sorbose aqueous solution was placed in a reactor with
n115 w 1%pi, 4wt%I)l) (NO3)
2 + 1wt% cd(N03)2 and 1 cp of JJJ's activated carbon powder catalyst) were charged, and the temperature was raised to 48°C. Normal pressure air was blown at 500 i/min from the air inlet at the bottom of the reaction tube to cause a reaction. As the reaction progressed, a caustic soda aqueous solution was injected at intervals to maintain Pl+ of the reaction solution at 7 to 8.
反応開始後１．５時間で苛性曹達水溶液の消費が遅くな
ったので、反応操作を停止し、反応液から触媒を分解ｌ
−だ。得られた反応終了液を、高速液体クロマトグラフ
ィーで分析した結果、２−ケトーＬ−グロン酸のナトリ
ウム塩が、８３ｗｔ％の収率で得られた。1.5 hours after the start of the reaction, the consumption of the caustic soda aqueous solution became slow, so the reaction operation was stopped and the catalyst was decomposed from the reaction solution.
-It is. As a result of analyzing the obtained reaction completed liquid by high performance liquid chromatography, the sodium salt of 2-keto L-gulonic acid was obtained in a yield of 83 wt%.
実施例−２
実施例−１と同様の方法と装置で、用いる触媒を３％ｐ
ｄ、 １％ｐｔ、３％（ＣＨ，ＣＯＯ）２ｐ ｂ 、
１％ｃｄ（ＮＯ３）２／炭素粉末触媒に変えて反応させ
た。Example-2 Using the same method and equipment as Example-1, the catalyst used was 3% p.
d, 1%pt, 3%(CH,COO)2p b,
The reaction was performed using a 1% cd(NO3)2/carbon powder catalyst.
反応の終了に２．５時間を要し収率７８ｗｔ％で２−ケ
トーＬ−グロン酸を得た。It took 2.5 hours to complete the reaction, and 2-keto L-gulonic acid was obtained in a yield of 78 wt%.
比較例−１
実施例−１と同様の反応装置を用い、同様の方法で用い
る触媒のみを変えて反応を実施した。触媒は、５ｗｔ％
ｐｔ、４ｗｔ％ｐｂ（ＮＯｓ）ｚを活性炭粉末に担持し
たものに使用した。Comparative Example-1 Using the same reaction apparatus as in Example-1, a reaction was carried out in the same manner except for the catalyst used. The catalyst is 5wt%
pt, 4 wt% pb(NOs)z supported on activated carbon powder was used.
反応の進行に伴ない、反応液の円］を７〜８に保つ様に
苛性曹達水溶液を反応液中に逐時注入した。反応開始２
．５時間で苛性曹達水溶液の消費が遅くなったので、反
応操作を停止した。実施例１と同様の方法で分析した結
果２−ケ）−Ｌ−グロン酸のナトリウム塩がＦＨ）ｗｔ
％の収率で得られた。As the reaction progressed, a caustic soda aqueous solution was injected into the reaction solution one after another so as to maintain the circle of the reaction solution at 7 to 8. Reaction start 2
．． Consumption of the caustic soda aqueous solution slowed down after 5 hours, so the reaction operation was stopped. As a result of analysis using the same method as in Example 1, the sodium salt of 2-ke)-L-gulonic acid was FH)wt
% yield.
比較例−２
実施例−１と同様の反応装置により、同様の方法で、用
いる触媒のみを変えて反応を実施した。Comparative Example-2 A reaction was carried out in the same manner as in Example-1 using the same reaction apparatus, except for changing the catalyst used.
触媒は３％ＩＭ＋、 １％ｐｉ、 ３％（ＣＨ３ＣＯＯ
）２ｐｂを活性炭粉末に４１Ｘ持したものを使用した。The catalyst is 3% IM+, 1% pi, 3% (CH3COO
) 2 pb in activated carbon powder with a concentration of 41X was used.
反応の進行に伴ない、反応液のＰＩ−１を７〜８に保つ
様に苛性曹達水溶液を注入した。反応の終了に３．５時
間を要し、収率７５ｗｔ％で２−ケトーＬ−グロン酸を
得た。As the reaction progressed, a caustic soda aqueous solution was injected to maintain the PI-1 of the reaction solution at 7 to 8. It took 3.5 hours to complete the reaction, and 2-keto L-gulonic acid was obtained in a yield of 75 wt%.
特許出願人 三井東圧化学株式会社patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
製造するに際し、白金または／およびパラジウムに鉛お
よびカドミウムを含有する触媒の存在下に、水溶液中で
反応液のＰＨを６〜１０に保ち含酸素ガスで酸化するこ
とを特徴とする２−ケト−１，−グロン酸の製造法。1) When oxidizing L-sorbose to produce 2-ke)-L-gulonic acid, the pH of the reaction solution is adjusted to 6 to 6 in an aqueous solution in the presence of a catalyst containing lead and cadmium in platinum or/and palladium. 1. A method for producing 2-keto-1,-gulonic acid, characterized by oxidizing it with an oxygen-containing gas at a temperature of 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58161888A JPS6054338A (en) | 1983-09-05 | 1983-09-05 | Preparation of 2-keto-l-gulonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58161888A JPS6054338A (en) | 1983-09-05 | 1983-09-05 | Preparation of 2-keto-l-gulonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6054338A true JPS6054338A (en) | 1985-03-28 |
| JPH0439474B2 JPH0439474B2 (en) | 1992-06-29 |
Family
ID=15743898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58161888A Granted JPS6054338A (en) | 1983-09-05 | 1983-09-05 | Preparation of 2-keto-l-gulonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6054338A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0247485A2 (en) * | 1986-05-30 | 1987-12-02 | Bayer Ag | Process for the preparation of oxetan-3-carboxylic acids |
| WO1994020448A1 (en) * | 1993-03-10 | 1994-09-15 | Südzucker Aktiengesellschaft | Method and device for producing monocarboxylic acids from carbohydrates, carbohydrate derivatives or primary alcohols |
-
1983
- 1983-09-05 JP JP58161888A patent/JPS6054338A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0247485A2 (en) * | 1986-05-30 | 1987-12-02 | Bayer Ag | Process for the preparation of oxetan-3-carboxylic acids |
| WO1994020448A1 (en) * | 1993-03-10 | 1994-09-15 | Südzucker Aktiengesellschaft | Method and device for producing monocarboxylic acids from carbohydrates, carbohydrate derivatives or primary alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0439474B2 (en) | 1992-06-29 |
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