JP2824394B2 - Catalyst for producing fumaric acid and method for producing fumaric acid using the catalyst - Google Patents
Catalyst for producing fumaric acid and method for producing fumaric acid using the catalystInfo
- Publication number
- JP2824394B2 JP2824394B2 JP6163492A JP16349294A JP2824394B2 JP 2824394 B2 JP2824394 B2 JP 2824394B2 JP 6163492 A JP6163492 A JP 6163492A JP 16349294 A JP16349294 A JP 16349294A JP 2824394 B2 JP2824394 B2 JP 2824394B2
- Authority
- JP
- Japan
- Prior art keywords
- fumaric acid
- catalyst
- maleic acid
- thiourea
- reaction
- 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 - Lifetime
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はフマル酸製造用触媒およ
びこの触媒を用いたフマル酸の製造方法に関し、詳しく
はマレイン酸の異性化反応により効率よくフマル酸を製
造するための触媒およびこの触媒を用いたフマル酸の製
造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst for producing fumaric acid and a method for producing fumaric acid using the catalyst, and more particularly to a catalyst for efficiently producing fumaric acid by a maleic acid isomerization reaction and this catalyst. And a method for producing fumaric acid using the same.
【０００２】[0002]
【従来の技術】近年、フマル酸はポリエステル樹脂の原
料、食品添加物、薬品向けだけではなく、浴剤や飼料添
加剤にも需要が見込まれるようになってきた。しかし、
需要の増加とともにフマル酸の品質の向上が一段と望ま
れるようになり、食品添加物および浴剤向けでは、残存
マレイン酸およびリンゴ酸の少ない品質、また工業用で
は耐熱安定性に優れた品質が要求されている。2. Description of the Related Art In recent years, demand for fumaric acid has been expected not only for raw materials of polyester resins, food additives and chemicals but also for bath additives and feed additives. But,
With the increase in demand, it has become increasingly desirable to improve the quality of fumaric acid.For food additives and bath additives, there is a demand for quality with less residual maleic acid and malic acid, and for industrial use, quality with excellent heat stability. Have been.
【０００３】フマル酸の製造法としては、マレイン酸を
チオ尿素などの触媒を用いてフマル酸に異性化する触媒
転位反応法およびマレイン酸を高温、高圧下に転位させ
てフマル酸とリンゴ酸とを併産する熱転位反応法が知ら
れている。[0003] As a method for producing fumaric acid, a catalytic rearrangement reaction method in which maleic acid is isomerized to fumaric acid using a catalyst such as thiourea or a method in which maleic acid is rearranged under high temperature and high pressure to produce fumaric acid and malic acid Is known.
【０００４】触媒転位反応法としては、例えば米国特許
第２，４５４，３８７号明細書にはチオ尿素またはその
誘導体を用いる方法、同第２，９１４，５５９号明細書
には臭素酸塩（例えば臭素酸カリウム）または臭素酸塩
と過ホウ酸塩（過ホウ酸ナトリウム）とを用いる方法、
特公昭４８−３０６１７号公報には特定構造を有するチ
オ尿素誘導体と塩酸または硫酸とを用いる方法、特開平
５−２７９２９２号公報には臭素酸塩と可変原子価金属
の水溶性塩（例えば、マンガン、セリウム、鉄、銅など
の硫酸塩など）を用いる方法が記載されている。As the catalytic rearrangement method, for example, US Pat. No. 2,454,387 discloses a method using thiourea or a derivative thereof, and US Pat. No. 2,914,559 describes a bromate (eg, Potassium bromate) or a method using bromate and perborate (sodium perborate),
JP-B-48-30617 discloses a method using a thiourea derivative having a specific structure and hydrochloric acid or sulfuric acid, and JP-A-5-279292 describes a bromate and a water-soluble salt of a variable valent metal (for example, manganese). , Sulphates of cerium, iron, copper and the like).
【０００５】しかし、これら公知の技術は総じて触媒使
用量が多く、効率的でなく、また得られるフマル酸は、
残存マレイン酸やリンゴ酸の濃度が高い、あるいはフマ
ル酸の熱安定性が低いなどの問題があって、最近の品質
のニーズを満足し得るものではない。However, these known techniques generally use a large amount of catalyst, are not efficient, and the resulting fumaric acid is
There are problems such as a high concentration of residual maleic acid and malic acid and a low thermal stability of fumaric acid, which cannot satisfy recent quality needs.
【０００６】また、熱転位反応法は、高圧容器が必要で
あって、腐食に対する配慮も不可欠であることから設備
費が高くつき、また多量のリンゴ酸が副生するなどの欠
点がある。In addition, the thermal rearrangement reaction method requires a high-pressure vessel and requires consideration for corrosion, so that equipment costs are high and a large amount of malic acid is produced as a by-product.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上記のよう
な従来技術の問題点を解決し、マレイン酸の触媒転位反
応により各種用途で要求される品質を備えた、詳しくは
高純度かつ熱安定性に優れたフマル酸を効率よく製造す
る触媒およびこの触媒を用いたフマル酸の製造方法を提
供することを目的とするものである。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has the quality required for various uses by the catalytic rearrangement reaction of maleic acid. An object of the present invention is to provide a catalyst for efficiently producing fumaric acid having excellent stability and a method for producing fumaric acid using the catalyst.
【０００８】[0008]
【課題を解決するための手段】本発明者らの研究によれ
ば、上記触媒転位反応における触媒として臭素酸塩とチ
オ尿素またはその誘導体とを組合せ使用することにより
上記目的が達成できることを知り、この知見に基づいて
本発明を完成するに至った。According to the study of the present inventors, it has been found that the above object can be achieved by using a combination of bromate and thiourea or a derivative thereof as a catalyst in the above catalyst rearrangement reaction. Based on this finding, the present invention has been completed.
【０００９】すなわち、本発明の一つは、マレイン酸の
異性化反応によるフマル酸製造用触媒であって、（Ａ）
臭素酸塩と（Ｂ）チオ尿素およびその誘導体から選ばれ
る少なくとも一種のチオ尿素化合物とを必須成分とする
ことを特徴とするフマル酸製造用触媒であり、また他の
発明は、この触媒を用いてマレイン酸から異性化反応に
よりフマル酸を製造する方法に関する。That is, one of the present invention is a catalyst for producing fumaric acid by an isomerization reaction of maleic acid, wherein (A)
A catalyst for producing fumaric acid, comprising a bromate salt and (B) at least one thiourea compound selected from thiourea and its derivatives as essential components. Another invention uses this catalyst. And a method for producing fumaric acid from maleic acid by an isomerization reaction.
【００１０】チオ尿素および臭素酸塩をそれぞれ単独で
触媒として用いることは公知であるが、これらを組合わ
せて用いることは試みられたことはなく、本発明のよう
に組合せて使用することにより一段と効率よく高品質の
フマル酸が得られることは予想外のことであった。It is known to use thiourea and bromate alone as catalysts, however, no attempt has been made to use them in combination, and they can be further used by combining them as in the present invention. It was unexpected that high quality fumaric acid could be obtained efficiently.
【００１１】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１２】本発明の成分（Ａ）である臭素酸塩の具体
例としては、臭素酸ナトリウム、臭素酸カリウム、臭素
酸アンモニウムなどが挙げられる。また、成分（Ｂ）の
チオ尿素誘導体の具体例としては、１，３−ジメチルチ
オ尿素、１，３−ジエチルチオ尿素などが挙げられる。
成分（Ｂ）としては、特に、チオ尿素が好適に用いられ
る。Specific examples of the bromate which is the component (A) of the present invention include sodium bromate, potassium bromate and ammonium bromate. Further, specific examples of the thiourea derivative of the component (B) include 1,3-dimethylthiourea and 1,3-diethylthiourea.
In particular, thiourea is suitably used as the component (B).
【００１３】成分（Ａ）および成分（Ｂ）の総添加量
は、マレイン酸に対し０．０５重量％以上であればよ
い。この総添加量が０．０５重量％より少ないと異性化
反応が十分に進行しない。総添加量の上限には特に制限
はないが、１重量％を超える量を添加しても、それ以上
の効果は期待できず、かえって経済的に不利になる。本
発明の触媒によれば、０．１〜０．５重量％、更には
０．１〜０．２重量％（対マレイン酸）という低い総添
加量によっても、高いマレイン酸反応率をもって異性化
反応を達成することができる。The total amount of component (A) and component (B) may be 0.05% by weight or more based on maleic acid. If the total amount is less than 0.05% by weight, the isomerization reaction does not proceed sufficiently. The upper limit of the total amount is not particularly limited. However, if the amount exceeds 1% by weight, no further effect can be expected, and it is economically disadvantageous. According to the catalyst of the present invention, isomerization with a high maleic acid conversion is achieved even with a low total amount of 0.1 to 0.5% by weight, and even 0.1 to 0.2% by weight (based on maleic acid). A reaction can be achieved.
【００１４】成分（Ａ）と成分（Ｂ）との使用割合（成
分（Ａ）／成分（Ｂ））は、上記総添加量の範囲内で適
宜決定することができるが、通常、成分（Ａ）／成分
（Ｂ）（重量比）を３：１〜５０：１の範囲内で選択す
ることにより高いマレイン酸反応率が得られる。かくし
て、成分（Ａ）／成分（Ｂ）（重量比）は、通常、３：
１〜５０：１であり、好ましくは４：１〜２０：１であ
る。The use ratio of component (A) to component (B) (component (A) / component (B)) can be appropriately determined within the above range of the total amount of addition. ) / Component (B) (weight ratio) in the range of 3: 1 to 50: 1 can provide a high maleic acid conversion. Thus, component (A) / component (B) (weight ratio) is usually 3:
It is 1-50: 1, preferably 4: 1-20: 1.
【００１５】本発明のフマル酸製造用触媒は上記成分
（Ａ）および成分（Ｂ）を必須成分として含むが、更に
セリウム、銅、マンガンおよび鉄の水溶性塩の少なくと
も一種の水溶性金属塩を含んでいてもよい。これら水溶
性金属塩を添加するとマレイン酸反応率が向上し、また
高品質のフマル酸が得られる。The catalyst for producing fumaric acid of the present invention contains the above components (A) and (B) as essential components, and further contains at least one water-soluble metal salt of cerium, copper, manganese and iron. May be included. When these water-soluble metal salts are added, the maleic acid reaction rate is improved, and high-quality fumaric acid is obtained.
【００１６】上記水溶性金属塩の具体例としては、硫酸
セリウム、硝酸セリウム、塩化セリウム、硫酸銅、硝酸
銅、塩化銅、硫酸マンガン、硝酸マンガン、塩化マンガ
ン、硫酸鉄、硝酸鉄、塩化鉄が挙げられる。水溶性金属
塩の添加量（金属換算）は、マレイン酸に対し０．１ｐ
ｐｍ以上であればよい。０．１ｐｐｍより少ないと十分
な添加効果が得られない。一方、水溶性金属塩の添加量
の上限については特に制限はないが、多量に添加しすぎ
ても一定以上の効果は期待できず、かえってフマル酸中
に残存して不都合を生じる場合もあることから、通常、
５０ｐｐｍ程度まで添加すれば十分である。かくして、
水溶性金属塩の添加量（金属換算）は、マレイン酸に対
し、通常、０．１〜５０ｐｐｍであり、好ましくは０．
３〜２０ｐｐｍである。Specific examples of the water-soluble metal salt include cerium sulfate, cerium nitrate, cerium chloride, copper sulfate, copper nitrate, copper chloride, manganese sulfate, manganese nitrate, manganese chloride, iron sulfate, iron nitrate, and iron chloride. No. The amount of the water-soluble metal salt added (in terms of metal) is 0.1 p with respect to maleic acid.
pm or more. If it is less than 0.1 ppm, a sufficient effect of addition cannot be obtained. On the other hand, the upper limit of the amount of the water-soluble metal salt is not particularly limited, but an effect exceeding a certain level cannot be expected even if it is added in a large amount, and it may remain in fumaric acid and cause problems. From, usually
It is sufficient to add up to about 50 ppm. Thus,
The amount of the water-soluble metal salt (in terms of metal) to be added is usually 0.1 to 50 ppm, preferably 0.1 ppm, based on maleic acid.
3 to 20 ppm.
【００１７】本発明のフマル酸の製造方法によれば、マ
レイン酸の異性化反応を上記のフマル酸製造用触媒の存
在下に行う。According to the method for producing fumaric acid of the present invention, the isomerization reaction of maleic acid is carried out in the presence of the above-mentioned catalyst for producing fumaric acid.
【００１８】本発明で使用する原料マレイン酸は精製品
でもよいし粗製品でもよい。精製品であれば、無水マレ
イン酸のタブレット品または液体品を水に溶解させて用
いることができる。また、粗製品であれば、無水フタル
酸製造プラントから回収される粗マレイン酸水溶液でも
よいし、無水マレイン酸製造プラントの中間工程から得
られる粗マレイン酸水溶液を用いてもよい。なお、粗製
品の場合、色調などの製品品質を満足させるため、活性
炭処理などの従来公知の精製手段を用いて予め精製する
のがよい。The raw material maleic acid used in the present invention may be a purified product or a crude product. As a purified product, a tablet or liquid of maleic anhydride can be used by dissolving it in water. In addition, if it is a crude product, a crude maleic acid aqueous solution recovered from a phthalic anhydride manufacturing plant may be used, or a crude maleic acid aqueous solution obtained from an intermediate step of a maleic anhydride manufacturing plant may be used. In addition, in the case of a crude product, in order to satisfy product quality such as color tone, it is preferable to purify in advance using a conventionally known purification means such as activated carbon treatment.
【００１９】無水マレイン酸を原料とする場合、先ず無
水マレイン酸を上水、好ましくは純水に溶解してマレイ
ン酸水溶液を調製する。この際、水和熱でマレイン酸水
溶液は通常４０〜５０℃程度まで昇温する。なお、水は
通常常温のものを使用するが、必要に応じて加温してお
いてもよい。水溶液中のマレイン酸濃度は通常１０〜５
０重量％であり、好ましくは３０〜４０重量％である。
濃度が高すぎると、生成するフマル酸のスラリー濃度が
高くなりすぎて抜き出しが困難となり、一方濃度が低す
ぎると生産効率が悪くなって好ましくない。When maleic anhydride is used as a raw material, first, maleic anhydride is dissolved in tap water, preferably pure water to prepare a maleic acid aqueous solution. At this time, the maleic acid aqueous solution is usually heated to about 40 to 50 ° C. by the heat of hydration. Note that water is usually used at room temperature, but may be heated if necessary. The maleic acid concentration in the aqueous solution is usually 10 to 5
0% by weight, preferably 30 to 40% by weight.
If the concentration is too high, the concentration of the fumaric acid slurry formed becomes too high, making extraction difficult, while if the concentration is too low, the production efficiency is poor, which is not preferable.
【００２０】このマレイン酸水溶液に本発明のフマル酸
製造用触媒、すなわち上記の成分（Ａ）としての臭素酸
カリウムおよび成分（Ｂ）としてのチオ尿素を添加し、
通常、７５〜１００℃の範囲の温度で、好ましくは８０
〜１００℃、更に好ましくは８５〜９５℃の範囲の温度
で異性化反応を行う。反応温度が７０℃以下では触媒を
相当多量に添加しないと反応が十分進行せず、一方１０
０℃を超えると得られるフマル酸の耐熱安定性が悪くな
る。To the maleic acid aqueous solution, the catalyst for producing fumaric acid of the present invention, that is, potassium bromate as component (A) and thiourea as component (B) are added,
Usually at a temperature in the range of 75-100 ° C, preferably 80
The isomerization reaction is carried out at a temperature in the range of -100C, more preferably 85-95C. At a reaction temperature of 70 ° C. or lower, the reaction does not proceed sufficiently unless a considerably large amount of catalyst is added.
If it exceeds 0 ° C., the heat stability of the obtained fumaric acid will be poor.
【００２１】臭素酸カリウムおよびチオ尿素の添加方法
については特に制限はなく、種々の方法によって実施す
ることができる。例えば、（１）臭素酸カリウムおよび
チオ尿素の水溶液をマレイン酸水溶液に一度に、あるい
は所定量に分けて、場合によっては少量づつ連続して添
加する方法、（２）臭素酸カリウムおよびチオ尿素各々
の水溶液を調製し、先ずチオ尿素水溶液を添加した後、
臭素酸カリウム水溶液を添加する、あるいはその逆の順
序で添加する方法、（３）臭素酸カリウムおよびチオ尿
素各々の水溶液を所定量に分けて交互に添加する方法、
（４）臭素酸カリウムまたはチオ尿素をマレイン酸水溶
液に粉末として直接添加する方法、などを採用すること
ができる。なお、（２）〜（４）においも、各水溶液あ
るいは粉末を一度に、あるいは所定量に分けて、場合に
よっては少量づつ連続して添加することもできる。これ
らの添加方法は、反応条件、特に、反応温度、反応圧
力、設備の規模などに応じて適宜変更して採用すること
ができる。The method for adding potassium bromate and thiourea is not particularly limited, and can be carried out by various methods. For example, (1) a method in which an aqueous solution of potassium bromate and thiourea is added to the maleic acid aqueous solution all at once or in predetermined amounts, and if necessary, continuously added in small amounts; (2) potassium bromate and thiourea An aqueous solution of thiourea is first prepared, and then an aqueous solution of thiourea is added.
(3) a method in which potassium bromate and thiourea are separately added in predetermined amounts and added alternately,
(4) A method of directly adding potassium bromate or thiourea as a powder to a maleic acid aqueous solution can be adopted. In (2) to (4), each aqueous solution or powder can be added all at once or in predetermined amounts, and in some cases, can be continuously added in small amounts. These addition methods can be appropriately changed and adopted depending on reaction conditions, particularly reaction temperature, reaction pressure, scale of equipment, and the like.
【００２２】例えば、上記方法（１）の場合、マレイン
酸水溶液を所定の反応温度まで昇温した後、所要量の臭
素酸カリウムとチオ尿素とを添加して異性化反応を行っ
ても、あるいは反応温度より低い温度のマレイン酸水溶
液に所要量の臭素酸カリウムとチオ尿素とを添加した
後、所定の反応温度まで昇温して異性化反応を行っても
よい。後者の方法において、反応熱によって所定の反応
温度まで昇温する場合には、昇温に必要な加熱手段を新
たに講ずる必要はない。なお、反応液の濃度によって
は、大きな反応熱が発生し、突沸のおそれがあるので、
このような場合を考慮し、臭素酸カリウムとチオ尿素と
の添加は、所定の反応温度よりも低い温度、例えば反応
が始まる温度以下で添加するのが好ましく、またこのよ
うな添加方法を採用することにより触媒をマレイン酸水
溶液中に均一に分散させることができる。For example, in the case of the above method (1), after the maleic acid aqueous solution is heated to a predetermined reaction temperature, a required amount of potassium bromate and thiourea are added to carry out the isomerization reaction, or After the required amounts of potassium bromate and thiourea are added to a maleic acid aqueous solution at a temperature lower than the reaction temperature, the isomerization reaction may be performed by raising the temperature to a predetermined reaction temperature. In the latter method, when the temperature is raised to a predetermined reaction temperature by the heat of reaction, it is not necessary to newly provide a heating means necessary for raising the temperature. Depending on the concentration of the reaction solution, a large amount of reaction heat may be generated and bumping may occur.
In consideration of such a case, the addition of potassium bromate and thiourea is preferably performed at a temperature lower than a predetermined reaction temperature, for example, at or below the temperature at which the reaction starts, and such an addition method is employed. This allows the catalyst to be uniformly dispersed in the maleic acid aqueous solution.
【００２３】また、上記方法（２）の場合、通常、臭素
酸カリウムおよびチオ尿素のいずれか一方、例えば臭素
酸カリウムの所要量を所定の反応温度よりも低い温度の
マレイン酸水溶液に添加し、昇温した後、チオ尿素の所
要量を添加し、所定の反応温度で異性化反応を完結させ
るのがよい。この方法（２）は、特にバッチ装置の場
合、反応によって生じる反応熱を抑制することもできる
ので、好ましい場合もある。In the case of the above method (2), one of potassium bromate and thiourea, for example, a required amount of potassium bromate is usually added to a maleic acid aqueous solution at a temperature lower than a predetermined reaction temperature. After raising the temperature, the required amount of thiourea is preferably added to complete the isomerization reaction at a predetermined reaction temperature. This method (2) may be preferable in the case of a batch apparatus in particular, because the reaction heat generated by the reaction can be suppressed.
【００２４】なお、上記水溶性金属塩の添加時期につい
ては特に制限はなく、例えば臭素酸カリウムおよびチオ
尿素と一緒に添加しても、あるいは臭素酸カリウムまた
はチオ尿素と一緒に添加してもよい。さらに、これら成
分を添加する前に添加してもよい。The timing of adding the water-soluble metal salt is not particularly limited. For example, it may be added together with potassium bromate and thiourea, or may be added together with potassium bromate or thiourea. . Furthermore, you may add before adding these components.
【００２５】[0025]
【発明の効果】触媒の面では、使用の絶対量が少ないに
もかかわらず、１００℃以下の比較的低温での異性化反
応を高いマレイン酸反応率をもって行うことが可能とな
った。これは高収率でフマル酸を製造することができる
ことであり、工業的に有利なプロセスである。According to the present invention, it has become possible to carry out the isomerization reaction at a relatively low temperature of 100 ° C. or lower with a high maleic acid conversion even though the absolute amount of the catalyst used is small. This means that fumaric acid can be produced at a high yield, which is an industrially advantageous process.
【００２６】また、生成フマル酸の品質の面では未反応
マレイン酸および副生リンゴ酸の含量がきわめて少な
く、着色もなく、また耐熱安定性に優れている。In terms of the quality of the produced fumaric acid, the content of unreacted maleic acid and by-product malic acid is extremely small, there is no coloring, and the heat resistance is excellent.
【００２７】[0027]
【実施例】以下、実施例を挙げて本発明を更に具体的に
説明する。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.
【００２８】実施例１ 撹拌装置と簡単な還流装置をセットした１リットルフラ
スコに無水マレイン酸のタブレット品１０１．４ｇおよ
び純水２９８．６ｇを仕込み、撹拌して溶解させて、濃
度３０重量％のマレイン酸水溶液を調製した。このマレ
イン酸水溶液の温度は約４０℃であった。Example 1 A tablet of 101.4 g of maleic anhydride and 298.6 g of pure water were charged into a 1 liter flask equipped with a stirring device and a simple refluxing device, and dissolved by stirring to obtain a 30% by weight solution. A maleic acid aqueous solution was prepared. The temperature of the maleic acid aqueous solution was about 40 ° C.
【００２９】このマレイン酸水溶液を８５℃まで昇温し
た後、臭素酸カリウム０．１８ｇとチオ尿素０．０２４
ｇとを添加し、８５〜９５℃の温度で６０分間十分な撹
拌下に保持して転位反応を完結させた。After the temperature of the maleic acid aqueous solution was raised to 85 ° C., 0.18 g of potassium bromate and 0.024 g of thiourea were added.
g was maintained at a temperature of 85 to 95 ° C. for 60 minutes with sufficient stirring to complete the rearrangement reaction.
【００３０】マレイン酸反応率、取得フマル酸収率、マ
レイン酸含量、リンゴ酸含量、溶解色および耐熱安定性
は次の方法により測定した。反応条件を表１に、また結
果を表２に示した。The conversion of maleic acid, the yield of obtained fumaric acid, the content of maleic acid, the content of malic acid, the dissolution color and the heat resistance were measured by the following methods. The reaction conditions are shown in Table 1 and the results are shown in Table 2.
【００３１】（Ａ）マレイン酸反応率 反応終了後、反応混合物を３０℃まで冷却し、析出した
結晶をろ別した。ろ液を液体クロマトグラフィー（カラ
ム：ＳＨＯＤＥＸ−ＤＭＧ１４、昭和電工（株）製、５
ψ×１５０ｍ／ｍ）で未反応のマレイン酸を測定してマ
レイン酸反応率を求めた。(A) Maleic acid conversion After the reaction was completed, the reaction mixture was cooled to 30 ° C., and the precipitated crystals were separated by filtration. The filtrate was subjected to liquid chromatography (column: SHOdex-DMG14, manufactured by Showa Denko KK).
(ψ × 150 m / m), the unreacted maleic acid was measured to determine the maleic acid conversion.
【００３２】（Ｂ）フマル酸収率 ろ別した結晶全量を純水で洗浄した後、４０℃の真空乾
燥器で５時間乾燥して、ｇ数を秤量し、フマル酸収率を
求めた。(B) Yield of fumaric acid The total amount of the filtered crystals was washed with pure water, dried in a vacuum dryer at 40 ° C. for 5 hours, weighed, and the yield of fumaric acid was determined.
【００３３】（Ｃ）マレイン酸、リンゴ酸含量 上記（Ｂ）で得られた乾燥品０．５ｇを純水に溶解させ
て全容量を１００ｍｌにした後、上記（Ａ）で使用した
のと同じ液体クロマトグラフィーでそれぞれの含量を求
めた。(C) Maleic acid and malic acid contents 0.5 g of the dried product obtained in the above (B) was dissolved in pure water to make the total volume 100 ml, and the same as that used in the above (A) Each content was determined by liquid chromatography.
【００３４】（Ｄ）溶解色、耐熱安定性 上記（Ｂ）で得られた乾燥品４ｇとモノエチレングリコ
ール１０ｍｌとを試験管に入れて、加熱溶解した後、直
ちに色調（ＡＰＨＡ）を測定し、結果を「溶解色」とし
て示した。また、同じ溶液を１５０℃のヒートブロック
で１時間加熱した後、色調（ＡＰＨＡ）を測定し、結果
を「耐熱安定性」として示した。(D) Melting color and heat stability 4 g of the dried product obtained in the above (B) and 10 ml of monoethylene glycol were placed in a test tube, heated and dissolved, and immediately the color tone (APHA) was measured. The results were shown as “dissolved color”. After heating the same solution in a heat block at 150 ° C. for 1 hour, the color tone (APHA) was measured, and the result was shown as “heat resistance stability”.
【００３５】実施例２〜４ ［触媒総添加量の変更］実施例１において、触媒添加量
を表１に示すように変更した以外は実施例１と同様に転
位反応を行った。結果を表２に示す。この結果から触媒
総添加量が０．１〜０．２重量％という条件下でも高い
マレイン酸反応率を示し、かつ品質のよい製品が得られ
ることが分かる。Examples 2 to 4 [Change in the total amount of catalyst added] A rearrangement reaction was carried out in the same manner as in Example 1 except that the amount of catalyst added was changed as shown in Table 1. Table 2 shows the results. From these results, it can be seen that a high-quality maleic acid reaction rate and a high quality product can be obtained even under the condition that the total catalyst addition amount is 0.1 to 0.2% by weight.
【００３６】実施例５〜８ ［臭素酸カリウム／チオ尿素重量比の変更］実施例１に
おいて、触媒添加量を表１に示すように変更した以外は
実施例１と同様に転位反応を行った。結果を表２に示
す。この結果から臭素酸カリウム／チオ尿素＝４：１〜
１０：１という条件下でも高いマレイン酸反応率を示
し、かつ品質のよい製品が得られることが分かる。Examples 5 to 8 [Change in weight ratio of potassium bromate / thiourea] A rearrangement reaction was carried out in the same manner as in Example 1 except that the amount of catalyst added was changed as shown in Table 1. . Table 2 shows the results. From these results, potassium bromate / thiourea = 4: 1 to 1
It can be seen that a high maleic acid reaction rate is exhibited even under the condition of 10: 1 and a good quality product is obtained.
【００３７】実施例９〜１３ ［水溶性銅塩の添加］実施例１において、触媒添加量を
表１に示すように変更し、また硫酸銅も０．３〜２０ｐ
ｐｍ（金属換算量）の範囲で変更した以外は実施例１と
同様に転位反応を行った。結果を表２に示す。この結果
から銅イオンは０．５〜１０ｐｐｍという添加量の少な
い条件下でも高いマレイン酸反応率を示し、かつ品質の
よい製品が得られることが分かる。Examples 9 to 13 [Addition of water-soluble copper salt] In Example 1, the amount of the catalyst added was changed as shown in Table 1, and the amount of copper sulfate was 0.3 to 20 p.
A rearrangement reaction was carried out in the same manner as in Example 1 except that the amount was changed in the range of pm (equivalent amount of metal). Table 2 shows the results. From these results, it can be seen that copper ions show a high maleic acid reaction rate even under the condition of a small addition amount of 0.5 to 10 ppm, and a product of good quality can be obtained.
【００３８】実施例１４〜１６ ［他の水溶性金属塩の添加］実施例１において、触媒添
加量を表１に示すように変更し、また水溶性金属塩の種
類も変更した以外は実施例１と同様に転位反応を行っ
た。結果を表２に示す。この結果からセリウム、マンガ
ンおよび鉄もマレイン酸反応率を高める効果を示し、か
つ品質のよい製品が得られることが分かる。Examples 14 to 16 [Addition of Other Water-Soluble Metal Salts] In the same manner as in Example 1, except that the catalyst addition amount was changed as shown in Table 1, and the kind of the water-soluble metal salt was also changed. A rearrangement reaction was carried out in the same manner as in Example 1. Table 2 shows the results. From these results, it is understood that cerium, manganese, and iron also have an effect of increasing the maleic acid reaction rate, and that a good quality product can be obtained.
【００３９】比較例１〜３ 実施例１において、触媒添加量などの反応条件を表３に
示すように変更した以外は実施例１と同様に反応を行っ
た。結果を表４に示す。Comparative Examples 1-3 Reactions were carried out in the same manner as in Example 1 except that the reaction conditions such as the amount of the catalyst added were changed as shown in Table 3. Table 4 shows the results.
【００４０】なお、表１、表３で用いた記号の意味は次
のとおりである。The meanings of the symbols used in Tables 1 and 3 are as follows.
【００４１】 Ａ：臭素酸カリウムの添加量（ｗｔ％対マレイン酸） Ｂ：チオ尿素の添加量（ｗｔ％対マレイン酸） Ａ＋Ｂ：臭素酸カリウムとチオ尿素との総添加量（ｗｔ
％対マレイン酸） Ａ／Ｂ：臭素酸カリウム／チオ尿素（重量比） 水溶性金属塩の量（ＰＰＭ）は対マレイン酸である。ま
た、表２、表４で用いた記号の意味は次のとおりであ
る。A: Addition amount of potassium bromate (wt% to maleic acid) B: Addition amount of thiourea (wt% to maleic acid) A + B: Total addition amount of potassium bromate and thiourea (wt
A / B: Potassium bromate / thiourea (weight ratio) The amount of the water-soluble metal salt (PPM) is based on maleic acid. The meanings of the symbols used in Tables 2 and 4 are as follows.
【００４２】ＭＡ反応率：マレイン酸反応率（モル％） ＦＡ反応率：フマル酸収率（モル％） ＭＡ分：残存マレイン酸量（ｐｐｍ） ＬＡ分：残存リンゴ酸量（ｐｐｍ）MA conversion: maleic acid conversion (mol%) FA conversion: fumaric acid yield (mol%) MA content: residual maleic acid content (ppm) LA content: residual malic acid content (ppm)
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【表２】 [Table 2]
【００４５】[0045]
【表３】 [Table 3]
【００４６】[0046]
【表４】 [Table 4]
Claims (6)
製造用触媒であって、（Ａ）臭素酸塩と（Ｂ）チオ尿素
およびその誘導体から選ばれる少なくとも一種のチオ尿
素化合物とを必須成分とすることを特徴とするフマル酸
製造用触媒。1. A catalyst for producing fumaric acid by an isomerization reaction of maleic acid, wherein (A) a bromate salt and (B) at least one thiourea compound selected from thiourea and its derivatives are essential components. A catalyst for producing fumaric acid.
（成分（Ａ）／成分（Ｂ））が３：１〜５０：１である
請求項１記載のフマル酸製造用触媒。2. The catalyst for producing fumaric acid according to claim 1, wherein the weight ratio of component (A) to component (B) (component (A) / component (B)) is 3: 1 to 50: 1.
水溶性塩から選ばれる少なくとも一種の水溶性金属塩を
含む請求項１記載のフマル酸製造用触媒。3. The catalyst for producing fumaric acid according to claim 1, further comprising at least one water-soluble metal salt selected from water-soluble salts of cerium, copper, manganese and iron.
を製造する際に、この異性化反応を請求項１または３記
載のフマル酸製造用触媒の存在下に行うことを特徴とす
るフマル酸の製造方法。4. A process for producing fumaric acid by the isomerization reaction of maleic acid, wherein the isomerization reaction is carried out in the presence of the catalyst for fumaric acid production according to claim 1 or 3. Production method.
酸に対し０．０５〜１重量％である請求項４記載のフマ
ル酸の製造方法。5. The method for producing fumaric acid according to claim 4, wherein the amount of the catalyst for producing fumaric acid is 0.05 to 1% by weight based on maleic acid.
レイン酸に対し０．１〜５０ｐｐｍである請求項４記載
のフマル酸の製造方法。6. The method for producing fumaric acid according to claim 4, wherein the amount of the water-soluble metal salt used (in terms of metal) is 0.1 to 50 ppm based on maleic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6163492A JP2824394B2 (en) | 1994-07-15 | 1994-07-15 | Catalyst for producing fumaric acid and method for producing fumaric acid using the catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6163492A JP2824394B2 (en) | 1994-07-15 | 1994-07-15 | Catalyst for producing fumaric acid and method for producing fumaric acid using the catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0824664A JPH0824664A (en) | 1996-01-30 |
| JP2824394B2 true JP2824394B2 (en) | 1998-11-11 |
Family
ID=15774898
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6163492A Expired - Lifetime JP2824394B2 (en) | 1994-07-15 | 1994-07-15 | Catalyst for producing fumaric acid and method for producing fumaric acid using the catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2824394B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001060780A1 (en) * | 2000-02-15 | 2001-08-23 | Showa Denko K.K. | Process for producing fumaric ester |
-
1994
- 1994-07-15 JP JP6163492A patent/JP2824394B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0824664A (en) | 1996-01-30 |
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