JPS61204149A - Production of succinic acid - Google Patents
Production of succinic acidInfo
- Publication number
- JPS61204149A JPS61204149A JP60043004A JP4300485A JPS61204149A JP S61204149 A JPS61204149 A JP S61204149A JP 60043004 A JP60043004 A JP 60043004A JP 4300485 A JP4300485 A JP 4300485A JP S61204149 A JPS61204149 A JP S61204149A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- catalyst
- maleic anhydride
- maleic
- succinic acid
- 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
- Catalysts (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】
［産業上の利用分野］
本発明は無水マレイン酸またはマレイン酸を貴金属触媒
を用いて水素化しコハク酸を製造する方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing succinic acid by hydrogenating maleic anhydride or maleic acid using a noble metal catalyst.
［従来の技術］
コハク酸を製造する方法として、無水マレイン酸または
マレイン酸を水性媒体中で貴金属触媒を用いて水素化す
る方法は、例えば特公昭４４−２９２４８号明細書に記
載されている。この方法では、例えばマレイン酸を水素
化した後、熱時に触媒を濾過して回収し、その濾液を冷
却してコＩ＼り酸を晶析せしめ、コハク酸結晶を濾別し
た後、その母液は再度水素化反応の水性媒体として、回
収触媒と共にマレイン斂の水素化反応に循環使用される
。[Prior Art] As a method for producing succinic acid, a method of hydrogenating maleic anhydride or maleic acid in an aqueous medium using a noble metal catalyst is described, for example, in Japanese Patent Publication No. 44-29248. In this method, for example, after hydrogenating maleic acid, the catalyst is collected by filtration while hot, the filtrate is cooled to crystallize the acid, the succinic acid crystals are separated by filtration, and the mother liquor is is reused as an aqueous medium for the hydrogenation reaction together with the recovered catalyst in the hydrogenation reaction of maleic acid.
［発明が解決しようとする問題点１
この水素化反応に使用する触媒は白金、ロジウム等の貴
金属が用いられ、極めて高価なものである。従って、で
きる限り長期間触媒として活性を保持していることが好
ましい、しかしながら、上記の方法において触媒の循環
再使用を繰返していくと、触媒は次第にその活性が低下
しく失活）、水素化に要する時間が長くなり、遂には実
用上触媒として再使用できなくなり、新規な触媒と交換
されることとなる。[Problem to be Solved by the Invention 1] The catalyst used in this hydrogenation reaction uses noble metals such as platinum and rhodium, and is extremely expensive. Therefore, it is preferable to maintain the activity as a catalyst for as long as possible. However, as the catalyst is repeatedly recycled and reused in the above method, the activity of the catalyst gradually decreases and becomes deactivated. The time required becomes long, and eventually it becomes impossible to reuse it as a catalyst in practice, and it has to be replaced with a new catalyst.
本発明の目的は、上記水素化反応において使用される貴
金属触媒の失活を防止し、該触媒の長期間にわたる循環
再使用を可能ならしめるにある。An object of the present invention is to prevent the noble metal catalyst used in the hydrogenation reaction from being deactivated and to enable the catalyst to be recycled and reused over a long period of time.
本発明者等は、上記水素化反応における触媒の失活につ
いて鋭意検討した結果、その原因は原料の無水マレイン
酸またはマレイン酸に含まれている不純物による被毒で
あり、この不純物を除去することにより触媒の失活を防
止しうろことを見出した。As a result of intensive study on the deactivation of the catalyst in the above hydrogenation reaction, the present inventors found that the cause was poisoning due to the raw material maleic anhydride or impurities contained in the maleic acid, and that it was necessary to remove this impurity. We have discovered that this method can prevent catalyst deactivation.
触媒の失活の原因となる不純物がどのような化合物であ
るかは、必ずしも明らかではないが１例えばマレイン酸
の重縮合物、あるいは無水マレイン酸の着色防止剤とし
て添加されている化合物。Although it is not necessarily clear what kind of impurity is the impurity that causes the deactivation of the catalyst, for example, it may be a polycondensate of maleic acid or a compound added as a color preventive agent to maleic anhydride.
例えば銅化合物等が考えられる。For example, copper compounds etc. can be considered.
［問題点を解決するための手段］
本発明はこれら原料中に含まれている不純物の処理に活
性炭を用いることによりその目的を達成したものである
。[Means for Solving the Problems] The present invention achieves its objectives by using activated carbon to treat impurities contained in these raw materials.
即ち本発明は、無水マレイン酸またはマレイン酸を水性
媒体中で貴金属触媒を用いて水素化してコハク酸を製造
する方法において、無水マレイン酸またはマレイン酸を
予め活性炭で処理した後。That is, the present invention provides a method for producing succinic acid by hydrogenating maleic anhydride or maleic acid in an aqueous medium using a noble metal catalyst, after the maleic anhydride or maleic acid is previously treated with activated carbon.
水素化反応に付することを特徴とするコハク酸の製造方
法である。This is a method for producing succinic acid characterized by subjecting it to a hydrogenation reaction.
本発明で原料として使用される無水マレイン醜またはマ
レイン酸は、一般にブテンおよびブタジェンなどのＣ４
留分、ブタン、あるいはベンゼン等の接触気相酸化反応
によって製造されたもの、もしくは、オルソキシレンの
接触気相酸化反応による無水フタル酸の製造の際の副生
無水マレイン酸やマレイン酸が挙げられる。特に通常市
販されている無水マレイン酸には、製造時の不純物のほ
かに、無水マレイン酸の貯蔵時における変質や変色を防
止する目的で、各種の薬剤が添加されており、これが触
媒を被毒せしめると考えられるので１本発明による処理
が必要であり、がっ、有効である。The maleic anhydride or maleic acid used as a raw material in the present invention is generally a C4 such as butene and butadiene.
Examples include those produced by the catalytic gas phase oxidation reaction of distillates, butane, or benzene, or by-product maleic anhydride and maleic acid during the production of phthalic anhydride by the catalytic gas phase oxidation reaction of ortho-xylene. . In particular, commercially available maleic anhydride contains impurities during manufacturing as well as various chemicals added to the maleic anhydride to prevent deterioration and discoloration during storage, which can poison the catalyst. Therefore, the treatment according to the present invention is necessary and effective.
本発明において、マレイン酸水溶液を使用する場合には
、市販の無水マレイン酸を水に溶解したものが用いられ
るが、マレイン酸を水素化した後、反応液を冷却して生
成したコハク酸を晶出せしめ、濾過によってコハク酸を
分離した母液に無水マレイン酸を所定量溶解したものを
使用することができる。即ち水素化反応の水性媒体を循
環再使用することができる。In the present invention, when using an aqueous solution of maleic acid, commercially available maleic anhydride dissolved in water is used, but after hydrogenating maleic acid, the reaction solution is cooled to crystallize the produced succinic acid. A predetermined amount of maleic anhydride dissolved in a mother liquor from which succinic acid has been separated by draining and filtration can be used. That is, the aqueous medium for the hydrogenation reaction can be recycled and reused.
本発明において用いられる活性炭としては、本発明に実
施した場合に効果がある限り、その種類および形状に特
に制限はない、即ち、粉末状、粒状、あるいは繊維状の
活性炭が用いられるが１通常、液相処理用のものが用い
られる。There are no particular restrictions on the type and shape of the activated carbon used in the present invention, as long as it is effective when implemented in the present invention.In other words, powdered, granular, or fibrous activated carbon is used; Those for liquid phase processing are used.
市販されている各種の活性炭は、その賦活方法が製造者
によって異なり、場合によっては活性炭の製造および賦
活の際に１本発明で使用される水素化触媒に対して好ま
しくない影響を与える汚れを含有している可能性がある
。従って、本発明を実施する際には、活性炭の汚れを予
め除去しておくことが好ましい。The activation method of various commercially available activated carbons varies depending on the manufacturer, and in some cases, during the production and activation of activated carbon, they may contain dirt that has an unfavorable effect on the hydrogenation catalyst used in the present invention. There is a possibility that it is. Therefore, when carrying out the present invention, it is preferable to remove dirt from activated carbon in advance.
活性炭の汚れを除去する方法としては、洗浄処理がある
が、その場合、活性炭中に残留する処理剤がマレイン酸
処理に際して脱着し、水素化反応系で貴金属触媒を被毒
せしめないことが必要である。このような洗浄剤で有効
な洗浄力を有するものとしては、酸の水溶液または有機
溶媒がある。Cleaning treatment is a method for removing dirt from activated carbon, but in this case it is necessary to ensure that the treatment agent remaining in the activated carbon does not desorb during the maleic acid treatment and poison the precious metal catalyst in the hydrogenation reaction system. be. Examples of such cleaning agents having effective cleaning power include aqueous acid solutions and organic solvents.
酸としては硫酸、硝酸等の鉱酸、あるいは酢酸、マレイ
ン酸等の有機酸が挙げられる。硫酸を使用する場合は、
濃度的０．１〜５ｚ、特に １〜３駕程度の希硫酸が好
ましい、有機酸の場合はその飽和濃度以下で使用される
。処理温度は常温〜約８０℃が好ましく、その理由は不
明であるが、８０℃以上の高温では洗浄効果が期待でき
ない、洗浄液の使用量は活性炭重量の５〜５０倍程度で
充分である。Examples of acids include mineral acids such as sulfuric acid and nitric acid, and organic acids such as acetic acid and maleic acid. When using sulfuric acid,
Dilute sulfuric acid with a concentration of 0.1 to 5z, particularly about 1 to 3 oz, is preferred; in the case of organic acids, it is used below its saturation concentration. The treatment temperature is preferably room temperature to about 80°C, and although the reason for this is unknown, no cleaning effect can be expected at high temperatures of 80°C or higher.The amount of cleaning liquid used is approximately 5 to 50 times the weight of activated carbon, which is sufficient.
洗浄液として１本発明の原料として使用される無水マレ
イン酸もしくはマレイン酸を用いることは好ましい態様
であって、後述するように、原料を充填塔または流動層
で活性炭処理を実施する場合に、初期汚れが流出する間
だけ得られた無水マレイン酸あるいはマレイン酸を水素
化処理に使用せず、汚れの流出が認められなくなった後
、本発明の水素化に使用するという形で活性炭の洗浄を
行うことができる。It is a preferred embodiment to use maleic anhydride or maleic acid, which is used as a raw material in the present invention, as the cleaning liquid. The activated carbon is cleaned by not using the maleic anhydride or maleic acid obtained during the hydrogenation process only while the maleic acid is flowing out, and using it in the hydrogenation of the present invention after no dirt is observed to flow out. I can do it.
洗浄液としての有機溶媒は、種々のものが用い得るが、
水と混和し得て、かつ、安価なメタノール等が好ましい
。Various organic solvents can be used as the cleaning liquid, but
Methanol, which is miscible with water and inexpensive, is preferred.
既に酸処理された市販の活性炭があれば、それを使用す
る方が好都合であることは勿論である。Of course, if there is commercially available activated carbon that has already been acid-treated, it is more convenient to use it.
本発明において、活性炭による無水マレイン酸またはマ
レイン酸水溶液の処理の方法としては。In the present invention, the method for treating maleic anhydride or maleic acid aqueous solution with activated carbon is as follows.
一般に活性炭を適用する場合に用いられる公知の方式、
例えば粒状の活性炭を使用して、 １段または多段の充
填塔、流動床等で連続的に処理する方式が採用されるが
１通常は充填塔が選ばれる。勿論、粉末活性炭または粒
状活性炭を使用して。A known method generally used when applying activated carbon,
For example, a system in which granular activated carbon is used and the treatment is carried out continuously in a one-stage or multi-stage packed tower, fluidized bed, etc. is adopted, but usually a packed tower is selected. Of course, using powdered activated carbon or granular activated carbon.
バー、チ方式（回分式）で処理することもできる。It is also possible to process by bar or chi method (batch method).
本発明における充Ｍｉ４塔による処理条件としては、無
水マレイン酸を活性炭で処理する場合には、処理温度は
無水マレイン酸が液状である必要があるので、その融点
（５２，８°Ｃ）以上、一般に １２０°Ｃ以下、通常
は６０〜１００℃の温度が採用される。ＳＶ （空間速
度）は一般に０．１〜１０ｈｒ’″１１通常０．２〜６
ｈｒ″である。マレイン酸水溶液を処理する場合にも
基本的には同様の処理条件で実施できるが、液性の相違
上から、マレイン酸の濃度は飽和濃度以下、通常２０〜
５０％濃度で、処理温度は常温以上、沸点以下、通常は
５Ｏ−ＩＱＯ”０の温度が採用される。Ｓｖは上記とほ
ぼ同様でよい。ただし該マレイン酸水溶液は、活性炭処
理後、そのまま水素化反応に付されので、その濃度は水
素化反応の濃度に合わせておくのが好都合である。活性
炭処理の際の圧力は特に限定されるものではなく、常圧
でも加圧してもよい。In the present invention, the treatment conditions using the Mi4-filled tower are as follows: When maleic anhydride is treated with activated carbon, the treatment temperature must be higher than its melting point (52.8°C), since the maleic anhydride must be in a liquid state. Generally a temperature of 120°C or less, usually 60 to 100°C, is employed. SV (space velocity) is generally 0.1~10hr'''11 usually 0.2~6
hr''.When treating an aqueous maleic acid solution, the treatment can basically be carried out under the same conditions, but due to the difference in liquid properties, the concentration of maleic acid is below the saturation concentration, usually 20 ~
At a concentration of 50%, the treatment temperature is above room temperature and below the boiling point, usually a temperature of 5O-IQO'0. Since the activated carbon is subjected to a hydrogenation reaction, it is convenient to adjust its concentration to that of the hydrogenation reaction.The pressure during activated carbon treatment is not particularly limited, and may be normal pressure or pressurized.
活性炭処理をバッチ方式で実施する際の条件は、処理温
度およびマレイン酸水溶液の濃度は、前記充填塔処理の
場合と同様でよいが、処理時間は一般に攪拌下に約１０
分以上１通常３０分〜２時間で充分である。この場合の
活性炭の使用量は、原料中の不純物量が少ないので、比
較的少量でよく、原料に対し約０．００５〜１重量ｔで
よい。The conditions for carrying out the activated carbon treatment in a batch manner are the treatment temperature and the concentration of the maleic acid aqueous solution, which may be the same as in the case of the packed column treatment, but the treatment time is generally about 10 minutes under stirring.
A time of at least 30 minutes to 2 hours is usually sufficient. In this case, since the amount of impurities in the raw material is small, the amount of activated carbon used may be relatively small, and may be about 0.005 to 1 t by weight based on the raw material.
無水マレイン酸またはマレイン酸の処理量は、活性炭の
吸着容量および原料中の不純物の種類またはその量に著
しく左右されるので一明確にはできないが、一般に活性
炭重量の１０，０００〜８０，０００倍のでレイン酸を
処理し得る。活性炭の吸着能の低下による不純物の破過
は、処理した後の原料の水素化反応における反応速度（
水素吸収速度）の低下によって容易に判定することがで
きる。The amount of maleic anhydride or maleic acid to be treated cannot be determined because it depends significantly on the adsorption capacity of activated carbon and the type or amount of impurities in the raw material, but it is generally 10,000 to 80,000 times the weight of activated carbon. Therefore, leic acid can be treated. The breakthrough of impurities due to a decrease in the adsorption capacity of activated carbon is due to the reaction rate (
This can be easily determined by the decrease in hydrogen absorption rate (hydrogen absorption rate).
本発明で処理した無水マレイン酸またはマレイン酸原料
を用いた場合、貴金属触媒で水素化しコハク酸を製造す
る方法は、公知の方法で実施される。例えば、濤度約３
０〜５０２のマレイン酸、無水マレイン酸水溶液を温度
約８０〜１００℃、水素加圧下、通常２〜３０ｋｇ／
ａｍ２Ｇで貴金属触媒の存在化で水素化し１反広賜、舘
触韓＊ａｉｅｉａａ＋−子の濾液を冷却し、析出したコ
ハク酸の結晶を濾過等で分離、屹燥し、一方、該触媒お
よび濾液は水素下反応に循環再使用する。＋１！液は副
生物が蓄積するので、通常は適宜一部排出するが、本発
明においては、既に原料中の不純物が処理されているの
で、循環母液中副生物の蓄積自体が少ないが、さらにこ
の母液を活性炭で処理して循環使用することにより、再
循環液中の不純物の蓄積を抑制することができる。When using the maleic anhydride or maleic acid raw material treated in the present invention, the method for hydrogenating with a noble metal catalyst to produce succinic acid is carried out by a known method. For example, the intensity is about 3
0 to 502 maleic acid or maleic anhydride aqueous solution at a temperature of about 80 to 100°C under hydrogen pressure, usually 2 to 30 kg/
Hydrogenate with am2G in the presence of a noble metal catalyst, cool the filtrate of Tatechihan*aieiaa+-, separate the precipitated succinic acid crystals by filtration, etc., and dry.Meanwhile, the catalyst and filtrate is recycled and reused in the reaction under hydrogen. +1! Since by-products accumulate in the liquid, a portion of the liquid is normally discharged as appropriate, but in the present invention, since impurities in the raw materials have already been treated, the accumulation of by-products in the circulating mother liquor is small, but in addition, this mother liquor By treating the liquid with activated carbon and recycling it, it is possible to suppress the accumulation of impurities in the recirculated liquid.
本発明で使用される貴金属触媒としては、例えばパラジ
ウム、ルテニウム、ロジウム、白金等の触媒が挙げられ
るが、一般にはこれらの貴金属が活性炭、シリカ、アル
ミナ、シリカ・アルミナ等に担持された触媒、もしくは
その酸化物が用いられ１例えば、担持率が２駕、５％ま
たは１０％のパラジウム−炭素（Ｐｄ−Ｃ）、 ５％ル
テニウム−炭素（Ｒｕ−Ｃ）、５ｚロジウム−炭素（Ｒ
ｈ−Ｃ：）あるいは酸化白金が挙げられる０通常は価格
的に有利で、かつ、選択性がよく被毒にも強いＰｄ−Ｃ
が用いられる。Examples of the noble metal catalyst used in the present invention include catalysts such as palladium, ruthenium, rhodium, and platinum, but generally these noble metals are supported on activated carbon, silica, alumina, silica/alumina, etc., or For example, palladium-carbon (Pd-C) with a loading of 2, 5% or 10%, 5% ruthenium-carbon (Ru-C), 5z rhodium-carbon (R
h-C:) or platinum oxide. Usually, Pd-C is advantageous in price, has good selectivity, and is resistant to poisoning.
is used.
触媒の使用量は、一般的にはマレイン酸に対して０．Ｏ
１〜２鬼、通常は ０．１〜１％である。The amount of catalyst used is generally 0.0% relative to maleic acid. O
1-2 demons, usually 0.1-1%.
［作用および発明の効果］
本発明はコハク酸の製造に際して、原料である無水マレ
イン酸またはマレイン酸を予め活性炭で処理することに
より、水素化反応に使用される貴金属触媒を被毒せしめ
る不純物が除去されるので、触媒の失活が防止され、長
期間にわたって触媒活性を保持することができる。また
、水素化反応における循環母液をさらに活性炭で処理す
ることにより、触媒寿命をさらに延長することができ、
コハク酸の製造における触媒コストを大幅に低減するこ
とが可能である。[Operation and Effects of the Invention] In the production of succinic acid, the present invention removes impurities that poison the precious metal catalyst used in the hydrogenation reaction by treating the raw material maleic anhydride or maleic acid with activated carbon in advance. Therefore, deactivation of the catalyst is prevented and the catalyst activity can be maintained for a long period of time. In addition, by further treating the circulating mother liquor in the hydrogenation reaction with activated carbon, the catalyst life can be further extended.
It is possible to significantly reduce catalyst costs in the production of succinic acid.
〔実施例］
以下、大発明の方法を実施例により詳細に説明するが、
水素化工反応における貴金属触媒の被毒失活は、触媒を
反復使用する為、その確認に長時間を要する。そこで反
復使用による触媒の活性低下を相対的に比較し得る方法
として、次に述べる強制的被毒処理試験法を採用した。[Example] Hereinafter, the method of the great invention will be explained in detail using examples.
Poisoning and deactivation of precious metal catalysts in hydrochemical reactions requires a long time to confirm because the catalyst is used repeatedly. Therefore, the following forced poisoning test method was adopted as a method to relatively compare the decrease in catalyst activity due to repeated use.
なお、本明細書中に使用されている１％」および「部」
は、特に指定されない限り「重量％」および「重量部」
を示す。In addition, "1%" and "part" used in this specification
"% by weight" and "parts by weight" unless otherwise specified
shows.
強制・ ″ ′ す
（１）被毒処理
試験しようとする無水マレイン酸またはマレイン酸２０
０部（触媒に対し２０００倍）を容器にとり、純水３０
０部を加えて溶解する。触媒として５鬼Ｐｄ−Ｃ：０．
１部を加え９５°Ｃで １時間、窒素雰囲気下に攪拌し
、被毒処理を行なう。熱時濾過し、２０部の温水で５回
洗浄した後、得られた触媒を８５°Ｃで乾燥する。(1) Maleic anhydride or maleic acid 20 to be tested for poisoning treatment
Take 0 parts (2000 times the amount of catalyst) in a container and add 30 parts of pure water.
Add 0 parts and dissolve. 5Ki Pd-C as a catalyst: 0.
1 part was added and stirred at 95°C for 1 hour under a nitrogen atmosphere to perform poisoning treatment. After hot filtration and washing 5 times with 20 parts of hot water, the catalyst obtained is dried at 85°C.
（２）水素化反応実験
市販の無水マレイン酸１０ｇを攪拌機および定圧の水素
導入管を備えたオートクレーブに採り、純水１００ｇを
入れ、８０℃、１０分で攪拌下に溶解する。(2) Hydrogenation reaction experiment 10 g of commercially available maleic anhydride was placed in an autoclave equipped with a stirrer and a constant pressure hydrogen inlet tube, and 100 g of pure water was added thereto, and the autoclave was dissolved under stirring at 80° C. for 10 minutes.
次いで（１）により被毒処理された触媒０ 、４５ｇを
加えて攪拌下、８０℃、８ｋｇ／ｃ＋ｏ２Ｇで水素の吸
収速度を測定する。Next, 0.45 g of the catalyst poisoned according to (1) is added, and the hydrogen absorption rate is measured at 80° C. and 8 kg/c+o2G while stirring.
対照として、新規な触媒を用いて同様に水素吸収速度を
測定し、被毒処理による活性低下の判断基準とする。As a control, the hydrogen absorption rate was similarly measured using a new catalyst and used as a criterion for determining the decrease in activity due to poisoning treatment.
実施例１および比較例１
（１）活性炭の洗浄
粒状活性炭（やし穀破砕炭）１部を無水マレイン酸とし
て１０部を含む４７％マレイン醜水溶液を用いて、４０
℃、攪拌下に洗浄処理し、濾過し、濾過ケーキを２０部
の純水でよく洗浄した後乾燥した。Example 1 and Comparative Example 1 (1) Cleaning of activated carbon Using a 47% maleic aqueous solution containing 1 part of granular activated carbon (crushed coconut charcoal) and 10 parts of maleic anhydride, 40%
The mixture was washed at 10°C with stirring, filtered, and the filter cake was thoroughly washed with 20 parts of pure water and then dried.
（２）活性炭による原料マレイン酸の処理市販の無水マ
レイン酸１００部に０．０１重量％の上記洗浄方法で得
られた活性炭を０４０１重量％加え、攪拌下に８０℃で
１時間処理し、熱時濾過した。該活性炭は、同様な方法
で繰返し再使用し１合計５回原料を処理した。(2) Treatment of raw maleic acid with activated carbon To 100 parts of commercially available maleic anhydride, 0.01% by weight of the activated carbon obtained by the above washing method was added, and the mixture was treated at 80°C for 1 hour with stirring and then heated. It was filtered at the time. The activated carbon was repeatedly reused in the same manner to treat the raw material five times in total.
各処理により得られた無水マレイン酸および比較例とし
て未処理の無水マレイン酸を用いて、前述の強制被毒処
理試験法を適用し、被毒処理された触媒の水素化反応の
水素吸収速度を反応率５０％、９０％および１００ｔの
到達時間により測定した。Using maleic anhydride obtained by each treatment and untreated maleic anhydride as a comparative example, the above-mentioned forced poisoning treatment test method was applied to evaluate the hydrogen absorption rate of the hydrogenation reaction of the poisoned catalyst. It was measured by the time required to reach a reaction rate of 50%, 90%, and 100t.
その結果を第１表に示す。The results are shown in Table 1.
第１表 ＭＡＮは無水マレイン酸を示す。Table 1 MAN indicates maleic anhydride.
この結果によれば、活性炭１重量部に対し、無水マレイ
ン醜を約４００００部処理ができることになる。即ち、
１回の活性炭０．０１部で処理できる無水マレイン酸の
量が１００部であり、該活性炭がさらに４回循環可能で
あるから、その無水マレイン酸の処理可能な量は
（＋００１０．０１）Ｘ ４ 、、＝ ４００００であ
る。According to this result, approximately 40,000 parts of anhydrous maleic acid can be treated with respect to 1 part by weight of activated carbon. That is,
The amount of maleic anhydride that can be treated with 0.01 part of activated carbon at one time is 100 parts, and the activated carbon can be recycled four more times, so the amount of maleic anhydride that can be treated is (+0010.01)X 4,,=40000.
実施例２
下部に調節コックおよび上部に無水マレイン酸液を８０
°Ｃに保温した分液漏斗を備え、８０℃に加温した内径
１０．２ｍｍ、高さ７２０ｍｍのガラス製の充填塔に、
実施例１の（１）と同様に処理した粒状活性炭５３ｍ１
を充填した。Example 2 Adjustment cock at the bottom and maleic anhydride solution at the top
A glass packed tower with an inner diameter of 10.2 mm and a height of 720 mm heated to 80 °C was equipped with a separating funnel kept at °C.
Granular activated carbon 53ml treated in the same manner as in Example 1 (1)
filled with.
市販の無水マレイン酸を上記の分液漏斗に入れ、ＳＶ
０．５ｈｒ−で８０℃の無水マレイン酸液を充填層に通
液した。合計的４，０００ｇの無水マレイン酸を処理し
、強制被毒処理試験法により測定した。その結果、粒状
活性炭処理した無水フタル酸の反応時間は、５ｏｚ反応
率の到達時間が１８分、３ｏｚで３５分、ｔｏｏｔでは
４４分であり、対照の新規触媒と実質的に変りがなく、
触媒の被毒による活性低下は見られなかった。Add commercially available maleic anhydride to the above separatory funnel and add SV
A maleic anhydride solution at 80° C. was passed through the packed bed for 0.5 hr. A total of 4,000 g of maleic anhydride was treated and measured using the forced poisoning test method. As a result, the reaction time of phthalic anhydride treated with granular activated carbon was 18 minutes to reach a 5oz reaction rate, 35 minutes for 3oz, and 44 minutes for toot, which was essentially the same as the new control catalyst.
No decrease in activity due to catalyst poisoning was observed.
水素化反応で得られたコハク酸は、常法に従って触媒を
熱時濾過し、濾液からコハク酸を品薄せしめ、濾別、乾
燥することにより、高純度のコハク酸が得られた。The succinic acid obtained in the hydrogenation reaction was filtered while the catalyst was hot in accordance with a conventional method, the succinic acid was depleted from the filtrate, and the succinic acid was separated by filtration and dried to obtain highly pure succinic acid.
実施例３
実施例１の（２）において無水マレイン酸１００部の代
わりに、市販の無水マレイン酸を純水に溶解したマレイ
ン酸の４０％溶液２５０部を用いて同様の方法で処理し
、得られたマレイン醜水溶液について、実施例１の方法
と同様な方法で強制被毒処理試験法を実施したところ、
実施例１と殆ど同様な結果が得られた。Example 3 In Example 1 (2), instead of 100 parts of maleic anhydride, 250 parts of a 40% solution of maleic acid, in which commercially available maleic anhydride was dissolved in pure water, was treated in the same manner. A forced poisoning test method was conducted on the malein-ugly aqueous solution in the same manner as in Example 1.
Almost the same results as in Example 1 were obtained.
実施例４
実施例２と同様な方法で粒状活性炭で処理した市販の無
水マレイン酸１００部を、攪拌機および定圧の水素導入
管を備えたオートクレーブに採り。Example 4 100 parts of commercially available maleic anhydride treated with granular activated carbon in the same manner as in Example 2 was placed in an autoclave equipped with a stirrer and a constant pressure hydrogen inlet tube.
純水２００部を入れ、撹拌下に溶解した０次いで、５％
Ｐｄ−Ｃ： ０．２部を加え、攪拌下ニ８０℃、 ８
ｋｇ／ｃｍ”Ｇで水素化反応を行った。水素の吸収がな
くなったところで反応を停止し、熱時に触媒を濾過し、
その濾液を冷却し、析出したコハク酸を濾過、乾燥した
ところ、高純度のコハク酸が得られた。Add 200 parts of pure water and dissolve 0 then 5% while stirring.
Pd-C: Add 0.2 part and stir at 80°C. 8
The hydrogenation reaction was carried out at kg/cm"G. The reaction was stopped when no hydrogen was absorbed, and the catalyst was filtered when hot.
The filtrate was cooled, and the precipitated succinic acid was filtered and dried to obtain highly pure succinic acid.
その母液および触媒は再度上記条件で繰返し水素化反応
に使用した。このように該触媒を５０回繰返して反応に
供したが、該触媒の活性は殆ど低下せず、実用上支障は
なかった。一方、未処理の市販の無水マレイン酸を原料
として使用して上記と同様に触媒を循環使用した場合は
、およそ２５回目位から水素吸収速度の低下が著しく、
マレイン酸の反応率１００ｔを達成するには長時間を要
するようになり、実質的に使用が不可能になった。The mother liquor and catalyst were again used in repeated hydrogenation reactions under the above conditions. Although the catalyst was subjected to the reaction 50 times in this manner, the activity of the catalyst hardly decreased and there was no problem in practical use. On the other hand, when untreated commercially available maleic anhydride is used as a raw material and the catalyst is recycled in the same manner as above, the hydrogen absorption rate decreases significantly from about the 25th time onwards.
It took a long time to achieve a reaction rate of 100 tons of maleic acid, making it virtually impossible to use.
Claims (5)
貴金属触媒を用いて水素化してコハク酸を製造する方法
において、無水マレイン酸またはマレイン酸を予め活性
炭で処理した後、水素化反応に付することを特徴とする
コハク酸の製造方法。(1) In a method for producing succinic acid by hydrogenating maleic anhydride or maleic acid in an aqueous medium using a noble metal catalyst, maleic anhydride or maleic acid is treated with activated carbon in advance and then subjected to a hydrogenation reaction. A method for producing succinic acid, characterized by:
である、特許請求の範囲第１項に記載のコハク酸の製造
方法。(2) The method for producing succinic acid according to claim 1, wherein the activated carbon is washed with an acid or an organic solvent in advance.
記載のコハク酸の製造方法。(3) The method for producing succinic acid according to claim 2, wherein the acid is maleic acid.
を水性媒体として水素化反応に循環する、特許請求の範
囲第１項から第３項までのいずれかに記載のコハク酸の
製造方法。(4) After the completion of the hydrogenation reaction, the mother liquor from which the crystallized succinic acid has been separated is recycled to the hydrogenation reaction as an aqueous medium, to produce succinic acid according to any one of claims 1 to 3. Method.
１項から第４項までのいずれかに記載のコハク酸の製造
方法。(5) The method for producing succinic acid according to any one of claims 1 to 4, wherein the circulating mother liquor is treated with activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60043004A JPH0611725B2 (en) | 1985-03-05 | 1985-03-05 | Method for producing succinic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60043004A JPH0611725B2 (en) | 1985-03-05 | 1985-03-05 | Method for producing succinic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61204149A true JPS61204149A (en) | 1986-09-10 |
| JPH0611725B2 JPH0611725B2 (en) | 1994-02-16 |
Family
ID=12651847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60043004A Expired - Fee Related JPH0611725B2 (en) | 1985-03-05 | 1985-03-05 | Method for producing succinic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0611725B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264548A (en) * | 1987-04-22 | 1988-11-01 | Mitsui Toatsu Chem Inc | Purification of lactic acid |
| JP2003002959A (en) * | 2001-06-18 | 2003-01-08 | Mitsubishi Gas Chem Co Inc | Method for producing aliphatic polyestercarbonate |
| US7520986B2 (en) | 2003-10-28 | 2009-04-21 | Nihon Genryo Co., Ltd. | Filtration device |
| JP2010180134A (en) * | 2009-02-03 | 2010-08-19 | Central Glass Co Ltd | Manufacturing method of 1,3,3,3-tetrafluoropropene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101671758B1 (en) * | 2014-12-26 | 2016-11-02 | 경북대학교 산학협력단 | Preparation method of non halogen-based flame-retardant polypropylene resin, polypropylene resin prepared thereby, and flame-retardant polymer resin composition comprising them |
-
1985
- 1985-03-05 JP JP60043004A patent/JPH0611725B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264548A (en) * | 1987-04-22 | 1988-11-01 | Mitsui Toatsu Chem Inc | Purification of lactic acid |
| JP2003002959A (en) * | 2001-06-18 | 2003-01-08 | Mitsubishi Gas Chem Co Inc | Method for producing aliphatic polyestercarbonate |
| US7520986B2 (en) | 2003-10-28 | 2009-04-21 | Nihon Genryo Co., Ltd. | Filtration device |
| JP2010180134A (en) * | 2009-02-03 | 2010-08-19 | Central Glass Co Ltd | Manufacturing method of 1,3,3,3-tetrafluoropropene |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0611725B2 (en) | 1994-02-16 |
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