WO2003059862A1 - Process for producing high-purity (meth)acrylic acid - Google Patents

Process for producing high-purity (meth)acrylic acid Download PDF

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Publication number
WO2003059862A1
WO2003059862A1 PCT/JP2003/000105 JP0300105W WO03059862A1 WO 2003059862 A1 WO2003059862 A1 WO 2003059862A1 JP 0300105 W JP0300105 W JP 0300105W WO 03059862 A1 WO03059862 A1 WO 03059862A1
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acrylic acid
meth
aldehyde
purity
crude
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PCT/JP2003/000105
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French (fr)
Japanese (ja)
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Shuhei Yada
Kenji Takasaki
Yasushi Ogawa
Yoshiro Suzuki
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Mitsubishi Chemical Corporation
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Priority to AU2003202485A priority Critical patent/AU2003202485A1/en
Publication of WO2003059862A1 publication Critical patent/WO2003059862A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification

Definitions

  • the present invention relates to a method for producing high-purity (meth) acrylic acid, and more particularly, to a method for producing high-purity (meth) acrylic acid by distilling crude (meth) acrylic acid containing aldehydes as impurities.
  • (meth) acrylic acid means one of acrylic acid and methacrylic acid or the rainy way.
  • Acrylic acid is produced, for example, by the following method. That is, first, propylene as a raw material is subjected to gas-phase catalytic oxidation, the obtained oxidation reaction mixture is absorbed with water to recover an aqueous solution of acrylic acid, and then the obtained aqueous solution is dissolved in the presence of an azeotropic agent. The crude acrylic acid is concentrated to obtain crude acrylic acid, and then the crude acrylic acid is purified by a distillation column to recover highly pure acrylic acid. In the case of methacrylic acid, it is manufactured by the same process as above using isobutylene as a raw material.
  • aldehydes such as furfural and benzaldehyde are produced as by-products.
  • aldehydes have a similar boiling point to (meth) acrylic acid, distillation is carried out. Is difficult to remove.
  • a method for removing aldehydes in crude (meth) acrylic acid a compound having one or more mercapto groups in the molecule (an aldehyde removing agent) and a reaction treatment with crude (meth) acrylic acid in the presence of an acidic catalyst
  • a known method is known (for example, Japanese Patent Publication No. 4-29695).
  • mercaptans such as methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, and n-butyl mercaptan have been proposed as the aldehyde removing agent.
  • aldehydes in crude (meth) acrylic acid The aldehydes are converted to other compounds by reaction with the aldehyde removal treatment agent and are removed.
  • the (meth) acrylic acid obtained by subsequent distillation treatment contains malodorous components and can be highly purified. There is no problem.
  • the present invention has been made in view of the above circumstances, and has as its object a method of reacting an aldehyde in crude (meth) acrylic acid with an aldehyde-removing agent to convert it into another compound, followed by a distillation treatment.
  • An object of the present invention is to provide a method for producing high-purity (meth) acrylic acid containing no malodorous components. Disclosure of the invention
  • the present inventors have earnestly studied and obtained the following findings. That is, in the case of performing a distillation treatment as a post-process, it is necessary to use an aldehyde removing agent capable of converting aldehydes into a compound having a higher boiling point than (meth) acrylic acid. From the viewpoint of solubility and reactivity, an aldehyde removal treatment agent containing an alkyl mercaptan having 12 to 16 carbon atoms as a main component is preferable. However, since alkyl mercaptans are produced via ethylene derivatives, it is inevitable that alkyl mercaptans having 10 or less carbon atoms are mixed into alkyl mercaptans having 12 to 16 carbon atoms.
  • the alkyl mercaptan having 10 or less carbon atoms has a boiling point similar to that of (meth) acrylic acid, so that it is difficult to separate by distillation and remains as a malodorous component.
  • the present invention has been completed based on the above-mentioned various findings, and the gist of the present invention is to produce high-purity (meth) acrylic acid by subjecting crude (meth) acrylic acid containing aldehydes as impurities to distillation treatment.
  • the aldehyde having a content of alkyl mercaptan having 12 to 16 carbon atoms of 98% by weight or more and a content of alkyl mercaptan of 10 or less carbon atoms of 5,000 ppm by weight or less is previously determined.
  • a method for producing high-purity (meth) acrylic acid comprising reacting crude (meth) acrylic acid in the presence of a removing agent and an acidic catalyst.
  • the present invention will be described in detail.
  • a crude (meta) acrylic acid containing an aldehyde as an impurity is subjected to a reaction treatment in the presence of an aldehyde removing treatment agent and an acidic catalyst to convert the aldehyde to a high boiling point compound.
  • an aldehyde removing treatment agent the content of alkylmercaptan having 12 to 16 carbon atoms is 98% by weight or more and the content of alkylmercaptan having 10 or less carbon atoms is 50,000. It is necessary to use an aldehyde removal treatment agent of 0 ppm by weight or less.
  • Alkyl mercaptans having more than 16 carbon atoms have poor solubility and reactivity with crude (meth) acrylic acid. If an aldehyde-removing agent with a content of alkyl mercaptan having 10 or less carbon atoms of more than 50,000 ppm by weight is used, this book will not produce high-purity (meth) acrylic acid containing no odorous components. The purpose of the invention cannot be achieved.
  • the content of the alkyl mercaptan having 12 to 16 carbon atoms in the aldehyde removing agent is preferably at least 99% by weight.
  • Specific examples of the alkyl mercaptan having 12 to 16 carbon atoms include n_dodecyl mercaptan, myristyl mercaptan, n-pentadecyl mercaptan, and n-hexadecyl mercaptan. Among these n- dodecyl Melka butane force? Particularly preferred.
  • the content of the alkyl mercaptan having 10 or less carbon atoms in the aldehyde removal treatment agent is preferably 100 wt% or less, more preferably 500 wt% or less.
  • the lower limit is usually 1 ppm in consideration of the effect and the cost for purification.
  • alkyl mercaptan having 10 or less carbon atoms examples include ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, 2-ethyl-n-hexyl mercaptan, and n-decyl mercaptan, n_decyl mercaptan and the like.
  • the aldehyde removal treatment agent used in the present invention is, for example, a method of reacting an alkyl halide with an alkali hydrosulfide, a method of reacting an alkyl halide with thiourea. After that, it can be obtained by a method of hydrolyzing with alcohol, a method of reacting an aliphatic alcohol with hydrogen sulfide in a gas phase, or a method of reacting olefin and hydrogen sulfide.
  • the acidic catalyst used in the present invention which is provided with a distillation (rectification) means having an increased number of stages as necessary, is not particularly limited.
  • the acidic catalyst is particularly preferably a sulfonated cation exchange resin.
  • the reaction treatment for converting aldehydes to high boiling compounds is preferably carried out as follows. That is, an aldehyde removal treatment agent is added to crude (meth) acrylic acid, and the crude (meth) acrylic acid is circulated through a fixed bed of a sulfonated cation exchange resin.
  • the amount of the aldehyde-removing agent varies depending on the impurity aldehyde concentration and the degree of removal, but is usually 1 to 10 times, preferably 3 to 5 times, the mole of the total amount of the impurity aldehyde.
  • the reaction temperature is usually 20 ° C to 90 ° C.
  • the reaction pressure is not particularly limited, but may be any pressure that can maintain a liquid phase.
  • the reaction time is generally 1 to 24 hours, preferably 0.1 to 3 hours.
  • the crude (meta) acrylic acid reacted with the aldehyde removing agent is subjected to a distillation treatment.
  • a conventionally known polymerization inhibitor can be added during the distillation.
  • the polymerization inhibitor include the following compounds. That is, as the N-oxyl compound, tertiary butyl dithroxide, 2,2,6,6-tetramethyl-4-hydroxypiperidyl-1-oxyl, 2,2,6,6-tetramethylpiberidyl-l-oxyl, 2, 2,6,6-tetramethylpiperidinoxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl, 4,4,, 4,4,1, tris-1 (2,2,6,6- Tetramethylpiperidinoxyl) Phosphite and phenolic compounds include hydroquinone, methquinone, pyrogallol, catechol, resorcinol, and phenothiazine compounds such as phenothiazine and bis-one.
  • the amount of the polymerization inhibitor (polymerization inhibitor) to be added is not particularly limited, but is usually from 1 to 100 ppm by weight.
  • the method of distillation is not particularly limited, and for example, various methods such as simple distillation and precision distillation can be employed. Further, the distillation may be carried out by either a notch system or a continuous system, but is preferably carried out industrially by a continuous system.
  • the distillation apparatus is not particularly limited. Generally, trays or packing are used inside the distillation column. As a tray, a bubble bell tray with a downcomer, many? There are dual trays without downcomers, such as plate trays, valve trays, super-flux trays, and max flux trays.
  • Examples of the packing include the following. That is, as the structured packing, “Sulza I-Pack” manufactured by Sulza I Brothers Co., Ltd., “Sumitomo Sulzer Packing” manufactured by Sumitomo Heavy Industries, Ltd., and “Merapack” manufactured by Sumitomo Heavy Industries, Ltd. "Gempak” manufactured by Glitch Co., Ltd.
  • the conditions for distillation are not particularly limited, but specifically, the residence time It is good to set the distillation temperature to 0.5 to 100 ° C for 0.5 to 20 hours.
  • the raw material used was crude acrylic acid containing 239 wt ppm of furfural and 238 wt ppm of benzaldehyde as impurities. Also, the aldehyde removal ⁇ treatment agent, was used pure 9 9.5 wt 0/0 of n- dodecyl Melka-butane (n- Okuchirumeru Kabutan content 4 0 wt ppm).
  • a sulfonated cation exchange resin (Mitsubishi Kagaku's cation exchange resin “PK-216 1”) was used as the acidic catalyst. The ion-exchange resin was passed through the packed tower.
  • the amount of the aldehyde removing agent added was such that the amount of ⁇ -dodecyl mercaptan was equivalent to 5 times the molar concentration of the aldehyde.
  • the flow was carried out at normal temperature and normal pressure at a speed of 50,000 kg Zh (residence time: 2 hours).
  • the liquid was sent to a packed column distillation apparatus to perform continuous distillation. In continuous distillation, a bottom temperature of 70 ° C., 9.9% by weight of the feed liquid were continuously distilled off, and a part of the distillate was used as a reflux liquid at a reflux ratio of 1.0 from the top of the column. It was introduced inside.
  • methquinone methoxyhydroxyquinone
  • polymerization inhibitor corresponding to 10 ppm by weight with respect to the amount of liquid introduced into the distillation column was dissolved in the reflux liquid and introduced into the column.
  • furfural and benzaldehyde in purified acrylic acid obtained as a distillate were 1 ppm by weight or less. The odor of the distillate from the top was confirmed, but not at all.
  • Example 1 as the aldehyde removal treatment agent, pure 9 8.5 wt 0/0 n -The same operation as in Example 1 was performed except that dodecyl mercaptan (n-octyl mercaptan content: 2000 ppm by weight, n-decyl mercaptan content: 600 ppm by weight) was used. An unpleasant odor was observed in the distillate from the top of the tower. As a result of confirming the composition of the distillate, it was found that 0.8 wt ppm of n-octyl mercaptan was present. Industrial applicability
  • the present invention relates to a method of reacting aldehydes in crude (meth) acrylic acid with an aldehyde-removing agent to convert the aldehydes into another compound, followed by distillation treatment, and comprises a high-purity (meth) acrylic acid containing no malodorous component. It has a high industrial value as a method for producing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

A process for producing high-purity (meth)acrylic acid by distilling crude (meth)acrylic acid containing an aldehyde as an impurity, which comprises reactively treating the crude (meth)acrylic acid beforehand in the presence of an acid catalyst and an aldehyde remover having a content of C12-16 alkyl mercaptans of 98 wt.% or higher and a content of C10 or lower alkyl mercaptans of 5,000 wt.ppm or lower. Thus, high-purity (meth)acrylic acid containing no ingredients emitting an offensive odor can be obtained.

Description

明 細 書 高純度 （メタ） アクリル酸の製造方法 技術分野  Description Manufacturing method of high-purity (meth) acrylic acid Technical field
本発明は高純度 （メタ） アクリル酸の製造方法に関し、 詳しくは、 不純物と してアルデヒド類を含有する粗 （メタ） アクリル酸を蒸留処理して高純度 （メ タ） アクリル酸を製造する方法に関する。 なお、 上記の 「 （メタ） アクリル酸 」 の表記は、 アクリル酸とメタクリル酸の一方または雨方を意味する。 背景技術  The present invention relates to a method for producing high-purity (meth) acrylic acid, and more particularly, to a method for producing high-purity (meth) acrylic acid by distilling crude (meth) acrylic acid containing aldehydes as impurities. About. In addition, the notation of the above-mentioned "(meth) acrylic acid" means one of acrylic acid and methacrylic acid or the rainy way. Background art
アクリル酸は例えば次の様な方法で製造されている。 すなわち、 先ず、 原料 のプロピレンを気相接触酸化し、 得られた酸化反応混合物を水で吸収してァク リル酸の水溶液を回収し、 次いで、 得られた水溶液を共沸剤の存在下に濃縮し て粗アタリル酸を得、 次いで、 粗ァクリル酸を蒸留塔で精製して高純度のァク リル酸を回収する。 そして、 メタクリル酸の場合は、 原料としてイソプチレン を使用し、 上記と同様のプロセスによって製造される。  Acrylic acid is produced, for example, by the following method. That is, first, propylene as a raw material is subjected to gas-phase catalytic oxidation, the obtained oxidation reaction mixture is absorbed with water to recover an aqueous solution of acrylic acid, and then the obtained aqueous solution is dissolved in the presence of an azeotropic agent. The crude acrylic acid is concentrated to obtain crude acrylic acid, and then the crude acrylic acid is purified by a distillation column to recover highly pure acrylic acid. In the case of methacrylic acid, it is manufactured by the same process as above using isobutylene as a raw material.
ところで、 （メタ） アクリル酸の製造方法においては、 フルフラール、 ベン ズアルデヒド等のアルデヒド類が副生するが、 斯かるアルデヒド類は、 （メタ ) アクリル酸との沸点が近似しているため、 蒸留による除去が困難である。 粗 （メタ） ァクリル酸中のアルデヒド類の除去方法として、 分子中に 1個以 上のメルカプト基を有する化合物 （アルデヒド除去処理剤） 及び酸性触媒の存 在下に粗 （メタ） アクリル酸を反応処理する方法が知られている （例えば特公 平 4 — 2 9 6 5 8号公報） 。 そして、 上記のアルデヒド除去処理剤としては、 メチルメルカプタン、 ェチルメルカプタン、 n—プロピルメルカプタン、 n _ ブチルメルカプタン等の各種のメルカブタンが提案されている。  By the way, in the method for producing (meth) acrylic acid, aldehydes such as furfural and benzaldehyde are produced as by-products. However, since such aldehydes have a similar boiling point to (meth) acrylic acid, distillation is carried out. Is difficult to remove. As a method for removing aldehydes in crude (meth) acrylic acid, a compound having one or more mercapto groups in the molecule (an aldehyde removing agent) and a reaction treatment with crude (meth) acrylic acid in the presence of an acidic catalyst A known method is known (for example, Japanese Patent Publication No. 4-29695). Various mercaptans such as methyl mercaptan, ethyl mercaptan, n-propyl mercaptan, and n-butyl mercaptan have been proposed as the aldehyde removing agent.
しかしながら、 上記の方法による場合、 粗 （メタ） アクリル酸中のアルデヒ ド類は、 アルデヒド除去処理剤と反応して他の化合物に変換されて除去される が、 その後に蒸留処理して得られる （メタ） アクリル酸は悪臭成分を含み、 高 純度化することが出来ないという問題がある。 However, according to the above method, aldehydes in crude (meth) acrylic acid The aldehydes are converted to other compounds by reaction with the aldehyde removal treatment agent and are removed. However, the (meth) acrylic acid obtained by subsequent distillation treatment contains malodorous components and can be highly purified. There is no problem.
本発明は、 上記実情に鑑みなされたものであり、 その目的は、 粗 （メタ） ァ クリル酸中のアルデヒド類をアルデヒド除去処理剤と反応させて他の化合物に 変換させた後に蒸留処理する方法であって、 悪臭成分を含まない高純度 （メタ ) アクリル酸の製造方法を提供することにある。 発明の開示  The present invention has been made in view of the above circumstances, and has as its object a method of reacting an aldehyde in crude (meth) acrylic acid with an aldehyde-removing agent to convert it into another compound, followed by a distillation treatment. An object of the present invention is to provide a method for producing high-purity (meth) acrylic acid containing no malodorous components. Disclosure of the invention
本発明者らは、 鋭意検討を重ねた結果、 次の様な知見を得た。 すなわち、 後 工程として蒸留処理を行なう場合は、 アルデヒ ド類を （メタ） アクリル酸より も高沸点化合物に変換し得るアルデヒド除丟処理剤を使用する必要があり、 粗 (メタ） アクリル酸との溶解性や反応性の観点から、 炭素数 1 2〜 1 6のアル キルメルカプタンを主成分とするアルデヒド除去処理剤が好適である。 ところ で、 アルキルメルカブタンはエチレンの誘導体を経由して製造されるため、 炭 素数が 1 0以下のアルキルメルカブタンが炭素数 1 2〜 1 6のアルキルメルカ ブタンに混入することは避けられず、 その混入量は、 製造方法や製品グレード によって異なる。 ところが、 炭素数が 1 0以下のアルキルメルカブタンは、 そ の沸点が （メタ） アクリル酸と近似しているため、 蒸留によって分離するのが 困難であり、 悪臭成分として残存する。  The present inventors have earnestly studied and obtained the following findings. That is, in the case of performing a distillation treatment as a post-process, it is necessary to use an aldehyde removing agent capable of converting aldehydes into a compound having a higher boiling point than (meth) acrylic acid. From the viewpoint of solubility and reactivity, an aldehyde removal treatment agent containing an alkyl mercaptan having 12 to 16 carbon atoms as a main component is preferable. However, since alkyl mercaptans are produced via ethylene derivatives, it is inevitable that alkyl mercaptans having 10 or less carbon atoms are mixed into alkyl mercaptans having 12 to 16 carbon atoms. The amount varies depending on the manufacturing method and product grade. However, the alkyl mercaptan having 10 or less carbon atoms has a boiling point similar to that of (meth) acrylic acid, so that it is difficult to separate by distillation and remains as a malodorous component.
本発明は、 上記の各種の知見に基づき完成されたものであり、 その要旨は、 不純物としてアルデヒド類を含有する粗 （メタ） アクリル酸を蒸留処理して高 純度 （メタ） アクリル酸を製造するに当たり、 予め、 炭素数 1 2〜1 6のアル キルメルカブタンの含有量が 9 8重量％以上であり且つ炭素数 1 0以下のアル キルメルカブタンの含有量が 5， 0 0 0重量 p p m以下のアルデヒド除去処理 剤および酸性触媒の存在下に粗 （メタ） アクリル酸を反応処理することを特徴 とする高純度 （メタ） アクリル酸の製造方法に存する。 以下、 本発明を詳細に説明する。 先ず、 本発明においては、 アルデヒド除去 処理剤および酸性触媒の存在下に不純物としてアルデヒド類を含有する粗 （メ タ） アクリル酸を反応処理し、 アルデヒド類を高沸点化合物に変換する。 本発明において、 アルデヒド除ま処理剤として、 炭素数 1 2〜 1 6のアルキ ルメルカブタンの含有量が 9 8重量％以上であり且つ炭素数 1 0以下のアルキ ルメルカプタンの含有量が 5， 0 0 0重量 p p m以下のアルデヒド除丟処理剤 を使用する必要がある。 The present invention has been completed based on the above-mentioned various findings, and the gist of the present invention is to produce high-purity (meth) acrylic acid by subjecting crude (meth) acrylic acid containing aldehydes as impurities to distillation treatment. The aldehyde having a content of alkyl mercaptan having 12 to 16 carbon atoms of 98% by weight or more and a content of alkyl mercaptan of 10 or less carbon atoms of 5,000 ppm by weight or less is previously determined. A method for producing high-purity (meth) acrylic acid, comprising reacting crude (meth) acrylic acid in the presence of a removing agent and an acidic catalyst. Hereinafter, the present invention will be described in detail. First, in the present invention, a crude (meta) acrylic acid containing an aldehyde as an impurity is subjected to a reaction treatment in the presence of an aldehyde removing treatment agent and an acidic catalyst to convert the aldehyde to a high boiling point compound. In the present invention, as the aldehyde removing agent, the content of alkylmercaptan having 12 to 16 carbon atoms is 98% by weight or more and the content of alkylmercaptan having 10 or less carbon atoms is 50,000. It is necessary to use an aldehyde removal treatment agent of 0 ppm by weight or less.
炭素数が 1 6を超えるアルキルメルカブタンの場合は、 粗 （メタ） アクリル 酸に対する溶解性や反応性に劣る。 炭素数 1 0以下のアルキルメルカブタンの 含有量が 5， 0 0 0重量 p p mを超えるアルデヒド除去処理剤を使用した場合 は、 悪臭成分を含まない高純度 （メタ） アクリル酸を製造せんとする本発明の 目的を達成することが出来ない。  Alkyl mercaptans having more than 16 carbon atoms have poor solubility and reactivity with crude (meth) acrylic acid. If an aldehyde-removing agent with a content of alkyl mercaptan having 10 or less carbon atoms of more than 50,000 ppm by weight is used, this book will not produce high-purity (meth) acrylic acid containing no odorous components. The purpose of the invention cannot be achieved.
アルデヒド除去処理剤中の炭素数 1 2〜 1 6のアルキルメルカブタンの含有 量は好ましくは 9 9重量％以上である。 炭素数 1 2〜 1 6のアルキルメルカプ タンの具体例としては、 n _ドデシルメルカブタン、 ミリスチルメルカプタン 、 n—ペンタデシルメルカブタン、 n—へキサデシルメルカブタン等力 s挙げれ る。 これらの中では n—ドデシルメルカブタン力 ?特に好ましい。 The content of the alkyl mercaptan having 12 to 16 carbon atoms in the aldehyde removing agent is preferably at least 99% by weight. Specific examples of the alkyl mercaptan having 12 to 16 carbon atoms include n_dodecyl mercaptan, myristyl mercaptan, n-pentadecyl mercaptan, and n-hexadecyl mercaptan. Among these n- dodecyl Melka butane force? Particularly preferred.
アルデヒド除去処理剤中の炭素数 1 0以下のアルキルメルカブタンの含有量 は、 好ましくは 1 0 0 0重量 p p m以下、 更に好ましくは 5 0 0重量 p p m以 下である。 なお、 その下限は、 効果と精製のためのコストを考慮し、 通常 1重 量 p p mである。 炭素数 1 0以下のアルキルメルカブタンの具体例としては、 ェチルメルカプタン、 n—プロピルメルカプタン、 n—ブチルメルカプタン、 n—へキシルメルカブタン、 シクロへキシルメルカプタン、 2—ェチルー n— へキシルメルカプタン、 n—才クチルメルカプタン、 n _デシルメルカプタン 等が挙げられる。  The content of the alkyl mercaptan having 10 or less carbon atoms in the aldehyde removal treatment agent is preferably 100 wt% or less, more preferably 500 wt% or less. The lower limit is usually 1 ppm in consideration of the effect and the cost for purification. Specific examples of the alkyl mercaptan having 10 or less carbon atoms include ethyl mercaptan, n-propyl mercaptan, n-butyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, 2-ethyl-n-hexyl mercaptan, and n-decyl mercaptan, n_decyl mercaptan and the like.
本発明で使用するアルデヒド除去処理剤は、 例えば、 ハロゲン化アルキルと 水硫化アルカリとを反応させる方法、 ハロゲン化アルキルとチォ尿素を反応さ せた後にアル力リで加水分解する方法、 脂肪族アルコールと硫化水素とを気相 接触反応させる方法、 ォレフィンと硫化水素とを反応させる方法により得るこ とが出来る。 そして、 段数を高めた蒸留 （精留） 手段が必要に応じて施される 本発明で使用する酸性触媒は、 特に制限されないが、 鉱酸、 パラ The aldehyde removal treatment agent used in the present invention is, for example, a method of reacting an alkyl halide with an alkali hydrosulfide, a method of reacting an alkyl halide with thiourea. After that, it can be obtained by a method of hydrolyzing with alcohol, a method of reacting an aliphatic alcohol with hydrogen sulfide in a gas phase, or a method of reacting olefin and hydrogen sulfide. The acidic catalyst used in the present invention, which is provided with a distillation (rectification) means having an increased number of stages as necessary, is not particularly limited.
ルホン酸、 スルホン化陽イオン交換樹脂などの強酸が好適である。 これらの中 では酸性触媒はスルホン化陽イオン交換樹脂が特に好ましい。 Strong acids such as sulfonic acid and sulfonated cation exchange resins are preferred. Of these, the acidic catalyst is particularly preferably a sulfonated cation exchange resin.
アルデヒド類を高沸点化合物に変換するための反応処理は、 好適には次の様 に行なわれる。 すなわち、 粗 （メタ） アクリル酸にアルデヒド除去処理剤を添 加し、 スルホン化陽イオン交換樹脂の固定床に流通させる。 アルデヒド除ま処 理剤の添加量は、 不純物アルデヒド濃度および除去程度により変化するが、 総 不純物アルデヒド量に対し、 通常 1〜 1 0倍モル、 好ましくは 3〜 5倍モルで ある。 反応処理温度は通常 2 0 °C〜9 0 °Cである。 反応圧力は、 特に制限はな いが、 液相を保持し得る圧力であれば充分である。 反応時間は、 通常 1〜 2 4時間、 好ましくは 0 . 1〜 3時間である。  The reaction treatment for converting aldehydes to high boiling compounds is preferably carried out as follows. That is, an aldehyde removal treatment agent is added to crude (meth) acrylic acid, and the crude (meth) acrylic acid is circulated through a fixed bed of a sulfonated cation exchange resin. The amount of the aldehyde-removing agent varies depending on the impurity aldehyde concentration and the degree of removal, but is usually 1 to 10 times, preferably 3 to 5 times, the mole of the total amount of the impurity aldehyde. The reaction temperature is usually 20 ° C to 90 ° C. The reaction pressure is not particularly limited, but may be any pressure that can maintain a liquid phase. The reaction time is generally 1 to 24 hours, preferably 0.1 to 3 hours.
次いで、 本発明においては、 アルデヒド除去処理剤と反応処理された粗 （メ タ） アクリル酸を蒸留処理する。  Next, in the present invention, the crude (meta) acrylic acid reacted with the aldehyde removing agent is subjected to a distillation treatment.
本発明においては、 蒸留の際に、 従来公知の重合防止剤 （重合抑制剤） を添 加することも出来る。 重合防止剤 （重合抑制剤） の具体例としては、 次の様な 化合物が挙げられる。 すなわち、 N—ォキシル化合物としては、 第 3ブチル二 トロォキシド、 2， 2 , 6 , 6—テトラメチルー 4—ヒドロキシピペリジルー 1ーォキシル、 2 , 2 , 6 , 6—テトラメチルピベリジルー 1ーォキシル、 2 ， 2， 6， 6—テトラメチルピペリジノォキシル、 4ーヒドロキシー 2 , 2， 6， 6—テトラメチルピペリジノォキシル、 4， 4， ， 4， ， 一トリス一 （2 ， 2， 6， 6—テトラメチルピペリジノォキシル） フォスファイト、 フエノー ル化合物としては、 ハイドロキノン、 メ トキノン、 ピロガロール、 カテコール 、 レゾルシン、 フエノチアジン化合物としては、 フエノチアジン、 ビス一 一メチルベンジル） フエノチアジン、 3， 7—ジォクチルフエノチアジン、 ビ スー （ひージメチルベンジル） フエノチアジン、 銅系化合物としては、 塩化第 2銅、 酢酸銅、 炭酸銅、 アクリル酸銅、 ジメチルジチ才力ルバミン酸銅、 ジェ チルジチォカルバミン酸銅、 ジブチルジチォカルバミン酸銅など力 ?挙げられる 。 これらの化合物は、 2種以上組み合わせて使用することも出来る。 重合防止 剤 （重合抑制剤） の添加量は、 特に制限されないが、 通常 1〜1 0 0 0重量 p p mでめる。 In the present invention, a conventionally known polymerization inhibitor (polymerization inhibitor) can be added during the distillation. Specific examples of the polymerization inhibitor (polymerization inhibitor) include the following compounds. That is, as the N-oxyl compound, tertiary butyl dithroxide, 2,2,6,6-tetramethyl-4-hydroxypiperidyl-1-oxyl, 2,2,6,6-tetramethylpiberidyl-l-oxyl, 2, 2,6,6-tetramethylpiperidinoxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl, 4,4,, 4,4,1, tris-1 (2,2,6,6- Tetramethylpiperidinoxyl) Phosphite and phenolic compounds include hydroquinone, methquinone, pyrogallol, catechol, resorcinol, and phenothiazine compounds such as phenothiazine and bis-one. 1-methylbenzyl) phenothiazine, 3,7-dioctyl phenothiazine, bis (h-dimethylbenzyl) phenothiazine, copper-based compounds such as cupric chloride, copper acetate, copper carbonate, copper acrylate, dimethyldithiate Sairyoku Rubamin copper, Jefferies chill di Chio carbamate copper, such as dibutyl Chio carbamic acid copper power? and the like. These compounds can be used in combination of two or more. The amount of the polymerization inhibitor (polymerization inhibitor) to be added is not particularly limited, but is usually from 1 to 100 ppm by weight.
本発明において、 蒸留の方法は、 特に制限されず、 例えば、 単蒸留、 精密蒸 留等の種々の方法を採用することが出来る。 また、 蒸留は、 ノ ツチ式または連 続式の何れで行ってもよいが、 工業的には連続式で行うのが好ましい。  In the present invention, the method of distillation is not particularly limited, and for example, various methods such as simple distillation and precision distillation can be employed. Further, the distillation may be carried out by either a notch system or a continuous system, but is preferably carried out industrially by a continuous system.
また、 蒸留装置については特に制限されない。 一般に蒸留塔内部にはトレイ 又は充填物が使用される。 トレイとしては、 ダウンカマーのある泡鐘トレイ、 多？し板トレイ、 バルブトレイ、 スーパ一フラック トレイ、 マックスフラクスト レイ等、 ダウンカマーの無いデュアルトレイ等がある。 充填物としては例えば 次の様なものがある。 すなわち、 規則充填物としては、 スルザ一 ·ブラザース (株） 製の 「スルザ一パック」、住友重機械工業 （株） 製の 「住友スルザーパ ッキング」 、 住友重機械工業 （株） 製の 「メラパック」 、 グリッチ （株） 製の 「ジェムパック」 、 モンッ （株） 製の 「モンッパック」、東京特殊金網 （株） 製の 「グッ ドロールパッキング」 、 日本ガイシ （株） 製の 「ハニカムパック」 、 ナガ才力 （株） 製の 「インパルスパッキング」 等がある。 不規則充填物とし ては、 ノートン （株） 製の 「インタロックスサドル」 、 日鉄化工機 （株） 製の 「テラレッ ト」 、 B A S F (株） 製の 「ポールリング」 、 マストランスファー (株） 製の 「カスケ一ド . ミニ . リング」 、 日揮 （株） 製の 「フレキシリング 」 等がある。 蒸留等を構成する装置の材質は、 （メタ） アクリル酸を取り扱う ため、 S U S 3 0 4、 S U S 3 0 4 L、 S U S 3 1 6、 S U S 3 1 6 L等のス テンレス鋼が好ましい。  The distillation apparatus is not particularly limited. Generally, trays or packing are used inside the distillation column. As a tray, a bubble bell tray with a downcomer, many? There are dual trays without downcomers, such as plate trays, valve trays, super-flux trays, and max flux trays. Examples of the packing include the following. That is, as the structured packing, “Sulza I-Pack” manufactured by Sulza I Brothers Co., Ltd., “Sumitomo Sulzer Packing” manufactured by Sumitomo Heavy Industries, Ltd., and “Merapack” manufactured by Sumitomo Heavy Industries, Ltd. "Gempak" manufactured by Glitch Co., Ltd. "Monpak" manufactured by Monk Co., Ltd., "Good Roll Packing" manufactured by Tokyo Special Wire Mesh Co., Ltd., "Honeycomb Pack" manufactured by NGK Insulators, Nagasai "Impulse packing" manufactured by Riki Co., Ltd. Examples of the irregular packing include “Interlock Saddle” manufactured by Norton Co., Ltd., “Terralet” manufactured by Nippon Steel Kakoki Co., Ltd., “Poll Ring” manufactured by BASF, and Mass Transfer Co., Ltd. "Cascade Mini Ring" manufactured by JGC Corporation and "Flexi Ring" manufactured by JGC Corporation. The stainless steel such as SUS304, SUS304L, SUS316, SSUS316L, etc. is preferable for the material of the equipment constituting the distillation or the like because it handles (meth) acrylic acid.
蒸留の際の条件については、 特に制限されないが、 具体的には、 滞留時間が 0 . 5〜 2 0時間、 蒸留温度が 5 0〜 1 0 0 °Cとなるように設定するのが良い The conditions for distillation are not particularly limited, but specifically, the residence time It is good to set the distillation temperature to 0.5 to 100 ° C for 0.5 to 20 hours.
発明を実施するための最良の形態 BEST MODE FOR CARRYING OUT THE INVENTION
以下、 本発明を実施例により更に詳細に説明するが、 本発明は、 その要旨を 超えない限り、 以下の実施例に限定されるものではない。  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
実施例 1  Example 1
原料には、 不純物としてフルフラール 2 3 9重量 p p m、 ベンズアルデヒド 2 3 8重量 p p mを含む粗ァクリル酸を使用した。 また、 アルデヒド除丟処理 剤には、 純度 9 9 . 5重量0 /0の n—ドデシルメルカブタン （n—ォクチルメル カブタン含有量 4 0重量 p p m) を使用した。 酸性触媒にはスルホン化陽ィォ ン交換樹脂 （三菱化学社製陽イオン交換樹脂 「P K— 2 1 6 Η」 ） を使用した 先ず、 上記の原料にアルデヒド除去処理剤を添加し、 スルホン化陽イオン交 換樹脂の充填塔内を流通させた。 アルデヒ ド除去処理剤の添加量は、 η—ドデ シルメルカプタンの量がァルデヒド濃度の 5倍モル相当量となる量とした。 流 通は、 常温常圧で 5 0 0 0 k g Z hの速度 （滞留時間 2時間） で行なった。 次いで、 充填塔蒸留装置へ送液して連続蒸留を行った。 連続蒸留は、 塔底温 度 7 0 °C、 供給液の 9 9重量％を連続的に留出させ、 留出液の一部を還流液と して塔頂より還流比 1 . 0で塔内に導入して行った。 なお、 連続蒸留に際して は、 蒸留塔に導入される液量に対して 1 0重量 p p mに相当するメトキノン （ メ トキシハイ ドロキノン） （重合禁止剤） を還流液に溶かして塔内に導入した 。 蒸留留出液として得られた精製ァクリル酸中のフルフラール及ぴベンズアル デヒドは共に 1重量 p p m以下であった。 塔頂からの留出液の臭いを確認した が、 全く確認されなかった。 The raw material used was crude acrylic acid containing 239 wt ppm of furfural and 238 wt ppm of benzaldehyde as impurities. Also, the aldehyde removal丟treatment agent, was used pure 9 9.5 wt 0/0 of n- dodecyl Melka-butane (n- Okuchirumeru Kabutan content 4 0 wt ppm). A sulfonated cation exchange resin (Mitsubishi Kagaku's cation exchange resin “PK-216 1”) was used as the acidic catalyst. The ion-exchange resin was passed through the packed tower. The amount of the aldehyde removing agent added was such that the amount of η-dodecyl mercaptan was equivalent to 5 times the molar concentration of the aldehyde. The flow was carried out at normal temperature and normal pressure at a speed of 50,000 kg Zh (residence time: 2 hours). Next, the liquid was sent to a packed column distillation apparatus to perform continuous distillation. In continuous distillation, a bottom temperature of 70 ° C., 9.9% by weight of the feed liquid were continuously distilled off, and a part of the distillate was used as a reflux liquid at a reflux ratio of 1.0 from the top of the column. It was introduced inside. At the time of continuous distillation, methquinone (methoxyhydroxyquinone) (polymerization inhibitor) corresponding to 10 ppm by weight with respect to the amount of liquid introduced into the distillation column was dissolved in the reflux liquid and introduced into the column. Both furfural and benzaldehyde in purified acrylic acid obtained as a distillate were 1 ppm by weight or less. The odor of the distillate from the top was confirmed, but not at all.
比較例 1  Comparative Example 1
実施例 1において、 アルデヒド除去処理剤として、 純度 9 8 . 5重量0 /0の n -ドデシルメルカブタン （n—ォクチルメルカブタン含有量 2 0 0 0重量 p p m、 n—デシルメルカブタン含有量 6 0 0 0重量 p p m) を使用した以外は、 実施例 1と同様に操作した。 塔頂からの留出液には悪臭が確認された。 留出液 の組成を確認した結果、 0 . 8重量 p p mの n—ォクチルメルカブタンが存在 していた。 産業上の利用可能性 In Example 1, as the aldehyde removal treatment agent, pure 9 8.5 wt 0/0 n -The same operation as in Example 1 was performed except that dodecyl mercaptan (n-octyl mercaptan content: 2000 ppm by weight, n-decyl mercaptan content: 600 ppm by weight) was used. An unpleasant odor was observed in the distillate from the top of the tower. As a result of confirming the composition of the distillate, it was found that 0.8 wt ppm of n-octyl mercaptan was present. Industrial applicability
本発明は、 粗 （メタ） アクリル酸中のアルデヒド類をアルデヒド除去処理剤 と反応させて他の化合物に変換させた後に蒸留処理する方法であり、 悪臭成分 を含まない高純度 （メタ） アクリル酸の製造方法として、 工業的価値が高い。  The present invention relates to a method of reacting aldehydes in crude (meth) acrylic acid with an aldehyde-removing agent to convert the aldehydes into another compound, followed by distillation treatment, and comprises a high-purity (meth) acrylic acid containing no malodorous component. It has a high industrial value as a method for producing.

Claims

請 求 の 範 囲 The scope of the claims
1 . 不純物としてアルデヒド類を含有する粗 （メタ） アクリル酸を蒸留処理し て高純度 （メタ） アクリル酸を製造するに当たり、 予め、 炭素数 1 2〜1 6の アルキルメルカブタンの含有量が 9 8重量％以上であり且つ炭素数 1 0以下の アルキルメルカブタンの含有量が 5， 0 0 0重量 p p m以下のアルデヒド除丟 処理剤および酸性触媒の存在下に粗 （メタ） アクリル酸を反応処理することを 特徴とする高純度 （メタ） アクリル酸の製造方法。 1. When crude (meth) acrylic acid containing aldehydes as impurities is subjected to distillation treatment to produce high-purity (meth) acrylic acid, the content of alkyl mercaptan having 12 to 16 carbon atoms must be 9 in advance. Reaction treatment of crude (meth) acrylic acid in the presence of an aldehyde-removing agent and an acidic catalyst having an alkyl mercaptan content of not less than 8 wt% and not more than 10 carbon atoms of not more than 50,000 wt ppm A method for producing high-purity (meth) acrylic acid.
2 . 酸性触媒がスルホン化陽イオン交換樹脂である 1に記載の製造方法。  2. The production method according to 1, wherein the acidic catalyst is a sulfonated cation exchange resin.
PCT/JP2003/000105 2002-01-15 2003-01-09 Process for producing high-purity (meth)acrylic acid WO2003059862A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0169254A1 (en) * 1984-07-21 1986-01-29 Mitsubishi Petrochemical Co., Ltd. Process for purification of 1,2-unsaturated carboxylic acids and/or esters thereof
JPH1087551A (en) * 1996-09-13 1998-04-07 Mitsubishi Rayon Co Ltd Purification of methacrylic acid
JP2001072643A (en) * 1999-09-01 2001-03-21 Mitsubishi Rayon Co Ltd Purification of methacrylic acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0169254A1 (en) * 1984-07-21 1986-01-29 Mitsubishi Petrochemical Co., Ltd. Process for purification of 1,2-unsaturated carboxylic acids and/or esters thereof
JPH1087551A (en) * 1996-09-13 1998-04-07 Mitsubishi Rayon Co Ltd Purification of methacrylic acid
JP2001072643A (en) * 1999-09-01 2001-03-21 Mitsubishi Rayon Co Ltd Purification of methacrylic acid

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