JP3781499B2 - Acrylic acid purification method - Google Patents
Acrylic acid purification method Download PDFInfo
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- JP3781499B2 JP3781499B2 JP02890297A JP2890297A JP3781499B2 JP 3781499 B2 JP3781499 B2 JP 3781499B2 JP 02890297 A JP02890297 A JP 02890297A JP 2890297 A JP2890297 A JP 2890297A JP 3781499 B2 JP3781499 B2 JP 3781499B2
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- Prior art keywords
- acrylic acid
- copper
- polymerization
- copper carbonate
- polymerization inhibitor
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Description
【０００１】
【発明の属する技術分野】
本発明は、アクリル酸の精製法に関する。詳しくは、重合禁止剤として、炭酸銅と特定の有機酸との接触混合液を用いるアクリル酸の精製法に関する。
【０００２】
【従来の技術】
アクリル酸の精製工程において酢酸銅の様な銅化合物或いは銅粉を重合禁止剤として用いる方法は古くから知られている。
しかしながら、大部分の銅化合物は水に難溶若しくは不溶であり、結果的に重合禁止剤として使用される銅化合物は酢酸銅、或いは、易水溶性として新たに合成した高価な銅化合物（例えば、ジブチルジチオカーバメイト銅等）が使用されているのみである。この中、最も汎用的な酢酸銅は、それ自身が熱的に分解を起こし、酢酸を発生し製品品質へ影響を与える可能性があるため、特開昭４９−１８８２０号公報においては、メタクリル酸製造工程での重合防止剤として、水酸化銅とメタクリル酸よりメタクリル酸銅を調製し、系内に添加する方法が提案されている。
【０００３】
【発明が解決しようとする課題】
このような背景の下、本発明は、重合禁止剤として安価で汎用的な銅化合物を用いるアクリル酸の精製法を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明者等は、上記課題を解決するために鋭意検討した結果、重合禁止剤として炭酸銅とアクリル酸とを攪拌下に混合して調製したアクリル酸銅を含む混合液を用いることにより優れた重合禁止効果が得られることを見出し、本発明を完成するに至った。即ち、本発明の要旨は、プロピレンの気相接触酸化反応により得られる粗アクリル酸を精製する方法において、重合禁止剤として、予め炭酸銅とアクリル酸とを攪拌下に混合して調製したアクリル酸銅を含む混合液の存在下（但し、アクリル酸を含む溶液に対する炭酸銅の使用量を２０〜３００ｐｐｍとする）、蒸留精製を行うことを特徴とするアクリル酸の精製法、にある。以下、本発明の方法について詳細に説明する。
【０００５】
【発明の実施の形態】
本発明に用いられる重合禁止剤は、炭酸銅とアクリル酸とを攪拌下に混合して調製したアクリル酸銅を含む混合液であるが、その原料である炭酸銅は下記化学式で表される化合物である。
【０００６】
【化１】
ｍＣｕＣＯ3 ・ｎＣｕ（ＯＨ）2 ・ｘＨ2 Ｏ
（通常、ＣｕＣＯ3 ・Ｃｕ（ＯＨ）2 ）
【０００７】
炭酸銅の使用量は、アクリル酸を含む溶液に対し２０ｐｐｍ以上３００ｐｐｍ以下の範囲より選ばれる。これより少ない量では、重合防止効果が十分ではなく、また、これより多い量では重合防止効果に差が無く、経済的に好ましくないばかりで無く、銅化合物の廃棄物も増える為、環境上も好ましくない。
【０００９】
アクリル酸は、市販の試薬を用いても気相接触反応により得られた粗製アクリル酸をそのまま用いても、また、粗製アクリル酸を蒸留精製したものを用いても良い。しかしながら、気相接触反応で得られた粗製アクリル酸を精製する方法にアクリル酸銅を調製し添加する場合には、粗製アクリル酸をそのまま用いる方法が経済的に好ましい。また、アクリル酸そのものとアクリル酸よりアクリル酸銅を調製出来るが、気相接触酸化反応で得られる反応液の様なアクリル酸の水溶液と炭酸銅からアクリル酸銅を調製することも出来る。また、高純度アクリル酸と水を適当な濃度に調製して得られるアクリル酸水溶液を用いることも出来る。
【００１０】
アクリル酸水溶液と炭酸銅よりアクリル酸銅を調製する場合、アクリル酸水溶液中のアクリル酸濃度は、用いる炭酸銅中の銅と等モル以上のアクリル酸が存在しておれば良いが、現実的には、１重量％以上、好ましくは５重量％以上のアクリル酸水溶液を用いるのが好ましい。
炭酸銅とアクリル酸或いはアクリル酸水溶液からのアクリル酸銅の調製方法は、特に制限は無いが、固（炭酸銅）・液（アクリル酸（水））の混合であるので撹拌槽にて混合する方法が好ましい。
【００１１】
混合温度は、炭酸銅とアクリル酸の反応速度を高める為には出来るだけ高温で行う方が好ましいが、好ましい温度範囲は、４０℃以上８０℃以下である。
また、混合時間は、混合温度により異なるが、通常、１分以上１時間以内より選ばれる。これより短いと炭酸銅とアクリル酸の反応が不十分となり、また、これより長くしても大きな効果が得られず、効率が悪くなるだけである。
【００１２】
本発明の方法では、重合防止剤として炭酸銅以外に、ハイドロキノン等のフェノール類、フェノチアジン、ジチオカーバメイト銅等の銅錯体、２，２，６，６，−テトラメチルピペリジン−１−オキシル等のＮ−オキシル化合物等の重合防止剤を併用できる。本発明の方法では、アクリル酸の精製工程にアクリル酸を配位子に持つ銅塩を添加するので、前記した様な酢酸銅を用いた場合に精製工程中に酢酸が留出する等不純物が系内に発生することが無く高品質のアクリル酸を製造する事が出来る。特に、アクリル酸回収塔の塔底液に存在するマイクル（Ｍｉｃｈａｅｌ）付加型の二量体、三量体等の多量体を高温で分解・回収・リサイクルする製造プロセスを含む工業的な製造方法に於いては、アクリル酸銅を使用する事による、上記したような酢酸等の不純物の発生・蓄積が無く好ましい。
【００１４】
【実施例】
以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。
【００１５】
実施例−１
プロピレン気相接触酸化法により得られた粗製アクリル酸を多段の蒸留塔にて精製して得られた高純度アクリル酸（純度＞９９％）と純水より７重量％アクリル酸水溶液を調製し、この水溶液９５．６ｇに炭酸銅０．６ｇ（５．０ｍｍｏｌ）及びハイドロキノン３．８ｇを添加して５０℃、３０分撹拌して重合禁止剤の水溶液を得た。一方、蒸留精製後のアクリル酸を更に冷却晶析して微量に含まれる重合禁止剤を除去した。この様にして得られた、高純度アクリル酸と先の重合禁止剤水溶液を２００：１で混ぜアンプル管に加え、空気雰囲気下、１３０℃で自己重合の誘導期間を測定した。測定は重合熱による発熱を温度で感知する方法で測定した。結果を表−１に示す。
【００１６】
比較例−１
実施例−１において炭酸銅の代わりに酢酸銅を１．０ｇ（５．０ｍｍｏｌ）及びハイドロキノン３．８ｇを廃酢酸９５．２ｇに添加した以外は実施例−１と同様の方法でアクリル酸の自己重合の誘導期間を測定した。結果を表−１に示す。
【００１７】
比較例−２
ハイドロキノン１９０ｐｐｍを上記晶析処理したアクリル酸に添加した以外は実施例−１と同様の方法でアクリル酸の自己重合の誘導期間を測定した。結果を表−１に示す。
【００１８】
比較例−３
酢酸銅５０ｐｐｍを上記晶析処理したアクリル酸に添加した以外は実施例−１と同様の方法でアクリル酸の自己重合の誘導期間を測定した。結果を表−１に示す。
【００１９】
実施例−２
実施例−１の方法において７％のアクリル酸水溶液の代わりに高純度アクリル酸そのものと炭酸銅よりアクリル酸銅を調製する以外は同様の方法で自己重合の誘導期間を測定した。結果を表−１に示す。
【００２０】
【表１】
【発明の効果】
本発明によれば、粗アクリル酸を蒸留精製する方法において、重合禁止剤として安価な炭酸銅とアクリル酸とを接触させた混合液を用いることにより酢酸銅と同等以上の重合禁止効果を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for purifying acrylic acid. Specifically, the present invention relates to a method for purifying acrylic acid using a contact liquid mixture of copper carbonate and a specific organic acid as a polymerization inhibitor.
[0002]
[Prior art]
A method of using a copper compound such as copper acetate or copper powder as a polymerization inhibitor in the purification step of acrylic acid has been known for a long time.
However, most copper compounds are insoluble or insoluble in water, and as a result, copper compounds used as polymerization inhibitors are copper acetate or expensive copper compounds newly synthesized as readily water-soluble (for example, Only dibutyldithiocarbamate copper) is used. Among these, the most general-purpose copper acetate itself may thermally decompose and generate acetic acid, which may affect the product quality. Therefore, in Japanese Patent Laid-Open No. 49-18820, methacrylic acid is used. As a polymerization inhibitor in the production process, a method of preparing copper methacrylate from copper hydroxide and methacrylic acid and adding it to the system has been proposed.
[0003]
[Problems to be solved by the invention]
Under such a background, an object of the present invention is to provide a method for purifying acrylic acid using an inexpensive and general-purpose copper compound as a polymerization inhibitor.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems, the present inventors have been excellent by using a mixed liquid containing copper acrylate prepared by mixing copper carbonate and acrylic acid under polymerization as a polymerization inhibitor. The inventors have found that a polymerization inhibition effect can be obtained, and have completed the present invention. That is, the gist of the present invention is an acrylic acid prepared by previously mixing copper carbonate and acrylic acid under stirring as a polymerization inhibitor in a method for purifying crude acrylic acid obtained by vapor phase catalytic oxidation reaction of propylene. In the purification method of acrylic acid, the distillation purification is performed in the presence of a mixed solution containing copper (however, the amount of copper carbonate used in the solution containing acrylic acid is 20 to 300 ppm) . Hereinafter, the method of the present invention will be described in detail.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The polymerization inhibitor used in the present invention is a mixed solution containing copper acrylate prepared by mixing copper carbonate and acrylic acid under stirring , but the raw material copper carbonate is a compound represented by the following chemical formula It is.
[0006]
[Chemical 1]
mCuCO 3 · nCu (OH) 2 · xH 2 O
(Usually CuCO 3 · Cu (OH) 2 )
[0007]
The amount of copper carbonate is selected from the solution pair to a range of 20 ppm or more 300ppm or less comprising acrylic acid. If the amount is less than this, the polymerization preventing effect is not sufficient, and if the amount is larger than this, there is no difference in the polymerization preventing effect, which is not economically preferable, and the waste of the copper compound also increases. It is not preferable.
[0009]
As the acrylic acid, a commercially available reagent may be used, or crude acrylic acid obtained by gas phase contact reaction may be used as it is, or a crude acrylic acid obtained by distillation purification may be used. However, when copper acrylate is prepared and added to a method for purifying crude acrylic acid obtained by gas phase contact reaction, a method using crude acrylic acid as it is is economically preferable. Further, although copper acrylate can be prepared from acrylic acid itself and acrylic acid, copper acrylate can also be prepared from an aqueous solution of acrylic acid and copper carbonate, such as a reaction solution obtained by a gas phase catalytic oxidation reaction. Further, an aqueous acrylic acid solution obtained by preparing high-purity acrylic acid and water at appropriate concentrations can also be used.
[0010]
When preparing copper acrylate from an acrylic acid aqueous solution and copper carbonate, the acrylic acid concentration in the acrylic acid aqueous solution should be equal to or greater than the molar amount of acrylic acid in the copper carbonate used. Is preferably 1% by weight or more, preferably 5% by weight or more of an acrylic acid aqueous solution.
Although there is no restriction | limiting in particular in the preparation method of copper acrylate from copper carbonate and acrylic acid or acrylic acid aqueous solution, Since it is mixing of solid (copper carbonate) and liquid (acrylic acid (water)), it mixes with a stirring tank. The method is preferred.
[0011]
The mixing temperature is preferably as high as possible in order to increase the reaction rate of copper carbonate and acrylic acid, but the preferable temperature range is 40 ° C. or higher and 80 ° C. or lower.
The mixing time varies depending on the mixing temperature, but is usually selected from 1 minute to 1 hour. If it is shorter than this, the reaction between copper carbonate and acrylic acid becomes insufficient, and if it is longer than this, a large effect cannot be obtained, and the efficiency only deteriorates.
[0012]
In the method of the present invention, in addition to copper carbonate as a polymerization inhibitor, phenols such as hydroquinone, copper complexes such as phenothiazine and dithiocarbamate copper, and N such as 2,2,6,6, -tetramethylpiperidine-1-oxyl -A polymerization inhibitor such as an oxyl compound can be used in combination. In the method of the present invention, since a copper salt having acrylic acid as a ligand is added to the purification step of acrylic acid, impurities such as acetic acid distilled out during the purification step when copper acetate as described above is used. High quality acrylic acid can be produced without being generated in the system. In particular, an industrial manufacturing method including a manufacturing process for decomposing, recovering and recycling multimers such as Michael addition dimers and trimers present in the bottom liquid of an acrylic acid recovery tower at high temperatures. In this case, it is preferable to use copper acrylate because there is no generation or accumulation of impurities such as acetic acid as described above.
[0014]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to these Examples, unless the summary is exceeded.
[0015]
Example-1
A 7% by weight aqueous acrylic acid solution was prepared from high-purity acrylic acid (purity> 99%) obtained by purifying crude acrylic acid obtained by the propylene gas phase catalytic oxidation method in a multistage distillation column and pure water, To 95.6 g of this aqueous solution, 0.6 g (5.0 mmol) of copper carbonate and 3.8 g of hydroquinone were added and stirred at 50 ° C. for 30 minutes to obtain an aqueous solution of a polymerization inhibitor. On the other hand, the acrylic acid after distillation purification was further cooled and crystallized to remove the polymerization inhibitor contained in a trace amount. The high-purity acrylic acid and the aqueous polymerization inhibitor solution thus obtained were mixed at a ratio of 200: 1, added to an ampule tube, and the self-polymerization induction period was measured at 130 ° C. in an air atmosphere. The measurement was performed by a method in which an exotherm due to the heat of polymerization was detected by temperature. The results are shown in Table-1.
[0016]
Comparative Example-1
In Example 1, instead of copper carbonate, 1.0 g (5.0 mmol) of copper acetate and 3.8 g of hydroquinone were added to 95.2 g of waste acetic acid. The induction period of polymerization was measured. The results are shown in Table-1.
[0017]
Comparative Example-2
The induction period of self-polymerization of acrylic acid was measured in the same manner as in Example 1 except that 190 ppm of hydroquinone was added to the crystallized acrylic acid. The results are shown in Table-1.
[0018]
Comparative Example-3
The induction period of self-polymerization of acrylic acid was measured in the same manner as in Example 1 except that 50 ppm of copper acetate was added to the crystallized acrylic acid. The results are shown in Table-1.
[0019]
Example-2
The induction period of self-polymerization was measured in the same manner as in Example 1 except that copper acrylate was prepared from high-purity acrylic acid itself and copper carbonate instead of 7% acrylic acid aqueous solution. The results are shown in Table-1.
[0020]
[Table 1]
【The invention's effect】
According to the present invention, in a method for distilling and purifying crude acrylic acid, a polymerization inhibition effect equal to or higher than that of copper acetate can be obtained by using a mixed solution obtained by contacting inexpensive copper carbonate and acrylic acid as a polymerization inhibitor. Can do.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02890297A JP3781499B2 (en) | 1997-02-13 | 1997-02-13 | Acrylic acid purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP02890297A JP3781499B2 (en) | 1997-02-13 | 1997-02-13 | Acrylic acid purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10218832A JPH10218832A (en) | 1998-08-18 |
| JP3781499B2 true JP3781499B2 (en) | 2006-05-31 |
Family
ID=12261349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP02890297A Expired - Lifetime JP3781499B2 (en) | 1997-02-13 | 1997-02-13 | Acrylic acid purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3781499B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100389848C (en) | 2001-10-30 | 2008-05-28 | 三菱化学株式会社 | Method for purifying (meth) acrylic acid |
| FR3015490B1 (en) * | 2013-12-20 | 2016-01-15 | Coatex Sas | PROCESS FOR POLYMERIZING (METH) ACRYLIC ACID IN SOLUTION |
-
1997
- 1997-02-13 JP JP02890297A patent/JP3781499B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10218832A (en) | 1998-08-18 |
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