JPH04187657A - Purification of acrylic acid - Google Patents
Purification of acrylic acidInfo
- Publication number
- JPH04187657A JPH04187657A JP31432690A JP31432690A JPH04187657A JP H04187657 A JPH04187657 A JP H04187657A JP 31432690 A JP31432690 A JP 31432690A JP 31432690 A JP31432690 A JP 31432690A JP H04187657 A JPH04187657 A JP H04187657A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- water
- distillation
- acetic acid
- column
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000746 purification Methods 0.000 title abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 93
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000004821 distillation Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000011109 contamination Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 20
- 239000007788 liquid Substances 0.000 description 15
- 235000019260 propionic acid Nutrition 0.000 description 10
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012223 aqueous fraction Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はアクリル酸の精製方法に関し、詳しくは、アク
リル酸の製造工程で生ずる副反応生成物である酢酸や、
製造工程で用いられる水などを簡単な蒸留操作だけで分
離してアクリル酸を効率よく精製する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for purifying acrylic acid, and more specifically, the present invention relates to a method for purifying acrylic acid.
This invention relates to a method for efficiently purifying acrylic acid by separating water and the like used in the manufacturing process with a simple distillation operation.
〔従来の技術及び発明が解決しようとする課題〕アクリ
ル酸は、プロピレンやアクロレインを、酸化触媒および
水蒸気の存在下、分子状酸素で酸化することにより得ら
れるか、このとき副反応生成物として、酢酸、ギ酸、プ
ロピオン酸、アセトアルデヒド、ホルムアルデヒド、二
酸化炭素、−酸化炭素なとか同時に生成される。このよ
うな反応生成物および未反応のプロピレンやアクロレイ
ンを含む混合ガスを冷却して水に吸収させると、アクリ
ル酸、酢酸、ギ酸、プロピオン酸およびアルデヒド類な
どを含む水溶液（粗アクリル酸）か得られる。[Prior art and problems to be solved by the invention] Acrylic acid can be obtained by oxidizing propylene or acrolein with molecular oxygen in the presence of an oxidation catalyst and water vapor, or as a side reaction product. Acetic acid, formic acid, propionic acid, acetaldehyde, formaldehyde, carbon dioxide, and carbon oxide are produced simultaneously. When this reaction product and a mixed gas containing unreacted propylene and acrolein are cooled and absorbed in water, an aqueous solution (crude acrylic acid) containing acrylic acid, acetic acid, formic acid, propionic acid, aldehydes, etc. is obtained. It will be done.
したかって、アクリル酸の製造にあたっては、最終的に
上記粗アクリル酸水溶液からアクリル酸を分離して精製
する工程か必要である。ところか水−酢酸−アクリル酸
の系では、各々の沸点が、１００−１１８−１４１°Ｃ
てあり、また各成分の２成分系気液平衡の関係から、蒸
留操作により水−酢酸の留分をアクリル酸から分離でき
ることが予想されながらも、実際には容易に分離するこ
とかできず、従来は抽出法や共沸蒸留法によりアクリル
酸の精製を行っているのか実情である。Therefore, in producing acrylic acid, a final step is required to separate and purify acrylic acid from the crude aqueous acrylic acid solution. However, in the water-acetic acid-acrylic acid system, the boiling points of each are 100-118-141°C.
Although it was expected that the water-acetic acid fraction could be separated from acrylic acid by distillation due to the two-component gas-liquid equilibrium relationship of each component, in reality it was not possible to separate it easily. The reality is that acrylic acid has traditionally been purified using extraction methods or azeotropic distillation methods.
しかし上記抽出法は、大規模な設備を必要とするたけて
なく、消費エネルギーも多大であるという欠点を有して
いる。However, the above extraction method has the drawbacks of requiring large-scale equipment and consuming a large amount of energy.
一方の共沸蒸留法は、特公昭６３−１０６９１号公報に
記載されるように、たとえばトルエンなとの共沸剤を添
加して蒸留操作を行い、アクリル酸と酢酸との分離を容
易にするものであるか、酢酸とアクリル酸とを分離する
という点ては効果的であるものの、共沸剤の回収設備か
必要であることと、精製後のアクリル酸に微量の共沸剤
が残留するという欠点かある。On the other hand, in the azeotropic distillation method, as described in Japanese Patent Publication No. 63-10691, a distillation operation is carried out by adding an azeotropic agent such as toluene to facilitate the separation of acrylic acid and acetic acid. Although it is effective in separating acetic acid and acrylic acid, it requires equipment to recover the entrainer, and a small amount of entrainer remains in the purified acrylic acid. There is a drawback.
そこで本発明者らは、前述の水−酢酸−アクリル酸の３
成分系の挙動に注目し、基礎的な２，３成分系の気液平
衡データの測定により、水の分率かある特定のところで
酢酸の濃縮に分岐点かあることを見出した。本発明は、
この知見に基ついて成されたものである。Therefore, the present inventors investigated the above-mentioned water-acetic acid-acrylic acid 3
By focusing on the behavior of component systems and measuring basic gas-liquid equilibrium data for two- and three-component systems, we found that there was a branching point in the concentration of acetic acid at a certain water fraction. The present invention
This study was based on this knowledge.
すなわち本発明は、酢酸および水を含有するアクリル酸
を蒸留により精製するにあたり、第１段の蒸留塔の塔底
から酢酸および１０重量％の以下の水を含有するアクリ
ル酸を缶出させ、この缶出物を第２の蒸留塔に供給し、
該第２の蒸留塔の塔頂から水および酢酸を留出させると
ともに、塔底からアクリル酸を缶出させることを特徴と
する方法を提供するものである。That is, in purifying acrylic acid containing acetic acid and water by distillation, the present invention allows acrylic acid containing acetic acid and less than 10% by weight of water to be taken out from the bottom of the first stage distillation column, and feeding the bottoms to a second distillation column;
The present invention provides a method characterized in that water and acetic acid are distilled out from the top of the second distillation column, and acrylic acid is distilled out from the bottom of the column.
まず、本発明ては、通常のアクリル酸製造工程を経て得
られる粗アクリル酸水溶液を原料として用いればよい。First, in the present invention, a crude acrylic acid aqueous solution obtained through a normal acrylic acid production process may be used as a raw material.
すなわち、前述のように、プロピレンやアクロレインを
酸化触媒および水蒸気の存在下、分子状酸素で酸化し、
得られた反応生成物および未反応のプロピレンやアクロ
レインを含む混合ガスを水に吸収させて粗アクリル酸を
得る。That is, as mentioned above, propylene and acrolein are oxidized with molecular oxygen in the presence of an oxidation catalyst and water vapor,
The resulting reaction product and a mixed gas containing unreacted propylene and acrolein are absorbed in water to obtain crude acrylic acid.
本発明では、このようにして得た粗アクリル酸を水や酢
酸を分離して精製し、高純度のアクリル酸を得るもので
あるか、この粗アクリル酸を得るまでの工程は従来と同
様にして行うことかできる。In the present invention, the crude acrylic acid obtained in this way is purified by separating water and acetic acid to obtain highly pure acrylic acid, or the process to obtain this crude acrylic acid is the same as conventional methods. You can do it.
また、このようにして得られたアクリル酸、酢酸。Also, acrylic acid and acetic acid obtained in this way.
水などを含む粗アクリル酸は、必要に応じてストリッピ
ング処理を行い、アルデヒド類を除去した後に本発明の
精製工程に供される。Crude acrylic acid containing water and the like is subjected to a stripping treatment as necessary to remove aldehydes, and then subjected to the purification process of the present invention.
本発明では、水、酢酸、アクリル酸を含む粗アクリル酸
を蒸留してアクリル酸を分離精製するものであるか、こ
のときの水の含有量は、通常全体の３０〜６０重量％で
ある。In the present invention, acrylic acid is separated and purified by distilling crude acrylic acid containing water, acetic acid, and acrylic acid, and the water content at this time is usually 30 to 60% by weight of the total.
第１の蒸留塔における操作条件は、粗アクリル酸の組成
、蒸留後の所望の水含有量により異なるか、通常は塔頂
温度を４０〜６０°Ｃ１塔底温度を８０〜１００″Ｃ２
圧力を５０〜１５０ｍｍＨｇ、還流比を０．１〜１０の
範囲に設定すればよい。このような条件下で蒸留を行う
ことにより、塔頂部から水、酢酸、プロピオン酸か留出
し、塔底部から酢酸および水を１０重量％以下、好まし
くは酢酸および水を０．１〜７重量％含有するアクリル
酸からなる缶出液を得ることかできる。水の含有量か１
０重量％を越えると、第２の蒸留塔でのエネルギー負荷
か増加し、水の含有量か極端に多くなると、酢酸の分離
かできな（なるので好ましくない。The operating conditions in the first distillation column vary depending on the composition of the crude acrylic acid and the desired water content after distillation, and usually the top temperature is 40-60°C, the bottom temperature is 80-100"C2
The pressure may be set in the range of 50 to 150 mmHg, and the reflux ratio may be set in the range of 0.1 to 10. By performing distillation under these conditions, water, acetic acid, and propionic acid are distilled out from the top of the column, and acetic acid and water are distilled out from the bottom of the column at 10% by weight or less, preferably from 0.1 to 7% by weight. It is possible to obtain a bottom liquor consisting of acrylic acid. Water content 1
If it exceeds 0% by weight, the energy load on the second distillation column will increase, and if the water content becomes extremely high, it will not be possible to separate acetic acid, which is not preferable.
次にこのように水の含有量を調節した粗アクリル酸を第
２の蒸留塔に供給し、該第２の蒸留塔における蒸留操作
により、塔頂から水および酢酸を留出させるとともに、
塔底から精製アクリル酸を缶出させる。この第２の蒸留
塔における操作条件は、製造工程あるいは第１の蒸留塔
から供給される粗アクリル酸の組成により異なるか、通
常は塔頂温度を４０〜６０°Ｃ２塔底温度を８０〜１０
０°Ｃ１圧力を５０〜１５０ｍｍＨｇ、還流比を１０〜
１５０の範囲に設定すればよい。このような条件下で蒸
留を行うことにより、塔頂部から水および酢酸を留出さ
せ、塔底部からは缶出液としてアクリル酸を得ることか
できる。Next, the crude acrylic acid with the water content adjusted in this way is supplied to a second distillation column, and water and acetic acid are distilled out from the top of the column by a distillation operation in the second distillation column.
Purified acrylic acid is discharged from the bottom of the tower. The operating conditions in this second distillation column vary depending on the manufacturing process or the composition of the crude acrylic acid supplied from the first distillation column, and usually the top temperature is 40-60°C2 the bottom temperature is 80-10°C.
0°C1 pressure 50~150mmHg, reflux ratio 10~
It may be set within the range of 150. By carrying out distillation under such conditions, water and acetic acid can be distilled out from the top of the column, and acrylic acid can be obtained as bottoms from the bottom of the column.
このように、本発明においては、共沸剤を用いることな
く水含有量を調整した状態て最終的な蒸留を行うたけて
アクリル酸を分離精製することかできるため、精製後の
アクリル酸に共沸剤、たとえばトルエン等が混入するこ
とか全くない。As described above, in the present invention, acrylic acid can be separated and purified before the final distillation with the water content adjusted without using an entrainer. There is no possibility of contamination with boiling agents such as toluene.
なお、粗アクリル酸における水含有量か上記のように３
０〜６０重量％の範囲内であれば２回の蒸留操作でアク
リル酸の精製を行うことかでき、水やアクリル酸の含有
量によっては３段階以上の蒸留操作を行ってもよい。In addition, the water content in crude acrylic acid is 3 as described above.
If the content is within the range of 0 to 60% by weight, acrylic acid can be purified by two distillation operations, and depending on the content of water and acrylic acid, three or more stages of distillation operations may be performed.
次に、本発明の詳細な説明する。 Next, the present invention will be explained in detail.
本実施例に使用した精製装置の構成を第１図に示す。こ
の精製装置は、第１の蒸留塔である脱水塔１０と、第２
の蒸留塔である脱酢酸基２０とを備えたもので、それぞ
れのトレイ段数は１８段とした。脱水塔１０の操作条件
は、塔頂部の圧力か８０ｍｍＨｇ、温度が４７°Ｃ１塔
底部の圧力か１５０ｍｍＨｇ、温度か９２°Ｃであり、
還流比は１．３２である。また、脱酢酸基２０は塔頂部
の圧力か５０ｍｍＨｇ、温度か５ピＣ１塔底部の圧力か
１１０ ｍｍＨｇ。The configuration of the purification apparatus used in this example is shown in FIG. This purification apparatus includes a dehydration tower 10, which is a first distillation tower, and a second distillation tower.
The distillation column was equipped with 20 deacetating groups, and the number of trays in each tray was 18. The operating conditions of the dehydration tower 10 are as follows: pressure at the top of the tower is 80 mmHg, temperature is 47°C, pressure at the bottom of the tower is 150 mmHg, and temperature is 92°C.
The reflux ratio is 1.32. In addition, the pressure of the deacetate group 20 at the top of the column was 50 mmHg, and the temperature was 110 mmHg at the bottom of the column.
温度が８８°Ｃてあり、還流比は１２１である。The temperature is 88°C and the reflux ratio is 121.
まず、アクリル酸、酢酸、水及びプロピオン酸を含む粗
アクリル酸を、粗アクリル酸供給管１１から脱水塔ｌＯ
の１５５段目トレイ部分に導入した。この粗アクリル酸
における上記成分の導入量は、アクリル酸３９．９９
ｇ／ｈ、酢酸２．００ ｇ／ｈ。First, crude acrylic acid containing acrylic acid, acetic acid, water and propionic acid is transferred from the crude acrylic acid supply pipe 11 to the dehydration tower lO
It was introduced into the 155th tray section of the 155th tray. The amount of the above components introduced into this crude acrylic acid was 39.99% of the acrylic acid.
g/h, acetic acid 2.00 g/h.
水３３．６９ ｇ／ｈ、 プロピオン酸０．０１ ｇ
／ｈとした。また、重合防止剤としてハイドロキノンを
用い、粗アクリル酸に０．０４ ｇ／ｈの量で混合した
。Water 33.69 g/h, propionic acid 0.01 g
/h. Further, hydroquinone was used as a polymerization inhibitor and was mixed with the crude acrylic acid in an amount of 0.04 g/h.
脱水塔１０の塔頂部の留出流体および還流液に合計０．
０６ ｇ／ｈの量でハイドロキノンを１．６３ｇ／ｈの
水とともに導入した。A total of 0.0% is added to the distillate fluid and reflux liquid at the top of the dehydration tower 10.
Hydroquinone was introduced in an amount of 0.06 g/h together with 1.63 g/h of water.
この脱水塔１０の塔頂部には、主として水が濃縮されて
管１２から導出され、冷却器１３て４゜°Ｃに冷却され
た後、気液分離器１４に導入される。Mainly water is concentrated at the top of the dehydration tower 10 and led out through a pipe 12, cooled to 4° C. by a cooler 13, and then introduced into a gas-liquid separator 14.
該気液分離器１４て分離した気相部に含まれる水０．２
１ｇ／ｈは管１５から排出され、気液分離器１４の液相
部は、ポンプ１６により抜き出されて、その一部か脱水
塔１０の塔頂部に還流し、残部が管１７から排出される
。この管１７から排出される廃液は、水３５．０１ ｇ
／ｈとプロピオン酸０．０１ｇ／ｈ、すなわち脱水塔１
０に導入されたほとんどの水とプロピオン酸とを含み、
ゎずかにアクリル酸０．２ｇ／ｈを含むものであった。Water contained in the gas phase separated by the gas-liquid separator 14 is 0.2
1 g/h is discharged from pipe 15, the liquid phase of gas-liquid separator 14 is extracted by pump 16, part of it is refluxed to the top of dehydration tower 10, and the remainder is discharged from pipe 17. Ru. The waste liquid discharged from this pipe 17 is 35.01 g of water.
/h and propionic acid 0.01g/h, that is, dehydration tower 1
containing most of the water and propionic acid introduced into the
It contained only 0.2 g/h of acrylic acid.
一方、塔底部から導出した缶出液の一部は、ポンプ１８
．加熱器１９を介して加熱された後に、再び１８８段目
トレイ部分に導入され、残部の缶出液か、ポンプ２１．
管２２を経て脱酢酸基２０の９段目のトレイ部分に導入
される。この管２２−により脱酢酸基２０に導入された
液は、アクリル酸３９．７９ ｇ／ｈ、酢酸２．００
ｇ／ｈ、水０．１８／ｈを含むもので、プロピオン酸は
ほとんど含まれていない状態となっている。このときの
水分含有量は、全液量に対して、約０．２重量％である
。On the other hand, a part of the bottoms drawn out from the bottom of the column is transferred to the pump 18.
．． After being heated through the heater 19, it is again introduced into the 188th tray section, and the remaining bottoms are pumped into the pump 21.
It is introduced into the ninth tray section of the deacetating group 20 through the pipe 22. The liquid introduced into the deacetic acid group 20 through this tube 22- is 39.79 g/h of acrylic acid and 2.00 g/h of acetic acid.
g/h, water 0.18/h, and almost no propionic acid. The water content at this time is about 0.2% by weight based on the total liquid amount.
脱酢酸基２０による蒸留操作ては、塔頂部に主として酢
酸か濃縮され、留出分として管２３から導出される。重
合防止剤としてはフェノチアジンを用い、脱酢酸基２０
の塔頂留出流体と還流液に合計０．０４ ｇ／ｈの量て
３．１６ ｇ／ｈのアクリル酸とともに導入した。この
留出分は、冷却器２４て４０°Ｃに冷却された後、気液
分離器２５に導入される。In the distillation operation using the acetic acid removal group 20, acetic acid is mainly concentrated at the top of the column and is discharged from a pipe 23 as a distillate. Phenothiazine is used as a polymerization inhibitor, and 20
A total of 0.04 g/h of acrylic acid was introduced into the overhead stream and reflux of 3.16 g/h of acrylic acid. This distillate is cooled to 40° C. in a cooler 24 and then introduced into a gas-liquid separator 25.
気液分離器２５で分離した気相部に含まれる酢酸０．９
１ ｇ／ｈと水０．０６ ｇ／ｈおよびアクリル酸０．
１９ ｇ／ｈは、管２６から排出される。また気液分離
器２５て分離した液相部は、ポンプ２７により抜き出さ
れて、その一部か脱酢酸基２０の塔頂部に還流し、残部
か管２８から排出される。この管２８から排出される廃
液は、酢酸１．０８ ｇ／ｈと水０．０４ ｇ／ｈおよ
びアクリル酸０．４０ ｇ／ｈを含むものであった。す
なわち、脱酢酸基２ｏに導入された酢酸と水のほとんど
は、上記管２６および管２８から排出されることになる
。Acetic acid contained in the gas phase separated by the gas-liquid separator 25: 0.9
1 g/h and 0.06 g/h of water and 0.06 g/h of acrylic acid.
19 g/h are discharged from line 26. The liquid phase separated by the gas-liquid separator 25 is extracted by a pump 27, a part of which is refluxed to the top of the acetate removal column 20, and the remainder is discharged from a pipe 28. The waste liquid discharged from this pipe 28 contained 1.08 g/h of acetic acid, 0.04 g/h of water and 0.40 g/h of acrylic acid. That is, most of the acetic acid and water introduced into the deacetating group 2o are discharged from the pipes 26 and 28.
一方、脱酢酸基２０の塔底には、この脱酢酸基２０にお
ける蒸留操作によりアクリル酸か濃縮され、缶出液とし
て管２９から導出される。管２９がら導出された缶出液
は、その一部かポンプ３０゜加熱器３１を介して加熱さ
れた後に１８８段目トレイ部分に再び導入され、残部の
缶出液が、ポンプ３２．管３３を経て回収される。On the other hand, acrylic acid is concentrated at the bottom of the column of the deacetate group 20 by the distillation operation in the deacetate group 20, and is led out from a pipe 29 as a bottom liquid. A portion of the bottoms drawn out from the pipe 29 is heated via the pump 30° heater 31 and then reintroduced into the 188th tray section, and the remaining bottoms are heated by the pump 32. It is collected via tube 33.
以上のような２段の蒸留操作によって精製アクリル酸４
２．３５ｇ／ｈを管３３がら回収することができた。こ
の時のアクリル酸の回収率は、約９８％であり、得られ
たアクリル酸中の酢酸とプロピオン酸はいずれも数ｐｐ
ｍであり、水はほとんと混入していなかった。また、当
然のことながら、従来のアクリル酸の精製に用いられて
いるトルエンなどの共沸剤成分は、全く含まれていない
。Purified acrylic acid 4 is obtained by the two-stage distillation operation as described above.
It was possible to recover 2.35 g/h from tube 33. The recovery rate of acrylic acid at this time was about 98%, and the acetic acid and propionic acid in the obtained acrylic acid were both several pp.
m, and almost no water was mixed in. Furthermore, as a matter of course, the entrainer component such as toluene used in conventional purification of acrylic acid is not included at all.
なお、上記実施例において、脱水塔１０の加熱器】９お
よび脱酢酸基２０の加熱器３１に要した熱負荷は、７１
．３１ ｋｃａｌ／ｈてあった。In the above example, the heat load required for the heater 9 of the dehydration tower 10 and the heater 31 of the deacetate group 20 was 71
．． It was 31 kcal/h.
以上説明したように、本発明によれば、蒸留という単純
なプロセスでアクリル酸の精製を行うことかできる。し
かもプロピオン酸の混入量か少なく、共沸剤を用いない
ので、共沸剤成分の混入か全くない高純度のアクリル酸
を得ることかてきる。As explained above, according to the present invention, acrylic acid can be purified by a simple process of distillation. Moreover, since the amount of propionic acid mixed in is small and no entrainer is used, it is possible to obtain highly pure acrylic acid with no entrainer components mixed in at all.
また、簡単な装置構成で実施することが可能であり、消
費エネルギーも僅かで済むため、低コストでアクリル酸
の精製を行うことかできる。Furthermore, it can be carried out with a simple device configuration and consumes only a small amount of energy, so that acrylic acid can be purified at low cost.
第１図は実施例で用いた精製装置の構成を示す系統図で
ある。
１０・脱水塔
１１：粗アクリル酸供給管
１２．１５．１？、２２，２３，２６，２８゜２９．３
３：管
１３．２４：冷却器
１４．２５：気液分離器
１６、 １８． ２１． ２７． ３０． ３２．ポン
プ１９．３１：加熱器
２０：脱酢酸基
特許出願人 出光石油化学株式会社
代理人 弁理士 大 谷 保FIG. 1 is a system diagram showing the configuration of a purification apparatus used in Examples. 10. Dehydration tower 11: Crude acrylic acid supply pipe 12.15.1? , 22, 23, 26, 28° 29.3
3: Pipe 13. 24: Cooler 14. 25: Gas-liquid separator 16, 18. 21. 27. 30. 32. Pump 19.31: Heater 20: Deacetate group Patent applicant: Idemitsu Petrochemical Co., Ltd. Agent Patent attorney: Tamotsu Otani
Claims (1)
精製するにあたり、第１段の蒸留塔の塔底から酢酸およ
び１０重量％の以下の水を含有するアクリル酸を缶出さ
せ、この缶出物を第２の蒸留塔に供給し、該第２の蒸留
塔の塔頂から水および酢酸を留出させるとともに、塔底
からアクリル酸を缶出させることを特徴とするアクリル
酸の精製方法。(1) In purifying acrylic acid containing acetic acid and water by distillation, the acrylic acid containing acetic acid and 10% by weight or less of water is taken out from the bottom of the first-stage distillation column. A method for purifying acrylic acid, which comprises supplying a substance to a second distillation column, distilling water and acetic acid from the top of the second distillation column, and distilling acrylic acid from the bottom of the column.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2314326A JP2980366B2 (en) | 1990-11-21 | 1990-11-21 | Acrylic acid purification method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2314326A JP2980366B2 (en) | 1990-11-21 | 1990-11-21 | Acrylic acid purification method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04187657A true JPH04187657A (en) | 1992-07-06 |
| JP2980366B2 JP2980366B2 (en) | 1999-11-22 |
Family
ID=18051991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2314326A Expired - Fee Related JP2980366B2 (en) | 1990-11-21 | 1990-11-21 | Acrylic acid purification method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2980366B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010503692A (en) * | 2006-09-15 | 2010-02-04 | ダウ グローバル テクノロジーズ インコーポレイティド | Acrylic acid production method |
| JP2012504618A (en) * | 2008-10-01 | 2012-02-23 | アーケマ・インコーポレイテッド | Control the process to purify (meth) acrylic acid using online near infrared analysis |
| JP2013049665A (en) * | 2011-07-14 | 2013-03-14 | Rohm & Haas Co | Method for removal of organic compound from waste water stream in process for production of (meth)acrylic acid |
| WO2018118700A1 (en) * | 2016-12-22 | 2018-06-28 | Eastman Chemical Company | Separation of propionic acid from acrylic acid via azeotropic distillation |
| CN110088074A (en) * | 2016-12-22 | 2019-08-02 | 庄信万丰戴维科技有限公司 | The method for purifying unsaturated carboxylic acid |
| CN110099889A (en) * | 2016-12-22 | 2019-08-06 | 伊士曼化工公司 | It is purified via the acrylic acid of dividing wall column |
-
1990
- 1990-11-21 JP JP2314326A patent/JP2980366B2/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010503692A (en) * | 2006-09-15 | 2010-02-04 | ダウ グローバル テクノロジーズ インコーポレイティド | Acrylic acid production method |
| US10294185B2 (en) | 2008-10-01 | 2019-05-21 | Arkema Inc. | Control of a process for the purification of (meth)acrylic acid using on-line, near IR analysis |
| JP2015063539A (en) * | 2008-10-01 | 2015-04-09 | アーケマ・インコーポレイテッド | Method for producing (meth)acrylic acid |
| US9745244B2 (en) | 2008-10-01 | 2017-08-29 | Arkeme Inc. | Control of a process for the purification of (meth)acrylic acid using on-line, near IR analysis |
| JP2012504618A (en) * | 2008-10-01 | 2012-02-23 | アーケマ・インコーポレイテッド | Control the process to purify (meth) acrylic acid using online near infrared analysis |
| JP2013049665A (en) * | 2011-07-14 | 2013-03-14 | Rohm & Haas Co | Method for removal of organic compound from waste water stream in process for production of (meth)acrylic acid |
| WO2018118700A1 (en) * | 2016-12-22 | 2018-06-28 | Eastman Chemical Company | Separation of propionic acid from acrylic acid via azeotropic distillation |
| CN110088074A (en) * | 2016-12-22 | 2019-08-02 | 庄信万丰戴维科技有限公司 | The method for purifying unsaturated carboxylic acid |
| CN110088075A (en) * | 2016-12-22 | 2019-08-02 | 伊士曼化工公司 | Propionic acid and acrylic acid are separated via azeotropic distillation |
| CN110099889A (en) * | 2016-12-22 | 2019-08-06 | 伊士曼化工公司 | It is purified via the acrylic acid of dividing wall column |
| US10968160B2 (en) | 2016-12-22 | 2021-04-06 | Eastman Chemical Company | Separation of propionic acid from acrylic acid via azeotropic distillation |
| US11214534B2 (en) | 2016-12-22 | 2022-01-04 | Eastman Chemical Company | Acrylic acid purification via dividing wall columns |
| CN110099889B (en) * | 2016-12-22 | 2023-04-04 | 伊士曼化工公司 | Purification of acrylic acid via a divided wall column |
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| Publication number | Publication date |
|---|---|
| JP2980366B2 (en) | 1999-11-22 |
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