JPH0615496B2 - Method for producing acrylic acid - Google Patents
Method for producing acrylic acidInfo
- Publication number
- JPH0615496B2 JPH0615496B2 JP58146528A JP14652883A JPH0615496B2 JP H0615496 B2 JPH0615496 B2 JP H0615496B2 JP 58146528 A JP58146528 A JP 58146528A JP 14652883 A JP14652883 A JP 14652883A JP H0615496 B2 JPH0615496 B2 JP H0615496B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- water
- acetic acid
- azeotropic
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 74
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000012808 vapor phase Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001882 dioxygen Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CYUZOYPRAQASLN-UHFFFAOYSA-N 3-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)CCOC(=O)C=C CYUZOYPRAQASLN-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 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 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- -1 steam Chemical compound 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明はプロピレンおよび／またはアクロレインからの
アクリル酸の製造方法に関する。詳しく述べると本発明
はプロピレンおよび／またはアクロレインを分子状酸素
含有ガスにより接触気相酸化し、えられる反応生成ガス
を急冷し凝集捕集しさらに未捕集物質を吸収水により吸
収捕集し、えられる主としてアクリル酸、酢酸および水
よりなるアクリル酸水溶液を常圧で１１０〜１３０℃の
範囲の沸点を有する共沸剤共存下に蒸留して共沸物とし
て実質的に水を留去し、共沸物より水を分離してこの水
を吸収水として循環使用し、一方塔底缶液として主とし
てアクリル酸および酢酸よりなる混合物をえ、この缶液
からアクリル酸を分離し精製することを特徴とするアク
リル酸の製造方法に関する。The present invention relates to a method for producing acrylic acid from propylene and / or acrolein. More specifically, the present invention comprises catalytic vapor phase oxidation of propylene and / or acrolein with a gas containing molecular oxygen, quenching of the resulting reaction product gas to coagulate and collect, and further to collect uncollected substances with absorbed water, The obtained acrylic acid aqueous solution mainly consisting of acrylic acid, acetic acid and water is distilled under normal pressure in the presence of an azeotropic agent having a boiling point in the range of 110 to 130 ° C. to substantially distill off water as an azeotrope, Characterized by separating water from the azeotrope and circulatingly using this water as absorption water, while obtaining a mixture consisting mainly of acrylic acid and acetic acid as the bottom liquid in the column, and separating and purifying acrylic acid from the liquid in the bottom. And a method for producing acrylic acid.
従来からのアクリル酸の製造方法はプロピレンおよび／
またはアクロレインを接触気相酸化してえられるアクリ
ル酸水溶液を有機溶媒により抽出処理しアクリル酸を抽
出し精製する工程よりなる。すなわち、水溶液から水を
分離する工程として抽出操作をすることが通常一般であ
る（たとえば特公昭46-30493号公報明細書参照）。しか
しながらこの抽出工程で排出される水は未回収のアクリ
ル酸や副生成物である有機酸、たとえば酢酸、プロピオ
ン酸、マレイン酸やアルデヒド類、たとえばアクロレイ
ン、アセトアルデヒド、さらにこれら化合物の重合物や
縮合物、たとえばアクリル酸２量体などの高沸点物質や
タール状物質などを含み、この廃水は、廃棄するにして
も活性汚泥法や濃縮燃焼法などにより無害化処理を必要
とし、そのための設備やユーティリティなどは、きわめ
てコストを要するものとならざるをえない。一方そのま
まアクリル酸捕集用の吸収水としてプロセスに使用する
としても該廃水中の酸分に帰因するプロセス内の酸分の
増加によりアクリル酸捕集装置でのアクリル酸の捕集効
率の低下をきたすことになり、かりにこの装置からの排
出ガスを原料ガスの不活性ガス源として再使用する場合
には、原料ガス中の酸分の増加をきたし、酸化反応にお
ける触媒活性の劣化を早める帰因ともなる（特開昭50-1
08208号および特開昭52-108917号公報明細書参照）。A conventional method for producing acrylic acid is propylene and / or
Alternatively, the method comprises a step of extracting an acrylic acid aqueous solution of acrylic acid obtained by catalytic vapor-phase oxidation of acrolein with an organic solvent to extract and purify acrylic acid. That is, it is generally common to perform an extraction operation as a step of separating water from an aqueous solution (see, for example, Japanese Patent Publication No. 46-30493). However, the water discharged in this extraction step is unrecovered acrylic acid and by-products such as organic acids such as acetic acid, propionic acid, maleic acid and aldehydes such as acrolein and acetaldehyde, as well as polymers and condensates of these compounds. , Such as acrylic acid dimer and other substances with high boiling points and tar-like substances, this wastewater requires detoxification treatment by the activated sludge method or the concentrated combustion method even if it is discarded, and equipment and utilities therefor are required. Such things must be extremely costly. On the other hand, even if it is used as it is in the process as absorbed water for collecting acrylic acid, the efficiency of collecting acrylic acid in the acrylic acid collector decreases due to the increase of acid content in the process due to the acid content in the waste water. If the exhaust gas from this equipment is reused as an inert gas source for the raw material gas, the acid content in the raw material gas will increase, which will accelerate the deterioration of the catalytic activity in the oxidation reaction. It is also a cause (Japanese Patent Laid-Open No. 50-1
08208 and Japanese Patent Application Laid-Open No. 52-108917).
また、近時上記酸化反応および捕集技術の向上により、
えられるアクリル酸水溶液の濃度もアクリル酸が５０〜
８０重量％にまで高めることも可能となってきている。In addition, due to recent improvements in the above oxidation reaction and collection technology,
The concentration of acrylic acid aqueous solution obtained is 50-
It has become possible to increase the amount to 80% by weight.
従って、本発明はこのような高濃度のアクリル酸水溶液
を使用して、従来のように抽出装作を施すことなく、直
接、脱水操作としての共沸蒸留法を採用し、さらにアク
リル酸と酢酸の塔頂への留出を痕跡程度に抑えることを
目的として検討し完成に至ったものである。Therefore, the present invention uses such a high-concentration aqueous solution of acrylic acid and directly adopts an azeotropic distillation method as a dehydration operation without performing extraction preparation as in the conventional method. The study was completed with the aim of limiting the amount of distillation to the top of the tower.
すなわち、本発明は以下の如く特定される。That is, the present invention is specified as follows.
(1)プロピレンおよび／またはアクロレインを分子状酸
素含有ガスにより接触気相酸化してアクリル酸を製造す
るに際し、該酸化反応によってえられる反応生成ガスを
急冷し凝集捕集しさらに未捕集物質を吸収水により吸収
捕集し、えられる主としてアクリル酸、酢酸および水よ
りなるアクリル酸水溶液を、理論段数１５〜２０の蒸留
塔であって、濃縮部と回収部との比率が0.8〜0.9である
蒸留塔に供給し、常圧で１１０〜１３０℃の範囲の沸点
を有し、かつ酢酸およびアクリル酸のそれぞれと共沸し
ない共沸剤の共存下に蒸留し、塔頂よりアクリル酸およ
び酢酸を含まない実質的に共沸剤と水とよりなる共沸組
成物を留出させ、この留出物より水を分離してえられる
水を吸収水として捕集装置に循環使用し、一方塔底より
水および共沸剤を含まない主としてアクリル酸と酢酸の
混合物をえることを特徴とするアクリル酸の製造方法。(1) When acrylic acid is produced by catalytic vapor-phase oxidation of propylene and / or acrolein with a molecular oxygen-containing gas, the reaction product gas obtained by the oxidation reaction is rapidly cooled to aggregate and collect uncollected substances. An acrylic acid aqueous solution mainly composed of acrylic acid, acetic acid and water, which is absorbed and collected by absorbed water, is a distillation column having a theoretical plate number of 15 to 20, and the ratio of the concentration part to the recovery part is 0.8 to 0.9. It is supplied to a distillation column and distilled under the coexistence of an azeotropic agent having a boiling point in the range of 110 to 130 ° C. under normal pressure and not azeotropic with acetic acid and acrylic acid, respectively. An azeotropic composition consisting essentially of an azeotropic agent and water that does not contain is distilled off, and the water obtained by separating water from this distillate is circulated and used as a absorbed water in the collector, while the bottom of the tower is used. Contains more water and azeotropic agents Mainly production method of acrylic acid, characterized by obtaining a mixture of acrylic acid and acetic acid are.
(2)蒸留塔に供給されるアクリル酸水溶液が、アクリル
酸を５０〜８０重量％の範囲、酢酸を２〜８重量％の範
囲で含有することを特徴とする特許請求の範囲(1)記載
の方法。(2) The acrylic acid aqueous solution supplied to the distillation column contains acrylic acid in the range of 50 to 80% by weight and acetic acid in the range of 2 to 8% by weight. the method of.
以下、本発明をさらに具体的に説明するが、それにより
本発明の目的もより明らかにされるであろう。Hereinafter, the present invention will be described in more detail, but the purpose of the present invention will be more apparent.
プロピレンおよび／またはアクロレインをモルブデンベ
ースの多元系触媒を用いて接触気相酸化してアクリル酸
を製造することは現在工業的に行なわれている。また最
近になって酸化反応およびアクリル酸捕集技術が長足の
進歩を示しえられるアクリル酸水溶液濃度が５０〜８０
重量％と高濃度化することが可能となっている。これは
従来法であるアクリル酸水溶液の抽出処理によるアクリ
ル酸および酢酸を水と分離する操作とくらべこの水溶液
から蒸留により直接水を分離することを好都合ならしめ
ることを意味する。しかもアクリル酸水溶液から水のみ
を効率よく分離し、実質的にアクリル酸と酢酸とが混合
物として取得できれば、従来プスセスへの適用にも好都
合である。本発明はかかる目的に適合すべく開発された
ものである。The catalytic gas phase oxidation of propylene and / or acrolein using a multi-component catalyst based on molbutene to produce acrylic acid is currently carried out industrially. Moreover, recently, the oxidation reaction and acrylic acid collection technology have shown great progress, and the acrylic acid aqueous solution concentration is 50-80.
It is possible to make the concentration as high as wt%. This means that it is convenient to directly separate water from this aqueous solution by distillation, as compared with the conventional method of separating acrylic acid and acetic acid from water by extraction treatment of the aqueous acrylic acid solution. Moreover, if only water is efficiently separated from the acrylic acid aqueous solution and substantially acrylic acid and acetic acid can be obtained as a mixture, it is convenient for the conventional process application. The present invention was developed to meet such a purpose.
本発明で使用される共沸剤としては、水の搬出能の大き
い化合物、すなわち共沸組成において水の割合が大きく
なるような化合物が好ましく、常圧で１１０〜１３０℃
の範囲の沸点を有する共沸剤が用いられる。具体的に
は、酢酸ｎ−ブチル、酢酸イソブチル、酢酸sec−ブチ
ル、メチルイソブチルケトンなどが挙げられる。As the azeotropic agent used in the present invention, a compound having a large ability to carry out water, that is, a compound having a large proportion of water in the azeotropic composition, is preferable.
An azeotropic agent having a boiling point in the range of is used. Specific examples include n-butyl acetate, isobutyl acetate, sec-butyl acetate, and methyl isobutyl ketone.
もちろん、これらの共沸剤は酢酸と沸点が近接してお
り、単に蒸留に供しただけでは、留出時酢酸をも水とと
もに留出せしめてしまうことにもなる。すなわち、留出
液組成が共沸剤−水−酢酸という組成となり再度煩雑な
分離操作を必要とする結果をもたらしてしまう。Of course, these azeotroping agents have a boiling point close to that of acetic acid, and if simply subjected to distillation, acetic acid will also be distilled out together with water at the time of distillation. That is, the composition of the distillate becomes the composition of azeotropic agent-water-acetic acid, resulting in the need for a complicated separation operation again.
ところが、本発明者らは、蒸留塔の塔頂蒸気を操作圧に
おける共沸組成となるように還流量を決めることにより
アクリル酸の留出が抑えられること、それだけでなくさ
らに蒸留塔の理論段数１５〜２０の蒸留塔であって、そ
の蒸留塔の回収部の理論段数を少なくとも１０に設定す
ると伴に、濃縮部と回収部との比率が０．８〜０．９で
ある蒸留塔に供給し、留出側の酢酸を痕跡程度となしう
ることを知見し、かくして共沸剤および水を含まない主
として酢酸およびアクリル酸とよりなる塔底液を取り出
しうることを見出したのである。However, the inventors of the present invention can suppress the distillation of acrylic acid by determining the reflux amount so that the overhead vapor of the distillation column has an azeotropic composition at the operating pressure, and not only that, but also the theoretical plate number of the distillation column. 15 to 20 distillation columns, wherein the number of theoretical plates of the recovery section of the distillation column is set to at least 10, and the ratio of the concentration section to the recovery section is 0.8 to 0.9 However, they have found that acetic acid on the distillation side can be made to be a trace amount, and thus, they have found that a bottom liquid mainly containing acetic acid and acrylic acid containing no azeotropic agent and water can be taken out.
上記蒸留操作において、本発明者らは、酢酸の濃縮ピー
ク段と水の濃縮ピーク段とが分離して存在することを見
出している。これは酢酸の留出を抑えるのに有効となっ
ていると考えられる。また供給液中の酢酸量が増加する
と酢酸の濃縮される段が広がり水の濃縮される段と接近
して重なり合ってき、酢酸の留出が若干生じてくる。し
たがって酢酸濃度が上昇してくるに応じて回収部の理論
段数も１０を越え１５段くらいにまで高める必要が生ず
る。アクリル酸水溶液中の酢酸濃度は２〜８重量％と変
化するからである。In the above distillation operation, the present inventors have found that the acetic acid concentration peak stage and the water concentration peak stage exist separately. This is considered to be effective in suppressing the distillation of acetic acid. Further, when the amount of acetic acid in the feed solution increases, the stage where acetic acid is concentrated expands and approaches the stage where water is concentrated and overlaps with each other, and distilling out of acetic acid slightly occurs. Therefore, as the acetic acid concentration increases, it is necessary to increase the theoretical plate number of the recovery section from 10 to 15 or so. This is because the acetic acid concentration in the acrylic acid aqueous solution changes to 2 to 8% by weight.
本発明方法により酢酸を含むアクリル酸水溶液の蒸留に
おいて常圧で１１０〜１３０℃の範囲の沸点を有する共
沸剤を用いつつアクリル酸のみならず酢酸も留出させな
い蒸留方法が確立され、これまで留出水は共沸剤を分離
後廃水処理とか酢酸の分離回収操作等によって無公害化
処理を必要としていたのに対し、留出液は共沸剤回収後
アクリル酸捕集用の吸収水として再使用され、きわめて
有効な無公害のクローズドシステム化プスセスが完成さ
れたことになる。According to the method of the present invention, a distillation method has been established which does not distill not only acrylic acid but also acetic acid while using an azeotropic agent having a boiling point in the range of 110 to 130 ° C. at atmospheric pressure in the distillation of an acrylic acid aqueous solution containing acetic acid. The distillate required a pollution-free treatment such as wastewater treatment after separation of the azeotrope or a separation and recovery operation of acetic acid, whereas the distillate was used as absorption water for collecting acrylic acid after the azeotrope was collected. It will be reused and a highly effective pollution-free closed systemized process has been completed.
以下に本発明の実施態様の１つである図１に従って、本
発明をさらに具体的に説明する。Hereinafter, the present invention will be described more specifically with reference to FIG. 1, which is one of the embodiments of the present invention.
プロピレン、空気および窒素、炭酸ガス、水蒸気を含む
不活性ガスよりなる反応用原料ガスをモリブデンをベー
スとする多元触媒を充填した第１反応器を通過させ、プ
ロピレンを主としてアクロレインへ酸化しそのガス状組
成物を、続いてモリブデン−バナジウムをベースとする
多元触媒を充填した第２反応器に通じ、アクロレインを
主としてアクリル酸へ酸化せしめる（以上図示せず）。
反応生成ガス中には目的とするアクリル酸のほかアクロ
レイン、アセトアルデヒド、酢酸、マレイン酸、水蒸
気、炭酸ガス、一酸化炭素、さらにはプロパン、プロピ
レンなどの炭化水素や窒素も含まれ、このガス状組成物
はライン１を通じてアクリル酸捕集装置１０１へ導入さ
れる。この捕集装置１０１において該ガスは急冷されて
まず凝縮せしめられ、大半のアクリル酸、酢酸はここで
水溶液となる。そして未凝縮部分はさらに捕集装置の上
方にてライン２によって供給される重合禁止剤を含んだ
冷却吸収水によって吸収捕集され、捕集装置１０１の下
部よりライン３によりアクリル酸水溶液の形で取出され
る。A reaction raw material gas consisting of propylene, air and an inert gas containing nitrogen, carbon dioxide, and steam is passed through a first reactor filled with a multi-way catalyst based on molybdenum, and propylene is mainly oxidized to acrolein, and the gaseous state thereof is obtained. The composition is then passed through a second reactor packed with a molybdenum-vanadium based multi-way catalyst to oxidize acrolein primarily to acrylic acid (not shown above).
In addition to the target acrylic acid, the reaction product gas also contains acrolein, acetaldehyde, acetic acid, maleic acid, steam, carbon dioxide, carbon monoxide, and hydrocarbons and nitrogen such as propane and propylene. The substance is introduced into the acrylic acid collecting device 101 through the line 1. In this collector 101, the gas is rapidly cooled and condensed first, and most of acrylic acid and acetic acid become an aqueous solution here. The uncondensed portion is further absorbed and collected by the cooling absorption water containing the polymerization inhibitor, which is supplied by the line 2 above the collector, and from the lower part of the collector 101 by the line 3 in the form of an aqueous solution of acrylic acid. Taken out.
アクリル酸捕集装置１０１の頂部からはライン４により
廃ガスが排出される。この中には非凝縮性の炭酸ガス、
一酸化炭素、プロパン、プロピレン、窒素および少量の
水蒸気とが含まれ酸分はほとんど含有されていないの
で、一部を反応用原料ガスに混入のため再使用され、残
りは接触燃焼器など（図示せず）により無害化されて大
気中に放出されたり、不活性ガスとしてプロセスの他の
部分で利用される。Waste gas is discharged from the top of the acrylic acid collecting apparatus 101 through the line 4. In this, non-condensable carbon dioxide,
It contains carbon monoxide, propane, propylene, nitrogen, and a small amount of water vapor, and contains almost no acid, so part of it is reused because it is mixed with the raw material gas for reaction, and the rest is included in the contact combustor (Fig. It is detoxified by (not shown) and released into the atmosphere or used as an inert gas in other parts of the process.
ライン３より取出されたアクリル酸水溶液は、必要によ
りアクロレイン、アセトアルデヒドなどの軽沸点物を回
収後、共沸脱水塔１０２へ供給される。該共沸脱水塔１
０２は理論段数１５以上好ましくは２０〜３０の範囲の
ものであり、かつ回収部の理論段数が１０以上とれるよ
うにせねばならない。脱水塔１０２の塔頂にはライン５
により共沸剤が供給され、塔頂からライン６により留出
する蒸気組成がほゞ水−共沸剤の共沸組成となるように
コントロールされる。The acrylic acid aqueous solution taken out through the line 3 is supplied to the azeotropic dehydration column 102 after recovering light boiling substances such as acrolein and acetaldehyde, if necessary. The azeotropic dehydration tower 1
02 has a theoretical plate number of 15 or more, preferably in the range of 20 to 30, and the number of theoretical plates of the recovery section must be 10 or more. Line 5 at the top of the dehydration tower 102
The azeotropic agent is supplied by the above, and the vapor composition distilled from the top of the column through the line 6 is controlled so that it becomes the azeotropic composition of almost water-azeotropic agent.
塔底からは水および共沸剤を含まないアクリル酸、酢酸
およびその他の高沸点物質がライン７を経て取り出さ
れ、この缶液は次に酢酸分離工程、アクリル酸精留工程
を経て製品化される（図示せず）。共沸脱水塔１０２の
塔頂より留出した液は、分離槽１０４において共沸剤相
と水相とに分離し、水相はライン８より共沸剤回収塔１
０３へ送られ、ここで塔頂より共沸剤と水の一部とを留
出せしめライン９を経て分離槽１０４へ送って回収され
る。一方共沸剤を含まぬプロセス水が塔底よりライン１
０を経て取り出され、アクリル酸捕集装置へ吸収水とし
て再利用される。かくして、廃水の発生を実質的にゼロ
とすることができる本発明プロセスが開発された。すな
わちこの捕集装置からの廃ガスの１部を第１反応器に循
環使用し、反応原料ガス中に必要な不活性ガス（窒素、
水蒸気など）を供給し、残部を系外へ排出せしめ、その
際含まれる水蒸気量は少なくとも接触気相酸化反応によ
り発生する水蒸気量となるよう調節せしめて実質的に廃
水を生ぜしめないプロセスが可能となる。From the bottom of the column, water and acrylic acid containing no azeotropic agent, acetic acid and other high-boiling substances are taken out through line 7, and this bottom liquid is then commercialized through an acetic acid separation step and an acrylic acid rectification step. (Not shown). The liquid distilled from the top of the azeotropic dehydration tower 102 is separated into an azeotropic agent phase and an aqueous phase in a separation tank 104, and the aqueous phase is separated from the line 8 through the azeotropic agent recovery tower 1
03, where the azeotropic agent and a part of the water are distilled off from the top of the column via line 9 to separation tank 104 for recovery. On the other hand, process water that does not contain an azeotropic agent is line 1 from the bottom of the tower.
It is taken out through 0 and reused as absorbed water in the acrylic acid collector. Thus, the process of the present invention has been developed which allows substantially zero wastewater generation. That is, a part of the waste gas from this collector is circulated to the first reactor, and the inert gas (nitrogen,
(Steam etc.) is supplied and the rest is discharged to the outside of the system, and the amount of steam contained at that time is adjusted to at least the amount of steam generated by the catalytic gas phase oxidation reaction, thereby enabling a process that practically does not generate wastewater. Becomes
本発明方法によってえられる実質的にアクリル酸と酢酸
とよりなる塔底液は、続いて酢酸分離操作を経てアクリ
ル酸精留装置にかけられ、製品アクリル酸となる。この
操作は工業的に長期間安定して遂行しうるものであっ
た。The bottom liquid obtained by the method of the present invention, which is substantially composed of acrylic acid and acetic acid, is subsequently subjected to an acetic acid separation operation and then applied to an acrylic acid rectification unit to obtain product acrylic acid. This operation could be stably carried out industrially for a long period of time.
実施例 １ プロピレンをモリブデンベース多元系触媒による２段酸
化反応に供し、えられた反応生成ガスをアクリル酸捕集
装置に導いた。この捕集装置は内径２００mmφのステン
レス製の塔で上部に５０段の泡鐘棚を備え、下部に多管
式の冷却部を備えており、塔の最上部から重合禁止剤の
ハイドロキノンを含むプロセス水を供給できるように設
計されたものである。Example 1 Propylene was subjected to a two-stage oxidation reaction using a molybdenum-based multi-component catalyst, and the obtained reaction product gas was led to an acrylic acid collector. This collector is a stainless steel column with an inner diameter of 200 mmφ, equipped with 50 stages of bubble cap racks in the upper part, and a multitubular cooling part in the lower part, and a process containing the polymerization inhibitor hydroquinone from the top of the column. It is designed to supply water.
アクリル酸5.9容量％、酢酸0.2容量％、水7.2容量％、
残り大部分が窒素であり、ほかにアクロレイン、プロピ
レン、プロパン、アセトアルデヒドを微量含有する反応
生成ガス２３Ｎm3／Ｈｒをこの捕集装置に導びき冷却凝
集せしめた。反応生成ガスは２００℃で供給され冷却部
にて７０℃に冷却され、吸収部へは６０℃のプロセス水
が2.4Kg／Ｈｒ供給されることにより、アクリル酸の補
集率は９９％以上に保持された。該捕集装置を出る廃ガ
ス温度は６０℃に調節された。Acrylic acid 5.9% by volume, acetic acid 0.2% by volume, water 7.2% by volume,
The reaction product gas 23Nm 3 / Hr containing a small amount of acrolein, propylene, propane, and acetaldehyde in addition to the remaining nitrogen, was introduced into this collector to be cooled and condensed. The reaction product gas is supplied at 200 ° C, cooled to 70 ° C in the cooling unit, and the process water at 60 ° C is supplied to the absorption unit at 2.4 kg / Hr, so that the collection rate of acrylic acid is 99% or more. Retained The temperature of the waste gas leaving the collector was adjusted to 60 ° C.
かくして、アクリル酸66.0重量％、酢酸2.2重量％、水3
1.2重量％、その他0.6重量％よりなるアクリル酸水溶液
が7.66Kg／Ｈｒえられた。このアクリル酸水溶液を１０
０mmφの無堰多孔板４８段を有する蒸留塔（理論段数１
９）の上より２３段目に供給した。共沸剤としてはメチ
ルイソブチルケトン（ＭＩＢＫ）を用い、塔頂圧１１０
mmHg（絶体圧）とし塔頂留出組成が水２１重量％、ＭＩ
ＢＫ７９重量％となるように塔最上部から重合禁止剤の
ハイドロキノンとともに投入した。塔底液としては5.3K
g／Ｈｒがえられ、その組成はアクリル酸96.5重量％、
酢酸3.3重量％であり、ＭＩＢＫおよび水はともに含ま
れていなかった。塔頂からの留出液は冷却により分離
し、水相は2.4Kg／Ｈｒをえ、この中には酢酸およびア
クリル酸は含まれず、わずかにＭＩＢＫ1.7重量％が含
有されていた。この水相を塔径５０mmφラシヒリングを
３メートルの高さに充填した蒸留塔で常圧下蒸留し塔頂
より0.1Kg／Ｈｒを留出させた。このＭＩＢＫを含む水
を分離槽１０４へ循環し、他方缶液2.3Kg／Ｈｒとして
ＭＩＢＫを含まないプロセス水をえた。この水は新たな
重合禁止剤を含んだ水0.1Kg／Ｈｒとともに上記の捕集
装置１０１に供給された。Thus, acrylic acid 66.0% by weight, acetic acid 2.2% by weight, water 3
An acrylic acid aqueous solution containing 1.2% by weight and other 0.6% by weight was obtained at 7.66 kg / hr. This acrylic acid aqueous solution 10
Distillation column with 48 plates of 0 mmφ non-weir perforated plate (1 theoretical plate)
It was supplied to the 23rd stage from the top of 9). Methyl isobutyl ketone (MIBK) was used as an azeotropic agent, and the column top pressure was 110.
mmHg (absolute pressure), top distillate composition is water 21% by weight, MI
It was charged together with hydroquinone as a polymerization inhibitor from the top of the tower so that the BK content was 79% by weight. 5.3K as the bottom liquid
g / Hr is obtained, the composition of which is acrylic acid 96.5% by weight,
The acetic acid content was 3.3% by weight, and neither MIBK nor water was contained. The distillate from the top of the column was separated by cooling, and the aqueous phase had a yield of 2.4 kg / hr, and did not contain acetic acid or acrylic acid, but contained only 1.7% by weight of MIBK. This aqueous phase was distilled under atmospheric pressure in a distillation column filled with a Raschig ring having a column diameter of 50 mm and a height of 3 meters to distill 0.1 kg / Hr from the top of the column. This MIBK-containing water was circulated to the separation tank 104, while process water containing no MIBK was obtained as a bottom liquid of 2.3 kg / Hr. This water was supplied to the above collector 101 together with 0.1 Kg / Hr of water containing a new polymerization inhibitor.
アクリル酸と酢酸とを含む共沸脱水塔缶液は酢酸分離塔
およびアクリル酸精留塔に順次供給されて製品アクリル
酸をえた。The azeotropic dehydration column bottom liquid containing acrylic acid and acetic acid was sequentially supplied to an acetic acid separation column and an acrylic acid rectification column to obtain product acrylic acid.
比較例 １ 実施例１における操作において、アクリル酸水溶液の供
給を蒸留塔の上から３１段目から行ない、あとは同様に
してアクリル酸水溶液の蒸留を行なった。塔頂からの留
出液は冷却により分離し、得られた水相中にはアクリル
酸は痕跡程度であったが酢酸が１．９重量％含まれてい
た。Comparative Example 1 In the operation of Example 1, the acrylic acid aqueous solution was supplied from the 31st stage from the top of the distillation column, and thereafter the acrylic acid aqueous solution was distilled in the same manner. The distillate from the top of the column was separated by cooling, and the obtained aqueous phase contained acrylic acid in a trace amount but contained 1.9% by weight of acetic acid.
図１は本発明の１つの実施態様を示すフローシートであ
る。FIG. 1 is a flow sheet showing one embodiment of the present invention.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭56−90034（ＪＰ，Ａ) 特開 昭60−38341（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-56-90034 (JP, A) JP-A-60-38341 (JP, A)
Claims (2)
分子状酸素含有ガスにより接触気相酸化してアクリル酸
を製造するに際し、該酸化反応によってえられる反応生
成ガスを急冷し凝縮捕集しさらに未捕集物質を吸収水に
より吸収捕集し、えられる主としてアクリル酸、酢酸お
よび水よりなるアクリル酸水溶液を、理論段数１５〜２
０の蒸留塔であって、濃縮部と回収部との比率が0.8〜
0.9である蒸留塔に供給し、常圧で１１０〜１３０℃の
範囲の沸点を有し、かつ酢酸およびアクリル酸のそれぞ
れと共沸しない共沸剤の共存下に蒸留し、塔頂よりアク
リル酸および酢酸を含まない実質的に共沸剤と水とより
なる共沸組成物を留出させ、この留出物より水を分離し
てえられる水を吸収水として捕集装置に循環使用し、一
方塔底より水および共沸剤を含まない主としてアクリル
酸と酢酸の混合物をえることを特徴とするアクリル酸の
製造方法。1. When producing acrylic acid by catalytically vapor-phase oxidizing propylene and / or acrolein with a gas containing molecular oxygen, the reaction product gas obtained by the oxidation reaction is rapidly cooled, condensed and collected, and further uncollected. The substance is absorbed and collected by absorbing water, and the obtained acrylic acid aqueous solution mainly consisting of acrylic acid, acetic acid and water is used in a theoretical plate number of 15 to 2
0 distillation column, the ratio of the concentration section and the recovery section is 0.8 ~
It is fed to a distillation column of 0.9 and distilled under the coexistence of an azeotropic agent having a boiling point in the range of 110 to 130 ° C. under normal pressure and not azeotropic with acetic acid and acrylic acid. And an azeotropic composition consisting essentially of an azeotropic agent and water that does not contain acetic acid is distilled, and water obtained by separating water from this distillate is circulated and used as a absorbed water in a collector, On the other hand, a method for producing acrylic acid, characterized in that a mixture of mainly acrylic acid and acetic acid containing no water and no azeotropic agent is obtained from the bottom of the column.
アクリル酸を５０〜８０重量％の範囲、酢酸を２〜８重
量％の範囲で含有することを特徴とする特許請求の範囲
(1)記載の方法。2. The acrylic acid aqueous solution supplied to the distillation column is
Claims containing acrylic acid in the range of 50-80% by weight and acetic acid in the range of 2-8% by weight.
(1) The method described.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58146528A JPH0615496B2 (en) | 1983-08-12 | 1983-08-12 | Method for producing acrylic acid |
| GB08420153A GB2146636B (en) | 1983-08-11 | 1984-08-08 | Process for producing acrylic acid |
| DE19843429391 DE3429391A1 (en) | 1983-08-11 | 1984-08-09 | METHOD FOR PRODUCING ACRYLIC ACID |
| KR1019840004818A KR900006901B1 (en) | 1983-08-11 | 1984-08-10 | Method of producing acrylic acid |
| MX202336A MX161562A (en) | 1983-08-11 | 1984-08-10 | PROCEDURE TO PRODUCE ACRYLIC ACID |
| FR8412731A FR2554809B1 (en) | 1983-08-11 | 1984-08-13 | PROCESS FOR THE PREPARATION OF ACRYLIC ACID |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58146528A JPH0615496B2 (en) | 1983-08-12 | 1983-08-12 | Method for producing acrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6038342A JPS6038342A (en) | 1985-02-27 |
| JPH0615496B2 true JPH0615496B2 (en) | 1994-03-02 |
Family
ID=15409679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58146528A Expired - Lifetime JPH0615496B2 (en) | 1983-08-11 | 1983-08-12 | Method for producing acrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615496B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW553929B (en) * | 1999-03-05 | 2003-09-21 | Rohm & Haas | Process for preparing (meth)acrylic acid |
| JP4920128B2 (en) * | 1999-12-02 | 2012-04-18 | 株式会社日本触媒 | How to prevent clogging of exhaust gas piping |
| CN110684470B (en) * | 2019-10-21 | 2022-03-01 | 江苏利田科技股份有限公司 | Method for preparing acrylate adhesive by using UV monomer wastewater and acrylate adhesive |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5690034A (en) * | 1979-12-25 | 1981-07-21 | Mitsubishi Petrochem Co Ltd | Purification of acrylic acid |
| JPH0615495B2 (en) * | 1983-08-11 | 1994-03-02 | 株式会社日本触媒 | Acrylic acid purification method |
-
1983
- 1983-08-12 JP JP58146528A patent/JPH0615496B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6038342A (en) | 1985-02-27 |
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