JPS6245219B2 - - Google Patents
Info
- Publication number
- JPS6245219B2 JPS6245219B2 JP11781282A JP11781282A JPS6245219B2 JP S6245219 B2 JPS6245219 B2 JP S6245219B2 JP 11781282 A JP11781282 A JP 11781282A JP 11781282 A JP11781282 A JP 11781282A JP S6245219 B2 JPS6245219 B2 JP S6245219B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- extraction
- aqueous solution
- bisulfite
- distillation
- 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
Links
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 52
- 238000000605 extraction Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 16
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- 238000004821 distillation Methods 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- -1 alkali metal salts Chemical class 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 description 16
- 239000000284 extract Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AOSFMYBATFLTAQ-UHFFFAOYSA-N 1-amino-3-(benzimidazol-1-yl)propan-2-ol Chemical compound C1=CC=C2N(CC(O)CN)C=NC2=C1 AOSFMYBATFLTAQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 229940090181 propyl acetate Drugs 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はアクリル酸の精製方法に関する。詳し
く述べると本発明はプロピレンまたはアクロレイ
ンの接触気相酸化反応によつてアクリル酸を製造
するプロセスにおいて、酸化反応器から出たアク
リル酸含有反応生成ガスの冷却・凝縮操作によつ
てえられるアクリル酸水溶液から、アクリル酸を
工業的に効率よく、何のトラブルもなく精製取得
するための方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for purifying acrylic acid. Specifically, the present invention relates to the production of acrylic acid by cooling and condensing the acrylic acid-containing reaction product gas discharged from the oxidation reactor in the process of producing acrylic acid by catalytic gas phase oxidation reaction of propylene or acrolein. This invention relates to a method for industrially and efficiently purifying and obtaining acrylic acid from an aqueous solution without any trouble.
アクリル酸が炭素数３の化合物たとえばプロピ
レンやアクロレインを接触気相酸化して製造しう
ることは近年酸化触媒の開発やプロセスの開発に
関する多くの文献により公知である。しかしなが
らえられたアクリル酸水溶液から高純度アクリル
酸を分離・精製する工程において、種々な困難に
遭遇するのも事実である。その原因は触媒性能が
高水準といえども反応生成物中の種々の副生物が
存在するからである。これら副生物を目的とする
アクリル酸から分離除去するのがきわめて困難で
あり、アクリル酸精製工程での種々のトラブルが
解決されるに至つていないのが現状だからであ
る。反応生成ガス中には、アクリル酸のほかにア
クロレイン、プロピオン酸、酢酸、アセトアルデ
ヒド、一酸化炭素、炭酸ガスなど比較的沸点の軽
いもの、さらにマレイン酸、芳香族カルボン酸た
とえば安息香酸やテレフタル酸など、それにター
ル状物質などの重質物といつた副生物が含有され
ている。このうち、比較的高沸点な物質がアクリ
ル酸の捕集および精製工程において種々のトラブ
ルの原因をなすものと考えられる。 In recent years, it has been known from numerous publications on the development of oxidation catalysts and process development that acrylic acid can be produced by catalytic gas phase oxidation of compounds having three carbon atoms, such as propylene and acrolein. However, it is a fact that various difficulties are encountered in the process of separating and purifying high purity acrylic acid from the obtained acrylic acid aqueous solution. The reason for this is that even though the catalyst performance is at a high level, various by-products are present in the reaction products. This is because it is extremely difficult to separate and remove these by-products from the intended acrylic acid, and various problems in the acrylic acid purification process have not yet been solved. In addition to acrylic acid, the reaction product gas also contains substances with relatively low boiling points, such as acrolein, propionic acid, acetic acid, acetaldehyde, carbon monoxide, and carbon dioxide, as well as maleic acid, aromatic carboxylic acids, benzoic acid, terephthalic acid, etc. It also contains heavy substances such as tar-like substances and other by-products. Among these, substances with relatively high boiling points are thought to cause various troubles in the collection and purification process of acrylic acid.
従来からアクリル酸を反応生成ガスの冷却・凝
縮操作によつて水溶液の形で捕集する方法が採用
されており、その際アクリル酸、水とともに上記
の多くの反応副生物も凝縮または溶解捕集され
る。アクリル酸水溶液中の比較的軽沸点な物質は
抽出操作前の工程において放散や蒸留操作によつ
てほゞ除去される。しかし、芳香族カルボン酸、
マレイン酸、重合物、タール状物質などの高沸点
物は依然としてアクリル酸水溶液中に残存してお
り、アクリル酸抽出時や抽出液よりアクリル酸を
分離・精製する蒸留工程において種々のトラブル
の原因となつている。これらのトラブルを軽減す
るために従来から種々提案がなされている。しか
し、副生物の分離除去は十分に達成できず長時間
の運転ではやはり抽出時の界面分離の不良や蒸留
時においてこれら副生物に帰因すると考えられる
重合が起こることが多く高価な重合禁止剤を多量
に使用しなければならないなどの不都合が発生し
たり、また装置の洗滌などを行うことで多くの廃
水を発生したりして、高純度アクリル酸を工業的
に安定して採用しうる方法とはなつていない。 Conventionally, a method has been adopted in which acrylic acid is collected in the form of an aqueous solution by cooling and condensing the reaction product gas, and in this process, many of the reaction by-products mentioned above are also collected by condensation or dissolution along with acrylic acid and water. be done. Substances with relatively low boiling points in the aqueous acrylic acid solution are substantially removed by dissipation or distillation in a step before the extraction operation. However, aromatic carboxylic acids,
High-boiling substances such as maleic acid, polymers, and tar-like substances still remain in the acrylic acid aqueous solution, causing various troubles during the extraction of acrylic acid and the distillation process to separate and purify acrylic acid from the extract. It's summery. Various proposals have been made to alleviate these troubles. However, separation and removal of by-products cannot be achieved sufficiently, and in long-term operation, poor interfacial separation during extraction and polymerization caused by these by-products often occur during distillation, which often requires expensive polymerization inhibitors. However, there are some disadvantages such as having to use a large amount of acrylic acid, and a large amount of waste water is generated when cleaning the equipment. It has not become familiar.
本発明は上記の如き欠点を克服しうるアクリル
酸の精製方法を提供することを目的とする。即
ち、本発明は以下のごとく特定される。 An object of the present invention is to provide a method for purifying acrylic acid that can overcome the above-mentioned drawbacks. That is, the present invention is specified as follows.
(1) プロピレンまたはアクロレインを接触気相酸
化してアクリル酸を製造するプロセスにおい
て、酸化反応器より出るアクリル酸含有反応生
成ガスの冷却・凝縮操作によつてえられたアク
リル酸水溶液をまず該水溶液に含まれる軽沸点
物質を蒸留または放散操作によつて除去し、つ
いでえられたアクリル酸水溶液に重亜硫酸塩を
添加して抽出工程に供し、当該抽出工程におけ
るスカムの発生を防止することを特徴とするア
クリル酸の精製方法。(1) In the process of producing acrylic acid by catalytic gas phase oxidation of propylene or acrolein, an aqueous acrylic acid solution obtained by cooling and condensing the acrylic acid-containing reaction product gas discharged from an oxidation reactor is first added to the aqueous solution. The light boiling point substances contained in the acrylic acid solution are removed by distillation or dissipation operation, and then bisulfite is added to the resulting acrylic acid aqueous solution and subjected to an extraction process, thereby preventing the generation of scum in the extraction process. A method for purifying acrylic acid.
(2) 重亜硫酸塩がアルカリ金属塩およびアンモニ
ウム塩よりなる群から選ばれた少なくとも１種
であることを特徴とする上記(1)記載の方法。(2) The method according to (1) above, wherein the bisulfite is at least one selected from the group consisting of alkali metal salts and ammonium salts.
つぎに、本発明をさらにくわしく説明する。 Next, the present invention will be explained in more detail.
モリブデン酸化物またはその複合酸化物を基礎
として調製された酸化触媒を用い、プロピレンま
たはアクロレインを一段酸化ないし多段酸化反応
に供するとアクリル酸を主体とする反応生成物が
えられる。そしてアクリル酸は通常は、アクリル
酸を含有する凝縮水溶液として捕集される。この
アクリル酸水溶液はついで軽沸点物の除去のため
蒸留や放散操作に供され、さらにメチルエチルケ
トンなどのケトン類や酢酸エステル類などの溶媒
による抽出操作にかけられる。 When propylene or acrolein is subjected to a single-stage or multi-stage oxidation reaction using an oxidation catalyst prepared based on molybdenum oxide or its composite oxide, a reaction product containing acrylic acid as a main component is obtained. The acrylic acid is then typically collected as a condensed aqueous solution containing acrylic acid. This aqueous acrylic acid solution is then subjected to distillation and dispersion operations to remove light boilers, and further subjected to extraction operations using ketones such as methyl ethyl ketone and acetic esters.
本発明者らは上記した軽沸点物を除去したアク
リル酸水溶液の抽出時に界面の分離状態及び蒸留
時の重合安定性の改良方法について種々検討した
ところ、当該アクリル酸水溶液にあらかじめ重亜
硫酸塩を添加することによつて副生物を分離・除
去することが容易となり抽出時の界面の分離状態
が良好となり蒸留時の重合安定性がよくなること
を見出し本発明を完成するに至つた。 The present inventors investigated various ways to improve the separation state of the interface during extraction and the polymerization stability during distillation of the above-mentioned aqueous acrylic acid solution from which light boilers had been removed, and found that bisulfite was added to the aqueous acrylic acid solution in advance The present inventors have discovered that by doing so, it becomes easier to separate and remove by-products, the separation state at the interface during extraction is improved, and the polymerization stability during distillation is improved, leading to the completion of the present invention.
本発明方法をとることにより抽出塔の上部界面
の分離状態が改良されるばかりでなく塔の内壁な
どへのスケールの付着も防止でき長期の連続運転
が可能となることが見出された。本発明者らは、
抽出塔の界面の分離が不良となるのは芳香族カル
ボン酸やタール状物質さらに若干の重合物よりな
ることを見出しているが、これらが、抽出前のア
クリル酸水溶液に添加される重亜硫酸塩によつて
何故抽出塔での工程で抽残側に除去されるのかは
知見していない。 It has been found that by employing the method of the present invention, not only the separation state at the upper interface of the extraction column is improved, but also the adhesion of scale to the inner wall of the column can be prevented, and long-term continuous operation becomes possible. The inventors
It has been found that aromatic carboxylic acids, tar-like substances, and some polymerized substances cause poor separation at the interface of the extraction tower, but these are caused by bisulfite added to the acrylic acid aqueous solution before extraction. It is not known why the raffinate is removed to the raffinate during the process in the extraction column.
しかもさらに驚くべきことは、本発明方法を採
用することによつて、この工程につづく抽出液か
らのアクリル酸精製工程におけるアクリル酸の重
合物の発生およびスケール発生も大巾に低減する
ことが見出されたのである。たとえば、抽出液の
溶媒放散のための蒸留塔やアクリル酸精留塔での
重合物発生の抑制、アクリル酸精製蒸留塔リボイ
ラー伝熱面への高沸点物によるスケール発生の軽
減などである。 What is even more surprising is that by employing the method of the present invention, it has been found that the generation of acrylic acid polymers and scale generation in the process of purifying acrylic acid from the extract following this process is greatly reduced. It was released. Examples include suppressing the generation of polymers in distillation columns and acrylic acid rectification columns for dissipating solvents in extracts, and reducing scale generation due to high boiling point substances on the heat transfer surface of the acrylic acid purification distillation column reboiler.
さらにまた抽出液中のマレイン酸の量も激減す
ることも判明し、かくして簡単なプロセスで高純
度のアクリル酸をえることも本発明方法で可能と
なつた。 Furthermore, it was also found that the amount of maleic acid in the extract was drastically reduced, and thus it became possible to obtain highly pure acrylic acid with a simple process using the method of the present invention.
本発明で使用する重亜硫酸塩としては、ナトリ
ウム、カリウム、セシウムなどのアルカリ金属塩
およびアンモニウム塩のうちから選ばれ、とく
に、ナトリウム塩、カリウム塩、アンモニウム塩
が好適に使用される。これらは10重量％以上の濃
度から飽和水溶液の形で用いられ、使用量は対象
とするアクリル酸に対して0.5〜15重量％、好ま
しくは１〜10重量％の範囲である。添加量が多す
ぎるとアクリル酸までもアルカリ塩となり抽出工
程での損失となる。また少なすぎるのも添加効果
が低下し好ましくない。添加方法は、アクリル酸
水溶液と上記重亜硫酸塩水溶液とを連続的にライ
ンミキサーで混合したり、撹拌槽で連続的ないし
半連続的に混合して抽出塔に供給する方法が好ま
しい。温度は高温を特別に必要とするものでなく
常温で十分であるが、50〜60℃に加熱して行なつ
てもよい。 The bisulfite used in the present invention is selected from alkali metal salts such as sodium, potassium, and cesium, and ammonium salts, and sodium salts, potassium salts, and ammonium salts are particularly preferably used. These are used in the form of a saturated aqueous solution with a concentration of 10% by weight or more, and the amount used is in the range of 0.5 to 15% by weight, preferably 1 to 10% by weight, based on the target acrylic acid. If the amount added is too large, even acrylic acid will turn into an alkali salt and will be lost in the extraction process. Also, if the amount is too small, the effect of addition will decrease, which is not preferable. As for the addition method, it is preferable to mix the acrylic acid aqueous solution and the above-mentioned bisulfite aqueous solution continuously in a line mixer, or to mix them continuously or semi-continuously in a stirring tank and supply the mixture to an extraction column. The temperature does not particularly require a high temperature, and room temperature is sufficient, but it may be heated to 50 to 60°C.
重亜硫酸塩を添加されたアクリル酸水溶液は抽
出塔にて、通常の溶媒たとえば、メチルエチルケ
トンなどのケトン類や酢酸エチル、酢酸プロピ
ル、酢酸イソプロピル、酢酸ブチルなどのエステ
ル類などによつて抽出され、塔上部からえられる
抽出液はそのまま溶媒放散塔に供給され、溶媒を
除去して粗アクリル酸がえられる。抽出操作にお
いて、通常の方法に従つて抽出液を水で洗滌する
こともできる。この場合、添加した重亜硫酸塩の
一部が分解し若干の二酸化硫黄が発生しているこ
ともあり、この二酸化硫黄を洗滌除去する意味も
かねて当該抽出液の水による洗滌方法が有効に使
用される。 The aqueous acrylic acid solution to which bisulfite has been added is extracted with a conventional solvent such as ketones such as methyl ethyl ketone or esters such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, etc. in an extraction tower. The extract obtained from the upper part is directly supplied to a solvent stripping tower, and the solvent is removed to obtain crude acrylic acid. In the extraction operation, the extract can also be washed with water according to a conventional method. In this case, some of the added bisulfite may have decomposed and a small amount of sulfur dioxide may have been generated, so washing the extract with water is an effective method to wash and remove this sulfur dioxide. Ru.
抽出液より高純度のアクリル酸をえる後工程、
すなわち溶媒放散塔、軽沸点ストリツパー、精製
塔においては重合を防止するために減圧下、温度
も120℃以下の条件下通常の重合禁止剤たとえ
ば、ハイドロキノン、メトキシハイドロキノン、
フエノチアジンなどおよび分子状酸素の存在下で
蒸留することが好ましい。 Post-process to obtain high-purity acrylic acid from the extract,
In other words, in the solvent stripping tower, light boiling point stripper, and purification tower, ordinary polymerization inhibitors such as hydroquinone, methoxyhydroquinone,
Distillation in the presence of a phenothiazine or the like and molecular oxygen is preferred.
実施例 １
前段反応用触媒としてモリブデン系複合酸化物
を用い、後段反応用触媒としてモリブデン−バナ
ジウム系複合酸化物を基盤とする触媒を用いて、
プロピレンを水蒸気の存在下に空気による接触気
相酸化反応を行ない、えられる反応生成ガスを冷
却凝縮せしめ、重合禁止剤としてハイドロキノン
を含むアクリル酸含有水溶液をえた。えられた水
溶液からアクロレインなどの軽沸点物質を蒸留除
去し、アクリル酸24重量％、酢酸0.8重量％、フ
タル酸類（オルソ、メタ、バラ）0.5重量％、マ
レイン酸0.8重量％、タール状物質1.0重量％を含
む水溶液20Kg／Hrをえた。Example 1 A molybdenum-based composite oxide was used as a catalyst for the first-stage reaction, and a catalyst based on a molybdenum-vanadium-based composite oxide was used as a catalyst for the second-stage reaction.
Propylene was subjected to a catalytic gas phase oxidation reaction with air in the presence of water vapor, and the resulting reaction product gas was cooled and condensed to obtain an aqueous solution containing acrylic acid containing hydroquinone as a polymerization inhibitor. Light boiling substances such as acrolein were removed by distillation from the resulting aqueous solution, resulting in 24% by weight of acrylic acid, 0.8% by weight of acetic acid, 0.5% by weight of phthalic acids (ortho, meta, rose), 0.8% by weight of maleic acid, and 1.0% by weight of tar-like substances. 20Kg/Hr of an aqueous solution containing % by weight was obtained.
この水溶液に、30重量％濃度の重亜硫酸ナトリ
ウム水溶液を0.25Kg／Hrの割合で添加混合し抽
出塔の上部から供給した。抽出塔下部からは酢酸
イソプロピルを20Kg／Hrの割合で供給し向流連
続的に、20日間抽出を行なつた。抽出操作は常温
常圧にて行なつた。抽出塔は内径70mm全高1800mm
の回転円板塔である。抽出は十分に抽出平衡に達
せしめたのち、抽出液（有機層）を26.9Kg／Hr
と抽残液（水性層）を13.4Kg／Hrの割合でえ
た。抽出塔の上部界面部分での分離不良による泡
状中間層はほとんどなく、またその後の工程であ
る抽出液の溶媒分離、軽沸点物分離および重質物
分離における各蒸留塔のカラムやリボイラ伝熱面
への高沸点物や重合物の付着は20日間の連続運転
後もきわめて少なく、さらに長期間の運転が可能
であつた。 To this aqueous solution, a 30% by weight aqueous sodium bisulfite solution was added and mixed at a rate of 0.25 Kg/Hr, and the mixture was supplied from the upper part of the extraction tower. Isopropyl acetate was supplied from the lower part of the extraction column at a rate of 20 kg/hr, and extraction was carried out continuously in countercurrent for 20 days. The extraction operation was performed at room temperature and pressure. The extraction tower has an inner diameter of 70mm and a total height of 1800mm.
It is a rotating disk tower. After sufficiently reaching extraction equilibrium, the extract (organic layer) was heated at 26.9Kg/Hr.
and a raffinate (aqueous layer) were obtained at a rate of 13.4 Kg/Hr. There is almost no foamy intermediate layer due to poor separation at the upper interface of the extraction tower, and the heat transfer surface of each distillation tower column and reboiler during the subsequent steps of solvent separation, light boiling point separation, and heavy substance separation of the extract. Even after 20 days of continuous operation, there was very little adhesion of high-boiling substances or polymers to the reactor, and it was possible to operate for an even longer period of time.
比較例 １
実施例１で用いたのと同じアクリル酸水溶液
を、実施例１におけると同じ装置および方法で抽
出処理した。ただし重亜硫酸ナトリウムは加えな
かつた。抽出平衡に達せしめたのち、抽出液（有
機層）として26.7Kg／Hr、抽残液（水性層）と
して13.1Kg／Hrがそれぞれえられた。抽出塔の
上部界面部分での泡状中間部は非常に多かつた。
また10日間の運転後溶媒分離塔、軽沸点物分離塔
でのカラムやリボイラには固形物の付着は認めら
れたが、運転を停止するほどではなかつたのに対
し、重質物分離塔のリボイラ伝熱面には固形物の
付着がきわめて多く、運転を継続しえない状態と
なつていた。Comparative Example 1 The same acrylic acid aqueous solution used in Example 1 was extracted using the same apparatus and method as in Example 1. However, sodium bisulfite was not added. After reaching extraction equilibrium, 26.7 Kg/Hr of the extract (organic layer) and 13.1 Kg/Hr of the raffinate (aqueous layer) were obtained. There were a large number of foamy intermediate parts at the upper interface part of the extraction column.
In addition, after 10 days of operation, solid matter was observed on the columns and reboilers of the solvent separation tower and light boiling point separation tower, but it was not enough to stop the operation, whereas the reboiler of the heavy material separation tower There was an extremely large amount of solid matter adhering to the heat transfer surface, making it impossible to continue operation.
実施例 ２
実施例１で用いたのと同じアクリル酸水溶液を
実施例１におけると同じ装置および方法で抽出処
理した。ただし、重亜硫酸ナトリウムのかわりに
重亜硫酸アンモニウムの30重量％濃度の水溶液を
0.5Kg／Hrの割合で添加混合した。十分に抽出平
衡に達せしめたのち抽出液（有機層）を26.8Kg／
Hrと抽残液（水性層）を13.7Kg／Hrの割合でえ
つつ20日間抽出を行なつた。抽出塔の上部界面部
分での泡状中間層はほとんどなく、また抽出液の
溶媒分離、軽沸点物分離および重質物分離におけ
る各蒸留塔のカラムやリボイラー伝熱面への高沸
点物や重合物の付着もきわめて少なく、さらに長
時間の運転が可能であつた。Example 2 The same acrylic acid aqueous solution used in Example 1 was extracted using the same apparatus and method as in Example 1. However, instead of sodium bisulfite, use an aqueous solution of ammonium bisulfite at a concentration of 30% by weight.
They were added and mixed at a rate of 0.5Kg/Hr. After sufficiently reaching extraction equilibrium, extract the extract (organic layer) to 26.8 kg/
Extraction was carried out for 20 days while obtaining Hr and raffinate (aqueous layer) at a ratio of 13.7 Kg/Hr. There is almost no foamy intermediate layer at the upper interface of the extraction tower, and high-boiling materials and polymers are present in the columns of each distillation tower and on the heat transfer surface of the reboiler during solvent separation, light boiling point separation, and heavy material separation of the extract. There was very little adhesion, and it was possible to operate for a longer period of time.
Claims (1)
化してアクリル酸を製造するプロセスにおいて、
酸化反応器より出るアクリル酸含有反応生成ガス
の冷却・凝縮操作によつてえられたアクリル酸水
溶液をまず該水溶液に含まれる軽沸点物質を蒸留
または放散操作によつて除去し、ついでえられた
アクリル酸水溶液に重亜硫酸塩を添加して抽出工
程に供し、当該抽出工程におけるスカムの発生を
防止することを特徴とするアクリル酸の精製方
法。 ２ 重亜硫酸塩がアルカリ金属塩およびアンモニ
ウム塩よりなる群から選ばれた少なくとも１種で
あることを特徴とする特許請求の範囲１記載の方
法。[Claims] 1. In a process for producing acrylic acid by catalytic gas phase oxidation of propylene or acrolein,
The acrylic acid aqueous solution obtained by cooling and condensing the acrylic acid-containing reaction product gas discharged from the oxidation reactor is first removed by distillation or dissipation to remove light boiling point substances contained in the aqueous solution. A method for purifying acrylic acid, which comprises adding bisulfite to an aqueous acrylic acid solution and subjecting it to an extraction step, thereby preventing the generation of scum in the extraction step. 2. The method according to claim 1, wherein the bisulfite is at least one selected from the group consisting of alkali metal salts and ammonium salts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11781282A JPS5910546A (en) | 1982-07-08 | 1982-07-08 | Method for purifying acrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11781282A JPS5910546A (en) | 1982-07-08 | 1982-07-08 | Method for purifying acrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5910546A JPS5910546A (en) | 1984-01-20 |
| JPS6245219B2 true JPS6245219B2 (en) | 1987-09-25 |
Family
ID=14720869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11781282A Granted JPS5910546A (en) | 1982-07-08 | 1982-07-08 | Method for purifying acrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5910546A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61218556A (en) * | 1985-03-25 | 1986-09-29 | Nippon Shokubai Kagaku Kogyo Co Ltd | Purification of acrylic acid |
-
1982
- 1982-07-08 JP JP11781282A patent/JPS5910546A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5910546A (en) | 1984-01-20 |
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