1242550 A7 B7 五、發明説明（1 ) 本發明係有關丙烯酸之製造方法，更詳細者係有關藉 由精製由接觸氣相氧化後取得粗丙烯酸後，經濟型進行製 造咼純度丙烯酸之方法。 (請先閲讀背面之注意事項再填寫本頁) 先行技術中，丙烯酸係爲反應性佳之化合物者，做爲 各種聚合物用單體，各種聚合性酯原料使用之重要化合物 者。此丙烯酸係於固體氧化觸媒之存在下，丙烯及/或丙 烯醛於氣相狀態下藉由分子狀氧進行氧化之方法，亦即， 藉由接觸氣相氧化進行工業製造者。藉由此丙烯酸之接觸 氣相氧化進行製造方法中，反應係於水蒸氣存在下被實施 者，因此，一般氧化生成物爲.含有丙烯酸氧化生成液（水 溶液）之狀態者。 此含有丙烯酸氧化生成液除丙烯酸之外，多半含有不 易與丙烯酸分離之糠醛、苯甲醛等醛類、馬來酸、無水馬 來酸、醋酸等羧酸類。由此含有丙烯酸水溶液進行回收丙 烯酸時，通常將生成液進行脫水處理後，利用精製方法藉 由蒸氣取得丙烯酸之方法。 經濟部智慧財4场：^工消費合作钍印製 其中，做爲該氧化生成液之脫水處理方法者，通常公 知者如使用酮、醋酸酯等溶劑之溶劑萃取法與使用與甲苯 、甲基異丁酮等之水共沸溶劑進行共沸脫水方法者。採用 此溶劑萃取法後，雖易於去除馬來酸類，惟，成本上不實 用，由經濟面觀之，以共沸脫水法爲有利者，工業上較爲 理想者。 丙烯酸近年來多半被用於高吸收性樹脂、高分子凝聚 劑等領域，惟，其聚合性極爲重要，含於粗丙烯酸之醛等 I纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 1242550 A7 B7__ 五、發明説明（2 ) 不純物造成極大問題點。因此，務必進行不純物之去除精 製，而被提出許多方法。 (請先閱讀背面之注意事項再填寫本頁) 例如，特公昭5 8 — 3 7 2 9 0號公報中被提出粗製 丙烯酸之脫水步驟中，於具有與丙烯酸同程度揮發性之醛 、酮類中使氫化胼進行反應後，變更爲縮合物之胼、曦後 ，分離去除之方法。惟，此精製方法其去除醛類之效率不 足而造成問題點。 又，特開平7 — 2 2 8 5 4 8號公報中被提出添加胼 化合物與二硫代月f酸銅於粗製丙烯酸後，於1 0 0 °C以下 溫度中進行蒸餾之方法。藉由採用此方法後，對於粗製丙 烯酸之精製步驟中之蒸餾塔進行丙烯酸聚合後，可抑制產 生附著，同時分離去除醛類等不純物後做成精製者，惟， 去除不純物之觀點上，亦即，由丙烯酸品質之觀點上，仍 出現與前項相同之問題點。 做爲其他丙烯酸之製造方法者如：於丙烯酸連續製造 方法之最終蒸餾柱體中，於2 5〜1 0 0 °C之溫度下，供 入粗丙烯酸與特定胺類該粗丙烯酸中醛及馬來酸以及無水 馬來酸之總莫耳數做爲基準者爲0 · 1〜2 · 0莫耳比之 含最少有效水準之供給流供給後，於最終蒸餾柱體上部供 與做爲該基準者爲〇·〇1〜1·〇莫耳比之其他特定胺 類之製造丙烯酸之製造方法者（特開平7 — 3 3 0 6 5 9 號公報、特開平9 — 1 2 4 5 4 6號公報）。 更被提出於共沸脫水處理之粗丙烯酸中添加至少1種 胼類等脫醛劑與脂肪族胺、複環式胺、芳香族單胺之胺類 本紙張尺度適用中國國家標準（CN'S ) A4規格（210X 297公釐）—: 5 - ' ""~ 1242550 A7 B7 五、發明説明（3 ) — ~ (請先閲讀背面之注意事項再填寫本頁) 後，進行蒸餾精製之丙烯酸製造方法（特開平9 -2 0 8 5 1 4號公報），於胼及氨之共存下進行蒸餾粗丙 烯酸之製造高純度丙烯酸之方法（特開平1 〇 -8 7 5 5 2號公報）’於共沸脫水處理前使含丙嫌酸水溶 液進行蒸發處理之方法中，可減輕製品化塔中之聚合附著 物之方法〔爲去除不純物仍使用胺類、胼類等〕（特開平 11 — 217350 號公報）。 此等丙烯酸之製造方法無論如何，係藉由添加胼類、 胺類、氨等使做爲含於粗丙烯酸之不純物者之醛類、馬來 酸、無水馬來酸做爲反應生成物被去除者。惟，此等丙烯 酸之製造方法中其藉由胼類等脫醛反應因馬來酸類而被阻 礙者爲公知者之問題點。 經濟部智慧时4-¾資工消費合itTi印製 因此，以胺等化學品去除馬來酸類後，進行確保醛與 胼類之反應性方法被利用之。惟，無法充份有效進行馬來 酸類或其反應生成物之殘存等脫醛作用，勢必造成過量使 用脫醛劑之同時，其精製度亦受限。又，此等方法中，添 加劑之反應生成物將形成殘渣，長期連續性運轉上亦出現 問題。更且，此等方法中，最後製品丙烯酸中之水份有出 現上昇之問題點。 本發明係以提供一種由接觸氣相氧化法取得之粗丙烯 酸進行製造高純度丙烯酸之方法者，可充份去除醛類、酮 類等不純物，抑制殘渣之生成，可長期連續運轉經濟面佳 之方法爲目的者。 本發明者針對製造丙烯酸之問題點，精密硏討脫醛劑 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐1 -6 - 1242550 A7 ____ —_B7 五、發明説明（4 ) 、胺等添加劑與添加量，殘渣之產生，殘存於精製丙烯酸 中之不純物量的關係後其結果發現由粗丙烯酸於特定水準 下去除馬來酸類時，可大幅減少丙烯酸蒸餾精製中添加齊U 之使用量，殘渣亦可，且明顯提高純度者。基於此發現， 進而完成本發明。 亦即，本發明係爲 (1 )將接觸氣相氧化取得含有丙烯酸之氧化生成物 進行共沸脫水處理取得之粗丙烯酸其該粗丙烯酸中馬來酸 及無水馬來酸之總濃度爲2，0 0 0 p p m以下，於胼類 之共存下進行蒸餾爲其特徵的製造丙烯酸之方法。 (2 )馬來酸及無水馬來酸之總濃度爲5 0 0〜 1，OOOppm之（1)所記載的丙烯酸製造方法。 (3 )胼類化合物如下記一般式（1 )所示之化合物 或其水和物（1 )或（2 )所載之丙烯酸製造方法。 R 1 ~ N — N Η 〇 · · · (1) (請先閱讀背面之注意事項再填寫本頁)1242550 A7 B7 V. Description of the invention (1) The present invention relates to a method for producing acrylic acid, and more specifically, it relates to a method for economically manufacturing a pure acrylic acid by purifying crude acrylic acid obtained by contact gas-phase oxidation by refining. (Please read the precautions on the back before filling this page.) In the prior art, acrylic acid is a compound with good reactivity, and it is an important compound for various polymer monomers and polymerizable ester raw materials. This acrylic acid is a method in which propylene and / or acrolein is oxidized by molecular oxygen in a gas phase state in the presence of a solid oxidation catalyst, that is, by an industrial manufacturer by contact gas phase oxidation. In the manufacturing method by contacting acrylic acid with gas phase oxidation, the reaction is performed in the presence of water vapor. Therefore, the general oxidation product is a state containing an acrylic acid oxidation solution (aqueous solution). In addition to acrylic acid, this acrylic acid-containing solution contains aldehydes such as furfural and benzaldehyde, maleic acid, anhydrous maleic acid, and acetic acid, which are not easily separated from acrylic acid. When acrylic acid is recovered by containing an acrylic acid aqueous solution in this way, the generated solution is usually subjected to dehydration treatment, and then the acrylic acid is obtained by steam by a purification method. 4 projects of the Ministry of Economic Affairs ’Smart Assets: printed with industrial and consumer cooperation. As the dehydration treatment method of this oxidation solution, generally known solvents such as ketone, acetate and other solvents are used for solvent extraction and use with toluene, methyl An azeotropic dehydration method using water azeotropic solvent such as isobutyl ketone. After using this solvent extraction method, although it is easy to remove maleic acid, it is not practical in terms of cost. From an economic point of view, the azeotropic dehydration method is advantageous and industrially desirable. Acrylic acid is mostly used in the fields of super absorbent resin and polymer flocculant in recent years. However, its polymerizability is extremely important. The paper size of aldehydes such as crude acrylic acid is applicable to Chinese National Standard (CNS) A4 (210X297). %) 1242550 A7 B7__ 5. Description of the invention (2) Impurities cause great problems. Therefore, it is necessary to carry out removal and purification of impurities, and many methods have been proposed. (Please read the precautions on the reverse side before filling out this page) For example, in the dehydration step of crude acrylic acid proposed in Japanese Patent Publication No. 5 8 — 3 7 2 9 0, aldehydes and ketones having the same degree of volatility as acrylic acid are used. After reacting hydrogenated hydrazone in the middle, it is changed to a method of separating and removing condensate after dysprosium and sunlight. However, this purification method is not efficient enough to remove aldehydes and causes problems. In addition, Japanese Patent Application Laid-Open No. 7-2 2 8 5 4 8 proposes a method of adding a sulfonium compound and copper dithioate f acid to crude acrylic acid, followed by distillation at a temperature of 100 ° C or lower. By adopting this method, after acrylic acid polymerization is performed on the distillation column in the purification step of crude acrylic acid, adhesion can be suppressed, and impurities such as aldehydes can be separated and removed, and refined, but from the viewpoint of removing impurities, that is, From the viewpoint of the quality of acrylic acid, the same problem as the previous paragraph still occurs. As other methods for producing acrylic acid, for example, in the final distillation column of the continuous acrylic acid manufacturing method, supply crude acrylic acid and specific amines at a temperature of 25 to 100 ° C, and the aldehydes and horses in the crude acrylic acid. The total number of moles of maleic acid and anhydrous maleic acid is 0. 1 ~ 2. 0. The molar ratio is the minimum effective level of the supply stream, and it is supplied on the upper part of the final distillation column as the reference. 〇1 ～ 1 · 〇 Morby's other specific amines to produce acrylic acid production method (Japanese Patent Application Laid-Open No. 7-3 3 0 6 5 9 and Japanese Patent Application Laid-open No. 9-1 2 4 5 4 6 Bulletin). It is also proposed to add at least one kind of dealdehyde agent such as fluorene and amines such as aliphatic amines, polycyclic amines, and aromatic monoamines to crude acrylic acid treated with azeotropic dehydration. This paper applies Chinese national standards (CN'S) A4. Specifications (210X 297mm) —: 5-'" " ~ 1242550 A7 B7 V. Description of the Invention (3) — ~ (Please read the precautions on the back before filling in this page), and then make distilled acrylic acid Method (Japanese Patent Application Laid-Open No. 9-2 0 8 5 14), a method for producing high-purity acrylic acid by distilling crude acrylic acid in the coexistence of tritium and ammonia (Japanese Patent Application Laid-open No. 10-8-8 5 5 2) In the method for evaporating the propionic acid-containing aqueous solution before the azeotropic dehydration treatment, a method for reducing the polymerized attachments in the productization tower [still using amines and amidines to remove impurities] (Japanese Patent Application No. 11-217350) Bulletin). In any case, the production methods of these acrylic acids are to remove aldehydes, maleic acid, and anhydrous maleic acid as the reaction products by adding amidines, amines, ammonia, etc. as impurities in crude acrylic acid. By. However, in these methods for producing acrylic acid, it is a known problem that those who are blocked by maleic acids by a dealdehyde reaction such as amidines. Printed by the Ministry of Economic Affairs of the Ministry of Economic Affairs and Industry, and it is printed by ItTi. Therefore, after removing maleic acid with chemicals such as amines, a method to ensure the reactivity of aldehydes and amidines is used. However, the inability to effectively perform dealdehyde removal such as the remnants of maleic acid or its reaction products will inevitably result in excessive use of the dealdehyde agent, and its refined system is also limited. Also, in these methods, the reaction products of the additives will form residues, and there will be problems in long-term continuous operation. Moreover, in these methods, there is a problem that the moisture content of acrylic acid in the final product rises. The present invention is to provide a method for manufacturing high-purity acrylic acid by contacting crude acrylic acid obtained by a gas phase oxidation method, which can sufficiently remove impurities such as aldehydes and ketones, suppress the formation of residues, and can run continuously for a long period of time with good economic performance. For the purpose. In view of the problem of manufacturing acrylic acid, the present inventors have discussed the dealdehyde agent precisely. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm 1 -6-1242550 A7 ____ — _B7. 5. Description of the invention (4), amine The relationship between the additives and the amount of addition, the generation of residues, and the amount of impurities remaining in the refined acrylic acid was found. When the maleic acid was removed from crude acrylic acid at a specific level, the amount of added Qi in the distillation and purification of acrylic acid could be greatly reduced. The residue can also be used, and the purity is significantly improved. Based on this finding, the present invention has been completed. That is, the present invention is (1) a crude crude obtained by contacting gas-phase oxidation to obtain an oxidation product containing acrylic acid and performing an azeotropic dehydration treatment. Acrylic acid: A method for producing acrylic acid with a characteristic that the total concentration of maleic acid and anhydrous maleic acid in the crude acrylic acid is below 2,000 ppm, and distillation is performed in the coexistence of amidines. (2) Maleic acid and The total concentration of anhydrous maleic acid is 5,000 to 1,000 ppm. The method for producing acrylic acid according to (1). (3) The amidine compound is a compound represented by the following general formula (1) And a water (1) or (2) a method for producing acrylic acid contained in R 1 ~ N -. N Η square · (1) (Read precautions and then fill the back side of this page)
R 經濟部智慧財是场員工消費合作社印製 R 中 式R The Ministry of Economy's Smart Money is printed by the staff consumer cooperative R Chinese
烷 之 3 - IX 數 碳 子 原 氫 表 代 別 分 2 R 或 / -基sfi 苯段中 之階} 基前3 代塔彳 取顧 ~ 有蒸 } 具於 1 /|\， \)/ 基 4 之 苯{類 ’ 胼 基 加 者 基 烴 式 環 匕曰 添做 時法 餾方 蒸造 行製 進之 中酸 塔烯 餾丙 蒸載 或所 者 旨 主 爲 的 類 醛 之 酸 烯 丙 粗 於 含 爲 量載 加所 添} 之 4 類C 胼之 \)/ 倍 5 量 ( 當 耳 莫 法 方 造 製 的 酸 烯 丙 8 本紙浪尺度適用中國國家標準（CNS) A4規格（210X 297公釐） 1242550 A7 B7 五、發明説明（5 ) 〔發明實施之最佳形態〕 (請先閲讀背面之注意事項再填寫本頁) 以下，針對本發明進行詳細說明。本發明中藉由接觸 氣相氧化所取得之粗丙烯酸係使用使丙烯及/或丙烯醛之 接觸氣相氧化取得之含有丙烯酸氧化生成液進行共沸脫水 處理後所成之粗丙烯酸者。此含有丙烯酸生成液可藉由丙 烯酸之一段氧化法取得反應生成液，亦可爲二段氧化法取 得之反應生成液者。此等含丙烯酸生成液係以水蒸氣於反 應中，故以丙烯酸水溶液狀態者宜。 此含有丙烯酸之氧化生成液組成依其氧化方法之形式 ，氧化反應條件等而異。惟，一般其各成成份之含有量爲 5 0〜80質量％ί之丙烯酸，20〜50質量％之水， 0 · 3〜2質量％之馬來酸，1〇〇〜5〇Op pm之糠 醛，100〜500ppm之苯甲醛者。本發明中，首先 爲經濟型之脫水方法者，藉由共沸脫水處理方法由含丙烯 酸氧化生成液去除水份後，取得粗丙烯酸者。 經濟部智慧財4^_工消費合itvi印髮 做爲此共沸脫水處理方法者，並無特別限定，丙烯酸 製造方法中可採用公知之方法者。例如，做爲共沸劑之例 者如：甲苯、二甲苯、乙苯、庚烷、甲基異丁酮、二異丁 酮、或此等混合物使用之，於1 0〜2 5 k P a左右之減 壓下進行共沸脫水處理者。 藉由此共沸脫水處理後，共沸脫水塔之塔底液中水份 濃度爲1， 0 0 0 ρ p m以下者。又，由共沸脫水塔之塔 頂去除水、醋酸、共沸劑、低沸點醛類。水與共沸劑以互 衣紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -8 - 1242550 Λ7 _ B7_ 五、發明説明（6 ) 爲不溶者宜，餾出液爲導住系外’油相做爲回流液往共沸 塔進行循環使用之。藉由此共沸脫水處理後’由塔底取得 粗丙烯酸。更且，必要時亦可去除醋酸等輕質成份。 接著，此粗丙烯酸進行重質成份分離處理’如：導入 重質成份分離塔，藉由一般蒸餾方法取得留出液。此留出 液中，取得含有水、醋酸、共沸劑、醛等低沸點物等不純 物之粗丙烯酸者。又，塔底液’呈馬來酸、無水馬來酸等 馬來酸類之高濃度丙烯酸適度導往系外進行去除之。 其中，重質成份分離塔之蒸餾條件其粗丙烯酸中馬來 酸及無水馬來酸之總濃度以2 , 0 0 0 P P m以下者宜， 較佳者爲1，500ppm以下’更佳者設定爲 1， 〇〇〇ppm者。本發明丙烯酸製造方法中’使此重 質成份分離塔之馬來酸類濃度調低者宜’而’後記實施例 可證明，做成500〜1， OOOppm者於以下蒸餾步 驟中可製造高純度之丙烯酸者。 亦即，高純度丙烯酸之製造方法中，存在含馬來酸類 之問題點，此一般藉由化學方法者。惟’由本發明硏討後 發現某程度之物理性去除之簡便方法可解決該問題點。因 此，爲使馬來酸完全去除’無需耗費高價之蒸餾塔’所採 蒸餾條件下即可以經濟型進行者乃本發明最大特徵者。 爲分離、去除此重質成份之蒸餾分離並無特別限定， 一般於壓力5〜15kPa ’塔底溫度60〜90°C之條 件下進行之。 以下，馬來酸類降低濃度之粗丙烯酸係於最終精製處 本紙張尺度適用中國國家標準（CNS) A4規格（210x297公釐） " —^ϋ —^1 ···--- --11 1;T m m - --- II I (請先閲讀背面之注意事項再填寫本頁) ,ν5 1242550 A7 B7_ 五、發明説明（7 ) 理之蒸餾塔進行處理之。此蒸餾處理於胼類存在下進行者 〇 (請先閲讀背面之注意事項再填寫本頁) 本發明中重要要件爲（1 )供與此蒸餾塔之粗丙烯酸 中馬來酸類濃度爲2， ΟΟΟρρπι以下者。（ii)針 對此條件之粗丙烯酸添加胼類者。 其中，添加胼類於馬來酸類降低濃度之粗丙烯酸條件 者並無特別限定，可於蒸餾塔前階段及/或蒸餾塔中進行 之。例如：與粗丙烯酸預先混合後供入蒸餾塔，可採用同 時於供給口供給之、或各別供給之方法者。其中，爲預先 混合供給時，可採用利用具有攪拌器、泵循環線之供給粗 丙烯酸桶之方法，設置靜力混合器，管線用攪拌器於供給 線之方法者。 做爲所添加胼類之例者，並無特別限定，以下記一般 式（1 )所式化合物或其水和物爲理想示例者。 R 1 - N - Ν Η 2 · · · ( ι )3-IX number of alkane protons represented by 2 R or /-radical sfi in the benzene segment} the first three radicals of the radical are taken care of ~ there is steaming} with 1 / | \ ， \) / radical 4 of the benzene {class' stilbene plus carbohydrocarbon ring ring is added when the time method distillation process steaming process in the distillation of acid tarene or aldehyde-like acid allyl crude The content of the type 4 C 胼 of the content is added to the content) and 5 times the amount (acid allyl produced by Dang Mofang method) This paper applies the Chinese National Standard (CNS) A4 specification (210X 297) (12%) 1242550 A7 B7 V. Description of the invention (5) [Best form of implementation of the invention] (Please read the precautions on the back before filling out this page) The following is a detailed description of the present invention. In the present invention, by contacting the gas phase The crude acrylic acid obtained by the oxidation is a crude acrylic acid obtained by subjecting propylene and / or acrolein to gas-phase oxidation in contact with an acrylic acid-containing oxidation solution containing azeotropic dehydration treatment. This acrylic acid-containing solution can be obtained by using acrylic acid. One-stage oxidation method to obtain the reaction solution, or two-stage Those obtained by the chemical reaction method. These acrylic acid-containing liquids use water vapor in the reaction, so those in the form of an acrylic acid aqueous solution are preferred. The composition of the oxidation-containing liquid containing acrylic acid depends on the form of its oxidation method, oxidation reaction conditions, etc. However, generally, the content of each component is 50 to 80% by mass of acrylic acid, 20 to 50% by mass of water, 0.3 to 2% by mass of maleic acid, and 100 to 50%. Op pm furfural, 100 ~ 500ppm benzaldehyde. In the present invention, the economic dehydration method is first, and the crude acrylic acid is obtained by removing water from the acrylic acid-containing oxidation solution by an azeotropic dehydration treatment method. Ministry of Wisdom 4 ^ _Industrial consumption and itvi printing and distribution is not particularly limited as the azeotropic dehydration treatment method, and known methods can be used in the production method of acrylic acid. For example, as examples of azeotropic agents: Those who use toluene, xylene, ethylbenzene, heptane, methyl isobutyl ketone, diisobutyl ketone, or a mixture thereof, and perform an azeotropic dehydration treatment under a reduced pressure of about 10 to 25 kPa. After this azeotropic dehydration treatment The water concentration in the bottom liquid of the azeotropic dehydration tower is below 1, 0 0 0 ρ pm. In addition, water, acetic acid, azeotrope, and low boiling point aldehydes are removed from the top of the azeotropic dehydration tower. Water and co-dehydration The boiling agent is compatible with the Chinese National Standard (CNS) A4 specification (210X 297 mm) at the scale of the intercoat paper. -8-1242550 Λ7 _ B7_ V. Description of the invention (6) It should be insoluble, and the distillate should be outside the guide system. The oil phase is recycled to the azeotropic column as a reflux liquid. After this azeotropic dehydration treatment, crude acrylic acid was obtained from the bottom of the column. Moreover, light components such as acetic acid can be removed when necessary. Next, this crude acrylic acid is subjected to heavy component separation treatment ', for example, it is introduced into a heavy component separation column, and the remaining liquid is obtained by a general distillation method. In this retentate, crude acrylic acid containing impurities such as low-boiling substances such as water, acetic acid, azeotrope, and aldehyde was obtained. In addition, the tower bottom liquid 'is a high-concentration acrylic acid containing maleic acids such as maleic acid, anhydrous maleic acid, etc., and is appropriately led out of the system for removal. Among them, the distillation conditions of the heavy component separation tower are those in which the total concentration of maleic acid and anhydrous maleic acid in crude acrylic acid is less than 2,000 PP m, and more preferably 1,500 ppm or less. It is 10,000 ppm. In the method for producing acrylic acid of the present invention, 'it is desirable to reduce the concentration of maleic acids in this heavy component separation tower', and the postscript example can prove that those with a concentration of 500 to 1,000 ppm can produce high-purity Acrylic. That is, the method for producing high-purity acrylic acid has a problem of containing maleic acid, and this is generally performed by a chemical method. However, after discussing the present invention, a simple method of physical removal to a certain degree can solve this problem. Therefore, the most characteristic feature of the present invention is that it can be carried out economically under the distillation conditions adopted for the complete removal of maleic acid 'without the need for an expensive distillation column'. Distillation separation for separating and removing this heavy component is not particularly limited, and it is generally performed under a pressure of 5 to 15 kPa ′ and a bottom temperature of 60 to 90 ° C. In the following, the crude acrylic acid with reduced maleic acid concentration is applied at the final refining place. The paper size applies the Chinese National Standard (CNS) A4 (210x297 mm) " — ^ ϋ — ^ 1 ··· --- --11 1 ; T mm---- II I (please read the precautions on the back before filling this page), ν5 1242550 A7 B7_ 5. Description of the invention (7) The distillation column is used for processing. This distillation process is carried out in the presence of amidines (please read the precautions on the back before filling this page). The important element in the present invention is (1) the concentration of maleic acid in the crude acrylic acid used in this distillation tower is 2, ΟΟρρπι The following. (Ii) For those who add 胼 to crude acrylic acid in this condition. Among them, the conditions for adding crude methacrylic acid to maleic acid to reduce the concentration of crude acrylic acid are not particularly limited, and they can be carried out in the pre-distillation stage and / or in the distillation column. For example, the crude acrylic acid is mixed with crude acrylic acid before being supplied to the distillation column, and it may be supplied simultaneously at the supply port or separately. Among them, in the case of pre-mixing and supplying, a method of supplying a crude acrylic barrel with a stirrer and a pump circulation line, a method of installing a static mixer, and a pipeline agitator on the supply line may be adopted. There is no particular limitation on the examples of the added amidines. The compounds represented by the general formula (1) or their water compounds are described below as ideal examples. R 1-N-Ν Η 2 · · · (ι)
I R 2 經濟部智慧財4¾¾工消費合作fi印製 〔式中，R1，R2分別代表氫原子，碳數1〜3之烷 基，苯基，具取代基之苯基或脂環式烴基。〕 做爲拼類之具體例者如：餅、苯脚、三餅、α ，α -甲基苯胼、α，α -二苯胼、/3 -萘胼等或此等水和物之 例。又，此等胼類或其水和物亦可複數使用之。 胼類添加量可依含於供入蒸餾塔之粗丙烯酸不純物之 濃度進行適當選取之。具體而言，爲不純物醛類之1〜8 本紙張尺度適用中國國家標準（CNS ) Α4規格（210X 297公羞)~]〇Ζ ' 1242550 A7 ______B7 五、發明説明（8 ) 倍者宜，較佳者爲3〜5倍〔各莫耳當量〕。 (請先閲讀背面之注意事項再填寫本頁) 做爲此粗丙烯酸蒸餾方法者，並無特別限定，可使用 各種蒸餾，其蒸餾條件之一例可採用壓力5〜1 0 k P a ，塔底液溫6 0〜9 0 °C之條件者。做爲此蒸餾之塔頂飽 出液之高純度丙烯酸可於所供給粗丙烯酸之6 0〜9 0容 量％範圍下取得。此精製丙烯酸係可藉由選定粗製條件後 ，使糠醛、苯甲醛、馬來酸等不純物爲1 p p m以下者。 本發明丙烯酸之製造方法係於共沸脫水處理，重質成 分分離處理，蒸餾處理等步驟下進行者。此等步驟、設備 、處理條件等依其處理方法、裝置尺寸、粗丙烯酸組成， 回收率，做爲精製丙烯酸目的之純度等而異，除本申請發 明特定以外，可做適當選擇。另外，丙烯酸爲極易聚合之 化合物者，因此，蒸餾等條件以採用極低壓，低溫之條件 者宜。 經濟部智慧时4^7H工消費合作社印发 又，本發明丙烯酸製造方法之蒸餾操作亦可分批蒸餾 者，惟，連續蒸餾者由工業面，生產性面爲較佳者。另外 ，爲防止丙烯酸聚合必要時可添加做爲聚合防止劑之公知 化合物，如：對苯二醛、甲氧基苯酚、對苯二酚單用甲醚 等之苯酚類、噻吩嗪、二苯胺、等胺類、二丁基二硫代胺 基甲酸銅等銅鹽、醋酸錳等錳鹽、硝基化合物、亞硝化合 物等者。 以下，藉由實施例及比較例進行本發明更詳細之說明 ，惟，本發明並非僅限於此等例者。又，丙烯酸中不純物 之定量係利用氣體層析法。 本紙張尺度適用中國國家標率（CNS ) A4規格（210X297公釐） -11 - 1242550 A7 B7 五、發明説明（1 2 3 4 5 6 7 8 9 10 ) 〔實施形態1〕 (請先閱讀背面之注意事項再填寫本頁) (1) 共沸脫水處理 於塡充塡充劑之小型蒸餾裝置（共沸脫水裝置）〔直 徑2 · 6mm、長度：660mm〕中使丙烯一般接觸氣 相氧化所取得之含丙烯酸氧化生成液以3 5 m 1 /小時之 速度’同時使做爲共沸溶劑之甲苯以1 3 5 m 1 /小時之 速度，連續供與後，於塔頂中壓力：1 7 . 5 k P a、溫 度：8 5 °C之條件下進行共沸脫水處理後取得粗丙烯酸① 。此粗丙烯酸①中，含有糠醛：470ppm、苯甲醛： 450ppm、馬來酸類：11，〇〇〇p p m。 經濟部皙慧財447M工消費合作社印製 1 重質成份分離蒸餾 2 於塡充塡充劑之小型蒸餾裝置（重質成份分離塔）〔 3 直徑2 · 6mm、長度：660mm〕中使該（1)取得 4 之粗丙烯酸①以3 0 m 1 /小時之速度下連續供與後，於 5 塔頂中壓力：5 · 3kPa 、溫度：65°C、塔底壓力： 6 1 0 · 0 k P a ，塔底溫度：8 2 °C之條件下進行蒸餾後 7 ，取得做爲餾出液之粗丙烯酸②。此粗丙烯酸②中，含有 糠醛：230ppm、苯甲醛：6〇PPm、馬來酸類： 8 880ppm。亦即，使馬來酸類含量去除至2， 00〇 9 p p m以下者。 10 (3 )丙烯酸之蒸餾處理 1242550 A7 B7 五、發明説明（i〇) (請先閱讀背面之注意事項再填寫本頁) 同時添加該（2 )取得：粗丙烯酸②與5 9 0 p p m 之胼1水和物〔醛類（針對糠醛與苯甲醛之和）爲4倍莫 耳當量〕後，以3 0 m 1 /小時之速度連續供入塡充塡充 劑之小型蒸館裝置（丙嫌酸蒸I留塔）〔直徑2 · 6 m m、 長度：660mm〕後，於塔頂中壓力：5 · 3kpa 、 溫度：6 5 °C、塔底壓力：1 0 · 0 k P a ’塔底溫度： 7 9 °C之條件下進行蒸餾後，針對做爲塔頂留出液之供給 液，取得粗製7 5容量％量之高純度丙烯酸。 所取得高純度丙烯酸中糠醛、苯甲醛、馬來酸類均爲 lppm以下，水份爲570ppm者。又，蒸餾塔塔底 液中之糠酸爲1 0 P pm、苯甲酸爲1 5 P pm、馬來酸 類爲5 0 P P ni者。另外’此時蒸餾塔塔底未出現析出物 〔實施例2〕 經濟部智慧財1¾吕：工消費合作社印製 實施例1中，預先使胼水和物與粗丙傭酸②進行混合 5分鐘後，連續供入丙烯酸蒸餾塔之外’與實施例1同法 操作取得做爲塔頂留出液所精製之高純度丙嫌酸。所取得 高純度丙烯酸中之糠醛、苯甲醛、馬來酸類均爲1 p pm 以下、水份爲5 9 0 P P m者。又，蒸態塔塔底液中之糠 醛爲7ppm、苯甲醛爲llPPm、馬來酸類爲4：3 m m p者。另外，此時蒸餾塔塔底未出現析出物。 〔比較例1〕 -13- 本纸張尺度適用中國國家標隼（CNS) A4規格（2ι〇χ 297公董） 1242550 A7 B7 五、發明説明（11) (請先閱讀背面之注意事項再填寫本頁) 同時添加實施例1之（1 )所取得含1 1，0 〇〇 p p m馬來酸類之粗丙烯酸①與1，8 3 0 P P m胼1水 和物〔針對醛類4倍莫耳當量〕之後’於丙烯酸蒸餾塔中 連續供與之外，與實施例1同法取得做爲塔頂留出液之精 製丙烯酸。所取得精製丙烯酸中糠醛爲8 p P ni、苯甲醒 1 p p m、馬來酸類爲1 5 p p m、水份爲1，7 5 0 p p m者。又，蒸館塔塔底液中之糠醛爲1 5 0 p p m、 苯甲醒爲240ppm、馬來酸類爲31， OOOppm 者。又，此時蒸觀塔塔底中出現大量析出物。 〔比較例2〕 同時添加1 1， 0 0 0 p p m實施例1之（1 )所取 經濟部智慧財4.^7:H工消#合作社印製 得之馬來酸類粗丙烯酸①與2，7 4 0 p p m之胼1水和 物〔爲胼類之6倍莫耳當量〕後，連續供入丙烯酸蒸餾塔 之外，與實施例1同法取得做爲塔頂留出液所精製之丙烯 酸。所取得精製丙烯酸中之糠醛爲5 p pm、苯甲醛爲1 ppm、馬來酸類爲l〇PPm、水份爲2，6 3 0 p pm者。另外，蒸餾塔塔底液中之糠醛爲1 1 〇 p pm 、苯甲醛爲180ppm、馬來酸類爲23， 000 p p m者。此時蒸態塔塔底中比比較例1之析出物更爲大 量。 〔比較例3〕 變更實施例1之（2 )中之蒸餾條件，取得含糠醛： 本紙張尺中Ϊ國^iTcNS ) A4規格（210/ 297公董1 :14 - 讎 1242550 A7 B7 五、發明説明（12) 290ppm、苯甲醛爲13〇PPm、馬來酸類： 2， 5 0 0 p p m之粗丙烯酸③。於此添加胼1水和物： 8 5 0 p p m，〔爲胼類之4倍莫耳當量〕後’連續供入 丙烯酸蒸餾塔之外，與實施例1同法取得做爲塔頂餾出液 之精製丙嫌酸者。所取得精製丙嫌酸中之糖輕爲2 P pm 、苯甲醛爲1 P P m、馬來酸類爲4 p p m、水份爲 8 1 0 p p m者。又，蒸餾塔塔底液中糠醛爲4 0 P P m 、苯甲醛爲30ppm、馬來酸類爲4， 5〇〇ppm者 。另外，此時蒸餾塔塔底中出現析出物。 〔產業上可利用性〕 本發明之製造方法係由藉由丙烯及或丙烯酸之接觸氣 相氧化所取得之粗丙烯酸可降低成本製造高純度丙烯酸’ 且於蒸餾精製時可抑制殘渣之產生。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產苟员工消費合作社印^ 本纸張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -15 - ^_____ 告本f 110032號專利申請案骑g -說明書修正頁 ί ' ..Α > 申請曰期 —_9° ^ 4 月 26 日 案 號 —X·__ 90110032 類 別 各櫊由本局填註 1242550 民國93年5月21日修正 A4 C4 f 2專利説明書 發明 新型 名稱 發明 創作 人 中文 英文 姓 名 丙烯酸之製造方法I R 2 Printed by the Ministry of Economic Affairs, Smart Wealth, Industrial and Consumer Cooperation, [printed in [where R1 and R2 respectively represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a phenyl group, a substituted phenyl group or an alicyclic hydrocarbon group. 〕 As specific examples of spelling, such as: cakes, benzene legs, three cakes, α, α-methylphenylhydrazone, α, α-diphenylhydrazone, / 3-naphthalene, etc. or examples of these water and substances . In addition, these tadpoles or their water and substances can also be used in plural. The amount of amidines can be appropriately selected according to the concentration of the crude acrylic acid impurities contained in the distillation column. Specifically, it is 1 ~ 8 of impure aldehydes. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 public shame) ~] 〇Z '1242550 A7 ______B7 5. The invention is better (8) The best is 3 to 5 times [each mole equivalent]. (Please read the precautions on the back before filling this page) There is no particular limitation on the method for distilling crude acrylic acid. Various distillations can be used. One example of the distillation conditions can be pressure 5 ~ 10 k P a, bottom of the column. Those with a liquid temperature of 60 to 90 ° C. High-purity acrylic acid used as the saturated liquid at the top of the distillation for this purpose can be obtained in the range of 60% to 90% by volume of the crude acrylic acid supplied. In this refined acrylic system, by selecting the crude conditions, the impurities such as furfural, benzaldehyde, and maleic acid can be reduced to 1 p p m or less. The method for producing acrylic acid of the present invention is performed under the steps of azeotropic dehydration treatment, heavy component separation treatment, and distillation treatment. These steps, equipment, and processing conditions vary according to their processing method, device size, crude acrylic acid composition, recovery rate, purity for the purpose of purifying acrylic acid, etc., except as specified in the present application, appropriate selections can be made. In addition, acrylic acid is a compound that is highly polymerizable. Therefore, conditions such as distillation and the use of extremely low pressure and low temperature are preferred. Printed and distributed by 4 ^ 7H Industrial and Consumer Cooperatives of the Ministry of Economic Affairs. Furthermore, the distillation operation of the acrylic acid manufacturing method of the present invention can also be performed in batches. However, continuous distillation is preferred from the industrial side and the productive side. In addition, in order to prevent the polymerization of acrylic acid, known compounds can be added as polymerization inhibitors if necessary, such as: phenols such as terephthalaldehyde, methoxyphenol, monomethyl ether, hydroquinone, diphenylamine, Such as amines, copper salts such as copper dibutyldithioaminoformate, manganese salts such as manganese acetate, nitro compounds, nitros compounds and the like. Hereinafter, the present invention will be described in more detail through examples and comparative examples. However, the present invention is not limited to those examples. The amount of impurities in acrylic acid was determined by gas chromatography. This paper size applies to China National Standards (CNS) A4 specifications (210X297 mm) -11-1242550 A7 B7 V. Description of the invention (1 2 3 4 5 6 7 8 9 10) [Embodiment 1] (Please read the back first Note: Please fill in this page again.) (1) Azeotropic dehydration treatment in a small distillation device (azeotropic dehydration device) [diameter 2 · 6mm, length: 660mm] in a small distillation unit filled with 塡 charge and 塡 charge. The obtained acrylic acid-containing oxidation solution was continuously supplied at a speed of 3 5 m 1 / h while the toluene as an azeotropic solvent was supplied at a speed of 1 3 5 m 1 / h. The pressure in the top of the tower was 1 7 Crude acrylic acid ① was obtained after azeotropic dehydration at 5 k P a and temperature: 8 5 ° C. This crude acrylic acid ① contained furfural: 470 ppm, benzaldehyde: 450 ppm, and maleic acids: 11,000 p p m. Printed by Xihuicai 447M Industrial and Consumer Cooperative of the Ministry of Economic Affairs 1 Separation and distillation of heavy components 2 In a small distillation device (heavy component separation tower) filled with tincture filling [3 diameter 2 · 6mm, length: 660mm] 1) Obtain crude acrylic acid of 4 ① After continuous supply at a speed of 30 m 1 / h, the pressure at the top of the tower: 5 · 3kPa, temperature: 65 ° C, the pressure at the bottom of the tower: 6 1 0 · 0 k P a, column bottom temperature: 8 2 ° C after distillation 7 to obtain crude acrylic acid as distillate ②. This crude acrylic acid ② contains furfural: 230 ppm, benzaldehyde: 60 ppm, and maleic acids: 8 880 ppm. That is, the content of maleic acids is reduced to less than 2,009 p p m. 10 (3) Distillation of acrylic acid 1242550 A7 B7 V. Description of the invention (i〇) (Please read the notes on the back before filling this page) Add this (2) at the same time to obtain: crude acrylic acid ② and 5 9 0 ppm 1 After the water and aldehydes [the aldehydes (for furfural and benzaldehyde) is 4 times the molar equivalent], it is continuously fed into a small steaming hall device filled with tincture at a speed of 30 m 1 / hour Acid distillation I retention tower) [diameter 2 · 6 mm, length: 660mm], pressure at the top of the tower: 5 · 3kpa, temperature: 65 ° C, pressure at the bottom of the tower: 1 0 · 0 k P a ' Temperature: After distillation at 79 ° C, a crude 75% by volume high-purity acrylic acid was obtained for the feed liquid remaining as the liquid at the top of the column. The furfural, benzaldehyde, and maleic acid in the obtained high-purity acrylic acid were all below 1 ppm, and the water content was 570 ppm. Further, the furfuric acid in the bottom liquid of the distillation column is 10 P pm, the benzoic acid is 15 P pm, and the maleic acid is 50 P P ni. In addition, at this time, no precipitates appeared at the bottom of the distillation column. [Example 2] Ministry of Economic Affairs, Intellectual Property 1¾, Lu: In Example 1 printed by the Industrial and Commercial Cooperative, the mash and the crude propionic acid were mixed for 5 minutes After that, it was continuously fed outside the acrylic acid distillation column, and the same procedure as in Example 1 was followed to obtain a high-purity propionic acid refined as a liquid left at the top of the column. The furfural, benzaldehyde, and maleic acid in the obtained high-purity acrylic acid were all below 1 p pm and the water content was 590 P P m. Further, the furfural in the bottom liquid of the vaporized tower was 7 ppm, the benzaldehyde was llPPm, and the maleic acid was 4: 3 m m p. In addition, no precipitates appeared at the bottom of the distillation column at this time. [Comparative Example 1] -13- This paper size applies to China National Standards (CNS) A4 (2ιχχ 297 public directors) 1242550 A7 B7 V. Description of the invention (11) (Please read the notes on the back before filling (This page) At the same time, the crude acrylic acid containing maleic acids 1 and 1,000 ppm obtained in Example 1 (1) was added together with 1,8 3 0 PP m 胼 1 water and compound [4 times mole for aldehydes. Equivalent] After that, it was continuously supplied in an acrylic acid distillation column, and purified acrylic acid was obtained as a liquid left at the top of the column in the same manner as in Example 1. In the obtained purified acrylic acid, furfural was 8 p P ni, benzophenone was 1 p p m, maleic acid was 15 p p m, and water content was 1,750 p p m. In addition, the furfural in the bottom liquid of the steaming tower tower was 150 p pm, the benzyl chloride was 240 ppm, and the maleic acid was 31,000 ppm. At this time, a large amount of precipitates appeared in the bottom of the steaming tower. [Comparative Example 2] At the same time, 1 1,000 ppm was added at the same time as Example 1 (1) of the Ministry of Economic Affairs, Smart Money 4. ^ 7: H 工 消 # Cooperatives printed crude maleic acid acrylic acid ① and 2, After 740 ppm of hydrazone 1 water [6 times the molar equivalent of hydrazone], it was continuously fed into the acrylic acid distillation column, and the acrylic acid refined as the liquid left over from the column was obtained in the same manner as in Example 1. . The furfural in the obtained purified acrylic acid was 5 p pm, the benzaldehyde was 1 ppm, the maleic acid was 10 PPm, and the water content was 2, 6 30 p pm. In addition, the furfural in the bottom liquid of the distillation column was 1 10 p pm, the benzaldehyde was 180 ppm, and the maleic acid was 23,000 p p m. At this time, the amount of precipitates in the bottom of the vaporized column was larger than that in Comparative Example 1. [Comparative Example 3] The distillation conditions in Example 1 (2) were changed to obtain furfural: The paper ruler iiTcNS) A4 specification (210/297 Gong Dong 1:14-雠 1242550 A7 B7 V. Invention Note (12) 290ppm, benzaldehyde is 13〇PPm, maleic acid: 2,500 ppm crude acrylic acid ③. Here is added 胼 1 water and substances: 850 ppm, [4 times as much as 胼Ear equivalent] After continuously feeding into the acrylic acid distillation column, the same method as in Example 1 was used to obtain the refined propionic acid as the overhead of the column. The sugar in the refined propionic acid obtained was 2 P pm, Those with benzaldehyde of 1 PP m, maleic acids of 4 ppm, and water of 810 ppm. Also, furfural in the bottom liquid of the distillation column is 40 PP m, benzaldehyde is 30 ppm, and maleic acids are 4, 5 〇ppm。 In addition, precipitates appear in the bottom of the distillation column at this time. [Industrial Applicability] The production method of the present invention is to reduce crude acrylic acid obtained by contact gas phase oxidation of propylene and acrylic acid. Cost-effective manufacturing of high-purity acrylic acid 'and suppresses the generation of residues during distillation and refining. (Please read the note on the back first Please fill in this page again) Printed by the Intellectual Property of the Ministry of Economic Affairs, Employees' Cooperatives, ^ This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) -15-^ _____ Notice F 110032 -Amendment page of the description ί '..Α > Application date—_9 ° ^ April 26th case number—X · __ 90110032 Each category is filled by this office 1242550 May 21, 1993 Amendment of A4 C4 f 2 patent Instructions Invention New Name Inventor Chinese and English Name Acrylic Manufacturing Method
Method for producing acrylic acid (1) 中川貴史 Nakagawa，Takashi (2) 田代裕統 Tashiro, Hironori (3) 富田幸次 Tomita，Kouji 國 籍 住、居所 姓 名 (名稱） (3) 曰本 (1)日本 （2)日本 (1) 日本國山口縣德山市新宮町--- 1Ί, Shinguuchou, Tokuyama-shi, Yamaguchi 745-8691 Jap (2) 日本國山口縣德山市新宮町--- 1Ί, Shinguuchou, Tokuyaina-shi, Yamaguchi 745-8691 Jap (3) 日本固山口縣德山市新宮町--- 1-1, Shinguuchou, Tokuyaraa-shi, Yamaguchi 745-8691 Japjan (1)出#石油化學股份有限公司 Idemitsu Petrochemical Co., Ltd. 裝 an 訂 線 部 !h ：/) * /.V it Ti 印 ¥ 國 籍 申請人 住、居所 (事務所） 代表人 姓 名 ¢1)日本 Π)日本國東京都墨田區横網一丁目六一一 6-1, Yokoami 1-chome, Suinida-ku, Tokyo 130Ό015 Japan ⑴富永一途 Tominaga，Ka2iito 本凡度4用中國國家標準（〔π 規格（2i〇'x297公釐） 1242550 S3. 5· 21 申請曰期 90 年 4 月 26日 案 號 90110032 A4 C4 類 (以上各櫊 a由^局或註） 業！專 利説明書 中 文 發明 新型 名稱 英 文 姓 名 國 籍 發明 創作 人 (4)長尾郁也 Nagao，Ikuya ⑻日本 (4)日本國愛知縣知多市南浜町—— 11, Minamihama-cho, Chita-shi, Aichi 478^8555 Japan 裝 住、居所Method for producing acrylic acid (1) Takaashi Nakagawa, Takashi (2) Tashiro, Hironori (3) Yuji Tomoda, Tomita, Kouji Nationality residence and residence name (name) (3) Japanese version (1) Japan (2) Japan (1) Shinguuchou, Tokuyama-shi, Yamaguchi 745-8691 Jap (2) Shinguuchou, Tokuyama-shi, Yamaguchi, Yamaguchi Prefecture, Japan (2) Shinguuchou, Tokuyaina- Tokuyama-shi, Yamaguchi, Japan shi, Yamaguchi 745-8691 Jap (3) Shinguuchou, Tokuyaraa, Tokuyaraa-shi, Yamaguchi 745-8691 Japjan (1) 出 # Petrochemical Co., Ltd. Idemitsu Petrochemical Co ., Ltd. Binding department! H: /) * /.V it Ti Print ¥ Nationality applicant's residence, residence (office) Representative name ¢ 1) Japan Π) Yokohama, Ichime, Sumida-ku, Tokyo, Japan 6-1, 6-1, Yokoami 1-chome, Suinida-ku, Tokyo 130Ό015 Japan Tomoagai Tominaga, Ka2iito Benfandu 4 uses the Chinese national standard ([π specification (2i〇'x297 mm) 1242550 S3. 5 · 21 Application No. 90110032 A4 C4 dated April 26, 1990 The above 櫊 a by ^ Bureau or Note) industry! Patent Specification Chinese Invention New Name English Name Nationality Inventor (4) Ikuya Nagao, Ikuya ⑻ Japan (4) Nanbei-cho, Chita-shi, Aichi Prefecture, Japan—— 11, Minamihama-cho, Chita-shi, Aichi 478 ^ 8555 Japan
IT 姓 名 (名稱） 國 籍 線 三、申請人 住、居所 (事務所） 代表人 姓 名 本纸张尺度過用中國國家標準（CNS ) A4規格（210X 297公釐）IT Surname (Name) Nationality Line III. Applicant's Residence, Domicile (Office) Representative's Surname This paper has been used in accordance with China National Standard (CNS) A4 specification (210X 297 mm)