TW201326115A

TW201326115A - Process for preparation of methacrylic and methacrylic acid ester

Info

Publication number: TW201326115A
Application number: TW101133298A
Authority: TW
Inventors: Jerald A Jones; Torsten Balduf; Henning Schaefer
Original assignee: Evonik Roehm Gmbh
Priority date: 2011-09-16
Filing date: 2012-09-12
Publication date: 2013-07-01
Also published as: WO2013037131A1; SG2014012637A; JP6092221B2; KR20140060529A; CN103796982A; JP2014528934A; TWI535696B; MY165642A; CN103796982B; SA112330847B1

Abstract

The invention relates to a process for preparation of at least one of methacrylic acid and a methacrylic acid ester, and a process for treatment of an aqueous phase comprising at least one organic compound comprising process steps: (a1) gas phase oxidation of at least one C4 compound to obtain a reaction phase comprising methacrylic acid; (a2) quenching of the reaction phase to obtain a crude aqueous phase comprising methacrylic acid; (a3) extraction of at least a part of the methacrylic acid from the crude aqueous phase comprising methacrylic acid into an organic solvent to obtain a crude organic phase comprising methacrylic acid and a first aqueous phase, wherein the first aqueous phase comprises components i. at least 65 wt.%, preferably in the range of from 65 wt.% to 99.9 wt.%, more preferably in the range of from 70 wt.% to 99.8 wt.% water, yet more preferably in the range of from 75 wt.% to 99 wt.%, more preferably in the range of from 76 wt.% to 98.5 wt.%, more preferably in the range of from 77 wt.% to 98 wt.%, even more preferably in the range of from 78 wt.% to 97.5 wt.%, even more preferably in the range of from 79 wt.% to 95 wt.%, yet more preferably in the range of from 80 wt.% to 90 wt.% water, based on the total weight of the first aqueous phase, and ii. not more than 35 wt.%, preferably in the range of from 0.1 wt.% to 35 wt.%, preferably in the range of from 0.2 wt.% to 30 wt.%, more preferably in the range of from 1 wt.% to 25 wt.%, yet more preferably in the range of from 1.5 wt.% to 24 wt.%, more preferably in the range of from 2 wt.% to 23 wt.%, even more preferably in the range of from 2.5 wt.% to 22 wt.%, even more preferably in the range of from 5 wt.% to 21 wt.%, yet more preferably in the range of from 10 wt.% to 20 wt.% of at least one organic compound other than the organic solvent used as extraction agent, based on the total weight of the first aqueous phase, wherein the sum of the weight amounts of i. and ii. is 100 wt.%; (a4) separation and optionally purification of at least a part of the methacrylic acid from the crude organic phase comprising methacrylic acid; (a5) optionally, esterification of at least a part of the methacrylic acid obtained in step (a4); (b) crystallisation of at least a part of the water from at least a part of the first aqueous phase obtained in process step (a3) to form a crystallised aqueous phase as second aqueous phase and a mother liquor, wherein the mother liquor comprises at least one component ii.; (c) at least partial separation of the crystallised aqueous phase from the mother liquor.

Description

製備甲基丙烯酸及甲基丙烯酸酯的方法 Method for preparing methacrylic acid and methacrylic acid ester

本發明關於一種製備甲基丙烯酸的方法，一種製備甲基丙烯酸酯的方法及一種處理包含至少一種有機化合物之水相的方法。 The present invention relates to a process for the preparation of methacrylic acid, a process for the preparation of methacrylates and a process for the treatment of an aqueous phase comprising at least one organic compound.

甲基丙烯酸(MAA)及甲基丙烯酸酯(諸如甲基丙烯酸甲酯(MMA)及甲基丙烯酸丁酯)被用於各種廣泛的應用中。甲基丙烯酸的商業化製造尤其係藉由異丁烯、第三丁醇、甲基丙烯醛或異丁醛的異相催化之氣相氧化反應而發生。因此獲得的氣態反應相係藉由冷卻和冷凝而轉變成甲基丙烯酸水溶液，隨意地自低沸騰物質(諸如乙醛、丙酮、乙酸、丙烯醛和甲基丙烯醛)分離且接著引入溶劑萃取塔中，俾以利用適合的萃取劑(諸如短鏈烴類)萃取且分離甲基丙烯酸。將分離之甲基丙烯酸以例如蒸餾而進一步純化，以分離高沸騰雜質(諸如苯甲酸、順丁烯二酸和對苯二甲酸)，俾以獲得純甲基丙烯酸。此已知的方法說明於例如EP 0 710 643、US 4,618,709、US 4,956,493、EP 386 117和US 5,248,819中。 Methacrylic acid (MAA) and methacrylates such as methyl methacrylate (MMA) and butyl methacrylate are used in a wide variety of applications. The commercial production of methacrylic acid occurs, inter alia, by a heterogeneously catalyzed gas phase oxidation reaction of isobutylene, tert-butanol, methacrolein or isobutyraldehyde. The gaseous reaction phase thus obtained is converted to an aqueous solution of methacrylic acid by cooling and condensation, optionally separated from low boiling materials such as acetaldehyde, acetone, acetic acid, acrolein and methacrolein and then introduced into a solvent extraction column. In the meantime, hydrazine is extracted and separated using a suitable extractant such as a short chain hydrocarbon. The separated methacrylic acid is further purified, for example, by distillation to separate high boiling impurities such as benzoic acid, maleic acid, and terephthalic acid, to obtain pure methacrylic acid. This known method is described, for example, in EP 0 710 643, US 4,618, 709, US 4, 956, 493, EP 386 117 and US 5,248,819.

此等已知的方法在各種過程階段產生大量廢水，其中最大的量係在自驟冷相萃取甲基丙烯酸之後餘留的水相形式。水主要來自添加至氣相氧化步驟中的蒸汽或水，及作為冷卻和冷凝步驟中的驟冷劑之水以及氧化反應本身的水。此廢水含有相當大量的有機化合物，且沒有進一步處理以移出至少部分該等有機化合物時不可再被使用或被安全地處置掉。此等有機化合物通常包括非所欲產物(諸如由於不完全萃取至有機萃取劑中的甲基丙烯酸)以及氧化步驟的其他副產物，諸如亦具有商業價值的丙烯酸、乙酸和丙酸。在此廢水中的有機物含量通常太高而與不需要顯著的稀釋、相當多的時間及非常大的處理設施之水處理方法(諸如生物處理，例如活化淤泥方法)不相容，使得常燃燒在甲基丙烯酸的商業化製造中之廢水，如例如在US 4,618,709中所述。然而，廢水的燃燒不利於環境和節約，需要輸入高能量，導致在釋放至環境之前可能需要進一步處理的放射，且亦導致存在於廢水中的具潛在價值之有機化合物的損失以及水本身的損失。 These known processes produce large amounts of wastewater at various stages of the process, the largest of which is in the form of an aqueous phase remaining after the methacrylic acid is extracted from the quenching phase. The water mainly comes from the steam or water added to the gas phase oxidation step, and the water as a quenching agent in the cooling and condensation steps and the oxidation reaction itself. water. This wastewater contains a significant amount of organic compound and can no longer be used or disposed of safely without further treatment to remove at least a portion of the organic compounds. Such organic compounds typically include undesired products (such as methacrylic acid due to incomplete extraction into the organic extractant) and other by-products of the oxidation step, such as acrylic acid, acetic acid, and propionic acid, which are also of commercial value. The organic content in this wastewater is usually too high to be incompatible with water treatment methods (such as biological treatments, such as activated sludge methods) that do not require significant dilution, considerable time, and very large treatment facilities, such that they are often burned at Waste water in the commercial manufacture of methacrylic acid, as described, for example, in US 4,618,709. However, the combustion of wastewater is not conducive to the environment and economy, requires the input of high energy, leads to radiation that may require further treatment before being released to the environment, and also results in the loss of potentially valuable organic compounds present in the wastewater and the loss of water itself. .

因此可能有利的是能夠回收存在於廢水中的至少部分的有機化合物。亦可能有利的是回收至少一些水本身，其具有足以對其施以生物處理及/或排放至環境中的低有機物含量(例如，沒有進一步的處理)，或具有足以使水可再使用(例如，用作為工業處理水)或用在反應本身中(例如，氧化及/或驟冷步驟中)的純度。CN 1903738提出使用薄膜分離器及接著以精餾塔純化來自丙烯酸製造的廢水且回收丙烯酸、甲苯和乙酸。薄膜過濾的缺點在於通常需要大量的水(常使用廢水本身)清洗掉不通過過濾器的組分。接著必須進一步處理或燃燒具有有機化合物濃度增加的此清洗水本身。 It may therefore be advantageous to be able to recover at least a portion of the organic compounds present in the wastewater. It may also be advantageous to recover at least some of the water itself, having a low organic content sufficient to be biologically treated and/or discharged into the environment (eg, without further processing), or having sufficient water to be reusable (eg, , used as industrial treated water) or used in the reaction itself (for example, in the oxidation and / or quenching steps) purity. CN 1903738 proposes the use of a membrane separator and subsequent purification of waste water from acrylic acid production in a rectification column and recovery of acrylic acid, toluene and acetic acid. A disadvantage of membrane filtration is that it usually requires a large amount of water (often using the wastewater itself) to wash away components that do not pass through the filter. This cleaning water itself having an increased concentration of the organic compound must then be further processed or burned.

本發明的目的概括地儘可能克服或避免先前技藝方法的缺點。 The object of the invention is to generally overcome or avoid the disadvantages of the prior art methods as far as possible.

進一步的目的係藉由自製程廢水回收有機化合物而增加甲基丙烯酸製造方法的總效率及/或總產率。 A further object is to increase the overall efficiency and/or overall yield of the methacrylic acid manufacturing process by recovering the organic compound from the proprietary process wastewater.

本發明的另一目的係藉由儘可能減低以有機化合物污染廢水，使得水可再使用，施以生物純化方法，或隨意地在生物或其他類型的純化方法之後排放至環境中，而不是與有機化合物一起燃燒。 Another object of the present invention is to reduce the consumption of wastewater by organic compounds, to make the water reusable, to apply biological purification methods, or to arbitrarily discharge to the environment after biological or other types of purification methods, rather than The organic compounds burn together.

解答上述目的的貢獻係由製造甲基丙烯酸及甲基丙烯酸酯中至少一者的方法而達成，其包含以下的方法步驟：a1)將至少一種C₄化合物氣相氧化，獲得包含甲基丙烯酸的反應相；a2)將反應相驟冷，獲得包含甲基丙烯酸的粗水相；a3)自包含甲基丙烯酸的粗水相將至少一部分的甲基丙烯酸萃取至有機溶劑中，獲得包含甲基丙烯酸的粗有機相和第一水相，其中第一水相包含以下組分：i.以第一水相總重量為基準計至少65重量%，較佳為從65重量%至99.9重量%之範圍內，更佳為從70重量%至99.8重量%之範圍內的水，又更佳為從75重量%至99重量%之範圍內，更佳為從76重量%至98.5重量%之範圍內，更佳為從77重量%至98重量%之範圍內，甚至更佳為從78重量%至 97.5重量%之範圍內，甚至更佳為從79重量%至95重量%之範圍內，又更佳為從80重量%至90重量%之範圍內的水，及ii.以第一水相總重量為基準計不超過35重量%，較佳為從0.1重量%至35重量%之範圍內，較佳為從0.2重量%至30重量%之範圍內，更佳為從1重量%至25重量%之範圍內，又更佳為從1.5重量%至24重量%之範圍內，更佳為從2重量%至23重量%之範圍內，甚至更佳為從2.5重量%至22重量%之範圍內，甚至更佳為從5重量%至21重量%之範圍內，又更佳為從10重量%至20重量%之範圍內的至少一種有機化合物(除了用作萃取劑的有機溶劑以外)，其中i.與ii.之重量總和為100重量%；a4)自包含甲基丙烯酸的粗有機相分離且隨意地純化至少一部分的甲基丙烯酸；a5)隨意地將步驟a4)中所獲得的至少一部分甲基丙烯酸酯化；b)自至少一部分方法步驟a3)中所獲得的第一水相結晶至少一部分的水，形成結晶水相作為第二水相和母液，其中母液包含至少一種組分ii.；c)將結晶水相與母液至少部分分離。 The contribution to the above object is attained by a method for producing at least one of methacrylic acid and methacrylic acid ester, which comprises the following method steps: a1) gas phase oxidation of at least one C ₄ compound to obtain a methacrylic acid-containing compound. a reaction phase; a2) quenching the reaction phase to obtain a crude aqueous phase comprising methacrylic acid; a3) extracting at least a portion of the methacrylic acid from the crude aqueous phase comprising methacrylic acid into an organic solvent to obtain a methacrylic acid a crude organic phase and a first aqueous phase, wherein the first aqueous phase comprises the following components: i. at least 65% by weight, preferably from 65% to 99.9% by weight, based on the total weight of the first aqueous phase More preferably, it is in the range of from 70% by weight to 99.8% by weight, still more preferably in the range of from 75% by weight to 99% by weight, more preferably from 76% by weight to 98.5% by weight, More preferably, it is in the range of from 77% by weight to 98% by weight, even more preferably in the range of from 78% by weight to 97.5% by weight, even more preferably from 79% by weight to 95% by weight, and even more preferably Is from 80% by weight to 90% by weight of water, and ii. with the first aqueous phase The weight is not more than 35% by weight, preferably from 0.1% by weight to 35% by weight, preferably from 0.2% by weight to 30% by weight, more preferably from 1% by weight to 25% by weight. More preferably, it is in the range of from 1.5% by weight to 24% by weight, more preferably from 2% by weight to 23% by weight, even more preferably from 2.5% by weight to 22% by weight. Even more preferably, in an amount ranging from 5 wt% to 21 wt%, still more preferably from 10 wt% to 20 wt%, in addition to an organic solvent used as an extractant, Wherein the sum of the weights of i. and ii. is 100% by weight; a4) separating from the crude organic phase comprising methacrylic acid and optionally purifying at least a portion of the methacrylic acid; a5) optionally at least the fraction obtained in step a4) a portion of methacrylated; b) crystallizing at least a portion of the water from at least a portion of the first aqueous phase obtained in process step a3) to form a crystalline aqueous phase as a second aqueous phase and a mother liquor, wherein the mother liquor comprises at least one component ii .) c) at least partially separating the crystalline aqueous phase from the mother liquor.

一種解答上述目的貢獻亦由處理包含至少一種有機化合物的水相之方法而達成，其包含以下的方法步驟： a)提供包含以下組分的第一水相：i.以第一水相總重量為基準計至少65重量%，較佳為從65重量%至99.9重量%之範圍內，更佳為從70重量%至99.8重量%之範圍內的水，又更佳為從75重量%至99重量%之範圍內，更佳為從76重量%至98.5重量%之範圍內，更佳為從77重量%至98重量%之範圍內，甚至更佳為從78重量%至97.5重量%之範圍內，甚至更佳為從79重量%至95重量%之範圍內，又更佳為從80重量%至90重量%之範圍內的水，及ii.以第一水相總重量為基準計不超過35重量%，較佳為從0.1重量%至35重量%之範圍內，較佳為從0.2重量%至30重量%之範圍內，更佳為從1重量%至25重量%之範圍內，又更佳為從1.5重量%至24重量%之範圍內，更佳為從2重量%至23重量%之範圍內，甚至更佳為從2.5重量%至22重量%之範圍內，甚至更佳為從5重量%至21重量%之範圍內，又更佳為從10重量%至20重量%之範圍內的至少一種有機化合物，其中i.與ii.之重量總和為100重量%，b)自至少一部分的第一水相結晶至少一部分的水，形成結晶水相作為第二水相和母液，其中母液包含至少一種組分ii.；c)將結晶水相與母液至少部分分離。 One solution to the above objective contribution is also achieved by a method of treating an aqueous phase comprising at least one organic compound, which comprises the following method steps: a) providing a first aqueous phase comprising: i. at least 65% by weight, preferably from 65% to 99.9% by weight, more preferably from 70% by weight based on the total weight of the first aqueous phase The water in the range of from 5% by weight to 99.8% by weight, more preferably from 75% by weight to 99% by weight, more preferably from 76% by weight to 98.5% by weight, still more preferably from 77% by weight In the range of 98% by weight, even more preferably in the range of 78% by weight to 97.5% by weight, even more preferably in the range of 79% by weight to 95% by weight, still more preferably from 80% by weight to 90% by weight Water in the range of % by weight, and ii. not more than 35% by weight, based on the total weight of the first aqueous phase, preferably from 0.1% by weight to 35% by weight, preferably from 0.2% by weight to Within the range of 30% by weight, more preferably from 1% by weight to 25% by weight, still more preferably from 1.5% by weight to 24% by weight, more preferably from 2% by weight to 23% by weight In the range, even more preferably in the range of from 2.5% by weight to 22% by weight, even more preferably in the range of from 5% by weight to 21% by weight, still more preferably in the range of from 10% by weight to 20% by weight At least one An organic compound wherein the sum of the weights of i. and ii. is 100% by weight, b) crystallizing at least a portion of the water from at least a portion of the first aqueous phase, forming a crystalline aqueous phase as the second aqueous phase and the mother liquor, wherein the mother liquor comprises at least one Component ii.; c) at least partially separates the aqueous crystalline phase from the mother liquor.

施以根據本發明之方法的步驟a1)中的氣相氧化反應之C₄化合物較佳為選自異丁烯、第三丁醇、異丁醛和甲基丙烯醛或二或多種其混合物的C₄化合物。在本發明較佳的態樣中，C₄化合物係衍生自甲基第三丁基醚(MTBE)或乙基第三丁基醚(ETBE)的***。 Subjected to gas phase oxidation reaction of a1) from the steps of the method according to the present invention is preferably a C ₄ compound selected from isobutylene, tert-butanol, methacrolein or isobutyraldehyde, and two or more C ₄ mixtures thereof Compound. In a preferred aspect of the present invention, C ₄ compound is derived from methyl tert-butyl ether (MTBE) or ethyl tert-butyl ether (ETBE) split.

在根據本發明之方法的步驟a1)中的氣相氧化反應較佳地發生在至少一種氧化觸媒的存在下。若C₄化合物為異丁烯或第三丁醇，則獲得包含甲基丙烯酸之氣相的氣相氧化反應可發生於一個步驟中，由此於本上下文中的一個步驟被認為意指初步氧化成甲基丙烯醛及進一步氧化成甲基丙烯酸實質上係發生在至少一種觸媒存在下的相同的反應區中。另一選擇地，在步驟a1)中的氣相氧化反應可發生於一個以上的步驟中，較佳為兩個步驟中，較佳為互相獨立的二或多個反應區，由此以二或多個觸媒存在較佳，各觸媒較佳地與各其他觸媒存在於獨立的反應區中。在兩步驟氣相氧化反應中，第一步驟較佳地將C₄化合物至少部分氧化成甲基丙烯醛，接著將甲基丙烯醛至少部分氧化成甲基丙烯酸。據此，例如較佳地至少一種適合於至少一種C₄化合物氧化成甲基丙烯醛的觸媒存在於第一反應步驟中及至少一種適合於甲基丙烯醛氧化成甲基丙烯酸的觸媒存在於第二反應步驟中。 The gas phase oxidation reaction in step a1) of the process according to the invention preferably takes place in the presence of at least one oxidation catalyst. If the C ₄ compound is isobutylene or tert-butanol, a gas phase oxidation reaction to obtain a gas phase comprising methacrylic acid can occur in one step, whereby a step in this context is considered to mean preliminary oxidation to a The acrolein and further oxidation to methacrylic acid occur substantially in the same reaction zone in the presence of at least one catalyst. Alternatively, the gas phase oxidation reaction in step a1) may occur in more than one step, preferably in two steps, preferably two or more reaction zones independent of each other, thereby A plurality of catalysts are preferred, and each catalyst is preferably present in a separate reaction zone with each of the other catalysts. In the two-step gas phase oxidation, the first step of C ₄ compound is preferably at least partial oxidation of methacrolein, followed by at least partial oxidation of methacrolein to methacrylic acid. Accordingly, for example, preferably at least one catalyst suitable for the oxidation of at least one C ₄ compound to methacrolein is present in the first reaction step and at least one catalyst suitable for the oxidation of methacrolein to methacrylic acid In the second reaction step.

適合於氣相催化氧化的反應條件為例如從約250℃至約450℃，較佳為從約250℃至約390℃之溫度及從約1大氣壓至約5大氣壓之壓力。空間速度的變化可從約100至約6000小時^-1(NTP)，而較佳為從約500至約3000小時^-1。C₄進料(諸如異丁烯)氧化(例如，氣相催化氧化)成甲基丙烯醛及/或甲基丙烯酸，以及為此之觸媒係從例如US 5,248,819、US 5,231,226、US 5,276,178、US 6,596,901、US 4,652,673、US 6,498,270、US 5,198,579、US 5,583,084之文獻中所熟知。 The reaction conditions suitable for gas phase catalytic oxidation are, for example, from about 250 ° C to about 450 ° C, preferably from about 250 ° C to about 390 ° C and from about 1 atmosphere to about 5 atm. The change in space velocity can range from about 100 to about 6000 hours ^-1 (NTP), and preferably from about 500 to about 3000 hours ^-1 . The C ₄ feed (such as isobutylene) is oxidized (e.g., gas phase catalyzed) to methacrolein and/or methacrylic acid, and the catalyst system for this purpose is, for example, from US 5,248,819, US 5,231,226, US 5,276,178, US 6,596,901, It is well known in the literature of US 4,652,673, US 6,498, 270, US 5, 198, 579, US 5, 583, 084.

適合於異丁烯或第三丁醇氧化成甲基丙烯醛及/或甲基丙烯酸之特別佳的觸媒和方法說明於EP 0 267 556中，及適合於甲基丙烯醛氧化成甲基丙烯酸之特別佳的觸媒和方法說明於EP 0 376 117中。該等文件特此引入以供參考且構成本發明揭示內容的一部分。 Particularly preferred catalysts and processes suitable for the oxidation of isobutylene or tert-butanol to methacrolein and/or methacrylic acid are described in EP 0 267 556 and are suitable for the oxidation of methacrolein to methacrylic acid. Preferred catalysts and methods are described in EP 0 376 117. The documents are hereby incorporated by reference in their entirety for all purposes in the extent of the disclosure.

在根據本發明之方法中，甲基丙烯醛成為甲基丙烯酸的氣相氧化反應較佳地發生在從約250至且低於約350℃之溫度下，在從約1至約3大氣壓之壓力下及在從約800至約1800 Nl/l/h之體積負荷下。 In the process according to the invention, the gas phase oxidation of methacrolein to methacrylic acid preferably occurs at a temperature of from about 250 to less than about 350 ° C at a pressure of from about 1 to about 3 atm. Below and under a volume load of from about 800 to about 1800 Nl/l/h.

通常使用氧作為氧化劑，例如以空氣形式，或以純氧或以至少一種在反應條件下為惰性之氣體(諸如氮、一氧化碳和二氧化碳中至少一者)稀釋之氧形式，由此以空氣作為氧化劑較佳及以氮及/或二氧化碳作為稀釋氣體較佳。若使用二氧化碳作為稀釋氣體，則較佳為從燃燒再循環之二氧化碳，較佳為反應氣體及/或副產物的催化或熱燃燒。施以根據本發明之方法的步驟a1)中的氣相氧化反應之氣體較佳地亦包含水，其通常以水蒸氣形式存在。可將氧、惰性氣體或氣體類及水在氣相反應之前或期間或之前及期間引入反應相中或與C₄化合物組合。 Oxygen is generally used as the oxidant, for example in the form of air, or in the form of oxygen or at least one of the gases which are inert under the reaction conditions, such as at least one of nitrogen, carbon monoxide and carbon dioxide, whereby air is used as the oxidant. Preferably, nitrogen and/or carbon dioxide is used as the diluent gas. If carbon dioxide is used as the diluent gas, it is preferably carbon dioxide recycled from combustion, preferably catalytic or thermal combustion of the reaction gas and/or by-products. The gas which is subjected to the gas phase oxidation reaction in the step a1) of the method according to the invention preferably also comprises water, which is usually present in the form of water vapor. Oxygen, and inert gas or gases such as water vapor may be introduced before, during or prior to the reaction or during the reaction phase and the C ₄ compound or composition.

在根據本發明之方法的較佳具體例中，將包含至少一種C₄化合物、空氣或氧及再循環之氧化反應器出口氣體(較佳為在循環前已燃燒之反應器出口氣體)之混合物供給至步驟a1)。反應器出口氣體係取決於分離條件及燃燒步驟的存在和作用而較佳地包含至少一種未反應之C₄化合物、至少一種氧化碳、氮和氧以及水。 In particular preferred embodiment the method according to the invention, comprising at least one C ₄ compound, air or oxygen oxidation and recycling the outlet gas of the reactor (preferably prior to the combustion cycle in the reactor outlet gas) mixture of Supply to step a1). Reactor off-gas separation system depends on the conditions and the presence and action of a combustion step preferably comprises C ₄ and at least one compound of the unreacted at least one carbon oxide, nitrogen and oxygen, and water.

在根據本發明的兩步驟氣相氧化反應中，在第一步驟中的C₄化合物：O₂：H₂O：惰性氣體之較佳的體積比通常為1：0.5-5：1-20：3-30，較佳為1：1-3：2-10：7-20。在第二步驟中的甲基丙烯醛：O₂：H₂O：惰性氣體之體積比較佳為1：1-5：2-20：3-30，較佳為1：1-4：3-10：7-18。 In the two-step gas phase oxidation reaction according to the present invention, the preferred volume ratio of the C ₄ compound:O ₂ :H ₂ O:inert gas in the first step is usually 1:0.5-5:1-20: 3-30, preferably 1:1-3:2-10:7-20. The methacrolein in the second step: O ₂ :H ₂ O: the volume of the inert gas is preferably 1:1-5:2-20:3-30, preferably 1:1-4:3- 10:7-18.

在根據本發明之方法的步驟a2)中，將包含甲基丙烯酸的氣相冷卻且冷凝(常已知為驟冷)，獲得包含甲基丙烯酸的粗水溶液形式的冷凝物。冷凝可以熟諳本技藝者已知且顯然適合的任何方式發生，例如藉由將包含甲基丙烯酸的氣相冷卻至低於其組分中至少一者(特別為水和甲基丙烯酸中至少一者)的露點之溫度。適合的冷卻方法為熟諳本技藝者所知，例如利用至少一個熱交換器，或以驟冷，例如以液體噴灑氣相，例如以水、水性組成物或有機溶劑，諸如芳族或脂族烴或至少兩種其之混合物的有機溶劑，由此較佳的有機溶劑在驟冷條件下具有相對低的蒸氣壓力，諸如庚烷、甲苯或二甲苯，由此以水作為根據本發明的驟冷液體較佳，且以驟冷步驟本身所形成之至少一部分的冷凝物甚至更佳。適合的驟冷方法為熟諳本技藝者所知，例如來自DE 21 36 396、EP 297 445、EP 297 788、JP 01193240、JP 01242547、JP 01006233、US 2001/0007043、US 6,596,901、US 4,956,493、US 4,618,709、US 5,248,819，將該等關於驟冷丙烯酸及甲基丙烯酸類之揭示內容特此併入且構成本發明的一部分。根據本發明較佳的是將氣相冷卻至介於40與80℃之間的溫度且以水及/或來自驟冷步驟的冷凝物清洗，獲得包含甲基丙烯酸的水溶液，其亦可包含不同的雜質量，諸如乙酸、順丁烯二酸、反丁烯二酸、檸康酸、丙烯酸和甲酸，以及醛類，諸如甲醛、乙醛、丙醛、丙烯醛、甲基丙烯醛，酮類和未反應之C₄化合物或化合物類。必須將該等雜質以及水以最大可能的程度與甲基丙烯酸分離，俾以獲得高純度的甲基丙烯酸。 In step a2) of the process according to the invention, the gas phase comprising methacrylic acid is cooled and condensed (often known as quenching) to obtain a condensate in the form of a crude aqueous solution comprising methacrylic acid. Condensation can occur in any manner known and apparently suitable to those skilled in the art, for example by cooling a gas phase comprising methacrylic acid to at least one of its constituents (particularly at least one of water and methacrylic acid) The temperature of the dew point. Suitable cooling methods are known to those skilled in the art, for example by using at least one heat exchanger, or by quenching, for example by spraying a liquid phase, for example with water, an aqueous composition or an organic solvent, such as an aromatic or aliphatic hydrocarbon. Or an organic solvent of at least two mixtures thereof, whereby the preferred organic solvent has a relatively low vapor pressure under quenching conditions, such as heptane, toluene or xylene, whereby water is used as the quenching according to the invention The liquid is preferred and at least a portion of the condensate formed by the quenching step itself is even better. Suitable quenching methods are known to those skilled in the art, for example, from DE 21 36 396, EP 297 445, EP 297 788, JP 01193240, JP 01242547, JP 01006233, US 2001/0007043, US 6, 596, 901, US 4, 956, 493, US 4, 618, 709. U.S. Patent No. 5,248,819, the disclosure of which is incorporated herein by reference in its entirety in its entirety in its entirety in the the the the the the the the the It is preferred according to the invention to cool the gas phase to a temperature between 40 and 80 ° C and to wash with water and/or condensate from the quenching step to obtain an aqueous solution comprising methacrylic acid, which may also comprise different Miscellaneous masses such as acetic acid, maleic acid, fumaric acid, citraconic acid, acrylic acid and formic acid, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, methacrolein, ketones And unreacted C ₄ compounds or compounds. The impurities and water must be separated from the methacrylic acid to the greatest extent possible to obtain high purity methacrylic acid.

自包含甲基丙烯酸的粗水溶液萃取至少一部分的甲基丙烯酸係利用有機萃取劑發生在方法步驟a3)中，例如利用至少一種有機溶劑，較佳為至少一種實質上與水不混溶之有機溶劑，使得可形成水相和有機相。可在根據本發明之方法的步驟c)中使用之較佳的有機溶劑具有與甲基丙烯酸沸點不同(較佳為較低)的沸點。在根據本發明之方法中，在方法步驟a3)中所使用之有機萃取劑較佳地具有在大氣壓力下所測量而低於161℃之沸點。接著在根據本發明之方法的步驟a4)中，有機萃取劑原則上可藉由例如蒸餾(較佳為至少部分蒸餾)而較佳地以相當的程度與甲基丙烯酸分離，較佳地在蒸餾裝置中比純甲基丙烯酸高的層至少部分移出作為低沸騰物的萃取劑。可將分離之有機萃取劑或其一部分引導返回方法步驟a3)，隨意地在至少一個冷卻及/或純化步驟之後。用於此步驟之較佳的有機溶劑特別選自烷烴及芳族，較佳為烷基芳族、烴，由此以至少一種選自C₆-C₈烴之有機溶劑較佳，由此以庚烷、甲苯及二甲苯特別佳，而以庚烷(較佳為正庚烷)最佳。萃取可以熟諳本技藝者已知且顯然適合的任何方式進行，較佳以逆向流萃取，例如利用溶劑萃取塔、脈衝式填充塔或填料塔、旋轉萃取器、清洗塔、相分離器或適合以有機溶劑萃取水相且自水相分離有機相的其他裝置。根據本發明較佳的是將至少部分，較佳為至少50重量%，較佳為至少約70重量%，較佳為至少約80重量%，更佳為至少約90重量%之包含在甲基丙烯酸水溶液中的甲基丙烯酸萃取至有機相中。 Extraction of at least a portion of the methacrylic acid from the crude aqueous solution comprising methacrylic acid takes place in process step a3) using, for example, at least one organic solvent, preferably at least one substantially water-immiscible organic solvent. So that an aqueous phase and an organic phase can be formed. Preferred organic solvents which can be used in step c) of the process according to the invention have a boiling point which is different (preferably lower) from the boiling point of methacrylic acid. In the process according to the invention, the organic extractant used in process step a3) preferably has a boiling point measured at atmospheric pressure and below 161 °C. In the step a4) of the process according to the invention, the organic extractant can in principle be separated from the methacrylic acid by, for example, distillation (preferably at least partial distillation), preferably in a distillation. The layer higher in the device than pure methacrylic acid is at least partially removed as an extractant of low boiling. The separated organic extractant or a portion thereof can be directed back to process step a3), optionally after at least one cooling and/or purification step. Preferred organic solvents for use in this step are particularly selected from the group consisting of alkanes and aromatics, preferably alkyl aromatics, hydrocarbons, whereby it is preferred to have at least one organic solvent selected from the group consisting of C ₆ -C ₈ hydrocarbons, thereby Heptane, toluene and xylene are particularly preferred, while heptane (preferably n-heptane) is most preferred. The extraction can be carried out in any manner known and apparently suitable to those skilled in the art, preferably in reverse flow extraction, for example using a solvent extraction column, a pulsed packed column or packed column, a rotary extractor, a washing column, a phase separator or suitable An organic solvent extracts the aqueous phase and separates the organic phase from the aqueous phase. It is preferred according to the invention to comprise at least a portion, preferably at least 50% by weight, preferably at least about 70% by weight, preferably at least about 80% by weight, more preferably at least about 90% by weight, in the methyl group. The methacrylic acid in the aqueous acrylic acid solution is extracted into the organic phase.

在根據本發明之方法的步驟a3)中因此獲得兩相：包含甲基丙烯酸的粗有機相，將其引導至根據本發明之方法的步驟a4)，及包含上文所述之量的組分i.和ii.(水和至少一種有機化合物)的第一水相。可包含在第一水相中作為組分ii.的有機化合物為氣相氧化反應期間所形成之任何有機化合物，諸如那些與驟冷步驟中所獲得的粗水相有關的上文述及者，以及未反應之C₄化合物和餘留在水相中的任何甲基丙烯酸。雖然第一水相可包含在方法步驟 a3)中用作萃取劑的少量有機溶劑(例如，由於不完全分離)，但是此有機溶劑較佳地不被視為根據本發明的組分ii.之有機化合物。 In step a3) of the process according to the invention, two phases are thus obtained: a crude organic phase comprising methacrylic acid, which is guided to step a4) of the process according to the invention, and a component comprising the amount described above The first aqueous phase of i. and ii. (water and at least one organic compound). The organic compound which may be included as component ii. in the first aqueous phase is any organic compound formed during the gas phase oxidation reaction, such as those described above in connection with the crude water phase obtained in the quenching step, and the unreacted C ₄ compound remaining in the aqueous phase and any methacrylic acid. Although the first aqueous phase may comprise a small amount of organic solvent used as an extractant in process step a3) (for example, due to incomplete separation), the organic solvent is preferably not considered to be component ii. according to the invention. Organic compound.

在根據本發明之方法的步驟a4)中，對步驟a3)中所獲得的包含甲基丙烯酸之粗有機相施以分離，較佳為熱分離方法，而將包含於其中的至少一部分甲基丙烯酸與用作方法步驟a3)中的萃取劑之有機溶劑分離。若使用熱分離，則此較佳為蒸餾，由此用於方法步驟a3)中之萃取的有機溶劑較佳地作為塔頂產物或在蒸餾塔的上層移出，而甲基丙烯酸或富含甲基丙烯酸之相係作為塔底產物或在比萃取溶劑低的蒸餾塔層移出。亦有可能使用例如分餾或精餾塔，使得具有沸點比甲基丙烯酸高的雜質餘留在塔底產物中，而較高純度的甲基丙烯酸可在比塔底高的塔層移出。若用於萃取的有機溶劑具有比甲基丙烯酸沸點高的沸點，則亦有可能在塔頂及/或更高的塔層移出甲基丙烯酸相。因此獲得的甲基丙烯酸或富含甲基丙烯酸之相的進一步純化可利用另外的熱方法，諸如蒸餾或精餾，或以其他方式，諸如結晶。根據本發明之方法亦可包含在方法步驟a4)之前或期間的中間步驟，諸如分離低沸騰物或高沸騰物的汽提或蒸餾、移出固體雜質的過濾、結晶、清洗及類似者中任一者或多者。純化及其他分離步驟的次數係取決於污染量及甲基丙烯酸最終產物的所欲純度而定。若甲基丙烯酸以其原樣子(例如，成為單體或共單體)用於製造甲基丙烯酸聚合物，則以較高的純度可能較佳，特別取決於最終應用而定。若將甲基丙烯酸酯化，則可接受較低純度的甲基丙烯酸，例如若酯最終產物可比甲基丙烯酸更簡單、更有效或更具效率地純化時。 In step a4) of the process according to the invention, the crude organic phase comprising methacrylic acid obtained in step a3) is subjected to a separation, preferably a thermal separation process, and at least a portion of the methacrylic acid contained therein Separated from the organic solvent used as the extractant in process step a3). If thermal separation is used, this is preferably distillation, whereby the organic solvent used for the extraction in process step a3) is preferably removed as an overhead product or in the upper layer of the distillation column, while methacrylic acid or methyl-rich The phase of the acrylic acid is removed as a bottom product or in a distillation column layer that is lower than the extraction solvent. It is also possible to use, for example, a fractionation or rectification column such that impurities having a higher boiling point than methacrylic acid remain in the bottom product, while higher purity methacrylic acid can be removed in the higher layer than the bottom of the column. If the organic solvent used for the extraction has a boiling point higher than the boiling point of methacrylic acid, it is also possible to remove the methacrylic acid phase at the top of the column and/or higher. Further purification of the methacrylic acid or methacrylic acid rich phase thus obtained may utilize additional thermal methods such as distillation or rectification, or otherwise, such as crystallization. The process according to the invention may also comprise intermediate steps before or during process step a4), such as separation of low boiling or high boiling stripping or distillation, removal of solid impurities filtration, crystallization, washing and the like Or more. The number of purification and other separation steps depends on the amount of contamination and the desired purity of the final product of methacrylic acid. If methacrylic acid is used in its original state (for example, as a monomer or a comonomer) for the production of a methacrylic acid polymer, it may be preferred to have a higher purity, particularly depending on Depending on the final application. If methacrylate is esterified, lower purity methacrylic acid can be acceptable, for example if the ester final product can be purified more simply, more efficiently or more efficiently than methacrylic acid.

至少一部分因此獲得的甲基丙烯酸在方法步驟a5)中的酯化可以熟諳本技藝者已知且顯然適合的任何方式進行，隨意地在聚合抑制劑的存在下，以防止甲基丙烯酸及/或甲基丙烯酸甲酯聚合。未特別限制在步驟a5)中進行酯化的方式。酯化可以例如US 6,469,202、JP 1249743、EP 1 254 887、US 4,748,268、US 4,474,981、US 4,956,493或US 4,464,229中所述來進行，將其關於丙烯酸及甲基丙烯酸之酯化的揭示內容特此併入且構成本發明的一部分。以液相酯化較佳。若酯化係利用甲基丙烯酸與醇之間的直接反應而發生，則較佳的是將反應以適合的觸媒催化。酯化觸媒為熟諳本技藝者所知且包括例如異相或均相觸媒，諸如固態觸媒或液態觸媒。酯化觸媒較佳為酸性離子交換樹脂，諸如那些在US 6,469,292、JP 1249743、EP 1 254 887中所述者或在市場上以商標名稱Amberlyst^®(Rohm and Haas Corp.)、Dowex^®(Dow Corp.)或Lewertit^®(Lanxess AG)取得者，或能夠催化酯化之酸，諸如硫酸H₂SO₄。 The esterification of at least a portion of the methacrylic acid thus obtained in process step a5) can be carried out in any manner known and apparently suitable to the skilled artisan, optionally in the presence of a polymerization inhibitor, to prevent methacrylic acid and/or Polymerization of methyl methacrylate. The manner in which esterification is carried out in the step a5) is not particularly limited. The esterification can be carried out, for example, as described in US 6,469,202, JP 1249743, EP 1 254 887, US 4,748, 268, US 4, 474, 981, US 4, 956, 493, or US 4, 464, 229, the disclosure of which is hereby incorporated herein in It forms part of the invention. Esterification in a liquid phase is preferred. If the esterification occurs by direct reaction between methacrylic acid and an alcohol, it is preferred to catalyze the reaction with a suitable catalyst. Esterification catalysts are known to those skilled in the art and include, for example, heterogeneous or homogeneous catalysts such as solid state catalysts or liquid catalysts. The esterification catalyst is preferably an acidic ion exchange resin such as those described in US 6,469,292, JP 1249743, EP 1 254 887 or on the market under the trade names Amberlyst ^® (Rohm and Haas Corp.), Dowex ^® (Dow). Obtained by Corp.) or Lewertit ^® (Lanxess AG), or an acid capable of catalyzing esterification, such as H ₂ SO ₄ sulfate.

在根據本發明之方法步驟a5)中所製造之甲基丙烯酸酯較佳地具有式〔CH₂=C(CH₃)C(=O)O〕_n-R，且可藉由將甲基丙烯酸與式R(OH)_m之醇酯化而形成，由此n及m代表從1至10之整數，較佳為從1至6，更佳為從1至5，更佳為從1至4，更佳為從1至3，且R係選自由直鏈或支鏈、飽和或不飽和，脂族或芳族，環或直鏈烴及含雜原子之直鏈或支鏈、飽和或不飽和，脂族或芳族，環或直鏈烴，例如烷基、羥烷基、胺烷基、其他含氮-及/或氧之殘基、乙二醇、二元醇、三元醇、雙酚、脂肪酸殘基，由此R較佳地代表甲基、乙基、丙基、異丙基、丁基(特別為正丁基、異丁基)、羥乙基(較佳為2-羥乙基)和羥丙基(較佳為2-羥丙基或3-羥丙基)、2-乙基己基、異癸基、環己基、異莰基、苯甲基、3,3,5-三甲基環己基、硬脂基、二甲基胺基乙基、二甲基胺基丙基、2-第三丁基胺基乙基、乙基三乙二醇、四氫呋喃基、丁基二乙二醇、甲氧基聚乙二醇-350、甲氧基聚乙二醇500、甲氧基聚乙二醇750、甲氧基聚乙二醇1000、甲氧基聚乙二醇2000、甲氧基聚乙二醇5000、烯丙基、乙二醇、二乙二醇、三乙二醇、聚乙二醇200、聚乙二醇400、1,3-丁二醇、1,4-丁二醇、1,6-己二醇、甘油、二胺甲酸乙酯、乙氧基化雙酚A、具有10個環氧乙烷單元之乙氧基化雙酚A、三羥甲基丙烷、乙氧基化C₁₆-C₁₈脂肪醇(諸如具有25個環氧乙烷單元)、2-三甲基銨乙基。 The methacrylate produced in step a5) of the process according to the invention preferably has the formula [CH ₂ =C(CH ₃ )C(=O)O] _n -R and can be obtained by methacrylic acid It is formed by esterification with an alcohol of the formula R(OH) _m , whereby n and m represent an integer from 1 to 10, preferably from 1 to 6, more preferably from 1 to 5, still more preferably from 1 to 4. More preferably from 1 to 3, and R is selected from linear or branched, saturated or unsaturated, aliphatic or aromatic, cyclic or linear hydrocarbons and linear or branched containing heteroatoms, saturated or not a saturated, aliphatic or aromatic, cyclic or straight chain hydrocarbon such as an alkyl group, a hydroxyalkyl group, an amine alkyl group, other nitrogen-and/or oxygen-containing residues, ethylene glycol, a glycol, a triol, a bisphenol, a fatty acid residue, whereby R preferably represents methyl, ethyl, propyl, isopropyl, butyl (especially n-butyl, isobutyl), hydroxyethyl (preferably 2- Hydroxyethyl) and hydroxypropyl (preferably 2-hydroxypropyl or 3-hydroxypropyl), 2-ethylhexyl, isodecyl, cyclohexyl, isodecyl, benzyl, 3,3, 5-trimethylcyclohexyl, stearyl, dimethylaminoethyl, dimethylaminopropyl, 2-tert-butylaminoethyl, ethyl three Glycol, tetrahydrofuranyl, butyl diethylene glycol, methoxy polyethylene glycol-350, methoxy polyethylene glycol 500, methoxy polyethylene glycol 750, methoxy polyethylene glycol 1000, Methoxy polyethylene glycol 2000, methoxy polyethylene glycol 5000, allyl, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 400, 1, 3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, ethyl diaminecarboxylate, ethoxylated bisphenol A, ethoxylate with 10 ethylene oxide units bisphenol A, trimethylolpropane, an ethoxylated C ₁₆ -C ₁₈ fatty alcohols (such as having 25 ethylene oxide units), 2-trimethylammonium ethyl.

甲基丙烯酸酯亦可藉由熟諳本技藝者已知的其他方法而從甲基丙烯酸甲酯製造，例如藉由轉酯化反應。在另一可能的羥酯衍生物製造中，根據本發明的甲基丙烯酸可與對應之含氧環(例如，環氧化物，特別為環氧乙烷或環氧丙烷)在開環反應中反應。 The methacrylate can also be made from methyl methacrylate by other methods known to those skilled in the art, for example by transesterification. In the production of another possible hydroxyester derivative, the methacrylic acid according to the invention can be reacted with a corresponding oxygen-containing ring (for example, an epoxide, in particular ethylene oxide or propylene oxide) in a ring opening reaction. .

較佳的甲基丙烯酸酯為甲基丙烯酸烷酯，特別為甲基丙烯酸甲酯、乙酯、丙酯、異丙酯、丁酯，特別為甲基丙烯酸甲酯、正丁酯、異丁酯、第二丁酯，特別為甲基丙烯酸甲酯、甲基丙烯酸正丁酯、甲基丙烯酸異丁酯；甲基丙烯酸羥酯衍生物，例如甲基丙烯酸羥乙酯(較佳為甲基丙烯酸2-羥乙酯)和甲基丙烯酸羥丙酯(較佳為甲基丙烯酸2-羥丙酯或甲基丙烯酸3-羥丙酯)；及其他的甲基丙烯酸烷酯，諸如甲基丙烯酸乙酯、甲基丙烯酸2-乙基己酯、甲基丙烯酸異癸酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯、甲基丙烯酸苯甲酯、甲基丙烯酸3,3,5-三甲基環己酯、甲基丙烯酸硬脂酯、甲基丙烯酸二甲基胺基乙酯、甲基丙烯酸二甲基胺基丙酯、甲基丙烯酸2-第三丁基胺基乙酯、三乙二醇甲基丙烯酸乙酯、甲基丙烯酸四氫呋喃酯、二乙二醇甲基丙烯酸丁酯、甲氧基聚乙二醇-350甲基丙烯酸酯、甲氧基聚乙二醇500甲基丙烯酸酯、甲氧基聚乙二醇750甲基丙烯酸酯、甲氧基聚乙二醇1000甲基丙烯酸酯、甲氧基聚乙二醇2000甲基丙烯酸酯、甲氧基聚乙二醇5000甲基丙烯酸酯、甲基丙烯酸烯丙酯、乙氧基化(隨意地例如具有25莫耳EO)C₁₆-C₁₈脂肪醇之甲基丙烯酸酯、2-三甲基銨甲基丙烯酸乙酯氯化物；乙二醇二甲基丙烯酸酯、二乙二醇二甲基丙烯酸酯、三乙二醇二甲基丙烯酸酯、聚乙二醇200二甲基丙烯酸酯、聚乙二醇400二甲基丙烯酸酯、1,3-丁二醇二甲基丙烯酸酯、1,4-丁二醇二甲基丙烯酸酯、1,6-己二醇二甲基丙烯酸酯、甘油二甲基丙烯酸酯、二胺甲酸乙酯二甲基丙烯酸酯、乙氧基化雙酚A二甲基丙烯酸酯、乙氧基化(隨意地例如具有10個EO)雙酚A二甲基丙烯酸酯；三羥甲基丙烷三甲基丙烯酸酯，由此以甲基丙烯酸甲酯、甲基丙烯酸丁酯和甲基丙烯酸羥酯衍生物特別佳。 Preferred methacrylates are alkyl methacrylates, especially methyl methacrylate, ethyl ester, propyl ester, isopropyl ester, butyl ester, especially methyl methacrylate, n-butyl ester, isobutyl ester a second butyl ester, especially methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; a hydroxy methacrylate derivative such as hydroxyethyl methacrylate (preferably methacrylic acid) 2-hydroxyethyl ester) and hydroxypropyl methacrylate (preferably 2-hydroxypropyl methacrylate or 3-hydroxypropyl methacrylate); and other alkyl methacrylates, such as methacrylic acid Ester, 2-ethylhexyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, benzyl methacrylate, methacrylic acid 3,3,5-three Methylcyclohexyl ester, stearyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, 2-tert-butylaminoethyl methacrylate, three Ethylene glycol ethyl methacrylate, tetrahydrofuran methacrylate, butyl glycol ethylene glycol methacrylate, methoxy polyethylene Alcohol-350 methacrylate, methoxy polyethylene glycol 500 methacrylate, methoxy polyethylene glycol 750 methacrylate, methoxy polyethylene glycol 1000 methacrylate, methoxy Polyethylene glycol 2000 methacrylate, methoxy polyethylene glycol 5000 methacrylate, allyl methacrylate, ethoxylated (optionally with, for example, 25 moles of EO) C ₁₆ -C ₁₈ fat Alcohol methacrylate, 2-trimethylammonium methacrylate ethyl chloride; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, Polyethylene glycol 200 dimethacrylate, polyethylene glycol 400 dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1, 6-hexanediol dimethacrylate, glycerol dimethacrylate, diurethane ethyl dimethacrylate, ethoxylated bisphenol A dimethacrylate, ethoxylation (optional, for example Having 10 EO) bisphenol A dimethacrylate; trimethylolpropane trimethacrylate, whereby methyl methacrylate, butyl methacrylate and Hydroxymethacrylate derivatives are particularly preferred.

在根據本發明之方法的方法步驟b)中，對至少一部分的第一水相施以結晶，獲得結晶水相，其中此相之水係以結晶形式存在，且母液包含至少一種組分ii.。在方法步驟b)中的結晶可藉由熟諳本技藝者已知的連續或分批方法而發生，較佳為連續結晶，諸如動態或靜態結晶或二者之組合，例如熔融結晶、刻痕冷卻(scratch cooling)結晶、分段結晶、層結晶、懸浮結晶、降膜結晶及類似者，或二或多者該等的任何組合，由此以懸浮式熔融結晶較佳，較佳為連續結晶方法。在根據本發明之方法的步驟b)之較佳態樣中，結晶可分兩個階段發生，由此於第一階段使晶體形成於例如冷卻之表面上，而於第二階段容許該等晶體成長且增加大小。兩個階段可發生在實質上相同的區域中，或各階段可發生在單獨的區域中。若在根據本發明之方法中進行懸浮式熔融結晶，則較佳的是結晶係以至少一次結晶及熔融循環而發生。在根據本發明之懸浮式熔融結晶的較佳態樣中，至少一部分的熔融結晶水被用以清洗至少一部分的結晶水。適合的方法說明於例如WO 02/055469、WO 99/14181、WO 01/77056、US 5,504,247中關於丙烯酸及/或甲基丙烯酸之純化，將其關於結晶的揭示內容(特別如在WO 01/77056及WO 02/055469中所揭示之懸浮式熔融結晶)特此併入以供參考且構成本發明的一部分。若水與第一水相中的一或多種組分ii.形成共熔混合物，則較佳地在共熔點僅結晶出水，俾能在結晶(第二水)水相中獲得儘可能純的水。 In method step b) of the process according to the invention, at least a portion of the first aqueous phase is crystallized to obtain a crystalline aqueous phase, wherein the aqueous phase of the phase is present in crystalline form and the mother liquor comprises at least one component ii. . The crystallization in process step b) can occur by a continuous or batch process known to those skilled in the art, preferably continuous crystallization, such as dynamic or static crystallization or a combination of both, such as melt crystallization, scoring cooling. (scratch cooling) crystallization, segmental crystallization, layer crystallization, suspension crystallization, falling film crystallization, and the like, or any combination of two or more, whereby suspension crystallization is preferred, preferably continuous crystallization. . In a preferred aspect of step b) of the process according to the invention, the crystallization can take place in two stages, whereby the crystal is formed on, for example, a cooled surface in the first stage and the crystal is allowed in the second stage. Grow and increase in size. Two phases can occur in substantially the same region, or each phase can occur in a separate region. If suspension melt crystallization is carried out in the process according to the invention, it is preferred that the crystallization occurs in at least one crystallization and melting cycle. In a preferred aspect of the suspension melt crystallization according to the present invention, at least a portion of the molten crystal water is used to clean at least a portion of the crystal water. Suitable methods are described in, for example, WO 02/055469, WO 99/14181, WO 01/77056, US 5,504,247 for the purification of acrylic acid and/or methacrylic acid, relating to crystallization The disclosure, in particular, the suspension of the molten crystals as disclosed in WO 01/77056 and WO 02/055469, is hereby incorporated by reference herein in its entirety in its entirety herein in its entirety in its entirety If the water forms a eutectic mixture with one or more of the components ii. in the first aqueous phase, preferably only water is crystallized at the eutectic point, and hydrazine is able to obtain as pure water as possible in the crystalline (second water) aqueous phase.

在根據本發明之方法的步驟c)中，作為第二水相的結晶水相與母液至少部分分離。分離可以熟諳本技藝者已知且顯然適合的任何方式進行，較佳地利用過濾、離心、相分離或其他的固體-液體分離方式中至少一者，較佳為過濾、離心或相分離，由此亦可包含晶體的清洗，例如以母液、熔融之結晶水相及水中至少一者清洗。此清洗-熔融型結晶及分離係說明於例如有關於方法步驟b)的上述引用之參考文獻中。在根據本發明之方法的步驟c)之較佳態樣中，使用較佳地在清洗塔中的相分離，例如在WO 01/77056中所揭示之清洗塔類型，由此使結晶相漂浮在母液上及/或母液中，及/或收集，及/或壓緊，例如利用可移動式平板，其在塔中向上移動且容許母液通過，而使結晶相保留在平板上，例如濾器形式的平板，使得結晶相可在清洗塔的塔頂或上層移出，而使母液通過平板且在比結晶相低的相分離器下層移出。亦有可能在相分離器的下層分離出結晶相，例如取決於結晶水相與母液的相對密度，或用於結晶及/或分離之裝置。在此態樣中，可將至少一部分的結晶相熔融，例如在熱交換器中，且較佳地以逆向流引導返回清洗塔，作為清洗在清洗塔中存在的結晶相之清洗液體。在根據本發明之方法的步驟c)之另一較佳的具體例中，分離係藉由離心來進行。在此具體例中，可將至少一部分的結晶相熔融，例如在熱交換器中，且引導返回離心裝置，作為清洗在離心裝置中存在的結晶相之清洗液體。因為母液中的水被耗盡，且母液包含與第一水相比較而更大比例的有機組分，所以有可能焚化在方法步驟c)中分離之後所獲得的母液。此焚化具有與第一水相比較而水含量減少的此大量有機相可充當燃料的優點，因此降低購買燃料的需求。此可為較佳的選擇，例如若燃料成本或相關的必要條件(諸如運輸的容易性及/或成本)不利時及/或組分ii.的有機化合物中之一或多者具有低的市場價值時，特別與彼等分離及/或純化所需之整體努力及開支比較時。 In step c) of the process according to the invention, the crystalline aqueous phase as the second aqueous phase is at least partially separated from the mother liquor. Separation can be carried out in any manner known and apparently suitable to those skilled in the art, preferably by filtration, centrifugation, phase separation or other solid-liquid separation means, preferably by filtration, centrifugation or phase separation. This may also include cleaning of the crystals, for example, cleaning with at least one of a mother liquor, a molten crystalline water phase, and water. This cleaning-melting type crystallization and separation is described, for example, in the above cited references relating to method step b). In a preferred aspect of step c) of the process according to the invention, phase separation, preferably in a washing column, is used, for example the type of washing column disclosed in WO 01/77056, whereby the crystalline phase floats On the mother liquor and/or in the mother liquor, and/or collected, and/or compacted, for example using a movable plate that moves upwards in the column and allows the mother liquor to pass, leaving the crystalline phase on the plate, for example in the form of a filter The plate is such that the crystalline phase can be removed at the top or top of the wash column while the mother liquor is passed through the plate and removed under the lower phase separator than the crystalline phase. It is also possible to separate the crystalline phase in the lower layer of the phase separator, for example depending on the relative density of the crystalline aqueous phase and the mother liquor, or the means for crystallization and/or separation. In this aspect, at least a portion of the crystalline phase can be melted, for example, in a heat exchanger, and preferably directed back to the cleaning column in reverse flow as a clearing of the crystalline phase present in the cleaning column. Wash the liquid. In another preferred embodiment of step c) of the method according to the invention, the separation is carried out by centrifugation. In this embodiment, at least a portion of the crystalline phase can be melted, for example, in a heat exchanger, and directed back to the centrifuge device as a cleaning liquid that cleans the crystalline phase present in the centrifuge device. Since the water in the mother liquor is depleted and the mother liquor contains a greater proportion of the organic component than the first water phase, it is possible to incinerate the mother liquor obtained after the separation in process step c). This incineration has the advantage that this large amount of organic phase, which has a reduced water content compared to the first aqueous phase, can act as a fuel, thus reducing the need to purchase fuel. This may be a preferred option, such as if the fuel cost or related requirements (such as ease of transport and/or cost) are unfavorable and/or one or more of the organic compounds of component ii. have a low market. Values are specifically compared to the overall effort and expense required to separate and/or purify them.

在根據本發明之方法的較佳態樣中，步驟b)和c)係連續進行。結晶步驟b)可發生在適合於進行根據本發明之方法的步驟b)之結晶單元中，其隨意地連接至適合於進行根據本發明之方法的步驟c)之分離單元，諸如上述之清洗單元或離心裝置。結晶單元可包含一或兩個階段，對應於方法步驟b)之可能的兩個階段。在結晶單元中或在結晶單元的第一階段中，通常將第一水相冷卻，使得水至少部分結晶。若晶體至少部分形成於結晶單元的冷卻表面上，則可將該等晶體刮掉。若包含第二階段，則接著將所得泥漿隨意地引導至結晶單元的第二階段，在此較佳地將泥漿攪拌，同時使更多晶體成長及/或增加晶體的大小。接著將來自結晶單元的晶體/母液泥漿引導至分離單元，在此分離至少部分的固體晶體且隨意地清洗，以移出至少部分雜質。可將至少一部分隨意清洗之晶體熔融且可將至少一部分的熔融部分引導至另外的方法步驟或於其中處理，如以下關於方法步驟f)中所述，或用作清洗液體，由此有可能將第一部分的熔融之結晶相如以下關於方法步驟f)中所述方式處置及將另一部分的熔融之結晶相用作清洗晶體的清洗液體。亦有可能將至少一部分的晶體作為晶種供給至結晶單元。亦可包含熔融步驟。熔融步驟可利用可在結晶單元和清洗單元中至少一者的內部或外部之裝置來實現。結晶單元可為熟諳本技藝者已知且顯然適合於自包含有機組分之水溶液結晶出水的任何結晶單元。適合的結晶單元以及併入清洗及/或熔融單元之結晶單元為那些在市場上取自Sulzer Chemtech AG,Switzerland或Niro Process Technology B.V.,The Netherlands之單元。適合的結晶單元、清洗單元及熔融單元，以及組合之結晶/清洗/熔融單元之實例係在有關於方法步驟b)之上述引用之文獻中提出。適合於根據本發明之方法的離心裝置為熟諳本技藝者所知。 In a preferred aspect of the method according to the invention, steps b) and c) are carried out continuously. The crystallization step b) can take place in a crystallization unit suitable for carrying out step b) of the process according to the invention, optionally connected to a separation unit suitable for carrying out step c) of the process according to the invention, such as the cleaning unit described above Or a centrifuge device. The crystallization unit may comprise one or two stages, corresponding to the two possible stages of method step b). In the crystallization unit or in the first stage of the crystallization unit, the first aqueous phase is typically cooled such that the water at least partially crystallizes. If the crystal is at least partially formed on the cooling surface of the crystallization unit, the crystals can be scraped off. If the second stage is included, the resulting slurry is then optionally directed to the second stage of the crystallization unit, where the slurry is preferably agitated while allowing more crystals to grow and/or increase crystals. size. The crystal/mother liquor slurry from the crystallization unit is then directed to a separation unit where at least a portion of the solid crystals are separated and optionally washed to remove at least a portion of the impurities. At least a portion of the randomly cleaned crystals may be melted and at least a portion of the molten portion may be directed to or processed in an additional process step, as described below in relation to method step f), or as a cleaning liquid, thereby making it possible The molten crystalline phase of the first portion is treated as described below in the manner described in method step f) and another portion of the molten crystalline phase is used as the cleaning liquid for cleaning the crystals. It is also possible to supply at least a portion of the crystal as a seed crystal to the crystallization unit. A melting step can also be included. The melting step can be accomplished using a device that can be internal or external to at least one of the crystallization unit and the cleaning unit. The crystallization unit can be any crystallization unit known to those skilled in the art and apparently suitable for crystallization of water from an aqueous solution comprising an organic component. Suitable crystallization units and crystallization units incorporated into the cleaning and/or melting unit are those commercially available from Sulzer Chemtech AG, Switzerland or Niro Process Technology B.V., The Netherlands. Examples of suitable crystallization units, cleaning units and melting units, as well as combined crystallization/cleaning/melting units are set forth in the above cited references to method step b). Centrifugal devices suitable for the method according to the invention are known to those skilled in the art.

方法步驟b)和c)可以但未必造成水自第一水相完全結晶，使得母液可或甚至通常確實包含某些水量。此為例如若水與第一水相中的組分ii.中之一或多者形成共熔混合物的特別情況。在此情況中，為了在結晶(第二水)水相中獲得儘可能純的水，較佳地在共熔點僅結晶出水，使得一部分的水餘留在母液中。餘留在母液中的水比例因此取決於與水形成共熔混合物之第一水相中的各個組分ii.之類型和量及水與此或該等組分ii.的各個共熔點而定。在根據本發明之方法的進一步態樣中，該方法進一步包含以下方法步驟中至少一者：d)將方法步驟c)中所分離的母液至少部分脫水，獲得至少部分脫水之母液；e)將至少一種組分ii.的至少一部分自方法步驟c)中所獲得的母液或自方法步驟d)中所獲得的至少部分脫水之母液分離。在根據本發明之方法的較佳態樣中，將結晶之後餘留在母液中的至少一部分水在方法步驟d)中與母液分離。在方法步驟d)中的脫水較佳地利用共沸蒸餾而發生，較佳為使用共沸添加劑的共沸蒸餾。可考慮熟諳本技藝者已知且顯然適合使方法步驟c)中所分離之母液至少部分脫水的任何共沸添加劑。根據本發明之特別佳的共沸添加劑為直鏈或支鏈烷烴(尤其為庚烷或己烷)、環烷烴(尤其為環己烷)、乙酸酯(尤其為乙酸異丁酯或乙酸乙酯)、芳族化合物(尤其為甲苯或苯)、或CS₂、CCl₄或溴甲烷。 Process steps b) and c) can, but do not necessarily, cause complete crystallization of water from the first aqueous phase, so that the mother liquor can or even does contain some amount of water. This is the special case, for example, if water forms a eutectic mixture with one or more of the components ii. in the first aqueous phase. In this case, in order to obtain as pure water as possible in the crystallized (second water) aqueous phase, it is preferred to crystallize only water at the eutectic point so that a part of the water remains in the mother liquor. The proportion of water remaining in the mother liquor therefore depends on the type and amount of each component ii. in the first aqueous phase which forms a eutectic mixture with water and the respective eutectic points of water and the component ii. . In a further aspect of the method according to the invention, the method further comprises at least one of the following method steps: d) at least partially dehydrating the mother liquor separated in process step c) to obtain at least partially dehydrated mother liquor; e) At least a portion of at least one component ii. is separated from the mother liquor obtained in process step c) or from the at least partially dehydrated mother liquor obtained in process step d). In a preferred aspect of the process according to the invention, at least a portion of the water remaining in the mother liquor after crystallization is separated from the mother liquor in process step d). The dehydration in process step d) preferably takes place by means of azeotropic distillation, preferably azeotropic distillation using an azeotropic additive. Any azeotrope additive known to the skilled artisan and apparently suitable for at least partial dehydration of the mother liquor separated in process step c) is contemplated. Particularly preferred azeotropic additives according to the invention are linear or branched alkanes (especially heptane or hexane), cycloalkanes (especially cyclohexane), acetates (especially isobutyl acetate or ethyl acetate) Ester), aromatic compound (especially toluene or benzene), or CS ₂ , CCl ₄ or methyl bromide.

在方法步驟e)中的分離較佳為熱分離方法，較佳為蒸餾、分餾或精餾，由此將至少一種組分ii.的至少一部分與母液或脫水之母液分離。除了至少一種待分離的組分ii.以外，母液或脫水之母液包含例如來自根據本發明之方法的步驟a3)之萃取劑或其他組分ii.。若一種以上的組分ii.包含在母液或脫水之母液中，例如二或多種組分ii.，則有可能在方法步驟e)中僅分離出一種組分ii.或分離出二或多種組分ii.。作為分離方式的蒸餾、分餾或精餾之選擇可由熟諳本技藝者輕易地決定，且取決於許多因素而定，例如待分離出至少一種組分ii.的母液或脫水之母液中的其他化合物數目和量，以及待分離的一或多種組分ii.及不意欲分離的母液或脫水之母液的組分之各個沸點，特別為母液或脫水之母液的其他組分之沸點接近於待分離的至少一種組分ii.之沸點，及若一種以上的組分ii.待分離時，則待分離的組分ii.之沸點互相接近。另一考慮因素為欲分離之至少一種組分ii.的所欲純度。 The separation in process step e) is preferably a thermal separation process, preferably distillation, fractionation or rectification, whereby at least a portion of at least one component ii. is separated from the mother liquor or the dehydrated mother liquor. The mother liquor or the dehydrated mother liquor comprises, for example, from the method according to the invention, in addition to at least one component ii. to be separated. Step a3) of the extractant or other component ii. If more than one component ii. is contained in a mother liquor or a dehydrated mother liquor, for example two or more components ii., it is possible to separate only one component ii. or separate two or more groups in process step e) Divided into ii. The choice of distillation, fractionation or rectification as a separation mode can be readily determined by those skilled in the art and will depend on a number of factors, such as the amount of other compounds in the mother liquor or dehydrated mother liquor from which at least one component ii. And the amount, and the respective boiling points of the component or components to be separated, and the components of the mother liquor or the dehydrated mother liquor which are not intended to be separated, in particular the boiling point of the mother liquor or other components of the dehydrated mother liquor, are close to at least the fraction to be separated The boiling point of one component ii., and if more than one component ii. to be separated, the boiling points of component ii. to be separated are close to each other. Another consideration is the desired purity of at least one component ii. to be separated.

在根據本發明之方法的較佳具體例中，該方法進一步包含以下的方法步驟：f)將結晶水相熔融，獲得熔融之結晶水相作為第三水相，其中對熔融之結晶水相施以下列中至少一者：引導至至少一種生物純化處理、用作處理水及引導至方法步驟a1)、a2)中至少一者。 In a preferred embodiment of the method according to the invention, the method further comprises the following method steps: f) melting the crystalline aqueous phase to obtain a molten crystalline aqueous phase as a third aqueous phase, wherein the molten crystalline aqueous phase is applied At least one of: directing to at least one biological purification treatment, serving as treatment water, and directing to at least one of method steps a1), a2).

結晶水相的熔融可以熟諳本技藝者已知且顯然適合的任何方式發生。特別地可對結晶水相施以使其熔融之溫度，例如在熔融裝置或熱交換器中。在方法步驟f)中的熔融可對應於方法步驟b)和c)的說明中已述及之熔融，及/或其可為另外的熔融。因此，例如第一次熔融可在方法步驟b)和c)的範圍內進行，例如為了提供用於清洗晶體之清洗液體。接著清洗液體本身較佳地在其與晶體接觸時至少部分結晶在晶體上。可將因此清洗及接著分離之晶體再熔融，以提供清洗液體，以必要的多次清洗-熔融循環獲得所欲晶體純度。一經獲得所欲純度時，接著可將晶體在根據本發明之方法的步驟f)中熔融，且進一步引導至生物純化處理，用作處理水及引導至方法步驟a1)和a2)中至少一者。 Melting of the crystalline aqueous phase can occur in any manner known to the skilled artisan and apparently suitable. In particular, the temperature at which the crystalline aqueous phase is allowed to melt, for example in a melting device or heat exchanger. The melting in process step f) may correspond to the melting already mentioned in the description of process steps b) and c), and/or it may be further melted. So, for example, the first melt can be It is carried out within the scope of process steps b) and c), for example in order to provide a cleaning liquid for cleaning the crystal. The cleaning liquid itself is then preferably at least partially crystallized on the crystal when it is in contact with the crystal. The crystal thus washed and subsequently separated can be remelted to provide a cleaning liquid, with the necessary multiple wash-melt cycles to achieve the desired crystal purity. Once the desired purity has been obtained, the crystals can then be melted in step f) of the process according to the invention and further directed to a biological purification process for use as treatment water and directed to at least one of process steps a1) and a2) .

若對第三水相施以至少一種生物純化處理，則此處理較佳為好氧處理及厭氧處理中至少一者。在具有二或多階段處理的一個具體例中，例如可以先厭氧處理及接著為好氧處理，可以先好氧處理及接著為厭氧處理，或可在例如相繼的分批反應器中依序使用厭氧及/或好氧處理。 If at least one biological purification treatment is applied to the third aqueous phase, the treatment is preferably at least one of aerobic treatment and anaerobic treatment. In a specific example having two or more stages of treatment, for example, anaerobic treatment followed by aerobic treatment may be performed first, followed by aerobic treatment followed by anaerobic treatment, or may be carried out, for example, in successive batch reactors. The procedure uses anaerobic and/or aerobic treatment.

根據本發明的熔融之結晶水相或第三水連通常具有足以直接可用作處理水或用作根據本發明之方法的方法步驟a1)或a2)中的添加水之純度。特別地，結晶水相或熔融之結晶水相較佳地包含以各個水相總重量為基準計少於5000 ppm，較佳為少於4000 ppm，更佳為少於3000 ppm，較佳為從1500至2500 ppm之範圍內，更佳為從1800至2200 ppm之範圍內，最佳為不超過2000 ppm之有機化合物。有可能特別藉由使用許多次在根據本發明之方法步驟c)中的清洗-熔融循環而達成更少的雜質量，例如少於約500 ppm或甚至少於100 ppm及在從0 ppm至100 ppm之範圍內。然而，該等較少的雜質量通常僅與減少的水量一起獲得。生物純化處理可在用作處理水或用作方法步驟a1)或a2)中的添加水之前隨意地進行。若熔融之結晶水相的水被用於其他目的或排放至環境中，則可能較佳但並不必然是此使用或排放係在生物純化之後。 The molten crystalline aqueous phase or third aqueous connection according to the invention generally has a purity sufficient to be used directly as process water or as added water in process step a1) or a2) of the process according to the invention. In particular, the crystalline aqueous phase or the molten crystalline aqueous phase preferably comprises less than 5000 ppm, preferably less than 4000 ppm, more preferably less than 3000 ppm, based on the total weight of the respective aqueous phases, preferably from It is preferably in the range of 1500 to 2500 ppm, more preferably in the range of 1800 to 2200 ppm, and most preferably not more than 2000 ppm. It is possible to achieve less of the amount of impurities, in particular by using the cleaning-melting cycle in step c) of the process according to the invention, for example less than about 500 ppm or even less than 100 ppm and from 0 ppm to 100. Within the range of ppm. However, such less impurity quality is usually only reduced A small amount of water is obtained together. The biological purification treatment can be carried out arbitrarily before use as treated water or as added water in process step a1) or a2). If the water of the molten crystalline water phase is used for other purposes or discharged to the environment, it may be preferred, but not necessarily, that the use or discharge is after biological purification.

在本發明的上下文中，術語〝生物純化處理〞意欲指利用一或多種生物有機體及/或微生物或生物或生化活性物質(例如，衍生自此等有機體或微生物的物質)來增加水的純度之任何處理，例如藉由移出污染物或雜質，較佳為有機污染物。以此方式移出之污染物及雜質通常為餘留在第三水相中的有機化合物。移出係藉由消化或分解一些或全部的有機化合物而實現。水純度的增加係例如藉由降低污染物及/或雜質，及/或藉由降低水的生化需氧量(BOD)或化學需氧量(COD)來測量，較佳地降低至代表廢水可再使用的水平，例如取決於所達成的純度而成為工業處理水，用在根據本發明之方法中，特別用於方法步驟a1)或a2)之一或二者中，或排放至環境中或水供給鏈中。生物純化處理為熟諳本技藝者所知且可為例如所謂的活化淤泥處理中之一或多者。此等處理為熟諳本技藝者所習知且熟知。生物純化處理可在一或多個階段中進行，或可為連續或不連續處理。 In the context of the present invention, the term "biopurification treatment" is intended to mean the use of one or more biological organisms and/or microorganisms or biological or biochemically active substances (for example substances derived from such organisms or microorganisms) to increase the purity of water. Any treatment, such as by removing contaminants or impurities, is preferably an organic contaminant. The contaminants and impurities removed in this manner are typically organic compounds remaining in the third aqueous phase. Removal is achieved by digesting or decomposing some or all of the organic compounds. The increase in water purity is measured, for example, by reducing contaminants and/or impurities, and/or by reducing the biochemical oxygen demand (BOD) or chemical oxygen demand (COD) of the water, preferably to representative wastewater. The level of reuse, for example industrial process water depending on the purity achieved, in the process according to the invention, in particular in one or both of process steps a1) or a2), or in the environment or Water supply chain. Biological purification treatments are known to those skilled in the art and can be, for example, one or more of the so-called activated sludge treatments. Such treatments are well known and well known to those skilled in the art. The biological purification treatment can be carried out in one or more stages, or can be continuous or discontinuous treatment.

若在根據本發明之方法的方法步驟e)中的分離為熱分離，則不可能總是或例如以可實施的經濟或技術方式使組分相互分離，例如若二或多種組分具有非常類似的沸點。此可為若施以方法步驟e)之母液或脫水之母液包含相對大量組分的特別情況，特別為若一或多種組分ii.具有類似於至少一種待在方法步驟e)中分離的組分ii.之沸點時，則更難在方法步驟e)中以微調只分離一種組分ii.。接著可在進一步的方法步驟g)中更適當或更實際地分離出二或多種組分ii.，在此可更輕易地達成此適應於各個組分ii.特殊的分離要求。據此，在根據本發明之方法的態樣中，在方法步驟e)中所分離之至少一種組分ii.為至少兩種組分ii.之混合物，且在以下進一步的方法步驟中：g)將至少一種組分ii.較佳地與此混合物至少部分分離。 If the separation in process step e) of the process according to the invention is thermal separation, it is not always possible to separate the components from each other, for example in an economically or technically feasible manner, for example if two or more components are very similar The boiling point. This may be if the mother liquor or dehydrated mother liquor of method step e) is included In particular, in the case of one or more components ii. having a boiling point similar to that of at least one component ii. to be separated in process step e), it is more difficult to process in process step e) Fine tuning separates only one component ii. It is then possible to separate two or more components ii. in a further method step g) more suitably or practically, which can be more easily achieved here in accordance with the particular separation requirements of the individual components ii. According to this, in the aspect of the process according to the invention, at least one component ii. separated in process step e) is a mixture of at least two components ii. and in a further process step: g At least one component ii. is preferably at least partially separated from the mixture.

在根據本發明之方法的方法步驟g)中的分離可包含一或多個分離步驟，諸如熱分離(如上文已根據本發明之方法中的其他分離步驟所討論)、層析術分離、化學分離(例如，藉由一種組分ii.的優先反應來形成更輕易與一或多種其他組分ii.分離之反應產物，或藉由二或多種組分ii.的反應來形成更輕易互相分離之反應產物)或熟諳本技藝者已知且顯然適合的任何其他的分離方式。 The separation in process step g) of the process according to the invention may comprise one or more separation steps, such as thermal separation (as discussed above in connection with other separation steps in the method of the invention), chromatographic separation, chemistry Separation (for example, by a preferential reaction of one component ii. to form a reaction product which is more easily separated from one or more other components ii., or by a reaction of two or more components ii. The reaction product) or any other separation means known to the skilled artisan and apparently suitable.

在根據本發明之方法的較佳具體例中，組分ii.的至少一種有機化合物(較佳為方法步驟g)中至少部分分離的至少一種組分ii.)為至少一種選自羧酸類、醛及酮之有機化合物。在該等之中，根據本發明較佳的是至少一種組分ii.(較佳為方法步驟g)中至少部分分離的至少一種組分ii.)為乙酸、丙烯酸、丙酸及甲基丙烯酸中至少一者。 In a preferred embodiment of the process according to the invention, at least one component ii.) at least partially separated from at least one organic compound of component ii. (preferably in process step g) is at least one selected from the group consisting of carboxylic acids, An organic compound of an aldehyde and a ketone. Among these, it is preferred according to the invention that at least one component ii.) which is at least partially separated in at least one component ii. (preferably in process step g) is acetic acid, acrylic acid, propionic acid and methacrylic acid. At least one of them.

若在方法步驟e)和g)中之至少一者所分離的至少一種組分ii.為或包含甲基丙烯酸，則在根據本發明之方法的較佳具體例中，將至少一部分的此甲基丙烯酸相添加至方法步驟a2)中所獲得的粗水相中及/或方法步驟a3)中所獲得的粗有機相中。此可為較佳的具體例，例如若在方法步驟e)和g)中之一或多者所分離之甲基丙烯酸不具有其最終用途所欲之純度時。例如，若所分離的甲基丙烯酸已與具有沸點比甲基丙烯酸低的一或多種其他組分一起分離，則以添加至粗水相中可能較佳。例如，若除了甲基丙烯酸以外的組分具有比甲基丙烯酸高的沸點，則以添加至粗有機相中可能較佳，因為此等較高沸點的沸騰物可在方法步驟a4)中分離。雖然甲基丙烯酸對其他組分(特別為其他的組分ii.)的相對比例亦可扮演一角色，但是在方法步驟e)和g)中之至少一者所分離的至少一種組分ii.中的其他組分之本性具有決定在方法步驟e)、f)和j)中至少一者所分離的此包含甲基丙烯酸的相添加至哪一相中的更大影響。例如，若在方法步驟e)和g)中之至少一者所分離之甲基丙烯酸比較純，包含例如少於約5重量%，較佳為少於約4重量%，較佳為少於約3重量%，較佳為少於約2重量%，較佳為從約1重量%至約2重量%之範圍內的雜質或其他組分ii.，則較佳的是可引入此甲基丙烯酸至方法步驟a4)之隨意的純化步驟中。 If at least one component ii. separated in at least one of method steps e) and g) is or comprises methacrylic acid, then the method according to the invention In a preferred embodiment, at least a portion of this methacrylic acid phase is added to the crude aqueous phase obtained in process step a2) and/or to the crude organic phase obtained in process step a3). This may be a preferred embodiment, for example if the methacrylic acid separated by one or more of method steps e) and g) does not have the desired purity for its end use. For example, if the isolated methacrylic acid has been separated from one or more other components having a lower boiling point than methacrylic acid, it may be preferred to add to the crude aqueous phase. For example, if components other than methacrylic acid have a higher boiling point than methacrylic acid, it may be preferred to add to the crude organic phase since such higher boiling boilings can be separated in process step a4). While methacrylic acid may also play a role in the relative proportions of other components, particularly other components ii., at least one component separated by at least one of method steps e) and g). The nature of the other components in the process has a greater effect on which phase the phase comprising methacrylic acid separated by at least one of process steps e), f) and j) is added to. For example, if the methacrylic acid separated in at least one of method steps e) and g) is relatively pure, it comprises, for example, less than about 5% by weight, preferably less than about 4% by weight, preferably less than about 3 wt%, preferably less than about 2 wt%, preferably from about 1 wt% to about 2 wt% of impurities or other components ii., it is preferred to introduce the methacrylic acid To the random purification step of method step a4).

在根據本發明之方法的另一態樣中，對在方法步驟e)和g)中之至少一者所分離的或包含在方法步驟d)中所獲得之脫水母料中的至少一種組分ii.的至少一部分，或在方法步驟a3)中所獲得之第一水相的至少一部分施以以下的方法步驟：h)酯化，獲得包含至少一種酯的酯相。 In a further aspect of the process according to the invention, at least one component of the dewatered masterbatch separated in process step e) and g) is contained in at least one of process steps e) and g) At least a portion of ii. or at least a portion of the first aqueous phase obtained in method step a3) is The following method steps: h) esterification to obtain an ester phase comprising at least one ester.

若至少一種各個組分ii.為羧酸，則此步驟可能較佳。酯化步驟之細節通常與根據本發明之方法的方法步驟a5)的上述者相同。將方法步驟e)和g)中之至少一者所分離的至少一種組分ii.(而不是或除了獲得至少一種各個組分ii.本身以外)酯化可能較佳，與組分ii.之酯比較，該酯化可取決於例如所分離的各個組分ii.可獲得之純度、各個組分ii.的市場或進一步應用而定。將方法步驟a3)中所獲得的第一水相中所包含的至少一種組分ii.酯化可能較佳，例如若第一水相僅包含低比例之不意欲分離的雜質及/或組分ii.，例如以第一水相總重量為基準計少於約6重量%，較佳為少於約5重量%，較佳為少於約4重量%，更佳為少於約3重量%之不意欲分離的雜質及/或組分ii.之雜質總量，特別為例如可比自組分ii.本身更容易自各個組分ii.之酯分離的雜質。 This step may be preferred if at least one of the individual components ii. is a carboxylic acid. The details of the esterification step are generally the same as those described above for process step a5) of the process according to the invention. It may be preferred to esterify at least one component ii. (other than or in addition to at least one of the individual components ii. itself) separated by at least one of method steps e) and g), with component ii. In contrast to esters, the esterification may depend, for example, on the purity of the individual components ii. achievable, the market for each component ii., or further applications. It may be preferred to esterify at least one component ii. contained in the first aqueous phase obtained in process step a3), for example if the first aqueous phase contains only a low proportion of impurities and/or components which are not intended to be separated. Ii., for example, less than about 6% by weight, based on the total weight of the first aqueous phase, preferably less than about 5% by weight, preferably less than about 4% by weight, more preferably less than about 3% by weight. The total amount of impurities and/or components ii. which are not intended to be separated, in particular, for example, impurities which are more easily separated from the ester of each component ii. from the component ii. itself.

在根據本發明的酯相中所包含之特別佳的酯係以C₁-C₄羧酸和C₁-C₄醇為底質，由此以C₂-C₄羧酸為底質之酯較佳。除了有關於方法步驟a5)中所述之甲基丙烯酸酯以外，特別佳的酯為乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸第二丁酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙烯酸正丁酯、丙烯酸異丁酯、丙烯酸第二丁酯、丙酸甲酯、丙酸乙酯、丙酸正丙酯、丙酸異丙酯、丙酸正丁酯、丙酸異丁酯、丙酸第二丁酯，在該等之中，以乙酸酯及丙烯酸酯較佳。 Particularly preferred esters which are included in the ester phase according to the invention are based on C ₁ -C ₄ carboxylic acids and C ₁ -C ₄ alcohols, whereby esters of C ₂ -C ₄ carboxylic acid are used as substrates. Preferably. In addition to the methacrylates described in process step a5), particularly preferred esters are methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, Second butyl acetate, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, methyl propionate, ethyl propionate, Among them, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, and second butyl propionate are preferred among the acetates and acrylates.

根據本發明有可能使酯相包含至少兩種酯。此可為若在方法步驟e)和g)中之至少一者所分離之至少一種組分ii.或在方法步驟a3)中所獲得的至少一部分第一水相包含至少兩種能夠反應形成酯的組分ii.(特別為至少兩種羧酸)之情況。此具體例可在若至少兩種能夠反應形成酯的組分ii.以例如熱或其他方式特別難分離時較佳，例如該等的性質(諸如沸點、在既定溶劑中的溶解度及/或揮發性)非常接近，而彼之酯可以較低的難度互相分離。 According to the invention it is possible to have the ester phase comprise at least two esters. This may be at least one component ii separated if at least one of process steps e) and g) or at least a portion of the first aqueous phase obtained in process step a3) comprises at least two capable of reacting to form an ester. The case of component ii. (especially for at least two carboxylic acids). This particular example may be preferred if at least two of the components ii which are capable of reacting to form an ester are particularly difficult to separate, for example by heat or other means, such as such properties (such as boiling point, solubility in a given solvent, and/or volatilization). Sex) is very close, and the esters of each other can be separated from each other with lower difficulty.

若酯相包含二或多種酯，則根據本發明之方法較佳地進一步包含以下的方法步驟：j)將至少一種酯與酯相至少部分分離；k)隨意地將方法步驟j)中所分離的至少一種酯純化。 If the ester phase comprises two or more esters, the process according to the invention preferably further comprises the following process steps: j) at least partially separating the at least one ester from the ester phase; k) optionally separating the process step j) Purification of at least one ester.

除了至少一種酯以外，酯相通常可包含溶劑，例如水或適合於酯化反應的至少一種有機溶劑或其混合物，以及未反應之組分ii.，及亦可能包含另外的酯或酯類。在方法步驟j)中的分離可為熟諳本技藝者已知且顯然適合於自酯相分離各個酯的任何分離分式。適合的分離方式之實例尤其為例如熱分離(諸如蒸餾、分餾或精餾)、以至少一種酯與酯相的其他組分相比而不同的溶解度為基礎之分離方式、固體-液體分離方式(諸如過濾)。若必要或有要求，亦可例如取決於各個酯意欲的最終應用而在方法步驟k)中進行在方法步驟j)中所分離的至少一種酯之純化作用。純化作用係取決酯而定，由此可全然考慮例如以熱方式、以層析術方式、以清洗或以結晶純化。 In addition to the at least one ester, the ester phase may generally comprise a solvent such as water or at least one organic solvent suitable for the esterification reaction or a mixture thereof, and unreacted component ii., and may also contain additional esters or esters. The separation in process step j) can be any separation fraction known to the skilled artisan and apparently suitable for separating the individual esters from the ester phase. Examples of suitable separation means are, for example, thermal separation (such as distillation, fractionation or rectification), separation methods based on solubility of at least one ester compared to other components of the ester phase, solid-liquid separation means ( Such as filtering). If necessary or required, the purification of at least one ester isolated in process step j) can also be carried out in process step k), for example, depending on the intended end use of the individual ester. use. Purification depends on the ester, from which it can be considered, for example, thermally, chromatographically, by washing or by crystallization.

在根據本發明之方法的具體例中，該方法進一步包含以下步驟：aa1)將甲基第三丁基醚***(MTBE)，獲得至少一種C₄化合物和甲醇，其中將至少一部分的至少一種C₄化合物作為進料供給至方法步驟a1)中至少一者的氣相氧化反應中。MTBE被廣泛地用作異丁烯之原料且MTBE的***為本技藝所熟知。MTBE的***可以熟諳本技藝者已知的任何適合的方式發生。適合的觸媒及反應條件說明於例如EP 1 149 814、WO 04/018393、WO 04/052809；Ullmann’s Encyclopedia of Industrial Chemistry,5^th Edition,Vol.A4,p.488；V.Fattore,M.Massi Mauri,G.Oriani,G.Paret,Hydrocarbon Processing,August 1981,p.101-106；Ullmann’s Encyclopedia of Industrial Chemistry,5^th Edition,Vol.A16,p.543-550；A.Chauvel,G.Lefebvre,“Petrochemical Processes,Technical and Economic Characteristics”,Vol.1,Editions Technip,Paris,1989,p.213 et seq.；US 5,336,841、US 4,570,026及其中引述之參考文獻中。將該等參考文獻的揭示內容特此併入以供參考且構成本發明揭示內容的一部分。 In a specific example of the method according to the invention, the method further comprises the steps of: aa1) splitting the methyl tert-butyl ether (MTBE) to obtain at least one C ₄ compound and methanol, wherein at least a portion of at least one C _The compound is supplied as a feed to the gas phase oxidation reaction of at least one of process step a1). MTBE is widely used as a raw material for isobutylene and the splitting of MTBE is well known in the art. The splitting of MTBE can occur in any suitable manner known to those skilled in the art. Suitable catalysts and reaction conditions are described for example in EP 1 149 814, WO 04/ 018393, WO 04/052809; Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, Vol.A4, p.488; V.Fattore, M.Massi mauri, G.Oriani, G.Paret, Hydrocarbon Processing , August 1981, p.101-106; Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, Vol.A16, p.543-550; A.Chauvel, G.Lefebvre, US Patent No. 5,336,841, US Pat. The disclosures of these references are hereby incorporated by reference in their entirety in their entirety in their entirety in the extent of the disclosure.

MTBE***的兩種主要產物為C₄化合物異丁烯和甲醇。另外的C₄化合物第三丁醇亦可包含在***反應產物相中。異丁烯和第三丁醇之一或二者可作為進料供給至方法步驟a1)中，組成此方法步驟的進料或除了來自另一來源之另外的C₄含量以外之C₄化合物總含量。一或多種中間分離及/或純化步驟亦可能在介於MTBE的***與供給因此獲得的至少一種C₄化合物至方法步驟a1)的氣相氧化反應之間，例如儘可能地將至少一種C₄化合物與甲醇互相分離且自***移出可能不利地影響氣相氧化反應的任何副產物。分離及/或純化可為熟諳本技藝者已知且顯然適合的任何方式。適合的純化及分離方法說明於例如EP 1 149 814、WO 04/018393及WO 04/052809中。在分離甲醇之後，包含C₄化合物異丁烯作為主要組分的***相接著可隨意地純化且作為進料提供至方法步驟a1)。適合的純化方法為熟諳本技藝者所知且較佳地包含蒸餾、萃取、吸附、吸收、層析術或清洗中至少一者，較佳為蒸餾及萃取中至少一者，較佳為至少一種蒸餾及至少一種萃取。未反應之MTBE可在此步驟中與C₄化合物相至少部分分離。可將分離之MTBE隨意地純化且至少部分再循環至***反應。 MTBE split two major products of C ₄ compounds isobutylene and methanol. An additional C ₄ compound, third butanol, may also be included in the split reaction product phase. One of or both of isobutylene and tert-butanol can be fed to the feed as a method step a1), the feed composition or method step in addition to other C ₄ content from another source the total content of C ₄ compound. The one or more intermediate separation and/or purification steps may also be between the splitting of the MTBE and the gas phase oxidation reaction of the at least one C ₄ compound thus obtained to the process step a1), for example as far as possible at least one C ₄ The separation of the compound from the methanol and the removal from the split may adversely affect any by-products of the gas phase oxidation reaction. Isolation and/or purification can be by any means known to the skilled artisan and apparently suitable. Suitable purification and separation methods are described, for example, in EP 1 149 814, WO 04/018393 and WO 04/052809. After the separation of the methanol, the split phase comprising the C ₄ compound isobutene as the main component can then be optionally purified and supplied as a feed to process step a1). Suitable purification methods are known to those skilled in the art and preferably comprise at least one of distillation, extraction, adsorption, absorption, chromatography or washing, preferably at least one of distillation and extraction, preferably at least one Distillation and at least one extraction. Unreacted MTBE can be at least partially separated from the _C4 compound phase in this step. The isolated MTBE can be optionally purified and at least partially recycled to the split reaction.

在根據本發明之方法的較佳具體例中，將方法步驟aa1)中所獲得的甲醇供給至方法步驟h)中。在根據本發明之方法的另一態樣中，可將方法步驟aa1)中所獲得的甲醇供給至方法步驟a5)中。可隨意地純化甲醇，較佳地利用熱純化，諸如蒸餾、分餾或精餾、結晶、萃取、塔或清洗，更佳為至少一種蒸餾。純化甲醇的實例說明於EP 1 254 887中。 In a preferred embodiment of the process according to the invention, the methanol obtained in process step aa1) is supplied to process step h). In a further aspect of the method according to the invention, the methanol obtained in process step aa1) can be supplied to process step a5). The methanol can be optionally purified, preferably by thermal purification such as distillation, fractionation or rectification, crystallization, extraction, column or washing, more preferably at least one distillation. An example of purifying methanol is described in EP 1 254 887.

本發明亦關於一種製造丙烯酸及甲基丙烯酸酯中至少一者的裝置，其包含互相流體引導連通的至少以下組件：A1)氣相氧化單元，A2)驟冷單元，A3)第一萃取單元，A4)第一分離單元，A5)隨意的第一酯化單元，B)用於自水相結晶水的結晶單元，C)隨意的第二分離單元。 The invention also relates to a device for making at least one of acrylic acid and methacrylate comprising at least the following components in fluid communication with each other: A1) a gas phase oxidation unit, A2) a quench unit, A3) a first extraction unit, A4) a first separation unit, A5) a random first esterification unit, B) a crystallization unit for crystallizing water from the aqueous phase, and C) a random second separation unit.

應瞭解術語〝以流體引導連通〞在此意指單元的連接使得流體(其可為液體、氣體、蒸氣、超臨界流體或任何其他流體中至少一者)可自一個單元引導至至少一個其他單元。此可以例如經由管子或導管(例如，由對試劑及當時條件具有抗性之材料所製成的，諸如不銹鋼或玻璃或熟諳本技藝者已知的任何適合的其他材料)直接連通或利用貯槽車或安排在單元之間的貯槽或貯存庫間接連通而達成。若欲引導氣體且應維持氣體的氣態形式，則引導氣體的設備較佳地維持在比氣體露點高的溫度下。若欲引導液體，則引導液體的設備較佳地維持在比液體及/或以液體存在的組分之固化及/或沉澱點高的溫度下。此可利用絕緣及/或加熱引導各個氣體或液體之設備而達成。所有的反應器、塔和其他裝置組件較佳地由對試劑及條件(諸如溫度及壓力條件，特別為施以該等的條件)具有抗性之材料所製成。 It should be understood that the term "flow-through communication" means that the connection of the unit is such that a fluid (which may be at least one of a liquid, a gas, a vapor, a supercritical fluid, or any other fluid) may be directed from one unit to at least one other unit. . This may be directly communicated or utilized by a tank truck, for example, via a tube or conduit (e.g., made of a material that is resistant to the reagents and conditions at the time, such as stainless steel or glass or any other suitable material known to those skilled in the art). Or arrange indirect communication between the tanks or reservoirs between the units. If the gas is to be directed and the gaseous form of the gas should be maintained, the means for directing the gas is preferably maintained at a higher temperature than the dew point of the gas. If the liquid is to be directed, the means for directing the liquid is preferably maintained at a temperature which is higher than the solidification and/or precipitation point of the liquid and/or the component present in the liquid. This can be achieved by means of insulation and/or heating of the individual gases or liquids. All reactors, columns and other plant components are preferably resistant to reagents and conditions, such as temperature and pressure conditions, particularly to the application of such conditions. Made of materials.

氣相氧化單元A1)較佳地包含至少一種適合於進行氣相反應的反應器，特別為壓力反應器，較佳為至少一種形成為例如管和殼反應器的多管反應器、及/或至少一種平板反應器及/或至少一種流化床反應器，由此以多管反應器較佳。特別佳的是至少一種多管反應器，其中將氧化觸媒安排在至少一個管中，其中較佳地將管以氧化觸媒填裝或塗佈(較佳為填裝)。根據本發明較佳的氧化觸媒為那些上文有關於本發明方法所述及者。反應器材料應對反應器內部的試劑及當時條件具有抗性且較佳地具有惰性。適合的反應器係於市場上取得，例如取自MAN DWE GmbH,Deggendorfer Werft,Germany，或取自IHI Corporation,Japan，且構成熟諳本技藝者之一般知識的一部分。 The gas phase oxidation unit A1) preferably comprises at least one reactor suitable for carrying out a gas phase reaction, in particular a pressure reactor, preferably at least one multi-tube reactor formed, for example, as a tube and shell reactor, and/or At least one plate reactor and / or at least one fluidized bed reactor, whereby a multi-tube reactor is preferred. Particularly preferred is at least one multi-tube reactor in which the oxidizing catalyst is disposed in at least one of the tubes, wherein the tube is preferably filled or coated (preferably filled) with an oxidizing catalyst. Preferred oxidizing catalysts in accordance with the present invention are those described above in connection with the process of the present invention. The reactor material should be resistant to, and preferably inert to, the reagents within the reactor and the conditions at the time. Suitable reactors are commercially available, for example, from MAN DWE GmbH, Deggendorfer Werft, Germany, or from IHI Corporation, Japan, and form part of the general knowledge of those skilled in the art.

在兩階段氣相氧化反應中，氣相氧化單元A1)可包含至少兩個反應區，各區包含氧化觸媒。至少兩個反應區可為在單一反應器中的至少兩個反應區，或為至少兩個反應器。在第一個反應區中的氧化觸媒較佳為氧化至少一種C₄化合物(較佳為異丁烯及/或第三丁醇)成為甲基丙烯醛之氧化觸媒，及在第二個反應區中的氧化觸媒較佳地適合於氧化甲基丙烯醛成為甲基丙烯酸。適合的觸媒為上文有關於根據本發明之方法所述及者。 In the two-stage gas phase oxidation reaction, the gas phase oxidation unit A1) may comprise at least two reaction zones, each zone comprising an oxidation catalyst. The at least two reaction zones can be at least two reaction zones in a single reactor, or at least two reactors. The oxidation catalyst in the first reaction zone is preferably an oxidation catalyst for oxidizing at least one C ₄ compound (preferably isobutylene and/or third butanol) to methacrolein, and in the second reaction zone. The oxidizing catalyst in the medium is preferably suitable for oxidizing methacrolein to methacrylic acid. Suitable catalysts are as described above in relation to the method according to the invention.

在本發明之裝置的較佳態樣中，至少一個用於至少一種氧化劑來源(較佳為氧，較佳為空氣)的送料器及至少一個用於水及/或蒸汽的送料器係與氣相氧化單元以流體連通。若氣相氧化單元包含至少第一及另外的氧化區，則裝置可包含用於各氧化區的至少一個用於至少一種氧化劑來源的送料器及至少一個用於水及/或蒸汽的送料器。裝置可另外包含用於稀釋劑的送料器，諸如氮、氬及/或二氧化碳，較佳為氮或二氧化碳，例如來自觸媒燃燒單元(CCU)或熱燃燒單元(TCU)(較佳為根據本發明之裝置下游的CCU或TCU)的包含二氧化碳之再循環氣體。各個送料器應由對試劑及當時條件具有抗性之材料(例如，不銹鋼或玻璃)所製成。在較佳的設計中，將氧、稀釋劑及水在進入各個反應器之前供給至C₄流，使得預形成之混合物進入反應器中。 In a preferred aspect of the apparatus of the present invention, at least one feeder for at least one oxidant source (preferably oxygen, preferably air) and at least one feeder and gas for water and/or steam The phase oxidation unit is in fluid communication. If the gas phase oxidation unit comprises at least a first and additional oxidation zone, the apparatus may comprise at least one feeder for each oxidation zone for at least one source of oxidant and at least one feeder for water and/or steam. The apparatus may additionally comprise a feeder for the diluent, such as nitrogen, argon and/or carbon dioxide, preferably nitrogen or carbon dioxide, for example from a catalytic combustion unit (CCU) or a thermal combustion unit (TCU) (preferably according to the present invention) A carbon dioxide-containing recycle gas from a CCU or TCU downstream of the inventive device. Each feeder should be made of a material that is resistant to the reagents and conditions at the time (for example, stainless steel or glass). In a preferred design the oxygen, diluent and water is supplied to the C ₄ flow before entering each reactor, such that the pre-formed mixture into the reactor.

根據本發明之方法的步驟a1)較佳地在氣相氧化單元中A1)進行。 Step a1) of the process according to the invention is preferably carried out in a gas phase oxidation unit A1).

在根據本發明之裝置的較佳具體例中，驟冷單元A2)為吸收單元，其中冷凝及/或吸收氣態氧化相，以形成液相。較佳的是將離開觸媒反應區之氧化相中存在的甲基丙烯酸在驟冷單元A2)中冷凝，以形成包含甲基丙烯酸為主要氧化產物的溶液(較佳為水溶液)。未反應之甲基丙烯醛亦可在吸收單元A2)中分離，且若要求時，引導返回氣相氧化區供進一步反應。適合用於根據本發明之裝置的驟冷單元為熟諳本技藝者所知。根據本發明之方法的步驟a2)較佳地在驟冷單元A2)中進行。 In a preferred embodiment of the apparatus according to the invention, the quench unit A2) is an absorption unit in which the gaseous oxidation phase is condensed and/or absorbed to form a liquid phase. Preferably, the methacrylic acid present in the oxidizing phase leaving the catalytic reaction zone is condensed in the quench unit A2) to form a solution (preferably an aqueous solution) comprising methacrylic acid as the main oxidation product. Unreacted methacrolein can also be separated in absorption unit A2) and, if desired, directed back to the gas phase oxidation zone for further reaction. Quench units suitable for use in the apparatus according to the present invention are known to those skilled in the art. Step a2) of the method according to the invention is preferably carried out in a quench unit A2).

在根據本發明之裝置的較佳具體例中，驟冷單元 A2)之後為第一萃取單元A3)。將驟冷單元A2)中所形成之包含甲基丙烯酸的水溶液引導至第一萃取單元A3)，在此提供有機溶劑，甲基丙烯酸較佳地被大量地萃取至該溶劑中。有機溶劑較佳地實質上與水不混溶，所以形成甲基丙烯酸至少部分被耗盡的水相及包含甲基丙烯酸的有機相。關於較佳的有機溶劑之細節於上文之方法步驟a3)的說明中提出。方法步驟a3)較佳地在第一萃取單元中進行。可考慮熟諳本技藝者已知且顯然適合於此萃取甲基丙烯酸的任何萃取單元用作第一萃取單元A3)。 In a preferred embodiment of the apparatus according to the invention, the quench unit A2) is followed by the first extraction unit A3). The aqueous solution containing methacrylic acid formed in the quenching unit A2) is guided to the first extraction unit A3) where an organic solvent is provided, and methacrylic acid is preferably extracted into the solvent in a large amount. The organic solvent is preferably substantially immiscible with water, thus forming an aqueous phase in which at least a portion of the methacrylic acid is depleted and an organic phase comprising methacrylic acid. Details regarding preferred organic solvents are set forth in the description of method step a3) above. Process step a3) is preferably carried out in a first extraction unit. Any extraction unit known to the skilled artisan and apparently suitable for extracting methacrylic acid can be considered for use as the first extraction unit A3).

根據本發明之裝置包含在第一萃取單元A3)下游的第一分離單元A4)。若根據本發明之裝置係用於製造甲基丙烯酸甲酯，則第一分離單元A4)係在第一酯化單元A5)的上游，較佳地在第一萃取單元A3)與第一酯化單元A5)之間且以流體連通。第一分離單元A4)較佳地適合於分離且較佳地純化甲基丙烯酸，特別用於自第一萃取單元A3)中所使用之萃取劑分離出甲基丙烯酸，且較佳地亦容許自根據本發明之裝置的第一萃取單元A3)排出之粗有機相(對應於根據本發明之方法的方法步驟a3)之粗有機相)中存在的其他組分分離出甲基丙烯酸。第一分離單元A4)較佳為熱分離單元，較佳地包含蒸餾塔、分餾塔、精餾塔和熟諳本技藝者已知且顯然適合於本發明方法的方法步驟a3)之分離的任何其他的熱分離設備中至少一者。第一分離單元A4)有可能包含一個以上的分離階段。 The device according to the invention comprises a first separation unit A4) downstream of the first extraction unit A3). If the apparatus according to the invention is used for the manufacture of methyl methacrylate, the first separation unit A4) is upstream of the first esterification unit A5), preferably at the first extraction unit A3) with the first esterification Units A5) are in fluid communication. The first separation unit A4) is preferably suitable for separating and preferably purifying methacrylic acid, in particular for separating methacrylic acid from the extractant used in the first extraction unit A3), and preferably also allowing The methacrylic acid is separated off from the other components present in the crude organic phase (corresponding to the crude organic phase of process step a3 according to the process according to the invention) of the first extraction unit A3) of the apparatus according to the invention. The first separation unit A4) is preferably a thermal separation unit, preferably comprising a distillation column, a fractionation column, a rectification column and any other known to those skilled in the art and which are apparently suitable for the separation of process step a3) of the process of the invention. At least one of the thermal separation devices. The first separation unit A4) may contain more than one separation stage.

用於純化在第一分離單元中所分離的甲基丙烯酸之隨意的第一純化單元亦可安排在第一分離單元的下游。隨意的第一純化單元可為例如熱純化單元，諸如蒸餾塔、分餾塔、精餾塔或類似者、結晶單元或熟諳本技藝者已知且顯然適合於純化甲基丙烯酸的任何其他裝置。 The optional first purification unit for purifying the methacrylic acid separated in the first separation unit may also be arranged downstream of the first separation unit. The optional first purification unit can be, for example, a thermal purification unit such as a distillation column, a fractionation column, a rectification column or the like, a crystallization unit or any other device known to those skilled in the art and which is obviously suitable for purifying methacrylic acid.

根據本發明之裝置有可能進一步包含一或多個在任何或所有所述單元或組件之間的額外組件，例如用於分離高及/或低沸騰組分的熱或汽提設備、用於固體/液體分離之設備，諸如至少一個過濾及/或離心，及/或冷卻及/或加熱單元。在較佳的設計中，例如將用於低沸騰物的蒸餾塔及隨意地亦將過濾器安排在驟冷單元的下游及萃取單元的上游。在兩階段氣相氧化單元之進一步較佳的態樣中，將驟冷單元安排在兩個階段之間。 The device according to the invention may further comprise one or more additional components between any or all of said units or components, such as heat or stripping equipment for separating high and/or low boiling components, for solids / Liquid separation device, such as at least one filtration and / or centrifugation, and / or cooling and / or heating unit. In a preferred design, for example, a distillation column for low boilers and optionally a filter downstream of the quench unit and upstream of the extraction unit. In a further preferred aspect of the two-stage gas phase oxidation unit, the quench unit is arranged between two stages.

可將未反應之甲基丙烯醛在驟冷單元、第一萃取單元、第一分離單元、第一純化單元中任一者或上述更多裝置組件中任一者中分離且引導返回氣相氧化單元供進一步反應。 The unreacted methacrolein may be separated and directed back to the gas phase oxidation in any of the quench unit, the first extraction unit, the first separation unit, the first purification unit, or any of the above-described more device components. The unit is for further reaction.

可將第一酯化單元A5)安排在第一分離單元A4)或隨意地在第一純化單元的下游。第一酯化單元A5)未受到特別的限制且可為適合於自甲基丙烯酸酯化形成甲基丙烯酸酯(較佳為甲基丙烯酸甲酯)之任何單元。其較佳地適合於液相酯化作用。第一酯化單元A5)較佳地包含酯化觸媒，其可為異相或均相觸媒，諸如固態觸媒或液態觸媒，且較佳為酸性離子交換樹脂，諸如那些在US 6,469,292、JP 1249743、EP 1 254 887中所述者或在市場上以商標名稱Amberlyst^®(Rohm and Haas Corp.)、Dowex^®(Dow Corp.)或Lewertit^®(Lanxess AG)取得者，或能夠催化酯化之酸，諸如硫酸H₂SO₄。 The first esterification unit A5) may be arranged in the first separation unit A4) or optionally downstream of the first purification unit. The first esterification unit A5) is not particularly limited and may be any unit suitable for forming a methacrylate (preferably methyl methacrylate) from methacrylate. It is preferably suitable for liquid phase esterification. The first esterification unit A5) preferably comprises an esterification catalyst which may be a heterogeneous or homogeneous catalyst such as a solid or liquid catalyst, and preferably an acidic ion exchange resin such as those in US 6,469,292. Acquired in JP 1249743, EP 1 254 887 or marketed under the trade names Amberlyst ^® (Rohm and Haas Corp.), Dowex ^® (Dow Corp.) or Lewertit ^® (Lanxess AG), or capable of catalyzing esterification Acid, such as sulfuric acid H ₂ SO ₄ .

可將第二純化單元安排在第一酯化單元A5)的下游，以純化其中所製造之甲基丙烯酸酯。隨意的第二純化單元可為例如熱純化單元，諸如蒸餾塔、分餾塔、精餾塔或類似者、結晶單元或熟諳本技藝者已知且顯然適合於純化甲基丙烯酸酯(特別為甲基丙烯酸甲酯)的任何其他裝置。 The second purification unit can be arranged downstream of the first esterification unit A5) to purify the methacrylate produced therein. The optional second purification unit can be, for example, a thermal purification unit such as a distillation column, a fractionation column, a rectification column or the like, a crystallization unit or a skilled person known to the skilled artisan and apparently suitable for purifying methacrylates (especially methyl groups). Any other device of methyl acrylate).

根據本發明之裝置進一步包含結晶單元B)。結晶單元B)適合自至少一部分的至少一種有機化合物(特別為至少一種組分ii.)分離出至少一部分在第一萃取單元A3)中所獲得之第一水相中所包含的水，如上文所述，獲得第二水相和有機相。根據本發明之方法的方法步驟b)較佳地在結晶單元B)中進行。根據本發明之裝置較佳地另外包含第二分離單元C)，其較佳為晶體分離單元。本發明方法的方法步驟c)較佳地在第二分離單元C)中進行。 The device according to the invention further comprises a crystallization unit B). The crystallization unit B) is suitable for separating at least a portion of the water contained in the first aqueous phase obtained in the first extraction unit A3) from at least one of the at least one organic compound (particularly at least one component ii.), as above Said to obtain a second aqueous phase and an organic phase. Process step b) of the process according to the invention is preferably carried out in crystallization unit B). The device according to the invention preferably further comprises a second separation unit C), which is preferably a crystal separation unit. Process step c) of the process according to the invention is preferably carried out in a second separation unit C).

在結晶單元B)中，通常將第一萃取單元A3)中所獲得的第一水溶液冷卻，使得水至少部分結晶。接著可將所得泥漿隨意地經由使晶體成長的滯留單元T1)(如上文有關於方法步驟b)和c)所述)運送至晶體分離單元C)，例如清洗塔或離心器，在此將固體晶體與母液至少部分分離，且較佳地清洗該晶體，以最大可能程度至少部分移出餘留的雜質。至少一個熔融裝置亦可包含在結晶單元B)及第二分離單元C)中至少一者中，且可在至少一者的內部或外部，較佳地與至少一個晶體分離單元以流體及/或固體引導連通。至少一部分隨意清洗之晶體較佳地在至少一個熔融單元中熔融，且使至少一部分的熔融部分通往下一個裝置組件或用作晶體分離單元C)中的晶體之清洗液體，或二者。亦有可能利用一或多個導管自晶體分離單元C)供給至少一部分的晶體至結晶單元B)及/或滯留單元中作為晶種。 In the crystallization unit B), the first aqueous solution obtained in the first extraction unit A3) is usually cooled, so that the water at least partially crystallizes. The resulting slurry can then be optionally transported via a retention unit T1) (as described above with respect to method steps b) and c) which crystallizes the crystals to a crystal separation unit C), such as a washing column or a centrifuge, where the solids are Crystal and mother liquor at least Partial separation, and preferably cleaning of the crystal, removes at least a portion of the remaining impurities to the greatest extent possible. At least one melting device may also be included in at least one of the crystallization unit B) and the second separation unit C), and may be fluid and/or internal or external to at least one, preferably with at least one crystal separation unit. Solids lead to communication. At least a portion of the randomly cleaned crystals are preferably melted in at least one of the molten units and pass at least a portion of the molten portion to the next device assembly or to the cleaning liquid used as crystals in the crystal separation unit C), or both. It is also possible to supply at least a portion of the crystals from the crystal separation unit C) to the crystallization unit B) and/or the retention unit as seed crystals using one or more conduits.

可將熟諳本技藝者已知且顯然適合於上述目的任何結晶單元、滯留單元及晶體分離單元用在根據本發明之裝置中，由此以容許連續結晶及分離之各個單元較佳。結晶單元可為熟諳本技藝者已知且顯然適合於自包含有機組分之水溶液結晶水的任何結晶單元，由此以懸浮結晶單元較佳，而甚至更佳的是配備有刮除器之懸浮結晶單元，用於至少部分刮掉在可形成晶體之冷卻表面上的晶體。若提供滯留單元，則其較佳為貯槽形式，較佳地配備有攪拌設備且具有至少一個入口與結晶單元以流體-及/或固體-引導連通及至少一個出口與晶體分離單元以流體-及/或固體-引導連通。結晶單元B)(隨意地與滯留單元T1)一起)較佳地適合於進行根據本發明之方法的步驟b2a)。晶體分離單元C)較佳地適合於進行根據本發明之方法的步驟c)，且較佳為清洗塔或離心裝置。適合的結晶單元以及併入清洗及/或熔融單元之結晶單元為例如在下游於水力或機械清洗塔中清洗晶體的懸浮結晶單元，如在Lancaster-Basel之Technomic出版公司(Publishing Co.Inc.)的G.F.Arkenbout之“Melt Crystallisation Technology”(1995)的書籍之第265-288頁中、Chem.Ing.Techn.(72)(10/2000)之1231-1233頁中所述。通常任何熔融物清洗塔係以強行輸送，例如在Chem.Ing.Techn.57(1985)No.2的第91-102頁與Chem.Ing.Techn.63(1991),No.9的第881-891頁中和WO 99/6348中所述。適合的熔融物清洗塔之實例說明於EP 97405、US 4735781、WO 00/24491、EP 920894、EP 398437、EP 373720、EP 193226、EP 191194、WO 98/27240、EP 305316、US 4787985中且在市場上取自例如TNO Institute in Apeldoorn,Netherlands、取自Niro Process Technology B.V.,Hertogenbosch,NL、或取自Sulzer Chemtech AG,Switzerland、TNO或Niro Process Technology B.V.,The Netherlands。適合的結晶單元、清洗單元及熔融單元，以及組合之結晶/清洗/熔融單元的更多實例亦在有關於方法步驟b2a)的上述引用之文獻中提出。適合作為根據本發明之裝置中的晶體分離單元之離心裝置為熟諳本技藝者所知且廣泛地取自於市場來源。 Any of the crystallization units, retention units, and crystal separation units known to those skilled in the art and which are apparently suitable for the above purposes can be used in the apparatus according to the present invention, whereby the respective units which permit continuous crystallization and separation are preferred. The crystallization unit may be any crystallization unit known to the person skilled in the art and apparently suitable for crystallization of water from an aqueous solution comprising an organic component, whereby a suspension crystallization unit is preferred, and even more preferably a suspension equipped with a scraper. A crystallization unit for at least partially scraping off crystals on a cooling surface capable of forming a crystal. If a retention unit is provided, it is preferably in the form of a sump, preferably equipped with a stirring device and having at least one inlet and crystallization unit in fluid- and/or solid-directed communication and at least one outlet and crystal separation unit in fluid-and / or solid - guided communication. The crystallization unit B) (optionally with the retention unit T1) is preferably suitable for carrying out step b2a) of the method according to the invention. The crystal separation unit C) is preferably suitable for carrying out step c) of the process according to the invention, and is preferably a washing column or a centrifugal device. Suitable crystallization unit and The crystallization unit incorporated into the cleaning and/or melting unit is, for example, a suspended crystallization unit that cleans the crystal downstream in a hydraulic or mechanical cleaning tower, such as GF Arkenbout of Technomic Publishing Co., Inc. of Lancaster-Basel ("Publishing Co. Inc.") Melt Crystallisation Technology" (1995), pages 265-288, Chem. Ing. Techn. (72) (10/2000), pages 1231-1233. Usually any melt cleaning tower is forcibly transported, for example, in Chem. Ing. Techn. 57 (1985) No. 2, pp. 91-102 and Chem. Ing. Techn. 63 (1991), No. 9, 881. -891 and WO 99/6348. Examples of suitable melt cleaning columns are described in EP 97405, US Pat. No. 4,739, 811, WO 00/24,491, EP 920,894, EP 398,437, EP 373, 720, EP 193 226, EP 191 194, WO 98/27240, EP 305 316, US Pat. Taken from, for example, TNO Institute in Apeldoorn, Netherlands, from Niro Process Technology BV, Hertogenbosch, NL, or from Sulzer Chemtech AG, Switzerland, TNO or Niro Process Technology BV, The Netherlands. Further examples of suitable crystallization units, cleaning units and melting units, as well as combined crystallization/cleaning/melting units are also proposed in the above cited documents relating to method step b2a). Centrifugal devices suitable as crystal separation units in the apparatus according to the present invention are known to those skilled in the art and are widely available from market sources.

至少一個焚化器或燃燒單元可包含在根據本發明之裝置中，例如用於焚化自結晶單元及/或晶體分離單元所獲得的母液。 At least one incinerator or combustion unit may be included in the apparatus according to the invention, for example for incineration of the mother liquor obtained from the crystallization unit and/or the crystal separation unit.

根據本發明之裝置亦可另外包含脫水單元D)。根據本發明之裝置亦可包含第三分離單元E)。脫水單元較佳地適合於進行本發明方法之方法步驟d)及第三分離單元較佳地適合於進行本發明方法之方法步驟e)。可考慮熟諳本技藝者已知且顯然適合使結晶單元及/或晶體分離單元中所分離之母液至少部分脫水的脫水單元用於根據本發明之裝置中。根據本發明之較佳的脫水單元為例如以不與至少一種組分ii.反應之脫水劑(諸如分子篩)填裝之塔，及蒸餾單元，特別為適合於共沸蒸餾之蒸餾單元。第三分離單元E)較佳為熱分離單元。可考慮熟諳本技藝者已知且顯然適合於進行方法步驟e)之分離的熱分離單元用於根據本發明之裝置中，諸如蒸餾塔、分餾塔或精餾塔中至少一者或類似者。 The device according to the invention may additionally comprise a dewatering unit D). The device according to the invention may also comprise a third separation unit E). The dewatering unit is preferably suitable for carrying out the process step d) of the process according to the invention and the third separating unit is preferably suitable for carrying out process step e) of the process according to the invention. It is contemplated that the dewatering unit known to the skilled artisan and which is apparently suitable for at least partially dehydrating the mother liquor separated in the crystallization unit and/or the crystal separation unit is used in the apparatus according to the invention. The preferred dewatering unit according to the invention is, for example, a column packed with a dehydrating agent (such as molecular sieves) which does not react with at least one component ii., and a distillation unit, in particular a distillation unit suitable for azeotropic distillation. The third separation unit E) is preferably a thermal separation unit. It is contemplated that a thermal separation unit known to the skilled artisan and apparently suitable for carrying out the separation of process step e) is used in the apparatus according to the invention, such as at least one of a distillation column, a fractionation column or a rectification column or the like.

更多的分離單元亦可包含在根據本發明之裝置中。較佳的另一分離單元的一個實例為適合於自包含至少兩種根據本發明之組分ii.的混合物(例如，在根據本發明之方法的步驟e)中所獲得的混合物)分離出至少一種組分ii.的分離單元。此等更多的分離單元較佳為熱分離單元，較佳地包含至少一個蒸餾塔、分餾塔、精餾塔或類似者。 Further separation units can also be included in the device according to the invention. An example of a preferred further separation unit is suitable for separating at least from a mixture comprising at least two components ii. according to the invention (for example the mixture obtained in step e according to the process of the invention) A separation unit of component ii. These more separation units are preferably thermal separation units, preferably comprising at least one distillation column, fractionation column, rectification column or the like.

根據本發明之裝置較佳地包含至少一個介於第三分離單元E)及/或至少一個另一分離單元與第一萃取單元A3)及/或第一分離單元A4)之間的導管，用於引導甲基丙烯酸及包含甲基丙烯酸之相中至少一者返回第一萃取單元A3)及第一分離單元A4)中至少一者。 The device according to the invention preferably comprises at least one conduit between the third separation unit E) and/or the at least one further separation unit and the first extraction unit A3) and/or the first separation unit A4) At least one of the first methacrylic acid and the methacrylic acid-containing phase is returned to at least one of the first extraction unit A3) and the first separation unit A4).

根據本發明之裝置隨意地包含至少一個用於酯化至少一種組分ii.的第二酯化單元H)，較佳地在結晶單元B)、第二分離單元C)及第三分離單元E)中至少一者的下游。本發明方法之方法步驟h)較佳地在第二酯化單元H)中進行。關於第二酯化單元H)之細節與那些上述的第一酯化單元A5)相同。 The apparatus according to the invention optionally comprises at least one second esterification unit H) for esterifying at least one component ii., preferably in the crystallization unit B), the second separation unit C) and the third separation unit E Downstream of at least one of them. Process step h) of the process according to the invention is preferably carried out in a second esterification unit H). The details regarding the second esterification unit H) are the same as those of the first esterification unit A5) described above.

根據本發明之裝置亦可包含至少一個用於一或多種酯至少部分互相分離的酯分離單元J)，特別用於自至少一個第二酯化單元中所獲得的酯相至少部分分離出至少一種酯，對應於本發明方法之方法步驟j)。可將熟諳本技藝者已知且顯然適合於分離酯的任何裝置用作酯分離單元J)。以已述及之類型的熱分離裝置，以及結晶裝置、萃取裝置、相分離裝置作為根據本發明之裝置中的酯分離單元較佳。 The device according to the invention may also comprise at least one ester separation unit J) for at least partial separation of one or more esters, in particular for at least partially separating at least one ester phase obtained from at least one second esterification unit The ester corresponds to step j) of the process of the process of the invention. Any device known to the skilled artisan and apparently suitable for separating esters can be used as the ester separation unit J). The thermal separation apparatus of the type already mentioned, as well as the crystallization apparatus, the extraction apparatus, and the phase separation apparatus are preferred as the ester separation unit in the apparatus according to the present invention.

至少一個另外的純化單元K)亦可提供至根據本發明之裝置中，用於純化在第二酯化單元中所獲得或在至少一個酯分離單元中所分離的酯及/或酯類。根據本發明之方法的方法步驟k)較佳地在至少一個另外的純化單元K)中進行。此另外的純化單元之細節對應於那些有關於第一酯化單元所述及之純化單元。 At least one additional purification unit K) may also be provided in the apparatus according to the invention for purifying the esters and/or esters obtained in the second esterification unit or separated in at least one ester separation unit. Process step k) of the process according to the invention is preferably carried out in at least one further purification unit K). The details of this additional purification unit correspond to those purification units described in relation to the first esterification unit.

在根據本發明之裝置的較佳態樣中，該裝置另外包含在氣相氧化單元A1)上游的MTBE***單元AA1)。***單元及適合於MTBE***的觸媒為本技藝中所熟知且構成熟諳本技藝者之一般知識的一部分，如在例如 Ullmann’s Encyclopedia of Industrial Chemistry,5^th Edition,Vol.A4,p.488；V.Fattore,M.Massi Mauri,G.Oriani,G.Paret,Hydrocarbon Processing,August 1981,p.101-106；Ullmann’s Encyclopedia of Industrial Chemistry,5^th Edition,Vol.A16,p.543-550；A.Chauvel,G.Lefebvre,“Petrochemical Processes,Technical and Economic Characteristics”,Vol.1,ditions Technip,Paris,1989,p.213 et seq.；US 5,336,841、US 4,570,026及其中引述之參考文獻中所述。 In a preferred aspect of the apparatus according to the invention, the apparatus additionally comprises an MTBE splitting unit AA1) upstream of the gas phase oxidation unit A1). MTBE splitting unit, and adapted to divide the catalyst in the present art is well known and constitute a part of those familiar with the general knowledge in the art, as for example in Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, Vol.A4, p.488; V .Fattore, M.Massi Mauri, G.Oriani, G.Paret , Hydrocarbon Processing, August 1981, p.101-106; Ullmann's Encyclopedia of Industrial Chemistry, 5 th Edition, Vol.A16, p.543-550; A. Chauvel, G. Lefebvre, "Petrochemical Processes, Technical and Economic Characteristics", Vol.1, Ditions Technip, Paris, 1989, p. 213 et seq.; US 5, 336, 841, US 4, 570, 026 and the references cited therein.

異丁烯分離單元S1)較佳地安排在MTBE***單元AA1)與氣相氧化單元A1)之間且各自以流體引導連通。異丁烯分離單元S1)適合於自第二觸媒反應區的流出物分離出異丁烯相及較佳地亦分離出甲醇相，該流出物包含異丁烯和甲醇為主要組分。異丁烯分離單元S1)可為萃取器、結晶器、塔、蒸餾裝置、精餾裝置、薄膜、滲透蒸發裝置、相分離器及清洗裝置中至少一者。異丁烯分離單元S1)較佳地包含異丁烯相出口及甲醇相出口。異丁烯相出口較佳地與氣相氧化單元A1)隨意地經由中間單元連接，諸如純化單元、熱交換器及/或穩壓器。甲醇相出口較佳地與第一酯化單元A4)及第二酯化單元H)中至少一者隨意地經由中間甲醇純化單元連接。可包含熟諳本技藝者已知且顯然適合於純化甲醇的任何裝置作為甲醇純化單元。適合的純化單元之實例較佳地包含至少一個蒸餾裝置、結晶器、萃取器、塔或清洗裝置，更佳為至少一個蒸餾裝置。用於甲醇之純化單元的實例說明於EP 1 254 887中。 The isobutylene separation unit S1) is preferably arranged between the MTBE splitting unit AA1) and the gas phase oxidation unit A1) and is each in fluid-directed communication. The isobutylene separation unit S1) is suitable for separating the isobutene phase from the effluent of the second catalyst reaction zone and preferably also separating the methanol phase, the effluent comprising isobutylene and methanol as main components. The isobutylene separation unit S1) may be at least one of an extractor, a crystallizer, a column, a distillation apparatus, a rectification apparatus, a membrane, a pervaporation apparatus, a phase separator, and a cleaning apparatus. The isobutylene separation unit S1) preferably comprises an isobutylene phase outlet and a methanol phase outlet. The isobutene phase outlet is preferably optionally connected to the gas phase oxidation unit A1) via an intermediate unit, such as a purification unit, a heat exchanger and/or a pressure regulator. The methanol phase outlet is preferably optionally connected to at least one of the first esterification unit A4) and the second esterification unit H) via an intermediate methanol purification unit. Any device known to the skilled artisan and apparently suitable for purifying methanol can be included as a methanol purification unit. Examples of suitable purification units preferably comprise at least one distillation apparatus, crystallizer, extractor, column or washing apparatus, more preferably at least one Distillation unit. An example of a purification unit for methanol is described in EP 1 254 887.

本發明亦關於一種根據本發明之方法，其中該方法係發生在根據本發明之裝置中。 The invention also relates to a method according to the invention, wherein the method occurs in a device according to the invention.

本發明係藉由以下的圖式和非限制性實例更詳細地例示說明。 The invention is illustrated in more detail by the following figures and non-limiting examples.

根據圖2的具體例，將C₄化合物引入氣相氧化單元A1中，在此以一-或兩-階段催化氣相氧化反應氧化成甲基丙烯酸。未顯示C₄化合物、氧、蒸汽及惰性稀釋劑氣體至氣相氧化單元A1的入口。C₄化合物可從MTBE***單元AA1(未顯示)經由異丁烯分離單元S1(未顯示)提供。將氣相氧化單元A1中所獲得的甲基丙烯酸氣相經由管線1引導至驟冷單元A2，在此冷卻且吸收至水或水相中，形成包含甲基丙烯酸之水相。未顯示驟冷液體至驟冷單元A2的入口。將甲基丙烯酸水相經由管線2引導至第一萃取單元A3，在此以作為萃取劑的有機溶劑萃取，形成有機相和水相(根據本發明之方法的第一水相)。該兩種相係在第一萃取單元A3中分離。 According to the specific example of Fig. 2, the C ₄ compound is introduced into the gas phase oxidation unit A1 where it is oxidized to methacrylic acid by a one- or two-stage catalytic gas phase oxidation reaction. The C ₄ compound, oxygen, steam, and inert diluent gas are not shown to the inlet of the gas phase oxidation unit A1. The C ₄ compound can be provided from the MTBE splitting unit AA1 (not shown) via an isobutylene separation unit S1 (not shown). The methacrylic acid gas phase obtained in the gas phase oxidation unit A1 is guided via line 1 to a quench unit A2 where it is cooled and absorbed into water or an aqueous phase to form an aqueous phase comprising methacrylic acid. The quench liquid is not shown to the inlet of the quench unit A2. The aqueous phase of methacrylic acid is directed via line 2 to a first extraction unit A3 where it is extracted with an organic solvent as an extractant to form an organic phase and an aqueous phase (first aqueous phase according to the process of the invention). The two phases are separated in the first extraction unit A3.

來自第一萃取單元A3的有機相係經由管線3引導至第一分離單元A4，在此蒸餾，分離出甲基丙烯酸及萃取劑。可將萃取劑經由管線6再循環至第一萃取單元A3。甲基丙烯酸可經由管線5收集且隨意地在下游的純化單元或單元等(未顯示)中純化或可經由管線4(隨意地經過純化(未顯示))引導至第一酯化單元A5。在第一酯化單元A5中，可將甲基丙烯酸以例如甲醇(例如，在分離單元S1(未顯示)中自MTBE***相所分離之甲醇)酯化，形成甲基丙烯酸甲酯。亦有可能將甲基丙烯酸在第一酯化單元A5中以上述其他的醇酯化。在第一酯化單元A5中所製造之酯係經由管線7收集且可隨意地在聚合單元A6(未顯示)中聚合，隨意地以中間及/或下游純化。 The organic phase from the first extraction unit A3 is directed via line 3 to a first separation unit A4 where it is distilled to separate methacrylic acid and an extractant. The extractant can be recycled via line 6 to the first extraction unit A3. Methacrylic acid can be collected via line 5 and optionally purified in a downstream purification unit or unit or the like (not shown) or can be directed to first esterification unit A5 via line 4 (optionally purified (not shown)). In the first esterification In unit A5, methacrylic acid can be esterified with, for example, methanol (for example, methanol separated from the MTBE split phase in separation unit S1 (not shown) to form methyl methacrylate. It is also possible to esterify methacrylic acid in the first esterification unit A5 with the above other alcohol. The esters produced in the first esterification unit A5 are collected via line 7 and optionally polymerized in polymerization unit A6 (not shown), optionally purified in the middle and/or downstream.

將第一萃取單元A3中所分離之水相引導至結晶單元B，通常在此冷卻，使得水至少部分結晶。若晶體至少部分形成於結晶單元B的冷卻表面上，則可將該等晶體刮掉。接著將所得泥漿隨意地引導至滯留單元T1(未顯示)，在此較佳地將泥漿攪拌，同時使更多的晶體成長及/或增加晶體的大小。接著將來自結晶單元B及/或滯留單元T1的晶體與母液之泥漿經由管線9引導至晶體分離單元C，在此將固體晶體與母液至少部分分離且隨意地清洗，以移出至少部分雜質。接著可將一部分的晶體自晶體分離單元C引導返回結晶單元B及/或滯留單元T1，以充當晶種(未顯示導管)。可將至少一部分隨意清洗之晶體熔融(未顯示熔融裝置)且將至少一部分的熔融部分再循環至例如氣相氧化單元A1(未顯示導管)，用作處理水，用作清洗晶體分離單元C中的晶體之清洗液體，經由管線20引導至生物純化單元(未顯示)或排放。可將晶體分離單元C中所分離之母液經由管線10(隨意地經過脫水單元D(未顯示))引導至第三分離單元E，在此可分離出至少一種組分ii.。若組分ii.之混合物係在第三分離單元E中分離，則可將此混合物引導至另外的分離單元，使組分ii.互相分離(未顯示)。若甲基丙烯酸或包含甲基丙烯酸之相係在第三分離單元E中分離，則可將此甲基丙烯酸或包含甲基丙烯酸之相經由管線15引導至第一萃取單元A3或經由管線16引導至第一分離單元A4。在第三分離單元E中所分離之至少一種組分ii.的至少一部分可經由管線11收集且在另外的純化單元(未顯示)中隨意地純化。亦有可能將第三分離單元E中所分離之至少一種組分ii.的至少一部分經由管線14引導至第二酯化單元H。可將晶體分離單元C中所分離之母液引導至第二酯化單元H。在第二酯化單元H中，將至少一種組分ii.以醇酯化，形成對應之酯。若醇為甲醇，則此甲醇例如可經由分離單元S1自MTBE***器AA1引入，隨意地經中間純化(未顯示)。若在第二酯化單元H中所獲得的酯相包含一種以上的酯，則至少一種酯可在酯分離單元J中分離。至少一種酯可在下游的酯純化單元K(未顯示)中純化。 The aqueous phase separated in the first extraction unit A3 is directed to the crystallization unit B, where it is typically cooled, such that the water at least partially crystallizes. If the crystal is at least partially formed on the cooling surface of the crystallization unit B, the crystals can be scraped off. The resulting slurry is then optionally directed to a retention unit T1 (not shown), where the slurry is preferably agitated while allowing more crystal to grow and/or increase the size of the crystal. The crystals from the crystallization unit B and/or the retention unit T1 and the mother liquor are then directed via line 9 to a crystal separation unit C where the solid crystals are at least partially separated from the mother liquor and optionally washed to remove at least a portion of the impurities. A portion of the crystal can then be directed back from the crystal separation unit C back to the crystallization unit B and/or the retention unit T1 to act as a seed crystal (the conduit is not shown). At least a portion of the randomly cleaned crystal may be melted (the melting device is not shown) and at least a portion of the molten portion is recycled to, for example, a gas phase oxidation unit A1 (a conduit not shown) for use as a treated water for use as a cleaning crystal separation unit C The crystal cleaning liquid is directed via line 20 to a biological purification unit (not shown) or discharged. The mother liquor separated in the crystal separation unit C can be directed via line 10 (optionally through a dewatering unit D (not shown)) to a third separation unit E where at least one component ii. can be separated. If the mixture of component ii. is in the third Separating from unit E, the mixture can be directed to another separation unit to separate components ii. from each other (not shown). If methacrylic acid or a phase comprising methacrylic acid is separated in the third separation unit E, this methacrylic acid or phase comprising methacrylic acid can be directed via line 15 to the first extraction unit A3 or via line 16 To the first separation unit A4. At least a portion of at least one component ii. separated in the third separation unit E can be collected via line 11 and optionally purified in an additional purification unit (not shown). It is also possible to direct at least a portion of at least one component ii. separated in the third separation unit E to the second esterification unit H via line 14. The mother liquid separated in the crystal separation unit C can be guided to the second esterification unit H. In the second esterification unit H, at least one component ii. is esterified with an alcohol to form the corresponding ester. If the alcohol is methanol, this methanol can be introduced, for example, from the MTBE splitter AA1 via separation unit S1, optionally by intermediate purification (not shown). If the ester phase obtained in the second esterification unit H contains more than one ester, at least one ester can be separated in the ester separation unit J. At least one ester can be purified in a downstream ester purification unit K (not shown).

實例1： Example 1:

此實例係在根據圖3的先導工廠中進行(自GEA租用的Niro法先導工廠)。將人造的第一水相混合且貯存在B-100中。將第一水相進料至表面刮乾淨的熱交換器(結晶器)中，第一水相在此冷卻至-15℃，其中冰晶體形成於冷表面上。將含有第一水相的冰晶體進料至再結晶器中，在此形成較大的晶體。將冰晶體在活塞型清洗塔中與濃縮液體分離。自清洗塔提取純水作為第二水相。此冰晶體流最終熔融，獲取純水的第三水相。自第一水相移出84%產率之水，而獲取之純水具有99.85%之水濃度及少量的乙酸(0.11%)和乙醇(0.04%)濃度。下一步的第二水相，自清洗塔提取母液，其具有55.5%之水濃度。將母液進料至蒸餾塔K-200，母液在此以共沸添加劑脫水。使用乙酸異丁酯(BuOAC)作為共沸添加劑。將蒸餾塔以以任意填裝方式填裝且在350毫巴下以經蒸氣加熱之蒸發器及以冷卻水操作之冷凝器連續操作。使用相分離容器作為蒸餾容器，且以輕質相用於回流及自系統抽取重質相。獲取徹底執行脫水而成無水的液槽流出物(脫水之母液)，具有少於0.01%之水濃度。最後，經由蒸餾物相分離容器的重質相而自系統提取出水，具有0.02%之乙酸濃度及2%之丙酮濃度。 This example was carried out in a pilot plant according to Figure 3 (Niro method pilot plant leased from GEA). The artificial first aqueous phase was mixed and stored in B-100. The first aqueous phase is fed to a surface-cleaned heat exchanger (crystallizer) where the first aqueous phase is cooled to -15 ° C, wherein the ice crystals Formed on a cold surface. The ice crystals containing the first aqueous phase are fed to a recrystallizer where larger crystals are formed. The ice crystals are separated from the concentrated liquid in a piston type cleaning column. Pure water is extracted from the washing tower as a second aqueous phase. This stream of ice crystals is finally melted to obtain a third aqueous phase of pure water. The 84% yield of water was removed from the first aqueous phase, and the obtained pure water had a water concentration of 99.85% and a small concentration of acetic acid (0.11%) and ethanol (0.04%). In the next second aqueous phase, the mother liquor is extracted from the washing column, which has a water concentration of 55.5%. The mother liquor is fed to a distillation column K-200 where the mother liquor is dehydrated with an azeotropic additive. Isobutyl acetate (BuOAC) was used as an azeotropic additive. The distillation column was continuously operated by charging in an arbitrary filling manner and at 350 mbar with a vapor-heated evaporator and a condenser operated with cooling water. A phase separation vessel is used as the distillation vessel, and the light phase is used for reflux and the heavy phase is extracted from the system. Obtain a water tank effluent (dehydrated mother liquor) that is thoroughly dehydrated to have a water concentration of less than 0.01%. Finally, water was extracted from the system via the heavy phase of the distillate phase separation vessel, having an acetic acid concentration of 0.02% and an acetone concentration of 2%.

A1‧‧‧氣相氧化單元 A1‧‧‧ gas phase oxidation unit

A2‧‧‧驟冷單元 A2‧‧‧Quench unit

A3‧‧‧第一萃取單元 A3‧‧‧First extraction unit

A4‧‧‧第一分離單元 A4‧‧‧ first separation unit

A5‧‧‧第一酯化單元 A5‧‧‧First esterification unit

B‧‧‧結晶單元 B‧‧ crystallization unit

C‧‧‧晶體分離單元第二分離單元 C‧‧‧Separation unit of crystal separation unit

E‧‧‧第三分離單元 E‧‧‧third separation unit

H‧‧‧第二酯化單元 H‧‧‧Secondization unit

J‧‧‧酯分離單元 J‧‧‧ ester separation unit

1-22‧‧‧管線 1-22‧‧‧ pipeline

a1‧‧‧本發明方法之步驟編號 a1‧‧‧Step numbering of the method of the invention

a2‧‧‧本發明方法之步驟編號 a2‧‧‧Step number of the method of the invention

a3‧‧‧本發明方法之步驟編號 A3‧‧‧Step number of the method of the invention

a4‧‧‧本發明方法之步驟編號 a4‧‧‧Step number of the method of the invention

a5‧‧‧本發明方法之步驟編號 a5‧‧‧Step number of the method of the invention

b‧‧‧本發明方法之步驟編號 b‧‧‧Step number of the method of the invention

c‧‧‧本發明方法之步驟編號 c‧‧‧Step number of the method of the invention

圖1係以流程圖形式顯示根據本發明之方法的較佳具體例。 Figure 1 is a flow chart showing a preferred embodiment of the method in accordance with the present invention.

圖2係以圖式顯示根據本發明之裝置的具體例。 Figure 2 is a diagram showing a specific example of the apparatus according to the present invention.

圖3顯示進行實例之先導工廠。 Figure 3 shows the pilot plant for the example.

Claims

一種製備甲基丙烯酸及甲基丙烯酸酯中至少一者的方法，其包含以下的方法步驟：a1)將至少一種C₄化合物氣相氧化，獲得包含甲基丙烯酸的反應相；a2)將該反應相驟冷，獲得包含甲基丙烯酸的粗水相；a3)自包含甲基丙烯酸的該粗水相將至少一部分的甲基丙烯酸萃取至有機溶劑中，獲得包含甲基丙烯酸的粗有機相和第一水相，其中該第一水相包含以下組分：i.以該第一水相總重量為基準計至少65重量%，較佳為從65重量%至99.9重量%之範圍內，更佳為從70重量%至99.8重量%之範圍內的水，又更佳為從75重量%至99重量%之範圍內，更佳為從76重量%至98.5重量%之範圍內，更佳為從77重量%至98重量%之範圍內，甚至更佳為從78重量%至97.5重量%之範圍內，甚至更佳為從79重量%至95重量%之範圍內，又更佳為從80重量%至90重量%之範圍內的水，及ii.以該第一水相總重量為基準計不超過35重量%，較佳為從0.1重量%至35重量%之範圍內，較佳為從0.2重量%至30重量%之範圍內，更佳為從1重量%至25重量%之範圍內，又更佳為從1.5重量%至24重量%之範圍內，更佳為從2重量%至23重量%之範圍內，甚至更佳為從2.5重量%至22重量 %之範圍內，甚至更佳為從5重量%至21重量%之範圍內，又更佳為從10重量%至20重量%之範圍內的至少一種有機化合物(除了用作萃取劑的該有機溶劑以外)，其中i.與ii.之重量總和為100重量%；a4)自包含甲基丙烯酸的該粗有機相分離且隨意地純化至少一部分的甲基丙烯酸；a5)隨意地將步驟a4)中所獲得的至少一部分甲基丙烯酸酯化；b)自至少一部分方法步驟a3)中所獲得的第一水相結晶至少一部分的水，形成結晶水相作為第二水相和母液，其中該母液包含至少一種組分ii.；c)將該結晶水相與該母液至少部分分離。 A method for preparing at least one of methacrylic acid and methacrylic acid, comprising the following method steps: a1) gas phase oxidation of at least one C ₄ compound to obtain a reaction phase comprising methacrylic acid; a2) the reaction Phase quenching to obtain a crude aqueous phase comprising methacrylic acid; a3) extracting at least a portion of the methacrylic acid from the crude aqueous phase comprising methacrylic acid into an organic solvent to obtain a crude organic phase comprising methacrylic acid and An aqueous phase, wherein the first aqueous phase comprises the following components: i. at least 65% by weight, preferably from 65% to 99.9% by weight, based on the total weight of the first aqueous phase, more preferably It is in the range of from 70% by weight to 99.8% by weight, more preferably from 75% by weight to 99% by weight, still more preferably from 76% by weight to 98.5% by weight, more preferably from In the range of 77% by weight to 98% by weight, even more preferably in the range of 78% by weight to 97.5% by weight, even more preferably in the range of 79% by weight to 95% by weight, still more preferably from 80% by weight Water in the range of % to 90% by weight, and ii. based on the total weight of the first aqueous phase More than 35% by weight, preferably from 0.1% by weight to 35% by weight, preferably from 0.2% by weight to 30% by weight, more preferably from 1% by weight to 25% by weight, More preferably, it is in the range of from 1.5% by weight to 24% by weight, more preferably from 2% by weight to 23% by weight, even more preferably from 2.5% by weight to 22% by weight, even more preferably. It is at least one organic compound (except for the organic solvent used as an extractant) in the range of from 5 wt% to 21 wt%, more preferably from 10 wt% to 20 wt%, wherein i. Ii. The sum of the weights is 100% by weight; a4) separating and arbitrarily purifying at least a portion of the methacrylic acid from the crude organic phase comprising methacrylic acid; a5) optionally at least a portion of the methyl groups obtained in step a4) Acrylate; b) crystallizing at least a portion of the water from the first aqueous phase obtained in at least a portion of process step a3) to form a crystalline aqueous phase as a second aqueous phase and a mother liquor, wherein the mother liquor comprises at least one component ii. c) at least partially separating the aqueous crystalline phase from the mother liquor.

一種處理包含至少一種有機化合物之水相的方法，其包含以下的方法步驟：a)提供包含以下組分的第一水相：i.以該第一水相總重量為基準計至少65重量%，較佳為從65重量%至99.9重量%之範圍內，更佳為從70重量%至99.8重量%之範圍內的水，又更佳為從75重量%至99重量%之範圍內，更佳為從76重量%至98.5重量%之範圍內，更佳為從77重量%至98重量%之範圍內，甚至更佳為從78重量%至97.5重量%之範圍內，甚至更佳為從79重量%至95重量%之範圍內，又更佳為從80重量%至90重量%之範圍內的水，及ii.以該第一水相總重量為基準計不超過35重量%，較佳為從0.1重量%至35重量%之範圍內，較佳為從0.2重量%至30重量%之範圍內，更佳為從1重量%至25重量%之範圍內，又更佳為從1.5重量%至24重量%之範圍內，更佳為從2重量%至23重量%之範圍內，甚至更佳為從2.5重量%至22重量%之範圍內，甚至更佳為從5重量%至21重量%之範圍內，又更佳為從10重量%至20重量%之範圍內的至少一種有機化合物，其中i.與ii.之重量總和為100重量%，b)自至少一部分的該第一水相結晶至少一部分的水，形成結晶水相作為第二水相和母液，其中該母液包含至少一種組分ii.；c)將該結晶水相與該母液至少部分分離。 A method of treating an aqueous phase comprising at least one organic compound, comprising the following method steps: a) providing a first aqueous phase comprising: i. at least 65% by weight based on the total weight of the first aqueous phase Preferably, it is in the range of from 65% by weight to 99.9% by weight, more preferably from 70% by weight to 99.8% by weight, still more preferably from 75% by weight to 99% by weight, more preferably It is preferably in the range of from 76% by weight to 98.5% by weight, more preferably in the range of from 77% by weight to 98% by weight, even more preferably from 78% by weight to 97.5% by weight, even more preferably from From 79% by weight to 95% by weight, more preferably from 80% by weight to 90% by weight Water in the range of % by weight, and ii. not more than 35% by weight, preferably from 0.1% by weight to 35% by weight, based on the total weight of the first aqueous phase, preferably from 0.2% by weight It is in the range of from 30% by weight, more preferably from 1% by weight to 25% by weight, still more preferably from 1.5% by weight to 24% by weight, still more preferably from 2% by weight to 23% by weight. Within the range, even more preferably in the range of from 2.5% by weight to 22% by weight, even more preferably in the range of from 5% by weight to 21% by weight, still more preferably in the range of from 10% by weight to 20% by weight At least one organic compound, wherein the sum of the weights of i. and ii. is 100% by weight, b) crystallizing at least a portion of the water from at least a portion of the first aqueous phase to form a crystalline aqueous phase as the second aqueous phase and the mother liquor, Wherein the mother liquor comprises at least one component ii.; c) at least partially separating the crystalline aqueous phase from the mother liquor.

根據申請專利範圍第1或2項之方法，其進一步包含以下方法步驟中至少一者：d)將方法步驟c)中所分離的該母液至少部分脫水，獲得至少部分脫水之母液；e)將至少一種組分ii.的至少一部分自方法步驟c)中所獲得的該母液或自方法步驟d)中所獲得的該至少部分脫水之母液分離。 The method according to claim 1 or 2, further comprising at least one of the following method steps: d) at least partially dehydrating the mother liquor separated in method step c) to obtain at least partially dehydrated mother liquor; e) At least a portion of at least one component ii. is separated from the mother liquor obtained in process step c) or from the at least partially dehydrated mother liquor obtained in process step d).

根據申請專利範圍第1或2項之方法，其進一步包含以下的方法步驟： f)將該結晶水相熔融，獲得經熔融之結晶水相作為第三水相，其中對該經熔融之結晶水相施以下列中至少一者：進行至少一種生物純化處理、用作處理水及進行方法步驟a1)和a2)中至少一者。 According to the method of claim 1 or 2, the method further comprises the following method steps: f) melting the crystallized aqueous phase to obtain a molten crystalline aqueous phase as a third aqueous phase, wherein the molten crystalline aqueous phase is subjected to at least one of the following: at least one biological purification treatment, used as treated water And performing at least one of method steps a1) and a2).

根據申請專利範圍第4項之方法，其中該至少一種生物純化處理為好氧處理和厭氧處理中至少一者。 The method of claim 4, wherein the at least one biological purification treatment is at least one of an aerobic treatment and an anaerobic treatment.

根據申請專利範圍第1或2項之方法，其中該結晶水相或該經熔融之結晶水相包含以各自水相總重量為基準計低於5000 ppm，較佳為低於4000 ppm，更佳為低於3000 ppm，較佳為從1500至2500 ppm之範圍內，更佳為從1800至2200 ppm之範圍內，最佳為不超過2000 ppm之有機化合物。 The method of claim 1 or 2, wherein the crystallized aqueous phase or the molten crystalline aqueous phase comprises less than 5000 ppm, preferably less than 4000 ppm, based on the total weight of the respective aqueous phases, more preferably It is preferably less than 3000 ppm, preferably in the range of 1500 to 2500 ppm, more preferably in the range of 1800 to 2200 ppm, and most preferably not more than 2000 ppm.

根據申請專利範圍第3項之方法，其中在方法步驟e)中所分離的該至少一種組分ii.為至少兩種組分ii.之混合物，且其中在進一步的方法步驟中，g)將至少一種組分ii.與該混合物至少部分分離。 The method of claim 3, wherein the at least one component ii. separated in method step e) is a mixture of at least two components ii. and wherein in a further method step, g) At least one component ii. is at least partially separated from the mixture.

根據申請專利範圍第1或2項之方法，其中該組分ii.的至少一種有機化合物為至少一種選自羧酸、醛和酮之有機化合物。 The method of claim 1 or 2, wherein the at least one organic compound of the component ii. is at least one organic compound selected from the group consisting of a carboxylic acid, an aldehyde and a ketone.

根據申請專利範圍第1或2項之方法，其中該至少一種組分ii.係為或包含乙酸、丙烯酸、丙酸和甲基丙烯酸中至少一者。 The method of claim 1 or 2, wherein the at least one component ii. is or comprises at least one of acetic acid, acrylic acid, propionic acid, and methacrylic acid.

根據申請專利範圍第7項之方法，其中在方法步驟e)和g)中至少一者中所分離的該至少一種組分ii.係為或包含甲基丙烯酸，且將至少一部分的該甲基丙烯酸添加至方法步驟a2)中所獲得的該粗水相及方法步驟a3)中所獲得的該粗有機相中之至少一者中。 According to the method of claim 7 of the scope of patent application, wherein in the method step The at least one component ii. separated in at least one of steps e) and g) is or comprises methacrylic acid, and at least a portion of the methacrylic acid is added to the crude obtained in process step a2) The aqueous phase is at least one of the crude organic phases obtained in step a3).

根據申請專利範圍第7項之方法，其中對在方法步驟e)和g)中之至少一者中所分離的或包含在方法步驟d)中所獲得之該脫水母液中的至少一種組分ii.的至少一部分，或在方法步驟a3)中所獲得之該第一水相的至少一部分施以以下的方法步驟：h)酯化，獲得包含至少一種酯的酯相。 The method according to item 7 of the patent application, wherein at least one component ii of the dehydrated mother liquor obtained in at least one of process steps e) and g) or contained in process step d) At least a portion of, or at least a portion of the first aqueous phase obtained in process step a3) is subjected to the following process steps: h) esterification to obtain an ester phase comprising at least one ester.

根據申請專利範圍第11項之方法，其中該酯相包含至少兩種酯。 The method of claim 11, wherein the ester phase comprises at least two esters.

根據申請專利範圍第11項之方法，其進一步包含以下的方法步驟：j)將至少一種酯與該酯相至少部分分離；k)隨意地將方法步驟j)中所分離的該至少一種酯純化。 According to the method of claim 11, further comprising the steps of: j) at least partially separating at least one ester from the ester phase; k) optionally purifying the at least one ester isolated in method step j) .

根據申請專利範圍第11項之方法，其中該至少一種酯係以C₁-C₄羧酸和C₁-C₄醇為底質。 The method according to item 11, patented range, wherein the at least one ester in a C ₁ -C ₄ carboxylic acids and C ₁ -C ₄ alcohol is sediment.

根據申請專利範圍第11項之方法，其進一步包含以下步驟：aa1)將甲基第三丁基醚***，獲得至少一種C₄化合物和甲醇，其中將至少一部分的該至少一種C₄化合物作為進料供給至該等方法步驟a1)中之至少一者的氣相氧化作用中。 According to the method of claim 11, further comprising the steps of: aa1) splitting methyl tert-butyl ether to obtain at least one C ₄ compound and methanol, wherein at least a portion of the at least one C ₄ compound is taken as The feed is supplied to the gas phase oxidation of at least one of the process steps a1).

根據申請專利範圍第15項之方法，其中將方法步驟aa1)中所獲得的甲醇供給至方法步驟h)。 The method according to claim 15 wherein the methanol obtained in process step aa1) is supplied to process step h).

一種用於製造甲基丙烯酸及甲基丙烯酸酯中至少一者的裝置，其包含互相流體引導連通的至少下列組件：A1)氣相氧化單元，A2)驟冷單元，A3)第一萃取單元，A4)第一分離單元，A5)隨意的第一酯化單元，B)自水相結晶水的結晶單元，C)隨意的第二分離單元。 A device for making at least one of methacrylic acid and methacrylic acid comprising at least the following components in fluid communication with each other: A1) a gas phase oxidation unit, A2) a quench unit, A3) a first extraction unit, A4) a first separation unit, A5) a random first esterification unit, B) a crystallization unit for crystallizing water from the aqueous phase, and C) a random second separation unit.