TWI627161B - Process for preparation of methacrylic acid and methacrylic acid esters - Google Patents

Process for preparation of methacrylic acid and methacrylic acid esters Download PDF

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TWI627161B
TWI627161B TW101133297A TW101133297A TWI627161B TW I627161 B TWI627161 B TW I627161B TW 101133297 A TW101133297 A TW 101133297A TW 101133297 A TW101133297 A TW 101133297A TW I627161 B TWI627161 B TW I627161B
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TW201329035A (en
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海寧 雪佛
托斯坦 波度夫
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贏創羅恩有限責任公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0004—Crystallisation cooling by heat exchange
    • B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/0036—Crystallisation on to a bed of product crystals; Seeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/004—Fractional crystallisation; Fractionating or rectifying columns
    • B01D9/0045—Washing of crystals, e.g. in wash columns
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/58—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment

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  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本發明關於甲基丙烯酸與甲基丙烯酸酯中之至少一者的製備方法，其包含以下的方法步驟：a1)將至少一種C4化合物氣相氧化，以獲得包含甲基丙烯酸的反應相；a2)將該反應相驟冷，以獲得包含甲基丙烯酸的粗製水相；a3)自該包含甲基丙烯酸的粗製水相萃取出至少一部分的甲基丙烯酸至有機溶劑中，以獲得包含甲基丙烯酸的粗製有機相和第一水相，其中該第一水相包含以下組份：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%；a4)自該包含甲基丙烯酸的粗製有機相分離出至少一部分的甲基丙烯酸且隨意地純化；a5)隨意地將步驟a4)中所獲得的甲基丙烯酸之至少一部分酯化；b)將步驟a3)中所獲得的該第一水相所包含之水的至少一部分與至少一部分的至少一種組份ii.分開，以獲得第二水相和有機相，其中該有機相包含至少一種組份ii，且在與該第一水相比較下，該第二水相中的至少一種組份ii.被耗盡；c)隨意地自方法步驟b)中所獲得的該第二水相分離出至少一部分的至少一種有機化合物，以獲得第三水相；d)隨意地自方法步驟b)中所獲得的該有機相分離出至少一部分的至少一種組份ii.，本發明亦關於包含至少一種有機化合物之水相的處理方法，及甲基丙烯酸與甲基丙烯酸酯中之至少一者的製造裝置。 The present invention relates to a process for the preparation of at least one of methacrylic acid and methacrylic acid ester comprising the following process steps: a1) gas phase oxidation of at least one C 4 compound to obtain a reaction phase comprising methacrylic acid; a2 Cooling 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 to an organic solvent to obtain a methacrylic acid-containing solvent The crude organic phase and the first aqueous phase, wherein the first aqueous phase comprises the following components: i. at least 65% by weight, based on the total weight of the first aqueous phase, preferably from 65% to 99.9% by weight 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, 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, More preferably from 80% by weight to 90% by weight of water, and ii. The total weight of the aqueous phase 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. In the range of up to 25% by weight, more preferably 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 Within the range of %, even more preferably from 5 wt% to 21 wt%, more preferably from 10 wt% to 20 wt% of at least one organic compound, wherein i. and ii. The sum is 100% by weight; a4) at least a portion of the methacrylic acid is separated from the crude organic phase comprising methacrylic acid and optionally purified; a5) optionally at least a portion of the ester of methacrylic acid obtained in step a4) And b) separating at least a portion of the water contained in the first aqueous phase obtained in step a3) from at least a portion of at least one component ii. to obtain a second aqueous phase and an organic phase, wherein the organic phase At least one component ii is included, and at least one of the second aqueous phases is compared to the first aqueous phase Part ii. is depleted; c) optionally separating at least a portion of the at least one organic compound from the second aqueous phase obtained in process step b) to obtain a third aqueous phase; d) optionally from method step b The organic phase obtained in the separation of at least a portion of at least one component ii. The invention also relates to a process for treating an aqueous phase comprising at least one organic compound, and at least one of methacrylic acid and methacrylic acid ester Manufacturing equipment.

Description

甲基丙烯酸與甲基丙烯酸酯的製備方法 Method for preparing methacrylic acid and methacrylic acid ester

本發明關於一種甲基丙烯酸的製備方法，一種甲基丙烯酸酯的製備及一種處理包含至少一種有機化合物的水相的方法。 The present invention relates to a process for the preparation of methacrylic acid, to the preparation of a methacrylate and to a process for treating an aqueous phase comprising at least one organic compound.

甲基丙烯酸(MAA)與甲基丙烯酸酯(諸如甲基丙烯酸甲酯(MMA)和甲基丙烯酸丁酯)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、異丁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、丙烯醛和異丁烯醛)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)萃取且分離出甲基丙烯酸。將分離之甲基丙烯酸以例如蒸餾而進一步純化，分離出高沸騰雜質(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 subsequently introduced into a solvent extraction column.俾 Extract and separate methacrylic acid using a suitable extractant such as a short chain hydrocarbon. The separated methacrylic acid is further purified, for example, by distillation, and high boiling impurities such as benzoic acid, maleic acid, and terephthalic acid are separated 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 the quenching agent in the cooling and condensation steps and the water of the oxidation reaction itself. . 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，其具有足以使其能接受生物處理及/或排放至環境中的低有機物含量，或具有足以使水可再使用的純度，例如作為工業處理用水或用在甲基丙烯酸/甲基丙烯酸甲酯製造方法本身。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份。接著必須進一步處理或燃燒具有增加之有機化合物濃度的此清洗水本身。 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 allow it to be biologically treated and/or discharged into the environment, or having a purity sufficient to render the water reusable, for example as industrial processing water or The method of making methacrylic acid/methyl methacrylate itself. 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 with an increased concentration of organic compounds must then be further processed or burned.

此外，各種方法步驟(特別為自萃取劑廣泛地蒸餾分 離出甲基丙烯酸，接著自驟冷水相萃取出甲基丙烯酸)導致形成為蒸餾物的甲基丙烯酸相及成為殘餘物的高沸騰物相(有時稱為塔底相、蒸餾殘餘物或廢油)，其仍含有大量的甲基丙烯酸。可能有利的是能夠自高沸騰相回收至少一些此甲基丙烯酸。已建議各種用於處理此等高沸騰物相的方法。 In addition, various method steps (especially for the extensive distillation of self-extracting agents) Leaving methacrylic acid followed by extraction of methacrylic acid from the quenched aqueous phase results in a methacrylic phase formed as a distillate and a high boiling phase that becomes a residue (sometimes referred to as a bottom phase, distillation residue or waste) Oil), which still contains a large amount of methacrylic acid. It may be advantageous to be able to recover at least some of this methacrylic acid from the high boiling phase. Various methods for treating such high boiling phases have been suggested.

EP 1 043 302提出以溶劑處理來自丙烯酸或甲基丙烯酸製造的廢油，以阻止廢油聚合及/或在廢油中產生沉澱物。US 2005/0054874揭示在丙烯酸或甲基丙烯酸合成中以該等的丙烯酸或甲基丙烯酸含量分類自個別步驟所排放之高沸騰重質成分且藉由將該等成分與來自其他工業方法的高沸騰相組合而處理該等成分，使等該等成分可經貯存而沒有固體沉澱。然而，未在該等任一文件中教示自廢油回收甲基丙烯酸。 EP 1 043 302 proposes to treat waste oils produced from acrylic acid or methacrylic acid with a solvent to prevent the polymerization of waste oil and/or to produce precipitates in the waste oil. US 2005/0054874 discloses the high boiling heavy components emitted from individual steps in the synthesis of acrylic acid or methacrylic acid by the fraction of acrylic acid or methacrylic acid and by boiling these components with other industrial processes. The components are treated in combination such that the components can be stored without solid precipitation. However, methacrylic acid has not been recovered from waste oil in any of these documents.

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

進一步的目的係藉由自高沸騰物相回收甲基丙烯酸而增加甲基丙烯酸及/或甲基丙烯酸甲酯製造方法的總產率。 A further object is to increase the overall yield of the methacrylic acid and/or methyl methacrylate manufacturing process by recovering methacrylic acid from the high boiling phase.

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此廢水而自製程廢水回收水，使得水可再使用，接受生物純化方法，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焚燒。 Another object of the present invention is to regenerate water by reusing the wastewater by self-contained wastewater by minimizing contamination of the wastewater with organic compounds, subjecting to biological purification methods, or optionally after biological or other types of purification methods. Emitted to the environment instead of being incinerated with organic compounds.

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.

解答上述目的的貢獻係由甲基丙烯酸與甲基丙烯酸酯中之至少一者的製備方法而達成，其包含以下的方法步驟：a1)將至少一種C4化合物氣相氧化，以獲得包含甲基丙烯酸的反應相；a2)將該反應相驟冷，以獲得包含甲基丙烯酸的粗製水相；a3)自該包含甲基丙烯酸的粗製水相萃取出至少一部分的甲基丙烯酸至有機溶劑中，以獲得包含甲基丙烯酸的粗製有機相和第一水相，其中該第一水相包含以下組份：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%；a4)自該包含甲基丙烯酸的粗製有機相分離出至少一部分的甲基丙烯酸且隨意地純化；a5)隨意地將步驟a4)中所獲得的甲基丙烯酸之至少一部分酯化；b)將步驟a3)中所獲得的該第一水相所包含之水的至少一部分與至少一部分的至少一種組份ii.分開，以獲得第二水相和有機相，其中該有機相包含至少一種組份ii，且在與該第一水相比較下，該第二水相中的至少一種組份ii.被耗盡；c)隨意地自方法步驟b)中所獲得的該第二水相分離出至少一部分的至少一種有機化合物，以獲得第三水相；d)隨意地自方法步驟b)中所獲得的該有機相分離出至少一部分的至少一種組份ii.。 The contribution to the above object is achieved by a process for the preparation of at least one of methacrylic acid and methacrylic acid ester, which comprises the following process steps: a1) gas phase oxidation of at least one C 4 compound to obtain a methyl group. a reaction phase of acrylic acid; a2) quenching the reaction phase to obtain a crude aqueous phase comprising methacrylic acid; a3) extracting at least a portion of methacrylic acid from the crude aqueous phase containing methacrylic acid into an organic solvent, Obtaining a crude organic phase comprising methacrylic acid and a first aqueous phase, wherein the first aqueous phase comprises the following components: i. at least 65% by weight, based on the total weight of the first aqueous phase, preferably from 65 It is in the range of from 70% 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 from 76% by weight. It is in the range of from 98.5% by weight, more preferably from 77% by weight to 98% by weight, even more preferably from 78% by weight to 97.5% by weight, even more preferably from 79% by weight to 95% by weight. Within the range of %, more preferably from 80% by weight to 90% by weight Water, 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 30% by weight More preferably, it is in the range of from 1% by weight to 25% by weight, still more preferably in the range of from 1.5% by weight to 24% by weight, even more preferably from 2% by weight to 23% by weight, even More preferably, it is in the range of from 2.5% by weight to 22% by weight, even more preferably from 5% by weight to 21% by weight, still more preferably from 10% by weight to 20% by weight of at least one organic a compound wherein the sum of the weights of i. and ii. is 100% by weight; a4) separating at least a portion of the methacrylic acid from the crude organic phase comprising methacrylic acid and optionally purifying; a5) optionally in step a4) At least a portion of the obtained methacrylic acid is esterified; b) separating at least a portion of the water contained in the first aqueous phase obtained in step a3) from at least a portion of at least one component ii. to obtain a second An aqueous phase and an organic phase, wherein the organic phase comprises at least one component ii, and in comparison to the first aqueous phase, the first At least one component of the aqueous phase ii. is depleted; c) optionally separating at least a portion of the at least one organic compound from the second aqueous phase obtained in process step b) to obtain a third aqueous phase; Optionally, at least one of the at least one component ii. is separated from the organic phase obtained in process step b).

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)提供包含以下組份的第一水相：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)將方法步驟a)所提供的該第一水相所包含之水的至少一部分與至少一部分的至少一種組份ii.分開，以獲得第二水相和有機相，其中該有機相包含至少一種組份ii，且在與該第一水相比較下，該第二水相中的至少一種組份ii.被耗盡；c)隨意地自方法步驟b)中所獲得的該第二水相分離出至少一部分的至少一種有機化合物，以獲得第三水相；d)隨意地自方法步驟b)中所獲得的該有機相分離出至少一部分的至少一種組份ii.。 A solution to the above object is also achieved by a process for treating an aqueous phase comprising at least one organic compound comprising the following method steps: a) providing a first aqueous phase comprising the following components: i. totaling the first aqueous phase At least 65% by weight based on the weight, preferably 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 More preferably, it is in the range of from 76% by weight to 98.5% by weight, more preferably from 77% by weight to 98% by weight, even more preferably from 78% by weight to 97.5% by weight. Internally, even more preferably in the range of from 79% by weight to 95% by weight, still more preferably in the range of from 80% by weight to 90% by weight, and ii. based on the total weight of the first aqueous phase 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 in the range of from 2% by weight to 23% by weight, even more preferably from 2.5% by weight to 22% by weight, or even more Preferably, it is in the range of from 5% by weight to 21% by weight, still more preferably from 10% by weight to 20% by weight, wherein the sum of the weights of i. and ii. is 100% by weight, b Separating at least a portion of the water comprised by the first aqueous phase provided by method step a) with at least a portion of at least one component ii. to obtain a second aqueous phase and an organic phase, Wherein the organic phase comprises at least one component ii, and at least one component of the second aqueous phase is consumed in comparison with the first aqueous phase; c) optionally from method step b) The obtained second aqueous phase separates at least a portion of at least one organic compound to obtain a third aqueous phase; d) optionally separates at least a portion of at least one component ii from the organic phase obtained in process step b) . . .

接受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、異丁醛和異丁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醚(MTBE)或乙基第三丁醚(ETBE)的***。 Receiving gas phase oxidation of C a1) in accordance with step 4 of the method of the present invention is preferably a compound selected from isobutylene, tert-butanol, methacrolein or isobutyraldehyde, and two or more C 4 compounds mixtures thereof. In a preferred aspect of the present invention, C 4 compound is derived from methyl tertiary butyl ether cleavage (MTBE) or ethyl tertiary butyl ether (ETBE) is.

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異丁烯醛及進一步氧化成甲基丙烯酸實質上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，較佳為互相分離的二或多個反應區，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分離的反應區中。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異丁烯醛，接著將異丁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化合物氧化成異丁烯醛的觸媒存在於第一反應步驟中及至少一種適合於異丁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 for obtaining a gas phase comprising methacrylic acid can occur in one step, whereby a step in the present context is considered to mean preliminary oxidation to isobutylene. The aldehyde 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 two steps, preferably two or more reaction zones separated from 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 is present in the second reaction. In the steps.

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每小時約100至約6000(NTP)，而較佳為從每小時約500至約3000 。C4進料(諸如異丁烯)氧化(例如，氣相催化氧化)成異丁烯醛及/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 may range from about 100 to about 6000 (NTP) per hour, and preferably from about 500 to about 3000 per hour. C 4 feed (such as isobutylene) oxide (e.g., vapor phase catalytic oxidation) to methacrolein and / or methacrylic acid, and the catalyst system for this example, from US 5,248,819, US 5,231,226, US 5,276,178 , US 6,596,901, US 4,652,673 It is well known in the literature of 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異丁烯醛及/或甲基丙烯酸之特別佳的觸媒和方法說明於EP 0 267 556中，及適合於異丁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 particularly preferred catalysts for the oxidation of methacrolein to methacrylic acid. 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，異丁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 and At a volumetric 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之至少一者)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。接受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、惰性氣體或氣體類和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 typically used as the oxidant, for example in the form of air, or in the form of oxygen, or in the form of oxygen diluted with at least one gas 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 undergoes the gas phase oxidation reaction in step a1) of the process according to the invention preferably also comprises water, which is usually present in the form of water vapour. Oxygen, and an 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氧化反應器出口氣體)之混合物供應至步驟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 a preferred embodiment of the process according to the invention, at least one C 4 compound, air or oxygen and recycled oxidation reactor outlet gas (preferably an oxidation reactor outlet gas which has been combusted prior to the cycle) will be included. The mixture is supplied 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。在第二步驟中的異丁烯醛：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 amount of methacrolein: O 2 :H 2 O: inert gas in the second step is preferably from 1:1 to 5:2 to 20:3 to 30, preferably from 1:1 to 4:3 to 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製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份中之至少一者(特別為水和甲基丙烯酸中之至少一者)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來冷卻，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，諸如選自芳族或脂族烴類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，例如從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所知，將該等關於驟冷丙烯酸和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、異丁烯醛，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自甲基丙烯酸分離，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 by any means 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 components (particularly at least water and methacrylic acid). One) the temperature of the dew point. Suitable cooling methods are known to those skilled in the art, for example by cooling with 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 selected from aromatics. Or an organic solvent of an aliphatic hydrocarbon or a mixture of at least two thereof, whereby the preferred organic solvent has a relatively low vapor pressure under quenching conditions, such as heptane, toluene or xylene, thereby using water as a basis The quench liquid of the present invention is preferred, and at least a portion of the condensate formed by the quenching step itself is even more preferred. 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. The disclosure of such quenched acrylic and methacrylic materials is hereby incorporated by reference and constitutes a part of the present disclosure. 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 the reaction of C 4 compound 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製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。方法步驟a3)亦包含將水相和有機相互相分離。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。接著有機萃取劑原則上可藉由例如蒸餾(較佳為部分蒸餾)而自甲基丙烯酸分離，較佳地分離至根據本發明之方法的步驟a4)中的實質程度，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。此步驟之較佳的有機溶劑特別選自烷烴類和芳族(較佳為烷基芳族)、烴類，由此以至少一種選自C6-C8烴之有機溶劑較佳，由此以庚烷、甲苯和二甲苯特別佳，而以庚烷(較佳為正庚烷)最佳。方法步驟a3)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、脈動式填充塔或填裝塔、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 occurs in process step a3) using, for example, at least one organic solvent, preferably at least one organic solvent which is substantially immiscible with water, This makes it possible to form an aqueous phase and an organic phase. Process step a3) also comprises separating the aqueous phase and the organic phase from each other. 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. The organic extractant can in principle be separated from the methacrylic acid by, for example, distillation (preferably partial distillation), preferably to the extent of the step a4) of the process according to the invention, preferably in a distillation apparatus. The layer higher 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 this step are particularly selected from the group consisting of alkanes and aromatics (preferably alkyl aromatics), hydrocarbons, and thus preferably at least one organic solvent selected from the group consisting of C 6 -C 8 hydrocarbons, whereby It is particularly preferred as heptane, toluene and xylene, and heptane (preferably n-heptane). Process step a3) can be carried out in any manner known and apparently suitable to the skilled person, preferably in reverse flow extraction, for example using a solvent extraction column, a pulsating packed column or a packed column, a rotary extractor, a washing column, phase separation Or other device suitable for extracting the aqueous phase with an organic solvent and separating 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製有機相，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份i.和ii.(水和至少一種有機化合物)的第一水相。可包含組份ii.之第一水相中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製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。雖然有可能於第一水相包含在方法步驟a2)中用於萃取的少量有機溶劑，例如由於自第一水相不完全分離之有機相，但是此溶劑不被視為組份ii.。 In step a3) of the process according to the invention, therefore, two phases are 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 amounts described above. The first aqueous phase of i. and ii. (water and at least one organic compound). The organic compound in the first aqueous phase which may comprise component ii. is any organic compound formed during the gas phase oxidation reaction, such as those described above in connection with the crude aqueous phase obtained in the quenching step, and C 4 compounds and unreacted remainder of the aqueous phase to remain in any methacrylic acid. Although it is possible to include in the first aqueous phase a small amount of organic solvent for extraction in process step a2), for example due to an organic phase which is not completely separated from the first aqueous phase, this solvent is not considered to be component ii.

在根據本發明之方法的步驟a4)中，使步驟a3)中所獲得的包含甲基丙烯酸之粗製有機相接受分離，較佳為熱分離方法，以使其中所含甲基丙烯酸的至少一部分與在方法步驟a3)中作為萃取劑之有機溶劑分開。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，較佳地在蒸餾塔的上半部之層，較佳地在蒸餾塔的上三分之一處的層，而甲基丙烯酸或富含甲基丙烯酸之相係在比萃取溶劑低的蒸餾塔層移出。在塔中的塔底產物被視為根據本發明的高沸騰物相，由此亦以術語〝塔底產物〞包含在比收集甲基丙烯酸相或相類之層或層類低的蒸餾塔層所收集之任何相。此塔底產物通常包含具有比甲基丙烯酸沸點高的組份，以及聚合物材料與不同量的甲基丙烯酸，由此可使甲基丙烯酸的量高達高沸騰物相總重量之約95重量%或甚至更多。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且較高純度的甲基丙烯酸可在比塔底產物高的塔層移出。在此例子中，塔底產物(高沸騰物相)的甲基丙烯酸含量可比使用簡單蒸餾塔者之該含量低。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/或在與移出萃取劑之層或層類相比而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為熟諳本技藝者所知的方式，諸如利用另外的熱方法，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、清洗及類似者中之任一者或多者。純化和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)用於製備甲基丙烯酸聚合物，則以較高的純度可能較佳，特別取決於最終應用而定。若欲酯化甲基丙烯酸，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。關於涉及甲基丙烯酸或甲基丙烯酸酯之熱方法，分離及/或純化較佳地在一或多種聚合抑制劑的存在下進行。 In step a4) of the process according to the invention, the crude organic phase comprising methacrylic acid obtained in step a3) is subjected to separation, preferably a thermal separation process, such that at least a portion of the methacrylic acid contained therein The organic solvent as the extractant is separated 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, preferably in the upper half of the distillation column. The layer of the portion, preferably at the upper third of the distillation column, while the methacrylic acid or methacrylic-rich phase is removed in a lower distillation column than the extraction solvent. The bottom product in the column is considered to be a high-boiling phase according to the invention, whereby the term "column product" is also included in the distillation column layer which is lower than the layer or layer of the methacrylic acid phase or phase. Any phase collected. The bottom product typically comprises a component having a higher boiling point than methacrylic acid, and a polymeric material with varying amounts of methacrylic acid, whereby the amount of methacrylic acid can be up to about 95% by weight of the total weight of the high boiling phase. Or even more. 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 and higher purity methacrylic acid can be removed in the higher layer than the bottom product. In this example, the bottom product (high boiling phase) may have a lower methacrylic acid content than would be the case with a simple distillation column. If the organic solvent used for the extraction has a boiling point higher than the boiling point of the methacrylic acid, it is also possible to remove the methacrylic acid phase at the top of the column and/or at a higher level than the layer or layer from which the extractant is removed. . Further purification of the methacrylic acid or methacrylic acid-rich phase thus obtained may be by methods known to those skilled in the art, such as by additional thermal methods such as distillation or rectification, or otherwise, such as crystallization. According to the invention The process 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. By. 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 as such (for example, as a monomer or co-monomer) for the preparation of methacrylic acid polymers, higher purity may be preferred, depending on the final application. If esterification of methacrylic acid is desired, lower purity methacrylic acid can be accepted, for example if the ester final product can be purified more simply, more efficiently or more efficiently than methacrylic acid. With regard to thermal processes involving methacrylic acid or methacrylic acid esters, separation and/or purification is preferably carried out in the presence of one or more polymerization inhibitors.

在根據本發明之方法的較佳具體例中，方法步驟a4)包含自粗製有機相分離出高沸騰物相之方法步驟aa4)。 In a preferred embodiment of the process according to the invention, process step a4) comprises process step aa4) of separating the high-boiling phase from the crude organic phase.

在根據本發明之方法的此具體例中，在粗製有機相之蒸餾中分離出成為塔底產物的高沸騰物相，如上述。在本上下文中的術語〝塔底產物〞意指在塔底或較低層已取出之產物，較佳地在蒸餾、精餾或分餾塔的約下三分之一處的層。高沸騰物相可包含以高沸騰物相總重量為基準計至多約95重量%，較佳為從約60重量%至約95重量%，更佳為從約65重量%至約90重量%，更佳為從約70重量%至約85重量%之甲基丙烯酸，高沸騰物相之餘留重量係由具有比甲基丙烯酸沸點高的組份所組成(〝高沸騰物〞)，例如高沸騰酸(諸如檸康酸、順丁烯二酸、對苯二甲酸、偏苯三甲酸及類似者)、醛(諸如對-甲苯醛和苯甲醛)、聚 合物材料(特別為甲基丙烯酸之聚合物)以及聚合抑制劑(諸如氫醌、氫醌單甲醚、啡噻、苯並啡噻)。 In this particular embodiment of the process according to the invention, a high boiler phase which is a bottom product is separated in the distillation of the crude organic phase, as described above. The term "bottom product" in this context means a product which has been taken off at the bottom or lower layer, preferably at about the lower third of the distillation, rectification or fractionation column. The high-boiling phase may comprise up to about 95% by weight, preferably from about 60% to about 95% by weight, more preferably from about 65% to about 90% by weight, based on the total weight of the high-boiling phase. More preferably, from about 70% by weight to about 85% by weight of methacrylic acid, the remaining weight of the high-boiling phase is composed of a component having a higher boiling point than methacrylic acid (〝high boiling matter 〞), for example, high. Boiling acids (such as citraconic acid, maleic acid, terephthalic acid, trimellitic acid and the like), aldehydes (such as p-tolualdehyde and benzaldehyde), polymeric materials (especially methacrylic acid) Polymer) and polymerization inhibitors (such as hydroquinone, hydroquinone monomethyl ether, thiophene Benzophenazophene ).

根據本發明較佳的是將至少一部分，較佳為至少50重量%，更佳為至少60重量%，更佳為至少70重量%，又更佳為至少80重量%，甚至更佳為至少90重量%，更佳為至少95重量%，又更佳為全部在方法步驟aa4)中所分離之高沸騰物相引入在方法步驟a3)中所獲得或在方法步驟a)中所提供之第一水相中。在此方式中，可將高沸騰物相與第一水相一起處理且可回收高沸騰物相所包含之至少一部分的甲基丙烯酸。在第一水相與高沸騰物相組合時可發生少量沉澱，使得若必要時可進行隨意的固體-液體分離，例如若沉澱物量足以負面影響一或多個另外的方法步驟時，或在引導液相至另外的方法步驟之前干擾液相的輸送(特別經過導管)時。根據本發明之方法的此具體例，在本發明方法之說明中提及之第一水相亦意欲指包含至少一部分高沸騰物相的第一水相。高沸騰物相與第一水相(二者皆於先前被視為〝廢相〞且通常被焚燒)的此處理亦具有彼等的處理係與甲基丙烯酸/甲基丙烯酸酯製造方法並行的優點。此避免可能藉由將該等相之一或二者至少部分直接再循環至甲基丙烯酸/甲基丙烯酸酯製造方法中而發生對甲基丙烯酸/甲基丙烯酸酯製造方法有任何可能的負面影響。 It is preferred according to the invention that at least a portion, preferably at least 50% by weight, more preferably at least 60% by weight, more preferably at least 70% by weight, still more preferably at least 80% by weight, even more preferably at least 90% More preferably, at least 95% by weight, more preferably all of the high-boiling phase separated in process step aa4) is introduced in process step a3) or in process step a) In the water phase. In this manner, the high-boiling phase can be treated with the first aqueous phase and at least a portion of the methacrylic acid contained in the high-boiling phase can be recovered. A small amount of precipitation can occur when the first aqueous phase is combined with the high boil, such that if desired, a random solid-liquid separation can be carried out, for example if the amount of precipitate is sufficient to negatively affect one or more additional process steps, or The liquid phase interferes with the transport of the liquid phase (especially through the conduit) before the further method step. According to this particular embodiment of the process of the invention, the first aqueous phase referred to in the description of the process of the invention is also intended to mean a first aqueous phase comprising at least a portion of the high-boiling phase. This treatment of the high boiling phase and the first aqueous phase (both of which were previously considered to be decadent and usually incinerated) also has their processing in parallel with the methacrylic/methacrylic acid manufacturing process. advantage. This avoidance may have any possible negative impact on the methacrylic acid/methacrylate manufacturing process by directly or at least partially recycling the phase to the methacrylic acid/methacrylate manufacturing process. .

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，將其關於丙烯酸和甲基丙烯酸類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 by the skilled artisan, optionally in the presence of a polymerization inhibitor, to prevent methacrylic acid and/or Polymerization of methyl acrylate. 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 incorporated herein And constitute a 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. Esterification catalyst is preferably an acidic ion exchange resins, such as those in US 6,469,292, JP 1249743, EP 1 254 887 or in the market in the trade name 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)中所製備之甲基丙烯酸酯較佳地具有式[CH2=C(CH3)C(=O)O]n-R，且可藉由甲基丙烯酸與式R(OH)m之醇酯化而形成，由此n和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，環或直鏈烴類及含雜原子之直鏈或支鏈、飽和或不飽和，脂族或芳族，環或直鏈烴類，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 prepared 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 supported by methacrylic acid An alcohol of the formula R(OH) m is esterified to form, 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 Saturated, aliphatic or aromatic, cyclic or linear hydrocarbons such as alkyl, hydroxyalkyl, amine alkyl, other nitrogen- and/or oxygen-containing residues, ethylene glycol, glycols, triols 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備，例如藉由轉酯化反應。在羥酯衍生物的另一可能的製備中，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 prepared from methyl methacrylate by other methods known to those skilled in the art, for example by transesterification. In another possible preparation of the hydroxy ester derivative, the methacrylic acid according to the invention may be reacted with a corresponding oxygen-containing ring (for example, an epoxide, in particular ethylene oxide or propylene oxide) in a ring opening reaction. reaction.

較佳的甲基丙烯酸酯為甲基丙烯酸烷酯類，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類，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 methacrylate Esters, second butyl esters, especially methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; hydroxy methacrylate derivatives, such as hydroxyethyl methacrylate (preferably methyl 2-hydroxyethyl acrylate) and hydroxypropyl methacrylate (preferably 2-hydroxypropyl methacrylate or 3-hydroxypropyl methacrylate); and other alkyl methacrylates such as methyl Ethyl acrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, benzyl methacrylate, methacrylic acid 3,3,5 - Trimethylcyclohexyl ester, stearyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, 2-tert-butylaminoethyl methacrylate , triethylene glycol ethyl methacrylate, tetrahydrofuran methacrylate, diethylene glycol butyl methacrylate, methoxy Ethylene glycol-350 methacrylate, methoxy polyethylene glycol 500 methacrylate, methoxy polyethylene glycol 750 methacrylate, methoxy polyethylene glycol 1000 methacrylate, A Oxypolyethylene glycol 2000 methacrylate, methoxypolyethylene glycol 5000 methacrylate, allyl methacrylate, ethoxylated (optionally having, for example, 25 moles EO) C 16 -C 18 fatty acid 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, thereby using methyl methacrylate, methacrylic acid Hydroxyethyl acrylate and methacrylate derivatives are particularly preferred.

在根據本發明之一個態樣中，在方法步驟b)中的分離 較佳地包含以下的方法步驟：b1a)將方法步驟a3)中所獲得或方法步驟a)中所提供之至少一部分的該第一水相以萃取劑萃取，以形成該第二水相和包含至少一種組份ii.的萃取相；b1b)將該第二水相與該萃取相至少部分分開。 In one aspect of the invention, the separation in method step b) Preferably, the method comprises the steps of: b1a) extracting at least a portion of the first aqueous phase obtained in process step a3) or provided in process step a) with an extractant to form the second aqueous phase and comprising At least one component ii. of the extract phase; b1b) at least partially separating the second aqueous phase from the extract phase.

在根據本發明之方法的方法步驟b1a)中，將包含組份i.和ii.的該第一水相的至少部分(較佳為全部)以萃取劑萃取，形成萃取相和第二水相。根據本發明較佳的是將至少一部分的至少一種組份ii.萃取至萃取相中，使得在與第一水相比較下，該第二水相中的至少一種組份ii.被耗盡。萃取較佳地發生在周圍或上升溫度下，較佳為從約20℃至約65℃之範圍內的溫度，更佳為從約30℃至約60℃之範圍內的溫度，又更佳為從約40℃至約55℃之範圍內的溫度。萃取較佳為液體-液體萃取。萃取可以熟諳本技藝者已知且顯然適合的任何方式進行，例如利用萃取塔、清洗塔、相分離器或熟諳本技藝者已知且顯然適合於液體-液體萃取的其他裝置。經發現適合於根據本發明之方法的方法步驟b1a)的萃取劑為有機溶劑類、離子液體類和有機或無機油類。適合於根據本發明之方法的方法步驟b1a)中使用的萃取劑(特別為有機溶劑類)較佳地以下列性質中之至少一者，較佳為至少兩者，更佳為至少三者，更佳為全部性質為特徵：i)根據本文所述之方法在25℃下所測定在系統萃取劑-水中的乙酸之平均k-值在從0.1至100之範圍內，較佳為從 0.2至90之範圍內，更佳為從0.3至80之範圍內，又更佳為從0.3至70之範圍內，更佳為從0.4至60之範圍內；ii)蒸發焓不超過2260仟焦耳/公斤，較佳為不超過2000仟焦耳/公斤，較佳為不超過1500仟焦耳/公斤，更佳為不超過1000仟焦耳/公斤，又更佳為不超過800仟焦耳/公斤；iii)沸點在從35至140℃之範圍內，較佳為從35至125℃之範圍內，更佳為從40至120℃之範圍內，又更佳為從40至110℃之範圍內；iv)在25℃之溫度下，較佳在35℃之溫度下，更佳在45℃之溫度下，又更佳在50℃之溫度下於水中的溶解度不超過150公克/公升，較佳為不超過130公克/公升，更佳為不超過110公克/公升，又更佳為不超過100公克/公升，甚至更佳為不超過90公克/公升。 In method step b1a) of the process according to the invention, at least part, preferably all, of the first aqueous phase comprising components i. and ii. is extracted with an extractant to form an extract phase and a second aqueous phase . It is preferred according to the invention to extract at least a portion of at least one component ii. into the extraction phase such that at least one component ii. of the second aqueous phase is depleted in comparison to the first aqueous phase. The extraction preferably occurs at ambient or elevated temperatures, preferably from about 20 ° C to about 65 ° C, more preferably from about 30 ° C to about 60 ° C, and more preferably Temperatures ranging from about 40 ° C to about 55 ° C. The extraction is preferably liquid-liquid extraction. The extraction can be carried out in any manner known and apparently suitable to those skilled in the art, for example using an extraction column, a wash column, a phase separator or other means known to those skilled in the art and which are clearly suitable for liquid-liquid extraction. The extractants which have been found to be suitable for process step b1a) of the process according to the invention are organic solvents, ionic liquids and organic or inorganic oils. The extractant (particularly an organic solvent) suitable for use in process step b1a) of the process according to the invention preferably has at least one of the following properties, preferably at least two, more preferably at least three, More preferably characterized by all properties: i) the average k-value of acetic acid in the system extractant-water as determined at 25 ° C according to the method described herein is in the range from 0.1 to 100, preferably from In the range of 0.2 to 90, more preferably in the range of 0.3 to 80, still more preferably in the range of 0.3 to 70, more preferably in the range of 0.4 to 60; ii) no more than 2260 angstroms in evaporation. / kg, preferably not more than 2000 仟 joules / kg, preferably not more than 1500 仟 joules / kg, more preferably not more than 1000 仟 joules / kg, and more preferably not more than 800 仟 joules / kg; iii) The boiling point is in the range of from 35 to 140 ° C, preferably from 35 to 125 ° C, more preferably from 40 to 120 ° C, still more preferably from 40 to 110 ° C; iv) The solubility in water at a temperature of 25 ° C, preferably at a temperature of 35 ° C, more preferably at a temperature of 45 ° C, more preferably at a temperature of 50 ° C, does not exceed 150 g / liter, preferably no more than 130 g / liter, more preferably no more than 110 g / liter, more preferably no more than 100 g / liter, and even more preferably no more than 90 g / liter.

除非另有其他聲明，上述性質係在約50℃和周圍壓力下測量。術語〝k-值〞係指分配係數，亦即本發明的組份ii.之各個有機化合物在有機相(萃取)與水相之間平衡的分布比。大於1的k-值意指更多的各個有機化合物存在於有機(萃取)相勝於水相中。雖然根據本發明之方法可使用具有k-值小於1的萃取劑有好的效應I，但是到較高的k-值程度較佳，例如大於1的k-值，因為該等值表明自第一水相更完全萃取出有機化合物至萃取相中。雖然k-值可能至多100，但是根據本發明具有至多約5、10、20、30、40、50、60、70、80或90之k-值的萃取劑亦可能較佳。亦 可接受例如較低(特別為低於5)及在上述範圍內的k-值，特別若萃取劑亦具有在有利範圍內其他較佳的性質中之一或多者時。若萃取劑為有機溶劑，則蒸發焓和沸點較佳地在儘可能低的實際限制內，特別的是萃取劑在進行萃取的溫度下較佳為液體。蒸發焓較佳地不低於約22仟焦耳/莫耳，而沸點較佳地大於0℃及更佳地不低於進行萃取的操作溫度。蒸發焓較佳地不超過水的蒸發焓2260仟焦耳/公斤或40.65仟焦耳/莫耳，俾以儘量降低在根據本發明之方法的步驟b1b)中自萃取相分離第二水相之後餘留在第二水相中的任何殘餘萃取劑的熱分離所必要之能量輸入。蒸發焓較佳地亦不超過組份ii.的有機化合物中之至少一者的蒸發焓，俾以儘量降低自組份ii.的一或多種有機化合物的熱分離萃取劑所必要之能量輸入。特別佳的是蒸發焓不超過甲基丙烯酸、丙烯酸和乙酸中之至少一者的蒸發焓。就相同的理由及促進萃取劑分離，萃取劑的沸點較佳地比組份ii.的有機化合物中之至少一者的沸點低，較佳地比甲基丙烯酸、丙烯酸和乙酸中之至少一者的沸點低，且較佳地在儘可能低的較佳範圍內。若使用離子液體或有機或無機油作為萃取劑，則較佳為儘可能高的蒸發焓和沸點，較佳地比水及組份ii.的至少一種有機化合物中之至少一者高。萃取劑較佳地在水中僅具有低的溶解度，特別在萃取溫度下，且較佳地實質上或完全不溶於水中，以及較佳地實質上或完全與水不混溶，俾以能夠儘可能地完全分離萃取相和第二水相。 The above properties are measured at about 50 ° C and ambient pressure unless otherwise stated. The term 〝k-value 〞 refers to the partition coefficient, that is, the distribution ratio of the respective organic compounds of the component ii. of the present invention to the equilibrium between the organic phase (extraction) and the aqueous phase. A k-value greater than 1 means that more individual organic compounds are present in the organic (extracted) phase than in the aqueous phase. Although the method according to the invention can have a good effect I using an extractant having a k-value of less than 1, a higher degree of k-value is preferred, such as a k-value greater than 1, since the equivalent indicates The aqueous phase more completely extracts the organic compound into the extract phase. While the k-value may be at most 100, extractants having a k-value of up to about 5, 10, 20, 30, 40, 50, 60, 70, 80 or 90 in accordance with the present invention may also be preferred. also For example, a lower (particularly below 5) and a k-value within the above range may be acceptable, especially if the extractant also has one or more of other preferred properties within the advantageous range. If the extractant is an organic solvent, the evaporation enthalpy and boiling point are preferably within as low practical limits as possible, in particular the extractant is preferably liquid at the temperature at which the extraction takes place. The evaporation enthalpy is preferably not less than about 22 Torr/mole, and the boiling point is preferably greater than 0 ° C and more preferably not lower than the operating temperature at which the extraction is carried out. The evaporating enthalpy preferably does not exceed the evaporation of water 焓 2260 仟 joules/kg or 40.65 仟 joules/mole, to minimize the remaining after separation of the second aqueous phase from the extract phase in step b1b) of the process according to the invention. The energy input necessary for the thermal separation of any residual extractant in the second aqueous phase. The evaporating enthalpy preferably also does not exceed the evaporation enthalpy of at least one of the organic compounds of component ii. to minimize the energy input necessary to thermally separate the extractant from one or more organic compounds of component ii. It is especially preferred that the evaporation enthalpy does not exceed the evaporation enthalpy of at least one of methacrylic acid, acrylic acid and acetic acid. For the same reason and to facilitate separation of the extractant, the boiling point of the extractant is preferably lower than the boiling point of at least one of the organic compounds of component ii., preferably at least one of methacrylic acid, acrylic acid and acetic acid. The boiling point is low and is preferably within the preferred range as low as possible. If an ionic liquid or an organic or inorganic oil is used as the extractant, it is preferred to have as high a vaporization enthalpy and a boiling point as possible, preferably higher than at least one of water and at least one organic compound of component ii. The extractant preferably has only low solubility in water, especially at the extraction temperature, and is preferably substantially or completely insoluble in water, and preferably substantially or completely immiscible with water, so as to be as The extract phase and the second aqueous phase are completely separated.

在根據本發明之方法的步驟b1b)中，將該第二水相至少部分與該萃取相分開。根據本發明之方法的步驟b1a)的萃取及方法步驟b1b)的分離可以熟諳本技藝者已知且顯然適合的任何方式進行，較佳地利用逆向流萃取，由此使方法步驟b1a)和b1b)較佳地在相同的裝置中進行，例如利用萃取塔、脈動式填充塔或填裝塔、旋轉萃取器(特別為那些使用離心力分離之裝置)、清洗塔、相分離器或適合自水相分離有機相或離子液體相的其他裝置。若有機溶劑被用作為方法步驟b1a)中的萃取劑，則有可能焚化在方法步驟b1b)分離之後所獲得的萃取相。此焚化具有使實質的有機萃取相充當燃料的優點，因此降低購買燃料的需求。此選擇可能是較佳的，例如若不利的燃料成本或相關要求，諸如運輸的容易性或成本，及/或組份ii.的有機化合物中之一或多者的低市場價值，特別與其分離及/或純化所必需之整體努力及支出比較。 In step b1b) of the process according to the invention, the second aqueous phase is at least partially separated from the extract phase. The extraction of step b1a) and the separation of process step b1b) according to the process of the invention can be carried out in any manner known to the skilled person and apparently suitable, preferably by countercurrent extraction, whereby method steps b1a) and b1b ) preferably in the same apparatus, for example using an extraction column, a pulsating packed column or packing column, a rotary extractor (especially those using centrifugal force separation), a washing column, a phase separator or a suitable self-aqueous phase Other means of separating the organic phase or the ionic liquid phase. If an organic solvent is used as the extractant in process step b1a), it is possible to incinerate the extract phase obtained after the separation of process step b1b). This incineration has the advantage of allowing the substantial organic extract phase to act as a fuel, thus reducing the need to purchase fuel. This option may be preferred, for example, if unfavorable fuel costs or related requirements, such as ease or cost of transportation, and/or low market value of one or more of the organic compounds of component ii. And/or the overall effort and expenditure comparison necessary for purification.

第二水相較佳地包含以第二水相總重量為基準計不超過5.0重量%，較佳為不超過4.5重量%，更佳為不超過4.0重量%，更佳為不超過3.5重量%，更佳為不超過3.0重量%，甚至更佳為不超過2.5重量%之方法步驟b)中所用萃取劑以外之有機化合物。在第二水相中除了萃取劑以外的有機化合物量較佳地儘可能少量，而較佳為0重量%，雖然可接受0.5重量%，0.8重量%，1.0重量%或1.2重量%之下限。在第二水相中不包括來自方法步驟b1a)的任何殘餘萃取劑之有機化合物的總量中，甲醛通常可以第二 水相總重量為基準計至多約1.5重量%存在，而餘留者係由C2或更高的C-鏈有機化合物所組成，特別為C2-C6或C2-C4化合物。此等有機化合物的總量係取決於方法步驟b1a)之萃取中所包含的萃取步驟或萃取循環次數及在此萃取中所使用之萃取劑量而定。越多次的萃取步驟造成第二水相越少的有機化合物含量，但是通常亦需要較長的及/或多階段萃取，及/或較多的萃取劑量，其可導致接著必須進一步處理或焚化的較大容積之萃取相。 The second aqueous phase preferably comprises not more than 5.0% by weight, preferably not more than 4.5% by weight, more preferably not more than 4.0% by weight, still more preferably not more than 3.5% by weight, based on the total weight of the second aqueous phase. More preferably, it is not more than 3.0% by weight, even more preferably not more than 2.5% by weight, of the organic compound other than the extracting agent used in the method step b). The amount of the organic compound other than the extracting agent in the second aqueous phase is preferably as small as possible, and is preferably 0% by weight, although the lower limit of 0.5% by weight, 0.8% by weight, 1.0% by weight or 1.2% by weight is acceptable. In the total amount of organic compound not including any residual extractant from process step b1a) in the second aqueous phase, formaldehyde may generally be present in an amount of up to about 1.5% by weight based on the total weight of the second aqueous phase, with the remainder remaining It consists of C 2 or higher C-chain organic compounds, in particular C 2 -C 6 or C 2 -C 4 compounds. The total amount of such organic compounds depends on the number of extraction steps or extraction cycles contained in the extraction of process step b1a) and the amount of extraction used in the extraction. The more extraction steps result in less organic compound content in the second aqueous phase, but generally also requires longer and/or multi-stage extraction, and/or more extraction dose, which may result in subsequent further processing or incineration. The larger volume of the extract phase.

在根據本發明之方法的選擇步驟c)中，自第二水相至少部分分離出至少一種有機化合物，以獲得第三水相，與第二水相比較，第三水相中的至少一種有機化合物被耗盡。第三水相較佳地包含以第三水相總重量為基準計不超過3重量%，較佳為不超過2.8重量%，更佳為不超過2.5重量%，更佳為不超過2.2重量%，更佳為不超過2.0重量%之方法步驟b1a)中所用萃取劑以外的有機化合物。在第三水相中的有機化合物量較佳地儘可能少量且較佳為0重量%。若有機化合物存在於第三水相中，則至多約1.5重量%可呈甲醛形式，而餘留者包含C2或更高的C-鏈化合物(除了在方法步驟b1a)中所使用之萃取劑以外)，特別為C2-C6或C2-C4化合物。第三水相因此較佳地包含以第三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，較佳在從0至3000 ppm之範圍內，更佳在從0至2500之範圍內，更佳在從0至2200 ppm之範圍內，最佳為不超過2000 ppm之有機化合物(除了C1 化合物(甲醛)及方法步驟b)中所使用之萃取劑以外)，由此可取決於第三水相意欲之進一步用途及/或處理而接受500 ppm或1000 ppm或1500 ppm或1800 ppm之下限。在方法步驟c)中的分離較佳為熱分離，諸如蒸餾或共沸蒸餾，較佳在大氣壓力下。較佳的是將來自方法步驟b1a)而餘留在第二水相中的殘餘萃取劑在方法步驟c)中以最大可能的程度分離。若在方法步驟b1a)中所使用之萃取劑與水形成共沸物，則分離可包含共沸蒸餾，例如使用共沸添加劑的共沸蒸餾。在根據本發明之方法的步驟c)的較佳態樣中，若在方法步驟c)中使用蒸餾分離(特別利用分餾或精餾)，則較佳的是低沸騰組份(特別為具有沸點比萃取劑低的組份)係在塔頂分離，萃取劑係在塔的側出口排出及任何組份ii.係與萃取劑或在塔的另一側出口排出，較佳在比排出萃取劑的側出口低的側出口。接著可將任何因此分離之萃取劑再循環至根據本發明之方法的步驟b1a)之萃取中，相當於根據本發明之方法的步驟h)。若組份ii的一或多種有機化合物經分離在與此步驟中所分離之任何萃取劑相同的相中，則可將此相添加至方法步驟b1b)中所分離之萃取相中。若組份ii的一或多種有機化合物經分離在與萃取劑不同的相中，則可將此不同的相引導至根據本發明之方法的步驟d)或步驟f)。在有機溶劑已被用作為本發明方法之方法步驟b1a)中的萃取劑時，則較佳地進行根據本發明之方法的步驟c)，但是若在方法步驟b1a)中使用離子液體或油萃取，則亦可進行此步驟c)。 In a selection step c) of the process according to the invention, at least one organic compound is at least partially separated from the second aqueous phase to obtain a third aqueous phase, at least one organic of the third aqueous phase being compared to the second aqueous phase The compound is depleted. The third aqueous phase preferably comprises no more than 3% by weight, preferably no more than 2.8% by weight, more preferably no more than 2.5% by weight, even more preferably no more than 2.2% by weight, based on the total weight of the third aqueous phase. More preferably, it is not more than 2.0% by weight of the organic compound other than the extractant used in the method step b1a). The amount of the organic compound in the third aqueous phase is preferably as small as possible and preferably 0% by weight. If the organic compound is present in the third aqueous phase, up to about 1.5% by weight may be in the form of formaldehyde, while the remainder comprises C 2 or higher C-chain compound (except for the extractant used in process step b1a) Other than), especially C 2 -C 6 or C 2 -C 4 compounds. The third aqueous phase thus preferably comprises less than 5000 ppm, preferably less than 4000 ppm, more preferably less than 3000 ppm, preferably from 0 to 3000 ppm, based on the total weight of the third aqueous phase. Preferably, in the range from 0 to 2500, more preferably in the range from 0 to 2200 ppm, optimally no more than 2000 ppm of organic compounds (except for the C 1 compound (formaldehyde) and method step b) In addition to the extractant used, the lower limit of 500 ppm or 1000 ppm or 1500 ppm or 1800 ppm may be accepted depending on the intended use and/or treatment of the third aqueous phase. The separation in process step c) is preferably thermal separation, such as distillation or azeotropic distillation, preferably at atmospheric pressure. Preference is given to separating the residual extractant from process step b1a) remaining in the second aqueous phase in the method step c) to the greatest extent possible. If the extractant used in process step b1a) forms an azeotrope with water, the separation may comprise azeotropic distillation, for example azeotropic distillation using an azeotropic additive. In a preferred embodiment of step c) of the process according to the invention, if distillation separation (particularly using fractionation or rectification) is used in process step c), it is preferred to have a low boiling component (especially having a boiling point) The component lower than the extractant is separated at the top of the column, and the extractant is discharged at the side outlet of the column and any component ii. is discharged with the extractant or at the other side of the column, preferably in the ratio of the extractant. The side outlet is a low side outlet. Any thus separated extractant can then be recycled to the extraction of step b1a) of the process according to the invention, corresponding to step h) of the process according to the invention. If one or more organic compounds of component ii are separated in the same phase as any of the extractants separated in this step, this phase can be added to the extract phase separated in process step b1b). If one or more organic compounds of component ii are separated in a different phase than the extractant, this different phase can be directed to step d) or step f) of the process according to the invention. When an organic solvent has been used as the extractant in step b1a) of the process according to the invention, step c) of the process according to the invention is preferably carried out, but if ionic liquid or oil is used in process step b1a) , you can also perform this step c).

在根據本發明之方法的此態樣中，在方法步驟d)中的分離較佳地包含以下的方法步驟：d1a)自該萃取相分離出至少一部分的萃取劑，獲得包含至少一種組份ii.的萃取物；d1b)隨意地自該萃取物分離出至少一部分的至少一種組份ii.。 In this aspect of the process according to the invention, the separation in process step d) preferably comprises the following process steps: d1a) separating at least a portion of the extractant from the extract phase, obtaining at least one component ii An extract; d1b) optionally separating at least a portion of at least one component ii. from the extract.

在根據本發明之方法的步驟d1a)中，自萃取相至少部分分離出在方法步驟b1a)中所使用之萃取劑，以獲得包含至少一種組份ii.的萃取物。若有機溶劑被用作為萃取劑，則在方法步驟d1a)中的分離較佳地利用熱分離方法而發生。適合的熱分離方法為熟諳本技藝者所知，由此根據本發明以蒸餾、分餾、精餾及類似者較佳，由此以真空蒸餾較佳。一或多種分離方法可包含在根據本發明之方法步驟d1a)中。在較佳的熱分離方法中，在此用作為方法步驟b1a)中的萃取劑之有機溶劑具有比欲分離之一或多種組份ii低的沸點，萃取劑係在蒸餾塔頂或在分餾塔或精餾塔的上層或上層等移出，較佳為在塔的上半層，及一或多種組份ii.或包含至少一種組份ii.的萃取物係在下層、在比移出萃取劑的層低的層或塔底移出。使用具有沸點比至少一種組份ii.低的有機溶劑作為方法步驟b1a)中的萃取劑之優點在於一些或全部的組份ii.(特別為甲基丙烯酸和丙烯酸)具有熱敏感性且在溫度增加時逐漸傾向二聚合、寡聚合或聚合。該等化合物在上升溫度下的熱處理因此通常需要添加聚合抑制劑。若欲分離低沸騰萃取劑及/或若分離 為真空蒸餾，則此分離可在比各個組份ii.之沸點低的溫度下進行，減低聚合傾向且因此亦降低對聚合抑制劑的需求。 In step d1a) of the process according to the invention, the extractant used in process step b1a) is at least partially separated from the extract phase to obtain an extract comprising at least one component ii. If an organic solvent is used as the extractant, the separation in process step d1a) preferably takes place using a thermal separation process. Suitable thermal separation methods are known to those skilled in the art, and thus distillation, fractionation, rectification, and the like are preferred in accordance with the present invention, whereby vacuum distillation is preferred. One or more separation methods can be included in step d1a) of the method according to the invention. In a preferred thermal separation process, the organic solvent used herein as the extractant in process step b1a) has a lower boiling point than one or more components ii to be separated, the extractant being at the top of the distillation column or at the fractionation column Or the upper or upper layer of the rectification column is removed, preferably in the upper half of the column, and one or more components ii. or the extract comprising at least one component ii. is in the lower layer, and the extractant is removed in the lower layer. The lower layer or the bottom of the column is removed. The use of an organic solvent having a boiling point lower than at least one component ii. as an extractant in process step b1a) has the advantage that some or all of the components ii. (especially methacrylic acid and acrylic acid) are thermally sensitive and at temperature When increasing, it tends to be dimerized, oligomerized, or polymerized. The heat treatment of such compounds at elevated temperatures therefore typically requires the addition of a polymerization inhibitor. If you want to separate the low boiling extractant and / or if it is separated For vacuum distillation, this separation can be carried out at a temperature lower than the boiling point of each component ii., reducing the tendency to polymerize and thus also reducing the need for polymerization inhibitors.

若使用離子液體或有機或無機油作為方法步驟b)中的萃取劑，則在方法步驟e)中的分離較佳地藉由相分離或蒸發而發生，較佳地藉由蒸發揮發性組份或組份類。 If an ionic liquid or an organic or inorganic oil is used as the extractant in process step b), the separation in process step e) preferably takes place by phase separation or evaporation, preferably by evaporation of the volatile components. Or component class.

在方法步驟d1b)中的分離較佳為熱分離方法，較佳為蒸餾、分餾或精餾，較佳為真空蒸餾，由此自萃取物分離出至少一部分的至少一種組份ii.。除了至少一種欲分離之組份ii.以外，萃取物包含例如萃取劑或其他組份ii.。若一種以上的組份ii.包含於萃取物中，例如二或多種組份ii.，則有可能在方法步驟d1b)中僅分離出一種組份ii.或分離出二或多種組份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，且主要取決於欲分離出至少一種組份ii.的萃取物中的其他化合物數目和量而定，以及取決於欲分離之一或多種組份ii.及不意欲分離之萃取物的組份之各個沸點而定，特別為萃取物之其他組份的沸點接近於欲分離之至少一種組份ii.的沸點，及若欲分離一種以上的組份ii.時，則欲分離之組份ii.的沸點互相接近。另一考慮因素為欲分離之至少一種組份ii.的所欲純度。在根據本發明之方法的步驟f)之後，可能希望或甚至有必要進一步純化至少一種組份ii.。 The separation in process step d1b) is preferably a thermal separation process, preferably distillation, fractionation or rectification, preferably vacuum distillation, whereby at least a portion of at least one component ii. is separated from the extract. The extract contains, for example, an extractant or other component ii., in addition to at least one component to be separated ii. If more than one component ii. is included in the extract, for example two or more components ii., it is possible to separate only one component ii. or two or more components ii in process step d1b). . The choice of distillation, fractionation or rectification as a separation mode can be readily determined by those skilled in the art and will depend primarily on the number and amount of other compounds in the extract from which at least one component ii. is to be separated, and The separation of one or more components ii. and the components of the extract which are not intended to be separated, in particular, the boiling point of the other components of the extract is close to the boiling point of at least one component ii. And if more than one component ii. is to be separated, the boiling points of the components to be separated ii. are close to each other. Another consideration is the desired purity of at least one component ii. to be separated. After step f) of the process according to the invention, it may be desirable or even necessary to further purify at least one component ii.

在根據本發明之方法的進一步態樣中，在方法步驟b)中的分離較佳地包含以下的方法步驟：b2a)自方法步驟a3)中所獲得的該第一水相的至少一部分 結晶出至少一部分的水，以形成作為第二水相的結晶水相和母液，其中該母液包含至少一種組份ii.；b2b)自該母液至少部分分離出結晶水相。 In a further aspect of the method according to the invention, the separation in method step b) preferably comprises the following method steps: b2a) at least a part of the first aqueous phase obtained from method step a3) At least a portion of the water is crystallized to form a crystalline aqueous phase and a mother liquor as the second aqueous phase, wherein the mother liquor comprises at least one component ii.; b2b) at least partially separates the aqueous crystalline phase from the mother liquor.

在根據本發明之方法的方法步驟b2a)中，使至少一部分的第一水相接受結晶，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份ii.。在方法步驟b2a)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、起跑式冷卻(scratch cooling)結晶、分步結晶、層結晶、懸浮結晶、降膜結晶及類似者，或二或多者其組合，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彼此相同的區域中，或各階段可發生在分離的區域中。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，參照丙烯酸及/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和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份ii.形成共熔混合物，為了獲得儘可能純的結晶(第二水)水相中的水，則較佳地在共熔點僅結晶出水。 In process step b2a) of the process according to the invention, at least a portion of the first aqueous phase is subjected to crystallization 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 b2a) 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, starting cooling. Scratch cooling, crystallization, layer crystallization, suspension crystallization, falling film crystallization, and the like, or a combination of two or more thereof, 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 stages can occur in regions that are substantially identical to one another, or stages can occur in separate regions. 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, for example, in WO 02/055469, WO 99/14181, WO 01/77056, US 5,504,247, with reference to the purification of acrylic acid and/or methacrylic acid, the disclosure of which relates to crystallization (especially as in WO 01/ Suspension melting crystals as disclosed in U.S. Pat. If The water forms one or more components of the first aqueous phase ii. forming a eutectic mixture. In order to obtain water in the purest crystalline (second water) aqueous phase, it is preferred to crystallize only water at the eutectic point.

在根據本發明之方法的步驟b2b)中，自母液至少部分分離出作為第二水相的結晶水相。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-液體分離方式中之至少一者，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、熔融之結晶水相和水中之至少一者清洗。此清洗-熔融型結晶及分離係說明於例如有關於方法步驟b2a)的上述引用之參考文獻。在根據本發明之方法的步驟b2b)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中所揭示之類型的清洗塔，由此使結晶相漂浮在母液上及/或中，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黏度，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份，所以有可能焚化在方法步驟b2b)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之此實質的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，例如若不利的燃料成本或相關的必要條件(諸如運輸的容易性及/或成本)及/或組份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和支出比較時。 In step b2b) of the process according to the invention, the aqueous crystalline 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 filtration, centrifugation or phase separation, It is thus also possible to include cleaning of the crystal, for example by washing 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 b2a). In a preferred aspect of step b2b) of the process according to the invention, phase separation, preferably in a washing column, such as a cleaning column of the type disclosed in WO 01/77056, is used, thereby floating the crystalline phase On 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 viscosity 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, such as in a heat exchanger, and preferably directed back to the cleaning column in a reverse flow as a cleaning liquid that cleans the crystalline phase present in the cleaning column. In another preferred embodiment of step c) of the method according to the invention, the separation is carried out by centrifugation. In this specific example, it can be A small portion of the crystalline phase is melted, for example in a heat exchanger, and directed back to the centrifuge as a cleaning liquid that cleans the crystalline phase present in the centrifuge. 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 separation in process step b2b). This incineration has the advantage that the organic phase, which is reduced in water content compared to the first water, can act as a fuel, thus reducing the need to purchase fuel. This may be a preferred option, for example if one or more of the adverse fuel costs or related requirements (such as ease of transport and/or cost) and/or organic compounds of component ii. have a low market Values are specifically compared to the overall effort and expenditure required to separate and/or purify them.

在根據本發明之方法的較佳態樣中，步驟b2a)和b2b)係連續進行。結晶步驟b2a)可發生在適合於進行根據本發明之方法的步驟b2a)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b2b)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b2a)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，同時使更多的晶體成長及/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，在此至少部分分離出固體晶體且隨意地清洗，至少部分移 出雜質。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，例如至少一種生物純化處理，用作為處理水或引導至如下述之方法步驟a1)和a2)中之至少一者，或用作為清洗液體，由此有可能將第一部分的熔融之結晶相如下述方式處置及將另一部分的熔融之結晶相用作為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應至結晶單元。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之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份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、清洗單元和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b2a)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 b2a) and b2b) are carried out continuously. The crystallization step b2a) may occur in a crystallization unit suitable for carrying out the step b2a) of the method according to the invention, optionally connected to a separation unit suitable for carrying out the step b2b) of the method 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 stages of method step b2a). 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 crystal to grow and/or increase the size of the crystal. The crystal/mother liquor slurry from the crystallization unit is then directed to a separation unit where the solid crystals are at least partially separated and optionally washed, at least partially 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 another method step, such as at least one biological purification treatment, used as treated water or directed to method step a1) as described below and At least one of a2) is used as a cleaning liquid, whereby it is possible to treat the molten crystalline phase of the first portion as follows and to use another portion of the molten crystalline phase as the cleaning liquid for cleaning the crystal. 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 the skilled artisan 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, and combined crystallization/cleaning/melting units are set forth in the literature cited above with regard to method step b2a). Centrifugal devices suitable for the method according to the invention are known to those skilled in the art.

方法步驟b2a)和b2b)可以但未必導致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份ii.中之一或多者形成共熔混合物的特別例子。在此例子中，為了獲得儘可能純的結晶(第二水)水相中的水，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組份ii.之類型和量及水與此或該等組份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，在方法步驟d)中的分離包含以下的方法步驟中之至少一者：d2a)將方法步驟b2b)中所分離之母液至少部分脫水，以獲得至少部分脫水之母液；d2b)自方法步驟b2b)中所獲得的母液或方法步驟d2a)中所獲得的至少部分脫水之母液分離出至少一部分的至少一種組份ii.。 Process steps b2a) and b2b) may, but do not necessarily, result in complete crystallization of water from the first aqueous phase, such that the mother liquor may or may not normally contain some amount of water. This is a particular example of the formation of a eutectic mixture, for example, if water and one or more of the components ii. in the first aqueous phase. In this case, in order to obtain water in the crystal phase (second water) as pure as possible, 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 is therefore taken Depending 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 the water and the component ii. In a further aspect of the method according to the invention, the separation in process step d) comprises at least one of the following process steps: d2a) at least partially dehydrating the mother liquor separated in process step b2b) to obtain at least Partially dehydrated mother liquor; d2b) at least a portion of at least one component ii. is separated from the mother liquor obtained in process step b2b) or the at least partially dehydrated mother liquor obtained in process step d2a).

在根據本發明之方法的較佳態樣中，在方法步驟d2a)中自母液分離出在結晶之後餘留在母液中之至少一部分的水。在方法步驟d2b)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b2b)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。 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 d2a). The dehydration in process step d2b) 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 b2b) 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d2b)中的分離較佳為熱分離方法，較佳為蒸餾、分餾或精餾，由此自母液或脫水之母液分離出至少一部分的至少一種組份ii.。除了至少一種欲分離之組份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)之萃取劑或其他組份ii.。若一種以上的組份ii.包含於母液或脫水之母液中，例如二或多種組份ii.， 則有可能在方法步驟d2b)中僅分離出一種組份ii.或分離出二或多種組份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，例如欲分離出至少一種組份ii.的母液或脫水之母液中的其他化合物數目和量，以及欲分離之一或多種組份ii.及不意欲分離之母液或脫水之母液的組份之各個沸點，特別為母液或脫水之母液的其他組份之沸點接近於欲分離之至少一種組份ii.的沸點，及若欲分離一種以上的組份ii.時，則欲分離之組份ii.的沸點互相接近。另一考慮因素為欲分離之至少一種組份ii.的所欲純度。 The separation in process step d2b) 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 dehydrated mother liquor comprises, for example, an extractant or other component ii. from step a3) of the process according to the invention, in addition to at least one component to be separated ii. If more than one component ii. is contained in a mother liquor or a dehydrated mother liquor, such as two or more components ii., It is then possible to separate only one component ii. or to separate two or more components ii. in process step d2b). 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 boiling point of the component of the mother liquor or the dehydrated mother liquor which is not intended to be separated, especially the mother liquor or the other components of the dehydrated mother liquor, are close to the boiling point to be separated. The boiling point of a component ii., and if more than one component ii. is to be separated, the boiling points of the 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.

根據本發明之方法的此態樣，該方法較佳地進一步包含以下的方法步驟：e2)熔融該結晶水相，以獲得熔融之結晶水相作為第三水相。 According to this aspect of the method of the present invention, the method preferably further comprises the following method steps: e2) melting the crystallized aqueous phase to obtain a molten crystalline aqueous phase as the third aqueous phase.

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。特別地可使結晶水相接受使其熔融之溫度，例如在熔融裝置或熱交換器中。在方法步驟e2)中的熔融可對應於方法步驟b2a)和b2b)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法步驟b2a)和b2b)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e2)中熔融，且進一步引導至生物純化處理，用作為處理水，及引導至方法步驟a1)和a2)中之至少一者。 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 e2) may correspond to the melting already described in the description of process steps b2a) and b2b), and/or it may be further melted. Thus, for example, the first melting can be carried out within the scope of the process steps b2a) and b2b), 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 is obtained, the crystal can be The body is melted in step e2) of the process according to the invention and further directed to the biological purification treatment, used as treated water, and directed to at least one of method steps a1) and a2).

根據本發明此態樣的熔融之結晶水相或第三水相通常具有足以直接用作為處理水或作為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5000ppm，較佳為少於4000ppm，更佳為少於3000ppm，較佳為從1500至2500ppm之範圍內，更佳為從1800至2200之範圍內，最佳為不超過2000ppm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-熔融循環而達成更低的雜質量，例如少於約500ppm或甚至少於100ppm及在從0ppm至100ppm之範圍內。然而，該等較少量的雜質通常僅與減少的水量一起獲得。可在用作為處理水或作為方法步驟a1)或a2)中的添加水之前隨意地進行生物純化處理。若熔融之結晶水相的水欲用於其他目的或排放至環境中，則可能較佳但並不總必然是此使用或排放係在生物純化之後。 The molten crystalline aqueous phase or the third aqueous phase according to this aspect of the invention generally has a purity sufficient to be used directly as treated 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, preferably from 1500 to 2500 ppm, based on the total weight of the respective aqueous phases. Within the range, it is more preferably from 1800 to 2200, and most preferably no more than 2000 ppm of organic compounds. It is possible to achieve a lower amount of impurities, in particular by using a number of cleaning-melting cycles in step c) of the process according to the invention, for example less than about 500 ppm or even at least 100 ppm and in the range from 0 ppm to 100 ppm. . However, such smaller amounts of impurities are typically only obtained with a reduced amount of water. 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 intended for other purposes or is discharged into the environment, it may be preferred, but not always, that the use or discharge is after biological purification.

根據本發明較佳的是使第三水相接受下列中之至少一者：引導至至少一種生物純化處理、用作為處理水和引導至方法步驟a1)和a2)中之至少一者。 It is preferred according to the invention that the third aqueous phase accepts at least one of: directing to at least one biological purification treatment, serving as treated water, and directing to at least one of method steps a1) and a2).

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和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/或藉由降低水的生物化學需氧量(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應鏈中。生物純化處理為熟諳本技藝者所知且可為所謂的活化污泥處理中之一或多者。此等處理為熟諳本技藝者所習知或熟知。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 water. Any treatment of the purity, 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 In the water supply chain. The biological purification treatment is known to those skilled in the art and may be one or more of the so-called activated sludge treatment. Such treatments are known or 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.

若第三水相接受至少一種生物純化處理，則此處理較佳為好氧處理和厭氧處理中之至少一者。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 the third aqueous phase is subjected to at least one biological purification treatment, the treatment is preferably at least one of an aerobic treatment and an 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.

若在根據本發明之方法的方法步驟d)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互相分離出組份，例如若二或多種組份具有非常類似的沸點。此可為若接受方法步驟d)之母液或脫水之母液包含相對大量組份的特別情況，特別為若一或多種組份ii.具有類似於至少一種欲在方法步驟d)中分離之組份ii.的沸點時，更 難在方法步驟d)中以微調分離出僅一種組份ii.而已。接著可在進一步的方法步驟f)中更適當或更實際分離出二或多種組份ii.，在此可更輕易地達成此適應於各個組份特殊的分離要求。據此，在根據本發明之方法的態樣中，在方法步驟d)中所分離之至少一種組份ii.為至少兩種組份ii之混合物，且在以下另外的方法步驟中：f)較佳地自此混合物至少部分分離出至少一種組份ii.。 If the separation in process step d) of the process according to the invention is thermal separation, it is not always possible or for example to separate the components from one another in an economically or technically feasible manner, for example if two or more components are very similar The boiling point. This may be a special case if the mother liquor or dehydrated mother liquor of process step d) comprises a relatively large amount of components, in particular if one or more components ii. have a composition similar to at least one which is intended to be separated in process step d) Ii. When the boiling point is more It is difficult to separate only one component ii. by fine adjustment in method step d). It is then possible to separate two or more components ii. in a further method step f), which can be more easily achieved in this particular adaptation to the individual components. According to this, in the aspect of the process according to the invention, at least one component ii. separated in process step d) is a mixture of at least two components ii, and in the following additional process steps: f) Preferably at least one component ii. is at least partially separated from the mixture.

在根據本發明之方法的方法步驟f)中的分離可包含一或多個分離步驟，諸如上文已根據本發明之方法中的其他分離步驟所討論之熱分離、層析術分離、化學分離(例如，藉由一種組份ii.的優先反應來形成更輕易自一或多種其他的組份ii.分離之反應產物，或藉由二或多種組份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 step f) of the process according to the method of the invention may comprise one or more separation steps, such as the thermal separation, chromatographic separation, chemical separation discussed above in accordance with other separation steps in the method of the invention. (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，組份ii.的至少一種有機化合物(較佳為方法步驟f)中至少部分分離之至少一種組份ii.)為至少一種選自羧酸類、醛類和酮類之有機化合物。在該等之中，根據本發明較佳的是至少一種組份ii.(較佳為方法步驟f)中至少部分分離之至少一種組份ii.)為乙酸、丙烯酸、丙酸和甲基丙烯酸中之至少一者。 In a preferred embodiment of the process according to the invention, at least one component ii.) of at least one organic compound (preferably in process step f) of component ii. is at least one selected from the group consisting of carboxylic acids, Organic compounds of aldehydes and ketones. Among these, it is preferred according to the invention that at least one component of the at least one component ii. (preferably in process step f) is at least partially separated ii.) is acetic acid, acrylic acid, propionic acid and methacrylic acid. At least one of them.

若在方法步驟d)和f)中之至少一者所分離之至少一種組份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)中所獲得的粗製水相中及/或方法步驟a3)中所獲 得的粗製有機相中。此可為較佳的具體例，例如若在方法步驟d)和f)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，若所分離之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的組份一起分離，則以添加至粗製水相中可能較佳。例如，若除了甲基丙烯酸以外的組份具有比甲基丙烯酸更高的沸點，則以添加至粗製有機相中可能較佳，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份(特別為其他組份ii.)的相對比例亦可扮演一角色，但是在方法步驟e)、f)和j)中之至少一者所分離之至少一種組份ii.中的其他組份之本性具有決定在方法步驟e)、f)和j)中之至少一者所分離之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d)和f)中之至少一者所分離之甲基丙烯酸比較純，包含例如不超過約5重量%，較佳為不超過約4重量%，較佳為不超過約3重量%，較佳為不超過約2重量%，較佳在從約1重量%至約2重量%之範圍內的雜質或其他組份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 by at least one of method steps d) and f) is or comprises methacrylic acid, then in a preferred embodiment of the method according to the invention at least a portion of this Adding the acrylic acid phase to the crude aqueous phase obtained in process step a2) and/or obtained in process step a3) In the crude organic phase. This may be a preferred embodiment, for example if the methacrylic acid separated by one or more of method steps d) and f) does not have the purity desired 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 a component other than methacrylic acid has a higher boiling point than methacrylic acid, it may be preferred to add to the crude organic phase because 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), f) and j) The nature of the other components in ii. has a greater effect on which phase the methacrylic acid containing phase separated by at least one of method steps e), f) and j) is added to. For example, if the methacrylic acid separated in at least one of the method steps d) and f) is relatively pure, it comprises, for example, no more than about 5% by weight, preferably no more than about 4% by weight, preferably no more than about 3 wt%, preferably not more 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，使方法步驟d)和f)中之至少一者所分離之至少一種組份ii.的至少一部分或方法步驟a3)中所獲得的第一水相的至少一部分接受方法步驟g)之酯化，獲得包含至少一種酯的酯相。 In another aspect of the method according to the invention, at least a portion of at least one component ii. separated by at least one of method steps d) and f) or the first water obtained in method step a3) At least a portion of the phase undergoes esterification of process step g) to obtain an ester phase comprising at least one ester.

若至少一種各個組份ii.為羧酸，則此步驟可能較佳。酯化步驟之細節與根據本發明之方法的方法步驟a5)的上 述者相同。使方法步驟d)和f)中之至少一者所分離之至少一種組份ii.酯化(不是或除了獲得至少一種各個組份ii.本身以外)可能較佳，與組份ii.之酯比較，該酯化可取決於例如所分離之各個組份ii.可獲得的純度、各個組份ii.的市場或進一步應用而定。例如，若第一水相僅包含低比例的不意欲分離之雜質及/或組份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%之不意欲分離之雜質及/或組份ii.的雜質總量，特別為例如可比自組份ii.本身更容易自各個組份ii.之酯分離的雜質，則使方法步驟a3)中所獲得的第一水相中所包含的至少一種組份ii.酯化可能較佳。 This step may be preferred if at least one of the individual components ii. is a carboxylic acid. The details of the esterification step and the method step a5) of the method according to the invention The same is true. Esterification of at least one component ii. separated by at least one of method steps d) and f) (not or in addition to obtaining at least one of the individual components ii. itself) may be preferred, and esters of component ii. In comparison, the esterification may depend, for example, on the purity of the individual components ii. available, the market for each component ii., or further applications. For example, if the first aqueous phase contains only a low proportion of impurities and/or components ii. which are not intended to be separated, for example, less than about 6% by weight, preferably less than about 5, based on the total weight of the first aqueous phase. % by weight, preferably less than about 4% by weight, more preferably less than about 3% by weight of the total amount of impurities which are not intended to be separated and/or components ii., in particular, for example, comparable self-component ii. Easier esterification of at least one component ii. contained in the first aqueous phase obtained in process step a3) may be preferred if the impurities are more readily separated from the ester of each component ii.

在根據本發明的酯相中所包含之特別佳的酯類係以C1-C4羧酸和C1-C4醇為基礎，由此以C2-C4羧酸為基礎之酯類較佳。除了有關於方法步驟a5)中所述之甲基丙烯酸酯以外，特別佳的酯類為乙酸甲酯、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，以乙酸酯類和丙烯酸酯類較佳。 Particularly preferred esters contained 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 based on C 2 -C 4 carboxylic acids 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 And n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, and second butyl propionate. Among them, acetates and acrylates are preferred.

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d)和f)中之至少一者所分離之至少一種組份 ii.或在方法步驟a3)中所獲得的至少一部分的第一水相包含至少兩種能夠反應形成酯的組份ii.(特別為至少兩種羧酸)之例子。此具體例可在若至少兩種能夠反應形成酯的組份ii.特別難分離時較佳，例如以熱或其他方式，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 that is separated if at least one of method steps d) and f) Ii. or at least a portion of the first aqueous phase obtained in process step a3) comprises at least two examples of components ii. (particularly at least two carboxylic acids) capable of reacting to form an ester. This particular example may be preferred if at least two components which are capable of reacting to form an ester ii. 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 The volatility is very close, and the esters can be separated from each other with a lower degree of difficulty.

根據本發明之方法可進一步包含以下的方法步驟：h)自該酯相至少部分分離出至少一種酯；j)隨意地將方法步驟h)中所分離出之該至少一種酯純化。 The process according to the invention may further comprise the following process steps: h) at least partially separating at least one ester from the ester phase; j) optionally purifying the at least one ester isolated in process step h).

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，以及未反應之組份ii.，及亦可能包含另外的酯或酯類。在方法步驟h)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出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份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，亦可進行在方法步驟h)中所分離之至少一種酯的純化作用。純化方式係取決於酯而定，由此可考慮例如以熱方式、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 components ii., and may also contain additional esters or esters. The separation in process step h) 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 ( Such as filtering). Purification of at least one ester isolated in process step h) can also be carried out if necessary or desired. The manner of purification depends on the ester and can thus be considered, for example, by thermal means, by chromatography, by washing or by crystallization.

在根據本發明之方法的較佳具體例中，在方法步驟g)、h)和j)中之至少一者所獲得的至少一種酯之至少一部分被用作為方法步驟b1a)中的萃取劑。 In a preferred embodiment of the process according to the invention, at least a portion of the at least one ester obtained in at least one of process steps g), h) and j) is used as the extractant in process step b1a).

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)將甲基第三丁醚(MTBE)***，以獲得至少一種C4化合物和甲醇，其中將該至少一種C4化合物的至少一部分作為進料供給至方法步驟a1)和□1)中之至少一者的氣相氧化反應中。MTBE被廣泛地用作為異丁烯之原料且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。適合的觸媒和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,5th Edition,Vol.A4,p.488；V.Fattore,M.Massi Mauri,G.Oriani,G.Paret,HydrocarbonProcessing,August 1981,p.101-106；Ullmann’s Encyclopedia of Industrial Chemistry,5th Edition,Vol.A16,p.543-550；A.Chauvel,G.Lefebvre,“Petrochemical Processes,Technical and Economic CharacteristicS”,Vol.1,Éditions 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 methyl tertiary butyl ether (MTBE) to obtain at least one C 4 compound and methanol, wherein the at least one C 4 compound At least a portion of the feed is supplied as a feed to the gas phase oxidation reaction of at least one of process steps a1) and □1). 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, HydrocarbonProcessing, 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 Characteristic S", Vol. 1, Éditions Technip, Paris, 1989, p. 213 et seq.; US 5, 336, 841, US 4, 570, 026 and references cited therein. 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應至方法步驟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。一或多個中間 分離及/或純化步驟亦可能介於***MTBE與供應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，例如儘可能地使至少一種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。適合的純化和分離方法說明於例如EP 1 149 814 A1、WO 04/018393 A1和WO 04/052809A1中。在分離甲醇之後，包含C4化合物異丁烯作為主要組份的***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、層析術或清洗中之至少一者，較佳為蒸餾和萃取中之至少一者，較佳為至少一種蒸餾和至少一種萃取。可在此步驟中自C4化合物相至少部分分離出未反應之MTBE。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. In one or both of isobutylene and tert-butanol may be supplied as a feed to a process 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. Between one or more intermediate separation and / or purification steps may also be interposed at least one C 4 compound to MTBE splitting process step thus obtained was supplied with a1) a gas phase oxidation reaction, for example at least one C 4 compound as possible Separation from methanol and 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 A1, WO 04/018393 A1 and WO 04/052809 A1. After separation of the methanol, a compound comprising C 4 isobutylene phase may then optionally purified and provided as feed to the process step a1 splitting group as the main component). 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. In this step can be from C 4 compound phase separating at least a portion of the unreacted MTBE. 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g)中。在根據本發明之方法的另一態樣中，可將方法步驟aa1)中所獲得的甲醇供應至方法步驟a5)中。可將甲醇隨意地純化，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 g). 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 purified methanol is described in EP 1 254 887.

本發明亦關於一種製造甲基丙烯酸與甲基丙烯酸酯中之至少一者的裝置，其包含互相以流體引導相通的至少以 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)第二分離單元，C)隨意的第三分離單元，D)隨意的第四分離單元，其中該第一分離單元為熱分離單元，其具有至少一個底部出口在其下三分之一處，該至少一個底部出口與該第二分離單元的至少一個入口以流體引導相通。 The invention also relates to a device for producing at least one of methacrylic acid and methacrylic acid, comprising at least Lower assembly: A1) gas phase oxidation unit, A2) quench unit, A3) first extraction unit, A4) first separation unit, A5) random first esterification unit, B) second separation unit, C) random a third separation unit, D) an optional fourth separation unit, wherein the first separation unit is a thermal separation unit having at least one bottom outlet at a lower third thereof, the at least one bottom outlet and the second At least one inlet of the separation unit is in fluid communication.

應瞭解術語〝以流體引導相通〞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之至少一者)可自一個單元引導至至少一個其他的單元。此可以例如經由管子或導管(例如，由對試劑和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)直接相通或利用貯槽車或安排在單元之間的貯槽或貯存庫間接相通而達成。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/或以液體存在的組份之固化及/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和條件(諸如溫度和壓力條件，特別為該等接受條件)具有抗性之材料所製成。 It should be understood that the term "flow-through" refers to the connection of a unit such that a fluid (which can be at least one of a liquid, a gas, a vapor, a supercritical fluid, or any other fluid) can 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 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 The reactor, column and other plant components are preferably made of materials that are resistant to reagents and conditions, such as temperature and pressure conditions, particularly those accepting conditions.

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之方法所述者。反應器材料應對反應器內部的試劑和當時條件具有抗性及較佳地具有惰性。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 oxidation catalysts in accordance with the present invention are those described above in relation to the process of the present invention. The reactor material should be resistant and preferably inert to the reagents and conditions at the time of the reactor. 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)成為異丁烯醛之氧化觸媒，及在第二個反應區中的氧化觸媒較佳地適合於氧化異丁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者。 In a two-stage gas phase oxidation reaction, the gas phase oxidation unit 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 oxidizing 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 is preferably suitable for oxidizing methacrolein to methacrylic acid. Suitable catalysts are those 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相通。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中的CCU或TCU下游)的包含二氧化碳之再循環氣體。各個送料器應由對試劑和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、稀釋劑和水在進入各個反應器之前供應至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 recycle gas comprising carbon dioxide in the CCU or downstream of the TCU in 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進行。 Step a1) of the process according to the invention is preferably carried out in a gas phase oxidation unit.

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)。亦可在吸收單元A2)中分離出未反應之異丁烯醛，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和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為第一萃取單元A3)。 In a preferred embodiment of the apparatus according to the invention, the quench unit A2) is followed by a 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 the extraction of methacrylic acid can be considered 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)較佳地在第一酯化單元A5)的上游，較佳地在第一萃取單元A3)與第一酯化單元A5)之間且以流體相通。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)排出之粗製有機相中存在的其他組份分離出甲基丙烯酸，相當於根據本發明之方法的方法步驟a3)之粗製有機相。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之至少一者。可能的是第一分離單元A4)包含一個以上的分離階段。第 一分離單元A4)較佳地包含至少一個底部出口，其可為在第一分離單元的底部或下三分之一處的出口。第一分離單元A4)的此安排較佳地容許自粗製有機相分離出高沸騰物相，對應於根據本發明之方法的方法步驟aa4)。至少一個底部出口較佳地與第二分離單元B)的至少一個入口以流體引導相通。此以流體引導相通可利用在第一分離單元的至少一個底部出口與第二分離單元的至少一個入口之間的直接導管。亦有可能在第一分離單元的至少一個底部出口與第二分離單元B)的至少一個入口之間安排至少一個中間裝置及/或組件R)，例如至少一個另外的分離裝置，諸如至少一個另外的熱分離裝置及/或至少一個固體/液體分離裝置，及/或至少一個混合裝置及/或至少一個貯存庫，例如能使第一分離單元A4)中所分離之高沸騰物相引入第一水相中，較佳地能使高沸騰物相與第一水相組合，及隨意地能使高沸騰物相及/或組合之高沸騰物相與第一水相之組份分離。熟諳本技藝者已知且顯然適合於所述目的的任何裝置和組件可包含在根據本發明的裝置中。 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 preferably upstream of the first esterification unit A5), preferably at the first extraction unit A3) The 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 other components present in the crude organic phase withdrawn from the first extraction unit A3) of the apparatus according to the invention separate methacrylic acid, corresponding to the crude organic phase of process step a3) of the process 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. It is possible that the first separation unit A4) contains more than one separation stage. First A separation unit A4) preferably comprises at least one bottom outlet, which may be an outlet at the bottom or the lower third of the first separation unit. This arrangement of the first separation unit A4) preferably allows separation of the high-boiling phase from the crude organic phase, corresponding to method step aa4) of the method according to the invention. The at least one bottom outlet is preferably in fluid communication with at least one inlet of the second separation unit B). This direct guiding of the fluid can utilize a direct conduit between at least one bottom outlet of the first separation unit and at least one inlet of the second separation unit. It is also possible to arrange at least one intermediate device and/or component R) between at least one bottom outlet of the first separating unit and at least one inlet of the second separating unit B), for example at least one further separating device, such as at least one additional Thermal separation unit and/or at least one solid/liquid separation unit, and/or at least one mixing unit and/or at least one reservoir, for example, capable of introducing a high boiling phase separated in the first separation unit A4) into the first Preferably, in the aqueous phase, the high-boiling phase is combined with the first aqueous phase, and the high-boiling phase and/or the combined high-boiling phase are optionally separated from the components of the first aqueous phase. Any device and component known to those skilled in the art and apparently suitable for the purpose can be included in the device according to the invention.

用於純化在第一分離單元A4)中所分離之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A4)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 A4) may also be arranged downstream of the first separation unit A4). 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/或低沸騰組份的熱或汽提設備、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, for example for separation high And/or a low boiling component hot or stripping device, a device for solid/liquid separation, such as at least one filtration and/or centrifugation, and/or a 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.

可將未反應之異丁烯醛在驟冷單元、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分離且引導返回氣相氧化單元供進一步反應。 Unreacted methacrolein may be separated from any of the quench unit, the first extraction unit, the first separation unit, the first purification unit, or any of the above-described more plant components and directed back to the gas phase oxidation unit for further processing 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 a Any other device of a acrylate (especially methyl methacrylate).

根據本發明之裝置進一步包含第二萃取單元B)。第二萃取單元B)適合自至少一部分的至少一種有機化合物(特別為至少一種組份ii.)分離出在第一萃取單元A3)中所獲得的第一水相中所包含之水的一部分，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)較佳地在第二萃取單元B)中進行。 The device according to the invention further comprises a second extraction unit B). The second extraction unit B) is adapted to separate a portion of the water contained in the first aqueous phase obtained in the first extraction unit A3) from at least a portion of the at least one organic compound, in particular at least one component ii. As described above, the second aqueous phase and the organic phase are obtained. Process step b) of the process according to the invention is preferably carried out in a second extraction unit B).

在根據本發明之裝置的較佳具體例中，第二分離單元B)包含第二萃取單元B1)。第二萃取單元B1)適合以萃取劑萃取至少一部分的第一水相，形成第二水相和萃取相，以及適合自萃取相以技術限度內可能的最大程度分離出第二水相。因此，根據本發明之方法的至少方法步驟b1a)及較佳為方法步驟b1a)和b1b)較佳地在第二萃取單元B1)中進行，最佳地以連續方式。第二萃取單元B1)較佳地包含至少一個萃取塔、清洗塔、相分離器或熟諳本技藝者已知且顯然適於液體-液體萃取，且較佳地亦適合於自水相分離出有機相或離子液相，更佳地以連續方法萃取和分離之其他裝置，例如至少一個萃取塔、至少一個脈動式填充塔及/或填裝塔、至少一個旋轉萃取器(特別為至少一個使用離心力分離之旋轉萃取器)、至少一個清洗塔及/或至少一個相分離器。第二萃取單元B1)較佳地能夠禁得起周圍溫度以及周圍溫度以外的溫度且在該等溫度下操作，特別在上升的溫度下，特別在有關於方法步驟b1a)和b1b)的上述溫度下。 In a preferred embodiment of the device according to the invention, the second separation unit B) comprises a second extraction unit B1). The second extraction unit B1) is adapted to extract at least a portion of the first aqueous phase with an extractant to form a second aqueous phase and an extract phase, and to separate the second aqueous phase from the extract phase to the greatest extent possible within technical limits. Thus, at least method step b1a) and preferably method steps b1a) and b1b) of the method according to the invention are preferably carried out in the second extraction unit B1), preferably in a continuous manner. The second extraction unit B1) preferably comprises at least one extraction column, washing column, phase separator or cooker known to the skilled person and is obviously suitable for liquid-liquid extraction, and preferably also suitable for separating organic from the aqueous phase. a phase or ionic liquid phase, more preferably a continuous extraction and separation of other means, such as at least one extraction column, at least one pulsation packed column and / or packed column, at least one rotary extractor (especially at least one using centrifugal force) A separate rotary extractor), at least one cleaning column, and/or at least one phase separator. The second extraction unit B1) is preferably capable of withstanding ambient temperatures and temperatures outside the ambient temperature and operating at such temperatures, in particular at elevated temperatures, in particular at the abovementioned temperatures with regard to method steps b1a) and b1b).

在根據本發明之裝置的另一較佳具體例中，第二分離單元包含B2a)結晶單元，及B2b)隨意的晶體分離單元。 In another preferred embodiment of the apparatus according to the present invention, the second separation unit comprises a B2a) crystallization unit, and a B2b) random crystal separation unit.

在結晶單元B2a)中，通常將第一萃取單元中所獲得的第一水溶液冷卻，使得水至少部分結晶。接著將所得泥漿隨意地經由使晶體成長的滯留單元T1)(如有關於方法步驟b2a)和b2b)之上文所述)運送至引導至晶體分離單元B2b)，例如清洗塔或離心器，在此自母液至少部分分離出固體晶體，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第二分離單元B2)中，且可在結晶單元B2a)和晶體分離單元B2b)中之至少一者的內部或外部，較佳地與至少一個晶體分離單元B2b)以流體及/或固體引導相通。至少一部分的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為晶體分離單元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B2b)供應至少一部分的晶體至結晶單元B2a)及/或滯留單元T1)中作為晶種。 In the crystallization unit B2a), the first aqueous solution obtained in the first extraction unit is usually cooled, so that the water at least partially crystallizes. The resulting slurry is then optionally transported via a retention unit T1) (as described in method steps b2a) and b2b) which grows the crystals to a crystal separation unit B2b), such as a washing column or a centrifuge, This at least partially separates the solid crystals from the mother liquor and preferably cleans the crystals to at least partially remove the remaining impurities to the greatest extent possible. At least one melting device may also be included in the second separation unit B2) and may be internal or external to at least one of the crystallization unit B2a) and the crystal separation unit B2b), preferably with at least one crystal separation unit B2b) The fluid and/or solid are guided to communicate. 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, or both. It is also possible to supply at least a portion of the crystals from the crystal separation unit B2b) to the crystallization unit B2a) and/or the retention unit T1) 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、滯留單元和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水自包含有機組份之水溶液結晶的任何結晶單元，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-引導相通及至少一個出口與晶體分離單元以流體-及/或固體-引導相通。結晶單元(隨意地與滯留單元一起)較佳地適合於進行根據本發明之方法的步驟b2a)。晶體分離單元較佳地適合於進行根據本發明之方法的步驟b2b)，且較佳為清洗塔或離心裝置。適合的結晶單元及以併入清洗及/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"Melt Crystallisation Technology"by G.F.Arkenbout,Technomic Publishing Co.Inc.,Lancaster-Basel(1995),pp.265-288、Chem.Ing.Techn.(72)(10/2000),1231-1233之書籍中所述。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,p.91-102 and Chem.Ing.Techn.63(1991),No.9,p.881-891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、清洗單元和熔融單元 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。 Any of the crystallization units, retention units and crystal separation units which are known to the skilled person and which are apparently suitable for the above purposes can be used in the apparatus according to the invention, whereby the individual units which permit continuous crystallization and separation are preferred. The crystallization unit may 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, 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 - guide the communication. The crystallization unit (optionally with the retention unit) is preferably suitable for carrying out step b2a) of the method according to the invention. The crystal separation unit is preferably adapted to carry out step b2b) of the method according to the invention, and is preferably a washing column or a centrifugal device. Suitable crystallization units and crystallization units incorporated into the cleaning and/or melting unit are suspended crystallization units for cleaning crystals, for example, downstream in a hydraulic or mechanical cleaning column, as in " Mel Crystallisation Technology " by GF Arkenbout, Technomic Publishing Co. Inc. ., Lancaster-Basel (1995), pp. 265-288, Chem. Ing. Techn. (72) (10/2000), 1231-1233. Typically any melt cleaning tower is forcibly transported, for example, in Chem. Ing. Techn. 57 (1985) No. 2, p. 91-102 and Chem. Ing. Techn. 63 (1991), No. 9, p. 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, and 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.

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，例如用於焚化在第二萃取單元中所獲得的萃取相或自結晶單元及/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 incinerating the extract phase obtained in the second extraction unit or the mother liquor obtained from the crystallization unit and/or the crystal separation unit.

根據本發明之裝置可進一步包含第三分離單元C)。第三分離單元C)特別包含在其中根據本發明之裝置包含萃取單元作為第二分離單元之具體例中，但是亦可包含在其中根據本發明之裝置包含結晶單元作為第二分離單元之具體例中。第三分離單元C)較佳地適合自第二水相分離出方法步驟b1a)中所使用之任何餘留的萃取劑。第三分離單元C)可為另外的萃取單元，但是較佳為熱分離單元，例如蒸餾塔、分餾塔、精餾塔或類似者，由此可考慮熟諳本技藝者已知且顯然適合於此分離之任何設備於根據本發明之裝置中。 The device according to the invention may further comprise a third separation unit C). The third separation unit C) is specifically included in a specific example in which the apparatus according to the invention comprises an extraction unit as the second separation unit, but may also comprise a specific example in which the apparatus according to the invention comprises a crystallization unit as the second separation unit in. The third separation unit C) is preferably adapted to separate any remaining extractant used in process step b1a) from the second aqueous phase. The third separation unit C) may be an additional extraction unit, but is preferably a thermal separation unit, such as a distillation column, a fractionation column, a rectification column or the like, from which the skilled artisan is known and apparently suitable for this purpose. Any device that is separated is in the device according to the invention.

根據本發明之裝置亦可進一步包含第四分離單元D)。在其中第二分離單元B)包含萃取單元B1a)之具體例中，第四分離單元D)較佳地包含至少一個用於自萃取相分離出至少一部分的萃取劑之熱分離裝置D1a)，獲得包含至少一種根據本發明之組份ii.的萃取物，對應於方法步驟d1a)。亦可包含至少一個另外的熱分離裝置D1b)，用於自萃取物分離出至少一部分的至少一種根據本發明之組份ii. ，對應於方法步驟d1b)。可考慮熟諳本技藝者已知且顯然適合於進行方法步驟d1a)和d1b)的分離之熱分解裝置用於根據本發明之裝置中，諸如蒸餾塔、分餾塔或精餾塔或類似者中之至少一者。 The device according to the invention may further comprise a fourth separation unit D). In a specific example in which the second separation unit B) comprises an extraction unit B1a), the fourth separation unit D) preferably comprises at least one thermal separation device D1a) for separating at least a portion of the extractant from the extraction phase, obtained An extract comprising at least one component ii. according to the invention corresponds to process step d1a). It may also comprise at least one further thermal separation device D1b) for separating at least one of the at least one component according to the invention from the extract. Corresponding to method step d1b). It is conceivable to use a thermal decomposition apparatus which is known to the person skilled in the art and which is obviously suitable for carrying out the separation of process steps d1a) and d1b) for use in a device according to the invention, such as a distillation column, a fractionation column or a rectification column or the like. At least one.

在其中第二分離單元包含結晶單元和晶體分離單元之具體例中，第四分離單元D)較佳地包含脫水單元D2a)和另外的分離單元D2b)中之至少一者。脫水單元D2a)較佳地適合於進行本發明方法之方法步驟d2a)。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份ii.反應之脫水劑(諸如分子篩)填裝之塔和蒸餾單元，特別為適合於共沸蒸餾之蒸餾單元。另外的分離單元D2b)較佳地適合於進行根據本發明之方法的步驟d2b)，且較佳為熱分離單元。可考慮熟諳本技藝者已知且顯然適合於進行方法步驟d1a)和d1b)的分離之熱分解裝置用於根據本發明之裝置中，諸如蒸餾塔、分餾塔或精餾塔或類似者中之至少一者。 In a specific example in which the second separation unit comprises a crystallization unit and a crystal separation unit, the fourth separation unit D) preferably comprises at least one of the dehydration unit D2a) and the further separation unit D2b). The dehydration unit D2a) is preferably suitable for carrying out the process step d2a) 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. Preferred dewatering units according to the invention are, for example, columns and distillation units packed with a dehydrating agent (such as molecular sieves) which are not reactive with at least one component ii., particularly distillation units suitable for azeotropic distillation. The further separation unit D2b) is preferably suitable for carrying out step d2b) of the method according to the invention, and is preferably a thermal separation unit. It is conceivable to use a thermal decomposition apparatus which is known to the person skilled in the art and which is obviously suitable for carrying out the separation of process steps d1a) and d1b) for use in a device according to the invention, such as a distillation column, a fractionation column or a rectification column or the like. At least one.

另外的分離單元亦可包含在根據本發明之裝置中。較佳的另外的分離單元之一個實例為適合自包含至少兩種根據本發明之組份ii.的混合物(例如，在根據本發明之方法的步驟d)中所獲得的混合物)分離出至少一種組份ii.的分離單元。此等另外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 one which is suitable for separating at least one from a mixture comprising at least two components ii. according to the invention (for example, a mixture obtained in step d according to the method of the invention) Component ii. Separation unit. These additional 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四分離單元D)和至少一個另外的分離單元中之至少一者與第一萃取單元A3)及/或第一分離單元A4)之間的導管，用於引導甲基丙烯酸和包含甲基丙烯酸之相中之至少一者自第四分離單元D)和至少一個另外的分離單元中之至少一者返回第一萃取單元A3)和第一分離單元A4)中之至少一者。 The device according to the invention preferably comprises at least one between at least one of the fourth separation unit D) and the at least one further separation unit and the first extraction unit A3) and/or the first separation unit A4) a conduit for directing at least one of methacrylic acid and a phase comprising methacrylic acid from at least one of the fourth separation unit D) and the at least one additional separation unit to return to the first extraction unit A3) and the first separation At least one of the units 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份ii.之第二酯化單元G)，較佳地在第二分離單元B)、第三分離單元C)和第四分離單元D)中之至少一者的下游。本發明之方法步驟g)較佳地在第二酯化單元G)中進行。關於第二酯化單元G)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 G) for esterifying at least one component ii., preferably in a second separation unit B), a third separation unit C) and a fourth separation Downstream of at least one of units D). Step g) of the process according to the invention is preferably carried out in a second esterification unit G). The details regarding the second esterification unit G) 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之酯分離單元H)，特別用於自至少一個第二酯化單元G)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h)。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為酯分離單元H)。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 H) for at least partial separation of one or more esters, in particular for at least partial separation of the ester phase obtained from at least one second esterification unit G) At least one ester corresponds to step h) of the process of the process of the invention. Any device known to the skilled person and apparently suitable for separating esters can be used as the ester separation unit H). The thermal separation apparatus of the type mentioned and 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J)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G)中所獲得或在至少一個酯分離單元H)中所分離之酯及/或酯類。根據本發明之方法的方法步驟j)較佳地在至少一個另外的純化單元J) 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 further purification unit J) can also be supplied to the apparatus according to the invention for the purification of the esters obtained in the second esterification unit G) or separated in at least one ester separation unit H) and/or Esters. Process step j) of the process according to the invention is preferably at least one further purification unit J) In progress. The details of this additional purification unit correspond to those purification units described in relation to the first esterification unit.

根據本發明之裝置亦可包含至少一個介於第二萃取單元B1)(如包含於裝置中)與第二酯化單元G)、酯分離單元H)和用於純化至少一種酯之另外的純化單元J)中之至少一者之間的酯導管。至少一個酯導管適合引導來自第二酯化單元G)、酯分離單元H)和用於純化至少一種酯之另外的純化單元J)中之至少一者的至少一種酯至第二萃取單元B1a)，在此可將至少一種酯隨意地用作為萃取劑。 The apparatus according to the invention may also comprise at least one additional purification between the second extraction unit B1) (as contained in the apparatus) and the second esterification unit G), the ester separation unit H) and for the purification of at least one ester. An ester conduit between at least one of the units J). At least one ester conduit is adapted to direct at least one ester from at least one of the second esterification unit G), the ester separation unit H) and the further purification unit J) for purifying the at least one ester to the second extraction unit B1a) Here, at least one ester can be used arbitrarily as an extractant.

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,5th 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,5th Edition,Vol.A16,p.543-550；A.Chauvel,G.Lefebvre,“Petrochemical Processes,Technical and Economic Characteristics”,Vol.1,Éditions 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, Éditions 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相通。異丁烯分離單元S1)適合分離出異丁烯相且較佳地亦自第二 觸媒反應區的流出物分離出甲醇相，該流出物包含異丁烯和甲醇為主要組份。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、相分離器和清洗裝置中之至少一者。異丁烯分離單元S1)較佳地包含異丁烯相出口和甲醇相出口。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和第二酯化單元中之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。甲醇的純化單元之實例說明於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 each is in fluid communication. The isobutylene separation unit S1) is suitable for separating the isobutylene phase and preferably also from the second The effluent from the catalyst reaction zone separates the methanol phase, which contains isobutylene and methanol as the major 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 and the second esterification unit 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 unit, crystallizer, extractor, column or cleaning unit, 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形和非限制性實例更仔細地例證。 The invention is illustrated more closely by the following graphical 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、蒸汽和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)。該兩種水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 inlet of the C 4 compound, oxygen, steam and inert diluent gas to the gas phase oxidation unit A1 is not shown. 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 aqueous 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，分離出甲基丙烯酸和萃取劑以及高沸騰物相。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引導至第一酯化單元A5，隨意地經過純化(未顯示)。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中以上述其他的醇類酯化。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，隨意地在中間及/或下游純化。將第一分離單元A4中所收集之高沸騰物相隨意地經由組合單元R(在此與在第一萃取單元A3中所分離之水相組合，若有這樣的要求時)引導至第二分離單元B。 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 the methacrylic acid and extractant as well as the high boiling phase. 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 via line 4 to first esterification unit A5, optionally purified (not shown). In the first esterification unit A5, methacrylic acid can be esterified with, for example, methanol (for example, methanol separated from the MTBE split phase in the 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 alcohols. 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. The high-boiling phase collected in the first separation unit A4 is optionally guided to the second separation via the combination unit R (here combined with the water separated in the first extraction unit A3, if such a requirement is required) Unit B.

將第一萃取單元A3中所分離之水相隨意地經由管線24和組合單元R(在此與高沸騰物相組合，若有這樣的要求時)引導至第二分離單元B(未顯示直接導管)。亦可省略組合單元R，而水相與高沸騰物相在第二分離單元B互相 直接組合。 The aqueous phase separated in the first extraction unit A3 is optionally directed via line 24 and combination unit R (here combined with high boilers, if so required) to the second separation unit B (direct conduit not shown) ). The combination unit R may also be omitted, and the aqueous phase and the high boiling phase are in the second separation unit B. Direct combination.

將組合之水相與高沸騰物相在第二分離單元B以作為第二萃取劑的有機溶劑萃取，形成水相(對應於本發明方法的第二水相)和有機相。將水相經由管線9引導至第三分離單元C，在此可將來自第二萃取步驟的餘留萃取劑至少部分分離且隨意地經由管線25再循環至第二分離單元B。對應於本發明方法的第三水相之餘留水相可經由管線20再循環至例如氣相氧化單元A1(未顯示導管)，用作為處理水，引導至生物純化單元(未顯示)或排放。在第二分離單元B中所分離之有機相可經由管線10引導至第四分離單元D，在此可分離出至少一種組份ii.。在第四分離單元D中所分離之至少一部分的至少一種組份ii.可經由管線11收集且隨意地純化(未顯示)。若組份ii.之混合物係在第四分離單元D中分離，則可將此混合物引導至另外的分離單元，使組份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四分離單元D中分離，則此甲基丙烯酸或包含甲基丙烯酸之相可經由管線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。亦有可能將第四分離單元D中所分離之至少一部分的至少一種組份ii.經由管線14引導至第二酯化單元G。可將第二分離單元B中所分離之有機相和水相或第三分離單元C中所分離之水相之任一者引導至第二酯化單元G。在第二酯化單元G中，將至少一種組份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G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H中分離。至少一種酯可在下游的酯純化單元J(未顯示)中純化。可將第二酯化單元G、酯分離單元H和酯純化單元J中之一或多者所獲得的至少一種酯引導至第二分離單元B，用作為萃取劑。 The combined aqueous phase and high boiling phase are extracted in a second separation unit B as an organic solvent as a second extractant to form an aqueous phase (corresponding to the second aqueous phase of the process of the invention) and an organic phase. The aqueous phase is directed via line 9 to a third separation unit C where the remaining extractant from the second extraction step can be at least partially separated and optionally recycled via line 25 to the second separation unit B. The remaining aqueous phase of the third aqueous phase corresponding to the process of the invention can be recycled via line 20 to, for example, a gas phase oxidation unit A1 (a conduit not shown) for use as treated water, directed to a biological purification unit (not shown) or discharged . The organic phase separated in the second separation unit B can be led via line 10 to a fourth separation unit D, where at least one component ii. can be separated. At least one component ii. of at least a portion separated in the fourth separation unit D can be collected via line 11 and optionally purified (not shown). If the mixture of component ii. is separated in the fourth separation unit D, the mixture can be directed to another separation unit to separate the components ii. from each other (not shown). If methacrylic acid or a phase comprising methacrylic acid is separated in the fourth separation unit D, 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 First separation unit A4. It is also possible to direct at least one component ii. of at least a portion separated in the fourth separation unit D to the second esterification unit G via line 14. Any one of the organic phase separated in the second separation unit B and the aqueous phase separated in the third separation unit C or the aqueous phase separated in the third separation unit C may be guided to the second esterification unit G. In the second esterification unit G, at least one component ii. is esterified with an alcohol to form the corresponding ester. If the alcohol is methanol, the methanol can be, for example, via the separation unit S1. The MTBE splitter AA1 was introduced and optionally purified intermediately (not shown). If the ester phase obtained in the second esterification unit G contains more than one ester, at least one ester can be separated in the ester separation unit H. At least one ester can be purified in a downstream ester purification unit J (not shown). At least one ester obtained by one or more of the second esterification unit G, the ester separation unit H, and the ester purification unit J may be introduced to the second separation unit B to be used as an extractant.

圖3顯示根據本發明之裝置的另一具體例，其中第二分離單元B為結晶單元。在此具體例中，關於裝置組件A1至A6、R、G、H、J、AA1和S1的細節係與圖2之具體例相同，而僅將不同的態樣說明於下。在圖2中示例之具體例中，通常將組合之水相與高沸騰物相在結晶單元B2a中冷卻，使得水至少部分結晶。若晶體至少部分形成於結晶單元B2a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B2a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B2b，在此自母液至少部分分離出固體晶體且隨意地清洗，至少部分移出雜質。接著可將一部分的晶體自晶體分離單元B2b引導返回結晶單元B2a及/或滯留單元T1，藉以充當晶種(未顯示導管)。 Figure 3 shows another embodiment of the apparatus according to the invention wherein the second separation unit B is a crystallization unit. In this specific example, the details regarding the device components A1 to A6, R, G, H, J, AA1, and S1 are the same as those of the specific example of Fig. 2, and only different aspects will be described below. In the specific example illustrated in Figure 2, the combined aqueous phase and high boiling phase are typically cooled in crystallization unit B2a such that the water at least partially crystallizes. If the crystal is at least partially formed on the cooling surface of the crystallization unit B2a, 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 B2a and/or the retention unit T1 and the slurry of the mother liquor are then directed via line 9 to the crystal separation unit B2b, where the solid crystals are at least partially separated from the mother liquor and optionally cleaned, at least partially removing the impurities. A portion of the crystal can then be directed back from the crystal separation unit B2b back to the crystallization unit B2a and/or the retention unit T1, thereby acting as a seed crystal (the conduit is not shown).

可將至少一部分的隨意清洗之晶體熔融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)，用作為處理水，用作為清洗晶體分離單元B2a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B2b中所分離之母液經由管線10引導至第四分離單元D，在此可分離出至少一種組份ii.。第四分離單元D可包含脫水單元D2a及/或熱分離單元D2b。若在第四分離單元D中分離出組份ii.之混合物，則可將此混合物引導至第四分離單元，使組份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四分離單元D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。在第四分離單元D中所分離之至少一部分的至少一種組份ii.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。亦有可能將第四分離單元D中所分離之至少一部分的至少一種組份ii.經由管線14引導至第二酯化單元G。可將晶體分離單元B2b中所分離之母液引導至第二酯化單元G。 At least a portion of the randomly cleaned crystal may be melted and at least a portion of the molten portion may be recycled to, for example, a gas phase oxidation unit A1 (a conduit not shown) for use as treated water for cleaning crystals in the crystal separation unit B2a The 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 B2b can be directed via line 10 to a fourth separation unit D where at least one component ii. can be separated. The fourth separation unit D may include a dehydration unit D2a and/or a thermal separation unit D2b. If a mixture of component ii. is separated in the fourth separation unit D, the mixture can be directed to the fourth separation unit to separate the components ii. from each other (not shown). If methacrylic acid or a phase comprising methacrylic acid is separated in the fourth separation unit D, 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 one component ii. of at least a portion separated in the fourth separation unit D can be collected via line 11 and optionally purified in an additional purification unit (not shown). It is also possible to direct at least one component ii. of at least a portion separated in the fourth separation unit D to the second esterification unit G via line 14. The mother liquid separated in the crystal separation unit B2b can be guided to the second esterification unit G.

試驗方法 experiment method 分配係數(k值)的測量 Measurement of distribution coefficient (k value)

將包含預定量之乙酸的水相與相同體積的有機溶劑(萃取劑)組合。將兩相在50℃下搖動及/或攪拌15-30分鐘，以確保達成乙酸遍及水相和有機相的平衡分布。接著容許混合物在50℃下分離返回成有機相和水相，且將該兩相互相分離。將分離之有機相中存在的乙酸量以氣相層析術(GC)或高壓液相層析術(HPLC)測量。 The aqueous phase containing a predetermined amount of acetic acid is combined with the same volume of organic solvent (extractant). The two phases are shaken and/or stirred at 50 ° C for 15-30 minutes to ensure an equilibrium distribution of acetic acid throughout the aqueous and organic phases. The mixture was then allowed to separate and return to an organic phase and an aqueous phase at 50 ° C, and the two phases were separated from each other. The amount of acetic acid present in the separated organic phase is measured by gas chromatography (GC) or high pressure liquid chromatography (HPLC).

實例1： Example 1:

實例1說明如圖4中所示之方法的一部分。將第一分離單元A4上因此產生之含有82.1重量%之MAA、14.3重量%之各種和部分未知的高沸騰物(二聚合和寡聚合之MAA、順丁烯二酸、對苯二甲酸、檸康酸、聚合物等)及3.6重量%之抑制劑(主要為對苯二酚(Hydrochinon))的高沸騰物相與自第一萃取單元A3因此分離之含有0.6重量%之MAA及5.0重量%之高沸騰物的第一水相以1：80之高沸騰物相對第一水相之比在組合單元R中組合。所得組合之相的濃度經測量為1.6重量%之MAA及5.1重量%之高沸騰物。將組合之相在第二分離單元B中以正己烷萃取。得到在有機相中的4.9重量%之MAA，相對於第一水相不與高沸騰物相組合時之比較例子中的3.9重量%之MAA。 Example 1 illustrates a portion of the method as shown in FIG. The first separation unit A4 thus produced contains 82.1% by weight of MAA, 14.3% by weight of various and partially unknown high-boiling substances (di-polymerized and oligomerized MAA, maleic acid, terephthalic acid, and lemon). The high boiling phase of the inhibitor (mainly hydrophobin) and 3.6% by weight of Hydrochonin is separated from the first extraction unit A3 by 0.6% by weight of MAA and 5.0% by weight. The first aqueous phase of the high boil is combined in the combination unit R at a ratio of 1:80 high boiling to first water phase. The concentration of the phase of the resulting combination was measured to be 1.6% by weight of MAA and 5.1% by weight of high boiling matter. The combined phases were extracted with n-hexane in a second separation unit B. 4.9 wt% of MAA in the organic phase was obtained, relative to 3.9 wt% of MAA in the comparative example when the first aqueous phase was not combined with the high boil.

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‧‧‧第二分離單元，第二萃取單元 B‧‧‧Second separation unit, second extraction unit

C‧‧‧第三分離單元 C‧‧‧ third separation unit

D‧‧‧第四分離單元 D‧‧‧fourth separation unit

G‧‧‧第二酯化單元 G‧‧‧Secondification unit

H‧‧‧酯分離單元 H‧‧‧ester separation unit

J‧‧‧酯純化單元 J‧‧‧ ester purification unit

R‧‧‧組合單元 R‧‧‧ combination unit

1-25‧‧‧管線 1-25‧‧‧ pipeline

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，其中第二分離單元B為萃取單元。 Figure 2 is a diagram showing a specific example of the apparatus according to the present invention, wherein the second separation unit B is an extraction unit.

圖3係以圖式顯示根據本發明之裝置的具體例，其中第二分離單元B為結晶單元。 Figure 3 is a diagram showing a specific example of the apparatus according to the present invention, wherein the second separation unit B is a crystallization unit.

圖4顯示如實例1中所述之方法的一部分。 Figure 4 shows a portion of the method as described in Example 1.

Claims (21)

一種製備甲基丙烯酸與甲基丙烯酸酯中之至少一者之方法，其包含以下的方法步驟：a1)將至少一種C4化合物氣相氧化，以獲得包含甲基丙烯酸的反應相；a2)將該反應相驟冷，以獲得包含甲基丙烯酸的粗製水相；a3)自該包含甲基丙烯酸的粗製水相萃取出至少一部分的甲基丙烯酸至有機溶劑中，以獲得包含甲基丙烯酸的粗製有機相和第一水相，其中該第一水相包含以該第一水相總重量為基準計作為組份i的65重量%至99.9重量%之水和作為組份ii的0.1重量%至35重量%之至少一種有機化合物；其中組份i與ii之重量總和為100重量%；a4)自該包含甲基丙烯酸的粗製有機相分離出至少一部分的甲基丙烯酸和高沸騰物相，其中至少一部分的該高沸騰物相係與步驟a3)中所獲得的該第一水相的至少一部分組合，且該組合相經至少一種有機溶劑萃取；a5)隨意地將步驟a4)中所獲得的甲基丙烯酸之至少一部分酯化；b)將步驟a3)中所獲得的該第一水相的至少一部分經萃取劑萃取，以形成第二水相和包含至少該組份ii的有機相，使得步驟a3)中所獲得的該第一水相所包含之水的至少一部分與至少一部分的該組份ii分開，其中該有機相包含該組份ii，且與該第一水相相比較，該第二水相中至少該組 份ii被耗盡；c)隨意地自步驟b)中所獲得的該第二水相分離出至少一部分的該至少一種有機化合物，以獲得第三水相；及d)隨意地自步驟b)中所獲得的該有機相分離出至少一部分的至少該組份ii。 A method of 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 is quenched to obtain a crude aqueous phase comprising methacrylic acid; a3) at least a portion of the methacrylic acid is extracted from the crude aqueous phase comprising methacrylic acid to an organic solvent to obtain a crude methacrylic acid-containing solvent. An organic phase and a first aqueous phase, wherein the first aqueous phase comprises from 65 to 99.9% by weight of water based on the total weight of the first aqueous phase, and from 0.1% by weight of component ii to 35 wt% of at least one organic compound; wherein the sum of the weights of components i and ii is 100% by weight; a4) separating at least a portion of the methacrylic acid and the high-boiling phase from the crude organic phase comprising methacrylic acid, wherein At least a portion of the high boiler phase is combined with at least a portion of the first aqueous phase obtained in step a3), and the combined phase is extracted with at least one organic solvent; a5) optionally obtained in step a4) At least a portion of the methacrylic acid is esterified; b) extracting at least a portion of the first aqueous phase obtained in step a3) with an extractant to form a second aqueous phase and an organic phase comprising at least the component ii, such that At least a portion of the water contained in the first aqueous phase obtained in step a3) is separated from at least a portion of the component ii, wherein the organic phase comprises the component ii and compared to the first aqueous phase, At least the component ii is depleted in the second aqueous phase; c) optionally separating at least a portion of the at least one organic compound from the second aqueous phase obtained in step b) to obtain a third aqueous phase; d) optionally separating at least a portion of at least the component ii from the organic phase obtained in step b). 根據申請專利範圍第1項之方法，其中該步驟b)包含以下的方法步驟：b1b)將該第二水相與該有機相至少部分分開。 The method of claim 1, wherein the step b) comprises the following method step: b1b) at least partially separating the second aqueous phase from the organic phase. 根據申請專利範圍第2項之方法，其中在步驟d)中的分離包含以下的方法步驟：d1a)自該有機相分離出至少一部分的該萃取劑，以獲得包含至少該組份ii的萃取物；d1b)隨意地自該萃取物分離出至少一部分的至少該組份ii。 The method of claim 2, wherein the separating in step d) comprises the following method step: d1a) separating at least a portion of the extractant from the organic phase to obtain an extract comprising at least the component ii ;d1b) optionally separating at least a portion of at least the component ii from the extract. 根據申請專利範圍第2項之方法，其中該第三水相包含以該第三水相總重量為基準計不超過3.0重量%之步驟b)中所用萃取劑以外的有機化合物。 The method of claim 2, wherein the third aqueous phase comprises no more than 3.0% by weight of the organic compound other than the extractant used in the step b) based on the total weight of the third aqueous phase. 根據申請專利範圍第1項之方法，其中該步驟b)包含以下的方法步驟：b2a)自步驟a3)中所獲得的該第一水相的至少一部分結晶出至少一部分的水，以形成作為第二水相的結晶水相和母液，其中該母液包含至少該組份ii；b2b)自該母液至少部分分離出該結晶水相。 The method of claim 1, wherein the step b) comprises the following method step: b2a) at least a portion of the first aqueous phase obtained in step a3) crystallizes at least a portion of the water to form a crystalline aqueous phase and a mother liquor of the aqueous phase, wherein the mother liquor comprises at least the component ii; b2b) at least partially separating the aqueous crystalline phase from the mother liquor. 根據申請專利範圍第5項之方法，其中在步驟d)中 的分離包含以下的方法步驟中之至少一者：d2a)將步驟b2b)中所分離之該母液至少部分脫水，以獲得至少部分脫水之母液；d2b)自步驟b2b)中所獲得的母液或步驟d2a)中所獲得的至少部分脫水之母液分離出至少一部分的至少該組份ii。 According to the method of claim 5, wherein in step d) The separation comprises at least one of the following method steps: d2a) at least partially dehydrating the mother liquor separated in step b2b) to obtain a mother liquor which is at least partially dehydrated; d2b) a mother liquor or step obtained from step b2b) The at least partially dehydrated mother liquor obtained in d2a) separates at least a portion of at least the component ii. 根據申請專利範圍第5項之方法，其進一步包含以下的方法步驟：e2)熔融該結晶水相，以獲得熔融之結晶水相作為第三水相。 According to the method of claim 5, further comprising the following method step: e2) melting the crystallized aqueous phase to obtain a molten crystalline aqueous phase as the third aqueous phase. 根據申請專利範圍第4或5項之方法，其中該第三水相或該結晶水相包含以該第三水相總重量為基準計1500至2500ppm之該有機化合物。 The method of claim 4 or 5, wherein the third aqueous phase or the crystalline aqueous phase comprises from 1500 to 2500 ppm of the organic compound based on the total weight of the third aqueous phase. 根據申請專利範圍第4項之方法，其中將該第三水相接受下列中之至少一者：進行至少一種生物純化處理、用作為處理水及進行步驟a1)和a2)中之至少一者。 The method of claim 4, wherein the third aqueous phase accepts at least one of: performing at least one biological purification treatment, using as the treated water, and performing at least one of steps a1) and a2). 根據申請專利範圍第1項之方法，其中在該步驟d)中所分離之該組份ii為至少兩種有機化合物之混合物，且其中在進一步的步驟f)中：f)自該混合物至少部分分離出該兩種有機化合物中的至少一種。 The method of claim 1, wherein the component ii separated in the step d) is a mixture of at least two organic compounds, and wherein in a further step f): f) at least a portion from the mixture At least one of the two organic compounds is isolated. 根據申請專利範圍第1項之方法，其中該組份ii的至少一者為至少一種選自羧酸、醛和酮之有機化合物。 The method of claim 1, wherein at least one of the components 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項之方法，其中該組份ii的至少一者係為或包含乙酸、丙烯酸、丙酸和甲基丙烯酸 中之至少一者。 The method of claim 1, wherein at least one of the components ii is or comprises acetic acid, acrylic acid, propionic acid, and methacrylic acid. At least one of them. 根據申請專利範圍第10項之方法，其中在步驟d)和f)中之至少一者所分離之該組份ii的至少一者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步驟a2)中所獲得的粗製水相中或步驟a3)中所獲得的粗製有機相中。 The method of claim 10, wherein at least one of the components ii separated by at least one of steps d) and f) is or comprises methacrylic acid, and at least a portion of the methyl group Acrylic acid is added to the crude aqueous phase obtained in step a2) or to the crude organic phase obtained in step a3). 根據申請專利範圍第10項之方法，其中將在步驟d)和f)中之至少一者所分離之該組份ii的至少一者或在步驟a3)中所獲得的該第一水相的至少一部分接受以下的方法步驟：g)酯化，以獲得包含至少一種酯的酯相。 The method of claim 10, wherein at least one of the component ii separated by at least one of steps d) and f) or the first aqueous phase obtained in step a3) At least a portion of the process steps are accepted: g) esterification to obtain an ester phase comprising at least one ester. 根據申請專利範圍第14項之方法，其中該酯相包含至少兩種酯。 The method of claim 14, wherein the ester phase comprises at least two esters. 根據申請專利範圍第14項之方法，其進一步包含以下的方法步驟：h)自該酯相至少部分分離出至少一種酯；j)隨意地將步驟h)中所分離出之該至少一種酯純化。 According to the method of claim 14, further comprising the steps of: h) at least partially separating at least one ester from the ester phase; j) optionally purifying the at least one ester isolated in step h) . 根據申請專利範圍第16項之方法，其中在步驟g)、h)和j)中之至少一者中所獲得的該至少一種酯之至少一部分被用作為步驟b)中的萃取劑。 The method of claim 16, wherein at least a portion of the at least one ester obtained in at least one of steps g), h) and j) is used as the extractant in step b). 根據申請專利範圍第14項之方法，其中該至少一種酯係以C1-C4羧酸和C1-C4醇為基礎。 The method of claim 14, wherein the at least one ester is based on a C 1 -C 4 carboxylic acid and a C 1 -C 4 alcohol. 根據申請專利範圍第1項之方法，其中作為進料供給至步驟a1)之氣相氧化反應的該至少一種C4化合物的 至少一部分係源自另一步驟aa1)：aa1)將甲基第三丁醚***以獲得該至少一種C4化合物和甲醇。 The method of claim 1, wherein at least a portion of the at least one C 4 compound supplied as a feed to the gas phase oxidation reaction of step a1) is derived from another step aa1): aa1) methyl third The butyl ether is cleaved to obtain the at least one C 4 compound and methanol. 根據申請專利範圍第19項之方法，其中將另一步驟aa1)中所獲得的甲醇供給至步驟g)。 The method according to claim 19, wherein the methanol obtained in the other step aa1) is supplied to the step g). 一種甲基丙烯酸與甲基丙烯酸酯中之至少一者的製造裝置，其包含互相以流體引導相通的至少下列組件：˙氣相氧化單元(A1)，˙驟冷單元(A2)，˙第一萃取單元(A3)，˙第一分離單元(A4)，˙隨意的第一酯化單元(A5)，˙組合單元(R)，˙第二分離單元(B)，˙隨意的第三分離單元(C)，˙隨意的第四分離單元(D)，其中該第一分離單元為熱分離單元，其包含至少一個底部出口於該單元的下三分之一處，該至少一個底部出口與該第二分離單元(B)的至少一個入口以流體引導相通。 A manufacturing apparatus for at least one of methacrylic acid and methacrylic acid comprising at least the following components in fluid communication with each other: a gas phase oxidation unit (A1), a quenching unit (A2), first Extraction unit (A3), ̇ first separation unit (A4), ̇ random first esterification unit (A5), ̇ combination unit (R), ̇ second separation unit (B), ̇ random third separation unit (C), optionally a fourth separation unit (D), wherein the first separation unit is a thermal separation unit comprising at least one bottom outlet at a lower third of the unit, the at least one bottom outlet At least one inlet of the second separation unit (B) is in fluid communication.
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