TW200407294A - Preparation of acrylic acid and/or its esters and also of propionic acid and/or its esters in an integrated system - Google Patents

Preparation of acrylic acid and/or its esters and also of propionic acid and/or its esters in an integrated system Download PDF

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Publication number
TW200407294A
TW200407294A TW92112452A TW92112452A TW200407294A TW 200407294 A TW200407294 A TW 200407294A TW 92112452 A TW92112452 A TW 92112452A TW 92112452 A TW92112452 A TW 92112452A TW 200407294 A TW200407294 A TW 200407294A
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Taiwan
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weight
acid
acrylic acid
propionic acid
stream
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TW92112452A
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Chinese (zh)
Inventor
Christoph Adami
Ralf Bohling
Otto Machhammer
Peter Zehner
Claus Hechler
Schliephake Volker
Thiel Joachim
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Basf Ag
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Priority claimed from DE2002120752 external-priority patent/DE10220752A1/en
Priority claimed from DE2002124341 external-priority patent/DE10224341A1/en
Application filed by Basf Ag filed Critical Basf Ag
Publication of TW200407294A publication Critical patent/TW200407294A/en

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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
    • C07C51/42—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
    • C07C51/16—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds

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

Abstract

In a workup zone, both acrylic acid of target product quality and an acrylic acid secondary mixture are removed from the product gas mixture which comprises acrylic acid and secondary components of a heterogeneously catalyzed gas phase partial oxidation. The target product quality has a lower content of secondary components than the secondary mixture. The acrylic acid present in the latter, optionally after preceding esterification, is converted by hydrogenation into propionic acid and/or its esters.

Description

200407294 玖、發明說明： 發明所屬之技術領域 丙烯酸及/或其酯 本發明係關於一種於整合系統中製備 以及丙酸及/或其酯之方法。 丙烯酸，其本身或其鹽或其酯之 〜八’對於製備用於高 度變化之應用領域内之聚合物（例如， v丨』如黏耆劑，超級吸收劑 ，黏合劑）尤其重要。將丙烯酸盥谪各 /、通*艾醉（例如烷醇）直接 酯化可得到丙烯酸酯。 以（例如㈣鹽或納鹽.之形式使用丙酸，以用於保存飼料 與食物或作為生產除草劑之起始物f。丙酸g§之應用包括 溶劑’增塑劑或共聚用單體（丙酸乙埽酯）。 先前技術 一種製備丙晞酸之方法，其藉由丙烷，丙烯及/或丙烯醛 之選擇性非均相催化氣相部分氧化進行製備。該等起始氣 體（其通常以惰性氣體、例如氮、C〇2、水蒸汽、氫分子、 惰性氣體、其它飽和及/或不飽和烴稀釋）係於高溫及視情 沉之高签下與起始氣體混合通過過渡金屬元素混合氧化物 觸媒’而氧化轉化為包含丙烯酸之產物氣體混合物（例如第 A 1090684號歐洲專利，第a 1〇 122027號德國專利，第 A 101 01 695號德國專利，第a 1005971 3號德國專利，第 A 100285 82號德國專利，第a 19955 168號德國專利，第 A 19955 176號德國專利，第a 1 159247號歐洲專利，第 A 19948248號德國專利以及第a 19948241號德國專利）。 以上所提及之藉由邵分氧化方法製備丙婦酸之一缺點在 於’其不僅會形成主要產物丙晞酸，亦會形成氣相催化氧 ㈣備路所常見之額外二級組份。其具體為境幾酸(如甲 酸，乙酸及/或丙酸）及/或趁（如丙_，甲基丙缔駿，丙酸 正丁醛，苯甲醛，糠醛，丁烯醛）以及丙烯酸烯丙酯。 基於所形成之丙烯酸之量，所提及之二級組份可形成高 達5重量％之總量（醛之情況下（包括丙缔酸缔丙酯））以及5 重量％之總量（烷羧酸之情況下）。 該等二級組份之缺點在於大多數該等二級組份之存在均 不利於對丙晞酸之使用。 例如，若使用該包含二級組份烷羧酸之丙烯酸自Ci_Cr 燒醇與丙烯酸製備酯，則將於二級反應中形成相應之甲酸 ’乙酸及/或丙酸酯，其將降低所需丙晞酸酯之產率（基於 所使用烷醇之數量）。 當將於醛存在之情況下所形成之丙婦酸g旨，或本身包本 有該醛之丙晞酸用於自由基聚合時，酸含量通常具有不利 性，例如，其會影響聚合反應之誘導時間，意即，達到聚 合溫度與聚合實際開始間之時段。其通常還會影響聚合程 度，且亦會導致聚合物之變色。丙晞酸晞丙酯亦同樣具有 不利性，因此於此文獻中可將丙晞酸烯丙酯視為一駿。 當自丙烷，丙烯及/或丙晞醛之選擇性非均相催化氣相部 分氧化之產物氣體混合物回收丙烯酸時，關於對該所回收 之丙缔酸之進一步使用，不僅需要將該丙烯酸自氣相移除 ，同時亦必須將該丙烯酸自上述二級組份充分移除。 為此目的，該程序通常為’視情況可在將其由適當吸收 200407294 劑吸收（通常為水或高沸點有機溶劑），自該產物氣體混合 物進行氣相氧化產物氣體混合物之直接及/或間接冷卻，其 後’藉由蒸餾’精餾，萃取及/或結晶過程將該丙烯酸自該 吸收劑以及二級組份充分移除之後，將伴有一部分相關二 級組份之丙烯酸首先取出（參看，例如，第Ai 〇115277號德 國專利’第A 982289號歐洲專利，第a 982288號歐洲專利 ’第A 982287號歐洲專利，第a 19606877號德國專利，第 A 19631645號德國專利與第A 1〇218419號德國專利，以及 该等文獻中所引用之先前技術）。或者，視情況可在對其進 行上述冷卻後，將來自於選擇性非均相催化氣相部分氧化 之產物氣體混合物分凝，如（例如）第A 1974〇253號德國專 利，第A 19627847號德國專利以及第A 19924532號德國專 利中所述。若需要，可進而藉由（例如）結晶作用處理自冷 凝塔所提取之丙烯酸之物質。 本文獻中將所有處理步驟之總和稱為處理區段。通常 (且此適用於根據本發明之方法），將取出丙烯酸含量大於 等於90重f %之丙烯酸物質。經常，自處理區段所提取之 丙烯酸物質的丙晞酸含量為（此亦適用於根據本發明之方 法）大於等於95重量％ ,經常為大於等於重量98%，在很多 情況下為大於等於99重量％，且於某些情況下為大於等於 99.5重量％。上述醛二級組份之丙烯酸物質（包括根據本發 明所提取者）之總量通常為以重量計小於等於百萬分之 2000，經常為以重量計小於等於百萬分之1〇〇〇，於很多情 況下為以重量計小於等於百萬分之5〇〇，於某些情況下為以200407294 (ii) Description of the invention: Technical field to which the invention belongs Acrylic acid and / or its ester The present invention relates to a method for preparing and propionic acid and / or its ester in an integrated system. Acrylic acid, itself or its salt or its ester, is especially important for the preparation of polymers for use in highly variable applications (for example, v 丨 ”such as adhesives, superabsorbents, adhesives). Acrylic acid esters can be obtained by directly esterifying acrylic acid esters with alcohol (such as alkanol). Use of propionic acid in the form of, for example, phosphonium salt or sodium salt, for preserving feed and food or as a starting material for the production of herbicides f. Applications of g§ include solvents' plasticizers or comonomers (Ethyl propionate). The prior art is a method for preparing propionic acid, which is prepared by selective heterogeneously catalyzed gas phase partial oxidation of propane, propylene and / or acrolein. The starting gases (which Usually inert gases, such as nitrogen, CO2, water vapor, hydrogen molecules, inert gases, other saturated and / or unsaturated hydrocarbons, are diluted at high temperatures and optionally at high levels. Mixed with the starting gas through the transition metal Elemental mixed oxide catalyst 'and oxidatively converted into a product gas mixture containing acrylic acid (for example, European Patent No. A 1090684, German Patent No. a 10122027, German Patent No. A 101 01 695, German Patent No. a 1005971 3 Patents, German Patent No. A 100285 82, German Patent No. a 19955 168, German Patent No. A 19955 176, European Patent No. a 1 159247, German Patent No. A 19948248, and German Patent No. a 19948241 ). One of the disadvantages of the above-mentioned preparation of propionic acid by the Shao oxidation method is that it will not only form the main product propionate, but also form an additional secondary component that is common in gas-phase catalytic oxygen preparation. . It is specifically chloric acid (such as formic acid, acetic acid and / or propionic acid) and / or while (such as propane, methyl propionate, n-butyraldehyde propionate, benzaldehyde, furfural, butenal) and acrylic acid Allyl esters. Based on the amount of acrylic acid formed, the secondary components mentioned can form up to 5% by weight (in the case of aldehydes (including allyl propionate)) and 5% by weight in total. The amount (in the case of alkanecarboxylic acid). The disadvantage of these secondary components is that the presence of most of these secondary components is not conducive to the use of propionic acid. For example, if the secondary component is used Acrylic acid of carboxylic acid is prepared from Ci_Cr alcohol and acrylic acid, and the corresponding formic acid 'acetic acid and / or propionate will be formed in the secondary reaction, which will reduce the yield of the desired propionate (based on the alkane used The amount of alcohol). When valproic acid is to be formed in the presence of aldehydes, When propionic acid containing the aldehyde itself is used in free radical polymerization, the acid content is usually unfavorable, for example, it will affect the induction time of the polymerization reaction, that is, the time between the polymerization temperature and the actual start of the polymerization. It usually also affects the degree of polymerization and also causes discoloration of the polymer. Propyl propionate is also disadvantageous, so in this document allyl propionate can be regarded as a block. When from propane, When recovering acrylic acid from the product gas mixture of propylene and / or propionaldehyde selectively catalyzed by gas phase partial oxidation, regarding the further use of the recovered acrylic acid, it is not only necessary to remove the acrylic acid from the gas phase, At the same time, the acrylic acid must be sufficiently removed from the above secondary components. For this purpose, the procedure is usually 'directly and / or indirectly, if appropriate, by absorbing 200407294 agents (usually water or high boiling point organic solvents) from the product gas mixture, as appropriate. After cooling, the acrylic acid is sufficiently removed from the absorbent and the secondary component by distillation, extraction and / or crystallization, and then the acrylic acid with a portion of the related secondary component is removed first (see For example, German patent No. Ai 〇115277 'European patent No. A 982289, European patent No. a 982288' European patent No. A 982287, German patent No. a 19606877, German patent No. A 19631645 and A 1〇 German Patent No. 218419, and prior art cited in those documents). Alternatively, the product gas mixture derived from the selective heterogeneous catalytic gas-phase partial oxidation may be subjected to partial condensation after being subjected to the above-mentioned cooling, as the case may be, for example, German Patent No. A 1974〇253, No. A 19627847 German patent and German patent No. A 19924532. If necessary, the substance of acrylic acid extracted from the condenser can be further processed by, for example, crystallization. The sum of all processing steps is referred to as a processing section in this document. Usually (and this applies to the method according to the invention), acrylic materials with an acrylic content of 90% f% by weight will be taken out. Often, the propionic acid content of the acrylic material extracted from the processing section is (this also applies to the method according to the present invention) 95% by weight or more, often 98% by weight or more, and in many cases 99 or more % By weight, and in some cases 99.5% by weight or more. The total amount of the acrylic material (including those extracted according to the present invention) of the above-mentioned aldehyde secondary component is usually 2000 parts per million or less by weight, often 1,000 parts per million or less by weight, In many cases it is less than or equal to 500 parts per million by weight, and in some cases it is

85187.DOC 200407294 重量計小於等於百萬分之250或以重量計小於等於百萬八 (100’且於較佳情況下甚至為以重量計小於等於百萬分刀 =以重量計小於等於百萬分之20或以重量計小於等：; 相對的，同時，上述丙晞酸物質（包括根據本發明所尸取 物質)内之燒叛酸之總含量通常為以重量計二 寺於百禹/刀芝5000，經常為以重量計小於等於百萬分、 鳩〇 ’於很多情況下為以重量計小於等於百萬分之2〇〇刀二 於較佳情況下為以重量計小於等於百萬分之500心重旦 計小於等於百萬分之跡且㈣切重量計小於等= 分之200或以重量計小於等於百萬分之100。、； 然而’所概述之自選擇性非均相催化氣相部分氧化對產 物氣體混合物進行處理而獲取丙締酸之方法之問題在於， 吾所不欲之二級組份之一部分的滞騰或結晶特性與丙缔酸 相似。 例如，數種越二級組份之滞點範圍於大氣屢力下為 或Ts±5Gt或Ts±靴，其中Ts為大氣壓力（1大氣壓 力）下丙浠酸之沸點。 以類似方式，丙烯酸與丙酸之㈣於大氣壓力下會際上 一致’而（例如）乙酸於結晶分離中附著於丙缔酸上。 因此’只可能由餾分之形成將二級組份自主要產物丙烯 酸移除，該餾分之形成一方面將二級組份冷凝，而另一方 面，由於分離困難，其仍然包含大量丙烯酸。 為避免處理區段内之丙埽酸損失過高，通常不會立即將85187.DOC 200407294 Less than or equal to 250 parts per million by weight or less than or equal to one million by weight (100 'and, in the best case, even less than or equal to one million parts by weight knife = less than or equal to one million by weight 20% or less by weight: etc. In contrast, at the same time, the total content of scorching acid in the above-mentioned propionic acid substances (including cadaveric substances in accordance with the present invention) is usually the weight of two temples in Baiyu / Daozhi 5000 is often less than or equal to million parts by weight, and in many cases is less than or equal to 200 parts per million by weight. Daoji is more preferably less than or equal to millions by weight. 500 parts per cent by weight and less than parts per million and cut weights equal to or less than 200 parts per million or 100 parts per million by weight.,; However, the self-selective heterogeneous catalysis as outlined The problem with the gas phase partial oxidation method of treating the product gas mixture to obtain acrylic acid is that the stagnation or crystallization characteristics of a part of the secondary component that we do not want are similar to that of acrylic acid. For example, several kinds of Yueji The stagnation range of the grade components is large Repeatedly, it is or Ts ± 5Gt or Ts ± boots, where Ts is the boiling point of propionic acid at atmospheric pressure (1 atmospheric pressure). In a similar manner, acrylic acid and propionic acid are occasionally consistent under atmospheric pressure. For example, acetic acid is attached to acrylic acid during crystallization. Therefore, 'the secondary component can only be removed from the main product acrylic acid by the formation of a fraction. The formation of this fraction condenses the secondary component on the one hand, and the other On the one hand, due to the difficulty of separation, it still contains a large amount of acrylic acid. To avoid excessive loss of propionic acid in the processing section, it is usually not immediately

85187.DOC 200407294 3餘分自處理區段排出，而將其回收至處理區段，至少 邵分回收至處理區段内之—部分（此部分非形成館分之部 分）。 然而，進行中之研究已顯示，此不利性在於至少一部分 一級組份能增加丙烯酸之聚合傾向，因此，該回收通常導 致處理區段聚合物形成之增加。 攸另一點看，區域内富含二級組份之餾分之形成亦為吾 所不欲。鑒於（例如）烷羧酸之腐蝕作用相當可觀，尤其於 甲酸之情況下，應當避免其局部累積。 發明内容 本發明之一目的在於提供一種製備丙烯酸之方法，其開 始於丙烷，丙烯及/或丙烯醛之選擇性非均相催化氣相部分 氧化，其中，以及目標產物物質之丙晞酸，將一包括二級 組份與丙烯酸之混合物自處理區段移除，而未因丙烯酸損 失對該方法之經濟適宜性產生顯著損壞。該方法同時為丙 缔酸醋之方法，因為可藉由類似方式將丙烯酸與適當之醇 直接反應而轉化為相應之丙烯酸酯。 吾人頃發現可藉由一方法達到本目的，該方法中，於一 整合系統中製備丙晞酸及/或其酯與丙酸及/或其酯，該方 法包括 a)於一區段内，即反應區段内，使丙烷，丙晞，及/或丙烯 醛經一選擇性非均相催化氣相部分氧化，從而形成一產 物氣體混合物A，其包括主要產物丙烯酸以及二級組份 醛及/或飽和烷羧酸， 85187.DOC -10- 200407294 b) 於一第二區段内，即處理區段内，自產物氣體混合物a 移除 Ο —方面，為一目標產物之一丙烯酸物質，其丙晞酸含 量為大於等於90重量％，以及同時 π)另一方面，一包含丙晞酸之二級混合物，其中醛之總 含量（莫耳％)(以所存在之丙烯酸數量計）及/或烷羧酸 之總含量（莫耳％)(以所存在之丙烯酸數量計）均大於〇 中所移除之丙烯酸物質内之醛及/或烷羧酸之總含量， 以及 c) 視情況可在將其酯化後，使用氫分子藉由氫化作用將於 Π)中移除之二級混合物内所存在之丙缔酸轉化為丙酸 及/或其酉旨。 根據本發明之方法之一基礎在於可使用氫分子藉由氫化 作用自丙烯酸及/或其酯中獲得丙酸及/或其酯。 例如，第A 2310754號德國專利推薦一非均相觸媒（所推 薦之觸媒為一載體觸媒，其上施加有鈀作為觸媒活性物質） 方法’其於液相中於加壓下進行。較佳情況為於一液體流 體化床内執行第A 23 10754號德國專利之方法。液相之基礎 為一溶劑。一有效溶劑之實例為水。然而，較佳溶劑為丙 酸。 為能夠控制丙烯酸之自然聚合傾向，於適度溫度下（例如 20至80°C )及適度壓力（例如1至10大氣壓力）下執行上述氯 化是有利的。 「多聚水」第15卷，第8冊，第1241-1251頁（1966)揭示 85187.DOC -11 - 200407294 了藉由液相（甲醇為較佳溶劑）内之非均相催化（使用釕磷 化氫錯合物）氫化而產生丙酸。一般反應溫度為60°C，且氫 壓力可為（例如）3 MPa。 第PL-94748號波蘭專利推薦藉由氣相内之非均相催化氫 化製備丙酸。將銅鋅觸媒應用於氧化鋁是有利的。該氫化 過程於（例如）溫度為250至3 50°C，壓力為大氣壓力至6個大 氣壓力時’於一固定觸媒床内進行，且丙酸選擇性至少為 95莫耳％。於氣相内用水蒸氣將丙婦酸稀釋是有利的。於 冷凝器内將丙酸蒸氣液化能立即提供成品。 「化學（Chem·)普魯姆（prum.)」，第37期（1987)，第651至 653頁揭示了藉由於氣相内借助載體金屬觸媒，Ni，cu ，Zn)彳隹化氫化丙晞酸而製備丙酸之可能性。 第A 2834691號德國專利揭示了（例如）一種藉由丙晞酸 乙酯之催化氫化製備乙烷丙酸之方法。所使用之觸媒為鍺 錯合物。 第A 40833 8號歐洲專利推薦了類似觸媒，其用於丙晞酸 衍生物之催化氫化。 「電分析化學與界面電化學」，第6〇期（1975)，第75_8〇 頁教示了於一鍍鉑電極上將丙烯酸陰極還原至丙酸。 根據「J·電分析化學」，Μ·伯恩（Byrne)，A.庫恩（Kuhn) ;第60期（1975)，第75_80頁，丙烯酸至丙酸之氫化甚至可 為細周性氯化。 原則上，可將所有上述程序應用於根據本發明之方法之 步驟c)中。85187.DOC 200407294 The remaining 3 points are discharged from the processing section, and they are recovered to the processing section, at least the Shao points are recovered to the part of the processing section (this part is not part of the formation of a museum). However, ongoing research has shown that this disadvantage is that at least a portion of the primary components can increase the propensity to polymerize acrylic acid, so this recovery usually results in increased polymer formation in the processing section. From another point of view, the formation of fractions rich in secondary components in the area is also undesirable. Given the considerable corrosive effects of, for example, alkanecarboxylic acids, especially in the case of formic acid, local accumulation should be avoided. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preparing acrylic acid, which starts from the selective heterogeneous catalytic gas-phase partial oxidation of propane, propylene, and / or acrolein, and the propionic acid of the target product substance will be A mixture comprising the secondary component and acrylic acid was removed from the processing section without significant damage to the economic suitability of the process due to the loss of acrylic acid. This method is also a method of acrylic acid, because acrylic acid can be directly converted into the corresponding acrylate in a similar manner by directly reacting acrylic acid with an appropriate alcohol. We have found that this can be achieved by a method in which propionic acid and / or its esters and propionic acid and / or its esters are prepared in an integrated system, the method comprising a) in a section, That is, in the reaction section, propane, propidium, and / or acrolein are partially oxidized by a selective heterogeneous catalytic gas phase to form a product gas mixture A, which includes the main product acrylic acid and the secondary component aldehyde and / Or saturated alkanecarboxylic acid, 85187.DOC -10- 200407294 b) in a second section, that is, in the treatment section, remove 0 from the product gas mixture a, which is an acrylic substance of a target product, Its propionic acid content is 90% by weight or more, and at the same time π) On the other hand, a secondary mixture containing propionic acid, wherein the total content of aldehyde (mol%) (based on the amount of acrylic acid present) and The total content of alkanoic acid (mol%) (based on the amount of acrylic acid present) is greater than the total content of aldehyde and / or alkanecarboxylic acid in the acrylic material removed in 0, and c) as appropriate Can be hydrogenated by using hydrogen molecules after esterifying them To [pi) is present within the mixture to remove two of the propionic acid is converted to acid association and / or unitary purpose. One basis of the method according to the invention is that propionic acid and / or its ester can be obtained from acrylic acid and / or its ester by hydrogenation using hydrogen molecules. For example, German Patent No. A 2310754 recommends a heterogeneous catalyst (the recommended catalyst is a carrier catalyst on which palladium is applied as the catalyst active material) Method 'It is performed in a liquid phase under pressure . Preferably, the method of German Patent No. A 23 10754 is performed in a liquid fluidized bed. The basis of the liquid phase is a solvent. An example of an effective solvent is water. However, the preferred solvent is propionic acid. To be able to control the natural polymerization tendency of acrylic acid, it is advantageous to perform the above-mentioned chlorination at a moderate temperature (for example, 20 to 80 ° C) and a moderate pressure (for example, 1 to 10 atmospheric pressure). "Polymeric Water" Volume 15, Volume 8, Pages 1241-1251 (1966) reveals 85187.DOC -11-200407294 by heterogeneous catalysis in the liquid phase (methanol is the preferred solvent) (using ruthenium Phosphine complex) is hydrogenated to produce propionic acid. The general reaction temperature is 60 ° C, and the hydrogen pressure can be, for example, 3 MPa. Polish patent No. PL-94748 recommends the preparation of propionic acid by heterogeneous catalytic hydrogenation in the gas phase. It is advantageous to apply a copper-zinc catalyst to alumina. The hydrogenation process is carried out, for example, at a temperature of 250 to 350 ° C, a pressure of atmospheric pressure to 6 atmospheres' in a fixed catalyst bed, and a propionic acid selectivity of at least 95 mole%. It is advantageous to dilute propionic acid with water vapor in the gas phase. The liquefaction of propionic acid vapor in the condenser can provide the finished product immediately. "Chem · Prum.", Issue 37 (1987), pages 651 to 653, reveals that the tritium hydrogenation of Ni, cu, Zn due to support metal catalysts in the gas phase The possibility of preparing propionic acid. German Patent No. A 2834691 discloses, for example, a method for preparing ethanepropionic acid by catalytic hydrogenation of ethyl propionate. The catalyst used is a germanium complex. A similar catalyst is recommended in European Patent No. A 40833 8 for the catalytic hydrogenation of malonic acid derivatives. "Electroanalytical Chemistry and Interfacial Electrochemistry", Issue 60 (1975), pages 75-8, teaches reduction of an acrylic cathode to propionic acid on a platinum-plated electrode. According to J. Electroanalytical Chemistry, Byrne, A. Kuhn; No. 60 (1975), pp. 75-80, the hydrogenation of acrylic acid to propionic acid can even be finely chlorinated . In principle, all the above-mentioned procedures can be applied to step c) of the method according to the invention.

85187.DOC -12- 200407294 然而’根據本發明、 7 A处人 万法耶基於一事實，即少量甲歒十 乙酸僅會輕微干涉大容 P/里甲鉍或 數丙故之使用。當應用報虔 之氫化作用變化形式睡…、、、用根據本發明 ^ _ 、目當於解決了將丙酸自丙烯酸 I异貝除上播法以蒸餾告 w敗 盆……： )移除之問題。因為未將丙酸及 其酉日使用於自由基聚合， 队夂 .± ^ ，、其内所包含又任何醛亦盔法ff 其產生不利影響。 ”、、床對 實施方式 進""步說明可應料根據本發明之方法内之兩個 或二個處理區段組態變化形式，以及包括㈣酸與二級組 伤《一級混合物’且將根據本發明將該二級組份有 並隨後將其用於氫化。 " 第A 職歐洲專利之程序為第一組態變化形式之基 礎。 土 以-本身已知之方式’首先於一反應區段内進行丙燒， 丙缔及/或丙烯醛之選擇性非均向催化氣相部分氧化，如 (例如）第A 982288號歐洲專利第3卷中所述。 通常會出現產物氣體混合物A，其包括：各個情況下以 總反應氣體混合物重量計1至3 0重量％之丙埽酸，〇〇5石1 重量％之丙烯，〇·〇5至1重量％之丙晞醛，〇〇5至1〇重量％之 氧分子，0·05至2重量％之甲酸，〇·05至2重量％之乙酸， 至2重量％之丙酸，0.05至1重量％之甲醛，0 〇5至2重量％之 其它醛（例如糠醛與苯甲醛），以總量計為〇.〇丨至〇 5重量％ 之順丁烯二酸與順丁烯二酐以及20至97重量％(較佳為5〇 至97重量％)之稀釋用惰性氣體。後者可特別包括飽和 85187.DOC -13- 20040729485187.DOC -12- 200407294 However, according to the present invention, the 7A treatment of Wanfaye is based on the fact that a small amount of formamidine acetic acid will only slightly interfere with the use of large volume P / limebismuth or acetone. When applying the hydrogenation change form of sacrifice to sleep ... ,, using the method according to the present invention ^ _, the purpose is to solve the problem of removing propionic acid from acrylic acid by isopropellation and distilling it ... :) Remove Problem. Because propionic acid and its next day are not used in free-radical polymerization, ±. ± ^, and any aldehydes contained in it also have an adverse effect. "", The step-by-step description of the implementation of the method according to the present invention can be expected in accordance with the method of the present invention, two or two processing section configuration changes, as well as including acetic acid and secondary group injury "primary mixture ' And the secondary component will be used in accordance with the present invention and subsequently used for hydrogenation. &Quot; The procedure of the European patent for position A is the basis for the first configuration variation. The first method is known in a manner known per se. Propylene calcination is carried out in the reaction section, with selective heterogeneous oxidation of propylene and / or acrolein to the catalytic gas phase, as described, for example, in European Patent No. A 982288, Volume 3. Product gas mixtures often occur A, which includes: in each case 1 to 30% by weight of propionic acid based on the weight of the total reaction gas mixture, 0.05% by weight of propylene, 0.05 to 1% by weight of propionaldehyde, 〇5 to 10% by weight of oxygen molecules, 0.05 to 2% by weight of formic acid, 0.05 to 2% by weight of acetic acid, to 2% by weight of propionic acid, 0.05 to 1% by weight of formaldehyde, 0.05 To 2% by weight of other aldehydes (such as furfural and benzaldehyde), total amount is 0.00丨 to 5% by weight of maleic acid and maleic anhydride and 20 to 97% by weight (preferably 50 to 97% by weight) of an inert gas for dilution. The latter may particularly include saturated 85187.DOC- 13- 200407294

CrC6-烴，例如〇至95重量％之甲烷基及/或丙烷，另外1至 3〇重量％之水蒸氣，〇.〇5至15重量〇/。之碳氧化合物與〇至95 重量％之氮’各個情況下基於1〇〇重量％之產物氣體混合物 A 〇 於該處理區段内，於一第一方法階段先使丙烯酸與二級 組份之一部分自產物氣體混合物A吸收吸收入一高沸點有 機溶劑内。 該高滞點有機溶劑之沸點於大氣壓力下較佳至少為2(rc ’尤其較佳為50°C，更佳為7(TC，其高於丙烯酸之沸點。 較佳溶劑（於本應用中，此術語”溶劑”亦包括溶劑混合物） <沸點（於大氣壓力下）為180至4〇(rc，尤其為22〇至36〇。(： 。有利之溶劑為高沸點疏水有機溶劑，其不具有外極性基 例如纟曰肪族或芳族烴（如來自石蠘蒸餾之中級油餾分，或 氧原子上具有龐大基團之醚，或其混合物），向其中加入一 極性落劑是有利的，如第A_43 〇8 〇87號德國專利所揭示之 I2 —甲基苯甲酸鹽。另外適合之溶劑包括具有包含1至8 個敌原子之直鏈醇的苯甲醯酸與苯甲酸之酯，如正苯甲酸 丁酉曰，苯甲酸甲酯，苯甲酸乙酯，苯甲酸二甲酯，苯甲酸 一乙酯，還包括熱載油，如聯苯，二苯醚或其氯衍生物， 以及二芳基烷，例如4-甲基_4、苯甲基二苯基甲烷與其異 構fa 2-甲基_2’_苯甲基二苯基甲烷，2-甲基-4，_苯甲基二苯 基甲烷與4-甲基_2，_笨甲基二笨基甲烷。一尤佳之溶劑為一 驷苯與二苯醚之溶劑混合物，較佳為共沸組份，具體為約 25重量％之聯苯（聯二苯）與以重量計約75%之二苯醚，例如CrC6-hydrocarbons, such as 0 to 95% by weight of methyl and / or propane, and another 1 to 30% by weight of water vapor, 0.05 to 15% by weight. Carbon dioxide and 0 to 95% by weight of nitrogen 'in each case based on 100% by weight of the product gas mixture A 0 in this processing section, in a first method stage, the acrylic acid and the secondary components are first mixed. A portion is absorbed from the product gas mixture A into a high-boiling organic solvent. The boiling point of the high stagnation point organic solvent is preferably at least 2 (rc ′, particularly preferably 50 ° C., more preferably 7 (TC), which is higher than the boiling point of acrylic acid under atmospheric pressure. A better solvent (in this application) The term "solvent" also includes solvent mixtures) < Boiling point (under atmospheric pressure) is 180 to 40 (rc, especially 22 to 36.) (:. A favorable solvent is a high boiling point hydrophobic organic solvent, which It does not have an external polar group such as an aliphatic or aromatic hydrocarbon (such as from a distillate of intermediate oil, or an ether having a large group on the oxygen atom, or a mixture thereof), and it is advantageous to add a polar precipitant thereto. , Such as I2-methylbenzoate disclosed in German Patent No. A_43 008 87. Another suitable solvent includes benzoic acid and benzoic acid having a linear alcohol containing 1 to 8 enemy atoms. Esters, such as butyl benzoate, methyl benzoate, ethyl benzoate, dimethyl benzoate, monoethyl benzoate, and also heat-carrying oils, such as biphenyl, diphenyl ether or its chlorine derivative, And diarylalkanes, such as 4-methyl-4, benzyldiphenylmethane and its isomers f a 2-methyl_2'_benzyldiphenylmethane, 2-methyl-4, _benzyldiphenylmethane and 4-methyl_2, _benzyldiphenylmethane. 1 A particularly preferred solvent is a solvent mixture of monobenzene and diphenyl ether, preferably an azeotropic component, specifically about 25% by weight of diphenyl (biphenyl) and about 75% by weight of diphenyl ether, E.g

85187.DOC -14- 200407294 可由商業途徑獲得之狄菲爾®(Diphyl®)。此溶劑混合物較 佳還包括一極性溶劑，如以整個溶劑混合物計〇. 1至25重量 %之苯甲酸二甲酯。 術語高沸物，中沸物與低沸物以及相應之形容詞術語於 下文中分別指於大氣壓力下其沸點高於丙烯酸之沸點的化 合物（高沸物），其沸點與丙烯酸沸點大體相同之化合物（中 沸物）以及其沸點低於丙烯酸之沸點之化合物（低沸物）。 於一直接冷凝器或淬火器内藉由溶劑之部分蒸發而進行 吸收之前，將該熱產物氣體混合物A冷卻是有利的。文氏 管（Venturi)洗滌器，氣泡塔與喷射冷凝器尤其適合此目的 。使反應氣體之高沸點二級組份冷凝入未蒸發之溶劑内。 於本發明之一較佳實施例中，將送至該吸收塔之該未蒸發 溶劑之一子流，較佳為1至10重量％之物質流，分流並由溶 劑淨化。蒸餾該溶劑，且於進一步冷凝後，如需要則將剩 餘高沸點二級組份除去，例如將其焚化。此溶液蒸餾過程 作用在於避免溶劑流内之高沸物濃度過高。較佳情況為將 蒸餾之溶劑自吸收塔送至負載溶劑流。 於一逆流吸收塔中實現吸收，該逆流吸收塔大體上提供 有各種類型之塔内構件，較佳為具有不規則或規整填料， 且該吸收塔自上方填充溶劑。將來自淬火器之氣態反應產 物與所有蒸發之溶劑自下方導入該塔，其後使其冷卻至吸 收溫度。冷卻迴路對該冷卻過程具有有利影響，意即：將 加熱之負載溶劑自塔内取出，於熱交換器内冷卻後，使其 於高於分流點之點返回塔内。進行吸收後，大體上所有高 -15-85187.DOC -14- 200407294 Commercially available Diphyl®. This solvent mixture preferably also includes a polar solvent such as 0.1 to 25% by weight of dimethyl benzoate based on the entire solvent mixture. The terms high-boiling, middle-boiling and low-boiling, and their corresponding adjectives are hereinafter referred to as compounds (high-boiling) whose boiling point is higher than the boiling point of acrylic acid at atmospheric pressure, respectively, and whose boiling points are substantially the same as those of acrylic acid (Middle boiling) and compounds whose boiling point is lower than the boiling point of acrylic acid (low boiling). It is advantageous to cool the hot product gas mixture A before absorption in a direct condenser or quencher by partial evaporation of the solvent. Venturi scrubbers, bubble columns and jet condensers are particularly suitable for this purpose. The high boiling point secondary components of the reaction gas are condensed into a non-evaporated solvent. In a preferred embodiment of the present invention, a substream of the non-evaporated solvent sent to the absorption tower, preferably a stream of 1 to 10% by weight, is split and purified by the solvent. The solvent is distilled, and after further condensation, if necessary, the remaining high-boiling secondary components are removed, for example, incinerated. The purpose of this solution distillation process is to avoid high boiler concentrations in the solvent stream. Preferably, the distilled solvent is sent from the absorption column to a supported solvent stream. Absorption is achieved in a counter-current absorption tower, which is generally provided with various types of internal components of the tower, preferably with irregular or structured packing, and the absorption tower is filled with solvent from above. The gaseous reaction product from the quencher and all evaporated solvents were introduced into the column from below, and then allowed to cool to the absorption temperature. The cooling circuit has a favorable effect on the cooling process, that is, the heated load solvent is taken out of the tower, and after cooling in the heat exchanger, it is returned to the tower at a point higher than the split point. After absorption, generally all heights -15-

85187.DOC 200407294 滞物’大多數丙烯酸以及㈣物之-部分皆處於該溶劑内。 將產物氣體混合物A之剩餘未吸收殘渣進一步冷卻，從 而藉由冷凝將其内所包含之低沸二級組份之可冷凝部分移 除，例如，水’甲醛與乙酸。此冷凝物於下文中被稱為稀 釋酸。仍然剩餘之氣體流主要由氮，碳氧化合物及未轉化 反應物組成。較佳為使其作為稀釋氣體部分返回反應區段 方、下文中被成為循環氣體。將其它部分作為廢氣排出且 較佳將其焚化。 於處理區段之下一方法階段，將丙烯酸自溶劑與中沸組 份以及所存在之低沸二級組份移除。 藉由精餾方法實現此移除過程，原則上可使用任何精餾 塔。使用具有雙流塔盤之塔是有利的。於塔之精餾區中， 蒸餾丙烯酸，使其基本與溶劑及中沸二級組份（如順丁烯二 酐）脫離。為降低丙烯酸内低沸物含量，將塔之精餾區有利 延長’且將丙烯酸作為一側流以大於等於95重量％之丙晞 酸的物質自塔取出。 邵分冷凝後，將一富含低沸物之物流於塔頂分流。然而 ，因為该物流仍然包含大量丙晞酸，通常應將其回收至吸 收階段。 然而，根據本發明，視情況在進行先前丙晞酸之酯化後 ，將該物流作為二級混合物自處理區段排出，並將其送至 其中所包含之丙烯酸之氫化過程是有利的。通常，以此方 式移除之二級混合物包括·· 98%重量之丙烯酸， -16-85187.DOC 200407294 Residuals' Most of the acrylic acid and the-part of the ammonium are in this solvent. The remaining unabsorbed residue of the product gas mixture A is further cooled, thereby removing the condensable part of the low-boiling secondary components contained therein by condensation, for example, water'formaldehyde and acetic acid. This condensate is hereinafter referred to as dilute acid. The remaining gas stream consists mainly of nitrogen, oxycarbons, and unconverted reactants. It is preferable to return it to the reaction section as a diluent gas, and it will be hereinafter referred to as a circulating gas. The other part is discharged as exhaust gas and is preferably incinerated. In a process stage below the treatment section, acrylic acid is removed from the solvent and middle boiling components and the low boiling secondary components present. By carrying out this removal process by a rectification method, in principle any rectification column can be used. It is advantageous to use a tower with a double-flow tray. In the rectification zone of the column, the acrylic acid is distilled so as to be substantially separated from the solvent and middle-boiling secondary components such as maleic anhydride. In order to reduce the content of low-boiling substances in acrylic acid, the rectification zone of the column is prolonged, and acrylic acid is taken out of the column as a side stream at a content of 95% by weight or more of propionic acid. After the Shao-Feng is condensed, a stream rich in low boilers is split at the top of the tower. However, because the stream still contains significant amounts of propionic acid, it should usually be recycled to the absorption stage. However, according to the present invention, it may be advantageous to discharge the stream as a secondary mixture from the treatment section after the previous esterification of propionic acid, as appropriate, to the hydrogenation process of the acrylic acid contained therein. Typically, the secondary mixture removed in this way includes 98% by weight acrylic acid, -16-

85187.DOC 200407294 〇·94重量％之乙酸， 〇·98重量°/〇之水， 以重Τ計百萬分之57之丙晞醛， 以重τ計百萬分之327之丙酸， 以重量計百萬分之35之糠醛， . 以重Τ計百萬分之3〇3之丙烯酸烯丙酯， 以重量計百萬分之11之順丁晞二酐，以及 以重量計百萬分之350之二丙稀酸。 相反’作為目標產物而移除之丙烯酸大體包括： _ 大於等於99重量％之丙烯酸， 以重嚴计小於等於百萬分之2〇〇〇之乙酸， 以重Τ計小於等於百萬分之丨5之丙烯醛， 以重量計小於等於百萬分之35〇之丙酸， 小於等於15重量％之糠醛， 小於等於150重量％之丙晞酸晞丙酯， 以重量計小於等於百萬分之2〇之順丁烯二酐， 以重量計小於等於百萬分之55〇之二丙晞酸，以及 ：泰 以重量計小於等於百萬分之1〇〇之水。 - 將一物流於精餾塔底部分流，其主要包括溶劑。為將其 回收至吸收階段，使該溶劑流基本與丙烯酸脫離，以能夠 再次將丙烯酸自產物氣體混合物A取出。較佳為藉由惰性 氣體汽提’更佳為藉由-循環氣體子流汽提，或當稀釋氣 體為丙烷時，藉由丙烷汽提，從而將溶劑中之丙烯酸耗倉乳 通常該汽提過程在壓力為約M至2〇巴，較佳壓力為^ 85187.DOC -17 200407294 至1·6巴，且其溫度為約80至120°C，較佳為110至120°C時 進行。在汽提方法中，於汽提塔頂部引導待淨化之溶劑流 ，·其經内部構件流向底部。將該汽提氣體逆流送至汽提塔 底部。當該汽提氣體流向塔頂部時，其將丙烯酸自液體溶 劑流中取出，使得能夠將淨化之溶劑流自氣流塔底部分流 ，其最大丙烯酸濃度為1重量％，較佳最大濃度為〇·5重量％ 。其後可使此基本無丙烯酸之溶劑再循環至吸收階段。 將丙晞酸負載汽提循環氣體循環至溶劑部分蒸發之階段 或循環吸收塔是有利的.。 於本發明之一較佳實施例中，該稀釋酸可同樣仍然包含 溶解之丙晞酸，以一溶劑餘分之子流對該稀釋酸進行萃取 處理，如上所述，該溶劑餾分已基本無丙烯酸。其後，可 將來自稀釋酸萃取之液態流冷凝，且隨後將其除去。同樣 將有機流回收至吸收階段。 所述之處理區段之精確方法條件可參見第A 982 288號 歐洲專利。 將二級混合物自處理區段排出（與將其循環至吸收階段 相比），會導致處理區段内聚合物形成減少，該處理區段内 ，如吾人之瞭解，個別處理步驟係於聚合抑制劑（如吩嘧嗪 或對苯二酚之單甲醚）存在之情況下以本身已知之方式進 行。 一第二組態變化形式基於第A 10115277號德國專利之程 序。對照第A 982 288號歐洲專利之處理過程，第a1〇U5277 號德國專利之處理方法包括自逆流吸收塔將底部流引導至 200407294 第一精餾塔i之上部區域，該吸收塔，以及溶劑，包括約i 〇 至40重量％之丙烯酸，大體上所有高沸物以及一部分低沸 物；其後於底部溫度為165至21(TC，較佳為180至200°C， 更佳為190至195°C，且適當壓力為1〇〇至5〇〇毫巴，較佳為 180至350毫巴，且更佳為25〇至29〇毫巴時，將該底部流於 精餾塔I内分離（意即按照約70至95重量％之比例）為一頂部 泥與一底邵流，該頂部流主要包括丙烯酸，大體上所有低 沸物，高沸物之一部分，以及溶劑殘渣，且該底部流主要 包括〉谷劑及約〇· 1至〇.5重量％之小部分丙烯酸。傳遞頂部流 以用於精餾回收目標產物物質之丙晞酸，且將底部流回收 至延况吸收塔之上部區域（於一具體實施例中，用一底部流 之小子泥對可能仍包含溶解之丙缔酸之稀釋酸進行萃取處 理。其後可將㈣釋酸萃取之㈣流除去，而同時同樣將 該有機流回收至吸收階段）。 朴關於精餘塔！之分離内部構件’其原則上無任何限制。筛 浮閥塔| ’不規㈣料或規整填料均可 同等使用。然而，較佳情況為雙流塔盤。 ，較佳為按照以下方法步驟將目標產物物質之丙晞酸自頂 部流移除： 考夕除歹欠餘流，藏殘餘流，以及㈣酸，包括㈣物以 及中/弗物纟#分與&滩物之—部分，以及—子流，該 子λπ'Ι»基本播低〉弗物，以及 自該子流回收目標產物物質之丙晞酸。 尤忑刀離問趨而5 ’較佳情況為使用一分隔壁精餾塔，85187.DOC 200407294 0.94% by weight acetic acid, 0.98% by weight / water, propionaldehyde 57 parts per million by weight T, propionic acid 327 parts per million by weight τ, Furfural at 35 parts per million by weight, .3 parts per million by weight of allyl acrylate, 11 parts per million by weight of maleic anhydride, and parts per million by weight 350 of bispropionic acid. On the contrary, the acrylic acid removed as a target product generally includes: _ 99% by weight or more acrylic acid, acetic acid less than or equal to 2000 parts per million by weight, or less than or equal to parts per million by weight 丨Acrolein of 5 is less than or equal to 35 parts per million by weight of propionic acid, 15% by weight or less of furfural, 150% by weight or less of propyl propionate, and less than or equal to parts per million by weight 20% of maleic anhydride, dipropionic acid of less than or equal to 55 parts per million by weight, and Thai's of less than or equal to 100 parts per million by weight of water. -Distilling a stream at the bottom of the rectification column, which mainly includes solvents. In order to recover it to the absorption stage, the solvent stream is substantially separated from the acrylic acid so that the acrylic acid can be taken out of the product gas mixture A again. Preferably, stripping by inert gas is more preferred. Stripping by -cycle gas sub-stream, or by propane stripping when the diluent gas is propane, so that the acrylic acid silo in the solvent is usually stripped. The process is carried out at a pressure of about M to 20 bar, preferably ^ 85187.DOC -17 200407294 to 1.6 bar, and its temperature is about 80 to 120 ° C, preferably 110 to 120 ° C. In the stripping method, the solvent stream to be purified is directed at the top of the stripper, which flows through the internal components to the bottom. The stripping gas is countercurrently sent to the bottom of the stripping column. When the stripping gas flows to the top of the tower, it takes the acrylic acid out of the liquid solvent stream, so that the purified solvent stream can be partially flowed from the bottom of the gas stream. The maximum acrylic acid concentration is 1% by weight, and the maximum concentration is preferably 0.5. % By weight. This substantially acrylic-free solvent can then be recycled to the absorption stage. It is advantageous to circulate the propionate-supported stripping cycle gas to the stage where the solvent is partially evaporated or to recycle the absorption column. In a preferred embodiment of the present invention, the dilute acid may still contain dissolved propionic acid, and the dilute acid is subjected to extraction treatment with a sub-stream of a solvent. As mentioned above, the solvent fraction is substantially free of acrylic acid. . Thereafter, the liquid stream from the dilute acid extraction can be condensed and subsequently removed. The organic stream is likewise recycled to the absorption stage. The precise method conditions of the treatment section can be found in European Patent No. A 982 288. Discharging the secondary mixture from the treatment section (compared to recycling it to the absorption stage) will result in reduced polymer formation in the treatment section. In this treatment section, as I understand it, individual processing steps are related to polymerization inhibition. Agents (such as phenpyrazine or monomethyl ether of hydroquinone) are carried out in a manner known per se. A second configuration variation is based on the procedure of German Patent No. A 10115277. In contrast to the processing procedure of European Patent No. A 982 288, the processing method of German Patent No. a10U5277 includes a self-counterflow absorption tower to direct the bottom flow to the area above the first distillation column i, 200407294, the absorption tower, and the solvent, Includes about 10 to 40% by weight of acrylic acid, substantially all high boilers and a portion of low boilers; thereafter, the bottom temperature is 165 to 21 ° C, preferably 180 to 200 ° C, more preferably 190 to 195 At a temperature of ° C and a suitable pressure of 100 to 500 mbar, preferably 180 to 350 mbar, and more preferably 25 to 290 mbar, the bottom is separated in the rectification column I (Meaning about 70 to 95% by weight) is a top mud and a bottom stream, the top stream mainly includes acrylic acid, substantially all low boilers, a part of high boilers, and solvent residues, and the bottom The stream mainly includes> cereals and a small portion of acrylic acid of about 0.1 to 0.5% by weight. The top stream is passed for rectification to recover the propionic acid of the target product substance, and the bottom stream is recovered to the extended state absorption tower. Upper area (in a specific embodiment, The zimu extracts the dilute acid that may still contain dissolved alanine. After that, the stream from the release acid extraction can be removed, and the organic stream is also recovered to the absorption stage at the same time. Park About Jingyu Tower! There are no restrictions on the separation of internal components in principle. Sieve float valve towers | 'irregular materials or structured packing can be used equally. However, a double-flow tray is preferred. It is better to follow the method steps below to target The propionate of the product material was removed from the top stream: Kao Xijuan owing residual stream, Tibetan residual stream, and osmic acid, including tritium and middle / Effective matter # 分 和 & 物 物 之 —Part, and- Substream, the sublaminar ππ'1 »basic soy> Ethyl alcohol, and the propionic acid of the target product substance recovered from the substream. You're better off 5 'and the best case is to use a dividing wall distillation column ,

85187.DOC -19- 其裝配有兩個冷凝器與一個蒸發器。尤其適合之内部構件 為雙流塔盤。 首先將離開該精餾塔之頂部流冷凝，其後，使其向下流 動至所使用之分隔壁塔之左副塔（汽提塔）。蒸汽自底部上 升，咸詻A主要為丙烯酸蒸汽，同時將低沸物自液體汽提 使得到達底部之液體流内幾乎無低沸物。冷凝後，於該 副塔頂部將-富含低滩物之物流分流。然而，因為此物流 仍/、、： G έ大£丙晞酸，通常使其回收至吸收階段及/或淬火 器。根據本發明，相反，視情況將丙烯酸酯化後，可將此 冨含低沸物之包含丙晞酸之物流作為二級混合物自處理區 #又排出’並且將其送至根據本發明之氫化過程。 總體而言，移除之二級混合物具有以下内容·· 87重量％之丙烯酸， 6重量％之乙酸， 5重量％之水， 0.7重量％之甲酸， 以重量計百萬分之15〇〇之丙烯醛 以重量計百萬分之1〇〇〇之丙晞酸晞丙酯 以重量計百萬分之400之順丁缔二酐 以重量計百萬分之150之丙酸，以及 以重量計百萬分之1〇之糠醛。 將目標產物物質之丙烯酸自到達分隔壁塔之右副挞、, 餾塔）底部之液體流中回收（此亦可由一結晶分離步驟替^1 。該汽提塔與該精餾塔具有一通用底部。其主要包括代 200407294 ’視情況將其淨化後（例如，藉由淬火内之蒸發），使該溶 ^循5哀至吸收階段。於精餾塔内，基本無低沸物之丙婦酸 备心上升’同時藉由液體回流將中沸物與高沸物沖洗出蒸 A °於塔之頂邵，該蒸汽冷凝，將一部分作為目標產物物 質之丙缔酸分流，且其剩餘物形成該液體回流。 目標產物物質之丙晞酸通常具有以下内容： 大於99重量％之丙晞酸， 以重量計小於百萬分之2〇〇〇之乙酸， 以重量計小於百萬分之1〇〇之水， 以重量計小於百萬分之10之甲酸， 以重量計小於百萬分之100之丙烯酸烯丙酯， 以重量計小於百萬分之1 00之順丁浠二肝， 以重量計小於百萬分之250之丙酸，以及 以重量計小於百萬分之260糠醛。 以上所述之處理區段之新穎方法條件可參見第A 1〇11527?9號德國專利。 將二級混合物自該處理區段排出（與將其循環至吸收階 段相比），會導致處理區段内聚合傾向降低，該處理區段内 ’如吾人之瞭解，個別處理步騾係於聚合抑制劑（如吩隹嗪 或對苯二酚之單甲醚（MEHQ))存在之情況下以本身已知之 方式進行。 以一完全相應之方式，第A 19 606 877號德國專利之圖4 ’ 5與6中，將頂部流自塔C30回收至吸收塔之過程亦可省 略，而將該頂部流作為二級混合物送至一根據本發明之氯85187.DOC -19- It is equipped with two condensers and one evaporator. A particularly suitable internal component is a dual-flow tray. The top stream leaving the rectification column is first condensed, after which it is allowed to flow down to the left side column (stripping column) of the dividing wall column used. The steam rises from the bottom. The salty A is mainly acrylic acid steam, and the low boilers are stripped from the liquid so that there is almost no low boilers in the liquid stream reaching the bottom. After condensation, the bottom-rich stream is diverted at the top of the sub-tower. However, because this logistics is still / ,: G is too large, and it is usually recycled to the absorption stage and / or the quencher. According to the present invention, on the contrary, after the acrylic acid is esterified as appropriate, this low boiling substance containing propionic acid-containing stream can be discharged again from the processing zone as a secondary mixture and sent to the hydrogenation according to the present invention. process. Overall, the removed secondary mixture has the following: 87% by weight of acrylic acid, 6% by weight of acetic acid, 5% by weight of water, 0.7% by weight of formic acid, and 15% by weight per million Acrolein is 100 parts per million by weight, propyl propionate is 400 parts by weight, maleic anhydride is 150 parts by weight, and propionic acid is 150 parts by weight, and by weight Furfural at 10 parts per million. The acrylic acid of the target product substance is recovered from the liquid stream reaching the bottom of the right side of the dividing wall tower, the distillation tower (this can also be replaced by a crystallization separation step ^ 1. The stripping tower and the rectification tower have a universal Bottom. It mainly includes the generation of 200407294 'after purification, as appropriate (for example, by evaporation in the quenching), so that the solvent can pass through to the absorption stage. In the distillation column, there is basically no low-boiling matter. The acid prepares the heart to rise 'At the same time, the medium and high boilers are flushed out by liquid reflux. At the top of the tower, the steam condenses, and a portion of the acrylic acid as the target product is diverted, and the remainder is formed. The liquid is refluxed. The propionic acid of the target product substance usually has the following content: greater than 99% by weight of propionic acid, less than 2000 ppm by weight of acetic acid, and less than 1 ppm by weight. Water of 0%, formic acid less than 10 parts per million by weight, allyl acrylate less than 100 parts per million by weight, cis-butanone dilivere less than 100 parts per million by weight, by weight Less than 250 parts per million of propionic acid Less than 260 furfural by weight. The novel process conditions of the above-mentioned treatment section can be found in German Patent No. A 1011527-9. The secondary mixture is discharged from the treatment section (and recycled Compared to the absorption stage), it will lead to a decrease in the polymerization tendency in the processing zone. In the processing zone, as I understand, individual processing steps are based on polymerization inhibitors (such as phenoxazine or hydroquinone monomethyl Ether (MEHQ)) is carried out in a manner known per se. In a completely corresponding manner, in Figures 4 '5 and 6 of German Patent No. A 19 606 877, the top stream is recovered from column C30 to the absorption column The process can also be omitted and the overhead stream is sent as a secondary mixture to a chlorine according to the invention

85187.DOC -21 - 200407294 匕私亦於此情況下，根據本發明之方法可導致處理區 段運行時間延長。 同樣方式亦可應用於以下情況，使第A 982 289號歐洲專 利之圖2中之塔VI_；[之頂邵流同樣不再循環至處理區段，而 進入根據本發明之一氫化過程。 第二組態變化形式基於文獻第A 19 833 〇49號德國專 利，第A 19 814 375號德國專利，第a 19 814 號德國專 利，第A 19 814 449號德國專利，第a 1〇〇53〇86號德國專 利，第A 19 740 252號德國專利，第a 19 814 387號德國專 利，第A 19 740 253號德國專利及第a 19 914 532號德國專 利所揭示之程序，其中將產物氣體混合物A視情況直接及/ 或間接冷卻後分凝。 上述文件揭示了，該包含於產物混合物A内之丙烯酸之 基本分離’其不僅可藉由使用一適當吸收劑將其吸收並隨 後經由萃取及/或精館分離過程自吸收劑分離而進行，亦可 藉由以下過程進行：視情況將該產物氣體混合物A直接及/ 或間接預冷卻後’使其分凝，同時於一提供有分離内部構 件之分離塔内上升至其本身，並經由自該分離塔分流之一 側流提取目標產物物質之丙烯酸，其丙烯酸含量通常為大 於等於95重量％。通常，將使該目標產物物質之丙晞酸送 至進一步蒸餾及/或結晶淨化階段，且至少將蒸餘及/或結 晶所產生之底部液體及/或母液之一部分回收至分凝塔。 然而，分凝方法之一缺點在於該中沸二級組份（例如乙酸） 會於冷凝塔長度上形成冷凝凸起。換言之，其於特定塔長 85187.DOC -22- 200407294 度(向度）累積，直至其根據沸點經由頂部或底部離開該塔 方、此特殊問題為水會與甲酸形成高沸點共滞混合物， =沸點於大氣壓力下位於水與丙烯酸之沸點之間，使得目 柃產物物質之側流分流上形成甲酸濃縮凸起，其可高達3〇 重量％。此會導致腐蝕問題，使得需要應用昂貴與不便之 措她，例如腐蝕抑制劑之使用，甲酸之觸媒分解，或甲酸 <酉曰化。其它二級組份之積累會為隨後之淨化階段帶來麻 煩。 根據本發明之方法於此亦能夠提供一補救方法。該方法 可^簡單方式實行：ϋ由允許將二級組份濃縮凸起刺破 而貝仃’其實際於經濟上並無重大缺點。換言之，於各個 濃：！起之高度，將各二級組份以及含有丙晞酸之液相自 、1 β «Ρ刀排出，視情況將其内所包含之丙缔酸酯化後， 藉由氫化過程利用氫原子將丙缔酸轉化為丙酸及/或其醋 。此措施可降低濃縮凸起之幅度’並更容易將：級組份自 丙缔酸移除（相繼之淨化階段可具有更小尺寸）。後者為本 發明之方法一極為普遍之優點。 分凝之詳細性能可如所引用之先前技術文獻（尤其為第 A 19 924 532?虎德國專利）中所述。其同樣亦可應用於抑制 分凝中之聚合。 根據本發明，較佳情況財為於氣相内而非液相内將丙 稀酸氫：為丙酸，因為氣相過程中丙稀酸聚合之問題無液 相中頭著為此目的’應藉由蒸發作用將作為液體提取之 二級混合物轉變至氣相。85187.DOC -21-200407294 In this case too, the method according to the invention can lead to an increase in the operating time of the processing section. The same method can also be applied to the case where the tower VI_ in Fig. 2 of European Patent No. A 982 289; [Zing Shao stream is also not recycled to the treatment section, but enters a hydrogenation process according to the present invention. The second configuration variation is based on the German Patent No. A 19 833 049, German Patent No. A 19 814 375, German Patent No. a 19 814, German Patent No. A 19 814 449, and German Patent No. a 1005 The procedures disclosed in German Patent No. 86, German Patent No. A 19 740 252, German Patent No. a 19 814 387, German Patent No. A 19 740 253, and German Patent No. a 19 914 532, in which the product gas Mixture A may condense directly and / or indirectly after cooling. The above document reveals that the basic separation of the acrylic acid contained in the product mixture A 'can be performed not only by absorbing it with an appropriate absorbent and then separating it from the absorbent through extraction and / or fine separation processes, but also This can be carried out by pre-cooling the product gas mixture A, directly and / or indirectly, as appropriate, to cause it to condense, and at the same time rise to itself in a separation tower provided with separation internal components, and pass from the The acrylic acid content of the target product substance is usually extracted by side stream in one of the separation towers, and its acrylic acid content is usually 95% by weight or more. Generally, the propionic acid of the target product substance is sent to a further distillation and / or crystallization purification stage, and at least a part of the bottom liquid and / or mother liquor produced by the distillation and / or crystallization is recovered to the fractionation column. However, one of the disadvantages of the partial condensation method is that the middle-boiling secondary component (such as acetic acid) can form condensation protrusions on the length of the condensation tower. In other words, it accumulates at a specific tower length of 85187.DOC -22- 200407294 degrees (dimension) until it leaves the tower via the top or bottom according to the boiling point. This particular problem is that water will form a high boiling point hysteresis mixture with formic acid, = The boiling point is between the boiling point of water and acrylic acid at atmospheric pressure, so that the formic acid concentrated protrusions are formed on the side stream of the mesh product product, which can reach 30% by weight. This can cause corrosion problems, making it necessary to apply expensive and inconvenient measures, such as the use of corrosion inhibitors, the decomposition of formic acid catalysts, or formic acid. The accumulation of other secondary components can cause annoyance to subsequent purification stages. The method according to the invention can also provide a remedy here. This method can be implemented in a simple way: it allows piercing of secondary component concentrated protrusions, but it does not have any major economic disadvantages. In other words, in each thick :! From the height, the secondary components and the liquid phase containing propionic acid are discharged from the 1 β «P knife, and the propionate contained in it is acidified as appropriate, and then hydrogen atoms are used to hydrogenate the Conversion of propionic acid to propionic acid and / or its vinegar. This measure can reduce the magnitude of the condensed bumps' and make it easier to remove: the fractions are removed from the acrylic acid (the successive purification stages can have smaller dimensions). The latter is a very common advantage of the method of the invention. The detailed properties of the segregation can be described in the cited prior art documents (especially the German patent No. A 19 924 532? Tiger). It can also be applied to inhibit polymerization in segregation. According to the present invention, it is preferable to use hydrogen propionate in the gas phase rather than in the liquid phase: it is propionic acid, because the problem of polymerization of acrylic acid in the gas phase process is no problem in the liquid phase. The secondary mixture extracted as a liquid is transformed into the gas phase by evaporation.

85187.DOC -23- 200407294 万、履相氫化過程中，吾人推薦使 或對苯二料甲基料㈣定。 μ本二驗 移除之二級混合物中所包含之丙稀酸於 二Γ丙二麵化時’有效之_旨具體為丙缔 Γ:要將—正丙稀酸丁酯以及第三-丙稀酸丁醋。 或其@旨自氫化產物混合物中移除時，可 " 6知《万法將其達成，例如藉由精㈣徑達成。 發明之方法尤其適合^藉由前述㈣之催化脫 致乍用獲侍用作選擇性非均相催化氣相氧化起始物質之丙 稀時’如世界專利第01/9627〇號，歐洲專利A 11 71 146號 ，德國專利第A 33 13 573號與美國專利第心61 67〇號中° 所述。可將所形成之氫分子相繼用於根據本發明之方法步 驟C)内之氳化。 實施例 a)對照例1 所有陳述皆關於德國專利第A 19 924 532號之圖。 一非均相催化氣相氧化提供了一產物氣體混合物（1)，於 溫度為270°c時，其具有以下内容： 11.5重量％之丙烯酸， 0.3重量％之乙酸， 以重量計百萬分之280之甲酸， 以重量計百萬分之30丙酸， 0.09重量％之順丁烯二酐， 〇.〇1重量％之丙烯醛，85187.DOC -23- 200407294 million, in the process of hydrogenation of the phase, we recommend to make or to the benzene dimethyl material. μ The acrylic acid contained in the secondary mixture removed in the second test is 'effective' when di-propionated to di-propane. The purpose is specifically propyl: To be butyl n-propionate and tertiary-propionate Dilute sour vinegar. When it is removed from the hydrogenation product mixture, it can be achieved by "Wafa, such as by precision path. The method of the invention is particularly suitable for the use of the above-mentioned catalytic desorption, which can be used as a starting material for selective heterogeneous catalytic gas-phase oxidation, such as World Patent No. 01/96270, European Patent A No. 11 71 146, German Patent No. A 33 13 573 and US Patent No. 61 67 °. The hydrogen molecules formed can be successively used for the tritiation in the method step C) according to the invention. Example a) Comparative Example 1 All statements relate to the drawing of German Patent No. A 19 924 532. A heterogeneous catalytic gas-phase oxidation provides a product gas mixture (1), at a temperature of 270 ° C, which has the following: 11.5% by weight acrylic acid, 0.3% by weight acetic acid, parts per million by weight 280 formic acid, 30 parts per million by weight of propionic acid, 0.09% by weight of maleic anhydride, 0.01% by weight of acrolein,

85187.DOC -24- 200407294 0.1重量％之甲醛， 以重量計百萬分之30糠醛， 0.001重量％之苯甲醛， 〇.3重量％之丙烯， 3.4重量％之氧， 5.3重量％之水， 1.7重量％之碳氧化合物，以及剩餘物N2。 於一喷射冷卻器（2)内將產物氣體混合物（3600 g/h)冷卻 至溫度136°C。所使用之喷射液體總計為7000 g/h之高沸點 餾分（6)之750 g/h(7)，其為經由收集塔盤（5)(於溫度為100 °C)時自分離塔（3)(無底部液體4)内提取。該噴射液體經由 管束熱交換器（8)循環，該管束熱交換器（8)由熱載油運轉。 自該循環迴路（9)持續提取40 g/h之高沸物。 將冷卻至溫度136°C之產物氣體混合物送至收集塔盤（5) 下之分離塔（10)。 該塔為一塔盤塔，自底部向上觀測，其具有第一 25雙流 以及50個泡帽塔盤（每個塔盤1泡帽）。塔盤厚度為49毫米。 該雙流塔盤每塔盤具有6個孔。頭五個雙流塔盤之孔徑為 9_5毫米。其後之10個塔盤之孔徑為9毫米，且最後5個雙流 塔盤之孔徑為8.7毫米。配置塔盤（15)上之塔盤以將其作為 一另外收集塔盤（11)。該塔盤用於將1800 g/h之丙烯酸（12) 之物質分流，該物質溫度為97°C，其包括·· 97.3重量％之丙烯酸， 0.8重量％之乙酸， 85187.DOC -25- 200407294 以重量計百萬分之154之甲酸， 以重量計百萬分之600之丙酸， 以重量計百萬分之700之糠醛， 以重量計百萬分之40之順丁烯二酐， 以重量計百萬分之200之苯甲醛，以及 1.3重量％之水。 並將其送至一懸浮結晶器（13)。於一管束熱交換器内將 所提取高沸物之一部分（6250 g/h)(14)加熱至105°C並將其 循環至塔内之第5塔盤（16)，該管束熱交換器由熱載油運轉。 結晶器為一攪拌容器（容量為31)，其具有一螺旋攪拌器 。經由該容器之夾套移除結晶之熱度。溶解之均衡溫度為 9.7°C。結晶過程所產生之懸浮液（固體含量約為25重量％) ，藉由2000轉數/分鐘之離心作用（離心直徑為300毫米）以 及3分鐘之離心時間被分批分離為晶體與母液。其後將該晶 體由熔融（預先洗滌）晶體（80克）以2000轉數/分鐘洗滌20秒 。將母液與洗滌液體回收至塔之第15塔盤（28)。 晶體（370 g/h)之分析值具有以下内容： 99.5重量％之丙烯酸， 〇.2重量％之乙酸， 0.1重量％之甲酸， 以重量計百萬分之200之丙酸， 以重量計百萬分之60之順丁烯二酐， 以重量計百萬分之200之糠醛， 30重量％之苯甲醛，以及 85187.DOC -26- 200407294 以重量計百萬分之1000之水。 於塔之頂部提取一氣態混合物（17)，於噴射冷卻器（18) 内使其部分冷凝。將480 g/h所產生之稀釋酸於溫度為30°C 時回收至塔之頂部（26)。持續提取220 g/h之稀釋酸（稀釋酸 包含之3重量％之丙烯酸與2.6重量％之乙酸）。將所提取之 90 g/h稀釋酸與MEHQ (22)混合，作為一0.5重.量％之液態穩 定劑溶液（2 1 )，使用冷卻水管束熱交換器（24)將其與稀釋酸 剩餘物（23)—起冷卻至18t，並將其用作喷射液體（25)。將 所提取之稀釋酸之另一部分用於製備一含有0.5重量％之4-羥基-TEMPO(4-羥基-2,2,6,6-四甲基呱啶-1-氧自由基）之 液態溶液，並將其以1 8 g/h之比率於溫度為20°C時送至分 塔之第75塔盤（27)。 所述之分離裝置可運行40天而無明顯聚合物形成。 b)實施例1 於a)之對照例1中，第30泡帽塔盤之高度上（自下）形成一 甲酸凸起（位於此塔高之回流液體包含28重量％之甲酸）。 於此高度提取10 g/h液體側流，從而使該甲酸凸起降低 至1 3重量％。 提取之液體側流之固定組份主要為： 3 8重量％之丙晞酸， 1 3重量％之甲酸， 12重量％之乙酸，以及 37重量％之水。 根據第A 23 10 754號德國專利將該提取之側流送至一氫 85187.DOC -27- 200407294 化過程中。 結晶之純度略有改良。 C)對照例2 ‘ 以下說明係關於第A 101 15277號德國專利之圖1或第 A 9 8 2 2 8 9號歐洲專利之圖2。 一來自氣相氧化之氣體流，其產生溫度為270°C，且壓力 為1.6巴之2900 Ι/h(標準溫度及壓力）丙烯酸，該氣體流所具 有之主要組份為（各為重量％) 氮（75)， 氧（3)， 丙烯酸（12)， 水（5)， CO(l)， C02(3)， 剩餘物，意即：其它組份（丨）。 於一文氏管（Venturi)淬火1内將該氣體流與淬火液體 (140-150 C)直接接觸’從而將該其冷卻至溫度為15〇。〇， 經由文氏官之截面最狹窄之區域上所提供之缝隙喷射該淬 火液體，其包括57.4重量％之二苯醚，2〇7重量％之聯苯， 20重里苯甲酸二甲酯以及其它組份之剩餘物。將淬 火液體《以液滴形式存在之一部分於一下游液滴分離器中 (具有向上氣體官迢儲存器）自氣相中移除，該氣相由反 應氣體與蒸發淬火㈣組成，同時將該淬火液體之部分回 收至文氏管（VentUn)洗㈣。麟劑蒸餘該回收之淬火液85187.DOC -24- 200407294 0.1% by weight of formaldehyde, 30 parts per million by weight of furfural, 0.001% by weight of benzaldehyde, 0.3% by weight of propylene, 3.4% by weight of oxygen, 5.3% by weight of water, 1.7% by weight of oxycarbons and the remainder N2. The product gas mixture (3600 g / h) was cooled to a temperature of 136 ° C in a spray cooler (2). The ejection liquid used is a total of 750 g / h (7) of the high boiling point fraction (6) of 7000 g / h, which is a self-separation tower (3 at a temperature of 100 ° C) through a collection tray (5) ) (No bottom liquid 4). The spray liquid is circulated through a tube bundle heat exchanger (8), which is operated by hot carrier oil. High-boiling matter of 40 g / h is continuously extracted from the circulation loop (9). The product gas mixture cooled to a temperature of 136 ° C is sent to a separation column (10) under a collection tray (5). The tower is a tray tower, viewed from the bottom, and has a first 25 double-flow and 50 bubble cap trays (1 bubble cap per tray). The thickness of the tray is 49 mm. The double-flow tray has 6 holes per tray. The diameter of the first five dual-flow trays is 9-5 mm. The diameter of the next 10 trays was 9 mm, and the diameter of the last 5 dual-flow trays was 8.7 mm. The tray on the tray (15) is configured as an additional collecting tray (11). The tray is used to divert a substance of acrylic acid (12) at 1800 g / h. The temperature of the substance is 97 ° C. It includes 97.3% by weight acrylic acid, 0.8% by weight acetic acid, 85187.DOC -25- 200407294 Formic acid 154 parts per million by weight, propionic acid 600 parts per million by weight, furfural 700 parts per million by weight, maleic anhydride 40 parts per million by weight, 200 parts per million by weight of benzaldehyde and 1.3% by weight of water. It is sent to a suspension crystallizer (13). A part of the extracted high boilers (6250 g / h) (14) was heated to 105 ° C in a tube bundle heat exchanger and circulated to the fifth tray (16) in the tower. The tube bundle heat exchanger Operated by hot carrier oil. The crystallizer is a stirring vessel (capacity is 31), which has a spiral stirrer. The heat of the crystals was removed through the jacket of the container. The equilibrium temperature of dissolution is 9.7 ° C. The suspension (solid content of about 25% by weight) produced by the crystallization process was separated into crystals and mother liquor in batches by centrifugation (centrifugation diameter of 300 mm) and centrifugation time of 3 minutes at 2000 rpm. The crystal was then washed from molten (pre-washed) crystals (80 g) at 2000 rpm for 20 seconds. The mother liquor and washing liquid are recovered to the 15th tray (28) of the column. The analytical value of the crystal (370 g / h) has the following contents: 99.5% by weight of acrylic acid, 0.2% by weight of acetic acid, 0.1% by weight of formic acid, 200 parts per million by weight of propionic acid, and one hundred by weight Maleic anhydride of 60 parts per million, furfural of 200 parts per million by weight, 30% by weight of benzaldehyde, and 85187.DOC -26- 200407294 water of 1,000 parts per million by weight. A gaseous mixture (17) is extracted at the top of the tower and partially condensed in a jet cooler (18). The dilute acid produced at 480 g / h was recovered to the top of the column at a temperature of 30 ° C (26). 220 g / h of dilute acid (3% by weight of acrylic acid and 2.6% by weight of acetic acid) was continuously extracted. The extracted 90 g / h diluted acid is mixed with MEHQ (22) as a 0.5 wt.% Liquid stabilizer solution (2 1), and it is left with the diluted acid using a cooling water tube heat exchanger (24). The object (23) is cooled to 18t and used as a spray liquid (25). The other part of the extracted dilute acid was used to prepare a liquid containing 0.5% by weight of 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpyridine-1-oxy radical) The solution was sent to the 75th tray (27) of the sub-column at a ratio of 18 g / h at a temperature of 20 ° C. The separation device can be operated for 40 days without significant polymer formation. b) Example 1 In Comparative Example 1 of a), a formic acid protrusion was formed at the height of the 30th bubble cap tray (from below) (the reflux liquid at this column height contains 28% by weight of formic acid). A liquid side stream of 10 g / h was extracted at this height, thereby reducing the formic acid bulge to 13% by weight. The fixed components of the extracted liquid side stream are mainly: 38% by weight of propionic acid, 13% by weight of formic acid, 12% by weight of acetic acid, and 37% by weight of water. According to German Patent No. A 23 10 754, the extracted side stream was sent to a hydrogen gas 85187.DOC -27- 200407294. The purity of the crystals was slightly improved. C) Comparative Example 2 ′ The following description is about Figure 1 of German Patent No. A 101 15277 or Figure 2 of European Patent No. A 9 8 2 2 8 9. A gas stream from gas phase oxidation, which produces acrylic acid at a temperature of 270 ° C and a pressure of 2900 l / h (standard temperature and pressure) of 1.6 bar. The main components of the gas stream are (weight% each) ) Nitrogen (75), oxygen (3), acrylic acid (12), water (5), CO (l), C02 (3), residue, meaning: other components (丨). This gas stream was brought into direct contact with the quenching liquid (140-150 C) 'in a Venturi quenching 1 to cool it to a temperature of 150. 〇, the quenching liquid is sprayed through the gap provided in the narrowest area of the Venturi official's section, which includes 57.4% by weight of diphenyl ether, 207% by weight of biphenyl, 20% by weight dimethyl benzoate and others The remainder of the components. A part of the quenching liquid in the form of droplets is removed in a downstream droplet separator (with an upward gas official storage) from the gas phase, which is composed of a reaction gas and an evaporative quenching radon. A part of the quenching liquid was recovered to VentUn for washing. The refining quenching fluid should be left over from the lin agent

85187.DOC -28- 200407294 體子流，從而將淬火液體蒸餾並將高沸點二級組份留下進 行焚化。 溫度為約15 0 °c時將氣相送至一不規則填充之吸收塔2之 低區，該吸收塔高3米；具有玻璃雙層夾套；内徑5〇毫米， 三個不規則填充區段之長度（自下而上）為9〇公分，9〇公分 與50公分，將該不規則填充區段自上而下按以下溫度調節 如下： 90°C，60°C，20。(：； -煙道塔盤將第二個至最後與最後 不規則填充區段分離；該不規則填充為不銹鋼金屬螺旋線 ，其螺旋直徑為5毫米，螺旋長度為5毫米；立即將吸收劑 送至中部不規則填充區段之上，並將其暴露至由2900 g/h 之吸收劑組成之逆流’該吸收劑同樣包括57·4重量％之二 苯醚，20.7重量％之聯苯，2〇重量％之〇_苯甲酸二乙酯以及 其它組份之剩餘物，且於溫度為5(rc時引導該吸收劑。 未吸收氣體混合物向上離開吸收塔2之第二不規則填充 區段，進而於第三不規則填充區段内冷卻，從而藉由冷凝 作用將其中所包含之二級組份之可冷凝組份（例如水與乙 酸）移除。該冷凝物被稱為一稀釋酸。為增加分離性能，使 稀釋酸之一部分於溫度為20°C時回收至吸收塔2，其位於吸 收i合2之第二任意包裝器上。於最高不規則填充區段下將該 稀釋酸自該處所安裝之煙道塔盤提取。循環與分流稀釋酸 之比率為200 g/g。除包含95.7重量％之水外，該稀釋酸亦 包括0.8重量％之丙烯酸。若需要，可如第19 6〇〇 955中德 國專利所述將其回收。1600 Ι/h(標準溫度及壓力）之氣體流85187.DOC -28- 200407294, so that the quenching liquid is distilled and the high-boiling secondary components are left for incineration. At a temperature of about 150 ° C, the gas phase is sent to the lower area of an irregularly packed absorption tower 2, which is 3 meters high; has a glass double jacket; an inner diameter of 50 mm, and three irregularly packed The length of the segment (bottom to top) is 90 cm, 90 cm and 50 cm. The irregularly filled segment is adjusted from top to bottom at the following temperature as follows: 90 ° C, 60 ° C, 20. (:;-The flue tray separates the second to the last and the last irregularly filled section; the irregularly filled is a stainless steel metal spiral with a spiral diameter of 5 mm and a spiral length of 5 mm; immediately absorbent Sent to the central irregularly filled section and exposed to a countercurrent consisting of an absorbent of 2900 g / h. The absorbent also includes 57.4% by weight of diphenyl ether and 20.7% by weight of biphenyl, 20% by weight of the residue of diethyl benzoate and other components, and the absorbent is guided at a temperature of 5 ° C. The unabsorbed gas mixture leaves the second irregularly packed section of the absorption tower 2 upwards , And then cooled in the third irregular filling section, so that the condensable components (such as water and acetic acid) of the secondary components contained therein are removed by condensation. The condensate is called a dilute acid In order to increase the separation performance, a part of the diluted acid is recovered to the absorption tower 2 at a temperature of 20 ° C, which is located on the second arbitrary packaging device of the absorption i-in 2. The diluted acid is placed under the highest irregular filling section. Flue trays installed from the premises Taken. The ratio of circulating and split dilution acid is 200 g / g. In addition to containing 95.7% by weight of water, the dilution acid also includes 0.8% by weight of acrylic acid. If necessary, it can be as described in German Patent No. 19600955 It is recovered. Gas flow of 1600 Ι / h (standard temperature and pressure)

85187.DOC -29- 200407294 最終離開吸收塔2，並作為循環氣體回收至丙晞氧化中。將 剩餘物焚化。 將吸收塔2之排出物送至一強迫循環閃蒸器5内，該閃蒸 器於60毫巴105°C時運行。將一 5230 g/h之負載丙烯酸之溶 劑流（主要組份各以重量百分比計或重量百萬分比計為：61 之溶劑，30之丙烯酸，百萬分之8118之乙酸，百萬分之200 之順丁烯二酐）分離為2160 g/h第一子流IIIA與3070 g/h第 二子流，該第一子流IIIA主要包含丙烯酸（主要組份各以重 量百分比計為·· 20之溶劑，77之丙烯酸與0.22之乙酸）；該 第二子流ΙΙΙΒ基本包含溶劑（主要組份各以重量百分比計 或重量百萬分比計為·· 8 3之溶劑，5之丙晞酸以及百萬分之 636之乙酸）。 將子流ΙΙΙΒ折合至汽提塔頂部3。所使用之汽提氣體為一 600 Ι/h(標準溫度及壓力）之空氣流。將來自蒸發器之子流 IIIB送至汽提塔3之頂部；該汽提塔此處作用為使溶劑與丙 烯酸脫離。與丙晞酸脫離後，將該溶劑自汽提塔3底部分流 ，並使其循環至吸收塔2之頂部。溶劑中之二丙烯酸含量為 2.0重量％。 將於該蒸發器5中所獲得之子流IIIA於100毫巴之壓力下 在一熱交換器6内冷凝，並將冷凝物送至精餾塔4之第28塔 盤，精餾塔4分隔為兩部分，確切地說將冷凝物送至其汽提 區。在精餾塔4之汽提區中，於逆流中使用丙烯酸蒸汽將低 沸物自子流IIIA汽提，同時使中沸物與高沸點物基本殘留 於液體中。自精餾塔4之汽提區底部提取一實際上無低沸物 85187.DOC -30- 200407294 之物流（主要組份各以重量百分比計或重量百萬分比計為 ·· 28之溶劑，71之丙烯酸，百萬分之721之乙酸，百萬分之 4026之順丁烯二酐）。將子流b送至氣流區與精餾塔4之精餾 區所共用之蒸發器7内，且將一殘渣流自蒸發器7分流（480 g/h，主要成分各以重量百分比計或重量百萬分比計為：87 之溶劑，10之丙婦酸，百萬分之7 0 0之順丁晞二纤），並將 其送至文丘管（Venturi)淬火1。為達到回收丙烯酸之所需物 質之目的，將來自蒸發器7之蒸汽流送至精餾塔4之精餾區 ，並由丙烯酸回流使其與中沸物及高沸物脫離。於精餾塔4 之精館區頂部，將一 420 g/h之目標產物流分流，該物流仍 然包含百萬分之1500之乙酸與百萬分之50之順丁烯二酐 (或者，醛總含量（包括丙烯酸晞丙酯）為以重量計小於百萬 分之300，且烷羧酸之總含量同樣為以重量計小於百萬分之 300)。將來自精餾塔4之汽提區之蒸汽冷凝為殘渣流a，其 包含87重量％之丙烯酸，以重量計百萬分之200之溶劑，以 重量計百萬分之15 10之醛，以重量計百萬分之1000之丙烯 酸烯丙酯，6重量％之乙酸以及0.7重量％之甲酸，將其與吩 嘧嗪混合，並同樣被送至文丘管（Venturi)淬火1。 使用一再循環溶劑流之子流將稀釋溶劑萃取後，送至焚 化之稀釋酸内之二丙烯酸含量為2.6重量％。 使用吩遠嗔抑制所有包含液態丙晞酸之物流之聚合。由 於聚合物之形成，每運行14日後，必須暫停處理。 d)實施例2 將c)之對照例2中之殘渣流自處理區段排出，並將其送至 85187.DOC -31 - 200407294 根據本發明之存在有丙烯酸之氫化方法。此使處理區段之 運轉時間增加至28天。 85187.DOC 32-85187.DOC -29- 200407294 finally left the absorption tower 2 and recovered as the circulating gas for the oxidation of propidium. The residue was incinerated. The effluent from the absorption tower 2 is sent to a forced circulation flasher 5 which is operated at 60 mbar and 105 ° C. A 5230 g / h acrylic acid-supported solvent stream (the main components are expressed by weight percentage or weight percent by weight: 61 solvent, 30 acrylic acid, 8118 ppm acetic acid, 1 ppm 200 maleic anhydride) is separated into a 2160 g / h first sub-stream IIIA and a 3070 g / h second sub-stream, the first sub-stream IIIA mainly contains acrylic acid (each of the main components by weight percentage as ... Solvent of 20, acrylic acid of 77 and acetic acid of 0.22); the second substream ΙΙΙΒ basically contains a solvent (the main components are each by weight percentage or weight percent by weight. · 8 3 solvent, 5 propionate Acid and 636 ppm of acetic acid). The substream llIB is reduced to the top 3 of the stripper. The stripping gas used was an air flow of 600 l / h (standard temperature and pressure). The substream IIIB from the evaporator is sent to the top of the stripping column 3; this stripping column functions here to remove the solvent from the acrylic acid. After being separated from the propionic acid, the solvent was partially flowed from the bottom of the stripping column 3 and recycled to the top of the absorption column 2. The diacrylic acid content in the solvent was 2.0% by weight. The sub-stream IIIA obtained in the evaporator 5 is condensed in a heat exchanger 6 at a pressure of 100 mbar, and the condensate is sent to the 28th tray of the rectification column 4, which is divided into Two parts, specifically the condensate is sent to its stripping zone. In the stripping section of the rectification column 4, the low-boiling matter is stripped from the sub-stream IIIA using acrylic acid steam in a countercurrent, while the middle-boiling and high-boiling substances are basically left in the liquid. From the bottom of the stripping zone of the rectification column 4, a stream with virtually no low boilers 85187.DOC -30- 200407294 (the main components are each by weight percentage or weight percent by weight of 28 solvents, Acrylic acid of 71, acetic acid of 721 ppm, maleic anhydride of 4026 ppm). The sub-stream b is sent to the evaporator 7 which is shared by the gas flow zone and the rectification zone of the rectification column 4, and a residue stream is split from the evaporator 7 (480 g / h, and the main components are each by weight percentage or weight The parts per million are: solvent of 87, acetic acid of 10, and cisbutadiene fiber of 700 / 000,000), and send it to the Venturi tube for quenching1. In order to achieve the purpose of recovering the desired material of acrylic acid, the steam stream from the evaporator 7 is sent to the rectification zone of the rectification column 4 and the acrylic acid is refluxed to separate it from the middle-boiling and high-boiling substances. At the top of the refinery section of the distillation column 4, a 420 g / h target product stream is split. The stream still contains 1500 parts per million acetic acid and 50 parts per million maleic anhydride (or, aldehydes) The total content (including propyl acrylate) is less than 300 parts per million by weight, and the total content of alkanecarboxylic acid is also less than 300 parts per million by weight). The steam from the stripping zone of the rectification column 4 is condensed into a residue stream a, which contains 87% by weight of acrylic acid, 200 parts per million by weight of a solvent, 15 parts per million by weight of an aldehyde, and Allyl acrylate of 1000 parts per million by weight, 6% by weight of acetic acid and 0.7% by weight of formic acid were mixed with phenpyrazine and sent to a Venturi tube for quenching 1 as well. The dilute solvent was extracted using a sub-stream of a recycled solvent stream, and the diacrylic acid content in the dilute acid to be incinerated was 2.6% by weight. Phenylpyridine is used to inhibit the polymerization of all streams containing liquid propionic acid. Due to the formation of the polymer, processing must be suspended after every 14 days of operation. d) Example 2 The residue stream in Comparative Example 2 of c) is discharged from the treatment section and sent to 85187.DOC -31-200407294 According to the present invention, there is a hydrogenation method of acrylic acid. This increases the operating time of the processing section to 28 days. 85187.DOC 32-

Claims (1)

200407294 拾、申請專利範園： 1· -種於m统中製備丙_及/或其酯以及丙酸及 /或其酯之方法，其包括 a) 於-第一區段内’即反應區段内，使丙烷，丙烯， 及/或丙烯醛進行選擇性非均相催化氣相部分氧化， 开y成產物氣體混合物A，其包含主要產物丙晞酸及二 級組份醛及/或飽和垸幾酸， b) 於一第二區段内，即處理區段内，自產物氣體混合 物A取出 1)一方面，目標產物丙烯酸物質，其丙烯酸含量係大 於等於90重量％，同時 另一方面’含有丙晞酸之二級混合物，其中酸以 所存在丙晞酸數量計之總含量（莫耳％)且/或烷羧 酸以所存在之丙晞酸數量計之總含量（莫耳％)均 大於在i)中所取出之丙烯酸物質内之醛及/或烷羧 酸之總含量， 及 C)於11)取出之二級混合物内所含丙烯酸係視情況於酯 化後使用分子氫進行氫化轉化成丙酸及/或其酯。 85187.DOC 200407294 柒、指定代表圖： (一) 本案指定代表圖為：第（ ）圖。 (二) 本代表圖之元件代表符號簡單說明： 1 捌、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 85187.DOC200407294 Patent application park: 1. A method for preparing propionate and / or its ester and propionic acid and / or its ester in the system, which includes a) in the first section, that is, the reaction zone In this section, propane, propylene, and / or acrolein are subjected to selective heterogeneous catalytic gas-phase partial oxidation to form a product gas mixture A, which includes the main product propionic acid and the secondary component aldehyde and / or saturation Arsenic acid, b) in a second section, that is, in the treatment section, is taken out from the product gas mixture A 1) on the one hand, the acrylic acid content of the target product acrylic acid is 90% by weight or more, and on the other hand 'Secondary mixture containing malonic acid, where the total content of acid (mol%) based on the amount of propionic acid present and / or the total content of alkanoic acid (mol%) based on the amount of propionic acid present ) Are greater than the total content of aldehydes and / or alkanecarboxylic acids in the acrylic material taken out in i), and C) acrylic acid contained in the secondary mixture taken out in 11) uses molecular hydrogen after esterification as appropriate Hydrogenation is performed to propionic acid and / or its ester. 85187.DOC 200407294 (1) Designated representative map: (1) The designated representative map in this case is: (). (2) Brief description of the element representative symbols of this representative figure: 1 若 If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: 85187.DOC
TW92112452A 2002-05-08 2003-05-07 Preparation of acrylic acid and/or its esters and also of propionic acid and/or its esters in an integrated system TW200407294A (en)

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DE2002120752 DE10220752A1 (en) 2002-05-08 2002-05-08 Production of propionic acid (ester), useful e.g. as an intermediate for herbicides, comprises hydrogenation of acrylic acid (ester) using hydrogen obtained from dehydrogenation of propane in a prior stage of the process
DE2002124341 DE10224341A1 (en) 2002-05-29 2002-05-29 Production of acrylic and propionic acid and/or their esters, useful as intermediates for e.g. adhesives, comprises catalytic gas-phase oxidation, and work-up to give pure acrylic acid and an acrylic acid by-product which is hydrogenated

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CN101589015A (en) * 2007-01-26 2009-11-25 巴斯夫欧洲公司 Produce acrylic acid

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BRPI0806767A2 (en) 2007-01-26 2011-09-13 Basf Se process for preparing acrylic acid
DE102007004960A1 (en) * 2007-01-26 2008-07-31 Basf Se Production of acrylic acid by partial gas phase oxidation, for use e.g. as monomer, includes extracting acrylic acid with organic solvent from acidic stream obtained in purification column
FR2913975B3 (en) * 2007-03-19 2009-01-16 Arkema France IMPROVED PROCESS FOR THE PRODUCTION OF ACROLEIN AND / OR ACRYLIC ACID FROM PROPYLENE
FR2934264B1 (en) * 2008-07-22 2012-07-20 Arkema France MANUFACTURE OF VINYL ESTERS FROM RENEWABLE MATERIALS, VINYL ESTERS OBTAINED AND USES THEREOF
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CN101589015A (en) * 2007-01-26 2009-11-25 巴斯夫欧洲公司 Produce acrylic acid
CN101589015B (en) * 2007-01-26 2013-11-13 巴斯夫欧洲公司 Method for the production of acrylic acid

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