CN117729967A - 丙烯酸酯连续蒸馏的方法 - Google Patents
丙烯酸酯连续蒸馏的方法 Download PDFInfo
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- CN117729967A CN117729967A CN202280052632.5A CN202280052632A CN117729967A CN 117729967 A CN117729967 A CN 117729967A CN 202280052632 A CN202280052632 A CN 202280052632A CN 117729967 A CN117729967 A CN 117729967A
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- rectification column
- feed
- evaporator
- acrylate
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Classifications
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- 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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
- B01D3/322—Reboiler specifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/52—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms containing halogen
- C07C57/54—Halogenated acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
公开的是一种借助精馏塔的丙烯酸酯连续蒸馏的方法,其特征在于精馏塔的进料线中的丙烯酸酯浓度为至少80重量%,精馏塔底部区域的液体通过蒸发器加热,与产物接触的蒸发器部件由不锈钢制成。
Description
本发明涉及一种借助精馏塔连续蒸馏丙烯酸酯的方法,其中进入精馏塔的进料中的丙烯酸酯含量为至少80重量%,精馏塔底部区域的液体借助蒸发器加热,与产物接触的蒸发器部件由不锈钢制成。
以丙烯酸酯为基础制备的聚合物分散体的形式的聚合物和共聚物具有重大的经济意义。例如,它们用作粘合剂、漆或织物、皮革和造纸助剂。
JP H01-180850 A记载了表面粗糙度对蒸馏塔中聚合物形成的影响。
JP 2001-213844 A记载了丙烯酸酯和甲基丙烯酸酯的制备。为了避免腐蚀,例如,由于使用了酸性催化剂,提议了由6重量%至20重量%的镍,14重量%至24重量%的铬和0.5重量%至5.5重量%的钴组成的合金。
WO 2005/040084 A1记载了含有足够铜的合金用以避免烯键式不饱和单体的聚合的用途。
丙烯酸酯典型地通过丙烯酸的酯化制备。在反应中得到的丙烯酸酯随后被蒸馏。为了纯化蒸馏,此处使用具有由非合金钢制成的蒸发器的精馏塔。
固态沉积物(污垢)在蒸发器表面上形成,这可能会阻碍热传递,甚至导致阻塞。这些固态沉积物必须定期以机械方式去除。
因此,目的是寻找一种改良的用于丙烯酸酯的蒸馏的方法,特别是在所用蒸发器中固态沉积物的水平较低的情况下。
所述目的借助精馏塔连续蒸馏丙烯酸酯的方法来实现,其中进入精馏塔的进料中的丙烯酸酯含量为至少80重量%,精馏塔底部区域的液体借助蒸发器加热,与产物接触的蒸发器部件由不锈钢制成。
合适的丙烯酸酯为,例如,丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯和丙烯酸2-乙基己酯。丙烯酸酯(acrylate)也被称为丙烯酸酯(acrylic ester)。
进入精馏塔的进料中的丙烯酸酯含量优选为至少85重量%,甚至更优选至少90重量%,甚至更优选至少95重量%。
进入精馏塔的进料的酸值优选为每g进料含中氢氧化钾不超过少于100mg,更优选每g进料含中氢氧化钾少于不超过10mg,最优选每g进料中含氢氧化钾少于不超过1mg。为了为进行测定酸值的测定,将1g进料用100ml乙醇稀释,并用0.1摩尔氢氧化钾在的乙醇中溶液用酚酞滴定。
精馏塔的设计本身是已知的,并由具有分离内构件的实际塔身、精馏塔底部区域中的蒸发器和精馏塔顶部区域中的冷凝器组成。在连续蒸馏中,进料连续计量加入到精馏塔中,蒸馏后的丙烯酸酯连续排出。
所使用的分离内构件原则上可以是所有标准的内部构件,例如塔板、规整填料和/或散装填料。在塔板中优选泡罩塔板、筛塔板、浮阀塔板、索尔曼塔板(Thormann tray)和/或穿流塔板;在散装填料中优选包括环形填料、螺旋填料、鞍形填料、拉西填料、Intos或鲍尔环填料、圆柱形填料或矩鞍填料、Top-Pak等、或编织物填料的那些。
蒸发器本身是一种已知的设计。与产物接触的蒸发器部件将热量从蒸发器转移到待蒸发液体。合适的蒸发器为,例如,壳管式换热器。壳管式换热器由壳体空间和管体空间组成。加热介质流经壳体空间。在蒸发器的情况下,加热介质典型地是加热蒸汽,加热蒸汽在壳体空间中的管的外部冷凝。待蒸发的液体流经管体空间,其由许多管组成。此处管的内部是与产物接触的蒸发器部件。
壳管式换热器可以作为内部的或外部的蒸发器操作。内部蒸发器直接存在于精馏塔的分离内构件下方。外部蒸发器存在于精馏塔的旁边并连接到精馏塔的下部区域。经过外部蒸发器的循环可通过泵(强制循环蒸发器)来推进。可以在强制循环蒸发器的回流中加入保压阀。这避免了在壳管式换热器中沸腾,蒸发只在膨胀到精馏塔下部区域(强制循环蒸发器)中时发生。后者尤其温和。
冷凝器本身同样是一种已知的设计。冷凝器可作为内部的或外部的冷凝器操作。外部冷凝器存在于精馏塔的旁边并连接到精馏塔的上部区域。合适的冷凝器有,例如,壳管式换热器。壳管式换热器由壳体空间和管体空间组成。冷却介质流经壳体空间。待冷凝的气体流经管体空间,其由许多管组成。一部分冷凝气体被回收作为回流进入精馏塔。
与产物接触的蒸发器部件由不锈钢制成。本发明上下文中的不锈钢是以铁为主要成分且含有至少10.5重量%铬的钢。
优选的不锈钢优选地含有10.5重量%至30.0重量%、更优选16.0重量%至26重量%、特别优选17.0重量%至20.5重量%、最优选18.0重量%至20.0重量%的铬,更优选地另外含有优选2.0重量%至35.0重量%、更优选8.0重量%至26.0重量%、特别优选10.0重量%至25.0重量%、最优选12.0重量%至24.0重量%的镍,和/或另外含有优选0.1重量%至8.0重量%、更优选2.0重量%至5.0重量%、特别优选2.5重量%至4.5重量%、最优选3.0重量%至4.0重量%的钼。
本发明基于这样的发现,即使用不锈钢可以明显地减少固态沉积物的形成。
在丙烯酸酯的制备中获得的具有高丙烯酸酯含量的物质流没有腐蚀性。因此在丙烯酸酯的纯化蒸馏中,使用由非合金钢制成的精馏塔和蒸发器。预期不会通过腐蚀造成材料的重大损失。然而,可能的情况是非常少量的铁被溶解,从而促进固态沉积物的形成。
下文说明丙烯酸酯的制备:
丙烯酸酯以本身已知的方式以各种途径通过丙烯酸与醇例如烷醇的酯化制备。丙烯酸酯通常通过均相或非均相催化酯化获得,例如,Kirk Othmer,Encyclopedia ofChemical Technology,第4版,1994,第301-302页,以及Ullmann's Encyclopedia ofIndustrial Chemistry,第5版,第A1卷,第167-169页中所述。
文献包括通过丙烯酸与醇的酯化制备丙烯酸酯的众多方法,例如在DE 196 04252 A1和DE 196 04 253 A1中。通过丙烯酸与正丁醇的酸催化酯化制备丙烯酸正丁酯的方法,例如,在WO 98/52904中公开。分批酸催化酯化的一个例子是EP 0 890 568 A1。
所使用的醇典型地是包含1至12个碳原子的任何醇,例如一元醇或多元醇,优选一元至四元醇,更优选一元至三元醇,最优选一元或二元醇,特别是一元醇。
实例有甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、异丁醇、叔丁醇、乙二醇单甲醚、乙二醇单乙醚、二乙二醇、1,3-丙二醇单甲醚、1,2-丙二醇、乙二醇、2,2-二甲基乙-1,2-二醇、1,3-丙二醇、1,2-丁二醇、1,4-丁二醇、二甲氨基乙醇、正己醇、正庚醇、正辛醇、正癸醇、正十二烷醇、2-乙基己醇、3-甲基戊-1,5-二醇、2-乙基己-1,3-二醇、2,4-二乙基辛-1,3-二醇、1,6-己二醇、环戊醇、环己醇、环辛醇、环十二烷醇、三乙二醇、四乙二醇、五乙二醇、正戊醇、十八烷醇、十六烷醇、十二烷醇、三羟甲基丁烷、三羟甲基丙烷、三羟甲基乙烷、新戊二醇及其乙氧基化和丙氧基化转化产物、新戊二醇羟基新戊酸酯、季戊四醇、2-乙基丙-1,3-二醇、2-甲基丙-1,3-二醇、2-乙基己-1,3-二醇、丙三醇、双三羟甲基丙烷、二季戊四醇、对苯二酚、双酚A、双酚F、双酚B、双酚S、5-甲基-5-羟甲基-1,3-二氧杂环己烷、2,2-二(4-羟基环己基)丙烷、环己烷-1,1-二甲醇、环己烷-1,2-二甲醇、环己烷-1,3-二甲醇和环己烷-1,4-二甲醇、环己烷-1,2-二醇、环己烷-1,3-二醇和环己烷-1,4-二醇。
优选的醇为甲醇、乙醇、正丁醇、异丁醇、仲丁醇、2-乙基己醇、正辛醇和二甲氨基乙醇。特别优选的醇为甲醇、乙醇、正丁醇、2-乙基己醇和二甲氨基醇。
非常特别优选的醇为甲醇、乙醇、正丁醇和2-乙基己醇。
可用的酸性催化剂优选为硫酸、对甲苯磺酸、苯磺酸、十二烷基苯磺酸、甲磺酸或它们的混合物;同样可能的有酸性离子交换剂或沸石。
特别优选使用硫酸、对甲苯磺酸和甲磺酸;非常特别优选硫酸和对甲苯磺酸。
基于该反应混合物的催化剂浓度为,例如,1重量%至20重量%,优选5重量%至15重量%。
在酸性或碱性催化剂的存在下通过酯交换制备丙烯酸酯是公知常识(Ullmann'sEncyclopedia of Industrial Chemistry,第5版,A1卷,第171页)。
文献中有许多用于由丙烯酸酯与醇制备丙烯酸酯的酯交换的实例,例如在EP 0906 902 A2中,通过丙烯酸甲酯与二甲氨基乙醇的酯交换制备丙烯酸二甲氨基乙酯。例如,在EP 1 078 913 A2中记载了分批的酯交换。
提议的催化剂尤其是钛烷氧化物,其中烷基基团为C1-C4-烷基,例如钛酸四甲基酯、钛酸四乙基酯、钛酸四异丙基酯、钛酸四丙基酯、钛酸四异丁基酯和钛酸四丁酯(参见EP1 298 867 B1,EP 0 960 877 A2)。DE 101 27 939 A1中还记载了其他的钛化合物。此外,在提议的催化剂之中还有钛酚盐(DE 200 86 18 A1),二丁基氧化锡(EP 0 906 902 A2),例如铪、钛、锆或钙的金属螯合化合物,碱金属醇盐和镁醇盐,有机锡化合物或钙和锂化合物,例如氧化物、醇盐、碳酸盐或卤化物。
合适的聚合抑制剂可为,例如,N-氧化物(硝酰基或N-烃氧基自由基,即具有至少一个>N-O.基团的化合物),例如4-羟基-2,2,6,6-四甲基哌啶N-烃氧基或4-氧代-2,2,6,6-四甲基哌啶N-烃氧基;酚类和萘酚例如对氨基苯酚、对亚硝基苯酚、2-叔丁基苯酚、4-叔丁基苯酚、2,4-二叔丁基苯酚、2-甲基-4-叔丁基苯酚、2,6-叔丁基-4-甲基苯酚或4-叔丁基-2,6-二甲基苯酚;醌类,例如对苯二酚或对苯二酚单甲醚;芳族胺,例如N,N-二苯胺,苯二胺,例如N,N'-二烷基-对苯二胺,其中烷基可以相同或不同,并且各自独立地由1至4个碳原子组成,并且可以是直链或支链的,例如N,N'-二甲基-对苯二胺或N,N'-二乙基-对苯二胺;羟胺,例如N,N-二乙基羟胺;亚胺,例如甲基乙基亚胺或亚甲紫;磺酰胺,例如N-甲基-4-甲苯磺酰胺或N-叔丁基-4-甲苯磺酰胺;肟,例如醛肟、酮肟或脒肟,例如二乙基酮肟、甲基乙基酮肟或水杨醛肟;磷化合物,例如三苯基膦、亚磷酸三苯酯或亚磷酸三乙酯;硫化合物,例如二苯硫醚或吩噻嗪;金属盐,例如醋酸铈(III)或乙基己酸铈(III),或其混合物。
优选地用吩噻嗪、对苯二酚、对苯二酚单甲醚、4-羟基-2,2,6,6-四甲基哌啶N-烃氧基、4-氧代-2,2,6,6-四甲基哌啶N-烃氧基、2,6-叔丁基-4-甲基苯酚或其混合物抑制聚合。
非常特别优选使用吩噻嗪作为聚合抑制剂。
实施例
实施例1
在底部区域带有壳管式换热器(62m2)且顶部区域带有外部冷却器的精馏塔(直径1000mm,15个双流塔板)的第一个塔板下方,连续地计量加入丙烯酸乙酯(99.88重量%的丙烯酸乙酯、0.05重量%的丙烯酸异丁酯、0.03重量%的N,N'-二仲丁基-对苯二胺、0.01重量%的4-羟基-2,2,6,6-四甲基哌啶基烃氧基)。精馏塔在400毫巴的压力下操作。回流比为0.2。回流用4-羟基-2,2,6,6-四甲基哌啶基烃氧基稳定。进入精馏塔的进料为6094kg/h。在精馏塔顶部,去除7386kg/h的馏出物。
与产物接触的蒸发器部件由不锈钢制成(根据DIN EN 10088的1.4571材料:16.5重量%至18.5重量%的铬、10.5重量%至13.5重量%的镍、2.0重量%至2.5重量%的钼,最高达0.7重量%的钛)。腐蚀率小于0.01mm/a。
在蒸发器中,100天后没有明显的聚合物沉积物。
实施例2(比较实施例)
在底部区域带有壳管式换热器(51m2)且顶部区域带有外部冷却器的精馏塔(直径1100mm,52个双流塔板)的第39个塔板处,连续地计量加入丙烯酸乙酯(99.88重量%的丙烯酸乙酯、0.05重量%的丙烯酸异丁酯、0.03重量%的N,N'-二仲丁基-对苯二胺、0.01重量%的4-羟基-2,2,6,6-四甲基哌啶基烃氧基)。精馏塔在1000毫巴的压力下操作。回流比为0.93。回流用4-羟基-2,2,6,6-四甲基哌啶基烃氧基稳定。进入精馏塔的进料为6399kg/h。从精馏塔底部排出6094kg/h的产物。
与产物接触的蒸发器部件由非合金钢(1.0425材料:最高达0.3重量%的铬、最高达0.3重量%的镍、最高达0.08重量%的钼、最高达0.03重量%的钛)制成。腐蚀率小于0.01mm/a。
在蒸发器中,100天后有明显的聚合物沉积物。
Claims (12)
1.一种借助精馏塔连续蒸馏丙烯酸酯的方法,其中进入精馏塔的进料中的丙烯酸酯含量为至少80重量%,精馏塔底部区域的液体借助蒸发器加热,与产物接触的蒸发器部件由不锈钢制成。
2.根据权利要求1所述的方法,其中丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁酯或2-乙基己基丙烯酸酯作为丙烯酸酯使用。
3.根据权利要求1或2所述的方法,其中进入精馏塔的进料中的丙烯酸酯含量为至少85重量%。
4.根据权利要求1或2所述的方法,其中进入精馏塔的进料中的丙烯酸酯含量为至少90重量%。
5.根据权利要求1或2所述的方法,其中进入精馏塔的进料中的丙烯酸酯含量为至少95重量%。
6.根据权利要求1至5中任一项所述的方法,其中所述蒸发器为壳管式换热器。
7.根据权利要求1至6中任一项所述的方法,其中与产物接触的蒸发器部件由不锈钢制成,所述不锈钢含有10.5重量%至30.0重量%的铬。
8.根据权利要求7所述的方法,其中与产物接触的冷凝塔部件由不锈钢制成,所述不锈钢额外含有2.0重量%至35.0重量%的镍。
9.根据权利要求7或8所述的方法,其中与产物接触的冷凝塔部件由不锈钢制成,所述不锈钢额外含有0.1重量%至8.0重量%的钼。
10.根据权利要求7至9中任一项所述的方法,其中进入精馏塔的进料的酸值为每g进料中氢氧化钾少于100mg。
11.根据权利要求1至10中任一项所述的方法,其中进入精馏塔的进料的酸值为每g进料中氢氧化钾少于10mg。
12.根据权利要求1至10中任一项所述的方法,其中进入精馏塔的进料的酸值为每g进料中氢氧化钾少于1mg。
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DE19728898A1 (de) | 1997-07-07 | 1999-01-14 | Henkel Kgaa | Verfahren zur lösemittelfreien Herstellung von ungesättigten Polyolestern |
DE69807406T2 (de) | 1997-10-01 | 2003-04-24 | Nippon Catalytic Chem Ind | Verfahren zur Herstellung von Alkylamino-(meth)Acrylat und eine Vorrichtung dafür |
FR2777561B1 (fr) | 1998-04-21 | 2000-06-02 | Atochem Elf Sa | Procede de fabrication en continu de (meth)acrylates de dialkylaminoalkyle |
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