CN100475767C - 脂肪酸的酯化方法 - Google Patents

脂肪酸的酯化方法 Download PDF

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CN100475767C
CN100475767C CNB2003101196213A CN200310119621A CN100475767C CN 100475767 C CN100475767 C CN 100475767C CN B2003101196213 A CNB2003101196213 A CN B2003101196213A CN 200310119621 A CN200310119621 A CN 200310119621A CN 100475767 C CN100475767 C CN 100475767C
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P·莫里茨
P·费斯勒
C·冯斯卡拉
O·拜勒
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Abstract

在带有一个或者多个部分填料部分(3、4)的塔(1)中进行脂肪酸F的酯化作用的方法。除了起反应器作用之外，该填料部分还具有汽提段的作用。它至少在上部形成进行脂肪酸F和相同或者过量摩尔比率的醇A多相催化的反应区(3)。在贮槽中通过汽化产生富含醇的气态逆流(5)。通过作为汽提气的逆流从该反应区除去水。负载的汽提气(60)在塔顶端至少部分液化。塔顶产物被分离变成富含水的馏分(63)以及富含醇的馏分(62)。富含醇的馏分作为酯化作用和生产汽提气的原料返回该流程。

Description

脂肪酸的酯化方法
本发明涉及一种脂肪酸的酯化方法和一种使用本发明的方法，通过多相催化生产脂肪酸酯的装置。在该方法中，一种C12-，C14-，C16-，C18-，C18′-或C18″-的脂肪酸，即月桂酸，肉豆蔻酸，棕榈酸，硬脂酸，油酸或者亚麻酸可以和一种如下醇类：甲醇，乙醇，正丙醇，异丙醇，正丁醇，异丁醇或者2-乙基己醇进行酯化反应。
根据常规的方法，预定量的脂肪酸是分批酯化的。在该方法中，将脂肪酸放置于一种带有搅拌机械的可加热的容器中并加热到大约100℃到250℃。加入催化剂，在保持恒定的温度下和恒定的醇类进料条件下进行酯化反应。将容器中的蒸气引导到分离塔中，在此把酯化期间生成的水从共汽化的醇中分离出来。通过这样从工艺中去掉水而改进了转化率。在所述的酯化反应完成后，进一步加热除去残余的水和醇。美国专利US-A6069261描述了一种脂肪酸的连续酯化方法，在该专利中用一种“持久”的辅助气体连续地除去水。这种辅助气体，例如氢或者氮气，不参与酯化反应物的化学反应。
本发明的目的在于提供另一种脂肪酸酯化的方法，该方法可以连续地进行而且不必使用辅助气体比如氢或者氮气。权利要求1中所描述的方法可以实现该目的。
脂肪酸F的酯化方法是在一个带有一个或者多个填料部分的塔中实施的。除作为反应器的功能之外，该填料还具有汽提段的作用。它至少在上部形成反应区，在那里，脂肪酸F与相同或者过量摩尔比率的醇A进行多相催化作用。在贮槽中通过汽化生成气态的富醇逆流，通过用作汽提气的逆流从反应区去掉水。该负载的汽提气在塔顶部至少部分液化。塔顶产物被分离成富含水的馏分和富含醇的馏分。富含醇的馏分作为酯化反应和生产汽提气的原料返回到所述工艺中。
根据上述方法，其特征在于，在汽提段的下部填料部分4中，来自于催化反应区3的液体混合物中的水和醇被汽提气50吸收。
根据上述方法，其特征在于另外的填料8装置在汽提段的上方，在这里，携带汽提气60的脂肪酸被富含醇并返回的馏分62的部分68捕获。
根据上述方法，其特征在于，醇进入催化反应区3或者其下方，其以气态形式与汽提气50，50’合并。
根据上述方法，其特征在于，在相分离器或者蒸馏塔中通过全蒸发过程把塔顶产物分离变成富含水的馏分63和富含醇的馏分62。
根据上述方法，其特征在于，原料A和F在预反应器2中进行部分的酯化作用，这样形成的脂肪酸F、醇A、酯E和水W的混合物进入塔1的催化反应区3。
根据上述方法，其特征在于通过弛豫蒸发器9或者蒸馏塔并在分离塔70中进一步地制备部分液态贮槽混合物，从而最后得到脂肪酸酯E，其纯度至少为99重量％。
根据上述方法，其特征在于，以下原料适合用作酯化作用的脂肪酸F和/或醇A：C12-，C14-C16-，C18-，C18′-或C18″-脂肪酸中的一种，即月桂酸，肉豆蔻酸，棕榈酸，硬脂酸，油酸或者亚麻酸，和甲醇，乙醇，正丙醇，异丙醇，正丁醇，异丁醇或者2-乙基己醇中的一种醇。
根据上述方法，其特征在于无机催化剂用作催化剂，或者使用离子交换树脂作催化剂，当在120℃以上和高达140℃的温度下时，所用离子交换树脂只有适度失活。
根据上述方法，其特征在于在150-230℃的温度下使用无机催化剂。
根据上述方法，其特征在于催化剂以强酸形式存在。
根据上述方法，其特征在于将离子交换树脂制备成大孔隙的离子交换树脂。
根据上述方法通过多相催化生产酯E的装置，其特征在于，塔1具有用于进行多相催化的填料部分的催化反应区3，该填料部分包括含有催化剂的颗粒状材料的层31和在催化剂的颗粒状材料之间作为汽提气50′的流动通道32，其中，在催化剂的颗粒状材料的孔中进行所述方法时，待处理的混合物形成直接向下流动的液体10′，汽提气形成直接向上流动的物流并且液相与气相直接接触以便发生物质交换。
下面将根据附图对本发明进行解释，图示如下：
图1一种带有塔的装置，其中设置有用于实施本发明方法的催化反应区，
图2催化反应区截面图，
图3塔的优选实施方案的塔顶部分，和
图4用于净化已生成的脂肪酸酯的一部分装置。
附图1所示的装置包括塔1，通过管路51可以从该塔贮槽中抽提中间产物，即含有按照本发明得到的脂肪酸酯的混合物并送到用于净化和浓缩的一部分装置7中。本发明的描述适用于比相应的脂肪酸F更容易汽化的脂肪酸酯E的制备，例如脂肪酸异丙酯。
按照本发明方法的起始原料是醇A和脂肪酸F。在塔1中得到的中间产物还含有残余的起始原料以及杂质。中间产物在装置7的分离塔中进一步地处理以便最终能得到纯度至少为99wt％的脂肪酸酯E。通过管路71抽出纯净产物。在分离塔中分离出来的残余的脂肪酸F通过管路72返回到该方法中。
塔1含有形成作为催化反应区3的填料部分，在该催化反应区中通过多相催化发生酯化作用。含醇A和脂肪酸F的混合物通过管路10和分配器30被送到催化反应区3中。第二个具有分配器40的下部填料部分4安装在催化反应区3的下方。另外的醇A通过管路11和分配器40进入该工艺中。
除了起反应器作用之外，由催化反应区3和下部填料部分4组成的填料部分还具有汽提段的作用。应用相同或者过量摩尔比率的醇A。因此通过汽化可以在贮槽中生成富含醇的气态逆流，该气态逆流起汽提气50′的作用，从反应区3中除去水W。通过加热支流53(供热Q+)而向设备5提供该蒸发需要的热量。在蒸馏的较低下部填料部分4中，来自从反应区3产生的液体混合物的水W以及醇A已被汽提气50吸收。
该负载的汽提气(箭头60)在设备6(排热Q-)塔顶部至少部分液化并且分离成两股馏分62和63。塔顶产物的馏分63富含水，例如含有水W的比例为80wt％。富含醇的馏分62，例如含95wt％-98wt％的醇A。它作为酯化原料返回到该流程并生成汽提气50。把塔顶产物分离成富含醇的馏分62和富含水的馏分63可以用以下方法进行，例如通过膜法，全蒸发过程，通过相分离器或者通过蒸馏塔。
通过下部分配器40进料的醇A在下部填料部分4上汽化，并入汽提气流50。必需的汽化热是由汽提气50提供，该汽提气在贮槽中通过汽化达到一种过热状态。
在所述的实例中，催化反应区3由垂直层31和作为汽提气50′的流动通道32组成。含原料A和F的混合物10′流向并流到层31上。反应区3的详图在截面图2的剖开部分中图解说明，即为含有汽提气50′的流动通道32和层31之间较宽的边缘区域，其包含催化剂的颗粒状材料310。由耐磨材料制造的纤维品311形成一个水的包封着催化剂的颗粒状材料310罩。混合物10′流入一个罩中和在纤维品311的外表面上流动，该罩内部具有蜿曲流径并且外部作为滴流薄膜。因为其中存在相对小的水的分压，所以水W通过滴流薄膜10″的表面进入汽提气流50′中。在EP-A0396650或者EP-A0631813中描述了适用于反应区3的填料。
原料A和F一起在预反应器2中已经有利地进行了部分反应，其中10-30％的脂肪酸F转化为酯E。这样醇A、脂肪酸F、酯E和水W的混合物通过管路10流入塔1。然后在反应区3中另有20％到70％的脂肪酸F被转化。
在汽提段的催化反应区3、下部填料部分4上面，另外的填料8和分配器80(参见图3)被有利地构建到塔1。携带汽提气60的脂肪酸F在该填料8中被富含醇并返回的馏分62的一部分68捕获。
图4展示了用于净化生成的脂肪酸的装置7的部分。弛豫蒸发器9是装置7部分的一个组成部分，管道52中的中间产物在此释放出大部分的残留气态醇A。该富含醇的蒸气通过管道92移出，它可进一步用于酯化反应。含醇量低的混合物通过管道91进入分离塔70，在这里萃取纯净酯E(管路71)。可以通过管路从冷凝器75收取的塔顶产物含有醇A和挥发性杂质，特别是空气。脂肪酸F(管路72)和不容易挥发的杂质(管道74)可以从贮槽提取出来，该贮槽中的热是使用加热电路73提供的。然而装置7的部分也可安装用作蒸馏塔。
在图4中描述了一个分离工艺，当脂肪酸酯E在比相应的脂肪酸F在更低的温度下沸腾时可以使用这一工艺。在脂肪酸用高级醇(例如2-乙基己醇)酯化的情况下，存在与装置7的部分净化相反的比例。脂肪酸酯在分离塔70的贮槽中接收并且必须进行进一步处理(未示出)。从分离塔70顶端抽取的脂肪酸和残留醇返回到工艺中。
以下原料可用作该酯化作用的脂肪酸F或者醇A。作为F，为C12-，C14-，C16-，C18-，C18′-或者C18″-的脂肪酸中的一种，即月桂酸，肉豆蔻酸，棕榈酸，硬脂酸，油酸或者亚油酸；作为A，为以下醇中的一种，甲醇，乙醇，正丙醇，异丙醇，正丁醇，异丁醇或者2-乙基己醇。
离子交换树脂或者无机催化剂被用作催化剂，其中该催化剂优选以强酸形式存在和该离子交换树脂优选制备成大孔隙的。如果醇A是甲醇，乙醇，正丙醇，异丙醇，正丁醇或异丁醇，那么催化剂-在这种情况下是离子交换树脂-必须能够在120℃-140℃的温度下使用，在此温度下，它必须只适度丧失活性。如果醇A是2-乙基己醇，那么催化剂-在这种情况下是无机催化剂一必须可以在温度为150-230℃下使用。
下面将给出适合于棕榈酸(PA)和异丙醇(IPA)酯化的几个方法参数值。
对于原料A＝IPA和F＝PA来说，优选纯度分别为95wt％和98wt％。然而其他的纯度值也是可以的，即对于IPA来说在88wt％-100wt％范围内和对于PA来说在95wt％-100wt％范围内。预反应器2在100℃和2巴下操作，然而也可以在温度高达140℃和相应多达4巴的较高压力下操作。一般说来，不同量的IPA通过管路21和11进料。管路21的IPA与管路11的IPA的比例优选2.5，但是也可以在1-4范围之内。塔1顶端压力为2-5巴，相应的反应区3的温度为120℃-140℃。中间产物(管路53)在加热装置5中被加热到温度高达170℃-200℃，然而也可以加热到250℃以上。
温度在115℃-140℃之间的汽提气60(图1)存在于该塔顶端填料8(图3)的上面，其含5％-12％的水W，在管路53里的中间产物含50％-80％的酯和2％-10％的IPA。
弛豫汽化器9在1巴和160℃-210℃下运行，在此IPA的比例减少到约0.5％。分离塔70在15-40毫巴下操作。在冷凝器75中温度降低到80-100℃之间，和在加热回路73中产生220℃-240℃之间的温度，该温度上限值还可以是250℃。
在下文中举出在实验性试验中得到的根据本发明的两个酯化作用的实例。
实施例1：
在大气压和下列条件下，在一个塔中连续进行棕榈酸和异丙醇的酯化反应：
反应塔：内径50毫米
增浓段和汽提段：Sulzer填料BX
反应区：catapak-S/装有强酸性离子交换剂，其在高达140℃的温度下稳定。
原料物流：棕榈酸(进料1)：2.16kg/h；
异丙醇(进料2)：1.44kg/h
产物物流：塔顶产物：1.2kg/h；贮槽产物：2.4kg/h
操作条件：塔顶压力：1013毫巴；回流比：0.2
反应区温度：大约98℃；贮槽温度：157.9℃
测定的贮槽浓度(wt％)：棕榈酸异丙酯：14.04；异丙醇：10.61；棕榈酸：74.5；水；0.83
实施例2：
在加压塔中实现与实施例1相同的合成。在这种方法中，使用已经预活化的原料，可以用此来模拟预反应器，利用轻微过压，将反应区的温度设定在大约为140℃的反应区的温度范围，以下操作条件显著地提高了反应转化率。
原料物流：
进料1：2.3kg/h，且该原料具有以下组(wt％)：
棕榈酸异丙酯：24.3；异丙醇：21.6；棕榈酸：52.1；水：2.0
进料2：异丙醇：1.84kg/h
产物物流：塔顶产物：1-43kg/h；贮槽产物：2.71kg/h
操作条件：塔顶压力：5100毫巴；回流比：0.2
反应区温度：大约140℃；贮槽温度：192℃
测定的贮槽浓度(wt％)：棕榈酸异丙酯64.0；异丙醇：7.7；棕榈酸：28.3水：0.06。

Claims (14)

1.一种用于脂肪酸F在具有一个或者多个部分填料的塔(1)中进行酯化的方法，该填料除了起反应器作用之外还具有汽提段作用，并形成催化反应区(3)，至少在填料上部固定有催化剂，在该方法中，进行脂肪酸F和相同或者过量摩尔比率的醇A的多相催化，通过汽化在贮槽中产生富含醇的气态逆流，
通过作为汽提气(50)的逆流从反应区除去水，
负载的汽提气(60)在塔顶端至少部分液化，
塔顶产物被分离成富含水的馏分(63)以及富含醇的馏分(62)，以及
富含醇的馏分作为酯化作用和生产汽提气(50)的原料回到该流程。
2.根据权利要求1的方法，其特征在于，在汽提段的下部填料部分(4)中，来自于催化反应区(3)的液体混合物中的水和醇被汽提气(50)吸收。
3.根据权利要求1的方法，其特征在于另外的填料(8)装置在汽提段的上方，且在所述填料(8)中，携带汽提气(60)的脂肪酸被富含醇并返回的馏分(62)的部分(68)捕获。
4.根据权利要求1-3中任一项的方法，其特征在于，醇进入催化反应区(3)或者其下方，其以气态形式与汽提气(50，50’)合并。
5.根据权利要求1-3中任一项的方法，其特征在于，在相分离器或者蒸馏塔中通过全蒸发过程把塔顶产物分离变成富含水的馏分(63)和富含醇的馏分(62)。
6.根据权利要求1-3中任一项的方法，其特征在于，原料A和F在预反应器(2)中进行部分的酯化作用，这样形成的脂肪酸F、醇A、酯E和水W的混合物进入塔(1)的催化反应区(3)。
7.根据权利要求1-3中任一项的方法，其特征在于通过弛豫蒸发器(9)或者蒸馏塔并在分离塔(70)中进一步地制备部分液态贮槽混合物，从而最后得到脂肪酸酯E，其纯度至少为99重量％。
8.根据权利要求1-3中任一项的方法，其特征在于，以下原料适合用作酯化作用的脂肪酸F和醇A：C12-、  C14-、C16-或C18-脂肪酸中的一种，和甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇或2-乙基己醇中的一种醇。
9.根据权利要求8的方法，其特征在于所述脂肪酸选自月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、油酸或亚麻酸。
10.根据权利要求1-3中任一项的方法，其特征在于无机催化剂用作催化剂，或者使用离子交换树脂作催化剂。
11.根据权利要求10的方法，其特征在于在150-230℃的温度下使用无机催化剂。
12.根据权利要求10的方法，其特征在于催化剂以强酸形式存在。
13.根据权利要求10的方法，其特征在于将离子交换树脂制备成大孔隙的离子交换树脂。
14.一种利用权利要求1-13中的任一项的方法通过多相催化生产酯E的装置，其特征在于，塔(1)具有用于进行多相催化的填料部分的催化反应区(3)，该填料部分包括含有催化剂的颗粒状材料的层(31)和在催化剂的颗粒状材料之间作为汽提气(50′)的流动通道(32)，其中，在催化剂的颗粒状材料的孔中进行所述方法时，待处理的混合物形成直接向下流动的液体(10′)，汽提气形成直接向上流动的物流并且液相与气相直接接触以便发生物质交换。
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US20060199971A1 (en) 2006-09-07
CN1504452A (zh) 2004-06-16
US20040106813A1 (en) 2004-06-03
TW200410933A (en) 2004-07-01
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US7091367B2 (en) 2006-08-15
MY142637A (en) 2010-12-15
KR101105256B1 (ko) 2012-01-17
JP2004175794A (ja) 2004-06-24
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JP4572067B2 (ja) 2010-10-27
MXPA03010593A (es) 2004-06-03

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