CN1296003A - 3－氯－2－羟丙基三甲基氯化铵有机副产物的分离方法 - Google Patents

3－氯－2－羟丙基三甲基氯化铵有机副产物的分离方法 Download PDF

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CN1296003A
CN1296003A CN 99112538 CN99112538A CN1296003A CN 1296003 A CN1296003 A CN 1296003A CN 99112538 CN99112538 CN 99112538 CN 99112538 A CN99112538 A CN 99112538A CN 1296003 A CN1296003 A CN 1296003A
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ammonium chloride
trimethyl ammonium
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CN1119320C (zh
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安丰发
菅秀君
刘燕
刘莹
万永翔
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Qilu Petrochemical Co of Sinopec
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Abstract

一种3－氯－2－羟丙基三甲基氯化铵中二氯丙醇和环氧氯丙烷的分离方法,在填料塔中用水蒸汽进行连续减压汽提。在汽液比0.5～5.0,真空度为0.060～0.098的条件下,能够使该产品中二氯丙醇的含量降为10ppm以下,环氧氯丙烷的含量降为5ppm以下,同时使产品提浓10%以上。该分离方法克服了共沸蒸馏、减压蒸馏后产品中二氯丙醇含量高和产品易变色的缺点,提高了产品质量,降低了能耗。

Description

3-氯-2-羟丙基三甲基氯化铵有机副产物的分离方法
本发明是关于3-氯-2-羟丙基三甲基氯化铵(简称CHPTMA)中有机副产物的分离方法。
CHPTMA是一种重要的带有活性基团的阳离子表面活性剂，可用作油田钻井助剂、相转移催化剂、乳化剂、固色剂、硬水软化剂等，它最大的用途是对淀粉、纤维素等高分子物质进行改性，生成可生物降解的阳离子淀粉或阳离子纤维素，广泛用于造纸工业中的增强剂、助留助滤剂、中性施胶的配套助剂。
以三甲胺、盐酸和环氧氯丙烷为原料合成CHPTMA的方法有两种：有机溶剂法和水溶液法。两种方法都易生成副产物1,3-二氯丙醇。1,3-二氯丙醇是环氧氯丙烷在酸性条件下水解得来的，在CHPTMA与淀粉反应的过程中，微量的二氯丙醇就能与淀粉发生交联作用，严重影响产品质量；另外，1,3-二氯丙醇沸点高，不与水等多种物质共沸，通常的蒸馏方法不易脱除干净。为了解决这一难题，国内外化学工作者做了大量工作，以去除有机副产物，提高CHPTMA的产品质量。例如JP90295952公开了在填料塔中减压水汽蒸馏去除CHPTMA产品中的环氧氯丙烷及二氯丙醇，所用填料为聚乙烯、聚丙烯等合成树脂或磁制填料。具体方法是：塔顶部装满填料CHPTMA粗反应液从塔顶加入，水蒸汽从塔下部对流通入塔内。反应液加完后，一次性排出釜底液。该工艺为半连续工艺，连续进料，间歇出料。对CHPTMA粗反应液连续水汽蒸馏3次，产品中环氧氯丙烷及二氯丙醇含量才能达到10ppm以下；蒸馏后产品浓度不变，与粗反应液一致。
本发明的目的在于提供一种同时脱除CHPTMA中的1,3-二氯丙醇及环氧氯丙烷并浓缩产品的有效方法—减压水蒸汽汽提法。使用该方法，连续汽提一次，二氯丙醇含量能达到10ppm以下。由于塔釜液连续不断地排出，避免了热敏性物料CHPTMA的分解，塔底产品为无色透明水溶液。
本发明所采用的技术方案是在填料塔中进行，在减压的条件下，CHPTMA粗水溶液和水蒸汽对流接触，同时汽提去除CHPTMA粗水溶液中的环氧氯丙烷和1,3-二氯丙醇，并将产品水溶液浓度浓缩10％(w)或以上。
具体的方法是：将填料装入汽提塔中，塔顶部连接冷凝器，冷凝器下部依次装有汽液分离器、废料罐，并与排气泵相连；塔内减压。塔釜带有夹套，可通油浴或蒸汽加热；其下部连接产品罐。产品罐通过缓冲罐与排气泵连接。由填料塔的上部加入CHPTMA的粗水溶液，质量流量计计量。水蒸汽由塔釜上部通入，通过蒸汽流量计计量，管道阀门控制流量大小。维持塔釜液位不变，成品经塔釜排入产品罐。
在汽提过程中，影响其产品中二氯丙醇含量的主要因素是汽液比和填料高度，塔的填料高度大，则所需汽液比小；塔的填料高度小，则需要汽液比大；适宜的汽液比为0.5～5.0，最好是0.8～3.0。汽液比太小，有机副产物脱除不干净，CHPTMA产品达不到使用要求；汽液比太大，容易引起泛塔，导致CHPTMA粗反应液从塔顶带出，产品收率下降。适宜的真空度为0.060～0.098mpa，最好是0.080～0.095mpa；真空度低于0.060mpa，产品中1,3-二氯丙醇含量明显增高。
影响汽提塔处理量的主要因素是塔径和填料高度。塔径和填料高度越大，每单位时间的粗液处理量是增加的，即汽提塔进料速度可以增大。
本发明所使用的填料要首先保证能被CHPTMA水溶液润湿良好，且对气液分布要均匀，填料可为不锈钢波纹填料，能被水溶液润湿的塑料波纹填料。
按照本发明提供的方法，汽提一次后产品中环氧氯丙烷≤5ppm,1,3-二氯丙醇≤10ppm，脱除彻底，有效地提高了产品的质量。同时，在汽提过程中，产品可以提浓10％，省去了进一步提浓工序，能耗降低；据本发明的方法，塔顶塔底都连续进料、连续出料，CHPTMA在塔内停留时间短，避免了间歇或半连续蒸馏法下的季铵盐水溶液变色的问题。
下面以实施例来进一步说明本发明。实施例中的组成％，都是质量单位。实施例1
在塔径48mm，填料高度1000mm的填料塔内，填料为6×6的不锈钢波纹填料。CHPTMA粗反应液中含CHPTMA38.4％，环氧氯丙烷0.1％,1,3-二氯丙醇0.9％。粗反应液以2L/h的速度从塔上部进入汽提塔中，水蒸汽从塔底进入，流速3～5Kg/h，操作条件为：汽液比1.5～2.0，真空度是塔顶0.085mpa，塔底0.080mpa；塔顶出料温度36℃～40℃，塔底无夹套，温度为50℃～53℃。每隔1小时取样分析塔釜排出液。釜液中产品浓度40％～43％。其它分析结果见表1。
         表1  汽提试验结果
序号 汽液比 DCH含量/ppm ECH/ppm
H-1H-2H-3H-4H-5H-6H-7H-8 1.51.51.51.52.02.02.02.0 5040404010101010 101010105454
实施例2
填料塔内径80mm，填料高度4000mm，填料为不锈钢波纹填料。CHPTMA粗反应液中含CHPTMA40.1％，环氧氯丙烷0.04％，1,3-二氯丙醇1.0％。粗反应液从塔顶进入，流速10L/h；水蒸汽从塔底上部进入，供给速度7～16Kg/h。汽提塔操作条件为：汽液比为0.80～1.5，塔底真空度为0.088～0.093mpa，塔顶真空度为0.090～0.097mpa；塔顶温度为31.0℃～35.0℃，塔底有夹套油浴加热，温度为52.0℃～56.0℃。每隔1小时分析塔釜排出液，其中CHPTMA产品浓度50％～52％。实验结果见表2。
   表2  产品中1,3-二氯丙醇含量随汽液比的变化
序号 汽液比 DCH含量/ppm ECH/ppm
V-1V-2V-3V-4V-5V-6 0.80∶10.80∶11.0∶11.0∶11.5∶11.5∶1 302820161010 545443
实施例3
与实施例2同样的填料塔及操作条件精制CHPTMA粗反应液。进料条件为：粗反应液中含CHPTMA58.1％，环氧氯丙烷0.1％,1,3-二氯丙醇2.5％；粗反应液供给速度10L/h，水蒸汽供给速度21～26Kg/h。塔釜排出液产品浓度68％～71％。实验结果见表3。
表3 1,3-二氯丙醇含量高的粗反应液汽提结果
序号 汽液比 DCH含量(ppm) ECH(ppm)
R-1R-2R-3R-4 2.0∶12.0∶12.5∶12.5∶1 50431010 8644

Claims (9)

1．一种3-氯2-羟丙基三甲基氯化铵中有机副产物的分离方法，包括连续减压水蒸汽汽提，除去产品中残留的环氧氯丙烷和二氯丙醇，从而使3-氯-2-羟丙基三甲基氯化铵产品中环氧氯丙烷和二氯丙醇的总含量不大于15ppm。
2．如权利要求1所述的方法，所述的3-氯2-羟丙基三甲基氯化铵为30％～70％的水溶液。
3．如权利要求1所述的方法，所需汽液比为0.5～5.0。
4．如权利要求1所述的方法，所需汽液比为0.8～3.0。
5．如权利要求1所述的方法，真空度为0.060～0.098mpa。
6．如权利要求1所述的方法，真空度为0.080～0.095mpa。
7．如权利要求1所述的方法，汽提塔所用的填料为波纹填料。
8．如权利要求1所述的方法，所用填料为塑料或不锈钢波纹填料。
9．如权利要求1所述的方法，在汽提过程中产品提浓10％以上。
CN99112538A 1999-11-10 1999-11-10 3－氯－2－羟丙基三甲基氯化铵有机副产物的分离方法 Expired - Fee Related CN1119320C (zh)

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