CN113754879A - 一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法 - Google Patents
一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法 Download PDFInfo
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Abstract
本发明涉及一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,其特征在于,先制备烯丙基聚氧乙烯醚,然后合成溴丙基聚氧乙烯醚,最终制得烷基聚氧乙烯醚季铵盐。本发明产品具有复配能力强、界面活性高、硬水中易分散的特点。本发明产品具有优良的乳化、润湿性能,在酸碱及高盐环境中不受影响,适合油田酸化、钻井、注水、稠油降粘等作业施工中使用。
Description
技术领域
本发明涉及一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法。
背景技术
阳离子表面活性剂是在日化、油田化学、工业清洗领域广发使用的一种表面活性剂。
在日化和工业清洗领域,阳离子表面活性剂具有去污、杀菌、气泡等优异性能,同时也可以让织物柔软、富有弹性,所以在织物柔顺剂、洗发液、护发素、杀菌洗手液等产品中被广泛使用。但是,在使用过程中阳离子表活剂无法与使用量最大的十二烷基苯磺酸钠、脂肪酸甲酯磺酸钠、脂肪酸皂等阴离子表活剂复配使用,很大程度上限制了其使用量和在日化品中性能的发挥。
在油田化学领域,阳离子表面活性剂能够与原油中的胶质、沥青质产生界面反应,从而具有良好的降低界面张力、乳化降黏、洗油驱油等能力,具有良好的应用前景。但是,阳离子表活剂易与驱油用聚合物(部分水解聚丙烯酰胺)反应,导致聚合物粘度降低,因此无法在油田二元复合驱中使用;地层岩石表面显负电性,阳离子表面活性剂极易在岩石表面吸附,从而失效,因此在大多数工况下无法使用;阳离子表活剂无法与油田化学驱中常用的十二烷基苯磺酸钠、重烷基苯磺酸、石油磺酸盐等阴离子表活剂复配使用。
基于以上阳离子表面活性剂在使用过程中存在的问题,本发明开发一种含有聚氧乙烯醚结构的季铵盐阳离子表面活性剂,通过在常规季铵盐类表活剂的尾部通过化学反应,接枝一定聚合度的聚氧乙烯醚,从而提高其亲水性、降低其正电中心的电荷强度、提高其正电中心与其他阴离子表活剂反应的位阻强度。
实现能够与阴离子表活剂复配的能力、提高其抗硬水能力、降低在油田化学驱过程中与地层岩石的吸附量,从而提高其应用范围。
发明内容
本发明的目的在于提供一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,该方法制备的产品具有复配能力强、界面活性高、硬水中易分散的特点。
为了解决上述技术问题,本发明采用以下技术方案:
一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,按照以下步骤进行:
1)制备烯丙基聚氧乙烯醚
将丙烯醇和催化剂氢氧化钾加入到不锈钢反应釜内,通入氮气置换5min,开启搅拌,设定转速为300r/min,设定反应温度130~135℃,当釜内温度稳定在设定温度时,开启进料泵,反应釜内注入环氧乙烷,环氧乙烷与丙烯醇的质量比为2~5:1,保持温度为130~135℃,反应5~6h,降温至30℃,得烯丙基聚氧乙烯醚;丙烯醇和氢氧化钾的质量比为99.5~99.9:0.1~0.5;
2)制备溴丙基聚氧乙烯醚乙醇溶液
将45%的氢溴酸水溶液、烯丙基聚氧乙烯醚和乙醇按照质量比1:2~5:2~5加入到三口烧瓶中;安装回流冷凝管,开启冷水;启动电动搅拌,转速为200r/min,在温度为20~30℃条件下,反应1~1.5h,加热至80℃,回流反应1~2h,得到溴丙基聚氧乙烯醚乙醇溶液。
3)制备烷基聚氧乙烯醚季铵盐
将十二十四烷基二甲基叔胺或十六十八烷基叔胺、溴丙基聚氧乙烯醚乙醇溶液和水,按照质量比1:2~7:1~5加入三口烧瓶中,安装回流冷凝管,并打开冷水;开启电动搅拌,设定转速为200r/min;在温度为80℃条件下,回流反应4~6h,当物料pH=6~6.5时,加入NaOH水溶液调节pH=7.5~8,;提高反应温度至105℃,回流反应4h,得烷基二甲基聚氧乙烯醚季铵盐;
步骤1)中所述加热为加热至温度为130~135℃;所述降温为降温至30~50℃。
所述氢氧化钠水溶液中氢氧化钠的浓度为32%。
发明具有以下有益技术效果:
1.本身制备的烷基聚氧乙烯醚季铵盐可以与常规阴离子表活剂复配使用,复配体系具有很低的表面张力和界面活性。
2.本身制备的烷基聚氧乙烯醚季铵盐可以在日化品中复配使用,在保证自身的杀菌、柔顺、保湿性能的同时,不会影响原有成分的洗涤性能。
3.本身制备的烷基聚氧乙烯醚季铵盐可以在油田化学品中添加使用,能够很大程度上提高产品的界面活性、洗油能力和乳化能力,不与聚合物、阴离子表活剂、石油磺酸盐等产品反应。
4.本身制备的烷基聚氧乙烯醚季铵盐具有良好的水溶性、抗硬水能力,可以应用在钙、镁含量较高的环境中。
具体实施方式
下面结合具体实例进一步说明本发明。
实施例1合成12/14烷基二甲基聚氧乙烯醚n5氯化胺
(1)将丙烯醇200g和催化剂氢氧化钾0.4g加入到不锈钢反应釜内,通入氮气置换5min,开启搅拌,设定转速300r/min。设定反应温度130℃,当釜内温度稳定在设定温度时,开启进料泵,从环氧乙烷钢瓶向反应釜内注入环氧乙烷900g。维持130℃反应5~6h,降温至40℃,得烯丙基聚氧乙烯醚n5;
(2)制备溴丙基聚氧乙烯醚乙醇溶液
将氢溴酸水溶液(45%)114g、烯丙基聚氧乙烯醚n5 200g和乙醇188g加入到三口烧瓶中;安装回流冷凝管,开启冷水;启动电动搅拌,转速为200r/min;设定反应温度30℃,反应1~h;加热至80℃,回流反应2h,得到溴丙基聚氧乙烯醚乙醇溶液。
取5~8g溴丙基聚氧乙烯醚乙醇溶液,放入锥形瓶中,加入150ml纯水,摇晃溶解,加入2~3滴酚酞指示剂,0.0988mol/L浓度NaOH标准溶液进行滴定,当溶液由无色变为粉红色时,停止滴定。平行滴定三次,取平均值,计算反应产率。
(3)制备烷基聚氧乙烯醚季铵盐
将12/14烷基二甲基叔胺50g、溴丙基聚氧乙烯醚n5乙醇溶液211.8g、水80g,加入三口烧瓶中。安装回流冷凝管,并打开冷水;开启电动搅拌,设定转速200r/min;温度为80℃,回流反应4h;提高反应温度至105℃,回流反应4h。完成12/14烷基二甲基聚氧乙烯醚季铵盐的制备;
通过酸碱滴定,计算剩余叔胺含量,进而计算产率。取12/14烷基二甲基聚氧乙烯醚季铵盐5~7g,放入锥形瓶中,加入50ml乙醇,100ml水,摇晃溶解。加入2~3滴酚酞指示剂,用0.0988mol/L浓度NaOH标准溶液进行滴定,当溶液由无色变为粉红色时,停止滴定。用0.1036mol/L浓度HCl标准溶液进行滴定,当粉红色刚刚退去,停止滴定。加入2~3滴甲基红~亚甲基蓝指示剂,用0.1036mol/L浓度HCl标准溶液进行滴定,当溶液由绿色变为红色时,停止滴定,记录消耗的HCl标准溶液的体积。滴定三次,取平均值进行计算。
在反应4h后,没有使用NaOH溶液进行pH值调节,最终产品收率偏低,只有76.40%。
实施例2合成12/14烷基二甲基聚氧乙烯醚n5氯化胺
选用实施例1合成的溴丙基聚氧乙烯醚n5直接进行季铵化反应。
将12/14烷基二甲基叔胺50g、溴丙基聚氧乙烯醚n5乙醇溶液211.8g、水80g,加入三口烧瓶中。安装回流冷凝管,并打开冷水;开启电动搅拌,设定转速200r/min;温度为80℃,回流反应4h;测定pH=6.3,加入5.17gNaOH水溶液(32%),此时pH=7.8;提高反应温度至105℃,回流反应4h。完成12/14烷基二甲基聚氧乙烯醚季铵盐的制备;
通过酸碱滴定,计算剩余叔胺含量,进而计算产率。取12/14烷基二甲基聚氧乙烯醚季铵盐5~7g,放入锥形瓶中,加入50ml乙醇,100ml水,摇晃溶解。加入2~3滴酚酞指示剂,用0.0988mol/L浓度NaOH标准溶液进行滴定,当溶液由无色变为粉红色时,停止滴定。用0.1036mol/L浓度HCl标准溶液进行滴定,当粉红色刚刚退去,停止滴定。加入2~3滴甲基红~亚甲基蓝指示剂,用0.1036mol/L浓度HCl标准溶液进行滴定,当溶液由绿色变为红色时,停止滴定,记录消耗的HCl标准溶液的体积。滴定三次,取平均值进行计算。
在反应4h后,使用NaOH对反应液进行pH调节,然后提高反应温度继续反应,最终12/14叔胺转化率提高到91.77%。可见,反应过程中的pH调节,对转化率有着直接的影响。
实施例3合成16/18烷基二甲基聚氧乙烯醚n10氯化胺
(1)将丙烯醇100g和催化剂氢氧化钾0.4g加入到不锈钢反应釜内,通入氮气置换5min,开启搅拌,设定转速300r/min。设定反应温度130℃,当釜内温度稳定在设定温度时,开启进料泵,从环氧乙烷钢瓶向反应釜内注入环氧乙烷900g。维持130℃反应5~6h,降温至40℃,得烯丙基聚氧乙烯醚n10;
(2)制备溴丙基聚氧乙烯醚n10乙醇溶液
将氢溴酸水溶液(45%)114g、烯丙基聚氧乙烯醚n10 400g和乙醇390g加入到三口烧瓶中;安装回流冷凝管,开启冷水;启动电动搅拌,转速为200r/min;设定反应温度30℃,反应1~h;加热至80℃,回流反应2h,得到溴丙基聚氧乙烯醚n10乙醇溶液。
取5~8g溴丙基聚氧乙烯醚n10乙醇溶液,放入锥形瓶中,加入150ml纯水,摇晃溶解,加入2~3滴酚酞指示剂,0.0988mol/L浓度NaOH标准溶液进行滴定,当溶液由无色变为粉红色时,停止滴定。平行滴定三次,取平均值,计算反应产率。
(3)制备烷基聚氧乙烯醚季铵盐
将16/18烷基二甲基叔胺60g、溴丙基聚氧乙烯醚n10乙醇溶液295g、乙醇100g,加入三口烧瓶中。安装回流冷凝管,并打开冷水;开启电动搅拌,设定转速200r/min;温度为80℃,回流反应4h;测定pH=6.3,加入2.9gNaOH水溶液(32%),调节pH=7.7;提高反应温度至105℃,回流反应4h。完成12/14烷基二甲基聚氧乙烯醚季铵盐n10的制备;
通过酸碱滴定,计算剩余叔胺含量,进而计算产率。取16/18烷基二甲基聚氧乙烯醚季铵盐n105~7g,放入锥形瓶中,加入50ml乙醇,100ml水,摇晃溶解。加入2~3滴酚酞指示剂,用0.0988mol/L浓度NaOH标准溶液进行滴定,当溶液由无色变为粉红色时,停止滴定。用0.1036mol/L浓度HCl标准溶液进行滴定,当粉红色刚刚退去,停止滴定。加入2~3滴甲基红~亚甲基蓝指示剂,用0.1036mol/L浓度HCl标准溶液进行滴定,当溶液由绿色变为红色时,停止滴定,记录消耗的HCl标准溶液的体积。滴定三次,取平均值进行计算。
在反应8h后,以16/18烷基二甲基叔胺计算,产率达到了93.83%。产品有效物浓度达到33.98%。
实施例4合成油酸酰胺丙基二甲基聚氧乙烯醚n10氯化胺
直接取用实施例3合成的溴丙基聚氧乙烯醚n10。
将油酸酰胺丙基二甲基叔胺60g、溴丙基聚氧乙烯醚n10乙醇溶液228g、乙醇100g,加入三口烧瓶中。安装回流冷凝管,并打开冷水;开启电动搅拌,设定转速200r/min;温度为80℃,回流反应4h;测定pH=6.4,加入3.5gNaOH水溶液(32%),调整pH=7.6;提高反应温度至105℃,回流反应4h。完成油酸酰胺丙基二甲基聚氧乙烯醚季铵盐n10的制备;
通过酸碱滴定,计算剩余叔胺含量,进而计算产率。取油酸酰胺丙基二甲基聚氧乙烯醚季铵盐n105~7g,放入锥形瓶中,加入50ml乙醇,100ml水,摇晃溶解。加入2~3滴酚酞指示剂,用0.0988mol/L浓度NaOH标准溶液进行滴定,当溶液由无色变为粉红色时,停止滴定。用0.1036mol/L浓度HCl标准溶液进行滴定,当粉红色刚刚退去,停止滴定。加入2~3滴甲基红~亚甲基蓝指示剂,用0.1036mol/L浓度HCl标准溶液进行滴定,当溶液由绿色变为红色时,停止滴定,记录消耗的HCl标准溶液的体积。滴定三次,取平均值进行计算。
本制备方法也可以使用在酰胺类叔胺制备聚氧乙烯醚季铵盐。
下面结合实验数据进一步说明本发明的有益效果:
本发明产品用于稠油降粘驱油剂:
本发明产品12/14烷基二甲基聚氧乙烯醚n5氯化胺应用于胜利油田某区块稠油降粘驱油剂。该区块注入水矿化度82506mg/L,矿化度较高,稠油相对密度0.985,稠油粘度12800mPa·s。要求产品能够对稠油具有乳化降粘能力,同时具有超低油、水界面张力,能够起到驱油的作用。12/14烷基二甲基聚氧乙烯醚n5氯化胺)用注入水配置成0.3%浓度的溶液,进行性能检测。检测结果如下表所示:
本专利产品12/14烷基二甲基聚氧乙烯醚n5氯化胺具有很高的界面活性,能够将稠油与注入水的界面张力降低至4.9×10~2mN/m。同时,阳离子表面活性剂可以与稠油中的胶质、沥青质产生界面化学作用,更加有利于稠油的乳化降粘。特别适合于油田稠油降粘驱油剂的使用。
本发明产品用于二元复合驱:
二元复合驱是胜利油田大规模使用的增产手段,要求驱油剂产品具有超低界面张力,优异的洗油能力,同时不能对聚合物粘度产生负面影响。
本专利产品实施例2制备的12/14烷基二甲基聚氧乙烯醚n5氯化胺与常规阴离子表活剂复配后,使用于二元复合驱,效果显著。
配方如下:
名称 | 浓度,% | 加入量,% |
12/14烷基二甲基聚氧乙烯醚n5氯化胺 | 33 | 30 |
十二烷基苯磺酸钠 | 40 | 20 |
脂肪醇聚氧乙烯醚硫酸钠 | 75 | 15 |
脂肪酸二乙醇胺 | 100 | 10 |
水 | 25 |
将上表中的各种表活剂,按照比例混合均匀配制成产品,用注入水配制成0.3%浓度的溶液,用注入水配制含有聚合物0.18%、产品0.3%的二元驱溶液,进行性能测试。为了对比12/14烷基二甲基聚氧乙烯醚n5氯化胺的性能,做了两组平行测试,测试1按照配方进行;测试2去除12/14烷基二甲基聚氧乙烯醚n5氯化胺后进行。测试结果如下:
如上表所示,在加入12/14烷基二甲基聚氧乙烯醚n5氯化胺后,产品的界面张力,加聚张力,都有明显的改善。这是因为12/14烷基二甲基聚氧乙烯醚n5氯化胺与十二烷基苯磺酸钠形成了界面活性非常强的离子对表活剂,这种离子对表活剂更易在油、水界面吸附,因此具有很高的降低界面张力的能力。随着界面张力的降低,加入12/14烷基二甲基聚氧乙烯醚n5氯化胺的产品,洗油效率也明显提升。
Claims (3)
1.一种烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,其特征在于,按照以下步骤进行:
1)制备烯丙基聚氧乙烯醚
将丙烯醇和催化剂氢氧化钾加入到不锈钢反应釜内,通入氮气置换5min,开启搅拌,设定转速为300r/min,设定反应温度130~135℃,当釜内温度稳定在设定温度时,开启进料泵,反应釜内注入环氧乙烷,环氧乙烷与丙烯醇的质量比为2~5:1,保持温度为130~135℃,反应5~6h,降温至30℃,得烯丙基聚氧乙烯醚;丙烯醇和氢氧化钾的质量比为99.5~99.9:0.1~0.5;
2)制备溴丙基聚氧乙烯醚乙醇溶液
将45%的氢溴酸水溶液、烯丙基聚氧乙烯醚和乙醇按照质量比1:2~5:2~5加入到三口烧瓶中;安装回流冷凝管,开启冷水;启动电动搅拌,转速为200r/min,在温度为20~30℃条件下,反应1~1.5h,加热至80℃,回流反应1~2h,得到溴丙基聚氧乙烯醚乙醇溶液;
3)制备烷基聚氧乙烯醚季铵盐
将十二十四烷基二甲基叔胺或十六十八烷基叔胺、溴丙基聚氧乙烯醚乙醇溶液和水,按照质量比1:2~7:1~5加入三口烧瓶中,安装回流冷凝管,并打开冷水;开启电动搅拌,设定转速为200r/min;在温度为80℃条件下,回流反应4~6h,当物料pH=6~6.5时,加入NaOH水溶液调节pH=7.5~8,;提高反应温度至105℃,回流反应4h,得烷基二甲基聚氧乙烯醚季铵盐。
2.如权利要求1所述的烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,其特征在于,步骤1)中所述加热为加热至温度为130~135℃;所述降温为降温至30~50℃。
3.如权利要求1所述的烷基聚氧乙烯醚季铵盐表面活性剂的合成方法,其特征在于,所述氢氧化钠水溶液中氢氧化钠的浓度为32%。
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