CN107033977A - 一种用于甲醇柴油的互溶剂及其制备方法 - Google Patents

一种用于甲醇柴油的互溶剂及其制备方法 Download PDF

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CN107033977A
CN107033977A CN201710315525.8A CN201710315525A CN107033977A CN 107033977 A CN107033977 A CN 107033977A CN 201710315525 A CN201710315525 A CN 201710315525A CN 107033977 A CN107033977 A CN 107033977A
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齐文刚
齐金梅
张荣海
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Abstract

本发明涉及一种用于甲醇柴油的互溶剂及其制备方法,本发明的甲醇柴油互溶剂为蓖麻油聚醚和蓖麻油聚醚酯，亲油基团主要是脂环、芳环、环氧丙烷，对柴油紧密的包覆；亲水基团主要是羟基、环氧乙烷，可以连接更多甲醇中的羟基；该助剂配制的甲醇柴油质量稳定，外观清澈透明，不浑浊，不分层，储存时间长，能够与国标柴油任意比例混合，不发生乳化现象;同时,蓖麻油、油酸、腐殖酸价廉、易得、环保。

Description

一种用于甲醇柴油的互溶剂及其制备方法
技术领域
本发明涉及一种互溶剂，具体涉及一种用于甲醇柴油的互溶剂及其制备方法。
背景技术
甲醇柴油是柴油、甲醇以及可选的添加剂按照一定的体积或质量比经过严格的流程调配而成的燃料。甲醇柴油的使用既可节约石油资源、降低成本，又能降低空气污染，是一种环保清洁的新型能源，受到了广泛的关注。
尽管甲醇柴油相对于传统的石化资源具有非常明显的优势，但其自身也存在各种缺陷，如腐蚀性高、互溶性差、闪点低、动力性差等，其中重要的一项就是甲醇和柴油的互溶性差。甲醇属于极性分子，柴油中的烷烃类成分属于非极性分子，根据相似相溶原理，甲醇和柴油很难相互融合。为克服现有甲醇柴油互溶性差、性能不佳等技术缺陷， 本发明旨在提供一种用于甲醇柴油的互溶剂及其制备方法，克服现有技术的缺点。
发明内容
本发明的目的在于提供一种用于甲醇柴油的互溶剂及其制备方法，本发明采用的技术方案为：
所述的甲醇柴油互溶剂为通式A和通式B，所述的通式A为：
所述的通式B为：
其中R为油酸、腐殖酸， EO为环氧乙烷，PO为环氧丙烷； m为4-16的整数，n为4-16的整数，n/m=1-2。
本发明进一步提供了甲醇柴油互溶剂的制备方法，包含以下步骤：
（1）蓖麻油聚醚的合成：将起始剂蓖麻油加入反应釜，同时加入催化剂氢氧化钾（温度低时反应较难，氢氧化钾可以多加点，温度高时反应较容易，氢氧化钾可以少点），开搅拌，升温至80～120℃，并通过抽真空或分子筛吸附脱水方式，去除水分至水分的重量比小于0.3%，然后升温至150～170℃，加入环氧乙烷，加完后在135～165℃保温熟化25-40min，然后加入环氧丙烷，其中环氧乙烷、环氧丙烷相对于起始剂蓖麻油的摩尔比为4～16：4～16：1，反应完成后在135～165℃保温熟化30-45min，降温到80-95℃后加入磷酸调节pH值至6-7，得到蓖麻油聚醚。
（2）蓖麻油聚醚酯的合成：将步骤（1）得到的蓖麻油聚醚与有机酸（如油酸或腐殖酸）混合，蓖麻油聚醚与有机酸的摩尔比为1-3：0.8-1.0，再加入催化剂对甲苯磺酸和溶剂甲苯，通过溶剂甲苯回流法在温度130～140℃条件下回流反应2-4小时，反应完全后回收甲苯，得到蓖麻油聚醚酯。
进一步的，所述通式A和通式B的重量份比值为30-70：30-70。
本发明的甲醇柴油互溶剂为蓖麻油聚醚和蓖麻油聚醚酯，亲油基团主要是脂环、芳环、环氧丙烷，对柴油紧密的包覆；亲水基团主要是羟基、环氧乙烷，可以连接更多甲醇中的羟基；该助剂配制的甲醇柴油质量稳定，外观清澈透明，不浑浊，不分层，储存时间长，能够与国标柴油任意比例混合，不发生乳化现象;同时,蓖麻油、油酸、腐殖酸价廉、易得、环保，具有较好的经济效益。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1
1、将起始剂1mol蓖麻油加入反应釜，同时加入1.2g氢氧化钾催化剂，开搅拌，升温至100-120℃，缓慢分批加入10mol环氧乙烷，加完后140±5℃保温熟化25min，然后分批加入10mol环氧丙烷，反应完成后140±5℃保温熟化45min，降温至85℃后用磷酸调节PH值至6-7，得到蓖麻油聚醚-1。
2、将步骤1中所制得的蓖麻油聚醚-1与油酸按摩尔比1：0.8的比例加入反应釜中，加入0.15mol的对甲苯磺酸作催化剂，同时加入甲苯溶剂15mol，搅拌升温至130-140℃回流反应2-4h，回收甲苯后，温度降至45-55℃后得到蓖麻油聚醚油酸酯。
3、将30份（重量比）蓖麻油聚醚-1和70份蓖麻油聚醚油酸酯投入到不锈钢反应釜，加热升温到50-60℃，搅拌2-3小时，即得到互溶剂-01。
实施例2
1、将起始剂1mol蓖麻油加入反应釜，同时加入1.2g氢氧化钾催化剂，开搅拌，升温至100-120℃，缓慢分批加入16mol环氧乙烷，加完后140±5℃保温熟化25min，然后分批加入8mol环氧丙烷，反应完成后140±5℃保温熟化45min，降温至85℃后用磷酸调节PH值至6-7，得到蓖麻油聚醚-2。
2、将步骤1中所制得的蓖麻油聚醚-2与腐殖酸按摩尔比3：0.8的比例加入反应釜中，加入0.15mol的对甲苯磺酸作催化剂，同时加入甲苯溶剂15mol，搅拌升温至130-140℃回流反应2-4h，回收甲苯后，温度降至45-55℃后得到蓖麻油聚醚的腐殖酸酯。
3、将70份（重量比）蓖麻油聚醚-2和30份蓖麻油聚醚腐殖酸酯投入到不锈钢反应釜，加热升温到50-60℃，搅拌2-3小时，即得到互溶剂-02。
以下通过实验结果说明本发明的效果性能:
以实施例一与实施例二制备出的甲醇柴油互溶剂的性能说明：
例一：表1.1为甲醇柴油的配方表，表1.2为表1.1配方中各项性能指标表。
表1.1
组分 重量百分比，%
柴油 60
互溶剂-01 20
甲醇 20
表1.2
外观 透明液体
密度，20摄氏度 0.849
常贮稳定性（6个月） 合格
例二：表2.1为甲醇柴油的配方表，表2.2为表2.1配方中各项性能指标表。
表2.1
组分 重量百分比，%
柴油 55
互溶剂-02 15
甲醇 30
表2.2
外观 透明液体
密度，20摄氏度 0.842
常贮稳定性（6个月） 合格

Claims (4)

1.一种用于甲醇柴油的互溶剂, 其特征在于,所述的甲醇柴油互溶剂为通式A和通式B，所述的通式A为：
所述的通式B为：
其中R为油酸、腐殖酸， EO为环氧乙烷，PO为环氧丙烷； m为4-16的整数，n为4-16的整数，n/m=1-2。
2.根据权利要求1所述的用于甲醇柴油的互溶剂的制备方法，其特征在于, 所述的互溶剂的制备方法包含以下步骤：
（1）蓖麻油聚醚的合成：将起始剂蓖麻油加入反应釜，同时加入催化剂氢氧化钾（温度低时反应较难，氢氧化钾可以多加点，温度高时反应较容易，氢氧化钾可以少点），开搅拌，升温至80～120℃，并通过抽真空或分子筛吸附脱水方式，去除水分至水分的重量比小于0.3%，然后升温至150～170℃，加入环氧乙烷，加完后在135～165℃保温熟化25-40min，然后加入环氧丙烷，其中环氧乙烷、环氧丙烷相对于起始剂蓖麻油的摩尔比为4～16：4～16：1，反应完成后在135～165℃保温熟化30-45min，降温到80-95℃后加入磷酸调节pH值至6-7，得到蓖麻油聚醚;
（2）蓖麻油聚醚酯的合成：将步骤（1）得到的蓖麻油聚醚与有机酸（如油酸或腐殖酸）混合，蓖麻油聚醚与有机酸的摩尔比为1-3：0.8-1.0，再加入催化剂对甲苯磺酸和溶剂甲苯，通过溶剂甲苯回流法在温度130～140℃条件下回流反应2-4小时，反应完全后回收甲苯，得到蓖麻油聚醚酯;
所述通式A和通式B的重量份比值为30-70：30-70。
3.根据权利要求1所述的用于甲醇柴油的互溶剂的制备方法，其特征在于, 所述的互溶剂的制备方法包含以下步骤：
（1）、将起始剂1mol蓖麻油加入反应釜，同时加入1.2g氢氧化钾催化剂，开搅拌，升温至100-120℃，缓慢分批加入10mol环氧乙烷，加完后140±5℃保温熟化25min，然后分批加入10mol环氧丙烷，反应完成后140±5℃保温熟化45min，降温至85℃后用磷酸调节PH值至6-7，得到蓖麻油聚醚-1;
(2）、将步骤1中所制得的蓖麻油聚醚-1与油酸按摩尔比1：0.8的比例加入反应釜中，加入0.15mol的对甲苯磺酸作催化剂，同时加入甲苯溶剂15mol，搅拌升温至130-140℃回流反应2-4h，回收甲苯后，温度降至45-55℃后得到蓖麻油聚醚油酸酯;
（3）、将30份（重量比）蓖麻油聚醚-1和70份蓖麻油聚醚油酸酯投入到不锈钢反应釜，加热升温到50-60℃，搅拌2-3小时，即得到互溶剂-01。
4.根据权利要求1所述的用于甲醇柴油的互溶剂的制备方法，其特征在于, 所述的互溶剂的制备方法包含以下步骤：
（1）、将起始剂1mol蓖麻油加入反应釜，同时加入1.2g氢氧化钾催化剂，开搅拌，升温至100-120℃，缓慢分批加入16mol环氧乙烷，加完后140±5℃保温熟化25min，然后分批加入8mol环氧丙烷，反应完成后140±5℃保温熟化45min，降温至85℃后用磷酸调节PH值至6-7，得到蓖麻油聚醚-2;
(2）、将步骤1中所制得的蓖麻油聚醚-2与腐殖酸按摩尔比3：0.8的比例加入反应釜中，加入0.15mol的对甲苯磺酸作催化剂，同时加入甲苯溶剂15mol，搅拌升温至130-140℃回流反应2-4h，回收甲苯后，温度降至45-55℃后得到蓖麻油聚醚的腐殖酸酯;
(3)、将70份（重量比）蓖麻油聚醚-2和30份蓖麻油聚醚腐殖酸酯投入到不锈钢反应釜，加热升温到50-60℃，搅拌2-3小时，即得到互溶剂-02。
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