CN114685276B - 一种乙烯羰基化制备丙酸酯类产品的方法 - Google Patents
一种乙烯羰基化制备丙酸酯类产品的方法 Download PDFInfo
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- 239000005977 Ethylene Substances 0.000 title claims abstract description 41
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 18
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- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
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Abstract
本发明涉及一种乙烯羰基化制备丙酸酯类产品的方法,以一氧化碳、乙烯和低碳醇为原料,加入均相催化剂和聚合物分散剂,于反应釜中反应,即得到目的产物,所述的聚合物分散剂为改性聚乙二醇。与现有技术相比,本发明通过引入聚合物分散剂,从而可以保持催化剂粒子的稳定,防止金属催化剂从溶液中沉降并附着在器壁上,改进从催化剂体系中损失的金属的回收。
Description
技术领域
本发明属于丙酸酯类产品制备技术领域,涉及一种乙烯羰基化制备丙酸酯类产品的方法。
背景技术
如丙酸甲酯等丙酸酯类产品作为一种优良的添加剂,在工业上有着多种用途,其催化反应工艺也是行业研究的热点与重点。现有的常规原料路线一般为以乙烯、一氧化碳和甲醇等醇类作为原料,并在金属钯盐类催化剂的作用下,使得乙烯进行羰基化得到对应的丙酸酯类产品。现有工艺路线在制备过程中存在以下缺陷:由于催化剂在反应过程中,活性钯失活会产生贵金属钯污染环境,所以需要对其进行回收重复利用,但是,金属钯容易发生聚集沉降,从而粘附在反应器内壁或不好清理的角落上,形成钯黑或者钯镜,不利于失活催化剂的回收再利用。
如中国专利ZL201310265124.8公开了一种乙烯合成丙酸甲酯的方法,原料乙烯、甲醇、一氧化碳和水在催化剂存在下通过羰基化合生成丙酸甲酯,采用的催化剂是以醋酸钯为主催化剂。该专利通过采用以醋酸钯为主催化剂,钴、镍或钌等金属离子为助催化剂的复合催化剂体系,可以实现在较低温度、较低压力下具有良好的催化活性和选择性,但是,其仍无法解决后续失活催化剂金属钯的回收再利用问题。而本发明正是为了解决上述问题而提出的。
发明内容
本发明的目的就是为了提供一种乙烯羰基化制备丙酸酯类产品的方法,以提高对钯催化剂的回收再利用。
本发明的目的可以通过以下技术方案来实现:
一种乙烯羰基化制备丙酸酯类产品的方法,以一氧化碳、乙烯和醇为原料,加入均相催化剂和聚合物分散剂,于反应釜中反应,即得到目的产物,所述的聚合物分散剂为改性聚乙二醇。
进一步的,所述的聚合物分散剂为羧基化PEG、磺酸化PEG、单甲基醚PEG或氨基化PEG中的一种或几种。更优选的,所述羧基化PEG可以为单羧基化PEG(HO-PEG-COOH)或双羧基化PEG(COOH-PEG-COOH);所述磺酸化PEG可以为单磺酸化PEG(HO-PEG-OSO3H)或双磺酸化PEG(HSO3O-PEG-OSO3H);所述氨基化PEG可以为单氨基化PEG(HO-PEG-NH2)或双氨基化PEG(NH2-PEG-NH2)。
进一步的,所述的均相催化剂为金属钯盐、有机磷化物与酸性助剂三者的复合。
更进一步地,金属钯盐的有机磷化物的摩尔比为1:1-5。
更进一步的,所述金属钯盐为醋酸钯、四(三苯基膦)钯或二苄叉丙酮钯中的一种或几种的组合。
更进一步的,所述有机磷化物为三苯基膦或三(3,4-二甲氧基苯基)膦等。
更进一步的,所述酸性助剂为对甲苯磺酸、硝酸、硫酸、磺酸或磷酸等。
进一步的,乙烯与CO的摩尔比为(1-10):1,乙烯进料体积空速为300-400h-1。优选的,乙烯与CO的摩尔比为5:1。
进一步地,所述聚合物分散剂与Pd元素的质量比为400:1-1:1。
进一步的,所述低碳醇为C1-C4一元饱和醇,优选的,其为甲醇等。
进一步的,反应温度为105-160℃,反应压力为0.5-8Mpa,反应时间为60-120min。
进一步的,反应在搅拌条件下进行,且搅拌速度为200-500rpm。
进一步的,反应釜内还加入有体系反应所需的溶剂,其可以为水等,也可以为其他本领域常用溶剂。
与现有技术相比,本发明具有以下优点:
(1)在反应介质中加入聚合物分散剂,使得贵金属钯粒子保持稳定,防止贵金属钯粒子在反应溶液中沉降并附着在反应器内壁或者不好清理的角落,从而改进催化剂体系中失活催化剂产生的贵金属的回收;
(2)聚合物分散剂加入后不影响反应转化率与产物选择性,且其成本低廉,添加方便,易于推广。
具体实施方式
下面结合具体实施例对本发明进行详细说明。本实施例以本发明技术方案为前提进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
以下各实施例中,所用羧基化PEG为自己制备,其制备过程参考如下:采用PEG与马来酸酐反应,控制PEG与马来酸酐的摩尔比为1:2.8,控制反应温度为170℃,在N2保护下反应6h,得到COOH-PEG-COOH。反应工艺路线具体为:
所用氨基化PEG也为自己制备,其制备过程参考如下:采用PEG与对甲苯磺酰氯进行酯化反应,然后进一步在140℃条件下与氨水密闭反应直接生成目标产物NH2-PEG-NH2,具体为:取105mmol PEG-400,309mmol对甲苯磺酰氯一次溶于100ml四氢呋喃中,向四氢呋喃中滴加8mol/L的氢氧化钾水溶液100ml,室温下反应7h,当然,上述制备过程中,如PEG-400等原料的添加量,以及反应温度等也可以根据需要做适应性的调整。
上述反应工艺路线具体为:
另外,磺酸化PEG也可以同样是自己制备,其制备过程参考如下:将氯磺酸在0℃下缓慢加入到1mmol PEG-600的CH2Cl2(10mL)溶液中,室温反应24h后,蒸除CH2Cl2、洗涤即得目的产物。同样,上述制备过程中,如PEG-600等原料的添加量,以及反应温度等也可以根据需要做适应性的调整。
其余如无特别说明的原料试剂或处理技术,则表明其均为本领域的常规市售产品或常规处理技术。
实施例1:
向容积为1L的高压反应釜中依次加入醋酸钯0.3g,对甲苯磺酸4.0g,三苯基膦,甲醇400.0g,聚合物分散剂(本实施例为COOH-PEG-COOH),使聚合物分散剂的质量与Pd元素的质量比为100:1,三苯基膦与醋酸钯的摩尔比约为1:1,乙烯与CO的摩尔比约为5:1(乙烯进料体积空速约为350h-1,加到反应压力即可)。反应过程中,控制搅拌速度为350rpm,保持反应温度为105℃,反应压力为0.5MPa,反应时间为90min时取样。
对取样结果进行测试,结果以乙烯计,丙酸甲酯选择性为98.5%,羰化时空收率为800g/gPd·h-1。同时,检测反应后的液相中的Pd含量(此处为钯原子含量,下同)为90%左右;观察反应釜内壁,可见内壁光滑且无钯黑粘附。
对比例1:
与实施例1相比,绝大部分都相同,除了省去了聚合物分散剂的添加。
对取样结果进行测试,结果以乙烯计,丙酸甲酯选择性为97.0%,羰化时空收率为600g/gPd·h-1。同时,检测反应后的液相中的Pd含量为70%左右;观察反应釜内壁,可见内壁上有明显的钯黑粘附和沉积。
可见,加入聚合物分散剂后,乙烯羰基化制备丙酸甲酯的转化率与选择性等基本不受影响,但是,聚合物分散剂的加入会提高金属钯保留在液相中的效果,有效避免金属钯的聚集沉积并在器壁上粘附。
对比例2:
与实施例1相比,绝大部分都相同,除了将聚合物分散剂改为等质量的PEG。
对取样结果进行测试,结果以乙烯计,丙酸甲酯选择性为97.4%,羰化时空收率为550g/gPd·h-1。同时,检测反应后的液相中的Pd含量为80%左右;观察反应釜内壁,可见内壁上有明显的钯黑粘附和沉积。
可见,PEG虽然可以提高金属钯保留在液相中的效果,但是提升不明显。
对比例3:
与实施例1相比,绝大部分都相同,除了将聚合物分散剂与Pd元素的质量比改为600:1。
对取样结果进行测试,结果以乙烯计,对丙酸甲酯选择性为97.2%,羰化时空收率为580g/gPd·h-1。同时,检测反应后的液相中的Pd原子含量为80%左右;观察反应釜内壁,可见内壁上没有明显的钯黑粘附和沉积。
实施例2:
向容积为1L的高压反应釜中一次加入醋酸钯0.3g,对甲苯磺酸4.0g,三苯基膦,甲醇400.0g,聚合物分散剂(本实施例为mPEG-COOH),使聚合物分散剂的质量与Pd元素的质量比为400:1,三苯基膦与醋酸钯的摩尔比为1:5,乙烯与CO的摩尔比为10:1(乙烯进料体积空速为400h-1,加到反应压力即可)。反应过程中,控制搅拌速度为350rpm,保持反应温度为120℃,反应压力为0.5MPa,反应时间为90min时取样。
对取样结果进行测试,结果以乙烯计,对丙酸甲酯选择性为98.4%,羰化时空收率为890g/gPd·h-1。同时,检测反应后的液相中的Pd含量为92%左右;观察反应釜内壁,可见内壁光滑且无钯黑粘附和沉积。
实施例3:
向容积为1L的高压反应釜中一次加入醋酸钯0.3g,对甲苯磺酸4.0g,三苯基膦,甲醇400.0g,聚合物分散剂(本实施例为mPEG-COOH),使聚合物分散剂的质量与Pd元素的质量比为1:1,三苯基膦与醋酸钯的摩尔比为1:2,乙烯与CO的摩尔比为1:1(乙烯进料体积空速为300h-1,加到反应压力即可)。反应过程中,控制搅拌速度为350rpm,保持反应温度为160℃,反应压力为8MPa,反应时间为120min时取样。
对取样结果进行测试,结果以乙烯计,对丙酸甲酯选择性为98.9%,羰化时空收率为800g/gPd·h-1。同时,检测反应后的液相中的Pd含量为82%左右;观察反应釜内壁,可见内壁光滑且无钯黑粘附和沉积。
实施例4:
与实施例1相比,绝大部分都相同,除了本实施例中将聚合物分散剂改为等质量的氨基化PEG。
对取样结果进行测试,结果以乙烯计,对丙酸甲酯选择性为97.8%,羰化时空收率为780g/gPd·h-1。同时,检测反应后的液相中的Pd含量为85%左右;观察反应釜内壁,可见内壁光滑且无钯黑粘附和沉积。
实施例5-实施例6:
与实施例1相比,绝大部分都相同,除了本实施例中将聚合物分散剂分别改为等质量的HO-PEG-NH2、磺酸化PEG;
其中,HO-PEG-NH2的制备过程为:以PEG为原料,采用氧化银和碘化钾催化系统催化PEG单磺酰化,通过氨基化反应将磺酰基转化为胺基,得到HO-PEG-NH2。
实施例8-实施例9:
与实施例1相比,绝大部分都相同,除了本实施例中将醋酸钯分别对应改为等摩尔量的四(三苯基膦)钯或二苄叉丙酮钯。
实施例10-实施例13:
与实施例1相比,绝大部分都相同,除了本实施例中将对甲苯磺酸分别改为等摩尔量的硝酸、硫酸、磺酸或磷酸。
实施例14:
与实施例1相比,绝大部分都相同,除了本实施例中将三苯基膦改为等摩尔量的三(3,4-二甲氧基苯基)膦。
上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。
Claims (9)
1.一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,以一氧化碳、乙烯和低碳醇为原料,加入均相催化剂和聚合物分散剂,于反应釜中反应,即得到目的产物,所述的聚合物分散剂为改性聚乙二醇;
所述的聚合物分散剂为羧基化PEG、磺酸化PEG、单甲基醚PEG或氨基化PEG中的一种或几种;
所述均相催化剂由金属钯盐、有机膦化物及酸性助剂组成。
2.根据权利要求1所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述的羧基化PEG为单羧基化PEG或双羧基化PEG。
3.根据权利要求1所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述的磺酸化PEG为单磺酸化PEG或双磺酸化PEG。
4.根据权利要求1所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述的氨基化PEG为单氨基化PEG或双氨基化PEG。
5.根据权利要求1所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述乙烯与CO的摩尔比为1-10:1,所述乙烯的进料体积空速为300-400h-1。
6.根据权利要求1或5所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述乙烯与CO的摩尔比为5:1。
7.根据权利要求1所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述反应的温度为105-160℃,所述反应的压力为0.5-8Mpa,所述反应的时间为60-120min。
8.根据权利要求1所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述金属钯盐的有机磷化物的摩尔比为1:1-5;所述有机磷化物选自三苯基膦或三(3,4-二甲氧基苯基)膦;所述酸性助剂选自对甲苯磺酸、硝酸、硫酸、磺酸或磷酸的一种或几种的组合。
9.根据权利要求8所述的一种乙烯羰基化制备丙酸酯类产品的方法,其特征在于,所述聚合物分散剂与Pd元素的质量比为400:1-1:1。
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