CN110256203B - 一种环氧丙烷废水中缩合醇醚资源化利用的方法 - Google Patents
一种环氧丙烷废水中缩合醇醚资源化利用的方法 Download PDFInfo
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- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
本发明提供一种环氧丙烷废水中缩合醇醚资源化利用的方法，将HPPO工艺产生的除盐后废水通过改性分子筛催化剂，使缩合醇醚水解成丙二醇和甲醇，以便从废水中回收丙二醇和甲醇，易于下游生化处理，提高经济性。
Description
技术领域
本发明属于石油化工技术领域，提供一种环氧丙烷废水中缩合醇醚资源化利用的方法。
背景技术
环氧丙烷是仅次于聚丙烯的第二大类丙烯衍生物，主要用于生产聚醚多元醇，进而制造聚氨酯，广泛用于化工、轻工、医药、食品等行业。目前国内生产环氧丙烷的工艺方法包括：氯醇法、共氧化法、过氧化氢直接氧化法(HPPO法)。HPPO法是在钛硅分子筛催化剂作用下，双氧水催化氧化丙烯合成环氧丙烷。HPPO法工艺简单，条件温和，产品单一，比氯醇法具有产生废水少的优势。
而在HPPO法生产环氧丙烷过程中，依然会产生有机废水，该部分废水的处理一直是环保的难题。HPPO法废水中的有机物主要为丙二醇、丙二醇单甲醚、丙二醇异甲醚，以及环氧丙烷与上述三种副产物发生缩合反应生成的醇醚。生成这些缩合醇醚的反应过程为：环氧丙烷水解生成丙二醇，环氧丙烷醇解生成丙二醇单甲醚或丙二醇异甲醚，然后环氧丙烷再与丙二醇、丙二醇单甲醚或丙二醇异甲醚发生缩合反应生成醇醚。这些缩合醇醚一部分吸附在钛硅分子筛催化剂孔道内，堵塞分子筛孔道，造成催化剂失活；而大部分溶于溶剂进入反应液，反应液经丙烯分离、环氧丙烷回收、溶剂回收后，缩合醇醚最后进入废水中，造成废水中COD含量高，后处理困难。生成缩合醇醚涉及的主要反应的方程式如下：
专利CN201510206710.4公开了一种环氧丙烷废水的处理方法。经过两级厌氧处理，使废水中大分子物质转化成小分子，提高废水可生化性；然后经过好氧活性污泥进一步处理，最后将好氧处理后的废水经高级芬顿氧化法深度处理，深度处理后的废水经气浮和中和沉淀反应达到间接排放标准。专利CN201710793051.8公开了一种PO生产废水强化预处理工艺。通过酸解曝气、汽提、Fenton氧化、混凝沉淀、臭氧氧化等步骤，对环氧丙烷废水强化预处理后，能够将环氧丙烷废水COD降低到500mg/L以下。
以上常规的处理环氧丙烷废水中有机物的方法为将有机物破坏，达标处理后排放，处理成本高，浪费资源。
发明内容
本发明的目的是提供一种环氧丙烷废水中缩合醇醚资源化利用的方法。将HPPO工艺产生的除盐后废水通过改性分子筛催化剂，使缩合醇醚水解成丙二醇和甲醇，以便从废水中回收丙二醇和甲醇，易于下游生化处理，提高经济性。涉及的反应方程式如下：
为达到上述目的，本发明的技术方案是这样实现的：
(1)在固定床反应器中装填改性分子筛催化剂；
(2)将来自上游的除盐后的环氧丙烷废水以一定空速通过固定床催化剂，控制一定的反应压力、反应温度；
(3)反应后冷凝取样分析。
上述步骤(1)中所述的改性分子筛催化剂，是在金属盐溶液作用下，通过传统浸渍法改性得到。
所述分子筛为SAPO-34、HZSM-5、MCM-22、MCM-41中的任意一种；
所述的金属盐溶液可以是氯化物、硝酸盐、碳酸盐、醋酸盐等，浸渍完毕后烘干、焙烧，即得金属改性的分子筛催化剂。
所述金属物质为Cu、Ag、Au、Fe、Co、Ni、Pt、Pd、Rh的任意一种、两种及以上以任意比例混合而成的混合物；
所述的改性分子筛催化剂中，金属物质的含量为0.1～10wt％；
上述步骤(2)中废水的空速为80～120h-1，反应压力为1.0～2.0MPa，反应温度为140～180℃。
本发明的有益效果：本发明对分子筛进行金属改性，在不改变分子筛结构的基础上，能有效的提高目的产物的收率和选择性，延长分子筛的使用寿命。本发明的处理方法可以将环氧丙烷废水中的缩合醇醚水解成丙二醇和甲醇，易于回收丙二醇、甲醇和下游生化处理。具有步骤简单，反应条件温和等特点，又具有明显的环境、经济效益和社会效益。
具体实施方式
本发明下述实施例中收率的计算公式为：
收率＝目的产物(实际)生成量/目的产物的理论生成量*100％。
实施例1改性分子筛催化剂的制备
(1)Fe-Ni改性SAPO-34催化剂的制备
Fe-Ni改性SAPO-34催化剂采用共浸渍法制备，称取一定量的硝酸铁固体和硝酸镍固体溶于适量去离子水中，缓慢加入SAPO-34分子筛原粉进行搅拌，搅拌均匀后静置浸渍12h；然后110℃干燥12h，550℃焙烧3h，得到(Fe-Ni)/SAPO-34催化剂，经压片、筛分处理后进行废水的缩合醇醚水解反应。其中Fe负载量为1.5wt％，Ni负载量为1.5wt％。
(2)Ag-Pd改性HZSM-5催化剂的制备
Ag-Pd改性HZSM-5催化剂采用共浸渍法制备，称取一定量的硝酸银固体和氯化钯固体溶于适量去离子水中，缓慢加入HZSM-5分子筛原粉进行搅拌，搅拌均匀后静置浸渍12h；然后110℃干燥12h，550℃焙烧3h，得到(Ag-Pd)/HZSM-5催化剂，经压片、筛分处理后进行废水的缩合醇醚水解反应。其中Ag的负载量为0.05wt％，Pd的负载量为0.05wt％。
(3)Cu-Pt改性MCM-22催化剂的制备
Cu-Pt改性MCM-22催化剂采用共浸渍法制备，称取一定量的硝酸铜固体和氯化铂固体溶于适量去离子水中，缓慢加入MCM-22分子筛原粉进行搅拌，搅拌均匀后静置浸渍12h；然后110℃干燥12h，550℃焙烧3h，得到(Cu-Pt)/MCM-22催化剂，经压片、筛分处理后进行废水的缩合醇醚水解反应。其中Cu的负载量为5.5wt％，Pt的负载量为0.5wt％。
(4)Co改性MCM-41催化剂的制备
Co改性MCM-41催化剂采用浸渍法制备，称取一定量的氯化钴固体溶于适量去离子水中，缓慢加入MCM-41分子筛原粉进行搅拌，搅拌均匀后静置浸渍12h；然后110℃干燥12h，550℃焙烧3h，得到Co/MCM-41催化剂，经压片、筛分处理后进行废水的缩合醇醚水解反应。其中Co的负载量为10wt％。
(5)Au改性MCM-22催化剂的制备
Au改性MCM-22催化剂采用浸渍法制备，称取一定量的氯化金固体溶于适量去离子水中，缓慢加入MCM-22分子筛原粉进行搅拌，搅拌均匀后静置浸渍12h；然后110℃干燥12h，550℃焙烧3h，得到Au/MCM-22催化剂，经压片、筛分处理后进行废水的缩合醇醚水解反应。其中Au的负载量为1wt％。
实施例2废水中的缩合醇醚资源化利用
(1)在固定床反应器中装填3wt％(Fe-Ni)/SAPO-34催化剂，使除盐后的环氧丙烷废水以80h-1泵入反应器中，在1.0MPa、180℃下进行水解反应。分析出料中丙二醇收率为74％，甲醇收率为81％。
(2)在固定床反应器中装填0.1wt％(Ag-Pd)/HZSM-5催化剂，使除盐后的环氧丙烷废水以120h-1泵入反应器中，在1.5MPa、160℃下进行水解反应。分析出料中丙二醇收率为70％，甲醇收率为75％。
(3)在固定床反应器中装填6wt％(Cu-Pt)/MCM-22催化剂，使除盐后的环氧丙烷废水以100h-1泵入反应器中，在1.2MPa、150℃下进行水解反应。分析出料中丙二醇收率为78％，甲醇收率为85％。
(4)在固定床反应器中装填10wt％Co/MCM-41催化剂，使除盐后的环氧丙烷废水以90h-1泵入反应器中，在2.0MPa、170℃下进行水解反应。分析出料中丙二醇收率为71％，甲醇收率为72％。
(5)在固定床反应器中装填1wt％Au/MCM-22催化剂，使除盐后的环氧丙烷废水以110h-1泵入反应器中，在1.7MPa、140℃下进行水解反应。分析出料中丙二醇收率为72％，甲醇收率为79％。
本发明所述内容并不仅限于本发明所述实施例内容。
本文中应用了具体个例对本发明结构及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (4)
1.一种环氧丙烷废水中缩合醇醚资源化利用的方法，由下列步骤组成：
(1)在固定床反应器中装填改性分子筛催化剂；
(2)将来自上游的除盐后的环氧丙烷废水以一定空速通过固定床催化剂，控制反应压力、反应温度，进行水解反应；
上述步骤(1)中所述的改性分子筛催化剂，是在金属盐溶液作用下，通过传统浸渍法改性得到,所述分子筛为SAPO-34、HZSM-5、MCM-22、MCM-41中的任意一种,所述金属物质为Ag、Au、Fe、Co、Ni、Pt、Pd、Rh的任意一种、两种及以上以任意比例混合而成的混合物。
2.根据权利要求1所述的一种环氧丙烷废水中缩合醇醚资源化利用的方法，其特征在于，所述的金属盐溶液是氯化物、硝酸盐、碳酸盐、醋酸盐中的一种或几种。
3.根据权利要求1所述的一种环氧丙烷废水中缩合醇醚资源化利用的方法，其特征在于，所述的改性分子筛催化剂中，金属物质的含量为0.1～10wt％。
4.根据权利要求1所述的一种环氧丙烷废水中缩合醇醚资源化利用的方法，其特征在于，上述步骤(2)中废水的空速为80～120h-1，反应压力为1.0～2.0MPa，反应温度为140～180℃。
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