CN1265104A - 钼环氧化催化剂的回收 - Google Patents

钼环氧化催化剂的回收 Download PDF

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CN1265104A
CN1265104A CN98807512A CN98807512A CN1265104A CN 1265104 A CN1265104 A CN 1265104A CN 98807512 A CN98807512 A CN 98807512A CN 98807512 A CN98807512 A CN 98807512A CN 1265104 A CN1265104 A CN 1265104A
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T·J·埃文斯
R·L·坎农
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Abstract

含有钼和钠有用成分的水法环氧化工艺物流进行焚化,含钼和钠的水溶液进行回收,酸化,在起初不加碱的情况下与钙化合物反应,以形成固体钼酸钙,然后分离钼酸钙。

Description

钼环氧化催化剂的回收
                    发明背景
发明领域
利用烯烃与有机氢过氧化物的催化反应生产环氧乙烷化合物例如1，2-环氧丙烷是工业上很重要方法。一般采用均相钼催化剂。本技术领域已例示说明了1，2-环氧丙烷和苯乙烯单体共生产的环氧乙烷法。
本发明方法涉及在这种环氧化法工艺中钼环氧化催化剂有用成分的回收。
相关技术描述
1，2-环氧丙烷和苯乙烯单体共生产的极其成功的方法包括：乙苯的分子氧氧化形成乙苯氢过氧化物，此氢过氧化物与丙烯的催化反应形成1，2-环丙烷和1-苯乙醇，和1-苯乙醇脱水形成苯乙烯单体。描述此方法的主要专利是美国专利3,351,635。
在此方法的实践中，环氧化反应混合物通常是在未反应的丙烯经蒸馏分离之后，要用苛性碱水溶液处理，苛性碱量要比与所含的有用成分钼反应形成钼酸钠所需的和与环氧酸盐中含有的有机杂质例如酸和酚的反应所需的碱量过量。例如可参见美国专利4,405,572，5,276,235和5,171,868。
在这种现有技术的实践中所存在的问题是，含有钼、钠和有机物的相当大量的工艺液流的形成和这种工艺液流的处置。钼的存在是特别麻烦的，因为在排出之前，为了满足环境条例，这种物质必须要除去。
本发明与共同转让的美国专利5,585,077紧密相关，该专利的公开并入本文作为参考。
在美国专利5,585,077中，含有钼和钠有用成分以及有机物的工艺水流被焚化。在焚化过程中，由钼和钠有用成分构成的灰粒下落通过含焚化炉气体的焚化炉。含灰气体经与水混合进行急冷，以形成焚化炉的泄料物。排出物是来自环氧化工艺物流的由纳有用成分和钼有用成分组成的水溶液，钠的有用成分一般以碳酸盐形式出现，而钼的有用成分一般以钼酸钠的形式出现。由于存在着与溶液所含重金属钼有关的环境危害，排污液不可直接排放。根据美国专利5,585,077的程序，排污水流例如用HCl酸化到pH小于5，因此碳酸盐转化为可以很容易除去的CO2。此后，不含碳酸根的液流的pH值用加入苛性碱来上调，加入有用的钙，使溶液所含的钼有用成分转化为CaMoO4，钼酸钙从溶液中沉淀下来，并加以回收。所得到的钼含量大大减少的水溶液然后可以很方便地进行处置，而此后仅需很少的处理。
虽然所述的美国专利5,585,077的方法对于回收钼的有用成分是高度成功的，但是由于沉淀的CaMoO4有用成分的粒度很小，利用过滤回收沉淀CaMoO4是相当慢的。常常应用过滤助剂来促进过滤，但是这样做是相当麻烦的，并且这样回收的固体例如在炼钢工业中几乎没什么用处。
发明简述
根据本发明，按美国专利5,585,077所述得到的含钼和钠的排出物流用加HCl的方法进行酸化，但只酸化到pH约5.1-6.5，以使碳酸盐有用成分转化为所加酸的钠盐和CO2，后者进行蒸发和分离。此后并不象美国专利5,585,077所公开的那样，即不加碱来使pH上调。加入有用的钙，这样最终形成的CaMoO4固体很容易利用过滤而分离。
附图说明
附图以流程图的形式例示说明了本发明的实施。
详细描述
根据本发明，如美国专利5,585,077所述，含有钼催化剂有用成分、苛性碱处理的钠有用成分和有机物的环氧化工艺水流根据已知的程序进行焚化。实质上实现了有机物的完全燃烧。主要以碳酸盐形式出现的钠有用成分，和钼有用成分作为焚化炉排出物流进行回收。
含钼和钠的排出物流然后酸化到pH在5.1-6.5范围内，和在合适的搅拌下大部分的碳酸盐有用或分转化为所加酸的钠盐和CO2，CO2蒸发并分离。为除去CO2可以采用25°～120℃的温度。为使残剩的溶解的CO2减至最少，较高的温度是优选的。如果需要或适宜，可以采用鼓泡或沸腾的步骤。借助酸化和汽提进行这种碳酸盐转化和除去二氧化碳对于所形成的CaMoO4浆液随后的处理是很重要的，因为由于与残剩  碳酸盐的反应将会形成CaCO3，这导致了钙的有用成分的消耗增加。又CaCO3固体增加了滤饼的体积，这将增加了处置费用。换句话说，碳酸钙固体将稀释了滤饼中钼的含量，因此降低了钼的回收价值。
在CO2除去后，酸化的排出物流然后进行处理，以使所含的钼的有用成分转化为不溶的钼酸钙，钼酸钙可以利用过滤进行回收。使用HCl酸化时，虽然也可以使用Ca(OH)2和CaO，但一般以酸化时所使用的酸的盐的形式例如CaCl2的形式来加入有用的钙。不管怎样，Ca(OH)2或CaO的使用对其后的过滤将总是有害的。
为了实现钼有用成分满意地转化为CaMoO4，所加的钙量必须至少是使Ca/Mo为1/1。Ca/Mo的比值越大，则形成CaMoO4的转化率就越大，因此钼的除去百分率就越大。优选地采用2/1-10/1的Ca/Mo比，3/1-10/1更优选。如果存在着竞争的污染物例如碳酸盐或硫酸盐，则需要更高的Ca/Mo比。
温度同样也是重要的考虑因素。为了以合理的Ca/Mo比进行的使钼有用成分形成CaMoO4的转化迅速，采用了至高达溶液沸点的约80℃的温度。在80℃或更高的温度下，大约数分钟内就形成了CaMoO4的固体，15钟到几小时一般是满意的。
根据本发明，所形成的CaMoO4是不溶性的颗粒，它很容易从溶液中沉淀析出。利用倾析或过滤或二者的结合，可以使固体物分离。合适的选择条件最终得到大于95％的钼自水溶液中的去除率，在某些条件下，获得了大于97％的去除率。
在美国专利5,585,077的程序中，含水的排放物酸化到pH5或更低，在CO2除去后，加碱使pH增加到6-9，所形成的CaMoO4晶体粒度极其小，例如10-15微米的平均粒度，这样的粒度使得过滤十分缓慢，有时需要使用过滤助剂例如硅藻土。
相比之下，根据本发明含水排放物只酸化到pH约5.1-6.5，在除去CO2后，不再加入苛性碱。依靠有用钙的加入，而CaMoO4很容易以更大的平均粒度，例如25-30微米的粒度结晶出来，这样的颗粒非常容易过滤分离。
显然，按美国专利5,585,077所述的那样，加入苛性碱改变了溶液中物种的平衡，以致CaMoO4晶体成核和成长的机制受到了有害的影响。
为了进一步说明本发明，将参照附图。焚化炉含水的排放物经管线2连同经管线3引入的足量的HCl一起进入区域1以降低所得到的溶液的pH到5.1-6.5的范围。区1溶液的温度可维持在80℃以上，由于焚化炉排放物中的碳酸盐有用成分的酸化，所形成的CO2经管4除去。可以将汽提气体例如氮气(未画出)引入区1，以促进CO2的除去。
大量不含碳酸根的溶液可以经管线5从区1送到过滤器6，其中在区1形成的少量的固体从溶液中滤出，经管线7除去。这些固体是由Mo、Fe和Na的化合物组成的。看来这些固体不会妨碍随后CaMoO4的形成或过滤，因此它们的除去是无条件的。
溶液经管线8由过滤器6送往区域9。CaCl2水流经管线11加入区9的料液中，CaCl2的加入量在区9足以提供至少1/1的Ca/Mo计量比，优选地至少2/1的Ca/Mo计量比。
在区9，溶液的温度维持在约80℃到沸点，停留时间15分钟或更长，由此形成了作为不溶固体沉淀物的CaMoO4。在区9利用适宜的方法提供了合适的混和。
区1，区6和区9所表示的方法可以以间歇的方式或连续的方式进行，间歇方式是优选的，可以在单个容器中进行。
含固体的溶液经管线12由区9送往过滤器13，在过滤器13中，固体沉淀物形成滤饼，经管线4分离，送去回收CaMoO4。经管线15则回收钼有用成分的含量已经大大地减少了的滤液。
实例
参照附图，来自1，2-环氧丙烷和苯乙烯单体工艺的含钼物流根据常规程序进行焚化，回收由钼和碳酸钠组成的排出物流。含有7％(重量)的碳酸钠，5％碳酸氢钠，1100ppm Mo，200ppm S和10ppm Fe的排出物流以18000磅/时的速度经管线2送入区1。由30～32％(重量)的HCl组成的盐酸物流以4400磅/时的速度经管线3也送往区1，以调节所得混合物的pH约为6。在区1，溶液维持在90℃，所形成的CO2以1100磅/时的速度经管线4除去。
大量的不含碳酸根的溶液经管线5由区1送到过滤器6，在过滤器6中，经管线7分离出25ppm的干固体。
滤液经管线8由过滤器6送往区9，与经管线11引入的1500磅/时的CaCl2水溶液(30％重量的CaCl2)混合。区9的混合物充分地混合，其温度维持在90℃，停留时间30分钟。在区9，在料液中的钼有用成分和引入的钙化合物之间进行反应，由此形成了钼酸钙，钼酸钙沉淀析出。区9的混合物经管线12由区9送往过滤器13，在过滤器13中，钼酸钙由溶液中滤出，滤饼经管线14，以100磅/时的速度除去，滤饼含约30％的水分。滤液以22500磅/时的速度经管线15被回收，含有25ppm的钼。该液流适于排放，无需进行进一步的实质性的处理。
与利用过滤助剂，根据美国专利5,585,077所述的程序实现的典型的约2.5加仑/分/英尺2的过滤速度形成明显的对照，本发明已经例示证明可达到超过12加仑/分/英尺2的过滤速度。

Claims (3)

1.从含钼和钠的环氧化工艺物流中分离钼环氧化催化剂有用成分的方法，该方法包括使所述物流焚化，从焚火分离出含有钼和钠有用成分的水相物流，使被分离出的水相物流酸化到pH约5.1-6.5，和分离生成的CO2，使剩余溶液与钙化合物在80℃到其沸点的温度下进行反应，溶液中所加Ca对Mo的比至少是1∶1，和分离生成的CaMoO4固体。
2.权利要求1的方法，其中所述被分离出的水流用HCl进行酸化。
3.权利要求1的方法，其中所加Ca/Mo的比是2/1到50/1。
CNB988075121A 1997-07-30 1998-06-29 钼环氧化催化剂的回收 Expired - Lifetime CN1134425C (zh)

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US08/903,082 US5776848A (en) 1997-07-30 1997-07-30 Molybdenum epoxidation catalyst recovery
US08/903,082 1997-07-30

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CN1265104A true CN1265104A (zh) 2000-08-30
CN1134425C CN1134425C (zh) 2004-01-14

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CN100372778C (zh) * 2006-05-25 2008-03-05 上海交通大学 具有中空结构的钼酸钙自组装体的制备方法
CN115304443A (zh) * 2022-07-25 2022-11-08 万华化学集团股份有限公司 一种异丁烷共氧化制备环氧丙烷工艺中环氧化反应浓缩液资源化利用的方法

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DE10008904A1 (de) 2000-02-25 2001-09-06 Degussa Verfahren zur Rückgewinnung von Katalysator-Übergangsmetallen aus salzhaltigen Reaktionsgemischen
US7223875B2 (en) * 2003-01-09 2007-05-29 Mobile Process Technology, Co. Process for manufacturing propylene oxide
EP1974783A1 (en) * 2007-03-22 2008-10-01 Holding AVR-Bedrijven B.V. Treatment of molybdate containing waste streams
ES2868952T3 (es) * 2017-06-08 2021-10-22 Lyondell Chemie Nederland B V Método de tratamiento de aguas residuales

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CA458253A (en) * 1949-07-19 C. Carosella Michael Preparation of molybdenum compounds
US3567433A (en) * 1968-02-14 1971-03-02 Universal Oil Prod Co Method of recovering metals from spent hydrorefining catalysts
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100372778C (zh) * 2006-05-25 2008-03-05 上海交通大学 具有中空结构的钼酸钙自组装体的制备方法
CN115304443A (zh) * 2022-07-25 2022-11-08 万华化学集团股份有限公司 一种异丁烷共氧化制备环氧丙烷工艺中环氧化反应浓缩液资源化利用的方法
CN115304443B (zh) * 2022-07-25 2023-12-19 万华化学集团股份有限公司 一种异丁烷共氧化制备环氧丙烷工艺中环氧化反应浓缩液资源化利用的方法

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BR9810730A (pt) 2000-08-08
JP2002511797A (ja) 2002-04-16
EP1009745B1 (en) 2003-03-26
ES2191323T3 (es) 2003-09-01
DE69812650D1 (de) 2003-04-30
JP4208971B2 (ja) 2009-01-14
KR20010022277A (ko) 2001-03-15
WO1999006386A1 (en) 1999-02-11
AU8853398A (en) 1999-02-22
KR100510213B1 (ko) 2005-08-26
DE69812650T2 (de) 2004-03-18
EP1009745A1 (en) 2000-06-21
CN1134425C (zh) 2004-01-14
US5776848A (en) 1998-07-07

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