CN1426485A - 用超临界水反应剂自有机贵金属组合物回收贵金属 - Google Patents
用超临界水反应剂自有机贵金属组合物回收贵金属 Download PDFInfo
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- 238000011084 recovery Methods 0.000 title description 3
- 239000000376 reactant Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 9
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 8
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- 229910052751 metal Inorganic materials 0.000 claims description 6
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- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
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- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
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- C22B11/042—Recovery of noble metals from waste materials
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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Abstract
在水中进行的超临界氧化能够氧化贵金属有机组合物如非均相(Pt/C)或均相贵金属催化剂中的“有机物”，并生成具有很少副产品和低贵金属损失的贵金属氧化物。
Description
本发明涉及贵金属精炼、更具体地有机贵金属组合物精炼的改进。
存在很多需要精炼的有机贵金属组合物。这些组合物包括所有种类的废催化剂，从非均相催化剂如在碳载体上的铂族金属，例如在碳上的4-5％Pd，到均相(液体)催化剂如基于铑膦配合物的那些、精炼厂和化学侧线馏分、含贵金属和有机物的废弃流体、废弃有机金属化合物和配合物以及很多其它固体和液体。在这些组合物中所含的贵金属价值使得回收贵金属重要。通常将含贵金属的废弃物和废催化剂焚烧。然而，所有这些焚烧方法主要以粉尘并且也可能以蒸气形式丢失大量贵金属，同时灰分仍然含有难以除去的相当量的碳/含碳材料。传统的焚烧方法还趋于生成相当大量的可能包括NOx和二噁英的污染物，并会产生难以处理的废水流。
已知有机材料可在超临界水中氧化(例如，参见USP 4,338,199)，但我们不相信已有的处理含贵金属的有机材料的任何建议。我们注意到一个学术上的建议：通过在MnO2催化剂存在下超临界水氧化处理作为废弃材料的苯酚。该建议未暗示存在或使用贵金属催化剂，并且这些材料的极高费用将是一个抑制因素。我们现在已发现，本发明方法可按安全、环境友好、能量有效的方式进行，并获得用于进一步加工的合适形式的贵金属产品。
用作本发明方法原料的有机贵金属组合物(这里以此术语使用)可为任何贵金属配合物、化合物或物理混合物(该术语拟包括贵金属本身或载在“有机”载体如活性炭上的贵金属化合物或配合物，尽管严格地说碳本身不是有机物质)。这些组合物包括贵金属或化合物或配合物与将被作为废弃物的有机材料的混合物。换言之，有机废弃物可与一定比例的贵金属或贵金属组合物掺混并根据本发明处理，由此氧化有机废弃物并回收贵金属，该贵金属用于进一步精炼或其它处理或在处理另外的废弃有机物中再循环。
本发明提供一种精炼有机贵金属组合物的方法，包括在含超临界水和氧源的反应液体中处理该组合物，使组合物的有机组分氧化并从反应产品中回收贵金属氧化物。
供氧方便地在伸长的管式反应器的入口处进行，与此同时将水加入反应器中，尽管氧可交替或另外在反应器入口下游加入，并且补充的氧可在沿反应器长度的一个或多个点加入。例如，补充的氧可在有机原料注入点下游加入反应器中。
各组分加入反应液体的顺序并不特别重要。本发明方法可通过如下操作完成：将有机贵金属组合物和水预混，将所得混合物加热至超临界温度或接近此温度，并加入氧化剂(反应热足以将温度升至临界温度以上)。氧化剂也可与一种或多种反应混合物组分预混。
尽管用连续方法操作是优选的，但也可以间歇方法操作。
使用的氧气量应达到原料在反应条件下完全氧化，该氧气量适当地通过来自反应器出口处的传感器反馈调节，该传感器显示游离氧和存在的任何一氧化碳。适宜的量为使所有的碳被氧化为二氧化碳的量。氧合适地自液氧罐供给。可以使用氧与一种或多种惰性气体的混合物，但目前优选不使用。
尽管目前优选使用氧作为氧化剂，但其它氧源，包括空气、过氧化氢和硝酸都可以考虑。
通常，水适宜地构成整个反应混合物的90wt％或更多，例如95wt％或更多。
水的超临界点为374℃和221巴。任一超临界反应器必须设计为很好地承受超过临界点的温度和压力。尽管实施该方法的装置(包括特殊的高压泵和阀门)的材料成本本身就高，但事实上本发明方法简单快速，低操作成本和低材料损失相结合，使该方法经济实用。
本发明方法合适地在温度400至600℃、优选500至580℃，且合适地在压力约230巴至约300巴，优选250巴至300巴下进行。当然，沿反应器长度存在压力降，取决于各反应器设计。起始温度，如上所述，可低于374℃。
根据本发明，有机物氧化放热；当反应器本身按绝热模式操作时，在注入原料2秒后已观察到反应器中温度升高150℃左右。该反应器优选为伸长的管式反应器，并合适地为隔热的。该反应器可合适地为盘管反应器。通过使用常规热交换器/节热器调节各入口和/或出口流体的热，通常可以使整个方法以自热方式，即不加入补充燃料的方式操作。实际上，该方法中生成的部分热可用于，例如生产高压蒸汽，该蒸汽可用于制造现场的其他处。
本发明方法的排出物为细碎的在超临界含水浆料或溶液(在卸压前)中的贵金属氧化物，其还含有其它氧化反应副产品，取决于原料有机组合物的实际化学组成。因此，若有机组分为无杂原子的碳或烃基的，则产品为水和二氧化碳，其在卸压后形成碳酸溶液。若在原料中存在磷、硫或氮原子，则该产品分别含磷酸、硫酸或氮。特别突出的是在该反应条件下不生成NOx，这是优于常规裂解型工艺的巨大优点。若需要，可将骤冷水加入反应产品中，并在此点或随后，通过加入碱如氢氧化钠中和形成的酸是适宜的。然而，通常我们宁可不这样做，因为可能形成不溶盐，这些盐会造成在超临界状态下堵塞，或污染贵金属氧化物产品，使得其进一步处理变复杂。
原料组合物的贵金属组分可仅为存在的金属，或其它金属可作为组分，例如作为催化剂的促进剂、或作为污染物，例如在使用期间积累的污染物存在。对于后一情况，本发明方法的产品将包括这些金属的最高氧化态。贵金属氧化物可通过不构成本发明部分的常规工艺与该污染的金属氧化物分离。
本发明将参考描绘实施本发明的装置的一个具体实施方案的附图进一步描述。参考附图，将一个例如数百米长并为盘管形式的伸长的管式反应器一般标记为1。向反应器中，在压力超过临界压力，如在约260巴下用泵抽入两股流体或水与氧气的混合流2。将氧气量优选通过来自反应器出口的氧传感器(未示)的反馈调节，例如在中试装置中达到出口气体中的10vol％或更多的O2。一个全规模的装置可合适地在低过量O2下操作。将水以确保高速通过反应器的速率加入，由此确保无固体沉降。将有机贵金属原料在特殊设计的中试装置中沿管式反应器约1/4路程处、在水为明显超临界的点加入。将原料本身以合适的速率加入以产生绝热温度升高。原料可为液体有机贵金属组合物，在此情况下将其直接泵入反应器中，或可为固体，在此情况下将其在水中淤浆化然后泵入反应器中。可将来自反应器的排出物用3显示的骤冷水流稀释和/或中和，尽管这是非必要的，然后通过合适的卸压装置4(以阀门显示)，然后通入气/液分离罐5中。过量的气体，例如O2、N2、CO2等通过管线6排出，贵金属氧化物浆料通过分离罐底处的管线7排出。贵金属氧化物趋于为极细粉末形式(若原料为液体)，和对应于原料金属形式的颗粒(若为固体)，例如若是在碳上的钯催化剂。然后可将固定分离出来并按需要进行进一步处理或精炼。
为经济地使用水，优选使用循环水。类似地，良好的工程设计提供流体之间的热交换。
应理解，附图和上面的具体描述涉及操作的“直接注入”模式。本领域熟练技术人员将懂得本发明可以多种细节不同的方式操作。例如，和特别对于固体原料如Pd/C或Pt/C，可将该原料合适地在水中淤浆化，经热交换器加入反应器中，然后注入氧气进行氧化反应。
现在本发明将以工作实施例的方式描述。
实施例1
将80Kg用过的在碳上的Pt催化剂用720Kg水淤浆化，将其通过研磨泵以降低颗粒尺寸，并以速率250Kg/hr加入超临界水氧化剂反应器中。该新催化剂为载在碳上的5wt％Pt，但分析用过的催化剂为载在碳上的1.6wt％Pt。将氧以调节至在出口气体中产生15％O2的速率加入反应器中。将排出物浆料过滤，得到细的黑色Pt氧化物和透明的浅黄色滤液。该滤液含0.5ppm以下的Pt。
实施例2
使用实施例1的方法处理未使用的掺有甲苯的5wt％Pd/碳催化剂。滤液含0.01ppm以下的Pd。通常，用过的催化剂含有在碳上的0.8wt％Pd，并且也可按照本发明处理。
实施例3
采用实施例1的方法，将含0.973wt％Rh的铑膦液体有机催化剂流体直接加入反应器中。该产品液体为极细黑色颗粒在无色溶液中的浆料。
在上面的所有实施例中，回收贵金属和破坏有机物都超过95wt％。可预期该方法经最佳组合后产生更好的结果。
Claims (8)
1.一种精炼有机贵金属组合物的方法，包括在含超临界水和氧源的反应液体中处理该组合物，至少使组合物的有机组分氧化并从反应产品中回收贵金属氧化物。
2.根据权利要求1的方法，其中有机贵金属组合物包括一种或多种铂族金属。
3.根据权利要求1或2的方法，其中氧源为氧。
4.根据权利要求3的方法，其中氧由液氧供给。
5.根据前述权利要求任何一项的方法，在温度400至600℃下进行。
6.根据前述权利要求任何一项的方法，在连续延长的反应器中进行。
7.根据权利要求6的方法，其中将有机贵金属组合物与水掺混并加入反应器中，然后加入氧。
8.根据权利要求7的方法，其中将混合物在温度低于水的临界温度下加入反应器中，并且自氧化放出的热提供超临界温度。
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| CN101608263A (zh) * | 2009-07-13 | 2009-12-23 | 中国科学院生态环境研究中心 | 废弃印刷线路板富集贵金属同时合成Cu2O/TiO2纳米光催化剂的工艺 |
| CN104060094A (zh) * | 2014-06-10 | 2014-09-24 | 福建工程学院 | 一种从废弃手机回收金和铜的方法 |
| CN110257636A (zh) * | 2019-07-11 | 2019-09-20 | 廊坊新奥龙河环保科技有限公司 | 超临界氧化回收催化剂中贵金属的方法 |
| CN111112295A (zh) * | 2019-12-27 | 2020-05-08 | 新地环保技术有限公司 | 含贵金属的废催化剂的预处理方法及系统 |
| CN113332927A (zh) * | 2021-05-25 | 2021-09-03 | 杭州灰弘环保科技有限公司 | 一种新型垃圾焚烧飞灰制浆水洗及碳中和耦合系统及方法 |
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| CN114477319B (zh) * | 2022-03-03 | 2024-06-11 | 湖南中先智能科技有限公司 | 一种硫酸镍制备工艺及设备 |
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| CN1308470C (zh) * | 2005-03-15 | 2007-04-04 | 深圳市伟雄机械设备有限公司 | 贵金属的无毒低成本提炼方法 |
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| CN111112295A (zh) * | 2019-12-27 | 2020-05-08 | 新地环保技术有限公司 | 含贵金属的废催化剂的预处理方法及系统 |
| CN111112295B (zh) * | 2019-12-27 | 2021-11-30 | 新地环保技术有限公司 | 含贵金属的废催化剂的预处理方法及系统 |
| CN113332927A (zh) * | 2021-05-25 | 2021-09-03 | 杭州灰弘环保科技有限公司 | 一种新型垃圾焚烧飞灰制浆水洗及碳中和耦合系统及方法 |
| CN113332927B (zh) * | 2021-05-25 | 2022-04-01 | 杭州灰弘环保科技有限公司 | 一种新型垃圾焚烧飞灰制浆水洗及碳中和耦合系统及方法 |
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| CN114477319B (zh) * | 2022-03-03 | 2024-06-11 | 湖南中先智能科技有限公司 | 一种硫酸镍制备工艺及设备 |
Also Published As
| Publication number | Publication date |
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| GB0010241D0 (en) | 2000-06-14 |
| ATE316585T1 (de) | 2006-02-15 |
| WO2001083834A1 (en) | 2001-11-08 |
| DE60116861D1 (de) | 2006-04-13 |
| JP2003531964A (ja) | 2003-10-28 |
| ZA200208042B (en) | 2003-10-07 |
| AU780392B2 (en) | 2005-03-17 |
| EP1294955A1 (en) | 2003-03-26 |
| JP5073143B2 (ja) | 2012-11-14 |
| US7122167B2 (en) | 2006-10-17 |
| KR100812623B1 (ko) | 2008-03-13 |
| CA2407605A1 (en) | 2001-11-08 |
| AU4441901A (en) | 2001-11-12 |
| BR0110344A (pt) | 2003-01-14 |
| ES2254383T3 (es) | 2006-06-16 |
| KR20020089499A (ko) | 2002-11-29 |
| US20030185733A1 (en) | 2003-10-02 |
| EP1294955B1 (en) | 2006-01-25 |
| DE60116861T2 (de) | 2006-08-10 |
| CA2407605C (en) | 2010-04-06 |
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