CN101147864A - 一种制备新型催化还原脱氯剂的方法 - Google Patents
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Abstract
本发明的目的是提供一种制备新型催化还原脱氯剂的方法，它是制备纳米Ni－Fe双金属复合催化还原脱氯剂的方法。该脱氯剂能够在纳米Fe0表面生成NiB非晶态合金团簇，进而提高了纳米Fe0的脱氯性能。本发明的特点在于所研制的纳米Ni－Fe双金属复合催化还原脱氯剂中，NiB非晶态合金均匀分布在纳米Fe0表面，在促进Fe0与反应物进行反应的同时，又不会将纳米Fe0的活性表面覆盖，保证Fe0能够充分与反应物接触，使脱氯反应效率大大提高。
Description
技术领域
本发明是涉及一种新型催化还原脱氯剂的制备方法，更具体的说是一种制备具有高脱氯效率的纳米Ni-Fe复合催化还原脱氯剂的方法。
背景技术
含氯有机化合物种类繁多，又是重要的化工原料、中间体和有机溶剂，因而被广泛应用于化工、医药、制革、机械、木材防腐等行业。它们通过挥发、容器泄漏、废水排放、农药和杀虫剂使用及含氯有机物成品的燃烧等途径进入环境，严重污染了大气、土壤、地下水和地表水。几乎所有的氯代芳烃及其衍生物都有毒性且难于降解，其中许多含氯有机物被列为美国EPA环境优先控制污染物。尤其是持久性有机污染物(Persistent Organic Pollutant，简称POPs)，具有“致癌、致畸、致突变”的“三致”效应和遗传毒性；同时，由于很多含氯有机物具有高挥发性和类酯物可溶性，易被皮肤、粘膜等吸收而对人体造成严重损害。因此，含氯有机污染物已经引起了各国政府、学术界、工业界和公众的广泛关注，成为一个全球性环境问题。近年来，随着纳米技术的发展，针对纳米Fe0和纳米M-Fe双金属体系(M＝Ni，Pt，Pd，Cu，Ag等)已经成为有机氯降解研究的新热点。纳米Fe0和纳米M-Fe双金属体系的比表面和表面反应性都较普通铁粉高。如，纳米Pd/Fe的BET比表面积为33.5m2/g，而Fe粉的BET比表面积为0.9m2/g；纳米级Pd/Fe的比反应速率常数(kSA)为商品Fe粉的几十倍到几百倍。此外，纳米级Fe微粒可以被注入被污染的土壤、沉积物或蓄水层进行原位修复，以替代传统铁反应墙或将地下水抽出后进行治理的方法。
目前，CN1868913报道了一种铁硅合金粉体与铝镁合金粉体作为脱氯材料去除水体中含氯有机物的方法。该类脱氯剂可以快速降解消除水体中的含氯有机物。CN1837106则报道了一种超声辅助强化金属还原有机氯化物脱氯的方法。选取零价金属或金属合金作为还原剂，在反应设备内设超声波发生器，超声波发生器向水体发射超声波，强化还原剂对废水中的有机氯的还原脱氯过程。另外，大量文献报道双金属催化剂具有单金属催化剂无法比拟的加氢活性和选择性。CN1831197和CN1183316报道了不同方法制备Pd-Fe复合催化还原脱氯剂脱除水中含氯有机物的过程。而由于贵金属Pd的价格昂贵，影响了这种脱氯剂的广泛应用。所以，使用过渡金属来替代贵金属是具有实用意义的。2002年，Thomas E.Mallouk报道了一种Ni-Fe双金属催化剂在氯代有机物脱除反应中的应用(Chem.Mater.2002，14，5140-5147)。作者使用KBH4还原Ni2+和Fe2+的混合溶液，得到纳米Ni-Fe复合催化还原脱氯剂。作者认为，Fe0起到还原剂的作用，沉积在Fe0表面的Ni起到催化的作用。而由于实验方法的限制，很难避免Fe0对Ni的包覆，使得部分Ni不能被利用。因此，寻找一种能使纳米Ni均匀沉积于纳米Fe0表面的制备双金属脱氯剂的方法是具有重大的理论和实际意义。
发明内容
本发明的目的是提供一种制备新型催化还原脱氯剂的方法，它是制备纳米Ni-Fe双金属复合催化还原脱氯剂的方法，该脱氯剂能够在纳米Fe0表面生成NiB非晶态合金团簇，进而提高了纳米Fe0的脱氯性能。
本发明的特点在于所研制的纳米Ni-Fe双金属复合催化还原脱氯剂中，NiB非晶态合金均匀分布在纳米Fe0表面，在促进Fe0与反应物进行反应的同时，又不会将纳米Fe0的活性表面覆盖，保证Fe0能够充分与反应物接触，Ni占脱氯剂的总重量的1％～45％。
催化还原脱氯剂的制备步骤如下：
将化学还原法制备的纳米Fe0(5～200nm)加入到5～350ml NiB化学镀液中，在20～90℃下搅拌5～120min。产物经去离子水洗涤至中性，再用无水乙醇洗去残留水分。产物经干燥后，可用于氯苯水溶液的脱氯反应。
所述的纳米Fe0尺寸在5～200nm内，优选团簇尺寸为60nm纳米Fe0。
所述的反应中加入的NiB化学镀液体积为5～350ml，优选220ml。
所述的反应温度为20～90℃，优选40℃。
具体实施方式
对比例1
本对比例说明催化还原脱氯剂的制备过程。
实施例1～10
这些实施例说明Ni-Fe双金属复合催化还原脱氯剂过程。
将1.0g尺度为60nm的纳米Fe0与70ml NiB化学镀液混合，在35℃下搅拌10min。产物经去离子水洗涤至中性，再用无水乙醇洗去残留水分。产物经干燥后，得到脱氯剂A。其中NiB化学镀液的组成为NiSO4·6H2O，乙二胺，NaOH，KBH4和去离子水。
同脱氯剂A制备过程一样，将60nm左右的纳米Fe0改成5nm纳米Fe0、100nm纳米Fe0和200nm纳米Fe0，得到脱氯剂B-D。
同脱氯剂A制备过程一样，改变NiB化学镀液的用量，控制Ni占脱氯剂总重量的1％和45％，得到脱氯剂E和F。
同脱氯剂A制备过程一样，将反应温度由35℃改变为20℃和90℃，得到脱氯剂G和H。
同脱氯剂A制备过程一样，将反应时间由10min改变为5min和120min，得到脱氯剂I和J。
对比例2
本对比例用于说明催化剂在氯苯水溶液脱氯反应中的催化性能，反应是在250ml三颈瓶中进行的，反应条件是：温度25℃，氯苯溶液浓度为200mg/L，脱氯剂用量为1∶400(重量比)，反应8h。
表1
| 催化剂 | 脱氯率(％) |
| NiB | 1.3 |
| 纳米Fe0 | 8.7 |
| A | 85.1 |
| B | 71.3 |
| E | 30.2 |
| F | 78.6 |
| H | 20.6 |
| J | 58.3 |
Claims (8)
1.本发明的目的是提供一种制备新型催化还原脱氯剂的方法，它是制备纳米Ni-Fe双金属复合催化还原脱氯剂的方法，该脱氯剂能够在纳米Fe0表面生成NiB非晶态合金团簇，进而提高了脱氯剂的脱氯性能。
本发明的特点在于所研制的纳米Ni-Fe双金属复合催化还原脱氯剂中，NiB非晶态合金均匀分布在纳米Fe0表面，在促进Fe0与反应物进行反应的同时，又不会将纳米Fe0的活性表面覆盖，保证Fe0能够充分与反应物接触，Ni占脱氯剂的总重量的1％～45％。
催化还原脱氯剂的制备：
将化学还原法制备的纳米Fe0(5～200nm)加入到5～350ml NiB化学镀液中，在20～90℃下搅拌5～120min。产物经去离子水洗涤至中性，再用无水乙醇洗去残留水分。产物经干燥后，可用于氯苯水溶液的脱氯反应。
2.按照权利要求1所述的纳米Fe0尺寸在5～200nm内，优选团簇尺寸为60nm纳米Fe0。
3.按照权利要求1所述的反应中加入的NiB化学镀液体积为5～350ml，优选220ml。
4.按照权利要求1所述的NiB化学镀液的组成为NiSO4·6H2O，乙二胺，NaOH，KBH4和去离子水。
5.按照权利要求1所述的反应温度为20～90℃，优选40℃。
6.按照权利要求1所述的搅拌时间为5～120min，优选10min。
7.按照权利要求1所述的纳米Ni-Fe双金属复合催化还原脱氯剂中，Ni占催化剂的总重量的1％～45％，优选21.7％。
8.权利要求1制备的催化还原脱氯剂应用于氯苯还原脱氯反应。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824718A (zh) * | 2012-09-07 | 2012-12-19 | 桂林市产品质量监督检验所 | 复合型催化脱氯剂 |
| CN104722774A (zh) * | 2015-03-09 | 2015-06-24 | 武汉科技大学 | 一种纳米铁/镍自组装微粒还原/催化剂及其制备方法 |
| CN107398271A (zh) * | 2016-05-19 | 2017-11-28 | 中国科学院大连化学物理研究所 | 炭载金原子簇催化剂及其在葡萄糖催化氧化中的应用 |
| CN117282431A (zh) * | 2023-09-22 | 2023-12-26 | 上海园林绿化建设有限公司 | 非晶态Co-Ni-Fe加氢脱氯催化剂及其制备方法和应用 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824718A (zh) * | 2012-09-07 | 2012-12-19 | 桂林市产品质量监督检验所 | 复合型催化脱氯剂 |
| CN102824718B (zh) * | 2012-09-07 | 2015-04-15 | 桂林市产品质量监督检验所 | 复合型催化脱氯剂 |
| CN104722774A (zh) * | 2015-03-09 | 2015-06-24 | 武汉科技大学 | 一种纳米铁/镍自组装微粒还原/催化剂及其制备方法 |
| CN107398271A (zh) * | 2016-05-19 | 2017-11-28 | 中国科学院大连化学物理研究所 | 炭载金原子簇催化剂及其在葡萄糖催化氧化中的应用 |
| CN107398271B (zh) * | 2016-05-19 | 2020-05-05 | 中国科学院大连化学物理研究所 | 炭载金原子簇催化剂及其在葡萄糖催化氧化中的应用 |
| CN117282431A (zh) * | 2023-09-22 | 2023-12-26 | 上海园林绿化建设有限公司 | 非晶态Co-Ni-Fe加氢脱氯催化剂及其制备方法和应用 |
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