CN113860358B - 一种利用制革含硫废水制备多元金属硫化物纳米片的方法 - Google Patents
一种利用制革含硫废水制备多元金属硫化物纳米片的方法 Download PDFInfo
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Abstract
本发明公开了一种利用制革含硫废水制备多元金属硫化物纳米片的方法。以硫化物浓度为1542~2700 mg/L的制革高浓度含硫废水为硫源，通过废水预处理、原位共沉淀、水热合成和冷冻干燥等工艺制得多元金属硫化物纳米片SnInxSy。采用本发明的方法处理后的废水可回用于制革脱毛工序或直接进入生化处理单元，制得的多元金属硫化物纳米片（SnInxSy）可见光催化剂兼具比表面积高、可见光响应强、稳定性好等特点，可应用于废水中重金属、有机物的可见光催化降解，达到“以废治废、变废为宝”的绿色发展目的，经济和社会效益显著。
Description
技术领域
本发明属于制革废水处理技术领域，具体涉及一种利用制革含硫废水制备多元金属硫化物纳米片的方法。
背景技术
资源短缺和环境污染是二十一世纪人类发展面临的主要问题，然而工业生产过程中却普遍存在资源浪费，并导致不同程度的环境污染。制革原料皮脱毛过程中产生大量高浓度的含硫废水，硫化物浓度高达4000～6000 mg/L，含硫废水中S2-离子和逸出的H2S气体具有毒性和腐蚀性，废水排放不仅对人体和环境生物危害较大，而且浪费了大量的硫资源。目前，高浓度含硫废水处理方法有超滤膜法、催化氧化法、酸化吸收法、化学沉淀法等，上述方法无法达到较高的脱硫效率，而且运行过程中容易产生二次污染，更无法实现硫资源回收。鉴于此，探索高浓度含硫废水资源化利用对上述行业的可持续发展具有重要意义。
半导体光催化技术能够直接利用太阳能将污染物转化为低毒或无毒的盐类、小分子、水和二氧化碳，在空气和水体净化方面表现出独特的优势，被认为是解决环境污染问题的理想途径。金属硫化物半导体是一种常见的可见光催化材料，与金属氧化物相比具有较负的价带位置和较窄的禁带宽度，因而在光解水产氢、还原CO2、降解污染物等领域具备广阔前景。传统的二元硫化物（如：CdS、ZnS）光腐蚀严重、可见光响应范围窄、无法进行能带位置调控等不足在实际应用受到限制。因此，设计出具备稳定性、可见光响应且有合适能带结构的金属硫化物半导体材料成为光催化领域研究的热点。三元金属硫化物半导体因具有稳定性好、可见光吸收强、禁带宽度和价带位置可调控等优点成为可见光催化领域的研究热点。此外，三元金属硫化物半导体可避免使用Cd、Pb、Hg等有毒有害金属，只需通过精确的化学计量就能实现能带位置的调控，从而实现在可见光或红外光条件下降解污染物。
针对制革高浓度含硫废水去除效率不高且没有资源化利用的问题，本发明以制革高浓度含硫废水作为硫源制备了一种三元金属硫化物（SnInxSy）可见光催化剂，并将其应用于制革废水中染料的光催化降解，实现了“以废治废”，为制革废水的深度处理和资源化利用提供一种新的途径。
发明内容
本发明的目的在于提供一种利用制革含硫废水制备多元金属硫化物纳米片的方法。该方法既能有效地回收制革含硫废水中的硫资源，同时又实现了制备的多元金属硫化物纳米片在可见光条件下对制革废水中的染料、Cr(VI)等污染物的高效降解，为制革高浓度含硫废水的资源化利用和制革行业的可持续发展提供新思路。
为实现上述目的，本发明采用如下技术方案：
一种利用制革高浓度含硫废水制备多元金属硫化物纳米片的方法，是以高浓度制革含硫废水制备一种多元金属硫化物（SnInxSy）可见光催化剂；其制备方法是采用原位化学共沉淀回收高浓度含硫废水中的硫化物（S2-、HS-、-SH），再通过水热法得到多元金属硫化物纳米片（SnInxSy），具体包括以下步骤：
（1）来源于制革厂脱毛工序产生的高浓度含硫废水通过高速离心沉淀去除废水中的皮毛、不溶性悬浮颗粒等杂质，加酸调节pH值至7~8，并按批次检测废水中硫化物的浓度；
（2）将Sn和In的金属盐溶解于醋酸溶液中，室温下搅拌形成无色透明溶液，加入表面活性剂后，继续搅拌形成得到金属盐前驱体；
（3）将步骤（1）预处理的高浓度含硫废水置于高压反应釜中，室温下持续搅拌，根据废水中硫化物浓度，按摩尔比缓慢滴加步骤（2）配备的金属盐前驱体，待滴加完毕，继续搅拌1~2h；再将体系置于160~200℃烘箱中恒温反应12~24h，待反应结束后冷却至室温，离心、洗涤、冷冻干燥，即得到SnInxSy金属硫化物纳米片。
本发明通过原位沉淀回收制革高浓度含硫废水中的硫化物，废水中硫化物的去除率达到99.6%，浓度低于20mg/L，可满足生物处理的进水要求。采用水热法生长晶体，利用废水中有机高分子诱导晶体生长，制备得到具有单分散、高比表面积、可见光吸收的三元金属硫化物纳米片（SnInxSy）。
本发明根据废水中硫化物的浓度，按摩尔比投加金属盐前驱体，通过原位化学沉淀法可高效的回收废水中的硫化物资源，脱硫效率高，可达到生物处理的进水标准。经过步骤1~3处理后的含硫废水中硫化物浓度1542~2700 mg/L下降为5.2~14.3 mg/L，硫化物去除率为99.3~99.6%；
本发明通过水热法制备的SnInxSy纳米片，具有较高的比表面积（102.7～111.5m2/g）和可见光吸收能力（吸收边落在可见光区域635～700 nm），可见光下（λ ≥ 420 nm）对RhB溶液的去除率为91.2～99.2%。
本发明涉及三元金属硫化物纳米片，通过调控Sn和In的摩尔比可调控带隙结构和带隙能，从而提高对太阳光的利用效率。
本发明的有益效果在于：
（1）本发明通过原位化学沉淀回收制革高浓度含硫废水中的硫化物，制备SnInxSy可见光催化剂，调节金属盐Sn4+和In3+的摩尔比以调控金属硫化物可见光催化材料的禁带宽度、价带和导带位置，提高光催化剂的氧化还原电势，从而显著提高光催化材料降解废水中染料和还原Cr(VI)的光催化活性，故可应用于制革废水浓度处理，实施例1-4数据表明，本发明SnInxSy纳米片在可见光条件下，光催化降解RhB效率明显高于商品TiO2(P25)。
（2）本发明属于废物资源化、高值化利用，制备方法简单，反应条件温和，生产成本低，适合大规模生产，可为制革行业可持续发展提供新方法和新思路。本发明将为其他废水资源化和高值化利用提供借鉴。
附图说明
图1为实施例1-4制备的光催化剂的XRD谱图；
图2为实施例1-4制备的光催化剂的DRS谱图；
图3为实施例1-4制备的光催化剂降解RhB反应速率。
实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例
（1）制革高浓度含硫废水预处理
将1000 mL制革脱毛工序产生的高浓度含硫废水（硫化物浓度2172mg/L、pH 11.2、SS 1250、COD 9285 mg/L），离心去除废水中的皮毛、不溶性悬浮颗粒等杂质，加入5%的盐酸溶液调节pH值至7~8，检测废水中硫化物的浓度为1522 mg/L；
（2）金属盐前驱体的制备
将476.8 mg SnCl4·5H2O和398.8 mg InCl3·4H2O溶解于10mL 20%醋酸溶液中，室温下搅拌形成无色透明溶液（Sn : In = 1 : 1），加入0.01 g十六烷基三甲基溴化氨，继续搅拌得到金属盐前驱体；
（3） 金属硫化物纳米片的制备
将100 mL步骤（1）预处理的高浓度含硫废水置于高压反应釜中，室温下持续搅拌，根据废水中硫化物浓度，按摩尔比缓慢滴加步骤（2）配备的金属盐前驱体，待滴加完毕，继续搅拌1h；再将体系置于160℃烘箱中恒温反应24 h，待反应结束后冷却至室温，离心、洗涤、冷冻干燥，即得到SnInS3.5金属硫化物纳米片。
所制备的光催化材料吸收边650 nm，比表面积为105.4 m2/g，对RhB溶液的降解率为98.6%。过滤后硫化物的浓度为15.8 mg/L，硫化物的去除率为99.3%。
实施例
（1）制革高浓度含硫废水预处理
将1000 mL制革脱毛工序产生的高浓度含硫废水（硫化物浓度硫化物浓度2236mg/L、pH 11.8、SS 1050、COD 10325 mg/L），离心去除废水中的皮毛、不溶性悬浮颗粒等杂质，加入5%的硫酸溶液调节pH值至7~8，检测废水中硫化物的浓度为1634 mg/L；
（2）金属盐前驱体的制备
将357.6 mg SnCl4·5H2O和598.2 mg InCl3·4H2O溶解于10mL 20%醋酸溶液中，室温下搅拌形成无色透明溶液（Sn : In = 1 : 2），加入0.008 g十二烷基硫酸钠，继续搅拌得到金属盐前驱体；
（3） 金属硫化物纳米片的制备
将100 mL步骤（1）预处理的高浓度含硫废水置于高压反应釜中，室温下持续搅拌，根据废水中硫化物浓度，按摩尔比缓慢滴加步骤（2）配备的金属盐前驱体，待滴加完毕，继续搅拌1h；再将体系置于180℃烘箱中恒温反应12h，待反应结束后冷却至室温，离心、洗涤、冷冻干燥，即得到SnIn2S5金属硫化物纳米片。
所制备的光催化材料吸收边650 nm，比表面积为105.4 m2/g，对RhB溶液的降解率为98.6%。过滤后硫化物的浓度为15.8 mg/L，硫化物的去除率为99.3%。
实施例
（1）制革高浓度含硫废水预处理
将1000 mL制革脱毛工序产生的高浓度含硫废水（硫化物浓度2602mg/L、pH 11.5、SS 1147、COD 9820 mg/L），离心去除废水中的皮毛、不溶性悬浮颗粒等杂质，加入5%的硝酸溶液调节pH值至7~8，检测废水中硫化物的浓度为1758mg/L；
（2）金属盐前驱体的制备
将274.8 mg SnCl4·5H2O和689.1 mg InCl3·4H2O溶解于10mL 20%醋酸溶液中，室温下搅拌形成无色透明溶液（Sn : In = 1 : 3），加入0.015 g十二烷基苯磺酸钠，继续搅拌得到金属盐前驱体；
（3） 金属硫化物纳米片的制备
将100 mL步骤（1）预处理的高浓度含硫废水置于高压反应釜中，室温下持续搅拌，根据废水中硫化物浓度，按摩尔比缓慢滴加步骤（2）配备的金属盐前驱体，待滴加完毕，继续搅拌1h；再将体系置于180℃烘箱中恒温反应18h，待反应结束后冷却至室温，离心、洗涤、冷冻干燥，即得到SnIn3S7金属硫化物纳米片。
所制备的光催化材料吸收边675 nm，比表面积为108.6 m2/g，对RhB溶液的降解率为99.2%。过滤后硫化物的浓度为9.2 mg/L，硫化物的去除率为99.6%。
实施例
（1）制革高浓度含硫废水预处理
将1000 mL制革脱毛工序产生的高浓度含硫废水（硫化物浓度2353mg/L、pH 12.3、SS 1012、COD 9488 mg/L），离心去除废水中的皮毛、不溶性悬浮颗粒等杂质，加入5%的硝酸溶液调节pH值至7~8，检测废水中硫化物的浓度为1758mg/L；
（2）金属盐前驱体的制备
将274.8 mg SnCl4·5H2O和689.1 mg InCl3·4H2O溶解于10mL 20%醋酸溶液中，室温下搅拌形成无色透明溶液（Sn : In = 1 : 4），加入0.5 mL曲拉通X-100，继续搅拌得到金属盐前驱体；
（3） 金属硫化物纳米片的制备
将100 mL步骤（1）预处理的高浓度含硫废水置于高压反应釜中，室温下持续搅拌，根据废水中硫化物浓度，按摩尔比缓慢滴加步骤（2）配备的金属盐前驱体，待滴加完毕，继续搅拌1h；再将体系置于200℃烘箱中恒温反应12 h，待反应结束后冷却至室温，离心、洗涤、冷冻干燥，即得到SnIn4S8金属硫化物纳米片。
所制备的光催化材料吸收边700 nm，比表面积为111.5 m2/g，对RhB溶液的降解率为97.6%。过滤后硫化物的浓度为14.1mg/L，硫化物的去除率为99.4%。
如表1所示，随着In含量的增加，所制备的光催化剂比表面积和孔容积有所增大，有利于增加反应活性点位。如图1所示，SnInxSy纳米片的衍射峰发生宽化，说明样品的粒径较小。实施例1-4的样品在27.5°和47.8°附近有明显的衍射峰，分别归属于（311）和（440）晶面。如图2所示，随着In含量的增加，其可见光吸收带发生红移，从而提高催化剂可见光利用效率，增强催化活性。如图3所示，In含量的增加，光催化降解罗丹明的效率相应提高，SnIn4S8对RhB溶液的降解率为97.6%。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (6)
1.一种利用制革含硫废水制备多元金属硫化物纳米片的方法，其特征在于：包括如下步骤：
（1）制革高浓度含硫废水预处理
将制革高浓度含硫废水离心，去除废水中不溶性杂质，加酸调节pH=7~8，检测废水中硫化物的浓度；
（2）金属盐前驱体的制备
将Sn和In的金属盐溶解于醋酸溶液中，室温下搅拌形成无色透明溶液，加入表面活性剂，继续搅拌均匀，得到金属盐前驱体；
（3）金属硫化物纳米片的制备
将步骤（1）预处理的高浓度含硫废水在室温下持续搅拌，根据废水中硫化物浓度，按摩尔比缓慢滴加步骤（2）配备的金属盐前驱体，滴加完毕后继续搅拌1~2h；在160~200℃下水热反应12~24h，自然冷却至室温，离心、洗涤、冷冻干燥，得到所述的多元金属硫化物纳米片SnInxSy，x=1~4，y=3.5~8；纳米片的比表面积为85.8~111.5 m2/g，带隙宽度小于2.06 eV，可见光吸收波长大于601nm。
2.根据权利要求1所述的方法，其特征在于：所述的高浓度含硫废水来源于制革及毛皮制革的脱毛或毁毛工序，毛皮为黄牛皮、水牛皮、牦牛皮、山羊皮、猪皮中的至少一种。
3.根据权利要求1所述的方法，其特征在于：步骤（1）中所述的制革高浓度含硫废水的主要水质特征为：
硫化物S2-和HS-：1542~2700 mg/L；
pH：11~12；
COD：8000~11000 mg/L；
悬浮物：1000~1200 mg/L。
4.根据权利要求1所述的方法，其特征在于：步骤（1）中所述的酸为盐酸、硫酸、硝酸中的至少一种。
5.根据权利要求1所述的方法，其特征在于：步骤（2）中Sn金属盐为SnCl4、SnBr4、乙酸锡(IV)、苯基三氯化锡中的至少一种，In金属盐为InCl3、In(NO3)3、醋酸铟中的至少一种，Sn和In的摩尔比为1:1~1:4。
6.根据权利要求1所述的方法，其特征在于：步骤（2）所述的表面活性剂为十二烷基硫酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化氨、曲拉通X-100中的至少一种，浓度为0.3~1.2mmol/L。
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