CN106914222B - 一种用于去除液相汞的吸附剂及其制备方法和使用方法 - Google Patents

一种用于去除液相汞的吸附剂及其制备方法和使用方法 Download PDF

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CN106914222B
CN106914222B CN201510999242.0A CN201510999242A CN106914222B CN 106914222 B CN106914222 B CN 106914222B CN 201510999242 A CN201510999242 A CN 201510999242A CN 106914222 B CN106914222 B CN 106914222B
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sulfide
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CN106914222A (zh
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李亚慧
姚鹏程
姜锐
臧晗宇
刘勇
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Shenyang Zhongke Envrionmental Engineering Technology Development Co Ltd
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Abstract

本发明涉及物理吸附、化学吸附净化技术领域，特别是涉及一种用于去除液相汞的吸附剂及其制备方法和使用方法。该吸附剂为负载在吸附剂载体上的硫醇自组装单分子膜和纳米硫化物，硫醇自组装单分子膜和纳米硫化物在载体上的负载量为15～50wt％。以高比表面积和大孔容的材料为载体，在其上负载硫化物和硫醇单分子自组装膜，将吸附剂制作成过滤柱对含汞废液进行过滤处理，制成的吸附剂单分子自组装膜具有较强的吸附能力，可以将液相中的汞单质或汞离子吸附包裹起来，与载体上的硫化物发生离子交换反应，锁定在载体的孔容内，达到除汞的目的。本发明吸附剂具有吸附容量大、吸附速率快的特点，适合油气田中含汞废水的治理。

Description

一种用于去除液相汞的吸附剂及其制备方法和使用方法
技术领域
本发明涉及物理吸附、化学吸附净化技术领域，特别是涉及一种用于去除液相汞的吸附剂及其制备方法和使用方法。
背景技术
汞由于具有持久性、易迁移性、生物累积性及高毒性等特点，汞污染已经引起国际社会的广泛关注。2013年1月联合国政府间谈判委员会通过了一项具有法律约束力的《国际防治汞污染公约》，将在全球范围内控制和减少汞排放。油气田中的汞会引起下游石油化工装里中的贵金属催化剂中毒，其含量一般为10～3000μg/L。目前，油气田脱汞主要采用化学吸附工艺，该工艺已在世界范围内的油气田脱汞装置中得到了广泛应用。传统的脱汞工艺具有一定的限制性，急需改进。当前废液中汞去除的方法大部分先是利用活性炭将汞吸附去除，或是利用硫化物与汞的反应生成HgS沉淀以去除液相中的汞。但是吸附剂的吸附容量一般比较小，如果大量使用会造成运行费用高，而利用硫化物生成HgS的方法很难使汞和硫循环利用；而且如果处置不当，这些方法可能造成二次污染。
发明内容
为了克服上述现有技术存在的缺陷，本发明的目的在于提供一种用于去除液相汞的吸附剂及其制备方法和使用方法，获得的液体吸附剂不仅适用于油气田处理厂内部的凝析油净化处理，还能用于含汞污水的净化，尤其是凝析油进料储量较大，有机汞含量较高的情况。
为实现上述目的，本发明的技术方案是：
一种用于去除液相汞的吸附剂，该吸附剂为负载在吸附剂载体上的硫醇自组装单分子膜和纳米硫化物，硫醇自组装单分子膜和纳米硫化物在载体上的负载量为15～50wt％。
所述的用于去除液相汞的吸附剂，纳米硫化物为锌、铁、铝和钛之一种或两种以上的金属硫化物。
所述的用于去除液相汞的吸附剂，硫醇自组装单分子膜为末端基团可离子化为正电荷的HS-R-NH2和带负电荷的HS-R-COOH，其中R代表具有2～20个碳原子的烷基、苯基或其衍生物。
所述的用于去除液相汞的吸附剂，吸附剂载体为具有大比表面积和孔容的材料，包括氧化铝、分子筛、硅藻土、凹凸棒土或活性炭之一种或两种以上。
所述的用于去除液相汞的吸附剂的制备方法，包括以下步骤：
第一步、选择吸附剂载体；
第二步、配置高浓度纳米硫化物溶液；
第三步、配置乙醇的水溶液，使乙醇的体积分数为20～40％，用3～5mol/L盐酸调节pH至3～4；搅拌均匀后向其中滴加硫醇，使硫醇的浓度为10～20wt％；超声处理5～15min后，室温下静置20～40min；
第四步、将吸附剂载体浸渍于高浓度纳米硫化物溶液中，并通过超声振荡0.5～1h，使其与吸附剂载体充分混合接触，将纳米吸附剂吸入到吸附剂载体的孔道内；
第五步、待到纳米吸附剂与吸附剂载体充分混合后，通过过滤将吸附剂载体分离出来，并于室温下干燥，得到载有纳米吸附剂的前驱体；
第六步、向步骤三中的溶液中滴加适量表面活性剂后，使表面活性剂的浓度为0.4～0.6wt％，加入载有纳米吸附剂的前驱体，磁力搅拌，60～80℃水浴加热冷凝回流5～7h；反应完全后冷却至室温，洗涤分离出固体于30～50℃下真空干燥20～30h，制得的产品即为载硫醇自组装单分子膜和纳米硫化物的吸附剂。
所述的用于去除液相汞的吸附剂的制备方法，高浓度纳米硫化物溶液是指锌、铁、铝和钛之一种或两种以上的金属硫化物水溶液，其浓度范围是0.1～10.0mol/L。
所述的用于去除液相汞的吸附剂的制备方法，第四步中所述的充分混合是指纳米吸附剂进入到吸附剂载体的空隙内，通过电镜扫描观察判断纳米吸附剂是否吸附在载体上。
所述的用于去除液相汞的吸附剂的制备方法，第六步中所述的表面活性剂为十六烷基三甲基溴化铵。
所述的用于去除液相汞的吸附剂的使用方法，包括以下步骤：
a.将制备好的吸附剂制作成过滤柱，利用自组装单分子膜来进行捕捉汞离子或汞单质，然后与孔内的纳米吸附剂反应生成沉淀，停留在载体内，形成的化合物结构稳定；
b.当过滤后的废液中汞含量达到10～3000μg/L，即对吸附剂进行更换，将失效的吸附剂进行深埋。
所述的用于去除液相汞的吸附剂的使用方法，通过由吸附剂制成的过滤柱，废液在过滤柱中的停留时间为60～120s。
与现有技术相比，本发明的优点及有益效果是：
1.本发明利用氧化铝、硅藻土等来源价格便宜的材料作为载体，负载金属硫化物采用由锌、铁、铝、钛中的一种或几种金属硫化物组合体。
2.本发明使用过程中通过自组装单分子膜用来捕捉溶液中的汞离子或汞单质，然后通过离子交换把汞离子锁定在孔容内，而进入液相中的金属离子本身无毒无害，不会造成二次污染。
3.本发明使用方法非常便捷，仅需将纳米除汞剂制成过滤柱，对含汞液体进行过滤处理，即可高效吸附液相中的汞离子及单质汞。
4.本发明使用油气田中的凝析油及其他涉汞行业的含汞废液去除。
总之，本发明以高比表面积和大孔容的材料为载体，在其内部负载上硫化物吸附剂，并在吸附剂上负载上硫醇自组装单分子膜用来吸附汞金属离子，自组装单分子膜用来捕捉溶液中的汞离子或汞单质，然后将吸附到的汞离子和汞单质与载体上的硫化物进行反应生成硫化汞锁定在载体孔内。
具体实施方式
在具体实施过程中，本发明用于去除液相汞的吸附剂为负载在吸附剂载体上的硫醇自组装单分子膜和纳米硫化物，硫醇自组装单分子膜和纳米硫化物在载体上的负载量为15～50wt％。
硫醇自组装单分子膜为末端基团可离子化为正电荷的HS-R-NH2和带负电荷的HS-R-COOH，其中R代表具有2～20个碳原子的烷基、苯基或其衍生物。纳米硫化物为锌、铁、铝、钛等无害金属硫化物。吸附剂载体为具有大比表面积和孔容的材料，包括氧化铝、分子筛、硅藻土、凹凸棒土、活性炭等。
在具体实施过程中，本发明用于去除液相汞的吸附剂的制备方法，包括以下步骤：
第一步、选择吸附剂载体；
第二步、配置高浓度纳米硫化物水溶液，其浓度为0.1～10.0mol/L；
第三步、配置一定比例的乙醇的水溶液，用4mol/L盐酸调节pH至3～4。搅拌均匀后，缓慢向其中滴加一定量硫醇。超声处理10min后，室温下静置30min；
第四步、将载体浸渍于高浓度纳米硫化物溶液中，并通过超声振荡0.5～1h，使其与载体充分混合接触，将纳米吸附剂吸入到载体孔道内，可以通过电镜扫描观察判断纳米吸附剂是否吸附在载体上；
第五步、待到纳米吸附剂与载体充分混合后，通过过滤将吸附剂载体从溶液中分离出来，并于室温下干燥，得到载有纳米吸附剂的前驱体；
第六步、然后向步骤三中的溶液中缓慢滴加一定量表面活性剂(十六烷基三甲基溴化铵CTAB)后立即加入载有纳米吸附剂的前驱体，磁力搅拌，70℃水浴加热冷凝回流6h。反应完全后冷却至室温，洗涤分离出固体于40℃下真空干燥24h，制得的产品即为载硫醇自组装单分子膜和纳米硫化物的吸附剂。
下面结合具体实施例对本发明进行详细说明。本实施例在以本发明技术方案前提下进行实施，给出了详细的实施方式和具体操作过程，但本发明的保护范围不限于下述的实施例。
实施例1
称取10g活性炭加入到盛有250ml浓硫酸的烧杯中，搅拌1h后，缓慢加入30g高锰酸钾并不断搅拌，形成分散液。分散液在室温下搅拌2h后，把反应液放入0.5L冰水浴中使反应停止。然后加入双氧水(质量分数为5％)10ml，使过量高锰酸钾反应完全，形成氧化活性炭。将氧化活性炭离心洗涤直至溶液中无SO4 2+，60℃真空干燥备用。然后将氧化活性炭在温度为95℃、超声振荡情况下，浸渍在1mol/L的硫化锌纳米吸附剂溶液中1h，将负载有硫化锌的氧化活性炭通过过滤分离出来，在25℃室温下干燥5h，制得载有纳米吸附剂的前驱体。配置乙醇的水溶液，使乙醇的体积分数为30％，用4mol/L盐酸调节pH至3～4。搅拌均匀后缓慢向其中滴加一定量γ-巯丙基三甲氧基硅烷(TMMPS)，使其浓度为15wt％。超声处理10min后，室温下静置30min。然后向其中缓慢滴加一定量十六烷基三甲基溴化铵(CTAB)，使其浓度为0.5wt％；加入5g载有纳米吸附剂的前驱体，磁力搅拌，70℃水浴加热冷凝回流6h。反应完全后冷却至室温，洗涤分离出固体于40℃下真空干燥24h。制得的产品即为载硫醇自组装单分子膜和纳米硫化物的吸附剂。
实施例2
与实施例1不同之处在于，将10g分子筛装入索氏抽提器中用乙醇抽提8h，抽提后用蒸馏水洗净，在60℃下用烘箱烘干，浸渍于2mol/L的硫化亚铁纳米吸附剂溶液中，在温度为95℃条件下，超声振荡1h，得到负载有硫化亚铁的分子筛，通过过滤洗涤分离出来，经干燥处理后，制得载有纳米吸附剂的前驱体。配置乙醇的水溶液，使乙醇的体积分数为35％，用4mol/L盐酸调节pH至3～4。搅拌均匀后缓慢向其中滴加一定量γ-巯丙基三甲氧基硅烷(TMMPS)，使其浓度为18wt％。超声处理10min后，室温下静置30min。然后向其中缓慢滴加一定量十六烷基三甲基溴化铵(CTAB)，使其浓度为0.6wt％；加入8g上述载有纳米吸附剂的前驱体，磁力搅拌，70℃水浴加热冷凝回流6h。反应完全后冷却至室温，洗涤分离出固体于40℃下真空干燥24h。制得的产品即为载硫醇自组装单分子膜和纳米硫化物的吸附剂。
实施例3
与实施例1不同之处在于，将10g具有大比表面积和孔容的硅藻土吸附剂载体置于配置好的硫化铝纳米吸附剂溶液中，95℃下超声振荡1h，通过过滤将吸附剂载体分离出来，并置于室温下干燥，制得载有纳米吸附剂的前驱体。配置乙醇的水溶液，使乙醇的体积分数为25％，用4mol/L盐酸调节pH至3～4。搅拌均匀后缓慢向其中滴加一定量γ-巯丙基三甲氧基硅烷(TMMPS)，使其浓度为12wt％。超声处理10min后，室温下静置30min。然后向其中缓慢滴加一定量十六烷基三甲基溴化铵(CTAB)，使其浓度为0.4wt％；加入10g上述载有纳米吸附剂的前驱体，磁力搅拌，70℃水浴加热冷凝回流6h。反应完全后冷却至室温，洗涤分离出固体于40℃下真空干燥24h。制得的产品即为载硫醇自组装单分子膜和纳米硫化物的吸附剂。
将上述吸附剂用于去除液相汞，包括以下步骤：
a.将制备好的吸附剂制作成过滤柱，利用自组装单分子膜来进行捕捉汞离子或汞单质，然后与孔内的纳米吸附剂反应生成沉淀，停留在载体内，形成的化合物结构稳定，无污染，达到液相除汞的目的。
b.当过滤后的废液中汞含量达到一定值，即对吸附剂进行更换，将失效的吸附剂进行深埋。
废液汞离子含量为10～3000μg/L，通过由吸附剂制成的过滤柱，吸附剂的使用量为20g，废液在过滤柱中的停留时间为60～120s。当过滤后的废液中汞含量达到相关排放标准限值后，即可以将过滤柱中的吸附剂替换下来，替换下来的吸附剂可直接深埋，对环境不会造成二次污染。
实施例结果表明，本发明以高比表面积和大孔容的材料为载体，在其上负载硫化物和硫醇单分子自组装膜，将吸附剂制作成过滤柱对含汞废液进行过滤处理，制成的吸附剂单分子自组装膜具有较强的吸附能力，可以将液相中的汞单质或汞离子吸附包裹起来，与载体上的硫化物发生离子交换反应，锁定在载体的孔容内，达到除汞的目的。该吸附剂具有吸附容量大、吸附速率快的特点，适合油气田中含汞废水的治理。

Claims (5)

1.一种用于去除液相汞的吸附剂的制备方法，其特征在于，该吸附剂为负载在吸附剂载体上的硫醇自组装单分子膜和纳米硫化物，硫醇自组装单分子膜和纳米硫化物在载体上的负载量为15～50wt%；
纳米硫化物为锌、铁、铝和钛之一种或两种以上的金属硫化物；
硫醇为γ-巯丙基三甲氧基硅烷，硫醇自组装单分子膜的 末端基团亲水基为-R-SH；
吸附剂载体为氧化铝、分子筛、硅藻土、凹凸棒土或活性炭之一种或两种以上；
所述的用于去除液相汞的吸附剂的制备方法，包括以下步骤：
第一步、选择吸附剂载体；
第二步、配置高浓度纳米硫化物溶液；
第三步、配置乙醇的水溶液，使乙醇的体积分数为20～40%，用3～5mol/L盐酸调节pH至3～4；搅拌均匀后向其中滴加硫醇，使硫醇的浓度为10～20wt%；超声处理5～15min后，室温下静置20～40min；
第四步、将吸附剂载体浸渍于高浓度纳米硫化物溶液中，并通过超声振荡0.5～1h，使其与吸附剂载体充分混合接触，将纳米吸附剂吸入到吸附剂载体的孔道内；
第五步、待到纳米吸附剂与吸附剂载体充分混合后，通过过滤将吸附剂载体分离出来，并于室温下干燥，得到载有纳米吸附剂的前驱体；
第六步、向步骤三中的溶液中滴加适量表面活性剂后，使表面活性剂的浓度为0.4～0.6wt%，加入载有纳米吸附剂的前驱体，磁力搅拌，60～80℃水浴加热冷凝回流5～7h；反应完全后冷却至室温，洗涤分离出固体于30～50℃下真空干燥20～30h，制得的产品即为载硫醇自组装单分子膜和纳米硫化物的吸附剂；
其中，高浓度纳米硫化物溶液是指锌、铁、铝和钛之一种或两种以上的金属硫化物水溶液，其浓度范围是0.1～10.0mol/L。
2.根据权利要求1所述的用于去除液相汞的吸附剂的制备方法，其特征在于，第四步中所述的充分混合是指纳米吸附剂进入到吸附剂载体的空隙内，通过电镜扫描观察判断纳米吸附剂是否吸附在载体的空隙内。
3.根据权利要求1所述的用于去除液相汞的吸附剂的制备方法，其特征在于，第六步中所述的表面活性剂为十六烷基三甲基溴化铵。
4.一种权利要求1所述的制备方法制备的用于去除液相汞的吸附剂的使用方法，其特征在于，包括以下步骤：
a.将制备好的吸附剂制作成过滤柱，利用自组装单分子膜来进行捕捉汞离子或汞单质，然后与孔内的纳米吸附剂反应生成沉淀，停留在载体内，形成的化合物结构稳定；
b.当过滤后的废液中汞含量达到10～3000μg/L，即对吸附剂进行更换，将失效的吸附剂进行深埋。
5.根据权利要求4所述的用于去除液相汞的吸附剂的使用方法，其特征在于，通过由吸附剂制成的过滤柱，废液在过滤柱中的停留时间为60～120s。
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