CN104525136A - 一种复合材料及其制备方法和用途 - Google Patents
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Abstract
本发明涉及一种可作为脱硫剂的复合材料，含有50～80质量份碳纳米管；20~40质量份壳聚糖；1~20份质量银。其制备方法包括：把壳聚糖、硝酸银和蒸馏水混合搅拌30min，然后搅拌状态下加入醋酸，搅拌至各原料全部溶解后加入碳纳米管，然后滴加硼氢化钠水溶液，使溶液中的银离子还原到纳米银，添加液体石蜡和交联剂，搅拌、洗涤、干燥处理后，即制得产品。本发明可用于烃类油尤其是变压器油的脱硫处理。吸附处理后把该吸附剂以乙醇-石油醚为萃取溶剂进行索氏提取，然后还原再生。本发明在提高载银量的方法上，采用壳聚糖作为絮凝助剂，利用高分子聚合物对金属离子的络合性能，实现对银粒子的纳米级分散和吸附剂的灵活性和更好渗透性，从而提高银的反应活性。
Description
技术领域
本发明涉及一种可作为脱硫剂的复合材料及其制备方法，主要用于烃类油的脱硫处理。
背景技术
变压器是保证用电的一个重要组成部分，其中变压器油运行长时间后易变质。硫在变压器油中大部分以五种形态存在：元素硫、硫醇、硫醚、二硫化物和噻吩。在这五种含硫物质中，较活泼的含硫物质称为腐蚀性含硫物，而比较稳定的含硫物如噻吩可以作为天然的抗氧化剂，但是在运行条件下可能会转化为腐蚀性硫，导致变压器油介损升高。因此在变压器油的再生工艺中应该尽量降低含硫量，在达到降低油介损的同时，延缓其在今后使用中油介损回升的趋势。
对于变压器油再生性能的评价主要有三个方面：脱色效果好；再生处理时间短；介损反弹慢，油处理精制程度深、寿命长。能够达到这些目标的有效处理方法之一就是要深度脱硫吸附处理。我们现有的XDK系列吸附剂已经投入生产应用，在变压器油再生处理中能够有效脱色、降低介损，但是总硫量的减少不明显，因此在原有的研究基础上，通过开发新型变压器油深度脱硫壳聚糖-碳纳米管-银吸附剂，以期达到实现变压器油更加高效的再生。
发明内容
鉴于变压器油再生深度脱硫的需要，本发明提供一种壳聚糖-碳纳米管-银脱硫剂复合材料及其制备方法，所得脱硫剂能够用于变质变压器油的脱硫处理，有效降低油品中的总硫量，吸附处理后的废油各项指标都达到国家标准。
本发明提供的技术方案是：一种壳聚糖-碳纳米管-银脱硫剂复合材料，所述复合材料含有碳纳米管20～100份；壳聚糖20~40份；银1~20份，所述份为质量份数。
本发明还提供了壳聚糖-碳纳米管-银脱硫剂复合材料的制备方法，包括以下步骤：把20~40质量份壳聚糖、5~35质量份硝酸银和1000~2000质量份蒸馏水混合搅拌30min，然后搅拌状态下加入醋酸，搅拌至各原料全部溶解后加入碳纳米管，然后滴加还原剂硼氢化钠水溶液，使溶液中的银离子还原到纳米银，添加液体石蜡（200~1000质量份）和交联剂，搅拌、洗涤、干燥处理后，即制得产品。
所述壳聚糖是重均分子量大于10kDa（优选12-200kDa）、脱乙酰度大于80%（优选82%-95%）的壳聚糖。
所述壳聚糖和硝酸银的重量比为1：0.2-0.8。
所述碳纳米管加入量为壳聚糖质量的0.5-3倍。
硼氢化钠水溶液的浓度为1-3wt%。
交联剂为25wt%戊二醛，交联剂和壳聚糖的重量比为0.4:1.0。
本发明所述的壳聚糖-碳纳米管-银脱硫剂可用于烃类油尤其是变压器油的脱硫处理。吸附处理后把该吸附剂以乙醇-石油醚为萃取溶剂进行索氏提取，然后还原再生。
本发明在提高载银量的方法上，采用壳聚糖作为絮凝助剂，利用高分子聚合物对金属离子的络合性能，实现对银粒子的纳米级分散和吸附剂的灵活性和更好渗透性，从而提高银的反应活性。
电子扫描显微镜（SEM，图1、图3、图5）测试显示负载后，壳聚糖-碳纳米管-银脱硫剂的微观形貌均一，说明在试验方法能够将壳聚糖-Ag均匀的负载到碳纳米管的表面，银的负载量能够通过原料比例和条件的改变实现可控制备，在实施例中X-射线能量色散谱测试测试表明材料表面的银元素质量百分比为39.69%（图2）、24.60%（图4）、11.79%（图6），通过原子吸收分光光度计测试确定脱硫剂的整体含银量分别为0.18g/g 、0.13 g/g、0.12 g/g，含量高于没有采用壳聚糖所得的吸附剂，也高于相关文献报道。该脱硫剂能够与变质变压器油充分接触，有效降低油品中的总硫量，吸附处理后的废油各项指标都达到国家标准。常温常压下操作，具有无毒、不易燃易爆等特点，其生产工艺简单，原料来源广泛，生产成本低廉，没有环境污染，而且处理后变压器油成品率高。该脱硫剂可以作为精脱硫剂使用，进行深度脱硫。
变压器油中的硫含量测定还没有具体的标准，本专利参考轻质石油产品硫含量的测定方法（电量法，SH/T0253-1992），采用微库仑法测定石油产品硫含量测定通常最小检出量可以达到100ppb。采用ASTMD 1275-2003（B法）进行绝缘油硫腐蚀测试：该方法是在规定条件（脱气、150℃下加热48小时）下铜片与试样（变压器油）接触，试样中的腐蚀性硫化物会导致铜片变质，根据铜片表面状态定性地检测试样中的腐蚀性杂质。采用恒温吸附进行脱硫处理，每100g脱硫剂处理1kg变压器油，控温80℃，吸附时间48h。
附图说明
图1是本发明实施例1的壳聚糖-碳纳米管-银脱硫剂的扫描电镜（SEM）图；
图2是本发明实施例1的壳聚糖-碳纳米管-银脱硫剂的X-射线能量色散谱（EDS）图；
图3是本发明实施例2的壳聚糖-碳纳米管-银脱硫剂的扫描电镜（SEM）图；
图4是本发明实施例2的壳聚糖-碳纳米管-银脱硫剂的X-射线能量色散谱（EDS）图；
图5是本发明实施例3的壳聚糖-碳纳米管-银脱硫剂的扫描电镜（SEM）图；
图6是本发明实施例3的壳聚糖-碳纳米管-银脱硫剂的X-射线能量色散谱（EDS）图。
具体实施方式
下面给出本发明的实施例，通过实施例对本发明进行具体描述。有必要在此指出的是，实施例只是对本发明进一步的说明，不能理解为对本发明范围的限制，该领域的技术人员可以对本发明的内容作出一些调整。
实施例1：
把1.0g壳聚糖（重均分子量约为12kDa、脱乙酰度92%）、0.6g硝酸银、100mL蒸馏水混合搅拌30min，然后搅拌状态下加入5mL纯醋酸到壳聚糖硝酸银水悬浮液，搅拌全部溶解后0.5g碳纳米管加入到上述溶液中，搅拌下20mL硼氢化钠水溶液（1.5%，wt%）滴加（1mL/min）到上述溶液中，搅拌，溶液的颜色变成黑色，然后添加100mL液体石蜡倒入溶液中。搅拌下0.5mL戊二醛（25%，wt%）溶液滴加到上述壳聚糖-银溶液。混合物再搅拌0.5小时，用1mol/L的氢氧化钠水溶液中和滴定，至pH为9，搅拌0.5小时，固液分离，将得到的固体产物用乙醇洗涤处理后在蒸馏水超声波分散洗涤10min，反复洗涤至pH值7.0-7.5，在80℃真空干燥，得到壳聚糖-碳纳米管-银吸附剂。制得的脱硫剂银含量为0.18g/g的产品。使用研制的三种复合材料（碳纳米管-壳聚糖-银、碳纳米管-壳聚糖、壳聚糖-银）对高硫变压器油（硫含量由1206mg/L）进行吸附处理，进行比较分析，试验结果表明三元复合材料的脱硫效果更好，通过载银能够有效降低油样的硫腐蚀性：
使用该脱硫剂吸附滤油，取样进行测试，结果如下：
实施例2：
把1.0g壳聚糖（重均分子量约为80kDa、脱乙酰度87%）、0.8g硝酸银、100mL蒸馏水混合搅拌30min，然后搅拌下加入5mL纯醋酸到壳聚糖硝酸银水悬浮液，搅拌全部溶解后2.5g碳纳米管加入到上述溶液中，搅拌下15mL 硼氢化钠水溶液（2%，wt%）滴加（1mL/min）到上述溶液中，搅拌，溶液的颜色变成黑色，然后添加120mL液体石蜡倒入溶液中。搅拌下0.8mL戊二醛溶液（25%，wt%）滴加到上述壳聚糖-银溶液。混合物再搅拌0.5小时，用1mol/L的氢氧化钠水溶液中和滴定，至pH为9，搅拌0.5小时，固液分离，将得到的固体产物用乙醇洗涤处理后在蒸馏水超声波分散洗涤10min，反复洗涤至pH值7.0-7.5，在80℃真空干燥，得到壳聚糖-碳纳米管-银吸附剂。制得的脱硫剂银含量为0.13g/g的产品。使用研制的三种复合材料（碳纳米管-壳聚糖-银、碳纳米管-壳聚糖、壳聚糖-银）对高硫变压器油（硫含量由1206mg/L）进行吸附处理，进行比较分析，试验结果表明三元复合材料的脱硫效果更好，通过载银能够有效降低油样的硫腐蚀性：
使用该脱硫剂吸附滤油，取样进行测试，结果如下：
实施例3：
把1.5g壳聚糖（重均分子量约为160kDa、脱乙酰度82%）、0.6g硝酸银、100mL蒸馏水混合搅拌30min，然后搅拌下加入5mL纯醋酸到壳聚糖硝酸银水悬浮液，搅拌全部溶解后1.5g碳纳米管加入到上述溶液中、搅拌情况下10mL硼氢化钠水溶液（2.6%，wt%）滴加（1mL/min）到上述溶液中，搅拌，溶液的颜色变成黑色，然后添加110mL液体石蜡倒入溶液中。搅拌下0.6mL戊二醛溶液（25%，wt%）滴加到上述壳聚糖-银溶液。混合物再搅拌0.5小时，用1mol/L的氢氧化钠水溶液中和滴定，至pH为9，搅拌0.5小时，固液分离，将得到的固体产物用乙醇洗涤处理后在蒸馏水超声波分散洗涤10min，反复洗涤至pH值7.0-7.5，在80℃真空干燥，得到壳聚糖-碳纳米管-银吸附剂。制得的脱硫剂银含量为0.12g/g的产品。使用研制的三种复合材料（碳纳米管-壳聚糖-银、碳纳米管-壳聚糖、壳聚糖-银）对高硫变压器油（硫含量由1206mg/L）进行吸附处理，进行比较分析，试验结果表明三元复合材料的脱硫效果更好，通过载银能够有效降低油样的硫腐蚀性：
使用该脱硫剂吸附滤油，取样进行测试，结果如下：
Claims (10)
1.一种复合材料，其特征在于：包括碳纳米管、壳聚糖和银；所述复合材料含有碳纳米管20～100份；壳聚糖20~40份；银1~20份，所述份为质量份数。
2.根据权利要求1所述的复合材料，其特征在于：所述壳聚糖是重均分子量大于10kDa、脱乙酰度大于80%的壳聚糖。
3.根据权利要求2所述的复合材料，其特征在于：所述壳聚糖的重均分子量为12-200kDa、脱乙酰度为82%-95%。
4.一种复合材料的制备方法，包括以下步骤：把20~40质量份的壳聚糖、5~35质量份硝酸银和1000~2000质量份蒸馏水混合搅拌30min，然后搅拌状态下加入醋酸，不断搅拌全部溶解后，加入碳纳米管，然后滴加还原剂硼氢化钠水溶液，使溶液中的银离子还原到纳米银，添加添加交联剂和200~1000质量份的液体石蜡，搅拌、洗涤、干燥处理后，即制得产品。
5.根据权利要求4所述复合材料的制备方法，其特征在于：所述壳聚糖和硝酸银的质量比为1：0.2-0.8。
6.根据权利要求4所述复合材料的制备方法，其特征在于：所述碳纳米管加入量为壳聚糖质量的0.5-3倍。
7.根据权利要求4所述复合材料的制备方法，其特征在于：硼氢化钠水溶液的浓度为1-3wt%。
8.根据权利要求4所述复合材料的制备方法，其特征在于：交联剂为25wt%戊二醛，交联剂和壳聚糖的质量比为0.4:1.0。
9.权利要求1或2或3所述复合材料用于烃类油的脱硫处理。
10.根据权利要求9所述的用途，其特征在于：所述烃类油为变压器油。
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