CN111001391B - 一种蒙脱石/硅酸钙复合吸附材料的制备方法 - Google Patents
一种蒙脱石/硅酸钙复合吸附材料的制备方法 Download PDFInfo
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052901 montmorillonite Inorganic materials 0.000 title claims abstract description 54
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 50
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 11
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Abstract
本发明公开了一种蒙脱石/硅酸钙复合吸附材料的制备方法,所述的方法为:将蒙脱石和硅酸钙混合在150℃~300℃温度下低温煅烧2~5小时,得到煅烧产物在质量分数为10~20%的过氧化氢溶液中搅拌0.5~4小时,过滤后得到预处理混合物配成质量浓度为1.0~15.0%的浆液,加入0.1~1.0质量份的硫酸铁、1.0~6.0质量份的柠檬酸、0.5~10.0质量份的葡萄糖酸钠和0.5~3.0质量份的过硫酸钠进行搅拌,过滤,滤饼在低于100℃温度下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。本发明制备的吸附材料可以同时吸附污染水样中有机污染物和重金属。该吸附材料具有原料来源广泛,制备工艺及操作简单,制备效率高,生产周期短,无需特殊化工设备,易于工业化批量生产。
Description
技术领域
本发明属于废水处理技术领域,涉及一种吸附材料的制备方法,具体地说涉及一种蒙脱石/硅酸钙复合吸附材料的制备方法。
背景技术
目前,冶炼、电镀、造纸、陶瓷制造等行业每年排放大量含有多种重金属的工业废水。重金属污染物具有潜在危害性,难被水中的微生物降解,可直接或间接对水生生物产生致毒致害作用,并通过生物富集、食物链放大等过程,进一步影响陆地生物和人类健康。重金属自身可随着水化学条件的变化而发生价态、形态的改变,并产生一系列物理化学反应,并可与水体沉积物、颗粒有机质或溶解有机质等相互作用,影响其沉降和迁移等地球化学过程。
有机污染物主要来源于化工企业排放的工业废水,其中含有大量的难以生化降解的有机化合物,主要包括酚类化合物、有机农药、多环芳烃等,其中很多有机污染物在环境中具有长期残留性、生物积蓄性、半挥发性和高毒性,具有致癌,致突变或致畸等潜在危害,给自然环境和人类健康造成很大的危害。其中酚类污染物在较低浓度时对生物体具有毒害作用,能够与生物体中的蛋白质结合,造成组织损伤。
目前,能够应用于同时吸附重金属和有机污染物的材料如石墨烯及其复合材料、磁性介孔氧化硅、碳纳米材料和微生物吸附剂,其生产工艺复杂、生产成本较高,限制了其在污染沉积物修复技术领域的实际应用。如:氧化石墨烯吸附膜的制备方法:在惰性气氛中制备杂化前驱体,其次将杂化前驱体与其他试剂进行反应,再将涂膜液进行涂膜得到氧化石墨烯吸附膜(刘俊生,武德伟,王凤侠,高腾,郑强松.一种脱除水中镍离子的氧化石墨烯吸附膜的制备方法:中国,CN110420621A[P].2019-11-08.)。介孔的氧化硅/碳纳米材料的制备方法:先溶解模板剂,加入其它试剂得到凝胶;再将凝胶在反应釜中晶化;进一步采用回流脱除模板剂,最后进行焙烧(朱正健,白诗扬,孙继红,武霞,尚慧.一种具有微孔及有序介孔的氧化硅/碳纳米材料的制备方法:中国,CN107117623A[P].2017-09-01.)。磁性碳纳米管复合材料的制备,需要将生产原料在200~300℃反应8~24h,该制备工艺虽制备过程简单,但其能耗较大(邓小娟,姚琲.一种磁性碳纳米管复合材料及其制备方法和应用:中国,CN103041773A[P].2013-04-17.)。对于废水处理来说,经济成本是首先要考虑的因素。因此,寻找和开发制备工艺高效简便、生产原料价格低廉的吸附材料是推进废水治理的关键和努力发展的方向。
蒙脱石具有一定的阳离子交换能力,可以用于吸附重金属离子。但天然蒙脱石的可交换阳离子容量大小限制了其对重金属离子的吸附容量。由于蒙脱石表面硅氧结构具有较强的亲水性,层间阳离子易发生水合,且键合能力较弱,对有机污染物的吸附性能较差。而硅酸钙由于原材料来源广、价格低廉从而在水污染处理中具有一定的应用价值,但天然硅酸钙因其比表面积较低使得其吸附性能较差。
发明内容
为了解决现有技术存在的问题,本专利提供一种生产工艺简单、生产成本较低,且对复合污染水样中的有机污染物和重金属同时具有去除效果的蒙脱石/硅酸钙复合吸附材料。
本专利的目的在于提供一种对污染水样中的有机污染物和重金属同时具有去除效果的蒙脱石/硅酸钙复合吸附材料。该吸附材料原料来源广泛,制备工艺及操作简单,制备效率高,生产周期短,无需特殊化工设备,易于工业化批量生产。
本发明将煅烧后的蒙脱石和硅酸钙同时加到过氧化氢溶液中进行预处理,将预处理的蒙脱石和硅酸钙浆液,同时加入硫酸铁、过硫酸钠、柠檬酸、葡萄糖酸钠进行改性,提高蒙脱石/硅酸钙复合吸附材料对重金属和有机污染物的吸附能力。
具体的化学原理为:低温煅烧蒙脱石和硅酸钙能够在不影响其晶体结构的前提下,失去表面孔隙中通过范德华力结合的水分子,产生更多的吸附质点。大部分土壤有机质通过吸附、交换和络合等作用结合在矿物表面或层间结构中。将低温煅烧蒙脱石和硅酸钙加到过氧化氢溶液中搅拌,可以将强烈分解有机质而不破坏其晶体结构,从而达到去除蒙脱石和硅酸钙中有机质的效果,使其吸附通道更宽,进一步提升其吸附性能。将预处理的蒙脱石和硅酸钙配成浆液,同时加入硫酸铁、过硫酸钠、柠檬酸、葡萄糖酸钠进行改性。其中柠檬酸作为还原剂将三价铁还原为二价铁,过硫酸钠在亚铁离子的催化作用下产生强氧化性过硫酸根自由基和羟基自由基,使改性后的蒙脱石/硅酸钙复合材料可以氧化降解废水中的有机污染物,同时亚铁离子水解产生络合物,也可以通过吸附去除有机污染物。柠檬酸的羧基官能团能够增加复合材料表面的活性吸附位点,提高材料的吸附性能。葡萄糖酸钠是一种绿色高效螯合剂,对多种金属离子都有很好的螯合能力,可以提高改性后的蒙脱石/硅酸钙复合材料对重金属的吸附能力。
为达成上述目的,本发明的技术方案是:
一种蒙脱石/硅酸钙复合吸附材料的制备方法,其包括如下步骤:
步骤一:将蒙脱石和硅酸钙混合在150℃~300℃温度下低温煅烧2~5小时,得到煅烧产物;所述的蒙脱石与硅酸钙的质量比为1.0~10.0:0.1~5.0;
步骤二:将步骤一得到的煅烧产物在质量分数为10~20%的过氧化氢溶液中搅拌0.5~4小时,得到的混合液过滤后得到预处理混合物;
步骤三:将5~15质量份的预处理混合物用去离子水配成质量浓度为1.0~15.0%的浆液,同时加入0.1~1.0质量份的硫酸铁、1.0~6.0质量份的柠檬酸、0.5~10.0质量份的葡萄糖酸钠和0.5~3.0质量份的过硫酸钠进行搅拌,过滤,滤饼在低于100℃温度下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
进一步,所述的蒙脱石采用钙基蒙脱石、钠基蒙脱石、铁基蒙脱石、有机改性蒙脱石或无机改性蒙脱石。
进一步,所述的过氧化氢溶液的加入量以所述的煅烧产物的质量计5~15mL/g。
相比现有技术,本发明具有以下优点:本发明所述的蒙脱石/硅酸钙复合吸附材料的制备方法,以蒙脱石和硅酸钙为原料,制备成复合吸附材料。与现有吸附材料相比,本发明制备的吸附材料可以同时吸附污染水样中有机污染物和重金属。该吸附材料具有原料来源广泛,制备工艺及操作简单,制备效率高,生产周期短,无需特殊化工设备,易于工业化批量生产。
附图说明
图1.蒙脱石/硅酸钙复合吸附材料对Cr6+、Cd2+、苯酚的吸附曲线图。
图2.蒙脱石/硅酸钙材料对Cr6+、Cd2+、苯酚的吸附曲线图。
具体实施方式
实施例中所涉及的原料:钙基蒙脱石由青阳非金属矿研究院提供;硅酸钙购自罗恩试剂公司,规格AR 250g;过硫酸钠购自国药集团化学试剂有限公司,规格AR 500g;柠檬酸(一水合柠檬酸)购自国药集团化学试剂有限公司,规格AR 500g;葡萄糖酸钠购自上海毕得化学试剂有限公司,规格AR 25g;硫酸铁购自上海山海工学团实验二厂,规格AR 500g;;重铬酸钾标准溶液0.0999mol/L,购自麦克林化学试剂有限公司,规格AR 45mL;苯酚购自华东化学试剂有限公司,规格AR 500g;硫化镉购自麦克林化学试剂有限公司,规格AR 150g;
实施例一
分别称取30g钙基蒙脱石和3g硅酸钙混合,在150℃温度下低温锻烧2小时;将低温煅烧后的产物与质量分数为10%过氧化氢溶液按质量体积比为100g:0.5L在165mL质量分数为10%的过氧化氢溶液中搅拌0.5小时,过滤后得到预处理的混合物待用;将预处理的10g混合物配成质量浓度为1.0%的浆液,加入3g硫酸铁、30g柠檬酸、1.5g葡萄糖酸钠和1.5g过硫酸钠进行改性,过滤后在80℃下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
实施例二
分别称取10g钙基蒙脱石和5g硅酸钙混合,在300℃温度下低温锻烧5小时;将低温煅烧后的产物与质量分数为20%过氧化氢溶液按质量体积比为100g:1.5L在225mL质量分数为20%的过氧化氢溶液中搅拌4小时,过滤后得到预处理的混合物待用;将预处理的10g混合物配成质量浓度为15.0%的浆液,加入1.0g硫酸铁、6.0g柠檬酸、10.0g葡萄糖酸钠和3.0g过硫酸钠进行改性,过滤后在80℃下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
实施例三
分别称取10g钙基蒙脱石和0.1g硅酸钙混合,在200℃温度下低温锻烧5小时;将低温煅烧后的产物与质量分数为20%过氧化氢溶液按质量体积比为100g:1.5L在225mL质量分数为20%的过氧化氢溶液中搅拌4小时,过滤后得到预处理的混合物待用;将预处理的10g混合物配成质量浓度为15.0%的浆液,加入1.0g硫酸铁、6.0g柠檬酸、10.0g葡萄糖酸钠和3.0g过硫酸钠进行改性,过滤后在80℃下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
实施例四
分别称取2g钙基蒙脱石和10g硅酸钙混合,在150℃温度下低温锻烧5小时;将低温煅烧后的产物与质量分数为10%过氧化氢溶液按质量体积比为100g:1.5L在180mL质量分数为10%的过氧化氢溶液中搅拌4小时,过滤后得到预处理的混合物待用;将预处理的10g混合物配成质量浓度为1.0%的浆液,加入2g硫酸铁、2g柠檬酸、20g葡萄糖酸钠和1g过硫酸钠进行改性,过滤后在80℃下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
实施例五
分别称取20g钙基蒙脱石和0.2g硅酸钙混合,在300℃温度下低温锻烧2小时;将低温煅烧后的产物与质量分数为20%过氧化氢溶液按质量体积比为100g:0.5L在100mL质量分数为20%的过氧化氢溶液中搅拌0.5小时,过滤后得到预处理的混合物待用;将预处理的10g混合物配成质量浓度为15.0%的浆液,加入0.2g硫酸铁、12g柠檬酸、1g的葡萄糖酸钠和6g过硫酸钠进行改性,过滤后在80℃下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
实施例六
分别配制500mL含K2Cr2O7、CdS、苯酚的浓度为200mg/L的模拟重金属和有机污染水样,加入3.5g以实施例五制备的蒙脱石/硅酸钙复合颗粒吸附材料,在25℃的恒温搅拌水浴中吸附,取样检测模拟重金属和有机污染水样的剩余浓度,计算Cr6+、Cd2+、苯酚的去除率。
图1表明,所述蒙脱石/硅酸钙复合吸附材料对Cr6+、Cd2+、苯酚的去除率分别为61.7%、63.5%、和28.2%。
对比例一
配制500mL含K2Cr2O7、CdS、苯酚的浓度为200mg/L的模拟重金属和有机污染水样,加入3.5g质量比为10.0:0.1的钙基蒙脱石和硅酸钙,在25℃的恒温搅拌水浴中吸附,取样检测模拟重金属和有机污染水样的剩余浓度,计算Cr6+、Cd2+、苯酚的去除率。
上述测试结果表明,所述蒙脱石/硅酸钙材料对Cr6+、Cd2+、苯酚的去除率分别为25.7%、31.5%、和10.7%。
Claims (3)
1.一种蒙脱石/硅酸钙复合吸附材料的制备方法,其特征在于:所述的制备方法包括如下步骤:
步骤一:将蒙脱石和硅酸钙混合在150℃~300℃温度下低温煅烧2~5小时,得到煅烧产物;所述的蒙脱石与硅酸钙的质量比为1.0~10.0:0.1~5.0;
步骤二:将步骤一得到的煅烧产物在质量分数为10~20%的过氧化氢溶液中搅拌0.5~4小时,得到的混合液过滤后得到预处理混合物;
步骤三:将5~15质量份的预处理混合物用去离子水配成质量浓度为1.0~15.0%的浆液,同时加入0.1~1.0质量份的硫酸铁、1.0~6.0质量份的柠檬酸、0.5~10.0质量份的葡萄糖酸钠和0.5~3.0质量份的过硫酸钠进行搅拌,过滤,滤饼在低于100℃温度下干燥至质量恒定不变,得到蒙脱石/硅酸钙复合吸附材料。
2.如权利要求1所述的制备方法,其特征在于:步骤一中,所述的蒙脱石为钙基蒙脱石。
3.如权利要求1所述的制备方法,其特征在于:步骤二中,所述的过氧化氢溶液的加入量以所述的煅烧产物的质量计5~15mL/g。
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