CN102513055A - 一种用于吸附富集有机磷农药的磁性材料制备方法 - Google Patents
一种用于吸附富集有机磷农药的磁性材料制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于吸附富集有机磷农药的磁性材料制备方法。以硅酸盐为骨架、抗静电剂SN为功能化剂,将抗静电剂SN与纳米四氧化三铁混合均匀后,加入镁盐溶液中混匀,再与硅酸盐水溶液混合反应,分离得到棕色絮凝状沉淀物即为用于吸附富集有机磷农药的液体磁性材料。将此磁性材料作为有机磷农药吸附剂,按0.05~0.5%加入到含有机磷的水样中,具有良好的吸附功能和磁分离性能。本发明具有原料易得、工艺简单、成本低廉、产品对多种有机磷农药吸附量大、分离效果好等优点,既可用于环境水体痕量有机磷农药的富集检测,又能用于有机磷农药废水的吸附处理。
Description
技术领域
本发明涉及一种用于吸附富集有机磷农药的磁性材料制备方法,具体是处理有机磷农药废水的吸附和萃取材料的生产工艺。属于环境污染控制与检测技术领域。
背景技术
有机磷农药由于广谱高效在我国广泛使用,农药滥用已经对生态环境及人体健康造成严重影响。目前,我国有2000多家农药生产厂,年产量80多万吨,其中有机磷农药约100多种,产量占80%以上。我国每年农药废水排放量达1.5亿吨,达标排放仅1%。有机磷农药污染已引起人们重视,尤其是疏水性有机磷农药毒性大、残存期长,对环境危害更为严重。
有机磷农药废水往往具有浓度高、毒性大、组分复杂等特点,其处理方法有焚烧法、活性污泥法等生物法、化学氧化、光催化、水解等化学法,包括吸附、混凝沉淀、萃取、水解、氧化等物理法和超声波法等。但生物法处理后的有机磷含量仍高达数10mg/L。化学法只能把有机磷转变为无机磷,磷仍然保留在水体中。物理法则可以将磷从废水中去除,但常常只是在废水预处理中使用,该方法所用的吸附剂种类很多,其中,活性炭和高分子树脂是有机磷废水预处理中常用的吸附剂。粉末活性炭吸附能力强,制备容易,价格较低,但再生困难。矿物材料常作为水溶性有机磷农药的吸附剂,如粉煤灰对乐果有良好的吸附性能,膨润土对甲胺磷、对硫磷等高毒有机磷农药有一定吸附作用,纳米氧化铝对草甘膦表现出良好的吸附作用。另外包括壳聚糖、腐殖质、微生物残体和植物废弃物的生物吸附材料,具有成本低、无二次污染等特点,但吸附量小。因此,研制开发高吸附容量、易分离和可再循环利用的吸附材料,是有机废水处理当务之急。
在环境水体有机磷农药检测方法中,水样的富集一般采用液-液萃取法、固相萃取(SPE)和固相微萃取法,但液-液萃取操作耗时,需使用大量对人体和环境有毒、有害的有机溶剂。因此SPE法近年来飞速发展,设计与制备快速高效、选择性好的固相萃取材料成为环境检测领域的研究热点。
虽然C18是最广泛使用的有机磷萃取剂。另外采用高分子多孔微球GDX树脂作为固相萃取材料,吸附富集-气相色谱法测定土壤中亲水性有机磷农药,该固相萃取材料对亲水性有机磷农药乐果、久效磷、甲基对硫磷表现出高回收率。还有通过多壁碳纳米管富集水样有机磷农药,效果良好。利用甲苯萃取剂,建立了水样中敌敌畏、二嗪农、毒死蜱、甲基对硫磷和对硫磷等5种有机磷农药的动态液相微萃取-气相色谱检测方法。用植物酶萃取乐果、对硫磷和甲基对硫磷三种有机磷农药,建立了水体中痕量有机磷农药的检测方法。利用活性炭纤维为固相萃取剂填料,萃取测定水样中微量有机磷农药。然而,上述这些材料必须置于SPE柱内使用,无法直接分散到有机磷水样中使用,因此存在时间长、吸附效率低等问题。
发明内容
本发明的目的在于公开一种用于有机磷农药吸附富集的磁性材料制备方法。用本发明方法得到的吸附富集有机磷农药的磁性材料,既可用于环境水体痕量疏水性有机磷农药的富集检测,又能用于有机磷农药废水的吸附处理,而且吸附容量大、易分离和可再循环利用。
为了实现上述目的,本发明选用镁盐、硅酸盐、磁性原料为无机原料,其中镁盐原料包括可溶性的氯化镁和硝酸镁,硅酸盐原料包括硅酸钠和硅酸钾,磁性原料采用纳米四氧化三铁。将抗静电剂SN与纳米四氧化三铁混合均匀后,加入镁盐溶液中混匀,再与硅酸盐水溶液混合反应,分离,得到沉淀物即为用于吸附富集有机磷农药的磁性吸附材料。
具体工艺如下:
第一步,原料的选择和配制
先分别将市售的工业级氯化镁或硝酸镁加水,配制成重量百分比浓度为2%~10%的溶液A;
将市售的工业级硅酸钠或硅酸钾加水配制成重量百分比浓度为1%~10%的溶液B;
接着,在抗静电剂SN中加水配制成浓度为0.1~0.5M的溶液C;
选择市售的工业级纳米四氧化三铁为磁性原料,先用0.1M稀盐酸清洗,再用水清洗到洗液的PH=6-8,最后加水配制成重量百分比浓度为2~10%的液体D;
上述抗静电剂SN为十八烷基二甲基羟乙基季铵硝酸盐。
上述纳米四氧化三铁由南京工业大学纳米应用研究中心提供,粒径为20~30nm的粉体;
第二步,磁性材料的制备
首先,按重量份数计量量取溶液A∶溶液B∶溶液C∶溶液D=5∶8∶1∶1份重量,接着,将溶液C与溶液D混合均匀,然后加入到放置了溶液A的反应器中,混匀,再将溶液B加入其中,搅拌均匀组成反应液,将反应液静置陈化10~20小时,最后,在反应器底部放置磁铁块2小时,弃去澄清液,反应器的底部留下的棕色絮凝状沉淀物,即为吸附富集有机磷农药的磁性材料。
将水加入上述吸附富集有机磷农药的磁性材料(棕色絮凝状沉淀物)中,即得到重量百分比为5~20%液体磁性材料,直接用于吸附富集有机磷农药。
或将棕色絮凝状沉淀物(吸附富集有机磷农药的磁性材料)烘干、粉碎,制得便于保存和运输的粉体产品。
上述在反应器底部放置磁铁块,是按照3000ml反应液使用市售的直径20厘米、厚2厘米的圆盘磁铁,磁铁块由上海金昆磁电科技有限公司提供。
所述直接用于吸附富集有机磷农药是,向浓度为痕量-120mg/L有机磷农药水样中加入制备得到的浓度为5~20%重量百分比的液体磁性材料,投加量为有机磷农药水样重量的0.05~0.5%重量百分比,搅拌5~30分钟,在有机磷农药水样底部放置直径10-20厘米,厚度为1-2厘米的磁铁10~30分钟,吸附沉淀物为富集了有机磷农药的残渣,澄清液直接通过气/液相色谱法检测有机磷农药浓度。残渣经高温焙烧,分解所吸附的有机磷物质,制备可循环利用的磁性无机材料。
上述浓度为痕量的有机磷农药水样中的澄清液通过气/液相色谱法检测有机磷农药浓度是,在每1g残渣中加入5ml-10ml甲醇,搅拌,吸取澄清液进行高效液相色谱分析,测定甲醇浓缩液中各有机磷农药含量,再除以100即得水中有机磷农药浓度。
本发明的优点如下:
1.本发明将抗静电剂SN与纳米四氧化三铁混合均匀后,加入镁盐溶液中混匀,再与硅酸盐水溶液混合反应,分离即可,因此具有工艺简单,原料易得、价格便宜等优点。
2.本发明得到的产品对疏水性有机磷农药具有良好的吸附性能,包括内吸磷、喹硫磷、甲基1605、杀螟松、辛硫磷、丙溴磷、倍硫磷、毒死蜱、甲拌磷、马拉硫磷、治螟磷等,吸附率70~96%。
3.与传统吸附剂相比,本发明得到的磁性材料可以直接分散到水样中吸附有机磷,然后通过磁铁分离吸附剂,不需使用过滤、离心等手段,具有效果好、速度快、省时省电等优点,在环境检测和污染控制中有较大应用潜力。
4.使用后的残渣可经高温焙烧,分解所吸附的有机磷物质,制备可循环利用的磁性无机材料。
5.本发明用途广泛,既可用于环境水体痕量有机磷农药的富集检测,又能用于有机磷农药废水的吸附处理。
具体实施方式
实施例1
第一步,原料的选择和配制
选用市售的工业级硅酸钠,用蒸馏水配制浓度为2%的硅酸钠溶液,简称为溶液B。
选用市售的工业级氯化镁,用蒸馏水配制浓度为2%的溶液,简称为溶液A。
选用江苏省海安和辰化工有限公司提供的抗静电剂SN(十八烷基二甲基羟乙基季铵硝酸盐),该抗静电剂SN为红棕色透明粘稠液体,含量55-60%,用蒸馏水配制浓度为02M抗静电剂SN溶液,简称为溶液C。
选用由南京工业大学纳米应用研究中心提供的纳米四氧化三铁粉体,粒径20~30nm,先用0.1M稀盐酸清洗纳米四氧化三铁5分钟,再用蒸馏水清洗到洗液的PH=6-8,最后配制成重量百分比浓度为5%的液体,简称为溶液D。
第二步,磁性材料的制备
取200mL四氧化三铁液体,简称为溶液D。200mL抗静电剂SN溶液,简称为溶液C。将溶液D和溶液C混合均匀,再倒入装有1000mL氯化镁溶液(溶液A)的烧杯中,混匀后,加入1600mL硅酸钠溶液(溶液B),混匀,静置陈化12小时,用上海金昆磁电科技有限公司提供的磁铁块(直径20厘米、厚2厘米)紧贴烧杯底部吸住烧杯中的底部留下的棕色絮凝状沉淀物,即为吸附富集有机磷农药的磁性材料。弃去澄清液。
将蒸馏水300mL加入上述吸附富集有机磷农药的磁性材料中,即得到外观为棕色,含量约为10%的液体磁性材料。直接用于吸附富集有机磷农药。
或将上述吸附富集有机磷农药的磁性材料烘干、粉碎,制得便于保存和运输的粉体产品。
实施例2
有机磷农药废水吸附处理:取100ml某农药厂甲基1605生产废水于烧杯中,加入实施例1制备得到的外观为棕色含量约为10%的液体磁性材料5ml,搅拌20分钟后,在烧杯下方贴底放置直径为10cm磁铁块,静置20分钟,吸取10ml澄清液,利用高效液相色谱仪检测清液中甲基1605浓度。实验结果表明:原废水中甲基1605浓度为120mg/L,吸附处理后澄清液中甲基1605浓度为15mg/L,去除率87.5%。对比实验表明,同量膨润土对甲基1605吸附率仅63%,粉末活性炭的吸附率略高于本产品,但其分离必须借助离心设备。因此,该材料对疏水性有机磷农药废水有良好的处理效果。
残渣经550度下高温焙烧2小时,分解掉所吸附的有机磷物质,粉碎成粉末后仍具有磁性,可作为砷吸附剂或磁性保温材料继续使用。
实施例3
湖水痕量有机磷农药的富集与检测
取500ml某湖水于烧杯中,该湖水含痕量有机磷农药,湖水中加入实施例1的10%液体磁性材料2.5ml,搅拌混合20分钟后,在烧杯下方贴底放置直径为10cm磁铁块,静置20分钟,将澄清液吸去,向留下的富集了有机磷农药的残渣中加入5ml甲醇,搅拌5分钟,吸取澄清液进行高效液相色谱分析,测定经过甲醇浓缩的澄清液中各有机磷农药含量,再除以100即得湖水中有机磷农药浓度。实验结果表明:湖水中甲基1605、毒死蜱浓度分别为0.021、0.006mg/L,加标回收率分别为94%、102%。该磁性材料对环境水体痕量疏水性有机磷农药富集效果好。
Claims (2)
1.一种用于吸附富集有机磷农药的磁性材料制备方法,其特征在于:
第一步,原料选择和配制
先分别在氯化镁或硝酸镁中加水,配制成重量百分浓度为2~10%的溶液A;在硅酸钠或硅酸钾中加水配制成重量百分浓度为1~10%的溶液B;接着,在抗静电剂SN中加水,配制成浓度为0.1~0.5M的溶液C;并选择纳米四氧化三铁为磁性原料,先用0.1M稀盐酸清洗后,再用水清洗,配制成重量百分浓度为2~10%液体D;
上述抗静电剂SN为十八烷基二甲基羟乙基季铵硝酸盐;
第二步,磁性材料的制备
首先,按重量份数计量量取溶液A∶溶液B∶溶液C∶溶液D=5∶8∶1∶1份重量,接着,将溶液C与溶液D混合均匀,然后加入到放置溶液A的反应器中,混匀,再将溶液B加入其中,搅拌均匀组成反应液,将反应液静置陈化10~20小时,最后,在反应器底部放置磁铁块,2小时后弃去澄清液,反应器的底部留下的棕色絮凝状沉淀物,即为吸附富集有机磷农药的磁性材料;
将水加入上述棕色絮凝状沉淀物中,配制成重量百分比为5~20%液体磁性材料,直接用于吸附富集有机磷农药;
或将棕色絮凝状沉淀物烘干、粉碎,制得便于保存和运输的粉体产品。
2.根据权利要求1所述的一种吸附富集有机磷农药的磁性材料制备方法,其特征在于:所述在反应器底部放置磁铁块,是按照3000ml反应液使用市售的直径20厘米、厚2厘米的圆盘磁铁计量。
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CN114262646A (zh) * | 2021-12-28 | 2022-04-01 | 山东中大药业有限公司 | 一种去除中药植株农残的洗涤剂及其制备方法 |
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CN114262646B (zh) * | 2021-12-28 | 2024-04-16 | 山东中大药业有限公司 | 一种去除中药植株农残的洗涤剂及其制备方法 |
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