CN106395966B - 一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法 - Google Patents
一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法 Download PDFInfo
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Abstract
本发明公开了一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法,该方法首先将2‑20重量份的由十六烷基三甲基溴化铵改性的有机膨润土与1‑10重量份的还原铁粉加入100重量份的天然钠基膨润土原土中,混匀,得垃圾填埋场衬垫材料;再将其平整铺设在填埋场底部,铺设的厚度为5cm以上,将垃圾填埋在垃圾填埋场衬垫材料上,垃圾产生的渗滤液流入衬垫材料,污染物被垃圾填埋场衬垫材料吸附并原位降解。本发明对垃圾填埋场渗滤液中有机污染物阻滞效果明显,同时可实现有机污染物的原位降解,可大规模用于填埋场建造。
Description
技术领域
本发明涉及一种垃圾填埋场自洁净防渗技术,尤其涉及一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法。
背景技术
人类生产生活产生大量垃圾需要处置。目前垃圾处置主要有填埋、焚烧、堆肥三种方式,其中填埋仍是最主要的处置技术。垃圾在填埋过程中将产生大量渗滤液,容易造成二次污染。渗滤液成分复杂,污染物种类繁多,其中卤代烃类化合物如四氯乙烯、氯仿等为毒性指数最高的一类污染物,且难以去除。此外如酚类、多环芳烃类和邻苯二甲酸酯类等化合物也在渗滤液中广泛存在。这些污染物若不加控制进入地下水将严重威胁人类健康。为保障地下水的安全,需要在填埋场底部铺设防渗衬垫。
目前常用的防渗衬垫材料主要有压实粘土衬垫(CCL)、高密度聚乙烯膜(HDPE)、土工膜(GCL)等。CCL通过压实粘土层使其渗透系数小于1×10-7cm/s,但通常需要1-2m的厚度。HDPE膜是一种高分子材料,一般厚度为2mm左右,具有防渗性能好、铺设简单、抗拉伸等优点,但不耐刺穿。若有破损,该处将成为渗滤液的泄漏点(Katsumi,T.,Benson,C.H.,Foose,G.J.,Kamon,M.,2001.Performance-based design of landfill liners.Eng.Geol.60,139-148.)。同时由于HDPE膜是石化产品,长时间使用也存在老化风险。GCL膜一般以两层无纺布中间夹一层5-10mm天然钠基膨润土制成,遇水溶胀后能得到很低的防渗系数,但其吸附能力有限,渗滤液中污染物容易通过分子扩散等方式穿透衬垫进入地下水(Foose,G.J.,Benson,C.H.,Edil,T.B.,2002.Comparison of solute transport in three compositeliners.J.Geotech.Geoenviron.128,391-403.)。
发明内容
本发明的目的在于针对现有技术的不足,提供一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法。
本发明的目的是通过以下技术方案实现的:一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法,包括如下步骤:
(1)将2-20重量份的由十六烷基三甲基溴化铵(CTMAB)改性的有机膨润土与1-10重量份的还原铁粉加入100重量份的天然钠基膨润土原土中,混匀,得垃圾填埋场衬垫材料。
(2)将步骤1所制得的垃圾填埋场衬垫材料平整铺设在填埋场底部,铺设的厚度为5cm以上。
(3)将垃圾填埋在垃圾填埋场衬垫材料上。
(4)垃圾产生的渗滤液渗入衬垫材料,有机污染物被垃圾填埋场衬垫材料吸附并原位降解。
进一步地,所述由十六烷基三甲基溴化铵改性的有机膨润土通过以下方法制备得到:
(1.1)将4重量份水通过水浴加热至70℃后,加入十六烷基三甲基溴化铵,搅拌溶解后,再加入1重量份膨润土,搅拌2h后,合成由十六烷基三甲基溴化铵改性的有机膨润土;所述十六烷基三甲基溴化铵与膨润土的可交换阳离子的物质的量相同。
(1.2)将步骤1.1中合成的CTMAB-膨润土过滤后于60℃烘箱中烘干,研磨并过100目筛,备用。
进一步地,所述膨润土的可交换阳离子包括钠和钙。
本发明的有益效果是:
1、有机膨润土、铁粉与膨润土机械混合即可,制备简单。
2、改善了膨润土衬垫吸附能力不足的缺点。添加有机膨润土后,衬垫对渗滤液中多种有机污染物阻滞能力均大幅提高,且对难降解持久性有机污染物阻滞效果更加显著。
3、衬垫能原位降解污染物,实现其自洁净能力,延长使用寿命。
附图说明
图1为不同CTMAB-膨润土含量膨润土衬垫的渗透系数关系图;
图2为菲在5cm含不同比例CTMAB-膨润土的衬垫中的穿透模拟曲线图;
图3为菲在不同厚度含20%CTMAB-膨润土的衬垫中的穿透模拟曲线图;
图4为苯酚在含不同CTMAB-膨润土量土柱中的穿透曲线图;
图5为邻苯二甲酸二甲酯(DMP)在不同CTMAB-膨润土含量土柱中的穿透曲线图;
图6为邻苯二甲酸二乙酯(DEP)在不同CTMAB-膨润土含量土柱中的穿透曲线图;
图7为氯仿在不同材料土柱中的穿透曲线图;
图8为经过一段时间淋洗后土柱中CTMAB-膨润土的剩余量柱状图;
图9为不同实验组经过72h反应后溶液中四氯乙烯剩余量柱状图,图中,1为0.5gCTMAB-膨润土;2为0.5g CTMAB-膨润土和0.1g铁;3为0.5g CTMAB-膨润土和0.25g铁;4为0.5g CTMAB-膨润土和0.5g铁;5为0.5g CTMAB-膨润土和0.5g SiO2;6为0.5g铁;7为对照。
具体实施方式
本申请发明人在研究中发现,衬垫中加入吸附性和降解性材料能增强衬垫对渗滤液中有机污染物的吸持能力,阻滞其迁移,并在原位进行降解,从而降低渗滤液污染的风险。有机膨润土是一种吸附能力强的材料,能同时吸附多种有机污染物,且饱和吸附容量大,将其加入衬垫可提高衬垫吸附渗滤液中有机污染物的能力。铁粉具有较强的还原能力,将其加入衬垫中能原位降解污染物,实现衬垫自洁净,延长衬垫使用寿命。
在此研究的基础上,得到以下技术方案请求专利保护。
一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法,包括如下步骤:
1、将2-20重量份的由十六烷基三甲基溴化铵(CTMAB)改性的有机膨润土与1-10重量份的还原铁粉加入100重量份的天然钠基膨润土原土中,混匀,得垃圾填埋场衬垫材料。
2、将步骤1所制得的垃圾填埋场衬垫材料平整铺设在填埋场底部,铺设的厚度为5cm以上。
3、将垃圾填埋在垃圾填埋场衬垫材料上。
4、垃圾产生的渗滤液流入衬垫材料,有机污染物被垃圾填埋场衬垫材料吸附并原位降解。
其中,所述由十六烷基三甲基溴化铵改性的有机膨润土通过以下方法制备得到:
1.1、将4重量份水通过水浴加热至70℃后,加入十六烷基三甲基溴化铵,搅拌溶解后,再加入1重量份膨润土,搅拌2h后,合成由十六烷基三甲基溴化铵改性的有机膨润土;所述十六烷基三甲基溴化铵与膨润土的可交换阳离子的物质的量相同。所述膨润土的可交换阳离子包括钠和钙。
1.2、将步骤1.1中合成的CTMAB-膨润土过滤后于60℃烘箱中烘干,研磨并过100目筛,备用。
本发明利用十六烷基三甲基溴化铵改性的有机膨润土吸附有机污染物的性能,阻滞渗滤液中有机污染物的迁移;利用铁粉的还原性能,原位降解吸附在衬垫中的有机污染物,实现衬垫自洁净能力,延长防渗衬垫使用寿命。本发明对垃圾填埋场渗滤液中有机污染物阻滞效果明显,同时可实现有机污染物的原位降解,可大规模用于填埋场建造。
下面结合具体实施例对本发明作进一步阐述,但本发明并不限于以下实施例。所述方法如无特别说明均为常规方法,所述药剂如无特别说明均能从公开商业途径而得。
实施例1
将几个含水率为30%、含不同CTMAB-膨润土量的膨润土材料放入环刀内,以击锤击实后,通过变水头渗透系数测定法测定材料渗透系数。
如图1所示,材料渗透系数的对数值与其中有机膨润土含量呈线性关系,相关系数r2为0.9965。材料中CTMAB-膨润土总含量为10%,渗透系数为1.13×10-9cm/s;材料中CTMAB-膨润土总含量为20%,渗透系数为2.97×10-9cm/s,均远低于国家标准的1×10-7cm/s。
实施例2
应用含对流、平流、层流的一维传递模型模拟菲在5cm含不同比例CTMAB-膨润土的衬垫中的迁移,设定初始浓度为1mg/L。
如图2所示,经过30年,菲穿透含5%CTMAB-膨润土的衬垫,峰值浓度为0.0116mg/L;其在含10%CTMAB-膨润土的衬垫中的穿透时间延长为50年,峰值浓度降为0.0058mg/L;进一步地,其在含20%CTMAB-膨润土的衬垫中的穿透时间延长为100年,峰值浓度降为0.0029mg/L;进一步地,其在含30%CTMAB-膨润土的衬垫中的穿透时间延长为120年,峰值浓度降为0.0017mg/L;进一步地,其在含40%CTMAB-膨润土的衬垫中的穿透时间延长为160年,峰值浓度降为0.0015mg/L。当衬垫中CTMAB-膨润土比例达到20%后,进一步增大CTMAB-膨润土的比例并不会明显增强衬垫对菲的阻滞效果。
实施例3
应用含对流、平流、层流的一维传递模型模拟菲在不同厚度含20%CTMAB-膨润土的衬垫中的迁移,设定初始浓度为1mg/L。
如图3所示,经过6年,菲穿透1cm厚该衬垫,峰值浓度为0.0601mg/L;进一步地,其穿透2cm厚该衬垫的时间延长为20年,峰值浓度降低为0.0151mg/L;进一步地,其穿透5cm厚该衬垫的时间延长为100年,峰值浓度降低为0.0029mg/L;进一步地,其穿透10cm厚该衬垫的时间延长为500年,峰值浓度降低为0.0008mg/L。考虑到垃圾填埋场使用年限一般可达60-80年,因此衬垫厚度应大于5cm。
实施例4
配置浓度为100mg/L的苯酚溶液。往4根内径为2.5cm玻璃柱中分别加入15g含0%,2%,5%,10%有机膨润土的膨润土材料并压实。将苯酚溶液分别加入4根玻璃柱中,保持溶液深度一致。连续收集下方滤出液,以10mL为一个测试样。以甲醇1:1稀释,过膜后进液相测定其中苯酚浓度。
如图4所示,膨润土衬垫中加入有机膨润土能延长苯酚的穿透时间,且延长时间与加入的有机膨润土含量呈正相关。未加有机膨润土的样品在滤出液量为30mL时可以检测出苯酚,添加2%CTMAB-膨润土样品在滤出液量为50mL时可检测出苯酚,添加5%CTMAB-膨润土样品在滤出液量为60mL时可检测出苯酚,10%CTMAB-膨润土样品在滤出液量为90mL时可检测出苯酚。
实施例5
配置浓度为100mg/L的DMP溶液。往4根内径为2.5cm玻璃柱中分别加入15g含0%,2%,5%,10%有机膨润土的膨润土材料并压实。将DMP溶液分别加入4根玻璃柱中,保持溶液深度一致。连续收集下方滤出液,10mL为一个测试样。以甲醇1:1稀释,过膜后进液相测定其中DMP浓度。
如图5所示,膨润土衬垫中加入有机膨润土能延长DMP的穿透时间,且延长时间与加入的有机膨润土含量呈正相关。未加有机膨润土的样品在滤出液量为60mL时可以检测出DMP,添加2%CTMAB-膨润土样品在滤出液量为160mL时可以检测出DMP,添加5%CTMAB-膨润土样品在滤出液量为190mL时可检测出DMP,10%CTMAB-膨润土样品在滤出液量为240mL时可检测出DMP。
实施例6
配置浓度为100mg/L的DEP溶液。往4根内径为2.5cm玻璃柱中分别加入15g含0%,2%,5%,10%有机膨润土的膨润土材料并压实。将DEP溶液分别加入4根玻璃柱中,保持溶液深度一致。连续收集下方滤出液,10mL为一个测试样。以甲醇1:1稀释,过膜后进液相测定其中DEP浓度。
如图6所示,膨润土衬垫中加入有机膨润土能延长DEP的穿透时间,且延长时间与加入的有机膨润土含量呈正相关。未加有机膨润土的样品在滤出液量为210mL时可以检测出DEP,添加2%CTMAB-膨润土样品在滤出液量为290mL时可检测出DEP,添加5%CTMAB-膨润土样品在滤出液量为350mL时可检测出DEP,10%CTMAB-膨润土样品在滤出液量为410mL时可检测出DEP。
实施例7
配置浓度为50mg/L的氯仿溶液。往3根内径为2.5cm玻璃柱中分别加入15g膨润土、水稻土及含10%CTMAB-膨润土的膨润土材料并压实。将氯仿溶液分别加入3根玻璃柱中,保持溶液深度一致,每根玻璃柱上加一个玻璃盖以防止氯仿挥发。连续收集下方滤出液,以10mL为一个测试样。以正己烷1:1萃取后,进气相测定其中氯仿浓度。
如图7所示,氯仿在渗流量为40mL时即穿透膨润土土柱,平衡浓度与初始浓度基本一致;天然粘土材料如水稻土对氯仿阻滞效果也有限,当渗流量为51mL时氯仿穿透水稻土土柱,平衡浓度也与初始浓度基本一致。而当渗流量为150mL时氯仿穿透含10%CTMAB-膨润土的膨润土土柱,平衡浓度也下降为初始浓度的80%左右。
实施例8
往3根内径为2.5cm玻璃柱中分别加入15g含10%,50%,100%有机膨润土的膨润土材料并压实,加水并保持溶液深度一致。待下方有溶液滤出后,每天收集一次滤出液并记录滤出量。将滤出液过膜后测定其中有机碳含量,并计算其中CTMAB含量。连续测定30天后,将所有CTMAB总量相加并计算出材料中CTMAB-膨润土剩余量。
如图8所示,三个土柱中CTMAB-膨润土剩余量分别为99.98%,99.99%,99.99%,实验过程中CTMAB-膨润土保持稳定。
实施例9
配置四氯乙烯溶液,浓度为200mg/L。往7组22mL离心管中分别加入0.5g CTMAB-膨润土,0.5g CTMAB-膨润土和0.1g铁,0.5g CTMAB-膨润土和0.25g铁,0.5g CTMAB-膨润土和0.5g铁,0.5g CTMAB-膨润土和0.5g SiO2,以及0.5g铁,并设一组空白对照。往所有管子中分别加入20mL四氯乙烯溶液,于25℃、200rpm振荡72小时后,以3000rpm离心15分钟。取4mL上清液,以正己烷1:1萃取后,通过气相测定其中四氯乙烯含量。
如图9所示,以对照组为基准,仅含有0.5g铁的管子内四氯乙烯剩余量为97.46%,而含有0.5g CTMAB-膨润土和含有0.5g CTMAB-膨润土和0.5g SiO2的管子内四氯乙烯剩余量分别下降为18.05%和17.29%;在含有0.5g CTMAB-膨润土和0.1g铁的管子内,四氯乙烯剩余量进一步下降为10.19%;在含有0.5g CTMAB-膨润土和0.25g铁的管子内,四氯乙烯剩余量进一步下降为4.16%;在含有0.5g CTMAB-膨润土和0.5g铁的管子内,四氯乙烯剩余量为2.96%。可见,还原铁粉与CTMAB-膨润土的比例为1:2时既能实现较好的降解效果又能保证一定的经济性。
以上实施例仅对发明做进一步说明,本发明范围不受所举实施例局限。
Claims (3)
1.一种高效阻滞迁移并原位降解渗滤液中有机污染物的方法,其特征在于,包括如下步骤:
(1)将2-20重量份的由十六烷基三甲基溴化铵改性的有机膨润土与1-10重量份的还原铁粉加入100重量份的天然钠基膨润土原土中,混匀,得垃圾填埋场衬垫材料;
(2)将步骤(1)所制得的垃圾填埋场衬垫材料平整铺设在填埋场底部,铺设的厚度为不少于5cm;
(3)将垃圾填埋在垃圾填埋场衬垫材料上;
(4)垃圾产生的渗滤液渗入衬垫材料,有机污染物被垃圾填埋场衬垫材料吸附并原位降解。
2.根据权利要求1所述的方法,其特征在于,所述由十六烷基三甲基溴化铵改性的有机膨润土通过以下方法制备得到:
(1.1)将4重量份水通过水浴加热至70℃后,加入十六烷基三甲基溴化铵,搅拌溶解后,再加入1重量份膨润土,搅拌2h后,合成由十六烷基三甲基溴化铵改性的有机膨润土;所述十六烷基三甲基溴化铵与膨润土的可交换阳离子的物质的量相同;
(1.2)将步骤(1.1)中合成的十六烷基三甲基溴化铵改性的有机膨润土过滤后于60℃烘箱中烘干,研磨并过100目筛,备用。
3.根据权利要求1所述的方法,其特征在于,所述膨润土的可交换阳离子包括钠和钙。
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