CN1298640C - 渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法 - Google Patents
渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法 Download PDFInfo
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- CN1298640C CN1298640C CNB2005100121914A CN200510012191A CN1298640C CN 1298640 C CN1298640 C CN 1298640C CN B2005100121914 A CNB2005100121914 A CN B2005100121914A CN 200510012191 A CN200510012191 A CN 200510012191A CN 1298640 C CN1298640 C CN 1298640C
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- nanofiltration
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- 239000007788 liquid Substances 0.000 title claims abstract description 30
- 239000012530 fluid Substances 0.000 claims abstract description 29
- 238000002485 combustion reaction Methods 0.000 claims abstract description 19
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 239000003337 fertilizer Substances 0.000 claims abstract description 12
- 238000001728 nano-filtration Methods 0.000 claims description 71
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- 238000001704 evaporation Methods 0.000 claims description 5
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- 238000001914 filtration Methods 0.000 abstract 6
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- 238000000926 separation method Methods 0.000 abstract 1
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- 239000012141 concentrate Substances 0.000 description 8
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- 238000005516 engineering process Methods 0.000 description 5
- 241000276438 Gadus morhua Species 0.000 description 4
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound 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- 238000006065 biodegradation reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound 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Abstract
渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法，属于垃圾处理技术领域。为了解决填埋场渗滤液“生物处理+纳滤工艺”膜截留液处理的问题，本发明公开了一种城市生活垃圾填埋场渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法，包括如下步骤：1)将渗滤液经“生物处理+纳滤工艺”后的膜截留液，泵入纳滤系统，操作压差为0.5～1.5Mpa，浓缩倍数为5～10倍，膜分离后得到浓缩液和透过液，所述纳滤系统所用膜是一种非软化纳滤膜，截留相对分子量为200～1000；2)让上述步骤得到的浓缩液流入浸没燃烧蒸发系统，燃烧室温度＞750℃，浸没深度0.3～0.6m，浓缩倍数为5～10倍，浓缩、净化后得到有机液体肥料。
Description
技术领域
本发明属于垃圾处理技术领域，特别涉及从城市生活垃圾填埋场渗滤液“生物处理+纳滤工艺”膜截留液中提取腐殖酸并浓缩为有机液体肥料的资源化方法。
背景技术
城市生活垃圾填埋场渗滤液是一种高浓度有机废水，目前国内大量已建成的采用常规工艺的渗滤液处理工程基本都达不到《生活垃圾填埋污染控制标准》中的一级排放标准。究其原因通常认为由渗滤液的水质波动大、可生化性随填埋时间的增长而下降、氨氮含量高、营养元素失衡等水质特点所致，而更本质的原因可能在于渗滤液中含有高浓度的难生物降解有机物一腐殖酸。
生物处理是有机废水的最基本处理方法，目前在渗滤液处理实际工程中也应用的最广泛。一方面，近年来一些新颖的生物脱氮途径不断被发现和揭示，对于通常含有高浓度的重碳酸氢盐和氨氮的渗滤液，这些现象表现的特别明显，许多渗滤液处理的小试、中试和工程实践均证明，只要合理选用生物反应器和优化工艺参数，即使氨氮浓度高至2700mg/l时，仍可通过生物硝化达标。另一方面，早期渗滤液中有机物由于主要是由大量易于生物降解的脂肪酸组成，因此采用生物处理是非常有效的。但是，由于渗滤液中还含有难生物降解有机物——腐植质，基本上从填埋场开始产生渗滤液，腐植质即存在其中，使得早期渗滤液经生物处理后仍有300～800mg/L的COD无法去除，单纯生物处理的出水难于达到直接排放要求。并且随着填埋时间的延续，渗滤液有机物中腐植质含量及所占的比例增加，进而导致渗滤液的可生化性下降，由此造成常规生物法处理渗滤液可能难于正常运行，所以，生物法处理老龄期渗滤液时效果不佳。虽然单靠生物处理不能使出水直接排放，但生物处理的设备简单、运行管理可靠、成本低，通过合理选取反应器、工艺参数和改进处理单元等措施，就可以充分发挥生物法处理渗滤液时高效生物硝化和净化可降解有机物的优点，目前国内外在许多工程实践中已成功用MBR法或在常规反应器中增加挂膜能力强的填料的厌氧+缺氧+好氧工艺来去除氨氮和可生物降解有机物，而生物处理出水中残留的难生物降解有机物则通过纳滤或RO进一步净化，最终出水可稳定达到一级排放标准。实际上，这种工艺组合已成为把渗滤液处理到一级排放标准的最佳技术之一，但也存在以下主要问题：截留浓缩液需进一步处理，投资和运行费用较大等。目前处理截留浓缩液的常用方法有回灌、浓缩焚烧、固化、回流到生物处理系统等，由于浓缩液中有机物为难生物降解，回灌、回流到生物处理系统效果不佳，并可能引起系统难于正常运行，而浓缩焚烧、固化等成本昂贵。因此，有必要寻求处理截留浓缩液在技术上可行、经济上更合理的方法。
发明内容
腐殖酸是渗滤液“生物处理+纳滤工艺”膜截留液中有机物的主要成分，比例可高达50～90％。从无害化角度看，它是造成渗滤液原液及其经“生物处理+纳滤工艺”后所产生的膜截留液难处理达标的主要污染物，从另一方面看，它又是有机肥料的主要成分，因此本发明提供了从渗滤液“生物处理+纳滤工艺”膜截留液中分离腐殖酸后再浓缩为有机液体肥料的资源化方法，同时本发明还解决了膜截留液难处理的问题。
本发明提供了一种城市生活垃圾填埋场渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法，其特征在于，该方法包括如下步骤：1)将渗滤液经“生物处理+纳滤工艺”后的膜截留液，泵入纳滤系统，操作压差为0.5～1.5Mpa，浓缩倍数为5～10倍，膜分离后得到浓缩液和透过液，所述纳滤系统所用膜是一种截留相对分子量为200～1000的纳滤膜；2)让上述步骤得到的浓缩液流入浸没燃烧蒸发系统，燃烧室温度＞750℃，浸没深度0.3～0.6m，浓缩倍数为5～10倍，浓缩、净化后得到有机液体肥料；当渗滤液经“生物处理+纳滤工艺”处理后出水中Ca2+＞150mg/L、Mg2+＞300mg/L时，所述纳滤系统中选用膜的截留相对分子量为500～1000。
纳滤系统的膜透过液和浸没燃烧蒸发系统的蒸发冷凝液可以回流至渗滤液“生物处理+纳滤工艺”系统的调节池中处理。
本发明的有益效果：1、渗滤液“生物处理+纳滤工艺”膜截留液中所含的难生物降解有机物以腐殖酸为主，根据其分子量较大，先选择技术可行、经济合理的纳滤工艺进行分离浓缩，又根据其难于挥发，再经浸没燃烧蒸发系统浓缩和净化，获得了产品一腐殖酸有机液体肥料，这样既对渗滤液“生物处理+纳滤工艺”膜截留液进行了资源化利用，又解决了其难于处理的难题。2、可利用本资源化方法对国内现有不能达标的渗滤液处理设施进行改造，一般是在原有工艺的后端(生物处理后)增加纳滤工艺，调整、优化生物处理设施及其工艺参数，再对纳滤工艺膜截留液采用本发明进行资源化利用，这样既可使整合后的渗滤液处理设施出水中有机物达标，又可使该组合工艺所产生的膜截留液变废为宝，从而达到环境效益、社会效益和经济效益的统一。3、本资源化方法可使填埋场产生的填埋气体得到了综合利用。4、本资源化方法实用、先进，流程简单，占地少，无二次污染，运行简便、可靠。
附图说明
图1是本发明渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法流程图。
具体实施方式
下面结合附图对本发明渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法作进一步描述。
首先阐述一下本发明的总体思路。渗滤液“生物处理+纳滤工艺”膜截留液难于处理，并且其含较高浓度腐殖酸，因此，本发明有别于处理的角度，提出了资源化方法，同时兼顾了资源化过程中产生废水的达标处理。渗滤液“生物处理+纳滤工艺”膜截留液的资源化思路主要在于进一步分离浓缩膜截留液中可资源化物质—腐殖酸并脱除盐，同时净化有毒有害物质。具体表现为：(1)采用了以膜和蒸发工艺组成的从渗滤液中物理分离浓缩腐殖酸制成有机液体肥料的资源化方法。(2)现有的用于处理渗滤液的膜工艺中主要为反渗透和纳滤，在渗滤液经生物处理后的后续工艺中，如果处理后出水不要求综合利用(如绿化浇灌)，仅为达标排放，则建议采用纳滤工艺，这是因为：反渗透一般对渗滤液中各溶质几乎不加选择地全部截留，因此膜截流液中无机盐分也和有机物同时被浓缩，从而使其难于资源化；纳滤通常对一价离子截留率低，对二价及以上离子有较高的截留，对于经生物处理后的渗滤液，其所含的无机盐分中主要为一价离子，因此可充分发挥纳滤能使大部分盐随出水排出的优点，同时纳滤可以较易获得更高的浓缩倍数，通常渗滤液“生物处理+纳滤工艺”中纳滤的浓缩倍数为5～10倍，而反渗透一般只能做到3～5倍；反渗透投资和运行费用比纳滤高。本发明涉及的渗滤液“生物处理+纳滤工艺”和资源化方法中的纳滤均应选用专门去除有机物而非软化的纳滤膜，这种膜的脱盐率应只有5-30％左右，是一种高通量荷电纳滤膜，渗滤液“生物处理+纳滤工艺”中所用的纳滤膜的截留相对分子量一般为200，而本发明的资源化方法中纳滤系统所用的膜截留相对分子量为200～1000之间，在Ca2+、Mg2+含量高时，如渗滤液经“生物处理+纳滤工艺”处理后出水中Ca2+＞150mg/L、Mg2+＞300mg/L，则应为资源化方法中纳滤选用截留相对分子量为500～1000之间的膜。(3)利用浸没燃烧蒸发系统来最后浓缩经纳滤系统分离后的浓缩液，由于此时浓缩液中有机物浓度达12～20g/L以上，TDS更可达35g/L以上，继续采用膜浓缩容易发生堵塞等问题，影响其正常运行，且运行费用也会迅速升高，因此，进一步浓缩不适宜采用纳滤系统。浸没燃烧蒸发系统是一种利用燃烧产生的高温气体与液体直接接触的蒸发器，其传热效率可高达95％以上，由于是直接传热，消除了固定的接触界面，因此克服了间壁传热界面结垢的问题，可以获得更高的含固率。浸没燃烧蒸发系统所需燃气可用填埋场产生的填埋气体，更是达到“以废治废”综合利用的效果，从而大大降低资源化的成本。通常，渗滤液在生物处理过程中，大部分有毒或有害有机物能被有效的降解或逸出到大气中而被去除，出水中重金属浓度也会降低，并保持在较低的水平上(通常低于排放标准)，而在浸没燃烧蒸发系统过程中，大量气体扰动沸腾液体，也会使浓缩液中有毒或有害微量有机物和少量的不稳定的低分子挥发性有机物被充分地蒸出，病原体也会被全部灭活，从而保证了产品的品质。(4)资源化方法所得的产品为腐殖酸有机液体肥料，有机物含量大于14％(重量比)，或总有机碳含量大于8％(重量比)。(5)经纳滤系统后的膜透过液和浸没燃烧蒸发系统的蒸发冷凝液，由于绝大多数难生物降解的腐殖酸等大分子有机物被分离出，因此可回流到渗滤液“生物处理+纳滤工艺”系统处理，不会影响系统的稳定运行。
如图1所示，渗滤液经“生物处理+纳滤工艺”后产生的膜截留液，经纳滤系统后分成两部分：一部分为膜截留的浓缩液，富含以腐殖酸为主的难生物降解有机物，浓度很高，而所含的以无机盐分为主体的非挥发性溶解性残渣(FDS)也会比膜分离前的进料高，但一般不高于2～2.5倍，即大部分无机离子在纳滤系统中可以良好通过，截留率不高于30％，浓缩液这部分水量占进水的10～20％；另一部分为膜透过液，水量占进水的80～90％，所含有机物分子量较小，相对容易生化降解，可回到渗滤液“生物处理+纳滤工艺”系统处理。膜截留下来含腐殖酸的浓缩液要用作腐植质有机液体肥料，在浓度和品质上还达不到产品的有关要求，因此，浓缩液流入浸没燃烧蒸发系统进一步浓缩，最终浓缩液的有机物质量含量一般可达12～25％，同时在此过程中微量可能影响产品品质的挥发性有机物被进一步净化，并全部灭活病原体，蒸发系统的产品基本上即可作为腐殖酸有机液体肥料。蒸发出的蒸汽经系统内部冷却实现了余热利用，节约能源，冷凝液回到渗滤液生物处理+纳滤工艺系统处理，因此本资源化方法没有二次污染。
下面以北京市某生活垃圾卫生填埋场渗滤液“生物处理+纳滤工艺”膜截留液为例，进一步说明本发明。
该卫生填埋场1997年开始运行，现已进入产甲烷阶段，日产生渗滤液200吨，水质如下：pH为7.67～8.48，CODcr为2220～3520mg/L，BOD5为230～617mg/L，TOC为841～1590mg/L，电导率为18.2～24.1ms/cm，重金属浓度均低于一级排放标准，颜色呈黄色至红褐色。该渗滤液主体处理系统即为现有的生物处理(MBR)+纳滤工艺，系统已正常运行一年，出水稳定达到一级排放标准。该渗滤液经“生物处理+纳滤工艺”后产生的膜截留液的水质为：pH为5.0～6.8，CODcr为10000～12500mg/L，TOC为4000～5200mg/L。膜截留液可直接由泵提升进入纳滤系统，纳滤膜的截留相对分子量(MWCO)为200～1000，操作压差为0.5～1.5Mpa，浓缩倍数为5～10倍，膜分离后得到浓缩液，其TOC为16000～45000mg/L，TDS为39000～100000mg/L，颜色呈深红褐色，表明含有很高浓度的腐殖酸。膜透过液透明、无色或黄色，回流入现有的渗滤液“生物处理+纳滤工艺”系统，经本发明所述的纳滤系统(所用膜是非软化纳滤膜，截留相对分子量为200～1000)分离浓缩后的浓缩液流入现有的浸没燃烧蒸发系统。浸没燃烧蒸发系统为利用填埋气体作燃气的一体式浸没燃烧蒸发器，包括燃烧室和蒸发室，燃烧室内部衬有耐火材料，下部浸入蒸发室的液体中，蒸发室上部的侧壁上设有排气管，中部设有输入渗滤液的进液管，底部设有排出浓缩液的出液管，燃烧室与蒸发室结为一体。所利用填埋气体中CH4含量为53～66％(体积比)，燃烧室温度＞750℃，浸没深度0.3～0.6m，浓缩倍数为5～10倍，蒸发后的最终浓缩液(即有机液体肥料)中TOC大于8％(重量比)，满足腐殖酸有机液体肥料对有机碳的含量要求。而蒸发出的蒸汽可用来预热进料液，从而在系统内部循环利用热量，部分蒸汽冷凝为水，还有部分未冷凝的蒸汽用渗滤液经处理达标后的出水喷淋冷却，回流入渗滤液“生物处理+纳滤工艺”系统处理。
本发明所述的渗滤液“生物处理+纳滤工艺”膜截留液资源化方法技术参数：1、渗滤液“生物处理+纳滤工艺”膜截留液的水质条件pH 5.0～6.8CODcr300～1500mg/LBOD5＜40mg/LTDS ＜15000mg/L2、纳滤系统工作压力 0.5～1.5Mpa浓缩倍数 5～10倍3、浸没燃烧蒸发系统燃烧室温度 ＞750℃浸没深度 0.3～0.6m浓缩倍数 5～10倍
Claims (3)
1.城市生活垃圾填埋场渗滤液“生物处理+纳滤工艺”膜截留液的资源化方法，其特征在于，该方法包括如下步骤：1)将渗滤液经“生物处理+纳滤工艺”后的膜截留液，泵入纳滤系统，操作压差为0.5～1.5Mpa，浓缩倍数为5～10倍，膜分离后得到浓缩液和透过液，所述纳滤系统所用膜是一种截留相对分子量为200～1000的纳滤膜；2)让上述步骤得到的浓缩液流入浸没燃烧蒸发系统，燃烧室温度＞750℃，浸没深度0.3～0.6m，浓缩倍数为5～10倍，浓缩、净化后得到有机液体肥料。
2.根据权利要求1所述的资源化方法，其特征在于：渗滤液经“生物处理+纳滤工艺”处理后出水中Ca2+＞150mg/L、Mg2+＞300mg/L时，所述纳滤系统中选用膜的截留相对分子量为500～1000。
3.根据权利要求1所述的资源化方法，其特征在于：将所述纳滤系统的膜透过液和所述浸没燃烧蒸发系统的蒸发冷凝液回流至渗滤液“生物处理+纳滤工艺”系统的调节池中处理。
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| CN100448917C (zh) * | 2006-09-27 | 2009-01-07 | 清华大学 | 一种从垃圾渗滤液膜处理浓缩液中提取腐殖酸的方法 |
| CN101701025B (zh) * | 2009-10-30 | 2013-03-20 | 华南理工大学 | 一种从浓缩垃圾渗滤液提取腐殖酸并治理废水方法 |
| CN102443178B (zh) * | 2011-09-15 | 2013-12-11 | 福州大学 | 腐植酸的提取方法 |
| CN102951741B (zh) * | 2012-08-14 | 2014-09-24 | 上海晶宇环境工程有限公司 | 垃圾渗滤液深度处理工艺及专用设备 |
| CN103626314B (zh) * | 2013-11-06 | 2016-04-13 | 上海晶宇环境工程有限公司 | 垃圾渗滤液的纳滤浓缩液处理工艺及专用装置 |
| CN103627008A (zh) * | 2013-11-06 | 2014-03-12 | 上海晶宇环境工程有限公司 | 从垃圾渗滤液中提取腐殖酸的工艺及专用装置 |
| CN104310659B (zh) * | 2014-11-12 | 2016-06-01 | 福州大学 | 含高浓度so42-的垃圾渗滤液mbr+nf浓缩液中腐植酸分离回收工艺 |
| CN105585196B (zh) * | 2016-01-26 | 2019-01-08 | 安徽普朗膜技术有限公司 | 生活垃圾渗滤液的处理系统 |
| CN111072433A (zh) * | 2020-01-22 | 2020-04-28 | 福州大学 | 腐植酸液肥中氯化钠的净化方法 |
| CN112607935A (zh) * | 2020-11-24 | 2021-04-06 | 南京万德斯环保科技股份有限公司 | 一种垃圾填埋场渗滤液全量化处理方法 |
| CN112777849A (zh) * | 2020-12-15 | 2021-05-11 | 南京万德斯环保科技股份有限公司 | 一种填埋场渗滤液综合处理系统及其处理方法 |
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