CN103787444B - 菱铁矿活性砂除磷方法 - Google Patents
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 21
- 239000011574 phosphorus Substances 0.000 title claims abstract description 21
- 239000004576 sand Substances 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 238000011010 flushing procedure Methods 0.000 claims abstract description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 4
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- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 abstract description 4
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- 241000894006 Bacteria Species 0.000 description 2
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- 238000012851 eutrophication Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
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- 239000004480 active ingredient Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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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 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种菱铁矿作为砂滤池滤料用于废水深度除磷的方法。其特征是把天然菱铁矿矿石破碎、筛分获得0.25-0.5mm颗粒并作为滤料填充砂滤池,以过滤方式进行低浓度含磷废水的深度除磷处理。其原理是菱铁矿被水中的溶解氧缓慢氧化形成新生水铁矿(铁氢氧化物),新生水铁矿吸附去除水中的磷。定期反冲洗使颗粒表面的水铁矿膜脱落,恢复菱铁矿氧化除磷作用。本发明的方法适合于生活污水、景观水体、受污染河水的深度除磷处理。
Description
一、技术领域
本发明涉及微污染源水深度处理的方法。
二、背景技术
随着经济快速发展和城市化,加之农田化肥过渡施用导致氮磷流失严重,大量营养元素氮磷进入湖泊等水体,使得诸如巢湖、太湖、滇池等湖泊以及城市景观水体严重的富营养化。国家设立水污染控制重大专项进行研究,投入巨资进行城市污水处理设施建设,提高城市生活污水的处理率。然而,目前城市生活污水处理普遍采用好氧活性污泥法工艺,但是好氧生物处理出水中总氮、总磷的浓度仍然分别达到20-35mg/L、0.3-3.0mg/L,是湖泊水体二类标准的10-50倍。很多情况下生活污水经过二级处理难以稳定达到国家一级A排放标准,需要增加深度处理设施以保证出水达标。生活污水处理即使达到排水标准,但对于已经富营养化的水体,需要对废水进行更严格的脱氮除磷才能保证水体的生态环境。尤其是生活污水处理后作为景观用水等实现废水资源化,生活污水处理厂二级处理出水需要进一步脱氮除磷才能满足废水资源化应用要求。
废水中高浓度磷的处理一般用石灰沉淀法、铁盐沉淀法、铝盐沉淀法处理。钙磷酸盐溶度积较大,用石灰处理低浓度磷不能达到预期效果。当水中磷浓度很低时铁、铝离子与磷酸根形成溶胶,很难用通常使用的沉淀池把磷酸盐沉淀从水中分离出来。为了提高沉淀除磷效果,必须投加远超过沉淀磷所需剂量的沉淀剂,导致铁、铝金属离子投加量大。
国内外已有很多学者在吸附法除磷方面做了研究,常用除磷吸附剂主要有沸石、方解石、膨润土、凹凸棒石、蛭石、赤泥、粉煤灰等天然矿物质和固体废物,这些粘土矿物和材料对磷有一定的吸附作用,但是吸附容量低。为了提高除磷吸附剂的吸附能力,很多学者进行除磷复合材料的制备研究,包括用有机废物作载体负载La、Ce、Fe等金属离子,用石英砂、蒙脱石、凹凸棒石、沸石等矿物做载体负载La、Al、Fe制备改性吸附剂,这些复合吸附剂具有较高的除磷吸附作用。从国内外研究结果来看,上述复合材料具有较好吸附作用的原因是吸附剂表面活性组分Fe3+、Al3+、La3+、Ce3+氢氧化物与磷酸根具有较强的化学键合作用。用稀土元素改性的吸附材料除磷效率高,但是价格昂贵,推广应用的前景不大。表面复合Fe3+、Al3+氢氧化物,或者能够不断释放活性铁、铝离子的廉价矿物材料在废水深度除磷吸附剂方面将具有更大的潜力,菱铁矿即是在好氧环境中可以不断缓慢释放铁离子的廉价矿物材料,在除磷吸附剂方面应具有潜力。吸附法因除磷工艺简单,除磷效果好而受到很多国内外研究者更多的关注。
三、发明内容
菱铁矿是分布广泛的一种碳酸盐矿物,晶体化学式为FeCO3。菱铁矿矿石常常在一些金属矿山作为伴生矿开采。高品位菱铁矿常常通过焙烧得到氧化铁用于炼铁,低品位菱铁矿通常情况下没有得到利用,常常在矿石开采中作为废石抛弃,既占用了土地,又破坏了环境。
发明人实验发现菱铁矿作为活性滤砂能够与水中溶解氧反应不断形成三价铁氢氧化物,新生铁氢氧化物具有很强的化学吸附除磷能力。
菱铁矿作为活性滤砂与水中溶解氧反应生成三价铁氢氧化物的速率,能够与去除水中低浓度磷所需的铁氢氧化物的量匹配,从而发明了菱铁矿作为活性滤料以过滤方式进行生活污水深度除磷的方法。
本发明方法是把菱铁矿含量不小于30%的天然菱铁矿矿石破碎、筛分获得0.25-0.5mm颗粒,并作为滤料填充砂滤池,进行低浓度含磷废水的深度除磷处理,菱铁矿被水中的溶解氧缓慢氧化形成新生水铁矿,新生水铁矿吸附去除水中的磷。反应方程可以表示如下:
FeCO3+O2+H2O——Fe(OH)3+CO3 2-
Fe(OH)3+H2PO4 -+H+——FePO4+3H2O
随着菱铁矿的氧化,铁氢氧化物不断在菱铁矿活性砂颗粒表面形成,导致菱铁矿氧化速率降低随着时间延长,活性砂去除磷的效率逐步降低,当处理出水不能够满足水质要求时,或者过滤速降低到设计滤速的70%时,反冲洗使颗粒表面的水铁矿膜脱落,恢复菱铁矿氧化除磷作用。
同时,活性滤砂还具有过滤截留水中颗粒物的作用,如沉淀不完全的微生物,对降低浊度也有一定的效果;随着活性滤砂的长期运行,活性砂颗粒表面附着微生物,形成硝化菌、反硝化菌、依赖硝酸盐的铁氧化菌占优势的微生物群落,使得菱铁矿活性颗粒滤砂在除磷的同时具有脱氮作用。
四、附图
图1活性菱铁矿滤砂照片
图2菱铁矿活性滤砂过滤去除低浓度的效果
五、具体实施方式
非限定实施例叙述如下。
选择菱铁矿矿石,菱铁矿含量不小于30%;
把菱铁矿矿石破碎、筛分获得0.25-0.5mm颗粒;
把菱铁矿颗粒滤料填充到直径30mm、高度1000mm玻璃管构建的砂滤柱中;
配制磷浓度1.0mg/L的模拟水,以水力停留时间3小时运行,进行废水除磷处理;
每隔5天取样检测出水磷浓度,运行225天出水磷浓度仍然保持在0.1mg/L以下(见图2),磷去除率大于90%,出水磷浓度达到地面水体二类标准。
Claims (2)
1.一种菱铁矿作为砂滤池滤料用于废水深度除磷的方法,其特征在于把天然菱铁矿矿石破碎、筛分获得0.25-0.5mm颗粒,并作为滤料填充砂滤池,以水力停留时间1-4小时进行低浓度含磷废水的深度除磷处理,菱铁矿被水中的溶解氧缓慢氧化形成新生水铁矿,新生水铁矿吸附去除水中的磷;
当处理出水不能够满足水质要求时,或者过滤处理滤速降低到设计滤速的70%时,反冲洗使颗粒表面的水铁矿膜脱落,恢复菱铁矿氧化除磷作用;
当反冲洗后仍然不能恢复吸附除磷活性时,更换滤料。
2.根据权利要求1所述的一种菱铁矿作为砂滤池滤料用于废水深度除磷的方法,制备活性滤砂的菱铁矿矿石中菱铁矿含量不小于30%。
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水铁矿的结构、组成及环境地球化学行为;王小明等;《地学前缘》;20110331;第18卷(第2期);第341页第1.1节第1-2行 * |
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