CN117342643A - 一种含铁锰多污染物废水处理方法 - Google Patents
一种含铁锰多污染物废水处理方法 Download PDFInfo
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- CN117342643A CN117342643A CN202311537370.4A CN202311537370A CN117342643A CN 117342643 A CN117342643 A CN 117342643A CN 202311537370 A CN202311537370 A CN 202311537370A CN 117342643 A CN117342643 A CN 117342643A
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- manganese
- iron
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 55
- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 46
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 31
- 239000011572 manganese Substances 0.000 title claims abstract description 31
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 231100000719 pollutant Toxicity 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 21
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005189 flocculation Methods 0.000 claims abstract description 9
- 230000016615 flocculation Effects 0.000 claims abstract description 9
- 239000003607 modifier Substances 0.000 claims abstract description 7
- 238000010979 pH adjustment Methods 0.000 claims abstract description 7
- 238000012216 screening Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000004062 sedimentation Methods 0.000 claims abstract description 5
- 238000005201 scrubbing Methods 0.000 claims abstract description 3
- 238000005507 spraying Methods 0.000 claims abstract description 3
- 239000008213 purified water Substances 0.000 claims description 16
- 239000002893 slag Substances 0.000 claims description 15
- 229910000616 Ferromanganese Inorganic materials 0.000 claims description 10
- 239000003124 biologic agent Substances 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 230000001580 bacterial effect Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 claims description 4
- 238000012258 culturing Methods 0.000 claims description 3
- 241000605222 Acidithiobacillus ferrooxidans Species 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 238000000889 atomisation Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 7
- 235000011941 Tilia x europaea Nutrition 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000011133 lead Substances 0.000 description 7
- 239000004571 lime Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008595 infiltration Effects 0.000 description 6
- 238000001764 infiltration Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VDGMIGHRDCJLMN-UHFFFAOYSA-N [Cu].[Co].[Ni] Chemical compound [Cu].[Co].[Ni] VDGMIGHRDCJLMN-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003673 groundwater Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 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 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000605272 Acidithiobacillus thiooxidans Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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Abstract
本发明公开了一种含铁锰多污染物废水处理方法，在含铁锰多污染物废水中加入吸附材料和处理药剂，经过pH调节‑配合反应‑絮凝反应‑沉降分离后的过程，同步深度脱除污染物。pH值调节到7‑10。吸附材料制备方法为：含铁、锰、铝多种金属元素的天然矿石，经筛分、破碎得到铁、锰、铝质量含量分别为2%‑20%，2%‑25%，2%‑14%的原料；原料在恒温恒湿的密闭容器中以雾化形式喷洒改性剂，静置后得基材；将基材搅拌擦洗筛分，得到吸附材料；吸附材料的投加量为0.1‑2.0 kg/m3废水。本发明工艺流程简单，固液分离效率高，适用性强、抗冲击负荷能力强，水处理的材料可通过返回循环使用。
Description
技术领域
本发明涉及水处理技术领域一种含铁锰多污染物废水处理方法。
背景技术
铁锰广泛存在于地壳中，当地壳被扰动或者受到地下水的侵袭，富含铁锰的岩石，经过风化、水的侵蚀作用，铁锰与一些含氧的离子或者分子结合，通过以下这些途径，最终进入水体环境：含有碳酸的地下水，可以溶解铁锰的氧化物，使其变成可溶的离子形态进入地下水；在还原性物质的存在条件下，铁锰被还原成低价态的离子，进一步被酸性水体溶解进入水体；地下环境中存在有机酸，有机酸溶解铁锰氧化物，使其进入水体。同时，在铁锰进入水体的过程中，多种污染物，如铜铅锌镉砷等重金属、钙镁等也一并进入水体，造成水体污染物存在形式多样、性质各异。对周边环境造成如重金属污染，色度、观感异常等问题。
针对含铁锰多污染物废水，常用的方法有空气氧化法、接触氧化法和生物氧化法，这些处理方法，对于铁锰含量较低、无其他污染物的情况，具有良好的效果，但对于铁锰含量高，尤其是铁锰含量达到0.8g/L以上，并且有其他污染物并存的废水，如铅、镉含量超标，处理难度较大。由于水体中的锰离子主要以+2价的形式存在，去除锰离子需要较高的氧化环境或者pH环境，造成废水处理的碱、氧化剂消耗大，水处理底渣处理难度大，同时其他重金属离子等污染物难以同步去除。因此，开发一种水质适用性好、效果优良、成本较低的含铁锰多污染物废水处理方法具有重要意义。
发明内容
本发明的目的是为解决含锰废水常规处理方法条件要求严格、处理效果不良、工艺复杂的问题，提供一种含铁锰多污染物废水处理方法。
本发明的一种含铁锰多污染物废水处理方法，在含铁锰多污染物废水中，先后加入吸附材料和处理药剂，经过pH调节-配合反应-絮凝反应-沉降分离后的过程，直接去除废水中的铁、锰等多种污染物。
所述的吸附材料的制备方法为：
a）含铁、锰、铝等多种金属元素的天然矿石，经过筛分、破碎，得到原料。原料中铁质量含量为2%-20%，锰质量含量为2%-25%，铝质量含量为2%-14%。
b）将步骤a）得到的原料，置于恒温恒湿的密闭容器中，以雾化形式喷洒改性剂，静置后得到基材。所述的改性剂，为氯化物、氢氧化物或过氧化物，改性剂用量为1-10 g/kg原料。所述的密闭容器，温度控制在30-70℃，相对湿度为50%-90%。
c）将步骤b）得到的基材，经过搅拌擦洗后，进行筛分，得到吸附材料。
当含铁锰多污染物废水的pH值不在7-10范围内时，将其调节到pH值为7-10。
所述的吸附材料粒度为200-600目，吸附材料的投加量为0.1-2.0 kg/m3废水。
所述的处理药剂，为生物制剂、氧气、次氯酸盐、过氧化物、过碳酸盐、过硫酸盐、碳酸盐中的一种或者多种。所述的生物制剂为专利ZL200810143860.5中的生物制剂，是以氧化亚铁硫杆菌、氧化硫硫杆菌为主的化能自养菌菌群培养得到的菌液，与铁盐或亚铁盐进行组分设计得到的产物。
所述的处理药剂，其投加量与废水中污染物质量总和的比值为10-0.4：1。
所述的pH调节、配合反应过程，是将废水进行搅拌，搅拌方式为机械搅拌、曝气搅拌、振荡搅拌中的一种或者多种。
所述的絮凝反应、固液分离过程为，向配合反应所得溶液中加入絮凝剂，加速沉淀，进行固液分离得净化水和底渣。所产生的底渣，一部分排出系统，另一部分需返回至配合反应过程，返回的比例为2%-20%。
本发明利用处理药剂、吸附材料的相互作用，处理以铁锰为主要污染物、其他多种污染物并存的废水，处理效率高。尤其是针对铁锰含量达0.8 g/L以上，并且存在其他如铅镉钙多污染物的废水，废水处理效率较中和法可以提高10%以上。克服了传统处理方法的pH设置过高、多种污染物难以同步去除的难题。
吸附材料中的铁、锰、铝等颗粒及其改性后的复合物，对废水中的污染物离子具有良好的催化活性及亲和力，并且添加的生物制剂，可以进一步强化吸附材料对污染物离子的亲和作用，在处理药剂的联合作用下，污染物在吸附材料表面、孔隙内部与吸附材料形成牢固的附着力，随吸附材料进入底渣，实现废水中污染物的去除；同时，吸附材料较传统水处理底泥，具有更高的比重，可以加速水处理的固液分离效率，提高水处理固液分离设备的表面负荷，节约工程占地面积。处理后的底渣，经部分返回，可以强化新形成的吸附材料的循环利用，进一步提高效率。
附图说明
图1为本发明实施例1处理流程图；
图2实施例1净化水与传统石灰中和法处理结果对比图；
图3为本发明实施例2处理流程图；
图4实施例2净化水与传统石灰中和法处理结果对比图；
图5为对比文件1（CN116332436B）处理流程图。
具体实施方式
以下是本发明的具体实施例，对本发明的技术方案作进一步的描述，但本发明并不限于该实施例。
实施例1
有色金属矿山酸性废水，含酸、铁、锰、锌、铜、钙污染物，采用pH调节-配合反应-絮凝反应-沉降分离的处理过程，去除废水中的污染物，处理流程如附图1。
吸附材料的制备方法为：铁质量含量为12%，锰质量含量为5%，铝质量含量为6%的天然矿石，经过筛分、破碎后，置于温度45摄氏度、相对湿度65%的密闭容器中，按1kg原料配3g过氧化氢的用量进行喷洒，静置48h后，经过擦洗、筛分，得到200-400目的吸附材料。
有色金属矿山酸性废水，采用石灰乳调节pH值至8。
配合反应过程中，按0.3 kg/m3废水的投加量，投加粒度为200-400目的吸附材料。并同步投加生物制剂、过碳酸盐，生物制剂投加量为0.6 kg/m3，过碳酸盐投加量为0.3 kg/m3。
pH调节、配合反应采用机械搅拌+曝气搅拌的方式。
向配合反应所得溶液中加入絮凝剂，加速沉淀，进行固液分离得净化水和底渣。所产生的底渣，一部分排出系统，另一部分需返回至配合反应过程，返回的比例为6%。有色金属矿山酸性废水、净化水取样并进行污染物指标检测，净化水中各污染物浓度稳定达到《铜镍钴工业污染物排放标准》（GB25467-2010）、《污水综合排放标准》（GB8979-1996）的要求。
对比例1 本实施例净化水与传统石灰中和法处理结果、对比文件1（CN116332436B）处理方法处理结果对比如附图2所示。
对于该有色金属矿山酸性废水，对比文件1处理方法为：
按如下方式制备除锰药剂：
（1）有色金属矿山含锰酸性废水，经液碱调节pH值至10，经搅拌反应后固液分离得到固相，经清水洗涤后得到沉渣，进行干燥、粉碎。其中锰质量含量为10%，铁质量含量15%。
（2）配置质量浓度为10%的浸润液，浸润液中聚合硫酸铁、硫酸锰、聚合硫酸铝三者的摩尔比为2：6：1。
（3）步骤（1）得到的沉渣、步骤（2）得到的浸润液，按固液比为1千克：10升混合进行搅拌浸润，浸润时间3h，得到基液。
（4）步骤（3）得到的基液，添加次氯酸钠，添加量为0.2mol有效氯/L基液。经120W、30KHz的超声活化处理30分钟，形成催化氧化载体。得到的溶液进行蒸发浓缩结晶，得到固态除锰药剂。
对于该有色金属矿山酸性废水，对比文件1的处理流程如附图5所示。有色金属矿山酸性废水先经曝气氧化20分钟，进行预氧化，再将固态除锰药剂按除锰药剂与锰离子质量比为0.6：1的比例投加至含锰酸性废水中，进行配合反应20分钟后，加入石灰调节废水体系pH值至7.2-7.5的区间，进行中和反应，再按2mg/L的比例加入絮凝剂溶液（浓度1g/L）进行絮凝反应，处理后的水进行固液分离，上清液进行污染物浓度检测。
对比本实施例净化水、中和法出水、对比文件1 出水的处理效果，本实施例净化水、对比文件1出水，其铁、锰含量均较低。但本实施例对于锌、钙，尤其是钙的处理效果更为突出，明显优于对比文件1出水的处理效果。本实施例出水，锌浓度满足《铜镍钴工业污染物排放标准》（GB25467-2010）的要求，对比文件1出水的锌浓度超出了GB25467-2010的要求；本实施例钙浓度降低至114 mg/L，对比文件1出水的钙浓度达到了482 mg/L。
实施例2
某含铁锰多污染物废水，pH值为7.5，含铁、锰、铅污染物，采用配合反应-絮凝反应-沉降分离的处理过程，去除废水中的污染物，处理流程如附图3。
吸附材料的制备方法为：铁含量为2%，锰含量为16%，铝含量为5%的天然矿石，经过筛分、破碎后，置于温度60摄氏度、相对湿度75%的密闭容器中，按1kg原料配3g氯化钠的用量进行喷洒，静置48h后，经过擦洗、筛分，得到300-600目的吸附材料。
配合反应过程中，采用机械搅拌的方式，按0.5 kg/m3废水的投加量，投加粒度为300-600目的吸附材料。并同步投加氧气、次氯酸盐，氧气投加量为0.05 kg/m3，次氯酸盐投加量为0.4 kg/m3。
向配合反应所得溶液中加入絮凝剂，加速沉淀，进行固液分离得净化水和底渣。所产生的底渣，一部分排出系统，另一部分需返回至配合反应过程，返回的比例为12%。含铁锰多污染物废水、净化水取样并进行污染物指标检测，净化水中各污染物浓度稳定达到《污水综合排放标准》（GB8979-1996）的要求。
对比例2 采用本实施例净化水与传统石灰中和法、对比文件1 （CN116332436B）处理方法处理结果对比如附图4所示。
对于该某含铁锰多污染物废水，对比文件1处理方法为：
按如下方式制备除锰药剂：
（1）有色金属矿山含锰酸性废水，经液碱调节pH值至10，经搅拌反应后固液分离得到固相，经清水洗涤后得到沉渣，进行干燥、粉碎。其中锰质量含量为10%，铁质量含量15%。
（2）配置质量浓度为10%的浸润液，浸润液中聚合硫酸铁、硫酸锰、聚合硫酸铝三者的摩尔比为2：6：1。
（3）步骤（1）得到的沉渣、步骤（2）得到的浸润液，按固液比为1千克：10升混合进行搅拌浸润，浸润时间3h，得到基液。
（4）步骤（3）得到的基液，添加次氯酸钠，添加量为0.2mol有效氯/L基液。经120W、30KHz的超声活化处理30分钟，形成催化氧化载体。得到的溶液进行蒸发浓缩结晶，得到固态除锰药剂。
对于该某含铁锰多污染物废水，对比文件1的处理流程如附图5所示。某含铁锰多污染物废水先经曝气氧化20分钟，进行预氧化，再将固态除锰药剂按除锰药剂与锰离子质量比为0.6：1的比例投加至某含铁锰多污染物废水中，进行配合反应20分钟后，加入石灰调节废水体系pH值至7.2-7.5的区间，进行中和反应，再按2mg/L的比例加入絮凝剂溶液（浓度1g/L）进行絮凝反应，处理后的水进行固液分离，上清液进行污染物浓度检测。
对比本实施例净化水、中和法出水、对比文件1 出水的处理效果，本实施例净化水、对比文件1出水，其铁、锰含量均较低，但对于铅的处理，本实施例出水，明显优于对比文件1出水的处理效果。本实施例出水，铅浓度满足《铜镍钴工业污染物排放标准》（GB25467-2010）的要求，对比文件1出水的铅浓度超出了GB25467-2010的要求。
Claims (6)
1.一种含铁锰多污染物废水处理方法，其特征在于：在含铁锰多污染物废水中，先后加入吸附材料和处理药剂，经过pH调节-配合反应-絮凝反应-沉降分离后的过程，直接去除废水中的铁、锰污染物；pH值控制为7-10；所述的处理药剂，投加量与废水中污染物质量总和的比值为10-0.4：1；
所述的吸附材料的制备方法为：
a）含铁、锰、铝多种金属元素的天然矿石，经过筛分、破碎，得到原料，原料中铁质量含量为2%-20%，锰质量含量为2%-25%，铝质量含量为2%-14%；
b）将步骤a）得到的原料，置于恒温恒湿的密闭容器中，以雾化形式喷洒改性剂，静置后得到基材；所述的改性剂，为氯化物、氢氧化物或过氧化物，改性剂用量为1-10 g/kg原料；所述的密闭容器，温度控制在30-70℃，相对湿度为50%-90%；
c）将步骤b）得到的基材，经过搅拌擦洗后，进行筛分，得到吸附材料；吸附材料的投加量为0.1-2.0 kg/m3废水。
2.根据权利要求1所述的一种含铁锰多污染物废水处理方法，其特征在于，所述的吸附材料粒度为200-600目。
3.根据权利要求1所述的一种含铁锰多污染物废水处理方法，其特征在于，所述的处理药剂，为生物制剂、氧气、次氯酸盐、过氧化物、过碳酸盐、过硫酸盐、碳酸盐中的一种或者多种；所述的生物制剂为以氧化亚铁硫杆菌、氧化硫硫杆菌为主的化能自养菌菌群培养得到的菌液，与铁盐或者亚铁盐配制得到的产物。
4.根据权利要求1或3所述的一种含铁锰多污染物废水处理方法，其特征在于，所述的处理药剂，投加量与废水中污染物质量总和的比值为6-0.4：1。
5.根据权利要求1所述的一种含铁锰多污染物废水处理方法，其特征在于，所述的pH调节、配合反应过程，是将废水进行搅拌，搅拌方式为机械搅拌、曝气搅拌、振荡搅拌中的一种或者多种。
6.根据权利要求1所述的一种含铁锰多污染物废水处理方法，其特征在于，所述的絮凝反应、固液分离过程为，向配合反应所得溶液中加入絮凝剂，加速沉淀，进行固液分离得净化水和底渣；所产生的底渣，一部分排出系统，另一部分返回至配合反应过程，返回的比例为2%-20%。
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