CN107686171B - 一种具备除磷除氨氮复合功能的综合型污水处理剂 - Google Patents
一种具备除磷除氨氮复合功能的综合型污水处理剂 Download PDFInfo
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- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000010865 sewage Substances 0.000 title claims abstract description 56
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000011574 phosphorus Substances 0.000 title claims abstract description 55
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 55
- 238000011282 treatment Methods 0.000 title claims abstract description 52
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000005189 flocculation Methods 0.000 claims abstract description 12
- 230000016615 flocculation Effects 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 22
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 14
- 239000011790 ferrous sulphate Substances 0.000 claims description 13
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 13
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical group [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 13
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 7
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 7
- 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 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 5
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- 238000003756 stirring Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 229910001868 water Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 12
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- 238000007664 blowing Methods 0.000 description 11
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- 239000003814 drug Substances 0.000 description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
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- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
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- 229910017119 AlPO Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
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- 238000011276 addition treatment Methods 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052567 struvite Inorganic materials 0.000 description 1
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5254—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using magnesium compounds and phosphoric acid for removing ammonia
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Abstract
本发明公开了一种具备除磷除氨氮复合功能的综合型污水处理剂，其质量百分比组成为：氧化剂3％～15％、氨氮生物硝化碳源增效剂3％～10％、氨氮絮凝去除剂1％～5％、除磷除氨氮复合无机絮凝剂70％～90％、有机絮凝剂1％～5％。本发明综合型污水处理剂通过氧化剂化学氧化除氨氮、碳源增效生物硝化除氨氮、物理絮凝除磷除氨氮相结合的综合方式，及各组分的协同作用有效去除污水中的磷和氨氮，具备综合处理效果好、反应速度快、大幅减少综合处理成本、使用简单、使用范围广等优势，实现了对污水综合指标的有效处理。
Description
技术领域
本发明属于污水处理技术领域，具体涉及一种具备除磷除氨氮复合功能的综合型污水处理剂。
背景技术
随着人类对环境资源的开发利用活动的增加以及工农业生产规模的加速，致使大量的含磷、含氨氮的生活污水以及工业污水排放到自然水体中，增加了水体富营养化，给工业、农业、水产业、旅游业及生活方面的用水都带来了极大的危害，氨氮、磷的去除也成为了水处理领域最关键的控制指标，如何有效的综合降低污水中的氨氮、磷对环境保护和水处理具备重要的意义。
目前，应用最多的污水除磷、除氨氮主要利用化学药剂和生物硝化降解两种方式。除磷主要是通过铝盐、铁盐等絮凝剂产生的金属离子与磷酸根生成难溶的磷酸盐沉淀物，同时利用混凝、絮凝作用的方法除去水中的磷。氨氮的去除方法，主要是利用投加氯气氧化法除氨氮、镁离子磷酸根和氨氮絮凝法除氨氮、微生物硝化反硝化菌降解除氨氮。
目前广泛应用的化学除磷、除氨氮的方法，均采用单独、有单一针对性的处理药剂，利用氧化、絮凝沉淀等方式分别去除污水中的氨氮和磷，但从处理原理角度又存在相同的重复作用，两种药剂没有协同和增效作用。造成污水综合处理加药浓度大、加药重复操作、药剂的重复作用效率降低、药剂残余金属离子浓度高、二次污染严重等问题。同时，单独针对药剂分别处理的方式，对复杂水体、氨氮和磷复合处理指标要求的水体，处理效率和效果都不能满足要求。
发明内容
本发明的目的在于解决上述污水处理中除磷除氨氮存在的问题，提供一种可以同时去除污水中氨氮和磷的综合型水处理剂。
实现上述目的所采用的综合型污水处理剂由下述质量百分配比的原料组成：
上述综合型污水处理剂优选由下述质量百分配比的原料组成：
上述的氧化剂为次氯酸钠、高铁酸钠、高铁酸钾中任意一种或两种以上，优选次氯酸钠。
上述的氨氮生物硝化碳源增效剂为醋酸铁和/或醋酸亚铁，优选醋酸铁。
上述的氨氮絮凝去除剂为氯化镁和/或硫酸镁，优选氯化镁。
上述的除磷除氨氮复合无机絮凝剂为聚合双酸铝铁、聚合硫酸铝铁、聚合硫酸铁、聚合氯化铝、三氯化铁、硫酸亚铁中至少两种，优选由下述质量百分比的原料组成：聚合双酸铝铁40％～60％、三氯化铁20％～40％、硫酸亚铁10％～20％。
上述的有机絮凝剂为阳离子聚丙烯酰胺和/或聚二甲基二烯丙基氯化铵，优选阳离子聚丙烯酰胺。
本发明综合型污水处理剂固体产品的制备方法为：将氧化剂、氨氮生物硝化碳源增效剂、氨氮絮凝去除剂、除磷除氨氮复合无机絮凝剂、有机絮凝剂在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂固体产品。
本发明综合型污水处理剂液体产品的制备方法为：在常温搅拌状态下，按照上述质量百分配比向去离子水中依次加入氨氮生物硝化碳源增效剂、氨氮絮凝去除剂、除磷除氨氮复合无机絮凝剂，待所用原料溶解并混合均匀后，加入有机絮凝剂再搅拌30～60分钟，得到综合型污水处理剂液体产品，该产品中有效成分的的含量为5wt％～15wt％，其余为水。
本发明综合型污水处理剂的除磷除氨氮的机理如下：
1、氧化剂可以将污水中的氨氮氧化为氮气形式分离除去。
NH4 ++1.5ClO-→0.5N2↑+1.5H2O+H++1.5Cl-
NH4 ++FeO4 2-→0.5N2↑+Fe3++4OH-
2、氨氮生物硝化碳源增效剂可以通过醋酸根增效，加速污水中的硝化反硝化微生物降解氨氮，变成氮气去除。
硝化反应：NH4 ++1.5O2→NO3 -+H2O+H+
反硝化反应：NO3 -+CH3COO-→0.5N2↑+2CO2+H2O+H+
3、氨氮絮凝去除剂中的镁离子可以通过与污水中的磷酸盐、氨氮共同形成沉淀，达到增效沉淀复合去除氨氮、磷的目的。
Mg2++NH4 ++PO4 3-+6H2O→MgNH4PO4·6H2O↓(鸟粪石沉淀)
4、除磷除氨氮复合无机絮凝剂可以通过铝盐或铁盐与磷酸根形成沉淀的方式去除，同时利用吸附桥架和络合絮凝作用，除去水中磷及氨氮。
Fe3++PO4 3-→FePO4↓
Fe2++PO4 3-→Fe3(PO4)2↓
Al3++PO4 3-→AlPO4↓
5、利用无机絮凝剂和有机絮凝剂的混凝、电性中和、吸附桥架等协同增效作用和互补优势，使水中的磷、氨氮和杂质脱稳、絮凝沉降达到除磷除氨氮的目的。
本发明综合型污水处理剂的使用方法为：根据污水中磷和氨氮含量浓度的高低，将综合型污水处理剂按照50～500mg/L的浓度添加到含磷、含氨氮污水中，搅拌1～3分钟，沉淀15～30分钟后，取上清液即可。
本发明综合型污水处理剂与现有除磷或除氨氮单一药剂相比较，具备以下有益效果：
1、本发明的综合型污水处理剂可以同时去除污水中氨氮和磷。针对除磷和除氨氮综合指标污水，通过碳源增效的方式，强化加速了硝化反硝化过程，降低了外加碳源的用量，节约成本的同时提高了除氨氮的效果。
2、本发明提高了除磷和除氨氮药剂组分的絮凝协同增效和综合去除效率。综合的处理方式、各组分的协同增效以及处理效率的提高，避免了因重复加药造成的过多药剂金属离子残留，减少了二次污染，避免了为了除磷和除氨氮，分别重复加药的处理方式，降低了除磷、除氨氮药剂的总投加量，提高了处理效率，实现了一次加药处理即可完成污水处理中磷和氨氮的综合性去除。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
将60g次氯酸钠、50g醋酸铁、30g氯化镁、470g聚合双酸铝铁、260g三氯化铁、100g硫酸亚铁、30g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例2
将60g高铁酸钾、50g醋酸亚铁、30g硫酸镁、470g聚合硫酸铝铁、260g聚合氯化铝、100g硫酸亚铁、30g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例3
将60g高铁酸钠、50g醋酸铁、30g氯化镁、470g聚合硫酸铁、260g聚合氯化铝、100g硫酸亚铁、30g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例4
将50g次氯酸钠、70g醋酸铁、40g氯化镁、450g聚合双酸铝铁、250g三氯化铁、100g硫酸亚铁、40g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例5
将30g高铁酸钾、30g醋酸亚铁、30g硫酸镁、530g聚合硫酸铝铁、300g聚合氯化铝、70g硫酸亚铁、10g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例6
将100g高铁酸钠、70g醋酸铁、40g氯化镁、450g聚合硫酸铁、230g聚合氯化铝、70g硫酸亚铁、40g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例7
将150g次氯酸钠、70g醋酸铁、50g氯化镁、400g聚合双酸铝铁、200g三氯化铁、100g硫酸亚铁、30g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例8
将50g高铁酸钾、50g醋酸亚铁、50g醋酸铁、50g硫酸镁、450g聚合硫酸铝铁、200g聚合氯化铝、100g硫酸亚铁、50g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例9
将100g高铁酸钠、100g醋酸铁、25g氯化镁、25g硫酸镁、450g聚合硫酸铁、250g聚合氯化铝、50g聚二甲基二烯丙基氯化铵在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例10
将60g次氯酸钠、30g醋酸铁、20g醋酸铁、30g氯化镁、465g聚合双酸铝铁、300g三氯化铁、85g硫酸亚铁、10g阳离子聚丙烯酰胺在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
实施例11
将60g次氯酸钠、50g醋酸铁、20g氯化镁、20g硫酸镁、400g聚合双酸铝铁、240g三氯化铁、160g硫酸亚铁、50g阳离子聚丙烯酰胺在固体搅拌混合器内常温碾磨、混合至粒径为50～150目，常温条件下鼓风干燥20～40分钟，即得具备除磷除氨氮复合功能的综合型污水处理剂。
为了证明本发明的有益效果，发明人采用实施例1～11的综合型污水处理剂对污水进行处理实验，具体实验情况如下：
取河北某地工业水与生活污水混合污水处理厂污水水样(总磷含量3.7mg/L，氨氮含量45.2mg/L)，按照药剂浓度为200mg/L添加本发明综合型污水处理剂，搅拌3分钟，沉淀20分钟后，取上清液，检测其总磷和氨氮，实验结果见表1。
表1总磷、氨氮去除实验数据
由表1可见，采用本发明综合型污水处理剂处理后水质指标均达到国标标准中要求的总磷含量＜0.5mg/L、氨氮含量＜8mg/L。
Claims (2)
1.一种具备除磷除氨氮复合功能的综合型污水处理剂，其特征在于它由下述质量百分配比的原料组成：
上述的氧化剂为次氯酸钠、高铁酸钠和高铁酸钾；
上述的氨氮生物硝化碳源增效剂为醋酸铁和醋酸亚铁；
上述的氨氮絮凝去除剂为氯化镁和硫酸镁；
上述的除磷除氨氮复合无机絮凝剂为聚合双酸铝铁、聚合硫酸铝铁、聚合硫酸铁、聚合氯化铝、三氯化铁以及硫酸亚铁；
上述的有机絮凝剂为阳离子聚丙烯酰胺和聚二甲基二烯丙基氯化铵。
2.根据权利要求1所述的具备除磷除氨氮复合功能的综合型污水处理剂，其特征在于：它由下述质量百分配比的原料组成：
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