CN112441805A - 利用高铁酸盐制备强化除磷及cod滤料的方法 - Google Patents
利用高铁酸盐制备强化除磷及cod滤料的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 34
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
- C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/144—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being a flue gas desulfurization product
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- C—CHEMISTRY; METALLURGY
- 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
- C02F1/52—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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
本发明涉及一种利用高铁酸盐制备强化除磷及COD滤料的方法,属于污水处理技术领域。本发明包括以下步骤:(1)将蒸压加气混凝土砌块废料粉碎过筛;(2)将其他物料粉碎过筛;(3)制备高铁酸盐溶液,并调节pH;(4)按质量百分比取以下组分混合:水泥15~25%,蒸压加气混凝土粉碎料40~50%,粉煤灰10~15%,石灰10~15%,石膏3~5%,造孔剂0.1%;(5)造粒成型:加入高铁酸盐溶液,并搅拌混合,制备成生料球;(6)将生料球进行蒸压养护,出料。本发明简单易行,制备的滤料孔隙率高,极大的增加微生物的附着能力,不但能满足除磷需求,还能快速降低污水COD值,降低了生产成本。
Description
技术领域
本发明具体涉及一种利用高铁酸盐制备强化除磷及COD滤料的方法,属于污水处理技术领域。
背景技术
随着我国经济的日益发展,大量污染物尤其是水体中氮磷的超标带来的水体富营养化问题,也日益严重。目前广泛使用的去除污水中氨氮的方法,主要有生物接触氧化法、曝气生物滤池、生物活性碳等,其主要原理是利用生物膜吸附氧化作用,将氨氮转化为硝酸盐或亚硝酸盐,达到去除水体中氨氮的目的。
高铁酸盐中铁离子价态为+6价,氧化性强,可氧化大多数有机物,且有选择性。高铁酸盐在碱性/弱碱性,中性/微酸性溶液及酸性溶液中的反应方程式分别如式(1)、(2)和(3)所示:
FeO4 2- + 4H2O + 3e- = Fe(OH)3+5H2O (1)
FeO4 2- + 4H+ + 3e- = Fe(OH)3 + OH- (2)
FeO4 2- + 8H++3e-=Fe3+ + 4H2O (3)
Fe(III)(即Fe3+)在污水中生成的Fe(OH)3具有絮凝、吸附作用,是高铁酸盐中Fe(VI)(即Fe6+)的还原产物,且对人体无害;在溶液中呈胶体,能将水中悬浮物聚集形成沉淀,能高效地除去水中的微细悬浮物。因此高铁酸盐同时具有氯气和明矾[KAl(SO4)2.12H2O]的净水效果,是一种新型的绿色净水剂。
CN 201410432978.5公开了一种利用混凝土搅拌站废弃灰浆制备免烧陶粒的方法。利用混凝土搅拌站废弃灰浆,结合水泥、粉煤灰、废弃灰浆粉、粘结剂、成孔剂等组分,利用蒸压技术制备免烧陶粒。该方法仅可重复利用其中15~25%的废弃灰浆粉,且废弃灰浆大部为实心颗粒,在该工艺中仅作普通填料使用,其他组分与普通蒸压加气混凝土砌块所用原料基本无异,必定会影响到最终陶粒的孔隙率及比表面积。
CN 201910888647.5公开了一种高铁酸盐强化反硝化除磷生物滤池脱氮除磷的方法。首先在污水中投加高铁酸盐,将水中难降解有机物氧化为易生物降解的有机物,提高污水的可生化性。同时反应产物羟基氧化铁可吸附去除污水中的部分磷。本发明可显著提高对微污染水源水,市政二级出水、工业废水的处理效率,特别适用于可生化性差污水的处理。但该方法仅简单的在反硝化除磷生物滤池前投加一定量的高铁酸盐,无形中多了一道工序,增加了污水处理成本。
蒸压加气混凝土制作加工过程中,能产生1~3%的废料,包括残次品、下脚料等,其中只有很少一部分被掺和在混凝土砂浆中被重复利用,再次制作蒸压砌块,大部分都作为建筑垃圾处理处置,造成资源的极大浪费。
发明内容
本发明要解决的技术问题是:克服现有技术的不足,提供一种利用高铁酸盐制备强化除磷及COD滤料的方法,其简单易行,充分利用蒸压加气混凝土砌块废料,制备的滤料孔隙率高,极大的增加微生物的附着能力,不但能满足除磷需求,还能快速降低污水COD值,降低了生产成本,具有较高的经济价值和环保效益。
本发明所述的利用高铁酸盐制备强化除磷及COD滤料的方法,包括以下步骤:
(1)将蒸压加气混凝土砌块废料粉碎至2mm以下,并过筛;
(2)将其他物料粉碎至0.5mm以下,并过筛;
(3)制备一定浓度的高铁酸盐溶液,并调节至pH=10,备用;
(4)原料预混:按质量百分比取以下组分混合:水泥15~25%,蒸压加气混凝土粉碎料40~50%,粉煤灰10~15%,石灰10~15%,石膏3~5%,造孔剂0.1%;
(5)造粒成型:向步骤(4)的混合料中加入步骤(3)中制备的高铁酸盐溶液,并搅拌混合,利用造粒机制备成6~10mm的生料球;
(6)将生料球送入蒸压加气混凝土砌块养护釜中进行蒸压养护,出料。
优选的,高铁酸盐为高铁酸钠或高铁酸钾,进一步优选为高铁酸钾。
优选的,使用氢氧化钠、氢氧化钾或氢氧化钙调节pH,进一步优选为氢氧化钙。
优选的,水泥为普通硅酸盐水泥,进一步优选为52.5MPa型,以增加所制备滤料的最终筒压强度。
优选的,石膏为二水石膏(CaSO4·2H2O),进一步优选为脱硫石膏。
优选的,造孔剂为铝粉、碳酸氢钙或碳酸氢钠,进一步优选为碳酸氢钙。
优选的,养护温度为110~120°C,养护时间为6~8小时。
本发明利用的蒸压加气混凝土砌块废料中,所含的硅酸钙盐类物质具有缓慢释放钙离子和碱度的能力,同时易于制成各种形状的多孔材料,对水体磷酸根具有较好的吸附效果;蒸压混凝土砌块中的托勃莫来石能提供钙离子,使其与水中磷酸根结合,并在其表面生成稳定的羟基磷酸钙(HAP)而实现除磷。
本发明利用蒸压加气混凝土砌块废料,包括次品及切割废料等,结合高铁酸盐强氧化及其生成物的絮凝作用,公开了一种制备强化除磷及快速降低污水COD值滤料的方法。该方法制取的滤料,孔隙率高,能极大的增加微生物的附着能力,不但能满足除磷需求,还能快速降低污水COD值,且能达到工业废物循环利用的目的,具有极高的经济及社会效益。
与现有技术相比,本发明的有益效果如下:
(1)本发明可将废弃加气混凝土砌块废料循环利用,变废为宝;
(2)本发明所提供配方组分配比合理,可使制备的生物滤料强度提高,筒压强度可达10MPa以上,并没有因为加入高铁酸物质而导致强度降低;
(3) 所述蒸压加气混凝土砌块本身密度低且比表面积大、多孔,本发明所制取的生物滤料比表面积更大,可达普通滤料4倍以上,且具有挂膜速度快的优点,缩短微生物降解启动时间;
(4)所述高铁酸盐氧化性强,可氧化大多数有机物,生成的Fe(OH)3具有絮凝、吸附作用,能将水中悬浮物聚集形成沉淀,高效地除去水中的微细悬浮物,达到快速降低水体COD值;
(5)本发明制取的滤料跟蒸压加气混凝土砌块内部结构类似,都含有大量的莫来石,使用过程中能缓慢释放钙离子,后者能与水体中的磷酸根生成沉淀或被氢氧化铁胶体絮凝,达到长期除磷之目的;
(6)本发明制备的滤料借用现有的蒸压加气混凝土生产工艺,生产成本更低,增强了产品的市场竞争力。
具体实施方式
下面结合实施例对本发明做进一步的说明。
实施例1
(1)蒸压加气混凝土砌块废料粉碎至2mm以下,并过筛;
(2)其他物料粉碎至0.5mm以下,并过筛;
(3)制备5wt%的高铁酸钠溶液,并调节至pH=10左右,备用;
(4)原料预混:按重量比取以下组分混合:水泥22%,蒸压加气混凝土粉碎料47%,粉煤灰12%,石灰14%,碳酸氢钠0.1%,余量石膏,并混合均匀;
(5)造粒成型:以步骤(4)中原料为基数,加入30%(重量比)步骤(3)中制备的高铁酸盐溶液,并搅拌混合均匀,利用造粒机制备成直径7mm的生料球;
(6)对生料球送入蒸压加气混凝土砌块养护釜中进行常规的蒸压养护,养护温度为110°C,养护时间8小时;出料。
实施例2
(1)蒸压加气混凝土砌块废料粉碎至1.5mm以下,并过筛;
(2)其他物料粉碎至0.5mm以下,并过筛;
(3)制备5 wt %的高铁酸钾溶液,并调节至pH=10左右,备用;
(4)原料预混:按重量比取以下组分混合:水泥15%,蒸压加气混凝土粉碎料50%,粉煤灰15%,石灰15%,碳酸氢钠0.1%,余量石膏,并混合均匀;
(5)造粒成型:加入以步骤(4)中原料为基数,加入35%(重量比)步骤(3)中制备的高铁酸盐溶液,并搅拌混合均匀,利用造粒机制备成直径8mm左右的生料球;
(6)对生料球送入蒸压加气混凝土砌块养护釜中进行蒸压养护,养护温度为115°C左右,养护时间7小时;出料。
实施例3
(1)蒸压加气混凝土砌块废料粉碎至2mm以下,并过筛;
(2)其他物料粉碎至0.5mm以下,并过筛;
(3)制备6 wt %的高铁酸钾溶液,并调节至pH=10左右,备用;
(4)原料预混:按重量比取以下组分混合:水泥25%,蒸压加气混凝土粉碎料40%,粉煤灰10%,石灰10%,碳酸氢钠0.1%,余量石膏,并混合均匀;
(5)造粒成型:加入以步骤(4)中原料为基数,加入33%(重量比)步骤(3)中制备的高铁酸盐溶液,并搅拌混合均匀,利用造粒机制备成直径9mm的生料球;
(6)对生料球送入蒸压加气混凝土砌块养护釜中进行常规的蒸压养护,养护温度为120°C,养护时间6小时;出料。
对比例1
(1)蒸压加气混凝土砌块废料粉碎至2mm以下,并过筛;
(2)其他物料粉碎至0.5mm以下,并过筛;
(3)原料预混:按重量比取以下组分混合:水泥24%,蒸压加气混凝土粉碎料50%,粉煤灰11%,石灰12%,碳酸氢钠0.1%,余量石膏,并混合均匀;
(4)造粒成型:以步骤(4)中原料为基数,加入33%(重量比)的水,并搅拌混合均匀,利用造粒机制备成直径8mm的生料球;
(5)对生料球送入蒸压加气混凝土砌块养护釜中进行常规蒸压养护,养护温度为120°C,养护时间7小时;出料。
对实施例1~3和对比例1所制备的生物滤料堆积密度、比表面积、孔隙率、筒压强度、脱氮/除磷效率等性能指标进行测定,具体测定结果见下表1。
原水指标:市政污水厂二级出水,pH=7.1,磷浓度为3ppm,COD浓度为48ppm。
表1 滤料物理指标及污水指标变化
区分 | 堆积密度kg/m<sup>3</sup> | 比表面积m<sup>2</sup>/g | 孔隙率% | 筒压强度Mpa | COD去除率% | 除磷效率% |
实施例1 | 624 | 11.6 | 62.4 | 9 | 61.4 | 96 |
实施例2 | 602 | 11.4 | 61.8 | 9.5 | 65.8 | 95.1 |
实施例3 | 612 | 11.7 | 63.9 | 8.9 | 67.1 | 95.4 |
对比例1 | 598 | 10.6 | 59 | 8.5 | 20.3 | 90.1 |
当然,上述内容仅为本发明的较佳实施例,不能被认为用于限定对本发明的实施例范围。本发明也并不仅限于上述举例,本技术领域的普通技术人员在本发明的实质范围内所做出的均等变化与改进等,均应归属于本发明的专利涵盖范围内。
Claims (7)
1.一种利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:包括以下步骤:
(1)将蒸压加气混凝土砌块废料粉碎至2mm以下,并过筛;
(2)将其他物料粉碎至0.5mm以下,并过筛;
(3)制备高铁酸盐溶液,并调节至pH=10,备用;
(4)原料预混:按质量百分比取以下组分混合:水泥15~25%,蒸压加气混凝土粉碎料40~50%,粉煤灰10~15%,石灰10~15%,石膏3~5%,造孔剂0.1%;
(5)造粒成型:向步骤(4)的混合料中加入步骤(3)中制备的高铁酸盐溶液,并搅拌混合,利用造粒机制备成7~9mm的生料球;
(6)将生料球送入蒸压加气混凝土砌块养护釜中进行蒸压养护,出料。
2.根据权利要求1所述的利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:高铁酸盐为高铁酸钠或高铁酸钾。
3.根据权利要求1所述的利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:步骤(3)中,使用氢氧化钠、氢氧化钾或氢氧化钙调节pH。
4.根据权利要求1所述的利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:水泥为普通硅酸盐水泥。
5.根据权利要求1所述的利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:石膏为二水石膏。
6.根据权利要求1所述的利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:造孔剂为碳酸氢钠。
7.根据权利要求1所述的利用高铁酸盐制备强化除磷及COD滤料的方法,其特征在于:养护温度为110~120°C,养护时间为6~8小时。
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