WO2020010678A1 - 一种新型河道浊度原位净化材料及其制备方法 - Google Patents

一种新型河道浊度原位净化材料及其制备方法 Download PDF

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WO2020010678A1
WO2020010678A1 PCT/CN2018/103392 CN2018103392W WO2020010678A1 WO 2020010678 A1 WO2020010678 A1 WO 2020010678A1 CN 2018103392 W CN2018103392 W CN 2018103392W WO 2020010678 A1 WO2020010678 A1 WO 2020010678A1
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weight
clay mineral
parts
mineral powder
acid
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PCT/CN2018/103392
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English (en)
French (fr)
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高卫民
程寒飞
詹茂华
孟溪
骆守鹏
张雷燕
陈志刚
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中冶华天南京工程技术有限公司
中冶华天工程技术有限公司
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Priority to MYPI2019005062A priority Critical patent/MY193933A/en
Publication of WO2020010678A1 publication Critical patent/WO2020010678A1/zh

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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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • 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
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • C02F2101/20—Heavy metals or heavy metal compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/007—Contaminated open waterways, rivers, lakes or ponds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/11—Turbidity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/16—Total nitrogen (tkN-N)

Definitions

  • the invention belongs to the field of water environment treatment, and relates to a novel in-situ purification material for river turbidity and a preparation method thereof.
  • the purification material is mainly composed of clay mineral powder, which is subjected to thermal activation, acid treatment and flocculation modification, and finally is compounded with adsorbent material. It can reduce the turbidity of the river water body quickly and at low cost, and purify the water quality.
  • the effect is single, only for suspended particles; the second is that the dosage is large, the cost is high, and the load on the environment is large; the third is the slow sedimentation rate, which requires a longer One process; the fourth is the inability to provide a carrier for microorganisms.
  • the present invention provides a method for preparing a novel in-situ purification material for river turbidity.
  • the preparation process includes the following steps:
  • Step 1 heat treatment of the clay mineral powder to obtain a heat-activated clay mineral powder
  • Step 2 The heat-activated clay mineral powder is immersed in an acid solution, filtered, washed with water to neutrality, and then dried to obtain hydrogen ion-modified clay mineral powder;
  • Step three spray the flocculant aqueous solution into the hydrogen ion-modified clay mineral powder under stirring, mix well, and then dry to obtain a mixed material;
  • Step 4 The mixed material and the adsorbent are combined to obtain the turbidity-reducing material of the present invention.
  • step one The method for preparing a novel in-situ purification material for river turbidity according to the present invention, wherein step one:
  • the clay mineral powder is selected from one or more of attapulgite, bentonite, diatomite, kaolin, and montmorillonite, and the particle diameter is preferably 100-200 mesh.
  • the heat treatment in step 1 is performed under the protection of an inert gas, the temperature is 200-300 ° C, and the treatment time is 2-6 hours.
  • step two The method for preparing a novel in-situ purification material for river turbidity according to the present invention, wherein step two:
  • the acid is selected from one or more of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid, acetic acid, malic acid, citric acid, and tartaric acid.
  • the sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid are inorganic acids, and the acetic acid, malic acid, citric acid, and tartaric acid are organic acids.
  • the acid solution concentration is 0.1-1M, and when the clay mineral powder is 100 parts by weight, the corresponding acid is 1-10 parts by weight.
  • the dipping temperature in step 2 is 10-40 ° C, and the dipping time is 1-4 hours.
  • the drying temperature in step 2 is 100-300 ° C.
  • the drying time is from hydrogen ion modified clay mineral powder to constant weight.
  • step three The method for preparing a novel in-situ purification material for river turbidity according to the present invention, wherein step three:
  • the flocculant is selected from the group consisting of polyaluminum chloride (referred to as PAC), polymerized ferric sulfate, polymerized ferric silicate, polymerized aluminum ferric silicate, starch, protein, animal glue, sodium alginate, sodium carboxymethyl cellulose, polymer One or more of dimethyldiallylammonium chloride, polyacryloyloxyethyltrimethylammonium chloride, polymethacryloyloxyethyltrimethylammonium chloride, and sodium polyacrylate.
  • PAC polyaluminum chloride
  • PAC polymerized ferric sulfate
  • polymerized ferric silicate polymerized aluminum ferric silicate
  • starch protein
  • protein animal glue
  • sodium alginate sodium carboxymethyl cellulose
  • polymer One or more of dimethyldiallylammonium chloride polyacryloyloxyethyltrimethylammonium chloride, polymethacryloyloxyethyltrimethylammonium chlor
  • PAC polymeric ferric sulfate, polymeric ferric silicate, polymeric ferric aluminum silicate are inorganic flocculants, starch, protein, animal gum, sodium alginate, sodium carboxymethyl cellulose, polydimethyldiallyl chloride Ammonium, polyacryloyloxyethyltrimethylammonium chloride, polymethacryloyloxyethyltrimethylammonium chloride, and sodium polyacrylate are organic flocculants.
  • the concentration of the flocculant is 10-50%.
  • the flocculant is 5-20 parts by weight.
  • the drying temperature in step 3 is 100-300 ° C, and the drying time is from hydrogen ion-modified clay mineral powder to constant weight.
  • step four The method for preparing a novel in-situ purification material for river turbidity according to the present invention, wherein step four:
  • the adsorbent is selected from one or more of zeolite powder, dolomite, sepiolite, and activated carbon.
  • the adsorbent is 10-50 parts by weight.
  • the invention also provides a novel in-situ purification material for river turbidity, which is characterized by comprising the following components: 100 parts by weight of clay mineral powder modified by thermal activation, hydrogen ions, and flocculant, and 10-50 weight of adsorbent material 5-20 parts by weight of flocculant when 100 parts by weight of thermally activated, hydrogen ion-modified clay mineral powder.
  • the purification material according to the present invention is a novel in-situ purification material for river turbidity prepared by any one of the above preparation methods.
  • the clay mineral powder, flocculant, adsorbent and the preferred scheme thereof in a novel river turbidity in-situ purification material provided by the present invention and a method for preparing a new river turbidity in-situ purification material provided by the present invention Definitions are consistent.
  • a novel in-situ purification material for river turbidity manufactured by the present invention is based on inorganic porous clay mineral powder and is activated by heat treatment; acid treatment; modified with a flocculant; and finally compounded with an adsorbent. Its action principle is that the flocculant is firmly loaded on the surface and pore channel of the activated large specific surface area clay mineral powder, and through the synergistic interaction with the adsorption material, the in-situ rapid purification effect of river water turbidity is achieved.
  • Thermal activation treatment of clay mineral powder can increase the reaction activity.
  • Acidic ion exchange treatment can improve the binding ability and strength of flocculated modified materials and clay mineral powder.
  • the flocculated material can be evenly and firmly dispersed in the channels and surfaces of clay mineral powder. Improve the flocculation and sedimentation effect.
  • the modified clay mineral powder and adsorption material can adsorb and fix heavy metals, N, P and other nutrient salts and difficult-to-degrade organic matter, as well as adsorb microorganisms, providing a good carrier for microorganisms.
  • the in-situ purification material for river turbidity prepared by the present invention can flocculate and adsorb suspended particles, quickly settle, and achieve the effect of river clarification;
  • the river turbidity in-situ purification material prepared by the present invention adsorbs and fixes heavy metals, nutrient salts such as N and P, and hardly degradable organic matter during the sedimentation process;
  • the in-situ purification material for river turbidity prepared by the present invention is porous and larger than the surface, which can adsorb microorganisms, provide a good breeding and growth place for microorganisms, and purify water quality for a long time;
  • the in-situ purification material for river turbidity prepared by the present invention is suitable for in-situ spraying construction in a river channel, while rapidly reducing river turbidity, adsorbing and fixing heavy metals, N, P and other nutrient salts and refractory organic matter;
  • the materials are safe and environmentally friendly, easy to construct, less used, and low cost.
  • FIG. 1 is a preparation process diagram of the novel in-situ purification material for river turbidity of the present invention.
  • Attapulgite ⁇ ⁇ BOTU SAO Co., Ltd., 150-200 mesh
  • Polydimethyldiallylammonium chloride Homemade (refer to CN103819607A)
  • Zeolite powder Huazhou Mineral Products Processing Plant, Lingshou County, 150-200 mesh
  • the preparation process is as follows:
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 250 ° C for 3 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 200g of the above-mentioned heat-activated attapulgite, immerse it in 10ml of 0.2M hydrochloric acid solution, treat for 2 hours, filter, wash with water to neutrality, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion exchange Attapulgite
  • Step 3 Weigh 100g of hydrogen ion-exchange attapulgite clay, and with stirring, spray 50g of a PAC aqueous solution with a mass concentration of 20%, mix well, and then dry at 105 ° C for 8 hours to constant weight to obtain a mixed material;
  • Step 4 100 g of the mixed material is compounded with 20 g of the zeolite powder to obtain the turbidity-reducing material A of the present invention, which is to be used.
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 250 ° C for 3 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 200g of the above-mentioned heat-activated attapulgite, immerse it in 10ml of 0.1M sulfuric acid solution, treat for 3 hours, filter, wash with water to neutral, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion exchange Attapulgite
  • Step 3 Weigh 100g of hydrogen ion-exchange attapulgite clay, and spray 50g of a polymer ferric sulfate aqueous solution with a mass concentration of 20% under stirring, mix well, and then dry at 105 ° C for 8 hours to constant weight to obtain a mixed material;
  • Step four 100 g of the mixed material is compounded with 20 g of the zeolite powder to obtain the turbidity-reducing material B of the present invention, which is to be used.
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 300 ° C for 2 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 200g of the above-mentioned heat-activated attapulgite, immerse it in 10ml of 0.2M hydrochloric acid solution, treat for 3 hours, filter, wash with water to neutral, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion exchange Attapulgite
  • Step 3 Weigh 100g of hydrogen ion-exchange attapulgite, and spray 50g of polydimethyldiallylammonium chloride aqueous solution with a mass concentration of 10% under stirring, mix well, and then dry at 105 ° C for 8 hours to constant weight. Get mixed material
  • Step four 100 g of the mixed material is compounded with 20 g of the zeolite powder to obtain the turbidity-reducing material C of the present invention, which is to be used.
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 500 ° C for 2 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 200g of the above-mentioned heat-activated attapulgite, immerse it in 10ml of 0.1M sulfuric acid solution, treat for 3 hours, filter, wash with water to neutral, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion exchange Attapulgite
  • Step 3 Weigh 100g of hydrogen ion-exchange attapulgite clay, and spray 50g of a polymer ferric sulfate aqueous solution with a mass concentration of 20% under stirring, mix well, and then dry at 105 ° C for 8 hours to constant weight to obtain a mixed material;
  • Step 4 100 g of the mixed material is compounded with 20 g of the zeolite powder to obtain the turbidity-reducing material D, which is to be used.
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 250 ° C for 3 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 200g of the above-mentioned heat-activated attapulgite, immerse it in 10ml of 0.1M sulfuric acid solution, treat for 3 hours, filter, wash with water to neutral, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion exchange Attapulgite
  • Step 3 Compound 100 g of attapulgite with hydrogen ion exchange and 20 g of zeolite powder to obtain turbidity-reducing material E, and set aside.
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 250 ° C for 3 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 100g of thermally activated attapulgite, and spray 50g of a 20% polymer ferric sulfate aqueous solution with stirring, mix well, and then dry at 105 ° C for 8 hours to constant weight to obtain a mixed material;
  • Step three 100 g of the mixed material is compounded with 20 g of the zeolite powder to obtain a turbidity-reducing material F, which is set aside.
  • Step 1 Weigh 200 g of attapulgite, immerse it in 10 ml of 0.2M hydrochloric acid solution, treat for 2 hours, filter, wash with water to neutrality, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion-exchange attapulgite ;
  • Step 2 Weigh 100g of hydrogen ion-exchange attapulgite, spray 50g of 20% PAC aqueous solution under stirring, mix well, and then dry at 105 ° C for 8 hours to constant weight to obtain a mixed material;
  • Step 3 The turbidity-reducing material G is obtained by compounding 100 g of the mixed material and 20 g of the zeolite powder, which is to be used.
  • Step 1 Weigh the attapulgite clay under the protection of 1KG nitrogen and heat it at 250 ° C for 3 hours to obtain heat-activated attapulgite clay.
  • Step 2 Weigh 200g of the above-mentioned heat-activated attapulgite, immerse it in 10ml of 0.1M sulfuric acid solution, treat for 3 hours, filter, wash with water to neutral, and then dry at 105 ° C for 8 hours to constant weight to obtain hydrogen ion exchange Attapulgite
  • Step 3 Weigh 100g of hydrogen ion-exchange attapulgite clay, and spray 50g of a 20% polymer ferric sulfate aqueous solution under stirring, mix well, and then dry at 105 ° C for 8 hours to constant weight to obtain turbidity-reducing material H. .
  • the high turbidity sewage was taken from the river during the rainy period after the treatment of a river in Nanjing.
  • the water quality parameters of the river are shown in Table 1 below.
  • the novel in-situ purification material for river turbidity prepared by the present invention has a porous structure, is larger than the surface, and has good flocculation and adsorption characteristics. Sprayed in the river can flocculate and adsorb suspended particles, quickly settle, and reduce turbidity. At the same time, it can also adsorb and fix difficult-to-degrade organic pollutants, total nitrogen, total phosphorus, and heavy metals. Water quality has been rapidly improved, river water transparency has been enhanced, sunlight has been enhanced, water organisms have grown and ecosystems have been accelerated.
  • the comparative example which is not the present invention, is inferior to the requirements of the patent protection material of the present invention in terms of turbidity reduction effect and other pollutant removal effect.

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
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Abstract

一种新型河道浊度原位净化材料，该材料包括如下组分：经热活化、氢离子、絮凝剂改性的粘土矿粉100重量份，吸附材10-50重量份。其中当热活化、氢离子、絮凝剂改性的粘土矿粉100重量份时，絮凝剂5-20重量份。还公开了该新型河道浊度原位净化材料的制备方法。

Description

一种新型河道浊度原位净化材料及其制备方法 技术领域
本发明属于水环境治理领域，涉及一种新型河道浊度原位净化材料及其制备方法，该净化材料以粘土矿粉为主体，经热活化、酸性处理和絮凝改性，最后与吸附材复合而成，可快速、低成本降低河道水体浊度，净化水质。
背景技术
随着我国经济的快速发展和城市化进程加速，我国城市区域内的河流段河水污染问题愈来愈严重，其河水水质污染状况加剧，河流环境恶化，河流生态平衡已逐渐失去，形成了大面积的黑臭水体，对环境也造成严重的不良影响。同时，城市污染河流的水污染加剧状况直接影响着河流周围的城市环境、城市社会经济的发展。因此，城市河流治理，尤其是城市河流内水污染治理刻不容缓。随着“水十条”的公布，国家政策的重视以及公民环保意识的提高，对黑臭水体的治理已上升到国家层面。
国内外研究表明，目前对黑臭水体治理的物理方法主要有人工曝气、底泥疏浚、物理化学法或生物法处理，其中在人工曝气技术的研究中采用了微气泡或低强度曝气法，底泥疏浚的技术主要是将河道底泥挖出进行固定化处理；物理化学法主要采用化学强化混凝、Fenton试剂氧化等，生物法主要包括生物膜法、微生物强化技术和曝气生物滤池。
当前，虽然针对黑臭河道治理的技术河方案很多，有些也比较成熟，但是对于河道治理以后出现的河水混浊的问题，相关新材料和新技术研究的比较少，尤其是针对河道治理以后，引水入河初期，会出现长期一段时间河水混浊，河底光照不充分，不利于水体生物生长和生态系统的构建；其次是雨水期，雨水携带河(湖)岸泥沙入河导致河水混浊，依靠自然沉降，周期较长，容易造成水体生态系统的破坏。目前大多简单投加絮凝剂，降低浊度，这样一是作用效果单一，只针对悬浮颗粒物；二是投加量大，成本高且对环境的负荷大；三是沉降速度慢，需要较长的一个过程；四是不能为微生物提供载体。
发明内容
针对上述问题，本发明提供了一种新型河道浊度原位净化材料的制备方法，其制备 工艺包括以下步骤：
步骤一：粘土矿粉加热处理得到热活化粘土矿粉；
步骤二：上述热活化粘土矿粉浸渍在酸溶液中处理，过滤、水洗至中性，再干燥得到氢离子改性粘土矿粉；
步骤三：搅拌下，向氢离子改性粘土矿粉中喷洒絮凝剂水溶液，混合均匀，再干燥得到混合材；
步骤四：混合材与吸附材复合得到本发明降浊材。
其制备工艺图参见附图1。
本发明的一种新型河道浊度原位净化材料制备方法，其中，步骤一：
所述粘土矿粉选自凹凸棒土、膨润土、硅藻土、高岭土和蒙脱土中的一种或多种，粒径优选在100-200目。
优选的，步骤一热处理在惰性气体保护下进行，温度为200-300℃，处理时间为2-6小时。
本发明的一种新型河道浊度原位净化材料制备方法，其中，步骤二：
所述酸选自硫酸、磷酸、盐酸、硝酸、乙酸、苹果酸、柠檬酸、酒石酸中的一种或多种。所述硫酸、磷酸、盐酸、硝酸为无机酸，所述乙酸、苹果酸、柠檬酸、酒石酸为有机酸。
优选的，酸溶液浓度为0.1-1M，当粘土矿粉100重量份，对应酸为1-10重量份。
优选的，步骤二浸渍温度为10-40℃，浸渍时间为1-4小时。
优选的，步骤二的干燥温度为100-300℃，干燥时间为氢离子改性粘土矿粉至恒重为止。
本发明的一种新型河道浊度原位净化材料制备方法，其中，步骤三：
所述絮凝剂选自聚合氯化铝(简称PAC)、聚合硫酸铁、聚合硅酸铁、聚合硅酸铝铁、淀粉、蛋白质、动物胶、藻朊酸钠、羧甲基纤维素钠、聚二甲基二烯丙基氯化铵、聚丙烯酰氧乙基三甲基氯化铵、聚甲基丙烯酰氧乙基三甲基氯化铵、聚丙烯酸钠中的一种或多种。PAC、聚合硫酸铁、聚合硅酸铁、聚合硅酸铝铁为无机絮凝剂，淀粉、蛋白质、动物胶、藻朊酸钠、羧甲基纤维素钠、聚二甲基二烯丙基氯化铵、聚丙烯酰氧乙基三甲基氯化铵、聚甲基丙烯酰氧乙基三甲基氯化铵、聚丙烯酸钠为有机絮凝剂。
优选的，絮凝剂浓度为10-50％，当氢离子改性粘土矿粉100重量份，絮凝剂5-20重量份。
优选的，步骤三的干燥温度为100-300℃，干燥时间为氢离子改性粘土矿粉至恒重为止。
本发明的一种新型河道浊度原位净化材料制备方法，其中，步骤四：
所述吸附材选自沸石粉、白云石、海泡石、活性碳中的一种或多种。
当混合材100重量份，吸附材10-50重量份。
本发明还提供了一种新型河道浊度原位净化材料，其特征在于，包括如下组分：经热活化、氢离子、絮凝剂改性的粘土矿粉100重量份，吸附材10-50重量份；其中当热活化、氢离子改性粘土矿粉100重量份时，絮凝剂5-20重量份。
优选的，本发明涉及的净化材料为上述任一项的制备方法制得的新型河道浊度原位净化材料。
其中，本发明提供的一种新型河道浊度原位净化材料中所述粘土矿粉、絮凝剂、吸附材及其优选方案与本发明提供的一种新型河道浊度原位净化材料的制备方法中定义一致。
本发明制造的一种新型河道浊度原位净化材料，以无机多孔粘土矿粉为基础，经热处理活化；酸处理；再用絮凝剂改性；最后跟吸附材复合而成。其作用原理是在活化后的大比表面积粘土矿粉的表面和孔道内牢固负载絮凝剂，通过与吸附材料协同作用，达到河道水体浊度原位快速净化效果。粘土矿粉的热活化处理，可以提高增加反应活性，酸性离子交换处理可以提高絮凝改性材料与粘土矿粉的结合能力和强度，絮凝材料可以均匀牢固的分散在粘土矿粉的孔道和表面，提高絮凝沉降效果，同时改性粘土矿粉和吸附材料又可以吸附固定重金属，N、P等营养盐及难降解有机物，以及吸附微生物，为微生物提供良好的载体。
本发明的有益效果：
1、本方法经特殊工艺和组成制备的河道浊度原位净化材料，原料来源广泛，制备工艺简单，成本低廉；
2、本发明制备的河道浊度原位净化材料可以絮凝、吸附悬浮颗粒物，快速沉降，达到河水澄清的效果；
3、本发明制备的河道浊度原位净化材料在沉降过程中，吸附固定重金属，N、P等营养盐及难降解有机物；
4、本发明制备的河道浊度原位净化材料多孔、比表大，可以吸附微生物，为微生物提供较好的繁殖和生长场所，长期净化水质；
5、本发明制备的河道浊度原位净化材料适合在河道原位喷撒施工，快速降低河水浊度的同时，吸附固定重金属，N、P等营养盐及难降解有机物；
6、材料安全环保、施工方便，用量少，成本低。
附图说明
下面结合附图对本发明进一步说明。
图1是本发明新型河道浊度原位净化材料的制备工艺图。
具体实施方式
下面结合实施例对本发明作进一步的描述。所描述的实施例及其结果仅用于说明本发明，而不应当也不会限制权利要求书中所详细描述的本发明。
凹凸棒土：盱眙博图凹土股份有限公司，150-200目
硫酸：试剂
盐酸：试剂
聚二甲基二烯丙基氯化铵：自制(参考CN103819607A)
PAC：巩义市美源净水材料有限公司，含量30％
聚合硫酸铁：湖南谊德化工有限公司，全铁含量22％
沸石粉：灵寿县华洲矿产品加工厂，150-200目
材料制备例1
制备工艺如下：
步骤一：称取凹凸棒土1KG氮气保护下加热250℃，保温热处理3小时，得到热活化凹凸棒土；
步骤二：称取上述热活化凹凸棒土200g，浸渍在10ml浓度为0.2M的盐酸溶液中，处理2小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤三：称取氢离子交换凹凸棒土100g，搅拌下，喷洒质量浓度为20％的PAC水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到混合材；
步骤四：混合材100g与沸石粉20g复合得到本发明降浊材A，待用。
材料制备例2
材料制备例1同样的方法：
步骤一：称取凹凸棒土1KG氮气保护下加热250℃，保温热处理3小时，得到热活化凹凸棒土；
步骤二：称取上述热活化凹凸棒土200g，浸渍在10ml浓度为0.1M的硫酸溶液中，处理3小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤三：称取氢离子交换凹凸棒土100g，搅拌下，喷洒质量浓度为20％的聚合硫酸铁水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到混合材；
步骤四：混合材100g与沸石粉20g复合得到本发明降浊材B，待用。
材料制备例3
材料制备例1同样的方法：
步骤一：称取凹凸棒土1KG氮气保护下加热300℃，保温热处理2小时，得到热活化凹凸棒土；
步骤二：称取上述热活化凹凸棒土200g，浸渍在10ml浓度为0.2M的盐酸溶液中，处理3小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤三：称取氢离子交换凹凸棒土100g，搅拌下，喷洒质量浓度为10％的聚二甲基二烯丙基氯化铵水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到混合材；
步骤四：混合材100g与沸石粉20g复合得到本发明降浊材C，待用。
比较材料制备例1
步骤一：称取凹凸棒土1KG氮气保护下加热500℃，保温热处理2小时，得到热活化凹凸棒土；
步骤二：称取上述热活化凹凸棒土200g，浸渍在10ml浓度为0.1M的硫酸溶液中，处理3小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤三：称取氢离子交换凹凸棒土100g，搅拌下，喷洒质量浓度为20％的聚合硫酸铁水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到混合材；
步骤四：混合材100g与沸石粉20g复合得到降浊材D，待用。
比较材料制备例2
步骤一：称取凹凸棒土1KG氮气保护下加热250℃，保温热处理3小时，得到热活化凹凸棒土；
步骤二：称取上述热活化凹凸棒土200g，浸渍在10ml浓度为0.1M的硫酸溶液中，处理3小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤三：氢离子交换凹凸棒土100g与沸石粉20g复合得到降浊材E，待用。
比较材料制备例3
步骤一：称取凹凸棒土1KG氮气保护下加热250℃，保温热处理3小时，得到热活化凹凸棒土；
步骤二：称取热活化凹凸棒土100g，搅拌下，喷洒质量浓度为20％的聚合硫酸铁水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到混合材；
步骤三：混合材100g与沸石粉20g复合得到降浊材F，待用。
比较材料制备例4
步骤一：称取凹凸棒土200g，浸渍在10ml浓度为0.2M的盐酸溶液中，处理2小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤二：称取氢离子交换凹凸棒土100g，搅拌下，喷洒质量浓度为20％的PAC水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到混合材；
步骤三：混合材100g与沸石粉20g复合得到降浊材G，待用。
比较材料制备例5
步骤一：称取凹凸棒土1KG氮气保护下加热250℃，保温热处理3小时，得到热活化凹凸棒土；
步骤二：称取上述热活化凹凸棒土200g，浸渍在10ml浓度为0.1M的硫酸溶液中，处理3小时，过滤、水洗至中性，再105℃干燥8小时至恒重，得到氢离子交换凹凸棒土；
步骤三：称取氢离子交换凹凸棒土100g，搅拌下，喷洒质量浓度为20％的聚合硫酸铁水溶液50g，混合均匀，再105℃干燥8小时至恒重，得到降浊材H，待用。
水处理实施例
高浊度污水取自南京某河道治理后雨水期河水，河水水质参数如下表1。
表1 原水水质参数
Figure PCTCN2018103392-appb-000001
取河水1L与2000ml烧杯中，搅拌下分别加入实施例1-3、比较例1-5降浊材0.1g，快速搅拌30s，低速搅拌30s，倒入1000ml量筒中，10min观测絮凝体容积，60min观测絮凝体容积，并测试上层清液中COD、总氮、总磷、铜和镉浓度，结果记录在表2中。
表2 处理后水质参数
Figure PCTCN2018103392-appb-000002
Figure PCTCN2018103392-appb-000003
从试验结果看：本发明制备的新型河道浊度原位净化材料具有多孔结构，比表大、絮凝吸附性好的特点，喷撒在河道中可以絮凝、吸附悬浮颗粒物，快速沉降，降低浊度，同时还能吸附固定难降解有机污染物、总氮、总磷以及重金属等污染物。水质得到快速改善，提高河水透明度，增强光照，促进水体生物生长和加快生态系统构建。而非本发明的比较例不论是浊度降低效果，还是其他污染物去除效果均不如本发明专利保护材料的要求。

Claims (11)

  1. 一种新型河道浊度原位净化材料，其特征在于，包括如下组分：经热活化、氢离子、絮凝剂改性的粘土矿粉100重量份，吸附材10-50重量份；其中当热活化、氢离子改性粘土矿粉100重量份时，絮凝剂5-20重量份。
  2. 如权利要求1所述的一种新型河道浊度原位净化材料的制备方法，其制备工艺包括以下步骤：
    步骤一：粘土矿粉加热处理得到热活化粘土矿粉；
    步骤二：上述热活化粘土矿粉浸渍在酸溶液中处理，过滤、水洗至中性，再干燥得到氢离子改性粘土矿粉；
    步骤三：搅拌下，向氢离子改性粘土矿粉中喷洒絮凝剂水溶液，混合均匀，再干燥得到混合材；
    步骤四：混合材与吸附材复合得到本发明降浊材。
  3. 如权利要求2所述的制备方法，其特征在于步骤一所述粘土矿粉选自凹凸棒土、膨润土、硅藻土、高岭土和蒙脱土中的一种或多种，粒径在100-200目。
  4. 如权利要求2所述的制备方法，其特征在于步骤一热处理在惰性气体保护下进行，温度为200-300℃，处理时间为2-6小时。
  5. 如权利要求2所述的制备方法，其特征在步骤二中所述酸选自硫酸、磷酸、盐酸、硝酸、乙酸、苹果酸、柠檬酸、酒石酸中的一种或多种。
  6. 如权利要求2和5任一项所述的制备方法，其特征在步骤二中酸溶液浓度为0.1-1M，粘土矿粉100重量份，对应酸为1-10重量份。
  7. 如权利要求2所述的制备方法，其特征在于步骤二中浸渍温度为10-40℃，浸渍时间为1-4小时，步骤二和步骤三干燥温度为100-300℃。
  8. 如权利要求2所述的制备方法，其特征在于步骤三所述絮凝剂选自聚合氯化铝、聚合硫酸铁、聚合硅酸铁、聚合硅酸铝铁、淀粉、蛋白质、动物胶、藻朊酸钠、羧甲基纤维素钠、聚二甲基二烯丙基氯化铵、聚丙烯酰氧乙基三甲基氯化铵、聚甲基丙烯酰氧乙基三甲基氯化铵、聚丙烯酸钠中的一种或多种。
  9. 如权利要求2和8任一项所述的制备方法，其特征在于步骤三絮凝剂浓度为10-50％，氢离子改性粘土矿粉100重量份，絮凝剂5-20重量份。
  10. 如权利要求2所述的制备方法，其特征在于步骤四所述吸附材选自沸石粉、白云石、海泡石、活性碳中的一种或多种。
  11. 如权利要求2和10任一项所述的制备方法，其特征在于步骤四混合材100重量份，吸附材10-50重量份。
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CN117125808A (zh) * 2023-09-28 2023-11-28 青岛鑫源环保集团有限公司 一种用于净水处理的特种除氮复合改性填料及其制备方法

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