CN108786717A - A kind of preparation method of modified copper water-supply pipe particle and its application in going water removal on phosphate - Google Patents
A kind of preparation method of modified copper water-supply pipe particle and its application in going water removal on phosphate Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 18
- 239000010452 phosphate Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 150000001879 copper Chemical class 0.000 title 1
- 239000010802 sludge Substances 0.000 claims abstract description 42
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011574 phosphorus Substances 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 23
- 239000010865 sewage Substances 0.000 claims abstract description 23
- 239000012798 spherical particle Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 231100000719 pollutant Toxicity 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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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
- 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
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
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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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Abstract
本发明公开了一种改性给水污泥颗粒的制备方法及其在去除水中磷酸盐上的应用，属于水处理技术领域。本发明的技术方案要点为：通过对给水厂的脱水污泥进行高温烘焙和酸活化以获得改性给水污泥颗粒，该改性给水污泥颗粒能够用于去除污水中的磷酸盐。本发明制备过程简单，可以合理利用给水厂的副产物，有助于资源回收，具有较好的环境效益，以该改性给水污泥颗粒为吸附剂，对高校家属区生活污水进行处理，可以获得良好的除磷效果。
The invention discloses a preparation method of modified feedwater sludge particles and its application in removing phosphate in water, belonging to the technical field of water treatment. The gist of the technical solution of the present invention is: the dewatered sludge of the water supply plant is subjected to high-temperature baking and acid activation to obtain modified feedwater sludge particles, and the modified feedwater sludge particles can be used to remove phosphate in sewage. The preparation process of the present invention is simple, and the by-products of water supply plants can be rationally utilized, which is conducive to resource recovery and has good environmental benefits. The modified water supply sludge particles are used as adsorbents to treat domestic sewage in family areas of colleges and universities, which can Get good phosphorus removal effect.
Description
技术领域technical field
本发明属于水处理技术领域，具体涉及一种改性给水污泥颗粒的制备方法及其在去除水中磷酸盐上的应用。The invention belongs to the technical field of water treatment, and in particular relates to a preparation method of modified feedwater sludge particles and its application in removing phosphate in water.
背景技术Background technique
磷是引起水体富营养化的重要因子，可通过化学沉淀、生物法和吸附的方式予以去除。化学沉淀法除磷效率高，但需要投加化学药剂，可能会产生二次污染。生物法处理效果不稳定且仅发生磷形态和位置的转移，并最终以剩余污泥的形式存在。吸附法除磷已被广泛应用于各类水体中磷的去除，除磷效率取决于吸附材料的选取。Phosphorus is an important factor causing eutrophication of water bodies, which can be removed by chemical precipitation, biological methods and adsorption. The phosphorus removal efficiency of chemical precipitation is high, but it needs to add chemicals, which may cause secondary pollution. The effect of biological treatment is unstable and only the transfer of phosphorus form and position occurs, and finally exists in the form of excess sludge. Phosphorus removal by adsorption has been widely used in the removal of phosphorus in various water bodies, and the efficiency of phosphorus removal depends on the selection of adsorbent materials.
以湖泊、水库等地表水水源取水的城市净水厂常采用混凝-沉淀-过滤-消毒等一系列过程去除水中的各类杂质，在获得符合《生活饮用水卫生标准》（GB5749-2006）的出水的同时也产生了大量污泥。因铁盐、铝盐等混凝剂的投加，给水污泥中常含有铝、铁、钙等金属元素，直接排放到环境存在潜在的危害，回收则比较困难。给水厂污泥中的铁和铝多以无定型形态存在，对给水污泥进行适当处理，如高温煅烧，可使其表面形成一种疏松多孔的结构，可作为吸附材料吸附水中的磷，实现“以废治废”。Urban water purification plants that draw water from surface water sources such as lakes and reservoirs often use a series of processes such as coagulation-sedimentation-filtration-disinfection to remove various impurities in the water. A large amount of sludge is also produced while effluent. Due to the addition of coagulants such as iron salts and aluminum salts, the feedwater sludge often contains metal elements such as aluminum, iron, and calcium, and there are potential hazards in direct discharge to the environment, and it is difficult to recycle. The iron and aluminum in the sludge of the water supply plant mostly exist in the form of amorphous form. Appropriate treatment of the sludge for water supply, such as high-temperature calcination, can form a loose and porous structure on the surface, which can be used as an adsorption material to absorb phosphorus in water and realize "Treating waste with waste".
发明内容Contents of the invention
本发明解决的技术问题是提供了一种制备过程简单且可操作性强的改性给水污泥颗粒的制备方法，该改性给水污泥颗粒能够用于去除污水中的磷酸盐。The technical problem solved by the invention is to provide a preparation method of modified feedwater sludge particles with simple preparation process and strong operability, and the modified feedwater sludge particles can be used to remove phosphate in sewage.
本发明为解决上述技术问题采用如下技术方案，一种改性给水污泥颗粒的制备方法，其特征在于具体步骤为：The present invention adopts following technical scheme for solving above-mentioned technical problem, a kind of preparation method of modified feedwater sludge particle is characterized in that concrete steps are:
（1）给水厂脱水污泥经自然风干后研磨成粉末状，并使之通过60目金属筛，封袋备用；(1) The dewatered sludge from the water supply plant is naturally air-dried, ground into powder, passed through a 60-mesh metal sieve, and sealed in bags for later use;
（2）将步骤（1）处理后的给水污泥颗粒与高岭土按照质量比为8:3～7:2的比例混合，再将混合物加水制成粒径为0.5-1.5cm的球状颗粒；(2) Mix the feedwater sludge particles treated in step (1) with kaolin at a mass ratio of 8:3 to 7:2, and then add water to the mixture to make spherical particles with a particle size of 0.5-1.5cm;
（3）将步骤（2）得到的球状颗粒置于105℃烘箱中干燥2～3h，成型；(3) Dry the spherical particles obtained in step (2) in an oven at 105°C for 2 to 3 hours, and shape them;
（4）将步骤（3）成型后的球状颗粒置于800℃马弗炉中焙烧2h，冷却后密封保存；(4) The spherical particles formed in step (3) were roasted in a muffle furnace at 800°C for 2 hours, and then sealed and stored after cooling;
（5）将步骤（4）焙烧后的球状颗粒浸泡于2mol/L的盐酸溶液中，室温下静置24h；(5) Soak the spherical particles roasted in step (4) in 2mol/L hydrochloric acid solution, and let stand at room temperature for 24 hours;
（6）将盐酸浸泡后的球状颗粒用蒸馏水冲洗至中性，并置于105℃烘箱中干燥至恒重，最终制得改性给水污泥颗粒。(6) Rinse the spherical particles soaked in hydrochloric acid until neutral with distilled water, and dry them in an oven at 105°C to constant weight to finally obtain modified feedwater sludge particles.
进一步优选，步骤（2）中所述给水污泥颗粒与高岭土的质量比为3:1。Further preferably, the mass ratio of feedwater sludge particles to kaolin in step (2) is 3:1.
本发明所述的改性给水污泥颗粒在去除水中磷酸盐上的应用，其特征在于具体过程为：处理前生活污水中磷酸盐的含量为7.5mg/L，改性给水污泥颗粒的投加量为每升生活污水添加6g改性给水污泥颗粒，将生活污水的pH值调为3，室温下于80r/min的转速震荡120h，处理后生活污水中磷酸盐的含量为0.28mg/L，除磷率为96.31%，满足《城市污水处理厂污染物排放标准》（GB18918-2002）一级A标准对磷0.5mg/L的排放要求。The application of the modified feedwater sludge particles in the present invention in removing phosphate in water is characterized in that the specific process is as follows: the content of phosphate in the domestic sewage before treatment is 7.5mg/L, and the input of the modified feedwater sludge particles The dosage is to add 6g of modified feedwater sludge particles per liter of domestic sewage, adjust the pH value of domestic sewage to 3, shake at a speed of 80r/min for 120h at room temperature, and the phosphate content in domestic sewage after treatment is 0.28mg/ L, the phosphorus removal rate is 96.31%, which meets the discharge requirements of 0.5mg/L of phosphorus in the first-level A standard of the "Urban Sewage Treatment Plant Pollutant Discharge Standard" (GB18918-2002).
本发明可操作性强，对污水中磷酸盐有较强的去除效果，与传统生物除磷方法相比，具有消耗动力少，对环境条件要求少等优点，同时有助于实现给水厂污泥的资源化利用。The invention has strong operability and strong removal effect on phosphate in sewage. Compared with the traditional biological phosphorus removal method, it has the advantages of less power consumption and less requirements on environmental conditions. resource utilization.
附图说明Description of drawings
图1是模拟废水磷浓度为10mg/L，在不调节原水pH值的情况下，不同投加量下改性给水污泥颗粒的除磷效果曲线；Figure 1 is the phosphorus removal effect curve of the modified feedwater sludge particles under different dosages when the phosphorus concentration in the simulated wastewater is 10 mg/L and the pH value of the raw water is not adjusted;
图2是以6g/L投加改性给水污泥颗粒，模拟废水磷浓度为10mg/L，在不同pH值条件下改性给水污泥颗粒的除磷效果曲线；Figure 2 is based on the addition of 6g/L of modified feedwater sludge particles, the simulated wastewater phosphorus concentration is 10mg/L, and the phosphorus removal effect curve of modified feedwater sludge particles under different pH conditions;
图3是以6g/L投加改性给水污泥颗粒，并调节水样pH值为3，于80r/min的转速震荡反应，改性给水污泥颗粒对不同浓度的模拟含磷废水的除磷效果曲线；Figure 3 is to add modified feedwater sludge particles at 6g/L, adjust the pH value of the water sample to 3, and react at a speed of 80r/min. Phosphorus effect curve;
图4是以6g/L投加改性给水污泥颗粒，并调节水样pH值为3，于80r/min的转速震荡反应，改性给水污泥颗粒对实际生活污水的除磷效果随时间的变化曲线。Figure 4 is to add modified feedwater sludge particles at 6g/L, adjust the pH value of the water sample to 3, and react at a speed of 80r/min. The phosphorus removal effect of modified feedwater sludge particles on actual domestic sewage varies with time. change curve.
具体实施方式Detailed ways
结合附图和具体实施方式对本发明的具体内容做进一步说明。The specific content of the present invention will be further described in conjunction with the drawings and specific embodiments.
实施例所制备改性给水污泥颗粒的除磷性能评价Evaluation of the phosphorus removal performance of the modified feedwater sludge particles prepared in the examples
给水厂脱水污泥经自然风干后研磨成粉末状，并使之通过60目金属筛，封袋备用；将上述处理后的给水污泥颗粒与高岭土按照质量比3:1的比例混合，混合物加水制成粒径为0.5-1.5cm的球状颗粒；将上述得到的球状颗粒置于105℃烘箱中干燥2～3h，成型；将成型后的球状颗粒置于800℃马弗炉中焙烧2h，冷却后密封保存；将焙烧后的球状颗粒浸泡于2mol/L的盐酸溶液中，室温下静置24h；将盐酸浸泡后的球状颗粒用蒸馏水冲洗至中性，并置于105℃烘箱中干燥至恒重，最终制得改性给水污泥颗粒。The dewatered sludge of the water supply plant is naturally air-dried, ground into powder, and passed through a 60-mesh metal sieve, sealed in bags for later use; the above-mentioned treated water supply sludge particles and kaolin are mixed in a mass ratio of 3:1, and the mixture is added with water Make spherical particles with a particle size of 0.5-1.5 cm; dry the spherical particles obtained above in an oven at 105°C for 2 to 3 hours, and shape them; place the formed spherical particles in a muffle furnace at 800°C for 2 hours, and cool sealed and stored; soak the roasted spherical particles in 2mol/L hydrochloric acid solution, and let stand at room temperature for 24 hours; rinse the spherical particles soaked in hydrochloric acid with distilled water until neutral, and dry them in an oven at 105°C until constant Heavy, finally made modified feedwater sludge particles.
取250mL某高校生活区污水（可溶性磷酸盐浓度为7.5mg/L）于500mL锥形瓶中，置于恒温振荡器上，按照图1得到的最佳投加量，投加6g/L（每升生活污水投加6g改性给水污泥颗粒）的改性给水污泥颗粒，按照图2确定的反应pH值，将该生活污水pH值调为3，结合图3的结果，将振荡器转速设置为80r/min，反应持续120h，并在反应过程中不同时间点取该生活污水，过滤后测定滤液中的磷酸盐含量，以此计算该改性污泥对实际生活污水中磷的去除效果，结果如图4所示。Take 250mL of sewage (soluble phosphate concentration is 7.5mg/L) in a university living area in a 500mL Erlenmeyer flask, place it on a constant temperature oscillator, and add 6g/L (per According to the reaction pH value determined in Figure 2, the pH value of the domestic sewage is adjusted to 3, combined with the results in Figure 3, the oscillator speed The setting is 80r/min, the reaction lasts for 120h, and the domestic sewage is taken at different time points during the reaction process, and the phosphate content in the filtrate is measured after filtration, so as to calculate the removal effect of the modified sludge on the phosphorus in the actual domestic sewage , and the result is shown in Figure 4.
本实施例中处理前生活污水中的磷酸盐含量为7.50mg/L，处理后生活污水中的磷酸盐含量为0.28mg/L，除磷率为96.31%，满足《城市污水处理厂污染物排放标准》（GB18918-2002）一级A标准对磷0.5mg/L的排放要求。由此可知，本实施例采用改性给水污泥颗粒作为吸附剂去除生活污水中的磷酸盐，可获得较好的处理效果。In this embodiment, the phosphate content in the domestic sewage before treatment is 7.50mg/L, the phosphate content in the domestic sewage after treatment is 0.28mg/L, and the phosphorus removal rate is 96.31%, which meets the requirements of the "Urban Wastewater Treatment Plant Pollutant Discharge" "Standard" (GB18918-2002) Class A standard has a discharge requirement of 0.5mg/L of phosphorus. It can be seen that in this example, the modified water supply sludge particles are used as the adsorbent to remove phosphate in domestic sewage, and a better treatment effect can be obtained.
以上显示和描述了本发明的基本原理，主要特征和优点，在不脱离本发明精神和范围的前提下，本发明还有各种变化和改进，这些变化和改进都要求落入本发明的保护范围之内。The basic principles, main features and advantages of the present invention have been shown and described above. On the premise of not departing from the spirit and scope of the present invention, the present invention also has various changes and improvements, and these changes and improvements all require to fall into the protection of the present invention. within range.
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