传统钙法除磷的机理及改良
摘要
磷污染可对人体、海洋生物、土壤、水体造成多种程度不同的危害,尤其是水体中以正磷酸盐离子、聚合磷酸盐及有机林化合物形式存在的磷,总质量浓度超过86ug/L(静止的水体)时,即判断该水体为富营养化,受磷污染。水体的过量的磷将会引起赤潮,藻类大量繁殖,鱼虾死亡等恶性现象。
人类生产活动中磷废水的排放是导致自然界水体富营养化的关键因素。其中汽车制造业的工艺环节里可产生涂装废水,其所含的磷浓度相当高,从30mg/L至300mg/L不等,还含有其他重金属等物质。若涂装废水不经处理直接排放,污染水体将无法有效的治理。
本文采用物化法中的传统钙法CaCl_2和熟石灰Ca(OH)_2除磷,研究其与磷酸盐反应的影响因素和机理。在此基础上再探寻一种基于两种除磷常见的含钙矿物(石灰石CaCO_3与熟石灰Ca(OH)_2)联合处理水样的改良方法,使在控制成本的情况下,二者除磷优势得到最大化发挥,缺点得以弥补,解决传统钙法存在机理不统一,出水泥水分离情况差一些影响其充分发挥作用的问题。
以重庆市长安汽车五厂的涂装废水为试验水样,通过FT-IR和孔径测量等手段对影响因素进行分析,获取最佳工艺参数。之后进行对传统钙法出水存在的问题的试验,通过定义污泥沉降比来重点考察出水的沉降性能。试验结果表明:
1.熟石灰法除磷:在废水含磷量为100mg/L的情况下,饱和石灰乳的投加量为25mL/L,溶液pH≥11.0,在25℃反应10~15min后,磷去除率可达99%;溶液pH值对反应过程具有控制性的作用,[OH-]含量的增多可促进出水磷去除率的升高。出水pH值较高,需要回调,消耗用酸量较大。
2.氯化钙法除磷:在废水含磷量为100mg/L的情况下,投加量大于0.1100g,pH≥11.0,室温下反应10min,磷去除率可达99%。CaCl_2除磷效果好,但对溶液的酸碱环境要求高,出水pH值也比较高,且药剂费用高于熟石灰。
3.结合除磷产物的FT-IR与XRF分析表明,传统石灰法除磷的主要机理是:在Ca2+离子和OH-离子浓度较高的体系中,磷酸根离子与二者逐步生成不同稳定程度的沉淀产物,即先由DCPD转化为高Ca/P、更加稳定的TCP,继而转化为HAP ,即DCPD→TCP→HAP。而吸附作用不是这一除磷过程的主要机理。
4.改良钙法(石灰石和熟石灰联合)除磷:在试验室废水磷浓度100mg/L,初始pH=4.5的室温下,石灰石投加量0.0300g,反应10min后,投加熟石灰0.0700g反应10min后,磷去除率可达99.32%。产物颗粒明显大于石灰法,沉降性能更好;出水pH值比石灰法低,可减少回调用酸。
5.在处理实际涂装废水时,原水样磷酸盐含量高达339.3mg/L ,在0.0200+0.0750g的投加比与5+10min的处理时间下,石灰石+熟石灰改良钙法工艺对实际废水中磷的去除率>99.5%。相比传统石灰法,改良钙法的除磷产物的颗粒粒径明显增大,沉降性能显著提高,出水pH更低一些,可减少约28%的回调用酸量。
Phosphorus pollution will cause various damages to the human body, marine organisms, soil and water. Especially for the phosphorus in water in the forms of orthophosphate ion and polymeric phosphate of which the total concentration is over 86ug/L (immobile water) will bring about eutrophication of water body.
Human production activity is the key reason causing water eutrophication in nature. Among these activities, the process of automobile manufactory and appliance industry will produce coating water containing quite a high phosphate concentration from 30mg/L to 300mg/L plus some heavy metals. There will be a series contaminationg if the coating water is discharged directly without effective treatment.
Through the experiments of phosphate removal by traditional methods (calcium chloride CaCl_2 and lime Ca(OH)_2 and limestone CaCO3), by means of FT-IR, XRF and chemical analysis, the influencing factors and the mechanisms when they react with phosphates were investigated. On basic of this, in prerequisite that the cost be under control, to maximize the advantages of both lime Ca(OH)_2 and limestone CaCO_3 ,to improve the bad separation of precipitations and solve the problem of acid waste for adjusting water of effluent.
The sample coating water obtained from an automobile factory was studied using combined method of lime Ca(OH)_2 and limestone CaCO3. The key influencing factors were analyzed to achieve the optimal technological parameters.
The results indicate:
1. Hydrated lime method: with a situation of TP in phosphate wastewater, dosage of hydrated lime, pH , temperature, oscillation time (separately 100mg/L, 25mL/L, more than 11.0, 25℃and 10-15min), the phosphate removal in supernatant reaches to 99%. The pH value plays a control role in the process of removing phosphates. Increasing [OH~-] can improve the P removal, but also increase the pH in effluent leading to extra acid quantity for adjusting pH near neuter.
2. Calcium chloride method: with a situation of TP in phosphate wastewater, dosage of hydrated lime, pH, temperature, oscillation time (separately 100mg/L, 0.1100g/L, more than 11.0, at room temperature and 10min), the phosphate removal in supernatant reaches to 99%. Its chemicals cost is higher than that of lime, and the reaction calls for a high pH acid-base environment, also the effluent has a quite high pH value.
3. Analysing the products of phosphate removing by FT-IR and XRF, the main mechanism is that: it appears that the phosphate is precipitated in the presence of Ca2+ and high pH in a transformation process DCPD→TCP→HAP where the Ca/P and thermal stability are higher. Adsorption does not play a significant role in phosphate removal with the two calcium methods.
4. Modified Calcium method (Limestone and lime combined method): on base of making phosphate wastewater, with initial pH=4.5, at room temperature, react with the limestone dosage of 0.0300g for 10min and lime dosage of 0.0700g for 10min, the process remove the phosphates by 99.32%. Its product partical size is significantly greater than that of lime method, the precipitatants of effluent are easy and quick to separated, and pH value is lower than lime method alone saving the usage of adjusting acid.
5. On base of actual coating wastewater, with a high TP of 339.3mg/L, the same initial pH, dosages of 0.0200+0.0750g and reaction time of 5+10min, the combined treatment remove more than 99.5% phosphates. Compared with traditional lime method, the particle size of products is bigger, settling performance is improved and the pH of effluent is lower which saving adjusting acid cost.
人类生产活动中磷废水的排放是导致自然界水体富营养化的关键因素。其中汽车制造业的工艺环节里可产生涂装废水,其所含的磷浓度相当高,从30mg/L至300mg/L不等,还含有其他重金属等物质。若涂装废水不经处理直接排放,污染水体将无法有效的治理。
本文采用物化法中的传统钙法CaCl_2和熟石灰Ca(OH)_2除磷,研究其与磷酸盐反应的影响因素和机理。在此基础上再探寻一种基于两种除磷常见的含钙矿物(石灰石CaCO_3与熟石灰Ca(OH)_2)联合处理水样的改良方法,使在控制成本的情况下,二者除磷优势得到最大化发挥,缺点得以弥补,解决传统钙法存在机理不统一,出水泥水分离情况差一些影响其充分发挥作用的问题。
以重庆市长安汽车五厂的涂装废水为试验水样,通过FT-IR和孔径测量等手段对影响因素进行分析,获取最佳工艺参数。之后进行对传统钙法出水存在的问题的试验,通过定义污泥沉降比来重点考察出水的沉降性能。试验结果表明:
1.熟石灰法除磷:在废水含磷量为100mg/L的情况下,饱和石灰乳的投加量为25mL/L,溶液pH≥11.0,在25℃反应10~15min后,磷去除率可达99%;溶液pH值对反应过程具有控制性的作用,[OH-]含量的增多可促进出水磷去除率的升高。出水pH值较高,需要回调,消耗用酸量较大。
2.氯化钙法除磷:在废水含磷量为100mg/L的情况下,投加量大于0.1100g,pH≥11.0,室温下反应10min,磷去除率可达99%。CaCl_2除磷效果好,但对溶液的酸碱环境要求高,出水pH值也比较高,且药剂费用高于熟石灰。
3.结合除磷产物的FT-IR与XRF分析表明,传统石灰法除磷的主要机理是:在Ca2+离子和OH-离子浓度较高的体系中,磷酸根离子与二者逐步生成不同稳定程度的沉淀产物,即先由DCPD转化为高Ca/P、更加稳定的TCP,继而转化为HAP ,即DCPD→TCP→HAP。而吸附作用不是这一除磷过程的主要机理。
4.改良钙法(石灰石和熟石灰联合)除磷:在试验室废水磷浓度100mg/L,初始pH=4.5的室温下,石灰石投加量0.0300g,反应10min后,投加熟石灰0.0700g反应10min后,磷去除率可达99.32%。产物颗粒明显大于石灰法,沉降性能更好;出水pH值比石灰法低,可减少回调用酸。
5.在处理实际涂装废水时,原水样磷酸盐含量高达339.3mg/L ,在0.0200+0.0750g的投加比与5+10min的处理时间下,石灰石+熟石灰改良钙法工艺对实际废水中磷的去除率>99.5%。相比传统石灰法,改良钙法的除磷产物的颗粒粒径明显增大,沉降性能显著提高,出水pH更低一些,可减少约28%的回调用酸量。
Phosphorus pollution will cause various damages to the human body, marine organisms, soil and water. Especially for the phosphorus in water in the forms of orthophosphate ion and polymeric phosphate of which the total concentration is over 86ug/L (immobile water) will bring about eutrophication of water body.
Human production activity is the key reason causing water eutrophication in nature. Among these activities, the process of automobile manufactory and appliance industry will produce coating water containing quite a high phosphate concentration from 30mg/L to 300mg/L plus some heavy metals. There will be a series contaminationg if the coating water is discharged directly without effective treatment.
Through the experiments of phosphate removal by traditional methods (calcium chloride CaCl_2 and lime Ca(OH)_2 and limestone CaCO3), by means of FT-IR, XRF and chemical analysis, the influencing factors and the mechanisms when they react with phosphates were investigated. On basic of this, in prerequisite that the cost be under control, to maximize the advantages of both lime Ca(OH)_2 and limestone CaCO_3 ,to improve the bad separation of precipitations and solve the problem of acid waste for adjusting water of effluent.
The sample coating water obtained from an automobile factory was studied using combined method of lime Ca(OH)_2 and limestone CaCO3. The key influencing factors were analyzed to achieve the optimal technological parameters.
The results indicate:
1. Hydrated lime method: with a situation of TP in phosphate wastewater, dosage of hydrated lime, pH , temperature, oscillation time (separately 100mg/L, 25mL/L, more than 11.0, 25℃and 10-15min), the phosphate removal in supernatant reaches to 99%. The pH value plays a control role in the process of removing phosphates. Increasing [OH~-] can improve the P removal, but also increase the pH in effluent leading to extra acid quantity for adjusting pH near neuter.
2. Calcium chloride method: with a situation of TP in phosphate wastewater, dosage of hydrated lime, pH, temperature, oscillation time (separately 100mg/L, 0.1100g/L, more than 11.0, at room temperature and 10min), the phosphate removal in supernatant reaches to 99%. Its chemicals cost is higher than that of lime, and the reaction calls for a high pH acid-base environment, also the effluent has a quite high pH value.
3. Analysing the products of phosphate removing by FT-IR and XRF, the main mechanism is that: it appears that the phosphate is precipitated in the presence of Ca2+ and high pH in a transformation process DCPD→TCP→HAP where the Ca/P and thermal stability are higher. Adsorption does not play a significant role in phosphate removal with the two calcium methods.
4. Modified Calcium method (Limestone and lime combined method): on base of making phosphate wastewater, with initial pH=4.5, at room temperature, react with the limestone dosage of 0.0300g for 10min and lime dosage of 0.0700g for 10min, the process remove the phosphates by 99.32%. Its product partical size is significantly greater than that of lime method, the precipitatants of effluent are easy and quick to separated, and pH value is lower than lime method alone saving the usage of adjusting acid.
5. On base of actual coating wastewater, with a high TP of 339.3mg/L, the same initial pH, dosages of 0.0200+0.0750g and reaction time of 5+10min, the combined treatment remove more than 99.5% phosphates. Compared with traditional lime method, the particle size of products is bigger, settling performance is improved and the pH of effluent is lower which saving adjusting acid cost.
引文
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