铈稀土吸附剂除磷脱氮实验研究
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摘要
近年来,随着经济的迅猛发展,全球范围内湖泊、河流富营养化问题日趋严重。其主要原因是由于入湖、河流的氮、磷等营养物质过多所致。研究表明,多数富营养化水体中的控制因素为氮、磷的输入量,因此,污水深度脱氮除磷对防止水体富营养化显得尤为重要。传统的脱氮除磷方法大都采用化学法和生物法。生物法脱氮除磷工艺运行稳定性较差,运行操作严格,受污水的温度、pH等影响较大,受污水中有机物浓度(BOD)依赖性很强,一般要求BOD:N:P比为100:5:1处理效果较好。而化学法要消耗大量的药物,产生的污泥量大,难以处理。与传统的化学法和生物法相比,吸附法具有工艺简单、高效等优点。从一定程度上弥补了生物法和化学法的不足。
本文针对造成水体富营养化的氮、磷,采用吸附法进行处理,以开发新型高效脱氮除磷吸附剂为目的,为废水的深度脱氮除磷提供一条切实可行的新途径。
研究结果表明:
(1)微波铈稀土吸附剂脱氮除磷的适宜条件是吸附剂用量为2g/L,反应时间为2.5小时,最佳pH值为4-6之间;
(2)镧铈不同比例的复合吸附剂除磷的效果差别不大,除氮的效果随着铈含量的增加而提高;
(3)焙烧法和微波合成法制备的吸附剂脱氮除磷的性能比较显示微波合成法优于焙烧法,对含磷1mg/L,含氨氮15mg/L的废水进行实验表明,吸附剂用量为2g/L,磷的去除率达到99%以上,氮的去除率达到80%以上,磷的最大吸附容量达到18.3mg/g;氮的最大吸附容量达到6.25mg/g;
(4)再生实验方面,再生液氢氧化钠适宜浓度为0.04mol/L,吸附剂再生10次后脱氮效率低于60%,吸附剂再生15次后除磷效率降至80%以下;
(5)成型方面,适宜的吸附剂成型压力为10MPa,造孔剂为碳酸氢钠,添加量为15%(质量比),烧结温度为900℃。当成型吸附剂用量为5g/L,磷的去除率达到61.7%,氮的去除率达到51.7%;
(6)结题实验方面,吸附剂用量为5g/L,8小时内脱氮除磷效率都达到了99%以上,实验达到了预期的效果。
With the development of economy in recent years, the eutrophication problem of lakes and rivers has become increasingly serious all over the world. The main reason is that many nutrients inputting into the water body, such as nitrogen, phosphorus. So many documents make clear that phosphorus and nitrogen quantity are the key role, and the removal of nitrogen, phosphorus are so urgent to eutrophication of water body, such as lakes and reservoirs.
The traditional methods of nitrogen and phosphorus removal are chemical and biological methods. However, biological treatment process is not steady for nitrogen and phosphorus removal because the pollutants are different in style, which result in operating badly, and at the same time temperature and pH value of influence play a great impact on removal ratio which relys on BOD in feed. When BOD: N: P is 100:5:1 can get a better treatment effect. To the chemical methods, which consume a large amount of medical flocculants and coagulating. Contemporarily a large amount of chemical sludge comes into being, and difficult to handle it. Adsorption which takes up the deficiency of biological and chemical measures, which is a high efficiency measure of removing nitrogen and phosphorus, and the technics is simple.
The thesis research takes adsorption method to deal with nitrogen and phosphorus which lead to eutrophication of water body, for the purpose of the depth of wastewater for nitrogen and phosphorus removal to provide a practical new ways. The results show that:
(1) The appropriate conditions of rare earth adsorbent treated by microwave for nitrogen and phosphorus removal is for the amount of adsorbent 2g/L, and reaction time is 2.5 hours, and the pH value is between 4-6;
(2) To La and Ce different proportion of Rare Earth adsorbent, there is not hardly difference in phosphorus removal, the efficiency gets better to nitrogen removal with the increaseing of Ce content;
(3) Comparison between roasting-adsorbent and microwave-adsorbent in nitrogen and phosphorus removal, the result shows microwave synthesis method is better than the roasting method. For the phosphorus-containing 1mg/L, nitrogen-containing 15mg/L wastewater, the amount of adsorbent of 2g/L, phosphorus removal rate is more than 99% ,nitrogen removal rate reached more than 80 percent; the largest phosphorus adsorption capacity is 18.3 mg/g; nitrogen adsorption capacity of the largest 6.25 mg/g respectively;
(4) On regeneration test, Appropriate regeneration liquid is NaOH concentration of 0.04mol/L, denitrification efficiency below 60% after 10 adsorbent regeneration, phosphorus removal efficiency below 80% after 15 adsorbent regeneration;
(5) On adsorbent Molding, appropriate adsorbent molding pressure is 10 MPa, additives of NaHCO_3 is 15% (mass ratio), and temperature of 900℃.when adsorbent dosage is 5g/L in dealing with wastewater , phosphorus removal rate reachex 61.7%,and nitrogen removal rate reachex 51.7%;
(6) The guitar experiment shows that, the amount of adsorbent is 5g/L nitrogen and phosphorus removal efficiency can also reach 99% after 8 h.
本文针对造成水体富营养化的氮、磷,采用吸附法进行处理,以开发新型高效脱氮除磷吸附剂为目的,为废水的深度脱氮除磷提供一条切实可行的新途径。
研究结果表明:
(1)微波铈稀土吸附剂脱氮除磷的适宜条件是吸附剂用量为2g/L,反应时间为2.5小时,最佳pH值为4-6之间;
(2)镧铈不同比例的复合吸附剂除磷的效果差别不大,除氮的效果随着铈含量的增加而提高;
(3)焙烧法和微波合成法制备的吸附剂脱氮除磷的性能比较显示微波合成法优于焙烧法,对含磷1mg/L,含氨氮15mg/L的废水进行实验表明,吸附剂用量为2g/L,磷的去除率达到99%以上,氮的去除率达到80%以上,磷的最大吸附容量达到18.3mg/g;氮的最大吸附容量达到6.25mg/g;
(4)再生实验方面,再生液氢氧化钠适宜浓度为0.04mol/L,吸附剂再生10次后脱氮效率低于60%,吸附剂再生15次后除磷效率降至80%以下;
(5)成型方面,适宜的吸附剂成型压力为10MPa,造孔剂为碳酸氢钠,添加量为15%(质量比),烧结温度为900℃。当成型吸附剂用量为5g/L,磷的去除率达到61.7%,氮的去除率达到51.7%;
(6)结题实验方面,吸附剂用量为5g/L,8小时内脱氮除磷效率都达到了99%以上,实验达到了预期的效果。
With the development of economy in recent years, the eutrophication problem of lakes and rivers has become increasingly serious all over the world. The main reason is that many nutrients inputting into the water body, such as nitrogen, phosphorus. So many documents make clear that phosphorus and nitrogen quantity are the key role, and the removal of nitrogen, phosphorus are so urgent to eutrophication of water body, such as lakes and reservoirs.
The traditional methods of nitrogen and phosphorus removal are chemical and biological methods. However, biological treatment process is not steady for nitrogen and phosphorus removal because the pollutants are different in style, which result in operating badly, and at the same time temperature and pH value of influence play a great impact on removal ratio which relys on BOD in feed. When BOD: N: P is 100:5:1 can get a better treatment effect. To the chemical methods, which consume a large amount of medical flocculants and coagulating. Contemporarily a large amount of chemical sludge comes into being, and difficult to handle it. Adsorption which takes up the deficiency of biological and chemical measures, which is a high efficiency measure of removing nitrogen and phosphorus, and the technics is simple.
The thesis research takes adsorption method to deal with nitrogen and phosphorus which lead to eutrophication of water body, for the purpose of the depth of wastewater for nitrogen and phosphorus removal to provide a practical new ways. The results show that:
(1) The appropriate conditions of rare earth adsorbent treated by microwave for nitrogen and phosphorus removal is for the amount of adsorbent 2g/L, and reaction time is 2.5 hours, and the pH value is between 4-6;
(2) To La and Ce different proportion of Rare Earth adsorbent, there is not hardly difference in phosphorus removal, the efficiency gets better to nitrogen removal with the increaseing of Ce content;
(3) Comparison between roasting-adsorbent and microwave-adsorbent in nitrogen and phosphorus removal, the result shows microwave synthesis method is better than the roasting method. For the phosphorus-containing 1mg/L, nitrogen-containing 15mg/L wastewater, the amount of adsorbent of 2g/L, phosphorus removal rate is more than 99% ,nitrogen removal rate reached more than 80 percent; the largest phosphorus adsorption capacity is 18.3 mg/g; nitrogen adsorption capacity of the largest 6.25 mg/g respectively;
(4) On regeneration test, Appropriate regeneration liquid is NaOH concentration of 0.04mol/L, denitrification efficiency below 60% after 10 adsorbent regeneration, phosphorus removal efficiency below 80% after 15 adsorbent regeneration;
(5) On adsorbent Molding, appropriate adsorbent molding pressure is 10 MPa, additives of NaHCO_3 is 15% (mass ratio), and temperature of 900℃.when adsorbent dosage is 5g/L in dealing with wastewater , phosphorus removal rate reachex 61.7%,and nitrogen removal rate reachex 51.7%;
(6) The guitar experiment shows that, the amount of adsorbent is 5g/L nitrogen and phosphorus removal efficiency can also reach 99% after 8 h.
引文
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