高浓度甲醛废水深度处理技术及评价
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摘要
本文采用真空膜蒸馏、膜吸收法、电化学氧化—絮凝法、催化转化法和催化转化—生物降解法处理高浓度甲醛废水,并对各处理技术的效果和成本进行分析和评价。主要研究结果如下:
1、真空膜蒸馏和膜吸收法处理高浓度甲醛废水
真空膜蒸馏法处理高浓度甲醛废水,考察了真空度、膜蒸馏时间等因素的影响。当料液温度为60℃,料液流速为5.24×10~(-3)m·s~(-1),真空度为0.088MPa,对起始浓度约为7500mg·L~(-1)的甲醛废水,膜蒸馏8h,甲醛去除率仅为27.83%。
以2%亚硫酸氢钠为膜吸收剂序批式处理高浓度甲醛废水,当吸收剂和甲醛废水温度和流速分别为60℃和5.24×10~(-3) m·s~(-1),膜吸收时间为2h,对起始浓度约为7500mg·L~(-1)的甲醛废水,序批式处理六次,甲醛累积去除率达到99.15%,剩余甲醛浓度小于100 mg·L~(-1)。
2、电化学氧化—絮凝法处理高浓度甲醛废水
在试验室自制的实验装置上,对影响甲醛电氧化去除效果的各因素进行了初步的研究。实验结果表明:电解时间是影响甲醛去除率的关键因素。当电压9.5V,电解5h,絮凝剂BMT-1用量为2.5%,甲醛浓度从7500mg·L~(-1)降低至324.75mg·L~(-1),去除率达到95.67%。
3、催化转化法预处理高浓度甲醛废水
选择适当的催化剂处理高浓度甲醛废水。考察了pH、温度、甲醛初始浓度和催化剂加入量等因素对甲醛去除效果的影响。实验结果表明:在温度为60℃,催化剂与甲醛摩尔比为1:5,反应41min,对初始浓度约为8000 mg·L~(-1)的甲醛废水,去除率可达99.91%,废水中甲醛残余浓度低于10mg·L~(-1)。提出了甲醛催化转化反应可能的反应历程,并进行了相关动力学研究。结果表明,甲醛催化转化反应属于化学反应控制过程。动力学方程可表示为r_A=-dC_A/dt=7.3831×10~(13)exp(-10510.6192/T)CA,反应的活化能为87.390 kJ·mol~(-1)。产物的定性试验结果证明甲醛催化转化的产物是糖类混合物,使处理后废水的可生化性增强。同时,废水处理后产生的废渣在重复使用时,仍可保持效高的催化性能。
4、催化转化—生物降解法深度处理高浓度甲醛废水
催化转化法预处理高浓度甲醛废水技术,尽管甲醛去除效率高,残余甲醛浓度小于10mg·L~(-1),但并不能够有效降低废水的COD,故必须要对预处理的甲醛废水进行生物降解法深度处理。
采用厌氧—好氧组合工艺深度处理催化转化法预处理后的废水甲醛废水(COD约为8000～100000 mg·L~(-1))。当UASB反应器OLR大约在8.0～10.0kg·m-3·d -1之间,pH7.0～7.5,温度35～40℃,HRT为9～12h, COD去除率达到87%～88%;好氧反应器OLR控制在1.0～1.8kg·m-3·d -1之间,DO为4mg·L~(-1),HRT为9～12h时,COD去除率达到93%～94%(进水COD1000～1800mg·L~(-1))。废水经过生化处理后COD总的去除率可达到98.81%,处理后的出水COD<100 mg·L~(-1)。
5、各处理技术的效果评价和成本分析
采用真空膜蒸馏法处理甲醛废水,尽管操作简便,成本低,但无论是采用调整真空度或延长真空膜蒸馏时间的方式,均不能有效处理高浓度甲醛废水。
以亚硫酸氢钠为膜吸收剂序批式处理高浓度甲醛废水,甲醛去除率高(99.15%),但处理过程中需要定时更换新鲜吸收剂,使处理成本增高。每处理一吨甲醛废水(甲醛浓度约7500mg·L~(-1)),其处理成本约为64.5元/吨(不计设备折旧费和人员工资)。同时反应产物的浓度亦低,回收和再利用的难度大。而伴生渗透蒸馏的存在,也会影响总处理效果。
电化学氧化—絮凝联合处理工艺,相比于单独的使用电化学氧化技术,可以缩短电解时间,降低电解能耗,节约处理成本。初步估算,以电化学氧化—絮凝法处理高浓度甲醛废水(甲醛浓度约7500mg·L~(-1)),其处理成本约为13.5元/吨。该处理技术比膜吸收法处理高浓度甲醛废水的成本降低了近80%。
催化转化法预处理高浓度甲醛废水,操作工艺简单,甲醛去除效率高。且甲醛催化转化的产物是糖类混合物,废水处理后的甲醛残余浓度低于10 mg·L~(-1),这将为进一步的深度处理提供了保障。另外,反应产生的废渣可以继续重复使用,处理成本进一步降低。每处理一吨高浓度甲醛废水(甲醛浓度约8000mg·L~(-1))所需药剂成本约1.6元。
生物降解法深度处理高浓度甲醛废水,出水达到《污水综合排放标准》(GB8978—1996)一级标准,其处理成本约3.90元/吨。
综上所述,若将催化转化—生物降解法组合,则有可能达到经济、高效处理高浓度甲醛废水的目的。
In this paper, several technologies, such as vacuum membrane distillation, membrane absorption, electrochemical oxidation– flocculation, catalytic transformation and catalytic transformation-biological degradation for the treatment of high concentration formaldehyde wastewater were developed. The efficiency and the cost of the technologies were analyzed and evaluated. The main research conclusions are as follows:
1、Treatment of high concentration formaldehyde wastewater with vacuum membrane distillation and membrane absorption
The effect of some important parameters,such as vacuum and time, on the treatment of high concentration formaldehyde wastewater with vacuum membrane distillation were studied. When the feed temperature was 60℃, liquid flow rate of feed was 5.24×10~(-3)m·s~(-1), the vacuum was 0.088MPa, the initial concentration of formaldehyde was about 7500mg·L~(-1) and the operation time was 8h, the removal efficiency of formaldehyde was only reached 27.83%.
The membrane absorption can effectively deal with high concentrations of formaldehyde wastewater by sequencing batch with 2% NaHSO3 as absorbent. When the temperature was 60℃, the flow rate of absorbent was 5.24×10~(-3)m·s~(-1), membrane absorption time was 2h and the initial concentration of formaldehyde was about 7500mg·L~(-1), the removal efficiency of formaldehyde was reached 99.15% and the concentration of residual formaldehyde was less than 100 mg·L~(-1) after 6 times sequencing batch treatment.
2、Treatment of high concentration formaldehyde wastewater with electrochemical oxidation–flocculation
The experiment was carried out in the lab self-constructed equipment. Experimental results revealed that electrolysis time was the key factor on the removal efficiency of formaldehyde. When the voltage was 9.5V, electrolytic time was 5h, the dosages of flocculant, BMT-1, was 2.5%, the concentrations of formaldehyde decreased from 7500mg·L~(-1) to 324.75mg·L~(-1) and the removal efficiency of formaldehyde was reached 95.67%.
3、Treatment of high concentration formaldehyde wastewater with catalytic transformation
A proper catalyst was adopted to treat the high concentration formaldehyde wastewater. The influence of some important parameters,such as pH, temperature, the initial concentration of formaldehyde and the catalyst dosages, etc, on the removal efficiency of formaldehyde were thoroughly studied. The experimental results indicated that the removal efficiency of formaldehyde reaches 99.91% after 41 minutes at 60℃when the initial concentration of formaldehyde was 8000 mg·L~(-1) and the molar ratio of HCHO and catalyst was 5:1.The concentration of formaldehyde in the outlet water could be less than 10mg·L~(-1). The possible mechanism of the reaction was suggested and the kinetics analysis was carried out. It showed that the reaction was a chemical reaction controlled process.The kinetic equation of the reaction could expressed as r_A =-dC_A/dt=7.3831×10~(13)exp(-10510.6192 /T) CA,the activation energy of the reaction was 87.390kJ·mol~(-1).The reaction products were mainly the combination of sugars by qualitative analysis, thus the biodegradability of the treated wastewater was increased. Moreover, the catalyst could still maintain high catalytic efficiency when it reused.
4、Treatment of high concentration formaldehyde wastewater with catalytic transformation–biodegradation
Although the treatment of high concentration of formaldehyde wastewater with the catalyst could reached high removal efficiency of formaldehyde and the concentration of formaldehyde in the outlet water could be less than 10 mg·L~(-1). The COD value of the wastewater did not decreased Therefore, the wastewater must be depth treated with biodegradation.
A anerobic-aerobic technics was chose to treat the wastewater which the COD was about 8000～100000mg·L~(-1). Under the proper operation conditions of the anerobic reactor(UASB), the OLR 8.0～10.0 kg·m-3·d-1, pH 7.0～7.5, the temperature 35～40℃, HRT 9～12 h, the removal efficiency of COD could reached 87%～88%. the proper operation conditions of the aerobic reactor, the OLR 1.0～2.0kg·m-3·d-1,DO 4mg·L~(-1),HRT 9～12h, the removal efficiency of COD could reached 93%～94% for the inlet COD 1000～1800mg·L~(-1). The overall COD removal efficiency of the biodegradation could be reached as high as 98.81%, and the value of COD of the outlet water could be less than 100 mg·L~(-1).
5、Evaluation of the effect and the cost of the technics
Although vacuum membrane distillation has several advantages, such as simple operation and low cost, it do not effectively deal with the high concentrations of formaldehyde wastewater whether it adjusted the vacuum or extended the time of vacuum membrane distillation.
The membrane absorption with 2% NaHSO3 as absorbent can effectively deal with the high concentrations of formaldehyde wastewater by sequencing batch. However, the cost of the technics will be increased for the requirement of continuous replacing fresh absorbent. The cost of the technology is about 64.5 Yuan / ton (excluding equipment depreciation and staff salaries).At the same time the concentration of the reaction product is so dilute that it is difficult to recycling and reuse. The present of coupled osmotic distillation can also influence the overall treatment effect.
Compared with electrochemical oxidation, the technics of the combining of the flocculation with the electrochemical oxidation can cut the electrolysis time, reduce electrolysis energy and cost. Preliminary estimation the cost of the technics is about 13.5 Yuan / ton. It can reduce the cost about 80% when it compared with the membrane absorption method.
The technics of catalytic transformation had several advantages, such as simple operation and high removal efficiency of formaldehyde. In addition, the reaction products were mainly the combination of sugars and the residual concentration of formaldehyde was lower than 10mg·L~(-1), which provided the foundation for further depth treatment with biodegradation. Moreover, the catalyst can be reused which can be reduced the cost . The cost of the technics is about 1.6Yuan / ton
The outlet water with the biodegradation of the formaldehyde wastewater after the catalytic transformation can achieved the standard "Integrated Wastewater Discharge Standard" (GB8978-1996). The cost of the technics is about 3.9Yuan / ton
Based on the experimental results and the evaluation of the technics, it can be found that the combining technics of the catalytic transformation-biological degradation can achieve the purposes of economical and efficient for the treatment of high concentrations of formaldehyde wastewater.
1、真空膜蒸馏和膜吸收法处理高浓度甲醛废水
真空膜蒸馏法处理高浓度甲醛废水,考察了真空度、膜蒸馏时间等因素的影响。当料液温度为60℃,料液流速为5.24×10~(-3)m·s~(-1),真空度为0.088MPa,对起始浓度约为7500mg·L~(-1)的甲醛废水,膜蒸馏8h,甲醛去除率仅为27.83%。
以2%亚硫酸氢钠为膜吸收剂序批式处理高浓度甲醛废水,当吸收剂和甲醛废水温度和流速分别为60℃和5.24×10~(-3) m·s~(-1),膜吸收时间为2h,对起始浓度约为7500mg·L~(-1)的甲醛废水,序批式处理六次,甲醛累积去除率达到99.15%,剩余甲醛浓度小于100 mg·L~(-1)。
2、电化学氧化—絮凝法处理高浓度甲醛废水
在试验室自制的实验装置上,对影响甲醛电氧化去除效果的各因素进行了初步的研究。实验结果表明:电解时间是影响甲醛去除率的关键因素。当电压9.5V,电解5h,絮凝剂BMT-1用量为2.5%,甲醛浓度从7500mg·L~(-1)降低至324.75mg·L~(-1),去除率达到95.67%。
3、催化转化法预处理高浓度甲醛废水
选择适当的催化剂处理高浓度甲醛废水。考察了pH、温度、甲醛初始浓度和催化剂加入量等因素对甲醛去除效果的影响。实验结果表明:在温度为60℃,催化剂与甲醛摩尔比为1:5,反应41min,对初始浓度约为8000 mg·L~(-1)的甲醛废水,去除率可达99.91%,废水中甲醛残余浓度低于10mg·L~(-1)。提出了甲醛催化转化反应可能的反应历程,并进行了相关动力学研究。结果表明,甲醛催化转化反应属于化学反应控制过程。动力学方程可表示为r_A=-dC_A/dt=7.3831×10~(13)exp(-10510.6192/T)CA,反应的活化能为87.390 kJ·mol~(-1)。产物的定性试验结果证明甲醛催化转化的产物是糖类混合物,使处理后废水的可生化性增强。同时,废水处理后产生的废渣在重复使用时,仍可保持效高的催化性能。
4、催化转化—生物降解法深度处理高浓度甲醛废水
催化转化法预处理高浓度甲醛废水技术,尽管甲醛去除效率高,残余甲醛浓度小于10mg·L~(-1),但并不能够有效降低废水的COD,故必须要对预处理的甲醛废水进行生物降解法深度处理。
采用厌氧—好氧组合工艺深度处理催化转化法预处理后的废水甲醛废水(COD约为8000～100000 mg·L~(-1))。当UASB反应器OLR大约在8.0～10.0kg·m-3·d -1之间,pH7.0～7.5,温度35～40℃,HRT为9～12h, COD去除率达到87%～88%;好氧反应器OLR控制在1.0～1.8kg·m-3·d -1之间,DO为4mg·L~(-1),HRT为9～12h时,COD去除率达到93%～94%(进水COD1000～1800mg·L~(-1))。废水经过生化处理后COD总的去除率可达到98.81%,处理后的出水COD<100 mg·L~(-1)。
5、各处理技术的效果评价和成本分析
采用真空膜蒸馏法处理甲醛废水,尽管操作简便,成本低,但无论是采用调整真空度或延长真空膜蒸馏时间的方式,均不能有效处理高浓度甲醛废水。
以亚硫酸氢钠为膜吸收剂序批式处理高浓度甲醛废水,甲醛去除率高(99.15%),但处理过程中需要定时更换新鲜吸收剂,使处理成本增高。每处理一吨甲醛废水(甲醛浓度约7500mg·L~(-1)),其处理成本约为64.5元/吨(不计设备折旧费和人员工资)。同时反应产物的浓度亦低,回收和再利用的难度大。而伴生渗透蒸馏的存在,也会影响总处理效果。
电化学氧化—絮凝联合处理工艺,相比于单独的使用电化学氧化技术,可以缩短电解时间,降低电解能耗,节约处理成本。初步估算,以电化学氧化—絮凝法处理高浓度甲醛废水(甲醛浓度约7500mg·L~(-1)),其处理成本约为13.5元/吨。该处理技术比膜吸收法处理高浓度甲醛废水的成本降低了近80%。
催化转化法预处理高浓度甲醛废水,操作工艺简单,甲醛去除效率高。且甲醛催化转化的产物是糖类混合物,废水处理后的甲醛残余浓度低于10 mg·L~(-1),这将为进一步的深度处理提供了保障。另外,反应产生的废渣可以继续重复使用,处理成本进一步降低。每处理一吨高浓度甲醛废水(甲醛浓度约8000mg·L~(-1))所需药剂成本约1.6元。
生物降解法深度处理高浓度甲醛废水,出水达到《污水综合排放标准》(GB8978—1996)一级标准,其处理成本约3.90元/吨。
综上所述,若将催化转化—生物降解法组合,则有可能达到经济、高效处理高浓度甲醛废水的目的。
In this paper, several technologies, such as vacuum membrane distillation, membrane absorption, electrochemical oxidation– flocculation, catalytic transformation and catalytic transformation-biological degradation for the treatment of high concentration formaldehyde wastewater were developed. The efficiency and the cost of the technologies were analyzed and evaluated. The main research conclusions are as follows:
1、Treatment of high concentration formaldehyde wastewater with vacuum membrane distillation and membrane absorption
The effect of some important parameters,such as vacuum and time, on the treatment of high concentration formaldehyde wastewater with vacuum membrane distillation were studied. When the feed temperature was 60℃, liquid flow rate of feed was 5.24×10~(-3)m·s~(-1), the vacuum was 0.088MPa, the initial concentration of formaldehyde was about 7500mg·L~(-1) and the operation time was 8h, the removal efficiency of formaldehyde was only reached 27.83%.
The membrane absorption can effectively deal with high concentrations of formaldehyde wastewater by sequencing batch with 2% NaHSO3 as absorbent. When the temperature was 60℃, the flow rate of absorbent was 5.24×10~(-3)m·s~(-1), membrane absorption time was 2h and the initial concentration of formaldehyde was about 7500mg·L~(-1), the removal efficiency of formaldehyde was reached 99.15% and the concentration of residual formaldehyde was less than 100 mg·L~(-1) after 6 times sequencing batch treatment.
2、Treatment of high concentration formaldehyde wastewater with electrochemical oxidation–flocculation
The experiment was carried out in the lab self-constructed equipment. Experimental results revealed that electrolysis time was the key factor on the removal efficiency of formaldehyde. When the voltage was 9.5V, electrolytic time was 5h, the dosages of flocculant, BMT-1, was 2.5%, the concentrations of formaldehyde decreased from 7500mg·L~(-1) to 324.75mg·L~(-1) and the removal efficiency of formaldehyde was reached 95.67%.
3、Treatment of high concentration formaldehyde wastewater with catalytic transformation
A proper catalyst was adopted to treat the high concentration formaldehyde wastewater. The influence of some important parameters,such as pH, temperature, the initial concentration of formaldehyde and the catalyst dosages, etc, on the removal efficiency of formaldehyde were thoroughly studied. The experimental results indicated that the removal efficiency of formaldehyde reaches 99.91% after 41 minutes at 60℃when the initial concentration of formaldehyde was 8000 mg·L~(-1) and the molar ratio of HCHO and catalyst was 5:1.The concentration of formaldehyde in the outlet water could be less than 10mg·L~(-1). The possible mechanism of the reaction was suggested and the kinetics analysis was carried out. It showed that the reaction was a chemical reaction controlled process.The kinetic equation of the reaction could expressed as r_A =-dC_A/dt=7.3831×10~(13)exp(-10510.6192 /T) CA,the activation energy of the reaction was 87.390kJ·mol~(-1).The reaction products were mainly the combination of sugars by qualitative analysis, thus the biodegradability of the treated wastewater was increased. Moreover, the catalyst could still maintain high catalytic efficiency when it reused.
4、Treatment of high concentration formaldehyde wastewater with catalytic transformation–biodegradation
Although the treatment of high concentration of formaldehyde wastewater with the catalyst could reached high removal efficiency of formaldehyde and the concentration of formaldehyde in the outlet water could be less than 10 mg·L~(-1). The COD value of the wastewater did not decreased Therefore, the wastewater must be depth treated with biodegradation.
A anerobic-aerobic technics was chose to treat the wastewater which the COD was about 8000～100000mg·L~(-1). Under the proper operation conditions of the anerobic reactor(UASB), the OLR 8.0～10.0 kg·m-3·d-1, pH 7.0～7.5, the temperature 35～40℃, HRT 9～12 h, the removal efficiency of COD could reached 87%～88%. the proper operation conditions of the aerobic reactor, the OLR 1.0～2.0kg·m-3·d-1,DO 4mg·L~(-1),HRT 9～12h, the removal efficiency of COD could reached 93%～94% for the inlet COD 1000～1800mg·L~(-1). The overall COD removal efficiency of the biodegradation could be reached as high as 98.81%, and the value of COD of the outlet water could be less than 100 mg·L~(-1).
5、Evaluation of the effect and the cost of the technics
Although vacuum membrane distillation has several advantages, such as simple operation and low cost, it do not effectively deal with the high concentrations of formaldehyde wastewater whether it adjusted the vacuum or extended the time of vacuum membrane distillation.
The membrane absorption with 2% NaHSO3 as absorbent can effectively deal with the high concentrations of formaldehyde wastewater by sequencing batch. However, the cost of the technics will be increased for the requirement of continuous replacing fresh absorbent. The cost of the technology is about 64.5 Yuan / ton (excluding equipment depreciation and staff salaries).At the same time the concentration of the reaction product is so dilute that it is difficult to recycling and reuse. The present of coupled osmotic distillation can also influence the overall treatment effect.
Compared with electrochemical oxidation, the technics of the combining of the flocculation with the electrochemical oxidation can cut the electrolysis time, reduce electrolysis energy and cost. Preliminary estimation the cost of the technics is about 13.5 Yuan / ton. It can reduce the cost about 80% when it compared with the membrane absorption method.
The technics of catalytic transformation had several advantages, such as simple operation and high removal efficiency of formaldehyde. In addition, the reaction products were mainly the combination of sugars and the residual concentration of formaldehyde was lower than 10mg·L~(-1), which provided the foundation for further depth treatment with biodegradation. Moreover, the catalyst can be reused which can be reduced the cost . The cost of the technics is about 1.6Yuan / ton
The outlet water with the biodegradation of the formaldehyde wastewater after the catalytic transformation can achieved the standard "Integrated Wastewater Discharge Standard" (GB8978-1996). The cost of the technics is about 3.9Yuan / ton
Based on the experimental results and the evaluation of the technics, it can be found that the combining technics of the catalytic transformation-biological degradation can achieve the purposes of economical and efficient for the treatment of high concentrations of formaldehyde wastewater.
引文
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