超临界水氧化法处理糖蜜酒精废液的研究
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摘要
本文总结了目前糖蜜酒精废液的治理技术，从超临界水的特性出发，阐述了超临界水氧化技术的特点，并对国内外有关超临界水氧化降解有机污染物的研究工作进行了比较全面地综述。在此基础上，提出了超临界水氧化法处理糖蜜酒精废液的新思路，进行了基于超临界水氧化技术应用问题的基础性研究，主要的研究内容和得到的结论如下：
对糖蜜酒精废液的特征进行了分析，结果表明：（1）废液的pH值为4.16，为避免酸性物质对反应器的腐蚀，在进行超临界水氧化前需调节废液的pH值并将产生的沉淀沉降除去。（2）糖蜜酒精废液在超临界水氧化过程中，每吨废液可产生1.93×106kJ的热量，产生的热量足够维持反应的自热，如处理后废水排出系统的温度以150℃计，每吨废液约可回收能量 1.42×106kJ ；（3）糖蜜酒精废液在165℃左右开设有部分有机物分解而析出炭，废液的预热不能超过该温度。
1、 对废液的中和－沉降预处理方法进行了研究。用石灰乳将pH值调到8.0，较适宜的絮凝沉降操作参数为：PAC浓度10～50mg/100ml废液，PHP－2浓度0.06～0.09mg/100ml废液，混合搅拌速度为100～300rpm，相应的混合时间为2min，反应搅拌速度50 rpm，相应的反应时间为15min。
2、 对影响超临界水氧化法处理糖蜜酒精废液过程的因素及其影响规律进行了研究，结果表明：在超临界水氧化过程中，增加反应温度、氧压力（氧的浓度）、反应时间，均能增大废液的CODCr去除率。在这些影响因素中，温度、反应时间对有机物氧化的CODCr去除率的影响较大；氧压力（浓度）对CODCr的去除率影响很小，CODCr的去除率随时间的变化，呈现出先快后慢的规律。在400℃下，反应1min，CODCr去除率可达到99.3%，出水达到《污水综合排放标准GB9878—1996》的三级标准；反应10min，CODCr去除率达99.9%以上，出水完全达到GB8978—1996的二级标准，如反应20min，出水可达到GB8978—1996的一级排放标准.
4、对超临界水氧化法处理糖蜜酒精废液的动力学进行初步研究，研究表明：CODCr的反应级数为2.45,氧气的反应级数为0，反应的活化能为275.89kJ/mol，频率因子为 1.66×1015.
5、对催化超临界水氧化法处理糖蜜酒精废液进行了初步探索，结果显示：Cu/Ce（3：1）和Cu：Mn：Fe（0.5：2：0.5）两种固体催化剂，在临界点附件
有较好的催化效果，但在较高的温度下，Cu/Ce（3：1）的催化效果不明显。
The paper systematically summarized current treatmeant technology of molasses
alcohol wastewater, reviewed the properities of supercritical water oxidation(SCWO) and universal research work in the field .The author prosposed applying SCWO to the treatmeant of molasses alcohol wastewater,and studied basic work on the application. The work and the results follow as:
1、 The characteristic of molasses alcohol wastewater was observeed. 1st ,the pH value of the wastewater is about 4.13,as an anti-corrosion method,pH value shoud adjust to about 8.0 and eliminate the flocculation created.2nd,the thermal energy the reaction created was about 1.93×106kJ per ton,in addition to sustain the reaction,the surplurs energy recycled was 1.42×106kJ per ton.3rd ,to avoid formation of carbon ,the temperture of preheated should keep under 165℃ .
2、 The pretreatmeant of neutralization-sedimentation has been studied.With the lime cream neutralization to adjust the pH value,the optimum condition obtained was, PAC 10~50mg/100ml wastewater ,PHP-2 0.06~0.09mg/100ml wastewater ,mixing 2 min, stirring velocity 100~300rpm ,and reacting 15min ,stirring velocity 50rpm.
3、 The factors and the regularity effecting the removal rate of COD has been studied, the result indicated that COD removal rate of organic pollutant will increase with the increment of reaction temperature, oxygen pressure , reaction time ,among which temperature and reaction time are main factors effecting the removal rate of organic pollutant. Oxygen pressure has little influence on the oxidation decomposition of the organic pollutant. Under the reaction temperature 400℃,after 1 min, the treated wastewater meet the 3rd grade of Comprehensive Wastewater Discharge Standard,(GB9878-1996 China);10 min ,the removal rate of COD reach up to 99.9%,meet 2nd grade;and, 20 min, the 1st grade.
4、 The kinetics of oxidation degradation of molasses alcohol wastewater were studied .The results indicates when the range of temperature were from 3600C to 4000C,the pressure of oxygen was 6.0MPa,Ea was 275.89kJ/mol ,A was 1.66×1015. The reaction order of organics pollutants was betweem1.0~2.45 and,oxygen was 0.
5、In the process of CSCWO, the catalysts Cu/Ce（3：1）and Cu：Mn：Fe（0.5：2：0.5） has little infullence on the oxidation decomposition of organic pollutants.
对糖蜜酒精废液的特征进行了分析，结果表明：（1）废液的pH值为4.16，为避免酸性物质对反应器的腐蚀，在进行超临界水氧化前需调节废液的pH值并将产生的沉淀沉降除去。（2）糖蜜酒精废液在超临界水氧化过程中，每吨废液可产生1.93×106kJ的热量，产生的热量足够维持反应的自热，如处理后废水排出系统的温度以150℃计，每吨废液约可回收能量 1.42×106kJ ；（3）糖蜜酒精废液在165℃左右开设有部分有机物分解而析出炭，废液的预热不能超过该温度。
1、 对废液的中和－沉降预处理方法进行了研究。用石灰乳将pH值调到8.0，较适宜的絮凝沉降操作参数为：PAC浓度10～50mg/100ml废液，PHP－2浓度0.06～0.09mg/100ml废液，混合搅拌速度为100～300rpm，相应的混合时间为2min，反应搅拌速度50 rpm，相应的反应时间为15min。
2、 对影响超临界水氧化法处理糖蜜酒精废液过程的因素及其影响规律进行了研究，结果表明：在超临界水氧化过程中，增加反应温度、氧压力（氧的浓度）、反应时间，均能增大废液的CODCr去除率。在这些影响因素中，温度、反应时间对有机物氧化的CODCr去除率的影响较大；氧压力（浓度）对CODCr的去除率影响很小，CODCr的去除率随时间的变化，呈现出先快后慢的规律。在400℃下，反应1min，CODCr去除率可达到99.3%，出水达到《污水综合排放标准GB9878—1996》的三级标准；反应10min，CODCr去除率达99.9%以上，出水完全达到GB8978—1996的二级标准，如反应20min，出水可达到GB8978—1996的一级排放标准.
4、对超临界水氧化法处理糖蜜酒精废液的动力学进行初步研究，研究表明：CODCr的反应级数为2.45,氧气的反应级数为0，反应的活化能为275.89kJ/mol，频率因子为 1.66×1015.
5、对催化超临界水氧化法处理糖蜜酒精废液进行了初步探索，结果显示：Cu/Ce（3：1）和Cu：Mn：Fe（0.5：2：0.5）两种固体催化剂，在临界点附件
有较好的催化效果，但在较高的温度下，Cu/Ce（3：1）的催化效果不明显。
The paper systematically summarized current treatmeant technology of molasses
alcohol wastewater, reviewed the properities of supercritical water oxidation(SCWO) and universal research work in the field .The author prosposed applying SCWO to the treatmeant of molasses alcohol wastewater,and studied basic work on the application. The work and the results follow as:
1、 The characteristic of molasses alcohol wastewater was observeed. 1st ,the pH value of the wastewater is about 4.13,as an anti-corrosion method,pH value shoud adjust to about 8.0 and eliminate the flocculation created.2nd,the thermal energy the reaction created was about 1.93×106kJ per ton,in addition to sustain the reaction,the surplurs energy recycled was 1.42×106kJ per ton.3rd ,to avoid formation of carbon ,the temperture of preheated should keep under 165℃ .
2、 The pretreatmeant of neutralization-sedimentation has been studied.With the lime cream neutralization to adjust the pH value,the optimum condition obtained was, PAC 10~50mg/100ml wastewater ,PHP-2 0.06~0.09mg/100ml wastewater ,mixing 2 min, stirring velocity 100~300rpm ,and reacting 15min ,stirring velocity 50rpm.
3、 The factors and the regularity effecting the removal rate of COD has been studied, the result indicated that COD removal rate of organic pollutant will increase with the increment of reaction temperature, oxygen pressure , reaction time ,among which temperature and reaction time are main factors effecting the removal rate of organic pollutant. Oxygen pressure has little influence on the oxidation decomposition of the organic pollutant. Under the reaction temperature 400℃,after 1 min, the treated wastewater meet the 3rd grade of Comprehensive Wastewater Discharge Standard,(GB9878-1996 China);10 min ,the removal rate of COD reach up to 99.9%,meet 2nd grade;and, 20 min, the 1st grade.
4、 The kinetics of oxidation degradation of molasses alcohol wastewater were studied .The results indicates when the range of temperature were from 3600C to 4000C,the pressure of oxygen was 6.0MPa,Ea was 275.89kJ/mol ,A was 1.66×1015. The reaction order of organics pollutants was betweem1.0~2.45 and,oxygen was 0.
5、In the process of CSCWO, the catalysts Cu/Ce（3：1）and Cu：Mn：Fe（0.5：2：0.5） has little infullence on the oxidation decomposition of organic pollutants.
引文
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