超临界水氧化处理煤气化生化污泥

采用超临界水氧化(SCWO)技术处理煤气化生化污泥,优化了处理工艺条件,考察了有机污染物和重金属的去除效果。实验结果表明,处理含水率为90%(w)的污泥的最佳工艺条件为:反应温度580℃、反应压力25MPa、氧化系数(初始反应加入的H_2O_2的摩尔数与理论上废水完全氧化所需的H2O2的摩尔数之比)4.0、反应时间2 min。SCWO处理后的气相产物为O2、CO2和少量N2,清洁环保,可直接排放或回收利用。液相产物中的主要有机污染物和重金属含量均大幅降低,出水达到GB 8978—1996《污水综合排放标准》,可直接排放或回用。固相残渣浸出液中重金属含量均低于GB 5085.3—2007《危险废物鉴别标准浸出毒性鉴别》,可直接进行填埋处理或资源化利用。     

Polyethylene conversion by partial oxidation in supercritical water

This paper gives the results of partial oxidation experiments of polyethylene (PE) in supercritical water (SCW). The experiments were carried out at a reaction temperature of 693K and a reaction time of 30 min using 6 cm³ of a batch-type reactor. The loaded sample weight was 0.3 g and there was 2.52 g water (0.42 g/cm³). The ratio of oxygen atoms to carbon atoms was 0.3. The results show a significant CO formation in O₂–SCW, and the 1-alkene/n-alkane ratio in partial oxidation was higher than that in SCW pyrolysis. These results suggest the possibility of the hydrogenation of hydrocarbon through partial oxidation followed by a water–gas shift reaction. Received: July 19, 2000 / Accepted: September 28, 2000     

超临界水氧化法处理含油污泥

采用间歇式超临界水氧化(SCWO)反应器处理采油过程产生的含油污泥,考察了反应参数对污泥COD去除率的影响。实验结果表明,当初始COD为1 000 mg/L、反应温度为420℃、反应时间为10 min,反应压力为24 MPa、溶液pH为10、过氧比为400%时,SCWO法对含油污泥的COD去除率为92.20%,收集液COD低于GB8978—1996规定的一级排放标准(100 mg/L)。     

Degradation of landfill leachate using transpiring-wall supercritical water oxidation (SCWO) reactor

Oxidation of landfill leachate wastewater was studied in a transpiring-wall SCWO reactor, operated under varied temperature and pressure 320–430 °C, 18–30 MPa. Effect of temperature and pressure on COD and BOD removal efficiency was investigated. COD and BOD removal efficiency being 99.23%, 98.06% were achieved at 430 °C, 30 MPa, which increased with temperature and pressure. The modified pseudo first-order rate model was regressed from experimental data, taking into account the induction time (t_ind) effect. The resulting pre-exponential factor A and activation energy E_a were 34.86 s^?1 and 32.1 kJ mol^?1, respectively, assuming that the reaction order for feed wastewater (based on COD) and oxidant were first order and zero order, respectively.     

铁碳微电解耦合光-Fenton氧化法降解水中的十溴联苯醚

采用铁碳微电解耦合光-Fenton氧化法降解模拟废水中的十溴联苯醚(BDE-209)。探索了铁碳微电解法降解BDE-209的影响因素,考察了铁碳微电解耦合光-Fenton氧化法对BDE-209的降解效果。实验结果表明:在模拟废水BDE-209质量浓度为1 mg/L、初始废水p H为2.0、铁碳质量比为1∶1、铁粉投加量为12 g/L、微电解温度为40 oC、微电解时间为60 min的条件下,铁碳微电解法的BDE-209降解率达到82.5%;当H2O2溶液投加量为4 m L/L时,铁碳微电解耦合光-Fenton氧化法的BDE-209降解率达到95.7%。说明添加H2O2的Fenton体系对BDE-209的降解有明显促进作用。     

Augmenting in-situ remediation by soil vapor extraction with six-phase soil heating

The use and performance of soil vapor extraction (SVE) as an in-situ remedial technology has been limited at numerous sites because of both geologic and chemical factors. SVE systems are not well suited to sites containing low permeability soils or sites contaminated with recalcitrant compounds. Six-phase soil heating (SPSH) has been developed by the Battelle Pacific Northwest Laboratories (Battelle) to enhance SVE systems. The technology utilizes resistive soil heating to increase the vapor pressure of subsurface contaminants and to generate an in-situ source of steam. The steam strips contaminants sorbed onto soil surfaces and acts as a carrier gas, providing an enhanced mechanism by which the contaminants can reach an extraction well. Full-scale applications of SPSH have been performed at the U.S. Department of Energy's Savannah River Site in Aiken, South Carolina; at a former fire training site in Niagara Falls, New York; and at Fort Richardson near Anchorage, Alaska. At each site, chlorinated solvents were present in low permeability soils and SPSH was applied in conjunction with SVE. The results of the three applications showed that SPSH is a cost-effective technology that can reduce the time required to remediate a site using only conventional SVE.     

Environmental assessment of supercritical water oxidation and other sewage sludge handling options.

Sustainable development relies on the eco-efficient use of all flows in society; more value created out of each resource unit. Supercritical water oxidation (SCWO) can be used for treatment of wet organic waste. The technology has been under development for over 20 years but has not yet been fully commercialized. SCWO allows for complete oxidation of all organics in sewage sludge and almost complete recovery of the inherent energy, essentially without harmful emissions. In this paper, a life-cycle assessment (LCA) of sewage sludge SCWO (Aqua-Critox) is presented and the results are compared with LCA results for other sludge handling options: agricultural use, co-incineration with municipal solid waste, incineration with subsequent phosphorus extraction (Bio-Con) and sludge fractionation with phosphorus recovery (Cambi-KREPRO). For SCWO, beneficial utilization of the heat of reaction is of crucial importance for the outcome. The electricity consumed by pumping and the nitrous oxide produced are other important parameters. The best sludge handling option from an environmental point of view depends on what aspect is considered more important in the impact assessment. Regarding global warming, the energy recovery methods perform better than agricultural use.     

Technical feasibility and conceptual design for using supercritical fluid to extract pesticides from aged soil

The demand for processes to clean up contaminated soils without introducing additional contaminants is increasing. One approach to solving this problem is the use of supercritical fluids like carbon dioxide, alone or with cosolvents, to extract contaminants from the soil. Carbon dioxide is readily available, inexpensive, and nonpolluting. Gases exhibit unique properties under supercritical conditions. They retain the ability to diffuse through the interstitial spaces of solid materials, plus they have the solvating power of liquids. Soil cleanup using supercritical fluid extraction (SFE) is being investigated as an alternative/complementary technology to other cleanup methods such as incineration and bioremediation. The objective of the studies included in this article was to collect and analyze data to support use of the SFE technology and to provide the conceptual design and operational processes needed for building a portable treatment unit.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.     

微纳米气泡耦合过渡金属离子催化氧化吸收甲醛

利用过渡金属离子Fe^2+和Mn^2+作为催化剂,耦合微纳米气泡催化氧化吸收HCHO,研究了各种反应参数变化对吸收效果的影响,并借助GC-MS技术探究了微纳米气泡氧化吸收HCHO的机理。实验结果表明:HCHO吸收率随着吸收液pH、NaCl浓度、SDS浓度及过渡金属离子浓度的增加均呈现出先升高后降低的变化规律,低浓度的NaCl有助于HCHO的吸收;在进气HCHO质量浓度0.4 mg/m^3、循环9次的设定工况下,最佳工艺条件为吸收液pH 4、NaCl质量浓度0.1 g/L、SDS质量浓度7 mg/L、Fe^2+/Mn^2+浓度2.0 mmol/L;在此条件下,Fe^2+和Mn^2+催化体系的HCHO吸收率分别达82.6%和90.4%。GC-MS分析结果显示,微纳米气泡氧化吸收HCHO的主要有机产物为乙二醇。     

臭氧氧化处理化工污水厂尾水

采用臭氧氧化工艺处理某化工污水厂尾水,考察了臭氧投加量对废水处理效果的影响,并进行了反应动力学研究。实验结果表明,最佳臭氧投加量为67 mg/L,在此条件下,处理后废水的COD去除率为19%,色度去除率为90%,UV254去除率为79%,BOD5/COD为0.11。反应动力学分析结果表明:臭氧氧化去除废水COD的反应适合采用二级反应动力学进行拟合,二级反应动力学方程为y=0.000 1x+0.000 3,相关系数为0.938 5;臭氧氧化去除废水色度的反应更适合采用一级反应动力学进行拟合,一级反应动力学方程为y=0.105 0x-0.018 4,相关系数为0.990 3。     

全自动消解-电感耦合等离子体质谱法测定土壤中16种元素

采用HNO_3-HF-HClO_4消解体系,建立了全自动消解-电感耦合等离子体质谱仪测定土壤中~(75)As、~9Be、~(51)V、~(55)Mn、~(59)Co、~(60)Ni、~(63)Cu、~(66)Zn、~(98)Mo、~(111)Cd、~(138)Ba、~(205)Tl、~(208)Pb、~(107)Ag、~(52)Cr、~(121)Sb等16种元素的新方法。通过碰撞池技术和编辑干扰元素校正方程有效校正了质谱干扰,并用内标校正了土壤基体干扰。用土壤标准物质GSS-13验证该方法,其校准曲线相关系数大于0.999 9,方法检出限在0.005~0.5μg/g之间,RSD为0.22%~2.35%,加标回收率为92%~114%。采用该方法测定实际土壤样品,加标回收率为93%~123%。     

Destruction of Aspergillus versicolor,Penicillium chrysogenum,Stachybotrys chartarum,and Cladosporium cladosporioides spores using chemical oxidation treatment process

The survival of aqueous suspensions of Penicillium chrysogenum, Stachybotrys chartarum, Aspergillus versicolor, and Cladosporium cladosporioides spores was evaluated using various combinations of hydrogen peroxide and Fe²⁺ as catalyst. Spore concentrations of 10⁶–10⁷ colony forming units per milliliter (CFU/mL) were suspended in water and treated with initial hydrogen peroxide and iron concentrations ranging from 0.05 to 10 percent and 100 to 200 ppm, respectively. After four hours of reaction time, samples were plated on agar plates, and the viable fraction of spores was determined by the number of colonies formed. Hydrogen peroxide concentrations above 50,000 ppm resulted in greater than 6‐log₁₀ reduction of viable spores for both catalyzed and noncatalyzed reactions. Iron had a strong catalytic effect when added to solutions with hydrogen peroxide concentration above 5,000 ppm and resulted in two to three orders of magnitude greater reduction compared to hydrogen peroxide alone. Additional samples taken after 24 hours of reaction time showed that the effect of the addition of 100 and 200 ppm of Fe²⁺ catalyst was mostly kinetic, and noncatalyzed hydrogen peroxide had sporicidal effects similar to catalyzed hydrogen peroxide. This study identified initial reagent concentrations of hydrogen peroxide and Fe²⁺ that accomplish a 6‐log₁₀ reduction of viable mold spores within reaction times of 4 and 24 hours. © 2007 Wiley Periodicals, Inc.     

超超临界锅炉高温管道内壁氧化皮的研究进展

分析了国内外超超临界锅炉高温管内氧化皮的研究现状,对高温受热面管内氧化皮的分析方法进行了归类,指出了目前的研究存在的不足之处。对目前的试验研究给予了建议,为进一步对高温管道的抗氧化性研究提供了发展方向,同时对提高机组的安全稳定运行具有重要的意义。     

紫外光谱结合正交试验设计同时测定水中苯系物

利用正交试验设计,以光谱预处理、特征筛选及多元校正方法为考察因素,每个因素的4种不同方法为水平,确定了水中3种苯系物（苯酚、苯胺及苯甲酸）紫外光谱数据的最佳分析方法,从而建立了其定量校正模型。对于苯酚、苯胺及苯甲酸,其光谱预处理、特征筛选及多元校正分别采用一阶导数+无信息变量消除法（UVE）+偏最小二乘回归（PLSR）,Savitzky-Golay平滑+变量结合种群分析法（VCPA）+PLSR,Savitzky-Golay平滑+移动窗口偏最小二乘法（MWPLS）+PLSR。在独立测试集上3组分的预测误差均方根（RMSEP）分别为0.809 4、0.796 3和0.945 4。水样加标回收实验的回收率为97.79%~103.84%,相对标准偏差（RSD）小于3%。该方法可作为一种同时测定水中苯系物的简便有效方法。     

超声吹脱-次氯酸钠氧化工艺处理酮连氮法制肼废水

采用超声吹脱-次氯酸钠氧化工艺处理酮连氮法制肼废水,优化了工艺条件,并进行了尾水处理与盐分回收。实验结果表明:在超声声能密度0.08 W/mL、吹脱气量2 000 L/h、次氯酸钠溶液(有效氯10%)投加量15mL/L、反应时间20 min的最优条件下,COD、氨氮和肼类物质去除率分别达到96.97%、99.02%和96.60%,处理成本约为30元/t(以废水计);尾水经蒸馏处理后可满足GB 8978—1996《污水综合排放标准》的一级B标准,回收NaCl纯度为98.92%,达到GB/T 5462—2015《工业盐》的精制工业盐一级标准。     

吡咯烷酮类离子液体萃取脱除模拟汽油中的噻吩

合成了3种N-甲基吡咯烷酮离子液体([HNMP]FeCl4,[HNMP]CuCl2,[HNMP]ZnCl3),并将其用于模拟汽油(噻吩溶于正辛烷,硫含量1381μg/g)中噻吩的萃取脱除。考察了[HNMP]FeCl4的深度脱硫和重复使用性能。实验结果表明:30℃下3种离子液体脱硫能力的强弱顺序为[HNMP]FeCl4[HNMP]CuCl2[HNMP]ZnCl3;在[HNMP]FeCl4与模拟汽油的体积比为1∶1、FeCl3与[HNMP]Cl的摩尔比为1、萃取时间为60min的优化条件下,单程脱硫率为70.7%,经4级萃取后模拟汽油中的硫含量降至61μg/g、总脱硫率为95.6%;利用真空加热法对[HNMP]FeCl4进行再生,[HNMP]FeCl4使用5次后脱硫率从70.7%降至59.5%,仍保持较好的脱硫性能。     

硫酸铵-锌试剂-Tween-80萃取分离废镍镉电池金属

以废旧镍镉电池为原料,探索盐酸溶解废镍镉电池的溶解条件,并用ICP仪检测镍镉电池溶液中金属离子含量.研究了硫酸铵-锌试剂-Tween-80体系萃取分离金属离子Ni(Ⅱ),Cd(Ⅱ),Co(Ⅱ)的行为.实验表明:Ni(Ⅱ),Co(Ⅱ)在pH 6～9范围内,与锌试剂形成的螯合物可被Tween-80相完全萃取,而Cd(Ⅱ)基本不被萃取.进而实现了镍镉电池溶液中的Ni(Ⅱ),Co(Ⅱ)离子与Cd(Ⅱ)离子的分离.     

臭氧氧化结合碱液吸收法烟气脱硝的工艺研究

利用臭氧将烟气中溶解度较小的NO氧化成NO2,再结合尿素、氢氧化钠、氢氧化钙溶液吸收脱除臭氧氧化产物,重点考察了O3与NO反应的摩尔比、进口NO浓度、烟气中SO2浓度和相对湿度等工艺参数对NO氧化的影响,并探明不同的吸收液脱除臭氧氧化产物的特性。结果显示O3与NO反应的最佳摩尔比为1.02,随着进口NO浓度的增加氧化效率下降,而烟气中的SO2和相对湿度对NO氧化影响较小。通过对氢氧化钙吸收臭氧氧化产物的特性分析得出,碱液对NO的吸收率相对较小,而对NO2的吸收率达到80%以上。     

表面活性剂与柠檬酸联合洗涤高黏性土壤中的重金属

以一水合柠檬酸（CA）为洗涤剂,分别采用吐温80（TW80）、十二烷基磺酸钠（SDS）、β-环糊精（BCD）和腐植酸（HA）4种表面活性剂与CA联合洗涤高黏性土壤中的重金属,考察表面活性剂与CA的联合洗脱效果。实验结果表明：添加4种表面活性剂均可提高CA对Cu、Zn和Pb的去除率;处理时无需调节体系pH;在表面活性剂与CA的混合液与土壤的液固比为10:1（mL/g）的条件下,采用一次洗涤即可。经4种表面活性剂与CA联合洗涤后,土壤中Cu、Zn和Pb的离子交换态、碳酸盐结合态和铁锰氧化结合态的占比均下降,而硫化物及有机结合态和残渣态的占比有所提升。