Toward cleaner production of hydrogen peroxide in China

Industrial production of hydrogen peroxide by anthraquinone (AO) process in China was briefly introduced. The pathways for cleaner production of hydrogen peroxide were discussed in detail from the viewpoint of process development and design, these included the replacement of Raney-Ni catalyst by highly active and highly selective Pd/Al₂O₃ catalyst, the reduction of raw materials, steam and power consumption, the usage of high boiling point, low water-soluble and low toxic solvents, the regeneration of degradations, the proper treatment of waste gas, water and solids. Because of these innovations and improvements, the AO process with Pd/Al₂O₃ catalyst for producing hydrogen peroxide was certified as a cleaner production technology by the Chinese government.     

金属化合物对发光菌的毒性效应及不同发光菌的敏感度差异研究

利用发光菌毒性测试技术,研究了5种重金属化合物HgCl2、Pb(NO3)2、Cd(NO3)2、K2Cr2O7、NaAsO2对3种常见发光菌种——青海弧菌Q67、明亮发光杆菌502、费氏弧菌的毒性效应差异.同时,对发光抑制率和金属化合物浓度进行线性回归分析后计算了EC50值(半数效应浓度值),并对比了不同菌种对各金属化合物的敏感度差异及特点.结果表明,5种重金属对青海弧菌Q67的毒性大小顺序为HgCl2Cd(NO3)2NaAsO2Pb(NO3)2K2 Cr2 O7;对明亮发光杆菌502的毒性大小顺序为:HgCl2NaAsO2Pb(NO3)2Cd(NO3)2K2 Cr2 O7;对费氏弧菌的毒性大小顺序为:HgCl2Pb(NO3)2Cd(NO3)2NaAsO2K2Cr2O7.研究结果对利用发光菌毒性测试技术测定不同废水污染时菌种的选择具有指导作用,在未知污染物的情况下应选用几种菌种同时检测,这样可以保证检测结果的可靠性.     

Photodegradation of amoxicillin by catalyzed Fe3+/H2O2 process

Three oxidation processes of UV-Fe³⁺(EDTA)/H₂O₂ (UV: ultraviolet light; EDTA: ethylenediaminetetraacetic acid), UV-Fe³⁺/H₂O₂ and Fe³⁺/H₂O₂ were simultaneously investigated for the degradation of amoxicillin at pH 7.0. The results indicated that, 100% amoxicillin degradation and 81.9% chemical oxygen demand (COD_Cr) removal could be achieved in the UV-Fe³⁺ (EDTA)/H₂O₂ process. The treatment efficiency of amoxicillin and COD_Cr removal were found to decrease to 59.0% and 43.0% in the UV-Fe³⁺/H₂O₂ process; 39.6% and 31.3% in the Fe³⁺/H₂O₂ process. Moreover, the results of biodegradability (biological oxygen demand (BOD₅)/COD_Cr ratio) revealed that the UV-Fe³⁺ (EDTA)/H₂O₂ process was a promising strategy to degrade amoxicillin as the biodegradability of the effluent was improved to 0.45, compared with the cases of UV-Fe³⁺/H₂O₂ (0.25) and Fe³⁺/H₂O₂ (0.10) processes. Therefore, it could be deduced that EDTA and UV light performed synergetic catalytic effect on the Fe³⁺/H₂O₂ process, enhancing the treatment efficiency. The degradation mechanisms were also investigated via UV-Vis spectra, and high performance liquid chromatography-mass spectra. The degradation pathway of amoxicillin was further proposed.     

Basic properties of sintering dust from iron and steel plant and potassium recovery

With the production of crude steel, China produces several million tons of sintering dusts which contain a great deal of valuable metals such as, K, Na, Zn, Pb. If discharged directly without adequate treatment, these elements can lead to adverse effects on the environment. Therefore, it is very necessary to determine how to separate these elements from the dust before discharge. Several physical and chemical detection methods were used to study the basic properties of sintering dust. At the same time, preliminary experiments on the recovery of the potassium resources from the sintering dust were carried out. The mean particle size of the electrostatic precipitator (ESP) dust determined by a laser granulometer was 41.468 μm. Multi-point BET and single-point BET analysis showed that the surface area of the ESP dust was 2.697 m²/g. XRD measurements detected the following phases in the ESP dust: Fe₂O₃, Fe₃O₄, KCl and NaCl, and Fe₂O₃, Fe₃O₄ and SiO₂ in the water-washed dust. SEM-EDS results proved that in the ESP dust, K mostly existed in the form of KCl particles without being coated. Leaching experiments showed that the KCl in the ESP dust could be separated and recovered by water leaching and fractional crystallization. Through the recovery experiments, the yield of K-Na vaporized crystalline salt was 18.56%, in which the mass fractions of KCl, NaCl, CaSO₄ and K₂SO₄ were about 61.03%, 13.58%, 14.03% and 9.97%, respectively. This process is technically viable and considerable in economic benefit. There was almost no secondary pollution produced in the whole recovery process.     

电-Fenton法降解低含盐量反渗透浓缩液中腐植酸

为研究采用碳毡-Pt电-Fenton体系处理模拟低含盐量反渗透浓缩液中的腐植酸的影响因素和降解机制,通过单因素试验,以COD_Cr去除率为评价指标,以Fe2+添加量、通氧量、电流密度、pH为考察因素,探讨了不同条件对电-Fenton体系ρ（H₂O₂）和COD_Cr去除率的影响.结果表明:采用电-Fenton法降解模拟反渗透浓缩液,较低的含盐量有助于COD_Cr的去除,与高含盐量（1 000~2 000 mg/L）相比,在低含盐量（500~1 000 mg/L）条件下COD_Cr去除率提高10%~20%;并且最佳条件下实际电流效率（GCE）达到15.6%,电化学能耗为32 kW·h/kg.最佳反应条件:通氧量为0.3 m3/L,Fe2+添加量为0.1 mmol/L,电流密度为3.5 mA/cm2,pH=3,在该条件下反应180 min时,电-Fenton体系产生的ρ（H₂O₂）为105 mg/L,可使ρ（COD_Cr）由150 mg/L降至16 mg/L,COD_Cr去除率达到90%.研究显示,较宽的pH范围（3~7）内碳毡-Pt电-Fenton体系对腐植酸的降解表现稳定,COD_Cr去除率均达到60%以上.      

含金属元素化合物和压力对工业污泥燃烧特性的影响

为了更好地利用工业污泥,有必要对它的燃烧特性进行研究,因而利用热重法研究了由3种典型的工业污泥按质量比1∶1∶1混合后的多组分试样在掺混含不同金属元素混合物、不同升温速率以及加压下的燃烧特性.实验结果表明,含金属元素化合物对污泥的燃烧能起到一定的催化作用,有助于改善工业污泥的着火性能,提高工业污泥的燃烧放热量和燃尽水平.含不同金属元素化合物对于污泥燃烧的催化机制和作用有所差异.实验中各种含金属元素化合物促进污泥燃烧过程的作用次序由大到小依次为:K2CO3、NaCl、Al2O3.随着压力的增大,污泥试样燃烧反应区间向低温区移动,各特征温度均呈下降趋势,综合燃烧特性指数有所提高;而随着升温速率的增大,污泥试样燃烧反应区间向高温区移动,各特征温度均有所增大,但综合燃烧特性愈好,对污泥燃烧越有利.     

过硫酸钾氧化去除Cu (CN)32-中的氰污染物

近年来,氰化物污染问题日益严重,冶金工业、电镀工业中含有大量氰化物.采用常规的物化法难以对Cu(CN)_3~(2-)中的CN~-达到很好的去除效果,因此探索高效、环保的氰化物处理方法迫在眉睫.过硫酸钾作为一种绿色清洁氧化剂,目前被广泛应用于有机污染物废水的处理.采用均相过硫酸钾对Cu(CN)_3~(2-)中CN~-进行降解,并分析其降解机制,详细研究过硫酸钾投加量、铜氰络合比对CN~-去除率的影响.CN~-的去除率随着过硫酸钾量的增加而升高,当过硫酸钾量为2 mmol·L~(-1),反应时间为60 min时,CN~-的去除率可达89.6%;铜氰络合比的增加促进CN~-的降解.Cu~+被氧化为Cu~(2+)并且以氧化铜的形式存在于沉淀中.采用电子自旋共振波谱仪和自由基猝灭实验对反应过程中可能的自由基进行研究,结果表明在过硫酸钾氧化去除CN~-的过程中,既存在硫酸根自由基氧化途径,又存在非自由基氧化途径.     

Effect of chromium oxide as active site over TiO2-PILC for selective catalytic oxidation of NO

This study introduced TiO2-pillared clays （TiO2-PILC） as a support for the catalytic oxidation of NO and analyzed the performance of chromium oxides as the active site of the oxidation process. Cr-based catalysts were prepared by a wet impregnation method. It was found that the 10 wt.% chromium doping on the support achieved the best catalytic activity. At 350℃, the NO conversion was 61% under conditions of GHSV = 23600 hr^-l. The BET data showed that the support particles had a mesoporous structure. Hz-TPR showed that Cr（10）TiP （10 wt.% Cr doping on TiO2-PILC） clearly exhibited a smooth single peak. EPR and XPS were used to elucidate the oxidation process. During the NO ＋ O2 adsorption, the intensity of evolution of superoxide ions （O2^-） increased. The content of Cr^3＋ on the surface of the used catalyst was 40.37%, but when the used catalyst continued adsorbing NO, the Cr^3＋ increased to 50.28%. Additionally, Oα/Oβ increased markedly through the oxidation process. The NO conversion decreased when SO2 was added into the system, but when the SO2 was removed, the catalytic activity recovered almost up to the initial level. FT-IR spectra did not show a distinct characteristic peak of SO4^2-.     

Simultaneous recovery of chromium and destruction of organics from LCD manufacturing process wastewater by supercritical water oxidation

The effectiveness of supercritical water oxidation (SCWO) process for the simultaneous recovery of chromium and destruction of organics from liquid crystal display (LCD) manufacturing process wastewater was investigated. The experiments were performed in an isothermal continuous-flow tubular reactor and H₂O₂ was used as an oxidant. The reaction temperatures ranged from 400 to 605 °C and the residence times ranged from 15 to 31 s at a fixed pressure of 25 MPa. The effect of temperature, oxidant concentration and residence time on chromium recovery and chemical oxygen demand (COD) conversion was investigated. The results of this study demonstrated that the SCWO process recovered chromium and decreased chemical oxygen demand up to 99.3% and 99.9%, respectively. The analyses showed that chromium are recovered as chromium oxide (α-HCrO₂ and Cr₂O₃). The SCWO process is an effective technique for simultaneously recovering chromium and for the destruction of hazardous organics in the LCD manufacturing process wastewater. Our study showed that there are two consequent reactions, chromium recovery reaction (hydrolysis) followed by the organic decomposition reaction (oxidation). The recovery of chromium can be achieved without major organic decomposition.     

超声、过硫酸钾协同去除水中诺氟沙星的效果

过硫酸钾活化可产生强氧化性硫酸根自由基(SO-4·),采用超声/过硫酸钾体系氧化降解诺氟沙星,考察了过硫酸钾浓度、诺氟沙星初始浓度、溶液初始p H值及自由基淬灭剂甲醇、叔丁醇对降解效果的影响.结果表明,超声/过硫酸钾体系能够显著降解和矿化诺氟沙星,与单独过硫酸钾、超声相比,超声/过硫酸钾对诺氟沙星的去除率分别提高了3.2和8.9倍,降解过程符合一级反应动力学.诺氟沙星的去除率随过硫酸钾浓度的增加趋于平缓.p H对诺氟沙星的降解影响较大,这是因为随p H的升高,体系中的氧化性物种由SO-4·转化为以SO-4·/HO·为主.TOC去除和大肠杆菌抗菌实验表明,反应180 min,超声/过硫酸钾能够实现49.12%的诺氟沙星矿化,且对大肠杆菌的抑菌圈直径由45 mm减小到14 mm(滤纸直径),完全去除其抗菌性.结果表明超声/过硫酸钾能够有效用于诺氟沙星废水处理.     

化学氧化法处理资源回收后的J-酸和吐氏酸染料中间体废液

萘系磺酸染料中间体Ｊ－酸和吐氏酸废母液经有用资源的回收后,尚须进行最终出水的达标处理．通过吐氏酸和Ｊ－酸废母液萃余液的后处理试验,确定了盐回收－混凝沉淀－化学氧化的达标处理工艺方案,并确定了相应的工艺参数．其中化学氧化采用Ｆｅｎｔｏｎ试剂（以双氧水作氧化剂,绿矾为催化剂）,在经济合理的投量范围内经２—４ｈ反应,萃余液ＣＯＤＣｒ去除率达８０％以上,最终出水ＣＯＤｃｒ在２００ｍｇ／Ｌ以下,满足有关工业废水排放标准．     

双功能介孔吸附材料的制备及其同时吸附废水中Cd2+和Cr2O72-的研究

采用直接法和后嫁接法成功制备出骨架掺杂Al原子,孔道表面接枝大位阻含胺基基团的双功能介孔硅基吸附材料.采用SAXRD、TEM、FTIR、NH3-TPD等手段对合成材料进行表征,结果表明合成的双功能AN-SBA-15具有有序的二维六方介孔结构,孔道表面的Al-OH与胺基不会发生自发复合反应.对模拟废水中Cd~(2+)和Cr_2O_7~(2-)的同时吸附去除实验研究表明AN-SBA-15具备同时吸附废水中Cd~(2+)和Cr_2O_7~(2-)离子的能力,吸附最佳pH值为5.0,吸附在40 min就达到平衡.AN-SBA-15对Cd~(2+)和Cr_2O_7~(2-)离子的吸附符合Langmuir模型,属于单层吸附.由Langmuir模型拟合出的AN-SBA-15对Cd~(2+)和Cr_2O_7~(2-)离子的最大吸附容量分别为125.9 mg·g~(-1)和156.5 mg·g~(-1).此外AN-SBA-15具备良好的脱附再生能力.     

A clean production process of sodium chlorite from sodium chlorate

This paper presents a novel cleaner production process for producing sodium chlorite by reducing sodium chlorate with hydrogen peroxide. In the new process, chlorine dioxide is generated by reducing chlorate ions with hydrogen peroxide in the presence of sulfuric acid: it then reacts with aqueous sodium hydroxide solution and hydrogen peroxide to produce sodium chlorite. The reaction conditions that were experimentally investigated included: reaction temperatures, concentrations of sodium chlorate solution, molar ratio of NaClO₃:H₂SO₄:H₂O₂, and acidity. Waste acid in the chlorine dioxide generator is dramatically reduced with recycling in the new process. The by-produced sodium sulfate in sulfuric acid is minimized and reclaimed.     

Economic use of renewable resources,LCA, cleaner batch processes and minimising emissions and wastewater

This editorial introduces and provides an overview of this Special Issue dedicated to papers from the 7th conference Process Integration, Modelling and Optimisation for Energy Saving and Pollution Reduction – PRES 2004. It contains 10 selected papers. The first three papers address important features of cleaner production – renewable resources, CO₂ emissions and Life Cycle Assessment. The second group of papers addresses cleaner production approaches to batch processed. The third set of papers studies reduction of emissions from industrial production including SO_x and NO_x. The last paper focuses upon minimisation of wastewater from industrial production.     

响应面法优化Fenton预处理精细化工废水

甘肃省某精细化工企业实际生产废水成分复杂、有机物含量高、可生化性差,为满足后续生化工艺需求,急需开展适宜的预处理技术研究.采用Fenton氧化工艺对该企业废水进行预处理,在单因素试验基础上,以初始pH、H₂O₂投加量、n（H₂O₂）:n（Fe2+）、反应时间为考察因素,COD_Cr去除效果为响应值,构建响应曲面模型,分析4个独立因素及各因素之间的交互作用对COD_Cr去除效果的影响;同时,对反应过程进行表观反应动力学分析,采用紫外光谱及傅立叶变换红外光谱分析废水有机物结构变化,探究该反应过程机理.结果表明:①废水预处理的最佳工艺条件为初始pH 4、H₂O₂投加量8 mL/L、n（H₂O₂）:n（Fe2+）12、反应时间88 min,废水COD_Cr去除率达30.15%;模型的实际运行结果与预测值接近,模型可靠.②Fenton氧化降解该精细化工废水中有机物途径复杂,难以通过单一的底物模型进行拟合.③Fenton氧化能有效降解废水中不饱和有机物,但出水中仍含有酰胺类、不饱和醛类和芳香类化合物.研究显示,Fenton预处理能有效降解废水中难降解有机物,但出水仍未达到后续生化处理要求,还需进一步优化或与其他预处理工艺组合.      

水中腐殖酸对高级氧化联用技术去除内分泌干扰物（DMP）的影响

使用腐殖酸模拟本底天然有机物进行试验,采用UV-H₂O₂、O₃、UV-O₃3种高级氧化工艺,研究了水中腐殖酸对3种高级氧化联用技术去除饮用水中内分泌干扰物(DMP)的影响.结果表明,UV-H₂O₂联用工艺氧化DMP的过程符合伪一级反应动力学,水中腐殖酸的存在对UV-H₂O₂联用工艺氧化DMP的影响非常大,伪一级反应的速率常数与本底TOC值的关系式为K=0.162 0[TOC]₀^{-0.817 1};同时水中腐殖酸对UV-O₃联用工艺氧化DMP的效果影响比较大,而总体上腐殖酸对O₃氧化DMP的去除影响不大.从效果分析知,在一定浓度腐殖酸本底条件下单独O₃氧化和UV-O₃联用工艺对DMP的氧化均以O₃分子对DMP的氧化起主导作用,当腐殖酸浓度变小,UV-O₃联用工艺体系中.OH自由基氧化DMP的重要性增大.水中腐殖酸对3种高级氧化工艺的影响程度顺序依次为:UV-H₂O₂>UV-O₃>O₃.     

Newly developed Fe3O4–Cr2O3 magnetic nanocomposite for photocatalytic decomposition of 4-chlorophenol in water

Chlorophenols, typically 4-chlorophenols are highly toxic and non-biodegradable organic contaminants which pose serious threat to the environment, particularly when released into aqueous medium. The removal of these pollutants by efficient method has received worldwide concern in recent past. A new Fe_3O_4–Cr_2O_3 magnetic nanocomposite was synthesized by wet chemical method under ultrasonic irradiation. Microstructure and morphology of the nanocomposite were characterized by powder X-ray diffraction(XRD),Fourier transform infrared(FT-IR), and a transmission electron microscope(TEM). Magnetic and optical properties were studied by a vibrating sample magnetometer(VSM) and an ultraviolet–visible(UV–Vis) spectrophotometer respectively. The magnetic nanocomposite(MNC) was used as photocatalyst for effective decomposition of 4-chlorophenol in water under ultraviolet(UV) irradiation.     

典型城市臭氧污染源贡献及控制策略费效评估

东莞是珠三角O_3污染最严重的城市,使用RSM/CMAQ(曲面响应模型)法分析了珠三角区域人为排放的NO_x和VOCs对东莞市O_3浓度变化源贡献.2014基准年分析结果表明,扣除模型域外区域传输及天然源排放对O_3本底浓度贡献(41.00%)后,东莞本地VOCs排放对O_3贡献最大(18.50%),珠三角区域NO_x减排率13%时可持续降低东莞市O_3浓度.进一步使用ABa CAS-SE(空气污染控制成本效益与达标评估系统)对2017、2020、2025东莞市3个未来年O_3污染控制情景进行了费效评估.评估结果显示,NO_x和VOCs控制比例相对较低的2017年控制情景人体健康效益/区域控制成本比约为1.1;而控制比例相对较高的2025年东莞O_3达标情景效益成本比仅为0.1.这说明,在高减排率情景下,以末端治理为主的控制措施经济可行性较差,需综合采取产业/能源结构调整、清洁生产等措施实现NO_x和VOCs的大比例减排,实现东莞O_3的稳定达标.今后将进一步研究NO_x和VOCs减排对PM_(2.5)环境浓度及健康效益影响,开展多目标污染物协同控制费效评估.     

外源亚精胺缓解荇菜(Nymphoides peltatum)Cr6+毒害的生理研究

研究了不同浓度的Cr^6 胁迫下，荇菜叶中叶绿素含量、可溶性蛋白含量、O2^-产生速率、保护酶——超氧化物歧化酶(SOD)、过氧化物酶(POD)、过氧化氢酶(CAT)活性的动态变化及外施亚精胺后对上述各指标的影响．结果表明：(1)单一Cr^6 处理下，叶绿素和可溶性蛋白含量在Cr^6 浓度为1mg／L时达到最大值，而后迅速下降；外施亚精胺(Spd)可显著提高二者的含量，延缓它们的下降速度．(2)单一Cr^6 处理下，SOD、POD、CAT活性分别在2、4、2mg／L Cr^6 处理下达到最大值．而后下降；外施亚精胺可提高这三种保护酶的活性，使其上升或稳定时期变长，从而降低O2^-等活性氧的产生速率．由此可见外源亚精胺可缓解Cr^6 对荇菜的胁迫效应．     

N2O decomposition over K/Na-promoted Mg/Zn-Ce-cobalt mixed oxides catalysts

Three groups of cobalt mixed oxide catalysts（Mg/Zn-Co, Mg/Zn-Ce-C, K/Na-Mg/Zn-Ce-Co）were prepared by sol-gel or impregnation methods. The synergistic effects of transition metal, rare earth metal and alkali metal on cobalt mixed catalysts for nitrous oxide（N2O）decomposing to N2 and O2were investigated. The experimental results revealed that the catalytic activity for N2 O decomposition was promoted as Co2＋was replaced partially by Zn2＋/Mg2＋, moreover, the characterization analysis by XRD and XPS showed that Zn2＋/Mg2＋replaced Co2＋successfully into the spinel structure of Co3O4 and promoted significantly the catalytic activity. Especially, the addition of CeO2 and K2O/Na2O decreased the binding energy and resulted in an increase in the density of the electron cloud around Co and an improvement of the catalytic activity. Of the investigated cobalt mixed catalysts, the best catalytic activity was shown by 2% K-Zn0.5-Ce0.05-Co catalyst.