糠醇生产中铜铬废触媒资源化研究

对已有的糠醇生产中产生的废渣回收工艺进行了改进。将糠醛液相加氢生产糠醇产生的废渣于130℃真空蒸馏回收废渣中的有机混合物，经过精馏获得糠醇与糠醛；剩余的固体废触媒与纯碱混合，经反射炉焙烧、水浸取、掺加石灰除硅、过滤得到铬酸钠水溶液；剩下的粗氧化铜经碱溶除铬、溶于硝酸得到硝酸铜溶液；将铬酸钠溶液、硝酸铜溶液按一定比例混合，加氨水搅拌，分离出的沉淀经传统方法焙烧活化、造粒制得新催化剂，回用于糠醛液相加氢生产糠醇。有机物、铬组分和铜组分的回收率均在90％以上。     

糠醇生产中铜铬废触媒资源化研究

对已有的糠醇生产中产生的废渣回收工艺进行了改进。将糠醛液相加氢生产糠醇产生的废渣于 130℃真空蒸馏回收废渣中的有机混合物 ,经过精馏获得糠醇与糠醛 ;剩余的固体废触媒与纯碱混合 ,经反射炉焙烧、水浸取、掺加石灰除硅、过滤得到铬酸钠水溶液 ;剩下的粗氧化铜经碱溶除铬、溶于硝酸得到硝酸铜溶液 ;将铬酸钠溶液、硝酸铜溶液按一定比例混合 ,加氨水搅拌 ,分离出的沉淀经传统方法焙烧活化、造粒制得新催化剂 ,回用于糠醛液相加氢生产糠醇。有机物、铬组分和铜组分的回收率均在 90 %以上     

糠醛加氢废催化剂的回收再利用

以糠醛液相加氢生产糠醇所用的废铜铬氧化物催化剂为原料，通过与纯碱氧化——钠化焙烧、浸取分离铜铬离子，分别制得铬酸钠和硝酸铜，并以此为原料进一步制得新催化剂，回用于糠醛液相加氢制糠醇。Cr(Ⅲ)与Cu(Ⅱ)的转化率均在90％以上，制得的新催化剂回收率大于85％，使用效果好。研究了铬转化率与焙烧温度、时间、返渣量等条件的关系。     

钢铁厂冷轧废水污泥中铬回收实验研究

钢铁厂冷轧废水污泥中含有10%以上的铬、20%以上的铁和1.5%以上的锌(均以质量分数计).为了从污泥中回收铬,首先研究了污泥中铬的形态,确定为Cr(Ⅲ);然后以碳酸钠为氧化助剂,将污泥与碳酸钠按一定比例混合后焙烧,再用水浸取.研究了碳酸钠的添加量、焙烧温度和时间、浸取时间和浸取方式对铬回收率的影响.研究表明,每克干污泥中添加0.6 g或以上碳酸钠,在固定床上700 ℃焙烧4 h以上,可实现60%以上的总铬浸出率,残渣为Fe2O3基脱硫剂原料.     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

铬渣的高温-快冷-等温转变固化研究

采用高温-快冷-等温转变对铬渣进行固化处理,通过调整配料成分确定最高固化温度,使铬渣的处理量最大且软化温度最低,以利节能和实际工业应用。结果显示,混合物以含铬渣35％～40％、粘土35％～45％、河沙10％、粉煤灰10％时,软化温度最低为1120～1125℃,固化产物经过标准毒性浸出,所测定的浸出液六价铬离子浓度低于0．8mg／L。该固化方法具有操作流程较短、铬渣处理量大等优点,可成功固化其中的六价铬离子。其固化原理是铬渣中铬离子在高温下迁移至相界面,在合理的冷却过程中稳定存在于相界面,而不易被浸出。     

制革铬鞣废液二次利用和铬回收的可行性研究

本文对制革废铬液的二次利用和铬回收进行了试验研究,并取得了最佳参数。实践表明,废铬液用于软化裸皮浸酸、浸酸裸皮初鞣和在废铬液中补充适量的新化铬鞣液用于鞣制二层皮,均取得了较好的效果,可分别节约红矾钠15％和60％。一个中型制革厂,全年可得经济效益7万元左右。环境效益也十分显著。     

从黄铜钝化废铬液中去除铜、锌离子的理论探讨

我厂黄铜保持架钝化液是一种高浓度的含铬液,在生产过程中由于产生大量的三价铬、铜、锌离子等杂质,使产品质量达不到要求而报废.六价铬以及铜、锌离子对生物     

海水中不同价态铬的极谱法分析

在NaNO3-NaHC（pH为6．2）缓冲介质中,加入DTPA（二乙烯三胺五乙酸钠,diethylenetriaminepentaacetate）,铬于-1．10--1．20V,峰电流达到一个稳定的最大值。通过对电解质选择、仪器参数优化,建立脉冲伏安法测定海水中总铬（Total）、铬（Ⅵ）、铬（Ⅲ）的分析方法。铬（Ⅵ）最低检出质量浓度是0．10汕g／L,样品加标回收率在92％-102％,1．00μg／L标准溶液测定的相对标准偏差为3．26％。该方法具有选择性好、灵敏度高、准确、简便的特点,适用于海水、饮用水和清洁地表水中微量铬的测定。     

电镀污泥氨浸渣中铬的回收

以电镀污泥氨浸渣为研究对象,采用钠化氧化焙烧方法,实现了铬物相的转化和回收。钠化氧化焙烧过程以Na_2CO_3作为钠化剂,掺量为20%(质量分数),在750℃下焙烧2.5h,铬的转化效果最佳。X射线光电子能谱结果表明,钠化氧化焙烧实现了氨浸渣中铬由非水溶态Cr(OH)_3向水溶态Na_2CrO_4的有效转变。在室温条件下水浸,固液比1g∶10mL,浸出5min,铬浸出率可达到91.36%。热力学计算结果显示,Cr(OH)_3与O_2、Na_2CO_3反应的吉布斯自由能为负值,表明Cr(OH)_3易于生成Na_2CrO_4,Na_2CrO_4易溶于水,易于回收。     

Linking plant tissue concentrations and soil copper pools in urban contaminated soils

Copper tissue concentrations of radish (Raphanus sativa cv. Cherry Belle), lettuce (Lactuca sativa cv. Buttercrunch) and ryegrass (Lolium perenne cv. Barmultra) grown in a greenhouse in urban contaminated soils are compared to total, soluble and free ion copper pools. The tissue concentrations of copper vary between 8.1 and 82.6 mg Cu kg(-1) dry tissue and the total soil copper content varies between 32 and 640 mg Cu kg(-1) dry soil. The linear regressions with cupric ion activity and total soil copper are both significant (p < 0.01), but cupric ion activity yields a higher level of statistical significance in every case. The results support the hypothesis that free metal in the soil solution is a better indicator of plant metal bioavailability than either total or soluble metal.     

Kinetics of oxidation of methylhydrazines in water. Factors controlling the formation of 1,1-dimethylnitrosamine

The kinetics of oxidation of methylhydrazine ($\text{MMH}$) and 1,1-dimethylhydrazine ($\text{UDMH}$) by dissolved oxygen in water has been measured at various acidities as a function of catalyst (cupric ion) concentration. In dilute solutions the oxidation occurs through a cupric ion catalyzed process as well as by an uncatalyzed step. The extent of formation of nitrosodimethylamine ($\text{NDMA}$) depends upon the initial $\text{UDMH}$ concentration. In dilute solutions $\text{NDMA}$ is not formed, but in more concentrated solutions, $\text{NDMA}$ formation increases with increasing $\text{UDMH}$ content, reaches a maximum at 60–80% $\text{UDMH}$ (by volume) and then decreases. The $\text{NDMA}$ yield appears to approximately parallel the viscosity of the medium, and it is speculated that the factors which control viscosity may also be responsible for governing $\text{NDMA}$ formation.     

Role of cupric ions in the H2O2/UV oxidation of humic acids

The purpose of this study is to reveal the role of cupric ions as a natural water contaminant in the H2O2/UV oxidation of humic acids. Humic acids are naturally occurring organic matter and exhibit a strong tendency of complexation with some transition metal ions. Chlorination of humic acids causes potential health hazards due to formation of trihalomethane (THM). The removal of THM precursors has become an issue of public concern. The H2O2/UV process is capable of mineralizing humic acids due to formation of a strong oxidant, hydroxyl radicals, in reaction solution. Experiments were conducted in a re-circulated photoreactor. Different cupric concentrations (0-3.8 mg/l) and different pH values (4-9) were controlled to determine their effects on the degradation of humic acids, UV light absorbance at 254 nm, and H2O2. The presence of cupric ions inhibits humic mineralization and decreases the rate of destruction of humic acids which absorb UV light at 254 nm. On the other hand, the higher the cupric concentration, the lower the H2O2 decomposition rate. In the studied pH range, the minimum of total organic carbon (TOC) removal occurs at pH = 6 in the presence of 2.6 mg/l of cupric ions; both acidification (pH = 4) and alkaline condition (pH = 9) lead to a better removal of TOC. It is inferred from this study that the cupric-complexed form of humic acids is more refractory than the non-complexed one.     

Effects of sulfur dioxide, hydrogen peroxide and sulfuric acid on the de novo synthesis of PCDD/F and PCB under model laboratory conditions

In a laboratory model system consisting of fly ash from municipal waste incinerator, CuCl2 x 2H2O, NaCl and activated carbon in N2 + 10% O2 atmosphere, the de novo synthetic reactions of formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) were studied under laboratory conditions in the presence of sulfur dioxide, hydrogen peroxide, and sulfuric acid. It has been found that the formation of PCDD is suppressed by sulfur dioxide more efficiently than the formation of PCDF. A similar effect has also been observed in the presence of hydrogen peroxide. The formation of PCDF is strongly suppressed in the presence of sulfuric acid. On the basis of the experimental results and thermodynamic calculations, the following mechanisms are proposed and discussed: oxidative destruction of PCDD and PCDF oxygen rings, conversion of cupric chloride and possibly also cupric oxide into the non-reactive sulfate, and the Deacon oxychlorination processes catalyzed by cupric chloride.     

Leaching behavior and chemical stability of copper butyl xanthate complex under acidic conditions

Although xanthate addition can be used for treating copper-containing wastewater, a better understanding of the leaching toxicity and the stability characteristics of the copper xanthate complexes formed is essential. This work was undertaken to evaluate the leaching behavior of copper xanthate complex precipitates by means of toxicity characteristics leaching procedure (TCLP) and semi-dynamic leaching test (SDLT) using 1 N acetic acid solution as the leachant. Also, the chemical stability of the copper xanthate complex during extraction has been examined with the studying of variation of chemical structure using UV-vis, Fourier transform infrared and X-ray photoelectron spectroscopies (XPS).Both TCLP and SDLT results showed that a negligible amount of copper ion was leached out from the copper xanthate complex precipitate, indicating that the complex exhibited a high degree of copper leaching stability under acidic conditions. Nevertheless, chemical structure of the copper xanthate complex precipitate varied during the leaching tests. XPS data suggested that the copper xanthate complex initially contained both cupric and cuprous xanthate, but the unstable cupric xanthate change to the cuprous form after acid extraction, indicating the cuprous xanthate to be the final stabilizing structure. Despite that, the changes of chemical structure did not induce the rapid leaching of copper from the copper xanthate complex.     

Cobalt-based alumina pillared zirconium phosphate catalysts for the selective catalytic reduction of NO by propane

A series of cobalt containing alumina pillared zirconium phosphate materials have been prepared by ion exchange or by impregnation, and fully characterised. The catalytic behaviour of these materials in the selective catalytic reduction of NO by propane, in excess of oxygen, at temperatures ranging between 350 and 550 degrees C, has been also evaluated. A maximum NO conversion close to 14% is obtained on Co-impregnated catalysts heated at 600 degrees C. The NO reduction seems to be related to the presence of Co3+, thus the calcination temperature of samples influences the resulting activity much more than the cobalt content.     

掺碘二氧化钛薄膜自组装制备、表征及光催化性能

通过自组装技术在低温液相反应体系中制备出大尺寸纳米二氧化钛及其掺碘薄膜。使用XRD、TEM、荧光发射光谱仪、激光拉曼光谱仪等手段对样品进行表征,发现掺I^5＋后的二氧化钛薄膜在可见光区也表现出明显的响应,而且合成的I^5＋／TiO2纳米薄膜在TEMggNT其晶型显示为金红石型,并且碘掺杂后样品的拉曼光谱强度减弱,峰位蓝移且宽化。掺杂I^5＋原溶液浓度为2mmol／L时,其可见光下光催化效果最优,5h后降解率可达到95％,较未掺杂的TiO2纳米薄膜提高了40％,I^5＋掺杂明显提高了TiO2对甲基橙溶液的光催化降解效率。     

污泥中重金属的去除及回收试验

论述了利用离子交换技术循环使用柠檬酸去除污泥中重金属,并置换回收重金属的适宜工艺条件.经柠檬酸处理后,污泥中90%以上的重金属被去除;柠檬酸处理液中的重金属用离子交换法回收,考察了树脂种类、流速、操作方式等因素对离子交换、再生效果的影响;在适宜工艺条件下,重金属的交换率均为100%,而洗脱率均接近90%;柠檬酸及离子交换树脂循环使用,重金属也得到回收,降低了处理成本.     

液-液萃取处理高氯难降解有机废水

农药化工厂生产苯肼、苯唑醇、乙基氯化物过程排放的废水是高氯难生物降解有机废水,采用三辛胺作萃取剂,用液-液萃取处理,三辛胺与水中Cl-离子形成萃合物而使Cl-转移到有机相.再经高效絮凝处理后,CODCr总去除率达89.8%,Cl-总去除率达83.2%,BOD/COD比从0.02上升到0.34,可生化性大幅度提高. 废水再经河水稀释进A/O池生化处理3d后,可达标排放.负载萃取液用5%NaOH水溶液反萃取.由于萃取剂回用降低了处理费用.