用废杂铜制备碱式碳酸铜

以废杂铜为原料,用稀硝酸浸出硝酸铜溶液,与碳酸氢钠反应得到碱式碳酸铜粗品,漂洗后得到高纯度碱式碳酸铜。实验结果表明,废杂铜与质量分数为30％的硝酸反应,开始比较平缓,后期反应剧烈,有少量红棕色的NO：生成,采用碱液吸收方式处理生成的NO：可减少其对大气的污染。碳酸氢钠与硝酸铜进行合成反应,反应温度50～80℃,反应液pH6．5～7．0,产品中铜的质量分数为55％-56％,产品质量较好。     

Release Characteristics of Nutrients from Polymer-coated Compound Controlled Release Fertilizers

Reliable information regarding release characteristics of nutrients from a polymer-coated controlled release fertilizer (CRF) is essential for beneficial agronomic and environmental results. Significant knowledge regarding nitrogen release from polymer-coated urea was gained while the information regarding the release of the different nutrients contained in polymer-coated compound N–P–K CRF remains limited. An experiment in which major factors affecting the differential release of nutrients from two coated compound CRF was performed in free water, water saturated sand and sand at field capacity. In general, nitrate release was the fastest, followed by ammonium and potassium whereas phosphate was significantly slower, with a rate of linear release in free water 45–70% slower than that of nitrate. Little differences were obtained for the lag periods of nitrate, ammonium and potassium release (2–10 days) under the experimental conditions, whereas for P they were one order of magnitude larger. The main factor slowing the release was assumed to be the lower solubility of ions with P being the least soluble. Release into free water was, expectedly, somewhat faster than that into saturated sand and significantly faster as compared to sand at field capacity and particularly so for P. Raising the temperature from 20 °C to 40 °C increased the rate of linear release of the different nutrients. The energy of activation, EA_rel, estimated for the linear release, of the different nutrients, was narrow ranging between 37 to 46 (KJ mol⁻¹) whereas the mean values obtained for the two CRF, differing by 50% in coating thickness, was non-significant. However, EA_rel was significantly different in different media. The complex effect of temperature on the lag period and nutrient interactions during release deserve further investigation.     

Release and fate of fluorocarbons in a shredder residue landfill cell: 1. Laboratory experiments

The shredder residues from automobiles, home appliances and other metal-containing products are often disposed in landfills, as recycling technologies for these materials are not common in many countries. Shredder waste contains rigid and soft foams from cushions and insulation panels blown with fluorocarbons. The objective of this study was to use laboratory experiments to estimate fluorocarbon release and attenuation processes in a monofill shredder residue (SR) landfill cell. Waste from the open SR landfill cell at the AV Miljø landfill in Denmark was sampled at three locations. The waste contained 1–3% metal and a relatively low fraction of rigid polyurethane (PUR) foam particles. The PUR waste contained less blowing agent (CFC-11) than predicted from a release model. However, CFC-11 was steadily released in an aerobic bench scale experiment. Anaerobic waste incubation bench tests showed that SRSR produced significant methane (CH₄), but at rates that were in the low end of the range observed for municipal solid waste. Aerobic and anaerobic batch experiments showed that processes in SRSR potentially can attenuate the fluorocarbons released from the SRSR itself: CFC-11 is degraded under anaerobic conditions with the formation of degradation products, which are being degraded under CH₄ oxidation conditions prevailing in the upper layers of the SR.     

从铜氨废液中回收铜

分别采用化学沉淀法和电解法从电镀污泥水热合成铁氧体后过滤分离的铜氨废液中回收铜。实验结果表明：采用化学沉淀法处理铜氨废液,以体积比为1：1的盐酸调节铜氨废液pH为5．4～6．4,沉淀出碱式氯化铜固体,铜回收率在98％以上,1L铜氨废液可回收碱式氯化铜5．83g（合铜3．50g）;采用电解法处理铜氨废液,在电流密度250A／m^2、电解时间5h、电解温度60℃的条件下,1L铜氨废液可回收3．54g铜粉,铜回收率超过99％,铜粉的粒径和纯度均可达到GB5246-85《电解铜粉》的要求。     

含铜废催化剂中铜的回收

采用热解—氨浸工艺处理含铜废催化剂（w（Cu）为23.6%）,优化了工艺条件,并通过蒸氨还原法制备出Cu₂O产品。实验结果表明：热解工段中,控制管式热解炉的空气流量为3.0 m³/min,在升温速率20 ℃/min、热解终温600 ℃、终温保持时间90 min的优化条件下,含铜废催化剂中的有机物热解完全;氨浸工段中,以NH₄Cl-NH₃-H₂O溶液为氨浸液,控制氨浸温度为40 ℃,在烧成料研磨时间90 min（粒径29.43 μm）、氨浸液总氨浓度4 mol/L、氨浸时间80 min的优化条件下,铜浸出率达到98%;经蒸氨还原法制得的Cu₂O产品的质量符合HG/T 2961—2010《工业氧化亚铜》中的一等品标准,产率为24%。     

利用含铜蚀刻废液生产碱式碳酸铜

介绍了利用含铜蚀刻废液生产碱式碳酸铜的生产工艺、技术特点、工艺流程和产品质量。以碳酸钠作蚀刻废液的除杂剂,对其进行除杂前处理,控制反应液的pH为3．5～4．0、反应液中碳酸钠的浓度为0．02～0．03mol／L。可除去其中大部分杂质。用碳酸钠与含铜溶液中的铜进行合成反应,控制反应温度为70～80℃、pH为8～9、碳酸钠和含铜溶液中铜的浓度均为1mol／L,反应生成碱式碳酸铜,此产品中铜的质量分数为56％,产品质量优于木材防腐用碱式碳酸铜国内外同类产品。     

煤及煤矸石中砷的释放

研究了煤及煤矸石中砷的释放特征。采用XRD技术对煤样中的主要矿物成分进行了分析。表征结果显示,煤样中的主要矿物组成为碳酸盐矿物、硅酸盐矿物,以及一定量的SiO2、TiO2、硫化物矿物和硫酸盐矿物。实验结果表明：煤中砷的赋存形态主要以残渣态和硫化物结合态为主;在煤燃烧过程中,当燃烧温度为1 000 ℃时,1号矿井的煤样燃烧后灰渣中的砷含量为1.385 μg/g,砷的释放率为40.10%,2号矿井的煤样燃烧后灰渣中的砷含量为1.531 μg/g,砷的释放率为56.04%;在煤矸石的淋溶过程中,在淋溶液体积为100 mL的条件下,当淋溶液pH为5时淋出液中的ρ（砷）为19.27 μg/L,当淋溶液pH为7时淋出液中的ρ（砷）为7.78 μg/L。     

提高异丙醇废水可生化性的试验研究

感光材料行业排出的异丙醇废水,BOD5／COD为0．40左右,经水解酸化处理后BOD5／COD提高至0．05左右,证实了水解酸化处理具有提高异丙酸废水可生化性的功能。在进水COD为2000－3000mg／L条件下,用水解酸化－好氧生化工艺处理,COD总去除率可达90％左右,BOD5总去除率可达95％左右,均明显优于平等对照组传统活性污泥法的处理效果。     

电镀污泥中铜和镍的回收

采用硫酸酸浸#x02014;铜镍分离#x02014;净化除杂#x02014;沉淀制取硫酸镍的工艺从电镀污泥中回收铜和镍,分别采用硫化钠沉淀法和铁粉置换法研究电镀污泥酸浸液中铜和镍的分离效果。实验结果表明,硫化钠沉淀法对铜和镍的分离效果较好,其最优工艺条件为：硫化钠加入量为理论需求量的1.2倍,硫化钠沉淀温度60℃,硫化钠沉淀时间30min。利用本回收工艺制得的硫酸镍产品中镍的质量分数为18%,镍的回收率达80%以上,铜的回收率达90%以上。     

用含硫化砷废渣制备砷酸铜

以湖北省某化工企业含砷废水处理过程中产生的含硫化砷废渣为研究对象,采用氧化碱浸—沉淀工艺制备砷酸铜。考察了沉淀反应液pH、沉淀反应温度、搅拌转速对砷沉淀效果的影响。采用XRD和SEM技术对砷酸铜的物相及形貌进行了表征。实验结果表明：废渣在氧化碱浸过程的砷浸出率为96.53%;沉淀反应时间为30 min时,沉淀步骤的最佳工艺条件为沉淀反应液pH 5.0、搅拌转速500 r/min、沉淀反应温度50 ℃。验证实验结果表明,在该工艺条件下,砷沉淀率均达93.96%以上。SEM表征结果显示,砷酸铜产品为颗粒状,粒径约为500 nm。XRD表征结果显示,砷酸铜产品中主要含有Cu₃As₂O₈,Cu₄O（AsO₄）₂,Cu₄（As₂O₇）O₂。该方法工艺简单、无二次污染,为废渣的综合利用提供了一种新的技术路线。     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

用含铜蚀刻废液制备碱式碳酸铜

以含铜蚀刻废液为原料,采用沉铜-浸铜-蒸氨三步法制备碱式碳酸铜。考察了反应物配比、提取温度、浸取时间等对实验结果的影响。最佳工艺条件：浸铜时,n（NH3）：n（CuO）为3．0,n（NH4HCO3）：n（CuO）为1．25,浸取时间为2h,无需加热;蒸氨时,在真空度为0．06MPa的条件下,采用在80—95℃范围内逐渐升温的方式蒸氨2．5h。实验结果表明,反应生成的碱式碳酸铜中Cu的质量分数为56％,产品质量优于木材防腐用碱式碳酸铜国内外同类产品。     

蚀刻液水合肼还原除铜

将电路板厂废弃的蚀刻液,经氢氧化铜沉淀法回收大部分铜后,再采用水合肼还原,进一步除铜。反应温度为50℃,水合肼质量分数为3．0％,溶液pH为6．0,废液中铜的去除率可达98.5％,处理后废液中铜的质量浓度低于0．2g／L,可作为碱性蚀刻液重复利用。     

Release of nitrogen and trace metal species from field stacked biosolids

Concerns over elevated nitrate (NO3-) levels found in groundwater near former biosolid stockpiling locations resulted in the Maine Department of Environmental Protection (MDEP) imposing stricter regulations governing the stockpiling of biosolids in October 2002. The goals of this study were to measure the amount and speciation of nitrogen (N) and trace metals leaving stockpiled biosolids and travelling through the soil column. The biosolids were placed on plastic-lined cells to collect all leachate. Ammonium (NH4+), ranging from 2000 to 4900 mg L(-1), was the dominant N species (90% of total N) in the leachate from the Class B lime-stabilized biosolids in the lined cell experiment. Nitrate (NO3-) and nitrite (NO2-) concentrations were negligible, remaining below 0.25 and 0.1 mg L(-1), respectively. Dissolved organic carbon (DOC) concentrations as high as 8900 mg L(-1) and chemical oxygen demand (COD) as high as 37 000 mg L(-1) were measured in the leachate leaving the lined cell. Fifteen zero-tension pan lysimeters (ZTP-lysimeter) were installed in a 90 m2 plot at depth intervals of 30, 60, and 100 cm. Leachate passing through the soil column underlying the biosolids stockpile was collected in the ZTP-lysimeters. The average ZTP-lysimeter NH4+ concentrations ranged from 1400 mg L(-1) at 60 cm depth to 145 mg L(-1) at 90 cm depth. The average ZTP-lysimeter DOC concentrations ranged from 2000 mg L(-1) at 60 cm to 525 mg L(-1) at 90 cm. Trace metal determinations of the leachate collected from the lined cell and ZTP-lysimeters showed arsenic loading rates exceeded the state limits of 0.5 kg ha(-1) year(-1) by an order of magnitude. Arsenic concentrations were in excess of several thousand milligrams per litre in the lined-cell leachate and several hundred milligrams per litre in the ZTP-lysimeters as deep as 90 cm under the biosolid stockpile. Phosphorus, iron and manganese in excess of several thousand milligrams per litre were observed in both the lined-cell leachate and ZTP-lysimeters. Significant concentrations of other trace metals were found at depth in the zero-tension ZTP-lysimeter plot. Trace metals were largely mobilized by the DOC from the biosolids and due to the presence of anaerobic environment, especially in the underlying soil.     

硼氢化钠还原法回收电镀废液中的铜

采用NaBH4作为还原剂回收电镀废液中的铜。正交实验结果表明,各因素对剩余铜离子质量浓度的影响的显著性顺序为n(NaBH4)∶n(CuSO4)反应时间反应温度。最佳实验条件为:n(NaBH4)∶n(CuSO4)=1.50,反应温度30℃,反应时间25min。经该工艺可获得平均粒径为33nm的近球形立方晶系纳米铜粉,处理后废液中铜离子质量浓度低至0.2mg/L。在铜粉制备过程中加入非离子型表面活性剂可有效阻止晶粒长大,并提高其分散性能,使产物粒径均匀。采用苯骈三氮唑处理后的铜粉抗氧化能力明显提高。     

A Comparison Between Corrosion Rates and Runoff Rates from New and Aged Copper and Zinc as Roofing Material

Recently there has been anincreased environmental concern in severalcountries in Europe, in particular in Sweden andin the Netherlands regarding the amount of copperand zinc that is released from building materialsinto society. Due to lack of runoff data, thelegislators have so far used corrosion ratesmeasured during the last 20 years to calculatequantities of metal released from buildingsassuming that the quantity of metal corrosionequals the quantity of metal runoff. Withdecreasing levels of environmental pollutantsduring the last decade in Europe, it is importantto determine more recent and hence morerepresentative corrosion and runoff rates to beused in the calculations. For this reason a field exposure program was implemented during 48 weeks in an urbanatmosphere in Sweden determining corrosion andrunoff rates for copper and zinc of differentage. New copper exposed for 48 weeks in the urbanatmosphere shows a corrosion rate of 6.7gm^-2y^-1 and an almost constant runoff rate of1.3 gm^-2y^-1 during the period. Therunoff rate is significantly lower than thecorrosion rate and represents only a fraction(20%) of the total amount of corroded metalduring this period. Zinc shows a graduallydecreasing corrosion rate with time being 5.0gm^-2y^-1 after 48 weeks of exposure. Therunoff rate is relatively stable with an averagerate of 3.1 gm^-2y^-1 during the sameperiod. This value represents 60% of the totalamount of corroded zinc. The effect of panel age has been investigatedin parallel field and laboratory studies. Theresults show that naturally aged copper exhibitssomewhat higher average runoff rates (2 gm^-2y^-1) than new copper, probably due to acombined effect of storage and weatherconditions. No significant difference in runoffrate can be found between new and naturally agedzinc. The field and laboratory investigationsshow that precipitation rate and amount influence the magnitude of the runoff rate forboth copper and zinc.     

用于有机污染物湿式氧化的铜系催化剂活性研究

对用铜系多相催化剂催化湿式氧化处理染料中间体Ｈ酸配水作了较为全面的研究。结果表明,铜氧化物催化剂在催化湿式氧化中的活性明显优于其他过渡金属氧化物,若能控制其溶出,则具有广阔的应用前景。