Catalysts based in cerium oxide for wet oxidation of acrylic acid in the prevention of environmental risks

Acrylic acid is a refractory compound for the non-catalytic wet oxidation (WO) process and can seriously damage the environment when released in industrial effluents. Oxidation of acrylic acid by catalytic wet oxidation (CWO) was studied in slurry conditions in a high-pressure batch reactor at 200 °C and 15 bar of oxygen partial pressure. Several solid cerium-based catalysts prepared in our laboratory were used (Ag/Ce, Co/Ce, Mn/Ce, CeO, MnO) and evaluated in terms of activity, selectivity and stability. Mn/Ce shows the higher activity in 2 h with 97.7% reduction of total organic carbon (TOC) followed by: MnO(95.5%)>Ag/Ce(85.0%)>Co/Ce(65.1%)>CeO(61.2%). Attempts were also carried out to analyze the influence of different Mn/Ce molar ratios. High percentages of Mn lead to practically total organic carbon concentration (TOC) abatements while low ratios lead to the formation of non-oxidizable compounds. Acrylic acid was readily degraded by all the catalysts pointing out the high importance of using a catalytic process. pH was an indicator of the reaction pathway and acetic acid was found as the major reaction intermediate compound; however it is completely oxidized after 2 h with exception for Co/Ce, CeO and MnO. Carbon adsorption and leaching of metals were poorly found for Mn/Ce indicating high stability. The catalyst microstructure after the reaction was analyzed and formation of whiskers of β-MnO₂ (or less probably MnOOH) were observed at the catalyst surface. Therefore, Mn/Ce revealed to be a promising catalyst for the treatment of effluents containing acrylic acid; nevertheless, its commercialization depends on further research.     

Fine coal desulphurization by leaching with bromine containing hydrobromic acid

Sulphur extraction from coal by leaching with bromine-containing aqueous hydrobromic acid has been investigated in the temperature range from ambient to 120 °C. This procedure was found to be selective for the removal of high levels of sulphate and pyritic sulphur within a few minutes of leaching, while no significant reduction of the organic sulphur could be observed. Leaching led to an appreciable reduction of the ash yield and the up-take of substantial quantities of bromine. The bromine can be removed as hydrogen bromide by thermal treatment under nitrogen, without significant loss of volatile matter; for reduction of the bromine level to below 0.1 wt%, treatment for at least 1 h at ≈ 500 °C was needed.     

二氧化硫浸锰制备高纯碳酸锰

采用湘潭低品位的贫软锰矿为原料，对二氧化硫气体湿法浸锰、浸出液除杂、碳化结晶制备高纯碳酸锰的工艺进行了研究。实验得到二氧化硫浸锰的最佳工艺条件为：浸锰温度150～155℃，液固质量比3：1，二氧化硫体积分数6％～7％、流速1．5～2．0mL／min，浸锰时间3．0～3．5h。按该条件浸锰，锰的浸出率可达95％以上。该工艺为贫软锰矿的开发利用及有色金属冶炼厂二氧化硫废气的综合治理开辟了一条新途径。     

表面活性剂对HCl-FeCl3溶液中锌精矿在浆萃取浸出率的影响

The effects of surfactant on the solvent extraction in leaching sphalerite were investigated. It is found that sodium dodecyl sulfonate is the effective surfactant in improving the zinc recovery from sphalerite in the aqueous FeCl3-HCl-tetrachloroethylene system. Through the measurements of surface tension and viscosity of the sphalerite slurry modified with different surfactants, it is concluded that sodium dodecyl sulfonate in the concentration range of 0.05 to 0.2g L-1 can improve the viscosity of sphalerite slurry in the water, decrease the surface tension of leaching solution, prevent the aggregation of ore particles, and give very high zinc extraction .     

乙烯废碱液处理装置存在问题分析及改进措施

分析了中国石油大庆石化分公司废碱液处理装置设备及管材存在问题的原因,提出了解决措施。此外针对装置运行中产生的有关问题,对其工艺进行了改进,其结果使装置能力在原设计的基础上提高到200%。     

渗漏溶蚀作用下碾压混凝土层(缝)面抗剪强度衰减规律试验研究

采用硝酸铵溶液循环浸泡的方式加速并模拟碾压混凝土层(缝)间渗漏溶蚀过程,应用直剪法测试抗剪强度,研究了溶蚀对混凝土层(缝)面抗剪强度的影响。结果表明,碾压混凝土层(缝)间渗漏溶蚀沿着缝面的法向逐渐向两侧混凝土的内部延伸,缝面溶蚀深度,即溶蚀前锋线至缝面的距离,用酚酞指示剂+电子探针线扫描技术测定,与钙离子累计溶出量呈线性关系,可以定量表征溶蚀程度。渗漏溶蚀引起缝隙两侧混凝土的孔隙率增大,微观结构变差,混凝土层(缝)面摩擦系数、黏聚力下降,但下降速率逐渐降低,衰减规律遵循牛顿冷却定律。试验数据拟合表明,基于牛顿冷却定律建立的以缝面溶蚀深度为自变量的抗剪强度衰减模型能够很好地反映碾压混凝土层(缝)面抗剪强度变化规律。     

湿式空气氧化法处理乙烯废碱液装置的技术改造

针对中国石化齐鲁石化公司烯烃厂乙烯装置废碱液处理系统在试运转过程中存在的问题,通过分析原因,提出并实施改进工艺的相关措施,得到一组适宜的工艺操作参数,保证了废碱液湿式空气氧化装置的稳定运行。     

Effects of soil solution on the dynamics of N2O emissions: a review

In this review, which consists of two parts, major interactions between nitrous oxide (N₂>O) and soil solution are described. In the first part, as an introduction, concentrations of dissolved N₂>O in different aqueous systems are summarized. An inventory of data on maximal N₂>O concentrations in soil solution (up to 9984 g N₂>O-N l^–1>) and in soil air (up to 8300 ppm) from literature is presented. The peak N₂>O concentrations represent a N₂>O supersaturation in the soil solution up to 30000 times with respect to ambient air and a soil air N₂>O concentration about 25000 times higher than in the atmosphere. The main physico–chemical parameters (solubility, diffusion) controlling N₂>O distribution between soil solution and soil air are outlined. The influences of cultivation practice, nitrogen turnover, water content and temperature on N₂>O a ccumulation in soil solution and soil air are reviewed. In the second part some models of N₂>O dynamics in soils are discussed with emphasis on N₂>O transport processes. A simple qualitative scheme is developed to categorize the effects of the soil solution on N₂>O dynamics in soils. In this scheme the temporary, intensive N₂>O oversaturation of the soil solution is interpreted as a result of gas diffusion inhibition by water (barrier function of soil solution) resulting in an accumulation of N₂>O. In addition, N₂>O supersaturation is an indication that transitory much N₂>O can be stored in the soil solution (storage function of soil solution). Where the soil solution flows up-, down- or sidewards it can act as a relevant transport medium for dissolved N₂>O (transport function of soil solution). This scheme is applied to examples from the literature.     

P_2O_5影响Na_2O-B_2O_3-SiO_2系玻璃结构与性质的特殊性

本文通过不混溶温度的确定,分相玻璃沥滤速率的测定以及NMR定量分析,研究了P_2O_6对Na_2O-B_2O_3-SiO_2系统玻璃结构和沥滤性质的影响。结果表明,P_2O_5在很大程度上促进钠硼硅分相玻璃的沥滤并非压抑“硼反常”所致,而是由以下三种因素综合作用的结果:(1)P_2O_5促进了钠硼硅玻璃的分相,使连通富硅相骨架尺寸增大;(2)P_2O_5的加入使富硅相骨架间隙中沉积的SiO_2量减少,减小了可溶相扩散阻力;(3)P_2O_5也使可溶相的溶解速率加快。     

Nitrate leaching from loamy soils as affected by crop rotation and nitrogen fertilizer application

Nitrate leaching as affected by cropping system/crop rotation, history of farmyard manure application or fertilizer nitrogen application (0 N, 0.5 N and 1 N) was studied at nine sites on loamy soils during 1986/87, 1987/88 and 1988/89. Soil solution from 80 to 90 cm soil depth was sampled every second week in the period November to May by the use of porous ceramic cups and analysed for NO₃-N and Cl. Climatical conditions were obtained from standard meteorological observations in the region. Drainage from soil profiles was calculated from measured and simulated values of precipitation and actual evapotranspiration, respectively.The results show that type of crop is of the utmost importance for the leaching magnitude of nitrate as 40% of the total variance in nitrate concentrations in the soil solution could be explained by the type of crop.The second factor of importance was the history of farmyard manure (FYM) application, which was able to explain 28% of the total variation in nitrate concentration in the soil solution. Nitrate concentration/leaching from arable land without FYM ever being applied was considerably lower than from arable land which received periodical FYM applications until the early 70's or from arable land which besides periodical FYM applications in the past presently still receives regular applications of FYM. Only about 1% of the total variation in nitrate concentration in the soil solution was explainable by the level of fertilizer nitrogen application.Differences between years explained 14% of the total variation in nitrate concentration in the soil solution due to differences between the years in soil temperatures and water run-off. The run-off during the autumn and winter of 1986/87, 1987/88 and 1988/89 was 95, 275 and 55 mm, respectively. As expected nitrate leaching increased with increasing run off. However, nitrate leaching at the 275 mm run off was considerably lower than expected, which seems explainable by a substantial denitrification. The soil at the sites in question seems thus partly to purify the soil solution for nitrate before it leaves the root zone at the observed high run off conditions.