Thermal hazard evaluation for γ-valerolactone production by using formic acid as hydrogen donor

Aiming at the green and sustainable energy substitution and supply, biomass valorization has become a potential strategy to face the energy crisis and increasing demand all over the world from long-term perspectives. Among the bio-based chemicals, γ-valerolactone (GVL) production from hydrogenation of levulinic acid (LA) and its esters has attracted great interests due to its wide applications, such as fuel, solvent, and additives. However, the safety evaluation for this hydrogenation reaction has received few attentions. To fill this gap, thermal hazard evaluation for GVL production from LA hydrogenation by using formic acid (FA) as hydrogen donor was first performed. The process conditions were optimized by using orthogonal experimental method for further calorimetry study. Thermal stability of chemicals and thermal risk of reaction process under adiabatic conditions were investigated by applying differential scanning calorimetry and accelerating rate calorimeter Phi-Tec II, respectively. The results revealed that the chemicals were stable in temperature range from 30 to 250 °C except FA due to its evaporation and decomposition with endothermic behaviors. The reaction process under isothermal and adiabatic conditions demonstrates that the decomposition of FA was rapid and followed by the hydrogenation of LA to GVL. Based on kinetic model under adiabatic conditions and risk matrix, the thermal runaway risk was found to be medium, indicating that certain safety measures should be properly designed and taken for loss prevention. This work could benefit the safety design and thermal risk prevention for GVL production by using FA as hydrogen donor.     

反硝化耐冷菌Acinetobacter johnonii DBP-3的低温除磷特性

通过批实验技术研究了不同条件下一株反硝化耐冷菌Acinetobacter johnonii DBP-3(Genbank登录号JN314436,保藏号CGMCC4753)的低温除磷特性.结果表明,菌株可分别利用氧气(O2)、硝酸根(NO3-)和亚硝酸根(NO2-)为电子受体吸收溶液中的磷酸盐,不同电子受体条件下吸磷效能的大小顺序为:氧气>硝酸根>亚硝酸根.NO3-的浓度为0～150mg·L-1时,菌株对磷酸盐的吸收能力随着NO3-浓度的增加而增加.亚硝酸盐浓度为0～20mg·L-1时菌株对磷酸盐的吸收能力随NO2-浓度的增加而明显增加;浓度为20～60mg·L-1时,菌株对磷酸盐的吸收能力受NO2-浓度的影响较小;浓度达80mg·L-1时,菌株的除磷能力明显下降.不同碳源条件下厌氧培养的菌体细胞在缺氧条件下培养时对磷酸盐的去除能力大小顺序为:乙酸钠>柠檬酸钠>葡萄糖.菌株除磷的适宜pH值范围为7～9.温度为5℃时,菌株仍保持一定的除磷能力,随着温度的升高除磷能力逐渐增加,当温度达35℃时,除磷能力开始下降.菌株对盐度的耐受性在好氧培养时大于缺氧培养.缺氧培养48h,菌体细胞中磷的平均含量可达5.7%,而厌氧培养的菌体细胞中磷的最低含量为2.6%,表现出了明显的聚磷和释磷特性.研究结果可为低温富营养化水体或富氮磷污水的生物处理提供理论依据.     

Photocatalytic degradation of perfluorooctanoic acid with β-Ga2O3 in anoxic aqueous solution

Perfluorooctanoic acid (PFOA) is a new-found hazardous persistent organic pollutant, and it is resistant to decomposition by hydroxyl radical (HO·) due to its stable chemical structure and the high electronegativity of fluorine. Photocatalytic reduction of PFOA with β-Ga₂O₃ in anoxic aqueous solution was investigated for the first time, and the results showed that the photoinduced electron (e_cb^-) coming from the β-Ga₂O₃ conduction band was the major degradation substance for PFOA, and shorter-chain perfluorinated carboxylic acids (PFCAs, C_nF_2n+1COOH, 1 ≤ n ≤ 6) were the dominant products. Furthermore, the concentration of F^- was measured by the IC technique and defluorination efficiency was calculated. After 3 hr, the photocatalytic degradation efficiency was 98.8% and defluorination efficiency was 31.6% in the presence of thiosulfate and bubbling N₂. The degradation reaction followed first-order kinetics (k = 0.0239 min^-1, t_1/2 = 0.48 hr). PFCAs (C_nF_2n+1COOH, 1 ≤ n ≤ 7) were detected and measured by LC-MS and LC-MS/MS methods. It was deduced that the probable photocatalytic degradation mechanism involves e_cb^- attacking the carboxyl of C_nF_2n+1COOH, resulting in decarboxylation and the generation of C_nF_2n+1·. The produced C_nF_2n+1· reacted with H2O, forming C_nF_2n+1OH, then C_nF_2n+1OH underwent HF loss and hydrolysis to form C_nF_2n+1COOH.     

铁还原环境四氯乙烯生物降解及其影响因素

通过实验研究了铁还原环境下四氯乙烯(PCE)的生物降解。以醋酸为共代谢基质,在20℃时,PCE可以顺序脱氯为TCE和DCEs。反应速率常数为0.2489d-1,半衰期为2.78d。在实验的第1天和第10天分别检测到了TCE和DCEs。TCE最高浓度为358.98nmol/L,是最主要的反应产物。碳平衡为88.7%～109.3%。在13d的实验周期中,微生物的数量和活性都有所增加。同时研究了不同的影响因素,如低温、不同pH和电子受体对PCE生物降解的影响。结果表明,在12℃时,PCE可以脱氯为TCE,半衰期为6.45d,降解速率为0.1075d-1,较20℃时的降解速率要低。脱氯的最佳pH值在7.0左右,较高和较低的pH值均会抑制脱氯微生物的活性。加入不同电子受体NO3-和SO42-,PCE脱氯受到不同程度的抑制,前者可能是由于NO3-是相对强的氧化剂,造成微环境中的氧化还原电位升高;后者则可能是SO42-的存在,会抑制脱氯菌的作用。     

可膨胀性层状粘土矿物对铜离子吸附机理的模拟研究

对 Cu-蒙脱石、Cu-蒙脱石的热产物及其复水产物进行了 XRD、EPR和 DTA研究 .在 Cu-蒙脱石的 EPR谱中同时记录到了 g=2 .1 4、g=2 .0 7(精细结构线 )、g～ 2 .7- 2 .2 (超精细结构线 ) 3组 Cu²⁺的信号 ,分别对应于蒙脱石层间水合铜离子、进入 Si-O四面体片复三方形孔洞和铝氧八面体空位中的 Cu²⁺,阐明了蒙脱石对重金属离子的吸附以交换吸附和专性吸附 2种方式进行 .     

不同基质作为电子供体时四氯乙烯的降解研究

将取回的厌氧污泥进行培养、驯化,并用驯化好的厌氧污泥进行PCE的厌氧生物降解研究。实验选用甲醇、乳酸盐和醋酸盐作为电子供体,对PCE的降解进行研究。实验结果表明:PCE通过还原脱氯实现其降解,在本实验条件下PCE的降解均符合一级反应动力学。通过对反应速率常数(k)的比较发现,乳酸盐是最有效的电子供体。     

ESEM–EDX characterisation of airborne particles from an industrialised area of northern Greece

The aim of this study was to characterise individual airborne particles collected from the Ptolemais-Kozani region (Western Macedonia), northern Greece. Throughout a 1-year period (March 2003 to February 2004), we collected several filters that captured airborne particles at seven sampling sites distributed throughout the area. The airborne particles captured on the filters were then characterised by environmental scanning electron microscopy (ESEM) coupled with energy-dispersive X-ray analysis (EDX). The particles were categorised as geogenic, biogenic and anthropogenic. The main anthropogenic airborne particles were fly ash (released from lignite-fired power plants) and carbonaceous (soot and char) and metalliferous (mainly iron- and copper-enriched) particulates. We present here characteristic ESEM and EDX spectra for the airborne particles and underline the presence of characteristic primary and secondary sulphates.     

生物膜内硫循环变化特征及其作用的研究动向

结合国内外的研究情况 ,阐述了生物膜内硫的存在形态随环境条件不同而发生的变化及其作用 ,提出了研究影响生物膜内硫循环的电子受体、硫酸盐还原菌 (SRB)及其与生物膜内脱氮菌、聚磷菌等功能微生物的关系 ,对提高生物膜的水处理效果有重要意     

电子束氨法烟气脱硫技术工艺研究

介绍了位于四川省绵阳市科学城热电厂的电子束氨法烟气脱硫脱硝工业试验装置和在该装置上进行的较全面的工艺研究 ,确定了影响SO2 脱除效率的主要参数 ,为北京京丰热电EA FGD工业示范工程设计提供了重要依据     

Nitrate removal to its fate in wetland mesocosm filled with sponge iron: Impact of influent COD/N ratio

• CW-Fe allowed a high-performance of NO₃^‒-N removal at the COD/N ratio of 0. • Higher COD/N resulted in lower chem-denitrification and higher bio-denitrification. • The application of s-Fe⁰ contributed to TIN removal in wetland mesocosm. • s-Fe⁰ changed the main denitrifiers in wetland mesocosm. Sponge iron (s-Fe⁰) is a porous metal with the potential to be an electron donor for denitrification. This study aims to evaluate the feasibility of using s-Fe⁰ as the substrate of wetland mesocosms. Here, wetland mesocosms with the addition of s-Fe⁰ particles (CW-Fe) and a blank control group (CW-CK) were established. The NO₃^‒-N reduction property and water quality parameters (pH, DO, and ORP) were examined at three COD/N ratios (0, 5, and 10). Results showed that the NO₃^‒-N removal efficiencies were significantly increased by 6.6 to 58.9% in the presence of s-Fe⁰. NH₄⁺-N was mainly produced by chemical denitrification, and approximately 50% of the NO₃^‒-N was reduced to NH₄⁺-N, at the COD/ratio of 0. An increase of the influent COD/N ratio resulted in lower chemical denitrification and higher bio-denitrification. Although chemical denitrification mediated by s-Fe⁰ led to an accumulation of NH₄⁺-N at COD/N ratios of 0 and 5, the TIN removal efficiencies increased by 4.5%‒12.4%. Moreover, the effluent pH, DO, and ORP values showed a significant negative correlation with total Fe and Fe (II) (P<0.01). High-throughput sequencing analysis indicated that Trichococcus (77.2%) was the most abundant microorganism in the CW-Fe mesocosm, while Thauera, Zoogloea, and Herbaspirillum were the primary denitrifying bacteria. The denitrifiers, Simplicispira, Dechloromonas, and Denitratisoma, were the dominant bacteria for CW-CK. This study provides a valuable method and an improved understanding of NO₃^‒-N reduction characteristics of s-Fe⁰ in a wetland mesocosm.