TA-FTIR/MS用于硝酸铵及其混合物的热化学行为研究

为评价物料混合对危险化学品热化学行为的影响,采用热分析-红外/质谱联用技术(TA-FTIR/MS)研究硝酸铵、柠檬酸和蔗糖的混合物的热化学行为。通过对硝酸铵及其混合物的分解温度和分解过程中逸出气体的分析,发现硝酸铵、柠檬酸和蔗糖的混合物热分解温度分别降低至135℃和153℃,而硝酸铵与甲基纤维素的混合物分解温度与硝酸铵基本相同为201℃,且各混合体系的气相分解产物均有氮氧化物(NOX),H2O和CO2。结果表明,混合物受热后其中的硝酸铵首先分解为硝酸和氨气;酸性物质和还原性物质由于对硝酸的分解反应有催化作用,使得混合物的热稳定性下降。     

碳源和硝酸盐对SBBR反硝化除磷影响的试验研究

研究碳源和硝酸盐对填加聚氨酯载体的SBBR反硝化除磷的影响。在SBR中填加聚氨酯载体,将生物膜法和活性污泥法相结合,形成序批式生物膜反应器(SBBR),在厌氧/缺氧交替运行条件下利用NO3-作为电子受体,研究NaAc浓度、NaAc与丙酸钠的比例、NO3-浓度及NO3-投加方式等因素对除磷效果的影响。PO43-质量浓度在9~11 mg/L之间,COD质量浓度为200 mg/L时,SBBR有较佳的除磷效果;当进水NaAc与丙酸钠配比为2时,进水COD自身降解速率较慢,且不影响除磷效果;分批次(这里分2次)投加硝酸盐有利于硝酸盐向亚硝酸盐的转化;NO3-质量浓度为65 mg/L左右时,能获得较好的除磷、除氮效果。填加聚氨酯载体的SBR装置除磷效果较理想;碳源和硝酸盐对SBBR反硝化除磷影响显著。     

熔融硝盐高温分解爆炸事故后果严重度评价

为评价热处理用硝盐槽熔融硝盐高温分解爆炸事故机理和后果严重度,结合某企业铝合金件硝盐固溶热处理工艺进行研究。 利用压缩气体容器爆炸能量计算模型、超压准则和TNT当量法估算热处理用硝盐槽内熔融硝盐高温分解爆炸事故后果,得出35 000 kg熔融硝盐在高温分解转化率为50%时爆炸的TNT当量为1 257.6 kg,爆炸会造成半径53.97 m范围内的人员轻伤,该结果和利用政府推荐的危险指数法得出的外部防护距离为50 m较为接近。 以上分析计算表明:超温爆炸过程中,熔融硝盐在硝盐槽中超温分解快速产生大量气体,在硝盐槽上盖及上部硝盐的阻挡下不能及时排出,致使硝盐槽内气体压力瞬间升高,形成类似于压力容器的空间,发生物理爆炸并引发高温硝盐喷溅。     

Small-scale fire performance assessment of intumescent coatings on metal tubes containing ammonium nitrate. A stepping-stone towards their application as a fire safety measure on road transportation tanks?

Ammonium nitrate is used in vast amounts globally, first and foremost as a component of fertilizers and explosive formulations. This usage necessitates its transportation which, as for most hazardous materials, involves certain risks. For oxidizing materials such as ammonium nitrate, the ultimate consequence of road transportation incidents is usually considered to be fire followed by explosion. Even though the probability in general is low, substantial reduction in its risk is a great gain for public safety. Thus, identifying novel and improving current safety measures for risk reduction, is an important aspect in the field of hazardous materials. Herein, a series of experiments are reported, which demonstrate the fire protection performance of two state-of-the-art intumescent passive fire protection materials on small-scale metal test tubes containing ammonium nitrate. Albeit being initial experiments on laboratory-scale, these results provide a promising starting point for further investigations on the potential of these materials for the fire protection of ammonium nitrate when carried in metal tanks. At its best, a prominent protection of ammonium nitrate from heat exposure was observed, as the temperature was kept well below its boiling point for more than 2.5 h. Successively, it resulted in a complete recovery of the sample material. This was in large contrast to the observed results for the unprotected test tubes, which led to complete decomposition of the sample after 11 min.     

Kinetics of nitrate reductive denitrification by nanoscale zero-valent iron

Nanoscale zero-valent iron (Fe⁰) was synthesized for nitrate denitrification. The reduction efficiency of nitrate decreased quickly with increasing initial pH value, increased considerably with the increasing dosage of nanoscale Fe⁰, and did not vary much with initial nitrate concentrations changing from 20 to 50 mg l^?1 when the excessive amount of nanoscale Fe⁰ was utilized. With reductive denitrification of nitrate by nanoscale Fe⁰, the removal rate of nitrate reached 96.4% in 30 min with nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7, and more than 85% of the nitrate was transformed into ammonia. Kinetics analysis in batch studies demonstrates that the denitrification of nitrate by nanoscale Fe⁰ involves reaction on the metal surface, which fits well the pseudo-first order reaction with respect to nitrate concentration. The observed reaction rate constant of reductive denitrification of nitrate was determined to be 0.086 min^?1 with a nanoscale Fe⁰ dosage of 1.0 g l^?1 and pH_in 6.7. Fast and highly effective denitrification can be achieved by nanoscale Fe⁰ compared with commercial Fe⁰ powder, this is due to the extremely high surface area and high reactivity for nanoscale Fe⁰, which can enhance the denitrification efficiencies remarkably.     

零价铁-反硝化菌在地下水硝酸盐污染修复中的应用

综述了应用零价铁-反硝化菌复合体系去除地下水中硝酸盐氮污染的研究进展.脱氮技术主要包括物理化学法、化学还原法和生物反硝化法,但单独使用任何一种方法都无法得到令人满意的处理效果.以零价铁在水中厌氧腐蚀所释放的氯气供给微生物进行反硝化,可以同时解决这两种技术单独使用时所存在的弊端.在此复合体系中,主要反应包括产氨、析氢和反硝化,降低脱氮产物中的氨氮比例就要减少产氨反应的发生几率.此外,使用纳米铁代替零价铁和反硝化细菌复合,可以大大提高脱氮反应速率.然而,该技术的研究在国内外尚处于起步阶段,在反应机理、产物控制、条件优化等方面都存在不足,还需要深入研究.     

莱州湾东岸地下水硝酸盐空间变异特征研究

应用经典统计学和地统计学对莱州湾东岸地下水NO3-质量浓度进行分析,采用Kriging方法对未观测点进行估值,分析研究区不同区域NO-3质量浓度的空间变异特征。同时,利用地理信息系统与Surfer软件分析研究区土地利用类型和NO-3质量浓度之间的关系。结果表明:1)莱州湾东岸地区地下水NO3-质量浓度平均值为118.51mg/L,变异系数为0.80,表现为中等强度变异;2)研究区地下水NO-3质量浓度的变异函数理论模型符合高斯模型,块金值/基台值为41.5%,表现为中等程度的空间相关性;3)不同土地利用类型中,耕地地下水中硝酸盐质量浓度平均值(136.09 mg/L)最高,其次是城镇用地(89.15 mg/L),水产养殖区(30.32 mg/L)最低,其中耕地超标率为81.25%,城镇用地超标率为76.92%,水产养殖区均未超标。农业生产过量使用化肥和城镇生活中的生活生产废水大量排放是造成地下水硝酸盐质量浓度过高的主要原因。而水产养殖区由于受人类生活、生产与耕作影响较少,地下水硝酸盐质量浓度相对较低。     

新型单级自养脱氮与反硝化除磷耦合工艺

反硝化除磷菌(Denitrifying Polyphosphate Accumulating Organisms,DPAOs)在缺氧段需要硝氮(NO-3-N)作为电子受体进行吸磷,而氨氧化细菌(Ammonia-Oxidizing Bacteria,AOB)和厌氧氨氧化细菌(Anaerobic ammonium oxidation,Anammox)恰好能够产生NO-3-N,基于此原理,将反硝化除磷菌与氨氧化细菌和厌氧氨氧化细菌进行联合培养,建立单级自养脱氮与反硝化除磷耦合工艺。该耦合工艺通过3个阶段的培养,在低碳氮磷比的条件下实现COD(Chemical Oxygen Demand)、氨氮及磷酸盐的同步高效去除(90%)。同时探讨了反硝化除磷细菌在不同碳源的条件下,各个化学指标(如挥发性脂肪酸、聚羟基脂肪酸等)的变化趋势及微生物群落多样性的变化情况。     

纤维素物质在生态浮床中的应用与发展

生态浮床是一种无占地、环境友好、集水体美化和污染物去除为一体的生态修复工程。首先分析了组合式生态浮床的原理、特点和弊端,以及生态浮床技术的研究现状,引出了湿地槽式生态浮床的概念;其次阐述了纤维素物质在生态浮床领域的应用现状和发展;最后探讨了纤维素物质在生态浮床领域应用急需解决的难题。为生态浮床技术的发展和革新提供参考。     

纤维素热裂解的二次反应研究

在热重红外联用分析仪上开展了纤维素的热裂解失重研究,通过对纤维素热裂解的TG和DTG曲线以及热解产物的红外析出图谱的分析研究,探讨了纤维素热裂解的二次反应过程及机理,并在经典Broido—Shafizdeh模型的基础上．提出了改进的纤维素热裂解模型。     

氰化物测定机理的研究

研究了酒石酸-硝酸锌法提取易释放氰化物，磷酸-EDTA提取总氰的机理；对异烟酸-吡唑啉酮光度法测定氰化物的条件作了探讨。     

湘江衡阳段沉积物对硝态氮的吸附特性研究

为探究沉积物对水体中硝态氮的吸附特性,以湘江衡阳段上游沉积物为研究对象,通过室内模拟吸附试验,探讨沉积物吸附硝态氮的影响因素、动力学规律及吸附等温线特征,并且利用SEM、FTIR等表征手段揭示吸附机理。结果表明,环境因素的改变会对硝态氮的吸附产生一定影响,泥水比的增大使沉积物的固体浓度效应明显,吸附量减小;硝态氮初始质量浓度越高,吸附量越大;温度越低越有利于沉积物对硝态氮的吸附;扰动速率偏高和偏低都会使吸附量减小。吸附过程在60 min后逐渐达到稳定,其吸附过程符合准二级动力学模型方程和Langmuir等温吸附方程,以化学吸附和单分子层吸附为主。SEM表征分析表明,沉积物呈粗糙多孔的片层结构,具有较多的吸附位点;FTIR表征分析表明,沉积物对硝态氮有一定的吸附作用,沉积物中含有羟基、酰基等多种基团,与硝态氮反应的机理主要表现为置换和吸附作用。     

Determination of heterogeneous reaction mechanisms: A key milestone in dust explosion modelling

Reaction kinetics is fundamental for modelling the thermal oxidation of a solid phase, in processes such as dust explosions, combustion or gasification. The methodology followed in this study consists in i) the experimental identification of the reaction mechanisms involved in the explosion of organic powders, ii) the proposal of simplified mechanisms of pyrolysis and oxidation, iii) the implementation of the model to assess the explosion severity of organic dusts. Flash pyrolysis and combustion experiments were carried out on starch (22 μm) and cellulose (53 μm) at temperatures ranging from 973 K to 1173 K. The gases generated were collected and analyzed by gas chromatography. In this paper, a semi-global pyrolysis model was developed for reactive systems with low Damköhler number. It is in good agreement with the experimental data and shows that both carbon monoxide and hydrogen are mainly generated during the pyrolysis of the solid, the generation of the latter compound being greatly promoted at high temperature. A simplified combustion model was also proposed by adding two oxidation reactions of the pyrolysis products. In parallel, flame propagation tests were performed in a semi open tube in order to assess the burning velocity of such compounds. The laminar burning velocity of cellulose was determined to be 21 cm s⁻¹. Finally, this model will be integrated to a predictive model of dust explosions and its validation will be based on experimental data obtained using the 20 L explosion sphere. The explosion severity of cellulose was determined and will be used to develop and adjust the predictive model.     

污泥中氮磷在灰潮土上的淋滤特性研究

污泥土地利用时,其中富含的氮、磷可能会对地下水造成污染.本研究通过测定模拟土柱淋洗液,分析了两种污泥中氮、磷在灰潮土中的迁移性.测定项目包括:pH、EC、硝态氮、全磷.结果表明,土壤淋洗液的pH变化不大,电导率、硝态氮、全磷则明显增大,并随淋洗次数的增多逐渐恢复到空白水平,而且淋洗液的电导率与硝态氮和全磷间存在较好的正相关关系.施用量程桥污泥控制在30%,竹园污泥在10%以内就不会对地下水造成氮、磷污染.     

青海湖氮素分布特征及其对藻类生长的影响

以青海湖水体的11个样点为研究对象,测定不同形态氮素(总氮、硝酸盐氮、亚硝酸盐氮、氨氮)质量浓度、藻类数量及叶绿素质量浓度,同时测定其他相关因子,并对氮素对藻类生长的影响进行分析。结果表明:青海湖水体中总氮、硝酸盐氮及氨氮质量浓度分别为0.80mg/L、0.28 mg/L和0.20mg/L,且湖心区(深水区)样点质量浓度大于岸边区(浅水区)样点,浅水区植物生长及沙柳河等外源输入均对氮素质量浓度有一定程度的影响;亚硝酸盐氮质量浓度为9.70μg.L-1,浅水区质量浓度高于深水区;浅水区氨氮的氧化作用可能是亚硝酸盐氮质量浓度在浅水区高于深水区的主要原因,同时溶解氧是此过程的限制因子;水体氮素与藻类数量为显著的负相关性,但与叶绿素质量浓度为显著正相关性。青海湖水体不同形态氮素分布具有不同特征,且氮素对藻类的生长和繁殖具有不同的影响。     

以硝酸盐为主要氮源的反硝化除磷细菌驯化

以活性污泥为种泥,通过序批式反应器(Sequencing Batch Reactor,SBR),在厌氧-缺氧-好氧交替的条件下驯化培养以硝酸盐为主要氮源的反硝化除磷细菌(Denitrifying Phosphorus-Accumulating Organisms,DPAO)。在330 d的培养时间内监测磷酸盐、硝酸盐和亚硝酸盐等常规指标,并研究驯化不同阶段的一个周期内各指标的变化及进行相应的动力学分析。结果表明,随着驯化的进行,厌氧阶段释磷速率逐渐增加,释磷量也相应增大,出水磷质量浓度最终维持在0.8mg/L,去除率达到91.8%,硝氮全部去除。通过对16S r RNA测序结果的比对,得到聚磷菌占总菌的76.93%,反硝化除磷菌占聚磷菌的一半以上。而聚糖菌仅占5.13%,聚磷菌成为优势菌种。此外,在整个驯化过程中,水质和环境条件的变化使出水中磷质量浓度出现波动,而出水硝氮的变化不大。研究表明,以硝酸盐作为主要氮源培养反硝化除磷细菌的方式是可行的,并有利于聚磷菌对聚糖菌的竞争,使聚磷菌成为优势菌种。     

Zero valent nano-sized iron/clinoptilolite modified with zero valent copper for reductive nitrate removal

Nitrates constitute one of the main toxic contaminants of groundwater. On the other hand, groundwater may be considered anoxic (oxygen concentration less than 9 μg L^?1). This fact justifies the use of nano zero valent metals for nitrate removal. In such conditions, zero valent metals are quite stable against oxidation due to the very low level of dissolved oxygen concentration. It has been shown that the performance of zero valent iron coated clinoptilolite zeolite for the reduction of nitrate anion in un-buffered conditions may be enhanced by coating small amounts of Cu⁰ onto the freshly prepared Fe⁰/zeolite composite. An optimum loading of Cu⁰ exists for which the rate of nitrate removal is maximal. For this optimal composition, the nitrite anion production curve with time passes through a maximum. Nitrite production, however, is slightly higher for the Cu modified zeolite. It has been shown that the nitrate removal process is only slightly dependent on the initial solution pH. In the temperature range of 20–60 °C, the process is controlled by both the liquid phase mass transfer and intrinsic reaction rate resistances. FESEM analysis of the zero valent metal/zeolite composite showed that upon the metal reduction reaction, an egg-shell distribution of zero valent metal in the zeolite agglomerate particle is produced.     

乳化炸药高压热分解试验研究

为分析压力在乳化炸药泵送事故中的影响,运用高压加速量热仪对乳化炸药、硝酸铵和含有10%水分的硝酸铵样品热分解特性进行研究。结果表明:压力对于乳化炸药,硝酸铵和含有10%水分硝酸铵样品的热分解有着显著的影响,压力条件下虽然起始分解温度基本没有变化,但是样品反应速率有了显著的升高,导致放热量增大。水分的存在阻碍硝酸铵的热分解,在乳化炸药配方中适当增加水份含量可以提高乳化炸药生产安全性。分析认为相比于温度,压力对于泵送事故的影响更为关键。     

杂质对硝酸铵水溶液临界爆炸温度的影响

利用自制装置对含杂质的硝酸铵水溶液临界爆炸温度进行测试研究.结果表明,Cl-单独作用在一定程度上抑制硝酸铵溶液的热分解,提高了其临界爆炸温度;pH值一定时,随着Cl-浓度的增大,硝酸铵水溶液的临界爆炸温度呈指数形式降低;Cl-浓度一定时,pH值越小,硝酸铵水溶液的临界爆炸温度越低;油脂会降低硝酸铵溶液的热稳定性.该结果...     

一体式好氧膜生物反应器的氮转化试验研究

一体式好氧膜生物反应器（Integrated aerobic membrane bio-reactor,简称IAMBR）内提供了世代时间较长的硝化菌生长环境，从而使得硝化作用增强。从氨氮浓度与亚硝酸氮浓度比值随天数变化，氨氮浓度与硝酸氮浓度比值随天数变化，亚硝酸氮浓度与硝酸氮浓度比值随天数变化角度分析了IAMBR内氮的转化情况，得出氨氮去除主要依靠膜生物反应器内的好氧污泥，并且IAMBR可用于去除氨氮的结论。