燃瓦斯气蓄热式加热炉再燃低氮改造数值模拟

为实现燃瓦斯气加热炉氮氧化物(NOx)排放低于200 mg/m3(O2体积分数3.5%)的要求,提出高效的再燃低氮改造方案.通过数值计算和工业试验相结合的方法对其进行验证.采用FLUENT软件计算不同再燃瓦斯气比例和当量比下,不同截面温度及NOx质量浓度分布,NOx生成还原特性和瓦斯气未燃尽率等.根据优化的数值计算结果对加热炉进行改造,进行连续一周的工业试验.结果表明:增加再燃比,燃烧空间高温区域比例降低,热力型NOx生成量减少且减幅增大,再燃作用对NOx的还原率先升高后降低.当再燃比为0.20时,再燃作用还原NOx的效率最高.增加再燃比或降低主燃区当量比将降低NOx浓度,但瓦斯气未燃尽率升高.通过与工业试验对比,验证了计算的可靠性.当再燃比为0.15~0.20,主燃区当量比为1.15~1.20时,NOx质量浓度最高值约160 mg/m3,均值约130 mg/m3(O2体积分数3.5%),且瓦斯气未燃尽率较低.     

NOx emission characteristics of hydrogen internal combustion engine

In order to investigate the NOxemission of hydrogen internal combustion engines.A test system for four-cylinder intake port-fuel-injection hydrogen internal combustion engine(H2ICE)is established to study the effect of fuel-air equivalence ratio,ignition advance angle,engine speed and exhaust gas recirculation on NOx emission.Experimental results show that the fuel-air equivalence ratio is the key factor to NOxemission,NOxemission concentration is always higher than 8 000×10-6 when the fuel-air equivalence ratio is larger than 0.8and lower than 500×10-6 when the fuel-air equivalence ratio is smaller than 0.5.The ignition advance angle and engine speed also play important roles on NOxemission formation.EGR is an useful method to reduce NOx emission concentration at large fuel-air equivalence ratio especially when engine speed is low and EGR ratio is high.     

华南沿海城市PM2.5污染特征及来源解析

基于2017年12月25日至2018年1月16日1 h时间分辨率的在线监测数据,对华南沿海城市——阳江市的大气PM_2.5质量浓度、化学组分和来源进行了分析.结果表明,采样时段阳江市PM_2.5中主要化学组分为OM、NO^-₃、SO^2-₄、NH⁺₄和EC,质量浓度占比分别为32.75%、25.59%、16.41%、12.37%和4.82%.相比清洁过程,两次污染过程期间NO^-₃质量浓度均为清洁过程时段的6倍以上,增量明显高于其他组分,占比则均为清洁过程时段的2倍以上,分别占29.38%和30.81%.PMF解析结果表明,二次转化源是最主要的源,其分担率高达51.41%,其中NO_x二次转化源分担27.18%,是阳江市PM_2.5分担率最大的二次转化源.首要的一次排放源是机动车源(15.11%).污染过程期间NO_x二次转化源的分担率显著提升,从11.85%分别增至33.15%和36.96%,是阳江市大气PM_2.5污染形成的主要原因.本研究表明阳江市冬季PM_2.5污染特征已类似于大型和特大城市,即面临严峻的二次污染,应着重加强对硝酸盐的防治,同时注重机动车管控.     

Effect of exhaust gas recirculation and intake pre-heating on performance and emission characteristics of dual fuel engines at part loads

Achieving simultaneous reduction of NO _x , CO and unburned hydrocarbon (UHC) emissions without compromising engine performance at part loads is the current focus of dual fuel engine research. The present work focuses on an experimental investigation conducted on a dual fuel (diesel-natural gas) engine to examine the simultaneous effect of inlet air pre-heating and exhaust gas recirculation (EGR) ratio on performance and emission characteristics at part loads. The use of EGR at high levels seems to be unable to improve the engine performance at part loads. However, it is shown that EGR combined with pre-heating of inlet air can slightly increase thermal efficiency, resulting in reduced levels of both unburned hydrocarbon and NO _x emissions. CO and UHC emissions are reduced by 24% and 31%, respectively. The NO _x emissions decrease by 21% because of the lower combustion temperature due to the much inert gas brought by EGR and decreased oxygen concentration in the cylinder.     

Effect of Moisture on Combustion Characteristics of High-Moisture-Content Coal Slime

水分对高水分煤泥燃烧特性的影响

王永堂1,王辉2,刘松霖2,杨海瑞3,吴江全2

（1. 哈电集团中央研究院,哈尔滨150028;2. 哈尔滨工业大学 能源科学与工程学院,哈尔滨 150001;3清华大学 能源与动力工程系,北京 100084）

摘要：

本文研究了煤泥中水分对其燃烧特性及孔隙结构变化的影响。在实验室规模的流化床反应器上获得了水分对床温变化、燃烧效率及NOx与SO2排放的作用规律,揭示了最低床温会随水分的增加而降低,而最高床温的变化与此不同。而且,随着水分的增加,观测到的烟气黑度增加并生成更多CO,从而导致煤泥燃烧效率降低。然而,水分的存在对降低NOx和SO2有利,随着水分增加,NOx和SO2的生成量趋于降低。水分对煤泥燃烧过程的影响主要体现在燃烧初期水分剧烈蒸发形成了较大的水蒸气通道,有利于水分的蒸发和散失,也有利于水分与煤燃烧产物的反应,例如CO的生成,NOx与SO2的降低等。由水蒸气作用形成的大孔会随着水分减少而减少,纳米级孔主要是蒸发结束后挥发分燃烧与焦炭形成过程所致,并会随着水分的减少而增加。

关键词：水分;燃烧特性;孔隙结构;煤泥

     

基于空气质量模拟的江苏省大气污染物排放清单比较研究

大气污染物排放清单是空气质量模拟和空气污染治理的重要依据.本研究比较分析了两套覆盖江苏省的2017年大气污染物排放清单，即分别由上海市环境科学研究院、江苏省环境科学研究院编制的"长三角清单"和"江苏省清单"，并结合区域空气质量模型CMAQ评估不同清单对长三角地区2017年1、4、7、10月的空气质量模拟的影响.清单比较结果表明，除二氧化硫（SO₂）以外，江苏省清单估算的各污染物排放量较长三角清单低.通过与观测数据比较，发现两套清单对SO₂、氮氧化物（NO_x）、臭氧（O₃）和细颗粒物（PM_2.5）的模型模拟性能均较好.江苏省清单与长三角清单两者的模拟结果空间分布接近，其中江苏省清单模拟的PM_2.5和O₃在长三角多数地区略低于长三角清单的模拟结果（1月O₃除外）.江苏省清单与长三角清单均能够用于空气质量模式模拟，可为江苏地区的细颗粒物和光化学烟雾污染的控制策略制定提供参考.     

Role of ammonium sulfate in sulfurization flotation of azurite: Inhibiting the formation of copper sulfide colloid and its mechanism

In this study, the role of (NH₄)₂SO₄ during the sulfurization of azurite and its response to flotation were investigated. The flotation results showed that adding (NH₄)₂SO₄ prior to sulfurization decreased the formation of colloid in flotation pulp, and the floatability of the suppressed azurite caused by excess sodium sulfide was restored. After adding (NH₄)₂SO₄ prior to sulfurization, the formation of Cu(NH₃)_n²⁺ intermediate products changed the path of the sulfurization reaction, which slowed the direct impact of HS^? on the azurite surface. The nucleation rate was reduced, and the growth of copper sulfide crystal was improved. Covellite (syn, CuS) with larger crystal grains was formed on the azurite surface, thereby enhancing the mechanical stability of copper sulfide products onto the mineral surface. Therefore, the generated copper sulfide colloid significantly reduced, ultimately promoting the effective adsorption of xanthate on the azurite surface.     

生物菌剂对蔬菜产量及菜地活性气态氮排放的影响

为了明确尿素配施生物菌剂对设施菜地活性气态氮(N₂O和NH₃)排放以及蔬菜产量的影响,分别采用静态暗箱-气相色谱法和通气室-氨捕获法对设施菜地N₂O和NH₃排放进行了原位观测.试验设置3个处理:空白处理(CK)、施用尿素(U)、尿素与生物菌剂配施(EM).结果表明:与CK处理相比,U处理蔬菜产量、N₂O排放量、NH₃排放量、活性气态氮累积排放量和活性气态氮排放强度分别增加了3.65%、43.40%、16.90%、38.60%和35.71%.与CK处理相比,EM处理蔬菜产量、N₂O排放量、NH₃排放量、活性气态氮累积排放量和活性气态氮排放强度分别增加了22.28%(P<0.05)、103.46%(P<0.05)、45.07%(P<0.05)、92.80%(P<0.05)和57.14%(P<0.05),差异显著.考虑EM处理显著增加了活性气态氮,并由此带来的环境损益,生物菌剂在菜地中的施用还需要进一步评估.     

重污染天气下大气污染排放源强的快速估算方法

针对以往大气污染排放源强估算时多采用排放因子法计算大气排放源强,存在着受排放源类别不全、排放清单的不确定性、人力物力财力因素制约,以及企业上报数据不准确,存在偷排多排的情况等问题,利用重污染天气城市各区域空气质量数据,采用泰森多边形确定区域特征长度、大气箱式模型估参的方法,快速确定各污染物的排放源强,建立较为简便的大气污染排放源强估算模式.对哈尔滨市采暖期的大气污染源强估算结果表明:NOx、SO2、CO总的估算排放源强为436.33,154.82和8 566.82 t/d.对源强估算算法进行精确度检验,其相对中值误差小于30%,适合作为区域大气污染物排放模拟与预测的模型理论基础.     

APEC期间河北省大气污染及PM_(2.5)来源变化特征

研究包括京津冀地区在内的13个城市APEC会议前、中、后三时段的大气污染特征,并通过PM_(2.5)采集和成分分析,对不同时段PM_(2.5)的来源进行解析。结果显示:与APEC会议前相比,APEC期间北京、石家庄、承德、廊坊、邢台、张家口、邯郸、唐山、天津、衡水、沧州、秦皇岛和保定的PM_(2.5)分别下降了58.7%、52.9%、50.1%、47.3%、43.5%、36.7%、34.9%、33.4%、29.6%、26.9%、20.2%、19.9%和12.8%,平均降低了35.9%,高于SO2、NO_2和CO的浓度降低比例(分别为17.5%、21.3%和22.0%);与APEC会议前相比,APEC期间邯郸市的NO_3~-、SO_4~(2-)和NH_4~+分别降低了32.0%、32.9%和39.1%;APEC会议前和APEC期间PM_(2.5)的来源变化不大,会议后,燃煤/生物质燃烧源、冶金、燃油源上升至21.7%、14.0%和20.8%,而扬尘源、工业源、二次源降至12.6%、11.8%和19.2%。     

Changes of hydrochemical composition and heavy metals concentration in shallow groundwater from karst hilly areas in Guiyang region, China

The quality changes of shallow groundwater from karst hilly areas in Guiyang region of China impacted by the urbanization were investigated. The results show that the major ions in shallow groundwater from the karst hilly areas are mainly composed of HCO₃ ⁻, SO₄ ²⁻, Ca²⁺ and Mg²⁺, and the concentrations scopes of NO₃ ⁻, Cl⁻, K⁺ and Na⁺ of the groundwater in agricultural, residential and industrial areas are 4.5–9.6, 2.8–7.1, 3.9–6.3 and 2.5–4.9 times higher than those in the forest areas, respectively. The concentrations of As, Pb and Cd of shallow groundwater in the industrial areas are also significantly enhanced, followed by those in the residential areas and the agricultural areas. The concentrations of NO₃ ⁻, SO₄ ²⁻, As, Pb and Cd of the groundwater in the industrial areas and those of NO₃ ⁻, SO₄ ²⁻, As and Cd of shallow groundwater in the residential areas reach grade III of the Groundwater Quality Standard of China (GB/T 14848-93), while the concentration of NO₃ ⁻ in the groundwater from the industrial areas exceeds grade V. With the process of urbanization, NO₃ ⁻ is the key factor to influence the groundwater quality in karst hilly areas, followed by SO₄ ²⁻, As, Pb and Cd.     

Evaluation of metal-doped manganese oxide octahedral molecular sieves in catalytic reduction of NOx from cigarette mainstream smoke

A series of Ag, Cu and Co-doped manganese oxide octahedral molecular sieves (OMS-2) were synthesized and evaluated to remove nitrogen oxides (NO _x ) from cigarette mainstream smoke. The three kinds of catalysts were added to cigarettes for studying the capabilities of reducing NO _x from cigarette mainstream smoke. The catalysis and reduction of NO in laboratory were studied. A mechanism for NO _x catalytic reduction from burning cigarettes with the catalysts adding to cigarettes was described. The catalysts show excellent catalytic activity for NO _x removal, especially the Ag-doped OMS-2 catalyst. 0.5% (mass fraction) Ag-doped OMS-2 catalyst has the best ability to remove NO _x from cigarette mainstream smoke. The use of Ag-doped OMS-2 as catalyst for removing carcinogenic compounds from cigarette smoke will be an effective strategy to protect the environment and public health.     

不同再燃技术降低燃煤锅炉NOx排放的对比分析

目前降低NO_x生成与排放技术中,再燃技术具有改造费用低、锅炉运行效率高、降低NO_x排放效率显著等特点。通过分析超细粉、生物质气、天然气和H₂作为再燃燃料的机理、影响因素、优缺点和实际应用情况,比较了不同再燃技术降低NO_x排放的技术参数和经济性,发现H₂再燃技术降低燃煤锅炉NO_x排放具有较大优越性。     

Selective catalytic reduction of NO with NH3 over sol-gel-derived CuO-CeO2-MnOx/γ-Al2O3 catalysts

Granular CuO-CeO₂-MnO _x /γ-Al₂O₃ catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO₂-MnO _x /γ-Al₂O₃ catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH₃ and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO₂-MnO _x /γ-Al₂O₃ catalysts is 300–400 °C. The catalysts maintain nearly 100% NO conversion at 350 °C. The °C NH₃ oxidation experiments show that both NO and N₂O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH₃, which improves the denitrification activity at low temperature. The over-oxidation of NH₃ at high temperature is the main cause leading to a decrease in the NO conversion. The NH₃ and NO desorption experiments show that NH₃ and NO can be adsorbed on CuO-CeO₂-MnO _x /γ-Al₂O₃ granular catalysts. The transient response of NH₃ and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process. Foundation item: Projects (50776037, 50721005) supported by the National Natural Science Foundation of China     

基于GAM的北京PM_(2.5)浓度变化的影响因素研究

为辨识与测度不同影响因子对PM_(2.5)浓度变化的作用机理,以2015年北京PM_(2.5)浓度时间演变模式为基础,建立PM_(2.5)与各大气污染物(PM_(10)、SO_2、NO_2、CO、O_3)及气象因素(日均温度、风力、风向)的GAM模型,探索不同因素对PM_(2.5)浓度变化的影响作用。结果显示:(1)北京PM_(2.5)浓度具有夏秋季低、春冬季高的时间分布特点;(2)2015年北京PM_(2.5)浓度变化与PM_(10)、SO_2、NO_2、CO大体呈线性正相关,且正相关程度由强到弱为:COPM_(10)SO_2NO_2,而与O_3、温度和风因子的关系更为复杂;(3)GAM模型的拟合优度R~2为0.725,线性回归模型的拟合优度R~2为0.519,相比较,GAM模型对PM_(2.5)浓度变化的解释度提高了20.6%。研究表明,GAM模型对于建立PM_(2.5)浓度变化与影响因素间综合性复杂关系更灵活、更可靠,优于线性回归模型。     

Octacalcium phosphate fiber synthesized by homogeneous precipitation method

Calcium phosphate fiber was synthesized by homogeneous precipitation method using urea as precipitation agent. Effects of the reactant concentration and hydrothermal temperature on the calcium phosphate morphology and composition were studied using SEM, FTIR and XRD. It is found that fine octacalcium phosphate(OCP)fiber can be synthesized when the reactant concentrations are 0.167 mol/L for Ca(NO3)2, 0.1 mol/L for (NH4)2HPO4, and 0.6-0.7 mol/L for (NH2)2CO, respectively, with the initial reactant solution pH value around 2.2, hydrothermal temperature 90 ℃ and termination reaction at pH value around 5.0. At very low urea concentration, the product size distribution is highly inhomogeneous, however, at an excessively high concentration the product becomes larger and shorter and a mixture of OCP and hydroxyapatite (HA). Increasing the hydrothermal temperature is favorable to the fast precipitation of OCP, higher productivity and finer product.     

Synthesis of γ-Al2O3 nanoparticles by chemical precipitation method

Highly pure active γ-Al₂O₃ nanoparticles were synthesized from aluminum nitrate and ammonium carbonate with a little surfactant by chemical precipitation method. The factors affecting the synthesis process were studied. The properties of γ-Al₂O₃ nanoparticles were characterized by DTA, XRD, BET, TEM, laser granularity analysis and impurity content analysis. The results show that the amorphous precursor Al(OH)₃ sols are produced by using 0.1 mol/L Al(NO₃)₃ · 9H₂O and 0.16 mol/L (NH₄)₂CO₃ · H₂O reaction solutions, according to the volume ratio 1.33, adding 0.024% (volume fraction) surfactant PEG600, and reacting at 40 °C, 1 000 r/min stirring rate for 15 min. Then, after stabilizing for 24 h, the precursors were extracted and filtrated by vacuum, washed thoroughly with deionized water and dehydrated ethanol, dried in vacuum at 80°C for 8 h, final calcined at 800 °C for 1 h in the air, and high purity active γ-Al₂O₃ nanoparticles can be prepared with cubic in crystal system, O _H ⁷ -FD3M in space group, about 9 nm in crystal grain size, about 20 nm in particle size and uniform size distribution, 131. 35 m²/g in BET specific surface area, 7 – 11 nm in pore diameter, and not lower than 99.93% in purity. Foundation item: Project(03JJY3015) supported by the Natural Science Foundation of Hunan Province     

功能型离子液体制备及应用的试验研究

综述了离子液体的制备方法及辅助合成手段的研究进展,包括一步合成法、两步合成法、微波合成法、超声波合成法,并介绍了其在CO_2,SO_2,NO_x及重金属Hg等多种污染物联合脱除技术中的应用.     

基于CMAQ-MCM模型的长三角地区夏季臭氧和大气氧化性影响的研究

传统的空气质量模型多使用简化的光化学反应机制来模拟大气污染物的形成.这些机制主要基于烟雾箱实验拟合的反应速率和产物来模拟二次产物（如臭氧（O₃））前体物的氧化反应，具有一定的不确定性，导致模拟结果产生偏差.针对该问题，本研究将详细的大气化学机理（MCMv3.3.1）与美国国家环境保护局研制的第三代空气质量预报和评估系统CMAQ相结合（CMAQ-MCM），模拟研究长三角地区2015年8月27—9月5日臭氧高发时段的空气质量.CMAQ-MCM模型可以较好地模拟长三角地区6个代表城市O₃和其前体物随时间的变化趋势.对模拟的O₃日最大8 h平均浓度的统计分析表明，徐州表现最好（标准平均误差=-0.15，标准平均偏差=0.23）.在长三角地区，居民源对挥发性有机物（VOCs）的贡献最大，占39.08%，其次是交通运输（33.25%）和工业（25.56%）.能源对总VOCs的贡献最小，约为2.11%.对活性氧化氮（NO_y）的分析表明，其主要组分是NO_x（80%），其次是硝酸（HNO₃）（<10%）.O₃的空间分布与NO_y和NO_x非常相似.HCHO等其他氧化产物的分布与NO_x相似，这很可能是由于在高NO_x条件下VOCs氧化产生的产物.甲基乙烯基酮（MVK）和甲基丙烯醛（MACR）的空间分布与自然源VOCs （BVOCs）非常相似，表明长三角地区MVK和MACR主要由BVOCs氧化生成.长三角地区受到人为源和自然源排放相互作用的影响.     

Adsorption of NO and NH3 over CuO/γ-Al2O3 catalyst

The selective catalytic reduction reaction belongs to the gas-solid multiphase reaction, and the adsorption of NH₃ and NO on CuO/γ-Al₂O₃ catalysts plays an important role in the reaction. Performance of the CuO/γ-Al₂O₃ catalysts was explored in a fixed bed adsorption system. The catalysts maintain nearly 100% NO conversion efficiency at 350 °C. Comprehensive tests were carried out to study the adsorption behavior of NH₃ and NO over the catalysts. The desorption experiments prove that NH₃ and NO are adsorbed on CuO/γ-Al₂O₃ catalysts. The adsorption behaviors of NH₃ and NO were also studied with the in-situ diffusion reflectance infrared Fourier transform spectroscopy methods. The results show that NH₃ could be strongly adsorbed on the catalysts, resulting in coordinated NH₃ and NH₄⁺ NO adsorption leads to the formation of bridging bidentate nitrate, chelating bidentate nitrate, and chelating nitro. The interaction of NH₃ and NO molecules with the Cu²⁺ present on the CuAl₂O₄ (100) surface was investigated by using a periodic density functional theory. The results show that the adsorption of all the molecules on the Cu²⁺ site is energetically favorable, whereas NO bound is stronger than that of NH₃ with the adsorption site, and key information about the structural and energetic properties was also addressed.