惰性粉体对蔗糖粉尘最小点火能的影响研究

为了预防蔗糖粉尘爆炸,利用1.2 L哈特曼管研究了NH₄H₂PO₄与Al(OH₄对蔗糖粉尘爆炸的抑制作用。在蔗糖粉尘质量分数一定的条件下,通过改变 NH₄H₂PO₄与Al(OH)₄的粒径和质量分数,测定其对蔗糖粉尘爆炸的抑制效果。结果表明:随着NH₄H₂PO₄和Al(OH)₄质量分数的增加,粒径的减小,蔗糖粉尘的最小点火能均逐渐增大,当惰性粉体增加到一定质量时,蔗糖粉尘被完全惰化,在蔗糖粉尘中分别加入粒径为48~74,38~47,25~37 μm的NH₄H₂PO₄和Al(OH)₄,3种粒径的NH₄H₂PO₄使蔗糖粉尘完全惰化的质量分数分别为40%,35%,30%,3种粒径的Al(OH)₃使蔗糖粉尘惰化的质量分数均为60%。因此(NH₄)H₂PO₄抑制蔗糖粉尘爆炸的效果比Al(OH)₃更显著。     

Fire and explosion risk assessment for large-scale oil export terminal

Now in Russian Federation and other countries large-scale oil terminals (volume of one tank exceeds 100 000 m³, total volume of tanks exceeds 300 000 m³) are designed and constructed. Therefore fire safety of such objects becomes a very important task, solution of which is hardly possible without detail fire risk assessment. This study is aimed to a solution of this problem. Potential, individual and social risks were calculated. The potential risk was defined as a frequency of occurrence of hazardous factors of fires and explosions in a given point of space (the so-called risk contours). The individual risk was defined as a frequency of injuring a given person by hazardous factors of fires and explosions. Time of presence of this person in hazardous zones (near the hazardous installation) is taken into account during calculations of the individual risk. Social risk was defined as a dependence of frequency of injuring a given number of people by hazardous factors of fires and explosions on this number. In practice the social risk is usually determined on injuring not less than 10 people.

The oil terminal under consideration includes the following main parts: crude oil storage consisting of three tanks of volume 100 000 m³ each, input crude oil pipeline of diameter 0.6 m, crude oil pumps, output crude oil pipeline of diameter 0.8 m, auxiliary buildings and facilities. The following main scenarios of tank fires have been considered: rim seal fire, pool fire on a surface of a floating roof, pool fire on a total cross-section surface of the tank, pool fire in a dyke, explosions in closed or semiclosed volumes. Fires and explosions in other parts of the terminal are also taken into account. Effects of escalation of accidents are considered.

Risk contours have been calculated both for the territory of the terminal and for the neighbouring space. The potential risk for the storage zone is near 10⁻⁴–10⁻⁵ year⁻¹, and at a distance 500 m from the terminal the potential risk values do not exceed 10⁻⁶ year⁻¹. The values of the individual risk for various categories of workers are in the range of 10⁻⁵–10⁻⁶ year⁻¹. Because of low number of the workers on the terminal and large distances to towns and villages the social risk value is negligible. These risk values are consistent with practice of the best oil companies, and fire hazard level of the terminal can be accepted as tolerable.     

Evaluation of the explosibility of malt grain dust based on static electrification during pneumatic transportation

The possibility of dust explosions by static electricity in a malt grain silo was investigated. Two kinds of experimental equipment were applied. One was to supply electrostatic charge in order to investigate the charge build up characteristics. The other was to transport the malt grain pneumatically in order to investigate the frictional charge accumulation in the transportation system.

The particle charge of the pulverized malt grain was in the order of 10⁻¹⁴ C. The particle charge of the malt grain was in the order of 10⁻⁹ C and the pipe charge in the transport system was also in the order of 10⁻⁹ C. The charge accumulated on both the pulverized particle and the grain particle were small in view of the incendiary potentiality. However, attention must be paid when the particles are dumped into isolated space. There might be a charge accumulation that will lead to the ignition of the dust cloud.     

MnO2/FeOOH复合材料对水中U(Ⅵ)的去除及机理试验研究

采用化学沉积法制备了二氧化锰/羟基氧化铁(MnO2/FeOOH)复合材料,并将其用于吸附去除水中的放射性重金属铀。通过静态吸附试验,考察了Fe/Mn物质的量比、pH值、吸附时间和干扰离子等因素对MnO2/FeOOH吸附U(Ⅵ)效果的影响,利用扫描电镜-能谱分析(SEM-EDS)、X射线衍射(XRD)、拉曼光谱(Raman)、红外光谱(FT-IR)和X射线光电子能谱(XPS)对材料结构和形貌进行表征,并分析其吸附机理。结果表明,在投加量为150 mg/L、温度为30℃、U(Ⅵ)初始质量浓度为10 mg/L、pH值为5、Fe/Mn物质的量比为1/2及吸附时间为120 min的条件下,MnO₂/FeOOH对U(Ⅵ)的去除率最大可达97.7%,且pH值对铀去除效果的影响最为明显。MnO₂/FeOOH对U(Ⅵ)吸附动力学符合准二级动力学模型,吸附等温线均能符合Langmuir和Freundlich模型,且最大吸附容量达260.34 mg/g。干扰离子试验表明,SO₄^2-、CO₃^2-和Fe³⁺对MnO₂/FeOOH吸附U (VI)几乎没有影响,而Ca²⁺和Cu²⁺具有明显的抑制作用,且抑制随浓度的增大而增强。FTIR和XPS分析表明MnO2/FeOOH对U(Ⅵ)的主要作用机制为表面羟基、Mn-O与铀的配位作用。因此,MnO2/FeOOH可作为一种潜在的铀吸附材料。     

Model for predicting hydroxylamine nitrate stability in plutonium process solutions

A mathematical model is described that may be used to determine the safety of hydroxylamine nitrate (HAN) solutions used in solvent extraction purification of plutonium. The most significant hazard associated with hydroxylamine use in processing plutonium is its rapid, autocatalytic reaction with nitric acid which can result in an explosion or pressurization of process vessels with radiological consequences to humans. In addition, heat is produced by the reaction that could potentially ignite process solvents. The HAN decomposition reaction can occur only under specific process conditions (temperature; HAN, plutonium and nitric acid concentrations) and the model is used to identify these conditions so that they can be avoided. A kinetics model has been developed using all of the known significant reactions that could occur in process solutions containing HAN and nitric acid as well as plutonium and iron. The reaction kinetics data (rate laws, rate constants, activation energies) used in the model were obtained from chemical literature sources. The model shows that the autocatalytic HAN reaction with nitric acid is very rapid and is catalyzed by Pu(III) and Fe(II) in process solutions. High temperatures and nitric acid concentrations also promote the reaction.     

Modelling Thiocyanate Adsorption onto Surfactant-Modified Coir Pith, an Agricultural Solid ‘Waste’

Thiocyanate (SCN⁻) is used in many industrial processes and is found in industrial wastewaters. Adsorptive removal of thiocyanate by surfactant-modified coir pith, an unwanted byproduct of coir fibre industry was studied. Cationic surfactant, hexadecyltrimethylammonium bromide was used as modifier. Optimum pH for maximum adsorption of SCN⁻ was found to be 2.0. Langmuir, Freundlich and Dubinin Radushkevich (D-R) isotherms were used to model the adsorption equilibrium data and the system followed all the three isotherms and the adsorption capacity of the adsorbent was found to be 8.6 mg g⁻¹. Kinetic studies show that the adsorption obeyed second order. Desorption studies showed that upto 90% recovery of SCN⁻ from the spent adsorbent was feasible. Effect of foreign anions on the adsorption of SCN⁻ was also examined.     

The effect of vent ducts on the reduced explosion pressures of vented dust explosions

An investigation into the effects of vent ducts on reduced explosion pressures is described. Experiments were made using an 18.5m³ explosion vessel and a modified 20 1 sphere, with dusts having K_st values ranging from 144 bar ms⁻¹ to 630 bar ms⁻¹. The vent area/vessel volume ratio bursting pressure of the vent cover, and the length to diameter ratio of the vent duct have been varied. Straight vent ducts, and ducts containing sharp 45° and 90° bends have been used.A simple model to describe the effect of vent ducts on the reduced explosion pressure has been derived and compared with the experimental results. Agreement is shown to be satisfactory in nearly all cases. A comparison between the experimental results and guidance on the effect of vent ducts already available in the literature is discussed.     

Methods for sizing dust explosion vent areas: a comparison when reduced explosion pressures are low

Various methods that are available for estimating the explosion venting requirements of weak dust handling equipment are compared. The regression analysis that Simpson has performed on the well known K_st nomographs is shown to extend to K_st values less than 50 bar m s⁻¹ and to reduced explosion pressures between 1.1 bar a and 1.2 bar a.     

Absorption kinetics of NO from simulated flue gas using Fe(II)EDTA solutions

The absorption of NO encountering flue gases in aqueous solutions of Fe(II)EDTA was determined using a semi-batch stirred tank with a plane gas–liquid interface at 50 °C. The concentrations of NO, SO₂ and O₂ in the feeding stream were 300–800 ppm, 500–2200 ppm and 0–20%, respectively. The pH value of the Fe(II)EDTA solutions varied from 3 to 11. The concentrations of Fe(II)EDTA were maintained between 0.01 and 0.05 M. Experiments were performed to evaluate the effect of operating parameters on the NO absorption rate, the reaction kinetics of the reactants in gas and liquid phases, and the effect of competition between various reactants on the mass transfer rate in the NO removal system. Results indicate that the average reaction rate constant is 3.70 × 10⁷ M⁻¹ s⁻¹. Adding NaOH does not increase the absorption capability of Fe(II)EDTA. The presence of O₂ decreases the NO absorption rate with Fe(II)EDTA. The absorption rate of NO with Fe(II)EDTA decreases at low concentrations of SO₂, but increases at high concentrations.     

Scaling parameters for vented gas and dust explosions

Results of experiments or calculations for vented explosions are usually presented by expressing a term containing the peak (reduced) pressure as a function of a vent parameter. In gas explosions, the reactivity of the system has been typically characterized through an effective burning velocity, u_f. In the case of dust explosions, a normalized peak rate of pressure rise, K(=V^1/3(dp/dt)_max), has been used instead. Depending on the chosen approach, comparisons between systems with the same “reactivity” take different meanings. In fact, correlation formulas resulting from these two approaches imply different scaling between important system parameters. In the case of a constant-u_f system, and for sufficiently large vent areas, the reduced pressure, Δp_r, is approximately proportional to the square of the peak unvented pressure, Δp_m. On the other hand, correlations developed for constant-K systems imply proportionality of Δp_r with Δp_m raised to a power between −5/3 and −1, with the exact value depending on the assumptions made on the shape of the pressure profile. While the ultimate resolution of the details of the scaling may require recourse to experiments, this theoretical analysis offers a tool for the planning of such experiments and for the interpretation of their results. The paper provides a discussion of these scaling issues with the help of predictions from an isothermal model of vented explosions.     

Evaluation of limits for effective flame acceleration in hydrogen mixtures

Results of experiments and data analysis on turbulent flame propagation in obstructed channels are presented. The data cover a wide range of mixtures: H₂/air, H₂/air/steam (from lean to rich) at normal and elevated initial temperatures (from 298 to 650 K) and pressures (from 1 to 3 bar); and stoichiometric H₂/O₂ mixtures diluted with N₂, Ar, He and CO₂ at normal initial conditions. The dataset chosen also covers a wide range of scales exceeding two orders of magnitude. It is shown that basic flame parameters, such as mixture expansion ratio σ, Zeldovich number β and Lewis number Le, can be used to estimate a priori a potential for effective flame acceleration for a given mixture. Critical conditions for effective flame acceleration are suggested in the form of correlations of critical expansion ratio σ^* versus dimensionless effective activation energy. On this basis, limits for effective flame acceleration for hydrogen combustibles can be estimated. Uncertainties in determination of critical σ^* values are discussed.     

Experimental study of flame acceleration and the deflagration-to-detonation transition under conditions of transverse venting

Results of experiments on critical conditions for flame acceleration and the deflagration-to-detonation transition in tubes with transverse venting are presented. Tests were made with hydrogen mixtures in two tubes (inner diameter of 46 and 92 mm) with obstacles. Ratios of vent area to total tube area were 0.2 and 0.4. Venting was shown to influence flame acceleration significantly. The greater the vent ratio, the more reactive the mixture necessary for development of fast flames. Critical conditions for flame acceleration in tubes with venting, expressed through a critical mixture expansion ratio σ_cr, were found to be σ_cr/σ₀1+2, where σ₀ is the critical value for a closed tube. Critical conditions for detonation onset in a vented tube were found to be very close to those in a closed tube with similar configuration of obstacles.     

An influence of oxygen content in an oxidizing atmosphere on inhibitive action of fluorinated agents on a hydrogen flame

An experimental investigation of the influence of inhibitors of various chemical natures on flammability limits in mixtures H₂+oxidizer (O₂+N₂)–suppressant (C₂HF₅; CHF₃; C₄F₁₀; inhibitor AKM, which is a mixture of olefins) was carried out. Compositions of N₂ and O₂ with elevated (25 vol%) and reduced (15 vol%) oxygen concentrations and air were used as oxidizing atmospheres. Experiments were done at room temperature and atmospheric pressure. Flammability limits were determined in a closed vessel of volume of 4.2 dm³ (internal diameter 20 cm). Mixtures were prepared immediately in the preliminary evacuated reaction vessel by partial pressures. The mixtures were ignited by an electrical spark of energy near 1 J in the center of the reaction vessel. A flame propagation was detected by a pressure transducer. Twelve flammability curves were measured, which allowed to compare effectiveness of the inhibitors at various oxygen contents in the atmosphere. A qualitative analysis of the obtained results was done, which showed an important role of an inhibitor regeneration.     

海州露天矿采空区地表CO2通量的试验研究

为探究海州露天矿东邦废弃采空区自然发火状态,基于采空区遗煤自燃特性和气体扩散理论,采用智能土壤气体通量监测系统,以月为单位,对东邦自燃采空区上覆地表CO₂通量开展长周期、多测点连续性监测试验;根据试验区域内地表CO₂通量和土壤温度分布特征,探究地下火区释放CO₂的地表涌出范围和变化情况;同时,着眼于温室气体排放的评估,计算试验区域内的CO₂涌出量,并分析其随时间的变化特征。结果表明:地表CO₂通量与土壤温度有明显正相关性;试验区域地表CO₂高通量区域呈逐月扩大和递增的趋势;CO₂涌出量随月份逐渐递增,试验区域年CO₂涌出量约为3.6×10⁶ m³。     

水泥窑用低氮燃烧器燃烧特性的试验研究

基于水泥生产线NO_x排放机理及控制方法,设计、研发了一种新型水泥窑用低氮燃烧器,并分析了天然气、煤制气及混合气的燃烧特性及其污染物的排放特性。结果表明:在过量空气系数α为1.2、二次风占比β为0.6时,新型低氮燃烧器燃烧天然气的效果较好,NO_x排放量为53 mg/m³,CO排放量为22 mg/m³;在相同燃烧条件下,煤制气燃烧温度及NO_x排放量比天然气高,CO排放量低于天然气;在过量空气系数α为1.2、二次风占比β为0.8时,NO_x排放量为57 mg/m³,CO排放量为6 mg/m³;天然气和煤制气掺烧时,其燃烧特性介于两者之间,且掺烧煤制气可提高天然气的燃烧速率。     

石墨烯电极电活化过硫酸盐降解含酚废水研究

以苯酚为目标污染物,利用石墨烯电极自身性质及电活化共同作用下活化过硫酸盐(PDS)产生氧化性自由基降解苯酚,对影响苯酚降解的因素(包括电流密度、初始pH值、PDS浓度及影响反应的主导自由基)进行探讨。通过系统中加入一定量的甲醇和叔丁醇作为自由基猝灭剂的猝灭试验确定降解过程中的主导自由基。结果表明,在未通电情况下石墨烯电极对苯酚也具有去除作用,可以吸附苯酚。在通电情况下,由于电活化和石墨烯活化的双重作用,相比于单一石墨烯体系和单一PDS体系,石墨烯/PDS体系对苯酚的降解率显著提高,在n(PDS)∶n (phenol)为50∶1、苯酚初始质量浓度为25mg/L、pH值为11、电流密度为30 mA/cm²的条件下,在90 min内苯酚的降解率可达98.91%。通过淬灭试验确定在石墨烯/PDS降解苯酚体系中以硫酸根自由基为主(SO₄^-·)、羟基自由基(·OH)为辅。综上所述,在未通电情况下,石墨烯可以利用自身吸附作用去除苯酚,在通电情况下,石墨烯电极利用自身性质以及电活化活化过硫酸盐,与单一PDS体系和单一石墨烯体系相比,有效提高了过硫酸盐的活化程度,提高了苯酚的降解率。     

Study on decomposition of hydroxylamine/water solution

The risk evaluation of decomposition of hydroxylamine(HA)/water solution was studied experimentally. The thermal property of HA/water solution was studied from the calorimetric data obtained using the differential thermal analysis (DTA). The intensity of decomposition was studied on the basis of the results of the mini closed pressure vessel test (MCPVT) and the pressure vessel test (PVT) in addition to the steel tube test.The thermal property of HA/water solution was evaluated on the basis of results of the DTA. The heat-release onset temperatures using the no-treated stainless steel cells were more than 70 K below those measured using the GSC. This result implies that the heat-release onset temperature depends on the materials of sample cell. On the other hand, the heat of reaction did not depend on the materials of sample cell.The intensity of the thermal decomposition was investigated on the basis of results of the MCPVT, the PVT and the steel tube test. The intensity of the thermal decomposition increased as the HA concentration increased in the MCPVT. The intensity of the thermal decomposition increased greatly when the HA concentration was beyond 80wt.% in the MCPVT. It was elucidated that the thermal decomposition of HA 70wt.%/water solutions was very violent in the PVT. In addition, HA/water solutions of more than 80wt.% concentration could detonate in the steel tube test. HA 80 wt.% water/solution was easily detonated by a detonator without RDX in the steel tube test.In addition, the decomposition hazard of HA/water solution by the metal ion and the iron powder was studied in this paper. The thermal stability of HA85%/water solution with the iron ion or the iron powder was discussed on the basis of the heat-release onset temperature by the DTA. The heat-release onset temperatures decreased when the concentration of the iron ion or the iron powder increased in the DTA measurements. The reactiveness of HA/water solution with the metal ion of iron, manganese, nickel, chromium and copper was examined by measuring the mass loss of HA/water solution after the metal ion was added to HA/water solution at room temperature. The reactiveness of HA/water solution with the iron powder was also studied in this paper. The ferrous ion, the ferric ion and the iron powder reacted with HA/water solution. Ignition automatically began when the 0.2wt.% ferric ion solution was added to HA85wt.%/water solution. The mass loss rate depended on the HA concentration greater than the iron ion concentration. The mass loss rate increased when an amount of the iron powder increased. On the other hand, the decomposition reaction of HA85wt.%/water solution with Cu²⁺ was calm compared to that of the iron ion. HA/water solution did not react with Mn²⁺, Ni²⁺ and Cr³⁺ at room temperature.     

纳米γ-Fe2O3对汞离子的吸附行为研究

为了研究用于含汞离子废水处理的新型高效材料,研究了纳米γ-Fe₂O₃对汞离子的吸附行为。探讨pH值(3、8和12)、温度(288 K、298 K、308 K、318 K)和离子强度(Ca²⁺,0.001 mol/L、0.01 mol/L、0.1 mol/L)对该吸附的影响。使用吸附动力学方程(拉格朗日准一级、准二级)和等温吸附方程(Langmuir和Freundlich)分别对吸附数据进行拟合,并讨论吸附机理。结果表明:pH值为3、8、12时,纳米γ-Fe₂O₃对汞离子的吸附动力学方程符合准二级动力学模型(R2=0.997~0.999);288 K、298 K、308 K、318 K时,纳米γ-Fe₂O₃对汞离子的吸附过程更符合Langmuir吸附模型(R²=0.970~0.995),并且随温度升高,吸附量增加;在不同pH值下,纳米γ-Fe₂O₃对汞离子的吸附等温式可使用Langmuir模式(R²=0.983~0.996)进行表征,随p H值降低,吸附量减少,中性环境有利于吸附;在不同Ca²⁺浓度下,可用Langmuir等温吸附式拟合(R²=0.990~0.996)。通过Langmuir等温吸附式推算出最大吸附量随Ca²⁺浓度增加而减少。     

Application of a hydroxylamine nitrate stability model to plutonium purification process equipment

A mathematical model that predicts hydroxylamine nitrate (HAN) (NH₂OH·HNO₃) stability is applied to aqueous solutions containing HAN, nitric acid and plutonium that are used in plutonium purification processes. The model estimates the stability of these solutions with respect to the rapid, hazardous, autocatalytic reaction of HAN with nitric acid that generates heat and gas. It also accounts for reaction kinetics, temperature changes, gas generation rates, solution volumes and flow rates, and distribution of plutonium and nitric acid between aqueous and organic phases. The model is applied to three typical process vessels used in solvent extraction purification of plutonium – a countercurrent aqueous/organic plutonium stripping column, an oxidation column used for HAN and hydrazine destruction, and a plutonium rework tank. Both normal and off-normal process scenarios are modeled. Two of the off-normal scenarios lead to the rapid autocatalytic reaction of HAN with nitric acid where heat and gas are generated and that could lead to damage of the process equipment and/or release of hazardous plutonium solution from the vessel. In these two cases, stationary aqueous solutions containing HAN, Pu(III), and nitric acid were allowed to slowly react until conditions for the autocatalytic reaction were reached.     

家庭厨余垃圾分布式就地厌氧消化工艺及效果研究

针对厨余垃圾收运后集中处理模式的收集难、成本高的问题,设计了分布式就地厌氧消化工艺,用研制的设备进行半连续试验.运行80 d左右趋于稳定,稳定后的VS去除率高于60％;VS进料产气率、VS进料甲烷产率分别为0.444 m3/kg VS、0.245 m3/kg VS,VS去除产气率、VS去除甲烷产率分别为0.737 m3...