Thermal diffusivity of fluids in a broad region around the critical point

Dynamic light scattering is a suitable method for the investigation of transport properties such as the thermal diffusivity of optically transparent fluids. The main advantages of the method are its quickness, the fact of the thermodynamic state of equilibrium of the sample (gradients are not required), and the relatively simple evaluation of data without the necessity of calibration. However, an insufficient production of intensity of scattered light may be a limiting effect. For that reason the vicinity of the gas-liquid critical point represents the classical range of application. In this paper, it is shown that by means of an appropriate choice of experimental apparatus, measurements are also feasible in an extended range of states. Broad regions around critical points of three pure fluids (sulfur hexafluoride, SF₆; ethane, C₂H₆; nitrous oxide, N₂O) over temperature ranges ¦T-T _c¦ of 0.02 to 50 K and density ranges (/_c) of 0.2 to 2 were investigated. In this region the thermal diffusivity shows great variations with temperature and density and cannot be described by means of ideal-gas behavior or relations for liquids. The measurements were carried out along the coexistence curve for both phases, along the critical isochore and along some isotherms with TT _c. The measured or calculated density, pressure, and thermal diffusivity data as well as some correlations are presented.     

Oxidation of Hydrogen Sulfide by Quinones: How Polyphenols Initiate Their Cytoprotective Effects

We have shown that autoxidized polyphenolic nutraceuticals oxidize H₂S to polysulfides and thiosulfate and this may convey their cytoprotective effects. Polyphenol reactivity is largely attributed to the B ring, which is usually a form of hydroxyquinone (HQ). Here, we examine the effects of HQs on sulfur metabolism using H₂S- and polysulfide-specific fluorophores (AzMC and SSP4, respectively) and thiosulfate sensitive silver nanoparticles (AgNP). In buffer, 1,4-dihydroxybenzene (1,4-DB), 1,4-benzoquinone (1,4-BQ), pyrogallol (PG) and gallic acid (GA) oxidized H₂S to polysulfides and thiosulfate, whereas 1,2-DB, 1,3-DB, 1,2-dihydroxy,3,4-benzoquinone and shikimic acid did not. In addition, 1,4-DB, 1,4-BQ, PG and GA also increased polysulfide production in HEK293 cells. In buffer, H₂S oxidation by 1,4-DB was oxygen-dependent, partially inhibited by tempol and trolox, and absorbance spectra were consistent with redox cycling between HQ autoxidation and H₂S-mediated reduction. Neither 1,2-DB, 1,3-DB, 1,4-DB nor 1,4-BQ reduced polysulfides to H₂S in either 21% or 0% oxygen. Epinephrine and norepinephrine also oxidized H₂S to polysulfides and thiosulfate; dopamine and tyrosine were ineffective. Polyphenones were also examined, but only 2,5-dihydroxy- and 2,3,4-trihydroxybenzophenones oxidized H₂S. These results show that H₂S is readily oxidized by specific hydroxyquinones and quinones, most likely through the formation of a semiquinone radical intermediate derived from either reaction of oxygen with the reduced quinones, or from direct reaction between H₂S and quinones. We propose that polysulfide production by these reactions contributes to the health-promoting benefits of polyphenolic nutraceuticals.     

城市垃圾渗滤液烟气脱硫体系气液吸收与解吸过程的数学模拟

针对垃圾渗滤液烟气脱硫体系气液吸收和解吸过程反应复杂的特性,基于经典双膜传质理论,建立了填料塔内湿法烟气脱硫模型,包括填料塔反应器模型和烟气SO2在垃圾渗滤液中吸收并伴随氨的解吸过程的数学模型。模型将系统内复杂的多组分反应分解为独立的离子反应,从而在确定的独立反应的条件下,可使模型的数值求解不依赖于特殊的假设条件以及可变的操作条件。根据工艺研究的实验条件对模型赋初值,结合模型参数估值确定适宜的边界条件,采用Maple 8.0对模型方程进行求解,得到了液膜内各组份的浓度分布特性曲线,以及气相分压、pH值、传质阻力、传质速率、吸收增强因子等沿塔高的分布特性,结果表明模型预测结果和实验结果吻合良好。所建立的模型为本工艺过程和其它湿法烟气脱硫过程的传质-反应现象提供了一个定量的理论分析和工程设计基础。     

化工过程熵增指数及其在磷复肥清洁生产评价中的应用

从热力学第二定律出发, 指出清洁生产的热力学本质是控制物质由有序结构向无序转化并从中获取最大效益, 其优劣可由过程熵增反映。 引用复杂体系非平衡定态过程最小熵产生原理,推导出依据与外界交换的物流和热流信息定量计算化工复杂系统过程熵增的方法, 并定义过程熵增指数ζ 。 评价了化工过程对环境热力学状态的综合影响。选择以硫和以氨为载能原料的磷复肥工艺为例进行了计算和对比,其过程熵增指数分别为6.753和4.571,反映出载能原料硫作为废物排放对环境热力学状态产生更大的影响。     

臭氧脱硝技术在稀贵多金属烟气治理中的应用

主要介绍在面临环境保护要求不断提升,废气排放指标不断降低的情况下,使用臭氧氧化+液碱脱硝技术对稀贵卡尔多炉和旋转顶吹炉生产回收金、银、硒、碲、铅、铋等金属产出的烟气的治理。治理后二氧化硫指标小于50mg/m3、氮氧化合物小于60mg/m3、尘指标小于10mg/m3,满足A类企业环保要求,同时其他重金属指标都满足国家国控指标要求,达到超低排放要求。     

解析参数对活性焦再生过程及再生效果的影响

 活性焦的热解析参数对再生活性焦的脱硫脱硝性能和机械强度至关重要。为了明确解析参数对活性焦再生过程和再生效果的影响规律,通过热解析试验探究活性焦硫残余比例、CO₂和CO生成量及再生活性焦脱硫脱硝性能随解析温度和解析时间的变化规律,继而明确适宜的活性焦热解析参数。结果表明,活性焦升温解析过程中,脱硫产物在317 ℃左右迅速分解,随后分解速率下降;在进入恒温解析阶段后脱硫产物分解速率先快速下降,而后进入缓慢解析状态。硫残余比例随恒温解析温度的升高而下降,在530 ℃下解析3 h可使脱硫产物完全解析;解析温度高于430 ℃后,活性焦表面的酚基、醌基、内酯基等含氧官能团分解量明显增加,并随恒温解析温度的升高而持续增加,分解所生成的CO和CO₂也随之大幅增加,这将使活性焦的孔隙结构进一步发展,继而不利于活性焦机械强度的保持;解析温度低于530 ℃时,硫残余比例随解析温度的升高而持续降低,使再生活性焦的脱硫脱硝性能持续提高;解析温度高于530 ℃后,含氧官能团分解量随解析温度的升高而持续增加,这将有利于提高活性焦表面SO₂氧化反应速率,继而使再生活性焦的脱硫性能持续升高,但酚基、内酯基等酸性含氧官能团的分解使再生活性焦对NH₃的吸附性能降低,进而使其脱硝性能降低。在兼顾再生活性焦脱硫脱硝性能、机械强度和生产效率等多方面因素时,430 ℃恒温解析3 h是相对较优的解析参数。在此解析条件下,再生活性焦的硫残余比例仅为1.8%,含氧官能团尚未发生大量分解,脱硫脱硝性能相对较为优良。     

锌湿法冶炼渣的自热焙烧无害化处理

针对湿法炼锌常压浸出渣和氧压浸出渣（均为危险废物）组成的高硫混合渣,系统考察了自热焙烧反应的各因素（温度、硫含量等）对渣中重金属固化效果的影响,并采用BCR连续提取法研究了焙烧前后渣中重金属的化学形态分布。结果表明,在焙烧温度1 000 ℃、混合物料硫质量分数20%、空气流速1.6 m3/h、焙烧时间7 h的条件下,渣中Zn、Pb、As、Cd等毒性浸出结果均可满足国家标准,渣率可降至约70%,焙烧热处理后渣中的Zn、Pb、As及Cd均以相对稳定的残渣态为主要化学形态,为锌湿法冶炼渣的低成本无害化与减量化处理提供了理论基础。     

Sulfur in chromia

The solubility of sulfur in chromia has been studied in H₂-H₂O-H₂S tagged with³⁵S at 973 and 1173 K at low oxygen and sulfur partial pressures typical for coal gasification-systems. For monocrystalline samples, it has been shown that sulfur-containing species are only present adsorbed on the surface of the specimens and can be removed by ultrasonic cleaning in acetone. The surface coverage after 4 weeks of exposure to H₂-H₂O-H₂S was between 2.8 and 19.3% of a monolayer. In polycrystalline chromia, sulfur was located only in pores and cracks of the sample. In dense, compact areas of the specimens the solubility of sulfur was below the detection limit of autoradiography, which was estimated to be better than 0.17 ppm.     

球团链箅机回转窑工艺中氯和硫元素迁移规律

摘要：对链箅机回转窑工艺中各段球团样品进行实验分析,研究了氯元素和硫元素在链箅机回转窑工艺中的迁移规律,明晰了烟气中HCl的生成机制。结果表明,球团原料中的氯元素主要是以NaCl的形式存在,氯元素有一部分在链箅机抽风干燥段会转变成HCl气体并进入烟气,一部分在链箅机预热Ⅱ段之后以NaCl的形式汽化进入烟气,剩余的氯元素仍以NaCl的形式存在于成品球团矿中。烟气中的HCl气体是在抽风干燥段,由富含SO2的烟气与含水球团料层中的NaCl发生反应生成的,烟气中SO2转变成Na2SO4重新固定于料层中。在预热Ⅰ段和预热Ⅱ段,烟气中的SO2与原料中碳酸钙分解生成的游离CaO反应生成CaSO4,也会重新固定烟气中的SO2。     

添加剂硫对Ni-Mn-Co粉末触媒合成金刚石的影响

本研究考察了高温高压条件下添加剂硫对Ni-Mn-Co粉末触媒合成金刚石的影响，并在此基础上，考察了含硫金刚石的机械性能。研究表明：硫对Ni70Mn25Co5粉末触媒合成金刚石的成核有明显的抑制作用，随着硫含量的增加，成核呈减少趋势；添加剂硫影响晶体的颜色和晶形，随添加剂含量的增加，晶体的颜色呈加深趋势，硫的添加使晶体的表面出现孔洞缺陷，当硫含量较低时，孔洞缺陷多分布在（100）晶面上，当硫含量较高时，（111）晶面上也出现孔洞，致使晶体的完整性受到制约；添加剂硫影响金刚石的机械性能，随着添加剂硫含量的增加，含硫金刚石的冷冲击强度（TI）和热冲击强度（TTI）呈明显的下降趋势。