垃圾水分对垃圾焚烧过程重金属迁移转化影响的实验研究(英文)

The effect of moisture in municipal solid waste (MSW) on partitioning of lead (Pb), zinc (Zn), copper (Cu) and cadmium (Cd) was studied in a laboratory tubular furnace by using simulated MSW. The moisture in MSW influences heavy metals in following ways, to increase the moisture in flue gas and decrease the combustion temperature, to prolong the combustion time, and to prolong the releasing time of volatiles with the furnace temperature decreased by increasing the moisture. The volatilization of Pb, Zn and Cd was enhanced by increasing the moisture in MSW because of the prolonged combustion time. For Pb and Zn, the combustion time was important at higher temperature, while for Cd, it was important at low temperature. The moisture content showed slight effect on Cu partitioning. When extra chlorine was added to MSW, such as 1%PVC + 0.5%NaCl, the volatilization of Pb, Zn and Cu was enhanced by increasing the moisture because water evaporation reduced the temperature and increased devolatilization time. At higher temperature, NaCl tends to decompose and generates more free chlorine, producing more metal chlorides. Since Cd is a strong volatile heavy metal in MSW, the effect of moisture content on its volatilization is less than that of Pb, Zn or Cu during the MSW incineration.     

ZL50活性炭吸附脱除二氧化硫的吸附动力学模型(英文)

A semi-empirical adsorption kinetic model was proposed with the time compensation method to describe the chemisorption of SO2 in flue gas by carbon adsorbents for flue gas purification. The change in adsorption capacity and adsorption rate with time at different water vapor concentrations and different SO2 concentrations was studied. The model was in good agreement with experimental data. The surface reaction was probably the rate controlling step in the early stage for SO2 adsorption by ZL50 activated carbon. The parameters m and n in the nth order adsorption kinetic model were related to the magnitude of the time compensation and adsorption driving force, respectively. The change of parameter n with water vapor concentrations and sulfur dioxide concentrations was studied and some physical implications were given. The sum of square errors was less than 1.0 and the average absolute percentage deviations ranged from 0.5 to 3.2. The kinetic model was compared with other models in the literature.     

负载金属氧化物分子筛催化氧化模拟汽油的脱硫研究

A simulated gasoline consisting of model sulfur compounds of thiophene （C4H4S） and 3-methythiophene （3-MC4H4S） dissolved in n-heptane was tested for the oxidative desulfurization in the hydrogen peroxide （H202） and formic acid oxidative system over metal oxide-loaded molecular sieve. The effects of the oxidative system, loaded metal oxides, phase transfer catalyst, the addition of olefin and aromatics on sulfur removal were investigated in details. The results showed that the sulfur removal rate of simulated gasoline in the H202/formic acid system was higher than in other oxidative systems. The cerium oxide-loaded molecular sieve was found very active catalyst for oxidation of simulated gasoline in this system. The sulfur removal rates of C4H4S and 3-MC4H4S were enhanced when phase transfer catalyst （PTC） was added. However, the sulfur removal rate of simulated gasoline was reduced with the addition of olefin and aromatics.     

TP316L在模拟生物质锅炉过热器气相和积灰条件下的腐蚀特性

Corrosion behavior of TP316L was investigated with simulated atmosphere and ash deposition for the superheater in biomass boiler. Corrosion dynamic curves were plotted by mass gain. The results showed that the corrosion was dependent on temperature and was greatly accelerated by ash deposition. The mass gain was distinctly reduced in the presence of SO2 with and without ash deposition on the specimens. Corrosion rates with ash deposit at different temperatures were calculated. Two feasible methods were provided to avoid serious high-temperature corrosion in the biomass boiler.     

表面活性剂双水相分离茶多酚生产废液中的茶氨酸(英文)

Extraction of theanine from waste liquid of tea polyphenol production was studied in aqueous surfactant two-phase system (ASTP) with cationic surfactant (CTAB) and anionic surfactant (SDS). Results indicate that the region of ASTP is narrow and there is only a two-phase region of cationic surfactant. The increase in concentrations of NaBr and Na2SO4 are beneficial to the formation of ASTP. Theanine concentration in the bottom phase increases with increasing concentration of theanine, whereas the partition coefficient and extraction rate only change a little when the concentration of theanine is above 0.2 g·L-1 . With the increase of SDS concentration, the phase ratio and the partition coefficient decrease, while the extraction efficiency of theanine increases and the concentration of theanine changes a little in the range from 2.4/7.5 to 2.8/7.2 for SDS/CTAB ratio. The temperature has a notable effect on the concentration of theanine in the bottom phase, partition coefficient and extraction rate of theanine. The increase of waste liquid decreases the phase ratio, increases the concentration and extraction rate of theanine in the bottom phase, since the protein and the saccharide enter the bottom phase with theanine.     

醇对正负离子表面活性剂双水相性质的影响

The effect of alcohol on the aqueous two-phase system properties of SDS/CTAB/H2O/Na2SO4 system was studied by the pseudo ternary phase diagram. The electrostatic forces (both attraction and repulsion) between cationic surfactant and anionic surfactant decreased because of the interaction of alcohol hydroxyl group and surfactant polar group. As a result, the phase area width of aqueous two-phase system increased. Long chain alcohol (more than five carbonatoms), which was in high concentration in the SDS/CTAB/H2O/Na2SO4) system, caused the anionic aqueous two-phase system area to vanish and the cationic aqueous two-phase system area to become wider. The CTAB rich phase turned from top phase to bottom phase.     

Removal of Cd（II） by Nanometer AIO（OH） Loaded on Fiberglass with Activated Carbon Fiber Felt as Carrier

A new nanometer material, nanometer AlO（OH） loaded on the fiberglass with activated carbon fibers felt（ACF） as the carrier, was prepared by hydrolytic reaction for the removal of Cd（II） from aqueous solution using column adsorption experiment. As was confirmed by XRD determination, the hydrolysis production loaded on fiberglass was similar to the orthorhombic phase AlO（OH）. SEM images showed that AlO（OH） particles were in the form of small aggregated clusters. The Thomas model was applied for estimating the kinetic parameters and the saturated adsorption ability of Cd（II） adsorption on the new adsorbent. The results showed that the maximum adsorption capacity of Cd（II） was 128.50 mg·g^-1 and 117.86 mg·g^-1 for the adsorbent mass of 0.3289 g and the adsorbent mass of 0.2867 g, respectively. The elution experiment result indicated that the adsorbed Cd ions was easily desorbed from the material with 0.1 mol·L^-1 HCl solution. Adsorption-desorption cycles showed the feasibility of repealed uses of the composited material. The adsorption capacities were influenced by pH and the initial Cd（II） concentration. The amount adsorbed was greatest at pH 6.5 and the initial Cd（II） concentration of 0.07 mg·L^-1, respectively. Nanometer AlO（OH） played a major role in the adsorption process, whereas the fiberglass and ACF were assistants in the process of removing Cd（II）. In addition, the adsorption capacities for Cd（II） were obviously reduced from 128.50 mg·L^-1 to 64.28 mg·L^-1 when Pb ions were present because Pb ions took up more adsorption sites.     

乙烯的物理吸附机理和化学吸附机理

An ab initio molecular orbital study connected with adsorption experiments was performed to determine the mechanism of physical adsorption and chemical adsorption of C2H4 on metals, and to compare the effects of the two kinds of adsorption. The results indicated that the adsorption styles were determined by whether there were local symmetry-adapted orbitals, whether the energy gap between symmetry-adapted orbitals was small and whether the electron occupancy of the symmetry-adapted orbitals was “occupancy vs. vacancy”. The different valence shells and orbital energies of Ag^ and Na^ resulted in different adsorption styles, chemical adsorption of C2H4 on Ag^ and physical adsorption of C4 H4 on Na respectively.     

Effect of processing on flavor precursor amino acids and volatiles of sesame paste (tehina)

The content of flavor precursor free amino acids in dehulled sesame seeds, subjected to roasting (R), steaming (S), roasting plus steaming (RS) and microwaving (M), was determined and compared with those of the raw (RW) seeds. R, RS, and S had major effects in reducing the content of free amino acids from 2360 μg/g to 582, 795 and 884 μg/g, respectively; M had no effect on the content of free amino acids. Meanwhile, flavor volatiles of the raw and processed seeds were compared by means of a dynamic headspace analyzer/gas chromatograph-mass spectrometer. Volatiles of RW seeds contained 85 compounds, whereas under the analytical conditions employed, seeds subjected to R, RS, S, and M had 117, 97, 93 and 87 compounds, respectively. Among volatiles identified in the RW seeds were 36 hydrocarbons, 8 aldehydes, 4 ketones, 8 alcohols, 2 acids, 2 esters, and 1 pyrazine. The only pyrazine identified in the RW seeds was 2,5-dimethylpyrazine. Pyrazines, generally recognized as contributors to the roasted aroma of foods, were more numerous (10 in R, 6 in RS, 2 in S, and 2 in M) and prevalent (8.71% in R, 2.97% in RS, 2.04% in S, 0.53% in M, and 0.25% in RW) in the volatiles of processed sesame seeds. The chemical nature of pyrazines also depended on the process employed. Multivariant analysis indicated a highly negative correlation between the loss of free amino acids and production of volatile flavor compounds in the R and RS samples, while the M sample remained unchanged. Furthermore, both R and RS seeds contained dimethyl sulfide and dimethyl disulfide, whereas no sulfur-containing compounds were present in other samples. Of the processed seeds, the flavors of R and RS samples were considered as acceptable, and the flavor intensity of the former was deemed stronger than that of the latter by the experimenters.     

表面活性素集成生产过程(Ⅲ)吸附柱的模型

The study is focused on modeling of separation process and optimization.An adsorption separation process is simulated.The surfactin production process by Bacillus subtilis ATCC 21332 followed by surfactin adsorption in a fixed-bed column packed with commercial active carbon is studied in laboratory.The adsorption column achieves high surfactin recovery(94%)by up-flow methanol elution at 25°C.The adsorption column is simulated with a complex one-dimensional plug flow dispersion model coupled with nonlinear adsorption equilibrium,based on the assumption that the adsorption of surfactin is monomolecular layer and no micelle is formed.The molecular diffusion coefficient of surfactin in water solution with electric neutrality is estimated to be 0.428×10 -5 cm 2 ·s -1 by molecular dynamics simulation.The model developed can describe the complex interplay of adsorption kinetics,fluid dynamics,and mass-transfer phenomena based on the assumption of no radial temperature and concentration gradients,and is of adequate precision.The work involved in this paper is valuable for the optimization of the production process of surfactin.     

PRECIPITATION IN THE Mg+2-Na+-SO3-2-SO4-2 AQUEOUS SYSTEM

Spontaneous precipitation in the aqueous system Mg₊₂-Na₊-SO₃^-2-SO₄^-2 affected by mixing solutions of MgSO₄ and Na₂SO₃, together was studied for temperature varying from 40 to 80°C and for pH from 5,5 to 9. The initial composition of a precipitating system was 0·67 and 1·17 mol of MgSO₃ and Na₂SO₄ per liter and 0·82 mol of MgSO₃ and Na₂SO₄ together with 0·83 mol of MgSO₄ per liter, respectively. Depending on the prevailing reaction conditions, solid phase consisting of MgSO₃ 6H₂O, MgSO₃ 3H₂O, Mg₂NaOH(SO₃)₂ H₂O or their mixture is formed. Each solid phase forms crystals of typical size and shape. The precipitation diagrams drawn in the temperature and pH coordinates for three different initial composition of the studied system are presented.     

Hot corrosion and protection of Ti2AlC against Na2SO4 salt in air

The hot corrosion behavior of Na₂SO₄-coated Ti₂AlC was investigated by means of thermogravimetric analysis, X-ray diffraction, and scanning electron microscopy/energy dispersive spectroscopy. This carbide displays good hot corrosion resistance below the melting point of Na₂SO₄ while the corrosion attacks become virulent when the salt is molten. A protectively continuous Al₂O₃ layer forms and imparts good corrosion resistance, and consequently, the corrosion kinetics is generally parabolic at 850 °C. However, porous oxide scales fail to protect the Ti₂AlC substrate at 900 and 1000 °C. The segregation of sulfur at the corrosion scale/substrate interface accelerates the corrosion of Ti₂AlC. Furthermore, a convenient and efficient pre-oxidation method is proposed to improve the high-temperature hot corrosion resistance of Ti₂AlC. An Al₂O₃ scale formed during pre-oxidation treatment can remarkably restrain the infiltration of the molten salt into the substrate and prevent the substrate from severe corrosion attacks.     

燃煤锅炉烟气中Na2SO4生成的化学动力学研究

准东煤燃烧过程中Na₂SO₄的形成会造成锅炉受热面沾污、尾部SCR催化剂失活等问题。烟气中Na₂SO₄形成及转化规律的研究对于预测和控制燃煤烟气中Na₂SO₄的形成有重要意义。发展了烟气中Na/Cl/S/O/H化学动力学模型,研究了烟气中Na₂SO₄的生成过程及转化机理,考察了含氧量、温度、SO₂浓度、H₂O浓度等因素对Na₂SO₄生成的影响。动力学计算结果表明,模型预测结果与实验数据吻合较好,验证了模型的准确性。烟气中的高氧气含量有利于Na₂SO₄的生成。高温加快化学反应的同时,抑制了Na₂SO₄的生成。SO₂和H₂O的影响效果受温度影响较大。反应路径分析表明,Na₂SO₄的生成路径有两个：一是依赖于SO₂直接氧化（NaCl→NaSO₃Cl→NaHSO₄→Na₂SO₄）,二是依赖于SO₂间接氧化（NaCl→NaO₂→NaSO₄→NaHSO₄→Na₂SO₄）。敏感性分析结果表明,Na₂SO₄的生成主要对系统中生成或消耗自由基的反应更为敏感。     

Hot-corrosion of silicon carbide in combustion gases at temperatures above the dew point of salts

To evaluate the performance of SiC to operating environments expected in future ceramic gas turbines, SiC samples were exposed in a low velocity burner rig at temperatures above the dew point of sodium sulphate (Na₂SO₄). Under these conditions, the corrosion behaviour should be independent of the sulphur content of the fuel, if Na₂SO_4(g) is not involved in the corrosion process. At 1000°C, SiC degradation was dependent on the sulphur levels in the fuel and the rates were controlled by the properties of the glassy corrosion products. Although there was an effect of P_SO3 on a_Na2O at 1300°C, the formation of an inner crystalline silica layer protected the material in both combustion gases so that the effect of p_SO3 on corrosion was concealed. These results indicate that Na₂SO_4(g) is involved in the corrosion process at temperatures above the dew point, contrary to what might be predicted from thermodynamic considerations. The role of sodium on enhancing the rate of corrosion is discussed.     

硫酸钠/氧化硅复合定形相变材料的溶胶凝胶法制备和表征简

A sodium sulfate （NaeSO4）/silica （SiO2） composite was prepared as a shape-stabilized solid-liquid phase change material by a sol-gel procedure using Na2SiO3 as the silica source. Na2SO4 in the composite acts as a latent heat storage substance for solid-liquid phase change, while SiO2 acts as a support material to provide structural strength and prevent leakage of melted NazSO4. The microstructure and composition of the prepared composite were characterized by the N2 adsorption, transmission electron microscope （TEM）, scanning electron microscope （SEM）, Fourier transform infrared spectroscopy （FTIR） and X-ray diffraction. The results show that the prepared Na2SOJSiO2 composite is a nanostructured hybrid of NazSO4 and SiO2 without new substances produced during the phase change. The macroscopic shape of the NazSO4/SiO2 composite after the melting and freezing cycles does not change and there is no leakage of Na2SO4. Determined by differential scanning calorimeter （DSC） analysis, the values of phase change latent heat of melting and freezing of the prepared NazSO4/SiO2 （50%, by mass） composite are 82.3 kJ.kg i and 83.7 kJ.kg-1, and temperatures of melting and freezing are 886.0 ℃ and 880.6 ℃, respectively. Furthermore, the Na2SOJSiO2 composite maintains good thermal energy storage and release ability even after 100 cycles of melting and freezing. The satisfactory thermal storage performance renders this composite a versatile tool for high-temperature thermal energy storage.     

Na2SO4掺杂含MgO铝酸钙熟料的结构表征及浸出性能

使用分析纯MgO、CaCO₃、SiO₂、Al₂O₃与Na₂SO₄在1350℃保温1 h合成了掺杂Na₂SO₄的含MgO铝酸钙熟料,在Na₂CO₃溶液体系下研究了其氧化铝浸出性能,通过XRD等分析手段对其晶体结构和自粉化性能进行了研究。结果表明,Na₂SO₄可以显著提升铝酸钙熟料的浸出性能,Na₂SO₄掺杂量由0%提高到4%,熟料的氧化铝浸出率由61.89%提高到92.01%,继续添加Na₂SO₄,浸出性能趋于稳定。由XRD结果可知,Na₂SO₄促使20CaO·13Al₂O₃·3MgO·3SiO₂（Q相）发生分解并使其转变为12CaO·7Al₂O₃（C₁₂A₇）。Na⁺进入C₁₂A₇晶格引起晶格畸变,从而提高C₁₂A₇的氧化铝浸出性能。Na₂SO₄的加入降低了熟料的自粉化性能,Na₂SO₄掺杂量由0%提高到6%,熟料的自粉率由97.46%下降到85.34%,当Na₂SO₄掺杂量达到10%后,熟料自粉率仅为36.3%。     

Differential capacitance of the platinum/aqueous-solution interphase

The differential capacitance of polycrystalline platinum in aqueous H₂SO₄ and NaOH solutions has been investigated as a function of bias potential. A capacitance minimum is observed at 0·56 V in H₂SO₄ and − 0·34 V in NaOH solution. There is strong evidence for the irreversible adsorption of oxygen/OH⁻ ions and oxide-film formation. Addition of n-butylamine hinders the adsorption of oxygen/OH⁻ ions and it is itself strongly adsorbed.     

Effect of anions and pH on the ethanol electro-oxidation at a platinum electrode

The electro-oxidation of ethanol and its inhibition by adsorbed chloride ions have been studied by cyclic voltammetry in 0.64 M HNO₃, 0.64 M HClO₄, 0.64 M NaNO₃, 0.64 M NaClO₄, 0.43 M NaNO₃/0.072 M Na₂SO₄ and 0.43 M NaClO₄/0.072 M Na₂SO₄ solutions at 25°C. The results show that these anions and the pH influence the peak current and potential for all three anodic waves. The anion effect is more pronounced in acidic solutions than in neutral solutions. The magnitude of the effect in the absence of chloride indicates that the surface coverage of these anions increases in the order perchlorate, sulfate, nitrate. The chloride inhibition is dependent on the anions and is smallest in sulfate solutions. Mechanisms proposed in an earlier study are found to be consistent with these results. It is also suggested that the ethanol system may be useful as a probe in studies of anion adsorption properties and platinum surface states.     

Thermoelectric characterization of NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe) polycrystalline materials

Layered -titanate materials, Na_xM_x/2Ti_1−x/2O₂ (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na_0.4Ni_0.2Ti_0.8O₂ were ca. 7×10³ S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm⁻¹ K⁻¹ at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na_0.4Ni_0.2Ti_0.8O₂ and Na_0.4Co_0.2Ti_0.8O₂ was about 1.9×10⁻⁴ and 1.2×10⁻⁴ K⁻¹ around 700 °C, respectively.     

Raman spectroscopic studies on the sulfation of cerium oxide

In the present study, we have examined sulfation of cerium oxide via impregnation of (NH₄)₂SO₄, followed by heating in the temperature range of 220–720°C, using Raman Spectroscopy. Based on the SO and SO stretching frequencies in the range of 900–1400 cm⁻¹, a wide range of surface oxysulfur species and bulk cerium-oxy-sulfur species are identified. At 220°C, a mixture of (NH₄)₂SO₄ crystals, SO²⁻_4(aq) and HSO¹⁻_r(aq) is found to have formed on ceria's surface, whereas complete conversion of (NH₄)₂SO₄ to SO²⁻_4(aq) and HSO¹⁻_4(aq) occurs at 280°C. At 350°C, formation of a mixture of surface pyrosulfate S₂O²⁻_7(surf.0, consisting of two SO oscillators and a bulk type compound identified as Ce(IV)(SO₄)_x(SO₃)_2−x (0 < x < 2) have been observed. Upon introduction of moisture, the former transforms to HSO¹⁻_4(surf.), whereas the latter remains unchanged. At 400°C, only the bulk type compound can be observed. At 450°C, only Ce₂(SO₄)₃ is generated and remains stable until 650°C. Further increase in the temperature to 720°C results in the formation of CeOSO₄. The present study not only provides a more thorough understanding of the sulfation of cerium oxide at a molecular level, but also demonstrates that Raman spectroscopy is a highly effective technique to characterize sulfation of metal oxides.