木质生物燃料与其半焦的混燃实验研究

生物质半焦作为生物质气化的副产物,其固定碳含量和热值均高于原生物质.若将生物质半焦充分利用将大幅提高生物质利用的能量效率,具有很大的经济和环境效益.在综合热分析基础上,考察了生物质半焦添加比例(掺烧比)对生物质微米燃料旋风炉燃烧炉膛温度、烟气及灰分的影响.试验研究发现掺烧比为20%(空气当量比为1.2,粉体粒径在0.177 mm以下,生物质含水率控制在8.1%以下),燃烧效果最好,燃烧效率高达98%,燃烧烟气中有害气体NOx和SO2的含量较少.     

水泥厂废旧除尘布袋热重分析及其形态特征

采用综合热重分析法,对水泥厂3种不同工段的废旧除尘布袋及相对应的同型号新布袋进行了热重(TG)分析实验研究.结果表明,废旧除尘布袋热重分析的升温过程中主要有3个失重峰,前两个失重峰与涤纶纤维的燃烧析出相对应,第3个失重峰主要是碳酸钙分解的结果.采用积分法(Coats-Redfern方程)计算得到各阶段燃烧反应的机理方程及相应的活化能参数.分析表明,在低温段废旧布袋中的灰尘对燃烧反应影响不大,而在高温段废旧布袋中的灰尘导致燃烧反应活化能升高,阻碍燃烧反应进行.从电镜扫描和能谱分析可知,废旧除尘布袋中的涤纶纤维几乎被焚烧殆尽,剩下的少量焚烧灰渣由C、O、Si、Ca等主要元素,以及Ti、Al、Mg、Mn、Fe等次要元素组成.这种灰渣与水泥成分类似,具有较高的回收利用价值.     

粉煤灰综合利用过程中汞的二次释放规律研究

我国粉煤灰年产生量4亿t左右,近年来利用率稳定在65%～68%,主要利用方式包括建材生产、道路施工、建筑工程和农业利用.建材生产包括高温工序,可能存在粉煤灰中汞的二次释放.本研究设计实验模拟了水泥生产、蒸养砖生产的主要环境因素,利用程序升温脱附的方法研究粉煤灰利用过程中的汞迁移转化规律,并对全国范围内粉煤灰利用过程汞的二次释放量做出估算.研究发现,粉煤灰中的汞以HgCl2(Hg2Cl2)、HgS和HgO的形式存在;水泥生产过程中,粉煤灰中98%以上的汞会释放;蒸养砖生产过程中,粉煤灰中汞的平均释放率为28%,释放率主要受到粉煤灰中的HgCl2(Hg2Cl2)比例的影响.我国粉煤灰利用过程中的汞二次排放量由2002年的4.07 t.a-1增至2008年的9.18 t.a-1,其中水泥行业的贡献率占到96.6%.     

燃煤电厂和垃圾焚烧电厂燃烧产物中卤代多环芳烃的赋存特征和毒性风险

研究了燃煤电厂和垃圾焚烧电厂燃烧产物中卤代多环芳烃（HPAHs）的赋存特征、生成机制和毒性效应.结果表明,燃煤电厂和垃圾电厂飞灰中氯代PAHs （Cl-PAHs）的含量为1.06~1.67 ng·g^-1和2.76 ng·g^-1,溴代PAHs （Br-PAHs）的含量为26.4~44.2 ng·g^-1和6.31 ng·g^-1;垃圾电厂飞灰中Cl-PAHs的含量明显高于燃煤电厂,主要是因为生活垃圾中含有大量的聚氯乙烯为代表的塑料.来自煤粉炉的飞灰中Br-PAHs和Cl-PAHs的含量明显低于循环流化床燃煤飞灰,主要是因为煤粉炉具有更高的燃烧温度和燃烧效率.燃煤电厂飞灰中主要为7-BrBaA和9-ClPhe;垃圾电厂除尘器飞灰中Br-PAHs主要为9-BrPhe和2-ClAnt.7-BrBaA和9,10-Br₂Ant在燃煤电厂除尘器飞灰的含量远高于其在底灰和脱硫石膏的含量,但摩尔质量相对较小的2-BrFle在飞灰、底灰和脱硫石膏中的含量相近.垃圾电厂除尘器飞灰经过半干法脱酸后Br-PAHs的含量减少50%以上,但是经过螯合剂稳固化作用之后飞灰中Br-PAHs的含量明显升高.Pearson相关分析结果表明,燃煤电厂不同燃烧产物的HPAHs生成机制相同,而垃圾焚烧电厂不同产物中HPAHs具有不同的生成机制,飞灰螯合化过程导致HPAHs的二次生成.垃圾电厂除尘器飞灰中HPAHs的TEQs值（10.0×10^-3 ng·g^-1）与燃煤电厂相近（8.87×10^-3~15.0×10^-3 ng·g^-1）.对于垃圾电厂不同燃烧产物,脱酸工艺能够显著去除7-BrBaA从而降低飞灰的TEQ值,而飞灰螯合化后TEQ值达到螯合前的5.4倍.燃煤电厂的飞灰因年产量较大,且总HPAHs的TEQs值相对较高,对其处理和资源化利用应考虑HPAHs带来的生态风险.     

Chemical composition and properties of ashes from combustion plants using Miscanthus as fuel

Miscanthus giganteus is one of the energy crops considered to show potential for a substantial contribution to sustainable energy production. In the literature there is little data available about the chemical composition of ashes from the combustion of Miscanthus and practically no data about their physical properties. However, for handling, treatment and utilization of the ashes this information is important. In this study ashes from two biomass combustion plants using Miscanthus as fuel were investigated. The density of the ashes was 2230 ± 35 kg/m~3, which was similar to the density of ashes from straw combustion. Also the bulk densities were close to those reported for straw ashes. The flowability of the ashes was a little worse than the flowability of ashes from wood combustion. The measured heavy metal concentrations were below the usual limits for utilization of the ashes as soil conditioner. The concentrations in the bottom ash were similar to those reported for ash from forest residue combustion plants. In comparison with cyclone fly ashes from forest residue combustion the measured heavy metal concentrations in the cyclone fly ash were considerably lower. Cl-, S and Zn were enriched in the cyclone fly ash which is also known for ashes from wood combustion. In comparison with literature data obtained from Miscanthus plant material the concentrations of K, Cl-and S were lower.This can be attributed to the fact that the finest fly ash is not collected by the cyclone de-dusting system of the Miscanthus combustion plants.     

Chemical looping combustion: A new low-dioxin energy conversion technology

Dioxin production is a worldwide concern because of its persistence and carcinogenic, teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction, pyrolysis gas oxidized by seven common oxygen carriers, namely, CuO, NiO, CaSO₄, CoO, Fe₂O₃, Mn₃O₄, and FeTiO₃, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers (CuO, NiO, Fe₂O₃, and FeTiO₃), the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste.     

Chemical looping combustion: A new low-dioxin energy conversion technology

Dioxin production is a worldwide concern because of its persistence and carcinogenic, teratogenic, and mutagenic effects. The pyrolysis-chemical looping combustion process of disposing solid waste is an alternative to traditional solid waste incineration developed to reduce the dioxin production. Based on the equilibrium composition of the Deacon reaction, pyrolysis gas oxidized by seven common oxygen carriers, namely, CuO, NiO, CaSO₄, CoO, Fe₂O₃, Mn₃O₄, and FeTiO₃, is studied and compared with the pyrolysis gas directly combusted by air. The result shows that the activity of the Deacon reaction for oxygen carriers is lower than that for air. For four typical oxygen carriers (CuO, NiO, Fe₂O₃, and FeTiO₃), the influences of temperature, pressure, gas composition, and tar on the Deacon reaction are discussed in detail. According to these simulation results, the dioxin production in China, Europe, the United States, and Japan is predicted for solid waste disposal by the pyrolysis-chemical looping combustion process. Thermodynamic analysis results in this paper show that chemical looping combustion can reduce dioxin production in the disposal of solid waste.     

Physicochemical characterization of forest and sugarcane leaf combustion's particulate matters using electron microscopy, EDS, XRD and TGA

Physical characteristics and quantitative elemental composition of PM and residual ash produced from sugarcane leaves (SCL) combustion were investigated using TEM-EDS compared with forest leaves (FRL). SEM-EDS was used to analyze the microstructure and chemical composition of biomass raw leaves and PM. XRD analysis was also performed to investigate the characterization of the crystalline nanostructure, structure of PM, and residual ash compared to the TEM image processing method. The oxidation kinetics of biomass raw materials, PM, and residual ash were investigated by TGA. The morphology of fine and ultrafine agglomerate structure of SCL soot and residual ash are not significantly different from the FRL soot and residual ash. The average diameter sizes of single primary nanoparticles of SCL and FRL soot are approximately 37 nm and 35 nm, while the sizes of residual ash are about 18 nm and 22 nm, respectively. The single primary nanoparticles of soot are mainly composed of curve line crystallites of carbon fringes, while residual ash is composed of straight-line lattice fringes. The average fringe lengths of SCL and FRL soot are about 1.25 nm and 1.04 nm from the outer shell and 0.89 nm and 0.74 nm from the inner core. The interlayer spacing of curve line carbon fringes of SCL and FRL soot is approximately 0.359 nm and 0.362 nm by the TEM image analysis and it was matched with XRD analysis. The biomass PMs are mainly composed of soot, Si, Ca, and K compounds: SiO₂, CaCO₃, and KCl.     

Experimental investigation of ash deposits on convection heating surfaces of a circulating fluidized bed municipal solid waste incinerator

Incineration of municipal solid waste(MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction, as well as a source of renewable energy.During MSW combustion, increased formation of deposits on convection heating exchanger surfaces can pose severe operational problems, such as fouling, slagging and corrosion.These problems can cause lower heat transfer efficiency from the hot flue gas to the working fluid inside the tubes. A study was performed where experiments were carried out to examine the ash deposition characteristics in a full-scale MSW circulating fluidized bed(CFB) incinerator, using a newly designed deposit probe that was fitted with six thermocouples and four removable half rings. The influence of probe exposure time and probe surface temperature(500, 560, and 700℃) on ash deposit formation rate was investigated. The results indicate that the deposition mass and collection efficiency achieve a minimum at the probe surface temperature of 560℃. Ash particles are deposited on both the windward and leeward sides of the probe by impacting and thermophoretic/condensation behavior. The major inorganic elements present in the ash deposits are Ca,Al and Si. Compared to ash deposits formed on the leeward side of the probe,windward-side ash deposits contain relatively higher Ca and S concentrations, but lower levels of Al and Si. Among all cases at different surface temperatures, the differences in elemental composition of the ash deposits from the leeward side are insignificant.However, as the surface temperature increases, the concentrations of Al, Si, K and Na in the windward-side ash deposits increase, but the Ca concentration is reduced. Finally,governing mechanisms are proposed on the basis of the experimental data, such as deposit morphology, elemental composition and thermodynamic calculations.     

Disposal of low concentration fume with solid waste modified by microwave

The feasibilities of two solid waste, smelting slag and fly ash, as desulfurization and denitrogenation absorbents and additives by microwave were investigated. The influences of operating parameters were also studied. Under the optimal operating conditions, the removal efficiencies of 65.9% and 65.0% were achieved for S0₂ and NOx respectively. Scanning Electron Microscope and energy dispersive spectroscopy were employed to study the micro-area characteristics of fly ash, smelting slag absorbent and the spent absorbent. In addition, the mechanisms of simultaneous removal of S0₂ and NO_x were investigated. The microwave-modified absorbent in fact played the role of solid catalyst in the process of S0₂ and NOx treatment from fume. S0₂ and NO_x were oxidized because of microwave-modified absorbent catalytic effect.     

粉煤灰用于碳捕集、利用及封存的研究进展

总结了国内外粉煤灰用于CO₂捕集、利用和封存的不同技术研究进展,同时对今后的研究和机遇进行了展望.粉煤灰自身可通过直接干式、半干式、湿式和间接方法对CO₂进行矿化捕集封存,在CO₂矿化的同时降低粉煤灰自身重金属的浸出,并且矿化后的粉煤灰因有效降低游离CaO和MgO的含量而更适合于制作混凝土添加剂.粉煤灰也可制成活性炭、沸石和多孔二氧化硅等产品,并对CO₂进行物理吸附捕集,制成产品的类型主要取决于粉煤灰自身的成分组成和理化性质.在CO₂利用方面,粉煤灰除了可拓展建材的利用途径外,还可制作CO₂多种化学工艺所需催化剂或催化剂载体,以及制作新型材料拟薄水铝石等.我国“双碳”目标的提出及燃煤电厂粉煤灰自身的理化特性为粉煤灰提供了一条新的综合利用途径.     

Influence of SO2 in incineration flue gas on the sequestration of CO2 by municipal solid waste incinerator fly ash

The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.     

飞灰和废大理石烟气脱硫的传质反应研究

在双搅拌釜上实验测定了飞灰和废大理石浆液的脱硫率η及pH值随过程时间t的变化关系,计算了不同t时的传质速率Nm、液膜传质系数kL、气相总传质系数KG、气膜传质系数kG、传质系数之比KG/kG以及反应增强因子E等,并分析了飞灰和废大理石脱硫的传质-反应过程.实验和计算结果表明,当进口SO2体积分数为4000×10-6时,飞灰和大理石浆液脱硫均受液相阻力控制;pH值越低,KG/kG就越小,液相阻力控制也就越明显,在pH＝4.5时,液相阻力占总阻力的90%; pH值越高,E就越大,化学反应对传质的影响也就越明显;pH＝6时飞灰浆液具有与大理石浆液相近的脱硫率,达70%左右.     

含金属元素化合物和压力对工业污泥燃烧特性的影响

为了更好地利用工业污泥,有必要对它的燃烧特性进行研究,因而利用热重法研究了由3种典型的工业污泥按质量比1∶1∶1混合后的多组分试样在掺混含不同金属元素混合物、不同升温速率以及加压下的燃烧特性.实验结果表明,含金属元素化合物对污泥的燃烧能起到一定的催化作用,有助于改善工业污泥的着火性能,提高工业污泥的燃烧放热量和燃尽水平.含不同金属元素化合物对于污泥燃烧的催化机制和作用有所差异.实验中各种含金属元素化合物促进污泥燃烧过程的作用次序由大到小依次为:K2CO3、NaCl、Al2O3.随着压力的增大,污泥试样燃烧反应区间向低温区移动,各特征温度均呈下降趋势,综合燃烧特性指数有所提高;而随着升温速率的增大,污泥试样燃烧反应区间向高温区移动,各特征温度均有所增大,但综合燃烧特性愈好,对污泥燃烧越有利.     

Abatement of SO2–NOx binary gas mixtures using a ferruginous active absorbent: Part I. Synergistic effects and mechanism

A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO₂–NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO₂ and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S + N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope (SEM) and an accessory X-ray energy spectrometer (EDS) were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO₂–NOx binary system were determined by thermodynamics.     

Abatement of SO2-NOx binary gas mixtures using a ferruginous active absorbent: Part I. Synergistic effects and mechanism

A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO2–NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO2 and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S + N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope(SEM) and an accessory X-ray energy spectrometer(EDS)were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO2–NOx binary system were determined by thermodynamics.     

垃圾焚烧中硫化合物对重金属Pb迁移分布影响

采用管式炉和模拟垃圾对垃圾焚烧中硫化合物(包括S、Na2S、Na2SO3、Na2SO4)、焚烧温度、重金属初始加入浓度以及焚烧停留时间对Pb迁移分布的影响进行了研究.使用ICP-AES分析技术(美国EPA消解方法)对重金属浓度进行测量.结果表明,垃圾焚烧中4种硫化合物的加入均使得Pb在底渣中的分布比例比未加入硫化合物时的分布比例降低.Pb在底渣中的分布比例随加入S和Na2S含量的增加而减少,相应地在飞灰中的分布随S和Na2S加入量的增加而增加,而Pb的迁移分布比例受Na2SO3和Na2SO4含量变化的影响不显著.温度的升高使得Pb向飞灰中的分布比例逐渐增加,整个试验温度范围内Pb在烟气中的分布均为0.初始浓度的增加也使Pb在底渣中的分布比例逐渐升高,飞灰中的分布比例逐渐下降.停留时间的增加会使得Pb在底渣中的分布比例降低,相应地在飞灰中的分布比例会增加.     

冶金尘泥混合垃圾燃烧飞灰熔融重构固化重金属的研究

针对冶金固废组分复杂且难以高附加值利用的特性,结合当前垃圾燃烧飞灰重金属污染现状,通过将两者混合进行熔融固化及成分重组,研究了重金属固化及浸出毒性.结果表明:随着温度升高,固化渣出现明显结块,且燃烧过程中矿物发生重组,Zn、Cu、Pb和Cr取代硅酸盐中Ca~(2+)、Al~(3+)等离子而被固熔于网状基体中,生成了Cu_6Zn_4Al_2O_4、FeCr_2O_4、Cd_(0.75)Zn_(0.25)Fe_2O_4、Zn(AlO0.5Fe1.5)O4、MgCr0.4Fe1.6O4及Cu0.5Zn0.5Fe2O4等物质;且随着温度升高,Ca-Fe-Si-O体系形成一种耐热硅酸盐稳定相CaFe_3(SiO_4)2OH,由于其覆盖或包裹住含有重金属的晶体,从而延缓并阻止了灰渣分解及重金属的浸出,降低了重金属对环境的污染.     

煤矸石资源充分利用的新工艺

从煤矸石中提取氧化铝，并用残渣直接煅烧硅酸盐水泥熟料，同时作废气、废液循环，是煤矸石资源开发利用的新工艺。通过对工艺原理的研究，揭示了煤矸石-石灰石-纯碱烧结过程的反应历程及影响氧化铝提取率的因素，分析了残渣直接煅烧水泥熟料的机理和废气、废液循环利用的可能性，实现了资源的合理利用。     

稻壳灰中温热处理稳固化垃圾飞灰重金属

利用稻壳灰与某垃圾电厂产生的飞灰为原料,对飞灰和稻壳灰与飞灰的混合物进行中温热处理,探究热处理工艺参数对稻壳灰稳固化垃圾飞灰重金属的影响.在一定温度范围内,反应主要产物为CSSF（即Ca₁₀（SiO₄）₃（SO₄）₃F₂）、Ca₃SiO₅等硅酸盐结晶相,这些物质会包覆重金属,同时,飞灰重金属Pb、Zn、Cu、Cd中相对不稳定的酸溶态和可还原态向更稳定的可氧化态或残渣态转变,使Pb、Zn、Cu、Cd的浸出浓度显著降低;热处理时间延长,稻壳灰添加量增加,会使热处理样中硅酸盐种类增多,结晶度提高,导致重金属的浸出浓度逐渐降低;稻壳灰添加量在2%~4%范围内,经中温热处理样品的重金属浸出浓度较低,添加量过高时（超过6%时）,重金属浸出浓度逐渐升高.