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.     

污泥烧结轻骨料调质影响研究

研究了污泥添加不同比例的SiO₂,Al₂O₃,CaCO₃和Na₂CO₃后的烧结体建材性能,并从晶体相反应机理角度讨论了添加剂改变烧结体建材性能的作用机理.结果表明,添加硅、铝能显著提高烧结体的抗压强度,硅是玻璃体成陶组分,对提高烧结体的抗压强度主要发挥物理作用;铝主要与污泥中的磷反应生成类似石英结构的AlPO₄高强晶体. 添加钠能增加烧结体的熔融液相,降低烧结体的吸水率,但烧结体变脆抗压强度降低. 添加钙增大吸水率,降低抗压强度. 此外,硅、铝会导致烧结体烧结温度提高,钠则能显著降低烧结温度.      

液相氧化-吸收脱除模拟烟气中NOx的研究

分别采用Na Cl O2和Na2SO3溶液作为氧化液和吸收液,在自行设计的鼓泡塔反应系统进行了液相氧化-吸收脱除模拟烟气NOx的研究,考察了气相SO2浓度、Na Cl O2和Na2SO3投加量以及p H值等因素对NO氧化和NOx脱除的影响.结果表明,SO2会优先于NO与氧化剂反应,从而增大氧化剂消耗量.偏酸性条件有利于NO氧化,但酸性太强会导致Na Cl O2分解为Cl O2逸出.碱性吸收液对NO几乎不具吸收脱除效果,但共存NO2能促进NO的吸收脱除.SO2对NO2吸收脱除具有促进作用.     

The chemical and mineralogical composition of the water-soluble fraction of power-plant ash and its effect on the process of crystallization of water

The content of the water-soluble fraction of power-plant fly ash from nine power plants burning brown and black coal varied in the range 0.43–1.34%. It was found, on the basis of chemical analysis and X-ray diffraction measurements, that the soluble fraction consists mostly of anhydrous CaSO₄, 3MgSO₄.CaSO₄, Na₂Ca(SO₄)₂ and other double sulphates. The sample from one power plant burning black coal also contained CaCO₃, CaO and K₂CO₃. The nucleation activity of the original ash sample, the ash without the water-soluble fraction and the separated fraction was found by the methods of nucleation deposition and the freezing of water drops. These measurements demonstrated that the soluble components, which, by themselves, exhibit low nucleation activity, considerably increase the nucleation activity of the ash when associated with the ash particles.     

Oxidation of SO2 in thin water films containing NH3

The reaction between NH₃ and SO₂ in thin water films was studied with a focus on the formation of sulfate. The reactions were conducted at 5 and 60% relative humidities or partial pressure of water vapor and at 0.04, 0.16 or 0.20 atm O₂ for temperatures between 20 and 50°C using a flow reactor and static flask reactors. In the presence of water vapor, the oxidation of SO₂ to sulfate was observed only when NH₃ was present. The product was primarily (NH₄)₂SO₄. Conversion of as much as 81% of the SO₂ to sulfate was observed after 10 min of reaction when the initial concentrations of SO₂ and NH₃ were 1 ppm and the relative humidity was 60%. Conversion was only 1–3% when NH₃ and/or water vapor were absent from the system. The surface of the reactor was found to influence the reaction by providing a place for a film of liquid water to form, and for the first several hours of reaction in the film, th e rate of sulfate formation was observed to be faster than oxidation in liquid water. In general, these results suggest that thin water films on environmental surfaces play a greater role in the deposition of atmospheric gases and the accumulation of their reaction products on surfaces than previously considered.     

The role of fly-ash particulate material and oxide catalysts in stone degradation

Studies of fly-ash composition identified the presence of calcium and sulphur, indicating their potential role as sources of calcium sulphate. Residual acidity (particularly for oil fly ash) suggested the possibility of enhanced chemical reaction, and the presence of transition metals, probably as oxides, might accelerate the oxidation of SO₂ to SO₄²⁻. Exposure tests in a laboratory-based rig simulating dry deposition on Portland and Monks Park limestone, either seeded or unseeded with fly-ash particulate material or transition metal oxide catalysts, were carried out using an SO₂-containing environment at 95% r.h. Enhanced sulphation of these seeded limestones due to the above factors was minimal; at high loadings of fly ash, there was even evidence of masking the limestone surface, reducing sulphation. However, pure CaCO₃ powder in the exposure rig showed increases in sulphation when seeded with metal oxide catalysts. Thus the limestones examined contained sufficient inherent catalysts for the oxidation of SO₂ to SO₄²⁻ to proceed at such a rate that external catalysts were superfluous. This implies that dissolution rate of SO₂ in moisture films controls the availability of species for reaction with these carbonate-based stones and that fly ash deposited from the atmosphere does not enhance the reaction.     

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.     

污泥焚烧过程中氯化物对Cd迁移行为的影响

采用固定层燃炉及向污泥中添加Cd方式,分别研究了污泥焚烧过程中有机氯(PVC)与无机氯(NaCl)对Cd迁移转化行为的影响,同时考察了不同焚烧条件下Cd的迁移及分布规律.结果表明,污泥焚烧过程中不同氯化物的加入均增强了Cd向飞灰或者烟气中迁移,但随着氯化物加入量的增加,Cd挥发增加的趋势并不明显.随温度的升高,有机氯(PVC)与无机氯(NaCl)均使得Cd在底渣中的分布减少,而焚烧时间及初始浓度对Cd迁移分布没有显著影响.底渣和飞灰的SEM-EDS和XRD分析表明,污泥焚烧过程中NaCl的加入导致Cd易与氯化物形成CdCl2、Na2CdCl4、K2CdCl6、K2CdSiO4和NaCdO2,而PVC的加入,除了与Cd形成Na2CdCl4和CdCl2外,还生成了K4CdCl6和K6CdO4氯化物,可见有机氯(PVC)与无机氯(NaCl)对Cd迁移转化影响主要与Cd的生成物种类及形态有关.     

Heterogeneous reaction of SO2 on CaCO3 particles: Different impacts of NO2 and acetic acid on the sulfite and sulfate formation

Despite the heterogeneous reaction of sulfur dioxide (SO₂) on mineral dust particles significantly affects the atmospheric environment, the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear. In this work, using the in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) technique, we employed a mineral dust particle model (CaCO₃) combined with NO₂ and acetic acid to investigate their effects on the heterogeneous reaction of SO₂ on CaCO₃ particles. It was found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate. The addition of NO₂ or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly. There was a synergistic effect between NO₂ and SO₂ that promoted the oxidation of sulfite to sulfate, and a competitive effect between acetic acid and SO₂ that inhibited the formation of sulfite. Moreover, light and water vapor can also affect the heterogeneous reaction of SO₂ with the coexistence of multiple gases. These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.     

外源含硫化合物对土壤挥发性有机硫化合物交换通量的影响

通过静态箱采样和Entech7100预浓缩仪-GC-MS分析了半胱氨酸、硫化钠和硫酸钠对土壤吸收或释放羰基硫（COS）、二甲基硫醚（DMS）、二硫化碳（CS2）和二甲二硫醚（DMDS）等4种挥发性有机硫化合物（VOSCs）的影响.结果表明,添加半胱氨酸后,土壤由COS和CS2汇转变为源,DMS和DMDS通量显著增加,且...     

基于碳捕集的富氧燃煤烟气联合脱硫脱硝试验研究

富氧燃煤烟气压缩液化CO2的高压低温工况为NO氧化为易溶于水的NO2提供了十分有利的条件.基于小型高压吸收试验装置,采用配制的富氧燃煤模拟烟气,在高压常温下进行了NO、SO2、O2与H2O的吸收反应试验.根据反应前后的气液产物分析,测定了不同组分比例与不同压力下混合气体中NO与SO2的转化率.NO氧化与吸收试验表明,NO转化为HNO3的比率随压力升高而增加,在0.5 ～2 MPa之间增加很快,在2 ～3 MPa之间增速趋丁平缓,压力达3 MPa以上时,90％以上的NO均转化为稀硝酸,且初始NO浓度越高,NO的转化率越大.混合气体中同时存在5O2与NO的联合吸收试验发现,只有少量的NO转化成了NO3-,SO2向H2SO4的转化率随压力升高而增加,初始SO2浓度越大,转化率越高.分析表明,SO2与NO同时存在时SO2先行转化为SO3,NO充当了催化剂,但SO2转化为SO3的一次转化率小于35％,反应酸液产物的多次循环能使SO2的转化率达到90％以上.建议的工艺流程中需采用两座吸收反应塔顺序脱除SO2与NO并回收稀酸溶液,有望在富氧燃煤发电捕集CO2系统中降低脱硫脱硝成本,部分地弥补富氧燃烧机组发电成本的增加.     

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.     

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.     

草浆造纸黑液ASF(活性炭、硫酸钠、糠醛)综合利用工艺研究

据统计,1988年我国造纸企业已达5360个,产量达1270×10⁴t,其中近5000个为年产5000t以下的小草浆厂,产量占总产量的43 ％左右.这些小草浆厂大多采用碱法制浆,这部分制浆蒸煮黑液,绝大多数直接排放江河,造成严重污染.开发多方面的综合利用途径,使草浆黑液变废为利,是一项有意义的研究课题,我们所开展的草浆造纸黑液ASF综合利用工艺,是一种将黑液作为制取活性炭、硫酸钠、糠醛的资源,同时也使其中绝大多数污染物得到去除的工艺.     

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.     

黔西拖长江流域水化学演化特征及驱动因素

拖长江为黔西典型的矿业型岩溶山地小流域,研究其水化学演化特征及驱动因素,对当地经济社会发展和水资源科学管理均具有重要的意义.通过采集拖长江流域河水、泉水和矿井水样品,利用水化学图解、数理统计和绝对因子分析-多元线性回归受体模型(APCS-MLR),研究了拖长江流域河水溶质来源及其对河水水化学组分的贡献.拖长江流域河水pH值为7.30～8.31,TDS值为40～520 mg·L^-1,TDS主要由Ca²⁺、 Na⁺、 HCO^-₃和SO₄^2-贡献.河水优势阳离子为Ca²⁺和Na⁺,优势阴离子为HCO^-₃和SO₄^2-,水化学类型从HCO₃-Ca过渡为HCO₃-Ca·Na和HCO₃·SO₄-Ca·Na型;矿井水主要为HCO     

A denuder technique for the measurement of nitrous acid in urban atmospheres

A new denuder set-up for the measurement of nitrous acid in polluted atmospheres is described here. The set-up is composed of one tetrachloromercurate-coated denuder for the removal of SO₂ and two downstream sodium carbonate-coated denuders for the determination of nitrous acid by the differential technique [Febo et al., 19, 1517–1530 1990]. The removal of SO₂ is necessary in order to avoid the formation of artifact nitrite on the sulfite layer which results from the interaction between atmospheric SO₂ and the Na₂CO₃ coating. Because of this mechanism, the measurement of HONO by means of the previously used NaClNa₂CO₃Na₂CO₃ denuder set-up is heavily biased in all cases when SO₂ and NO₂ are present at high concentration levels (e.g. urban environments).     

钠盐对高负荷餐厨垃圾和剩余污泥中温厌氧混合发酵过程的抑制作用

针对高负荷餐厨垃圾和剩余污泥混合发酵系统在实际应用过程中存在的盐度抑制问题,通过批次试验探究了不同钠盐（CH₃COONa、NaCl和Na₂SO₄）对中温混合发酵体系的影响,考察了添加不同浓度钠盐时混合发酵体系的甲烷累积产量、有机物去除率、挥发性脂肪酸（VFAs）累积量及水解、酸化、乙酸化和产甲烷速率的抑制作用.结果表明,随着CH₃COONa浓度的增加,相应的甲烷产量逐渐增加,但在高浓度时理论甲烷产量降低,当Na⁺浓度为8 g·L^-1时,对产甲烷抑制率为21%.此外,NaCl和Na₂SO₄对甲烷累积产量具有抑制作用,相同Na⁺浓度下,Na₂SO₄对混合发酵体系甲烷产量的抑制作用更大;当SO₄^2-浓度为8.3 g·L^-1时,相应甲烷抑制率为23%.相反,Cl^-浓度为3.1~6.2 g·L^-1时,对混合发酵过程中甲烷抑制率为4.6%~7.7%;但随着Cl^-浓度增至9.3~12.3 g·L^-1时,甲烷产量提升了14.5%~37.6%.分析认为,NaCl对混合发酵过程有机物去除率的抑制作用主要是Na⁺的影响,而Na₂SO₄的抑制作用主要来源于SO₄^2-和Na⁺的协同作用.NaCl和Na₂SO₄对水解速率和产甲烷速率的抑制作用较大,而对酸化速率和乙酸化速率抑制作用较小.     

贵州乌都河流域雨季河水水化学特征及其控制因素

乌都河是贵州西部典型的矿业型岩溶山地流域.对乌都河流域干流、支流、泉水和矿井水进行采样分析,通过Gibbs图、Piper图和数理统计分析等方法,研究了乌都河流域水化学特征及控制因素,并计算了不同因子对河水的贡献率.结果表明,乌都河流域水体pH值范围为7.87~8.52,均值为8.14;ρ（TDS）范围为135~243 mg ·L^-1,均值为191.7 mg ·L^-1.天然河水和泉水中阳离子以Ca²⁺和Mg²⁺为主,阴离子以HCO₃^-为主,水化学类型为HCO₃-Ca型;但受矿业活动影响后,部分支流河水中阳离子以Ca²⁺和Na⁺为主,水化学类型过渡为HCO₃ ·SO₄-Ca和HCO₃ ·SO₄-Ca ·Na型.乌都河流域河水离子组分受矿井水排放和阳离子交换作用、碳酸盐岩风化、硅酸盐岩风化和农业施肥这4个因子的影响.矿井水中具有较高浓度的SO₄^2-和Na⁺,是乌都河支流河水中SO₄^2-和Na⁺的主要来源.化学物质平衡法计算表明,碳酸盐岩风化的贡献率为44.12%~86.92%,均值为74.32%;矿业活动的贡献率为3.28%~37.07%,均值为11.61%;碳酸盐岩风化是乌都河流域河水水化学的主控因素,矿业活动对河水水化学组分也有不可忽视的贡献.大气降水、硅酸盐岩风化、农业活动和生活污水的贡献率均值分别为3.75%、4.67%、2.85%和2.81%,对流域水化学的影响有限.