垃圾焚烧过程中影响重金属分布因素的研究

在转式垃圾焚烧炉和固定床加热炉中,研究了有机垃圾焚烧过程中温度、水分、无机氯及有机氯对几种重金属分布的影响。研究结果表明,焚烧垃圾过程中焚烧温度对重金属分布特性的影响特性不一,重金属锌和铅容易转移到气相中去,而重金属镍和铬大部分是以固态形式残留在底渣中;水能与重金属及其化合物发生反应,引起物质转变,影响重金属的分布;氯的存在也影响重金属的分布特性,氯的参与使重金属更易向飞灰或烟气中迁移。     

Trace metal emissions from co-combustion of refuse derived and packaging derived fuels in a circulating fluidized bed boiler

Energy recovery from refuse derived fuels (RDF) and packaging derived fuels (PDF) is one option in integrated waste management. Nine RDF and PDF co-combustion tests with peat and coal in a circulating fluidized bed boiler were carried out in this work. Heavy metal emissions in flue gas and fly ash were measured. Multivariate data analyses were used to find out the most important parameters affecting metal emissions in the flue gas.

The results showed that total heavy metal emissions were low. Although RDF and PDF had more heavy metals than peat and coal, the multivariate data analysis showed that an increase of the RDF or PDF share in the fuel mixture up to 20% did not correlate directly with the metal emissions in the flue gas. Distribution of Cd, Cu, Zn and Sn between flue gas and fly ash correlated with each other. Injection of limestone to bind sulphur and chlorine did not have a significant effect on heavy metal emissions in the flue gas. Heavy metals concentrated on the fly ash, but all fly ashes passed the EPA-TCLP tests.     

城市生活垃圾焚烧过程中二次污染物的生成与控制

在我国 ,采用焚烧法处理城市固体垃圾 ,逐渐得到推广和应用。然而焚烧带来的二次污染物 ,如二、细颗粒、重金属、HCl以及SOx、NOx 等也随之引起了广泛关注。对垃圾焚烧过程中各种二次污染物的产生机理及其控制方法进行了综述。并且指出近期我国城市固体垃圾焚烧烟气污染物的重点控制对象应为颗粒物、HCl、SOx 和NOx。     

Metal partitioning in products of incineration of municipal solid waste

Metals contained in the waste transfer to the waste incineration products, including flue gas, fly ash, and bottom ash, as different oxide, nitride, carbides, and other phases. Most of the metal-based phases formed in incineration are toxic and their emissions need to be strictly controlled. Therefore, behavior of metal species during incineration must be well understood. Such understanding is possible based on the experimental identification of the metal phases formed in the waste combustion and determination of their concentration in various incineration products. To avoid well-known experimental difficulties of the industrial waste incinerators associated with the poor fuel/conditions reproducibility and limited instrumentation, a 140,000 Btu/h pilot-scale, laboratory burner was constructed, characterized and operated at NJIT. A synthetic fuel representative of the municipal solid waste in the US was formulated and produced in 600-Lb batches. The solid fuel contained Fe and SiO2 as main constituents, and was doped with trace amounts of Al, Ni, Cr, Hg and PbO. Several experiments have been conducted on combustion of the synthetic fuel in the pilot-scale incinerator with varying fuel-air equivalence ratio. Both gaseous and condensed combustion products were sampled and analyzed. Atomic absorption spectroscopy and X-ray diffraction were used to analyze total metal contents and metal containing phases in the incineration products. Thermodynamic equilibrium computations were performed to obtain the adiabatic flame temperature and identify the phases of the metal-containing products formed at the equilibrium conditions. The results of the equilibrium computations performed at the varied fuel/air ratios were compared with the observed experimental results.     

Application of fluidized bed combustion to industrial waste treatment

Landfill and sea-dumping appear to be on their way out as acceptable methods for the disposal of untreated industrial wastes in Taiwan. Recently, there has been interest in the application of fluidized bed technology to waste incineration for efficient energy utilization and environmental protection. A pilot fluidized bed combustion system was used to investigate the incineration performance and parametric test for the waste from an industrial park. According to the experimental results, the appropriate operating conditions, including temperatures of 800-840 degrees C, aeration rates of U(0)/Um(f)-2.0 or so, and on-bed feeding, were recommended to treat such waste. The emissions of SO(x), NO(x) and CO in flue gas meet the ROC-EPA regulation.     

Comparison of CaO’s effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023–1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)₂ and CaCO₃ in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO₄. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO₄ formation and lowered Cr leaching concentration.     

采用循环流化床技术焚烧城市生活垃圾

根据目前我国城市生活垃圾热值偏低的实际情况 ,提出以煤为辅助燃料 ,采用循环流化床焚烧技术处理生活垃圾 ,可大幅度降低运行成本 ,符合国情。阐述了循环流化床焚烧技术在降低NOx、SO2 和二噁等方面的优越性。尾气处理建议采用喷活性碳 +布袋除尘组合工艺 ,飞灰处理建议采用高温熔融处理     

Halogen production from aqueous tropospheric particles

Box model studies have been performed to study the role of aqueous phase chemistry with regard to halogen activation for marine and urban clouds and the marine aerosol as well. Different chemical pathways leading to halogen activation in diluted cloud droplets and highly concentrated sea salt aerosol particles are investigated. The concentration of halides in cloud droplets is significantly smaller than in sea-salt particles, and hence different reaction sequences control the overall chemical conversions. In diluted droplets radical chemistry involving OH, NO(3), Cl/Cl(2)(-)/ClOH(-), and Br/Br(2)(-)/BrOH(-) gains in importance and pH independent pathways lead to the release of halogens from the particle phase whereas the chemistry in aerosol particles with high electrolyte concentrations is controlled by non-radical reactions at high ionic strengths and relatively low pH values.For the simulation of halogen activation in tropospheric clouds and aqueous aerosol particles in different environments a halogen module was developed including both gas and aqueous phase processes of halogen containing species. This module is coupled to a base mechanism consisting of RACM (Regional Atmospheric Chemistry Mechanism) and the Chemical Aqueous Phase Radical Mechanism CAPRAM 2.4 (MODAC-mechanism). Phase exchange is described by the resistance model by Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, 1986.It can be shown that under cloud conditions the bromine atom is mainly produced by OH initiated reactions, i.e. its concentration maximum is reached at noon. In contrast, the concentration level of chlorine atoms is linked to NO(3) radical chemistry leading to a smaller amplitude between day and night time concentrations.The contribution of radical processes to halogen atom formation in the particle phase is evident, e.g. by halogen atoms which undergo direct phase transfer. Furthermore, the application of the multiphase model for initial concentrations for sea-salt aerosols shows that the particle phase can act as a main source of halogen containing molecules (Cl(2), BrCl, Br(2)) which are photolysed in the gas phase to yield halogen atoms (about 70% of all Cl sources and more than 99% for Br).     

Sulfidation treatment of molten incineration fly ashes with Na2S for zinc, lead and copper resource recovery

The present study focuses on the conversion of heavy metals involved in molten incineration fly ashes to metal sulfides which could be thereafter separated by flotation. The sulfidation treatment was carried out for five molten incineration fly ashes (Fly ash-A to Fly ash-E) by contacting each fly ash with Na(2)S solution for a period of 10 min to 6h. The initial molar ratio of S(2-) to Me(2+) was adjusted to 1.20. The conversion of heavy metals to metal sulfides was evaluated by measuring the S(2-) residual concentrations using an ion selective electrode. The formation of metal sulfides was studied by XRD and SEM-EDS analyses. In the case of Fly ash-A to Fly ash-D, more than 79% of heavy metals of zinc, lead and copper was converted to metal sulfides within the contacting period of 0.5h owing to a fast conversion of metal chlorides to metal sulfides. By contrast, the conversion of about 35% was achieved for Fly ash-E within the same contacting period, which was attributed to a high content of metal oxides. Further, the S(2-) to Me(2+) molar ratio was reduced to 1.00 to minimize Na(2)S consumption and the conversions obtained within the contacting period of 0.5h varied from 76% for Fly ash-D to 91% for Fly ash-C. Finally, soluble salts such as NaCl and KCl were removed during the sulfidation treatment, which brought about a significant enrichment in metals content by a factor varying from 1.5 for Fly ash-D to 4.9 for Fly ash-A.     

垃圾焚烧重金属迁移特性及其影响因素

综述了城市固体垃圾(MSW)焚烧过程中的Hg、Cd、Pb、Cu、Zn、As和Cr等几种主要重金属污染源在焚烧过程中的迁移特性及其主要影响因素。将重金属在焚烧过程中的迁变归结为:蒸发、气相和表面反应、冷凝成核团聚和飞灰吸附等4个主要过程;而垃圾中重金属的初始浓度、原始垃圾的基体盐分(如A l、S i和K、Na等的存在形式)、垃圾中的C l(PVC和NaC l)和S的含量、垃圾的含水量以及焚烧过程中的运行参数(温度、滞留时间、氧化-还原气氛)等都会对焚烧过程的迁移规律产生影响。     

Fate of antimony in municipal solid waste incineration

The average antimony concentration in municipal solid waste is estimated to be about 10-60 ppm. Thermodynamical models predict a volatile behavior for antimony compounds, yet literature mass balances show that about 50% of the antimony input remains in the grate ashes. This fact can be explained by the formation of thermally stable antimonates in the fuel bed due to interactions with alkali or earth-alkali metals. Thermogravimetric experiments revealed an increased thermal stability for antimony oxide in presence of oxygen and calcium oxide. Spiking experiments on the test incinerator TAMARA showed that chlorination processes have a strong effect on antimony volatilization whereas high fuel-bed temperatures and addition of antimony oxide only have a moderate effect. In the grate ashes, antimony shows a pH-depending leaching property, which is typical for anionic species. This fact supports the thesis that antimony is present in the grate ashes in an anionic speciation.     

Mass Burn Incineration with a Presorted MSW Fuel

This research, supported by the U.S. Dept. of Energy, investigates potential benefits to mass burn incineration from burning a presorted MSW fuel. Comparative boiler efficiency tests at three mass burn incineration sites utilizing as-received MSW and a presorted MSW fuel are reported. Test results indicate that waste presorting can provide substantial benefits to the mass burn process. Flue gas and ash heavy metals are found to be significantly reduced. Discarded automobile batteries are found to substantially contribute to lead levels in the waste stream. Reductions in emissions of CO, HC, HC1, HF, and NO_X are reported. Increases in facility boiler efficiency and MSW disposal capacity are measured.     

Formation and destruction of PCDD/F inside a grate furnace

Formation and destruction of polychlorinated dibenzo-p-dioxins and dibenzofurans PCDD/F during the combustion process was investigated experimentally in a pilot plant. All important process steps like the burnout of the fuel bed on the grate, the burnout of the flue gas inside the combustion chamber, the heat recovery in a boiler as well as influences of the fuel composition are described in detail.

High concentrations especially of PCDF are formed during the burnout of the fuel bed. The formation reaction is mainly influenced by the fuel composition and the burnout characteristic of the fuel bed. Fuels with low chlorine and low metal content (Cu) result only in negligible concentrations of PCDD/F.

Under stable combustion conditions characterized by an excellent flue gas burnout PCDD/F will almost be completely destroyed already inside the combustion chamber. “Cold strands” of unburned flue gas (high CO concentrations) caused by disturbed combustion conditions will result in high concentrations of PCDD and especially of PCDF in the raw gas.

A second place of PCDD/F formation is the well-known boiler section. Here fly ash deposits containing residual carbon (mainly soot particles) are the source for the formation reaction. Under stationary effective combustion conditions, they are dominant for PCDD/F concentrations in the raw gas over a very long period of time.

Stationary efficient flue gas burnout (especially soot) together with effective boiler cleaning will guaranty low concentrations of PCDD/F in the flue gas in front of the flue gas cleaning system.     

市政污泥与生活垃圾混烧技术验证

对市政污泥与生活垃圾混烧进行了验证研究。结果表明，与生活垃圾单独焚烧相比，污泥与生活垃圾混烧后烟气中NOx、CO和HCl的浓度没有出现明显变化，而SO2浓度出现了下降（从82～93mg／m3下降至41～70mg／m3）；Hg、Pb、Sn、Cr和Zn的浓度均表现为不同程度的上升，但仍然符合GB[g485；二恶英从0．0087μgTEQ／m3降至O．0047μgTEQ／m3。掺烧半干污泥比例为10％、12％和15％时，吨物质的发电量分别为311．8kWh／t、306．7kWh／t和296．1kwh／t。混烧污泥在一定程度上降低了系统的发电量，因此建议混烧污泥的比例不应大于15％。测算的污泥混烧成本约209元／t（80％含水率）。     

Formation and mitigation of PCDD/Fs in iron ore sintering

The sintering of iron ore is presently a significant industrial source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) worldwide owing to the fundamental requirement of the operation of a high temperature process to pre-treat fines and to recycle plant by-products arising from the integrated iron and steelworks. The process is a noteworthy contributor of PCDD/F indirectly due to decreasing PCDD/F releases from municipal solid waste incineration. Commonly PCDD/F formation from the process is associated with the addition of oily mill scales although raw material containing a combination of C, Cl and specific metal catalyst has been shown to drastically increase PCDD/F formation in the process. The degenerate graphitic structure of carbon present in coke fuel and soot formed and the chemistry of catalytic metals and Cl are important factors. A review on PCDD/F emission in this process has been carried out, including examination of its formation mechanism, congener distribution, contributing factors and mitigation strategies, with emphasis on the use of inhibiting compound to achieve suppression. A detailed analysis of the de novo and precursor theories of formation and the contributing factor is given since the subject of PCDD/F formation is still controversial. The de novo formation pathway identified in sinter plants and controlled studies performed in the laboratory as well as at pilot-scale are discussed; where appropriate, a comparison is drawn between sintering and other thermal processes emitting PCDD/Fs. Summary of the latest developments in PCDD/F downstream abatement strategies presently employed in full scale industrial plants is provided. Potential inhibiting compounds are discussed in terms of their mode of action and merits under sintering conditions.     

危险废物回转式流化冷渣多段焚烧系统焚烧特性研究

危险废物的处理和处置是摆在我国各级市政府面前的紧迫任务。然而我国已经运行的危险废物焚烧装置普遍存在回转窑挂壁结渣、热灼减率偏高和污染排放超标等问题,作者通过将回转窑和流化床特点相结合的方法提出了一种新型危险废物回转式流化冷渣多段焚烧处置装置。该装置采用回转窑(一燃室)、二燃室和流化床结合的热解-流化焚烧工艺,特别是采用控制窑头温度避免了回转窑挂壁结渣;采用流化冷渣装置延长未燃烬渣的焚烧时间,解决了热灼减率偏高问题;水冷式烟气急冷装置可以将烟气温度从1 100℃降到200℃,防止了二恶英的尾部低温再生成。该系统运行稳定可靠,可以处理医疗垃圾和大多数的固态和液态危险废物,实现了烟气污染物尤其是二恶英排放达到国家标准的目标。同时对该系统运行时窑头温度分布、二燃室炉膛出口氧量变化、回转窑和炉膛升温特性、燃烧室外壁温度分布等几方面运行数据都进行了详细的介绍,为危险废物焚烧炉的运行提供了宝贵的经验数据。     

城市生活垃圾并流竖炉焚烧模拟实验研究

气化熔融焚烧技术能够避免重金属和二恶英的二次污染，被公认为实现零排放和环境友好型的焚烧方法。在这样的背景下提出了生活垃圾并流竖炉气化熔融焚烧工艺。该工艺以竖炉为气化熔融主体设备，垃圾料层与助燃空气在炉内都是至上而下并流流动，从而使垃圾热解气化产生的可燃气体在竖炉下部完全燃烧，以提供灰渣熔融耗热。并流竖炉热态模拟试验表明，并流时垃圾料层中各点的温度明显高于逆流情况，并流时产生的CO₂量明显高于逆流情况。因此说并流竖炉更适合气化熔融焚烧工艺的要求。     

城市生活垃圾在机械炉排炉内焚烧过程研究及数值模拟

研究城市生活垃圾在机械炉排炉内焚烧过程，建立了垃圾在炉排炉移动床内燃烧过程中垃圾体积变化、水分蒸发、挥发分析出及燃烧、垃圾颗粒的移动、气-固两相热传递、焦炭燃烧等各个反应阶段的热化学模型，采用一维非稳态模型分别建立了床层内气固两相介质控制方程。通过对炉排上垃圾焚烧过程的数值模拟研究，获得料层中温度分布、料层高度、炉床机械负荷、气相中反应物组分和污染物浓度分布。利用建立的模型对某大型垃圾焚烧炉的燃烧过程进行数值仿真，对燃烧过程、烟气成分进行预测，为垃圾焚烧炉排炉的设计和燃烧控制提供理论依据。     

流化床垃圾焚烧炉产生的有毒二噁英同类物分布研究

测定了流化床垃圾焚烧炉焚烧产生的飞灰、烟尘和烟气中的2，3，7，8位氯取代二噁英同类物的含量及其毒性当量。结果表明，产生的二噁英主要存在于飞灰中，烟气中的含量很少。飞灰中二噁英总浓度和毒性当量分别为8.44ng／g和0．80ng／g，经过布袋除尘器后的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为0．34ng／m^3和0．02ng／m^3，而布袋除尘器前的烟尘和烟气中二噁英的浓度之和与毒性当量之和分别为40．78ng／m^3和3．0ng／m^3。飞灰和烟尘中2，3，7，8位氯取代二噁英同类物的分布相似，但是与烟气中2，3，7，8位氯取代二噁英同类物的分布差别较大。通过了解有毒二噁英同类物的分布，可以进一步优化流化床垃圾焚烧炉的焚烧条件，降低二噁英的排放量，减少垃圾焚烧对环境的污染。     

Changes in PCDD/PCDF formation processes during instationary phases of combustor operation--exemplified by the use of Cl4DD isomer patterns

In this paper results of various measurement campaigns at different municipal waste incineration (MWI) plants concerning the change of the PCDD/PCDF isomer distribution in the crude gas during transiently impaired combustion conditions are presented. The focus is on the Cl4DD isomer distributions exemplarily for all other homologue groups to demonstrate the change in PCDD/PCDF formation mechanism at transient combustion conditions. Additionally to crude gas samples, at one plant filter and boiler ash were investigated simultaneously to determine if there is any difference in the isomer distribution between the matrices. For the ash from an electrostatic precipitator (ESP ash), the boiler ash and the corresponding crude gas sample, nearly identical changes in the Cl4DD isomer distribution under transient combustion conditions in relation to the normal operation process could be detected. By comparing the Cl4DD isomer distributions from different incineration plants (two municipal waste incinerators and one little incinerator burning wood chips for heating domestic household) under transient combustion conditions, in all cases the 1,3,6,8- and 1,3,7,9-Cl4DD were dominating the isomer distribution, whereas under normal operation other isomers were predominant. Obviously PCDD/PCDF formation mechanisms under transient combustion conditions are independent from the type of incinerator and of the burned fuel, respectively. Data sets were analyzed with respect to the possible reaction mechanism via chlorophenols and a good correlation of 2,4,6-trichlorophenol during the second phase of a start-up process and during a CO experiment was found. To get more detailed information about possible formation mechanisms, at one plant the dependence of the PCDD/PCDF isomer distribution on the different matrices was studied. Separate analysis of fly ash collected at the boiler exit, subsequent gas phase, ESP ash and boiler ash under normal operation conditions showed that, apart from the fly ash, the Cl4DD isomer distributions are nearly the same in the different matrices. Surprisingly, the Cl4DD isomer distribution of the fly ash was more similar to the distributions found under transient combustion conditions.