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.     

生活垃圾低温热解过程二噁英控制试验

针对垃圾热解烟气中二噁英排放不达标的现象,在分析垃圾热解机理及二噁英产生机制的基础上,提出了定量供氧、分层控制二噁英的方法;并采用数值分析和试验测试相结合的方法,对炉内气流组织及垃圾热解过程进行模拟分析。结果表明：热解炉内部气流整体分布较为均匀,能够保证垃圾稳定热解。热解炉沿轴向方向上存在温度分层,与理论分析结果一致,但燃烧层与热解层之间的过渡层存在二噁英合成气氛;热解炉温度实测结果与模拟结果整体吻合较好;空气过剩系数为0.3时热解炉运行情况更有利于减少二噁英的产生。现场试验发现,热解炉出口烟气中除颗粒物浓度超标外,其余常规污染物及二噁英排放浓度均满足GB 18485—2014《生活垃圾焚烧污染控制标准》;而市面上常见炉型二噁英出口浓度为0.44 ng-TEQ/m³,超过GB 18485—2014限值0.1 ng-TEQ/m³;2种炉型试验结果对比证明,在热解炉布气均匀的基础上,通过定量供氧、分层控制的方法可以有效抑制烟气中二噁英的生成。该成果可为生活垃圾低温热解过程二噁英的控制提供理论参考。     

30t/d新型村镇垃圾热解气化炉二噁英排放特性

针对目前处置村镇垃圾的小型热处理炉运行不稳定、排放难以达标等问题,介绍了一种新型村镇垃圾热解气化炉(30 t/d),并对其系统烟气及炉渣的二噁英生成排放特性进行研究。结果表明：炉渣中的二噁英浓度为0.723μg I-TEQ/kg,可满足GB 16889—2008《生活垃圾填埋场污染控制标准》中二噁英排放的要求;在正常喷射活性炭时尾部烟气二噁英浓度为0.029 ng I-TEQ/Nm³,低于GB 18485—2014《生活垃圾焚烧污染控制标准》中二噁英排放限值;气化燃烧过程的烟气二噁英原始排放浓度较低,低温异相合成反应是该垃圾炉烟气二噁英的主要来源;在质量浓度分布上占优势的为高氯代PCDD/Fs,对总毒性当量起主导作用的为2,3,4,7,8-PeCDF,喷射活性炭对二噁英具有良好的去除效果。以期为村镇垃圾热解气化规范处置提供示范,并为热解气化炉二噁英排放控制提供参考。     

Negative emissions of carbon dioxide through chemical-looping combustion (CLC) and gasification (CLG) using oxygen carriers based on manganese and iron

Carbon capture and storage (CCS) is an economically attractive strategy for avoiding carbon dioxide (CO₂) emissions from, e.g., power plants to the atmosphere. The combination of CCS and biomass combustion would result in a reduction of atmospheric CO₂, or net negative emissions, as plant growth is a form of sequestration of atmospheric carbon. Carbon capture can be achieved in a variety of ways, one of which is chemical looping. Chemical-looping combustion (CLC) and chemical looping gasification (CLG) are two promising technologies for conversion of biomass to heat and power or syngas/methane with carbon capture. There have been significant advances made with respect to CLC in the last two decades for all types of fuel, with much less research on the gasification technology. CLG offers some interesting opportunities for production of biofuels together with carbon capture and may have several advantages with respect to the bench mark indirect gasification process or dual-bed fluidized bed (DFBG) in this respect. In CLG, an oxygen carrier is used as a bed material instead of sand, which is common in indirect gasification, and this could have several advantages: (i) all generated CO₂ is present together with the syngas or methane in the fuel reactor outlet stream, thus in a concentrated stream, viable for separation and capture; (ii) the air reactor (or combustion chamber) should largely be free from trace impurities, thus preventing corrosion and fouling in this reactor; and (iii) the highly oxidizing conditions in the fuel reactor together with solid oxide surfaces should be advantageous with respect to limiting formation of tar species. In this study, two manganese ores and an iron-based waste material, LD slag, were investigated with respect to performance in these chemical-looping technologies. The materials were also impregnated with alkali (K) in order to gauge possible catalytic effects and also to establish a better understanding of the general behavior of oxygen carriers with alkali, an important component in biomass and biomass waste streams and often a precursor for high-temperature corrosion. The viability of the oxygen carriers was investigated using a synthetic biogas in a batch fluidized bed reactor. The conversion of CO, H₂, CH₄, and C₂H₄ was investigated in the temperature interval 800–950 °C. The reactivity, or oxygen transfer rate, was highest for the manganese ores, followed by the LD slag. The conversion of C₂H₄ was generally high but could largely be attributed to thermal decomposition. The K-impregnated samples showed enhanced reactivity during combustion conditions, and the Mangagran-K sample was able to achieve full conversion of benzene. The interaction of the solid material with alkali showed widely different behavior. The two manganese ores retained almost all alkali after redox testing, albeit exhibiting different migration patterns inside the particles. LD slag lost most alkali to the gas phase during testing, although some remained, possibly explaining a small difference in reactivity. In summary, the CLC and CLG processes could clearly be interesting for production of heat, power, or biofuel with negative CO₂ emissions. Manganese ores are most promising from this study, as they could absorb alkali, giving a better conversion and perhaps also inhibiting or limiting corrosion mechanisms in a combustor or gasifier.

     

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.     

Thermogravimetric coupled with Fourier transform infrared analysis study on thermal treatment of monopotassium phosphate residue

In China, safe disposal of hazardous waste is more and more a necessity, urged by rapid economic development. The pyrolysis and combustion characteristics of a residue from producing monopotassium phosphate (monopotassium phosphate residue), considered as a hazardous waste, were studied using a thermogravimetric, coupled with Fourier transform infrared analyzer (TG-FTIR). Both pyrolysis and combustion runs can be subdivided into three stages: drying, thermal decomposition, and final devolatilization. The average weight loss rate during fast thermal decomposition stage in pyrolysis is higher than combustion. Acetic acid, methane, pentane, (acetyl) cyclopropane, 2,4,6-trichlorophenol, CO, and CO₂ were distinguished in the pyrolysis process, while CO₂ was the dominant combustion product.     

生活垃圾焚烧飞灰二噁英控制技术研究进展

生活垃圾焚烧飞灰含有二噁英等有机物和Cr、Hg等重金属,是高度危险的固体废物,已成为二噁英污染的主要来源之一。针对飞灰中二噁英的不同解毒技术研究现状,系统阐述了近年来不同技术的原理、研究现状及发展趋势等,指出具有较大工业化应用前景的是水泥窑协同处置和低温热解技术。水泥窑协同处置技术可实现二噁英高效降解,且无二次污染物产生,局限性是该技术需要依托熟料生产线,飞灰水洗预处理投资运行成本相对较高;低温热解技术可高效实现飞灰中二噁英的脱除,局限性是存在二噁英从固相转移至气相,通常集成其他气相二噁英降解技术,如催化氧化等技术,可实现气相二噁英的高效降解,能耗及投资成本相对较低。并对飞灰中二噁英未来的降解技术和发展方向进行了展望,旨在为飞灰二噁英解毒技术的实用研究提供理论研究基础。     

A new gasification and melting incineration process of MSW with co-current shaft furnace

In all the municipal solid waste (MSW) disposal technology, incineration with gasification and melting has been taken as a environmentally sound and zero emission technology owing to avoiding second-pollution of heavy metals and dioxin. In this background, a new direct gasification and melting incineration process with co-current shaft furnace is put forward. In this process, MSW and combustion-supporting air are co-current from top to bottom in a shaft furnace. Fuel gas from pyrolysis and gasification burns completely in the bottom in order to offer energy for slag melting. The simulation experiment of the co-current shaft furnace has been done. The results of simulation experiment show that the temperature on the condition of co-current is much higher than on the condition of countercurrent at the bottom of reaction tube and so is the CO₂ quantity discharged from reaction tube. It can be concluded that the co-current shaft furnace is more suitable for direct gasification and melting incineration process.     

催化臭氧氧化过程中溴酸盐的生成机制研究

以黄河下游某水厂滤后水为目标物,选择了9种催化剂,在间歇反应装置中研究了单独臭氧和催化臭氧氧化过程中溴酸盐（BrO 3-）的生成情况,结果表明,在催化臭氧氧化过程中,NiO、CuO、Fe3O4、Al2O3加入使BrO 3-质量分数分别降低34.0%、32.8%、29.2%、20.8%.选取Fe3 O4作为催化剂研究催化...     

中国危险废物和医疗废物焚烧处置行业二（口恶）排放水平研究

通过调研全国危险废物和医疗废物焚烧处置设施,对包含二噁英排放水平的设施按处置对象、炉型和处理量分类,并作系统分析和研究.结果表明现有危险废物焚烧设施烟气中二噁英的浓度比医疗废物低,达标率为74.19%;危险废物选用回转窑处置效果较好,达标率为66.67%;而医疗废物选用回转窑或热解炉,要综合考虑处置规模、生产成本和二英排放总量等因素;危险废物介于10~30 t·d-1和医疗废物介于10~20 t·d-1的处置设施要尤其注意二噁英的排放问题;医疗废物焚烧飞灰中二噁英的均值浓度为危险废物6倍以上,仅有16.67%满足填埋要求.二者烟气中二英的浓度分布以1,2,3,4,6,7,8-HpCDF、2,3,7,8-TCDF和OCDD为主.     

Sulfur evolution in chemical looping combustion of coal with MnFe2O4 oxygen carrier

Chemical looping combustion （CLC） of coal has gained increasing attention as a novel combustion technology for its advantages in CO2 capture. Sulfur evolution from coal causes great harm from either the CLC operational or environmental perspective. In this research, a combined MnFe2O4 oxygen carrier （OC） was synthesized and its reaction with a typical Chinese high sulfur coal, Liuzhi （LZ） bituminous coal, was performed in a thermogravimetric analyzer （TGA）-Fourier transform infrared （FT-IR） spectrometer. Evolution of sulfur species during reaction of LZ coal with MnFeaO40C was systematically investigated through experimental means combined with thermodynamic simulation. TGA-FTIR analysis of the LZ reaction with MnFe2O4 indicated MnFe2O4 exhibited the desired superior reactivity compared to the single reference oxides Mn304 or Fe203, and SO2 produced was mainly related to oxidization of H2S by MnFe2O4. Experimental analysis of the LZ coal reaction with MnFe2O4, including X-ray diffraction and X-ray photoelectron spectroscopy analysis, verified that the main reduced counterparts of MnFe2O4 were Fe304 and MnO, in good agreement with the related thermodynamic simulation. The obtained MnO was beneficial to stabilize the reduced MnFe2O4 and avoid serious sintering, although the oxygen in MnO was not fully utilized. Meanwhile, most sulfur present in LZ coal was converted to solid MnS during LZ reaction with MnFe2O4, which was further oxidized to MnSO4. Finally, the formation of both MnS and such manganese silicates as Mn2SiO4 and MnSiO3 should be addressed to ensure the full regeneration of the reduced MnFe2O4.     

Spatio-temporal variation of landfill gas in pilot-scale semi-aerobic and anaerobic landfills over 5 years

Variation of CH₄, CO₂, and O₂ concentrations in layers of different depths in semi-aerobic and anaerobic landfills was analyzed over a period of 5 years. The results showed that most of the municipal solid waste became basically stable after 5 years of landfill disposal. In the upper and middle layer, the concentration of CH₄ in the semi-aerobic landfill was significantly lower than that in the anaerobic landfill in different landfill periods, while in the lower layer, there was little difference in the CH₄ concentration between the semi-aerobic and anaerobic landfills. The average concentration of CH₄ and CO₂ in the anaerobic landfill was always higher than that in the semi-aerobic landfill, while the O₂ concentration showed an opposite variation in different landfill periods. This was related to the aerobic reaction of landfill waste around the perforated pipe in the semi-aerobic landfill, which inhibited effective landfill gas generation.     

Biomass chemical looping gasification for syngas production using modified hematite as oxygen carriers

Syngas is a clean energy carrier and a major industrial feedstock. In this paper, syngas was produced via biomass chemical looping gasification(CLG) process. Hematite, the most common Fe-based oxygen carrier(OC), was modified with different metal oxides(CeO₂, CaO and MgO) by the impregnation method. The hematite modified by CeO₂, CaO and MgO was namely as CeO₂-hematite(CeO₂-H), CaO-hematite(CaO-H) and MgO-hematite(MgO-H), respectively. The introduction...     

Quantifying and managing regional greenhouse gas emissions：Waste sector of Daejeon, Korea

A credible accounting of national and regional inventories for the greenhouse gas （GHG） reduction has emerged as one of the most significant current discussions. This article assessed the regional GHG emissions by three categories of the waste sector in Daejeon Metropolitan City （DMC）, Korea, examined the potential for DMC to reduce GHG emission, and discussed the methodology modified from Intergovernmental Panel on Climate Change and Korea national guidelines. During the last five years, DMC＇s overall GHG emissions were 239 thousand tons C02 eq./year from eleven public environmental infrastructure facilities, with a population of 1.52 million. Of the three categories, solid waste treatment/disposal contributes 68%, whilst wastewater treatment and others contribute 22% and 10% respectively. Among GHG unit emissions per ton of waste treatment, the biggest contributor was waste incineration of 694 kg CO2 eq./ton, followed by waste disposal of 483 kg CO2 eq./ton, biological treatment of solid waste of 209 kg CO2 eq./ton, wastewater treatment of 0.241 kg CO2 eq./m3, and public water supplies of 0.067 kg CO2 eq./m3. Furthermore, it is suggested that the potential in reducing GHG emissions from landfill process can be as high as 47.5% by increasing landfill gas recovery up to 50%. Therefore, it is apparent that reduction strategies for the main contributors of GHG emissions should take precedence over minor contributors and lead to the best practice for managing GHGs abatement.     

城市废弃物处理温室气体排放研究:以厦门市为例

城市废弃物处理是城市人为活动产生温室气体的来源之一.参考IPCC国家温室气体清单指南2006推荐的方法建立了厦门市废弃物处理的温室气体排放计算模型,对厦门市2005～2010年废弃物处理的温室气体排放情况进行了估算,包括固体废弃物填埋、焚烧以及污水处理等过程.结果表明,2005年温室气体总排放量折合二氧化碳当量(CO2e)为406.3 kt,2010年温室气体总排放量(以CO2e计)达到704.6 kt,随着废水处理工艺的提高和城市生活垃圾量的迅速增长,主要排放源由废水处理转变为固体废弃物填埋.2005年填埋产生的温室气体排放占固体废弃物处理排放量的90%左右,2010年所占比例下降到75%.厦门市废水处理温室气体排放量2007年最高,以CO2e计达到325.5 kt,化学原料及化学品制造业从2005～2010年一直是厦门市CH4排放量最高的产业,占工业废水处理CH4排放总量的55%以上.     

Fe2O3(1-12)作用下CO化学链燃烧反应机理研究

在化学链燃烧(CLC)过程中,载氧体表面的原子结构和电子特性决定了其化学反应活性.本文以Fe_2O_3为载氧体,探讨了其自然条件下主要裸露的高米勒数指表面(1-1 2)的结构性质,研究发现表面不同配位数的氧和铁原子(包括O2f、O3f、O4f、Fe4f和Fe5f)的键参数、电子态密度及电荷布居等存在明显差异.为探究这种差异对Fe_2O_3反应活性的影响,对比分析了CO在表面5种氧和铁原子位生成CO_2的吸附-反应机理.CO在表面低配位O原子O2f和O3f首先形成物理吸附,然后被晶格氧氧化生成CO_2,反应需要克服能垒分别为3.657 e V和3.401 e V;然而,CO在O4f位吸附时,首先克服1.864 e V能垒形成二齿形碳酸盐物种,之后克服1.097 e V的能垒形成CO_2.当CO在Fe4f和Fe5f位吸附时,CO与Fe原子成键,后经过活化与表面O原子成键,形成二齿形碳酸盐物种,能垒分别为0.416和0.219 e V,最终碳酸盐物种分别克服0.500和1.462e V的能垒生成CO_2.因此,可以推断表面高配位数的O4f、Fe4f和Fe5f原子,由于其较高的氧化态,在化学链燃烧过程中充当活性位的作用.本研究有助于了解铁基载氧体表面化学链燃烧反应的微观机理,并为载氧体表面结构性能调控制备提供理论借鉴.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

Fe2O3/MIL-53(Al)催化类芬顿氧化性能及其作用机制研究

以MIL-53(Al)和铁盐为原料,采用浸渍-焙烧的方法,制备了Fe_2O_3/MIL-53(Al)类芬顿催化剂.通过扫描电子显微镜(SEM)、射透射电子显微镜(TEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)及X射线光电子能谱仪(XPS),对Fe_2O_3/MIL-53(Al)、MIL-53(Al)及Fe_2O_3 3种材料的理化性质进行了表征.以亚甲基蓝为相关材料催化类芬顿反应氧化性能的指示剂,考察了Fe_2O_3/MIL-53(Al)、MIL-53(Al)及Fe_2O_3 3种材料催化类芬顿反应的活性.探讨了Fe_2O_3/MIL-53(Al)催化活性强化的相关作用机制.研究结果表明,Fe_2O_3/MIL-53(Al)的物化结构特征是以赤铁矿为主的纳米Fe_2O_3颗粒均匀、离散地分布在MIL-53(Al)之上,纳米Fe_2O_3颗粒尺寸大多集中在1～5 nm.与未负载纳米Fe_2O_3相比,其分散性和颗粒尺寸都展现出潜在优越性.Fe_2O_3/MIL-53(Al)材料催化类芬顿反应降解水溶液中亚甲基蓝的效果是未负载纳米Fe_2O_3的4.8倍(以反应速率常数计),且TOC去除率亦有明显优势.自由基猝灭实验结果表明Fe_2O_3/MIL-53(Al)催化类芬顿降解污染物的主要活性氧类物质为羟基自由基.MIL-53(Al)孔结构发达、孔分布均匀及孔尺寸较小且均一等结构特征,导致负载其中的Fe_2O_3具有孔道负载量大、颗粒分布离散且均匀、颗粒粒径小且均一等特点,从而强化了纳米Fe_2O_3催化类芬顿反应氧化降解水中污染物的性能.     

柴油表征燃料在高浓度CO2氛围下燃烧机理的分析

为研究高浓度CO₂在高温高压情况下对柴油燃烧特性的影响,提出了柴油表征燃料在CO₂/O₂氛围下的燃烧反应机理.通过量子化学计算了化学反应路径并对反应路径进行分析,最后进行柴油表征燃料燃烧的仿真.通过搭建定容燃烧弹试验台架和可视化系统进行试验与仿真分析,结果表明：在50% CO₂+50% O₂氛围下,对仿真与实验的火焰燃烧极限长度和火焰纵截面面积进行对比,最小误差分别为0.39%和0.64%,最大误差分别为8.54%和4.94%,说明此机理适用于高浓度CO₂氛围下柴油燃烧特性的研究;CO₂的化学效应在柴油表征燃料燃烧时具有促进作用,CO₂在2600 K时发生热解,热解产物CO与H自由基等发生反应可以生成着火促进剂·OH;柴油在50% CO₂+50% O₂、43% CO₂+57% O₂和35% CO₂+65% O₂氛围下的燃烧效率比空气氛围分别提高了28.2%、30.4%和33.3%.     

典型农药废盐热处理特性及适用性

随着我国农药行业的迅速发展,农药废盐的管理和无害化处置已经成为亟待解决的环境问题.为了解决农药废盐热处理适用性的问题,推进废盐热处理工业化进程,选择盐城某企业典型农药废盐开展热重试验和动力学模型研究,分析废盐的热处理特性;基于热重试验和动力模型获取的优化参数,进一步利用管式炉模拟试验研究循环流化床焚烧炉处置废盐的可行性.结果表明:该农药废盐热解和燃烧的失重过程相似,在升温过程中一直处于缓慢失重状态,但均只有一个明显的失重阶段.其中,热解的失重阶段为170~298℃,700℃时减重率达到84.08%,燃烧的失重阶段为194~315℃,700℃时减重率达到81.45%,为了使废盐充分反应,根据热重结果确定热处理温度为350℃.热处理动力学分析表明,燃烧和热解在失重阶段反应机理相同,氧气的存在可以促进废盐的热处理过程,确定了热处理的组分为空气组分,该农药废盐属于低热值成分复杂的固体废物.在上述条件下,利用管式炉模拟试验进一步优化了废盐的热处理条件为温度350℃、停留时间45 min、空气组分、空气流量40 mL/min.对热处理后的残留物及烟气进行GC/MS分析发现,热处理法可有效降低废盐中有机污染物含量,烟气中有害物质以苯系物为主,含有少量氯苯及氯代烃类有机物.研究显示,经过管式炉热处理试验后,废盐中有机污染物的去除率达82.93%,可以有效降低有机污染物含量,从而验证了该类废盐热处理的适用性.