废茶活性炭脱硫脱硝性能的应用研究

为探讨废茶活性炭对于SO2和NO脱除作用的制约因素,分别考察了材料孔径结构、石墨化程度及表面结构对其脱硫脱硝性能的影响,同时研究了其吸附机制及动力学过程.结果表明,较高的石墨化程度是影响材料脱硫性能的主要因素,微孔径较小且含氮碱性基团较高时有利于SO2的脱除;发达的中孔结构是制约NO脱除效率的关键因素,含氮碱性基团对NO的脱除具有一定的促进作用;烟气中SO2和NO共存时,材料的脱硫脱硝性能均有所降低,氧气和水蒸气的加入能够改善其脱硫脱硝效率;废茶活性炭在无水环境下对于SO2和NO的吸附作用均以物理吸附为主,水蒸气的存在促进了材料对SO2的化学吸附;通过动力学模型的拟合发现,Bangham吸附模型能够很好地描述材料脱硫脱硝的动力学过程,其R2均高于0.989,材料对于SO2和NO的吸附速率常数均随氧气和水蒸气的加入而减小.     

烧结烟气湿式氨法同时脱硫脱硝实验研究

在鼓泡反应器中进行烧结烟气湿式氨法同时脱硫脱硝的实验研究,考察了添加剂/NO物质的量比、吸收液NH3-NH+4浓度和烟气性质对烧结烟气脱硫脱硝的影响。实验结果表明:随着添加剂/NO物质的量比、烟气温度和NO浓度的增加,脱硝率均呈现先增大后减小的趋势。脱硝率随着吸收液中NH3-NH+4浓度的增大而增大。随着SO2浓度的增大,脱硝率逐渐减小。在所有实验条件下,脱硫率均接近或达到100%。在最佳实验条件下,脱硝率可达61.49%。通过添加添加剂部分氧化烧结烟气,可使烧结烟气湿式氨法脱硫工艺的脱硝率提高20%~30%。     

煤制气废水总酚负荷对反硝化的抑制效应研究

在高负荷酚类污染物的煤制气废水中,人们往往关注酚类对硝化菌的活性和效率抑制,对反硝化过程的抑制研究不多.为了探明煤制气废水中酚类化合物对反硝化脱氮效率和污泥活性的抑制作用,以缺氧反硝化小试系统为对象,考察了不同酚负荷对反硝化效率(NO~-_3-N和NO~-_2-N去除效率)、对污泥应激活性、降解活性和污泥毒性的影响.结果表明,当总酚浓度从50mg·L~(-1)提高到200 mg·L~(-1)时,NO~-_3-N和NO~-_2-N的去除率分别由83%和80.6%降至55%和25%,且NO~-_2-N的浓度随着NO~-_3-N浓度的降低呈现先上升后下降的趋势.在不同酚负荷的污泥驯化过程中,反硝化污泥的过氧化氢酶活性、脱氢酶活性以及污泥毒性变化趋势基本不变,但随着总酚浓度的升高,过氧化氢酶活性和污泥毒性会上升,脱氢酶活性会下降.     

钢铁行业典型烧结机污染物排放特征对比研究

钢铁工业排放是引起空气污染的重要原因之一,烧结工序又是钢铁行业中的排放大户.鉴于此,选取了一台工艺相对落后但仍在我国中西部地区大量存在的90 m2小型步进式烧结机和一台工艺较为先进的450 m2大型带式烧结机,对两台烧结机不同点位的SO₂、NO_x、颗粒物以及烟气Hg等进行实测,并对颗粒物中的元素、水溶性离子、OC和EC进行分析,从而获取不同技术水平、不同污控措施下烧结机污染物排放特征以及与2019年生态环境部办公厅印发的《关于推进实施钢铁行业超低排放的意见》中的超低排放限值之间的差距.结果表明:①烧结机头SO₂、NO_x、CO、颗粒物和烟气Hg排放浓度分别为54.69~123.04 mg/m3、187.28~312.58 mg/m3、6 746.04~7 790.83 mg/m3、11.04~19.93 mg/m3和78.97~2 537.07 ng/m3,烧结机尾颗粒物排放浓度为0.76~16.22 mg/m3,机头颗粒物以PM_2.5为主,占比为81.02%~91.49%,机尾颗粒物主要为PM₁₀,占比为71.17%~73.01%.烧结机头SO₂、NO_x、颗粒物以及烧结机尾颗粒物还需分别减排36.00%~71.55%、73.30%~84.00%、9.40%~49.82%和0~38.35%才能满足超低排放限值.②烧结颗粒物主要成分为K、Ca、Na、Mg、Fe、Cl-、SO₄2-、NH₄+、OC和EC等,其占比与烧结机类型、烧结原辅料以及污染物控制措施等因素有关,石灰石-石膏法脱硫后SO₄2-占比增加28.12%,活性炭移动床脱硫后EC占比增加2.15%.③布袋除尘器对烧结机不同粒径颗粒物和烟气Hg的脱除能力比双室五电场静电除尘器分别高出1.25%~5.06%和9.51%,活性炭移动床系统对烧结不同粒径颗粒物以及烟气Hg的去除效果分别比石灰石-石膏法脱硫系统高出9.40%~11.38%和4.31%.研究显示,不同工艺、不同污控措施烧结机大气污染物排放特征存在一定差异,SO₂、NO_x排放浓度与超低排放限值差距较大,烟尘排放浓度与超低排放限值差距较小.      

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.     

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.     

CFB锅炉钙基飞灰的雾化喷水悬浮式脱硫特性

以循环流化床(CFB)锅炉钙基飞灰为原料,实验研究了不同条件下飞灰的雾化喷水悬浮式脱硫工艺技术特性。结果表明:增湿飞灰具有良好的低温脱硫能力,其脱硫过程分为快速、慢速反应2个阶段,增湿前后脱硫剂的总钙利用率从41%提高到70%左右。飞灰颗粒的增湿效果与反应温度是影响硫盐化速率的主要因素。采用50 μm雾化水粒径、增湿水分级喷入方式,可使飞灰颗粒获得更好的增湿效果,并延长快速反应的持续时间,使反应更充分;反应温度对增湿脱硫同时存在促进与抑制2方面作用,最佳反应温度在80℃左右;SO₂浓度对脱硫的影响不显著;飞灰经过雾化喷水活化后,颗粒表面的孔隙、裂缝增多,改善的微观结构促进了气固传质和脱硫反应。     

焚烧飞灰水泥窑共处置过程As的迁移特征

为了明确焚烧飞灰水泥窑共处置过程中As的迁移特性,对大量国外工业水泥窑As的监测数据进行了统计分析,研究As或Cl输入总量对As迁移特性的影响.同时,采用CHEMKIN软件对水泥窑煅烧过程中As的物相进行热力学模拟,并使用水泥回转窑系统的简化模型讨论了窑灰循环对As迁移的影响.结果表明,焚烧飞灰中As的酸可提取态、可还...     

DNBF-O3-GAC组合工艺深度脱除氮磷及代谢产物

为提高污水厂尾水水质,本研究采用新型缓释碳源复配海绵铁、活性炭作为反硝化生物滤池的复合填料,分别以模拟二级处理出水和实际污水厂尾水为进水,考察了复合缓释碳源填料反硝化生物滤池-臭氧-活性炭(DNBF-O_3-GAC)组合工艺同步脱氮除磷及去除微生物代谢产物的性能,并借助Mi Seq高通量测序技术分析了反硝化生物滤池生物膜中的微生物群落结构特征.结果表明,组合工艺取得了较好的脱氮除磷及微生物代谢产物的效果:模拟配水阶段和实际尾水阶段NO_3~--N平均去除率分别达到88.87%、79.99%;TP平均去除率分别达到87.67%、65.51%;UV254平均去除率分别达到45.51%、49.23%.组合工艺各处理单元具有不同的功能:NO_3~--N、TN、TP、TFe的变化主要发生在反硝化生物滤池反应器中;UV254、三维荧光强度的变化主要发生在臭氧-活性炭反应器中.微生物在属水平进行聚类分析结果表明,反硝化脱氮系统存在硫自养反硝化菌和异养反硝化菌,当实际尾水阶段碳源相对不足时,硫自养反硝化作用有了显著加强,Thiobacillus(硫杆菌属)的占比由7.44%上升至29.62%,硫自养反硝化与异养反硝化形成的这种互补作用延长了新型缓释碳源的使用周期.     

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.     

燃煤锅炉低氮氧化物燃烧特性的神经网络预报

大型燃煤电站锅炉的低NO_x燃烧技术日益受到关注,但NO_x的排放特性复杂,受煤种、锅炉设计结构和操作参数等多种因素影响.在对某台600MW四角切圆燃煤电站锅炉的NO_x排放特性和飞灰含碳量特性进行多工况热态测试的基础上,应用人工神经网络的非线性动力学特性及自学习特性,建立了大型四角切圆燃烧锅炉NO_x排放特性和燃烧经济性的神经网络模型,并对此模型进行了校验.结果表明,该模型能根据燃煤特性及各种操作参数准确预报锅炉在不同工况下的NO_x排放和飞灰含碳量特性,可为大型电站锅炉通过燃烧调整降低NO_x排放和提高锅炉燃烧效率提供有效手段.     

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere

The heterogeneous degradation of nitrogen dioxide (NO₂) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NO_x analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO₂, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO₂ varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO₂ degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.     

Mercury removal from coal combustion flue gas by modified fly ash

Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.     

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.     

钢铁行业烧结烟气脱硫脱硝技术研究进展

钢铁行业是我国重要的基础行业,也是典型的高污染行业,每年排放大量的二氧化硫(SO₂)和氮氧化物(NO_x)等大气污染物。随着钢铁行业超低排放标准的实施,对大气污染有主要贡献的烧结工序亟须改造现有的或新建先进的脱硫脱硝设施。在介绍烧结烟气特点和排放标准变化的基础上,综述了目前主流应用的单独脱硫技术、单独脱硝技术和同时脱硫脱硝技术的应用现状,以及实验研发阶段的同时脱硫脱硝技术的研发进展,并系统展望了各类技术的未来发展前景。指出在单独脱硫和脱硝技术中,半干法和低温选择性催化还原法(SCR)更具应用潜力,且半干法脱硫+袋式除尘+SCR的工艺组合环境效益最高;同时脱硫脱硝技术中,氧化法和活性焦法尚需进一步提高效率和降低成本,同时脱硫脱硝技术具有潜在发展前景。     

废水同步脱硫脱氮关键工艺参数及微生物群落结构的研究

大量未经处理的含硫化物和硝酸盐废水的排放将带来严重的环境问题.根据以废治废原则,使用厌氧滴滤塔反应器构建的同步脱硫耦联反硝化脱氮反应(SDD)能很好的去除废水中S~(2-)和NO-x-N.其中以聚氨酯泡沫为填料的厌氧滴滤塔反应器中生物活性最强,脱氮脱硫效果最好.体系中功能菌优先将S~(2-)氧化成S0,待S~(2-)去除完全后,再进一步将S0氧化成SO_4~(2-).同时,SDD反应降解NO_3~--N的速率快于NO_2~--N.进水S/N摩尔比越大,产物中SO_4~(2-)相对含量越低.结合实际工程考虑,应控制进水S/N摩尔比在5/3~5/2之间,S~(2-)浓度控制在538 mg·L-1以下.微生物群落结构分析结果表明,Thiobacillus属在4组反应器上占绝对优势,其相对丰度均高于40%.其次相对丰度较高的Rhodanobacter、Arenimonas和Truepera属与厌氧反硝化作用密切相关.对4组反应器中微生物进行Alpha-多样性分析结果表明取得较好脱硫耦联反硝化效果的体系中物种多样性指数也较高.     

采用含硫铁化学污泥作为反硝化电子供体进行焦化废水中总氮深度去除

城市污水处理和大部分的工业废水处理工艺的出水总氮普遍难以达标排放,基于进水水质的C/N值不稳定、提高回流比造成水力负荷增大、降低反应动力学并且耗能、投加有机碳源带来二次污染以及高污泥产率等问题,急需寻求一种节能降耗、操作简单的深度脱氮方法.对此,利用含硫工业废水预处理产生的含硫铁化学污泥作为固相电子供体进行自养反硝化深度脱氮,实验过程中,以焦化废水二级生物出水作为研究对象,考察脱氮性能、硫铁泥转变过程及微生物群落变化,求出废水深度脱氮新工艺的优化反应条件与效果范围.当进水NO_3~--N、NO_2~--N浓度分别是(74.54±0.57)mg·L~(-1)、(1.11±0.19)mg·L~(-1),水力停留时间为18 h时,对应出水浓度分别降低至(2.78±1.08)mg·L~(-1)、(2.87±0.71)mg·L~(-1);TON(NO_3~--N+NO_2~--N)去除率高达90.0%;NO_3~--N还原速率和NO_2~--N累积速率分别为12.06 mmol·(L·d)-1、7.74 mmol·(L·d)-1.结果表明,以副产物化学硫铁泥作为电子供体深度脱氮有潜在的工程应用价值,以水处理工艺过程中原位利用废物,解决部分富硫铁化学污泥后续处理问题,表现出资源化利用的综合特征.     

不同吸附剂处理废水中磷的对比研究

为了降低富营养化,实验中讨论了粉煤灰、活性炭两种吸附剂对人工配制的含磷废水的去除效果。从投药量、废水pH值以及振荡时间三个方面考察了对吸附作用的影响。实验结果显示：粉煤灰对磷的去除效果远比活性炭的好,而且还可达到以废治废的效果。粉煤灰、活性炭的最佳投药量分别为0．06g／ml、0．05g／ml;最佳pH值均为6;最佳振荡时间分别为5h、7h;在上述条件下,粉煤灰对磷的吸附率可达90．38％,而活性炭则为31．54％。