金属卤化盐改性沸石脱汞性能

为了获得性价比较高的燃煤烟气脱汞吸附及氧化材料,采用碱金属卤化盐、过渡金属卤化盐等溶液浸渍改性人造沸石,通过固定床吸附实验考查改性沸石对模拟烟气中汞的脱除能力,讨论改性沸石对汞的脱除机理。结果表明:碱金属卤化盐改性会略微降低沸石对汞的脱除能力,过渡金属卤化盐改性会显著提高沸石对汞的脱除能力。提高溶液浓度会提高过渡金属卤化盐溶液改性沸石的脱除能力。改性导致沸石的比表面积减小、孔容积减小,吸附能力减弱,但有效官能团的增加使得氧化及催化氧化能力增强。过渡金属卤化盐改性沸石对汞的脱除机理为化学吸附占主导地位,Hg~0被物理吸附的比例小于5%,其余的均被氧化成汞氧化物。     

氯化铜改性石墨相氮化碳吸附剂的脱汞性能

针对燃煤电厂汞污染物排放控制的问题,以尿素为前驱体,通过直接热聚合法制得绒毛状石墨相氮化碳(gC_3N_4),并用于低温条件下吸附脱除单质汞(Hg~0)。利用透射电子显微镜(TEM)、X射线衍射(XRD)、氮气吸附-脱附、X射线光电子能谱(XPS)等手段对吸附剂进行表征。结果表明:未改性g-C_3N_4具有良好的低温脱汞活性,在120°C时其脱汞效率可达84.7%;CuCl_2改性可以有效提高g-C_3N_4的脱汞性能,其脱汞效率在40～200°C范围内均可达到97%以上;温度对吸附剂脱汞效率的影响较小。XPS表征测试结果表明,铜离子和共价态氯原子均参与了单质汞的吸附脱除反应,Hg~0被Cu~(2+)离子和共价态Cl原子氧化成了Hg~(2+)离子,再吸附于g-C_3N_4表面而脱除。CO_2、SO_2和水蒸气对吸附剂脱汞效率影响较小,但水蒸气可提高汞吸附量。     

椰壳碳基吸附剂的脱汞特性

为研究来源于生物质的椰壳活性炭对单质汞的脱除性能,采用化学浸渍法对椰壳活性炭进行化学改性处理,并在小型实验台架上考察了椰壳碳基吸附剂的脱汞性能。并对改性前后的样品进行了BET和SEM表征分析以研究改性前后椰壳活性炭的变化规律。结果表明,改性后椰壳活性炭具有较强的脱汞能力,特别是在140℃、180℃时的脱汞效率仍保持在95%以上。改性后椰壳活性炭具有更多的利于脱汞的官能团,其主要靠化学吸附脱汞。烟气中低浓度的SO_2与NO对汞的脱除有一定的抑制作用,而HCl有一定的促进作用。     

飞灰-氢氧化钙/聚苯硫醚(PPS)滤料对烟气中单质汞的脱除

在汞固定床实验台上进行了飞灰-氢氧化钙和PPS滤料负载飞灰-氢氧化钙吸附单质汞,以及不同温度、气体成分对滤料负载吸附剂脱除汞影响的实验研究。实验结果表明,质量配比为2∶1的飞灰-Ca(OH)2吸附剂对Hg0的脱除效果最好,最高可达到34.5%左右,比纯飞灰条件下的脱除效率提高了近10%。120℃条件下,PPS滤料负载飞灰-Ca(OH)2吸附剂对汞的脱除率最高达72%,远高于滤纸薄膜上吸附剂的脱除率。随着温度升高,PPS滤料负载吸附剂的脱除效率降低。HCl、SO2和NO对PPS负载吸附剂脱除汞表现出不同程度的促进作用,HCl具有很强的促进作用,少量HCl足以大幅度提高脱除效果,SO2有一定的促进作用,NO的促进效果并不明显。     

天然和巯基改性沸石吸附水溶液中重金属Hg2+的特征研究

为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg²⁺浓度和吸附时间对沸石和巯基改性沸石吸附Hg²⁺的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg²⁺受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg²⁺的化学反应。而天然沸石对Hg²⁺的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1 h、巯基改性沸石在0.5 h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg²⁺的吸附能力得到了很大的提高,吸附容量由8.06 mg/g 提高到19.88 mg/g,提高了146.65%。     

天然和巯基改性沸石吸附水溶液中重金属Hg^2＋的特征研究

为了提高沸石对汞的吸附性,利用半胱胺盐酸盐对天然斜发沸石进行改性,制得巯基改性沸石。研究了吸附剂用量、pH值、温度、Hg^2＋浓度和吸附时间对沸石和巯基改性沸石吸附Hg^2＋的影响,并进一步研究了吸附机理。结果表明,巯基改性沸石吸附Hg^2＋受pH值、温度的影响较小,吸附机制主要是沸石表面的硫与Hg^2＋的化学反应。而天然沸石对Hg^2＋的吸附主要是离子交换作用,受温度、pH值等的影响较大,随温度的升高吸附量下降。整个吸附过程以较快的速度进行。天然沸石在吸附时间为1h、巯基改性沸石在0．5h时基本达到吸附平衡。吸附条件试验和Langmuir等温吸附模型都表明,巯基改性沸石对Hg^2＋的吸附能力得到了很大的提高,吸附容量由8．06mg／g提高到19．88mg／g,提高了146．65％。     

卤化铵改性竹炭对单质汞吸附性能的影响

为了研究廉价吸附剂竹炭的脱汞性能,将经过CO_2活化并采用NH_4Cl、NH_4I超声浸渍改性的竹炭(BC)应用于单质汞的吸附,并对比不同负载量的NH_4Cl以及NH_4I改性和温度等因素对竹炭的汞脱除性能的影响。采用了元素分析、扫描电镜分析、XPS表征、比表面积及孔径分布等对材料进行研究。结果表明,NH_4Cl和NH_4I改性显著提高竹炭的脱汞能力,并且在同等条件下NH_4I改性剂效果优于NH_4Cl。研究表明提高负载量会造成吸附材料孔堵塞,但在0~8wt.%的负载量情况下,孔道的堵塞不足以抵消化学吸附带来的积极作用,表明改性竹炭对汞的吸附主要表现为化学吸附。同时改性竹炭存在随着温度升高其吸附效率先降低后升高的趋势,暗示竹炭对汞的吸附在低温时物理吸附占优势,温度升高时化学吸附占优势。     

改性粉煤灰基脱汞吸附剂制备及性能分析

以燃煤电厂粉煤灰为主要原料制备了具有一定强度的脱汞吸附剂,并用卤盐溶液NaCl和NaBr进行改性,获得了具有较高单质汞脱除效率的粉煤灰基吸附剂,并对吸附剂的理化性能进行了分析。结果表明,改性溶液浓度越高,改性时间越长,改性剂越易进入吸附剂内部堵塞孔隙,吸附剂比表面积越小,但改性剂并没有改变吸附剂的物相组成。改性剂会附着在吸附剂孔隙表面,增加微孔数量,并与单质汞反应生成汞的化合物填充于表面微孔中。5%NaCl溶液浸渍改性3 h获得的吸附剂具有最优的汞脱除效果,达到92.6%,吸附寿命为1 430 min,吸附饱和量为930 ng·g~(-1)。     

硝基苯酚和硝酸改性酚醛泡沫脱除烟气中Hg~0

以酚醛泡沫作为基体材料,选择对硝基苯酚和硝酸作为改性剂,制备改性酚醛泡沫PF-12%NO_2和PF-HNO3-5,并研究其对模拟烟气中Hg~0的脱除能力。通过红外和热重表征发现,2种改性剂均可在样品表面引入硝基,且硝酸改性样品PF-HNO_3-5的热解温度更低,可能是由于其表面产生了大量羰基。脱汞实验发现,未改性样品PF-0的汞吸附量仅有0.46μg/g,而PF-12%NO_2的汞吸附量为1.45μg/g,PF-HNO_3-5的汞吸附量为14.63μg/g,表明硝基和羰基确实可以提升吸附剂对烟气中Hg~0的吸附能力。PF-12%NO_2和PF-HNO_3-5的汞吸附曲线均符合颗粒内扩散模型及Bangham模型。     

羟基金属柱撑膨润土吸附氟的性能研究

将膨润土进行改性制得4种羟基金属柱撑膨润土,用XRD考察了层间结构,并将它们应用于含氟废水的吸附处理中,研究了各种吸附剂的吸附速率、介质的pH、吸附剂用量、饱和吸附曲线和吸附剂的重复使用性.结果表明,改性得到的羟基金属柱撑膨润土的层间距都明显变大,在实验条件下对氟离子的吸附性能为羟基铁铝复合柱撑膨润土>羟基铁柱撑膨润土>羟基铝柱撑膨润土.该类吸附剂对氟离子还具有较好的重复使用性.     

铁基膨润土对水中磷酸根的吸附热力学及动力学研究

采用铁盐改性制得铁基膨润土,研究了其对水中磷酸根的吸附性能及影响因素,结果表明,通过对膨润土的改性提高了磷的去除率,含磷废水初始pH值的大小对磷的去除率影响不大,初始浓度越低越有利于磷的去除。磷的去除率随改性膨润土的投加量增大而提高,随温度升高而增大。进一步研究表明,改性膨润土对磷的吸附是吸热反应,其吸附等温线可采用Langmuir等温吸附方程拟合;改性膨润土对磷的吸附是快速吸附,在20 min内,磷去除率达70%以上,符合准二级吸附动力学模型。     

Sorption kinetics and isotherm modelling of imidacloprid on bentonite and organobentonites

Bentonite was modified by quaternary ammonium cations viz. cetytrimethylammonium (CTA), cetylpyridinium (CP), rioctylmethylammonium (TOM) and pcholine (PTC) at 100% cation exchange capacity of bentonite and was characterized by X-ray diffraction, CHNS elemental analyser and Fourier transform infrared spectroscopy. The sorption of imidacloprid on organobentonites/bentonite was studied by batch method. Normal bentonite could adsorb imidacloprid only upto 19.31–22.18% while all organobentonites except PTC bentonite (PTCB), enhanced its adsorption by three to four times. Highest adsorption was observed in case of TOM bentonite (TOMB) (76.94–83.16%). Adsorption kinetic data were fitted to pseudo-first-order, pseudo-second-order and intraparticle diffusion models. For normal bentonite data were best fitted to pseudo-first-order kinetic, while for organobentonites fitted to pseudo-second-order kinetics. Sorption data were analysed using Freundlich, Langmuir, Temkin and Dubinin–Radushkevich isotherm models. Data were well fitted to Freundlich adsorption isotherm. Product of Freundlich adsorption constant and heterogeneity parameter (K_f.1/n) was in following order: TOMB (301.87) > CTA bentonite (CTAB) (152.12) > CP bentonite (CPB) (92.58) > bentonite (27.25). Desorption study confirmed hysteresis and concentration dependence. The present study showed that the organobentonite could be a good sorbent for removal of imidacloprid from natural water sample also. Percentage adsorption and Distribution coefficient (mL g^?1) value of different adsorbent was in following order: TOMB (74.85% and 297.54) > CTAB (55.78% and 126.15) > CPB (45.81% and 84.55) > bentonite (10.65% and 11.92).     

Pore Structure Effects on Ca-Based Sorbent Sulfation Capacity at Medium Temperatures: Activated Carbon as Sorbent/Catalyst Support

Abstract

The reaction between three different Ca-based sorbents and SO₂ were studied in a medium temperature range (473–773 K). The largest SO₂ capture was found with Ca(OH)₂ at 773 K, 126.31 mg SO₂?g Ca(OH)₂ ^?1, and the influence of SO₂ concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sul-fated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO₂, one kind of CaO/activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO₂ than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO₂ and Ca-based sorbents and the prepared CaO/AC sorbents/cata-lysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the des-ulfurization reaction. AC acting as the support can play a role to supply O₂ to increase the affinity to SO₂. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO₂ adsorption.     

适宜处理分散性生活污水的人工湿地除磷填料的筛选及改性

为提高人工湿地除磷效能,从沸石、陶粒、萤石、膨胀蛭石、石灰石、麦饭石、火山岩、牡蛎壳、钢渣和废砖块这10种具有较高磷素饱和吸附量的填料中,筛选出钢渣、沸石和石灰石3种适宜处理分散性生活污水的人工湿地填料,并分别使用不同浓度梯度的酸(碱)、盐对3种填料进行改性,以增强其除磷能力。研究结果表明,钢渣、沸石和石灰石分别经2 mol/L AlCl3、2 mol/L NaOH及2 mol/L AlCl3、0.5 mol/L AlCl3溶液改性后,磷素吸附量达到最高值(0.272、0.0801和0.351 mg/g),而双常数方程能更好地描述优选填料对生活污水中磷的吸附动力学过程,综合考虑填料的吸附效果、成本及来源,改性石灰石是人工湿地处理分散性生活污水时较为理想的除磷填料;此外,填料经铝改后,氮磷吸附效果普遍优于其他改性条件,且Al-P有利于植物直接吸收利用,含铝废水来源广泛,故利用铝改液处理人工湿地填料具有较高的应用推广价值。     

改性铁覆膜砂的制备及吸附性能研究

制备了4种改性铁覆膜砂,并对其吸附性能进行了全面的实验,分析比较了4种改性剂的作用和效果.实验中发现,添加改性剂对铁覆膜砂吸附性能的促进作用各不相同,改性剂和铁氧化物的性质共同决定了改性铁覆膜砂的性质.吸附等温线和连续动态过滤实验结果表明,活性炭和硅藻土对提高铁覆膜砂吸附性能有促进作用,但膨润土和粉煤灰的作用不明显,甚至还可能降低吸附容量.活性炭改性铁覆膜砂的吸附等温式符合Langmuir模型,硅藻土改性铁覆膜砂、膨润土改性铁覆膜砂和粉煤灰改性铁覆膜砂对Langmuir模型和Freundlich模型都有较好的相关性.改性铁覆膜砂对天然有机物(NOM)的吸附属于单分子层吸附,吸附的主要机理为静电相互作用、配位交换-表面络合作用和疏水/憎水作用等.溶液pH值对改性铁覆膜砂吸附NOM有很大的影响,表现为低"pH值去除效率高,高pH值去除效率低"的特点,其变化规律取决于添加物质的性质.磷酸盐会和腐殖酸在改性铁覆膜砂表面产生竞争吸附,磷酸盐对粉煤灰改性铁覆膜砂的吸附能力影响最大.     

改性膨润土作为垃圾渗透液防渗层的实验研究

本文以天然钠基膨润土为原料,采用水溶液聚合法,在室温条件下,通过改性聚丙烯酰胺对膨润土进行直接插层改性,制备了一种新型聚丙烯酰胺改性膨润土防渗材料。以此防渗材料作为防渗层,选用沈阳大辛填埋场的垃圾渗透液为处理对象,在动态实验下,就其对实际垃圾渗滤液中主要污染物去除的有效性和控制垃圾渗滤液渗透的可行性进行研究。抗渗性能测试结果表明,改性膨润土防渗性能较好,渗透系数为1．0×10^-7cm/s,达到固体废物填埋场的防渗材料国家标准1．0×10^-7cm／s的使用要求。改性膨润土防渗层对COD、氨氮、重金属离子去除效果较好,吸附作用较强,COD和氨氮最大去除率分别达到81％和91％,TFe、Zn^2＋和TCr的最大去除率分别达到71％、58％和73％。实验结果验证了本研究所制备的改性膨润土防渗材料具有优良的抗渗、截污性能。     

Adsorption of elemental mercury vapors from synthetic exhaust combustion gas onto HGR carbon

An activated carbon commercially available named HGR, produced by Calgon-Carbon Group, was used to adsorbe metallic mercury. The work is part of a wider research activity by the same group focused on the removal of metallic and divalent mercury from combustion flue gas. With respect to previously published papers, this one is aimed at studying in depth thermodynamic equilibria of metallic mercury adsorption onto a commercial activated carbon. The innovativeness lies in the wider operative conditions explored (temperature and mercury concentrations) and in the evaluation of kinetic and thermodynamic data for a commercially available adsorbing material. In detail, experimental runs were carried out on a laboratory-scale plant, in which Hg° vapors were supplied in a nitrogen gas stream at different temperature and mercury concentration. The gas phase was flowed through a fixed bed of adsorbent material. Adsorbate loading curves for different Hg° concentrations together with adsorption isotherms were achieved as a function of temperature (120, 150, 200°C) and Hg° concentrations (1.0?7.0 mg/m³). Experimental runs demonstrated satisfying results of the adsorption process, while Langmuir parameters were evaluated with gas–solid equilibrium data. Especially, they confirmed that adsorption capacity is a favored process in case of lower temperature and they showed that the adsorption heat was –20 kJ/mol. Furthermore, a numerical integration of differential equations that model the adsorption process was proposed. Scanning electron microscopy (SEM) investigation was an useful tool to investigate about fresh and saturated carbon areas. The comparison between them allowed identification of surface sites where mercury is adsorbed; these spots correspond to carbon areas where sulfur concentration is greater.

Implications: Mercury compounds can cause severe harm to human health and to the ecosystem. There are a lot of sources that emit mercury species to the atmosphere; the main ones are exhaust gases from coal combustion and municipal solid waste incineration. Furthermore, certain CO₂ capture processes, particularly oxyfuel combustion in a pulverized fuel coal-fired power station, produce a raw CO₂ product containing several contaminants, mainly water vapor, oxygen, and nitrogen but also mercury, that have to be almost completely removed; otherwise these would represent a strong drawback to the success of the process.     

沸石改性及其去除水中氨氮的实验研究

通过实验研究了沸石改性条件及其对水中氨氮吸附去除的影响。结果表明,加热改性与无机酸改性不能显著提高沸石对氨氮的吸附量。利用NaOH改性的最佳浓度为1 mol/L,此条件下对氨氮吸附量可提高到650.68 mg/kg,为天然沸石的2.82倍。利用无机盐改性时,对氨氮吸附效果最好的是NaCl改性沸石,其次为KCl改性沸石与CaCl₂改性沸石。随着NaCl溶液浓度和改性时间的增加,改性沸石对氨氮的吸附量显著增加,可达天然沸石的3～4倍;在NaCl浓度为150 g/L与改性时间为18 h条件下,改性沸石对氨氮吸附量可达887.35 mg/kg,为天然沸石的3.84倍。