ZnCl_2溶液对褐煤半焦表面性质及其中高温脱汞性能的影响

利用ZnCl_2溶液对褐煤进行浸渍后在700℃条件下热解制备改性半焦,采用N2吸附/脱附、傅里叶变换红外光谱、X射线光电子能谱等手段对ZnCl_2处理前后两种半焦表面物化性质进行了表征,在小型固定床反应器上研究了ZnCl_2溶液浸渍处理前后褐煤半焦对气态单质汞(Hg~0)的脱除性能.结果表明,经过ZnCl_2处理得到的半焦(ZSC)具有发达的孔隙结构,其表面含氧官能团含量和数量有所提高,并出现了新的C-Cl基团;在100~360℃温度范围内,制备的改性半焦ZSC的脱汞效率随温度升高而降低,但在中高温条件下仍表现出良好的脱汞性能;在化学吸附过程中,气态Hg0被C-Cl基团氧化为HgCl或HgCl_2,同时Hg~0与半焦表面含氧官能团结合生成HgO,Hg~0最终以HgCl_2或HgO的形式附着在半焦表面.     

改性褐煤半焦的表面性质及对气态Hg0的吸附特性

以廉价的褐煤为原料制备褐煤原料半焦,通过化学改性研制脱除烟气中气态Hg⁰的改性半焦(MnO_x/褐煤半焦)吸附剂,运用N₂吸附-脱附、SEM(扫描电镜)、XRD(X射线衍射仪)及XPS(X射线光电子能谱)等对吸附剂的表面特性进行表征与分析,利用固定床吸附试验考察2种吸附剂对气态Hg⁰的吸附特性. 结果表明:原料半焦与改性半焦均具有较发达的孔隙结构,并且以2~5 nm的介孔结构为主;经化学改性后,半焦表面石墨化程度有所提高,石墨碳C─C所占比例由51.37%增至76.17%;MnO_x主要以高度分散的无定形状态均匀分布于改性半焦表面. 固定床吸附试验结果表明,温度为140 ℃时,原料半焦对气态Hg⁰的吸附性能较差,而改性半焦则表现良好,其最高吸附效率可达85.6%;初始ρ(Hg⁰)分别为10.1、20.3、30.0、40.6 μg/m³时,改性半焦的吸附性能随初始ρ(Hg⁰)升高而增强;当吸附温度由30 ℃升至140 ℃时,改性半焦的吸附性能也随着吸附温度的升高而增强. 改性半焦对气态Hg⁰的吸附作用应主要为化学吸附,被吸附后的汞主要以氧化态(Hg²⁺)形式存在.     

KI改性黏土脱除烟气中单质汞的研究

卤素改性材料对烟气中单质汞的去除具有较高的效率,黏土(膨润土)在我国分布广,资源丰富且廉价易得.为探究KI改性黏土对烟气中单质汞的脱除效率,以浸渍法制得了KI改性膨润土,研究了不同KI负载量、不同吸附温度及不同烟气氛围下,改性膨润土对Hg0的脱除效率和累积吸附量,并与原始膨润土进行对比.运用比表面分析(BET)、傅里叶红外光谱仪(FTIR)及热重分析法(TGA)等方法对材料的物理化学特性进行了分析.结果表明,KI改性大大提升膨润土对Hg0的脱除效率,并且Hg0的脱除效率随着KI负载量的加大而上升.温度提高了吸附剂吸附Hg0的性质,吸附剂主要表现为化学吸附.O2有利于吸附剂对Hg0的吸附.SO2对吸附剂吸附Hg0有轻微的促进作用,H2O的存在对吸附剂吸附Hg0具有很强的抑制作用.     

酸-碘改性壳聚糖-膨润土脱除单质汞特性及机理分析

为探明烟气中酸性气体(SO2,NO,HCl)和H2O对酸-碘改性壳聚糖-膨润土吸附剂脱除单质汞(Hg0)的影响和脱除机理,在小型固定床试验台架上开展了Hg0脱除的实验研究.结果表明:由于SO2与Hg0在吸附剂表面活性位上存在竞争吸附,SO2抑制吸附剂对Hg0的脱除.H2O和较高浓度(1000μg/m3)的NO对脱汞具有明显地促进作用.由于低温下HCl与Hg0较高的反应能垒,HCl对脱汞没有影响.与单一烟气成分影响相比,在SO2、NO、HCl和H2O的联合作用下,吸附剂的长时间脱汞性能得到大幅提高.机理分析表明壳聚糖首先被酸中的H+质子化,之后再吸附酸与KI反应生成的I2,进而有效地吸附Hg0.量子化学计算表明壳聚糖在酸性条件下对I2具有良好的吸附特性,改性壳聚糖吸附剂对Hg0具有较好的吸附能力,其吸附能约为127kJ/mol.     

低温等离子强化复合钙基吸附剂脱汞实验研究

在固定床吸附实验台上对低温等离子改性前后的复合钙基吸附剂进行脱汞实验,深入探究SO₂和O₂对具有较高孔隙率和比表面积的复合钙基吸附剂脱汞性能的影响.并通过多种表征手段和方法分析复合钙基吸附剂对Hg⁰的吸附机理.实验结果表明,由于等离子改性提高了吸附剂表面的含氧官能团的相对含量,经等离子改性的复合钙基吸附剂的脱汞效率有明显提高.在N₂+0.07% SO₂+6% O₂气氛下,吸附剂脱汞效率相比于无氧气氛由23.7%增至91.2%,吸附剂脱汞效率明显提高.此时吸附剂表面的羟基、酯基官能团作为主要反应活性位点,而羰基官能团的作用不明显.O₂的存在促使活性炭表面由碳原子不饱和键形成的活性位增加,促进了Hg⁰的吸附,同时生成多种汞化合物.随着SO₂浓度升至0.15%,改性复合钙基吸附剂表面活性位再次出现不足,此时SO₂抢夺Hg⁰的吸附位点,脱汞效率降至23.3%.     

FeCl3改性MOFs在低温下对Hg0的吸附性能

为提高吸附剂对Hg0（零价汞）的吸附效率,利用MOFs（金属有机框架）材料发达的孔隙结构和高比表面积（1 997.010 0 m2/g）,采用FeCl₃溶液浸渍改性,制备了吸附剂FeCl₃@MIL-101（Cr）用于脱除Hg0.在小型固定床反应器上考察了浸渍浓度、反应温度、氧含量等对Hg0去除的影响.结果表明:FeCl₃@MIL-101（Cr）在进口ρ（Hg0）为2×10-3 mg/L,c（FeCl₃）为0.2 mol/L,反应温度60℃,气体流速400 mL/min,φ（O₂）为1%的条件下,吸附穿透时间长达62 h,相应的吸附容量为14.27 mg/g.在此基础上,进一步利用BET（比表面积测试）、SEM（扫描电镜）-EDX（能量色散X射线光谱）、XRD（X射线衍射）、XPS（X射线光电子能谱）等常用表征手段研究了改性前后吸附剂的物理化学特性,证明了吸附剂FeCl₃@MIL-101（Cr）吸附零价汞是物理吸附与化学吸附共同作用的结果,含氯官能团在吸附Hg0过程中也发挥了相当大的作用,并且氧气可促进其吸附效果.最后,分析了其吸附机理.研究显示,该种吸附剂在低温条件下具有较为优良的脱汞性能,应用前景良好.      

FeCl3改性钢渣脱除燃煤烟气中Hg0的研究

以钢铁厂废弃钢渣为原料,以丙酮溶液为分散剂制备FeCl₃改性材料,在固定床吸附评价装置上考察了钢渣在FeCl₃改性前后对模拟烟气中Hg脱除效果的影响,并结合吸附试验与微观表征对改性催化剂的脱汞性能进行分析.结果表明:氯是FeCl₃改性钢渣吸附剂的主要活性组分,FeCl₃的掺入使钢渣的比表面积由1.06 m2/g提高到1.32 m2/g,进而提高吸附剂的汞吸附容量,经FeCl₃改性后废弃钢渣对汞的脱除效率比未改性前提升了3.2倍.SO₂的存在降低了FeCl₃改性钢渣材料的脱汞性能,持续通入的SO₂与吸附剂接触占据了部分孔道和表面活性位点,使得对单质汞的吸附效率下降,200℃时含有SO₂时的FeCl₃改性钢渣吸附剂吸附量比未通入SO₂气体的改性材料降低了75.57%;在含有HCl气体的烟气体系中,FeCl₃改性钢渣材料对汞的脱除效率从3432.70 ng/g升至10341.10 ng/g,并且随着反应温度的升高零价汞向氧化态汞转化的效率增加.研究显示,SO₂的存在降低了FeCl₃改性钢渣吸附剂的脱汞性能,而HCl气体有效地促进了FeCl₃改性钢渣吸附剂对零价汞（Hg0）的脱除.      

载溴竹炭的脱汞特性研究

为获得脱汞性能高的烟气汞吸附剂,采用化学浸渍法对廉价的生物质竹炭进行溴化学改性,并在小型实验台架上考察了载溴竹炭的脱汞性能。对改性前后的样品进行了BET和XPS表征分析以研究表面官能团在改性过程中的转化规律和脱汞机理。结果表明:改性后竹炭具有超强的脱汞能力,特别是在140℃时,其脱汞效率仍保持在100%。改性后竹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SO2与NO对汞的脱除有一定的抑制作用,在相同的实验条件下,SO2对吸附剂脱汞的抑制作用更加明显。     

壳聚糖吸附剂脱除燃煤模拟烟气中汞的试验研究

采用在线检测法检测了纯氮气气氛下及模拟烟气气氛下高分子化合物壳聚糖吸附剂对单质汞的吸附特性,结果表明,温度升高有利于脱汞反应的进行,纯氮气氛下脱除汞单质效率不高,60℃时为28.85%, 120℃时升为38.46%;氮氧化物、硫氧化物对汞的脱除有一定的促进作用,在模拟烟气气氛下120℃时吸附剂出口平衡吸附率为48.05%,平均吸附率约68%.红外光谱分析揭示了壳聚糖吸附剂吸附烟气中汞的机理为2个游离氨基与2个羟基鳌合1个汞原子或汞离子.     

腐殖酸定向修饰Ce-Co铁基生物焦汞吸附机理

使用腐殖酸对铁基改性生物焦进行定向修饰,并借助固定床吸附装置考察改性后生物焦汞吸附性能,探究了不同腐殖酸负载量下的铁基改性生物焦的汞吸附能力.采用BET、XPS、FTIR表征手段,考察了定向修饰后生物焦的孔隙结构、表面元素价态及表面功能基团的组成,通过SEM扫描电镜探究生物焦微观形貌,并利用EDS能谱分析生物焦表面活性金属成分分布.结果表明,使用腐殖酸对铁基改性生物焦定向修饰后的生物焦汞脱除性能大幅提高,使用5%质量分数包裹后的生物焦汞脱除性能最高,3h单位累积汞吸附量为18025ng/g,相较于未被修饰的铁基改性生物焦汞吸附性能提高65%;负载腐殖酸后的生物焦以介孔为主,表面活性金属种类丰富,有利于单质汞的氧化;样品表面羧基、醇羟基等含氧官能团数量增加,定向修饰后生物焦表面出现大量氨基等利于重金属吸附的含氮官能团;定向修饰后的生物焦表面出现团聚现象,包裹量过高会将生物焦表面活性位点完全包裹,阻碍了氧化还原反应的进行,不利于汞的进一步氧化;汞在生物焦表面的吸附过程同时存在化学吸附与物理吸附.     

Mercury oxidation and adsorption characteristics of potassium permanganate modified lignite semi-coke

The adsorption characteristics of virgin and potassium permanganate modified lignite semi-coke (SC) for gaseous Hg⁰ were investigated in an attempt to produce more effective and lower price adsorbents for the control of elemental mercury emission. Brunauer-Emmett-Teller (BET) measurements, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) were used to analyze the surface physical and chemical properties of SC, Mn-SC and Mn-H-SC before and after mercury adsorption. The results indicated that potassium permanganate modification had significant influence on the properties of semi-coke, such as the specific surface area, pore structure and surface chemical functional groups. The mercury adsorption efficiency of modified semi-coke was lower than that of SC at low temperature, but much higher at high temperature. Amorphous Mn⁷⁺, Mn⁶⁺ and Mn⁴⁺ on the surface of Mn-SC and Mn-H-SC were the active sites for oxidation and adsorption of gaseous Hg⁰, which oxidized the elemental mercury into Hg²⁺ and captured it. Thermal treatment reduced the average oxidation degree of Mn^x+ on the surface of Mn-SC from 3.80 to 3.46. However, due to the formation of amorphous MnO_x, the surface oxidation active sites for gaseous Hg⁰ increased, which gave Mn-H-SC higher mercury adsorption efficiency than that of Mn-SC at high temperature.     

Simultaneous removal of gaseous CO and elemental mercury over Cu-Co modified activated coke at low temperature

Cu-Co multiple-oxides modified on HNO₃-pretreated activated coke (AC_N) were optimized for the simultaneous removal of gaseous CO and elemental mercury (Hg⁰) at low temperature (< 200 °C). It was found that 2%CuOx-10%CoOx/AC_N catalyst calcined at 400°C resulted in the coexistence of complex oxides including CuO, Cu₂O, Co₃O₄, Co₂O₃ and CoO phases, which might be good for the simultaneous catalytic oxidation of CO by Co-species and removal of Hg⁰ by Cu-species, benefiting from the synergistic catalysis during the electro-interaction between Co and Cu cations (CoO ? Co₃O₄ and Cu₂O ? CuO). The catalysis removal of CO oxidation was obviously depended on the reaction temperature obtaining 94.7% at 200 °C, while no obvious promoting effect on the Hg⁰ removal (68.3%-78.7%). These materials were very substitute for the removal of CO and Hg° from the flue gas with the conditions of 8–20 vol.% O₂ and flue-gas temperature below 200 °C. The removal of Hg° followed the combination processes of adsorption and catalytic oxidation reaction via Langmuir-Hinshelwood mechanism, while the catalysis of CO abided by the Mars-van Krevelen mechanism with lattice oxygen species.     

Investigation on activated semi-coke desulfurization

An activated semi-coke with industrial-scale size was prepared by high-pressure hydrothermal chemistry activation, HNO3 oxidation and calcination activation in proper order from Inner Mongolia Zhalainuoer semi-coke, which is rich in resource and cheap in sale.SO2 adsorption capacity on this activated semi-coke was assessed in the fixed bed in the temperature range of 60-170℃, space velocity range of 500-1300 h^-1, SO2 concentration of 1000-3000 ppmv, and N2 as balance. The surface area, elemental and proximate analysis for both raw semi-coke and activated semi-cokes were measured. The experimental results showed that the activated semi-coke has a high adsorption capacity for sulfur dioxide than the untreated semi-coke. This may be the result of increase of surface area on activated semi-coke and surface oxygen functional groups with basicity characteristics. Comparison to result of FTIR, it is known that group of-C-O-C-may be active center of SO2 catalytic adsorption on activated semi-coke.     

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.     

影响大气汞化学过程的敏感因子分析

为了分析汞在大气中的化学行为,在一个化学模式中加入汞的气相、气液平衡和液相反应,模拟大气汞及其化合物的演变规律,并分析了气象因子(云、光解率、温度)和化学因子(气态O3、H2O2、HO2、OH和气态零价汞Hg0(g))的初始体积分数对各形态汞及其化合物浓度和Hg0(g)转化率的影响.模拟结果表明,在中等大气污染条件下,Hg0(g)的每小时平均转化率为2.91%.敏感性试验结果表明,云量、光解率、温度、O3和Hg0(g)的初始体积分数对不同形态汞的影响较为显著.云量的增加、光解率的增加、臭氧初始体积分数的升高,各形态汞的平衡时间缩短,除气态氧化汞和一价汞离子外,其他形态汞的平衡浓度均会降低,Hg0(g)的转化率增加.温度增加将抑制Hg0(g)的转化.Hg0(g)的初始体积分数增加,各形态汞的浓度升高,但其平均转化率没有显著变化.不同因子对汞化学过程的相对作用对区域或全球大气汞的环境模拟具有指导意义.     

Ce掺杂低钒V2O5-WO3/TiO2催化剂脱除烟气元素汞的研究

制备了Ce掺杂的低矾V₂O₅-WO₃/TiO₂催化剂,在模拟燃煤烟气条件下开展Hg⁰的脱除实验.结果表明该催化剂具有很好的Hg⁰脱除能力,在200～500℃的温度范围内能脱除烟气中95%的Hg⁰.催化剂表征结果表明,比表面积、 孔容和孔径与汞脱除能力没有显著相关性.XPS的结果表明,催化剂表面的Ce是以Ce⁴⁺的形式存在,有利于Hg⁰的脱除反应.抗硫抗水实验表明,H₂O会轻微抑制Hg⁰的脱除反应,主要原因是H₂O和Hg⁰在样品表面的竞争吸附;SO₂会促进Hg⁰的脱除反应,原因是SO₂能增加样品表面的酸吸附位且增加表面Hg⁰的吸附量.     

利用改性钒钛钢渣和飞灰吸附模拟烟气中的Hg0

固体废弃物钒钛钢渣(VTS)、飞灰(FA)含有Fe、V、Ti等可促进Hg0氧化吸附的过渡金属氧化物,为提高VTS吸附Hg0性能、改性FA的抗硫特性,利用蒸汽活化、浸渍FeCl₃方法改性FA/VTS、FA/CaO,在固定吸附床上研究了不同改性方法、反应温度(T)、烟气ρ(SO₂)和ρ(HCl)对η(吸Hg0效率)的影响. 结果表明:蒸汽活化对提高η的作用有限. 经浸渍FeCl₃方法改性的FA/VTS,其η显著提高,在200 ℃下,吸附20 min时可达93%,吸附10 h后的Q(吸附容量)为0.42 mg/g;而浸渍FeCl₃方法改性的FA/CaO,其η随温度呈先升后降趋势,在120 ℃、吸附20 min时达到最高(74%). SO₂抑制Hg0的吸附,但FA/VTS的抗硫性能较FA/CaO有显著提高,具有低温抗硫吸附Hg0的潜势,可能与VTS中Ti的质量分数高有关. HCl可促进Hg0的吸附,在ρ(HCl)为30 mg/m3条件下,浸渍FeCl₃方法改性的FA/VTS吸附2 h的η在90%以上. 研究表明,经FeCl₃浸渍改性的FA/VTS是较好的Hg0吸附剂,具有实际应用的潜势.