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.     

抑制双碱法烟气脱硫浆液中SO_3~(2-)的重金属催化氧化

双碱法烟气脱硫浆液中累积的重金属对SO23-有强烈的催化氧化作用,导致有效脱硫组分损耗.投加Na2S去除浆液中的重金属离子,研究不同重金属离子浓度下SO23-的氧化速率,以揭示Na2S沉淀法对重金属催化氧化SO32-的抑制作用.实验表明,Mn2+对SO32-氧化的催化作用很显著,1.0 mmol/L Mn2+可使SO32-的初始氧化速率提高2.0倍,达0.65mmol/(L.min);SO23-的催化氧化在前60 min内快速进行,Mn2+的反应级数为0.169,故此时段内控制Mn2+浓度对抑制其催化作用尤为重要.初始pH6.50~8.50时,Na2S能有效去除浆液中重金属离子,且碱性条件更有利于重金属离子的去除.初始pH为8.50、Na2S投加量为240.0 mg/L时,脱硫浆液中Mn2+、Zn2+、Ni2+、Cd2+的去除率分别为91.0%、88.1%、85.5%和99.9%.Mn2+对脱硫浆液中的重金属离子浓度具有指示作用.投加Na2S将Mn2+浓度由1.0 mmol/L降为5.0×10-3mmol/L,SO32-的初始氧化速率降低64.6%,为0.23 mmol/(L.min).在双碱法烟气脱硫中试装置中投加Na2S可使脱硫效率提高3.8%~5.1%.故以Mn2+为指示、用Na2S控制重金属离子浓度从而抑制SO23-被催化氧化,有利于降低脱硫剂消耗、提高脱硫效率.     

中小型燃煤烟气脱硫脱硝实验研究

介绍了选用熟石灰Ca(OH)2作脱硫剂的半干法烟气脱硫工艺来脱除SO2;选用NH3作还原剂,活性炭作催化剂,在低温(＜200℃)和氧气存在的条件下选择性催化还原(SCR法,属干法)NOx的技术来脱除NOx.实验表明:脱硫率＞92.5%,脱硝率＞74.6%,半干法烟气脱硫工艺和干法(SCR法)烟气脱硝技术适宜于中小型燃煤烟气的脱硫脱硝.     

抑制双碱法烟气脱硫浆液中SO2-3的重金属催化氧化

双碱法烟气脱硫浆液中累积的重金属对SO23-有强烈的催化氧化作用,导致有效脱硫组分损耗.投加Na2S去除浆液中的重金属离子,研究不同重金属离子浓度下SO23-的氧化速率,以揭示Na2S沉淀法对重金属催化氧化SO32-的抑制作用.实验表明,Mn2+对SO32-氧化的催化作用很显著,1.0 mmol/L Mn2+可使SO32-的初始氧化速率提高2.0倍,达0.65mmol/(L.min);SO23-的催化氧化在前60 min内快速进行,Mn2+的反应级数为0.169,故此时段内控制Mn2+浓度对抑制其催化作用尤为重要.初始pH6.50~8.50时,Na2S能有效去除浆液中重金属离子,且碱性条件更有利于重金属离子的去除.初始pH为8.50、Na2S投加量为240.0 mg/L时,脱硫浆液中Mn2+、Zn2+、Ni2+、Cd2+的去除率分别为91.0%、88.1%、85.5%和>99.9%.Mn2+对脱硫浆液中的重金属离子浓度具有指示作用.投加Na2S将Mn2+浓度由1.0 mmol/L降为5.0×10-3mmol/L,SO32-的初始氧化速率降低64.6%,为0.23 mmol/(L.min).在双碱法烟气脱硫中试...     

零价汞在MnOx/α-Al2O3-氯气体系中的催化氧化

为强化烟气中零价汞向二价汞的转化,利用模拟含汞烟气研究了以MnOx/α-Al2O3作为催化剂、利用氯气作为氧化剂催化氧化零价汞的方法.着重考察了氯气浓度、温度、空速和SO2对催化氧化零价汞性能的影响,并与HCl作为氧化剂的结果进行了对比.同时,对催化剂进行表征,探讨了催化剂表面吸附态汞的形态.研究结果表明,Cl2较HCl更易活化且活性温度区间更广,在100～300℃范围内,Cl2体积分数为2.0×10-6时的催化氧化效率即可达80%以上;在1.6×104-6.4×104 h-1空速范围内,零价汞氧化率保持在90%以上.空速继续提高到1.92×105h-1时,零价汞氧化率呈现线性下降趋势;烟气中的SO2与Cl2:反应会消耗Cl2,Cl2体积分数低时对催化氧化反应抑制作用显著,但Cl2体积分数增至5.0×10-6时对催化氧化反应的抑制效果较弱,仅为10%左右.     

O2+、O3同时脱硫脱硝实验

针对目前的烟气同时脱硫脱硝方法中存在的投资成本、运行费用、占地面积大等问题,研究强电离放电方法产生高浓度氧活性粒子(O2+、O3)注入烟气外排管道中,进行O2+、O3消除烟气中的NO, SO2转化成HNO3, H2SO4的等离子化学反应.描述强电离介质阻挡放电制取O2+、O3原理和烟道中O2+与H2O反应形成·OH及其氧化脱硫脱硝反应机制,分析回收酸液中的酸根离子种类及浓度.在O2+、O3与NO+SO2的物质的量比为5,烟气温度为65℃,H2O体积浓度为10%,停留时间为1s的实验条件下,脱硝脱硫率分别为97.4%,83.2%.     

模拟环境条件下δ-MnO2氧化As(III)的搅拌流动动力学特征

采用搅拌流动法研究了酸性水钠锰矿及水羟锰矿2种δ-MnO2矿物氧化As(Ⅲ)的动力学过程,构建了可用于多相体系的搅拌-流动氧化还原反应动力学模型.经过As吸附量的校正后,该模型对酸性水钠锰矿及水羟锰矿氧化As(III)动力学数据拟合度分别为0.980和0.951,模型拟合得到pH 7时2种矿物单位比表面上氧化As(III)的初始反应速率常数k分别为0.131,0.014min-1×m-2.相比而言,该速率常数明显高于批量法得到的表观速率常数kobs,0.021,0.001min-1×m-2更接近真实的化学动力学参数.搅拌流动法与批量法得到的不同矿物的速率常数大小趋势一致,即尽管酸性水钠锰矿对As(III)的氧化率低于水羟锰矿,单位比表面上酸性水钠锰矿氧化As(III)初始反应速率却远高于水羟锰矿.反应过程分析表明,反应初始阶段,As(III)的吸附为主要限速步骤;而随着反应的进行,矿物表面反应位点逐渐钝化或减少,反应位点数量成为限速步骤.     

O_2~+、O_3同时脱硫脱硝实验

针对目前的烟气同时脱硫脱硝方法中存在的投资成本、运行费用、占地面积大等问题,研究强电离放电方法产生高浓度氧活性粒子(O2+、O3)注入烟气外排管道中,进行O2+、O3消除烟气中的NO,SO2转化成HNO3,H2SO4的等离子化学反应.描述强电离介质阻挡放电制取O2+、O3原理和烟道中O2+与H2O反应形成·OH及其氧化脱硫脱硝反应机制,分析回收酸液中的酸根离子种类及浓度.在O2+、O3与NO+SO2的物质的量比为5,烟气温度为65℃,H2O体积浓度为10%,停留时间为1s的实验条件下,脱硝脱硫率分别为97.4%,83.2%.     

粒径与前驱体对活性炭催化臭氧氧化的影响

利用煤质、木质、椰壳3种前驱体活性炭制得6种粒级共18种活性炭样品,作为催化剂进行催化臭氧降解草酸的效果研究.结果表明,减小活性炭粒径对催化臭氧氧化效率提升效果显著,160~300目活性炭催化臭氧氧化降解草酸速率常数是10~20目颗粒活性炭的9.2~19.0倍.煤质160~300目活性炭催化臭氧氧化降解效果最佳.活性炭粒径的倒数与催化臭氧氧化伪一级动力学速率常数呈线性关系.对官能团的滴定表明,活性炭表面的羟基数量与催化臭氧氧化一级动力学速率常数存在较为明显的指数关系.     

废催化剂再生后对甲基橙的吸附动力学研究

废催化剂为生产醋酸乙烯过程中产生的废弃物,经过热处理直接得到ZnO／活性炭。以ZnO／活性炭为吸附剂,进行了吸附水溶液中甲基橙（MO）实验,在优化条件下,实验浓度范围内甲基橙溶液的吸附去除率均高于97％,表明ZnO／活性炭适于吸附甲基橙。采用准二级动力学模型和粒子内扩散模型研究ZnO／活性炭对水溶液中甲基橙的吸附动力学,并计算得到动力学参数和相关系数。结果表明,两种模型较好地描述了实验数据,其吸附过程的速率控制步骤为膜扩散控制,并随溶液初始浓度的增加准二级速率常数降低,面内扩散速率常数增加。     

Regeneration performance and carbon consumption of semi-coke and activated coke for SO2 and NO removal

To decrease the operating cost of flue gas purification technologies based on carbon-based materials, the adsorption and regeneration performance of low-price semi-coke and activated coke were compared for SO₂ and NO removal in a simulated flue gas. The functional groups of the two adsorbents before and after regeneration were characterized by a Fourier transform infrared (FTIR) spectrometer, and were quantitatively assessed using temperature programmed desorption (TPD) coupled with FTIR and acid–base titration. The results show that semi-coke had higher adsorption capacity (16.2% for SO₂ and 38.6% for NO) than activated coke because of its higher content of basic functional groups and lactones. After regeneration, the adsorption performance of semi-coke decreased because the number of active functional groups decreased and the micropores increased. Semi-coke had better regeneration performance than activated coke. Semi-coke had a larger SO₂ recovery of 7.2% and smaller carbon consumption of 12% compared to activated coke. The semi-coke carbon-based adsorbent could be regenerated at lower temperatures to depress the carbon consumption, because the SO₂ recovery was only reduced a small amount.     

改性颗粒活性炭对水中溴酸根的吸附特性研究

采用阳离子表面活性剂氯化十六烷基吡啶(CPC)改性颗粒活性炭以提高活性炭对溴酸根的吸附能力.通过小试研究了改性颗粒活性炭(GAC-CPC)对溴酸根的吸附特性,考察了BrO-3初始浓度、pH、共存阴离子等因素对吸附过程的影响.结果表明,CPC改性能显著提高GAC对BrO-3的吸附能力,吸附量随着初始浓度升高而增大;在碱性条件下GAC-CPC对BrO-3的吸附量减小;共存阴离子与BrO-3在GAC-CPC上存在竞争吸附,其影响顺序为:NO-3SO2-4PO3-4CO2-3.用准一级、准二级和颗粒内扩散动力学模型拟合GAC-CPC吸附BrO-3的动力学过程,结果表明,准二级动力学能更好的描述吸附过程,且孔扩散可能是改性GAC吸附BrO-3初始阶段的主要速率控制因素.用Langmuir和Freundlich等温吸附模型拟合不同温度下BrO-3的吸附平衡过程,结果表明,Langmuir等温吸附模型能很好的描述吸附平衡过程,GAC-CPC吸附BrO-3的过程是自发且放热的,温度升高不利于吸附.     

消除烟道气中二氧化硫的活性炭催化剂——SO2在催化剂上动态吸附研究

本文考察了流动态体系中,烟气主要组分(O₂和水蒸汽)的含量对SO₂在活性炭上吸附量的影响;研究了SO₂吸附动力学。结果表明,在一定空速和吸附温度下,烟气中O₂和水蒸汽含量分别为5%和8%(Ⅴ%)左右时,SO₂吸附量为最大。SO₂在活性炭上吸附动力学曲线很好地遵循Elovich方程;SO₂吸附活化能E_a⁰为21.939×10³J/mol以及Elovich参数,进而得出吸附活化能E_a,与吸附温度的关系。     

电厂烟气中SO2对活性炭吸附单质铅(Pb0)的影响机理

利用密度泛函理论系统研究了SO_2对活性炭吸附单质铅(Pb~0)的影响,其中,结构优化与频率计算采用B3LYP/def2-SVP级别方法和基组,单点能计算采用B3LYP/def2-TZVP级别方法和基组.同时,利用玻尔兹曼分布函数分析了SO_2与Pb~0在活性炭表面的竞争吸附关系,结果表明,Pb~0在纯净活性炭上的吸附能力大于SO_2.此外,本研究发现,SO_2的预吸附会增强活性炭对Pb~0的吸附效果.通过静电势分布揭开了SO_2促进活性炭吸附Pb~0的深层原因,结果发现,吸附SO_2以后活性炭表面静电势极大值增大,极小值减小,吸附剂吸附能力因此增强.最后,利用电子密度差分图揭示出SO_2改性活性炭在吸附Pb~0时,SO_2对Pb~0吸附的影响可以分为直接影响和间接影响两种.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

Adsorption and desorption of SO2, NO and chlorobenzene on activated carbon

Activated carbon (AC) is very effective for multi-pollutant removal; however, the complicated components in flue gas can influence each other''s adsorption. A series of adsorption experiments for multicomponents, including SO₂, NO, chlorobenzene and H₂O, on AC were performed in a fixed-bed reactor. For single-component adsorption, the adsorption amount for chlorobenzene was larger than for SO₂ and NO on the AC. In the multi-component atmosphere, the adsorption amount decreased by 27.6% for chlorobenzene and decreased by 95.6% for NO, whereas it increased by a factor of two for SO₂, demonstrating that a complex atmosphere is unfavorable for chlorobenzene adsorption and inhibits NO adsorption. In contrast, it is very beneficial for SO₂ adsorption. The temperature-programmed desorption (TPD) results indicated that the binding strength between the gas adsorbates and the AC follows the order of SO₂ > chlorobenzene > NO. The adsorption amount is independent of the binding strength. The presence of H₂O enhanced the component effects, while it weakened the binding force between the gas adsorbates and the AC. AC oxygen functional groups were analyzed using TPD and X-ray photoelectron spectroscopy (XPS) measurements. The results reveal the reason why the chlorobenzene adsorption is less affected by the presence of other components. Lactone groups partly transform into carbonyl and quinone groups after chlorobenzene desorption. The chlorobenzene adsorption increases the number of C = O groups, which explains the positive effect of chlorobenzene on SO₂ adsorption and the strong NO adsorption.     

Formation of sulfur oxide groups by SO2 and their roles in mercury adsorption on carbon-based materials

The presence of SO₂ display significant effect on the mercury (Hg) adsorption ability of carbon-based sorbent. Yet the adsorption and oxidation of SO₂ on carbon with oxygen group, as well as the roles of different sulfur oxide groups in Hg adsorption have heretofore been unclear. The formation of sulfur oxide groups by SO₂ and their effects on Hg adsorption on carbon was detailed examined by the density functional theory. The results show that SO₂ can be oxidized into SO₃ by oxygen group on carbon surface. Both C-SO₂ and C-SO₃ can improve Hg adsorption on carbon site, while the promotive effect of C-SO₂ is stronger than C-SO₃. Electron density difference analyses reveal that sulfur oxide groups enhance the charge transfer ability of surface unsaturated carbon atom, thereby improving Hg adsorption. The experimental results confirm that surface active groups formed by SO₂ adsorption is more active for Hg adsorption than the groups generated by SO₃.     

中孔结构对活性炭吸附卷烟烟气中有机物的影响

卷烟烟气中复杂化合物对大气环境的污染已经引起了全世界的关注.因此,本文以颗粒活性炭为原料,通过硝酸钙、水蒸气调控得到比表面积、微孔容量丰富且含有较高中孔率的介孔活性炭,研究了孔结构对三醋酸甘油酯和挥发性有机物吸附的影响.结果表明:活性炭对三醋酸甘油酯的吸附主要受到比表面积和微孔的影响,中孔对其吸附性能没有太明显的作用;中孔结构对苯、甲苯、丙酮的吸附可以起到明显的通道效应,大大提高了活性炭对挥发性有机物的去除能力.     

活性炭纤维对活性染料的吸附动力学研究

研究了活性炭纤维从水溶液中吸附4种活性染料（活性艳红K-2BP、活性翠蓝KN-G、活性金黄K-3RP、活性黑KN-B）的吸附特性,从动力学角度探讨了吸附机理.结果表明,活性炭纤维对4种染料的平衡吸附量q_e均随着初始浓度和温度的增加而升高,相同条件下,q_e的大小顺序为：活性艳红＞活性金黄＞活性黑＞活性翠蓝.吸附过程符合伪二级吸附速率方程,染料分子的空间结构、大小和极性是影响初始吸附速率的主要因素.活性炭纤维对4种染料的吸附活化能都比较低,依次为16 .42、3 .56、5 .21和26 .38 kJ·mol^-1,说明吸附过程以物理吸附为主.