离子液体R3NANR3的制备及其脱硫性能

以二元酸和短链叔胺为原料,合成了已二酸三乙胺盐离子液体———R3NANR3。对该离子液体进行SO2气体的循环吸收和解吸行为的研究。实验结果表明,R3NANR3离子液体能对SO2气体进行有效的化学吸收。该吸收过程分二步进行,以第一步吸收为主。室温下(20℃)该离子液体在3 h以内吸收速率较快,3 h后吸收速率减慢并逐渐达到平衡。R3NANR3离子液体与SO2气体饱和吸收量的物质的量之比为1.08。较高温度将导致SO2气体的解吸,在90℃时饱和吸收液能较充分地解吸,残留量为0.0010 mol/L。多次吸收和解吸测试表明,R3NANR3离子液体能实现对SO2气体的循环吸收和分离,将成为烟气中SO2气体的脱除和利用的重要循环吸收剂。     

醇胺离子液体对烟气硫的高效脱除

燃煤烟气中的SO_2对人体健康和生态环境危害很大,传统的除硫装置大都存在二次污染。离子液体作为新型吸收剂有着广泛的应用前景。制备柠檬酸三乙醇胺离子液体作为脱硫剂,在模拟烟气条件下对SO_2的吸收性能进行研究。结果表明:柠檬酸三乙醇胺离子液体具有高效脱硫性能,在70 min时脱硫率仍能达到80%以上;温度升高不利于脱硫过程的进行;而SO_2浓度增加,离子液体的吸收量增加;离子液体的解吸工艺简单,在90℃下加热80 min可完全解吸,再生性能良好。柠檬酸三乙醇胺离子液体对SO_2的吸收主要以化学吸收为主,同时伴有物理吸收过程,吸收摩尔比达到3.38~3.68 mol·mol~(-1)。     

采用可再生胺法脱除烟气中SO_2

为加快可再生胺法脱硫工艺的工业化进程,开发了一套撬装式脱硫再生中试装置,通过SO_2连续吸收解吸实验验证装置性能。分别考察吸收剂质量分数、pH、液气比(L/G)、解吸温度、SO_2进口含量对吸收和解吸效率的影响,结果表明:随吸收剂质量分数、pH、液气比的增大吸收率升高,而解吸率下降;解吸温度升高,吸收率变化不大,解吸率增速较快;SO_2进口浓度增大,吸收率和解吸率迅速降低。确定适宜工艺条件为:吸收剂质量分数30%,pH=6~8,吸收温度30℃,解吸温度(90±5)℃,液气比L/G=5.0 L·m-3。通过微分法导出体积总传质系数KGa的计算公式,并与相关工艺参数进行关联拟合,回归出填料吸收塔K_Ga经验模型:K_Ga=0.081(L/G)~(0.232 0)(8.91 w~(0.107 3)pH~(0.24)8e-0.32yA-1)。     

碱性硫酸铝吸收与解吸二氧化硫的机理及性能

采用实验的方法研究了碱性硫酸铝溶液吸收和解吸SO_2机理,同时探讨了碱度20%、铝量20 g·L~(-1)的碱性硫酸铝溶液温度变化对SO_2吸收率的影响效果。结果表明,SO_2进入碱性硫酸铝溶液中首先发生的是与活性Al~(3+)的结合反应,当活性Al~(3+)消耗殆尽后,则进行与H_2O的结合反应;而在解吸过程中,首先是与H_2O结合的SO_2发生解吸反应,其后是与活性Al~(3+)结合的SO_2发生解吸反应。当吸收液温度低于50℃,且每升溶液中SO_2通入量不高于5 L时,其吸收率均能维持在95%以上。     

微波解吸柠檬酸盐溶液中SO2实验研究

结合微波具有的热效应、非热效应特性，利用经改装的微波反应装置，研究了微波场下柠檬酸浓度、微波作用时间、微波功率、SO2初始浓度和搅拌速率对解吸柠檬酸盐溶液中SO2的影响，得出了影响SO2解吸率的基本规律和最佳解吸条件，并进行了分析。     

低浓度硫化氢废气的液相催化氧化法净化实验研究

针对H2S浓度为750~1500mg/m3的气体的液相催化氧化技术进行了动力学实验研究。配制了以铁基离子作为主催化剂的复合吸收净化溶液,同时加入稳定剂和表面活性剂提高催化剂在碱性吸收溶液的活性。分别考察了原料气中H2S、O2含量以及吸收液中催化剂离子浓度、温度等因素对吸收速率的影响;确定了较为理想的吸收操作条件并获得了较好的吸收净化效果;饱和吸收液易于再生,净化性能恢复良好,可重复使用。     

微波解吸柠檬酸盐溶液中SO2实验研究

结合微波具有的热效应、非热效应特性,利用经改装的微波反应装置,研究了微波场下柠檬酸浓度、微波作用时间、微波功率、SO2初始浓度和搅拌速率对解吸柠檬酸盐溶液中SO2的影响,得出了影响SO2解吸率的基本规律和最佳解吸条件,并进行了分析.     

未燃尽碳表面卤化汞的解吸反应机理

研究燃煤电厂未燃尽碳表面卤化汞的解吸反应机理对于燃煤电厂飞灰的再利用具有重要的指导意义。建立未燃尽碳表面饱和簇模型以及未燃尽碳表面卤化汞模型,采用量子化学中的密度泛函理论对未燃尽碳表面卤化汞的解吸特性进行了研究,详细讨论了解吸过程中间态产物的能量变化,计算了298~1 500 K温度范围内的热力学参数、动力学参数以及反应速率常数,拟合得到了解吸反应的反应速率计算公式。结果表明,在未燃尽碳表面含汞卤化物的解吸反应为吸热反应,在高于1 070 K时各解吸才可以自发进行,并且随着温度的升高各解吸反应吸收的热量减少、自发性增强;Hg Cl_2在未燃尽碳表面解吸反应的活化能最低,其次为Hg Br_2Hg BrHg Cl;在同一温度下卤化汞在未燃尽碳表面发生解吸的反应速率由快到慢依次为Hg Cl_2、Hg Br_2、Hg Br、Hg Cl。     

土壤颗粒级配对镉吸附-解吸规律的影响

利用甘肃金川某地土壤通过批实验进行等温吸附和动力学解吸实验,研究不同颗粒级配的中砂对镉的吸附、解吸特征,并采用Freundlich和一级动力学方程对其吸附解吸方程进行拟合。结果表明,(1)Freundlich和一级动力学方程对该土壤吸附、解吸镉的实验适用;(2)等温吸附实验中4组不同颗粒级配的中砂对镉的吸附性很强,最大平衡吸附量依次为260.667、286.107、299.362和292.232 mg/kg,吸附性能与颗粒级配中的细粒土相对含量大小成正比;(3)4组土壤对镉的解吸在初期2 h内解吸速率均较快,在3 h左右达到吸附-解吸平衡。平衡后4组土样Ⅰ、Ⅱ、Ⅲ和Ⅳ的最大解吸量依次为0.752、0.561、0.44和0.54 mg/kg,解吸速率和平衡时最大解吸量均与颗粒级配中细颗粒相对含量密切相关。     

低浓度硫化氢废气的液相催化氧化法净化实验研究

针对H2S浓度为750～1500 mg/m^3的气体的液相催化氧化技术进行了动力学实验研究.配制了以铁基离子作为主催化剂的复合吸收净化溶液,同时加入稳定剂和表面活性剂提高催化剂在碱性吸收溶液的活性.分别考察了原料气中H2S、O2含量以及吸收液中催化剂离子浓度、温度等因素对吸收速率的影响;确定了较为理想的吸收操作条件并获得了较好的吸收净化效果;饱和吸收液易于再生,净化性能恢复良好,可重复使用.     

鼓泡反应器中液相络合催化同时脱硫脱硝的研究

在鼓泡反应器中考察了[Co(en)3]2+同时吸收去除SO2和NO的影响因素,实验结果表明,pH值和脱硫剂种类是影响乙二胺合钴同时脱除NO和SO2的最重要影响因素,烟气中的氧促进乙二胺合钴吸收NO和SO2,烟气中的SO2,CO2和NO2对乙二胺合钴吸收NO具有抑制作用。在实验条件温度为20℃,pH为13.0,[Co(en)3]2+浓度为0.025 mol/L,加入1 g NH3.H2O的脱硝率更好,连续吸收60 min,脱硝率均保持在93.5%,加入NaOH和NH3.H2O的脱硫效果最好。乙二胺合钴络合同时脱除NO和SO2完全可以在一个装置中完成。     

膜吸收法处理高浓度甲醛废气资源化技术研究

采用疏水性中空纤维膜接触器,以NaHSO₃为吸收液处理高浓度甲醛废气。研究了吸收液流量、吸收液温度、吸收液浓度、气体进口流量和气体进口浓度等因素对甲醛去除率和总传质系数的影响。结果表明,当吸收液流量为4.17×10^-6m³/s,吸收液温度为60℃,甲醛进气流量为3.7×10^-6m³/s,甲醛进气浓度为566 mg/m³时,甲醛出气浓度可低至2.8 mg/m³,甲醛的去除率可达99.5%,总传质系数为4.46×10^-5m/s。反应产物（ɑ-羟基磺酸钠）易分离,并可作为重要的有机合成原料或用于制备高纯甲醛而得到充分利用,NaHSO₃溶液经适当稀释后仍可作为吸收液循环使用。表明膜吸收法可基本实现高浓度甲醛废气处理的资源化。     

CuCoOx／TiO2催化氧化NO性能研究

采用浸渍法制备了CuCoOx／TiO2催化剂,考察了焙烧温度、反应温度、氧含量、NO浓度和空间速度对催化剂催化氧化NO性能的影响,并考察了催化剂的抗硫抗水性能。XRD、TPR和BET分析表明,350℃焙烧的催化剂具有CuCo2O4尖晶石结构,比表面积大,对NO的氧化效果好。在空速为5000h^-1,NO进口浓度500mg／m^3,含氧量10％的条件下,反应温度300℃时NO转化率可达79．5％,250℃时NO转化率接近50％。该催化剂具有良好的单独抗SO2、抗H2O毒化性能,H2O和SO2同时存在时很快失活。该催化剂可用于不同时含H2O和SO2的含NO气体催化氧化后再吸收处理。     

聚丙烯酸水凝胶对氯化-1-丁基-3-甲基咪唑离子液体的吸附热力学和动力学研究

通过水溶液聚合法制备了聚丙烯酸水凝胶（polyacrylic acid,PAA）,研究了溶液酸碱度和温度对聚丙烯酸水凝胶吸附氯化1-丁基3-甲基咪唑离子液体的影响。结果表明,水凝胶对氯化1-丁基3-甲基咪唑离子液体的吸附量随溶液pH值增大而逐渐增大,pH=2～4时增幅明显,而pH大于4时变化趋于缓慢;随温度的升高而逐渐降低。该等温吸附行为基本符合Langmuir吸附等温式,由二级吸附动力学模型获得的吸附过程活化能（Ea=52.470 kJ/mol）可以看出,PAA对氯化1-丁基3-甲基咪唑的吸附属于化学吸附范畴。     

Absorption of NO and NO2 in Caprolactam Tetrabutyl Ammonium Halide Ionic Liquids

ABSTRACT

To explore environmentally benign solvents for the absorption of NO and NO₂, a series of caprolactam tetrabutyl ammonium halide ionic liquids were synthesized. The solubility of NO and NO₂ was measured at temperatures ranging from 298.2 to 363.2 K and atmospheric pressure, and the following trend in the solubility of NO and NO₂ in ionic liquids with various halide anions was observed, respectively: F > Br > Cl and Br > Cl > F. Moreover, as the temperature increased from 308.15 to 363.15 K and the mole ratio of caprolactam increased from 2:1 to 6:1, the solubility of NO increased. Alternatively, the solubility of NO₂ decreased as the temperature increased from 298.15 to 363.15 K, and the mole ratio of caprolactam increased from 2:1 to 6:1. The absorption and desorption of NO and NO₂ was practically reversible in the ionic liquids, which was characterized by nuclear magnetic resonance. The method, which is at least partially reversible, offers interesting possibilities for the removal of NO and NO₂.

IMPLICATIONS Basic ionic liquids with amino groups were synthesized and used to capture CO₂, SO₂, and H₂S, and to promote hydrogenation of CO₂. In this paper, the authors used caprolactam tetrabutyl ammonium halide ionic liquid (IL) as absorbing medium in which NO_x could be absorbed. NO_x desorbed from the absorbent could be efficiently reduced by right catalysts at high temperature. The absorbed NO and NO₂ gas could be desorbed at higher temperature, allowing the ionic liquids to be reused several times without loss of capability. It was believed that caprolactam tetrabutyl ammonium bromide (CPL-TBAB) ILs may be useful for NO_x removal reagent for pollution control.     

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.     

菌丝体表面分子印迹壳聚糖吸附剂对Cr3+的吸附性能研究

菌丝体表面分子印迹吸附剂所保留的印迹对过渡金属离子有着良好的吸附作用,以Cr3 作为吸附离子,系统研究了该吸附剂的吸附特性和影响因素.结果表明:吸附剂对Cr3 的饱和吸附容量可达60 mg/g;其吸附行为满足Langmuir方程式.初始浓度为200 mg/L时,最佳吸附pH在3～4,吸附容量可达到50 mg/g左右,离子强度对吸附没有影响,用0.5 mol/L硝酸或硫酸解吸Cr3 ,解吸率在90%以上.     

Sorption and desorption of imidazolium based ionic liquids in different soil types

This study investigates the influence of the two different clay minerals kaolinite and smectite as well as of organic matter on the cation sorption and desorption behaviour of three imidazolium based ionic liquids -1-butyl-3-methyl-imidazolium tetrafluoroborate (IM14 BF(4)), 1-methyl-3-octyl-imidazolium tetrafluoroborate (IM18 BF(4)) and 1-butyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide (IM14 (CF(3)SO(2))(2)N) - in soil. The German standard soil Lufa 2.2 - a natural soil classified as a loamy sand - was the basis substrate for the different soil compositions and also served as a reference soil. The addition of organic matter and clays increases the sorption of the substances and in particular smectite had striking effects on the sorption capacity for all three ionic liquids indicating that ionic interactions play an important role for sorption and desorption processes of ionic liquids in soil. One exception was for kaolinite-containing soils and the IM14 cation: with (CF(3)SO(2))(2)N(-) as an anion the sorption was identical at either 10 wt% or 15 wt% clay content, and with BF(4)(-) sorption was even lower at 15 wt% kaolinite than at 10 wt%. Desorption was weak for IM18 BF(4), presumably owing to the longer alkyl side chain. With regard to the influence of kaolinite on desorption, the same pattern was observed as it was found for the sorption of IM14 BF(4) and IM14 (CF(3)SO(2))(2)N.     

An alternative to additional SO3 injection for fly ash conditioning

Small concentrations, approximately 2-10 parts per million (ppm), of injected sulfur trioxide (SO3) have improved particulate collection efficiencies of electrostatic precipitators burning lower-sulfur coal. However, the addition of extra SO3 not only incurs costs but also presents negative environmental effects. This work explored a method that could be applied to existing coal-fired power plants to convert the sulfur dioxide (SO2) already present in the flue gas to sufficient levels of SO3 for fly ash conditioning as an alternative to adding SO3 by burning elemental sulfur. During this research, a pre-mixed natural gas flame was used to promote the conversion of SO2 to SO3 in a drop-tube furnace with average non-flame, free stream gas temperatures of 450 and 1000 K. SO3 concentrations measured by wet chemistry and confirmed using elemental balances of other sulfur species measured by gas chromatography revealed that as much as 7% of SO2 was homogeneously transformed to SO3. The results also showed that at low temperatures, the rate at which SO3 is converted back to SO2 decreased, thus extending the time period during which SO3 concentrations would be sufficient for ash conditioning. An additional benefit of this technique is speculated to result from increased flue gas humidity.     

水吸收法处理低浓度氮氧化物废气的中试研究

对水在中试规模下吸收低浓度的氮氧化物废气进行了研究。分别研究了喷淋密度、温度、压力、气速以及氮氧化物浓度对吸收效果的影响,结果表明,综合考虑各种因素,喷淋密度在20 m3/（m2·h）,水温在15℃以下,气速小于0.28 m/s,废气浓度在400 mg/m3左右时,氮氧化物的平均脱除率可以达到50%左右;同时,随着压力的增大,吸收效率也增加。