粉尘对高温煤气脱硫反应的影响

研究了在400℃-550℃范围内粉尘对氧化铁高温脱硫剂的硫容和脱硫反应速度的影响。结果表明随着温度的升高,粉尘对脱硫剂的硫容和脱硫反应速度的影响增大。并利用收缩核模型计算比较了由于粉尘加入引起的H2S有效扩散系数的变化,发现有效扩散系数由于粉尘的作用,随温度升高显著降低。为脱硫除尘一体化工艺的开发提供了一定的理论依据。     

EDTA-HEDTA复配络合铁体系脱H2S性能研究

配制了一种EDTA-HEDTA复配络合铁脱硫液,配方溶液组成为n(EDTA)∶n(HEDTA)∶n(Fe3+)∶n(Fe2+)=1.2∶6∶5∶1,pH=8.5。研究了进气H2S含量、温度与稳定剂对配方溶液脱硫性能和稳定性的影响。结果表明,配方溶液对H2S质量浓度35%以内的气体有良好吸收效果,脱硫率可达98%以上;随着温度升高,配方溶液脱硫率几乎不变,但穿透时间呈降低趋势;添加稳定剂Na2S2O3或苯甲酸钠可减缓络合剂的降解。硫容测试表明,配方溶液硫容为2.0g/L,具有良好的脱硫潜力。     

无氧下低浓度硫化氢在浸渍活性炭上的吸附研究

为了考察常温、无氧下浸渍Na2CO3改性、原料气相对湿度对活性炭吸附硫化氢的促进作用，用动态吸附法分别测试了不同湿度下原活性炭和浸渍活性炭对低浓度硫化氢的吸附，同时考察了温度对该吸附过程的影响。结果表明，吸附平衡数据均符合Freundlich吸附等温方程。与原活性炭相比，浸渍活性炭的孔容和比表面积略有降低，但对硫化氢的吸附能力却显著提高，说明硫化氢与浸渍剂在活性炭表面上发生了化学反应。相对湿度增加，活性炭和浸渍活性炭对H2S的吸附能力均显著增强。温度升高，平衡吸附量均略有下降。     

脱除低浓度硫化氢的改性活性炭纤维的再生研究

用改性的活性炭纤维（ACF）脱除低浓度的H2S是一种十分有效的方法,但脱硫后的改性ACF容易达到脱硫饱和而失活。用溶剂再生和气体热再生的方法可以对失活后的改性ACF进行再生。在固定床反应器上考察了再生后ACF的脱硫性能。实验结果表明,与溶剂再生相比,气体热再生是更有效的再生方法。不同再生方法的效果的不同,是由ACF脱除H2S的反应机理的不同和再生机理的不同造成的。     

活性炭基水解催化剂的制备及其脱硫性能的研究

分别通过溶胶-凝胶法、浸渍法制备Cu/活性炭(AC)水解催化剂,考察了不同制备方法对水解脱硫性能的影响。利用XRD、BET、SEM等对载体及催化剂进行表征,分析了预处理对AC表面性质及不同制备方法对脱硫效率的影响,并探讨了水解脱硫的机理。结果表明,浸渍法所制备的水解催化剂活性优于溶胶-凝胶法制备的催化剂,在通过预处理增大了AC的比表面积、丰富了AC的孔道结构的基础上,浸渍法能均匀地将活性组分分散在载体表面及其孔道中,而溶胶-凝胶法制备的催化剂活性组分主要覆盖在载体的表面,不能有效进入孔道内,造成脱硫效率下降。在反应温度80℃、羰基硫浓度1.33g/m~3、空速1500h~(-1)、氧化铜质量分数为5%时,浸渍法制备的水解催化剂具有较高的硫容,可达29mg S/g。     

新型Mn-Fe/Al_2O_3高温脱除H_2S的实验研究(Ⅱ)

本文首先研究了粒度dp=07mm脱硫剂的脱硫反应和再生反应性能。研究表明当Mn∶Fe=2∶1(w)、载体在1000℃焙烧后,脱硫剂有较好的脱硫反应性能,其最佳的脱硫反应温度为550℃,且在710℃、O2浓度低于1083%(v)、空速2000～3000h-1再生条件下,可完全对脱硫剂进行再生;H2S浓度影响脱硫剂的初始脱硫反应速率和穿透反应时间,但对脱硫剂的脱除率和穿透硫容影响不大。并研究了粒度dp=3mm脱硫剂的脱硫情况。实验结果表明,小颗粒脱硫剂的脱硫反应主要为化学反应控制,大颗粒脱硫剂主要为扩散控制。为此对大颗粒脱硫剂进行了工程设计,即采用活性组分非均布脱硫剂。研究表明,非均布脱硫剂明显提高了脱硫剂的平均脱硫反应速率和硫容,同均布脱硫剂相比,非均布脱硫剂再生后具有较好的脱硫稳定性能。     

Ni含量对负载型NiO/ZnO-TiO2吸附剂结构及吸附脱硫性能的影响

以ZnO-TiO₂为载体,采用等体积浸渍法制备了不同Ni含量的NiO/ZnO-TiO₂汽油脱硫吸附剂。采用X射线衍射（XRD）、压汞、H₂程序升温还原（H₂-TPR）和H₂程序升温脱附（H₂-TPD）等手段对吸附剂进行了表征。同时,采用FCC轻汽油为原料,在固定床反应装置中对不同Ni含量的NiO/ZnO-TiO₂吸附剂进行脱硫性能评价,以考察Ni含量对该吸附剂脱硫性能的影响。结果表明,Ni含量适量增加对于吸附剂比表面积、内部孔道分布和颗粒强度影响较小,同时能够增加具有脱硫活性的Ni⁰物种,促进吸附剂脱硫活性。当吸附剂中Ni质量分数达到5.48%后,吸附剂的内部孔道分布改变,吸附剂的比表面积和颗粒强度明显降低,对吸附剂脱硫活性极为不利。当Ni质量分数为4.45%时,吸附剂具有最佳脱硫性能,能够将FCC轻汽油中3×10^-4的总硫含量降低至5×10^-6以下,并维持脱硫时间达152 h,穿透硫容达11.24%（112.4 mg S/g吸附剂）,且脱硫后FCC轻汽油烯烃含量变化较小。     

活性炭及甲酸催化过氧化氢氧化噻吩脱硫研究

以噻吩代表汽油中的有机硫化合物,将其溶解于正辛烷配制成反应原料,考察了活性炭对噻吩的吸附脱硫情况,研究了质量分数为30％的过氧化氢水溶液为氧化剂,在活性炭和甲酸的催化作用下,反应原料中噻吩氧化脱硫。考察了活性炭的催化性能及反应条件对其催化性能的影响。实验结果表明,30％H2O2-HCOOH-AC（活性炭）三元体系产生的过氧甲酸和羟基自由基能将模型有机硫化合物氧化,噻吩的氧化脱硫率可达到85％以上;活性炭和甲酸的催化氧化性能明显优于单纯使用甲酸催化性能。甲酸浓度、活性炭加入量、过氧化氢初始浓度及温度对噻吩硫的氧化脱除均有影响。     

（NH_4）_2MOS_4在活性炭上浸渍过程的研究Ⅰ．浸渍参数对（NH_4）_2

（ＮＨ＿４）＿２ＭＯＳ＿４在活性炭上浸渍过程的研究Ⅰ．浸渍参数对（ＮＨ＿４）＿２ＭＯＳ＿４在活性炭上分布的影响秦慧芳，张成芳，陆岗，俞丰，朱子彬（华东理工大学无机化工研究所，上海２００２３７）关键词硫代钼酸铵，浸渍，活性炭，钼分布负载型催化剂制备一般...     

纳米ZnO室温选择氧化H2S特性的研究

碱式碳酸锌在不同焙烧温度下制得的纳米ZnO具有六方晶系纤锌矿结构，平均粒径为15.4 nm、19.1 nm、22.9 nm和33 nm，以其为脱硫剂，对H2S室温脱硫性能进行了研究。利用XRD和XPS技术对脱硫反应前后的样品进行了表征。实验结果表明，纳米ZnO的脱硫性能随粒径的增大而降低，常温、常压下，260 ℃焙烧的纳米ZnO对H2S有高的去除率，并且H2S可选择性地被氧化为单质硫。     

COS hydrolysis in the presence of oxygen： Experiment and modeling

A mathematical model of COS hydrolysis on Al2O3, with fouling of catalyst, has been developed. Kinetic studies were carried out in a fixed bed reactor under atmospheric pressure and low temperature （40-70℃）. The effects of the COS inlet concentration, temperature, and relative humidity were analyzed. Experimental results of breakthrough curves were used to obtain kinetic parameters, which accounted for effects of S deposition on the inner-face of the catalyst. The model described the experimental breakthrough curves satisfactorily and well explained the performance of COS hydrolysis in the presence of oxygen. The exothermic heat of adsorption and activation energy, assuming Arrhenius type of temperature dependence of the equilibrium constant, were determined. Activation energy of COS hydrolysis and H2S oxidation were 35.9 kJ/mol, 19.6 kJ/mol; adsorption heat of H2O and H2S on Al2O3 were 45.1 and 60.1 kJ/mol respectively. Deactivation coefficient （α） was used to quantify the behavior of COS hydrolysis at different operating conditions. The effect of relative humidity on α is significant in the relative humidity range under study. Experimental data accorded well with model data in the studied range.     

Kinetics of carbon dioxide absorption from air in a flow reactor with a fixed bed of K<Subscript>2</Subscript>CO<Subscript>3</Subscript>-based sorbent

Sorption of carbon dioxide from air in a flow reactor with a bulky fixed bed of the K₂CO₃/Al₂O₃ composite sorbent was studied. The dynamic sorption capacity of the material was shown to depend on the relative humidity of the inlet air. A numerical model was constructed for evaluating the profile of СО₂ concentration in the layer and kinetic curves of CO₂ breakthrough at the outlet of the reactor. The results of simulation allowed us to adequately describe the experimental kinetic curves at 20–40% humidity.     

纳米α-FeOOH催化剂一段法脱除COS和H2S性能的研究

利用均相沉淀法、氨水滴定法制备纳米α-FeOOH粒子，以该粒子为活性组分制备催化剂，利用微反－色谱联用活性评价技术，在常压、空速10 000 h－1、25 ℃～60 ℃温度范围内考察了纳米α-FeOOH催化剂对COS催化水解的活性。采用热重法对纳米α-FeOOH催化剂脱除H2S的性能进行了研究。结果表明：纳米α-FeOOH催化剂对COS水解在低温度、大空速下具有高的活性，系列Ⅰ和系列Ⅱ催化剂分别在60 ℃和40 ℃～45 ℃时COS转化率达到100%。在60 ℃时各种催化剂吸附H2S的能力最强，最高饱和硫容可达到21.72w%。催化剂表面能量分布不均匀，COS催化水解在低温时存在补偿效应。     

On the adsorption/oxidation of hydrogen sulfide on activated carbons at ambient temperatures

Activated carbons of various origins (bituminous coal, wood, coconut shells, and peat) were studied as adsorbents of hydrogen sulfide. Before the experiments the surface of the adsorbents was characterized by using the sorption of nitrogen, Boehm and potentiometric titrations, thermal analysis, and FTIR. The adsorbents were chosen to differ in their surface areas, pore volumes, and surface acidities. To broaden the spectrum of surface acidity, carbons were oxidized by using nitric acid and ammonium persulfate. After hydrogen sulfide adsorption the species present on the surface were analyzed using thermal analysis, ion chromatography, and elemental analysis. The H(2)S breakthrough capacity tests showed that the performances of different carbons differ significantly. For a good performance of carbons as hydrogen sulfide adsorbents a proper combination of surface chemistry of carbon and porosity is needed. It was demonstrated that a more acidic environment promotes the formation of sulfur oxides and sulfuric acid despite yielding small H(2)S removal capacities. On the other hand, a basic environment favors the formation of elemental sulfur (sulfur radicals) and yields high capacities. The presence of a sufficient amount of water preadsorbed on the carbon surface to facilitate dissociation also plays an important role in the process of H(2)S adsorption/oxidation. The results showed that there is a critical value in carbon surface acidity, which when exceeded results in a negligible hydrogen sulfide breakthrough capacity. This is consistent with the mechanism of H(2)S adsorption on unmodified carbons, where the rate-limiting step is the reaction of adsorbed hydrogen sulfide ion with dissociatively adsorbed oxygen. When the acidity is expressed as pH, its value should be higher than 5 to ensure the effective removal of hydrogen sulfide from the gas phase. Study of carbon regeneration using water washing and heat treatment showed that the adsorbents can be regenerated to about 40% of their initial capacity.     

Adsorption tests of water vapor on synthetic zeolites for an atmospheric detritiation dryer

Tritiated hydrogen and hydrocarbon are usually oxidized to a tritiated water vapor to make the tritium adsorbable and easy to treat. The adsorption system as a subsequent process plays an important role in a tritium recovery and its performance affects the overall detritiation efficiency significantly. In order to quantify an adsorbent's utilization and its dynamic capacity against an inlet humidity and a flow rate, a series of quantitative tests based on the breakthrough behavior were carried out in an isothermal fixed bed of synthetic zeolites such as molecular sieve 4A, 5A, 13X and mordenite. The amount of water vapor breaking during the adsorption was estimated to provide a breakthrough capacity at the various inlet flow rates and humidity conditions. The molecular sieve 13X exhibited a better adsorption performance at a given bed height. The existence of CO₂ in a humid atmosphere had a minor effect on the net adsorption capacity and the hydrogen isotopic water (HDO) in the elution stream showed a delayed behavior during a thermal desorption.     

The diffusion coefficient of H2S in liquid sulfur

The diffusion coefficient of H₂S in liquid sulfur is a key kinetic parameter that has been missing in literature. In this paper, a pressure decay method was applied to measure the diffusion coefficients of H₂S in liquid sulfur at 403 and 423 K. This pressure decay process was then modeled by taking the simultaneous diffusion and reversible chemical reactions between H₂S and liquid sulfur into consideration. The diffusion coefficients and reaction rate constants were numerically determined by fitting theoretical curves to experimental data using Finite Element Method and Genetic Algorithm. The solubility of H₂S in liquid sulfur at 403 and 423 K was also calculated and the results agreed with the semi-empirical correlation lately reported in literature. This study further extended the validity of the correlation to higher partial H₂S pressure conditions.     

Fixed bed phosphate adsorption by immobilized nano-magnetite matrix: experimental and a new modeling approach

Nano-sized magnetite impregnated charcoal granular activated carbon (nFe-GAC) was utilized for the removal of phosphate from aqueous solutions using a fixed bed column. The dynamic of the phosphate adsorption was analyzed using a new approach to the Thomas model based on a two-step differential sorption rate process. The initial adsorption was found to be external mass transfer controlled, while intra-particle diffusion was the predominant mechanism in the latter stage. Consequently, two kinetic coefficients were calculated for each breakthrough curve resulting in an excellent model prediction. By implementing this approach a transition point, at which diffusion becomes the predominant adsorption mechanism, can be accurately determined. The effect of varying parameters, such as feed flow rates, feed pH, initial phosphate concentrations and adsorbent bed height were examined and described using the modified Thomas model. Reaction rates increased with augmentation of the flow rates from 1 to 40 mL/min while the adsorption capacity and transition point decreased. Similar transition points were obtained for initial phosphate concentrations between 10 and 100 mg/L. The unique characteristics of the nFe-GAC were evident as it exhibited very high phosphate adsorption capacity, at a wide range of pH values (4–9) with negligible effect of competing ions and short critical bed depth.     

A study of the influence of modifying iron and aluminum chloride additives on the water-absorbing capacity and thermal stability of peat

The influence exerted by modifying additives of inorganic nature on the hydrophilicity of peats from the Orlovskoe deposit in Tomsk oblast and on their thermal stability was studied. The acid-base, equilibrium, and kinetic properties of the starting peat samples and those modified with solutions of iron(III) and aluminum chlorides were examined. Their physicochemical parameters were determined: total exchange capacity, acidity by acid and basic groups, relative humidity, distribution coefficients, effective diffusion coefficients, and activation energy. The effect of modifying cations on the thermal decomposition of peat was analyzed.     

Comparison between mass transfer properties of weak-anion-exchange resins with graft-functionalized polymer layers and traditional ungrafted resins

Glycidylmethacrylate was grafted to Toyopearl HW-65M and subsequently modified with diethylamine to obtain a weak anion exchanger. The degree of grafting was varied from 11 to 50%. The binding capacity for bovine serum albumin was 11 mg/ml for the lowest degree of grafting and 97 mg/ml for the highest degree of grafting. The maximum binding capacity was observed at 27% degree of grafting. The mass transfer properties of the grafted resins and an ungrafted resin(Toyopearl DEAE 650M) were investigated assuming rectangular isotherms. Simple models for reaction kinetics, pore- and surface diffusion and film diffusion were used to describe the concentration-time data in batch mode. The data were best fitted by a pore diffusion model. The estimated pore diffusion coefficients (D(P)) for bovine serum albumin were fitted by a polynome to the degree of grafting with an maximum value at 27% of D(P) = 1.95-10(-11) m2/s. Compared to published data of other ungrafted resins and to the molecular diffusion coefficient of bovine serum albumin in free solution of D(P) = 5.6 10(-11) m2/s, the diffusion in grafted layers seems to be accelerated. The breakthrough curves for columns packed with various resins showed a decrease in sharpness with increasing degree of grafting which could not be described by a simple pore diffusion model using the calculated transport coefficients from batch mode. The shape of the breakthrough curves could be well described by a combined film and pore diffusion model. For the ungrafted Toyopearl DEAE 650M resin the breakthrough curve is more favorable and the influence of film diffusion to the mass transfer is reduced. It can be concluded that grafting will increase the capacity and the pore diffusion in batch mode but in column operation the grafting layer has a film resistance which plays an important role in the overall mass transfer.