碳酸钠溶液吸收H2S气体的传质性能及数学模型分析

采用Na2CO3溶液在填料塔中分别吸收高、低浓度H2S气体,通过测定总体积传质系数(KGa),采用基于Box-Behnken设计的响应面分析方法研究吸收液流量、浓度和气体流量对KGa的影响,建立了Na2CO3溶液吸收高、低浓度H2S的二次响应曲面模型. 结果表明,在高、低H2S吸收体系中,各因素对KGa的影响规律基本一致,在低浓度H2S吸收体系中对KGa的影响更大. KGa与3个因素之间不是简单的单调函数关系,吸收液流量和浓度具有较强的相互增效作用. 处理H2S浓度为2.16%(j)、气体流量为720 L/h的体系时,当吸收液浓度为0.082 mol/L、其流量为11.28 L/h时,KGa最大;处理H2S浓度为20.1%(j)、气体流量为720 L/h的体系时,吸收液浓度为0.764 mol/L、其流量为11.28 L/h时,KGa最大.     

H2S Reactive Absorption from Off‐Gas in a Spray Column: Insights from Experiments and Modeling

H₂S removal from an off‐gas stream was performed in a spray column by H₂S reactive absorption into a NaOH solution. The individual and interactive effects of three independent operating variables on the percentage of absorbed H₂S were investigated: the initial pH of the scrubbing solution, the initial scrubbing solution temperature, and the volumetric liquid‐to‐gas ratio. The optimum operating variables were determined by response surface methodology (RSM) attaining a percentage of absorbed H₂S of 98.7 ± 0.2 %. Additionally, the process performance was modeled by an artificial neural network (ANN) to predict the percentage of absorbed H₂S. The results showed that the experimental data agreed better with the ANN model than with the RSM results.     

Experimental Study and Mathematical Modeling of NO Removal Using the UV/H2O2 Advanced Oxidation Process

An experimental study on NO removal via UV/H₂O₂ process was conducted in a semi‐continuous bubble‐column reactor and the effect of some operation parameters including NO initial concentration and gas flow rates on removal efficiency was investigated. Applying UV light increased the efficiency significantly. The steady‐state removal efficiency was found to be higher at the lower gas flow rates. The bubble size as an important factor in mass transfer calculations and modeling procedure was determined at different gas flow rates using bubble photographs and image processing technique. In the ranges of flow rates studied here, the gas flow rate had no significant effect on the bubble diameter. A mathematical model was developed to describe the NO removal process. The model predictions were compared with existing experimental data, confirming a good agreement of the data.     

H2S固体氧化物燃料电池的制备及其性能

采用尿素燃烧法制备La0.6Sr0.4Co0.2Fe0.8O3-δ(记作LSCF,下同)钙钛矿型阴极催化剂前体粉末,经800℃锻烧后具有典型的钙钛矿结构。在400～950℃温度范围内,催化剂具有较高的电导率,满足固体氧化物燃料电池阴极的要求。研究了以H2S为燃料气时,单体固体氧化物燃料电池(CoS-Mo2S)/BaCe0.9-xZrxY0.1O3/LSCF在不同温度下的电化学性能以及脱硫性能。结果表明:电池的最大电流密度、最大功率密度以及对H2S的脱除率均随温度的升高而增大;在反应温度为850℃,燃气流量为50 mL/min的条件下,电池的最大电流密度和最大功率密度分别为39.52 mA/cm2,6.38 mW/cm2;900℃时,H2S的脱除率达72%。     

Modeling and Parametric-Sensitivity Analysis of Nonisothermal Reactive Absorption

We address the uniqueness and multiplicity of the equilibrium solutions in a specific class of chemically reactive system involving nonisothermal reactive gas absorption. A film model that is not restricted to a particular reaction regime is developed for (m,n)th-order irreversible reactions. Lower and upper bounds for the interfacial temperature rise are proposed, and tested by application to real systems, including the chlorination of n-decane, chlorination of toluene, and sulfonation of dodecylbenzene (DDB). We further develop a categorization of the possible bifurcation parameters, and propose lower and upper bounds for each of the new parameters in the generalized model. A parametric-sensitivity analysis in the kinetic- and reactor-parameter spaces is presented. It is shown that the steady-state multiplicity behavior of the system is more sensitive to the kinetic parameters, whereas a few of the new reactor parameters are of significant impact.     

氧化铝生产赤泥附液吸收H_2S实验研究

对氧化铝生产附产赤泥吸收净化H2 S废气进行了实验研究 ,赤泥附液吸收H2 S具有吸收效率高、吸收容量大、易控制 ,操作简便等优点 ,在较少时间内对H2 S的吸收效率保持在 90 %以上。     

粗合成气净化系统脱硫塔的结构改进及应用

介绍中石油吉林石化公司化肥厂合成气装置脱硫系统生产工艺,由于原料渣油含硫量大幅度提高,装置投运时间长设备存在腐蚀与老化问题,粗合成气脱硫塔无法满足合成气中H2S含量低于5 mg/m3的要求,经改造,脱硫塔出口H2S含量降到2 mg/m3以下,延长了后部氧化锌精脱硫催化剂的使用周期.     

ABSORPTION OF H2S INTO AQUEOUS METHYLDIETHANOLAMINE

The absorption of H₂S into aqueous methyldiethanolamine (MDEA) was studied experimentally over the temperature range 15 to 35°C and for MDEA concentrations from 10 to 25 wt% using a laminar liquid jet device and a stirred-cell absorber. The contact times ranged from 2 × 10^-3 to 1 × 10^-2 seconds for the jet absorber and from 6 to 38 seconds for the stirred-cell absorber. It was found that the absorption rate data for both devices could be modelled assuming an instantaneous reaction regime for the reaction between H₂S and MDEA. The experimental results were interpreted to give an estimate for the diffusion coefficient of MDEA in water. Diffusion coefficient results are consistent for the two apparatuses. A lower bound for the second-order rate constant for the reaction between H₂S and MDEA is estimated from the experimental data to be 1.4 × 10¹⁰cm³/g mole s at 25°C     

粗煤气中硫化氢脱除与利用的探讨

分析了采用克劳斯硫回收装置脱除硫化氢工艺生产过程中存在的问题。在对生产实际分析和科学化验的基础上,探讨采用WSA技术,利用粗煤气中的废气硫化氢生产工业浓硫酸的可行性。     

H2S在线分析仪的开发与研究

介绍基于比尔定律开发的H2S在线分析仪。该仪器主要应用于克劳斯硫磺回收系统，替代价格昂贵的进口仪表。     

H2S选择性氧化催化剂的侧线试验研究

主要介绍了H2S选择性氧化脱硫催化剂在某30万t合成氨装置上的现场考核，实验证明了在适宜的条件下，该催化剂可以处理复杂气源中低浓度H2S，经过500h的考核，催化剂显示了很好的活性、选择性及稳定性。     

Comparison of Overall Gas‐Phase Mass Transfer Coefficient for CO2 Absorption between Tertiary Amines in a Randomly Packed Column

The mass transfer performance of CO₂ absorption into an innovative tertiary amine solvent, 1‐dimethylamino‐2‐propanol (1DMA2P), was investigated and compared with that of methyldiethanolamine (MDEA) in a packed column with random Dixon‐ring packing. All experiments were conducted under atmospheric pressure. The effects of inert gas flow rate, amine concentration, liquid flow rate, CO₂ loading, and liquid temperature on mass transfer performance were analyzed and the results presented in terms of the volumetric overall mass transfer coefficient (K_Ga_v). The experimental findings clearly indicate that 1DMA2P provided better mass transfer performance than MDEA. For both 1DMA2P and MDEA solutions, the K_Ga_v increased with rising amine concentration and liquid flow rate, but decreased with higher CO₂ loading. The inert gas flow rate only slightly affected the K_Ga_v. A satisfactory correlation of K_Ga_v was developed for the 1DMA2P‐CO₂ system.     

SIMULTANEOUS ABSORPTION OF C02 AND H2S IN SULFINOL SOLUTIONS IN A SET OF PACKED ABSORBER-STRIPPER

Simultaneous absorption of CO₂ and H₂S in a Sulfinol solution have been studied in a set of small pilot scale packed absorber-stripper. Data were presented on the effects of varying liquid circulation rate, feed gas flow rate, feed gas composition and steam pressure at bottom of stripper, on the individual gas removal %, steam stripping efficiency and overall volumetric gas-phase mass transfer coefficient for absorption. A comparison with an earlier work on absorption into 20% hot potassium carbonate solution in the same apparatus show that the influence of operating variables on the performance of the absorber-stripper unit is qualitatively similar for both types of solvents except that the steam stripping efficiency of the Sulfinol system is much more superior than the 20% hot carbonate system under similar conditions. This shows that the hybrid nature of the Sulfinol solvent gives a much better regeneration efficiency than chemical solvents in simultaneous CO₂ and H₂S removal     

锰系可再生高温脱硫剂的制备及其性能测试

煤气的高温脱硫净化是 IGCC 和 DRI 生产的瓶颈,直接影响整个过程的热效率。在50℃、pH值约为9的条件下采用硝酸锰、硝酸铝混合溶液与氨水进行共沉淀,制备了锰含量不同的脱硫剂,在固定床反应器中考察了脱硫剂的硫化及再生性能,并利用XRD、SEM、BET等手段表征了脱硫剂在硫化/再生过程中的物相和结构变化。共沉淀法制备的脱硫剂Mn/Al分散性好,在850℃高温下进行脱硫反应可以定量快速进行。脱硫硫容与脱硫剂锰含量呈正比,Mn-S/Mn-O交换原子比在0.90~0.95之间,改变空速和进口H₂S含量并不改变脱硫硫容。采用O₂浓度为3%的稀释空气在850℃下再生,再生后的硫容稳定,说明所制备的脱硫剂可用于高温可再生脱硫。     

生物质与煤混合热解过程中H2S的排放特性

选取麦秆、玉米秆、棉秆、杨木屑与无烟煤、烟煤进行H2S排放特性的混合热解实验研究,实验过程中采用热重-色谱-质谱连用技术对混合热解过程中产生的H2S气体进行了在线测量,研究和分析了热解温度和生物质的掺混比例对H2S排放的影响。结果表明：生物质的加入使煤析出H2S提前,随着生物质比例的增加,H2S在更低的温度下有更大的析出速度;生物质对烟煤和无烟煤析出H2S的影响都存在一个温度分界点,在分界点前后有着较大的区别。     

焦炉煤气脱硫脱氰工艺的优化

通过对焦炉煤气脱硫系统中HCN分解装置的运行状况和存在的问题进行总结,找出了其堵塞原因,并在理论和实践分析的基础上对生产工艺进行改造、操作方法进行改进。经过改造后工艺实际生产效果明显改善,脱硫工序开工率、硫磺产量明显提高,取得了较好的经济效益和环境效益。     

Mathematical Modeling and Optimization of Combined Steam and Dry Reforming of Methane Process in Catalytic Fluidized Bed Membrane Reactor

Mathematical modeling of the methane-combined reforming process (steam methane reforming–dry reforming methane) was performed in a fluidized bed membrane reactor. The model characterizes multiple phases and regions considering low-density phase, high-density phase, membrane, and free board regions that allow study of reactor performance. It is demonstrated that the combined effect of membrane and reaction coupling provides opportunities to overcome equilibrium limits and helps to achieve higher conversion. Additionally, the influence of key parameters on reactor performance including reactor temperature, reactor pressure, steam to methane feed ratio (S/C), and carbon dioxide to methane feed ratio (CO₂/C) were investigated in the multi-objective genetic algorithm to find the optimal operating conditions. Finally, the process of steam reforming was simulated in selected optimal conditions and the results are compared to those of the combined reforming process. Comparison reveals the superiority of the combined reforming process in terms of methane conversion, catalyst activity, and outlet H₂/CO ratio in the syngas product in being close to unity.     

硫化氢在 Primene JM-T 中溶解度的测定与模型建立简

The primary aliphatic amine Primene JM-T was investigated as a potential absorbent for H2S removal. The solubility of HzS in JM-T was measured at 298, 313,333,353, and 368 K with H2S partial pressures from 20 to 760 kPa and HzS loading from 0.02 to 0.8 mol H2S per mol JM-T. Relevant physical properties, such as density, viscoslty and dielectric constant, ot the matenal were measured. ＇The thermodynamlc model with two-suttlX Margules equation was used to correlate the experimental vapor-liquid equilibrium data. Furthermore, the absorption mechanism in non-aqueous system is suggested and the difference between non-aqueous and aqueous absorption system is pointed out.     

HPF湿式氧化法焦炉煤气脱硫脱氰技术

介绍了HPF法脱硫脱氰工艺的原理、流程、特点以及实际操作数据。     

Modeling of Direct H2S Fueled Solid Oxide Fuel Cells with Reforming Chemical Kinetics

A direct H₂S fueled SOFC model is developed based on Ni‐YSZ/YSZ/YSZ‐LSM button cell test stand. The model considers the detailed reforming chemical processes of H₂S and multi‐physics transport processes in the fuel cell and fuel supply tubes. The model is validated using experimental data. Extensive simulations are performed to study the complicated interactions between multi‐physics transport processes and chemical/electrochemical reactions. The results elucidate the fundamental mechanisms of direct H₂S fueled SOFCs. It is found that suitably increasing the H₂O content in the supplied H₂S fuel can improve SOFC electrochemical performance; high operating temperature may facilitate the reforming of H₂S and improve the electrochemical performance. The sulfur poisoning effect may be mitigated by increasing the H₂O content in the fuel, increasing the operating temperature, decreasing the flow rate, and/or making the cell work at low voltage (or high current) conditions.