水力喷射-空气旋流器用于湿法烟气脱硫及其传质机理

在一种新型高效的气液传质设备--水力喷射-空气旋流器(WSA)中,以Ca(OH)₂料浆为吸收剂进行了模拟烟气湿法脱硫的实验研究。结果表明:脱硫率随进口气速增加而增加;随液体喷射速度增加先增加,增加到一定程度后几乎不变;随烟气中SO₂的进口浓度增加而减小,存在一适宜的Ca(OH)₂浓度和回流比。在气体流量24～72 m³·h^-1、循环液体量0.4～0.8 m³·h^-1、料浆中Ca(OH)₂浓度7500 g·m^-3时,对SO₂浓度为1891～6373 mg·m^-3的烟气进行湿法脱硫,脱硫率达88.9%～97.7%,且WSA的旋流气体和喷射液体在湿法脱硫中具有自清洁能力,未发现内部结垢和喷孔堵塞现象。总体积传质系数K_Ga、有效相界面积a均随进口气速u_G增大而增大,而总传质系数K_G随u_G增加变化较小;当液体喷射速度 u_L≤0.26 m·s^-1时,K_Ga和K_G随u_L增加快速增大,之后增加缓慢,而a随u_L几乎线性增加,K_Ga和K_G随吸收剂中Ca(OH)₂浓度c_L增加有一最大值。结合实验数据拟合得到了相关的经验公式,这些关联式能较好地预测WSA的湿法脱硫传质性能。气体旋流场强度对总体积传质系数K_Ga和有效相界面积a起支配作用,脱硫传质过程同时受气膜和液膜阻力控制,但以液膜控制为主。     

燃煤烟气中SO2对氨法脱碳的影响

利用湿壁塔实验台对燃煤烟气中SO₂对氨水溶液［1%～7%(质量）］吸收CO₂的影响进行了实验研究,具体分析了不同反应温度（20～80℃）和CO₂体积分数（5%～20%）条件下,CO₂传质通量及传质系数随SO₂浓度和SO₂负载量的变化规律。结果表明, SO₂浓度由0增至11428 mg·m^-3,CO₂传质通量及传质系数均有一半左右降幅,而SO₂负载量［0.1～0.4 mol SO₂·（mol NH₃）^-1］的增加,同样导致CO₂传质通量及传质系数明显减小。氨水浓度及反应温度增加可有效提高CO₂传质通量和传质系数,相对降低SO₂对CO₂传质的影响。CO₂浓度的增加可明显提高其传质通量,但是CO₂的传质系数有所降低。     

电石渣喷淋吸收烟气二氧化硫工艺及动力学

在喷淋吸收装置中对电石渣浆液吸收SO₂进行了系统研究。研究结果表明：脱硫效率随烟气SO₂浓度的增加先升高,然后下降;随体系pH的增加而升高,pH从3升到13时,脱硫效率由52.3%升到94.7%;增加浆液电石渣浓度和减小电石渣粒径均有利于SO₂的吸收去除;液气比从10 L·m^-3增加到50 L·m^-3时,脱硫效率提高了59.9%;以电石渣烟气脱硫的化学反应为基础,建立电石渣烟气脱硫反应动力学模型,总反应级数n=α+β=1.67,反应活化能E_a=51396.59 J·mol^-1,频率因子k₀=0.37894×10⁶(mol·m^-3)^-0.67·s^-1。     

水力喷射-空气旋流器中气液传质特性及其机理

对一种新型高效的气液传质设备--水力喷射-空气旋流器(WSA)的传质机理进行了研究。分别采用化学吸收法(CO₂-空气-NaOH体系)和物理吸收法(CO₂-空气-H₂O体系)测定了不同进口气速、不同液体喷射速度下的有效相界面积a和液膜传质系数k_L,并由此得到体积传质系数k_La。结果表明,由于WSA中气液间的强交互作用,a、k_L以及k_La均随进口气速和液体喷射速度增大而增大。采用量纲分析法对实验数据进行了归纳,拟合出了a、k_L和k_La随气相Reynolds数Re_g、液相Weber数We_L之间的经验公式:a=0.0024Re_g^1.25We_L^0.079,Sh_L=35.31Re_g^0.2303We_L^0.13,k_La=6.52×10^-8Re_g^1.48We_L^0.21,这些关联式能较好地预测WSA的传质性能。研究还表明,在WSA中的气液射-旋流传质体系中,传质过程符合双膜理论、表面更新理论和溶质渗透理论,但以表面更新机理为主。     

微通道内离子液体/乙醇混合溶液吸收CO2的传质特性

采用高速摄像仪对微通道内离子液体/乙醇混合溶液吸收CO₂的传质行为进行了实验研究。考察了弹状流型下气液两相流量比和离子液体浓度对液侧体积传质系数k_La和液侧传质系数k_L的影响。当离子液体浓度不变时,k_La、k_L均随气液流量比的升高而增大并逐渐趋于恒定。当液相流量不变时,对于不同浓度的离子液体溶液,液侧体积传质系数k_La和液侧传质系数k_L随气液流量比的变化曲线出现了交叉点。在交叉点之前,k_La和k_L均随着离子液体浓度的增大而减小;在交叉点之后,k_La和k_L均随着离子液体浓度的增大而增大。提出了用于预测液侧体积传质系数k_La的新的量纲1经验关联式,预测效果良好。     

NaOH-CO2体系下并流立体旋流筛板塔传质性能

二氧化碳捕集是应对全球气候变暖问题的重要技术之一。本文使用NaOH溶液和CO₂作为实验体系,在并流塔中对立体旋流筛板（TRST）的传质性能进行实验研究,测定并计算出全塔及塔板段的气相总体积传质系数[K_Ga_e,(K_Ga_e)_t],重点考察塔板安装数量和方式、空塔气相动能因子和喷淋密度、CO₂和NaOH浓度等参数的影响规律。研究结果表明,塔板段是传质过程的主要区间,增加塔板数量以及采用塔板逆向安装方式是提升传质性能的有效技术手段;塔板段的气相总体积传质系数随空塔气相动能因子和NaOH浓度的增加呈先增大后减小的趋势,随喷淋密度和CO₂浓度的增加而减小,最高可达12.18kmol/(m³·h·kPa);建立塔板段的气相总体积传质系数的经验模型,模型计算值与实验数据的吻合性较好,相对误差小于20%。     

沼气提纯过程中醇胺溶液吸收CO2传质性能

醇胺溶液吸收CO₂是沼气提纯领域重要的研究课题。在实验填料吸收塔中,以乙醇胺(MEA)、二乙醇胺(DEA)为吸收剂,研究了吸收剂浓度、进气流量、CO₂浓度、进液温度对吸收过程转化率η、吸收速率N以及气相总体积传质系数K_Ga_e的影响。结果表明,吸收剂浓度增加可有效提高η、N及K_Ga_e;进气流率增加,η逐渐降低,N先增加后降低,K_Ga_e先增加后降低最终趋于稳定;随着CO₂浓度增加,η和K_Ga_e不断降低,N逐渐增加;随着进液温度升高,η和K_Ga_e均先升高后降低;MEA、DEA的最佳进液温度在40～60℃之间,并随CO₂负载量增大而逐渐降低。研究结果对于醇胺溶液吸收法沼气提纯技术的研究开发和实际应用有参考作用。     

自发式气调共混膜的制备及性能分析

以磺化聚醚醚酮（SPEEK）和聚偏氟乙烯（PVDF）为原材料,制备自呼吸式气调共混膜,并对其气调特性及保藏效果进行分析。利用SEM、DSC等手段研究SPEEK与PVDF之间的相容性,杂合制备共混膜,通过一系列测试手段分析共混膜的孔径分布、透气性等,并应用于花椰菜的气调保藏。结果表明：通过改变SPEEK与PVDF的混合比例,可以制备出不同透气性的气调膜。不同比例的共混膜对纯CO₂的渗透系数范围为1.05×10^-10~1.495×10^-9cm³·cm/（cm²·s·cmHg）,对纯O₂的渗透系数范围为0.19×10^-10~2.97×10^-10cm³·cm/（cm²·s·cmHg）。将所制备的共混膜应用于花椰菜的气调保藏时,气调包装内CO₂浓度在3.7~9.1h后达到平衡状态,终浓度保持在体积分数4.4%~7.8%;O₂的浓度在5.5~9.6h后到达平衡状态,终浓度保持在体积分数4.2%~9.2%,该气体组分适宜花椰菜的长期气调保鲜。根据膜的调节范围和保藏实验可推测,该共混膜可应用于多种新鲜果蔬产品的自发性气调保藏。     

乙醇胺捕集燃煤烟气二氧化碳工艺模拟

有机胺法是最有效的燃煤烟气二氧化碳（CO₂）捕集技术之一。使用Aspen plus模拟乙醇胺（MEA）捕获烟气CO₂的过程,先进行单独的吸收塔与再生塔模拟,在单独系统模型收敛的基础上,再进行吸收-解吸的综合模拟。在入塔烟气流量为8.22 m³/min、CO₂物质的量分数为0.18、MEA流量为2 311.3 kg/h、MEA物质的量分数为0.12条件下,MEA捕集燃煤烟气中CO₂的模拟结果: CO₂脱除率为69.3%,净化气中CO₂物质的量分数为5.33×10^-2,再生塔顶再生气中CO₂物质的量分数为0.956,基本达到了设计要求。此为更深入地开展胺法吸收CO₂的研究提供了依据。     

微通道内MEA/MDEA混合溶液吸收CO2的传质特性

研究了T形微通道内N-甲基二乙醇胺（MDEA）和单乙醇胺（MEA）混合水溶液吸收CO₂的传质过程。考察了弹状流型下气液两相流量、MEA和MDEA浓度对液侧传质系数k_L和体积传质系数k_La的影响。液侧传质系数和体积传质系数均会随着MEA浓度的升高而升高。与MEA相比,MDEA浓度的提高对传质影响较小。传质系数会随着液体流量的增大而增大,但气体流量的变化对其影响较小。体积传质系数随液体流量的增大而增大,但随气体流量的增大先增大,之后趋于稳定。考虑到化学反应对传质的强化作用,引入了Hatta数,提出了一个新的体积传质系数预测式,预测效果良好。     

Gas separation using sol-gel derived microporous zirconia membranes with high hydrothermal stability☆

A microporous zirconia membrane with hydrogen permeance about 5 × 10?8 mol·m?2·s?1·Pa?1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 kPa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexafluoride, around Knudsen values. A much lower CO2 permeance (3.7 × 10?9 mol·m?2·s?1·Pa?1) was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination tem-perature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular siev-ing property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 kPa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10?8 and~3 × 10?9 mol·m?2·s?1·Pa?1, respectively. Both H2 and CO2 permeances of the zirconia membrane de-creased with exposure time to 100 kPa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10?8 mol·m?2·s?1·Pa?1 and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.     

Electrochemical analysis and convection-enhanced mass transfer synergistic effect of MnOx/Ti membrane electrode for alcohol oxidation

The different electrocatalytic reactors could be constructed for the electrocatalytic oxidation of 2,2,3,3-tetrafluoro-1-propanol(TFP) with two typical MnO_x/Ti electrodes, i.e.the electrocatalytic membrane reactor(ECMR) with the Ti membrane electrode and the electrocatalytic reactor(ECR) with the traditional Ti plate electrode.For the electro-oxidation of TFP, the conversion with membrane electrode(70.1%) in the ECMR was 3.3 and 1.7 times higher than that of the membrane electrode without permeate flow(40.8%) in the ECMR and the plate electrode(21.5%) in the ECR, respectively.Obviously, the pore structure of membrane and convection-enhanced mass transfer in the ECMR dramatically improved the catalytic activity towards the electro-oxidation of TFP.The specific surface area of porous electrode was 2.22 m~2·g~(-1).The surface area of plate electrode was 2.26 cm~2(1.13 cm~2× 2).In addition, the electrochemical results showed that the mass diffusion coefficient of the MnO_x/Ti membrane electrode(1.80 × 10~(-6) cm~2·s~(-1)) could be increased to 6.87 × 10~(-6) cm~2·s~(-1) at the certain flow rate with pump, confirming the lower resistance of mass transfer due to the convection-enhanced mass transfer during the operation of the ECMR.Hence, the porous structure and convection-enhanced mass transfer would improve the electrochemical property of the membrane electrode and the catalytic performance of the ECMR,which could give guideline for the design and application of the porous electrode and electrochemical reactor.     

微通道内单乙醇胺水溶液吸收CO2/N2混合气的传质特性

采用高速摄像仪对400 μm×400 μm T形微通道内单乙醇胺（MEA）水溶液吸收混合气中CO₂过程的气液两相流及传质特性进行了实验研究,微通道内的压力降采用压力传感器进行测量。考察了弹状流型下气液两相流量及MEA浓度对压力降、比表面积和传质性能的影响。结果表明,当MEA浓度不变,气液两相流量增大时,压力降、比表面积、传质系数、体积传质系数和增强因子均增大,并逐渐趋于恒定。当气液流量不变,MEA浓度增大时,压力降、传质系数、体积传质系数和增强因子增大,但比表面积减小。实验条件下,压力降范围为2.00~5.23 kPa,化学吸收过程的传质系数范围为7.74×10^-4~2.97×10^-3 m·s^-1。对于伴有快速化学反应的传质过程,以Sherwood数、Reynolds数、Schmidt数及增强因子为变量建立了体积传质系数的预测关联式,平均偏差为5.09%,具有良好的预测性能。     

Experimental study of the mass transfer behavior of carbon dioxide absorption into ternary phase change solution in a packed tower

Phase change absorbents for CO₂ are of great interest because they are expected to greatly reduce the heat energy consumption during the regeneration process. Compared with other phase change absorbents, monoethanolamine (MEA)-sulfolane-water is inexpensive and has a fast absorption rate. It is one of the most promising solvents for large-scale industrial applications. Therefore, this study investigates the mass transfer performance of this phase change system in the process of CO₂ absorption in a packed tower. By comparing the phase change absorbent and the ordinary absorbent, it is concluded that the use of MEA/sulfolane phase change absorbent has significantly improved mass transfer efficiency compared to a single MEA absorbent at the same concentration. In the 4 mol·L^-1 MEA/5 mol·L^-1 sulfolane system, the CO₂ loading of the upper liquid phase after phase separation is almost zero, while the volume of the lower liquid phase sent to the desorption operation is about half of the total volume of the absorbent, which greatly reduces the energy consumption. This study also investigates the influence of operating parameters such as lean CO₂ loading, gas and liquid flow rates, CO₂ partial pressure, and temperature on the volumetric mass transfer coefficient (K_Ga_V). The research shows that K_Ga_V increases with increasing liquid flow rate and decreases with the increase of lean CO₂ loading and CO₂ partial pressure, while the inert gas flow rate and temperature have little effect on K_Ga_V. In addition, based on the principle of phase change absorption, a predictive equation for the K_Ga_V of MEA-sulfolane in the packed tower was established. The K_Ga_V obtained from the experiment is consistent with the model prediction, and the absolute average deviation (AAD) is 7.8%.     

硫代杯[4]冠-4在硝酸体系中对Sr2+的萃取

乏燃料后处理的高放废液分离过程中,发展新型分离材料实现对锶的高效萃取至关重要。合成了1,2交替构象的硫代杯[4]冠-4(TCACE),利用FT-IR、¹H NMR和MS对目标产物进行了表征。研究不同稀释剂对萃取的影响,优化得出CH₂Cl₂为稀释剂,在硝酸浓度为3 mol·L^-1,有机相中硫代杯[4]冠-4浓度为1×10^-3 mol·L^-1,水相中Sr²⁺浓度为5×10^-4 mol·L^-1,萃取温度为25℃,萃取80 min条件下,平均传质系数为1.36×10^{-5 m}·s^-1,Sr²⁺的分配比为0.69。分析了不同条件对硫代杯[4]冠-4对Sr²⁺的萃取影响,研究了萃取计量方程式,实验结果表明萃合物为{Sr(NO₃)₂}·{TCACE}。研究了TCACE对其他金属离子Mo⁶⁺、Ni²⁺、Ag⁺、Sn⁴⁺等的萃取效果,表明对Sr²⁺具有较好的选择性。     

气体喷射-气液旋流式冷氢箱的传质特性

开发了一种具有多重旋流结构的气体喷射-气液旋流式冷氢箱,并通过大型冷模实验对其进行传质性能测试。在气体喷射速度10～80 m·s^-1和液体进口速度0.2～0.7 m·s^-1条件下,采用氧吸收法测量了液相体积传质系数k_La,采用空气-Na₂SO₃溶液化学吸收法测量了相界接触面积a。结果表明:k_La和a均随气体喷射速度和液体进口速度增大而增大,其中受气体速度变化影响更为明显;由测定的传质参数数值可知新型冷氢箱传质效果较传统冷氢箱大幅提高,与机械输入设备处于相同量级,具有优异的气液混合性能。还采用量纲分析法对数据进行了归纳拟合,得到传质参数与气相Reynolds数、液相Weber数之间的关联式,可以较好地关联预测冷氢箱的传质性能。     

CO2 absorption performance in a rotating disk reactor using DBU-glycerol as solvent

Gas–liquid mass transfer of rotating disk reactor was studied in CO_2 absorption using 1,8-diazabicyclo-[5.4.0]-undec-7-ene(DBU)-glycerol solution as solvent. Effects of the rotating disk structure and various operation parameters on the CO_2 absorption rate and CO_2 removal efficiency were investigated. The rotating disk with optimal holes is conducive to mass transfer of CO_2 and the formation of thin liquid film at the opening increases the gas–liquid contact area. With the increase of rotating speed, the liquid flow pattern on the rotating disk surface changes from thin film flow to separated streams and creates extra liquid lines attached to the rim of the disk,which leads to a very complicated change on the CO_2 absorption rate and CO_2 removal efficiency. The overall gas-phase mass transfer coefficient increases 138% as the rotating speed increasing from 250 to 1400 r·min~(-1).Increasing temperature from 298 to 338 K can enhance the CO_2 absorption rate due to lowering the viscosity of the solvent. The rate-determined step for the absorption is focused on the gas side. The rotating disk reactor can effectively enhance the absorption of CO_2 with viscous DBU-glycerol solvents.