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。     

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。     

烟气飞灰在θ环填料塔中对单乙醇胺溶液脱除CO2传质性能的影响

本文将烟气飞灰加入液相中,采用小型散堆θ环填料塔分析了飞灰对于单乙醇胺(MEA)溶液脱除CO₂传质性能的主要影响规律与机理,着重研究了各种操作参数条件下体积总传质系数K_Ga_v所受飞灰的影响。所得结果显示:在加入飞灰之后,减小了K_Ga_v值;而溶液温度的增加将会影响K_Ga_v值的提高,此外,K_Ga_v受飞灰的负面效应呈现出逐渐提高的趋势;而增大液气比则会使体积总传质系数K_Ga_v线性提高,同时,飞灰的影响则逐步地变弱;增加填料高度,K_Ga_v增加,而飞灰对K_Ga_v的负面影响逐渐增强;在逐渐增大飞灰浓度之后,飞灰对于体积总传质系数K_Ga_v所起的抑制作用也相应增强。     

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。     

二段式吸收塔强化水洗技术提纯沼气过程

压力水洗技术已成为提纯沼气的关键技术之一。采用填料吸收塔进行CO₂脱除实验研究,考察了液气比、吸收压力、吸收温度、CO₂初始含量、填料层高度对CO₂脱除率的影响,以及液气比、沼气流量对总体积吸收系数的影响,并运用填料塔与喷雾塔结合的二段式吸收塔进行压力水洗提纯沼气的过程强化实验。实验结果表明,吸收压力和液气比的增大、吸收温度的降低、填料层高度的增加有利于CO₂的脱除,体积总吸收系数随着液气比及沼气流量的增加而增大。二段式吸收塔能够提高CO₂吸收效果,当沼气处理量为10 L·min^-1,填料层高度为100 cm,CO₂含量小于3%时,与填料塔相比二段式吸收塔可以减少约12%的吸收液用量,并且采用110 cm填料的二段式吸收塔获得最佳的提纯效果,CO₂脱除率达到97.4%。     

填料吸收塔内乙醇胺溶液吸收CO2增强因子

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NaOH水溶液吸收低浓度CO₂的实验结果估算了填料的有效相界面积,建立了乙醇胺（MEA）溶液吸收高浓度CO₂增强因子的数学模型,并从数学模型和实验的角度研究了MEA浓度、进气流率、CO₂浓度等工艺参数对MEA吸收CO₂增强因子的影响。结果表明,增强因子数学模型计算值与实验值能够良好吻合,MEA吸收CO₂化学反应增强因子随进气CO₂浓度增加而降低,随MEA浓度增加而增加,随进气流率增加而减小。     

水力喷射-空气旋流器中微粒强化气液传质及其机理

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,研究了第三相固体粒子对气液传质的影响。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)测定了不同固含率c_s、进口气速u_g、液体喷射速度u_L下的有效相界面积a和液膜传质系数k_L,并由此得到总体积传质系数k_La和增强因子E。结果表明,随着粒子固含率增大,k_L、a、k_La和E先增大后减小,存在一适宜固含率。在不同进口气速和液体喷射速度下,加入微粒后,k_L、a、k_La均增大,但E随进口气速和液体喷射速度增加而减小。微粒加入后,主要从a、k_L和表面更新频率S这3方面强化了气液传质,但主要是通过增强表面更新频率S而实现的。     

旋流气液两相强化吸收CO2的传质性能

为强化二氧化碳的吸收过程,采用一类旋流逆向气液多级接触的方式,以NaOH溶液为吸收剂,研究其与大跨度浓度CO₂(2.5%～15%)接触反应的传质性能。分别探讨了吸收剂浓度、吸收剂流量、烟气CO₂浓度、烟气流量及反应温度对气相总体积传质系数(K_ga)的定量影响。结果表明,在实验条件下,其K_ga可达(4.53×10^-5)～(9.22×10^-5)kmol·m^-3·s^-1·kPa^-1。与双级直流喷雾和单级旋流喷雾相比,旋流逆向气液多级接触能够有效强化大跨度浓度CO₂的吸收过程。K_ga随吸收剂浓度、流量和反应温度的增加而增加,随CO₂浓度增加呈现先增加后减小(CO₂浓度大于5%)的非线性关系,随气体流量增加先增加后趋于稳定。     

阵列凸起微通道内气液两相传质特性研究

研究了阵列凸起微通道内N-甲基二乙醇胺（MDEA）吸收CO₂过程的气液两相传质特性。在弹状流型下,考察了气液两相流量、MDEA浓度对体积传质系数、CO₂吸收效率、压力降以及能量损耗的影响。弹状气泡受到阵列凸起的挤压作用发生形变,促进了气液两相间的传质。与平滑通道相比,阵列凸起微通道在实验条件下具有更好CO₂吸收效率。在相同的能量损耗时,阵列凸起微通道具有更大的体积传质系数。     

鼓泡床中电石渣加速碳酸化分析与响应面优化

搭建了鼓泡床碳酸化反应器,研究常温常压下电石渣直接液相碳酸化矿化封存CO₂的能力,揭示了重要操作参数表观气速、液固比和CO₂浓度对电石渣矿化封存CO₂能力和碳酸化效率的影响规律。同时构建响应面模型,分析各参数对电石渣碳酸化效率的影响强度,优化获得最大碳酸化效率及相应操作工况。结果表明,增加气速有利于钙离子溶解和CO₂吸收,但反应器中过高气速易导致气相通道效应,不利于气液充分接触。当液固比降低,溶液中钙离子浓度提高,更有利于碳酸化反应,但液固比过低会影响固液间传质。适当增加CO₂浓度有利于提高碳酸化效率,但CO₂浓度增至到一定值后,对碳酸化效率影响降低。响应面建模分析发现,各因素对碳酸化效率影响顺序为：液固比>CO₂浓度>表观气速。优化结果发现碳酸化效率最高为93.58%,工况为表观气速0.07m/s,液固比为8.26mL/g和CO₂体积分数为20.91%。研究可知,鼓泡床中常温常压下电石渣直接液相加速碳酸化反应,具有较大的CO₂固定量和高的碳酸化效率,实验结果为电石渣加速矿化封存CO₂技术的发展提供了基础数据。     

填料型预碳化塔的数学模型与模拟 ‘

硕酸化反应为一典型的连串、可逆放热反应，液膜内的快反应与液相本体的慢反应相互耦合，共同决定着ＣＯ２的化学吸收速率。本文在以往工作的基础上，通过对碳化机理和动力学的全面分析，建立了填料型预碳化塔的数学模型。对有关工业过程进行了模拟，指出了影响填料行为的关键因素并提出了相应的改进措施。     

MDEA-TBEE复合溶液选择性吸收H_2S性能评价

将一种强空间位阻胺TBEE(叔丁氨基乙氧基乙醇)添加于MDEA(N-甲基二乙醇胺)溶液中形成复合溶液MDEA-TBEE,以填料柱为反应器,采用常压吸收-常压再生操作流程,研究了复合溶液从混合气中选择性吸收H2S吸收性能,并与单组分吸收剂MDEA溶液吸收性能作比较,以脱除率、选择性、溶液负载和容量为评价指标,评价了再生温度、原料气CO2/H2S摩尔比、气液比和贫液负载等因素对复合溶液选择性吸收H2S性能的影响。结果表明,复合溶液比MDEA溶液易于再生,H2S脱除率高于MDEA溶液;复合溶液的容量大于MDEA溶液,平均是MDEA的1.25倍;随着气液比增大,H2S脱除率下降,选择性有所上升。     

Absorption of NOx in packed column (II)

An absorption efficiency of packed column removing nitrogen oxides with water and NaOH solution under atmospheric pressure was studied. The efficiency and the acidity produced by absorption of NO, were measured in a packed column. The model developed that was based on the mass-transfer information for packed column and absorption mechanism accompanying the chemical reaction was compared with experimental results. Predictions using the model presented by the previous paper (part 1) was shown well to agree with from the experimental results (part II). The efficiency of NO_x, absorption is largely dependent on the height of packing material and the partial pressure of NO_x in the feed gas. The efficiency of NO_x absorption decreases with the increase of the acidity produced by recycling of water as a scrubber liquid. For the recycle mode with an aqueous NaOH solution as a scrubber liquid, NO_x absorption efficiency is shown to be constant until all of the C_OH- in the scrubber liquid are converted into C_H+.     

KINETICS AND ABSORPTION RATE OF CO2 INTO PARTIALLY CARBONATED AMMONIA SOLUTIONS

In this research, kinetics and absorption rate of CO₂ were studied using partially carbonated ammonia solutions. A correlation was proposed to calculate CO₂ absorption rate based on two dimensionless parameters: conversion film parameter and carbonation ratio. Absorption rate experiments have been performed employing a laboratory absorption packed column. More than 60 items of experimental data were used for obtaining the correlation parameters. In the experiments, total ammonia concentration range was 30 to 750 (mol · m^?3), carbonation ratio range was 0.22 to 0.785, and CO₂ partial pressure in the gas mixture was 10, 14, or 18 (kPa). A comparison of the predictions indicated that the proposed correlation was more accurate than other correlations reported in the literature.     

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%.     

Experimental model validation of an integrated process for the removal of carbon dioxide from aqueous ammonia solutions

In this work modelling and experimental validation of an integrated process for the removal of carbon dioxide from ammonia solutions - the so called decarbonisation - is presented. In this process, carbon dioxide and small amount of ammonia is stripped out from the solution at ambient pressure in a packed column. Recovery of the stripped ammonia can be reached by combining absorption of ammonia and condensation of stripping steam. The integration of stripping, absorption and direct-contact condensation (DCC) can be achieved in one compact unit in which stripping takes place in the lower part of the packed column, and the DCC and ammonia absorption in its upper part. This unit has been modelled in a rigorous way considering heat and mass transfer as well as reaction rates in multicomponent reactive stripping, absorption and direct-contact condensation in packed columns (Ma?kowiak et al., 2009). Extensive experimental investigations in a pilot scale packed column with diameters of 0.15 and 0.32 m have been performed for both, the stripping and for DCC. Relevant operation parameters as well as column dimensions were varied during the experiments in order to investigate their influence on the selectivity of the decarbonisation and to achieve a broad data base for the validation. Experimental validation of the two sub-processes and the entire decarbonisation shows good agreement between calculated and experimental values. Based on the validated model a successful optimisation of the decarbonisation process in industrial scale has been performed, leading to increased carbon dioxide removal and reduction of ammonia losses.     

氨吸收装置技术改造总结

为扩大合成氨系统氨水排放量,增加吸收负荷,对氨吸收装置提出了技术改造方案：利用原装置吸收弛放气中的气氨制成氨水,新增1套氨水精馏制液氨装置,制成的氨含量为99．0％的液氨用作合成尿素。对比了改造前后氨吸收工艺流程;论述了氨水精馏塔的结构特点、填料类别和塔内液体分布器的特性参数;对改造前后运行参数进行了对比,结果表明,改造后尾气中氨含量从未出现超标现象,实现了氨水零排放。     

离子液体水溶液-气体水合物对CO2的双捕获工艺

设计了以离子液体[APMIM]Br水溶液吸收-生成水合物捕获CO2工艺流程,并利用CO2在该离子水溶液中的溶解度数据和在其中生成CO2水合物的相平衡实验数据进行物料衡算. 考察了水含量、压力和液气流量比对气体吸收-水合物生成的CO2双重捕获效果的影响,对比了气体水合物与离子液体水溶液捕获CO2的能力. 结果表明,在较高压力和水含量条件下,水合物捕获CO2的效应强于离子液体溶液;较低压力下离子液体溶液吸收CO2起主要作用. 与纯水合物法相比,双捕获工艺具有一定优势,且突破了单纯水合物脱碳的压力和CO2含量要求高的局限性. 当原料气中CO2低于65%(j)时,系统的脱碳效率低于40%,对于CO2含量较低的气体,其CO2的脱除性能回归至单纯离子液体溶液体系.