膜气体吸收过程中复合溶液化学增强因子预测

建立了一个膜吸收复合溶液化学增强因子计算模型,实验测定和模型预测了胺类复合溶液膜吸收CO2的增强因子,研究了Hatta准数Ha、气液流速、吸收剂浓度等因素对增强因子的影响,通过比较评价了模型的准确性。结果表明:当Ha>2,增强因子E值近似等于Ha,胺类膜吸收CO2的反应可作为拟一级快速反应处理;吸收剂浓度对增强因子的影响很大,随吸收剂浓度增大增强因子迅速增大;液速增大,增强因子也增大,但增大幅度有限;气速对增强因子几乎无影响。数学模型能较好地预测复合溶液膜吸收CO2的化学增强因子,预测的平均相对偏差为8.7%,最大为15.5%。     

中空纤维膜组件分离酸性气体

研究了气体膜分离与溶剂吸收相结合的分离技术.以NaOH水溶液为吸收剂,在中空纤维膜组件中实现二氧化硫气体的选择性吸收.研究了在三种不同结构的疏水性聚丙烯中空纤维膜组件中,吸收剂浓度、液速、气速、气液两相在膜组件内的流程、膜结构等对分离过程的影响;根据膜结构的实际参数确定了多孔膜的曲率因子,总传质系数的计算值与实验值相符.     

膜吸收法回收烟气CO_2传质过程研究

在0.1~2 m~3/h模拟烟气膜吸收处理装置上,进行了膜吸收法捕集CO_2传质过程研究。在其他条件不变的情况下,考察了气体流量、吸收液流量和吸收液浓度对传质过程的影响;结合吸收溶剂的化学反应增强因子及中空膜本身的参数,建立了膜吸收过程的传质计算模型。试验结果表明:在有化学吸收推动的膜吸收传质过程中,膜吸收的传质阻力集中在气相和膜的界面,而反应发生在液膜界面,所建立的计算模型也很好地反映了这一现象。通过建立传质模型,可以推算出膜表面吸收传质过程,从而为膜吸收过程的工业放大提供支撑。     

膜基-氨基酸盐及其复合溶液吸收CO2的性能

选择了氨基乙酸(GLY)和氨基丙酸(ALA)的盐溶液作为CO2吸收剂,将高效活化剂哌嗪(PZ)添加于GLY形成新型氨基酸基复合溶液,采用膜接触器-再生循环装置,研究了液速、吸收剂浓度等因素对总传质系数和脱除率的影响,评价和比较了GLY和ALA及其复合溶液的吸收性能。结果表明:GLY的传质推动力大于ALA,GLY的总传质系数和脱除率大于ALA;在吸收剂浓度对总传质系数的影响程度上,GLY大于ALA;复合溶液的吸收性能明显优于单一的氨基酸盐溶液,少量的PZ能显著地增强传质效率。     

煤基合成气(CO+H_2)合成二甲醚——产品分离中传质的研究

在溶剂法回收二甲醚过程中 ,考察了吸收压力、气液比 G/L、空塔线速、进塔气体中的 DME浓度以及吸收温度等因素对 DME体积传质系数 Kyα的影响。结果表明 :随着吸收压力、空塔线速、进塔气体中 DME浓度的增加 ,Kyα值上升 ;随吸收温度和 G/L的升高 ,Kyα值降低     

煤基合成气（CO＋H2）合成二甲醚：产品分离中传质的研究

在溶剂法回收二甲醚过程中,考察了吸收压力、气液比G/L、空塔线速、进塔气体中DME浓度以及吸收温度等因素对DME体积传质指数Kya的影响,结果表明：随着吸收压力、空塔线速、进塔气体中DME浓度的增加,Kya值上升,随吸收温度和G/L的升高,Kya值降低。     

MDEA与MEA脱碳反应动力学

通过双模理论及反应釜吸收实验的方法,建立了胺液脱碳拟一级传质反应模型,并对其进行了实验验证。通过模型中的增强因子、二级反应速率常数及传质速率分析了伯胺MEA(乙醇胺)及叔胺MDEA(甲基二乙醇胺)的动力学特性,以此为基础进一步分析了MDEA+MEA混合胺液的交互作用、动力学特性,并得到了较优的胺液配比。研究结果表明:伯胺MEA的增强因子及传质速率数值大于叔胺MDEA,随着气液传质过程进行,传质速率逐渐减小;对于混合胺液,表观反应速率常数以及增强因子随着MEA浓度的增加以及温度的升高而逐渐增大;当总胺浓度为3mol·L^-1时,MDEA+MEA(2mol·L^-1+1mol·L^-1)的混合胺液增强因子数值为0.5,传质速率较大,为最优混合胺液配比。     

二乙醇胺溶液吸收CO2过程

运用双膜理论对气液两相传质进行分析,针对二乙醇胺溶液吸收CO2建立数学模型,该模型精确描述CO2传质速率对溶液pH值依赖程度及速率强化因子随化学反应进行的变化情况. 从每种含碳离子(包括CO32-, HCO3-与RNHCOO-)在不同反应阶段的浓度分布角度分析了各自对总传质速率的影响规律,实验中分别控制溶液浓度、进气流量和复合溶液配比等工艺参数. 结果表明,CO2传质速率主要受CO32-与HCO3-控制,而RNHCOO-的作用有限. 吸收液浓度提高促进传质,但当pH值降至8.2后其作用减弱;传质速率随进气流量升高而加快,70 mL/min后趋于稳定;复配溶液较单一溶液对CO2吸收速率和吸收量均有促进作用,但复配比例变化对离子贡献率影响微弱.     

湿壁塔氨法烟气脱硫的非平衡模型

针对氨法烟气脱硫体系,基于经典双膜传质理论,建立了湿壁塔氨法烟气脱硫的非平衡模型,包括烟气中SO2在氨水溶液中吸收模型以及反应器模型。该模型考虑了传质和反应之间的相互影响以及液相中电解质存在的影响,用传质速率方程表征二相间的传递过程。对直径为100 mm,列管高度为1 200 mm的吸收塔不同条件下氨水吸收模拟烟气中SO2进行了预测,得到了液膜内各组分的浓度分布曲线,增强因子沿塔高的分布。所得到的实验结果与预测结果基本一致。该模型可以为湿式氨法烟气脱硫的工艺设计及操作提供参考。     

MDEA与MEA脱碳反应动力学

通过双模理论及反应釜吸收实验的方法,建立了胺液脱碳拟一级传质反应模型,并对其进行了实验验证。通过模型中的增强因子、二级反应速率常数及传质速率分析了伯胺MEA(乙醇胺)及叔胺MDEA(甲基二乙醇胺)的动力学特性,以此为基础进一步分析了MDEA+MEA混合胺液的交互作用、动力学特性,并得到了较优的胺液配比。研究结果表明:伯胺MEA的增强因子及传质速率数值大于叔胺MDEA,随着气液传质过程进行,传质速率逐渐减小;对于混合胺液,表观反应速率常数以及增强因子随着MEA浓度的增加以及温度的升高而逐渐增大;当总胺浓度为3mol·L~(-1)时,MDEA+MEA(2 mol·L~(-1)+1 mol·L~(-1))的混合胺液增强因子数值为0.5,传质速率较大,为最优混合胺液配比。     

膜基气体吸收过程中活化剂的活化性能比较

将AMP(2-甲基-2-氨基-1-丙醇)和PZ(哌嗪)作为活化剂,分别添加于MDEA(N-甲基二乙醇胺)溶液中组成复合溶液,在膜吸收装置上考察了其吸收CO2性能. 通过气液流速、气相组成、液相浓度、负载、膜组件结构和膜结构形态等对总传质系数Kov影响的比较,研究了具有多氨基环状结构的化合物PZ和空间位阻结构的化合物AMP在膜气体吸收过程中对传质的加强作用. 结果表明,多氨基化合物PZ比空间位阻胺AMP活化效应更大,PZ对传质的加强作用高于AMP,流体力学因素对传质的影响有限,活化剂的化学活化作用对传质的影响是关键性因素,动力学因素对传质具有本质上的作用.     

Implementation of electrolyte CPA EoS to model solubility of CO_2 and CO_2+ H_2S mixtures in aqueous MDEA solutions

The electrolyte version of SRK plus association equation of state(e SRK-CPA Eo S) was employed to correlate CO_2 solubility in MDEA aqueous solutions. The applied model comprises the classic form of CPA Eo S including SRK Eo S plus Wertheim association term in addition to MSA theory and Born terms so that the two last terms are responsible for the long-range interactions. A reaction-containing bubble pressure computation technique comprising two nested loops was utilized to model the systems. The internal loop, calculates the liquid phase concentrations via reaction, mass and charge balance equation solving, whereas, the vapor phase concentrations will be obtained in the external one. 470 experimental data were used to correlate binary subsystems and the H_2O + MDEA + CO_2 ternary system. Since, there not exist any binary VLE data for MDEA + CO_2 subsystem, two fitting scenarios were applied. At the first scenario, the binary interaction parameter was assumed equal to zero, while, in second approach the parameter was obtained through ternary system correlation. Both scenarios show very good accuracy in that the Absolute Average Deviation percentages(AAD) obtained were 19.12% and 18.85%, respectively. Also, to show the efficiency of the used model, a comparison between our results and those of the best-known models was made.Finally, having model parameters for H_2S solubility from our previous work [A. Afsharpour, Petroleum Science and Technology 35(3)(2017) 292-298], simultaneous solubility of CO_2+ H_2S mixtures in MDEA solutions was predicted using the e SRK-CPA Eo S with no new optimizable parameters. As the results show,the applied model has a good performance for correlation and prediction of acid gas solubility in a wide range of pressures, temperatures, acid gas loadings, and MDEA concentrations.     

旋转填充床中伴有可逆反应的气液传质

应用CO2-MDEA气液吸收体系,对旋转填充床中伴有可逆反应的气液传质过程进行了定量的模型研究。在所有反应都可逆的情况下,根据Higbie渗透理论建立了旋转床中CO2-MDEA体系的扩散-反应传质模型。通过模型对传质过程的定量描述以及实验结果对模型的验证,超重力旋转床的强化作用可进一步被揭示为:由于不断更新的液膜使得可溶性气体在液膜内形成较大的浓度梯度,从而极大地增大了传质系数,强化了传质;旋转床的强化作用是在动态的传质过程中完成的,液膜的寿命越短则传质系数越大。在不同转速、温度、MDEA浓度和气液流量条件下进行了实验,本文模型的模拟值和实验结果吻合较好。     

Removal of carbon dioxide by absorption in mixed amines: modelling of absorption in aqueous MDEA/MEA and AMP/MEA solutions

This work presents an investigation of CO₂ absorption into aqueous blends of methyldiethanolamine (MDEA) and monoethanolamine (MEA), as well as 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine (MEA). The combined mass transfer–reaction kinetics–equilibrium model to describe CO₂ absorption into the amine blends has been developed according to Higbie's penetration theory following the work of Hagewiesche et al. (Chem. Eng. Sci. 50 (1995) 1071). The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (MDEA+MEA+H₂O) of this work and into (AMP+MEA+H₂O) reported by Xiao et al. (Chem. Eng. Sci. 55 (2000) 161), measured at higher contact times using wetted wall contactor. The good agreement between the model predicted rates and enhancement factors and the experimental results indicate that the combined mass transfer–reaction kinetics–equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer for the aqueous amine blends MDEA/MEA and AMP/MEA.     

复合溶液膜吸收CO2的性能及其对膜孔润湿的影响

利用自行搭建的CO₂膜吸收实验台，采用聚丙烯（PP）膜组件，以质量分数10%的N-甲基二乙醇胺（MDEA）作为主体胺溶液，添加不同配比的哌嗪（PZ）、乙醇胺（MEA）、甘氨酸钾（PG），考察CO₂脱除效率和传质速率的变化，比较不同复配比的复合溶液表面张力以及对PP膜的浸润性，并以10%MDEA+10%PG混合溶液作为吸收液进行长时间实验。结果表明：添加少量的添加剂对MDEA溶液膜吸收CO₂均有显著的促进作用，当配比小于0.2时，促进作用大小为PZ>MEA>PG；当配比大于0.2时，促进作用大小为PZ>PG>MEA；PZ和MEA均随着添加配比的增加，溶液表面张力减小，而PG相反；表面张力小的溶液对膜浸润性较强，容易造成膜润湿；添加剂质量分数均为10%时，对膜溶胀性和疏水性以及膜孔结构影响大小为PZ>MEA>PG；在20天内，PG/MDEA混合溶液作用下的CO₂脱除效率从89.56%下降为83.09%，对PP的疏水性影响较小，膜组件可以稳定运行。吸收液表面张力对膜吸收法脱除CO₂性能的影响显著。所得结果可为膜吸收CO₂吸收剂复配提供依据，并可为揭示膜吸收CO₂过程中膜润湿导致膜失效的机理以及抑制膜润湿提供实验数据。     

Theoretical and Experimental Studies on Acetylene Absorption in a Polytetrafluoroethylene Hollow‐Fiber Membrane Contactor

The separation of acetylene from a gas mixture was investigated using a polytetrafluoroethylene hollow‐fiber membrane contactor and 1‐methyl‐2‐pyrrolidinone as absorbent. The effects of the gas velocity, the liquid velocity, the feed gas concentration, and the module length on the acetylene mass transfer were investigated. The results showed that the acetylene mass transfer flux increased with increasing liquid velocity, gas velocity, and feed gas concentration, but decreased with increasing membrane module length. A mathematical model was used to predict the wetting extent of the membrane and the mass transfer resistance in the acetylene mass transfer process. The wetting extent of the membrane was found to increase with increasing liquid velocity and to be effectively restrained with increasing gas velocity. The liquid phase resistance and the wetted‐membrane phase resistance controlled the acetylene mass transfer in the acetylene absorption process. The acetylene absorption efficiency was maintained at 90 % for 114 h of the C₂H₂ membrane absorption–thermal desorption cycle process.     

Experimental investigation of the effects of different chemical absorbents on wetting and morphology of poly(vinylidene fluoride) membrane

Membrane wetting is of one the most important factor that affects the CO₂ absorption efficiency in membrane contactors due to the increase of mass transfer resistance. In this study, the effects of different absorbents on the wettability of poly(vinylidene fluoride) membranes were investigated. Four absorbents including monoethanolamine, potassium carbonate–piperazine (PZ), potassium carbonate–monoethanolamine, and methyldiethanolamine–PZ were applied to investigate the effects of different absorbents on membrane wetting. Membrane properties before and after contact with absorbents were investigated using methods of thermogravimetric analysis, Fourier transform infrared spectroscopy, electron scanning microscope, and contact angle measurements. The results revealed that methyldiethanolamine and mixed absorbents containing methyldiethanolamine caused the most morphological changes in membrane. The results showed that reduction percentages of contact angle for water, K2CO3/PZ, K2CO3/MEA, MEA, and MDEA/PZ solutions were 14.52, 16.9, 21.19, 23.7, and 28.33, respectively, after 30 days immersion. The results also showed that potassium carbonate–PZ solution caused the least change in membrane wettability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45543.     

DEGRADATION OF AQUEOUS SOLUTIONS OF ALKANOLAMINE BLENDS AT HIGH TEMPERATURE, UNDER THE PRESENCE OF CO2 AND H2S

An experimental study on the degradation of aqueous solutions of alkanolamine blends, under the presence of carbon dioxide and hydrogen sulfide, was carried out. The studied alkanolamines were: diethanolamine (DEA), methyldiethanolamine (MDEA), and 2-amino-2-methyl-1-propanol (AMP). Degradation experiments were carried out at a temperature of 200°C. The mass fraction of DEA and MDEA in the studied aqueous solutions was 10% and 35%, respectively. AMP was incorporated into the MDEA-DEA aqueous solutions, with concentrations of (0-8) mass fraction. Partially degraded alkanolamine aqueous solutions were analyzed, after about 90 hours, by gas chromatography.

It was found that in all the studied alkanolamine aqueous solutions the MDEA degrades more slowly than DEA under the same experimental conditions. Degradation of both alkanolamines was found to be almost independent of the AMP concentration. AMP exhibits an intermediate stability; it is more resistant to degradation than DEA but less than MDEA. In addition, thermal degradation of DEA and MDEA is minimal up to 200°C.     

氨基酸离子液体-MDEA混合水溶液的CO_2吸收性能

为改善N-甲基二乙醇胺(MDEA)水溶液对CO2气体的吸收性能,选择了四甲基铵甘氨酸([N1111][Gly])、四乙基铵甘氨酸([N2222][Gly])、四甲基铵赖氨酸([N1111][Lys])、四乙基铵赖氨酸([N2222][Lys])4种功能性离子液体作为活化剂与其复配组成新型CO2吸收剂。用恒定容积法考察了总质量分数为30%的混合溶液吸收CO2的性能,分析了离子液体在水溶液中与MDEA通过质子传递相互促进吸收CO2的机理。实验结果显示离子液体能够显著提高MDEA水溶液吸收CO2的速率,且吸收速率随着添加量的增加而提高。在本文所用的几种混合吸收剂中,阴离子为赖氨酸的离子液体混合吸收剂具有较高的吸收负荷;而[N1111][Gly]-MDEA混合溶液对CO2的初期吸收速率最快,同时[N1111][Gly]-MDEA混合吸收剂的再生效率高于其他离子液体混合吸收剂,达到98%。     

膜蒸馏脱盐中膜污染与膜润湿的研究进展

膜蒸馏作为一种脱盐的新兴技术受到广泛关注。然而,因为实际水质组分复杂,可能含有如表面活性剂、油类物质、易结垢盐和有机溶剂等污染物,导致一般疏水膜在长时间运行情况下极易发生膜污染或者膜润湿,最终造成膜通量或截留性能降低。本文首先简述了不同种类的膜污染和膜润湿的特点及形成原因,并分析了膜污染和膜润湿之间的区别和联系。对膜蒸馏过程中膜污染和膜润湿的监测和预测手段进行了简要介绍,最后针对膜蒸馏脱盐过程,重点介绍了近几年国内外预防膜污染和膜润湿的研究进展。研究者一般从污染物与疏水膜的相互作用力着手对疏水膜进行表面改性制备全疏膜和Janus复合膜,避免污染物在膜面的吸附以及抑制表面或孔道润湿。越来越多的研究人员采用致密亲水膜的渗透汽化脱盐来从根本上避免疏水膜带来的润湿。除此之外,对进料液进行预处理也能显著延迟膜的污染和润湿,如混凝/沉淀、膜过滤、煮沸、pH调控等,还可通过改变进料方式、辅助外加磁场等措施控制膜表面局部区域的流体力学状态,减少污染物的附着。适当的膜后处理措施也能恢复膜性能。最后,文章指出了解决膜蒸馏中膜污染和膜润湿的研究方向。