Selective Removal of H2S from Gas Streams with High CO2 Concentration Using Hollow‐Fiber Membrane Contractors

Selective and simultaneous separation of H₂S and CO₂ from CH₄ was accomplished in a hollow‐fiber membrane contactor (HFMC). The absorption of both H₂S and CO₂ using an aqueous solution of methyldiethanolamine (MDEA) was almost complete and acid gases were totally removed. Despite the large difference between H₂S and CO₂ concentrations, the rate of H₂S absorption was not significantly influenced by CO₂ absorption. The independent effect and interactions of several process variables on the separation performance of H₂S and CO₂ were investigated. The results indicated that the membrane contactor could be a highly efficient choice for removal of almost all H₂S in the presence of a large CO₂ content even at high gas/liquid flow ratio. The selectivity of H₂S was about three times higher compared to the conventional absorption packed towers.     

CO2 removal by single and mixed amines in a hollow‐fiber membrane module—investigation of contactor performance

This work investigates CO₂ removal by single and blended amines in a hollow‐fiber membrane contactor (HFMC) under gas‐filled and partially liquid‐filled membrane pores conditions via a two‐scale, nonisothermal, steady‐state model accounting for CO₂ diffusion in gas‐filled pores, CO₂ and amines diffusion/reaction within liquid‐filled pores and CO₂ and amines diffusion/reaction in liquid boundary layer. Model predictions were compared with CO₂ absorption data under various experimental conditions. The model was used to analyze the effects of liquid and gas velocity, CO₂ partial pressure, single (primary, secondary, tertiary, and sterically hindered alkanolamines) and mixed amines solution type, membrane wetting, and cocurrent/countercurrent flow orientation on the HFMC performance. An insignificant difference between the absorption in cocurrent and countercurrent flow was observed in this study. The membrane wetting decreases significantly the performance of hollow‐fiber membrane module. The nonisothermal simulations reveal that the hollow‐fiber membrane module operation can be considered as nearly isothermal. © 2014 American Institute of Chemical Engineers AIChE J, 61: 955–971, 2015     

Al2O3/Yttria‐Stabilized Zirconia Hollow‐Fiber Membrane Incorporated with Iron Oxide for Pb(II) Removal

Removal by absorptive ceramic membranes can simultaneously absorb and separate metal ions from water. Alumina/yttria‐stabilized zirconia (Al₂O₃/YSZ) hollow‐fiber membranes, fabricated using phase inversion and sintering process, were deposited with iron oxide by an in‐situ hydrothermal process. The results showed that α‐Fe₂O₃ was produced and incorporated across the membranes. A reduction in flux was recorded with the deposition of α‐Fe₂O_3. However, it improved the adsorption capacity for heavy metal adsorption. The adsorption‐separation test demonstrated that the optimized membrane is able to completely remove Pb(II) ions after two hours.     

Transient Simulation of Hollow‐Fiber Membrane Filtration with Nonuniform Permeability Distribution

Transient simulation of filtration in hollow‐fiber membranes with nonuniform permeability distribution was conducted. The diversity of permeability distributions caused different initial flux and transmembrane pressure distributions. Manipulating the permeability distribution enables a hollow‐fiber membrane to achieve its maximum volumetric flow rate. During solid‐liquid separation, the inter‐adjustment between flux and cake distributions improved their uniformities simultaneously. The reciprocal of the volumetric flow rate of the membranes all increased linearly with water production. Severely nonuniform permeability distribution caused low water production. The numerical results could be applicable to account for the non‐ideal performance of industrial hollow‐fiber membrane modules.     

Interaction Parameter Method for Investigating BTEX Extraction Using the Hollow‐Fiber Microporous Membrane Liquid/Liquid Extraction Technique

This work focused on the extraction of BTEX from aqueous solution by a hollow‐fiber microporous membrane liquid/liquid extraction (HF‐MMLLE) technique. A simple and rapid method based on the Hansen solubility parameters (HSP) theory was adopted to theoretically determine the interaction parameter (χ₁₂) between the extractants and BTEX. Experiments were carried out to establish the relationship between the interaction parameter and the extraction performance. Furthermore, the distribution coefficient and permeability coefficient related to the extraction performance were also discussed, which verified the relationship from a quantitative idea. It was observed that the liquid/liquid extraction was based on the strong affinities between the extractants and the target pollutants. This method should be paid more attention for its potential application in other solvent‐sensitive processes.     

Fick's First Law of Diffusion and Binary Gas Separation by Hollow‐Fiber Asymmetric Membrane

For calculating mass transfer through a hollow‐fiber asymmetric membrane, a fundamentally new theoretical method based on Fick's first law of diffusion is proposed. The main features of this method, and the ones currently used for the same purpose, have been compared. The current methods, also based on Fick's first law of diffusion, are shown to be theoretically less than adequate. Recommendations are given for the practical implementation of the new method.     

Long‐term study of CO2 absorption by PVDF/ZSM‐5 hollow fiber mixed matrix membrane in gas–liquid contacting process

In order to fabricate hollow fiber mixed matrix membrane (HFMMM) for long‐term CO₂ absorption process, ZSM‐5 (Zeolite Socony Mobil–5) zeolite was modified using hexadecyltrichlorosilane for increasing hydrophobicity and then added to the polyvinylidene fluoride (PVDF) spinning dope. The in‐house made HFMMMs were characterized in terms of gas permeance, overall porosity, average pore size, effective surface porosity, surface roughness, mechanical stability, and wetting resistance. The morphology of the HFMMMs was studied using SEM. The cross‐sectional SEM images indicated that the membrane structure has changed from sponge‐like to finger‐like by ZSM‐5 loading. The surface roughness increased by increasing ZSM‐5 concentration in the spinning dope. The HFMMM spun from the spinning dope with 0.5 wt % of ZSM‐5 zeolite showed that the CO₂ absorption flux decreased 18.9% in the initial 115 h of the operation and then the absorption flux remained constant until the end of the operation. For plain PVDF HFM the absorption flux decreased 36% from the initial value in the first 15 h of the experiment. Thus it could be concluded that the long term stability of HFM was improved by the incorporation of ZSM‐5. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44606.     

Absorption of carbon dioxide by the absorbent composed of piperazine and 2-amino-2-methyl-1-propanol in PVDF membrane contactor

This paper tests the performance of microporous polyvinylidinefluoride (PVDF) hollow fiber in a gas absorption membrane process (GAM) using the aqueous solutions of piperazine (PZ) and 2-amino-2-methyl-1-propanol (AMP). Experiments were conducted at various gas flow rates, liquid flow rates and absorbent concentrations. Experimental results showed that wetting ratio was about 0.036% when used with the aqueous alkanolamine solutions, while that was 0.39% with aqueous piperazine solutions. The CO₂ absorption rates increased with increasing both liquid and gas flow rates at N_Re < 20. The increase of the PZ concentration showed an increase of absorption rate of CO₂. The CO₂ absorption rate was much enhanced by the addition of PZ promoter. The resistance of membrane was predominated as using a low reactivity absorbent and can be neglected as using absorbent of AMP aqueous solution. The resistance of gas-film diffusion was dominated as using the mixed absorbents of AMP and PZ. An increase of PZ concentration, the resistance of liquid-film diffusion decreased but resistance of gas-film increased. Overall, GAM systems were shown to be an effective technology for absorbing CO₂ from simulated flue gas streams, but the viscosity and solvent-membrane relationship were critical factors that can significantly affect system performance.     

Experimental study on membrane wetting in gas–liquid membrane contacting process for CO2 absorption by single and mixed absorbents

The membrane wetting by the liquid absorbents is an important problem in the operation of gas–liquid membrane contacting process. In order to gain a better understanding on the role of absorbents on membrane wetting, monoethanolamine (MEA, primary amine), diethanolamine (DEA, secondary amine), and 2-amino-2-methyl-1-propanol (AMP, sterically hindred amine) were applied as absorbent solutions. The membrane used for the experiments was the hollow fiber polyvinylidenefluoride (PVDF) membrane. The performance of both single and mixed amine solutions on the CO₂ absorption capacity and membrane wetting potential were investigated. In addition, sodium chloride (NaCl, inorganic salt) and sodium glycinate (SG, organic salt) were added into the MEA aqueous solution to observe CO₂ flux and membrane wetting.The results revealed that the use of MEA solution and SG as absorbents gave highest CO₂ flux. The overall mass transfer coefficients obtained from the experiments also showed the same trend as CO₂ flux, i.e, the values were in the following order: MEA> AMP > DEA. However, the long-term flux was monitored and it was found that MEA also gave lowest flux decline due to the membrane wetting. The use of mixed amine solutions and the addition of NaCl did not help protect the membrane wetting. On the contrary, the addition of SG in to MEA solution can improve flux and resulted in stable CO₂ flux indicating that the membrane wetting was negligible.     

Sulfur dioxide non‐dispersive absorption in N,N‐dimethylaniline using a ceramic membrane contactor

BACKGROUND: Removal of sulfur dioxide from gas emissions by selective absorption is a common method to separate and concentrate sulfur dioxide and to reduce air pollution and environmental risks. N,N‐dimethylaniline is an organic solvent used in some industrial applications for its sulfur dioxide affinity, leading to a regenerative process. However, the use of scrubbers and equipment in which direct contact between gas and liquid takes place leads to solvent losses due to evaporation and drops dragging. RESULTS: In this work, an innovative procedure based on non‐dispersive absorption in a ceramic hollow fibre membrane contactor was studied in order to avoid drops dragging. The absorption efficiency ranged between 40 and 50%, showing the technical viability of the process. The sulfur dioxide flux through the membrane has a linear relationship with the concentration of SO₂ in the gas stream and an overall mass transfer coefficient K_overall = (1.10 ± 0.11) × 10^?5 m s^?1 has been obtained. CONCLUSIONS: The mass transfer behaviour of a ceramic hollow fibre membrane contactor for sulfur dioxide non‐dispersive absorption in N,N‐dimethylaniline has been studied. The main resistance is found to be the ceramic membrane and the effective diffusivity has been inferred. The mass transfer model and parameters allow the evaluation of equipment design for technical applications. Copyright © 2008 Society of Chemical Industry     

Investigation of CO2 removal by immobilized carbonic anhydrase enzyme in a hollow‐fiber membrane bioreactor

Gas–liquid membrane contactors are compelling candidate bioreactors for implementing CO₂ capture because of large mass transfer rates and liquid–solid interfaces, low pressure drop, low axial dispersion and mixing, modularity, simple scale‐up or scale‐down, and operational suppleness. Binding the carbonic anhydrase (CA) enzyme on the membrane surface adds extra advantages due to the impressive large hydration turnover number and offers an attractive way for CO₂ capture. This novel approach to CO₂ removal by immobilized CA in a hollow‐fiber membrane bioreactor (HFMB) was investigated via a multiscale steady‐state model, under gas‐filled and partially liquid‐filled membrane pores conditions. The impact of CA loading, buffer acid‐base constant and concentration, membrane wetting, uncatalyzed/catalyzed CO₂ hydration in the wetted membrane zone, operating conditions, and cocurrent/countercurrent flow orientation on the HFMB performance was analyzed. The results showed that this low‐cost, green, and environmentally friendly technology could be an appealing alternative to CO₂ capture from stationary emissions sources. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2996–3007, 2017     

Phenol recovery with tributyl phosphate in a hollow fiber membrane contactor: Experimental and model analysis

The extraction and stripping of phenol using a solution of tributyl phosphate in kerosene in a hydrophobic polypropylene hollow fiber membrane contactor has been studied. The effect of the aqueous and the organic phase flow rates on the overall mass transfer coefficient for both extraction and stripping steps was investigated. Experimental values of the overall mass transfer coefficient were determined and compared with predicted values from the resistance in series model. Results showed that the overall mass transfer coefficients for extraction were about one order of magnitude greater than those measured during the stripping process. The experimental values were in good agreement with the predicted values for the extraction module. However, the predicted values were slightly overestimated for the stripping module. The individual mass transfer resistances were analyzed and the rate-controlling steps of mass transfer were also identified in both extraction and stripping modules. The major resistance in extraction and stripping was in the aqueous phase and in the membrane phase, respectively.     

Egg‐Yolk Sphingomyelin and Phosphatidylcholine Attenuate Cholesterol Absorption in Caco‐2 Cells

Phospholipids have been shown to modulate intestinal cholesterol absorption in cells and animals, a process that is regulated by several transporter proteins. Of these proteins, Niemann–Pick C1‐Like 1 (NPC1L1) is a major contributor to this process. The mechanism by which phospholipids modulate cholesterol absorption remains unknown. Here, we evaluate the effects of egg‐yolk phospholipids on cholesterol absorption and transport in human colon carcinoma cell line (Caco‐2 cells) and on the expression of NPC1L1 and others proteins associated with cholesterol absorption (ABCG5, ABCG8, ABCA1, ACAT2, MTP, CAV‐1, ANX‐2). The roles of SREBP‐1 and SREBP‐2 in this process were also investigated. The results show that egg‐yolk sphingomyelin (CerPCho) and phosphatidylcholine (PtdCho) inhibit cholesterol transport in the Caco‐2 monolayer in a dose‐dependent manner. These might be due to the decrease of the cholesterol solubility in micelles as well as to the increases in the micellar sizes and the bile acid‐binding capacity. Furthermore, the treatments with egg‐yolk CerPCho or PtdCho at 1.2 mmol/L reduced the expression levels of NPC1L1 protein to 21 or 22%, respectively, and its mRNA to 9 or 31% of that in the control group (p < 0.05). Moreover, there was a general inhibitory effect of egg‐yolk PtdCho and CerPCho on the mRNA levels of SREBP‐1, and SREBP‐2. These results suggest that the inhibitory effect of egg‐yolk CerPCho and PtdCho on cholesterol transport might be due to their interference with the physicochemical properties of micelles and their regulations on the expression of the NPC1L1 gene.     

Pd‐Ag/α‐Al2O3 Catalyst Deactivation in Acetylene Selective Hydrogenation Process

The selective hydrogenation of acetylene to ethylene over Pd‐Ag/α‐Al₂O₃ catalysts prepared by different impregnation/reduction methods was studied. The best catalytic performance was achieved with the sample prepared by sequential impregnation. A kinetic model based on first order in acetylene and 0.5th order in hydrogen for the main reaction and second‐order independent decay law for catalyst deactivation was used to fit the conversion time data and to obtain quantitative assessment of catalyst performances. Fair fits were observed from which the reaction and deactivation rate constants were evaluated. Coke deposition amounts showed a good correlation with catalyst deactivation rate constants, indicating that coke formation should be the main cause of catalyst deactivation.     

Hollow‐fiber dispersion‐free extraction and stripping of Pb(II) in the presence of Cd(II) using D2EHPA under recirculating operation mode

Lead(II) and cadmium(II) solvent extraction (SX) with D2EHPA dissolved in heptane and kerosene from aqueous chloride media was studied. Extraction reaction stoichiometries and extraction equilibrium constants were evaluated. Application of a dispersion‐free membrane‐based extraction and stripping technique with two hollow‐fiber contactors under recirculating operation mode allowed a quantitative (>97%) removal of lead from the aqueous solution in the extraction module with a separation factor of 19 and a 62% recovery in the back‐extraction module with a separation factor of 6.3 after 7 h under optimum conditions. Mass‐transfer coefficients for the system were evaluated. Optimal conditions for transport and separation are reported and compared using SX and the membrane‐based technique. Copyright © 2004 Society of Chemical Industry     

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.     

Polyvinylidene fluoride and polyetherimide hollow fiber membranes for CO2 stripping in membrane contactor

Porous polyvinylidene fluoride (PVDF) and polyetherimide (PEI) hollow fiber membranes incorporating polyethylene glycol (PEG) were prepared via spinning process for CO₂ membrane stripping. CO₂ loaded diethanolamine solution was used as liquid absorbent while N₂ was used as a strip gas. The characterization study of the fibers was carried out in terms of permeation test, contact angle measurement and liquid entry pressure (wetting pressure). Performance study via membrane contactor stripping was carried out at specific operating condition. The experimental results showed that PVDF membrane have high gas permeation, effective surface porosity and contact angle despite having lower liquid entry pressure in comparison with PEI membrane. PVDF-PEG membrane showed the highest stripping flux of 4.0 × 10⁻² mol m⁻² s⁻¹ at 0.7 ms⁻¹ compared to that of PEI membrane. Although the stripping flux for PEI-PEG membranes was slightly lower than PVDF membrane (e.g. 3.5 × 10⁻² mol m⁻² s⁻¹ at liquid velocity of 0.85 ms⁻¹), the membrane wetting pressure of PEI membrane is higher than hydrophobic PVDF membrane. Long term performance of both membranes showed severe flux reduction but started to level-off after 30 h of operation.