Chemical kinetic modeling of i‐butane and n‐butane catalytic cracking reactions over HZSM‐5 zeolite

A chemical kinetic model for i‐butane and n‐butane catalytic cracking over synthesized HZSM‐5 zeolite, with SiO₂/Al₂O₃ = 484, and in a plug flow reactor under various operating conditions, has been developed. To estimate the kinetic parameters of catalytic cracking reactions of i‐butane and n‐butane, a lump kinetic model consisting of six reaction steps and five lumped components is proposed. This kinetic model is based on mechanistic aspects of catalytic cracking of paraffins into olefins. Furthermore, our model takes into account the effects of both protolytic and bimolecular mechanisms. The Levenberg–Marquardt algorithm was used to estimate kinetic parameters. Results from statistical F‐tests indicate that the kinetic models and the proposed model predictions are in satisfactory agreement with the experimental data obtained for both paraffin reactants. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2456–2465, 2012     

Extraction of tocopherols from the deodorized distillate of soybean oil with liquefied petroleum gas

Deodorizer distillate, produced during the last processing step of edible oil refinement, is a mixture of tocopherols, sterols, fatty acids, glycerides, hydrocarbons, water and other materials. The amount of tocopherols in deodorizer distillate is large enough to be considered as raw material for vitamin E preparation. In this work, separation of tocopherols from sterols has been achieved using liquefied petroleum gas (LPG) extraction. LPG was chosen as extraction solvent in order to improve extract recovery and prevent tocopherol degradation.     

Olefin production by cofeeding methanol and n‐butane: Kinetic modeling considering the deactivation of HZSM‐5 zeolite

The joint transformation of methanol and n‐butane fed into a fixed‐bed reactor on a HZSM‐5 zeolite catalyst has been studied under energy neutral conditions (methanol/n‐butane molar ratio of 3/1). The kinetic scheme of lumps proposed integrates the reaction steps corresponding to the individual reactions (cracking of n‐butane and MTO process at high‐temperature) and takes into account the synergies between the steps of both reactions. The deactivation by coke deposition has been quantified by an expression dependent on the concentration of the components in the reaction medium, which is evidence that oxygenates are the main coke precursors. The concentration of the components in the reaction medium (methanol, dimethyl ether, n‐butane, C₂? C₄ paraffins, C₂? C₄ olefins, C₅? C₁₀ lump, and methane) is satisfactorily calculated in a wide range of conditions (between 400 and 550°C, up to 9.5 (g of catalyst) h (mol CH₂)^?1 and with a time on stream of 5 h) by combining the equation of deactivation with the kinetic model of the main integrated process. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Transient kinetics of n‐butane partial oxidation at elevated pressure

A transient Mars‐van Krevelen type kinetic model was developed for n‐butane partial oxidation over vanadyl pyrophosphate (VPP) catalyst. The model validity was verified over a relatively wide range of redox feed compositions as well as higher reactor pressure (410 kPa). Oxygen and n‐butane conversion increased with higher pressure while maleic anhydride (MA) selectivity decreased by as much as 20%. However, the overall MA yield was enhanced by up to 30%. High pressure maintains the catalyst in a higher oxidation state (as long as there is sufficient oxygen in the gas phase) and as a consequence, the catalytic activity is improved together with MA yield. High pressure also affects the redox reaction rates and activation energies. © 2012 Canadian Society for Chemical Engineering     

Formation of microporous membrane of isotactic polypropylene in dibutyl phthalate‐soybean oil via thermally induced phase separation

Isotactic polypropylene (iPP) microporous membranes were prepared via the thermally induced phase separation (TIPS) process with the diluents being dibutyl phthalate (DBP) and soybean oil mixture. By changing the weight ratio of DBP to soybean oil systematically, it was determined experimentally that the cloud‐point curves were influenced to a great extent, while the crystallization curves showed much less dependence on the diluents composition. Scanning electron microscopy (SEM) showed that the resulting membrane morphologies changed significantly by varying the composition of the diluents, i.e., by changing the interaction parameter and other characteristics of diluents, the interwoven or celluar structure can be fabricated successfully at a fixed polymer concentration under the same cooling conditions. Different growth rates of iPP spherulite were obtained in the diluents with different composition. It is shown that the spherulites growth rates may be also attributed to the great variations of the final microporous morphology to a certain extent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Reactive extraction of propionic acid using tri‐n‐octylamine,tri‐n‐butyl phosphate and aliquat 336 in sunflower oil as diluent

BACKGROUND : Propionic acid is widely used in chemical and allied industries and can be produced by biocultivation in a clean and environmentally friendly route. Recovery of the acid from the dilute stream from the bioreactor is an economic problem. Reactive extraction is a promising method of recovering the acid but suffers from toxicity problems of the solvent employed. There is thus a need for a non‐toxic solvent or a combination of less toxic extractants in a non‐toxic diluent that can recover acid efficiently. RESULTS: The effect of different extractants (tri‐n‐butylphosphate (TBP), tri‐n‐octylamine (TOA) and Aliquat 336) and their mixed binary solutions in sunflower oil diluent was studied to find the best extractant‐sunflower oil combination. Equilibrium complexation constant, K_E, values of 4.02, 3.13 and 1.87 m³ kmol^?1 were obtained for propionic acid extraction using Aliquat 336, TOA and TBP, respectively, in sunflower oil. The effect of different modifiers (1‐decanol, methylisobutyl ketone, butyl acetate and dodecanol) on the extraction was also studied and it was found that modifiers enhance extraction, with 1‐decanol found to be the best. CONCLUSION: The problem of toxicity in reactive extraction can be reduced by using a non‐toxic diluent (sunflower oil) or a modifier in a non‐toxic solvent, with the extractant. The addition of modifiers was found to improve the extraction. Copyright © 2008 Society of Chemical Industry     

Synthesis and properties of multihydroxy soybean oil from soybean oil and polymeric methylene‐diphenyl‐ 4,4′‐diisocyanate/multihydroxy soybean oil polyurethane adhesive to wood

The reactive multihydroxy soybean oil (MHSBO) was synthesized from epoxidized soybean oil (ESBO). The ESBO was reacted with ethylene glycol to obtain MHSBO having high functionality. This study investigated a feasibility to prepare wood adhesive through the reaction of polymeric methylene‐diphenyl‐4,4′‐diisocyanate (pMDI) with MHSBO. Different polyurethane adhesives were prepared with a variety of equivalent mole ratios (eq. mole ratios) of MHSBO to pMDI. The chemical reactions of adhesives were analyzed using ¹H NMR and Fourier transform infrared (FTIR), and their thermal studies were investigated by DSC and TGA. The MHSBO/pMDI resins (3 : 1 and 2 : 1 eq. mole ratios) showed endothermic peaks, whereas the MHSBO/pMDI resins (1 : 2 and 1 : 3 eq. mole ratios) showed exothermic peaks. The best adhesion strength was found when plywood was bonded with the adhesive of a eq. mole ratio of 2 : 1 (MHSBO : pMDI). These results indicated that the bond strength was not related to the reactivity obtained from the FTIR spectra. But it was explained that the adhesion strength increased as the residual  NCO groups in the adhesive reacted with the hydroxy groups of wood during the manufacturing of plywood. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electro‐membrane process for the separation of amino acids by iso‐electric focusing

BACKGROUND: Amino acids (AAs) are usually produced commercially using chemical, biochemical and microbiological fermentation methods. The product obtained from these methods undergoes various treatments involving extraction and electrodialysis (ED) for salt removal and AA recovery. This paper describes an electro‐membrane process (EMP) for the charge based separation of amino acids. RESULTS: Iso‐electric separation of AAs (GLU–LYS) from their mixture, using ion‐ exchange membranes (IEMs) has been achieved by an efficient and indigenous EMP. It was observed that electro‐transport rate (flux) of glutamic acid (GLU) at pH 8.0 (above its pI) was extremely high, while that for lysine (LYS) (pH 9.6) across the anion‐exchange membrane (AEM) was very low, under similar experimental conditions. Under optimum experimental conditions, separation of GLU from GLU–LYS mixture was achieved with moderate energy consumption (12.9 kWh kg^?1), high current efficiency (CE) (65%) and 85% recovery of GLU. CONCLUSIONS: On the basis of the electro‐transport rate of AA and membrane selectivity, it was concluded that the separation of GLU–LYS mixture was possible at pH 8.0, because of the oppositely charged nature of the two amino acids due to their different pI values. Moreover, any type of membrane fouling and deterioration in membrane conductivity was ruled out under experimental conditions. This work clearly demonstrates the great potential of EMP for industrial applications. Copyright © 2010 Society of Chemical Industry     

超滤和纳滤膜分离提取纳他霉素

为提高纳他霉素(natamycin)生产提取得率,减少溶剂使用,本文采用超滤、纳滤操作对工业生产的纳他霉索发酵液进行处理。实验结果表明:操作压力、操作时间及料液流速对超滤过程有很大影响。通过超滤可将蛋白质等大分子杂质去除,然后再用纳滤膜对超滤渗透液进行浓缩纯化,对纳滤工艺的操作条件如进料压力、料液pH、浓缩倍数等进行了研究。采用超滤、纳滤技术提取纳他霉素,其收率可达62.74%。     

Catalytic Oxidative Dehydrogenation of n‐Butane on Gallium Nitride‐Containing Titanosilicate Catalyst

GaN‐containing titanosilicate catalysts were used for the first time for the oxidative dehydrogenation (ODH) of n‐butane at a relatively low reaction temperature (460 °C). Commercially available GaN powder with a wurtzite crystal structure showed superior reactivity and stability for the ODH of n‐butane. The catalytic property of GaN catalyst for ODH strongly depends on the GaN particle size. The effects of the GaN weight percentage and GaN particle size on the catalytic performance are investigated in a fixed bed reactor. Based on the physicochemical properties of the catalyst characterized via TEM, DLS, N₂ adsorption‐desorption, XRF, O₂‐TPD, XRD, XPS, and in‐situ FTIR, the textural and structural properties of catalyst were obtained. The catalytic results reveal that the presence of GaN increases the activity of the catalysts, indicating that GaN can be used as a new active phase for the ODH of n‐butane. XRD, XPS, O₂‐TPD, DLS, TEM, and in‐situ FTIR results show that activated O species exist on the surface of the GaN catalyst and enhance the catalytic performance with a decreasing GaN particle size, suggesting that smaller GaN particles possess a remarkable capability to activate O species in O₂ and C‐H bonds in light alkanes.     

聚酰亚胺膜的制备及对有机物系的纳滤分离

针对以均苯四甲酸二酐(PMDA)和4,4′-二氨基二苯醚(ODA)为原料合成聚酰亚胺的过程,研究了亚胺化方法、凝胶浴组成与温度等条件对膜的结构和分离性能的影响。实验结果表明,当聚酰胺酸铸膜液质量分数为15%、凝胶浴为30%乙醇(质量)的醇水溶液时,所制得的聚酰亚胺纳滤膜具有最佳的分离性能。操作压力为2MPa下稳态操作时,该膜对酮苯脱蜡工艺后的溶剂与润滑油基础油混合物的截留率达66%,通量为4.26L/(m2.h),为有机溶剂体系的纳滤膜分离技术的工业应用提供了基础。     

Synthesis of bio‐based polyurethanes from epoxidized soybean oil and isopropanolamine

Epoxidized soybean oil (ESO) and isopropanolamine were used to synthesize a new polyol mixture for preparation of bio‐based polyurethanes. The chemical synthetic route for reaction of ESO with isopropanolamine was analyzed by ¹H‐NMR. The results suggested that both ester groups and epoxy groups in ESO had reacted with amino group of isopropanolamine through simultaneous ring‐opening and amidation reactions. Epoxy groups in various situations exhibited different reactivity, and the unreacted epoxy groups were further opened by hydrochloric acid. The synthesized polyol mixture had high hydroxyl number of 317.0 mg KOH/g. A series of polyurethanes were prepared by curing the synthesized polyol mixture with 1,6‐diisocyanatohexance along with different amount of 1,3‐propanediol (PDO) as chain extender. Tensile tests showed that yield strengths of the polyurethanes ranged from 2.74 to 27.76 MPa depending on the content of PDO. Differential scanning calorimetry analysis displayed one glass transition temperature in the range of 24.4–28.7°C for all of the polyurethane samples, and one melt peak at high content of PDO. Thermogravimetric analysis showed that thermal degradations of the polyurethanes started at 240–255°C. In consideration of simple preparation process and renewable property of ESO, the bio‐based polyurethane would have wide range of applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Selective separation of n‐butanol from aqueous solutions by pervaporation using silicone rubber‐coated silicalite membranes

BACKGROUND: To use butanol as a liquid fuel and feedstock, it is necessary to establish processes for refining low‐concentration butanol solutions. Pervaporation (PV) employing hydrophobic silicalite membranes for selective recovery of butanol is a promising approach. In this study, the adsorption behavior of components present in clostridia fermentation broths on membrane material (silicalite powder) was investigated. The potential of PV using silicone rubber‐coated silicalite membranes for the selective separation of butanol from model acetone–butanol–ethanol (ABE) solutions was investigated. RESULTS: The equilibrium adsorbed amounts of ABE per gram of silicalite from aqueous solutions of binary mixtures at 30 °C increased as follows: ethanol (95 mg) < acetone (100 mg) < n‐butanol (120 mg). The amount of butanol adsorbed is decreased by the adsorption of acetone and butyric acid. In the separation of ternary butanol/water/acetone mixtures, the enrichment factor for acetone decreased, compared with that in binary acetone/water mixtures. In the separation of a model acetone–butanol–ethanol (ABE) fermentation broth containing butyric acid by PV using a silicone rubber‐coated silicalite membrane, the permeate butanol concentration was comparable with that obtained in the separation of a model ABE broth without butyric acid. The total flux decreased with decreasing feed solution pH. CONCLUSION: A silicone rubber‐coated silicalite membrane exhibited highly selective PV performance in the separation of a model ABE solution. It is very important to demonstrate the effectiveness of PV in the separation of actual clostridia fermentation broths, and to identify the factors affecting PV performance. Copyright © 2011 Society of Chemical Industry     

膜分离技术分离纯化泰乐菌素的研究

简要介绍膜分离技术,采用超滤膜、纳滤膜对泰乐菌素发酵液进行脱色除蛋白试验。通过考查该体系膜通量、发酵液浓缩情况及滤液质量等,发现采用膜系统处理泰乐菌素发酵液在工艺、技术上是可行的,比传统过滤方式具备很多优越性。     

引入更多的膜分离装置推动氯碱工业技术进步

介绍了采用纳滤膜去除盐水中SO42-,采用超滤和反渗透相结合处理废水并回用,采用在活性污泥处理中引入超滤提高处理后废水的质量等。建议引入更多的膜分离装置以推动氯碱工业的发展。