Membrane distillation for dilute ethanol: Separation from aqueous streams

Air-gap membrane distillation was examined as a possible technique for ethanol–water separation using PVDF membranes. The composition and flux of the permeate were monitored as feed concentration, feed temperature, feed flow rate, cooling temperature and cooling flow rate were varied. The effect of salt addition to the feed mixture was also examined. The upper feed concentration tested was 10 wt.% ethanol. Within the feed temperature range of 40–70°C, ethanol selectivity of 2–3.5 was achieved. Two versions of a general mathematical model were solved numerically for the ethanol–water system; one did not include temperature and concentration polarization effects while the other did. Good agreement between experimental and predicted values was obtained with the latter version of the model.     

Comparison of membrane processes with distillation for alcohol/water separation

The overall objectives of this study were to summarize and evaluate the performance of currently available membranes for purification of fermentation alcohol and to compare the economics of membrane processes with a modern-day energy-efficient distillation scheme.Literature survey showed that very little work had been done on the development of membrane processes for alcohol concentration.Based on laboratory work, it was found that the present-day thin-film composite desalination membranes can be used for partial concentration of beer solution to about 20 to 30% alcohol concentration. The water permeation coefficient for these membranes in reverse osmosis with 7.6% alcohol feed at 60 atm was about 10 kg/m²-day-atm (2 lb/ft²-day-atm).Due to the high osmotic pressures of ethanol/water mixtures, reverse osmosis can be used only for the initial concentration of beer solution and for the final dehydration of 95% alcohol to produce 199 proof alcohol. Thus, a distillation unit would have to be used for the intermediate concentration of alcohol solution. Membrane concentration schemes using distillation for intermediate concentration were prepared for comparison with a conventional distillation process. Based on preliminary analysis it was concluded that while the capital cost of the membrane-augmented distillation schemes can be significantly than that of the conventional system, the annualized cost of these schemes will be approximately equal to that for distillation. The capital and the annualized costs of the membrane process for the final dehydration of alcohol can be significantly lower than those for the conventional dehydration still.     

内部热耦合精馏系统节能研究

针对传统精馏塔系统和内部热耦合精馏塔系统两种不同的精馏系统,以苯―甲苯物系和丙烯―丙烷物系两种理想的二组分物系分别作为研究对象,以系统的热力学效率、公用工程费用和节能百分率作为研究评价基准,模拟并研究分析压缩比、进料热状态等参数对传统精馏塔和内部热耦合精馏塔节能效果的影响,两种不同的理想物系下内部热耦合精馏系统之间的差异,并分析内部热耦合精馏节能的影响因素,为内部热耦合精馏塔内部节能研究提供参考。     

Dehydration of Ethanol by Facile Synthesized Glucose-Based Silica

Bioethanol is considered a potential liquid fuel that can be produced from biomass by fermentation and distillation. Although most of the water is removed by distillation, the purity of ethanol is limited to 95–96 % due to the formation of a low-boiling point, water–ethanol azeotrope. To improve the use of ethanol as a fuel, many methods, such as dehydration, have been proposed to avoid distillation and improve the energy efficiency of extraction. Glucose-based silica, as an adsorbent, was prepared using a simple method, and was proposed for the adsorption of water from water–ethanol mixtures. After adsorption using 0.4 g of adsorbent for 3 h, the initial water concentration of 20 % (water, v/v) was decreased to 10 % (water, v/v). For water concentrations less than 5 % (water, v/v), the adsorbent could concentrate ethanol to 99 % (ethanol, v/v). The Langmuir isotherms used to describe the adsorption of water on an adsorbent showed a correlation coefficient of 0.94. The separation factor of the adsorbent also decreased with decreasing concentration of water in solution.     

Optimization of the reflux ratio for methanol–water stage distillation column

In this paper, the enthalpy-concentration method was applied in order to model a steady-state continuous methanol–water mixture distillation column. This work includes three steps; first, to develop a code in MATLAB v.7.6 to apply to the mathematical model of the column. The second step is to simulate the column using HYSIS v.3.2. While the third is the calculation of the optimized reflux ratio to minimize the operating cost. For a distillation tower such as the methanol–water splitter in this study, there are relatively few degrees of freedom that can be manipulated in order to minimize operating costs; the reflux ratio can influence the steady-state operating point and therefore the daily costs. In this paper, we have discussed the trade-offs between reflux ratios and operating costs. A correlation is derived to define the optimum value of the reflux ratio as an exponential function of a certain economic parameter of energy prices and depreciation costs. We demonstrate that, at low energy prices or high equipment depreciation costs, the optimum reflux factor is high.     

Experimental techniques,data treatment for studying the dynamics of ethanol production/consumption in baker's yeast

The dynamics of ethanol production/consumption in baker's yeast were studied under feed- rate controlled conditions. The yeast was grown on molasses in an 8-l fed-batch reactor and experiments were done at cell concentrations between 5 and 65 g l^?1. Small changes in the feed rate were made around a feed rate corresponding to the critical growth rate, at which the yeast cell metabolism switches between ethanol consumption and production. A membrane gas sensor was used for on-line measurement of the ethanol concentration in the broth. The measured ethanol signal was used for control and the system was excited through changes in the regulator set-point. The closed-loop experiments ensured that feed variations were within the critical range, and thus facilitated reproducible experiments. Data were fitted to a second-order difference equation by statistical methods. Results were compared with a theoretically derived model. The process gain could be understood in terms of the underlying stoichiometry by using the “bottleneck” view of yeast glucose metabolism. The process time constant was found to be longer than is implied by a simple Monod relation between glucose uptake rate and concentration.     

Elevated viscosities in a simulated moving bed for γ‐aminobutyric acid recovery

Process streams of agro‐food industries are often large and viscous. In order to fractionate such a stream the viscosity can be reduced by either a high temperature or dilution, the former is not an option in case of temperature sensitive components. Such streams are diluted prior to chromatographic fractionation, resulting in even larger volumes and high energy costs for sub‐sequential water removal. The influence of feed viscosity on the performance of simulated moving bed chromatography has been investigated in a case study of the recovery of a γ‐aminobutyric acid rich fraction from tomato serum. This work addresses the chromatographic system design, evaluates results from a pilot scale operation, and uses these to calculate the productivity and water use at elevated feed concentration. At the two higher feed viscosities (2.5 and 4 mPa·s) water use is lower and productivity higher, compared to the lowest feed viscosity (1 mPa·s). The behavior of the sugars for different feed viscosities can be described well by the model using the ratio of feed to eluent as dilution factor. The behavior of γ‐aminobutyric acid is highly concentration dependent and the recovery could not be accurately predicted.     

Phase behaviour of ethanol + water + ethyl acetate at 101.3 kPa

Must distillation processes simulation is a challenging task, due to the lack of thermodynamic interaction parameters and accurate studies of phase equilibria. The presence of polar substances, those different from ethanol and water, and their low concentrations make it very difficult to model industrial distillation. Several of the congeners are essential enological components of the organoleptic matrix. In this work, we are concerned with the study of phase behaviour of ethanol + water + ethyl acetate at 101.3 kPa, this being the third compound, the legal congener of the highest composition in common alcoholic distillation. The experimental results showed partial miscibility and four azeotropes into a complex medium. Group contribution models yield poor results. Disposable literature was compared and commented upon. The lack of experimental data in multicomponent alcoholic distillation mixtures and the low reliability of the group contribution methods suggest a prudent application to process simulation.     

Transport of binary water–ethanol mixtures through a multilayer hydrophobic zeolite membrane

Transport of water–ethanol mixtures through a hydrophobic tubular ZSM-5 (Si/Al = 300) zeolite membrane during pervaporation was studied experimentally and theoretically. The zeolite membrane was deposited on a support made of pure titania coated with three intermediate ceramic titania layers. The influence of feed concentration, feed temperature and permeate pressure on permeate fluxes and permeate concentrations was investigated in a wide range. Dusty gas model parameters of the support and all ceramic intermediate layers were calculated on the basis of gas permeation data. Mass transfer resistances and pressure drops in the different membrane layers during pervaporation were calculated for several process conditions. In particular the influence of the undesired but unavoidable pressure drop in the support and the intermediate layers on the effective driving force for pervaporation was evaluated and found to be relevant for predicting the overall process performance. The membrane prepared was found to be suitable for the recovery of highly concentrated ethanol from feed mixtures of relatively low ethanol concentrations at relatively low feed temperatures.     

Separation of ethanol—water mixtures by pervaporation through thin,composite membranes

This paper reports on the separation of ethanol—water mixtures using pervaporation for several membrane types. The FT30 and RC100 membranes pass ethanol selectively at feed concentrations similar to fermentation beers, and the FT30 membrane continues to pass ethanol selectively at higher ethanol feed concentrations. As the ethanol concentration in the feed increases, the ethanol selectivity of both the FT30 and RC100 membranes decreases; near the ethanol—water azeotrope, both membranes pass water selectively. At lower ethanol concentrations, the selectivity of the FT30 membrane increases as the feed temperature increases above 23°C.     

Biodiesel Production from Integration Between Reaction and Separation System: Reactive Distillation Process

Biodiesel is a clean burning fuel derived from a renewable feedstock such as vegetable oil or animal fat. It is biodegradable, non-inflammable, non-toxic, and produces lesser carbon monoxide, sulfur dioxide, and unburned hydrocarbons than petroleum-based fuel. The purpose of the present work is to present an efficient process using reactive distillation columns applied to biodiesel production. Reactive distillation is the simultaneous implementation of reaction and separation within a single unit of column. Nowadays, it is appropriately called “Intensified Process”. This combined operation is especially suited for the chemical reaction limited by equilibrium constraints, since one or more of the products of the reaction are continuously separated from the reactants. This work presents the biodiesel production from soybean oil and bioethanol by reactive distillation. Different variables affect the conventional biodiesel production process such as: catalyst concentration, reaction temperature, level of agitation, ethanol/soybean oil molar ratio, reaction time, and raw material type. In this study, the experimental design was used to optimize the following process variables: the catalyst concentration (from 0.5 wt.% to 1.5 wt.%), the ethanol/soybean oil molar ratio (from 3:1 to 9:1). The reactive column reflux rate was 83 ml/min, and the reaction time was 6 min.     

加碱萃取精馏制取无水乙醇

乙醇-水体系存在共沸点,难以通过普通精馏方法制取高纯度乙醇,萃取精馏是分离共沸体系的有效途径。目前常用的萃取溶剂是乙二醇。在分离乙醇-水体系的过程中,将适当的盐类(醋酸钾)溶于乙二醇形成溶盐萃取剂,会有效提高溶剂的选择性。本文用萃取精馏方法并加入乙二醇分离效果更明显。     

A new approach to improving the performance ofZymomonas in continuous ethanol fermentations

Although most fermentation ethanol is currently produced in traditional batch processes with yeast, the ethanologenic bacteriumZymomonas mobilis is recognized as an alternative process organism for fuel alcohol production. Different strategies for improving the productivity of ethanol fermentations are reviewed. In batch and open-type continuous fermentations the advantage of replacing yeast byZymomonas relates principally to the 10% higher fermentation efficiency (product yield), whereas in high cell density, closed-type continuous systems (operating with cell recycle or retention) the superior kinetic properties ofZymomonas can be exploited to affect about a five-fold improvement in volumetric productivity. Unlike yeast, the rate of energy supply (conversion of glucose to ethanol) inZymomonas is not strictly regulated by the energy demand and a nongrowing culture exhibits a maintenance energy coefficient that is at least 25 times higher than yeast. As an alternative to process improvement through genetic engineering of the process organism this investigation has taken a biochemical and physiological approach to increasing the kinetic performance ofZ. mobilis through manipulation and control of the chemical environment. Energetically “uncoupled” phenotypes with markedly increased specific rates of ethanol production were generated under conditions of nutritional limitation (nitrogen, phosphate, or potassium) in steady-state continuous culture. The pH was shown to influence energy coupling inZymomonas affecting the maintenance coefficient (m _e ) rather than the max growth yield coefficient (Y _x ^sάx ). Whereas the pH for optimal growth ofZ. mobilis (ATCC 29191) in a complex medium was 6.0–6.5, the specific rate of ethanol production in continuous fermentations was maximal in the range 4.0–4.5. Fermentation conditions are specified for maximizing the specific productivity of aZymomonas-based continuous ethanol fermentation where the potential exists for improving the volumetric productivity in dense culture fermentations with an associated 35–40% reduction in capital costs of fermentation equipment and an estimated savings of 10–15% on cost of product recovery (distillation), and 3–7% on overall production costs based on the projected use of inexpensive feedstocks.     

Membrane separations in ethanol recovery: an analysis of two applications of hyperfiltration

With further development, membrane separations have the potential to contribute to process improvements, especially for energy conservation, in ethanol fuel production. Two applications of hyperfiltration (reverse osmosis) in the recovery and purification of ethanol from fermentation beer are defined and analyzed for energy requirements and economics. These analyses are performed for a complete plant, including a recovery subprocess with and without the use of hyperfiltration. The hyperfiltration processes are designed using existing data for available membranes and hypothetical data for advanced membranes. The overall purpose of these analyses is to identify process modifications and membrane-related research that can contribute to decreasing the energy requirements of ethanol fuel production.

In one application, hyperfiltration is used in a lignocellulose-to-ethanol plant to preconcentrate low-proof (2 wt% beer prior to further purification by fractional and azeotropic distillation. This application requires ethanol-rejecting membranes, which are developed. When lignocellulose is used as a feedstock for ethanol production, a low-proof beer is usually produced. The energy requirements of ethanol recovery from low-proof beer by conventional distillation exceed the energy content of ethanol and frequently preclude the feasibility of producing ethanol from lignocellulose. The use of hyperfiltration to preconcentrate ethanol can significantly reduce the energy requirements of ethanol recovery from low-proof beer. The analyses are based upon process designs using existing and hypothetical membranes. This application is found to conserve 19 to 20 GJ/m³ (67,000 to 72,000 Btu/gal) of anhydrous ethanol as compared to only fractional and azeotropic distillation and to be economically competitive (with a 2 to 4% lower price). The analysis indicates that this application of hyperfiltration is promising and that future research should be devoted to increasing flux (while maintaining or improving ethanol rejection) and to assessing and improving membrane life.

In the other application, hyperfiltration is used to dehydrate high-proof (93 to 95 wt%) ethanol in a corn-to-ethanol plant. Ethanol dehydration is an energy-intensive separation, generally requiring 2.0 to 2.8 GJ/m³ (7,000 to 10,000 Btu/gal) of anhydrous ethanol. This application was designed based upon hypothetical, water-rejecting hyperfiltration membranes, which are not pres ently developed. Although the hyperfiltration process is found to conserve 0.8 GJ/m³ (2,900 Btu/gal) of anhydrous ethanol, it is not found to have an economic advantage over a conventional ethanol purification process. Therefore, this application is not found to be promising and little incentive exists for performing research aimed at development of a water-rejecting membrane for the dehydration of ethanol by hyperfiltration.

Finally, thoughts regarding the use of membrane separations in the chemical/fuel industry are presented.     

Recovery of volatile products from dilute high-fouling process streams

As biomass hydrolysis, and fermentation technologies approach commercial viability, advancements in product recovery technologies will be required. For cases in which fermentation products are more volatile than water, recovery by distillation is often the technology of choice. Distillation technologies that will allow the economic recovery of dilute volatile products from streams containing a variety of impurities have been developed and commercially demonstrated. Distillation tower and tray designs, along with specialized heat-exchanger designs, allowing for extended processing intervals on solutions containing lignocellulosic residues, organic acids, and inorganic salts concentrations >100 g/L are in commerical operation. In the case of ethanol, distillation energy consumption efficiencies for processing solutions containing <40 g/L of desired product can approach demonstrated energy consumption efficiencies for solutions containing concentrations >120 g/L. These proprietary technologies have been applied individually at commercial scale, and designs have been developed that incorporate the combined technologies with only a marginal increase in capital investment compared to traditional methods.     

Production of process water using integrated membrane processes

Application of ultrafiltration, nanofiltration, reverse osmosis, membrane distillation, and integrated membrane processes for the preparation of process water from natural water or industrial effluents was investigated. A two-stage reverse osmosis plant enabled almost complete removal of solutes from the feed water. High-purity water was prepared using the membrane distillation. However, during this process a rapid membrane fouling and permeate flux decline was observed when the tap water was used as a feed. The precipitation of deposit in the modules was limited by the separation of sparingly soluble salts from the feed water in the nanofiltration. The combined reverse osmosis—membrane distillation process prevented the formation of salt deposits on the membranes employed for the membrane distillation. Ultrafiltration was found to be very effective removing trace amounts of oil from the feed water. Then the ultrafiltration permeate was used for feeding of the remaining membrane modules resulting in the total removal of oil residue contamination. The ultrafiltration allowed producing process water directly from the industrial effluents containing petroleum derivatives. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Continuous culture studies of xylose-fermentingZymomonas mobilis

The continuous cofermentation performance of xylose-fermentingZymomonas mobilis at 30°C and pH 5.5 was characterized using a pure-sugar feed solution that contained 8 g/L glucose and 40 g/L xylose. Successful chemostat start up resulted in complete utilization of glucose and greater than 85% utilization of xylose, but was only reproducibly achieved using initial dilution rates at or less than 0.04/h; once initiated, cofermentation could be maintained at dilution rates of 0.04 to 0.10/h. Whereas xylose and cell-mass concentrations increased gradually with increasing dilution rate, ethanol concentrations and ethanol yields on available sugars remained approximately constant at 20–22 g/L and 80–90% of theoretical, respectively. Volumetric and specific ethanol productivities increased linearly with increasing dilution rate, rising from approx 1.0 each (g/L/h or g/g/h) at a dilution rate of 0.04/h to approx 2.0 each (g/L/h or g/g/h) at a dilution rate of 0.10/h. Similarly, specific sugar-utilization rates increased from approx 2.0 g/g/h at dilution rate 0.04/h to approx 3.5 g/g/h at dilution rate of 0.10/h. The estimated values of 0.042 g/g for the maximum Z.mobilis cell-mass yield on substrate and 1.13 g/g/h for the minimum specific substrate utilization rate required for cellular maintenance energy are within the range of values reported in the literature. Results are also presented which suggest that long-term adaptation in continuous culture is a powerful technique for developing strains with higher tolerance to inhibitory hemicellulose hydrolyzates.     

Production of ethanol from starch by co-immobilizedZymomonas mobilis-glucoamylase in a fluidized-bed reactor

The production of ethanol from starch was studied in a fluidized-bed reactor (FBR) using co-immobilizedZymomonas mobilis and glucoamylase. The FBR was a glass column of 2.54 cm in diameter and 120 cm in length. TheZ. mobilis and glucoamylase were co-immobilized within small uniform beads (1.2-2.5 mm diameter) of κ-carrageenan. The substrate for ethanol production was a soluble starch. Light steep water was used as the complex nutrient source. The experiments were performed at 35κC and pH range of 4.0-5.5. The substrate concentrations ranged from 40 to 185 g/L, and the feed rates from 10 to 37 mL/min. Under relaxed sterility conditions, the FBR was successfully operated for a period of 22 d, during which no contamination or structural failure of the biocatalyst beads was observed. Volumetric productivity as high as 38 g ethanol/(Lh), which was 74% of the maximum expected value, was obtained. Typical ethanol volumetric productivity was in the range of 15-20 g/(Lh). The average yield was 0.49 g ethanol/g substrate consumed, which was 90% of the theoretical yield. Very low levels of glucose were observed in the reactor, indicating that starch hydrolysis was the rate-limiting step.     

Co-eluent effect in partition chromatography. Rhamnose-xylose separation with strong and weak cation-exchangers in aqueous ethanol

The effect of ethanol in aqueous eluent on the chromatographic separation was studied at 298 K. Two sugars, L-rhamnose and D-xylose, were separated by using strong and weak cation-exchangers as a stationary phase. The ionic form of the resins was Na+ or Ca2+. The separations were carried out with sugar feed concentrations up to 35 wt% and with both low (about 1%) and high (about 10%) feed volume to bed volume ratios. The separation of the sugars was improved by adding ethanol into the eluent. The separation was also significantly enhanced when the weak cation-exchangers with the greatest affinity for water were used instead of strong cation-exchangers as a separation medium for the sugars having different hydrophilicities. The experimental data were successfully explained with a rate-based column model, which accounted for the volume changes of the stationary phase. A thermodynamic sorption model was utilized in column calculations.     

Ethanol fermentation in a tower fermenter using self-aggregatingSaccharomyces uvarum

A self-aggregating strain ofSaccharomyces uvarum (U4) was used as a biocatalyst to carry out continuous ethanol fermentation in a tower fermentor equipped with a cell separator. Cell aggregates (2–3 mm) formed a stable packed bed in the fermentor, and the cell separator retained yeast cells effectively. Corn steep liquor was used as a nitrogen source for the fermentation of corn syrup and black strap molasses. An ethanol productivity of 54 g/L/h was reached using corn syrup at a dilution rate of 0.7/h, and sugar concentration in the feed was 15% (w/v). For molasses fermentation, an ethanol productivity of 22 g/L/h was obtained at a dilution rate of 0.7/h, and sugar concentration in the feed was 12.5% (w/v). Ethanol yields obtained from tower fermentation are higher than those obtained from flask fermentation (96% for corn syrup fermentation and 92% for molasses fermentation). No significant loss in fermentation activity was observed after 3 mo of operation.