Reducing the energy demand of corn‐based fuel ethanol through salt extractive distillation enabled by electrodialysis

The thermal energy demand for producing fuel ethanol from the fermentation broth of a contemporary corn‐to‐fuel ethanol plant in the U.S. is largely satisfied by combustion of fossil fuels, which impacts the possible economical and environmental advantages of bioethanol over fossil fuels. To reduce the thermal energy demand for producing fuel ethanol, a process integrating salt extractive distillation—enabled by a new scheme of electrodialysis and spray drying for salt recovery—in the water‐ethanol separation train of a contemporary corn‐to‐fuel ethanol plant is investigated. Process simulation using Aspen Plus® 2006.5, with the electrolyte nonrandom two liquid Redlich‐Kwong property method to model the vapor liquid equilibrium of the water‐ethanol‐salt system, was carried out. The integrated salt extractive distillation process may provide a thermal energy savings of about 30%, when compared with the contemporary process for separating fuel ethanol from the beer column distillate. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Molecular Orbital Based Design Guideline for Hypergolic Ionic Liquids

Currently, monomethyl hydrazine is the most widely used hypergolic rocket fuel. Due to its high toxic vapor, there is a thrust towards developing low‐toxic hypergolic fuels. Ultra‐low vapor pressure ionic liquids are one such potential category of fuels. However, designing ionic liquid with ignition delay comparable to monomethyl hydrazine is a challenge, because fundamental understanding of the hypergolic nature of ionic liquids is far from clear. This work used the computed energy gap values between the highest occupied molecular orbitals (HOMO) of the anions for a series of ionic liquids and the lowest occupied molecular orbital (LUMO) of HNO₃, and variation in the computed relative heats of formation, ΔH_f, of these anions to develop correlations to predict hypergol activity between an ionic liquid fuel and nitric acid as the oxidizer. The observed trends in HOMO LUMO energy gap and ΔH_f values can be used successfully to verify not only hypergolicity of known systems but also the lack of this phenomenon in OH⁻ and BF₄⁻ based ionic liquids. It was shown that through suitable substitution of electron withdrawing or electron donating groups in the anion, the energy gap and the ΔH_f values could be tailored into an optimal range that would have a high probability for the new system to exhibit hypergolic reactivity. To validate our method, we suggest herein new ionic liquid structures for synthesis and experimental screening.     

Pressure-Driven Pervaporation

Abstract

Pervaporation is a promising method for the fractionation, purification, and recovery of volatile liquids (1).Current interest in ethanol as a fuel and the possibility to obtain this fuel by biomass fermentation, which yields dilute (8–12% w/w) aqueous ethanol solutions, led to considerable research effort in ethanol purification and dehydration by pervaporation (2–4).     

Butanol production in a sugarcane biorefinery using ethanol as feedstock. Part I: Integration to a first generation sugarcane distillery

Butanol production from renewable resources has been increasingly investigated over the past decade, mostly for its use as a liquid biofuel for road transportation, since its energy density is higher than that of ethanol and it may be used in gasoline driven engines with practically no changes, but also for use as a feedstock in the chemical industry. Most of the research concerning butanol production focuses on the ABE process (fermentation of sugars into a mixture of acetone, butanol and ethanol), which has several drawbacks regarding microorganism performance and product inhibition. An alternative to ABE fermentation, ethanol catalytic conversion to butanol can produce a higher quality product with less retrofitting than ABE in existing ethanol producing facilities. There are different types of catalysts for the chemical conversion of ethanol to butanol being developed in laboratory scale, but their actual use in a sugarcane processing plant has never before been assessed. Butanol production from ethanol in a sugarcane biorefinery, using data from the literature, was assessed in this study; different technological alternatives (catalytic routes) were evaluated through computer simulation in Aspen Plus (including production of electricity, sugar, ethanol and other products) and economic and environmental impacts were assessed. Results indicate that vapor-phase catalysis presents higher potential for industrial implementation, and commercialization of butanol for use as a chemical feedstock has an economic performance similar to that of current, optimized first generation sugarcane distilleries, but can potentially contribute to cost reduction that will allow commercialization of butanol as a fuel in the future.     

四氟硼酸盐类离子液体对典型柴油的萃取脱硫研究

The extractive removal of sulfur compounds （S-compounds） from Dongying and Liaohe diesel fuels with [BF4]^--based ionic liquids were systematically investigated. The results show that the absorption capacity of an ionic liquid for the S-compounds in diesel fuels relies on its structure and its size. In the case of the two examined diesel fuels, both elongating the cation tail length and increasing the mass ratio of ionic liquid/diesel fuel promote the desulfurization ability of the examined ionic liquids. The results also show that imidazolium-based ionic liquids display higher extraction efficiencies than pyridinium-based ionic liquids, presumably owing to the fact that the rings of the S-compounds are similar to the imidazolium head ring. With the 1 ： 1 mass ratio of ionic liquid/diesel fuel, the rates of the first desulfurization of Dongying and Liaohe diesel fuels using [C8mim][BF4] amount to 29.96% and 39.76%, suggesting that [C8mim][BF4] is a promising extractant for desulfurization of these diesel fuels.     

The role of butanol in the development of sustainable fuel technologies

OVERVIEW: The development of innovative methods to efficiently convert biomass to fuels and industrial chemicals is one of the grand challenges of the current age. n‐Butanol is a versatile and sustainable platform chemical that can be produced from a variety of waste biomass sources. The emergence of new technologies for the production of fuels and chemicals from butanol will allow it to be a significant component of a necessarily dynamic and multifaceted solution to the current global energy crisis. IMPACT: The production of butanol from biomass and its utilization as a precursor to a diverse set of fuel products has the potential to reduce petroleum use worldwide. In concert with other emerging renewable technologies, significant reductions in greenhouse gas emissions may be realized. The rapid incorporation of renewables into the world fuel supply may also help to offset predicted increases in transportation fuel prices as the supply of oil declines. APPLICATIONS: Recent work has shown that butanol is a potential gasoline replacement that can also be blended in significant quantities with conventional diesel fuel. These efforts have transitioned to research focused on the development of viable methods for the production of an array of oxygenated and fully saturated jet and diesel fuels from butanol. The technologies discussed in this paper will help drive the commercialization and utilization of a spectrum of butanol based sustainable fuels that can supplement and partially displace conventional petroleum derived fuels. Published 2010 by John Wiley and Sons, Ltd.     

Production of fuel ethanol from softwood by simultaneous saccharification and fermentation at high dry matter content

BACKGROUND: The production of bio‐ethanol from softwood is considered a promising alternative to fossil fuels in Sweden. In order to make fuel ethanol economically competitive with fossil fuels, it is important to reduce the production cost, which can be done by increasing the dry matter content of the fermentation medium, thus reducing the energy demand in the final distillation of the fermentation broth. Running simultaneous saccharification and fermentation (SSF) at higher dry matter content has, however, been found to decrease the ethanol yield. RESULTS: The use of different stirrer types and stirring speeds in the present study has shown to have an influence on the final ethanol yield in SSF with 10% water‐insoluble solids (WIS). Also, higher concentration of pretreatment hydrolysate, i.e., with increased inhibitor concentration, at the same WIS resulted in a decreased ethanol yield. However, despite stirring problems and high inhibitor concentration, ethanol was produced at 12% WIS with an ethanol yield in the SSF step of 81% of the theoretical based on the content of fermentable sugars in the fermentor. CONCLUSION: The decrease in ethanol yield in SSF at high dry matter content has been shown to be a combined effect of increased mass transfer resistance and increased inhibitor concentration in the fermentation broth. Copyright © 2008 Society of Chemical Industry     

Alternatives for the Purification of the Blend Butanol/Ethanol from an Acetone/Butanol/Ethanol Fermentation Effluent

Biobutanol is a biofuel with potential to substitute gasoline. It can be generated through fermentation of lignocellulosic material, by which acetone, butanol, and ethanol (ABE) are obtained and subsequently separated. Nevertheless, the blend ethanol/butanol itself is a fuel, so its separation could be not even necessary. An alternative is proposed to simplify the purification step of the ABE mixture, avoiding the separation of the ethanol/butanol blend. Intensification alternatives are suggested for the resulting structure. The proposed schemes are optimized through a stochastic approach, minimizing the total annual cost and the eco‐indicator 99. The individual risk index is computed for selected designs. The suggested designs reduce the individual risk index by around 30–66 %.     

Butanol production in a sugarcane biorefinery using ethanol as feedstock. Part II: Integration to a second generation sugarcane distillery

Production of second generation ethanol and other added value chemicals from sugarcane bagasse and straw integrated to first generation sugarcane biorefineries presents large potential for industrial implementation, since part of the infrastructure where first generation ethanol is produced may be shared between both plants. In this context, butanol from renewable resources has attracted increasing interest, mostly for its use as a drop in liquid biofuel for transportation, since its energy density is greater than that of ethanol, but also for its use as feedstock in the chemical industry. In this paper, vapor-phase catalytic production of butanol from first and second generation ethanol in a sugarcane biorefinery was assessed, using data available from the literature. The objective is to evaluate the potential of butanol either as fuel or feedstock for industry, taking into account economical/environmental issues through computer simulation. The results obtained show that, although promising, butanol sold as chemical has a limited market and as fuel presents economic constraints. In addition, investments on the butanol conversion plant could be an obstacle to its practical implementation. Nevertheless, environmental assessment pointed out advantages of its use as fuel for road transportation, if compared with gasoline in terms of global environmental impacts such as global warming.     

木质纤维素的生物转化综述

随着不可再生资源的石油的不断消耗,人们把目光转到许多再生能源甚至粮食来产生燃料。纤维素是全球产量最多的可再生有机物,如何使它转化成有用的资源如乙醇、丁醇等化工产品日益受到人们的重视。文章就是从此出发,探讨如何使用生物转化的方法把木质纤维素等原料通过预处理、酶水解和发酵等方法变成乙醇、丁醇等物质的过程。通过对SHF、SSF、SSCF、CBP等热点方法进行探讨其优缺点和国内外的最新研究成果,试图找出成本低、效率高的最佳生产途径。     

Kinetic study on ethanol production using Saccharomyces cerevisiae ITV‐01 yeast isolated from sugar cane molasses

BACKGROUND: Bio‐ethanol production from renewable sources, such as sugar cane, makes it a biofuel that is both renewable and environmentally friendly. One of the strategies to reduce production costs and to make ethanol fuel economically competitive with fossil fuels could be the use of wild yeast with osmotolerance, ethanol resistance and low nutritional requirements. The aim of this work was to investigate the kinetics of ethanol fermentation using Saccharomyces cerevisiae ITV‐01 yeast strain in a batch system at different glucose and ethanol concentrations, pH values and temperature in order to determine the optimum fermentation conditions. RESULTS: This strain showed osmotolerance (its specific growth rate (µ_max) remained unchanged at glucose concentrations between 100 and 200 g L^?1) as well as ethanol resistance (it was able to grow at 10% v/v ethanol). Activation energy (Ea) and Q₁₀ values calculated at temperatures between 27 and 39 °C, pH 3.5, was 15.6 kcal mol^?1 (with a pre‐exponential factor of 3.8 × 10¹² h^?1 (R² = 0.94)) and 3.93 respectively, indicating that this system is biologically limited. CONCLUSIONS: The optimal conditions for ethanol production were pH 3.5, 30 °C and initial glucose concentration 150 g L^?1. In this case, a maximum ethanol concentration of 58.4 g L^?1, ethanol productivity of 1.8 g L^?1 h^?1 and ethanol yield of 0.41 g g^?1 were obtained. Copyright © 2010 Society of Chemical Industry     

Microalgal biomass as a fermentation feedstock for bioethanol production

BACKGROUND: The increasing cost of fossil fuels as well as the escalating social and industrial awareness of the environmental impacts associated with the use of fossil fuels has created the need for more sustainable fuel options. Bioethanol, produced from renewable biomass such as sugar and starch materials, is believed to be one of these options, and it is currently being harnessed extensively. However, the utilization of sugar and starch materials as feedstocks for bioethanol production creates a major competition with the food market in terms of land for cultivation, and this makes bioethanol from these sources economically less attractive. RESULT: This study explores the suitability of microalgae (Chlorococum sp.) as a substrate for bioethanol production via yeast (Saccharomyces bayanus) under different fermentation conditions. Results show a maximum ethanol concentration of 3.83 g L^?1 obtained from 10 g L^?1 of lipid‐extracted microalgae debris. CONCLUSION: This productivity level (～38% w/w), which is in keeping with that of current production systems endorses microalgae as a promising substrate for bioethanol production. Copyright © 2009 Society of Chemical Industry     

A review on production,storage of hydrogen and its utilization as an energy resource

Energy price is rising due to rapid depletion of fossil fuels. Development of renewable and non-polluting energy resources is necessary for reducing pollution level caused by those conventional fuels. Researchers have recognized hydrogen (H₂) as such an energy source. Hydrogen is a potential non-carbon based energy resource, which can replace fossil fuels. Hydrogen is considered as the alternative fuel as it could be generated from clean and green sources. Despite many advantages, storage of hydrogen is a serious problem. Due to high inflammability, adequate safety measures should be taken during the production, storage, and use of H₂ fuel. This review article elucidates production methods and storage of hydrogen. Besides this safety related to H₂ handling in refilling station, and automobiles has also been discussed. Study shows that safety program and awareness could be fruitful for increasing the acceptance of hydrogen as fuel.     

Absence of 14C in PM2.5 Emissions from Gasohol Combustion in Small Engines

PM2.5 combustion emissions from small engines (string trimmer and chainsaw) using gasoline containing biogenic ethanol were collected and analyzed for their ¹⁴ C content. The sampling methodology was designed to minimize potential bias from organic artifact effects. The ¹⁴ C in the PM2.5 emissions was found to be drastically smaller (approximately a factor of 40) than the ¹⁴ C amounts measured in the fuels. This suggests that the current method of using ¹⁴ C measurements on ambient aerosol to estimate the contribution from fossil fuel combustion will be little affected by increased use of ethanol-containing gasoline.     

Waste paper sludge as a potential biomass for bio-ethanol production

This review describes the utilization of paper sludge (PS), which is waste from the pulp and paper industry. Its advantages make PS the cellulosic biomass with the most potential for bio-refinery research and applicable for industrial scale. Some of the grain based biofuels and chemicals have already been in commercial operation, including fuel ethanol or biochemical products. Unfortunately, research and application of PS are yet in their infancy and suffer from large scale because of low productivity. Reviewing the many researches that are working at the utilization of PS for bio-refineries could encourage the utilization of PS from laboratory research to be applied in industry. For this reason, PS usage as industrial raw material will be effective in solving the environmental problems caused by PS with clean technology. In addition, its conversion to bio-ethanol could offer an alternative solution to the energy crisis from fossil fuel. Two methods of PS utilization as raw material for bio-ethanol production are introduced. The simultaneous saccharification and fermentation (SSF) using cellulase produced by A. cellulolyticus and thermotolerant S. cerevisiae TJ14 gave ethanol yield 0.208 (g ethanol/g PS organic material) or 0.051 (g ethanol/g PS). One pot bioethanol production as a modified consolidated biomass processing (CBP) technology gave ethanol yield 0.19 (g ethanol/g Solka floc) and is considered to be the practical CBP technology for its minimizing process.     

Simultaneous saccharification and fermentation of alkaline-pretreated corn stover to ethanol using a recombinant yeast strain

Bio-ethanol converted from cheap and abundant lignocellulosic materials is a potential renewable resource to replace depleting fossil fuels. Simultaneous saccharification and fermentation (SSF) of alkaline-pretreated corn stover for the production of ethanol was investigated using a recombinant yeast strain Saccharomyces cerevisiae ZU-10. Low cellobiase activity in Trichoderma reesei cellulase resulted in cellobiose accumulation. Supplementing the simultaneous saccharification and fermentation system with cellobiase greatly reduced feedback inhibition caused by cellobiose to the cellulase reaction, thereby increased the ethanol yield. 12 h of enzymatic prehydrolysis at 50 °C prior to simultaneous saccharification and fermentation was found to have a negative effect on the overall ethanol yield. Glucose and xylose produced from alkaline-pretreated corn stover could be co-fermented to ethanol effectively by S. cerevisiae ZU-10. An ethanol concentration of 27.8 g/L and the corresponding ethanol yield on carbohydrate in substrate of 0.350 g/g were achieved within 72 h at 33 °C with 80 g/L of substrate and enzyme loadings of 20 filter paper activity units (FPU)/g substrate and 10 cellobiase units (CBU)/g substrate. The results are meaningful in co-conversion of cellulose and hemicellulose fraction of lignocellulosic materials to fuel ethanol.     

Formulation of Canola-Diesel Microemulsion Fuels and Their Selective Diesel Engine Performance

Vegetable oils have been considered as an alternative to diesel fuel due to their comparable properties and performance. However, the high viscosity of vegetable oil causes engine durability problems with long-term usage. Vegetable oil viscosity can be reduced by blending with diesel fuel in thermodynamically stable mixtures using microemulsion fuel formulation techniques. This work focuses on the formulation of microemulsion fuels comprising diesel fuel and canola oil as the oil phase with ethanol and sec-butanol as viscosity reducers as well as 1-octanol and oleyl amine as surfactant/cosurfactant. Selective tests on an instrumented diesel engine were performed for formulated microemulsion fuels and No. 2 diesel fuel for comparison. The results show that formulated microemulsion fuels have fuel properties that meet the ASTM requirements for viscosity, cloud point, and pour point for biodiesel. Even more important, they have phase stability over a wide range of temperatures (−10 to 70 °C). Although all of the microemulsion fuels showed higher fuel consumption than diesel fuel, some of the microemulsion fuels had significantly reduced CO and NO_x emissions as well as reduced particulates when compared to baseline diesel fuel. The research demonstrates the potential of these microemulsion fuels as alternative to neat diesel fuel.     

Desulfurization of Diesel Fuel by Extraction with Lewis-Acidic Ionic Liquid

Abstract

Ionic liquids were found to be highly selective for the extractive removal of aromatic sulfur compounds from fuels at room temperature. The efficiency of ionic liquids for the removal of aromatic sulfur compounds is dependent on the properties and structure of the ionic liquids. In this work, the Lewis-acidic ionic liquid 1-butyl-3-methylimidazolium tetrahalogenoferrate(III) ([BMIM] [FeCl₄]) was synthesized and demonstrated to be more effective for the removal of aromatic sulfur compounds from diesel over ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] [BF₄]) because of its Lewis-acidic property. The ionic liquids favorably extracted organic compounds with a higher density of aromatic π-electrons. [BMIM][FeCl₄] ionic liquid can be regenerated through reextraction by hexane, and could be used in multiple steps for the removal of sulfur compounds from diesel.     

Experimental determination of laminar burning velocity for butanol and ethanol iso-octane blends

The potential of butanol as an additive in iso-octane used as gasoline fuel was characterized with respect to laminar combustion, and compared with ethanol. New sets of data of laminar burning velocity are provided by using the spherical expanding flame methodology, in a constant volume vessel. This paper presents the first results obtained for pure fuels (iso-octane, ethanol and butanol) at an initial pressure of 0.1 MPa and a temperature of 400 K, and for an equivalence range from 0.8 to 1.4. New data of laminar burning velocity for three fuel blends containing up to 75% alcohol by liquid volume are also provided. From these new experimental data, a correlation to estimate the laminar burning velocity of any butanol or ethanol blend iso-octane-air mixture is proposed.     

Separation of Ionic Liquid Dispersions in Centrifugal Solvent Extraction Contactors

Abstract

Separations of dispersions formed by mixing immiscible organic room‐temperature ionic liquids (IL)/hydrocarbon/and aqueous systems using a centrifugal solvent‐extraction contactor have been successfully demonstrated in proof‐of‐concept testing. This accomplishment is significant in that physical property factors that are typical of ionic liquid systems (e.g., similar densities of the bulk phases, low interfacial tensions, and high viscosities) are typically unfavorable for dispersion separation, particularly in continuous processes. Efficient separation of dispersions containing ionic liquid solvents is essential for utilization of these compounds in liquid‐liquid extraction applications to maximize both solute transfer efficiency and solvent recovery. Efficient solvent recovery is of particular concern in IL applications because of the high cost of most IL solvents.

This paper presents the results of initial experiments with three hydrophobic ionic liquids to determine how their physical properties affect phase mixing and phase disengagement in contact with an aqueous solution using a centrifugal contactor. While the results of the reported work are promising, additional work is needed to optimize existing mathematical models of contactor hydraulics to address special considerations involved in IL‐based processes and to optimize the equipment itself for IL applications.