Biodiesel Feedstock from Emulsions Produced by Aqueous Processing of Yellow Mustard

The multi-stage treatment of stable oil-in-water emulsions produced during non-enzymatic aqueous processing of dehulled yellow mustard flour with cyclic ethers [tetrahydrofuran (THF) and 1,4-dioxane] was investigated to produce a single-phase oil-solvent-water miscella suitable for biodiesel production. While the single-stage treatment of yellow mustard emulsion recovered 97 % and 95 % of the oil by using 4:1 THF:oil and 9:1 dioxane:oil weight ratios, respectively, miscella phases containing more than 7 % water formed, which made them unsuitable as biodiesel feedstock. Multi-stage treatments of the emulsion using lower THF:oil and dioxane:oil weight ratios were further developed to produce oil-solvent-water miscella phases with low water content. While three-stage extraction of emulsions using 0.5:1, 1:1, 1.5:1, and 2:1 dioxane:oil weight ratios did not destabilize the emulsion, three-stage extraction using 0.5:1 and 0.75:1 THF:oil weight ratios effectively recovered over 97 % of the oil, resulting in the production of oil-rich miscella phases containing only 1 % and 1.5 % water, respectively. These miscella phases were analyzed for free fatty acid and phosphorus contents and proved to be excellent feedstocks for the preparation of high-purity methyl esters through single-phase base-catalyzed transmethylation.     

Destabilization of Yellow Mustard Emulsion Using Organic Solvents

An aqueous extraction process was developed consisting of aqueous contact with dehulled yellow mustard flour to recover protein followed by dissolution of the released emulsion in dimethylformamide (DMF) or isopropyl alcohol (IPA) to recover the released oil in the form of single-phase oil–solvent miscellae suitable for industrial applications. Only some 38 ± 3 % of the oil in the yellow mustard emulsion was extracted using DMF even at high weight ratios since DMF is widely miscible with water, preventing separation of the oil from the emulsion. A ternary phase diagram of DMF/oil/water was prepared and confirmed the limited solubility of the oil in DMF in the presence of water. The use of 31:1 IPA:oil weight ratio could effectively recover over 94 % of the oil in the emulsion; however, multiple-stage treatment of the emulsion was proven to be more efficient with lower volumes of IPA required to achieve high oil extraction yields. The results suggest that the optimal conditions for multiple-stage process were four stages using 2:1 IPA:oil weight ratio, with 96 ± 1 % oil recovery from the emulsion.     

Application of a Ternary Phase Diagram to the Phase Separation of Oil-in-Water Emulsions Using Isopropyl Alcohol

The oil-in-water emulsion formed during an aqueous extraction of yellow mustard seed flour was destabilized using isopropyl alcohol (IPA) in a four stage extraction process, with concurrent recovery of oil and water in separate phases. The emulsion was extracted using two different approaches: phase separation extraction (PSE) that used fresh IPA as the extraction solvent at each stage, and phase separation extraction with recycle (PSER) that reused the extracted water-rich phase, containing IPA, as the extraction solvent. Extraction processes by both approaches were modeled by the ternary liquid phase diagram of IPA, canola oil and water to characterize the extraction progress. PSER resulted in improved oil–water separation and IPA usage efficiency than PSE, but achieved only 84.0?% oil recovery, compared to 92.3?% by PSE. The ternary diagram of IPA, canola oil and water offered good approximation of the oil and water separation behavior of PSE and PSER by closely predicting the compositions of the separated phases; however, the weight ratio of the separated phases were not as closely predicted.     

Flaking and extrusion as mechanical treatments for enzyme-assisted aqueous extraction of oil from soybeans

Flaking and extruding dehulled soybeans were evaluated as a means of enhancing oil extraction efficiency during enzyme-assisted aqueous processing of soybeans. Cellulase, protease, and their combination were evaluated for effectiveness in achieving high oil extraction recovery from extruded flakes. Aqueous extraction of extruded full-fat soy flakes gave 68% recovery of the total available oil without using enzymes. A 0.5% wt/wt protease treatment after flaking and extruding dehulled soybeans increased oil extraction recovery to 88% of the total available oil. Flaking and extruding enhanced protease hydrolysis of proteins freeing more oil. Treating extruded flakes with cellulase, however, did not enhance oil extraction either alone or in combination with protease. Discrepancies in oil extraction recoveries were encountered when merely considering crude free fat because some oil became bound to denatured protein during extrusion and/or sample drying. Bound fat was unavailable for determination by using the hexane extraction method, but was accounted for by using the acid hydrolysis method for total oil determination. Oil extraction recovery from extruded soybean flakes was affected by oil determination methods, which was not the case for unextruded full-fat soy flour.     

Destabilization of Emulsion Formed During Aqueous Extraction of Peanut Oil: Synergistic Effect of Tween 20 and pH

To destabilize the emulsion formed during aqueous extraction processing (AEP) of peanuts, Tween and Span series surfactants (Tween 20, Tween 80, Span 20, and Span 80) were used alone or in combination to break the emulsion. Results indicate that only Tween surfactants had a pronounced demulsifying effect that was dependent on Tween concentration and system pH. When 1.2 wt% Tween 20 aqueous solution was used for oil extraction at pH 10.0, the highest free oil yield was achieved at 76.1 %, which was similar to the oil recovery of using proteases as a destabilization agent. The results obtained using a model emulsion system containing peanut oil and Tween 20/peanut protein isolates (PPI) showed that when Tween 20 and PPI coexisted in extraction medium at pH 10.0, the dynamic interfacial tension and droplet size distribution curves were very similar to those when Tween 20 was used alone, suggesting that Tween 20 dominated at the interface, instead of PPI. Destabilization of the model emulsions relied on three important factors: inclusion of Tween 20 at the initial mixing stage, high pH, and a gentle mixing speed. A synergistic destabilization mechanism of using Tween 20 at high pH during AEP was proposed. The discovery of Tween 20 as an effective demulsifier significantly contributes to the development of AEP of oilseeds.     

Separating Oil from Aqueous Extraction Fractions of Soybean

Previous research has shown that enzyme-assisted aqueous extraction processing (EAEP) extracts 88–90% of the total soybean oil from extruded full-fat soy flakes into the aqueous media, which is distributed as cream (oil-in-water emulsion), skim, and free oil. In the present work, a simple separatory funnel procedure was effective in separating aqueous skim, cream and free oil fractions allowing mass balances and extraction and recovery efficiencies to be determined. The procedure was used to separate and compare liquid fractions extracted from full-fat soy flour and extruded full-fat soy flakes. EAEP extracted more oil from the extruded full-fat soy flakes, and yielded more free oil from the resulting cream compared to unextruded full-fat soy flour. Dry matter partitioning between fractions was similar for the two procedures. Mean oil droplet sizes in the cream and skim fractions were larger for EAEP of extruded flakes compared to non-enzymatic AEP of unextruded flour (45 vs. 20 μm for cream; 13 vs. 5 μm for skim) making the emulsions from EAEP of extruded flakes less stable. All major soy protein subunits were present in the cream fractions, as well as other fractions, from both processes. The cream could be broken using phospholipase treatments and 70–80% of total oil in the extruded full-fat flakes was recovered using EAEP and a phospholipase de-emulsification procedure.     

Biodiesel Production from Mustard Emulsion by a Combined Destabilization/Adsorption Process

Tetrahydrofuran, added to the oil‐in‐water emulsions formed by the aqueous processing of yellow mustard flour, produced oil/water/THF miscellas containing 1–2 % water. The high water content prevented the direct conversion of the system to fatty acid methyl esters (FAME) through a single‐phase base‐catalyzed transmethylation process. Dehydration of these miscellas by adsorption on 4A molecular sieves at room temperature using either batch or continuous fixed‐bed systems successfully reduced the water content to the quality standards needed for biodiesel feedstock (0.3 %). Equilibrium adsorption studies for the uptake of water from oil/THF/water miscella phases at room temperature allowed quantitative comparison of the water adsorption capacity based on the oil and THF concentrations of the miscellas. Batch contact was used to investigate the dominant parameters affecting the uptake of water including miscella composition, adsorbent dose and contact time. The adsorption of the water was strongly dependent on adsorbent dose and miscella oil concentrations. The regeneration of molecular sieves by heating under nitrogen at reduced pressure for 6 h at 275 °C resulted in incomplete desorption of miscella components. The adsorption breakthrough curves in terms of flow rates, initial water and oil miscella concentrations were determined. The dehydrated miscella phases were reacted with methanol in a single‐phase base‐catalyzed transmethylation process with high yields (99.3 wt%) to FAME. The resulting FAME met the ASTM international standard in terms of total glycerol content and acid number.     

Destabilization of the Emulsion Formed during Aqueous Extraction of Soybean Oil

Characterization and destabilization of the emulsion formed during aqueous extraction of oil from soybean flour were investigated. This emulsion was collected as a cream layer and was subjected to various single and combined treatments, including thermal treatments and enzymatic treatments, aimed at recovery of free oil. The soybean oil emulsion formed during the aqueous extraction processing of full fat flour contains high molecular weight glycinin and β-conglycinin proteins and smaller oleosin proteins, which form a multilayer interface. Heat treatment alone did not modify the free oil recovery but freeze–thaw treatment increased the oil yield from 3 to 22%. After enzymatic treatment of the emulsion, its mean droplet size changed from 5 to 14 μm and the oil recovery increased to 23%. This increase could be attributed to the removal (due to enzymatic hydrolysis) of large molecular weight polypeptides from the emulsion interface, resulting in partial emulsion destabilization. When enzymatic treatment was followed by a freeze–thaw step, the oil recovery increased to 46%. This result can be attributed to the thinner interfacial membrane after enzymatic hydrolysis, partial coalescence during freeze–thaw, and coalescence during centrifugation. Despite the reduction in emulsion stability achieved, additional demulsification approaches need to be pursued to obtain an acceptably high conversion to free oil.     

Recovery and Recycling of Isopropyl Alcohol Used in Biodiesel Production From Yellow Mustard Oil

The recovery of solvents used during biodiesel synthesis is an important factor in the economic feasibility and sustainability of the entire process. In this study, we looked at the use of isopropyl alcohol (IPA) for oil extraction and biodiesel production, as well as its potential for recovery and recycling. We found that multistage extraction improved oil recovery, with up to 86% oil yield using four stages of extraction at an IPA:mustard flour (volume:weight) ratio of 1.5:1 at room temperature. Using acid–base‐catalyzed transesterification, 99% of the mustard oil was converted to biodiesel. At the end of this process, IPA was recovered from the azeotrope by salting out using potassium carbonate or sodium carbonate. The solubility behavior of the components was evaluated by means of ternary‐phase diagrams of IPA/water/sodium carbonate and IPA/water/potassium carbonate, which determined their liquid–liquid–solid equilibrium constants at ambient pressure and at room temperature. Using 20% (w:w) potassium carbonate, 95% of the IPA was recovered at 99% purity from a starting mixture of IPA containing 13% water. Azeotropic distillation of the IPA–water azeotrope with 10% potassium carbonate resulted in the recovery of 99% of the IPA at 94% purity. These results suggest that IPA is not only a suitable solvent for mustard‐oil extraction but also for salt‐enhanced azeotropic distillation resulting in near‐complete recovery from aqueous solutions.     

Oil-free protein isolates from full-fat,dehulled mustard flour by microfiltration

New microfiltration (MF)-based aqueous processes for the extraction of oil-free protein isolates from full-fat, dehulled mustard flour have been developed. The processes used hydrophilic MF membranes to separate oil and protein. The most successful processing sequence consisted of alkaline extraction of oil and protein from the flour at pH 11, centrifugation to remove undissolved solids, and an initial microfiltration step to separate oil and dissolved protein. This was followed by proteolytic enzyme treatment of the retentate and a second-stage MF step to recover further protein. The proteolytic enzyme treatment was designed to break aggregated proteins into smaller fractions to permit their passage through the MF membrane. The permeates from the two microfiltration steps were ultrafiltered to concentrate the protein and remove antinutritional compounds and highly fragmented peptides. With this process, 60% of the protein originally in the flour was separated from the oil phase. Approximately 40% of the protein present in the flour was recovered in the form of two oil-free protein isolates—a soluble protein isolate containing 91% protein and a precipitated protein isolate containing 100% protein. The process proves the potential of MF as an effective method of extracting oil-free protein isolates from oilseeds without the use of organic solvents. Based on a presentation at the 16th Annual Meeting of the Canadian Section of AOCS held in Winnipeg, Manitoba, Canada, September 29–October 1, 2001.     

Effect of dehulling methods and desolventizing temperatures on proximate composition and some functional properties of sesame (Sesamum indicum L.) seed flour

Sesame seeds were dehulled mechanically and in 10% sodium chloride solution before oil extraction and drying to obtain the flour. The effect of these dehulling methods on the proximate composition, oil and water absorption, emulsification, and foaming properties of the flour was investigated. The effect of desolventizing temperatures (80, 90, and 100°C) on these properties was also investigated. Protein contents of seeds, dehulled mechanically (MDSF) and in 10% NaCl solution (SDSF), were 58.5 and 52.1%, respectively. Carbohydrate and ash contents of both flours also varied. The oil and water absorption capacities of the flours were 268 and 252% for MDSF and 370 and 410% for SDSF, respectively. The emulsion capacity of the MDSF sample was slightly lower (20.0 mL oil/g sample) but more stable than the SDSF sample, whose value was 20.4 mL oil/g sample. The foam capacity of MDSF was, however, higher (48.5%) but less stable than SDSF (33.7%). An increase in desolventizing temperatures of the meal led to increases in oil and water absorption capacities of the flours. Foam and emulsion capacities, on the other hand, decreased with increase in temperature. Desolventizing temperatures had no effect on the stability of the formed emulsion but had a decreasing effect on the stability of the foam.     

Functional Properties of Protein Isolates Produced by Aqueous Extraction of De-hulled Yellow Mustard

Two types of protein isolates were prepared from de‐hulled yellow mustard flour by aqueous extraction, membrane processing and isoelectric precipitation. The precipitated and soluble protein isolates had 96.0 and 83.5% protein content on a moisture and oil free basis, respectively. Their functional properties were evaluated and compared with commercial soybean and other Brassica protein isolates. The soluble protein isolate exhibited high values for all properties. The precipitated protein isolate showed excellent oil absorption and emulsifying properties but poor solubility, water absorption and foaming properties due to its high lipid content (~25%). Storage temperature had limited effect on lipid oxidation, and hence the stability of the precipitated protein isolate at 25–45 °C. Flavor of wieners and bologna prepared with 2% of this isolate as binder was comparable to those prepared with soy protein isolate.     

Enzymatic extraction of mustard seed and rice bran

Aqueous enzymatic extraction was investigated for recovery of oil from mustard seed and rice bran. The extraction process was reproducible based on statistical analysis of extraction data under different extraction conditions. The most significant factors for extraction were the time of digestion with enzymes, seed or bran concentration in water, volume of hexane added before recovery, and amount of enzyme(s) used. The pretreatment steps of each material before enzyme digestion influenced oil yield. Quality of enzyme-extracted mustard oil was better with respect to color and odor than commercial expeller-extracted and Soxhlet-extracted oils. Most of the characteristics of rice bran oil were identical to those of commercial solvent-extracted oils, but rice bran oil had a lower content of colored substances and higher acidity (free fatty acid). Enzymatic extraction led to recovery of a protein concentrate with increased protein and reduced fiber and ash contents in the mustard and rice bran meals.     

Isopropyl Alcohol Extraction of De‐hulled Yellow Mustard Flour

Vegetable oils are typically extracted with hexane; however, health and environmental concerns over its use have prompted the search for alternative solvents. Mustard oil was extracted with isopropyl alcohol (IPA) to produce an IPA‐oil miscella suitable for industrial applications. Single‐stage extraction resulted in 87.6 % oil yield at a 10:1 (v/w) IPA/flour ratio. Multiple‐stage extraction resulted in higher extraction efficiency with lower IPA use. Four‐stage cross‐current extraction at an IPA/flour ratio of 2:1 (v/w) per stage resulted in 93.7 % oil yield. At 45 °C, a 91.5 % oil yield was achieved with three‐stage extraction using a 2:1 (v/w) IPA/flour ratio. Any changes to the pH of the mixture resulted in reduced oil yield. Water also reduced the extraction efficiency. The azeotropic IPA solution containing 13 % water extracted ~40 % less oil than did dry IPA in both single and multiple‐stage extractions. Some polar compounds were also extracted, including sugars; however, protein extraction was negligible. The protein left in the extracted meal was not degraded or lost during the extraction. The results suggest that IPA is an excellent solvent for mustard oil, but water content exceeding 5 % in the solvent adversely affects the oil extraction and reuse of the IPA.     

Polyacrylamide-reactive styrene/unsaturated polyester microgel composites

Reactive microgels (RM) were prepared by the copolymerization of styrene and an unsaturated polyester in an emulsion of oil (styrene + unsaturated polyester) in water. The adsorption of the unsaturated polyester on the water–oil interface ensured the stability of the emulsion. Furthermore, polyacrylamide (PAAM) crosslinked with RM was obtained by suspending RM particles in an aqueous AAM solution and polymerizing the system at 70°C to obtain a PAAM–RM composite. The extraction experiments of the RM with dioxane and of the PAAM with water indicated the presence of small amounts of soluble PAAM homopolymers and negligible amounts of free RM, the materials being PAAM crosslinked by RM. The extent of swelling of these materials in water decreased with increasing weight ratio of RM/AAM and was independent of the composition of RM. When the final polymerization temperature was increased to 130°C, RM reacted not only with AAM to form a crosslinked polymer, but also with itself to form semi-interpenetrating reactive polymer networks (SIRPN). The extent of swelling of PAAM–RM SIRPN in water was much lower than that of the PAAM–RM material. Membranes were also prepared by hot pressing at 200°C the PAAM–RM and PAAM–RM SIRPN composites. The swelling behavior of these membranes in water, acetone, tetrahydrofuran, acrylic acid, ethyl alcohol, and dioxane, as well as in the mixtures of ethyl alcohol–water, acetone–water, tetrahydrofuran–water, and acrylic acid–water, was investigated. © 1995 John Wiley & Sons, Inc.     

Production of Isopropyl and Methyl Esters from Yellow Mustard Oil/IPA Miscellas

Using an isopropyl alcohol (IPA):flour [volume:weight (ml:g)] ratio of 1.5:1 per stage of extraction resulted in an oil yield of 86.3%. The combined miscella (IPA + oil), which contained 90.6 wt% IPA, 9.8 wt% oil, and 2.1 wt% water, was used as a feedstock for biodiesel production by transesterification. Transesterification of the IPA/oil miscella dehydrated using adsorption on 4Å molecular sieves with 1.2 wt% (based on oil) potassium hydroxide for 2 h at 72 °C converted only 29% of the feed to esters. The addition of methanol (MeOH) resulted in an ester yield of 87%, consisting of 79% methyl ester and 7% isopropyl ester when starting with an IPA:oil:MeOH molar ratio of 146:1:30. By increasing the KOH catalyst to 3 wt%, the ester yield increased to 94%. To increase the ester yield, the miscella was pretreated with sulfuric acid. This resulted in a reduction of the IPA content, the removal of other impurities such as phospholipids, and reduction of the water mass fraction to less than 1%. When IPA was used as a cosolvent with methanol in the transesterification process, a very high ester conversion (>99%) was achieved. The biodiesel produced was compliant with ASTM standards, showing that IPA can be used as a solvent for oil extraction from yellow mustard flour.     

Solvent extraction of oil from soybean flour II— pilot plant and two-solvent extractions

The process of grinding soybeans to a fine flour and extracting the flour with hexane was studied on a pilot plant scale. The crude oil from the pilot plant study had 15 ppm phosphorus and was suitable for physical refining after a light acid pretreatment and bleaching. The refined oil showed a Lovibond color of 1.4 yellow and 0.3 red. The pilot plant study also showed that grinding of the soybeans and the separation of solid from miscella were the most difficult steps in solvent extraction with fine flour. A laboratory study on separation of miscella from meal by aqueous ethanol reduced the hold-up volume, but it did not remove all the miscella. A test with betacarotene showed that only the miscella outside the flour particles was displaced. Aqueous ethanol solutions used as a second solvent extracted additional nontriglyceride materials (primarily phospholipids) from the meal. Also, the free fatty acid content of the oil was increased with aqueous ethanol solution wash. The quality of the extracted crude oil was lowered by using a second solvent, but it had the advantage of needing only one centrifugation to separate miscella from meal.     

The combined application of extrusion and enzymatic technology for extraction of soybean oil

This paper describes a new technological process for soybean oil extraction. The process deals with the combined effect of thermoplastic extrusion of beans and the subsequent action of hydrolytic and proteolytic enzymes in aqueous medium to recover the oil, thus, avoiding solvent application. The thermoplastic extrusion is fundamental for the process, because it facilitates the action of enzymes in oil containing cells, reduces the non-hydratable phosphatides and promotes protein denaturation by reducing the emulsion stability and thus enhancing the oil extraction. The main parameters affecting the oil yield are: the temperature and diameter of the die in the extrusion process, the dilution, the concentration of enzymes and the incubation time of the enzymatic treatment. The highest yield was obtained under the following conditions: extrusion of beans at 90°C and exit die of 6 mm, enzymatic incubation time of 6 h, extruded soy/water dilution ratio 1:10 and concentration of enzyme 6%. With these conditions 88% of the oil were obtained after centrifugation. Moreover, the aqueous enzymatic extraction is easier than solvent extraction, and leads to high value products: a solvent-free meal more suitable for human consumption, a protein hydrolysate that can be used as ingredient for liquid foods and an oil of better quality. The non-hydrolyzed meal contains ca 25% of original soybean protein and the residual oil. The protein hydrolysate in the liquid phase contains ca 75% of the total protein in the original grain with a molecular weight below 20 kDa.     

Growth mechanism and pH-regulation characteristics of composite latex particles prepared from Pickering emulsion polymerization of aniline/ZnO using different hydrophilicities of oil phases

A Pickering emulsion polymerization of aniline, using different hydrophilicities of oil phases, was stabilized by ZnO nanoparticles and performed to synthesize composite latex particles of polyaniline/ZnO. Ammonium peroxydisulfate (APS) was used as an oxidizing agent. The morphologies and growth mechanisms of the resulted composite latex particles were studied. The pH-regulation capacity of the composite latex particles was discussed. When toluene was used as the oil phase, the composite latex particles showed hollow structure, irregular morphology, and hundreds of nanometer in size. It was ascribed to the polymerization of aniline on the interfaces of droplets/water. ZnO nanoparticles, with 50-100 nm in size, acted as surfactants to stabilize the emulsion. When THF was used as an oil phase, the composite latex particles showed spherical morphology and enwrapping ZnO nanoparticles. It was attributed to the homogeneous nucleation of polyaniline in the aqueous phase. ZnO nanoparticles acted as templates for the polyaniline particles. The stability of the Pickering emulsion polymerization was affected by the volume ratio of the oil phase to water. The aqueous solution with pH 3-9 could simply be regulated to about pH 7 by the composite latex particles. It was contributed by the dissolution of ZnO nanoparticles and doping-dedoping of polyaniline in the acidic and alkaline aqueous solutions.     

煤油-司班80-氢氧化钠液膜分离氨基苯酚的研究

对煤油-司班80-氢氧化钠乳化液膜处理氨基苯酚(邻、间、对氨基苯酚)水溶液的过程作了系统研究,当液膜质量百分比组成为煤油95%,Span 80 5%,内水相的质量百分比浓度为2.5%,油内比1∶1,乳水比1∶5(均为体积比),乳水混合搅拌速率为200 r/min,萃取时间为20 min时,对氨基苯酚脱除率可达75%以上。