Progress 09/01/06 to 08/31/08
Outputs
OUTPUTS: Outputs. Advanced Materials and Processes (AMP) conducted and analyzed experiments and developed novel high yield, high efficiency processes for degumming, decolorizing, neutralization, and washing of vegetable oils and vegetable oil miscella using a static Fiber Reactor (FR). The FR eliminates emulsions and does not require centrifuges. The neutralization and washing processes were also applied to fats and cooking oil. AMP also visited/surveyed 1) soybean oil, cottonseed oil, and biodiesel processing plants, 2) manufacturers of processing plants, 3) industry consultants, and 4) manufacturers of fiber processors for the petroleum industry. AMP surveyed fiber and pump suppliers. Events. Conferences and symposia attended included the American Oil Chemists Society annual meetings (2007-8), the American Chemical Society national meetings (2006-8), and a National Biodiesel Conference (2007). A workshop in vegetable oil processing at the 2007 AOCS meeting was attended. Technology exchange events occurred with ADM; TechnoChem; InstaPro; Rapid Energy Services; AgBioEnergy; Valley COOP Oil Mill; Crown Iron Works; Desmet Ballestra; and Frazier Barnes & Associates Consulting. Products. Databases were created for research and development investigating the effect of the following on processes: oil viscosity; oil:caustic flow rates/ratios; ability of co-solvents to dissolve fatty acid salts/gums; caustic utilization; effect of time/temperature; washing effectiveness; oil losses; and reactor length. FRs constructed included 1/2" o.d. x 9" to 60" and 1" o.d. x 24". Fibers used included 316 stainless steel, 8 and 12 micron diameter. A one inch o.d. FR with 8 micron glass fibers was used to wash product. One inch and three inch o.d. separators were constructed. Collaborations fostered by the project included those with ADM; Rapid Energy Services; AgBioEnergy; and Valley COOP. Technology generated by the project includes new ethanol extraction processes to degum, neutralize, bleach and wash vegetable oils/miscella and fats. This technology includes the ability to accomplish the following: 99+% removal and isolation of gum fraction with 0.14% oil loss; Large reduction in color; 99+% removal and isolation of FFA fraction with 0.18% oil loss; Effective water wash of miscella, instant clean separation of phases (No rag layer); Total oil loss of only ~0.3% compared to typical 1-1.5% oil lost in soap stock; Fast processing without dispersions; Virtually instantaneous separation of the two phases; Elimination of soap stock (5% by-product stream composed of gums/soap/oil/water); Production of gum and FFA concentrates; Reduced water pollution; Simplicity of operation; Low temperature, low pressure, low maintenance, static contacting process; and Low energy requirement (eliminate centrifuges) Dissemination. Presentation of results at AOCS annual meetings (2007-8) and Industrial Oil Products Division Luncheon (2008); and at ADM; TechnoChem; InstaPro; Rapid Energy Services; AgBioEnergy; Valley COOP Oil Mill; Crown Iron Works; Desmet; and FBA. Outreach activities to current and potential partners and collaborators are continuing. PARTICIPANTS: (1) principal investigator/project director: John L. Massingill, Jr. (2) Post-doc Student: Pulin Patel (3) Graduate Student: Maheedhar Guntupalli (4) Undergraduate student: Nathan Raemsch Partner Organizations: Texas State University; Tennessee Technological University; ADM; Rapid Energy Services; TechnoChem; Bekaert Steel Collaborators: Chang Ji and Linette Watkins, Texas State University Department of Chemistry and Biochemistry; Holly Stretz, Tennessee Tech Training or professional development: Postdocs, Graduate students, and Undergraduate students were trained in the construction and operation of a fiber reactor, including chromatographic analyses. Process chemistry, continuous operation, and mass balance around an operating reactor. TARGET AUDIENCES: Target audiences: Vegetable oil, fat, and biodiesel processors; Manufacturers of process equipment; Farmers; Farm cooperatives. Efforts: informal laboratory instruction and experiential learning opportunities. PROJECT MODIFICATIONS: Hurricane Dolly has caused a delay in the pilot plant demonstration planned for Valley COOP Oil Mill in Harlingen, TX in the summer of 2008. The pilot plant will be rescheduled.
Impacts
Process intensification is a major outcome of the Fiber Reactor processes for biorefining vegetable oils and fats. Process intensification that impacts product yield; capital efficiency, energy efficiency, and water utilization rates. The impact of this is that less equipment is needed and less energy is needed to run the remaining equipment. The FR degum/bleach/neutralize/wash processes impacts result from its high mass transfer efficiency and instantaneous separation of phases right out of the reactor. The large interfacial area, the minute diffusion distance, and the continuous renewal of the fiber phase combine to yield mass transfer efficiencies far greater than possible with conventional treatment. Efficiencies that have the following impacts: Improved high value oil yields; Reduction/elimination of lower value byproduct soap stock; Improved FFA quality; Reduced energy consumption by replacing centrifuges with static FR and eliminating multiple stages; Reduced capital cost of new plants by replacing multiple reactors and centrifuges with appropriately sized static Fiber Reactors; Reduced maintenance by replacing centrifuges and their moving parts with static FRs with 100% onstream time between turnarounds, no routine maintenance; Reduced oil pollution in plant waste water by elimination of aqueous phase carryover - because the aqueous phase clings to the fibers, rather than dispersing into the hydrocarbon phase, carryover is virtually eliminated; Minimized water treatment costs; Reduced water consumption; and Potentially isolate phytonutrients for additional revenue. AMP developed fundamental applied knowledge of the behavior and operation of the Fiber Reactor in biorefining processes that were published. The Fiber Reactor is a game changer for two phase chemical processes and is expected to impact the biorefining, biodiesel, specialty chemical, and pharmaceutical industries from now on.
Publications
- John L. Massingill, Jr., Pulinkumar N. Patel, Maheedhar Guntupalli, Claude Garret, and Chang Ji, 2008, High Efficiency Nondispersive Reactor for Two-Phase Reactions, Org. Process Res.Dev.12, 771.
- John Massingill, High Efficiency Non-Dispersive Reactor for Processing Oils and Fats, INFORM, 2008, Vol. 19, (9) 637. John Massingill, Maheedhar Guntupalli and Nathan C. Raemsch, High Yield, High Efficiency Bio-Refining, 97th AOCS Annual Meeting, St. Louis, MO, 2006.
- John L. Massingill Jr., Maheedhar Guntupalli, and Nathan C Raemsch, Non-Dispersive Reactors: The Next Wave in Chemical Processing, Process Intensification Symposium, Division of Industrial & Engineering Chemistry, The 232nd ACS National Meeting, San Francisco (2006)
- John L. Massingill Jr., Pulin Patel, Maheedhar Guntupalli, and Nathan C Raemsch, High Efficiency Biorefining and Biodiesel Manufacturing, 98th AOCS Annual Meeting, Quebec City, 2007.
- John Massingill, Pulin Patel, and Austin Shelton, Neutralization and Degumming in a Fiber Reactor, Poster, 99th AOCS National Meeting (2008).
- John Massingill, Pulin Patel, Nathan Raemsch, and Austin Shelton, Ultra-efficient Biodiesel Processing, 99th AOCS Annual Meeting, (2008).
|
Progress 09/01/06 to 08/31/07
Outputs
The purpose of this SBIR Phase II project is to commercialize a novel high yield, high efficiency bio-refining process for degumming and neutralization of vegetable oils/animal fats that eliminates emulsions and does not require centrifuges. Notable features of the novel FIBER processes compared to current processes are: Fast processing without dispersion; Virtually instantaneous separation of the two phases; Degumming; Neutralization; Reduced soap stock formation-- improved oil and free fatty acid yield; Reduced water pollution; Simplicity of operation; Low temperature, low pressure, low maintenance operation; and Low energy requirement. The goal of this project is to convert Fiber technology from petroleum processing to bio-oil refining which requires adapting the approach for higher viscosity of vegetable oil, hydrolytic instability of the triglycerides, higher level of acidic impurities, poor solubility of fatty acid salts in water, and poor solubility of
phospholipids. Research Description: Fiber contactors one-half inch i.d. by 4"-36" long were built from stainless steel tubing, fittings, and fibers. Oil flow rates were typically 10 mL/min. The results were scaled up to one inch o.d. by 12" and 24" s.s. pipe units, which had typical flow rates of 50 mL/min. Clear 1" PVC pipe contactors with glass fibers were made for washing operations. Processes evaluated and being evaluated are: Neutralizing soybean miscella (5-70% hexane), Neutralizing degummed soybean oil, Neutralizing and degumming crude soybean oil, Neutralizing chicken fat and tallow in hexane, Research findings: Neutralization of miscella (70% hexane-30% oil) is highly efficient with 94+% free fatty acid removal at stoichiometric caustic, 97+% removal at 2% excess caustic, and 99+% removal at 6% excess caustic. Tertiary miscella with only 15% hexane can also be handled efficiently. High levels of free fatty acids (16+% in the oil) can be handled. Processing of neat oil is
less efficient and may require a pressurized unit to allow higher temperature operation to reduce oil and fat viscosity. Extraction processes have successfully degummed crude vegetable oil (93+% removal) and studies to optimize degumming are in progress. Both degumming and neutralization have essentially zero separation time. In Phase I, AMP identified solubility of soaps, such as sodium stearate, in the constrained aqueous phase as the limiting critical parameter in this process and now routinely uses co-solvent ethanol to overcome this limitation. Scale-up: Neutralization was scaled up to the one inch reactor without difficulty. Commercialization: Negotiations are in progress to form a joint venture to continue R&D, demonstrate technology in a pilot plant (eight inch Fiber unit, one million pounds/yr rate), manufacture hardware, and market the technology. Patents and Inventions. United States Patent Application 20060157411, Massingill; John Lee (July 20, 2006). "Use of fiber film
reactors to effect separation and reaction between two immiscible reaction components".
Impacts
Anticipated yield improvements for soybean oil processing include: 0.2-1.5% free fatty acids (FFA) recovered in a FFA concentrate and 1-1.5% oil yield improvement through elimination of soapstock emulsions. A process cost savings for the soybean industry of about $900 MM/yr for using FFC technology as follows: Fiber units have the potential to reduce vegetable oil degumming/neutralization /washing costs by an order of magnitude or more; A highly efficient process can deliver a yield improvement of up to 3% by a less energy intensive, environmentally friendly process; Being able to treat oil efficiently without forming dispersions will result in reduced water clean-up costs and less water pollution; Replacing multiple high speed centrifuges with static Fiber units will make a significant impact on energy cost reduction. The static contactor is inherently simpler and is less expensive to operate and maintain than high speed centrifuges and uses no additional electricity.
Maintenance is virtually nil for FFC operations. Payback Period. A Fiber unit is expected to cost about as much as a centrifuge. The four centrifuges in the refining process are estimated to cost $500,000 each and each consumes about $250,000/yr of electricity for operation at industrial rates of about $0.04/kWh. Replacing 4 centrifuges with three FFC units would have an energy saving payback period of about 18 months for electricity alone.
Publications
- No publications reported this period
|