Source: SARTEC CORPORATION submitted to
CONTINUOUS BIODIESEL PRODUCTION FROM MULTIPLE SOURCE FEEDSTOCKS USING ZIRCONIA CATALYST
 
PROJECT DIRECTOR: McNeff, C. V.
 
PERFORMING ORGANIZATION
(N/A)
SARTEC CORPORATION
ANOKA,MN 55303
 
NON TECHNICAL SUMMARY: Biodiesel is a renewable petroleum diesel substitute whose use can improve air quality and help combat global warming. We propose to test the feasibility of using a novel and innovative process to synthesize biodiesel that could change the economics and commercial practices of the biodiesel industry. Our research will evaluate the feasibility of using a novel, highly efficient heterogeneous zirconia-based catalyst in a continuous flow packed-bed reactor for synthesizing biodiesel from a variety of feedstocks. The surface chemistry of zirconia is dominated by Lewis acid-base chemistry, which will allow for the controlled adsorption of acid or base moieties that can be used for catalysis of both esterification and transesterification reactions. In this research, both base, acid and unmodified forms of zirconium dioxide will be evaluated at elevated temperature and pressure for efficient, continuous transesterification of triglycerides (TGs) and esterification of free fatty acids. Phase I research will test the capability of this catalyst to produce biodiesel using a variety of feedstocks (i.e. soybean oil, algae oil, yellow grease, beef tallow and acidulated soapstock) without significant catalyst deterioration over extended periods of use. Furthermore, we will purposefully foul the catalyst with dirty feedstocks and evaluate if the catalyst can be regenerated by pyrolysis of adsorbed organic matter in order to restore its original catalytic activity. If successful, we believe this research will overcome the most significant limitations currently experienced by the biodiesel industry, namely the difficulty in using inexpensive feedstocks that contain high levels of free fatty acids, the necessity to continuously add catalyst to the reaction (in either batch or semi-continuous production modes), resulting in the need to dispose of waste products harmful to the environment and eliminating the need for extensive washing of the biodiesel with water. If successful the proposed fixed bed catalysts should stimulate use of inexpensive feedstocks, thereby lowering the cost of biodiesel production significantly. In summary, a successful phase I project will demonstrate the feasibility of using zirconia at elevated temperature and pressure to change the economics of biodiesel production and expand its role as a renewable, environmentally friendly energy source.
 
OBJECTIVES: Zirconia (zirconium dioxide) is a chemically and thermally stable transition metal oxide widely used in a variety of metallurgical and chromatographic applications. This metal oxide is chemically stable over the entire pH range and at elevated temperatures and pressures. Chemically, its surface is dominated by Lewis acid-base chemistry. The use of various metal-oxides including titania- and zirconia-based catalysts for esterification and transesterification has been previously reported. However, all of the previously cited work used high surface area, metal or metal oxide powders which are unsuited for packing in a continuous flow reactor. There have been no reports describing the use of modified spherical porous zirconia microspheres in a fixed bed reactor operated at high temperature and pressure in a fixed bed reactor, as we propose in this Phase I feasibility research. Our approach will differ significantly from all prior work by drawing upon our extensive expertise in the production of thermally and chemically stable porous transition metal oxide (zirconia) microspheres that can be used to produce a continuous flow reactor. The catalytic materials we propose to use will have a well defined pore structure and be stable under both high pressure and high temperature conditions. A careful survey of the current scientific literature and published patents reveals that the approach we propose to study in Phase I, specifically the use of spherical porous microspheres of modified and unmodified zirconia that can withstand high temperature and pressure conditions as fixed bed catalysts for biodiesel production, has not been reported before. We anticipate demonstrating the feasibility of using these mechanically and thermally stable catalysts for the continuous production of biodiesel that can meet the accepted ASTM fuel standards and justify scale up to large-scale biodiesel production in Phase II research. The main Phase I research objectives will be four-fold: 1. Test the feasibility of using porous zirconia microspheres (with and without acid or base pre-use modification) for continuous fixed-bed production of biodiesel from refined and used lipid feedstocks. 2. Explore the effect of temperature and pressure upon production rate and byproduct formation. 3. Optimize the production parameters of biodiesel to meet ASTM specifications while maintaining high production rates using the newly developed fixed-bed continuous flow reactor. 4. Demonstrate the feasibility of regenerating a zirconia-based catalyst to its original activity after the fixed-bed reactor has been used purposely fouled.
 
APPROACH: Production and purchase of substrate porous zirconia particles: At the beginning of the project, porous zirconia particles will be prepared as a single large batch of porous zirconia particles that will be used for all subsequent studies. The use of a single batch of substrate zirconia will allow for the direct comparison of data obtained from different surface modifications and eliminate any variations due to the substrate particles. Surface modification of zirconia particles to produce base and acid modified surfaces: The preparation of acid and base modified porous zirconia catalysts will be performed using published methods of synthesis. Packing of modified zirconia particles into high pressure and temperature stable flow reactors: Different porous zirconia-based reactors will be produced by packing the particles into all-stainless steel column hardware outfitted with stainless steel frits. The particles will be packed into stainless steel high performance liquid chromatographic column hardware using a downward slurried method. When the pressure has been fully released, the column will be disconnected from the apparatus and the frit and end fitting will be attached to the inlet to complete construction of the reactors. Initial testing of modified zirconia particles: Initially the different types of zirconia catalyst will be evaluated to see if they show a potential for the transesterification of triglycerides to the fatty acid methyl esters under initial testing conditions. The purpose of these initial experiments is to determine feasibility and select the most promising materials for further optimization of reactor conditions with the ultimate goal of selecting the best material and determining conditions to produce biodiesel fuel that meets or exceeds the ASTM standards for biodiesel (B100) fuel. Initial testing of the catalysts will be performed using refined soybean oil and methanol. Use of optimized conditions for biodiesel production from different feedstock lipids: After the optimized conditions have been determined for each catalyst, different feedstocks will be tested (both crude and refined stocks). Biodiesel production under each condition will be analyzed and glycerol production will be monitored. Regeneration of reactor catalyst and report preparation: An important goal of this project will be to demonstrate that the zirconia-based catalyst can be regenerated to its original performance after it has been purposefully fouled with dirty feedstock lipids and performance has likely decreased from its original production efficiency. A significant advantage of using a zirconia-based catalyst is that it is chemically and thermally stable so very aggressive cleaning conditions may be used without degradation of the porous particles.
 
CRIS NUMBER: 0213571 SUBFILE: CRIS
PROJECT NUMBER: MINK-2008-00176 SPONSOR AGENCY: NIFA
PROJECT TYPE: SMALL BUSINESS GRANT PROJECT STATUS: TERMINATED MULTI-STATE PROJECT NUMBER: (N/A)
START DATE: May 1, 2008 TERMINATION DATE: Dec 31, 2008

GRANT PROGRAM: SMALL BUSINESS AND INDUSTRY GRANTS
GRANT PROGRAM AREA: Small Business

CLASSIFICATION
Knowledge Area (KA)Subject (S)Science (F)Objective (G)Percent
511741020002.1100%

CLASSIFICATION HEADINGS
KA511 - New and Improved Non-Food Products and Processes
S7410 - General technology
F2000 - Chemistry
G2.1 - Expand Domestic Market Opportunities


RESEARCH EFFORT CATEGORIES
BASIC (N/A)%
APPLIED 100%
DEVELOPMENTAL (N/A)%

KEYWORDS: biodiesel, alternative and renewable energy, zirconia, catalyst,; fixed-bed reactor, transesterification, esterification, biofuel,; diesel oxygenate

PROGRESS: May 1, 2008 TO Dec 31, 2008
OUTPUTS: During the course of this research project the Mcgyan Process was demonstrated to a wide variety of groups, mainly through laboratory tours conducted by Drs. McNeff and Yan. Two congresspeople from the State of Minnesota visited our laboratory facility. Various Minnesota state and local representatives came to see the process in action. Lay people and students from across the country and business people from around the world also visited SarTec Corporation to learn more about this exciting new technology. In addition, various brochures, publications and electronic media (such as a DVD tour of the facility) were created to disseminate the outcomes of this important research. PARTICIPANTS: Dr. Clayton V. McNeff (Principal Investigator) oversaw all research performed under this project. Dr. Bingwen Yan (Senior Scientist) supervised both laboratory technicians and performed all key tasks related to the project including the preparation of the zirconia-based catalyst reactors. Sharon Franklin (Senior Laboratory Technician) conducted the analysis of biodiesel samples (gas and liquid chromatography). Guo Xiong Liu (Laboratory Technician) conducted experiments described in the project narrative using the zirconia-based catalyst reactors. TARGET AUDIENCES: Not relevant to this project. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.

IMPACT: 2008-05-01 TO 2008-12-31 During the course of this research project we successfully demonstrated the feasibility of using fixed bed porous zirconia-based catalytic reactors for the continuous production of biodiesel (using inexpensive high FFA content feedstocks) that passed all ASTM D 6751 specifications. The five main findings of the project were: 1. We demonstrated the feasibility of using porous zirconia microspheres (with and without acid or base modification) for continuous fixed-bed production of biodiesel from crude and refined lipid feedstocks. 2. We documented the effect of temperature and pressure upon production rate and product formation. 3. We optimized the production parameters of biodiesel to meet ASTM D 6751 specifications while maintaining high production rates using the newly developed fixed-bed continuous flow reactor. 4. We demonstrated that different feedstocks (both crude and refined stocks) may be used including: refined canola oil and sunflower oil, corn oil, yellow grease and beef tallow. 5. We documented the feasibility of regenerating a zirconia-based catalyst to its original activity after the fixed-bed reactor has been used and purposely "fouled". These findings demonstrate that this technology has the potential to significantly lower the overall cost of biodiesel production in the United States with no significant production of waste products during the synthesis. In Phase II research we will scale up the work demonstrated in Phase I in order to demonstrate biodiesel production at a pilot plant scale using inexpensive feedstocks that typically contain high free fatty acid content. Upon completion of successful Phase II research we believe this novel technology will change the economics of biodiesel production and expand the role of biodiesel as a renewable, environmentally friendly energy source by making it more cost competitive with petroleum-based diesel fuel.

PUBLICATION INFORMATION: 2008-05-01 TO 2008-12-31
C. McNeff, B. Yan, A. Gyberg, B. Krohn, T. Hoye, 2008, A Novel Continuous Catalytic System for Biodiesel Production, 99th AOCS Meeting, IOP 2: Alternative Feedstocks Section (also see http://wcco.com/energy/algae.energy.independence.2.731183.html; http://www.wccoradio.com/topic/play_window.phpaudioType=Episode&audi oId=3033275; and http://www.mn2020.org/index.aspType=B_BASIC&SEC=%7B6AB5EF94-CA10-4A6 D-B9D9-686B8FE40772%7D&DE)

PROJECT CONTACT INFORMATION
NAME: McNeff, C. V.
PHONE: 800-472-7832
FAX: 763-421-2319