Source: BIOPLASTIC POLYMERS & COMPOSITES, LLC submitted to NRP
IMPROVED QUALITY SOY-OIL BASED BIODIESEL FUEL- PHASE II
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
SMALL BUSINESS GRANT
Reporting Frequency
Annual
Accession No.
0204188
Grant No.
2005-33610-16116
Cumulative Award Amt.
(N/A)
Proposal No.
2005-03241
Multistate No.
(N/A)
Project Start Date
Sep 1, 2005
Project End Date
Aug 31, 2007
Grant Year
2005
Program Code
[8.8]- (N/A)
Recipient Organization
BIOPLASTIC POLYMERS & COMPOSITES, LLC
(N/A)
MIDLAND,MI 48640
Performing Department
(N/A)
Non Technical Summary
The benefits of biodiesel are well documented. Problems related to fuel quality, filter plugging, injector failure, material compatibility, and fuel economy persist and must be resolved before wide spread use of biodiesel can be addressed. Most of these problems are due to the presence of double bonds in the fatty acid residues, which impacts its oxidation and storage stability. These inherent problems hinder the use of biodiesel in cold temperatures, negatively affect fuel economy, increase particulate emission, and lead to power loss. We have demonstrated a potentially simple and efficient chemical modification whereby the soy-based oil is cleaved at the double bonds, thus eliminating all unsaturation and reducing the overall molecular weight of the fuel. This one-step process is fast, selective and simple which, is expected to provide an economical route to improve the quality of vegetable-based biodiesel fuels. Our process should increase the cetane number, decrease NOx emission and alleviate filter plugging and gumming. Our modification can also extend the low temperature flow characteristics of current biodiesel and thus eliminate cold flow issues. The replacement of 1% of current on-road diesel fuel with biodiesel would require 300 million gallon biodiesel or 215 million bushels of soybeans. The gross impact on the farm economy would be of the order of $800million. At this level a small reduction in imported crude oil would result, however, much higher market penetration would result in significant reductions in imported oil.
Animal Health Component
100%
Research Effort Categories
Basic
(N/A)
Applied
100%
Developmental
(N/A)
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
51118202000100%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
1820 - Soybean;

Field Of Science
2000 - Chemistry;
Goals / Objectives
The overall objective of this phase II proposal is to introduce biofuel derived from the esterification and ozonation of fats and vegetable oils that has better low temperatures flow properties, it is more volatile (lower viscosity), and has higher thermal and oxidative stability than current biodiesels. This phase II effort will be completed in 24 months for a total budget of $298,780 following the tasks described below. Demonstrate ozonolysis process using LowSat methyl soyate The use of LowSat methyl soyate will enhance the cold temperature properties of the biofuel and the ozone treatment will extend its oxidation and storage stability. This objective can be achieved by extending our phase I work and using LowSat soy oils, which contains less than 6% saturated fatty acids. Determine effect of temperature in the ozonolysis reaction We plan to study the effect of temperature on the rate of the reaction. Since ozone has a very high oxidation potential, the reaction of ozone with the double bond is not expected to be greatly affected by the temperature. However, since the solubility of ozone in the reaction mixture is inversely proportional to the temperature, the reaction rate will undoubtedly be affected. . Study the effects of different catalysts We plan to evaluate several common alkali oxides catalysts on the rate and extent of the reaction. We would then determine the effect of particle shape and size (e.g. surface area) and porosity in this reaction. The data will further be used in the design of the process as detailed below. Determine optimal process conditions In order to develop a commercially viable process, we plan to study key process variables in the catalytic ozonolysis reaction. These include reaction kinetics, structure characterization, physical properties, oxidation performance and cold temperature flow. These data are important and will provide the foundation for the rest of the project. As such, we anticipate that a significant amount of time will be spent initially to complete this task. Plant Design To assess the commercial feasibilities of a proposed pilot plant, complete process simulations will be carried out using Aspen simulation package. The procedures for process simulation will involve defining chemical components, selecting an appreopriate thermodynamic model, determining plant capacity, choosing proper operating units and setting up input conditions (flow rate, temperature, pressure, and other conditions). Economic evaluation We plan to use common sensitivity analysis of each process step to identify the major factors affecting the economic viability of the integrated biodiesel ozonation and production facility.
Project Methods
Temperature Effect: Previously, due to safety considerations most of the work was done at low temperature. We found that the catalyst leads to rapid decomposition of the ozonide intermediates, eliminating formation of polymeric peroxides. Thus, we plan to run the ozonolysis process at different temperatures. Catalyst: We have used NaOH and various amines previously. These catalysts are effective but the amines were partially oxidized by the ozone and both catalysts had to be neutralized and removed at the end of the reaction. Preliminary results indicate that metal alkaline oxides such as CaCO3 and MgO are effective catalysts. These heterogeneous catalysts are readily available, relatively inexpensive, easily removed by filtration and easily used in a continuous process. Determine Optimal Conditions: We plan to run all the reactions isothermally. The solubility of ozone in the reaction mixture is inversely related to the temperature, thus, it is expected that ozone mass transfer will be the rate limiting factor. We plan to determine the reaction order with respect to each of the reactants. The reaction rates will be determined from the slope of a plot of the change in the concentration over time. Structure characterization: The reaction product will be analyzed primarily by FTIR, and GC to identify the composition of the reaction products and determine their structure. Particular attention will be given to the composition of the product mixture, residual double bonds and any presence of carboxylic acid species. Physical properties: We plan to test properties that were identified as most critical problems. These problems include: fuel quality standards, cold flow properties, storage stability and exhaust emissions. Since the feedstock in our process is methyl soyate, which has been thoroughly tested, we do not intend to repeat these tests. Instead, we plan to focus on selected tests as follows: Cold temperature properties will be evaluated using cold filter plugging point (CFFP) test. Additionally cloud point, pour point and crystallization onset will be tested. Engine performance will be evaluated to determine any adverse effects by varying the biodiesel content in the fuel and in particular testing for potential clogging and degradation of fuel system performance. It is anticipated that the research work in this area will be done in cooperation with the ME Department at MSU. Plant design: The determination of plant capacity will be based on the reported availability of biodiesel manufactured at Zeeland Farm Services and available waste oil from Michigan State University. We will use continuous stirred tank reactor and a common fill factor for the reactor design. Economic Evaluation will be determined using a small regional plant model to produce biodiesel from LowSat soy oil and recycled cooking oil from MSU. An important advantage of employing a local plant to produce biodiesel from local, low cost feedstocks for local market consumption is reduced cost. Smaller regional plants having lower transportation and feedstock costs will reduce overall cost and boost market share for biodiesel among farmers and others in rural communities.

Progress 09/01/05 to 08/31/07

Outputs
OUTPUTS: Significant Results: We established a continuous catalytic ozonation process to cleave the double bonds in the fatty esters (biodiesel) and convert the new chain-ends to methyl esters. The resulting fuel is thermally stable, oxidatively resistant, more volatile (lower MW), and retains all other desirable properties of Biodiesel. A prototype reactor was built and tested under different process conditions to enable us to produce the fuel with the desired properties under most economical conditions. Some key points related to this process are: Air vs. Oxygen: Ozone is obtained and used from air instead of oxygen, which significantly affect the economics of the process. Compressed, dry air is allowed to flow through the ozone generator to create a 6 wt% ozone. Excess air, including unreacted ozone, is directed from the top of the reactor through an ozone destruction step before releasing back into the atmosphere. Process conditions: Unlike conventional ozonation reactions, which require extremely low temperatures (ca -70C), high dilution in non-flammable solvents and dilute concentrations, our catalytic process is run with no additional solvents at ambient temperatures using cooling water (or ice) to maintain operating temperatures. Furthermore, the process is relatively simple, and the product is recovered with no need for distillation, neutralization, filtration, etc. Catalysis: The catalyst is a low cost calcium carbonate. We have shown that porous, small particles are effective in this process. Further, this heterogeneous catalyst remains effective for many hours of operation and does not require any neutralization and separation steps as is the case with homogeneous catalysts. Elimination of the Unsaturation: Our goal was to eliminate the unsaturation in Biodiesel fuel in the most efficient way by choosing the appropriate process parameters. The results indicate several possible process conditions where all the double bonds are removed. It is apparent from these (and similar data) that the efficiency of the process is a complex function of the operating conditions. Thus, the iodine number is increased through a maximum by either varying the oil flow rate (A) or the gas flow rate (B) at a constant generator power. Hence, the efficiency of the process decreases as the oil flow or air (ozone) flow are increased through a maximum (e.g. residual double bonds) and then increases again at higher flows. The Biofuel was further characterized by FTIR to determine the effect of the process conditions on the structure of the product mixture. By calculating the contribution of the C=C peak (ca 3008 reciprocal cm) to the overall carbon-carbon complex peak in this region, it was possible to determine the extent of the unsaturation present in the product mixtures. The results were identical to the results obtained for the Iodine number and indicate the effect of the processing parameter on the efficiency of the catalytic ozonation reaction. Based on these (and other supporting data) optimal processing parameters were obtained. PARTICIPANTS: No new participant information TARGET AUDIENCES: Target audiences include fuel additives Manufacturers and blenders. At this time there is considerable interest in various coomercial organizations in the U.S., Japan, Australia and Brasil PROJECT MODIFICATIONS: In the course of this work, attention was directed toward fuel oxigenator additives in addition to improving the thermal properties of the Biodiesel. Such fuel additives could serve as oxigentor replacement in gasoline as well as diesel fuels.

Impacts
Accomplishments: The most notable accomplishment is the path to commercialization of this technology through Zeeland Biobased Products, LLC. This newly created company, which is a partnership between Zeeland Farm and Service and BioPlastic Polymers and Composites, is charged with commercialization of the technology that is based on this USDA grant funding. This partnership was secured with a convertible $1.1M loan agreement secured by the state of Michigan through the Michigan Economic Development Corporation (21st century Jobs Fund). The partnership provides a direct link to the largest soybean crushing facility in the state of Michigan, Zeeland Farm Services (This is a family owned Michigan business with over 50 years of service to the agricultural and transportation industries with 150 employees and annual gross sales revenue of over $150 MM. It processes about 26,000 bushels of soybeans per day, operating 24 hours a day, 360 days a year, to produce two primary products: soybean meal and soybean oil. Most notably, in the last few years 90% of the total soybean crop processed in Michigan was pressed by Zeeland). The fundamental chemistry and technology obtained by this grant will be used to commercialize the following products: Fuel Additives for Gasoline and Diesel Bio-Based, Thermally Stable and Biodegradable Lubricants Polyols for Polyurethane and Unsaturated Polyester Resins for Resin Manufacturers At this time there is considerable interest in the lubricant product line potential in the U.S.(Valvoline), Japan (Japan Electric), Australia (Innoplas)and Brasil (Corn Products)and discussions are in hand with two large companies in the U.S. with interest in the other two product line concepts. The design, construction and optimization of the continuous ozonation process are also key achievements. To the best of our knowledge this is the first of a kind continuous ozonation process. Since ozonation employs a powerful oxidizer (e.g. ozone), safety issues dictates special processing conditions, which are not suitable for large batch processes. Furthermore, the continuous process improves mixing and mass transfer in this demanding gas-liquid-solid reaction, it provides excellent heat transfer and safe operating conditions as the actual reaction chamber is relatively small with a short residence time. We have also minimized side reactions and incomplete reduction of the double bonds by optimizing the process conditions. The fundamental understanding of the catalytic ozonation process allowed us to design and built a continuous process. Preliminary economic evaluation indicates that this process is highly profitable.

Publications

  • Biodiesel additive and its preparation method. Narayan, Ramani; Graiver, Daniel; Farminer, Kenneth W. (Board of Trustees of Michigan State University, USA). U.S. Pat. Appl. Publ. (2006), 7pp. CODEN: USXXCO US 2006194975 A1 20060831 Patent written in English. Application: US 2006-363193 20060227. Priority: US 2005-656679 20050228. CAN 145:252050 AN 2006:894282
  • Modifications of soybean oil using novel ozone-based chemistry. Graiver, Daniel; Tran, Phuong; Patrick, Laura; Farminer, Ken; Narayan, Ramani. Department of Chemical Engineering and Material Science, Michigan State University, East Lansing, MI, USA. ACS Symposium Series (2006), 939(Degradable Polymers and Materials), 76-100. Publisher: American Chemical Society, CODEN: ACSMC8 ISSN: 0097-6156. Journal; General Review written in English. CAN 147:164643 AN 2007:514652 .
  • Value-added chemicals from catalytic ozonation of vegetable oils. Graiver, Daniel; Narayan, Ramani. Department of Chemical Engineering and Material Science, Michigan State University, East Lansing, MI, USA. Lipid Technology (2006), 18(2), 31-35. Publisher: PJ Barnes & Associates, CODEN: LITEEI ISSN: 0956-666X. Journal written in English. CAN 145:474496 AN 2006:180656 .
  • Application of Catalytic Ozone Chemistry for Improving Biodiesel Product Performance. Baber, Tylisha M.; Graiver, Daniel; Lira, Carl T.; Narayan, Ramani. Department of Chemical Engineering & Materials Science, Michigan State University, East Lansing, MI, USA. Biomacromolecules (2005), 6(3), 1334-1344. Publisher: American Chemical Society, CODEN: BOMAF6 ISSN: 1525-7797. Journal written in English. CAN 143:29257 AN 2005:312861 CAPLUS .
  • Modifications of soybean oil using novel ozone based chemistry. Farminer, Kenneth W.; Graiver, Daniel; Narayan, Ramani; Tran, Phuong. BioPlastic Polymers and Composites, Okemos, MI, USA. Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2005), 46(1), 282. Publisher: American Chemical Society, Division of Polymer Chemistry, CODEN: ACPPAY ISSN: 0032-3934. Journal; Computer Optical Disk written in English. CAN 143:213319 AN 2005:200988 CAPLUS .
  • Modifications of soybean oil using novel ozone based chemistry. Farminer, Kenneth W.; Graiver, Daniel; Narayan, Ramani; Tran, Phuong. BioPlastic Polymers & Composites, Okemos, MI, USA. Abstracts of Papers, 229th ACS National Meeting, San Diego, CA, United States, March 13-17, 2005 (2005), POLY-157. Publisher: American Chemical Society, Washington, D. C CODEN: 69GQMP Conference; Meeting Abstract written in English. AN 2005:194255 CAPLUS .


Progress 09/01/05 to 08/31/06

Outputs
Objective 1: Demonstrate ozonolysis process using LowSat methyl soyate. Overcoming the poor pour point and low temperature flow of the fuel was addressed by using LowSat soy oils. Conventional soy oil contains about 15 wt % saturated fatty acids in the triglycerides mixture (about 11% pamitic and 5% stearic acids). By comparison LowSat soy oil contains less than 8% of these saturated fatty acids. Catalytic ozonation of LowSat methyl soyate oil gave biofuel having better low temperature characteristics than conventional biodiesel. Key observations were: No crystallization temperature related to the unsaturated fatty acid residue-these acid residues were cleaved by the ozone at the double bond. The heat of crystallization (at -5C) related to the saturated fatty acid residues, which are not affected by the ozonation process, is significantly smaller and can easily be suppressed by additives. The larger number of double bonds in the lowSat oil yielded a lower average molecular weight (and more volatile) products more similar to petroleum diesel than those derived from conventional soy oil. FTIR, GC, and some GC-MS data confirmed the structure of the product from LowSat oil and clearly showed the total amount of double bonds that were reduced as well as the correspondent methyl esters and diesters that were obtained. Objective 2: Determine effect of temperature in the ozonolysis reaction Most of the work using ozone is done at low temperatures (around -56C) whereby the reaction mixture is kept cold by dry ice/acetone mixture. This is a common practice due to safety procedures using ozone. However, we have now confirmed that in the presence of the catalyst in the system, the unstable intermediates quickly react with methanol to yield stable methyl esters. TGA and DSC data showed no accumulation of the peroxides during the reaction. Thus, the process can safely be run at room temperature. It was observed that the solubility of ozone in the reaction mixture increased as the temperature was reduced but the reaction rate was proportional to the temperature. These results are very important as it enable us to run the process at room temperature at a much lower cost compared with identical process that requires continuous cooling. Furthermore, running our catalytic ozonation process at room temperature avoids any risks associated with possible phase separation due to premature crystallization of saturated methyl esters which could plug-up an opening in the reactor.. Objective 3: Effects of different catalysts Different size calcium carbonate catalysts were used and the results show that the rate of the reaction is inversely proportional to the size of the catalyst. However, very fine particle size calcium carbonate (few microns) was difficult to filter out of the reaction. Furthermore, when very large particle size (10 mm range) was used, the reaction was not totally selective and some carboxylic acid functional groups were observed (due to incomplete esterification with methanol). The effect of moisture content and catalyst porosity were also examined. These results allowed us to choose the optimum catalyst for all other planned experiments.

Impacts
Successful completion of the project will produce biofuel from fats and vegetable oils having better oxidative and thermal stability, improved cold temperature flow properties and higher volatility than current biodiesel without adversely affecting the benefits of biodiesel.

Publications

  • No publications reported this period