Fats, Oils and Animal Coproducts Research UnitFats & oils, biodiesel, biopolymers, surfactants, hides & leather, wool, rendered protein
WILLIAM N. MARMER, Ph.D.Research LeaderFats, Oils and Animal Coproducts Research Unitfats & oils, biodiesel, biopolymers, surfactants, hides & leather, woolrendering products
United States Eastern Regional Research CenterDepartment of 600 East Mermaid LaneAgriculture Wyndmoor, PA 19038
Voice: (215) 233-6585FAX: (215) [email protected]://www.ars.usda.gov/naa/errc
AgriculturalResearchService
NP307 (213) BIOENERGY PLANNING AND COORDINATION MEETINGBeltsville, November 29th – December 1st, 2006
ERRC SY’s Who Work on Biodiesel
CWU 1935-41000-066 CWU 1935-41000-067 (bioenergy in part; CWU coded NP306) (coded NP306)
Victor WyattBill Marmer
Tom Foglia Rick AshbyDan Solaiman
EASTERN REGIONAL RESEARCH CENTERWYNDMOOR, PENNSYLVANIAJohn P. Cherry, Center Director
Mike Haas
Research Project 1935-41000-066(Tom Foglia, LS)
PRODUCTION OF VALUE-ADDED LIPIDS, BIOFUELS,AND BIOBASED PRODUCTS FROM FATS AND OILS
Termination date: June 19, 2009
Objective 4 (of 5), Biofuels and additives: Develop alternative processes for producing biodieselfrom intact oils and fats and/or less expensive lipid feedstocks.
Develop methodologies for improving the quality and performanceof biodiesel fuels.
Objective 5 (of 5), Glycerol utilization:Convert glycerol to prepolymers for prospective use in the synthesis of polyesters and polyamides or for use as polydispersants.
glycerol
• Hyperbranched and dendrimeric polymers • Reactive intermediates for production of adhesives, elastomers and foams• Linear condensation prepolymers (2-5 polyester/amide monomers)
Research Project 1935-41000-067(Dan Solaiman, LS)
INTEGRATIVE PROCESSES FOR THE BIOCONVERSION OF FATS, OILS AND THEIR DERIVATIVES INTO BIOBASED MATERIALS AND PRODUCTS
Termination date: July 1, 2009
Objective 1 (of 2): Develop fermentation-based bioconversion systems…that utilize…fats, oils and coproducts as feedstocks to produce value-added biobased products and materials with enhanced properties and minimal environmental footprints
Sub-objective 1.1: Broaden the application expanse of the feedstocksExplore their suitability for use in the fermentative or cell-based production of value-added bioproducts such as water-soluble biopolymers, biosurfactants, chemical intermediates, biolubricants, thickening agents, and bioemulsifiers
Sub-objective 1.2: Implement strain improvement…
Sub-objective 1.3: Explore the use of inexpensive feedstocks and of alternativefermentation techniques such as fed-batch culture
produce new bio-based materialsmaximize the yields of existing technologies glyce
rol
Benchtop fermentorstest engine at ERRC
Biodiesel ResearchResearch capabilities/instrumentation/facilities
GC-MS and HPLC-MS ERRC Pilot Plant: “SUPER” Group support
Biodiesel ResearchProduction from Alternative Feedstocks
veg. oil, animal fat, restaurant grease
Direct (in situ) production from
soy flakes DDGS meat & bone meal
Before Biodiesel Aftertransesterication product transesterification
Soapstock trap grease
Biodiesel ResearchProduction: Process simulation and cost engineering
ASPEN+ and SuperPro Designer Software
Model for refined soy oil Andy McAloon
Biodiesel
BIODIESEL COPRODUCT STREAM
OIL
MEOH
METHANOL
CATALYST
NAOCH3
MEOH -SOL
MEOH1
HTOIL
ES1 -OUT
MEOH2
SEP1T
ES2 -OUT
SEP1 -TOP
SEP1 -BOT
WASH1
SEP2 -BOT
SEP2 -TOP
WBOT
MIXGLY
MGLY2
GLY -H2O
REMEOH
GLYH2O
HCL2
FATTYM
GLYWAT TOEVAP2
GLYCERIN
RWATER
MGLYIN
RWATER2
HD2
RCWATERHTWAT
HCL
H2O
WASH WDESEL
W2
TO-EVAP
RWATER3
HD4
WATER
HD6
REMEOH2
HD3
RWATER4
WDL
RWATER5
VAP
BIODISEL
NAOH
W1
TANK2 TANK3
MIXER
MIXER
ESTER1 ESTER2
SPLIT
SEP2
SEP1
SEP2
SEP2
MIXER
GLYMH2O
DISTILL
SEP
FMSEPEVAP1
RSTOIC
RXN
HX4
MIXER2
CFUGE
EWASH
HX2
HX1
HX5
HX11HX13
HX8
HX7
HX9
HX6
HX12 HX10
VDRYER
RSTOIC
PHTANK
WASH1
SPLIT2
Methanol Alkali
Refined O
il ,
Glycerine
Methanol
Cost modeling:Alkali-Catalyzed Transesterification
min0 10 20 30 40 50
mAU
0200
400
600
800
11.3
81 Analysis of Minor Constituents by HPLCSME andGlycerides Steryl
Glycosides
min0 5 10 15 20 25
mV
100
200
300Total Glycerol by HPLC
SME DAG and Sterols MAG Glycerol
Analysis of Biodiesel Blends
GCB20 Blend
mV
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 min
DieselHPLCB5 Blend
SME biodiesel
Soy oil
Biodiesel Research:Assessment of Fuel Quality
(1) Synthesis and characterization of oligomers:(a) with iminodiacetic acid (b) with dicarboxylic acids
(succinic or azelaic)
(2) Conversion to hyperbranched polymers:Anticipated: some will be water-solubleMost will be soluble in polar organic solvents
Potential uses: adhesives, films, elastomers, surgical applications
Uses for Glycerol Coproduct StreamHyperbranched Polymers from Glycerol
(Victor Wyatt, Tom Foglia)
ON
O
O
O H O
O
N
O
H
OO
N
O
H
O
OO
N
O
O
H
ON
O
O H O
OO O
O
O
O
O
O
OO
OO= glycerol residue
(a) (b)
HN
O OH
O
[ ]x
Microbial ScreeningMicrobial Screening
Fermentation ManipulationFermentation Manipulation
Strain Improvement
Strain Improvement
Sophorolipids
Poly(hydroxyalkanoates)
Glycerol
O
O
O
O
O
HOO
OH
OHHO
HO HO
Biosurfactants
Biopolymersγ-Poly(glutamic acid)
O
R O
[ ]x
Pure (99%)Semi-refined (80%)Crude (40%)
Uses for Glycerol Coproduct StreamGlycerol as a Fermentation Feedstock
(Rick Ashby, Dan Solaiman)
Activities planned for next couple of years
Feedstocks:In situ conversions: continuous processes, assessment of defatted meal as feedGrease applications: improve conversion processes
Enzymatic and solid acid catalysisAnalytical: Adoption of new methods for trace constituents
Partial glycerides, steryl glycosides, residual sulfurRapid determination of blend levelsApplications of methods to identify and eliminate the problems
Glycerol: Production, characterization and application of hyperbranched polymersSynthesis of new reactive monomersFermentation products: effect of feedstockon yields and properties
Biosurfactants and biopolymers Intact fats and oils: use as heating fuel
Biodiesel and Related Biofuels: American Collaborations(other than Pennsylvania)
EASTERN REGIONAL RESEARCH CENTER, WYNDMOOR, PENNSYLVANIAFats, Oils and Animal Coproducts Research Unit
William N. Marmer, Research Leader [email protected]
National Biodiesel BoardJefferson City, MO
Minnesota
Fats & Proteins Res. Found.Alexandria, VA
Runyon IndustriesMemphis, TN
Procter & GambleCincinnati
ADM, Decatur, IL
Moscow, ID
Golden, CO
SRRC, New Orleans
Hagerman, ID
Laughing Stock FarmFreeport, MERalph Turner
NCAUR, Peoria,IL
Biodiesel and Related Biofuels: Pennsylvania Collaborations
The Energy CooperativePhiladelphia Fry-o-Diesel, LLCBiodiesel from Trap Grease
Nadia Adawi
AgComNew Oxford
Soy Diesel AnalysisDan Sharrer
Pennsylvania State UniversityEnergy InstituteState College
Fuel Evaluation & Engine TestingAndré Boehman, Joseph Perez
SpringhouseUtilization of Glycerol
A Biodiesel Co-ProductTom Kauffman
Greater Philadelphia Clean Cities ProgramERRC: Silver Member
Nathalie Shapiro
HarrisburgERRC: Member, Biodiesel Feasibility Working Group
David Bingaman
Changing World TechnologiesPhiladelphia
Renewable Fuels fromAgricultural Co-Products
Brian Appel
EASTERN REGIONAL RESEARCH CENTER, WYNDMOOR, PENNSYLVANIAFats, Oils and Animal Coproducts Research Unit
William N. Marmer, Research Leader [email protected]
Regional Economic Development District Initiatives
Renewable Harrisburg, August 2005Energy Symposium
ERRC: SponsorRuss Montgomery, Organizer
Energy Symposia for SchoolsAbington, 2003-2006
ERRC: PresenterOrganizer: Ellen Bard
Biodiesel Feasibility Study
ReadingM. Rt. UllmanLeola
Direct combustion of fats and oils
PPG IndustriesPittsburghCoproduct
fermentation to industrial products
Biodiesel and Related Biofuels: Worldwide Collaborations
EASTERN REGIONAL RESEARCH CENTER, WYNDMOOR, PENNSYLVANIAFats, Oils and Animal Coproducts Research Unit
William N. Marmer, Research Leader [email protected]
Karl-Franzens University, Graz, Austria
Martin Mittelbach
Nigerian Institute for Oil Palm Research, Benin, Nigeria
Roland Abigor
CIRADMontpellier, FrancePierre Villeneuve
Prof. Paulo A. Z. Suarez, Univ of BrasiliaProf. Ramos,
Univ. Federal do Paranà, Curitiba, Brazil
ARS-FSU Coop. Res. Prgm.GosNIIOKhT
Moscow, Russia
Marcel LieHong Kong University
ГосНИИОХТ
Int’l Congress on BiodieselVienna, Nov. 2007
Mike Haas, General Chair