Sevim_Erhan Use of Vege Oils in Biobased Products

7/30/2019 Sevim_Erhan Use of Vege Oils in Biobased Products

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The Use of Vegetable Oils inThe Use of Vegetable Oils inBiobasedBiobased ProductsProducts

SevimSevim Z.Z. ErhanErhan

National Center forNational Center forAgricultural UtilizationAgricultural Utilization

ResearchResearchUSDA/ARS, Peoria, ILUSDA/ARS, Peoria, IL


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Agricultural Research ServiceAgricultural Research Service

Area OrganizationArea OrganizationNorth AtlanticNorth Atlantic

AreaArea

MidwestMidwestAreaArea

South AtlanticSouth AtlanticAreaArea

Mid SouthMid SouthAreaArea

SouthernSouthernPlains AreaPlains Area

PacificPacificWestWest

AreaArea

NorthernNorthernPlains AreaPlains Area

Peoria, IllinoisPeoria, Illinois

BeltsvilleBeltsvilleAreaArea


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The NCAUR Mission

Invent new usesof agricultural commodities forindustrial and food products

Develop new technologyto improveenvironmental quality

Provide technical supportto Federal regulatoryand action agencies


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NCAUR Research Units

Bioproducts and Biocatalysis Cereal Products and Food Science Research Crop Bioprotection Research Fermentation Biotechnology Research

Food and Industrial Oils Research Microbial Genomics and Bioprocessing Research Mycotoxin Research

New Crops and Processing Technology Research

Plant Polymer Research


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Food and Industrial Research UnitUSDA, ARS, NCAUR, Peoria, IL

Chemical Systems for the conversion of vegetableoils to industrial products.

Vegetable oil-based alternative to diesel fuels,extenders and additives

Optimizing flavor quality and oxidative stability of

commodity vegetable oils Functionality, structure, and quality interactions in

food oil systems


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Chemical Systems for the Conversionof Vegetable Oils to Industrial Products

Investigate and develop economically feasible new industrialproducts from vegetable oils (with emphasis on soybean oil)

and thus, expand their domestic and export markets.

Objective:

Modifying chemical and physical properties of vegetable oilsto enhance their use as additives, or major components of:Lubricants, Inks, Surface Coatings, Fuels, Polymers,Composites, Surfactants and other Industrial Chemicals

Focus:


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World Oilseed Production

Palm Kernel 2%Copra 2%

Sunflowerseed 7%

Peanut 10%

Cottonseed 11%

Rapeseed 12% Soybeans 56%


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World Vegetable OilConsumption

Palm 27%

Olive 3%

Sunflowerseed

10%

Peanut

5%

Rapeseed

15%

Soybeans 29%

Palm Kernel 3%

Coconut 4%Cottonseed 4%


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World Soybean Production

United States 45%Brazil 21%

Other 5%

Paraguay 2%India

3%

China

15%

Argentina

15%


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U.S. Soybean Oil Consumption

Salad or

cooking oil

47%

Baking and Frying fats

36%

Margarines

12%

Other edible

Products


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Biobased Products

Biobased products are industrialproducts (including fuels but notfood or feed) made from renewable

agriculture and forestry resources.


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Potential Benefitsof Biobased Products

New markets for agriculture commodities

Add value to commodities/wastes

Economic development

Reduced dependence on imports

Environmental advantages


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Issues with Biobased Products

Cost

Performance

Availability

Energy efficiency


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E.O. 13101 Greening theGovernment Through WastePrevention, Recycling, and

Federal Acquisition (Sept. 1998)


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E.O. 13134 Developing andPromoting Biobased ProductsAnd Bioenergy (August 1999)

Stimulate the creation and early adoptionof technologies needed to make biobased

products and bioenergy cost-competitivein large national and international markets

Goal of tripling U.S. use of biobasedproducts and bio-energy by 2010


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Biomass Research &Development Act of 2000

Improve interagency coordination and focusthe federal R&D efforts on conversion ofbiomass into biobased products

Establishes Technical Advisory Committeeand Biomass R&D Board

Authorizes additional funding at USDA forbiomass R&D Initiative


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Biomass Industrial Products:Priorities for Research andCommercialization (NRC, 2000)

Proposed intermediate- and long-term targetsfor adoption and use

Recommended increased Federal R&D support

Recommended research priorities for biology

and engineeringEnvisioned government-industry partnership


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USDA Biobased Products & BioenergyCoordination Council (BBCC)

1995, Secretary of Agriculture created NewUses Coordinating Council

1997, Renamed Biobased ProductsCoordination Council

2002, Biobased Products and BioenergyCoordination Council established byDepartmental Regulation


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USDA working group on biobased products

& bioenergy

13 USDA Agencies/Offices

Coordinate USDA activities

Work with other Federal agencies, public andprivate sector

Research priorities and policyrecommendations to Secretary


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Biobased Products & Bioenergy Initiative

http://www.ars.usda.gov/bbcc

Pertinent Websites

http://www.bioproducts-bioenergy.gov/

USDA Biobased Industrial Products Site

http://www.usda-biobasedproducts.net

ARS National Programs 306 & 307

http://www.nps.ars.usda.gov/


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Lubricants


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World Lubricant Consumption

Industrial Uses 2.25 billion gallons

Automotive Uses: - 5.63 billion gallons


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Industrial Lubricants

Lubricant market in the U.S. is about

$8 billion

More than 90% of all lubricants are

based on petroleum

The demand for biodegradable lubricants

is expected to grow at about 10% annualrate


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ConcernsEnvironmental

Pollution Air, Water and SoilEcological Balance

Handling and ToxicityHealthContamination

DisposalBiodegradabilityCost


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Primary Functions of Lubricants

Reduce friction and minimize wearDissipate heat

Disperse depositsInhibit rust/corrosion

Seal critical contact joints


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Consumption of Lubricants

~ 20 M tons / year in US

Chain saw lubricantsDrilling oils

Food industry fluidsGear oilsGreasesHydraulic fluids

Motor Oils

OtherHydraulicFluids

Commercial Uses of

Biodegradable Lubricants

Marine lubricantsPump oils

Railroad lubricantsShock absorber fluidsMould release oilsTwo stroke engine oils

Biodegradability is delivered by basestock,not additives


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Basestock: 80-100% of Lubricant

Specifications?

Lubricant

Additives

Screening Protocol

Basestock

No

Yes

Bench/field testing

Meets specs?

No

Yes

Flowchartof Lubricant

Development

Screeningprotocolsdepend onapplication


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Properties to be Included inBasestock Screening

BiodegradabilityViscosityLow temperature solidification

Deposit formingVolatilityOxidative stability

Hydrolytic stabilitySolvency, miscibilitySeal compatibility

Special requirements

(e.g. electricalconductivity,

transparency, density,heat conductivity etc.)


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Properties to be Controlled byAdditives

Wear protectionCorrosionFoaming, air release

Shear stabilityDemulsibility, water rejection

Friction, tractionAdhesionSurface tension

Special requirements(e.g. color, purity,Magnetic properties, etc.)


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Vegetable Oils as LubricantsVegetable Oils as Lubricants

Low volatilityLow volatility

Advantages:Advantages:

Due to high molecular weight of the triglyceride moleculeDue to high molecular weight of the triglyceride molecule

Good boundary lubrication propertiesGood boundary lubrication propertiesPolar ester groups are able to adhere to metal surfacesPolar ester groups are able to adhere to metal surfaces

Excellent viscosityExcellent viscosity temperature characteristicstemperature characteristics

Narrow range of viscosity changes with temperatureNarrow range of viscosity changes with temperature

BiodegradabilityBiodegradability

Compatibility with mineral oil and additive moleculesCompatibility with mineral oil and additive molecules

CH3(CH2)4 (CH2)7O

O

CH3(CH2)7 (CH2)7O

O

CH3(CH

2)4

(CH2)7 O

O


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Vegetable Oils as LubricantsVegetable Oils as Lubricants

Poor oxidative stabilityPoor oxidative stability

Disadvantages:Disadvantages:

Due to the presence ofDue to the presence of bisbis--allylicallylic protonsprotons

Poor low temperature fluidityPoor low temperature fluidity

Due to high molecular weightDue to high molecular weight

Hydrolytic instabilityHydrolytic instabilityDue to the presence of ester functionalityDue to the presence of ester functionality


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Rate of Oxidation

C C CC O O OO

Allylic

Methylene

DoublyAllylic

Methylene

Stearic (18:0)1

Oleic (18:1)10

Linoleic (18:2)100

Linolenic (18:3)200

Rate

O O OO


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General Solutions to the ProblemsGeneral Solutions to the Problems

Modification of vegetable oilsModification of vegetable oils

Chemical modificationsChemical modifications

Genetic modificationsGenetic modifications

AdditivesAdditives

Antioxidants, pour point depressantsAntioxidants, pour point depressants

BlendingBlending

With diluents or functional fluids to achieve enhancedWith diluents or functional fluids to achieve enhancedperformanceperformance


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Chemical Modification

Converting the C=C bond into epoxy group

Attaching branched strructures at epoxy sites

of triglyceride chains


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Triacylglycerol Structure of Vegetable Oil

(Soybean Oil)

O

O

O

O

O

O

CH3

CH3

CH3

epoxidation

O

O

O

O

O

O

CH3O

O

CH3O

OCH3

O


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H2O, HClO4 (H+)

Reflux, 100 oC, 48 hrs

HC CH

OH OH

CH

O

HC

Epoxy Ring Opening and Di-hydroxylation


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HC CH

OH OH

Pyridine, room temperature

Stir for48 hrs

HC CH

OR ORanhydride,

Reaction with Anhydride

to Form Diester Derivative

(CH3CO)2O

[CH3(CH2)2CO]2O

[CH3(CH2)4CO]2O

R = COCH3

R = CO(CH2)2CH3

R = CO(CH2)4CH3


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BF3HC CH

O O

CHHC

BF3

+

-

R O

OO

R

BF3-

O

CHHC

O

RO

O

R+

O

OR

HC CH

_BF3 O

OR

Catalytic Ring Opening and Reaction

with Anhydride


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161.3177.4

135.7

140.1

171.9

SBOESBO

OAc-SBO

OBu-SBO

OHx-SBO

Start Temperature(Ts)C)

Test oils

Pressurized Differential Scanning Calorimetry of theOils @ 10C/min.; Air at 200 Psi; Constant Pressure

178.2203.9

165.1

170.2

196.6

Onset Temperature(To)C


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-18OHx-SBO

-3OBu-SBO

-3OAc-SBO0ESBO

-6SBO

Pour point (C)Test oils

Pour Point of the Oils - ASTM D 97


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-3920 : 801OHx-SBO

-300 : 1001OHx-SBO-180 : 1000OHx-SBO

Pour point(C)Diluent : oil(ratio)PPD(%)Test oil

Pour Point Improvement with Additive and Diluent


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Conclusions

Chemical modification of vegetable oil is achievedwith significant improvement in thermo-oxidative

and low temperature stability Basic vegetable oil structure is retained with high

biodegradability

The methodology can be applied to any vegetable oilwith triacylglycerol structure The modified oil can be used as an industrial base

fluid; the chemical technology being cost effective

has a good potential for commercial production This technology has been patented, U.S. patent

6,583,302 (2003)


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Base FluidsBase Fluids

Soybean oilSoybean oil alkali refined (SO)alkali refined (SO)

HighHigh LinoleicLinoleic Soybean Oil (Soybean Oil (HLSOHLSO))

Mid Oleic Soybean Oil (Mid Oleic Soybean Oil (MOSOMOSO))

High Oleic Soybean Oil (High Oleic Soybean Oil (HOSOHOSO))

PolyalphaolefinPolyalphaolefin ((PAOPAO))


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AdditivesAdditives

Antioxidant additiveAntioxidant additive

AlkylatedAlkylated diphenyldiphenyl amine (AO1)amine (AO1)

ButylatedButylated hydroxyhydroxy toluene (AO2)toluene (AO2)

Mixture ofMixture of alkylatedalkylated phenol/phenol/dithiophosphoricdithiophosphoric acid ester/acid ester/diphenyldiphenyl amine (AO3)amine (AO3)

ZincZinc diamyldiamyl dithiocarbamatedithiocarbamate (AO)(AO)

AntiwearAntiwear additivesadditivesAntimonyAntimony diakyldiakyl dithiocarbomatedithiocarbomate (AW1)(AW1)

AmineAmine--phosphate compound (AW2)phosphate compound (AW2)

MolybdenumMolybdenum diakyldiakyl phosphorodithioatephosphorodithioate (AW3)(AW3)

Pour Point DepressantPour Point Depressant

PP--methylmethyl methacrylatemethacrylate


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Test MethodsTest Methods

Pressurized Differential Scanning Colorimeter (Pressurized Differential Scanning Colorimeter (PDSCPDSC))

Temperature ramping methodTemperature ramping method(measures onset temperature OT)(measures onset temperature OT)

Rotary Bomb Oxidation Test (Rotary Bomb Oxidation Test (RBOTRBOT))

ASTM D 2272ASTM D 2272

Low Temperature Flow PropertyLow Temperature Flow Property

ASTM D 97 Pour Point TestASTM D 97 Pour Point Test


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Oxidation Stability

of Soybean Oil

Good correlation between UN and OT R-sq 0.99

Oxidation stability of vegetable oils is predictable using its fattyacid composition rather than individual fatty acid percentage.

0.94

1.14

1.40

1.50

UN OT0C)

Linolenic

C18:3

Linoleic

C18:2

Oleic

C18:1

Stearic

C18:0

Palmitic

C16:0

Vegetable

oils

1736.2953.6024.204.7711.14SO

1981.761.0886.783.307.08HOSO

1901.6524.1860.714.339.13MOSO

179-56.2727.495.6310.61HLSO

S C


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Synergistic Effect of Additive Combinations

in Soybean Oil

AO reached a limit in effectivenessat 2%

AW2 and AW3 acts as pro-oxidant

Only AW1 showed synergistic effecton antioxidant capability of AO

AO-AW1 will be used.

150

175

200

225

SO 1%AO2%AO

3%AO

2%AO+2%AW1

2%AO+2%AW2

2%AO+2%AW3

2%AW

1

Temp.,

degC

PDSC Results RBOT Results

0

35

70105

140

SO 1%AO2%AO

3%AO

2%AO+2%AW1

2%AO+2%AW2

2%AO+2%AW3

2%AW

1

RBOTtime

(min)

AO Zinc diamyl dithiocarbamateAW1 Antimony diakly dithiocarbamateAW2 Amine-phosphate compoundAW3 Molybdenum dialkyl phosphorodithioate

Eff f A i id A i (AO AW ) Addi i


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Effect of Antioxidant-Antiwear (AO-AW1) Additive

Mixture on Vegetable Base Oils and Formulated Lubes

PDSC Onset Temp. PAO oxidatively more stable base fluid with OT of 188 C. additive combination increased the oxidation stability by 50 C.

150

175

200

225

250

275

PAO8 SO HLSO MOSO HOSO COM

neat20%PAO8additive

20%PAO8+additive

OT(C)

RBOT Results of


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RBOT Results of

Formulated Vegetable Oil Based Lubes

RBOT time of 100 min and above considered good for industrial lubricants. Excellent oxidation stability of VO formulations compared with COM

0

100

200

300

400

500

600

700

800

SO HLSO MOSO HOSO COM

additive20%PAO+additive

R

BOTTime(min)


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Pour Point improvement using PAO and PPD

PAO added as diluent (PP -57 C) to improve LTP 20% PAO improved the PP by -3 to -6 C Addition of up to 40% PAO made no significant improvement Further improvement using 1% PPD

-60

-50

-40

-30

-20

-10

0

P

ourpoint(de

gC)

PAO8 SO HLSO MOSO HOSO

neat20%PAO8additive20%PAO8+additive


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Crystal growth without

Pour

Point

Depressant (PPD)

Crystal growth withPPD

Crystal sizelimited by

hindrance ofp- methacrylate

backbone


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ConclusionsConclusions

Additive combinations need to be evaluated in variousAdditive combinations need to be evaluated in variousbase fluids to assess effectivenessbase fluids to assess effectiveness

AntioxidantAntioxidant ZDDCZDDC (zinc(zinc diamyldiamyl dithiocarbamatedithiocarbamate))performed better then diphenylamine, hindered phenol,performed better then diphenylamine, hindered phenol,or their mixtureor their mixture

All antioxidants showed more synergism withAll antioxidants showed more synergism with antiwearantiwearadditiveadditive ADDCADDC (antimony(antimony diakyldiakyl dithiocarbamatedithiocarbamate))compared to molybdenumcompared to molybdenum phosphorodithioatephosphorodithioate, while, whileamineamine--phosphate did not show any synergismphosphate did not show any synergism

ZDDCZDDC andand ADDCADDC combination showed the best resultscombination showed the best resultsin vegetable oilsin vegetable oils


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Conclusions ContinuedConclusions Continued

This additive combination improves the performanceThis additive combination improves the performance

ofof MOSOMOSO to make it acceptable for most industrialto make it acceptable for most industrialapplicationsapplications

The overall approach provides VO based lubricantsThe overall approach provides VO based lubricants

that exhibit superior performance then commerciallythat exhibit superior performance then commerciallyavailable bioavailable bio--based industrial lubricants and arebased industrial lubricants and arecomparable with petroleumcomparable with petroleum--based lubricants.based lubricants.


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S i Z E h


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[email protected]

Sevim Z. Erhan

Research LeaderFood and Industrial Oil ResearchUSDA/ARS/NCAUR1815 N. University St. Peoria, IL 61604

Phone: 309-681-6532

Fax: 309-681-6340

Sevim_Erhan Use of Vege Oils in Biobased Products

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