689

INDUSTRIAL SPECIALTY CROPS

Lubricants and additives from plant oilsEarly efforts in plant oil lubri-

cant and lubricant additivesinvolved the use of jojoba oil

derivatives in an automatic transmis-sion fluid supplement (additive mix-ture). This development was stimu-lated, in part, by the disappearance ofsperm oil from the marketplace whenthe sperm whale was placed on theendangered species list in 1972. Atthat time, sperm oil and its deriva-tives were used in highly successfulhigh-performance automatic trans-mission fluids.

Since the development of jojobaoil-based fluids, interest in plant oil-based lubricants has broadened 10encompass a variety of plant oils.There are several reasons for thisinterest. and these are summarized inthe advantages that accrue from plantoils.

These advantages include bio-

~

,,""•TIW article wa.t' prepa~d lorINFORM by Phillip S. LtuuJisand Alta Shanallan. of JU.7930 Occ/de""" Sooth. s.anJe.1IIu/IIng, .. 98108.

degradability, non toxicity, noncar-cinogenicity, and resource renewa-bility.

In contrast to mineral oils, plantoils have double bonds and carboxylgroups which facilitate catalyzed oxi-dation and hydrolysis by bacteria andmolds. Mineral oils must undergo aslow oxidation to form reactive sitesto which bacteria can attach them-

AdductEP anti wear

Sulfurized esterantiwear/amioxidant

Dibutyl phospblte-, 12-17% S

/Linear ester

(low-temperature modifier)

t Roloctioo

I Transesterification

o

"R-C-O-CH2

~ IR-C-O-CH

I__~3-=5~%:..::S_~. Adduct

• antioxidant.. Dibut)'1 phO!iphiteAdduct

EP entiwear o

"R-C-O-CH2

Rapeseed oil

1H~~m1

3000, SOOO,6OClO,MWT

To ......VI improver

Friction medlfler

FIgUre 1. Synthesle ~ with rapeseed 011

,. <;1IiII~

selves. Thus, depending upon the typeof mineral oil, a plant oil might biode-grade 50-100 times faster than a min-eral oil.

Some mineral oils, particularlythose derived from bright stocks(residual oils) contain small but mea-surable quantities of polycyclic(polynuclear aromatic) compoundsthat are toxic and carcinogenic. Thereare no such toxic compounds presentin plant oils.

As a renewable resource, plant oilsoffer a small but important steptoward reducing U.S. dependence oncrude oil. Obviously, when crude oil isremoved from the ground, it is goneand cannot be replaced, while plantoils can be regenerated annually or, insome cases, semiannually.

There are some obvious disadvan-tages to the use of plant oils as fullyformulated lubricating oils. There is alimited volume or plant oils availablefor such an application. Indeed theworld supply of plant oils would suf-fice to satisfy only 5-10% of U,S.demand for lubricants. However, ifselective use of plant oils is used as analternative to mineral oils-for exam-ple, use in only industrial lubri-cants-then plant oils could providethe necessary volume.

At current costs, plant oils cannotcompete with mineral oil lubricants.This is not the case with plant oil-derived additives which can be manu-factured at costs that are competitivewith mineral oil derivatives. Also,plant oil costs are competitive withsynthetic lubricants currently pro-duced from petrochemicals.

Plant oils also suffer from somespecific inferior properties including

INFORM, VOl. 5, no. 6 (June 1994)

690

INDUSTRIAL SPECIALTY CROPS

Table 1The thickening power of Eruclchem T6000

Telomer(%) Base oil I Base oil 2

"'·C lOOGC VI "'·C 100°C VI0 18.80 353 34 17.93 3.73 ss2 20.64 3.82 52 20.40 4.26 '07• 23.00 4.27 83 22.09 4.39 1106 25.14 4.55 90 24.46 4.89 .2.8 27.38 '.94 .04 25.58 5.27 .'"

fixed viscosity (mineral oil lubricantscan be tailored 10 a variety of viscosi-ty grades). And plant oils are lessoxidatively stable and require moreand different antioxidants to achievestability equivalent to that of mineraloils.

One approach 10 plant oil lubri-

cants involves the use of three basefluids and a sequence of additivesbased on plant oil chemistry. Thebase fluids include canola or rape-seed oil, an ester derived from rape-seed oil fatty acids, and mineral oil.The additives include a plant oiltelomer to provide viscosity index

EXPERIENCE &RELIABILITY

from villoge scole up 10turnkey (ontrocting

PRESSESlor pre-press ond lull-pren

REGENT, SOVEREIGN, STERLING

PARTStecllni<olly superior porl$ to give

optimum perlormonce

0. Smet !"roc ...... Tech .... ogT In<?lJ91'oc .. f.e«y food, s...;.. 110, AlIonIo. ~ 303J9. USA

tool: 110I00I10&36.00.61 foa: '/oIOoI/~2Ui,l' n.:984'20E.5METfJSAAo._Go-.~

For Infofmafion circle 1203

(VI) improvement and to modifyfriction, a sulfurized plant oil deriva-tive to provide anti wear and antioxi-dant activity. and a phosphorousderivative for load-carrying orextreme pressure wear activity.

The industrial oils and supplementsinclude gear oils, automatic transmis-sion fluids, hydraulic oils, tractor flu-ids. way lubricants. metal cutting flu-ids and power steering fluids.

Antioxidants. extreme pressure(EP) additives. anti wear agents. fric-tion modifiers and viscosityimprovers can be synthesized start-ing with rapeseed oil. as shown inFigure I.

A recently developed new plant oilderivative. Erucichem T6000. is atelomer derived from rapeseed oil. Itis a unique new product that is totallyseed-based, easily biodegraded, pro-

0. s.n., .DSetIoWM UmitHC-s..--......,...,.,~HU2QAO,UnitedIiolgdomtool: .... /42/,..... f.oa: .... /42/U8fIl n., ~ ORHUU

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INFORM, Vol. 5, no. 6 (June 1994)

691

Table 2Four Ball Wear Test (ASTM 0-4172)

RPM-1200; temp.-7SoCilime-60 min; load--40 kg

Wear scardiameter(mm)

1.281.120.790.710.960.39

LVI base oilLVI ... 1% telcrnerLVI + 2.5% telomerLVI + 5.0% telomerMV) base oilMY) + 2.5% telorner

vides lubricity and oil thickening. andis a blending agent for both plant oilsand mineral oils.

The telarner is prepared in pilotplanl or larger quantities at atmo-spheric pressure using a reactionIlask fitted with an air condenser.thermometer and nitrogen inlet lube.The nitrogen is saturated with watervapor by bubbling the nitrogenthrough water contained in a smailflask heated to 60°C. The reactorcontents are heated at 300--320°C for12-15 hours while water is removedcontinuously. After completion ofthe reaction. the products are cooledto room temperature under a steamof dry nitrogen. About 15 hours at315°C are required to obtain a tetom-er of 6000 molecular weight.

Erucichem T6000 contains70-75% of telomer, 10-15% of fanyacids including dimer acids and10-15% of triglyceride. Typical phys-ical properties include color. yellow tolight brown; kinetic viscosity at 40°C.1286 centistokes (5957 Saybott Uni-versal Seconds); kinetic viscosity at100°C. 101 cemisrokes (470 SaybonUniversal Seconds): VI. 167: neutral-izaticn number. 15-20; and iodinenumber. 55.

The telomerization reaction is notlimited to rapeseed oil but can be car-ried out with any highly polyunsatu-rated oil including crambe, canola,corn oil or safflower oil. In actualcommercial practice. linseed oil isadded to rapeseed oil to facilitate thetelomerization.

Erucichem T6000 thickens mineraloil and plant oils and provides a baseto incorporate other additive functionssuch as anti wear, detergency andantioxidation. It has potential for use

in grease. paints, plastics and the coat-ings industries.

The thickening power of Eruci-chern T6000 is illustrated in Table I.As a low-molecular weight polymer.it is shear stable as demonstrated bythe Sonic Oscillator Shear Test; andit provides hydrodynamic lubricationas illustrated in the Four Ball WearTest (ASTM 0-4172), shown inTable 2.

A notice of allowance has beenissued on a patent application cover-ing this telomer. It is currently beinglest marketed and will be used in agear oil formulation, a hydraulic andtractor oil formulation, a way lubri-cant, and in a water-soluble cuningoil.

Wood listed five major forces thathe said are driving emerging indus-trial bic-oil markets in some coun-tries:

• Agricultural land use programs.In the European Union (EU), farmerscan plant rapeseed intended for indus-trial use on set-aside acreage. Woodestimated 450,000 metric tons ofindustrial rapeseed were harvested in1993 from 420,000 acres, "Most ofthis production is used in the biodieselindustry," he said.

• Alternate disposal programs forsurplus crops. In the United States, theneed to use excess com supplies andhelp support prices is behind the drivefor ethanol-blended fuels, Wood said.He reponed that approximately 8% ofU.S. gasoline sales are ethanol-blend-ed fuel, consuming about 360 millionbushels of com.

o Rural economic development. InCanada, agriculture and ruraleconomies benefit from bio-oil pro-duction "when measured against fed-eral and provincial subsidies" grantedto an ethanol plant and feedlot opera-tion near Lanigan. Saskatchewan,Wood said.

• Safety and environment concerns.In the United States. federal Environ-mental Protection Agency (EPA)clean air standards for urban areas willbecome more Strict. fostering interestin diesel-type fuels derived from soy-bean oil. Wood said.

o Superior performance in selectapplications. Examples of suchapplications are thin-film coatings onmetals, solvent cleaning of metalsand printing ink for newspapers-allniche markets in Canada. Severalother papers noted the same or simi-lar forces around the world.

Rio-Oils Symposiumproceedings availableIs there nothing new under the sun?Rudolph Diesel used vegetable oils inhis engine. Castor oil fueled the firstdiesel engine to arrive in Argentina in1916, And a French engineer pub-lished a paper in 1928 discussing veg-etable oils in diesel engines. This briefhistory was presented by Mark Sturn-borg of Agriculture and Agri-FoodCanada at the Bio-Oils Symposium inearly March in Saskatoon,Saskatchewan, Canada.

Papers at the meeting reviewed thegrowth of the bto-cits industry inCanada, Europe and the United States,properties of bio-cils. and outlooks forthe Canadian and U.S. bio-cil industry(Table I). The meeting was organizedby the Saskatchewan Canola Develop-ment Commission.

The first commercial production ofrapeseed in Western Canada was dur-ing 1942 to produce an oil for use inlubricants during World War II,according to Mike Wood of Agricul-ture Canada, who spoke on "Status ofBio-Oils in Canada." Although Cana-dian research later focused successful-lyon edible applications of rapeseedoil, "Canada has never had a leader-ship position in closing the loop backagain and developing markets forcanola in industrial applications suchas bio-oils," he said.

BiodieselBiodiesel feedstocks include tallow,lard, poultry fat. used frying oil, soy-bean oil. sunflower oil, cottonseedoil, coconut oil, palm and palm ker-nel oil, corn oil and rapeseed oil.reported Steve Howell of Marc-IV, abicdiesel consulting firm in Bucyrus.Kansas.

In Europe. biodiesel product spec-ifications and engine warranties"appear to be well defined," accord-ing to Werner Korbitz, a biodiesel

INFORM, Vol. 5, no. 6 (June 199.:1)

692

INDUSTRIAL SPECIALTY CROPS

T_'B60dIesei prodoc:tion and planta in deYek)pment, Europe and North AITHM1ca

Operating plants Proposed plants

CeentrySmall (CliIpllcityin meme tons)

(capacity inmetric Ions)

Industrial (tapadtyin metrje tons)

1(15.000)4 (uxal of 110.000)

I (30.000)123 (120.000 each)

I (10.00~1(30,000)15 (smaJl-K:alc)I (lab-scale)"4 (total of 190,000)

AustriaF~

10>1,Cu<:h Republic

4 (500 each)I (1.000)

Variom (lIltlII of 100.(00)

3-4 (1.000 each)

Slovak Republico.~,BelgiumDenmarks_,HungaryI~,,",

United Stales

4 (l.000eacb)1(300)

2 (1OtBl of 16.(00)

I (880:f

1(50,000)11

~ing ..sed " frying oil: b ",nnower oil; t npeoced: d 10)'; rCCllbtocu (or other planu not Ipedfled.Sourr~:~ KorbilZ, VICM&, AIUUi.

consultant in Vienna, Austria. Sturn-borg said thai rapeseed methyl ester(RME) fuel is suited for use in Cana-da except in winter.

U.S. standards agencies are justbeginning to address the need for aconsensus standard for ester-basedbiodiesel fuels, according to AIWong of Arbokem Inc. in Vancou-ver, British Columbia, Canada, andthree co-authors. Lack of standardsis a barrier to warranty coverage forengines using biodiesel fuels, hesaid. The U.S. Department of Agri-culture (USDA) announced in mid-March that it awarded a $140.000grant to the American BiofuelsAssociation to establish biodieselstandards and to clarify terminology.In the study. the Southwest ResearchInstitute, a private facility approvedby the EPA, will test emissions froma Detroit Diesel 6V92 engine fueledwith soydiesel. Theengine is stan-dard for ci.ty bus fleets, according toUSDA's announcement. Levels ofemissions .for unburned hydrocar-bons, carbon monoxide. particulatematter and oxides of nitrogen will bedetermined, and the engine's dura-bility will be tested to determine ifnew lubricants need to be developed

1(60.000)1(40.000)

1(30.000)1(5.000)

16 (unl or 18.000>"1 (30.000)1'

for use with biodiesel.Key European tractor producers

agreed during 1991 to provide war-ranty coverage for engines running onRME. Korbitz said. followed by simi-lar action by truck manufacturers.RME can be used in unmodifiedEuropean diesel engines and is com-patible with fossil diesel, he said.However, rransesteriftcetlon process-ing increases cost.

To help keep biodiesel fuelspriced competitively with standarddiesel fuel, France and Italy do nOIassess regular fuel taxes on bio-diesel fuels, Korbitz reported. No taxincentives have been extended tobiodiesel in the United States. wherefederal regulations are a prime factorin its development. Howell said.Such regulations include the Alterna-tive Motor Fuels Act of 1988. CleanAir Act of 1990 and the NationalEnergy Policy Act of 1992. hereported.

"There is some legislation inprogress that wiU look al lax Incen-lives" for biodiesel, said KentonJohannes of the National SoyDieselDevelopment Board in Jefferson City.Missouri. in late March.

Howell also said that raw oil costs

account for 70.5% of the total cost ofproducing biodiesel fuel in the Unit-ed States. Other costs aresales/administration, 9%; cost of cap-ital, 6.5%; utilities. maintenance.etc .. 5.5%; methanol. 4.5%; labor,2.5%: and catalyst. 1.5%.

Production economics was thesubject of two papers. Stumborgreported on computer studies of on-farm oil extraction equipment andmethods and transesterification ofcanola oil based on a hypothetical270,OOO-liter community-scale plant,the characteristics and performanceof processed and blended oils andtheir effects on various engines. Bio-oils will be used only as fuel addi-tives in Canada because the countryproduces only 1.2 billion liters in anaverage year and consumes 15.3 bil-lion liters of fossil diesel, Stumborgconcluded. Engines running onbiodiesel in Canadian tests werecomparable in power generation andfuel consumption with engines run-ning on No.2 diesel fuel, but withbio-diesel exhaust emissions gener-ally improved, except for an increasein aldehydes, which are not regulat-ed. U.S. test results, however.showed a drop in aldehyde em is-

INFORM. Vol. 5, no. 6 (June 1994)

693

siena, said Howell. Stumborg report-ed that on-farm extraction test resultswere not encouraging, and he recom-mended larger scale facilities, suchas community-scale or targer toachieve the lowest unit cost.

Community-scale ethanol produc-tion was the topic for University ofMissouri agricultural economist J.Alan Weber. Although there is no U.S.community-scale biodiesel produc-tion, there is a community-scaleethanol production plant. Reeves Cat-tle Company in Garden City, Kansas,produces ethanol and uses co-productsin its other agricultural enterprises,Weber reported. The ethanol plant'sannual capacity, which was 750,000gallons in 1981, is now 8 million gal-lons.

Weber reported that a community-scale biodiesel facility is serving rural

fuel and feed needs of a cooperative inNeulangbach, Austria. Weberdescribed a computer program hedeveloped that enables farmers, busi-nessmen and others in the communityto evaluate the profit potential ofinvesting in a community-scalebiodiesel plant, using data specific totheir agricultural activities and com-munity.

range of most plant oils, eliminatesoxygen and hydrogenates any unsat-urated compounds. "Hydroprocess-ing canola oil results in a straight-chain hydrocarbon with no aromaticor cyclic compounds, making it agood fuel additive with a high cetanevalue," Soveran reported. The tech-nology can be used to produce otherproducts, depending on the chemicalmakeup of the starting material."The process provides a means ofproducing unique saturated hydro-carbons efficiently and cost effec-tively," Soveran said.

New production techniques couldbe necessary to meet biodieseldemand, which Howell of Marc-IVsaid will continue to grow because ofthe fuel's improving performancecompared with fossil diesel as wellas its environmental status, lubricity,

Future, competition for biodieselEmerging technology for convertingbio-oils to fuels or other high-valueproducts was discussed by D.W.Soveran of the SaskatchewanResearch Council, which appliedconventional petroleum technology[0 the conversion of bio-oils. Calledthe supercetane process, the newtechnology is a catalytic hydrocrack-ing process. It reduces the boiling

TWO, WHO GOTO EXTREMESOILS AND FATSOilseed- and rendering proc-ess materials put tremendouswear and tear on screw pressparts.For our parts we use thefinest steels, hightech weldingand hardening process, expe-rience gathered over genera-tions and combine them withmost modern technologies.Result: Wear characteristics,that are pace setters aroundthe world. For more informa-tion, call or write us.

INFORM. Vol. 5. no. 6 (June 1994)

694

INDUSTRIAL SPECIALTY CROPS

(.~",.~.

!@\!t-

Our Renewal Parts DiilisiDn.... add the Crowningc~uchw",

I!!" .. ,-~

low toxicity and high safety. Themost likely markets are bus fleets,marine applications. wetlands con-struction, togging, mining, recre-ational equipment in "green" areas,and government fleets such as thearmed forces, National Park Serviceand Department of Agriculture.

Tests of biodiesel performanceand effects on engines were providedby M.R. Goyal of Deere Power Sys-tems Group in Waterloo, Iowa,including performance of two tur-bocharged Deere engines running ontwo fuels-RME, a methyl ester ofrapeseed oil. and Methyl Soyate, amethyl ester of soybean oil. Goyalsaid that bus systems in more than10 U.S. municipalities are testingbio-diesel. The National Soy DieselDevelopment Board was conductingmore than 150 test programs

throughout the United States."We've logged about seven millionmiles to date with no reportableproblems," Johannes said. More than30 programs involve bus fleets andtwo fleets have gone more than amillion miles in testing.

But biodiesel and ethanol fuels arenot without competition. Programs areunderway to test vehicle performanceon liquid propane gas, natural gas,methanol, ethers, electricity, hydrogenand solar power.

A report on growth of alternativefuels as projected by Business Com-munications Company (BCC) inNorwalk. Connecticut, was reportedin the March 21, 1994, issue ofChemical Marketing Reporter. Com-pressed natural gas (CNG) is predict-ed to dominate the U.S. alternativefuels market in 2003 with a 60%

share, according to the report. About500 U.S. service stations pumpedCNG in 1993, with another 100 sta-tions per year adding CNG service,the report said.

Propane will have a 17% share ofthe U.S. alternate-fuels market, elec-tricity 13% and others (ethanol andmethanol) 10%. (The study did notinclude biodiesel.) In 2003, alterna-tive fuels are expected to accountfor only about 2% of the total ener-gy consumed by motor vehicles inthe United States. the BCC studysaid.

Vehicles using alternative fuels willproliferate, BCC projected, risingfrom 74,000 on the road in 1993 to655,000 in 1998 and 3.6 million in2003, with alternate fuel vehiclesaccounting for 1.6% of all vehicles inU.S. traffic. •

Crown Iron Works Company

Over the years our reputation forsupplying the best available oilextraction and processing equipmenthas been growing worldwide.

Our Renewal Ports Division maintainsthe same standards of excellenceand is dedicated to providing aservice which is second to none.

For a prompt and competitiveresponse contact:Crown· Renewal Parts DivisionP.O. Box 1364, Mlnneapolli, Minnesota 5S440·1364, U.s.A.Teleph_: 612 639 8900 h.: 612 639 8051,Tete.: 290204 Crown Iron Mpi

INFORM. Val. 5. no. 6 (June 1994)

Wurster & Sanger

For Information circle *112

ter & S

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ter & 5