Inventory of Concepts for Mixed Diesel Fuels Containing Renewable

SE0007520

ALTD-00/5

Inventory of concepts for mixed diesel fuels containing renewable components Final report Inventering av koncept for dieselblandningar innehallande fornyelsebara ravaror Slutrapport B Kronberg R Berg J Berg

Rapporterna kan besfallas fran Studsvikbiblioteket, 61182 Nykoping. Tel 0155-22 10 84. Fax 0155-26 30 44 e-post [email protected]

Statens energimyndighet Box 310, 631 04 Eskilstuna Energimyndigheten iBUTION OF THIS DOCUMENT IS UNLIMT FOREIGN SALES PROHIBITED 00-08-24

Energimyndigheten JAN 0 4 2001 o 8II" f

Xitel: Inventory of concepts for mixed diesel fuels containing renewable components Final report Inventering av koncept for dieselblandningar innehallande fomyelsebara ravaror Slutrapport

Forfattare: Bengt Kronberg YKI Rolf Berg Befri Konsult Johan Berg SLR FoU/Agro Oil

RAPPORT INOM OMRADET ALTERNATIVA DRIVMEDEL

Rapportnummer: ALTD 00/5

Projektledare: Johan Berg

Projektnummer: P9560-2

Projekthandlaggare pa Statens Energimyndighet: Bjorn Rehnlund

Box 310 • 631 04 Eskilstuna • Besoksadress Kungsgatan 43 Telefon 016-544 20 00 • Telefax 016-544 20 99 [email protected] • www.slem.se DISCLAIMER

Portions of this document may be illegible in electronic image products. Images are produced from the best available original document. Inventory of concepts for mixed diesel fuels containing renewable components

Inventering av koncept for dieselblandningar innehallande fomyelsebara rdvaror

Final report June 2000

Bengt Kronberg, YKI Rolf Berg, Befri Konsult Johan Berg SLR FoU / Agro Oil Inventory of concepts for mixed diesel fuels containing renewable components

The present project has involved the assembly of two sub-reports, which have been put together to form this final report. Both of the sub-reports deal with the incorporation of ethanol in diesel fuels. The potential advantages are the decreased net emissions of carbon dioxide, due to the renewable nature of ethanol (if obtained from renewable raw materials), and the decrease of NOx emissions, due to the decreased combustion temperature.

The first sub-report is a compilation of scientific articles and patents/patent applications regarding the possibility to blend ethanol into diesel to form a stable solution in the form of a so-called microemulsion, with the aid of surfactants and/or cosolvents. This sub-report was assembled by Bengt Kronberg, Institute for Surface Chemistry (YKI), Stockholm, Sweden.

The second sub-report briefly describes the test work, both in the laboratory and in field tests, that is being done in various countries, regarding the blending of ethanol into diesel fuel. This report was assembled by Rolf Berg, Beffi Konsult, Solna, Sweden.

The project coordinator has been Johan Berg, SLR FoU / Agro Oil AB.

The support for this project from Swedish National Energy Administration (Energimyndigheten, Project No. 9560-2) is gratefully acknowledged. This support also coveredpart of the work of assembling an EU project proposal; part of this proposal assembly work was funded by means supplied from YKI.

Inventering av koncept for dieselblandningar innehallande fomyelsebara ravaror

Inom detta projekt har sammanstallts tva delprojekts-rapporter, som har lagts ihop till en slutrapport. Bada dessa rapporter behandlar inblandning av etanol i dieseldrivmedel. De potentiella fbrdelama med detta ar minskade netto-emissioner av koldioxid, pa grund av att etanol ar fomyelsebart (om det erhalls fran fomyelsebara ravaror), och minskningen av NOx- emissionema, p g a sankt forbranningstemperatur.

Den forsta delprojekts-rapporten ar en sammanstallning av vetenskapliga artiklar och patent/patentansokningar rorande mojligheten att blanda etanol i diesel, med hjalp av tensider och andra airmen, sa att en s k mikroemulsion erhalls. Denna rapport har sammanstallts av Bengt Kronberg, Ytkemiska Institutet (YKI), Stockholm.

Den andra delprojekts-rapporten beskriver det test-arbete som pagar med etanol-inblandning i diesel, i ett antal lander. Bade laboratorietester och falttester refereras. Denna rapport har sammanstallts av Rolf Berg, Befri Konsult, Solna.

Projektledare har varit Johan Berg, SLR FoU / Agro Oil AB.

Projektet har erhallit ekonomiskt stod av Energimyndigheten (projektnummer 9560-2). Detta stod har ocksa tackt en del av arbetet med att sammanstalla en EU-ansdkan; en del av detta arbete har ocksa tackts med medel hos YKI. Literature reviewof work related to microemulsion mixtures of aqueous ethanol and Diesel oil for the combustion in Diesel engines

Bengt Kronberg Institute for Surface Chemistry P.O. Box 5607 SE-114 56 Stockholm Sweden

Microemulsion fuels are clear stabletwo-phase dispersions that form spontaneously upon adding the components. They are comprised of a continuous non-polar hydrocarbon phase and a discontinuous polar phase. Because of the small droplet size of the discontinuous phase (2 - 200nanometers) these fuels appear to be clear.

The use of technical alcohol introduces as small amount of water into the fuel. The resulting W/O microemulsion is said to improve combustion properties. The water serves as a heat sink, lowering the combustion temperatures and reducing NOx emissions. Its volatility serves to improve fuel atomisation.

Below is given an account of various references, found in literature, both as published papers and as patents. The papers have not been sorted and hence there is no order of appearance.

YTKEMISKA INSTITUTE? / Institute for Surface Chemistry

Mailing address: Visiting address / Reg. office: Tel: +46 8 790 99 00 VAT No. SE902002656401 Box 5607 Drottning Kristinas vag 45 Fax: +46 8 20 89 98 Reg. No. 902002-6564 SE-114 86 Stockholm Stockholm e-mail: [email protected] Sweden Sweden web site: www.surfchem.kth.se Low Emissions Diesel fuel.

Us Patent 5,746,783 (May 5 1998) A.L. Compere, W.L. Griffith, G.F. Dorsey, B.H. West. For Martin Marietta Energy Systems.

A method and matter of composition for controlling NOx emissions from existing Diesel engines. The method is achieved by adding a small amount of material to the Diesel fuel to decrease the amount of NOx produced during combustion. Specifically, small amounts, less than about 1% of urea of a triazine compound (methylol melamines) are added to Diesel fuel. Because urea and triazine compounds are generally insoluble in Diesel fuel, microemulsion technology is used to suspend or dissolve the urea or triazine compound in the Diesel fuel. A typical formulation includes 5% t-butyl alciohol, 4.5%% water, 0,5% urea or triazine compound, 9% oleic acid and 1% ethanolamine. The subject innovation provides improved emissions in heavy Diesel engines without the need for major modifications.

Example: The following materials were mixed to prepare a fuel: 5g methylol amine 45g water 50g t-butyl alcohol 90g oleic acid 10g ethanolamine 800g Phillips D2 10 g Mach I superfine alpha Fe203 catalyst

Oxygenated Microemulsion Diesel Fuel

H.S. Kesling Jr., F.J. Liotta, J.M. McdFarland Preprints of papers-American Chemical Society, Division Fuel Chemistry 39(2), 322 (1994).

Gives a discussion of the choice of alcohol as cosurfactant in the microemulsion. Specifically t-butyl alcohol annd 1-phenylethanol are mentioned. These are available on a large scale world wide. No specific formulations are given. Also C1-6 alcohols, benzyl alcohol and glycols are mentioned.

Diesel Review, Ytkemiska Institutet 2 Microemulsion Diesel fuel compositions and method of use.

A.K. Smith, M.L. Robbins, S.J. PaceP.G. Grimes for Exxon Research and Engineering Co. Eur. Pat Nr. 0 475 620 A2, 91-08-23.

The inventors claim microemulsion formulations where the aqueous phase is enriched with an ashless oxidising agent, such as ammonium nitrate, ammonium nitrite, hydrogen peroxide, ammonium hypochlorite, ammonium chlorite, ammonium perchlorate, ammonium chlorate, perchloric acid, chlorous acid, hypochlorous acid, ammonium hypobromide, ammoniumbromate, bromic acid, ammoniumhypoiodide, ammoniumperiodate, , 2,4 dinitrophenyl hydrazine, 2,5 dinotrophenol, 2,6 dinotrophenol, 2,4 dinitrforecorcinol, nitroguanidine, 3 nitro- 1,2,4-triazole, 2 nitro imidazole, 4 nitro imidazole, picric acid, cumene hydroperoxide, cyanuric acid, nitroglycerin, nitrobenzene trinitrotoluene and mixtures thereof.

One interesting example of formulation is giving using surfactants without any sulfur content. In order to attain a temperature insensitivity the inventors blend two or more surfactants with opposing temperature dependencies; MEA-oleate becomes more hydrophilic while the ethoxylated alkyl ammonium oleate become more lipophilic with increasing temperature. Blends of these surfactants give temperature insensitive microemulsions. Otherwise the patent only cites examples where sulphur containing surfactants are used.

Hybrid Diesel fuel composition

C. Genova, I Blute, R. Pappa for Enirecherche S.p.a. Eur pat nr. 0 399 620, (90-11 28).

The patent claims a hybrid Diesel fuel composition in the form of a microemulsion comprising a Diesel fuel, water a glycolipid surfactant and an aliphatic alcohol co surfactant. The term glycolipid surfactant means surface active compounds generally definable by the formula A-X-R, where A represents the glucide group or a mono-, di , tri-, or tetra-saccaride, R represents a saturated or unsaturated linear of branched chain alkyl group containing at least 10 carbon atoms, the two groups A and R being connected together by a function X chosen from ester, ether acetal and hemiacetal functions. Among the alcohol co-surfactants the primary alcohols n-butanol, n- pentanol and n-hexanol are preferred. One example of a formulation is: Oleyl saccarose ether 2.9 -4.2 % n-pentanol 6.8 - 9.8% water 1—6% Diesel fuel 80 - 89.3%

No tests of these blends have been performed.

Diesel Review, Ytkemiska Institute! 3 Methanol as co-surfactant for microemulsions

S.G. Schon and E.A. Hazbun for Arco Chemical Technology Inc., US pat nr., 5,004,479 (1991-04-02)

Stable microemulsion fuel compositions are provided which comprise (a) a hydrocarbon fuel such as Diesel fuel, jet fuel, gasoline or fuel oil; (b) water and (c) co surfactant combination of methanol and a fatty acid partially neutralised by a nitrogeneous base. The compositions of the invention have a high degree of phase stability over a wide range of temperature, and reduce combustion emissions. The patent rests on experiments with Emersol 315 as emulsifier. This emulsifier is a commercial soy-derived fatty acid mixture from Emery Industries containing linoleic, oleic, linolenic, and palmitic acids with a free acid content of 99 wt%. It is shown that neither of the hydroxides NaOH or KOH were effective neutrilizers when methanol was the used as a “co-surfactant ”. The water uptake was less than 0.03gH20 / g Dieselover the entire neutralisation range. On the other hand using NH3 (ammonia), MEA (monoethanol amine), DMEA (dimethyl ethanol amine), MIPA (mono isopropanol amine) water uptakes in the range 0.1 - 0.33 g H20 /g Diesel can be obtained. Furthermore for some of these systems stability is obtained over a wide temperature range (0 to 70° C) It is emphasised that the large water tolerance of the systems is only valid for a limited range of degree of neutralisation, varying between 40 - 80%.

Diesel fuel aqueous alcohol microemulsions

A.W. Schwab for The United States of America as represented by the Secretary of Agriculture, Washington D.C. US pat nr 4,451,265 (1981-04-21).

Hybrid fuel microemulsions are prepared from Diesel fuel, water, alcohol, and an novel surfactant system comprising N,N-dimethylethano!amine and al long chain fatty acid substance. These fuels are characterised by high water tolerance and low temperature stability, and are particularly adaptable to the utilisation of aqueous ethanol as the alcohol source.

The patent rests on experiments with Emersol 315 as emulsifier. This emulsifier is a commercial soy-derived fatty acid mixture from Emery Industries containing linoleic, oleic, linolenic, and palmitic acids with a free acid content of 99 wt%. The following formulation was found to be able to incorporate 2.2 vol% water: Diesel fuel 66.8 vol% Ethanol 11 vol% Emersol 315 16.7 vol% DMEA 5.5 vol% Where DMEA is N,N-dimethylethanolamine.

Diesel Review, Ytkemiska Institute! 4 Experiments with Alcohol/Diesel Fuel Blends in Compression Engines

C.A. Moses, T.W. Ryan and W.E. Likos, Proc. Int. Symp., Alcohol Fuel Technology, 4th , vol. 2 493 (1980).

The authors have tested a single microemulsion formulation for engine tests. Over a hundred surfactants were screened and a stable microemulsion was obtained with “SOA” from Scher Chemicals Inc., No further description of the surfactant is given.

Microemulsion Fuel System

E.A. Hazbun, S.G. Schon and R.G. Gray for Arco Chemical Co. US Pat. Nr. 4,744,796 (1986-02-04).

Stable microemulsion fuel compositions are provided which comprise (a) diesel fuel, (b) water and/or methanol (c) a surfactant combination of tertiary butyl alcohol (TBA) and an ionic or non-ionic surfactant. The compositions of the invention exhibita high degree of phase stability even over wide variations of temperature, greatly improved salt tolerance and reduce smoke particulate and NOx emissions. The patent is focussed on the effect of TBA as a co-surfactant. It is found that TBA renders good temperature stability while normal butyl alcohol does not.

Fire Resistant Microemulsions Containing Phenyl Alcohols as Co-Surfactants

E.A. Hazbun and S.G. Schon for Arco Chemical Co. US Pat. Nr. 4,477,670 (1986-12 22)

It is shown that if phenyl alcohols are substituted for the lower alcohols in microemulsion fuel formulations there will be an increase in the flash point. The phenyl alciohols include benzyl alcohol, phenethyl alcohol, methyl benzyl alcohol, phenyl propanolisomers, and the phenyl butanol isomers. Of these methyl benzyl alcohol (MBA) and benzyl alcohol are preferred for reasons of cost and availability.

Microemulsion from Vegetable oil and lower alcohol with octanol surfactant as alternative fuel for Diesel engines

A.W. Schwab and E.H. Prydefor The United States of America as represented by the Secretary of Agriculture, Washington D.C. US pat nr 4,557,734 (1985-12-10).

Hybrid fuel emulsions are prepared from vegetable oil, methanol or ethanol, a straight chain isomer of octanol, and optionally water. The fuels are characterised by relatively high water tolerance acceptable viscosity and performance properties comparable to no. 2 Diesel fuel. It is shown that in going from butanol to tetradecanol the water uptake increases up to octanol and then decreases. Hence the maximum

Diesel Review, Ytkemiska Institutet 5 water tolerance is found for octanol. Furthermore if 4 octanol is used even a higher water uptake is found. Furthermore using 1-octanol, or 4-octanol, the critical solution temperature stays at ca -15°C up to a water content of ca 1.2 vol %.

Soy-oil -ethanol microemulsions as Diesel Fuel

C.E. Goering, A.W Schwab, R.M. Companion and E.H. Pryde, ASAE, 26(6), 1602 (1983).

Microemulsion Fuels were compared with ordinary Diesel fuel in engine tests. It was shown that a microemulsion based on 1-butanol and ethanol produced nearly as much engine power as the reference Diesel fuel at the same speed, despite having a 19% lower heating value.

Triglyceride/aqueous ethanol/1-butanol microemulsions

A.W. Schwab, H.C. Nielsen, D.D. Brooks and E.H. Pryde, J. Dispersion Sci. Technol., 1, 1 (1983).

The authors have formed solutions of ethanol and triglyceride or hexadecane using 1-butanol as surfactant, see Figure below.

1-Butanol

x Triolein a Trilinolein © Hexadecane

95% Ethanol Ternary phase diagram at 25° C for pure systems of hexadecane, trilinolein and triolein woth 95% ethanol and 1-butanol.

Diesel Review, Ytkemiska Institute! 6 There is evidence that 1-butanol in combination with ethanol associates and interacts with water to form systems exhibiting microemulsion features. Preliminary data also indicate metastable states sin the region of the plait point and support the microemulsion model of an alternative microstructure ion which oil-rich and water rich domains are randomly interdispersed at equilibrium.

Microemulsion from vegetable oil and aqueous alcohol with 1-butanol surfactant as alternativefuel for Diesel engines.

A.W. Schwab and E.H. Pryde for the United States of America as represented by the Secretary of Agriculture, Washington D.C., US pat. Nr. 4,526,586 (1985.07.02).

The patent claims a fuel composition containing 40-65 (vol)% vegetable oil, a lower (C1 to C3) alcohol and 1-butanol, according to the shaded area in the phase diagram below.

1-BUTANOL

/'ONE PHASE'\ (MICROEMULSION)

/ TWO PHASES \ (MACROEMULSION ) :—- X -10-¥——

SOYBEAN 95% OIL ETHANOL

Ternary phase diagram for soy bean oil aqueousethaniol and butanol.

Microemulsion from vegetable oil and aqueous alcohol with trialkylamine surfactantas alternative fuel for Diesel engines.

A.W. Schwab and E.H. Pryde for the United States of America as represented by the Secretary of Agriculture, Washington D.C., US pat. Nr. 4,451,267 (1984.05.29).

The patent claims fuel compositions of vegetable oils and the following surface active constituents. Trialkylamine, or a reaction product of trialkylaamine and a fatty acid.

Diesel Review, Ytkemiska Institute! 7 The trialkylamine could be tremethylamine, triethylamine, tripropylamine or tributylamine. Phase diagrams are given for four systems in the Figure below.

SURFACTANT

SURFACTANT AQUEOUS CURVE EtOH (Vo) Et-,N :ACIDS:1-BuOH

------Y-7Q-X ------67.72 \ ONE PHASE / : 21.52 67.72 ( MICROEMULSION) EM-1

S *

/ TWO PHASES ' (MACROEMULSION i——X-10-X-—

AQUEOUS SOYBEAN ETHANOL

Ternary phase diagram for soy bean oil aqueous ethaniol and surfactant mixtures

Diesel fuel - aqueous ethanol microemulsions

A.W. Schwab, R.S. Fattore and E.H. Pryde, J. Dispersion Sci. and Technology, 3, 45 (1982).

The authors discuss two different microemulsion formulae. The first one is given in figure 1 below and here 1 butanol is used as a surfactant.

Diesel Review, Ytkemiska Institute! 8 Hmtanol

,40/60 $

# 50/50,

# 60/40,

2 Phases 90/10 80/20 70/30 60/40 50/50 40/60 30/70 20/80 10/90 Diesel Fuel No. 2 Volume Percent (A/6) Ternary phase diagram for 95% ethanol, Diesel fuel and butanolat 30° C and 50° C

It should be noted that as little as ca 8% of the butanol is needed to form a microemulsion of 15% ethanol in Diesel. In the second formulation the surfactant was formed in situ by reacting N, N dimethylethanolamine with a fatty acid in a 1.05 ratio. The phase diagram is shown in figure 2 below.

Want C

# 60/40, ,60/40 %

Oieta) Fuel Ha. 2 90/10 80/20 70/30 60/40 50/50 40/60 30/70 20/80 10/90 Volume Percent (A/B) Ternary phase diagram at 30° C for 95% ethanol, Diesel fuel and N, N dimethylethanolamine soybean acids surfactant

Diesel Review, Ytkemiska Institute! 9 Also in this system we note that as little as ca 8% of the surfactant is needed to form a microemulsion of 15% ethanol in Diesel. Various formulations were tested with respect to clouding temperature and the effect of added water as shown in figure 3 below. The figure reveals that the latter microemulsion is superior in keeping a low clouding temperature irrespective of water content under a wide concentration range of water.

Soybean Oil Acids N,H-dimethylethanolamine + Soybean Oil tods Allylamine + Soybean Oil Acids 2-ami na-2-methyl-1 - prop ana i + Soybean Oil Acids /-Butylamine + Soybean Oil Acids

Volume Percent of Dispersed Phase (Hz0)

Critical solution temperatures of Diesel fuel aqueous ethanol microemulsions prepared with different surfactants.

Performance of stabilised Diesel fuels containing alcohols and water in single and muliticylinder direct injection engines.

R.T. Johnsson and J.O. Staffer, Soc Automot Eng., SP-542, 91 (1983).

The authors have blended alcohol and Diesel using either hexanol or Tergitol 15.S-5 (Union Carbide) for engine tests. The fuels containing hexanol behaved similar to ordinary Diesel fuel in terms of gaseous emissions, efficiency , and engine performance These fuels also produced a consistent reduction in the smoke and particulate emissions for both engines. The microemulsion fuels produced a distinct increase in the HC and Co emissions. This is attributed to changes in the injection timing of the engine caused by the fuel.

Diesel Review, Ytkemiska Institute! 10 Evaluation of Diesel fuel - ethanol mixtures

P.A. Boruff, A.W. Schwab, C.E. Goering and E.H. Pryde, Trans. ASAE25, 47 (1982).

The authors have evaluated the engine performance of two different microemulsions of Diesel and ethanol . The formulations are given in the table below:

Reference Nr. 1 Nr. 2 Nr 2 Diesel oil 100 66.7 66.7 95% ethanol 16.7 Emersol 315 (Soybean acids) 12.5 N, N dimethylethanloamine 4.1 1-butanol 22.2

Estimated cost (US $/litre) 0.26 0.47

Some problems were first encountered with vapour locks of ethanol. The peak power obtained with Nr2 was 92% of that for Diesel oil reflecting the lower energy content of the butanol blend. Similarly the peak power of Nr 1 was 93% of that for Diesel oil. These reductions in peak power could easily be overcome by readjusting the stop on the injector pump for a higher fuel rate. The microemulsions resulted in lower exhaust temperatures than the

Microemulsions as Diesel fuels

G. Gillberg and S. Friberg, Adv. Chem. Ser., 166 (Evaporation-combust. Fuels), 221 (1978)

A useless paper, with a lot of results from systems where the fuel compositions are not given. No surfactants are named.

Diesel engine evaluation of a non-ionic sunflower oil - aqueous ethanol microemulsion.

M. Ziejewski, KR. Kaufman, A.W. Sshwab, J. Am. Oil Chem. Soc., 10 (October 1984), 1620.

A microemulsion of sunflower oil and ethanol was formulated as 240 gal sunflower oil, 60 gal 190 proof ethanol, 150 gal 1-butanol and compared in a durability test with Phillips 2D reference. The reason of the work was to test sunflower oil as a Diesel fuel alternative. The fuel was formulated as a microemulsion in order to lower the viscosity. The major problem encountered was an incomplete combustion process at low load - engine operation. Significant lubrication oil dilution was observed initially, followed by an abnormal increase in viscosity o fth4e lubricating oil. Heavier carbon residue in the piston lands, in the piston ring grooves and in the intake ports was

Diesel Review, Ytkemiska Institute! 11 noted. In addition, premature injection-nozzle deterioation (sticking of the needle) was experienced.

Microemulsions stabilise ethanol-Diesel oil blends.

Chem. Eng. News Dec 15, 1980.

This is a journalist ’s report on the work of Schwab and Pdryde. It is claimed that blends containing 8 parts (by volume) of Diesel oil, 2 parts 95% ethanol, 1.5 parts mixed soy faattyacids and 0.5 partsN.N dimethyl ethanol amine, formed a microemulsion that was stable at temperatures down to -18°C, even though the blend contained more than 0.5% water. Using tert-butylamine instead of N,N- dimethylethanolamine provided even greater water tolerance and also resulted in lower viscosity. Another solution was also tested consisting of 9 parts Diesel oil, 1.5 parts 95% ethanol and 3 parts 1-butanol. This formulation was also stable down to -18°C. Diesel engine tests gave that the formulations above were comparable although not identical to operation with straight Nr 2 Diesel furl. The formulations gave lower smoke and carbon monoxide but the unburned hydrocarbonswere higher.

High Alcohol Microemulsion Fuel Performance in a Diesel Engine

BH West, AL Compere and WL Griffith. International Fuels and Lubricants Meeting and Exposition, Tulsa, Oklahoma, 1990

This is a useful reference where 5the authors have tested microemulsions of Diesel and ethanol, blended with various surfactants and co-surfactants. Engine tests, ignition delay as swell as cetane numbers have been determined. Best results, with respect to cetane numbers (values above 50), were obtained using linolenic acid as a surfactant and butanol, with or without methyldodecanate, as co-surfactant.

Low Emission Diesel Fuel

A.L. Compere, W.L. Griffith, G.F. Dorsey, B.H. for West Martin Marietta Energy System, Inc. US Patent 5,746,783, May 5 1998

This invention uses urea, or triazine compounds, to lower NOx. The compounds are effective in concentrations less than, or equal to, one per cent and are dissolved in the Diesel by means of a microemulsion. A typical microemulsion is composed of water 4.5% urea, or a triazine compound 0.5% Oleic acid 9.0% ethanol amine 1.0% tert-butyl alcohol 5.0%

Diesel Review, Ytkemiska Institute! 12 Effectof Composition on Sizes of w/o Etanolamine-Oleic Acid Microemulsions by Small-Angle Neutron Scattering

E. Camponetti, A. Lizzio, R. Triolo, A.L. Compere, W.L. Griffith and S.J. Johnsson., Langmuir, 5, 357-363, 1989.

The authors have studied the microemulsion droplets in system comprised of D20, oleic acid ethanol amine, 1-pentanol and hexadecane by means of small angle neutron scattering giving the size and shape of the water droplets.

Effect of Surfactant Neutralisation on Hexadecane/Water/1-Pentanol/Oleic Acid/Ethanolamine Microemulsions - A SANS Study

E. Caponetti, W.L. Griffith, J.S. Johnsson, R.Triolo, A.L. Compere; Langmuir, 4, 606 -610 (1988)

The system on hexadecane/water/1-pentanol/oleic acid/ethanolamine was varied in oleic acid concentration and degree of neutralisation. To a first approximation, aqueous core size is a function of the concentration of neutralised surfactant, giving similar particle sizes for half the concentration of fully neutralised surfactant and full concentration of half neutralised surfactant. Thus it appears that fully neutralised ethanolamine system is similar to fully neutralised potassium oleate systems of similar composition. This implies that substitution of ethanolamine for potassium does not significantly affect the systems compositions.

Microemulsions Fuel compositions fort the internal combustion engine and for fuel furnaces

H.W. Steinmann, US Pat 6,017,368 Jan 2000.

This patent claims a low viscosity microemulsion that is stable over a wide temperature range, including temperatures below the freezing point of water. The additives are fatty acids neutralised with amonia, ethoxylated non-ionic surfactants, water insoluble aliphatic alcohols, water nitrogen oxide scavengers (urea and ethyl carbamate).

Diesel Review, Ytkemiska Institute! 13 A SUMMARY OF RESEARCH AND FIELD TESTS.

ROLF BERG

March 2000 Summary Page 3 - 4

Background Page 5

Tests with "Oxygenated diesels" in Page 6-11

Australia Page 6

Brazil Page 6

Finland Page 6-7

France and the Netherlands Page 7

India Page 7

Sweden Page 7 - 9

United States of America Page 10-11

Conclusions Page 11

References. Page 12 - 14 SUMMARY

In many parts of the world there is a large interest to use a better diesel fuel than the one currently used. One of the possibilities is to use a mixture of alcohol, mainly ethanol, and diesel.

The development and testing of this type of fuel is currently carried out in many parts of the world today, in Australia, South and North America, Asia and in Europe. The reasonfor this varies between different areas. In Australia the main driver has been a development of an emulsifier; in Brazil the surplus of ethanol; in USA the demand for domestic renewable components in the fuel; in India the desire to find a locally produced renewable fuel; in Sweden as well as in the rest of Europe the main driver is the environment.

Although the main reasons for development vary, they all aim for the same goal: "obtaining a stable mixture of bio-ethanol in the local diesel formulation." By stable is meant, in this case, either a stable solution or a "quasi-stable" emulsion, which does not separate to any significant degree for, say, 90 days. The tests performed so far demonstrate the possibility to produce such a stable mixture of a given diesel quality and alcohols with the use of various additives.

The expression "Diesel fuel" does not mean the same thing to an American as it means to a Central European or to a Swede. The "Diesel fuel" has its different specifications in different countries. In many of the tests it is shown that a diesel of one specification is easy to blend with ethanol while another diesel specification is very difficult to get in blend or may need a lot more additive or a different formulated additive to get in blend with the ethanol. Also the quality of ethanol is of importance for the possibility to make stable blends.

At the moment there is a lot of activity in the field of developing additives to make it possible to blend ethanol and diesel. Not only the companies mentioned in the present report are interested in products and processes making it possible to blend ethanol and diesel. It is likely that that in the future we will see a broad competition, involving many more companies, in this additive market.

Emissions tests show that there is a large potential for improvement of the emissions, especially NOx and particulates, when using ethanol blended in diesel fuels. The decrease of the particulates may be up to 50%. This will give rise to better air quality and decrease the adverse health effects. Also, the contribution tothe greenhouse effect will decrease, due to the partly renewable nature of the fuel. ------1 ! Additive/ Amount 95% Lab Fleet Country Year of or tests tests 1 Producerf alcohol 99,5% alcohol Project used

Australia 1990 Dalco 15% 95% Yes Yes

Sweden 1992 - 99Dalco* 5-50% 95% Yes Yes 1997 BI07 -10% 95% Yes No 1998-AKZO MoM -15% 95% Yes No 1997- DER* -15% 95% Yes No 1999-Pure Energy -15% 95% Yes Not yet 1998- Technoferm* -15% Unknown Yes Not yet 1997 - 99Esterol** -30% Unknown Yes Yes

Brazil 1997 - 98Dalco -15% 95% Yes No 1998-No additive -7% 99,50% Yes Yes 1999-Pure Energy -15% Unknown Yes Not yet 1999BI07 -10% Unknown Yes No

USA 1998-Pure Energy -15% 95% Yes Yes 1999-Unknown -10% Unknown Yes Not yet 1999-8107 -10% Unknown Yes Not yet

Finland 1999-Dalco 15% 95% Yes No

India 1999-No additive -7% 99,50% Yes No

France 1998-Unknown Unknown Unknown Yes No 1998-Unknown*** Water,-10% Unknown Yes No,

The Netherlands 1998-Unknown Unknown Unknown Yes '

Tests with both ethanol and RME in Diesel **- Tests with RME and Ethanol without any diesel *** Tests with blend of diesel and up to 10% of water 4 BACKGROUND

During the 1980's SSEU (The Swedish Ethanol Development Foundation) (7) together with governmental authorities, the industry and transport companies had worked to develop ethanol driven vehicles and the infrastructure for these vehicles. The main work was directed to heavy-duty diesel driven vehicles where the environmental problems are considerable. To speed up the use of ethanol in existing diesel engines SSEU looked for other possibilities, resulting in a program to mix diesel and ethanol. This program was based on an emulsifying additive from Australia called Dalco. The Swedish program with this emulsifier started with laboratory tests at Chalmers Technical University, Gothenburg and continued in three stages. Engine drivability tests and emissions tests where performed on a test stand. Health influence was tested at the University of Stockholm and Fleet Tests were held in the areas of Gothenburg, Stockholm and Solleftea (for more details, see below). During 1992 to 1997 SSEUmade tests in Sweden with diesel -ethanol blends, supported by The Swedish Communication Research Board, KFB (8). The aim was to produce a blended fuel, diesel - ethanol that could be used instead of today's diesel fuels in existing diesel engines without any changes or timing on the engines. At the same time the aim was to reduce harmful emissions. At the start of the Swedish test program with mixed fuel diesel - emulsifier - ethanol KFB financed a literature review. This study was carried out by Lars-Ola Olsson at LU/LTH (1). He summarizes reports of tests attempting to make medium-term stable fuels by mixing alcohols with diesel. His conclusion is that "there are no major technical problems with fuels consisting of blends between diesel and low concentrations of ethanol." This report includes a good technical description of how a diesel engine works as well as a comparison between ethanol and diesel as fuel forthis type of engines.

5 OXYGENATED DIESELS IN:

AUSTRALIA

During the 1980's, Dr Russel Reeves at APACE Research Limited, tested an emulsifier, (2,3, 4 and 5) in order to make it possible to blend diesel and ethanol, producing a "stable" blend. The fuels were tested on both an engine dynamometer and in vehicles on a chassis dynamometer with good results. These results made it possible to start field tests with buses and trucks in Australia. This is the same emulsifying additive as has been used in the Swedish trials. Today there is very little activity regarding this fuel in Australia. An American based company, Methanex Corporation (6) has bought the rights for the product, Dalco. Methanex Corporation has no activities in Australia with diesel methanol blends but is active in South America, especially in Chile using methanol in blend with diesel.

BRAZIL

In Sao Paulo, Brazil, a large laboratory test is carried out, examining possibilities to blend ethanol into their quality of diesel fuel. They have tested the same additives as have been tested in Sweden, Dalco and Bio7, but they have had some problems and are not satisfied with the results so far. So far, the results have not been as good as those obtained in the tests in Sweden. This is probably due to the difference in diesel quality between Sweden and Brazil. They are today looking for other additives and have had contacts with Pure Energy in New York, USA. Laboratory tests have been made with a British additive, Bio7 from AAE. (9)

Tests have also been made with a very low percentage, 3 - 7%, of anhydrous ethanol in the diesel. In this case the tests are made without any additive and the anhydrous ethanol is blended directly into the diesel fuel. This will be tested on a small fleet of vehicles in Sao Paulo. In another Brazilian City, Curitiba, tests are carried out with a new additive. This project is now ready for the fleet testing stage, on buses in the city of Curitiba.

FINLAND

Tests with ethanol-blended diesel havebeen performed at VTT, theTechnical Research Centre of Finland, in Helsinki. (10) These tests have been ordered by Swedish companies and are a part of the Swedish tests with different additives.

6 1EA, the International Energy Agency, has a program on tests with new diesel fuels run by VTT. In this program there are tests planned for ethanol-blended diesel fuels. They have received a fuel from Sweden made with the additive Dalco for these tests. At present, reports are not available. But the results will be reported in an IEA-report.

FRANCE AND THE NETHERLANDS

In continenalEurope several actors are interested in using a mixture of ethanol and diesel. Tests are made in France and in the Netherlands. In both of these countries there are oil companies involved in the testing and a lot of secrecy is surrounding these tests. In France an independent laboratory, ETS, has made tests with mixtures of diesel and ethanol. These tests were made for an oil company and no reports have been published. In France, there have also been lab tests with up to 10% water in blend with diesel. This fuel have been presented to working groups in the Auto Oil 2 program and there have been a few minor articles in newspapers on this issue.

INDIA

Some tests are performed in India but so far no results are available. The tests involve "low" blends, i.e., 2 - 7 % of anhydrous ethanol blended into their quality of diesel fuel without any stabilizing additive. This is very similar to the tests made in Brazil showing the possibility to blend a small percentage of anhydrous ethanol in diesel without any additive.

SWEDEN

In 1992 SSEU realized that the development and the knowledge was sufficient for making fleet tests with ethanol-blended diesel. The fuel used in the fleet tests contained 15% hydrous (95%?)ethanol, 0.6% active substance of the additive Dalco (Dalco is the name of a product developed by the Australian company Apace Research Ltd.) and the remainder being Swedish diesel of environmental class 1 (Mkl). The first stage was performed in laboratories at Chalmers University in Gothenburg. (11)

Fleet tests with trucks and buses were carried out in the following three areas in Sweden: the coastal area south of Gothenburg, Stockholm and the area around the city of Solleftea in the northern parts of Sweden. Both infrastructure, costs, environmental benefits and emissions tests were taken into account. A special investigation was made on the injection systems in two of the trucks. They were retrofitted with new injectors and injection pumps at the start of the project. These injection systems were taken out of the trucks after the fleet test was finished and the systems were sent to a Bosch workshop in Stockholm for investigation. The

7 results of these investigations are reported in one of the reports from the fleet tests. In summary, the injection systems showed no evidence of any injector related problems. (12)

These data provide the background to for introducing these types of fuels on the market in the future. The test program has been reported in several Swedish reports. (13, 21 - 24)

The official tests were finished during 1997. After this there has been no governmental support for further tests of this kind of mixed fuels.

Since late 1997, when the governmental support for the test was terminated it has not been economically feasible to use the mixed fuel diesel-Dalco emulsifier-ethanol. The costs for this kind of fuel is much too high and the environmental benefits can not alone motivate the users to carry this cost for the fuel. However, tests involving a few small-sized fleets have been using this Dalco mixed fuel motivated only by environmental reasons. In these fleets no problems have been reported concerning any kind of problems with the injection systems (as pointed out above, the diesel fuel in Sweden is substantially different from diesel fuel in Brazil where the success has been very limited). The trucks using this mixed fuel are working in the city area of Stockholm and are mostly used forstreet maintenance.

The use of the additive Dalco makes the fuel very expensive compared to neat diesel base fuel. The production process,-(i. e., the mixing of the fuel diesel-Dalco emulsifier -ethanol) is very labor intensive and requires long time, generating costs that result in a price that is not acceptable for the fuel market in Sweden.

With the objective of making the mixed fuel less expensive several projects are working to find other methods to blend ethanol and diesel fuel to a stable fuel. Many different additives have been tested but so far none has been completely successful. The additive that we are looking for is a biological, renewable product that gives us the possibility to blend, by simply mixing (splash blend) 10 to 15% hydrous ethanol with diesel at a price that makes the resulting mixture only marginally more expensive than ordinary diesel. There is a demand for a fuel of this kind in Sweden for environmental reasons. Some city authorities have declared that they will use at least 10% renewable fuels in their cars, trucks and machines during the year 2000. This is mainly because of the C02 problem but also because of other, more local, environmental benefits, connected to renewable fuels, such as decreasing particulate and NOx emissions. The results from the tests show that these emissions will be reduced, compared to neat diesel fuel, when a blend of diesel and ethanol is used. (14) Particulate emissions will decrease more than proportionally (up to 50% reduction) to the amount of ethanol in the blend. NOx emissions will decrease slightly. Also the health effects will change. The test shows that the biological activity in the exhausts is reduced, indicating that the exhausts are less dangerous and the risk for cancer and

8 mutations is lower compared to exhausts from neat diesel fuels. (15)

These tests in Sweden have received attention in other nations in Europe (theiNetherlands and France), but also in Brazil, India, Mexico and USA.

This work has also initiated development of a more useful additive, easier to blend and more cost effective. Forthis reason tests have been made with the following products.

Bio7 has been tested during 1998 in blend with Swedish diesel Mkl. The lab tests show unsatisfying results concerning drivability. Reports not available. (9)

Samples of the mixed fuel using Dalcoas the emulsifier have been sent to VTT in Finland for testing. These tests are a part of an IEA program on "new diesel fuels". Will be reported in an IEA report.

There is a discussion between Pure Energy Corporation and a Swedish company to test their additive together with the Swedish Mkl. (20)

Akzo Nobel is performing lab work in order to find a suitable additive. They have some promising results but have not, so far, found an additive ready to use. No reports available. (16)

Svenska Technoferm is another company working in this field. They have started to make tests with a renewable additive in Swedish diesel Mkl. Reports not available.

SLR has a program to make a mixture of ethanol - RME - diesel Mkl. This program is in cooperation with YKI (Institute for Surface Chemistry, Ytkemiska Institutet). The program has progressed to become a project with support from the European Commision (17)

There has also been a project of similar character, mixing ethanol and biodiesel (RME), Esterol. This project has had support from the ALTENER program in EU. No reports are available at present. According to the project manager, the first part of the project is reported to the European Commission program ALTENER, but he has no copies of the report availablefor distribution at this moment. (18)

9 UNITED STATES of AMERICA

In Illinois, tests are made with a blend of diesel and 15% hydrous ethanol, (95% ethanol, 5% water). The additive used is a product from the company Pure Energy Corporation, New York. It is a biologically produced additive, 5% of the additive is used in the blends. This is the first generation of this additive and the company is working on developing it further. This project is supported by the US Department of Energy (DOE), (19) and by the ethanol industry and engine manufacturers. The project started late 1998 and had at that time two truck running on the blend, which is called ”Oxy-diesel”. Results from the tests are published on the homepage of Pure Energy Corporation. (20)

The fleet of test vehicles expanded during May 1999 from two trucks in Decatur, Illinois, with some 15 buses in Chicago. Emissions tests have started at a university in Illinois. This project is planning to run long time tests with engines on an engine dynamometer. Producers of fuel systems are involved in the project as well as the engine manufacturer, Cummins.

A report has been released from emissions tests made at South West Research Laboratories in San Antonio, Texas. This report shows that particulate matter (PM) is reduced with 41% using a blend with 15% ethanol and 5% additive compared to driving on U.S. diesel no 2. At the same time there is a reduction of NOx with 5% and CO with 27% while HC emissions increase with 110%. Tests have also been performed with 10% ethanol and 5 % additive with the following results: Reduction of PM 27%, NOx 4% and CO 20% increase of HC with 71 %. The report also mentions the loss of power; almost 10% compared with running on neat diesel. The report is published at the homepage of Pure Energy Corporation.

Personal at Pure Energy Corporation have indicated that there are problems connected with using the same formulation for the additive on all diesels fuels. For a given diesel formulation, the additive needs to be optimized concerning composition and dosage. Development work is also underway with the additive to make it more active and to make it less costly to produce. (20)

The British company AAE have tested their additive, Bio7, with Swedish diesel MK1 without success, drivability problems occurred. AAE is now active in USA. In cooperation with U S Department of Energy they are starting a project with a blend of 7% anhydrous ethanol in diesel. They claim that their additive is ofrenewable origin enabling them to have more than 10% renewable fuel components in the diesel. (9)

The company Methanex, (6) has gained the rights for the Americas concerning the additive that was used in some Sweden tests, Dalco. This is an Australian product, which has been tested also in Australia and in Argentina with some work going on also in the western parts of 10 South America, mainly in Chile. Methanex uses methanol, produced from fossil gas (natural gas), i.e., is not a renewable blending component.

At the moment there are many activities in this field in the USA. Not only the companies mentioned above are interested in products to make it possible to blend ethanol and diesel. It is likely that in the future we will see a broad competition in the additive market to blend ethanol into diesel fuels.

CONCLUSIONS

It is possible to make a "new", more environmentally friendly fuel for use in existing diesel engines by mixing ethanol and diesel. There are potential benefits from using this kind of fuel: less harmful emissions and health effects, as well as improved air quality.

A number of countries are showing great interest in this kind of diesel fuel. The ethanol-diesel blend is tested in many parts of the world today: Australia, South and North America, Asia, Europe. The main reason for this varies between different areas. In Australia the main driver has been development of an emulsifier; in Brazil the surplus of ethanol; in USA the demand for domestic renewable components in the fuel; in India the desire to find a locally produced renewable fuel; in Sweden, as well as in the rest of Europe, the main driver is the environment.

Although the main reasons for development vary, they may all lead to the same goal: obtaining a stable mixture of bio-ethanol in the local diesel formulation.

The tests performed so far show the possibility to come up with a stable mixture of a given diesel quality and alcohols using various additives. The expression "Diesel fuel" does not mean the same thing to an American as it means to a Central European or to a Swede. The fuel "Diesel" has its different specifications in different areas. In many of the tests it is shown that a diesel of one specification is easy to blend with ethanol while another diesel specification is very difficult to get in blend or may need a lot more additive to get in blend with the ethanol. Also the quality of ethanol is of importance for the possibility to make stable blends.

Most of the tests show better emissions results, compared with running on neat diesel fuel, from measurements on an engine test stand as well as from tests with vehicles on a chassis dynamometer. These lower emissions can help to make the air quality better and to reduce the health risks. Also, the renewable part of the fuel, the bio-ethanol, will reduce the amount of produced green house gases.

11 REFERENCES.

1. Lars-OIa Olssort En litteraturstudie om Blandbransle best&ende av Diesel och Etanol Lu/LTH Varme och Kraftteknik. ISRN LUTMDN/TMVK-3160-SEaug 1993. (KFB 93-61-742)

2. Apace Research Ltd, Exhaust emissions of in-service trucks using diesohol E 15 compared to diesel fuel.

3. Apace Reseach Ltd, Use of dieseohol emulsions in compression ignition engines. A brief summary of the salient points to be considered when using ethanol/diesel emulsions.

4 . R.R Reeves and E.J. Lorn Blending of alcohol with diesel fuel. The United Nations Industrial Development Organisation -85 Project number: US/GLO/83/039.

Homepage of Apace: www.pactok.net/DOCS/apace

6. Homepage of Methanex Corporation: www.methanex.com

7. Homepage of SSEU (now BAFF): www.sseu.se ......

8. Homepage of KFB: www.kfb.se

9. AAE Homepage: http://members.aoi.com/AAEGroup

10. Contact persons at VTT are Nils-Olof Nylund and Paivi Aakko, phone number +358 9 456 5757

11. Henrik Simonsen Studier av tandegenskaper hos etanolbranslen. Delrapport TFB (Transportforskningsberedningen numera Kommunikationsforskningsberedningen) projekt Dnr 92-69-742

12 ISSN 1101-9972.

12. KFB rapport 1997:35 Blandbransle etanol/diesel. Siutrapporl (ink! emissionsbiiaga) Rolf Berg, Befri Konsult och Karl-Erik Egeback.

13. In a special English summary report written by ProfessorK-E Egeback at the University of Lulea, Sweden ail the reports from the different tests are summarized.

14. KFB meddelande 1997:17 Chemical and biological characterization Roger Westerholm, of exhaust emissions from ethanol and A. Christensen, M. Tomqvist. ethanol blended diesel fuels in Lars Ehrenberg, D Haupt. comparison with neat diesel fuels.

15. KFB meddelande 1997:16 Undersokning av reglerade och nagra Dan Haupt, Nordstrom, oreglerade emissioner fran motorer Merja Niva, L Borgenudd. drivna med blandbransle, dieselolja Stig He 11 berg, Lulea Univ. och elanol.

16. Contact person at Akzo Nobel is Urban Lowenberg phone +46 303 85000.

17. Contact person at SLR is Johan Berg, phone number +468 657 4365.

18. The project manager can be reached at the following telephone number: +46 155 211 607.

19. Homepage of DOE: www.doe.gov/

20. Pure Energy homepage: www.pure-energy.com

21. KFB rapport 1997:23 Diesohol - dieselbransle med 15% etanol. Slutrapport. Lars Alin, ASPEN Petroleum

22. KFB rapport 1997:29 Fordon drivna med blandbransle diesel - etanol Jan Lothigius (red)