Improved Cold-Flow Additives

for B100 and B20

Kelly Jezierski
10/22/07
WSU AET Program Thesis Topic
Intro
Problem BD has been known to gel in cold weather,
which plugs filters and can prevent it from being pumped
to engine.

According to the NBB, if it is desired to reduce the cold flow
properties of B20 blendsusers implement the same
solutions as they would with Number 2 diesel fuel
*blend with kerosene,
use cold flow enhancing additives,
*turn on fuel filter or fuel line heaters, or
*store vehicles near or in a building.

Cold Flow Impacts, National Biodiesel Board.,
http://www.me.iastate.edu/biodiesel/pages/biodiesel16.html. p 4.

*This is not always practical, and when no such precautions
are required for regular diesel, why use biodiesel?...
Thesis Summary
Experimental Design
The following types of biodiesel will be investigated:
1. Soybean oil-based (SBO) 4. Palm oil-based (PO)
2. Rapeseed oil-based (RO) 5. Yellow grease (YG)
3. Cottonseed oil-based (CSO) 6. Poultry fat-based (PF)

Effects of various cold-flow additives on B100 and B20
Measure the following values using 0.5%, 1%, 1.5%, 2%, and 3% by volume of both
proprietary and generic biodiesel cold-flow improvers on B100 and B20 to
determine the best additive(s):
1. CP 3. TAN 5. Viscosity
2. PP 4. CFPP 6. CN 7. IP

Effects of amount of additive(s) on B100 and B20
Use different amounts of additive mixtures, from 0.5% to 3% by vol., to run
same tests and determine an optimal additive formulation.

Outcome
Understanding of the chemical nature, concentration effects, and mechanism
of cold-flow reduction.
Help to identify the optimal formulation to develop an improved pour point
depressant.
Composition Performance Effects
Saturated fatty compounds => higher melting points than unsaturated.
In a mixture they crystallize at higher temperature than the unsaturates.
Fuels from fats/oils with significant amounts of satd fats => higher CPs and PPs.

G. Knothe / Fuel Processing Technology 86 (2005),1065.

D. Baker, Ford Research and Advanced Engineering / Biodiesel, A Role for SAE, SAE Motor Vehicle
Council (2006),10.
Cold Flow Depends on
Saturation Content
D. Baker, Ford Research and Advanced Engineering / Biodiesel, A Role for SAE, SAE Motor Vehicle
Council (2006),11.
Recommended Generic Additives for
Reducing PP
1. Kerosene or petro-diesel
2. Fatty compound-derived materials with bulky moieties (ex., alcohols)
in the chain
3. Branched esters such as iso-propyl, iso-butyl and 2-butyl instead of
the methyl esters, which have lower MPs in the neat form.
4. Usu. polymeric additives
EVAs (ethylene vinyl acetate copolymers) used to lower PP for
petro-diesel, some 'compatible with biodiesel,' but usu. dont lower
PP much
5. Noteworthy Tertiary fatty amines and amides reportedly enhanced
ignition quality w/o negatively affecting the low temp properties.
Satd fatty OHs of chain lengths > C12 increased the PP
substantially.
Ethyl laurate weakly decreased the PP.



G. Knothe / Fuel Processing Technology 86 (2005),1065-1066.

Studies from Literature
Chiu et al., tested four cold flow improver additives at 0.12% in B80,
B90, and B100 SB blends.
They reported that two of the four additives Bio Flow-875 from Octel Starreon and OS-
110050 from SVO Specialty Products, Inc. significantly decreased the PPs, with the
Bio Flow-875 being most effective, but they also used a significant amt of kerosene.
But all had little effect on CPs.
A mixture of 0.2% Bio Flow-875 additive, 79.8% biodiesel, and 20% kerosene (D#1)
reduced the pour point of B100 by 27 C.
Ming et al. studied samples of palm oil FAMEs and blends with 1-2% of
the following additives: Tween-80, dihydroxy fatty acid (DHFA),
acrylated polyester pre-polymer, palm-based polyol (PP), a blend of
DHFA and PP at a 1:1 ratio (DHFAPP), an additive synthesized using
DHFA and ethyl hexanol (DHFAEH), and castor oil ricinoleate.
All had good results, with more significant reductions of PP and CP values observed for
POME, PKOME, POMEPO, POMESO and PKOMESO samples.
The biggest PP reduction was about 7.5C (by addition of 1.0% DHFA to POMEPO), while
the biggest reduction of the CP value was about 10.5C (by addition of 1.0% DHFA 1 1.0%
PP to POME).

1. C.-W. Chiu et al., Impact of cold flow improvers on soybean biodiesel blends, Biomass and
Bioenergy 27 (2004) 485491
2. T. C. Ming et al., Strategies for decreasing the pour point and cloud point of palm oil products,
Eur. J. Lipid Sci. Technol. 107 (2005) 505512 DOI 10.1002/ejlt.200400944

Studies from Literature
Sern et al. investigated the PP properties of palm FAMEs and blends,
as well with commercially available polymers/surfactants.
These included poly(ethylene glycol), poly(methyl methacrylate), poly(ethylene-co-vinyl
acetate), poly(styrene-co-maleic anhydride), poly(ethylene glycol) distearate, poly-
(octadecyl methacrylate), poly(1-decene), poly(maleic anhydride-alt-1-octadecene),
caprylic acid sodium salt, N-lauroylsarcosine sodium salt, polyoxyethylene(2) cetyl ether
and polyoxyethylene(10) cetyl ether.
Seven out of the twelve polymeric compounds tested were miscible in palm oil methyl
esters due to similar polarities of the solute and biodiesel.
Poly-(maleic anhydride-alt-1-octadecene) was able to improve the PP of palm oil methyl
esters from 12 to 6 C when 2 wt-% was added.
The CP was reduced from 12.9 to 8.1 C, and the CFPP was reduced from 12 to 7 C, whilst the flash point value
remained unchanged at 156 7C when 2 wt-% of poly (maleic anhydride-alt-1-octadecene) was added to the palm oil
methyl esters.

1. C.H. Sern et al., The effect of polymers and surfactants on the pour point of palm oil methyl
esters, Eur. J. Lipid Sci. Technol. 109 (2007) 440444, DOI 10.1002/ejlt.200600242.
Studies from Literature
Kazancev et al. investigated various blends of rapeseed oil methyl
esters, linseed oil methyl esters, pork lard methyl esters and fossil diesel
fuel were prepared, and both CP and CFPP were analyzed using:
Wintron XC- 30 (Biofuel Systems, UK); Viscoplex 1035 (ROHM GmbH, Germany); Chimec
6635 (Chimec SpA, Italy); Clarinat Sosi Flow (Clariant (Norge) AS, Norway); Infineum R-
442 (Infineum, UK); Grotamar 71 (Yachticon, Germany).
The mixtures whose CFPP are -5 C and lower may contain even up to 25% palm FAMEs,
while the proportion of petro-diesel and rapeseed FAMES may vary over a wide range --
such mixtures without additional additives may be used in in the summer only (no surprise).
In the transitory periods (Autumn/Spring), it is possible to use up to 20% FAME mixtures
with winter diesel, and the 5% FAME additive may be added to the fuel used in winter.
Viscoplex 1035 @ 5000 mg/kg was found to be the most effective on properties of the RME
mixture with PME and LME at a ratio of 20 : 4 : 1, decreasing the CFPP by -10C.
Chimec 6635 @ 1000 mg/kg was most effective for rapeseed FAMEs, decreasing the CFPP from -5 to -
19 C.

1. K. Kazancev et al., Cold flow properties of fuel mixtures containing biodiesel derived from animal
fatty waste, Eur. J. Lipid Sci. Technol. 108 (2006) 753758 DOI 10.1002/ejlt.200600074.
1. VISCOPLEX 10-171 (canola) and 10-310 or 10-35
(rapeseed & comparable) degussa (now a unit of Evonik
Ind.) [1.]

Note 2., 3., and 4. below contain small amounts of toxics, usu. toluene
2. Wintron XC30 Biofuel Systems Limited [2.]
3. Arctic Express Biodiesel Antigel Power Service Products
[2.]
4. Lubrizol 8056 J Pour Point Depressant for Vegetable
Oils and Biodiesel
[2.]
5. Bio Flow-875 Octel Starreon LLC [3.]

1. http://www.rohmax.com/rohmax/en/productsapplications/productsbyseries/series10/
2. http://journeytoforever.org/biodiesel_winter.html#adds
3. C.-W. Chiu et al., Impact of cold flow improvers on soybean biodiesel blend, Biomass and
Bioenergy 27 (2004) 485491


Recommended Proprietary Additives
for Reducing PP
PROJECT % Done
Sept-07 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08
Overall Program
A Preparation 33%
A.0 Select Research Topic 100%
A.1 Write Thesis Summary 100%
A.2
Perform Literature Search & List Needed
Materials
50%
A.3 Select Cold Flow Additives to Test 50%
A.4
Contact/Query Experts on Pour Point
Depressants
0%
A.5 Order Materials 0%
A.6
Train on Use of NBEL Equipment and
Experimentation
0%
A.7
Draft Experimental Procedure for Effects
of Cold Flow Additives
0%
A.8
Draft Experimental Procedure for
Amount of Additives Experimentation
0%
Fall 2007 Semester Winter 2008 Semester
Timeline
Schedule of Project Action Items
AET Master Thesis: Improved Biodiesel Cold-Flow Additives for Various Types of B100 and B20
Proposed Schedule (Part A)
= Full task schedule
= Sub-task timing
= Sub-task on schedule
= New or extended sub-task
=
Sub-task behind schedule but end result
still achievalbe
=
Sub-task behind schedule - end result
attainability doubtful
= Activity complete
Proposed Schedule (Part B)
PROJECT % Done
Sept-07 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08
Overall Program
B Experimentation 0%
B.0
Finalize Experimental Procedure for
Effects of Cold Flow Additives
0%
B.1 Perform Dry Run of Experimentation 0%
B.2
Further Refine Experimental Procedure
for Effects of Cold Flow Additives Based
on Dry Run Results
0%
B.3
Perform Final Experiments to Determine
Effects of Cold Flow Additives
0%
B.4
Analyze Experiments on Effects of Cold
Flow Additives
0%
B.5
Refine Procedure for Amount of
Additives Experimentation in Detail,
Based on Results of Effects of Cold
Flow Additives Experiments
0%
B.6
Analyze Amount of Additives
Experimentation Results
0%
AET Master Thesis: Improved Biodiesel Cold-Flow Additives for Various Types of B100 and B20
Fall 2007 Semester Winter 2008 Semester
Timeline
Schedule of Project Action Items
Proposed Schedule (Part C)
PROJECT % Done
Sept-07 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08
Overall Program
C Thesis 0%
C.0
Write First Draft of Thesis for WSU
Review
0%
C.1
Present to NBEL Team for Review
Commentary
C.2
Refine Draft for Final Submisison,
Based on Commentary
0%
C.3 Submit Final Paper for Publication 0%
C.4 Thesis Published 0%
C.5 Present Results to NBEL Consortium 0%
AET Master Thesis: Improved Biodiesel Cold-Flow Additives for Various Types of B100 and B20
Fall 2007 Semester Winter 2008 Semester
Timeline
Schedule of Project Action Items
= Full task schedule
= Sub-task timing
= Sub-task on schedule
= New or extended sub-task
=
Sub-task behind schedule but end result
still achievalbe
=
Sub-task behind schedule - end result
attainability doubtful
= Activity complete