Transcript Improved Cold-Flow Additives for B100 and B20 Biodiesel

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 blends…users implement the same
solutions as they would with Number 2 diesel fuel —
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*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 sat’d 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.
2.
Kerosene or petro-diesel
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. don’t lower
PP much
5.
Noteworthy – Tertiary fatty amines and amides reportedly enhanced
ignition quality w/o negatively affecting the low temp properties.
•
Sat’d fatty –OH’s 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 0.1–2% in B80,
B90, and B100 SB blends.
 They reported that two of the four additives – Bio Flow-875 from Octel Starreon and OS110050 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.
2.
C.-W. Chiu et al., “Impact of cold flow improvers on soybean biodiesel blends,” Biomass and
Bioenergy 27 (2004) 485–491
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) 505–512 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) 440–444, 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 10–35 (ROHM GmbH, Germany); Chimec
6635 (Chimec SpA, Italy); Clarinat Sosi Flow (Clariant (Norge) AS, Norway); Infineum R442 (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 10–35 @ 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) 753–758 DOI 10.1002/ejlt.200600074.
Recommended Proprietary Additives
for Reducing PP
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.
3.
4.
5.
1.
2.
3.
Wintron XC30 – Biofuel Systems Limited [2.]
Arctic Express Biodiesel Antigel – Power Service Products
[2.]
Lubrizol 8056 J – Pour Point Depressant for Vegetable
Oils and Biodiesel
[2.]
Bio Flow-875 – Octel Starreon LLC [3.]
http://www.rohmax.com/rohmax/en/productsapplications/productsbyseries/series10/
http://journeytoforever.org/biodiesel_winter.html#adds
C.-W. Chiu et al., “Impact of cold flow improvers on soybean biodiesel blend,” Biomass and
Bioenergy 27 (2004) 485–491
Proposed Schedule (Part A)
AET Master Thesis: Improved Biodiesel Cold-Flow Additives for Various Types of B100 and B20
Schedule of Project Action Items
Timeline
PROJECT
% Done
Fall 2007 Semester
Winter 2008 Semester
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
A.3 Select Cold Flow Additives to Test
A.4
Contact/Query Experts on Pour Point
Depressants
A.5 Order Materials
50%
0%
0%
Train on Use of NBEL Equipment and
Experimentation
Draft Experimental Procedure for Effects
A.7
of Cold Flow Additives
A.6
A.8
50%
Draft Experimental Procedure for
Amount of Additives Experimentation
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Activity complete
Proposed Schedule (Part B)
AET Master Thesis: Improved Biodiesel Cold-Flow Additives for Various Types of B100 and B20
Schedule of Project Action Items
Timeline
PROJECT
% Done
Fall 2007 Semester
Winter 2008 Semester
Sept-07 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08
Overall Program
B
Experimentation
Finalize Experimental Procedure for
B.0
Effects of Cold Flow Additives
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B.1 Perform Dry Run of Experimentation
0%
Further Refine Experimental Procedure
B.2 for Effects of Cold Flow Additives Based
on Dry Run Results
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Perform Final Experiments to Determine
Effects of Cold Flow Additives
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B.3
Analyze Experiments on Effects of Cold
Flow Additives
Refine Procedure for Amount of
Additives Experimentation in Detail,
B.5
Based on Results of Effects of Cold
Flow Additives Experiments
Analyze Amount of Additives
B.6
Experimentation Results
B.4
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Proposed Schedule (Part C)
AET Master Thesis: Improved Biodiesel Cold-Flow Additives for Various Types of B100 and B20
Schedule of Project Action Items
Timeline
PROJECT
% Done
Fall 2007 Semester
Winter 2008 Semester
Sept-07 Oct-07 Nov-07 Dec-07 Jan-08 Feb-08 Mar-08 Apr-08 May-08
Overall Program
C
C.0
C.1
C.2
C.3
C.4
C.5
Thesis
Write First Draft of Thesis for WSU
Review
Present to NBEL Team for Review
Commentary
Refine Draft for Final Submisison,
Based on Commentary
Submit Final Paper for Publication
Thesis Published
Present Results to NBEL Consortium
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Sub-task timing
Sub-task on schedule
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Sub-task behind schedule - end result
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attainability doubtful
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