Improved Cold-Flow Additives for B100 and B20

Kelly Jezierski

10/22/07

WSU AET Program Thesis Topic

IntroProblem – 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 — *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 SummaryExperimental DesignThe 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 B20Measure 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. Viscosity2. 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. Kerosene or petro-diesel2. 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 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) 485–4912. 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 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 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.

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#adds3. C.-W. Chiu et al., “Impact of cold flow improvers on soybean biodiesel blend,” Biomass and

Bioenergy 27 (2004) 485–491

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.2Perform Literature Search & List Needed Materials

50%

A.3 Select Cold Flow Additives to Test 50%

A.4Contact/Query Experts on Pour Point Depressants

0%

A.5 Order Materials 0%

A.6Train on Use of NBEL Equipment and Experimentation

0%

A.7Draft Experimental Procedure for Effects of Cold Flow Additives

0%

A.8Draft Experimental Procedure for Amount of Additives Experimentation

0%

Fall 2007 Semester Winter 2008 SemesterTimeline

Schedule of Project Action ItemsAET 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.0Finalize Experimental Procedure for Effects of Cold Flow Additives

0%

B.1 Perform Dry Run of Experimentation 0%

B.2Further Refine Experimental Procedure for Effects of Cold Flow Additives Based on Dry Run Results

0%

B.3Perform Final Experiments to Determine Effects of Cold Flow Additives

0%

B.4Analyze 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.6Analyze 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 SemesterTimeline

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.0Write First Draft of Thesis for WSU Review

0%

C.1Present to NBEL Team for Review Commentary

C.2Refine 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 SemesterTimeline

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