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Dr. Philip Steele Professor Mississippi State University.

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1 Dr. Philip Steele Professor Mississippi State University

2 Production of Multiple Fuel Types from Bio-oil
Philip H. Steele Venkata K Penmetsa Satish K Tanneru Forest Products Department Mississippi State University

3 Bio-oil properties: 40-50% oxygen content is the primary factor causing the negative properties of bio-oil: High acidity Aging problem (polymerization) Immiscibility with petroleum-derived fuels Pungent odor Low energy density (35 – 40% petroleum fuels)

4 Olefination of bio-oil requires reaction of an olefin (10%) with the bio-oil; a relatively high HHV boiler fuel is produced (fuel 1): Olefination requires alcohol addition at a relatively low percentage (20%) An aqueous fraction is produced that reduces water content of the fuel after being separated from the organic fraction

5 Olefination reaction scheme:
The reaction predominantly produces ethers and esters; a small percentage of water (<5%) is converted to alcohol

6 Mass balance of olefination process:
Olefinated bio-oil

7 Olefination fuel properties:
Raw Bio-oil Boiler Fuel Acid value 98.0 19.2 HHV, MJ/kg 16.1 34.0 Water, % 30.6 1.7 C, % 36.2 71.1 H, % 7.8 10.0 N, % 0.03 0.1 O, % 55.9 18.8

8 Product testing: A highly combustible boiler fuel is produced by olefination as the test below indicates:

9 Esterification to bio-diesel (fuel 2):
R-COOH + R’-OH R-COOR’+ H2O Complete conversion of the acids, aldehydes, and ketones require moles of alcohol per kg of bio-oil; not economically viable The high water content (20-30%) in raw bio-oils plus water from the esterification reaction create equilibrium limitations Catalyst

10 Esterification to bio-diesel (fuel 2):
Our research has focused on reducing the amount of alcohol to accomplish the reaction and to provide adequate stability such that equilibrium reaction reversal due to presence of water was slowed Aqueous fraction for 20% alcohol is about 20% with about 55% boiler fuel yield

11 Esterification to bio-diesel (fuel 2, early results):
Raw Bio-oil Bio-diesel ASTM D 6751 bio-diesel Acid value 98.0 16.7 0.5 HHV, MJ/kg 16.1 36.5 36 Water, % 30.6 5.3 0.05 C,% 36.2 78.2 77 H,% 7.8 9.7 12 N,% 0.03 0.4 O,% 56.0 11.7 11

12 Continuous stirred tank reactor
Bio-oil hydroprocessing to hydrocarbons: Bio-oil Packed bed reactor Continuous stirred tank reactor Using 100% hydrogen Low hydrogen* (<50%) *Provisional patent filed

13 Both packed bed reactor hydrogen processing and low hydrogen autoclave HT a high-quality hydrocarbon mix is produced: Removal of oxygenated compounds 100%Hydrogen/ Hydrocarbons Low Hydrogen* Water Bio-oil Upgraded bio-oil *Provisional patent filed

14 Packed bed reactor plugging and catalyst deactivation occurs quickly:
Hydrotreating plugging Catalyst deactivation Elliott (2007) Coke plugging 48 h Elliott (2009) 100 h Elliott (2010) 10 – 100 h Elliott (2012) 90 – 91.5 h MSU experiments (2012) 28 h and improving

15 MSU continuous packed bed reactor:

16 Hydroprocessing with the MSU continuous packed bed reactor (fuel 3):
Raw bio-oil MSU hydrocarbons *Elliott et al 2012 Acid value 98.0 13.4 HHV, MJ/kg 16.1 41.3 Water, % 30.6 1.9 0.3 Yield % 38 42 C,% 36.2 79.0 84.0 H,% 7.8 10.6 10.4 N,% 0.03 0.1 O,% 56.0 2.1 *Energy and Fuels 26(6):  doi: /ef

17 Hydrotreating bio-oil with low hydrogen:
MSU has developed a hydroprocessing technique (provisional patent filed) utilizing low hydrogen rather than 100% hydrogen for the hydrotreating stage This can allow a low hydrogen hydrotreating closer to the resource rather than at a methane cracking facility; the stabilized bio-oil can then be transported and stored without aging

18 1st stage hydrotreating comparing 100% hydrogen and low hydrogen results (fuel 4):
Raw Bio-oil Hydrogen Low Hydrogen Acid value 98.0 55.5 51.6 HHV, MJ/kg 16.1 34.7 36.5 Water, % 30.6 3.1 2.7 C,% 36.2 73.7 76.4 H,% 7.8 9.7 9.1 N,% 0.03 O,% 56.0 15.2 14.0

19 Comparison of diesel fuel with hydrocarbon mix produced with low hydrogen HT followed by 100% hydrogen HC and comparison with diesel fuel (fuel 4, early results): Raw Bio-oil HC bio-oil (H2) Diesel Acid value 98.0 < 0.1 HHV, MJ/kg 16.1 43.0 45.8 Water, % 30.6 0.5 C,% 36.2 86.2 85.1 H,% 7.8 12.1 12.2 N,% 0.03 0.01 O,% 56.0 1.5

20 Simulated distillation of hydrocarbon mix produced by low hydrogen HT followed by 100% hydrogen HC:
Gasoline, 55%

21 Summary: MSU has explored both traditional and new approaches to upgrading bio-oil Olefination is a novel method of producing a boiler fuel (fuel 1) with low water content and a relatively high HHV of 34 MJ/kg (patent pending) Esterification of bio-oil to biodiesel produces a high energy (36.5 MJ/kg) boiler fuel (fuel 2) with the potential to produce biodiesel meeting ASTM transportation fuel quality MSU has progressed to production of mixed hydrocarbons with packed bed technology (fuel 3); improvement is ongoing

22 Summary: MSU has pioneered the utilization of low hydrogen in the hydrotreating stage to conserve hydrogen. The resulting mixed hydrocarbons (fuel 4) contain the petroleum molecular weight equivalents of 55% gasoline, 30% jet fuel and 15% diesel

23 Acknolwedgement: This research is based upon work funded through the Sustainable Energy Research Center at Mississippi State University and is supported by the Department of Energy under Award Number DE-FG3606GO86025.

24 Production of Multiple Fuel Types from Bio-oil
Philip H. Steele Venkata K Penmetsa Satish K Tanneru Forest Products Department Mississippi State University

25 Dr. Philip Steele Professor Mississippi State University

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