Conversion of Bio-oil to Hydrocarbons Via a Low Hydrogen Route Philip H. Steele and Sathish K. Tanneru

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1 Conversion of Bio-oil to Hydrocarbons Via a Low Hydrogen Route Philip H. Steele and Sathish K. Tanneru Forest Products Department Mississippi State University 1

2 Pyrolysis auger reactor: MSU has developed a 7 kg/h auger fast pyrolysis reactor to produce bio-oil from biomass. Bio-oil yields are 65% from pine wood. Pine wood bio-oil was utilized in our experiments. 2

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) 3

4 Alternate bio-oil hydroprocessing methods to produce hydrocarbons: Pretreated bio-oil Hydrotreating via 100% H 2 or bio-syngas* Hydrocracking via 100% H 2 *Patent pending HT bio-oil 4

5 Hydrotreating bio-oil with syngas: MSU has developed a technique (patent pending) utilizing a proprietary bio-oil pretreatment process. This pretreated bio-oil allows hydrotreating (HT) with syngas containing 18% vs 100% H 2. Required HT H 2 is produced by the water gas shift reaction (WGS). Biomass syngas can be produced near the resource by gasifying biomass not suitable for pyrolysis. This will allow HT near the resource rather than at a centralized methane cracking facility; following HT the bio-oil is stabilized and can then be transported and stored without aging. 5

6 Materials and Methods: Raw bio-oil required for this research was produced from loblolly pine wood chips in the Department of Forest Products, MSU. The syngas was produced by a down-draft gasifier and compressed to 1500 psi in laboratory tanks. We thank Dr. Fei Yu for supplying this compressed syngas for our experiments. Catalysis was performed with nickel-based proprietary heterogeneous catalysts. Hydroprocessing treatments were performed in a stirred batch autoclave. 6

7 1 st stage hydrotreating (HT) comparing 100% H 2 and syngas results: Property Raw bio-oil Hydrogen HT product Syngas HT product Acid value HHV, MJ/kg Water, % C,% H,% N,% O,% Syngas HT product 7

8 Hydrocarbon mix vs diesel properties compared to both syngas and 100% H 2 HT with 100% H 2 HC; there is little diff. between fuel properties: Property Acid value HHV, MJ/kg Raw biooil Hydrocarbon mix H 2 HT and H 2 HC Hydrocarbon mix syngas HT and H 2 HC Diesel Yield,% Water, % C,% H,% N,% O,%

9 Yield % Simulated distillation of hydrocarbon mix produced by syngas HT followed by 100% H 2 HC: Jet fuel, 30% o C Gasoline, 55% o C Diesel, 15% o C Temperature o C 9

10 Yield % Simulated distillation of hydrocarbon mixture produced by both 100% H 2 HT and HC: Gasoline, 88% o C Jet fuel, 11% o C Diesel, 1% o C Temperature ( o C) 10

11 WGS reaction: CO + H 2 O H 2 + CO 2 Syngas HT exit gas shows the consumption of 17% CO to produce H 2 via the WGS. This supplemented the low 18% of syngas H 2 ; 39% of CO 2 (+28%). For the 100% H 2 HT, exit gas shows 49% of H 2 was consumed. For H 2 HC for both syngas and H 2 HT, 21 and 33% of H 2 was consumed; CO 2 is low without WGS. Sample Name Hydrogen% CO% CO 2 % Syngas Syngas HT exit gas (17.0) 38.8 H 2 HT exit gas 51.0 (49.0) H 2 HC exit gas (From Syngas HT) H 2 HC exit gas (From H 2 HT) Syngas and reactor exit gas components 79.0 (21.0) (33)

12 Total H2 consumed using syngas HT vs H2 HT; both followed by 100% H2 HC: 17% syngas H2 was consumed for HT 21% H2 consumed for H2 HC 39% total H2 consumed 49% H2 consumed for H2 HT 33% H2 consumed for H2 HC 82% total H2 consumed Therefore, H2 consumption reduced by (82 39%) 43% if syngas HT is applied 12

13 MSSTATE pilot plant 2-t/h fast pyrolysis auger feed reactor:

14 Infeed to biomass handling system for pyrolysis reactor:

15 Summary: MSU has developed a pretreatment method that allows the utilization of syngas for HT of bio-oil. The potential of using syngas, rather than hydrogen, for HT was tested. Results show that much of the HT H 2 required is supplied by the WGS reaction. H 2 consumption was reduced by 43% by use of syngas for the HT step. The respective HT intermediate products differed little between syngas treated and H 2 treated. Likewise, there was little difference between the final H 2 HC products whether the HT was performed by syngas or H 2. 15

16 Summary: The ratio of hydrocarbon fuel types differed between syngas HT and H 2. MSU is near completion of fabricating a 2-ton/day pyrolysis pilot plant with biomass feed capability and fuels conversion technology. 16

17 Acknowledgement: 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- FG3606GO Thank you 17

18 Conversion of Bio-oil to Hydrocarbons Via a Low Hydrogen Route Philip H. Steele and Sathish K. Tanneru Forest Products Department Mississippi State University 18

19 DHA analysis of hydrocarbon mixture produced by syngas HT and 100% H 2 HC and both 100% H 2 for HT and HC: M a s s % Syngas hydrocarbon mix H2 hydrocarbon mix Paraffins I-Paraffins Olefins Class type Napthnes Aromatics Unknowns Total C14+ 19

20 Syngas and reactor exit gas components: Water gas shift reaction (WGS): CO + H 2 O H 2 + CO 2 Syngas HT exit gas shows the consumption of 17% CO to produce H 2 via the WGS This supplemented the low 18% of syngas H 2 ; 39% of CO 2 was produced from the WGS For the 100% H 2 input for HT, Sample Name Hydrogen% CO% CO 2 % Syngas Syngas HT exit gas H 2 HT exit gas 51.0 (49.0) exit gas shows that 49% of H 2 was consumed For H 2 HC for both syngas and H 2 HT, 21 and 33% of H 2 was consumed, respectively; CO 2 produced is low without WGS H 2 HC exit gas (From Syngas HT) H 2 HC exit gas (From H 2 HT) 79.0 (21.0) (33)

21 Total H2 consumed using syngas HT vs H2 HT; both followed by 100% H2 HC: 17% syngas H2 was consumed for HT 21% H2 consumed for H2 HC 39% total H2 consumed 49% H2 consumed for H2 HT 33% H2 consumed for H2 HC 82% total H2 consumed Therefore, H2 consumption reduced by (82 39%) 43% if syngas HT is applied 21

22 Input of H 2 vs H 2 consumed from that produced by the WGS: Water gas shift reaction (WGS): CO + H 2 O H 2 + CO 2 When 100% H 2 was applied for HT, 49% of it was consumed for the HT reaction. It is probable that less total hydrogen than 49% was produced by the 18% H 2 contained in the syngas added to that produced by the WGS. However, the quality of the syngas HT bio-oil indicates that the reaction had adequate hydrogen to produce an HT product quite similar to that produced by 100% H 2 HT. Evidence that the WGS produced H 2 was provided by the high 39% production of CO 2 for syngas HT compared to 16% for H 2 HT.

23 Hydrocarbon mix vs diesel properties produced with syngas HT and100% H 2 hydrocracking (HC): Property Raw bio-oil Hydrocarbon mix from 100% H 2 HC Diesel Acid value HHV, MJ/kg Water, % C,% H,% N,% O,%

24 Hydrocarbon mix vs diesel properties produced with both 100% H 2 HT and HC: Property Raw Bio-oil Hydrocarbon mix Diesel Acid value HHV, MJ/kg Water, % C,% H,% N,% O,%

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