Sustained Hydrotreatment of Biomass Pyrolysis Bio –oil with Minimal Catalyst Deactivation

Zia Abdullah, PhD Versa Renewables, LLC

Rachid Taha, PhDBattelle Memorial Institute

Huamin Wang, PhDPacific Northwest National Laboratory

Created by Battelle and Equinox Chemicals

Bio-Chemicals & Products Drop-in Bio-Fuel

Our mission is to produce biomass-based renewable chemicals and fuels

which are cost-competitive with existing petroleum-based technologies.

2

We are well equipped with pyrolysis, hydrotreatment, bio fuels & chemical production and analytical capabilities

3

50 #/day bench scale auger Pyrolysis System (ABRI Tech)

1 ton/day Proprietary Downflow Pyrolysis System

Bench Scale Hydrotreatment System& Analytical Capabilities 1 gal/day Hydrotreatment Pilot System Bio oil to biochemical pilot reactors

Commercial Scale Fuels & Chemicals Production Capability

The industry’s bio oil upgrading problem

Upgrading

Biomass PyrolysisSulfided CatalystHydrotreatment

BiofuelBio Oil

Upgrading

Biomass PyrolysisSulfided CatalystHydrotreatment

BiofuelBio OilN.M. CatalystStabilization

Hypotheses:

• Noble Metal stabilization catalyst deactivates first because of coke formation

• Unstabilized bio oil rapidly deactivates the catalyst & plugs the reactor

• Non carbon supported stabilization catalysts along with a decoking procedure will solve the problem

4

TiO2 supported stabilization catalysts and a regeneration procedure were developed

Catalyst Stage I: 3%Ru/TiO2

Stage II: 3%Ru/TiO2-ZSM5

LHSV - Total 0.2-1

LHSV – Stage I 0.4-2

LHSV – Stage II 0.4-2

Stage I temperature 150-200oC (170

oC)

Stage II temperature 200-400oC (380

oC)

Reactor Pressure 1,800 psig

H2/Bio-oil Ratio (L/L) 3,000

TOS (hrs.)~50 between regeneration cycles

PNNL Developed TiO2 Supported Catalysts Fresh catalyst

Hydrotreatment

In situ rinse with solvent

Hydrogen reduction at 400oC

Catalyst characterization

5

Catalysts were still losing activity over 200 hrs. TOS

CH4OH Rinse + H2 Reduction @ 400oC Removes all Carbon

Some Loss of Acidity in Both Stage I and Stage II Catalyst Contaminated by Metals and S

Metal Dispersion Loss not Significant

6

Metal poisoning was confirmed using synthetic bio oil with and without additives

Synthetic Bio oil Composition

Element(ppm)

Actual Bio oil

Synthetic bio oil

Aluminum 161 186

Calcium 84 113

Iron 130 117

Magnesium 17 101

Phosphorus 48 72

Potassium 29 103

Sodium 13 63

Zinc 18 58

Sulfur 50 6

Total 1309 819

Additives to Synthetic Bio oil to Simulate Poisons in Actual Bio oil

7

An ion exchange resin treatment was used for bio oil cleanup

8

• Filtration of bio-oil via 0.2 µm to remove resin • Blended bio-oil with 30% methanol to improve the

homogeneity of the bio-oil and enable use of fixed bed catalyst.

• No CH4 or unaccounted H2O produced in Stage I at steady state.

• Other solvents, including water are being considered.

• Bio-oil/Resin: 10• Reaction : 2 hrs. at 40oC• N2 at atmospheric

pressure• Mechanical stirring

Blended bio-oil with 30% methanol to improve

homogeneity

0 20 30

Mechanic Mixer

N2

relief valve

Thermocouple

Heating media

Mechanical Mixer

Relief Valve

Thermocouple

N2

8

(ppm) Al Ca Fe K Mg Na Si S

Bio oil1 41 160 47 <10 <45 <.1 <50

Bio oil (present study)

5 18 16 57 5 4 11 10

Cleaned up Bio oil

<3 <3 <3 6 <3 3 1 9

Bio oil cleanup was integrated with hydrotreatment

Hydrocarbon Product

Ru/TiO2Catalyst

Zone I

0.2 µm filtration

Conventional sulfided catalyst

Ion Exchange

Zone II

Solventrecycle

Bio Oil

1 Diebold, J.P., “A Review of the chemical and physical mechanisms of the storage stability of bio oils”, in Fast Pyrolysis of Biomass: A Handbook, Vol 2., Bridgewater, A.V., IEA Bioenergy, 2002.

9

This process was successful at hydrotreatment for 1,200 hrs. TOS

H/C Product yield: 60 gal./ton

%Wt.

Paraffins 24.1

Total aromatic 5.6

Napththelenes 67.9

Olefins 2.4

Total 100

RON ~70

Chain length C6-C14

Refineryexample

Battelle Results

Density (kg/m3) 0.8-0.9 0.81-0.85

BSW (wt%) 0.5 NA (<0.5)

Total S (wt%) 0.082 <0.005

Total N2 (wt%) 0.015 <0.05

TAN (mg KOH/g) 0.5 <0.5

Pour Point (oC) 21-36 NA(<<20)

Viscosity (cPs) 3-236 <2

10

Summary

This project has enabled a commercially viable bio oil hydro-treatment process to produce renewable blend stock for transportation fuels.

• Novel, low cost bio oil cleanup process to enable long-term operation of a bio oil stabilization catalyst

• A non carbon supported catalyst and successful regeneration, allowing long-term hydrotreater operation

• New process has demonstrated stabilization and hydrotreatment catalysts for over 1,200 hrs. TOS

Acknowledgements

The experimental work was done at the Battelle Memorial Institute and the Pacific Northwest National Laboratories.

Financial Support was provided by Battelle and by the Department of Energy / EERE / BETO.

11