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Optimization of Biomass Pretreatment using Response Surface Method

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Paper prepared for 7th European Design of Experiment (DOE) User Conference, Paris, France 6th – 8th June 2018

Ashraf Zin.1* , Noor Haida Sebran.1, Law Poh Gaik.1,Jofry Othman1, Azlan Shah Hussain.1

1Level 17, Tower 3, PETRONAS Twin Towers, Kuala Lumpur City Centre, 50088 Kuala Lumpur, Malaysia*Corresponding author. Tel.: +603 8928 1130. Fax: +603 8925 9549E-mail: ashraf.zinzawawi@petronas.com.my

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1. Background and Problem Statement

2. Response Surface Method and Results

3. Conclusion

Presentation Outline

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Four key drivers to participate in Malaysia biomass industry, especially in the bio-chemical space

Growth in bio-based platform chemical is forecasted at a CAGR of ~8.7% until 2021

4.785.29

5.876.52

7.24

2017 2018 2019 2020 2021Bio-based platform chemicals provide alternative and green

feedstock for the fast growing chemical segment

RevenueUSD billion

Large availability of oil palm-based biomass waste across Malaysia present business opportunity

This will also support Malaysia bio-economy agenda and “go-green” effortsDiversification to petrochemical industry

21Major

biomass resource

18Biomass

waste

13Agricultural

waste

Oil palmwaste

Not competing with food

Abundant domestic

availability

Highest availability

Screening criteria

Policy/ProgramCommercialisation status (non-exhaustive)

Commercialized• Acetic Acid• Iso-Butanol• Ethylene• Ethylene glycol

Demonstration• n-butanol

Pilot• P-xylene

1 2

78 mtpa80% total

biomass waste

3 4Leverage on existing knowhow in petchem business

Capability

Customer/market

Supply chain

Technology

Creates RM 30 billion in additional GNI, 66,000 high value jobs and 12% reduction in carbon emissions

Promotes a knowledge-based bio-economy

Objective

Mobilise participation of Malaysian SMEs and position biomass industry towards high value creation

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Background: Why do we need to remove lignin from empty fruit bunch (EFB) prior to hydrogenolysis?• To increase the accessible surface area of the cellulose and hemicellulose 1

• Base-catalyzed delignification (BCD) or alkaline wash delignification is proven to be a cost effective pretreatment 2

• The important parameters for BCD include the base concentration, temperatures, duration and size of the EFB fibers 3,4

• Lignin content of untreated empty fruit bunch (EFB) can range between 24 wt.% to 31 wt.% 5

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1. Taherzadeh MI, Karimi K (2008) Pretreatment of lignocellulosic wastes to improve ethanol and biogas production: a review. Intl Jour Mol Sci 9:1621–16512. Katahira R, Mittal A, McKinney K, Chen X, Tucker MP, Johnson DK, Beckham GT (2016) Base catalysed depolymerisation of biorefinery lignin. ACS Sustainable Chem

& Eng 4:1474–14863. Akhtar J, Teo CL, Lai LW, Hassan N, Idris A, Aziz RA (2015) Factors affecting delignification of oil palm empty fruit bunch by microwave-assisted dilute acid/alkali

pretreatment. Bioresources 10(1):588–5964. Choi, W. I.,Park,J.Y.,Lee, J.P.,Oh,Y. K.,Park,Y. C., Kim, J.S., Park, J. M., Kim, C. H., Lee, J. S. (2013) Optimization of NaOH catalyzed steam pretreatment of empty fruit

bunch, Biotechnology for Biofuels, 6 (170) 5. Zawawi, A., Gaik, L. P., Sebran, N., Othman, J., & Hussain, A. S. (2017). An optimisation study in biomass delignification process using alkaline wash. Biomass

Conversion and Biorefinery.6. H. V. Lee et al.,The Scientific World Journal (2014)

Picture taken from [6]Picture taken from www.ankurscientific.com

Utilizing RSM (Box-Behnken) method as DoE , 17 runs of biomass EFB pretreatment including 5 center points were carried out to investigate the effects of 3 factors on lignin content, which is analyzed by methods of NREL6 and Van Soest7

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6. Sluiter, A. Ruiz, R., Scarlata, C., Sluiter, J., D. Templeton and D. Crocker (2008) Determination of structural carbohydrates and lignin in biomass. Colorado: National Renewable Energy Laboratory. Laboratory Analytical Procedure. NREL/TP-510-42618.7. Chaves, A. V., G. C. Waghorn and M. H. Tavendale. (2002). A Simplified Method for Lignin Measurement in a Range of Forage Species. Proceedings of the New Zealand Grassland Association. 64:129-133.8. Mirahmadi K, Kabir MM, Jeihanipour A, Karimi K, Taherzadeh MJ (2010) Alkaline pretreatment of spruce and birch to improve bioethanol and biogas production. Bioresources 5(2):928–9389. Muryanto, Eka T, Haznan A, Agung. C, Effendi TC, Yanni S (2015) Alkaline delignification of oil palm empty fruit bunch using black liquor from pretreatment. Procedia Chemistry 16:99–105

Base concentration

Tem

pera

ture

A – Base Concentration : 0.5 wt% to 3.0 wt%

B – Temperature: 373K to 423K

C – Duration : 60min to 120min

Box-Behnken was chosen over CCD because the design of a CCD model that has axial points outside the box will cause too extreme conditions for the pretreatment purpose; i.e. high temperature and high base concentration

Design Expert ® helped to carry out ANOVA showing that the main factors of Base Concentration and Duration to be significant for delignification, plus the factor interaction between Temperature-Base Concentration

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Since the overall model is significant and the LoF is not significant, the way forward is to move within the fitted model and the contour plots produced

Pretreatment strategy is to maximize the cellulose-rich material while minimizing lignin content using alkali wash. The model was developed and confirmed that lignin content can be reduced from 26 wt.% to < 12.0 wt.%

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Optimized Conditions: 1.75 wt.% NaOH, 150 °C (423K) and 90 minutes

Quality Control Study of the Pretreated EFB indicates good reproducibility & repeatability for the predictive model based on random sampling

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Lignin Content Control Chart

Cellulose Content Control Chart

12.86

9.30

11.08

75.50

58.50

67.00

Summary:1. Random samples were made over 15

times from 40 kg of cellulose rich materials (pretreated biomass) indicates good reproducibility and repeatability with standard deviation of 0.67 (lignin) and 3.20 (cellulose)

Note: Virgin materials have 26% lignin, 39.5% cellulose and remaining is hemicellulose

© 2018 Petroliam Nasional Berhad (PETRONAS) 10

• Biomass EFB pretreatment using low base concentration is a cost effective process that could

lower the lignin content prior to conversion to chemicals

• Response Surface Method (RSM) helped to ascertain the significant parameters for biomass

base wash pretreatment i.e temperature, base concentration and duration

• Design Expert is an excellent tool to develop a predictive model for the lignin content of the

pretreated biomass.

Conclusion

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For further reading: Biomass Conv. Bioref. DOI 10.1007/s13399-017-0246-x

Zawawi, A., Gaik, L. P., Sebran, N., Othman, J., & Hussain, A. S. (2017). An optimisation study in biomass delignification process using alkaline wash. Biomass Conversion and Biorefinery.

© 2018 Petroliam Nasional Berhad (PETRONAS) 11

The authors would like to acknowledge PETRONAS and PETRONAS Chemical Group Bhd. (PCGB)

for funding this work.

Acknowledgement

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Questions?

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Thank you

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