Removal Effects of Alkali and Ash from Palm Empty Fruit Bunch for Enhanced Bio-Oil Production

1. Removal Effect of Alkali and Alkaline Earth Metallic Species and Ash from Biomass(Palm Empty Fruit Bunch) on Pyrolytic Characteristics to Produce Oil Prof. Yong-ChilSeo Directors of WtE Center and BK21+Program Heung-Min Yoo, Hang-Seok Choi, Jae-Joon Kang Yonsei University 2015. 08. 25

2. 01 Introduction Contents Experiment & Method 02 03 Results & Discussion 04 Conclusions

3. Introduction

4. INTRODUCTION What is EFB? Empty Fruit Bunch Palm Kernel & Shell Fresh Fruit Bunch • World-wide EFB generation and predicted bio-oil production from EFB in 2008 * MT = metric ton Amount of EFB: about18 millionton/year from Malaysia 1

5. INTRODUCTION Why do we have to develop a technology recycling EFBs? • Energy supply : lack of fossil fuels • Secure alternative energy using biomass • Lack of biomass which is usable in Korea; Need substitute resources • Secure a sustainable biomass and technology development • Lack of disposal technology of palm wastes(EFB) • Many EFBs have been discharged as increasing palm oil industry • Need a clean and efficient technology • Need a research for efficient disposal of palm wastes(EFB) • Selecting the most efficient disposal technology • Considerng the balance of demand and supply 2

6. INTRODUCTION Application of various BtE technologies • Possibility for using EFB as a biomass energy source • Discharging amount of EFB will increase continuously • Lack of biomass being usable in Korea; replacing biomass source • Additionally, thermochemical process can consume EFB faster than other processes Biomass-Groundwork • Bio-Ethanol • Bio-Butanol • Bio-Diesel • Bio-Oil • Bio-Gas • Secure the Biomass • Pre-Treatment • Sugar platform establishment • Fermentation • High Efficiency Technology • (Biomass To Energy) Fuel • Chemical Products • Plastics • Medical Products • Cosmetic Products • Electronic Products Conversion Solve the Technical Bottleneck Core of a New Economic Generation Chemical Product Generation of Fossil Fuel 3

7. INTRODUCTION The problems for using EFBs as a biomass • (Physical characteristics) Need to grind for proper feeding • Density of EFB is too low ⇒ It caused ‘bridging’, when it feed into a reactor • Shape of EFB is like needle ⇒ It also caused ‘bridging’ • (Chemical characteristics) Removal ash and AAEM • Sample of EFB has high ash content (approximately 6 wt. %) • ⇒ It affects to yield of biocrude oil and disturbpyrolytic reaction • Problems by AAEM(Alkali & Alkaline Earth Metallic Species) content (Na, K, Mg, Ca) • - Homogeneity on biocrude oil • - Moisture content • - Agglomeration at a fluidized bed AAEM mass (%) AAEM mass (%) (Reference)Mallee wood fast pyrolysis: Effects of alkali and alkaline earth metallic species on the yield and composition of bio-oil 4

8. INTRODUCTION Physico-chemical characteristics of EFBs • Comparison results on EFB and other biomass • (The sample of EFB) non-hazardous for environment / high HHV value as over 4,000 kcal/kg • However, it has highest ash content as approximately 6 wt. % Ash & AAEM has to be removed to increase a yield of biocrude oil 5

9. Experiment & Method

10. Experiment & Method Pre-treatment (crushed by mill) Pre-treatment / Washing / Physico-chemical Analysis / Pyrolysis/ Bio crudeoil Analysis The experimental process using EFBs Physico-chemical Analysis Physico-chemical Analysis Dried • Elemental Analysis • HHV analysis • Thermo-gravimetric analysis • Proximate analysis • Chemical composition • ICP Analysis Pyrolysis Bio crudeoil Analysis Feedstock 500 ㎛ - 1 mm > 1 mm < 500 ㎛ Washing Dried Crushed (to 500㎛) • Thermo-gravimetric analysis • Proximate analysis • Chemical composition • ICP Analysis • (Tap water) Washing for 3days • (Nitric acid) Washing for 3days • (Samples) Unwashed & Washed EFBs • ※ sample size was selected to ‘< 500 ㎛’ • (GC-MS) Chemical Composition Biocrude oil • (Microscopy) Homogenity • (Temperature) 400 ~ 650 ℃ 6

11. Experiment & Method Pre-treatment/ Washing / Physico-chemical Analysis / Pyrolysis/ Bio crudeoil Analysis Preparing sample of EFB • (Step 1) Decision of sample size • A sample of the EFB was imported from Malaysia • From advanced research, it showed a highest yield, when used sample of EFB of 500 ㎛ • For proper feeding, it has to be grinded as a powder(under 500 ㎛) • ⇒ Thus, we have grinded it using variety mills(cutter mill and herb mill) • (Step 2) Drying for decreasing moisture content • Because of the palm oil process, its initial moisture content is high as 60 wt.% • At 110℃, the EFB was dried for 72hr • ⇒ It can be decreased from 60 wt. % to9 wt.% Dried Grinded Grinded Grinded Feedstock 500 ㎛ - 1 mm < 500 ㎛ > 1 mm 7

12. Experiment & Method Pre-treatment / Washing/ Physico-chemical Analysis / Pyrolysis/ Bio crudeoil Analysis Washing sample of the EFB for removal ash • (Step 1) Select water for removal ash • Abdullah and Gerhauser suggested that to wash the EFB by distilled water for removal of the ash • It takes too much time to gather and produce a distilled water • ⇒ It is difficult to apply to commercial plant • Thus, it was compared with tap water under the same experimental conditions • ※ (Experiment)itwas washed for 1~3days, and then analyzed on proximate analysis • (Step 2) Removal of the AAEM(Alkali & Alikaline Earth Metallic Species) • Daniel Mourant et. al, were washed EFB using nitric solution(0.1wt.%) for removal AAEM • It was also compared with tap water under the same experimental conditions • ※ (Experiment)itwas washed for 1~3days, and then analyzed it on proximate analysis • (Step 3) Drying and crushing • After washing, sample of EFBs were dried and crushed again for analysis and experiments 8

13. Experiment & Method Pre-treatment / Washing / Physico-chemical Analysis / Pyrolysis/ Bio crudeoil Analysis Basic Characteristics on sample of the EFBs • Thermo-gravimetric analysis • (Purpose)To find out the reaction rateby thermal energy • ⇒ It would be a critical factor in thermochemical process • (Temperature range) From 20℃ to 950℃ • Proximate analysis • (Analytic Target)Moisture content, Volatile Content, Fixed-carbon content, Ash content • ⇒ In this study, it focused on moisture and ash contents • (Purpose)To evaluate on removal effect of ashwashed by tap water or nitric acid • (Analytic condition)From 20℃ to 950℃, oxidation and reduction conditions • Chemical composition analysis • (ICP analysis) An evaluation on removal effect of AAEM, washed by tap water or nitric acid • (Composition analysis) Cellulose, Hemi-cellulose and lignin composition • ⇒ The pyrolytic temperature depended on chemical composition 9

14. Experiment & Method Pre-treatment / Washing / Physico-chemical Analysis / Pyrolysis / Bio crudeoil Analysis Conditions for fast pyrolysis experiment • Conditions for variety technologies • The experimental conditions → The Residence Time of Fast Pyrolysis : 2 sec Cold-bed Hot-bed 10

15. Experiment & Method Pre-treatment / Washing / Physico-chemical Analysis / Pyrolysis / Bio crudeoil Analysis The schematic diagram on process Pre-Heater Screw feeder & Reactor Cyclone Quencher (I, II) TC display 1. Pre-Heater, 2. MFC, 3.Screw Feeder, 4. Reactor, 5. Distributor & Wind-box, 6. Furnace, 7. Drain, 8. Cyclone, 9. Quencher (I), 10. Dry ice Quencher, 11. Dry Gas Meter, 12. Filter, 13. Micro-GC. Micro-GC Dry gas meter 11

16. Experiment & Method Pre-treatment / Washing / Physico-chemical Analysis / Pyrolysis/ Bio crudeoil Analysis Quality analysis of biocrude oils • GC-MS analysis • (Purpose)To find out the chemical composition • ⇒ It expected to decrease oxygen content with decreasing of phenolic compounds • Homogeneity analysis • (Purpose)To evaluate quality of bio-crude oils, using microscopic images • (Equation) • ⇒ For quantify the homogeneity of the biocrude oils Biocrude oil 12

17. Results & Discussion

18. Results & discussion (Ash) Removal efficiency • Comparison results for washing time • Considering economic, tap water was also used for ash removal • Removal efficiency is similar between water types (5.94 wt.% ⇒ 2 wt.%) • (Nitric Acid Solution)It makes to decrease a moisture content (under 0.2 wt.%) Nitric acid & Tap water were chosen as a solution for ash removal 13

19. Results & discussion Thermo-gravimetric analysis • Comparison on TG results by washing solution • (Nitric Acid Solution)Fastest reaction rate among those (ranging from 200 to 400℃) • ⇒ The pyrolytic temperature could be lower than others 14

20. Results & discussion Chemical composition • Changing of composition by washing • (Nitric Acid Solution) Lignin was cracked by acid solution • ⇒ Expect to convert into gaseous product faster than others • (Lignin) It produces phenolic compounds • ⇒ It might affect to decrease oxygen content in bio-crude oil 15

21. Results & discussion Thermo-gravimetric analysis • Removal effect on AAEM • (Nitric Acid Solution)Especially, the removal effect on Potassium was highest, • when it washed for 2 days • ⇒ Expect to decrease to produce agglomeration (Potassium) removed up to 95 wt.% The EFB washed by Nitric acid (for 2days) was chosen as a feedstock 16

22. Results & discussion Yield of bio-crude oil • Results on characteristics of fast pyrolysis • (Yield)The highest yield(48 wt.%) showed at 500℃,when used washed EFB (tap water) • (Impurity droplets) It decreased by washing treatment by tap water and nitric acid • (Conversion)From results, conversion into the gaseous showed an increasing trend • ⇒ It needs to test EFB gasification using washed EFB 17

23. Results & discussion The yield of bio-crude oil • The homogeneity analysis • (Image Digitized) The homogeneity was calculated by area of impurities • (Homogeneity) It was highest yield of oil at 500 ℃ ⇒ improved from 55.85% to 98.62% Homogeneity 98.62 % 90.96 % <Unwashed EFB> 55.85 % <WashedEFB_by tap water> <WashedEFB_by nitric acid> homogeneity improvement was clear < Image Processing > < Microscopic Image > 18

24. Results & discussion The result of GC-MS for biocrude oils • The phenolic compounds ratio in bio-crude oils • Phenolic compoundsshowed highest content, when use washed EFB by tap water • It can be used not only fuel, but also manufacturing of synthesis resin • When sample of the EFB is applied bypyrolysis process, it is good to use washed EFB (by tap water) • ⇒ Considering the yield of bio-crude oil, economic and so on 42.11 % 89.72 % 42.27 % 19

25. Results & discussion Additional gasification test for EFBs (at 900oC & ER=0.6) • Comparison on EFB gasification results with agglomerations • (Syngas yield)Showed highest conversion to gaseous, when using washed EFB by nitric acid • ⇒ H2 ratio has increased to 35 %, and syngas yieldhas increased to 73 % • (Agglomeration) reduced from 9 wt.% to 1.39 wt.% ⇒ good for continuous operation (↑) Syngas(H2+CO) yield H2 H2 H2 20

26. Conclusions

27. Conclusions Removal efficiency on ash and AAEM 1. • Considering cost and removal efficiency of ash and AAEM • Tap water(washing for 1 day)and nitric acid(washing for 2days)were selected, respectively • Especially, in the case of potassium, it was removed 95 % by nitric acid washing • Effects by washing treatment 3. • Bio-crude oil yield increased to 48.4 wt. %,when using the washed EFB by tap water • According to washing nitric acid, the lignin contentwas decreasing from 26 % to 10 % • ⇒ Leading to decrease bio-crude oil yield and phenolic compounds • ⇒ Gas conversion increased • ⇒ The highest homogeneity in oil was showed • ⇒ The char produced showed less agglomeration (from9 wt.% to 1.39 wt. %) 2. Removal of AAEM & ash gives positive effects thermochemically For fast pyrolysis, the tap water treatment is enough for high yield of oil A nitric acid solution treatment would be appropriate method to prevent agglomeration product in char and increase gas conversion 21

28. Thank you for your attention Contact : Yong-Chil SeoYonsei Universityseoyc@yonsei.ac.kr +83-10-5373-2114