Removal Effect of Alkali and Alkaline Earth Metallic

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