introduction 01 experiment & method 02 results & discussion 03 conclusions 04

Introduction01

Experiment & Method

02

Results & Discussion03

Conclusions04

INTRODUCTION

Palm Kernel & Shell Empty Fruit BunchFresh Fruit Bunch

Amount of EFB : about 18 million ton/year from Malaysia

Palm oil (MT)* FFB (MT) EFB (MT)

World-wide 43×106 100% 195×106 43×106

Malaysia 18×106 41% 82×106 18×106

Indonesia 19×106 45% 86×106 19×106

Others 6×106 14% 27×106 6×106

* MT = metric ton

World-wide EFB generation and predicted bio-oil production from EFB in 2008

What is EFB?

1

INTRODUCTION

• Secure alternative energy using biomass

• Lack of biomass which is usable in Korea; Need substitute resources

• Secure a sustainable biomass and technology development

Energy supply : lack of fossil fuels

Why do we have to develop a technology recycling EFBs?

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

INTRODUCTIONApplication of various BtE technologies

• Secure the Biomass• Pre-Treatment• Sugar platform establishment• Fermentation• High Efficiency Technology (Biomass To Energy)

Biomass-Groundwork

Generation of Fossil Fuel

Conversion

•Bio-Ethanol

•Bio-Butanol

•Bio-Diesel

•Bio-Oil

•Bio-Gas

•Chemical Products

•Plastics

•Medical Products

•Cosmetic Products

•Electronic Products

Fuel

Chemical Product

Solve the Technical BottleneckCore of a New Economic Generation

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

3

INTRODUCTIONThe problems for using EFBs as a biomass

• 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’

(Physical characteristics) Need to grind for proper feeding

• Sample of EFB has high ash content (approximately 6 wt. %) ⇒ It affects to yield of biocrude oil and disturb pyrolytic 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

(Chemical characteristics) Removal ash and AAEM

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

INTRODUCTION

• (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. %

Comparison results on EFB and other biomass

Physico-chemical characteristics of EFBs

EFBJatropha

SeedPKS Sawdust

Elemental analysis[wt%]

C 41.81 57.88 44.6 45.93H 5.73 7.36 6.50 6.65N 0.84 2.92 2.92 0.68O 37.36 25.18 40.20 46.00S N/D ND 0.1 0.16

Proximate analysis[wt%]

Moisture 9.63 6.99 5.92 6.27Volatile 64.95 80.63 71.31 78.11Fixed

carbon19.48 8.98 17.81 15.04

Ash 5.94 3.41 4.96 0.58

Composition

[wt%]

Lignin 26.74 39.61 20.41 25.22Cellulose 31.75 36.64 30.59 41.06

Hemicellulose

20.83 4.82 30.64 30.64

HHV [kcal/kg] 4,036 5,780 4,406 4,196Ash & AAEM has to be removed to increase a yield of biocrude oil

5

The experimental process using EFBs

Feedstock

> 1 mm 500 ㎛ - 1 mm < 500 ㎛

• Elemental Analysis• HHV analysis• Thermo-gravimetric analysis• Proximate analysis• Chemical composition• ICP Analysis

• (Tap water) Washing for 3days

• (Nitric acid) Washing for 3days

Dried

• Thermo-gravimetric analysis• Proximate analysis• Chemical composition• ICP Analysis

Dried

Crushed(to 500 ㎛ )

• (Samples) Unwashed & Washed EFBs ※ sample size was selected to ‘< 500 ㎛’

• (Temperature) 400 ~ 650 ℃

• (GC-MS) Chemical Composition

• (Microscopy) Homogenity Biocrude oil

Experiment & MethodPre-treatment / Washing / Physico-chemical Analysis / Pyrolysis / Bio crudeoil Analysis

6

Preparing sample of EFB


• 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 1) Decision of sample size

• 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. % to 9 wt.%

(Step 2) Drying for decreasing moisture content

Feedstock > 1 mm 500 ㎛ - 1 mm < 500 ㎛

Dried

Grinded Grinded Grinded

7

Experiment & MethodPre-treatment / Washing / Physico-chemical Analysis / Pyrolysis / Bio crudeoil AnalysisWashing sample of the EFB 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) it was washed for 1~3days, and then analyzed on proximate analysis

(Step 1) Select water for removal ash

• 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) it was washed for 1~3days, and then analyzed it on proximate analysis

(Step 2) Removal of the AAEM(Alkali & Alikaline Earth Metallic Species)

• After washing, sample of EFBs were dried and crushed again for analysis and experiments

(Step 3) Drying and crushing

8

Experiment & MethodPre-treatment / Washing / Physico-chemical Analysis / Pyrolysis / Bio crudeoil AnalysisBasic Characteristics on sample of the EFBs

• (Purpose) To find out the reaction rate by thermal energy

⇒ It would be a critical factor in thermochemical process

• (Temperature range) From 20℃ to 950℃

Thermo-gravimetric 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 ash washed by tap water or nitric acid

• (Analytic condition) From 20℃ to 950℃, oxidation and reduction conditions

Proximate 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

Chemical composition analysis

9

Experiment & Method

Conditions for fast pyrolysis experiment

Parameter Unit Value

Reactor type

-(BFB)Bubble Fluidized Bed

Capacity Kg/hr 1

Feeding Rate

g/min 10

Feeding Amount

g 500

Reactor Temperature

℃ 400~650

Uo/Umf - 2

Uo L/min 25

Residence Time

sec 1.3~2.0

Particle Size

mm 0.5

Condenser Type

-ㆍ Shell & Tubeㆍ Dry Ice

The experimental conditions

Conditions for variety technologies

Pre-treatment / Washing / Physico-chemical Analysis / Pyrolysis / Bio crudeoil Analysis

TechnologyHeating

RateResidence

Time

Temp. ℃

Products

CarbonationConventionalFastFlash-liquidFlash-gasUltraVacuumHydro-pyrolysisMethanol-pyrolysis

Very lowLow

Very highHighHigh

Very highMedium

HighHigh

Days5-30 min0.5-5 s

<1 s<1 s

<0.5 s2-30 s<10 s<10 s

400600650

<650<6501000400

<500>700

CharcoalOil, gas,

charBio-oilBio-oil

Chemicals, gas

Chemicals, gas

Bio-oilBio-oil

Chemicals

→ The Residence Time of Fast Pyrolysis : 2 sec

Cold-bed Hot-bed

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The schematic diagram on process

Pre-Heater


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.

Screw feeder & Reactor

Cyclone Quencher (I, II)

TC display

Micro-GC Dry gas meter

11

Quality analysis of biocrude oils


• (Purpose) To find out the chemical composition

⇒ It expected to decrease oxygen content with decreasing of phenolic compounds

GC-MS analysis

• (Purpose) To evaluate quality of bio-crude oils, using microscopic images

• (Equation)

⇒ For quantify the homogeneity of the biocrude oils

Homogeneity analysis

Biocrude oil

12

Results & discussion

• 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.%)

Comparison results for washing time

(Ash) Removal efficiency

Moisture Volatile Ash Fixed Carbon

Distilled Water

1 day 3.38 77.57 2.15 16.9

2 days 2.23 80.18 1.71 15.87

3 days 2.06 80.11 1.66 16.17

Tap Water

1 day 3.76 78.44 1.68 16.12

2 days 2.43 79.47 2.39 15.71

3 days 2.41 78.92 2.03 16.64

Nitric Acid

(0.1 wt. %)

1 day 0.1 81.33 2.38 16.19

2 days 0.2 81.15 2.05 16.6

3 days 0.16 83.86 1.53 14.45

Nitric acid & Tap water were chosen as a solution for ash removal

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• (Nitric Acid Solution) Fastest reaction rate among those (ranging from 200 to 400℃)

⇒ The pyrolytic temperature could be lower than others

Comparison on TG results by washing solution


14

Chemical composition

• (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

Changing of composition by washing

Cellulose (%) Hemi-cellulose (%) Lignin (%)

Unwashed EFB 31.75 20.83 26.74

Washed EFB(Tap Water)

37.36 19.47 22.33

Washed EFB(Nitric Acid)

39.03 22.43 10.04


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• (Nitric Acid Solution) Especially, the removal effect on Potassium was highest, when it washed for 2 days

⇒ Expect to decrease to produce agglomeration

Removal effect on AAEM

(Potassium) removed up to 95 wt.%

The EFB washed by Nitric acid (for 2days) was chosen as a feedstock


16

Yield of bio-crude oil

• (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

Results on characteristics of fast pyrolysis

Elemental Analysis [wt. %]

Moisture Content[wt. %]

HHV[kcal/kg]

pHC H O N S

Bio-crude oil of EFB 53.27 7.73 37.30 0.83 ND 22.28 4,319 2.5


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Homogeneity

55.85 %

90.96 %98.62 %

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%

< Image Processing >

<Unwashed EFB>

<WashedEFB_by tap water>

<Washed EFB_by nitric acid>

< Microscopic Image >

homogeneity improvement was clear


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The result of GC-MS for biocrude oils

The phenolic compounds ratio in bio-crude oils

Bio-crude oil Total Compoundspeak areaof phenolic

compounds (%)

Unwashed EFB

Analyzed 94 compounds 42.11 / 100

Washed EFB(tap water)

Analyzed 8 compounds 89.72 / 100

Washed EFB(Nitric acid

solution)Analyzed 62 compounds 42.27 / 100

42.11 %

89.72 %

42.27 %

• Phenolic compounds showed 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 by pyrolysis process, it is good to use washed EFB (by tap water)

⇒ Considering the yield of bio-crude oil, economic and so on


19

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 yield has increased to 73 %

• (Agglomeration) reduced from 9 wt.% to 1.39 wt.% ⇒ good for continuous operation (↑ )

Syngas(H2+CO) yield

H2

H2H2

20

Considering cost and removal efficiency of ash and AAEM

Conclusions

• 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• Bio-crude oil yield increased to 48.4 wt. %, when using the washed EFB by tap water

• According to washing nitric acid, the lignin content was 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 (from 9 wt.% to 1.39 wt. %)

Removal of AAEM & ash gives positive effects thermochemically

For fast pyrolysis, the tap water treatment is enough for high yield of oilA nitric acid solution treatment would be appropriate method toprevent agglomeration product in char and increase gas conversion

21

Contact :Contact :

Yong-Chil SeoYong-Chil SeoYonsei UniversityYonsei [email protected]@yonsei.ac.kr+83-10-5373-2114+83-10-5373-2114

introduction 01 experiment & method 02 results & discussion 03 conclusions 04

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