NEW UTILIZATION TECHNOLOGIES FOR LOW RANK COALS

NEW UTILIZATION TECHNOLOGIES

FOR LOW RANK COALS

MASAAKI TAMURA General Manager, Kobe Steel

2

Coal & Energy Technology Dept., KOBE STEEL, Ltd.

New Utilization Technologies

For Low Rank Coals

Upgraded Brown Coal (UBC)

Hyper Coal Process (HPC)

1st International Symposium on the Sustainable Use of Low Rank Coals

Masaaki Tamura

Kobe Steel Ltd.

3


New technology developments have been derivative from

the Brown Coal Liquefaction (BCL) process

Brown coal Liquefaction (BCL) process has been proceeding since the early 1970s, aiming at

developing beneficial use for the abundant Victorian brown coal. The 50t/d pilot plant

operation (1985-1990) had been carried out at Morwell, Victoria. In 1993, the pilot plant

project completed successfully attaining all the development objects.

UBC

Hyper

Coal

SPH

4


Targets of the New Utilization Technologies

Direct Coal Liquefaction Technology

(BCL Process Development)

Upgraded Brown Coal

（UBC）

Based on the high efficiency

dewatering technology

↓

・Utilization of low rank coals

・High calorie fuel with low

environmental impact

Governmental support projects

between Japan and Indonesia

・3t/d Pilot Plant

・600t/d Demonstration Plant

Ultra-heavy Residue

Hydrocracking（SPH)

Based on the slurry phase

hydrocracking technology

for coal

↓

Utilization of ultra-heavy

resources to produce clean

transportation fuels

・Vacuum Residue

・Oil Sand

・Other unconventional heavy

residue

Hyper Coal

（Ash Free Coal）

Based on the solvent de-ashing

technology for coal residue

↓

Coal refining and up-grading

Governmental support projects

(2002～2007)

（CO2 reduction by direct

injection

to gas turbine combined cycle）

・New additive for coke oven

・Nonferrous metallurgical

reagent

5


Low Rank

CoalMining Shipping Utilization

Coal ChainMissing

Demerit• Low Heat Value

Merit• Rich and inexpensive

• Low Sulfur & Low Ash

★1,2,3 ★4

Low Rank Coal is not yet well utilized but attractive

UBC would make LRC business as follows.

UBC

Plant

★1 Plant Construction★2 UBC Production★3 License Business

★4 UBC Utilization

6


Background of the UBC Projects

1. Best Mix of Coal Energy

2. Reduction of Ash Disposal

Cost

1. Decreasing of Oil &

Bituminous Coal

Production

2. Utilization of Low Rank

Coals

Economical Processing for Calorie Up

Stability for Bulk Handling

KALIMANTAN

JAVA

UBC Demonstration

plant 600t/d 2006～2010

UBC Pilot Plant 3t/d

2001～2004

7


0.1 t/ d BSU Kakogawa, Japan 3 t/ d PP Palimanan, Indonesia 600 t/ d DP Satui, Indonesia

History and Schedule of UBC Commercialization

Sample Typeton/day

(1) Scouting Test 0.00001 Batch

(2) Beaker Test 0.0001 ↓

(3) Autoclave 0.001 ↓

(4) Bench Scale 0.1 ↓

(5) Pilot Scale 3 Continuous ▼Now

(6) Demonstration 600 ↓

(7) Commercial 5000 ↓

R&D Stage 1990 2000 2010

8


Objective and Outline of UBC Demonstration Project

Objective

Outline

1 Establishing Technology for Commercial level2 More Accurate Feasibility3 Marketing based on the Bulk Sample (5,000-10,000tons)

Item Details1 Scale 600t/d（Product Base）2 Place Satui Area in South Kalimantan, Indonesia3 Coal Several Lignites（4,000～5,000kcal/kgAD）4 Period / Budget 2006～2010 / 100M$5

System etcBy "JCOAL" joined with Kobe Steel Ltdwith the partnership of Arutmin and BumiResources. Indonesian Government alsosupports the project.

6 ProductEvaluation

By several companies （Kobe steel Ltd,Power company etc）

9


UBC Process Flow

Asphalt

Raw

Coal

Slurry

Making

Slurry

Dewatering

Waste

Water

Oil

Recovery

UBC BriquetteUB

C

Recycle

Oil

Briquetti

ng

Coal/Oil

Separation

10


Heavy Residual oil is absorbed

by the micro pores and oil color is

lost

Water Proof

Stabilized

Principle of UBC Processing

Before Slurry Dewatering After Slurry Dewatering

Capillary Water

Surface Water Asphalt

Oil soaks into the pores and

asphalt is selectively adsorbed.

11


100

1000

10000

100000

0 100 200 300 400 500

温度（℃）

圧力

（ｋ

Pa)

B D

A

C

React i on Boundar y

St ur at ed Vaper Pr essur e of Wat er

Evapor at i ve

Non Evapor at i ve

React i veNon React i ve

Temperature (degree C)

Pressure

(kPa)

More Expensive

Processing Condition of UBC

G r. Evaporation Reaction Exam ple of the ProcessA × × Press D ew ateringB ○ × U B C、Steam Fluidzed bed D rier、Steam Tube D rierC × ○ Fleissner、Hot W ater D ew atering、KFUEL+D ○ ○ ENC O AL、SYNC O AL、KFUEL

12


0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

Bitum inous C oal Liginite A UBC（Lignite A)

Weight % M oisture

Ash

D ry C oal

6,400kcal/kg

26,400kj/kg

Sulfur 0.5 %db

4,100kcal/kg

17,200kj/kg

Sulfur 0.14%db

6,350kcal/kg

26,600kj/kg

Sulfur 0.14%db

UBC

Calorie Improvement by UBC

13


NOX & Unburnt (at A/ C=2.2, O2=6%)

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

0 100 200 300 400 500

NOX(ppm) O2=6%

Carb

on C

onte

nt

in A

sh (

%)

UBC- A

UBC- B

UBC- C

Bituminous

Tested by 100kg/h test burner furnace (CRIEPI)

Combustion Test of 3t/d sample

Excellent Burning out with less emission of NOX

14


UBC Mixing Ratio and NOx Emission, Unburnt

Relation between mixing ratio and NOx concentration and unburnt ratio (OFA ratio=0)

•Both NOx emission and unburnt can be reduced by UBC mixing to steaming coal

0

100

200

300

400

500

600

0 20 40 60 80 100Mixing ratio

based on bituminous Coal A [%]

NO

x [

pp

m]

(6%

O2

)

0.0

0.2

0.4

0.6

0.8

1.0

1.2

Un

bu

rn

t ra

tio

[%

]

Coal B-NOx UBC C-NOx

UBC D-NOx Coal B-UcUBC C-Uc UBC D-Uc

15


B ench Test

0

50

100

150

200

250

0 40 80 120 160 200 240

Tim e（ｈ）

Temperature（

℃）

UBC -A

UBC -B

UBC -C

Bitum inous C oal-G

Bitum inous C oal-H

UBCBituminous

H TR

N 2

D RY AIR

Sam ple

106O x350H

C onstant Tem perature B ox

H TR

N 2

D RY AIR

Sam ple

106O x350H

C onstant Tem perature B ox

Spontaneous Combustion Test of 3t/d sample

Bench Scale Test Facility

UBC A,B,C are more stable than current coal.

16


Grind Test (Hardgrove Tester)

50

60

70

80

90

100

110

120

0 20 40 60 80 100

Briquette Blend Ratio（%）

ＨＧＩ

Raw Coal-A

100%

UBC-A 100%

HGI of blend coal

is linier to the

blending ratio

HGI

17


Technical and Business Know How for UBC

Handling

•Unloading & Piling

•Crushing

•Spontaneous Combustion

Combustion

•Emission & Burning out

•Fouling & Slagging

Transportation

Flue Gas

•Pollutant Emission

•Fly Ash Specification

UBC

Production

Resource

Evaluation

Furnac

e

R/HTR,

S/HTR

AIR

HTRCrush

Dust

Collector

De-

SOX

StorageUnloading

Conveyor

G/H G/H

Economizer

脱硝

Stack

UBC

FOB

CIF

Furnace End

De-

NOX

18


UBC Commercial Plant Study Base Flow

MP STM

UBC Fine

R/Oil★ 4

Steam Tube Dryer

Fine

Coal

Bunker

Coal

Crusher

Slurry Making Evaporator Super Heater

Vapor Compressor

CW

Recycle Oil

LP STM

HP STM

Cond.

UBC Cake

Decanter

Recycle Oil　★ 3

M

R/Oil

★ 1,2,4

Oil TankHot BRQ

Briquette

Machine

PCWS

PCWR

UBC BRQ

BRQ Cooler

★ 1

★ 3

★ 2

Raw Water TreatmentFresh

Water

Waste Water

TreatmentCW system

PCW

(Process Cooling

Water System)

BFW

System

Raw Coal

Generator

MP Steam

LP Steam

HP Steam

Boiler

Reject

Coal

BFW ☆ 1

☆ 1 BFW

BD ☆ 2

BD ☆ 3

Oil/WTR Separation

W/Water ☆ 4

☆ 4

Raw Water

Treatment

Waste

Water

N2 Supply

System

IA Supply

System

PA Supply

System

L/Oil &

H/Oil

IW

5000t/d UBC Process Flow Sheet

#100 Coal Handling

#200 Slurry Dewatering#300 Coal Separation

#400 Oil Recovering #500 UBC Briquetting

#700 Utility System

BD ☆ 2

19


UBC Plant

95M$ @5,000t/d with

Power Generation

UBC Commercial Plant Balance (25% moisture case)

6,385t/d (25%Moisture)

43t/d Oil

5,000t/d (3.5% Moisture)

Boiler & Generator

Steam Power

79M$ @5,000t/d without

Power Generation

Preliminary

624 t/d (25%Moisture)

20


UBC Plant Capacity & Construction Cost

Capacity and construction cost depends on moisture content.

m ositure Feed Product Plant *1 Plant *2t/d t/d M $ M $ $/t-U B C $/t-raw coal

25%M -coal 6385 5000 95 79 8.2 6.2

38%M -coal 7723 5000 110 91 9.2 5.750%M -coal 9592 5000 121 101 10.3 5.2

*1: including Pow er G eneration

*2: excluding Pow er G eneration

Processing C ost*1

Preliminary

21


Up Graded Brown Coal (UBC) Summary

Target

Technology

Utilization of low rank coals which accounts for 50% of coal resources

●Expansion of procurement option for steaming coal

High Calorie and water resist coal by the slurry de-watering

●Low temp. de-watering without chemical reactions

●Original technology from the BCL direct liquefaction process

Steaming coal for power stations (for blending)

●Advantage in ash disposal cost and low NOx combustion

600t/d demonstration plant in operation at Satui, South Karimantan

1,500ton combustion test carried out in 2nd quarter of 2010

5,000ton combustion test carried out in 4th quarter of 2010

●First commercial plant (5,000t/d）could be commissioned in 2012

Status

Market

22


Characteristics and Application of Hyper Coal

Contents

1．Features of Hyper Coal

2. Hyper Coal Production Process

3. Coal extraction behaviors and Product features

4. Hyper Coal application studies

23


Gas Turbine

Features of Hyper Coal

・Ash Free

・ Control ash content from few 100ppm～

few 1,000ppm

・ Sulfur and heavy metals virtually removed.

・ But organic sulfur remained.

・High Calorie

（HPC : 8000～8500 kcal/kg Steaming Coal : 6500 kcal/kg)

Excellent thermal plasticity

・HPC obtains an excellent thermal plasticity even though the

parent coals have no thermal plasticity.

・HPC maintains thermal plasticity in the wide range of

temperature.

Direct Reduction Plant

Coke Oven

Coal

Fired

Boilers

HPC process is a coal refining process, not only

to produce an ash-free coal but also produce an

upgraded coal by re-arrangement

of the extracted coal molecule.

24


Coal extraction Settling After solvent recovery

Over flow

Under flow

HPC

Hyper-coal

Insoluble

The molecular associations

are thermally loosened and

molecules are dissolved into

solvent

The solids (ash and insoluble

molecules) are settled by

gravity in the liquid (solution).

Clarified solution is obtained

by removing the insoluble.

HPC and insoluble coal

are obtained after

vaporizing the recycle

solvent.

The solvent de-ashing technology applied

HPC Process Concept

25


HPC Process FeaturesSolvent

recovery

HPC

RC

Briquetting

coal

Slurry

make-up

Recycle-

solvent

Pre-heater

Extraction

Extractor

Solid-Liquid

separation

Settler

Recycle-

solvent

Recycle-

solvent

Extracted

Insoluble

Solvent recycling

Coal derived 2-ring aromatics

Non use of

hydrogen

Simple and mild

<2MPa, <400℃

Filter

26


Experimental

0 0.1 0.2 0.3 0.4 0.5

0.2

0.4

0.8

1.0

0

0.6

Coal

ST

KR

GR

MO

NT

EN

GN

ML

H/C

ato

mic

ratio

Bituminous coal

Sub-bituminous coal

Brown coal (Lignite)

O/C atomic ratio

Raw coal Solvent

So far, more than 80 different type of coals

have been tested.

Recycling solvent

for continuous test

or 1-MN

1-MN-d10,

Tetralin-d12, for 1H-NMR

Component conc. [%]

1-methylnaphthalene 56.54

2-methylnaphthalene 37.76

naphthalene 1.03

27


FIGURE: Relation between coal extraction temperature and coal extraction yield

（Holding time: 60min.)

Experimental results

－Extraction yields－

Peak temperature range

Thermal relaxation and

radical cross-

linking/polymerization

reactions are in

competitive

0

20

40

60

80

100

240 280 320 360 400

Coal extraction temperature [oC]

Coa

lextr

act

ion

yie

ld[w

t%d

af]

GN

EN

ML

KR

ST

GR

28


Thermal decomposition products

Raw coal

FIGURE: Changing in thermal decomposition products with temperature (Holding time: 60 min.)

CO+CO2CO+CO2

0

2

4

Yie

ld[w

t%,d

af]

C1-C4 gases

0

1

2

260260 300 340340 380380 420 260260 300 340340 380380 420

H2O

0

2

4

Yie

ld[w

t%,

daf]

0

2

4

6

8

1010

260260 300 340340 380380 420

OilOil

260260 300 340340 380380 420

Temperature [ºC] Temperature [ºC]

6

63

ST

GR

GN

ML

Bituminous

Sub-bituminous

Brown Coal

29


Coal band

LigniteSub-bituminousBituminous

H/C

O/C

0 0.1 0.2 0.3 0.4 0.50

0.2

0.4

0.6

0.8

1.2

1.0

decarboxylationn

dehydrationndemethylationn

O/C

0 0.1 0.2 0.3 0.4 0.5

330

360

370

400410

420

RC

HPC

decarboxylationn


O/C

0 0.1 0.2 0.3 0.4 0.50

0.2

0.4

0.6

0.8

1.2

1.0

300

330360

370

RC

HPC

400

420440

460

H/C

decarboxylationn


RC

HPC

Raw coal: GR Raw coal: GN Raw coal: ML

FIGURE:

Moving on the Krevelen‘s coal band with increase in the

extraction temperature （ 10 ℃/min, Holding time: 60min.)

30


Component structure

0 100 200 300 400

Temperature [℃]

0 100 200 300 400

Temperature [℃]

NT KR

G

L2

L1

G L2

L1

L1: Mobile component (Liquid-like)

L2: Intermediate component (Gel-like)

G: Immobile component (Solid-like)

Extraction residue = L2 + G

0

0.2

0.4

0.6

0.8

1F

ract

ion

al

inte

nsit

y [

-]

31


5000

6000

8000

Hea

tv

alu

e[k

cal/

kg

](d

af)

7000

Raw

coal

9000

300 340 380 420 460

5000

6000

8000

7000

Raw

coal

9000

300 340 380 420 460

HV HPC HV RC

Heat value

Extraction temperature [ºC] Extraction temperature [ºC]

Bituminous (GR)

Sub-bituminous (GN)

Brown Coal (ML)

FIGURE:

Relation between coal extraction temperature and heat value estimated using Künle’s equation（ 10 ℃/min, Holding time: 60min.)

32


Bituminous

Sub-

bituminous

Brown Coal

Fuel

Coal Product ash VM C H N S O diff. ratio Heat value

[wt%]db [wt%] (daf basis) [kcal/kg] gross

M Raw coal 12.2 41.3 82.9 5.5 2.0 0.6 9.1 1.4 6920

HPC 0.06 44.7 84.9 5.5 1.8 0.6 7.2 1.2 8630

RC 20.4 27.9 82.8 4.3 2.0 0.7 10.2 2.6 6060

GN Raw coal 8.2 40.8 76.4 5.5 1.9 0.9 15.4 1.5 7030

HPC 0.08 49.6 83.2 6.0 1.6 0.6 8.6 1.0 8560

RC 18.5 27.9 82.8 4.8 2.0 0.9 9.6 2.6 6140

ML Raw coal 2.8 53.3 71.1 5.4 1.1 0.2 22.2 0.9 4710

HPC 0.07 77.1 82.9 6.4 0.7 0.2 9.8 0.3 8240

RC 4.5 51.4 81.4 3.5 1.4 0.2 13.5 0.9 6710

Ultimate & Proximate analysis

33


Measurement of fluidity

Viscosity

Constant share rate

Torque

Temp.

To

rqu

e

Gieseler plastometry

Dial divisions

Constant torqueTemp.

Div

./m

in

Max. fluidity

Resolidification

Softening

34


150 250 350 450

Temperature [oC]

1

10

100

1000

10000

100000F

luid

ity [

Div

.min

]

Gieseler plastometer curve

Coking coal (ST)

HPC from coking coal

(ST-HPC)

HPC from brown coal

(ML-HPC)

HPC from sub-bituminous

(GN-HPC)

Thermoplasticity

35


HPC Application studies

・ Coke additive

・ Fuel

・ Catalytic gasification

・ Nonferrous metallurgical reagent

36


Why coke is strengthen by addition of HPC?

Heating

HPC starts to plasticize at low temperature then solidify at around 500℃.

During this period, HPC fills surrounding voids also dissolves coal to form

solid cokes.

HPCCoal

300～500ºC 1000ºC

High strength coke

300 kg test furnace, 3 ºC/min., 1000 ºC

B.D.: 720 kg/m3, Moist.: 7.8 wt%

HPC for coke additive

37


Production of high strength and

high reactive coke using HPC

Slightly

coke

＋HPC

Merit:

・Compatible strong coke with high reactivity

・Reinforcement against the price rising of coking coal by using

quantities of slightly coking coal and HPC from steaming coal

Slightly Coking Coking

Composition

0 20 40 60 80 100 78 80 82 84 86 20 30 40 50

Base

HPC

Composition Ratio [wt%] Drum Index DI15015 [%]

Strength Reactivity

Hot Reactivity index RI [%]

Base Base

HPC Addition HPC Addition

Slightly

15% 85%

Coking Coal

50% 40%10

%

38


77.4

85.4

66

70

74

78

82

86

66

70

74

78

82

8684.0

86.5

Base-1 + HPC 10%

Base-2 + HPC 10%

Coking coal 75 65 50 40

Slightly coking coal 25 25 50 50

HPC 0 10 0 10

Coal blending ratio (%)

Result of large scale test

High amount of coking coal High amount of slightly coking coal

Coke Oven

39


Reduction of reducing agent by strong coke

(DI

450

500

550

600○

：Japan’s Blast Furnaces

82 84 86 88 90

Red

uci

ng A

gen

t R

ati

o (

kg/t

-pig

iro

n)

450

500

550

600

82 84 86 88 90150

15)

450

500

550

600

82 84 86 88 90

Coke Drum Index

450

500

550

600

82 84 86 88 90

40


Zero emission H2 production by catalytic gasification

C O C O C O

C O 2C O 2

C O 2

H 2

H 2

H 2

0

25

50

75

100

125

Gas yield　[m

mol/g-char]

C oal C oal+K2C O 3 HyperC oal+K 2C O 3

T= 650 oC

0

20

40

60

80

100

0 30 60 90

C har gasification tim e [m in]

Char conversion [%, daｖcf] T= 650 oC

C oal+K 2C O 3

C oal

H yperC oal+K 2C O 3

H2+CO2 rich gasT= 650 ºC; High gasification rate

0

0.02

0.04

0.06

0.08

0 1 2 3 4

C atalyst recycling count

Gasification rate, k [min-1]

H yperC oal

C oal

No catalyst deactivation in catalyst recycling

HyperCoal

Steam

Ga

sfi

re

Residu

al coal

Coal

Bo

iler

H2O

H2/C

O2

se

pa

ratio

n

CatalystCatalyst

recovery

ash

H2 = > 59 %

CO2 = > 39 %

CO2 to

Storage

H2

Product gas

Zero emission H2 production process

41


HPC Reactivity for Silicon Production

SiO (g) + 2C ⇒ SiC + CO (g)

0 500 1000 1500 2000

Residual SiO gas [mL]

Petroleum coke

(High VM) Coal (Low VM)

Charcoal

HPC-char

1650 ºC

High reactivity

High density HPC char (1.27 g/cc)

HPC-char has similar reactivity to charcoalNo slag layer - impurities in feed report to product

Need to use low (~1%) ash carbons (chars/coals)

Hypercoal as a carbon source potential for production of solar-grade silicon (solar cells)

Solar-grade silicon has large increase in value compared to standard grade silicon

The increase in product value could justify the use of premium ultra-low impurity

carbon product with lower reactivity

42


RC Reactivity for Synthetic Retile Production

FeO.TiO2 + C = Fe.TiO2 + CO(g)

FeO.TiO2 + CO(g) = Fe.TiO2 + CO2(g)

C + CO2 = 2 CO

Roller Bed Furnace used for

Synthetic Rutile production (CSIRO)

Raw coal (Collie)

RC

2 4 6 8

0

20

40

60

80

1200

1000

100

800

600

400

200

Time [h]C

on

versi

on

[%]

Tem

pera

ture [

ºC]

Temp.

1.6h

3.4h

RC briquettes

RC has much higher reactivity than raw coal.

RC could be an excellent candidate material for

use in synthetic retile production.

(RC is a byproduct of HPC)

43


Hyper Coal (HPC) Summary

Target

Technology

Utilization of steaming coals for metallurgical uses● Against recent booming in coking coal market

Ash free coal by the solvent de-ashing technology● Extraction under the relatively mild operation condition

● Original technology from the BCL direct liquefaction process

● Clean fuel for boilers

● Ideal feedstock for gasifier

● Additive to produce high strength and high reactive coke

0.1t/d pilot plant in operation at Takasago, Japan.

10t/d pilot plant could be constructed in 2012.Status

Market

Feature The process is a coal refining process, not only to produce an ash-free

coal but also produce an upgrading coal by re-arrangement of the

extracted coal molecule.● Negligible Ash (< 0.5%), Moisture (<0.5%), and high heat value (> 36 MJ/kg)

● Homogeneous maceral structure, vitrinite-like

● Excellent thermoplasticity

44


Acknowledgement

The both technology developments have been supported

by Agency of Natural Resources and Energy, METI and

New Energy and Industrial Technology Development

Organization (NEDO). We would like to express

appreciation to them and joint researchers of Japan Coal

Energy Center (JCOAL), Advanced Industrial Science

and Technology (AIST).

NEW UTILIZATION TECHNOLOGIES

FOR LOW RANK COALS

MASAAKI TAMURA General Manager, Kobe Steel

QUESTIONS?

NEW UTILIZATION TECHNOLOGIES FOR LOW RANK COALS

Documents

Transcript of NEW UTILIZATION TECHNOLOGIES FOR LOW RANK COALS