IX JAPAN-BRAZIL SYMPOSIUM ON DUST PROCESSING - ENERGY - ENVIRONMENT IN METALLURGICAL INDUSTRIES

September, 8-11, 2013 Gorceix Fundation Auditorium, Ouro Preto, Brazil

THE STATE-OF-THE-ART EMPLOYMENT OF WOODY BIOMASS AND BIOGAS IN MANUFACTURING INDUSTRIES CENTERING AROUND STEEL INDUSTRY
Tateo USUI ( Osaka Univ., Japan; now at Univ. Federal de Ouro Preto, Brazil ) Hirokazu KONISHI , Kazuhira ICHKAWA , Hideki ONO, Hirotoshi KAWABATA ( Graduate School of Engneering, Osaka Univ., Japan ) Paulo Santos Assis ( Univ. Federal de Ouro Preto, Brazil)

1. INTRODUCTION
The purpose of this paper is to show the idea of an excellent employment of woody biomass and biogas in manufacturing industries centering around steel industry. In the beginning, how come to recognize the present research theme is explained by looking back on our previous works.

2. BACKGROUND FOR THE PRESENT WORK

The first author and coworkers used to be, carried out experimental studies on carbonization of coal and wood in Graduate School of Engineering, Osaka University, in order to use both carbonization gas and coal-char or charcoal in the following ironmaking processes. semi-coal-char or semi-charcoal

2.1 Pre-reduction of iron oxide pellets by coal carbonization gas ( Iron bath smelting reduction process )

In the first step, three sorts of bituminous

coal were carbonized under various rising temperature conditions (see Figs.1 and 2).

Carbonization experiment
Carbonization conditions Carrier gas: N2 1.0 L/min (s.t.p.) Heating rate: 200 K/h TC, max : 823 K, 873 K, 973 K, 1073 K, 1273 K
Carbonization furnace N2 inlet Thermocouple 81 I.D. Heater Condenser

850

Coal particles

280

Water inlet (273 K) Exhaust gas Gas chromatograph Ribbon heater

320 100
Alumina balls

155 I.D. Tar filter

Fig. 1

Experimental apparatus

Backgrounds (Iron bath smelting reduction total process Image ) Carbonization furnace Coal Char Pre-reduction furnace Fe2O3 Fe3O4, FeO, Fe

Utilization of V.M. of coal in an iron bath smelting reduction total process Exhaust gas

Smelting furnace

Smelting furnace

Coal

Pellets

Carbonization gas Fe Iron bath smelting reduction total process

Smelting furnace

Backgrounds (Pre-reduction of iron oxide with carbonization gas of coal)

Utilization of volatile matter (V.M.) of coal

Tc, max=1073 K

Application
Pre-reduction of iron oxide in an iron bath smelting reduction total process
Carbonization conditions Coal: Muswellbrook coal Carrier gas: N2 1.0 L/min (s.t.p.) Maximum carbonization temperature (TC, max): 1073 K Heating rate: 200 K/h

Fig. Mole fraction of carbonization gas before reduction as a function of carbonization time.

Fig. 3

Reference T. Usui, T. Yokoyama, T. Nakahashi and Z. Morita, 1993 Ironmaking Conference Proceedings (Iron and Steel Society), pp. 389-398.

Final fractional reductions F and FH

Muswellbrook coal

Newlands coal

Fractinal reduction F, FH ()

0.4

Fractional reduction (gravimetric method) Fractional reduction due to H

Fractinal reduction F, FH ()

0.4

Fractional reduction (gravimetric method) Fractional reduction due to H

Tar filter: room temperature

Tar filter: room temperature

0.2

0.2

0 800 1000 1200 Reduction temperatureTR (K)

0 800 1000 1200 Reduction temperature TR (K)

Fig. Variations of final fractional reductions F and FH with reduction temperature TR.

Reduction temperature 1173, 1273 K

Reduction of iron oxide by hydrogen in hydrocarbons

2.2 Carbon composite iron oxide pellets using semi-coal-char

It was found in the above-mentioned carbonization
experiments under rising temperature conditions that when the carbonization was interrupted halfway, the volatile matter release was interrupted corresponding to the interrupted carbonizing temperature, i.e., the maximum carbonizing

temperature Tc,max ; and that when the carbonization was

started again the release of the residual volatile matter began at the very interrupted carbonizing temperature Tc,max and the

same total amount of carbonization gas was released as the

one without interruption.

From these findings we proposed the novel carbon composite pellets, in which the semi-coal-char including the residual volatile matter was used as carbonaceous material. When we use fully carbonized coal char as carbonaceous material, the reduction of carbon composite pellets starts at first as solid / solid reaction under rising temperature condition like in a blast furnace. Whereas, when we use the semi-coal-char as carbonaceous material, the reduction of carbon composite pellets starts from the beginning as gas / solid reaction just after the reduction temperature arrives at Tc,max .

Therefore, the first merit is the decrease in starting temperature of reaction and the second one is the rate enhancement of reduction reaction by the residual volatile matter (see Fig.5). The

decrease in starting temperature of reduction

reaction of iron ore in a blast furnace leads to the

decrease in consumption of reducing agent.

Heating pattern
temperature Carbonization TC (K) temperature Carbonization
1400
TC , max ==1273 1273K K Tc,max

1200 1073 K 1000 800 600 400 0 120 240 360 973 K 873 K 823 K

Fig. 2

Carbonization time Carbonization time t (min)

In order to obtain the semi-coal-char, Newcastle blend coal was carbonized from room temperature to TC, max = 823, 873, 973, 1073 and 1273 K at 200 K/h, and kept at TC, max until arrival time of 6 h.

Carbonization experiment (total gas volume)

0.3

Total gas volume [m3 (s.t.p.) ]

0.25 0.2 0.15 0.1 0.05 0

C2H4 C2H6 C3H8 CH4

CO2 CO H2

Fig. 4

823

873

973

1073

1273

Maximum carbonization temperature TC, max (K)

Total gas volume ( Newcastle blend coal ) H2 gas releases more than any other gases at TC, max = 873, 973, 1073, 1273 K. The higher TC, max is, the more H2 gas releases. Char contained much hydrogen at TC, max = 823 K.

Analysis of the char obtained by carbonization TC, max 823 K

Table. Analysis of Char carbonized at Tc, max = 823 K

F.C. V.M. Ash 72.2 15.9 11.9

S C H O N 0.53 75.3 2.87 7.31 2.06

(mass%)

TC, max 1073 K

Table. Analysis of Char carbonized at Tc, max = 1073 K (mass%)

F.C. V.M. Ash S 82.7 4.43 12.9 0.42

C H O N 81.5 1.54 1.91 1.74

TC, max 1273 K

Table. Analysis of Char carbonized at Tc, max = 1273 K (mass%) F.C. V.M. Ash S C H O N 83.2 2.51 14.3 0.52 81.7 0.90 1.34 1.27

Reduction of carbon composite iron oxide pellets

Preparation of carbon composite iron oxide pellets Char : Fe2O3 = 1 : 4

Binder Bentonite (1 mass% added) Particle size: under 45 63 mm Pellets size: about 15 mm Keeping at 378 K for 24 h to remove water Reduction experiment and analysis Reduction conditions Ar or N2 gas atmosphere Heating rate: 0 or 3K/min Analysis Gas chromatography, SEM, XRD

Ar gas inlet

Pellets

Electric furnace

Alumina crucible
Thermocouple

Gas outlet

Relation between fractional reduction and reduction time of carbon composite pellets at 1073 K in N2 atmosphere

25
Fractional reduction F (-)

Semi-coal-char
TR = 1073 K

20 15 10 5 0 0 10 20

10 %

Reduction behavior
F of carbon composite pellet at TC, max = 823 K was higher than any other pellets by about 10 %. When TC, max was lower, namely the pellet had more residual V.M., the reduction of carbon composite pellet was much enhanced.

Char TC, max = 823 K TC, max = 1073 K TC, max = 1273 K

30

40

50

60

Reduction time t (min)

( Fig. 5 )

100
Fractional reduction F (-)
Semi-coal-char

80 60 40 20 0 0

TC, max = 823 K TC, max = 1073 K TR = 1173 K TC, max = 1273 K

20

40

60

80

Reduction time t (min)

Fig. 5. Reduction curves for semi-coal-char composite pellets ( TR = 1173 K ).

Influence of several kinds of carbon materials

Reduction at 1273 K in N2 gas atmosphere Fractional reduction F [%] 100 80 60 40 20 0 0 10 20 30 40 50 60 Reduction time t [min] Char (TC, max = 823 K) (V.M. 15.9 %) Coke Graphite (Purity 98 %) (V.M. 0.6 %)

Reduction rate Early stage Char Coke, Graphite Later stage Char, Coke Graphite

Effect of V.M. and crystallization Reduction rate

2.3 Carbon composite iron oxide pellets using semi-charcoal

The above-mentioned carbonization

experiments on coal were expanded into

those on charcoal; semi-charcoal including

the residual volatile matter was used as

carbonaceous material in the novel carbon

composite pellets.

The rate enhancement effect of reduction for semi-charcoal composite pellets is stronger than that for semi-coal-char composite pellets, because the gasification rate of semi-charcoal is higher than that of semi-coal-char. This is caused by the following reasons: amorphous nature of semi-charcoal is stronger than that of semicoal-char (see Fig.6) and the activation energy of semi-charcoal is lower than that of semi-coal-char (see Table 1).

Reduction of iron oxide by woody biomass A lot of steel engineers researched various means to decrease coke in a blast furnace in order to reduce CO2 emission.

Biomass
Carbon neutral (No CO2 emission) Rich resources

Woody biomass

Application
(Carbonaceous material) Injection into a blast furnace

Japanese Japanese Biomass cedar waste cypress

Preparation of carbon composite iron ore agglomerate

Sample Sample for carbonization experiment Carbonaceous material Japanese cypress

Table. Analysis of Japanese cypress (mass%)
F.C. V.M. Ash T.S T.C H O N 8.12 90.8 1.05 0.014 50.7 6.16 41.1 1.01

Sample for reduction experiment of iron oxide pellets Iron oxide: Reagent grade hematite (Fe2O3) (95 mass%, Wako Pure Chemical Industries Ltd.)

Binder Bentonite (1 mass% added)

Table. Chemical analysis of Bentonite (mass%)
SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O 58.79 14.27 2.99 0.70 1.28 0.70 3.42

Heating pattern of carbonization of Japanese cypress

Carbonization temperature TC (K)
1400 1200 1000 800

TC, max = 1273 K 1073 K 823 K

600
400 0 120 240 360

Carbonization time t (min)

In order to obtain the semi-charcoal, Japanese cypress was carbonized from room temperature to TC, max = 823, 1073 and 1273 K at 200 K/h, and kept at TC, max until arrival time of 6 h.

Total gas volume generated by carbonization

Total gas volume [m3(s.t.p.)]
0.04 0.03 0.02 0.01 0 823 1073 1273

C2H4 C2H6 C3H8 CH4

CO2 CO H2

Maximum carbonization temperature Tc, max (K)

Total gas volume generated by carbonization H2 gas was released more than any other gases at TC, max = 1273 K, but was released less than CO, CO2 and CH4 gases at TC, max = 823 K. The higher TC, max was, the more H2 gas was released. Semi-charcoal retained much V.M., namely H2 gas, at Tc, max = 823 K.

Analysis of the semi-charcoal obtained by carbonization

Table Analysis of semi-charcoal obtained by carbonization of Japanese cypress. (mass%)
Component Japanese cypress Semicharcoal Coke TC,max = 823 K TC,max = 1073 K TC,max = 1273 K F.C. 8.12 80.60 89.35 91.80 V.M. 90.8 Ash 1.08 0.76 1.01 1.16 S 0.01 0.01 0.03 0.04 C 50.7 85.8 91.2 92.6 H 6.16 O 1.01 9.89 5.89 4.81 N 41.1 0.60 0.55 0.82

18.65 9.64 7.00

0.97

2.93 1.33 0.56

0.26

87.1

11.97

0. 60

84.6

1.35

1.22

Volatile matter (V.M.)

Tc, max = Tc, max =

Hydrogen
Tc, max =

823 K

1073 K

1273 K

It was confirmed that the semi-charcoal of TC, max = 823 K retained much V.M., namely hydrogen.

Semi-charcoal obtained by carbonization

Semi-charcoal has many micro pores with the size of about 10 mm.

Tc, max = 823 K

Tc, max = 1073 K

Tc, max = 1273 K

Gasification of semi-charcoal
Experimental conditions Semi-charcoal Tc, max = 823, 1073, 1273 K CO2 1.0 L/min (s.t.p.) TG = 1073, 1173, 1273 K 6375 m Binder 2 mass% Pellets

TG

Weight loss measurement

600 [K/h] N2 CO2

Reaction rate

R.T.

Fig. Schematic of reduction furnace.

Gasification of semi-charcoal
TG = 1173 K
0 Weight loss [ % ] -20 -40 -60 Coke Weight loss [ % ] 0 -20 -40 -60

TG = 1273 K

Semi-charcoal Tc,max = 1273 K -80 Tc,max = 1073 K Tc,max = 823 K

-80
-100 0

-100 0

20 40 60 Reaction time [min] Fig. Weight loss curves of semi-charcoals obtained by carbonization at Tc, max = 823, 1073, 1273 K and coke at TG = 1173 K in CO2 gas atmosphere.

20 40 60 Reaction time [min] Fig. Weight loss curves of semi-charcoals obtained by carbonization at Tc, max = 823, 1073, 1273 K and coke at TG = 1273 K in CO2 gas atmosphere.

Tc, max is low

Reaction rate is high

Gasification of semi-charcoal
Arrhenius plots of reaction rate of gasification
Reaction rate : ln k C, CO2 [ 1/min ]
-2 1400 1300 TG [K] 1200 1100 1000

Gradient Activation energy

Tc, max 823 K 1073 K 1273 K Coke

-4
E [kJ/mol]

138

139

162

219

-6

Semi-charcoal
-10 0.7 -8 Tc,max = 823 K Tc,max = 1073 K Tc,max = 1273 K Coke 0.8 0.9 -1 1/TG [K ]

Tc, max is low Activation energy is low

[10-3] 1.0

Fig. Reaction rate per unit mass at TG = 1073, 1173, 1273 K in CO2 atmosphere.

This result of activation energy might be influenced by specific surface area and crystallization of these samples.

Table 1. Comparison of activation energies for various carbonaceous materials. (27)

Carbonaceous material Graphite Bintyo char Bamboo char Coke Glassy carbon Activated carbon Semi-charcoal at Tc,max = 823 K Semi-charcoal at Tc,max = 1073 K Semi-charcoal at Tc,max = 1273 K Semi-coal-char at Tc,max = 1073 K Coke * Present work Activation energy (kJ/mol) 217 (29) 182 (29) 181 (29) 200 (29) 211 (29) 149 (29) 138 * 139 * 162 * 174 * 219 *

The crystal structures of semi-coal-char and semi-charcoal

(a) Semi-coal-char
Diffraction intensity / arb. unit
: Carbon : Unknown

(b) Semi-charcoal
Diffraction intensity / arb. unit
: Carbon

TC, max = 1273 K

TC, max = 1273 K

1073 K

1073 K 973 K
20 30 40 50 60 70

823 K
20 30 40 50 60 70

2(Cu-K) /degree

2(Cu-K) /degree

Semi-coal-char Crystalline structure

Semi-charcoal Amorphous structure

Fig. 6

Reduction of semi-charcoal composite iron oxide pellets Preparation of semi-charcoal composite iron oxide pellets Semi-charcoal : Fe2O3 = 1 : 4 Binder Bentonite (1 mass%) Particle size: 2335, 6375, 105150 m Pellets size: about 15 mm Keeping at 378 K for 24 h to remove water

Reduction experiment and analysis Reduction conditions N2 gas atmosphere Analysis Gas chromatography

Reduction behavior of iron oxide in semi-charcoal composite pellets at TR = 1073 K in the N2 gas atmosphere

TR = 1073 K
30

Fractional reduction Tc,max 823 K 1073 K 1273 K Coke Reduction behavior

F of semi-charcoal composite pellet at TC, max = 823 K was 19 % for 60 min and higher than any other pellets by 78 %. When TC, max was lower, namely the pellet had more residual V.M., the reduction of semicharcoal composite pellet was much enhanced.

Particle size: 6375 mm

Tc,max = 823 K

Fractional reduction F [%]

15

Tc,max = 1073 K Tc,max = 1273 K

0 0 30

Coke
60

Reduction time [min] Fig. Reduction curves of semi-charcoal composite pellets using semi-charcoal at Tc,max = 823, 1073, 1273 K and coke at TR = 1073 K in N2 gas atmosphere.

Reduction behavior of iron oxide in semi-charcoal composite pellet at TR = 1173 K in N2 gas atmosphere

TR = 1173 K
50

Fractional reduction Tc,max 823 K 1073 K 1273 K Coke Reduction behavior

F of semi-charcoal composite pellet at TC, max = 823 K was 40 % for 60 min and higher than any other pellets. When TC, max was lower, namely the pellet had more residual V.M., the reduction of semicharcoal composite pellet was much enhanced.

Particle size: 6375 mm

TC,max = 823 K TC,max = 1073 K TC,max = 1273 K
Coke

Fractional reduction F [%]

25

0
0 30 60

Reduction time [min] Fig. Reduction curves of semi-charcoal composite pellets using semi-charcoal at Tc,max = 823, 1073, 1273 K and coke at TR =1173 K in N2 gas atmosphere.

Reduction behavior of iron oxide in semi-charcoal composite pellets at TR = 1273 K in N2 gas atmosphere

TR = 1273 K
100

Fractional reduction
Tc,max 823 K 1073 K 1273 K Coke Reduction behavior
F of semi-charcoal composite pellets at TC, max = 823, 1073 and 1273 K were over 90 % for 60 min and indicated the same behavior at TR = 1273 K. These reducibility of semi-charcoal composite pellets were high and were not dependent on residual V.M. at TR = 1273 K.

Particle size: 6375 mm

Fractional reduction F [%]

50

0 0 30

Tc,max = 823 K Tc,max = 1073 K Tc,max = 1273 K Coke

60

Reduction time [min] Fig. Reduction curves of semi-charcoal composite pellets using semi-charcoal at Tc,max = 823, 1073, 1273 K and coke at TR = 1273 K in N2 gas atmosphere.

The influence of crystallinity of semi-charcoal on reduction of iron oxide in semi-charcoal composite pellet at TR = 1273 K

Fractional reduction
100

Semi-charcoal composite pellet

Fractional reduction F [%]

80

Semi-coal-char composite pellet

Reduction rate Reduction rate of semi-charcoal composite pellets are higher than that of semi-coal-char composite pellets. Amorphous structure Crystalline structure

60

40

20

Charcoal Char Tc,max (K) 823 1073 1273

0 10 20 30 40 50 60

Reduction time [min]

Fig. Reduction curves of carbon composite pellets using semi-charcoal and semi-coal-char at Tc,max = 823, 1073, 1273 K with time at TR = 1273 K in N2 gas atmosphere.

Reducibility
Semi-charcoal Semi-coal-char

Total gas volume generated by carbonization of Japanese cypress, Japanese cedar and Newcastle blend coal at Tc,max = 1273 K.
0.3 0.25 0.2 0.15 0.1 0.05 0

Total gas volume [m3(s.t.p.) / kg]

C2H4 C2H6 C3H8 CH4 CO2 CO H2

Japanese cypress Japanese cedar Newcastle blend coal

Fig. Total gas volume generated by carbonization of Japanese cypress, Japanese cedar and Newcastle blend coal at a maximum carbonization temperature Tc, max = 1273 K.

CO gas contained in woody biomass is larger than that in coal.

Utilization of iron oxide reduction process

Total gas volume generated by carbonization

Total gas volume [m3(s.t.p.)]
0.04 0.03 0.02 0.01 0 823 1073 1273

C2H4 C2H6 C3H8 CH4

CO2 CO H2

Japanese cypress

Maximum carbonization temperature TC, max (K)

Total gas volume generated by carbonization H2 gas was released more than any other gases at TC, max = 1273 K, but was released less than CO, CO2 and CH4 gases at TC, max = 823 K. The higher TC, max was, the more H2 gas was released. Semi-charcoal retained much V.M., namely H2 gas, at TC, max = 823 K.

O/C, H/C mole ratio (Van Krevelen diagram)

0.6
demethanation

Calorific power low

mole ratio

0.4

Semi-coal-char TC, max = 823 K Semi-coal-char TC, max = 873 K TC, max = 823 K Semi-charcoal TC, max = 973 K Tc, max = 823 K TC, max = 1073 K TC, max = 1173 K TC, max = 1273 K 873 K Semi-charcoal TC, max = 823 K TC, max = 1073 K TC, max = 1273 K Coke

1073 K

0.2
1273 K

973 K

1073 K 1273 K

Coke
The higher TC, max was, the lower O/C and H/C values were.

1173 K

0 0

0.05

0.1

mole ratio

Dehydration, decarboxylation

3. OUTLINE OF THE PRESENT STUDY From the accumulated date mentionedabove on semi-charcoal, in the first step, the first author is going to study the optimum conditions for the use of both semi-charcoal and carbonization gas (biogas) released at carbonization in ironmaking such as carbon

composite agglomerates by data analyses in

Univ. Federal de Ouro Preto with Prof. Assis;

we can expect that the lower the

carbonizing temperature Tc,max is, the

better the reactivity of semi-charcoal becomes but the less the amount of

carbonization gas releases in the

carbonizing step.

As the carbonizing temperature Tc,max decreases, the activation energy of semicharcoal decreases gradually, while the amount of carbonization gas release in the carbonizing step, namely, the amount of biogas, decreases rather drastically. There will be some optimum carbonizing temperature Tc,max in an actual process for both preparing reactive semi-charcoal and producing much biogas.

In the second step, the experimental program will be proposed to search the optimum conditions for the use of both semi-charcoal and carbonization gas released in the carbonizing step. Of course, the experimental program has to be expanded from wood to various kinds of biomass.

In addition, literatures on various kinds of biomass will be collected and analyzed. Application of semicharcoal to another manufacturing industry will also be searched. In the third step, the experimental apparatus will be designed for the next year research period.

CONCLUDING REMARKS From the previous study on pre-reduction of iron oxide pellets by coal carbonization gas, we proposed a novel carbon composite pellets; semicoal-char was used as carbonaceous material to enhance the rate of reduction and at the same time to decrease the starting temperature of reduction reaction. We expanded these results to semi-charcoal. The first author is going to study the optimum conditions for the use of both semi-charcoal and carbonization gas released at carbonization in ironmaking by data analyses in Univ. Federal de Ouro Preto with Prof. Assis.

Muito obrigado.

O/C, H/C mole ratio (Van Krevelen diagram)

0.6
demethanation

Calorific power low

mole ratio

0.4

Semi-coal-char TC, max = 823 K Semi-coal-char TC, max = 873 K TC, max = 823 K Semi-charcoal TC, max = 973 K Tc, max = 823 K TC, max = 1073 K TC, max = 1173 K TC, max = 1273 K 873 K Semi-charcoal TC, max = 823 K TC, max = 1073 K TC, max = 1273 K Coke

1073 K

0.2
1273 K

973 K

1073 K 1273 K

Coke
The higher TC, max was, the lower O/C and H/C values were.

1173 K

0 0

0.05

0.1

mole ratio

Dehydration, decarboxylation