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ISIJ International,

Vol,

33

(1

993), No.

11 pp. 1136-1 143


,

Study on Blast Furnace lronmaking System Integrated


with Methanol Synthesis for Reduction of Carbon Dioxide Emission
and Effective Use of Exergy
Feasibility

Tomohiro AKIYAMA.Hirotaka SATO.Atsushi


Institute

for

and Jun-ichiro
MURAMATSU

AdvancedMaterials Processing. Tohoku University,


(Received on February 25. l993. accepted in

final

Katahira,

YAGl

Aoba-ku. Sendai, Miyagi-ken. 980 Japan.

form on September24. 1993)

replacement of coke by natural gas and production of methanol from the off gas wil[ result in the
blast furnace ironmaking system with methanol synthesis. According to the requirement of
reduction of CO.emission and energy savings, the feasibility study of the integrated system
wasconducted.
Operating data of the newsystem was calculated by a mathematical model based on the heat and mass
balances. The effect of operating conditions, such as replacement amount of coke and conversion factor
to methanol, on the total emission of greenhouse effect gas (GEG) and on the exergy loss was examined.
The exergy loss and the GEGemission decreased with increase in the replacement amount of coke by
natural gas and the conversion factor. In the operation case that has 300 kg-coke/thm and 21 Nm'-natural
9
gas/thm in fuel ratio and 2.3/ in conversion factor, the total amount of GEGdecreased from 542 to
454kg/thm and the sumof exergy loss also decreased from 9.0 to 8.2 GJ/thm.
Partial

integrated

ironmaking,
KEYWORDS:
analysis;

blast furnacei

carbon dioxide; methanol synthesis; natural gas

1.

Introduction

lronmaking industry consumesmuchenergy and then


generates significant amountof waste gas. The waste gas
emitted during combustion contaminates the environment, to the extent affecting the global climate and
threatening the future habitability
of the earth. The
in
dioxide
the
of
carbon
atmosphere makesup
content
only a thirtieth of "/o of atmosphere. But together with
other greenhouse effect gases (GEG) it plays a role in
changing the earth's climate by catching and trapping
the heat radiated from the earth near the surface. The
previous papersl'2) of the authors revealed the location
emission and exergy loss
and magnitude of both
within the ironmaking systems.
Reduction in the C02emission rate probably will not
be accomplished without a massive switch to nonfossileenergy sources, Until such energy sources supplant coal,
oil and natural gas, the technology challenge
must be
directed to: l) exploit the fuels moreefficiently,
2) replace
coal by natural gas and 3) reconvert and sequester C02
emissions. The most important item is efficiency
improvement, because it is often economically and
environmentally attractive.
Somebasic thermodynamic
laws tell us how to reduce energy consumption.
According to the laws energy is neither consumednor
created. Whatis consumedis the capacity of energy to
do work. This is exactly the concept of exergy,1 ~ 6) which
gives system designers a 'new point of view' for op-

GEG

C 1993 ISIJ

injection;

exergy

system integration.

1136

'

i ,.ri

'

timization.
Second, any practical transformation that
converts energy from one form to another is accompanied
by exergy loss. Therefore, an even better solution than
is
using energy efficiently
no use of energy at all. As a
result, someprocesses that apparently have little relation
to energy in agglomeration process of ore and coal, such
as the recycling of scrap or iron-bath type smelting
reduction, may have an enormous impact on energy
consumption. Recycling and smelting reduction processes bypass the most energy-intensive steps for processing the charging material.1,2)
Consequently, reduction of exergy inflow and increase in exergy efficiency
are the most successful method to enhance effective use
of exergy.
The natural gas option leads to improvements in
efficiency,
and it is appealing for various reasons. From
of fuel, C02 converted from natural gas is
viewpoint
a
around 500/0 of that from coal in a unit calorific value.
Moreover, in comparison with coal, the use of natural
gas as fuel has various advantages such as simplicity of
gas-handling equipment, Iow useless componentsand less
sulfur content. Onthe other hand, in order to realize a
plan to substitute natural gas for coal in the ironmaking
system, technologies to solve following problems must
be established. First, natural gas is muchless abundant.
Therefore, nonfossile energy technology must be ac=
cepted until natural gas is entirely consumed. Second,
leakage of natural gas during extraction and transport
could partially offset the advantage of its use, because

ISIJ International,

Vol.

33

993). No.

11

the decrease in coke rate. This system needs also oxygen


enrichrnent in blast air to maintain the desired flame
emission from the blast
temperature. To reduce
furnace, two operation methodscan be considered. One
methodis to reconvert the top gas from a blast furnace

a kind of greenhouseeffect gas and is moreefficient


absorber of infrared radiation than C02'
Historically,
the changing price structure and availabllity of natural gas have often madeit competitive with
of
coke. Operation of a blast furnace with injection

CH4is

GEG

remove carbon content in fossil fuel


advance. In the first method, a part
carbon
is
the
of
assumedto be converted to methanol
top gas
(CH30H). Methanol, which is currently consumedat
the rate of ca. 2Mt/year in Japan, is becomingan essential
raw material for a chemical product such as formaldehyde. Moreover, it has been recently focussed as
secondary energy, which will be use for vehicles or power
generation. Also, the natural gas injection is employed
to advantage to the methanol synthesis where the
production rate is accelerated by the higher hydrogen

and another

natural gas has been carried out in several countries, for


example USA,7) Australia,8) CIS9~11) (formerly USSR)
and Hungry.12) Particularly, there were manyreports in
1960's in CIS, which showed practical operations of
natural gas injection up to about 100Nm3perIt-hot
metal. Recently, natural gas injection to a blast furnace
has been also focussed from a viewpoint of C02problem
is to
as mentioned above. The purpose of this study
natural
using
propose an improved ironmaking system

is

to

as solid

GEG

emission and for effective use


gas for reduction of
natural
of exergy. In the system,
gas Is Injected to a blast
is
synthesized
from the top gas.
furnace and methanol
based
The mathematical model
on heat and mass
data which is
the
operating
various
predicted
balances
Effect
analysis.
of operating
for
the
exergy
necessary
conditions, such as amountof coke replaced by natural
emission
gas and conversion ratio to methanol, on
the
for
loss
examined
assessment of the
and exergy
was

in

concentration, because H2 concentration of the top gas


is expected to increase with
increasing the injection
will be described later.
details
natural
of
gas;
amount
The second method is adopted whenthe C02 problem
must be solved even if energy efficiency were decreased.
Namely, carbon in methane is removed in the form of
carbon fiber by chemical vapor deposition (CVD)method
(CH4= + 2H2) before the injection of natural gas. This
leads to hydrogen injection into the blast furnace. Since
carbon fiber has hlgh electric conductivity and good
mechanlcal property, it is focussed as a newhigh grade

GEG

system proposed.
2.

(1

Improved lronmaking System Proposed

Figure I shows a typical conventional blast furnace


ironmaking system, which consists of five unit processes:
coke oven, sintering machine, rotary kiln, hot stove and
blast furnace. The conventional ironmaking system
in each process from coal and limestone,
generates GEG
which are marked by superscript of ~ Limestone emits
carbon dioxide in agglomeration processes according to

method has two unavoidable


low energy efficiency due to no
combustion of carbon and another is slow reaction rate
of CVD.Therefore, the improved ironmaking system in
this study adopts only the first method.
Figure 2 shows schematic dlagram of the industrial
methanol synthesis system. This system consists of three
unit processes: steam reformer, catalytic
reactor and
distillation
towers. First, natural gas is reformed to gas
mixture of H2-CO-C02at 750 K by steam. Next, the
gas is introduced to the catalytic reactor at 523 K under
high pressure condition for production of crude methanol. To improve productivity
and decrease pressure required for met,hanol synthesis, various catalysts have
been developed. During the period of 1952 to 1965, all
material.

However,

disadvantages: one

the reaction of CaC03 CaO


+ C02' The blast furnace
=
off gas (BFG) and the coke oven gas (COG)are mostly
utilized in other processes within the system. The outfiow
ratio of the byproduct gas from the system depends on
the operation conditions of the ironmaking system.
indicate the improved ironDotted lines in Fig,
making system proposed here. Considerable amount of
natural gas is injected to a blast furnace resulting in

600

this

is

i___> Methanol
Dvst

BFG
PCI=0

Coat~

Coa[#

Coke

Oven

500

E 400

!:
\o

cp

COG
300

~
O
LU 200
O
l OO
o

Ore

CaCO~

Fi ne

Fvrnace
Si

#
CaC03

Hot

nter

Machirie

Coke

CoaL#

Biast

Rotary
Ki [n

'

LDO

Stove

Ai r

A
S[

Hot Metai

'~----ir-- vi

ag

-- Natural

Gas

+ 02

(Carbon Rber)

Ore

~l BF ~] Coke ~] Sinter
~l pe I Iet ~~ EIect ri cit y
Fig,

l,

Schematic diagram of blast furnace ironmaking system and summation of greenhouse effect gas
(#; original
source of GEG)

(GEG)

emission.

1137

@1993, ISIJ

33

Vol.

ISIJ International,

G)

993), No.

(1

11
Methano]

G)

@
50-300kglcm2

45(~C

'--':-':~Fr~Tlir~';

C02+3H2

Compressor

=CH30H+H20

Reformer

5i

*i

40C

75(Pc

Cooling tower

---{lF----'

Reactor c0+2H2=cH30H

18(~C

~~

{i

=~*

~'
Lrji~~ ~

~ ~{

Crude methanol
storage

waste Heat Boiler

distillation

tower
Natural gas

Separator

+C02

l
2

CH4

CO

22.0
1.0

18.5

C02
7.0
Il.O

H20

H2

N2

O 5 70 5
O5 .

69.0

27

4
5

Table

1.

35
.

Fig.

2.

unit

CH30H
72 5
lOO O
92 . O
.
.

O2
.

45
.

mol~
mol~

!uass~

mass~
mass%

Typical methanol synthesis system.

emission in a methOperating data and GEG


anol synthesis system of 600 t/day scale. (Unit: per
a ton of methanol)

Distallation

Methanoll2Mt/yearl

NG

Rawmaterials

CH4; 590Nm3.C02; 190Nm3

'

Topgas
Hot Metal[100Mt/year]

Coke

Utility

BF -

45 kwh

CH4; 550 Nm3.Electricity:

GEGemission
massbalance

(a)

(590 x,12122.4+ 190 x 12/22.4)(b)

utility

(c)

total

550,x 12122.4 + 45 x

O.

1677

I OOOx 12132= 43 kg-C

Top gas

= 302 kg-C

Methanol

345 kg-C

lutegrated

conventional catalysts were composed of ZnO and


03, which was effective in the ranges of 600 to 650
Cr
an~
34 to 40 MPa. Cu-based catalysts were lately
developed and employedunder the moderate conditions;
viz. 520
and less than 10 MPa.Besides, someindustrial
processes can produce pure methanol at the extremely
low pressure, 5MPa, where reduction of energy consumption progresses considerably. Since the reactions
+H20,
of methanol synthesis (C02+3H2=CH30H
device
cooling
exothermic,
CH30H)
a
re
2H20
a
CO+
=
is generally required to be annexedto the reactor. Crude
towers to remove
methanol goes through the distillation
impurities.
Table 1 Iists the operating data and
emission in the industrial methanol synthesis system in
of 600 t/d. Here, the consumption of
the productivity
natural gas for the system is 1140Nm3/t-methanol as
raw material and fuel. Consequently the system emits
of 345 kg-C/t-methanol. The ironmaking system
integrating with the methanol synthesis system is shown
in Fig. 3. In this system the steam reforming process in
the methanol synthesis system is unnecessary because
methaneis reformed in the blast furnace. Hence, the top
gas froin the blast furnace is directly introduced into the
catalytic reactor, where methanol can be obtained. Even
if the top gas pressure is about 0.25 MPa,markedly lower

Fig.

GEG

GEG

C 1993 ISIJ

1138

3.

BF

Concept for the integration of blast furnace ironmaking and methanol synthesis systems.

than that in the conventional methanol synthesis systems,


the gas conversion to methanol is thermodynamically

Assumingthat all methanol demandedin Japan


produced only from the top gas of the existing blast

possible.
is

furnaces, the conversion to methanol is calculated to be


~/, of
and C02in the gas. Therefore, the target
ca.
in the present study is not be so high
the
conversion
of

CO

it
should be
as the conventional process and then
determined on the basis of the energy balance within the
whole system. It is to be noted that methanol is yielded
at atmospheric pressure.13)
by

H2-C02-COgas even
Natural gas injection into a blast furnace and the
methanol synthesis from the off gas result in the following

advantages:
1)
reduction of
from a blast furnace due to the
injection of natural gas which has low C/H ratio.
2) reduction of
from a coke oven due to decrease
of coke rate in the blast furnace.
3)
reduction of
from BFGdue to the methanol
synthesis from the blast furnace off gas.
4)
reduction of
from the present industrial meth-

GEG

GEG

GEG

GEG

ISIJ [nternational.

Vol.

33 (1993), No,

anol synthesis systems due to decrease in produc-

Method

Calculated

(4)

CO

Gasutilizations

and nH, = 0.483.1


(5)

No soot

ofCOand H2 are to

Onthe other hand, quantity of heat generated in the


partial
oxidation of the carbon (C + 0.502=CO) is
expressed by H298(CO)
= - 21 7.94 kJlkg-C = a4). Additional
reduction of iron ores is conducted by
produced in the partial oxidation of carbon due to
combustion or reduction to an extent determined by the
The quantity of heat generated here per I kg carbon in
coke will be expressed below.

H298(C02)=

be nco =0.5

partial

oxidation

of carbon in natural gas will be

- 1461.51 =al

CO
CO+ O. 502 = C02'

10 12.62

Therefore, the thermal effect of the oxidation of natural


gas with oxygenin air or iron ore is.described as follows:

H*g = (al

+ a2nco+ a3nH,)y

where y is injection rate of natural gas (Nm3/thm).


Oxidation of carbon in coke with oxygen in air or iron
ore:

=-

released by the oxidation of carbon monoxide from


m3of natural gas (at 298 K).
Hydrogen liberated in the course of the partial
oxidation of the natural gas also contributes to the
reduction of iron oxides to an extent determined by the
utilization
of hydrogen according to the equation of

is

where x is coke rate (kg/thm) and C, is carbon content


of coke (kg-C/kg-coke).
Since equality of H~g=H*~k*is assumedfor coke to
natural gas, the replacement ratio
y (Nm3-natural gas)/x
(kg-coke) is given by the following relationship

in I m3 of
given by the following

H2+0.502=H20.For hydrogen contained


natural gas, the heat generation
equation.

is

y/x

which

AQcokt= QCH4+ QCo+ Ql{2

is

= (a4 + a5nco)

'

of

+ a2nco+ a3nH,)

C./(al

5 as a function

represented in Fig.

nH,. Utilization

CO

affects

more intensively

(1)
........

of nco and
than that

of H2' Under the assumptions of nc0=0.5 and nH,=


0.483, the replacement ratio is found to be I I Nm3natural gas/kg-coke. Estimation of the operation data
was conducted on the basis of this replacement ratio.
,

MassBalance

3.2.

Heat Balance

+a5nco)x'C*

(a

H*.k*

H298(C02)=- 10 112.62 kJlkg-CO


= (- 10 112.62) 28/24.46nco kJ/m3-CH4
I1576,18nc0=a2nco kJ/m3-CH4

kJlkg-CO

The energy of

Coke

= (- 10 112.62) 28/12nco kJ/kg-C


= -23 596. Inco = a5nco kJ/kg-C

kJ/m3-CH4

Carbonmonoxideproduced in partial oxidation of the


natural gas participates in the indirect reduction at the
utilization
according to the basic reaction of
rate of

CO

CO(CO+ 0.502 = C02)'

of

utilization

generates in a blast furnace.

The quantity of heat generated by

5)

lj298(CO)=

kJ/m3-CH4
19 561 .24nH, a3nH, kJ/m3-CH4
=

=-

Heat Balancel2)
Figure showsschematically assumptions for deriving
heat and mass balance equations for the blast furnace
operation with natural gas injection. The assumptions
are briefly explained as follows:
(1)
Main componentof natural gas is methane.
(2)
Natural gas and oxygen are injected from the
tuyere resulting in decrease of coke rate.
(3)
According to the equation of CH4+0.502=
2H2,
and H2 are generated in the raceway.
+

3.1.

CO

I19617,1 kJ/kg-H2
119617, l)2 2/24.46nH,

H298(H20)== (-

tion.
3.

11

Operating data for the blast furnace off gas is estimated


by massbalance equations. The amountof slag (S+ dS)

Qcoke 1lc0=0.500
~r
IIH2 o 483

O95

4~

0.5

1.00

1.05
1.10

C0+0.50 =CO.+Q
H +0.50 =H.0+QH2

el
:~

1.15

F 0.4

1 20
y/x=1.25

C in
Airi*

-~-~'

r
CH4+02
CH

CH+0.50 =C0+2H+QcH4

0.3

O3

4.

0.5

0.4

+0.

Fig.

T1

Fig.

Assumptions for deriving heat and mass balances for

5.

Coke;88("/.)

co (

~)

Relation between replacement ratio y/x (Nm3/kg) and


gas utilizations.

the blast furnace operation with natural gas injection.

1139

C 1993 Is[J

Vol.

ISIJ International,

decreases slightly
when coke rate is reduced,
calculated by the following equation.

x=Csoa(S+dS)-CsocaS....

C*.

and

33

..........(2)

(22.

(3)

2y=(YH2+YH20)(V+dV)-(IH2+1H20)V..................

(4)

141/12)Co x + OIN= (Yco+ 2Yc02+ YH20)(V+dV)


'

-(Ic0+2lc02 +1H20)V ....

O= YN2(V+dV) -IN2V

(5)

GEG

operating datal5)
it

of carbon monoxide and hydrogen are 0.500

and O.483,

respectively.

nc0= Yc02/(Yc0+ Yc02)=0.500

GEG

assumedthat

is

utilization

mass(C-kg).
(2)
converted to another
Evenif one species of GEG
species of GEG
due to combustion or oxidation within
a system, they were not counted again.
(3)
GEGemission by consuming electricity was
assumedto be O, 1677kg-C/kwh which was the standard

(7)

.......,..

......

nH2=YH20/(YH2+YH20)=0.483 .......
Yc0+Yc02+YH2+YH20+YN2=I ...
Table

GreenhouseEffect Gas Emission


in the ironmaking system
Total emission of
was
estimated according to the following method;
(1)
etc.)
All species of
emitted (CO. C02,CH4
estimated
equivalent
unit
value
by
carbon
C02
as
were
a

3.4.
(6)

..............................................

Additionally,
based on the practical
in the blast furnace with oil injection,

(8)

..........

(9)

..........

emission for
GEG

the generation of electricity.


This value
electricity
the
obtained
that
the
assumption
on
was
was
generated in steam-power station.

Fundamentalexergy equations and environmental

2.

conditions.

Formof

8= 8c + sr

+ ep + 8M

Equation

exergy

Chemical
Temperature
Pressure

8T=(~niCpf)1 T- To ~ To In(T/To)
8p = (~ ni)RTOIn
P Po)
eM= RTO [ni In ni/(~ni) I]

Table 3 gives the operating data and the profile of a


conventional blast furnace. Inner volume of this blast furnace is 500 m3 and nominal productivity is 10000thot metal per a day. The furnace operating conditions
were 500 kg in coke rate; o/, pellet and 78.6 "/* sinter in
the constitution of burden charged; 0.2456 MPain top
in top gas temperature. Folgas pressure and 478
10wing analysis used the operating data which were
the actual operating data averaged during a period of a
month under a stable condition was partially modified
to satisfy mass balances on major elements (N, Fe, C,
H, O, Ca) within the error of 0.010/0. Simulation of
operations with natural gas injection was conducted on

I~( J l
I

To = 298. 15 K, Po= I atm

Condensedphase:

Gasphase:

H20(1) at To' Po
Substances

Mole fraction

N2
02

O.7560
0.2034

H20
C02

0.03

Ar

O.009 l

12

0.0003

Table

Results and Discussion

4.

ec=~n,g,o

Mixing

is

The process exergy analysisl~4) was applied to the


integrated system for ironmaking and methanol synthesis. Fundamental equations for the exergy analysis
and the environmental condition are lited in Table
without derivation because the concept and the calculation method of exergy were reported previously in
detail.4)
Exergy loss was estimated in each process and
within the system.
summarized
was

'

.................

value

Exergy

3.3.

tively.

x
Yc02)(V+dV)-(Ic0+1c02)V
(Yc0+
=

11

given to the coke rate, x kg,


operating data of y, Yj (j=H2, H20, CO. C02, N2), dV
and OIN are predicted by solving Eqs. (1), (3) to (9),
simultaneously.

Equations (3) to (6) correspond mass balance equaon carbon, hydrogen, oxygen and nitrogen, respec(22.414112)C.

993), No,

Whenarbitrary

is

tions

y-

(1

Operating data and profile

3.

of the blast furnace of 10000t/d

scale.

Input

Rawmaterials
Coke
Blowing gas
Electricity

Lumpore/Sinter/Pellets

('/.)

= 18.3/78.6/3.0, 1632 kg/t-pig,

303 K,

T.Fe/FeO/Si02/Al203/CaO/MgO/Ti02/Mn= 58.735/4.58/4.32/1.71/7.41/1.39/0.232/0.25
500 kg/t-pig, 303 K. F.C./T.S./Ash ('/,)
= 87.76/0.42/1 1.80
l I 19Nm3/t-pig, I 189K, 4.250 atm, 02 enrichment 21.8 Nm3/t-pig. H20enrichment 40g/Nm3, N2/02('/,) =77.5122.5
Blowing+ Blast furnace = 850 103 + 77. I 103 =927. I 103 kwh/d = I 11 .2 (= 927. I 103/8 337) kwh/t-pig,
'

'

TRT= 77, I -

54.4

(=

453 322/8 337)

'

'

22.7 kwh/t-pig

Output

Top gas (BFG)


Pig iron
Slag

l 641 Nm prg 478 K CO/CO/H2/N2 21 7/22 2/2 2/53 9 nc0=49,4, 727kcal/Nm3, 2.456atm
8337 t/d = I OOOkg/t-pig, 1766 K, Fe/C/Si/Mn/P/S/Ti ('/.) = 94.732/4.53/0.26/0.29/0, I 16/0.022/0.05
('/*)
300 kg/t-pig, FeO/Si02/Al203/CaO/MgO/Ti021MnO
= O.36/33 .38/ 14.69/4 1.65/7 13/ I .09/0. 39
21.O kg/t-pig. C/T.Fe/FeO/Si02/Al203/CaO/MgO/Ti02/Mn('/.) = 42.4/33 .83/2.64/2,49/0.98/4.27/0.80/0.
/t

Dust
Profile

Capacity

Volume

lOOOOt/d

4500 m3

C 1993 ISIJ

Hearth diameter
14.

Im

Top pressure (Max)


2.

5atm

1140

Charging device

PWBell-less

top

Shaft support
Free standing

13/0. 14

Numberof

cooling boxes
Stave/Closed 664/168

Vol.

ISIJ International,

the basis of these operating data. Figure showspredicted


operating data. In the calculation, natural gas and oxygen
replaced coke at the interval of 50 kg-coke and heat loss
ratlo through wall was identical as the base operation.
content
It is seen that in concentration of the top gas
decreases and
content increases with the natural gas
injection.
This change in the operating data is ad-

vantageous for methanol synthesis, because production


of I mol methanol needs hydrogen of 2 to 3mol.
Figure 7 shows effect of the natural gas injection on
Since
sumof exergy loss within the ironmaking system.
the operating conditions of blast air, charging ratio of
agglomerates are assumedto be the same as the base
operation, energy loss in the agglomeration processes
and in the hot stove is almost same. However, a coke
oven consumesless exergy due to reduction of charging
coke with the increase in natural gas injection. On the
contrary, exergy for the production of oxygen increases
because Linde process for producing pure oxygen
in the form of
high exergy, particularly

consumes

Theblast furnace also consumeshigher exergy


whennatural gas is injected. Methaneand carbon have
electricity.

chemical exergy of 830 and 41lkJ/mol, respectively.


Therefore, methanehas higher chemical exergy compared
with carbon, which is a negative factor in natural gas

Coke rate (kg/tHM)

300
2400

400

500
60
N2

'

1600

~1

Natural gas injection(Nm3/thm)

~~

_____c_O, co 2

800

~
Fl

>

'~

\~'

----~20

(!)
F~~
(J,

Fig.

Natural gas (Nm3/tHM)


6.

Flow rate and composition of blast


against natural gas injection.

200

8.

o
1~ 500o
o
\-l 400
300o
= 200o
= lOOi
a

SOO

8.2G

eJO:~

e)>,

~I

~l Sinter&Pellet
Fig.

7.

400

28

356

327

500

400

300

Coke ratiO (kg/thm)

~lc

oven

~ls

machine

~iR

kiln

~~02 ~lElectricitv

Changes of total GEGemission in a blast furnace


ironmaking system with natural gas injection.

219

110

Cokeratio(kglthm)
~1 Hstove ~~ c oven

71

37

386

~~IBF

,:

500

4T

29

71

furnace off gas

9.0G

9
S8
~
~~ 7
e6
5
h4
3
2
1
o

46lkg

71

300

Fig.

29

29

400

Natural gas injection(Nm3/thm)

10

219

1OO

200

I oo

Enriched

110

535kg

500

,1

H2

600

~
4,

in the exergy

20

11

consumption. Considering all the


factors mentioned above, sum of exergy loss in each
process within the ironmaking system decreased from 9.0
to 8.2 GJ/thrn which is 8.8 ~/..
emission in the
Figure 8 shows changes of total GEG
ironmaking system with natural gas injection to the blast
furnace. Being similar to exergy loss, total amount of
GEGchanges withis natural gas injection from 535 to
461 kg/thm, which 13.80/. In the constituent processes,
emission decreases 59kg in the blast
amount of GEG
furnace; 19 kg in the coke oven and increases 4kg in the
oxygenprocess. In the ironmaking system integrated with
methanol synthesis, additional reduction of GEGis
expected by methanol synthesis of the blast furnace off
depends on howmuchof
gas. Reduction ratio of GEG
off
converted
the
to methanol. Methanol
gas can be
synthesis from blast furnace off gas has just begun to
be studied.13) It is, therefore, not easy to predict possible
conversion ratio under the condition of the blast furnace
off gas. Here, three conversion ratio, l, 5and 50"/. on
the basis of carbon mass, wer~ assumedfor estimation.
Figure 9 shows effect of conversion ratio on total GEG
emission in the integrated ironmaking system. Total
double
GEGis found to be remarkably decreased bysynthesis.
effects of natural gas injection
and methanol
For instance, in the case Cwhere conversion ratio is 5olo,
since GEG
decreases by 16 kg due to methanol synthesis,
will decrease from 461 to 445 kg. The case C
total GEG

Z_

~~

O
~.

993), No.

injection

ON 40

(1

G_a_~

l'op

~~5)

t~

33

300

Fig.

02 ~~ BF

9.

~~0%~il%~i5%l~50%

Conversion factor

Case
Effect

Case

of conversion ratio

case

blast furnace off gas


emission in a blast fur(Case, y/x)=(A, 0/500), (B,

from

methanol on total GEG


nace ironmaking system

to

Changesof total exergy loss in a blast furnace ironmaking system with natural gas injection.

l 10/400),

1141

(C, 219/300).

C 1993 ISIJ

ISIJ International,

Table

4.

Case

Vol.

33 (1993), No,

Operation cases ibr the estimation of exergy

emission.
and GEG

loss

A* 1

Conventional

11

C- I

A-2

C-2

lronmaking

Coke

(kg)

Natural gas
Methanol converslon

(Nm*)
(~/.)

By-produced Methano]

(kg)

5oo
o

500

500

500
219

o
l .9

lO
10

l .O
9

20

Synthesis

Methanol

(kg)

20

lO

Natural gas

(Nm')

23

ll

I OOOkg-hotmetal

Production;

700

300
219

o
o

2.3

20

o
o

ll

13

and 20kg-methanol

lOOOkg-HetMetal

~l BFironmaking

[~

& 20kg-Methanoi

Mothanol synthesls

60O
~42

534

528

500
4f2

4s4

~,

.,

40O

~:

.:2

~
~~

300
200

Fig.

lO.

GEG

of integrated system on total


emisa blast furnace ironmaking system with
methanol synthesis for the production condition
of I OOO
kg-hot metal and 20 kg-methanol.
Effect

sion in

l OO
o
Conventiona]

CaseA- l

has 300kg/thm in coke rate and


of natural gas.

CaseC- l

CaseA-2

219Nm3/thmin

the

CaseC-2

Conclusron

5.

injection

The ironmaking system


synthesis

affects

also

integrated

GEGemission

with
in

emission, an improved
To reduce exergy loss and GEG
ironmaking system wasproposed, which consisted of the

methanol

the existing

conventional blast furnace with the injection

methanol synthesis system. In Japan, annual productions


of crude steel and methanol are about 100 Mt and 2Mt,
respectively.

From this production

ratio of crude steel


production per I t-hot
metal will makethe existing methanol synthesis system
unnecessary. According to thls data, conversion ratlos
to compensatethe existing systems are I .9 o/o in the case
A and 2.3 o/o in the case C. Table 4Iists five cases for the
estimation of total
emission. The computation was
conducted for the productions of I OOO
kg-hot metal and
20kg-methanol. In the conventional case of Table 4,
ironmaking and methanol synthesis systems exlst
independently. This is the present state of industry. The
other cases stand for integrated ironmaking system with
methanol synthesis. In the cases of A-1 and C-1 where
conversion ratio to methanol Is assumedto be I o/o, the
integrated system partly supports methanol production
in the existing methanol system. In the
cases of A-2 and
C-2, the proposed system replaces the existing methanol
system compietely. Figure 10 showsthe effect of methanol
synthesis from blast furnace off gas
on total
emission. For example, total
decreases from 542

to methanol, only

?-O kg-methano]

GEG

GEG

GEG

GEG

GEG

GEG

Acknowledgment
The authors wish to express their

sincere thanks to

Foundation for the Development of Environments


Protection Technology in lron and Steel Industries and
Nlppon Steel Corporation for the partial financial
support, and to Kawasaki Steel Corporation for the
supply of operating data of a blast furnace.
Nomenclature

454kg/thm in the case C-2 where no methanol is


produced by the present industrial
system. This
computation shows clearly the effectiveness of the
integration
of ironmaking and methanol synthesis
to

al,a

2,

a3,

C.. :

C. :

systems.

@1993 ISIJ

of natural
gas and the methanol synthesis system. The feasibility
study clarified advantage of this system from exergy loss
emission. Operating data which were necessary
and
in the feasibility
study wasestimated by the mathematical
model derived on the basis of heat and mass balances.
In the calculation of operating data, principal parameters
selected were l) replacement amountof coke by natural
gas, and 2) conversion ratio from the blast furnace off
gas to methano]. As replacement amountand conversion
ratio increased, not only exergy loss but also
emission from the system decreased significantly.
Both
effects of natural gas injection
and conversion ratio on
emission were clarified quantitatively.

C****:

1142

a4, a5 :

constant (-)

Ca content

Ccontent

in
in

coke (-)
coke (kg(C)/kg(coke))

C.a content in slag in the base operation

(-)

ISIJ International,

Vol.

33

(1

993). No.

: Ca content in slag (-)


C:o oxygen content in coke (-)
Hng heat increased by the injection of natural gas
(k J/m3-CH4)
Hcoke heat decreased by decrease of charged coke

s:

11

solid

5ca

REFERENCES

'

l)

'

li:

O~N:
S:
dS:

dV:
x:
y:
Yi:

(k J/kg-C)
volume fraction

of

nH, :
subscript

species of gas in the

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amountof oxygen injected (Nm3)
amountof slag in the base operation (kg/thm)
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C 1993 ISIJ

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