Professional Documents
Culture Documents
Vol,
33
(1
993), No.
for
and Jun-ichiro
MURAMATSU
final
Katahira,
YAGl
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
1.
Introduction
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
CH4is
GEG
and another
is
to
as solid
GEG
in
GEG
system proposed.
2.
(1
However,
disadvantages: one
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
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%
Distallation
Methanoll2Mt/yearl
NG
Rawmaterials
'
Topgas
Hot Metal[100Mt/year]
Coke
Utility
BF -
45 kwh
GEGemission
massbalance
(a)
utility
(c)
total
550,x 12122.4 + 45 x
O.
1677
Top gas
= 302 kg-C
Methanol
345 kg-C
lutegrated
Fig.
GEG
GEG
C 1993 ISIJ
1138
3.
BF
Concept for the integration of blast furnace ironmaking and methanol synthesis systems.
possible.
is
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,
Method
Calculated
(4)
CO
Gasutilizations
No soot
ofCOand H2 are to
H298(C02)=
be nco =0.5
partial
oxidation
- 1461.51 =al
CO
CO+ O. 502 = C02'
10 12.62
H*g = (al
+ a2nco+ a3nH,)y
=-
is
in I m3 of
given by the following
is
y/x
which
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
MassBalance
3.2.
Heat Balance
+a5nco)x'C*
(a
H*.k*
kJlkg-CO
The energy of
Coke
kJ/m3-CH4
CO
of
utilization
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
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.
5.
Coke;88("/.)
co (
~)
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)
O= YN2(V+dV) -IN2V
(5)
GEG
operating datal5)
it
and O.483,
respectively.
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
3.4.
(6)
..............................................
Additionally,
based on the practical
in the blast furnace with oil injection,
(8)
..........
(9)
..........
emission for
GEG
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]
I~( J l
I
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
4.
ec=~n,g,o
Mixing
is
'
.................
value
Exergy
3.3.
tively.
x
Yc02)(V+dV)-(Ic0+1c02)V
(Yc0+
=
11
Equations (3) to (6) correspond mass balance equaon carbon, hydrogen, oxygen and nitrogen, respec(22.414112)C.
993), No,
Whenarbitrary
is
tions
y-
(1
3.
scale.
Input
Rawmaterials
Coke
Blowing gas
Electricity
Lumpore/Sinter/Pellets
('/.)
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
(=
'
'
22.7 kwh/t-pig
Output
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
5atm
1140
Charging device
PWBell-less
top
Shaft support
Free standing
13/0. 14
Numberof
cooling boxes
Stave/Closed 664/168
Vol.
ISIJ International,
consumes
300
2400
400
500
60
N2
'
1600
~1
~~
_____c_O, co 2
800
~
Fl
>
'~
\~'
----~20
(!)
F~~
(J,
Fig.
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
~lc
oven
~ls
machine
~iR
kiln
~~02 ~lElectricitv
219
110
Cokeratio(kglthm)
~1 Hstove ~~ c oven
71
37
386
~~IBF
,:
500
4T
29
71
9.0G
9
S8
~
~~ 7
e6
5
h4
3
2
1
o
46lkg
71
300
Fig.
29
29
400
10
219
1OO
200
I oo
Enriched
110
535kg
500
,1
H2
600
~
4,
in the exergy
20
11
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
from
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,
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
sion in
l OO
o
Conventiona]
CaseA- l
CaseC- l
CaseA-2
219Nm3/thmin
the
CaseC-2
Conclusron
5.
injection
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
to methanol, only
?-O kg-methano]
GEG
GEG
GEG
GEG
GEG
GEG
Acknowledgment
The authors wish to express their
sincere thanks 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))
(-)
ISIJ International,
Vol.
33
(1
993). No.
s:
11
solid
5ca
REFERENCES
'
l)
'
li:
O~N:
S:
dS:
dV:
x:
y:
Yi:
(k J/kg-C)
volume fraction
of
nH, :
subscript
exergy (kJ)
nco :
i-th
CO
utilization
H2 utilization
i-th
2)
3)
4)
5)
6)
7)
8)
9)
1O)
l 1)
J.
May, 337.
(-)
(-)
12)
l 3)
l4)
S, Fujita,
component
O:
standard condition
g:
gas
15)
1143
5(1992),
Il61.
CATSJMeeting
205 (1967), 630.
C 1993 ISIJ