-------
68
Refinery Energy Consumption Data. Knowing that the size
variable can be accounted for by using unit energy consumptions (energy consumption.3
per unit of throughput) and having Nelson's correlations for the complexity
variable, typical refinery energy consumption data are needed to compare the
energy consumption of the model refinery with that of the U.S. refining in-
dustry as a whole. The Bureau of Mines publishes data on the energy consumed
at refineries in the U.S., breaking this down by states (or state groups)
and sources of energy(20)^ Table 17 summarizes the national totals, in-
cluding the breakdown by sources, for the last 3 years for which the data
are available. Table 18 presents the state-by-state breakdown of the energy
consumptions for the most recent year available (1973). This table also
includes the 1973 and 1975 crude oil capacities for all the states and the
unit energy consumptions and average refinery complexities for the states
with the larger refinery capacities. As backup information, Table 19 contains
the fuel energy contents used by the Bureau of Mines(22) 3^ developing their
tabulations.
Types of Fuels Used
Because refinery gas is a major source of energy in most refineries,
it will be instructive to consider the quantities of refinery gas available for
fuel users in various refineries. Two aspects in which they have available for
fuel use are concerned with the two processes which generate the greatest share
of the refinery gas at the model refinery—catalytic reforming and catalytic
cracking.
Hydrogen From Catalytic Reforming. As mentioned previously,
the catalytic reforming process generates as a byproduct considerable quantities
of hydrogen. This hydrogen can be used in hydro-treating processes to remove
sulfur from liquid fuels. The feed to the catalytic reformer itself requires
a mild hydro-treating to remove traces of sulfur which would otherwise poison
the catalyst. The quantity of hydrogen needed for other hydro-treating operations
depends primarily upon the sulfur content of the crude oil being processed.
Also, some refineries use hydrocracking as a conversion process, either instead
of, or in addition to, catalytic cracking, and hydrocracking requires rela-
tively large quantitites of hydrogen. There are some refineries at which the
-------
69
TABLE 17. CRUDE RUNS AND ENERGY CCNSUMPTION
DATA FOR U. S. REFINERIES(2'>
Crude Oil Capacity, 103 B/CD(a)
Crude Run, 10 3 B/CD
Capacity Utilization, percent
Consumption of Energy Sources
Oil, 103 B 3
Liquefied petroleum gas, 10 B
Natural gas, 10 ,scf
Refinery gas , 10 scf
Petroleum coke, 10 tons
Coal, 10 tons
Electricity, 106 kwhr
Steam, 10b Ib
9
Energy Consumption, 10 Btu
Oil
Liquefied petroleum gas
Natural gas
Refinery gas
Petroleum coke
Coal
Electricity
Steam
TOTAL
3
Energy Consumption, 10 Btu/B crude
Total
Ex. refinery gas and coke
Natural gas and LPG only
1971
12,884.31
11,199.48
86.92
38,072
6,850
1,062,938
981,557
10,444
405
20,720
36,762
239,359
27,475
1,095,889
971,742
314,573
9,728
70,697
44,114
2,773,577
678.5
363.8
274.8
1972
13,235.09
11,728.39
88.62
44,324
13,418
1,040,746
1,053,492
11,230
339
22,612
38,870
276,318
53,820
1,073,009
1,042,957
338,247
8,143
77,152
40,644
2,910,290
679.8
357.2
263.2
1973
13,799.62
12,430.83
90.08
49,574
10,136
1,073,742
1,083,363
13,282
329
23,382
33,945
309,095
40,655
1,107,028
1,072,529
400,054
7,902
79,779
40,734
3,057,776
673.9
349.4
252.9
1974
14,530.85
12,689.32
87.33
(a) Average of values at beginning and end of year. Oil and Gas Journal.
-------
TABLE 18. STATE-BY-STATE BREAKDOWN OF 1973 CRUDE RUNS AND ENERGY CONSUMPTION FOR U.S. REFINERIES
(20)
1973 Crude RunCe;
States (103 B/CD) Oil
Arkansas
Calif., Wash., Ore.,
Alasks, Hawaii
Colorado
Delaware, Mass.,
R.I., Virginia
Georgia, N. Car.,
S. Car., Florida
Illinois 1
Indiana
Kansas
Kentucky, Tennessee
Louisiana 1
Maryland
Michigan
Minnesota, Wise.,
N. Dak., S. Dak.
Mississippi, Alabama
Missouri, Nebraska
Montana
New Jersey
New Mexico
Jiew York
Ohio
Oklahoma
Pennsylvania
Texas 3
Utash
West Virginia
Wyoming
Arizona
TOTAL 12
Percent of Energy
Consumption
48
,971
38
113
57
.79
.42
.84
.40
.76
,031.12
491
373
175
,462
18
122
242
287
101
119
593
46
100
500
447
604
,209
115
13
141
3
,430
.61
.27
.15
.09
.58
.88
.35
.59
.07
.08
.21
.39
.49
.32
.16
.28
.11
.97
.72
.23
.95
.83
1,978
37,942.
1,041
4,267
1,362
54,274
36,944
4,602
9,537
15,443
2,223
3,628
10,575
1,776
346
5,042
38,493
163
3,911
10,104
1,374
45,763
8,681
3,805
2,534
3,288
309,095
10.1
1973 Energy Consumption (109 Btu) ^
LPG
205
13,649
421
40
373
2,403
325
999
1,656
6,811
—
650
148
365
2,254
453
192
610
2,238
734
433
16
4,966
586
—
128
40,655
1.3
Nat. Gas
5,236
146,111
2,169
1,041
801
11,182
4,542
34,889
5,791
116,835
—
3,244
1,524
25,411
4,446
5,653
9,826
3,600
--
20,677
49,739
20,390
612,382
5,625
1,235
15,012
1,107,028
36.3
Ref. Gas
2,914
184,618
3,086
24,744
—
88,626
42,301
30,425
12,072
116,917
11
7,172
15,997
20,099
8,606
11,370
37,280
3,126
8,460
47,974
42,867
64,549
280,330
8,864
967
10,154
1,072,529
35.1
Coke &
Coal
— _
58,284
994
13,614
—
42 , 108
15,753
14,126
4,790
32,951
—
2,319
9,940
4,458
4,217
5,693
19,879
1,175
2,530
14,456
13,012
21,688
113,523
4,789
552
6,385
407,956
13.3
1973 Energy Consumption
(103 Btu/B Crude Run) Nelson
Ex.
Elec. & Ref. Gas
Steam Total Total and Coke
239
25,604
300
8,876
20
7,363
983
2,289
1,242
28,060
31
778
1,501
2,975
157
972
10,092
188
652
3,975
2,351
4,481
16,033
624
263
464
120,513
3.9
10
466
• 8
52
2
205
100
87
35
316
2
17
39
55
20
29
115
8
17
97
109
156
1,035
23
5
35
3,057
,572
,748 648.7 310.3
,038
,582
,555
,955 547.2 199.9
,848 562.0 238.5
,330
,268
,017 592.2 313.2
,265
,971
,685
,084
,026
,183
,763 534.6 270.7
,862
,791
,920 536.2 196.3
,776 672.6 330.2
,887 711.3 352.0
,915 884.4 548.2
,933
,551
,431
,776 673.9 349.4
N.G., Complexity
LPG Factor
and Oil 1973
274.8 9.26
180.3 8.89
"233.0 8.11
260.6 9.05
224.0 9.02
172.6 8.52
315.8 9.51
300.0 10.07
534.5 9.36
321.1 9.24
100.0
o
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71
TABLE 19. FUEL ENERGY CONTENTS USED BY BUREAU OF MINES(22)
Enerev Content
Fuel
Metric Units
English Units
Crude oil
Distillate fuel oil
Residual fuel oil
Liquefied petroleum gas
Natural gas
Refinery gas
Petroleum coke
Coal
Electricity
Steam
9,032 kcal/liter
9,270 kcal/liter
10,006 kcal/liter
6,383 kcal/liter
9,211 kcal/std m3
8,845 kcal/std m3
8,400 kcal/kg
6,699 kcal/kg
863 kcal/kwhr
669 kcal/kg
5.675 x 10 Btu/bfal
5.825 x 106 Btu/bfal
6.287 x 106 Btu/bbl
4.011 x 106 Btu/bbl
1,031 Btu/scf
990-Btu/scf
30.12 x 106 Btu/ton
24.02 x 106 Btu/ton
3,412 Btu/kwhr
1,200 Btu/lfa
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72
demand for hydrogen is too great to be satisfied by the reformer byproduct
and a separate hydrogen generation plant is used.
The number of refineries in the U.S. using various hydrotreating
processes is shown in Table 20. In this table, "hydrotreating" refers to
the mildest type of process (such, as that used for the reformer feed), "hydro-
refining" to more severe processes, and "hydrocracking" to the conversion
process mentioned above. The use of hydrotreating processes in this country
is expected to increase as more crude oil having higher sulfur content is
processed and as the restrictions on the sulfur contents of fuels are tightened.,
TABLE 20. NUMBER OF REFINERIES USING
HYDROTREATING PROCESSES< I 7)
Crude Oil Capacity Range, I03 B/CD 25 25-100 100 All Sizes
Number of Refineries Using
Hydrocracking
Hydroref i n i ng •
Hydrotreat i ng
Al 1 Refineries in U.S.
5
2
41
124
13
24
82(a)
92
26
18
43
43
44
44
166
259
(a) Model refinery included here.
Off Gas From Catalytic Cracking. The catalytic cracking
process produces considerable quantities of light hydrocarbons (C-^-C.) which
are collected as a gaseous stream. Much of this stream is made up of un-
saturated (olefinic) hydrocarbons such as ethylene, propylene, and butylene.
Since these olefins are not as desirable in fuel products as are other types
of hydrocarbons, it is common practice to include with a catalytic cracker
another process to utilize the olefins produced by the catalytic cracker.
The two processes which can be used for this purpose are alkylation and poly-
merization. Both processes yield a high octane product containing mostly
-------
73
branched-chain paraffin compounds, a product which is blended into gasoline.
In alkylation, isobutane is added to the olefins to form branched-chain com-
pounds in the gasoline boiling range. In polymerization, the light olefins
combine with each other to form a similar product. A refinery which has
either of these olefin utilization processes will not have large quantities
of light olefins available for fuel use.
Adaptability to Firing
Low-Energy Gas
Land Area. The amount of land area occupied by the processing
equipment is important in analyzing the possibility of retrofitting refineries
to low-energy gas because it determines the distances over which the gas must
be piped. The processing equipment usually occupies only a small part of the
total refinery area. Storage tanks usually occupy the largest part of the
area. With the increasing emphasis on pollution abatement, water treatment
facilities can use a considerable fraction of the refinery area. As examples
of typical refinery layout, the plot plans of two refineries recently built
in the United States are shown in Figures 21 and 22.
The land area required by a refinery depends on the size and com-
plexity of the refinery. W. L. Nelson(25) has determined some average land
usages per unit of refinery throughput and has expressed them in terms of the
refinery complexity factor. These data are plotted in Figure 23. They include
the land in use for process equipment and storage but not for administration
buildings and buffer zones around the plant. Based on some available refinery
plot plans, such as those shown in Figures 21 and 22, it appears that the
process equipment typically occupies 1/3 to 1/5 of the area included in the
correlation of Figure 23.
Access to Waterways. Although not absolutely essential, access
to a waterway is an attractive feature of a site for a coal gasification facility.
Considerable quantities of cooling water are required for such a facility, even
when a recirculating system is used. If the waterway is navigable, it may be
desirable to transport at least part of the coal to the facility by barge.
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74
Clai
Holding &
Lf ication /
P°nd~"o\/^
Decanting >N
Basin *(j/
Flares &
Slowdown
i •
R
o
1
Stora
^
\S O Sul
Reco1
ik
Amine_>
Sulfur
Unit
.— — i ^e^
1 ' Co
0 O
O 0
o o
o o
•Jaste W<
fur
/ery
U £1
ater Treatment
C^A — Administration 1
, m
Main Processing Area [
i/
jU
r~u
1
t t
.ayed tt
ker i
0 0
0 0
0 0
0 0
o ::
o
«-flv<
Hydre
— Lij
1 'FT
J U
faphtha
leformer
0 0
0
0 0
o
o
, .
O T^O
ge Area
O
LO)
o
0
o
irogen Unit
^cracker
?ht Ends
Crude &
'Vacuum
Unit
0 O
O O 0 '
O
O
l
V
1
FIGURE 21. PLOT PLAN OF AROO'S CHERRY POINT REFINERY
Capacity: 1,000,000 B/SD
Total Area: 450 Acres
(23)
-------
75
Waste Water Treatment
FCC
Feed}.
j oo
OOOO
OOO
OQO
000
•Product Storage
*-LP Gas Spheres
Coker
o
o
o
„
TO OP
j-Amine Sulfur Un i t
P~j Main/ Reformer /
I I Processing ..' Alkylatio*
f Area
Administration
o
o
o
f
Crude
Storage
FIGUEE 22. PLOT PLAN OF MDBIL OIL'S JOLIET, ILLINOIS, REFINERS
Capacity: 164,000 B/SD
(24).
-------
50
40
30
20
10
Land in Use for Process Equipment and Storage
(acres per 10,000 B/D crude capacity)
I
Complexity of
U.S. Industry
I
8 10
Nelson Refinery Complexity
12
14
16
FIGURE 23. LAND IN USE FOR PROCESS EQUIPMENT AND STORAGE AT REFINERIES(25)
-------
77
• Description of Model Refinery
Size and Products
The model petroleum refinery used in this study has a crude oil
capacity of about 3.97 x 106 liter/day (25,000 barrel/day). The products
of the refinery are propane, butane, gasoline, kerosene, distillate, residual
(No. 6) fuel oil, and asphalt. There are seasonal variations in the quanti-
ties of these products produced. More gasoline is produced in the sunnier,
and more residual fuel oil is produced in the winter. Asphalt is produced
only in the suttmer. Such seasonal variations are normal for petroleum refineries.
Processes
The following refining processes are used in the model refinery:
• Fractionation of crude oil and petroleum fractions
• Catalytic cracking
• Catalytic reforming (including feed hydro-treating)
• Polymerization.
Catalytic cracking is a process for reducing the molecular weight
of hydrocarbons and is used to produce hydrocarbons boiling in the gasoline
range from higher boiling hydrocarbons. Catalytic reforming and polymeri-
zation are processes for producing high octane streams for blending into gasoline.
In catalytic reforming, paraffinic and naphthenic hydrocarbons are converted
into aromatic hydrocarbons, which high higher octanes. Hydrogen is liberated
in this process. In polymerization, light olefins such as ethylene, propylene,
and butyLanes are combined to form branched-chain hydrocarbons in the gasoline
and boiling range. Branched-chain compounds have relatively high octanes. The
light olefins are produced in the catalytic cracker.
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78
Current Fuel Use Patterns
The primary fuel used in the model refinery is a blend of off gases
from various units within the refinery. Off gases are collected from a number
of processing units, the major sources being the catalytic cracker and the
catalytic reformer. The quantity and quality of the blended refinery gas
varies daily, but the average quantity is 1.45 x 105 ]Sfcn3/day (5.12 x 106 scf/day)
and the average composition is
Specie Mole, percent
H2 29.7
C, 32.7
C2's 13.0
C3's 10.4
C4's 6.9
N2 7.2.
The average heating value of this gas is about 37.3 MJ/Nm3 (1000
6 9
Btu/scf). Thus, the refinery gas supplies about 5.40 x 10 MJ/day (5.12 x 10
Btu/day) of heat.
The collected off gases go to a fuel gas drum which provides for
gas mixing and surge volume. Purchased natural gas is added to the fuel gas
drum as needed to maintain a desired pressure level which is usually about
45 to 50 psig. The blend of refinery gas and natural gas is then distributed
to the various burners in the refinery.
The model refinery manufactures asphalt from a portion of its
residual oil. Due to the high demand for this product in the summer and
negligible demand in winter, the refinery would vary its operations between
summer and winter accordingly. The average amount of natural gas required
would be 19,000 Nm3/day (673,000 scf/day) during the summer (May through
November) and 570 Nm3/day (20,000 scf/day) during the winter (October through
April). These quantities correspond to heating values of 0.21 x 10 MJ/day
g
(0.02 x 10 Btu/day) in the winter.
-------
79
6 9
During the winter, an additional 2.17 x 10 MJ/day (2.06 x 10
Btu/day) of heat would be supplied by burning residual (No. 6) fuel oil.
This fuel oil has a heating value of about 43,000 kJ/kg (18,500 Btu/lb).
When this fuel oil is used, it is atomized with steam and fed to the burners
along with the refinery gas/natural gas blend. For the processes which are
set up to burn the oil, the heat input from the oil is restricted to about
10 percent of the total heat input of the furnace. This is necessary to
minimize operating problems, since the process heaters were not designed for
oil.
Mding the above figures, the total heat supplied by refinery gas,
6 9
natural gas, and residual fuel oil is about 6.11 x 10 MJ/day (5.79 x 10
6 9
Btu/day) in the summer and 7.60 x 10 MJ/day (7.20 x 10 Btu/day) in the winter.
Geographic Considerations
The model refinery is assumed located close to plentiful supplies
of coal which could be used for the production of low-energy gas. The model
refinery would also be bounded by a navigable waterway which could be used
for barging coal into a gasification plant and for supplying the water needs
of such a plant. The refinery could also be accessed by rail transport.
Refineries typically are located near to a number of other industrial
facilities, which introduces the possibility that a single gasification plant
could supply low-energy gas to this refinery plus other nearby facilities. This
concept is beyond the scope of this study.
Other Considerations
The model refinery processes low-sulfur crude oil (normally less
than 1 weight percent sulfur). The refinery has no sulfur plant and uses no
hydrodesulfurization processes except for the removal of trace amounts of
sulfur from the feed to the catalytic reformer, which is always a required
operation. The products of the refinery are low in sulfur content. The
residual fuel oil produced contains less than 2 weight percent sulfur.
-------
30
Potential Demand for Low-Energy Gas
In considering the retrofitting of this refinery to use low-energy
gas, the first priority is for replacing the purchased natural gas. The second
priority is for replacing the residual fuel oil burned during the winter.
Since this is low-sulfur fuel oil, it should be regarded as a premium fuel
which could be used in a number of industrial facilities for which other means
of controlling sulfur oxide emissions would be less practical. The residual
fuel oil is also difficult to use in the existing furnaces at the refinery.
The third priority is for replacing several species in the refinery
gas which have, other uses for which they are better suited. One of these
species is hydrogen, which can be used in hydro-treating operations in the
refinery. Hydro-treating not only reduces the sulfur content of petroleum
fractions, but also increases the volume of the products by adding hydrogen
to them. Thus, the hydrogen can be used to produce more and cleaner liquid
fuels. Hydrogen can also be marketed for other uses. The other species which
could be displaced from the refinery gas are propane and butane. These are
premium fuels which are normally recovered and marketed, either separately or
as "liquified petroleum gas" (LPG). Propane and butane are normal products
of the model refinery;. the amount of these products normally recovered depends
on available storage and market demand. The recovery of additional quantities
of these species from the refinery gas is attractive considering the in-
creasing price and demand for these premium fuels.
Table 21 shows the potential demand for low-energy gas at the model
refinery. Based on displacing the purchased natural gas, the residual fuel
oil burned, and 98 percent of the hydrogen, propane, and butane from the re-
6 9
finery gas, the potential demand is about 3.51 x 10 MJ/day (3.33 x 10 Btu/day)
6 9
in the surtmer and 5.00 x 10 MJ/day (4.74 x 10 Btu/day) in the winter.
Comparison of the Model Refinery
With Other Refinerie's"
Size. The model refinery, with a crude oil capacity of about 3.97
x 10 liter/day (25,000 barrel/day), is close to the median size but less than
the average size U.S. refinery. Because it is close to the median size, it is
felt to be a good model with respect to size.
-------
TABLE 21. POTENTIAL DEMAND FOR LOW-ENERGY GAS AT MODEL REFINERY
Fuel
Purchased
Res idua 1
Hydrogen
Propane i
Butane in
TOTAL
Di sp laced
natural gas
fuel oi 1 burner
(a)
in refinery gas
(a)
n refinery gas
refinery gas
Summer
(May-Nov)
0.17
—
0. 10
0.31
0.26
0.84
IOV MJ/day
Winter
(Dec-Apr)
0.01
0.52
0. 10
0.31
0.26
1 .20
Heating Va
Annua 1
Average
0. 10
0.22
0. 10
0.31
0.26
0.99
1 ue Demand
Summer
(May-Nov)
0.67
—
0.41
1.21
1 .04
3.33
IOV Btu/day
Winter
(Dec-Apr)
0.02
2.06
0.41
1.21
1 .04
4.74
Annua I
Average
0.40
0.86
0.41
1.21
1 .04
3.92
CO
(a) Heating value demand based on 98 percent recovery of specie from refinery gas.
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82
Complexity. The Nelson complexity factor for the model refinery
is 5.92 and that for the U.S. refining industry as a whole is 8.88. Thus, the
model refinery is less complex that the average U.S. refinery. As a result of
this difference in complexity, one would expect (based on Figure 19) the unit
energy consumption for the model refinery to be about 34 percent less than that
of the average U.S. refinery.
Refinery Energy Consumption. A comparison of the energy
consumption of the model refinery with the U.S. average value is shown in
Table 22. The annual average consumption of refinery gas, natural gas, and
residual fuel oil by the model refinery corresponds to about 1.55 MJ/liter
crude oil (233,000 Btu/B crude oil). This is not a total energy consumption in
the sense of the Bureau of Mines data^O) since it does not include coke or
purchased electricity. The amount of coke consumed as fuel is difficult to
estimate because this includes the coke deposited on catalysts in process
units and then burned off, such as is done in catalytic crackers. The amount
of electricity used for process units at the model refinery must be included
to determine total energy use. In order to obtain an approximate comparison
with the Bureau of Mines data^20) one can add to the known energy consumption
of the model refinery the average values for coke and electricity for the state
(or group) in which the model refinery is located. This gives a total energy
consumption of about 2.20 MJ/liter crude oil (330,000 Btu/B crude oil).
For comparison with the model refinery, the U.S. average energy
consumption has to be adjusted for the differences in time (fuel cost) and
complexity. Using Nelson's correlation (Figure 19) to correct the U.S.
average value to the time and complexity of the model refinery cases gives
a total energy consumption of about 2.38 MJ/liter crude oil (358,000 Btu/B
crude oil). This agrees reasonably well with the value of 2.20 MJ/liter
cited above. Thus, the total energy consumption of the model refinery appears
to fall in line reasonably well with other industry data when the effects of
the pertinent variables are properly considered.
-------
TABLE 22. COMPARISON OF ENERGY CONSUMPTIONS FOR
MODEL REFINERY WITH U.S. AVERAGE VALUES
Energy Source
Net Energy
1973 U.S.
Refinery
Average
Consumpt
May-Nov
ion, J/l
Mode 1
itre ( I03 Btu/B
Refinery, 1975
Dec-Apr
crude)(a)
Annua 1
Average
Crude oi I 0.331 (0.05)
Distillate fuel oil 47.1 (7.09)
Residual fuel oil 404.7 (60.98 0.0 (0.0) . 548.2 (82.6) 228.3 (34.4)
Liquefied petroleum gas 59.5 (8.96)
Natural gas 1619.2 (243.99) 184.5 (27.8) 5.3 (0.8) 109.5 (16.5) £
Refinery gas 1568.7 (236.38 1206.5 (181.8) 1206.5 (181.8) 1206.5 (181.8)
Petroleum coke 585.1 (88.17)
Coal I 1.6 (1.74)
Purchased electricity 116.7 (17.58)
Purchased steam 59.6 (8.98) _ -- _
TOTAL 4472.5 (673.92)(b) . 1544.3 (232.7)(c)
Refinery Complexity 9.24 5.92
(a) MJ/Mter crude = (1.591) ( I03 Btu/B crude).
(b) Adjusting from 1973 to 1975 and from complexity 9.24 to 5.92 using Figure 3 yields
(6.73.92)(|£) = 358 x 10 Btu/B.
664
(c) Does not include coke or purchased electricity. Adding average values of these for
state (or group) of model refinery gives total of 330 10-* Btu/B.
-------
84
Types of Fuels Used. The model refinery is heavily de-
pendent upon the refinery gas as. an energy source. While this is a major
energy source in most refineries, there are many refineries in which it is
not nearly so dominant as was assumed for the model refinery. The data in
Table 18 indicate that, on a national basis, refinery gas provides about
35 percent of the total energy needs of refineries. This compares with
about 55 percent for the model refinery (including the estimated coke and
electricity).
For the model refinery, low-sulfur crude oil is processed, no
other hydrotreating operations are used, and, hence, much of the hydrogen
from the catalytic reformer can be used for fuel. In many other refineries,
the crude oil will contain more sulfur, more of the hydrogen will be re-
quired for hydrotreating operations, and, hence, less of the fuel needs will
be satisfied with refinery off gases. Polymerization is used in the model
refinery, but aUcylation is much more widely used in other refineries.
Therefore, most of the C^-C. compounds in the refinery gas of the model
refinery are assumed to be saturated hydrocarbons (paraffins).
Land Area. The model refinery occupies a total of about 32
acres, of which only about 3 acres are used for the processing equipment.
As can be seen from Figure 23, the area per unit throughput for the model
refinery is somewhat less than the general correlation would indicate. Thus,
the model refinery is probably somewhat more compact than many other refineries.
Access to Waterway. The model refinery is located on a navi-
gable waterway, and this is true for most other refineries as well. Re-
fineries, crude oil is received and refined products are shipped by tankers
and/or barges.
-------
85
Gasification Plant Design
Due to the low overall energy demand of the model refinery, an
air-blown fixed-bed, Wallman-Galusha gasification system was selected for
study. The gasification plant would supply about 5.00 x 10 MJ/day (4.74
x 10 Btu/day) in the winter and 3.51 x 10 MJ/day (3.33 x 109 Btu/day) in
the summer. Figure 24 shows the flow sheet for the Wellman-Galusha gasi-
fication plant. The mixture of refinery waste gas at 39.6 MJ/Nm (1062
Btu/scf) and low-energy gas from the Vfellman-Galusha at 6.26 MJ/Nm (168
Btu/scf) would have a heating value of about 9.84 MJ/Nm (264 Btu/scf) in
the winter and 8.72 MJ/Nm (234 Btu/scf) in the summer. A complete material
balance for this plant is given in Appendix B. Table 23 summarizes the
pertinent characteristics of the refinery model gasification plant.
TABLE 23. GASIFICATION PIANT DESIGN FOR REFINERY MODEL
Gasifier - Wellman-Galusha C3 units!
Desulfurization - Stretford
Maximum gas production rate - 5.0. x 1Q5 MJ/day
(.4.77 x I09 Btu/day)
Gas high heat value - 6.619 MJ/Nrrv5 (.168 Btu/scf 1
Coal consumption - 228 metric ton/day
(252 ton/day)
Efficiency - 76.7 percent
The coal selected for use in this system was an Eastern bituminous-
type coal with 6 percent moisture, 8 percent ash, and sulfur content of 3.9
percent. The free-swelling index of this coal is about 5, dictating the use
of an agitator-type fixed-bed gasifier. A complete analysis of the coal is
given in Table 24.
-------
Coal
preparation
Coal storage
©Cooling water
Scrubber/o. Copier
^.v ^ (7) ^.A ^
Stretford
absorber|j~
•Clean gas
© Makeup water
Cooling pond
20)
^•Sulfur
CO
Tar oil
separator
-Ammonia
stripping
JL©
.Phenol
removal
FIGURE 24. FLOW SIffiET FOR THE WELIJ1AN-GALUSHA GASIFICATION PLANT
(See Appendix B for complete material balance.)
-------
87
TABLE 24. REFINERY MODEL PLANT COAL ANALYSIS
Proximate
Moisture
Volati le Matter
Fixed Carbon
Ash
Ultimate Analysis
Hydrogen
Carbon
Nitrogen
Oxygen
Sulfur
Ash
HHV (Btu/lb)
Grindab i 1 ity
Free-Swelling Index
Wt. Percent
6. 1
32.7
48.3
8.4
4.8
68.0
2. 1
6.8
3.9
8.4
13690
60
5
Due to the snail size of the gasification plant it was not felt
practical to install coal preparation facilities, therefore, crushed-sized
coal would be purchased from the mine and stored at the gasification plant.
The gas plant would consist of three 10-ft diameter Wellman-Galusha units
capable of producing a total of 5.03 x 10 MJ/day (4.77 x 10 Btu/day) of
fuel gas with a heating value of 6.26 MJ/Nm (168 Btu/scf). The coal con-
sumed would be about 278 metric ton/day (252 ton/day) and the overall thermal
efficiency of the plant would be 76.7 percent. The raw gas from the gasifier
is processed directly through a scrubber for the removal of tars, oil, phenols,
and airmonia, and then through a cooler section where additional ammonia, tars,
and other condensible constituents are removed. The gas is then fed into a
Stretford-type desulfurization system which oxidizes sulfur compounds to
elemental sulfur in solution, eliminating the need for a Glaus plant. The
final gas product would contain 300 ppm of sulfur, or less, and would be
mixed with refinery gas and distributed to the various processes in the refinery.
-------
88
Figure 25 shews an overall plot plan of the refinery with
gasification and coal storage facilities and also the required cooling
pond. The processing facilities of the refinery itself occupy about
2
16,200 m (4 acres) of ground, and storage capacity requires an
2
additional 93,000 m (23 acres) of ground. The gasification plant
2
for the refinery is estimated to require about 4,050 m (1 acre)
2
of ground with an additional 4,050 m (1 acre) required for a cooling
pond. Coal-storage facilities for 1-month supply of coal would require
2
an additional 4,050 m (1 acre).
Potential Impact of Low-Energy Gas
The petroleum refining industry is a promising candidate for
retrofitting to the use of low-energy gas because the consumption of
energy, and particularly natural gas, by the industry is high and because
much of the industry is located in regions of high coal availability. The
industry includes a wide range of refinery sizes and energy requirements.
The model refinery used in this study is somewhat small when one considers
the economic justification of a coal-gasification facility to serve a
single refinery. It is important to look at some of the larger refineries
in the United States in order to appreciate the impact which the use of
low-energy gas from coal could have on the nation's refining industry.
Table 25 lists the 24 largest petroleum refineries in the
United States. For each of these refineries, the table gives the Nelson
complexity factor and estimates of the consumptions of energy in the form
of natural gas and oil. The latter were obtained by
(1) Determining the unit energy consumption (all
sources) from the complexity using Nelson's
correlation (Figure 19)
(2) Multiplying the above by the fraction of the
total energy supplied by natural gas and oil,
using the Bureau of Mines data for the state
or state group in which the refinery is located
(Table 18).
-------
Coal storage
I acre
Gasifica-
tion &
Cleaning
1.0 acre
Cooling pond
I .acre
Rivet
bank
Processing, 4 acres
1
1
1
I
Gasoline
Production
I
i Process
! Support
~| r ~~>
i
1 i Light gas MCatalytic
1 [Recovery'
1
I
j
'Crocking
~l
l
1
_J
j Crude
Oil
( Distillation
l
1
I
i
. _ i
CO
Refinery storage, 23 acres
FIGURE 25. REFINERY PLOT PLAN
-------
TABLE 25. CAPACITIES AND ESTIMATED ENERGY CONSUMPTION^1 7 )
OF LARGEST REFINERIES IN THE UNITED STATES
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(ID
(12)
(13)
(14)
(IS)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
State
Louisiana
Texas
Texas
Indiana
Texas
Texas
Texas
Texas
Illinois
Louisiana
New Jersey
Louisiana
Mississippi
California
Texas
Illinois
California
California
Pennsylvania
Louisiana
Illinois
Pennsylvania
Ohio
Pennsylvania
Company
Exxon
Texaco
Exxon
Amoco
Amoco
Mobil
Gulf
Shell
Shell
Cities
Exxon
Shell
Std (Calif)
Std (Calif)
Atlantic-
Richfield
Marathon
Std (Calif)
Atlaatic-
Richfield
Atlantic-
Rich field
Gulf
Mobil
Gulf
Sohio
Sun
Coal
City Availability
Baton Rouge
Port Arthur
Bay town
Whiting
Texas City
Beaurcont
Port Arthur
Deer Park
Wood River
Lake Charles
Linden
Norco
Pascagoula
£1 Segundo
Hous ton
Robinson
Richmond
Carson
Philadelphia
Belle Chaase
Jollet
Philadelphia
Lima
Marcus Hook
High
High
High
High
High
High
High
High
High
High
High
High
High
High
High
Crude Oil
Capacity, '•1/-'1
103 B/CD
445
406
400
360
333
325
312
294
283
268
265
240
240
230
213
195
190
185
185
180.4
175
174.3
168
165
Nelson
Complexity
9.
8.
12.
9.
10.
9.
10.
9.
10.
9.
8.
7.
6.
7.
10.
5.
12.
8.
5.
8.
8.
7.
7.
13.
45
69
99
26
23
18
24
77
15
52
15
27
99
94
12
84
45
28
75
17
62
83
50
73
Unit Natural Gas and
Oil Consumption
MJ/liter crude 10 Bt"/B crude
396
500
749
366
590
528
590
563
318
399
325
304
333
320
584
183
504
334
231
342
270
315
229
554
249
314
471
230
371
332
371
354
200
251
204
191
209
201
367
115
317
210
145
215
170
198
144
348
Total Natural Gas and
Oil Consumption
10 MJ/day 10 Btu/day
28.1
32.1
47.6
21.0
31.4
27.3
29.3
26.3
14.4
17.0
13.7
11.6
12.7
11.6
19.7
5.6
15.2
9.9
6.8
9.9
7.6
8.9
6.1
14.4
111
127
188
83
124
108
116
104
57
67
54
46
50
46
78
22
60
39
27
27
30
35
24
57
O
-------
91
"Cable 25 also indicates which refineries are located in states considered as
having a high coal availability (production or reserves).
Among the refineries listed in Table 25 are
• Seven refineries having estimated natural gas
and oil consumption greater than 83 x 106 MJ/day
(79 x 109 Btu/day) and located in states having
high coal availability.
• Nine refineries having estimated natural gas and
oil consumption of 21-83 x 106 MJ/day (20-79 x
109 Btu/day) and located in states having high
coal availability
• Eight refineries located in states not having
high coal availability.
With regard to coal availability, it should be noted that there may be
cases in which transporation of coal from a nearby state is feasible.
Cft the other hand, there may be cases in which coal reserves in a given
state are not feasible for use at a site within the same state but are
fairly far away.
For these large refineries, the estimated natural gas and oil
consumptions are high enough to justify on-site coal gasification facili-
ties. It appears that there are quite a number of refineries in the United
States for which the energy needs and locations are such that retrofitting
them to use low-energy gas from coal could make considerable sense. The
impact of this option upon the petroleum refining industry could be quite
significant.
Burners and Furnaces in
a Refinery Plant
This section describes.typical furnaces and burners used in a
refinery plant similar to that described in this study and the possibilities
of converting these processes to low-energy gas.
-------
92
Burners
In the case of the refinery discussed in this study, because of
the relatively small fuel needs, the use of a Wallman-Galusha air-steam gas
producer is proposed. This gas would be mixed with refinery gas from which
marketable components such as hydrocarbon, propane, and butane had been
stripped leaving CH,, C2H6' an<^ N~ as components in a gas of 41.8 MJ/Nm
(1062 Btu/scf) high heating value (HHV). The HHV of the fuel mixture is
10.4 MJ/Nm (264 Btu/scf) during the summer (when the mixtures contain 10.8
percent by volume refinery gas). Ihe HHV during the winter is 9.25 MJ/Nm
(235 Btu/scf) (when the fuel gas contains 7.5 percent by volume of refinery
gas). The summer and winter Wobbe numbers would be 291 and 258. Ihe flash-
back velocity gradient at stoichiometric and the heat release rate at stoi-
chiometric are very slightly below the values given in Table A-2 for Wellman-
Galusha gas, and somewhat above those for natural gas.
For the fuel mixture the flash-back velocity gradient times the
higher heating value, a probably important criterion for nozzle-mix type
3 44
burners, varies from 591 to 512 MJ/Nm -sec (15 x 10 to 13 x 10 Btu/scf-sec).
These values are far below the value for natural gas, but still an improvement
over Wellman-Galusha gas.
For the typical refinery considered in this study, Table 26 lists
characteristics of the furnaces used for process heating and steam raising.
Figure 26 shows an inspirating burner used on refinery furnaces. Figure 27
shows the burner used in refinery boilers.
Cn changeover to the mixed fuel from natural gas, it is probable
that all the furnace burners would have to be changed to gas burners of the
general type shown in Figure 28, when sufficient draft is available. When
sufficient draft was not available, exhaust fans could be added, or nozzle-
mix burners with blowers would be used.
Because of the low-heating values of the gas, the burners in
boilers would require changing. (See discussion of secondary steel plant
boilers.) One boiler manufacturer would recommend a vortex burner for the
lew heating value gases. They would also recommend replacing the multiple
-------
TABLE 26. FURNACES IN A SMALL REFINERY
No.
1
2
3
4
5
6
7
8
9
Type
Pref lash reboi ler
Crude heater
Vacuum tower heater
Light oi 1 heater
Tar stripper heater
Unifier heater
Platforming heater
Raw oi 1 heater
Boi lers
Des i gn
I03 MJ/hr
8.2
20.3
14.2
29.7
38.8
10.5
21. 1
5.9
47-65
Capacity,
(I06 Btu/hr)
(7.8)
(19.5)
(13.5)
(28.2)
(36.8)
(10.0)
(20.0)
(5.6)
(45-62)
Temperature, F (
Stack
516
504
574
493
643
609
—
527
—
(960)
(940)
(1065)
(920)
(1 190)
(1128)
—
(980)
F)
Furnace
668
757
689
654
663
—
649
677
—
(1235)
(1395)
(1270)
(1210)
(1225)
(1200)
(1250)
—
02 Efficiency,
3ercent Percent Fuels
4.5
2.0
4.5
3.5
4.8
2.6
4.8
9.2
-
69.6
71.5
66.8
71.6
63.0
64.0
—
54.0
—
Gas,
Gas,
Gas,
Gas,
Gas,
Gas
Gas
Gas
Gas,
No.
No.
oi 1
No.
No.
No.
6 oi 1
2 oi 1
6 oi 1
6 oil
6 oi 1
CO
-------
94
Spider
Secondary
Air
Primary
Air
FIGURE 26. ZUS1K VPM VEETICAL GAS BURNER
FOR HIGH HYDROGEN GAS
Spider with radial arms distributes
primary air-fuel mixture evenly over
secondary air stream. No adjustment
needed in shifting from start-up gas
to high hydrogen fuel.
-------
95
Oil-
Steanf*
Air
Air
Swirl
'Vanes
A
X
X
X
\
N
X
\
FIGUEE 27. REFESEPY BOILER BURNER
-------
96
Tip Cone
FIGURE 28. ZINK VYR VERTICAL GAS BURNER
FOR PROCESS HEATERS
Burner designed to use raw gas at
appreciable pressure, and natural draft
to supply air. Has a high turndown
ratio and can use a wide variety of
gases. Gas-tip cone is perforated with
slots to permit passage of air into re-
circulation zone.
-------
97
burners with a single large capacity burner. This would cut down cost of
replacing air ducting. However, because of the high cost of field work, it
is quite possible that the replacement of the entire boiler-burner systems
with new package units would be the most economical approach.
To summarize, it is probable that all the burners in a refinery
might have to be replaced when a change is made from the natural gas.
Further, it may be most economical to replace the boilers with new
package boilers rather than attempt to make field changes on their
burners.
-------
98
V. CONSIDERATIONS IN DISTRIBUTING LOW- AND
INTERMEDIATE-ENERGY GAS IN INDUSTRY
Volume and Pressure
Considerations
Industrial gas distribution systems are often intricate and
extensive. The model steel plant in this study would have approximately
9144 m (30,000 ft) of gas piping with diameters ranging from 38 to 254 mm
(1-1/2 to 10 inches). The refinery model would have approximately 762 m
(2500 ft) with sizes ranging from 25 to 152 mm (1 to 6 inches) in diameter.
These piping systems would be carbon steel with some brass valves and
fittings. Natural gas distribution systems are commonly rated at about
1030 kPa gage (150 psig). In most plants in the two industries considered
in this study, however, natural gas would be distributed at much lower
pressures of about 276 to 345 kPa gage (40 to 50 psig).
A schematic of an industrial piping system is shown in Figure 29.
The gas is supplied to the system at some supply pressure, Ps, and exits
the system at the burner at pressure, ?„. The difference between Ps and P..,
ij hi
is the pressure drop through the system which for turbulent flow is propor-
tional to the gas density (p) times the square of the velocity (V). Prior
to being admitted to the burner, the exit pressure, ?„, is further reduced
£1
by an orifice to a pressure normally less than 6.9 kPa gage (1 psig).
Because natural gas is often distributed at much less than the
design pressure of the distribution system, it is useful to look at the
possibility of using the same system for a lower energy gas. The governing
equation relating the supply and exit pressures for two gases (1 and 2)
assuming the same energy supply rate for both cases is
2 21 "> ">
p - p = -i- ip * - p 2)
s2 E2 w 2 ( si El ;
where W = Wobbe number = HHV /p" at standard conditions. An extreme,
simplified case would be where ?„, = ?„„ = 0. The equation then reduces to
-------
Supply Pressure P
Exit Pressure P,
Burner Pressure < 1 psig
Gas Distribution System
FIGURE 29. INDUSTRIAL GAS DISTRIBUTION SYSTEM
-------
100
Figure 30 shows this relationship for 3 cases: Wellman-Galusha gas,
Wellraan-Galusha gas mixed with refinery gas for the refinery model, and
Koppers-lbtzek gas for the steel plant model.
As can be seen in Figure 29, for a natural gas supply pressure
of 207 kPa gage (30 psig) , a pressure of 1070 kPa gage (155 psig) would be
necessary for the Koppers-Totzek gas in the steel mill model and over 1380
kPa gage (200 psig) would be necessary for the Wellman-Galusha gas and
refinery gas. Both the steel mill model plant and the refinery model plant
were assumed to have a natural gas supply pressure of from 276 to 345 kPa
gage (40 to 50 psig) . It would be concluded, therefore, that using the
existing distribution system would require pressures that would exceed the
design pressure of the existing system. It would be assumed that at least
part or all of the gas distribution system would have to be replaced. The
required pipe size would depend on the pressure at which the gas is supplied.
If the gas were supplied at the same pressure as the natural gas and the
total pressure drop through the system were kept constant, then the required
pipe areas for two gases are related by
For the three cases shown in Figure 29, the area ratios would be as shown
in Table 27.
TABLE 27. REQUIRED PIPE SIZE FOR GAS DISTRIBUTION*
Natural Gas
Wellman-Galusha Gas
Wellman-Galusha Refinery
Gas Mixture
Koppers-Totzek Steel Mi 1 1 Gas
HHV
Btu/scf
973
168
235
286
W
1244
183
256
338
Pipe
Area
Ratio
1
6.8
4.8
3.7
Pipe
Diameter
Ratio
1
2.61
2.19
1 .92
* Assuming the same supply pressure and heat delivery rate.
-------
101
200
ca
J2
CO
"O
8
1-1
g-
150
oo
•H
05
-------
102
The size of pipe and its cost would have to be weighed against the available
space and costs of compression. Compression could require a significant
amount of energy depending on the final gas pressure. The itiost efficient
way to compress the gas is with interceding in an isothermal process.
Most large compression systems use interceding. The other extreme is
adiabatic compression where no heat is transferred from the gas as it is
compressed. Figures 31 and 32 show the power requirements for both adiabatic
and isothermal compression for the steel and refinery plant models, respec-
tively. Compression of fuel gas to 6.9 x 10 Pa (100 psig) (P9/Pi =7.8)
6 9
in both model industry cases would require 0.40 x 10 MJ/day (0.38 x 10
Btu/day) for the steel mill model (which is 1.8 percent of the total energy
in the clean gas) and 0.15 x 106 MJ/day (0.14 x 109 Btu/day) for the
refinery model (which is 2.9 percent of the total energy in the clean gas).
Corrosion Considerations on Substituting Low-
or Intermediate-Energy Gas for Natural Gas
Potential corrosion problems in gas distribution systems and
process equipment resulting from the substitution of low- or intermediate-
energy gas from coal for natural gas are also an important consideration.
Corrosive constituents in the produced fuel gas can increase degradation of
carbon steel, brass, and other materials found throughout fuel systems.
Specific interest is given here to retrofitting a steel plant to fuel gas;
however, the discussion has general applicability to a variety of industrial
processes.
While the composition of gases produced by coal gasifiers is some-
what unique, a broad experience exists for handling of corrosive gases from
other sources, e.g., coke oven gas, sour gases from petroleum production,
gases generated in chemical processes, and refinery industries. Experience
with distribution of town gas, used extensively in Europe, is directly
applicable. The approach taken in this study was to identify the corrosive
species in fuel gas and, where possible, to establish acceptable limits for
distribution. Also, corrosion mitigation and monitoring procedures were
reviewed.
-------
103
1.0
10 MJ/day
= (LO9 Ktu/day)
0.5
2468
Pressure Ratio P2/P1 ^For Pl =
10
FIGURE 31. COMPRESSION POWER FOR STEEL MILL MODEL
GAS SUPPLY
-------
104
0.3
0.2
106 MJ/day
(109 Btu/day)
0.1
Pressure Ratio P2/P1 ^For Pl
10
FIGURE 32. COMPRESSION POWER FOR REFINERY
MODEL GAS SUPPLY
-------
105
Corrosive Species in Low- and
Intermediate-Energy Gas from Coal
A variety of materials is used in the distribution and usage of
fuel gas. Carbon steel for pipes and fittings is the most prevalent
material with lesser amounts of brass found in valves and high-alloy steels
and nickel alloys in process equipment. Constituents in fuel gas in the
presence of water support corrosion of these materials. Of primary concern
are conditions resulting in general corrosion, but those which promote
stress-corrosion cracking are also considered.
Constituents of fuel gas can be divided into three groups:
corrosive, inhibitive, and inert. Carbon dioxide (CC^)/ hydrogen sulfide
(H2S) and other sulfur-containing species, ammonia (NH3), and hydrogen
cyanide (HCN) promote corrosion. Carbon monoxide (CO) inhibits corrosion;
whereas hydrogen (H-), methane (CHJ , and nitrogen (N~) do not significantly
affect corrosion. The acid gases, carbon dioxide and hydrogen sulfide,
readily corrode mild steel. Copper alloys are corroded by sulfur compounds
and are susceptible to corrosion or stress-corrosion cracking in the presence of
ammonia. Nickel and nickel alloys are corroded by sulfur compounds.
Although the effect of a given species on corrosion is generally known, the
corrosivity of a mixture of gases is not readily predictable because of
complex interaction and temperature effects.
Of all the constituents in fuel gas, hydrogen sulfide is the most
deleterious because even small amounts can greatly accelerate corrosion. An
early study of the corrosion of steels by natural gas containing traces of
H-S recommends that H9S content be controlled to less than 2.28 mg/m (0.1
(26)
grain per 100 cubic feet of gas) . Corrosion is not severe in the absence
of water. Corrosion of steel in refinery condensing systems was found to
(27)
increase with sulfide concentration . Inhibitor treatment and pH
(28)
control were necessary to control corrosion of steel in storage of high-
pressure sour gas (13 percent H-S, 5 percent C02)• Monel and Inconel alloys
were substituted for austenitic stainless steel in special equipment operating
at ambient temperatures. Many other instances are recorded in which severe
corrosion problems arose from handling of moist hydrogen sulfide containing
gases.
-------
106
In addition to general corrosion, stress-corrosion cracking (SCC)
is promoted by H~S. Susceptibility to SCC for a range of ferrous materials
increases as hardness increases. In sour gas service, most failures of
tubular components occurred with alloys, the hardness of which exceeded
(29)
R 22 . Field failure data and laboratory studies form the basis for
NACE's publication IF 166, "Sulfide Cracking Resistant Metallic Materials
for Valves for Production and Pipeline Service" which recommends R 22 as
c
the maximum hardness level for this service. The recomnendation has seen
much broader application than just for valves.
Based upon laboratory data, 0.001 atmosphere was chosen as the
critical partial pressure of H2S at which SCC will occur . Under
more severe conditions, higher temperature and pressure, the value is lower
(32)
still . The point to be made is that even small amounts of H2S can
promote SCC.
Carbon dioxide dissolves in water to form carbonic acid, a
corrosive agent to mild steel. Corrosion rates in excess of 100 mils per
year have been observed for partial pressures of approximately 690 kPa
(100 psia). Obrect identified CCU as a major corrodent in steam-
condensate systems. It is also recognized as a primary contributor to
corrosion in handling of sour gases. A rule-of-thumb for natural gas
transmission is that no special corrosion mitigation procedures are required
for partial pressures of CO- below 35 kPa (5 psia). This level is not
absolute as evidenced by a steady lowering of the acceptable limit over the
years. Presence of both H2S and C02 lowers the tolerable limits of each
gas.
Mixtures of carbon dioxide-carbon monoxide-water were shown to
promote SCC of a high-strength steel. Steel specimens failed in 65 percent
CO - 35 percent C0~ mixtures at total pressure as low as 2 atmospheres at
(34) z
20 C . This system has also resulted in SCC of mild steed in town gas
composition . Recent work at Battelle has shown SCC of mild steel to
occur in C02-CO-CH4-H20 at C02 and CO partial pressures of 6.9 kPa (1 psia)
and less. All three constituents (C02/ CO, and H2O) must be present to
support SCC.
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107
Ammonia accelerates the corrosion of mild steel, but is presence
in fuel gas is of greater consequence because of its deleterious effect on
copper and copper alloys. Stress-corrosion cracking of many of the copper
alloys is readily promoted by NEL, even at trace levels. At high concentra-
tions, general corrosion of copper alloys is a serious problem.
Copper alloys are also corroded by sulfur-bearing canpounds.
Nickel and nickel alloys are susceptible to sulfidation in aqueous phase
and at high temperatures. The latter is of concern when burning sulfur-
containing fuel.
Other constituents of fuel gas can participate in corrosion
processes, but the primary contributions to corrosivity of fuel gas are
made by species discussed above: hydrogen sulfide, carbon dioxide, and
ammonia.
In addition to corrosive gases, fuel gas contains condensable
tars and ash, which can cause plugging and blockage if not controlled. A
beneficial effect of condensable organics is that they can coat the metal
surfaces and retard corrosion.
Mitigation and Monitoring
of Corrosion by Fuel Gas
In the above section, it was shown that raw fuel gas contains
several species which promote corrosion of materials commonly found in gas
distribution systems and processes equipment burning fuel gas. Here,
procedures to mitigate and monitor corrosion by fuel gas are discussed.
"Control of Internal Corrosion in Steel Pipelines and Piping Systems",
NACE Standard KP-01-75, presents recommended practice for corrosion control
of pipeline systems, including gas transmission and gas distribution systems.
Relevant portions of the recommended practice are presented below with
experience from comparable service conditions, namely, transport of coke
oven and town gas, transmission of natural gas, and handling of sour gases
during production.
Corrosion control can be achieved in this service by several
procedures: (1) elimination of corrosive species in the fuel gas, (2) use
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108
of corrosion inhibitors, (3) application of coatings, and (4) substitution
of more corrosion-resistant material. Choice of procedure is made on the
basis of economics and ease of application to a specific problem area.
In view of the number of corrosive species present in fuel gas
v
and the variety of materials in contact with the gas, removal of water
provides the most general means to control corrosion. In the absence of
water, corrosion throughout the distribution system would be negligible.
(Corrosion in town gas systems in Europe was controlled by removal of water
/o/r\
and desulfurization .) Water can be removed by water separators, by
refrigeration, or by dehydrators. Various types of dehydrators are available
including glycol and desiccant. Using these means, the dewpoint of the gas
is maintained below service temperatures to prevent condensation in the
system. Commercial units are available to dehydrate large volumes of gas.
It may be advantageous to remove other corrosive constituents in
addition to water. Conmercial processes are available to remove acid gases,
annvDnia, and other corrosive species. Removal of sulfur prior to use of
fuel gas decreases corrosion throughout the system (in addition to elimina-
ting the need for flue-gas clean-up units).
Addition of corrosion inhibitor can be used in conjunction with
other corrosion control procedures. Several types of inhibitors are avail-
able for either continuous or batch application. Filming inhibitors are
effective for gas distribution systems. Application of protective coatings
is not seen to be necessary for the bulk of the piping system, but it can
be beneficial in specific areas.
In process equipment when a specific corrosion problem is identi-
fied, selection of a more corrosion resistant material may provide a ready
solution. For example, nickel and high-nickel alloys are susceptible to
sulfidation and are not recommended for use with high temperature sulfur
bearing gases. Alloys resistant to sulfidation should be used.
The need for corrosion mitigation and the evaluation of its
effectiveness are determined by analysis of corrosion monitoring data. The
level of sophistication required is determined in part by the consequences
of a failure. A leak in a fuel gas system is less tolerable than a leak in
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109
a natural gas system, because, in the addition to fire and explosion
hazards, noxious carbon monoxide would escape. Prior to conversion to
fuel gas, the entire system should be inspected and a list of materials
throughout the system compiled. Any questionable components, because of
present condition or known corrosion susceptibility, should be replaced.
A sample of each type of component in the system should be reinspected
periodically for corrosion damage after conversion to fuel gas. These
inspections can be supplemented by data from corrosion coupons and probes
installed throughout the system as necessary. Analysis of gas, residue,
and deposits found in the system also provides valuable information.
Experience gained following conversion to fuel gas will dictate the
frequency and amount of inspection required.
Handling of fuel gas presents similar corrosion problems to
those of handling coke oven gas, i.e., a variety of acid gases and other
corrosive components are produced in a moist gas. Corrosion control
practiced varies with the severity of corrosion problems experienced at
different plants. Except for special instances, distribution systems of
carbon steel have provided good service. For mitigation, where corrosion
was excessive, the coke oven gas was either dried or partially dried and
desulfurized. low corrosion rates of carbon steel have been observed in
some moist coke oven gas service with no applied conversion control.
These low rates were attributed to condensable hydrocarbons coating the
steel surface. Austenitic stainless steel has been used successfully to
carry moist coke oven gas. However, it must be recognized that austenitic
stainless steel, particularly in the sensitized condition, is susceptible
to SCC in presence of polythionic acid , chloride, or fluoride
Polythionic acid and chloride can form from, or are found in, the
environment, while fluoride can result from use of some welding fluxes.
Internal corrosion of natural gas transmission lines is
controlled primarily by dehydration of the gas and inhibitor treatment.
Inhibitor can be injected continually or by batch treatment in a pigging
operation. Monitoring of internal corrosion in pipelines transporting
(39)
natural gas containing CO- and Hos was recently reviewed . Corrosion
data obtained on an operating system are presented for corrosion coupons,
hydrogen probes, electrical resistance probes, and corrosion spools.
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110
Corrosion problems related to oil and gas production (drilling
operation) in the presence of H-S and CO- are not amenable to mitigation
by dehydration or removal of corrosive species. Corrosion is controlled
under these conditions by inhibition, pH control, and selection of
corrosion resistant materials. Much information is available in the
literature describing corrosion and sulfide stress corrosion cracking
behavior of a variety of materials in sour gas service. These data can
be applied to material selection and corrosion mitigation for fuel gas
service.
Conclusions
Conversion to fuel gas from natural gas will require additional
corrosion-control procedures. Corrosive constituents are present in fuel
gas but are not found in appreciable amounts in natural gas, e.g., acid
gases and ammonia, corrode common materials found in gas distribution
systems. While fuel gas compositions are somewhat unique in relative
amounts and mix of corrosives, experience in corrosion control in similar
services is directly applicable. One of the most certain and perhaps most
economical means of corrosion mitigation is to remove water from the gas
prior to injection in the distribution system. Individual corrosives can
also be eliminated; desulfurization is common practice. These techniques
are successfully applied to the transport of coke oven gas. In specific
process units, selection of more corrosion resistant materials may be
necessary. An example of the latter is the elimination of high nickel
alloys from units for direct burning of coke oven gas because of severe
sulfidation.
It is recommended that a thorough corrosion survey of systems for
materials compatibility as affected by gas conversion be made prior to any
conversion, and be repeated periodically after conversion. In this way
corrosion problems can be identified and suitable corrosion mitigation
procedures selected.
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Ill
VI. ENVIRONMENTAL CONSIDERATIONS IN RETROFIT
Emissions from the Gasification Processes
Model Steel Plant
Table 28 summarizes the major emissions from the gasification
process for the model steel plant. The major points of emissions in this
process are the coal storage, coal pulverizing and preparation facilities,
the oxygen, plant, the filter which separates water from slag and clarifier
sludge, cooling tower, and the Glaus sulfur recovery process.
Snissions from the coal storage pile will involve fugitive dust
picked up by the wind and leachate resulting from rain water filtering
through the coal pile. The coal pile should be packed tight to limit dust
loss and prevent air from entering the pile causing oxidation and spon-
taneous combustion. Conveyors should be hooded with the hood exhaust
processed through a baghouse or electrostatic precipitator. Leachate
from the coal pile would resemble acid mine drainage in many respects—
containing acids, organics, and soluble metals. This water should be col-
lected and ponded for biological reduction of pollutants before being dis-
charged to a water source.
Fugitive dust problems can be minimized by coating the coal pile
with a plastic material and drawing from it only during periods of emergency.
The coal normally would then be taken directly from unit train or barge
by covered conveyors. The logistics of such an operation, however, would
have to be carefully planned to ensure proper operation of such a system.
However, care must be taken to prevent breaks in the coating which would
create a chimney effect causing aspiration of air into the pile resulting
in oxidation and combustion.
Emissions from the coal pulverizing preparation step consists
of pollutants in the gas used in drying the coal, plus possibly some volatile
constituents from the coal. A portion of the final product gas is combusted
to heat air which is then supplied to the pulverizer for drying purposes.
This stream is then vented from the pulverizer. The stream consists pri-
marily of carbon dioxide, nitrogen, some water vapor, and oxygen. The stream
would also contain particulates and possibly some small amounts of sulfur
dioxide oxidized from the coal.
The vent stream from the coal preparation step should be pro-
cessed through a baghouse or electrostatic precipitator or some other
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112
TABLE 28. DISCHARGES FROM STEEL MILL
MODEL GASIFICATION PLANT
Source
Coal storage —
fugitive dust and
leachate from rain
Coal pulverizing
Oxygen plant
Fi Iter
Cool i ng tower
p 1 ume
Claus
Glaus tai 1 gas
Area of
Impact
Ai r,
Water
Air
(or
Air
Water,
Sol id Waste
Air
Sol id Waste
(by-product)
Air
Flow Rate
Dependent on
wind and rain
conditions
492, 160 Ib/hr
1 12, 144 scfm)
72,704 scfm
21,616 Ib/hr
17,500 Ib/hr
1,704 Ib/hr
675 scfm
Discharge
Ma i n
Composition
Coal dust
Acids
Organ ics
Soluble Metals
C09
M
H20
Oo
CH4
S02
Particulates
N2
C02,H20,02
C
Ash
H20
H20
Dissolved and
suspended sol i ds
S
H?S
C02
Percent(a)
— _
2 (v)
68 (v)
13 (v)
17 (v)
Trace
Trace
Trace
99 (v)'
Trace
17.8 (w)
72.2 (w)
10.0 (w)
100 (v)
—
100 (w)
2.7 (v)
97.3 (v)
(a) (v) volume percent
(w) weight percent.
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113
efficient particulate removal device for controlling particulate emissions.
Emissions of other constituents would include some sulfur compounds such as
SCU, though these emissions should be relatively small. Also, in any coal
crushing operation, considerable noise is generated and the pulverizing
operation should be housed in a building to minimize this effect.
To limit dust loss, the entire coal pulverization facility
should be located in a building with positive ventilation control. The
exhaust from the building would then be processed through a particulate
control device.
The discharge from the oxygen plant would involve primarily
nitrogen which is not considered a harmful emission and would require no
control.
Wet slag from the gasifier along with clarifier sludge from the
water scrubbing operation is processed through a filtration step for
liquid/solids separation. The slag from the gasifier contains a variety
of constituents typical of coal ash but due to the high temperature in
the gasifier is relatively inert and not expected to be a pollution
problem; however, actual operating data will be necessary to verify this.
Sludge from the clarifier, however, would contain dissolved gases such as
H-S which could present an odor problem. Lime could be added to the
clarifier circuit to fix the H~S in a nonvolatile form, or with highly
alkaline coals, the alkalinity in the slag from the gasifier may be
sufficient to alleviate the problem^ ' 6 \
A significant discharge to the atmosphere would be the cooling
tower plume. The cooling tower water would contain dissolved constitutents
from the scrubber circuit that overflows from the clarifier. These con-
stituents would be present to some extent in the drift loss or plume from
the cooling tower. Although many of these compounds may be present only
in infinitesimal amounts when combined with the water in the plume, they
may create a corrosion or health menace in the area around the plant. A
solution to this problem is to use dry cooling towers or a cooling pond
either of which would involve much greater cooling area.
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114
About 772 kg/hr (1704 Ib/hr) of elemental sulfur would be pro-
duced from the Glaus plant in this process. This sulfur would be of
marketable quality and could be stored and shipped. The Glaus process,
however, only removes about 95 percent of the sulfur compounds of the
inlet stream. The resulting tail gas or vent stream from the Glaus process,
therefore, would contain hydrogen sulfide and CO-- With the system shown
and if meeting regulations with the least direct cost were an objective, then
this tail gas could be blended with the product gas from the gasifier and
combusted without exceeding even the strictest state limitations on sulfur
dioxide emissions.
Model Refinery Plant
The major emissions from the refinery model gasification plant
are shown in Table 29. Sources of emissions are coal storage, the gasifier
itself, scrubber effluent, and emissions from the Stretford desulfurization
process.
Effluents from coal storage would involve similar considerations
to those discussed for the steel plant model. Because crushed, sized coal
would be purchased from the mine, however, dust loss for the refinery would
be less than for the steel plant due to the lower percentage of fines or
small particles. Also, air and noise pollution from drying and crushing
operations in the coal preparation step would not be present. If these
operations were installed, similar consideration to those for the steel plant
model would have to be employed.
About 801 kg/hr (1768 Ib/hr) of dry ash would be emitted from
the gasifier in the form of bottom ash. The Wellman-Galusha is a "dry ash"
or nonslagging process and the bottom ash may have characteristics similar to
that from a stoker or pulverized fired boiler. Common practice in boiler
installations is to truck or sluice the ash to pond or landfill.
The effluent from the scrubber system contains significant amounts
of tars, ammonia, and phenols, which would have to be treated prior to
disposal. In some cases these products may be able to be used in the
industrial plants or marketed. For instance, in the case of the refinery,
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115
TABLE 29. DISCHARGES FROM REFINERY MODEL
GASIFICATION PLANT
Source
Coal storage —
fugitive dust and
leachate from rain
Scrubber effluents
Tar separation
NH, stripping
Phenols
Cyanide
Hydrocarbons
Pond
Evaporation
Discharge
Area of Main
Impact Flow Rate Composition
Solid waste Depends on wind Coal dust
and rain condi- Acids
tions Organ ics
Sol uble meta Is
Water
1 153 Ib/hr Tar
1095 Ib/hr NH3
H20
120 Ib/hr Phenols
HCN
CxHy
Air
Trace Ammon i a
Phenol s
W\/r1 r*<"»^a r*h/~mc
Percent
— —
91
9
20
80
• 100
—
—
Trace
it
Stretford
Sol id waste
(by-product)
777 Ib/hr
HCN
Sulfur
Sod i urn
Th iosuI fate
& sodium
Th iocyanate
100
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116
the recovered tars could possibly be used to supplement residual oil in
making of asphalt. However, this would have to be evaluated as to the
effect of these tars on the asphalt production process of the plant. Tars
would be recovered by decantation and would result in a composition of
about 91 percent tar, and 9 percent water. Ammonia and other compounds,
such as trace amounts of hydrogen sulfide which may be dissolved in the
scrubber water, could be steam stripped and recovered for sale. Phenols
could also be recovered for use by use of the Phenolsolvan process, or
they could be biologically reduced to sludge and separated from the water
for disposal. There is no inmediate use for phenols in the refinery so
biological reduction would probably be employed. The economics of this
versus recovery of the phenols in a potentially more expensive process
would have to be evaluated further.
In addition to tars, ammonia, and phenols, the scrubbing water
could also contain small amounts of hydrogen cyanide (HCN) and hydrogen
fluoride (HF). Hydrogen cyanide in the water stream can be very detrimental
to a biological control process, and it may have to be treated separately.
Otherwise, it would be expected to follow hydrogen sulfide through the
process. Hydrogen fluoride would react with the ash in the coal and be
disposed of in a neutralized form with the ash.
Because many of the constituents in the scrubbing water are
highly volatile and odorous, care must be taken throughout the water
scrubbing and treatment system to minimize leaks and evaporation. Reaction
vessels should be covered and vented either back to the scrubbers or to
some other control process. Also, if the volatile and odorous constituents
are not removed from the water before being discharged to the settling
pond, odors could result from pond evaporation.
The recovery or disposal of tars, ammonia, phenols, and other
gas liquor constituents will involve some hydrocarbon emissions. These
emissions result from leaks around seals in pumps and storage facilities.
Refineries, in general, are accustomed to dealing with the problems
associated with handling these compounds, however, and should be able to
handle the additional load supplied by a coal gasifier.
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117
The Stretford desulfurization process for this particular
design would produce 349 kg/hr (770 Ib/hr) of elemental sulfur which
could be stored and sold. The Stretford purge stream will contain
sodium salts of anthraquinone disulfonate, metavanadate, citrate,
thiosulfate, and thiocyanate. This stream may require special treatment
or disposal methods (40).
Emissions from Combustion Processes
Qnissions from combustion processes result generally from four
types of pollutants; emissions of sulfur dioxide, oxides of nitrogen,
particulates, and trace constituents, such as polycyclic organic matter
or heavy metals.
Emissions of Sulfur Dioxide
In the gasification process many sulfur compounds in the coal are
converted to sulfur compounds in the gas. The major sulfur-bearing consti-
tuent is hydrogen sulfide with minor amounts of carbonyl-sulfide (COS),
carbon disulfide (CS~), and mercaptans. If these compounds are not removed
from the fuel gas prior to combustion, they are oxidized quantitatively
to sulfur dioxide in the products of combustion. These expected emissions,
if all the sulfur in the coal is converted to sulfur in the gas, are shown
in Figure"33 as a function of coal sulfur and heat content.
Standards have not yet been developed specifically for dealing
with sulfur emissions from coal gasification applications as described in
this study. There is currently debate on whether sources fired with gas
from coal should be treated as solid fuel fired or gas fired sources and as
to whether emissions should be based on the heating value of the gas or solid
fuel.
If emissions are based on the heat content of the coal, then they
are a function of coal sulfur and heat content as shown in Figure 33. As can
be seen from Figure 33, a coal-sulfur content of less than 0.5 to 0.8 percent
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118
10.0
8.0
m
126,
in
c
o
en
to
4.0
UJ
CJ
O
CO
2.0
0.0,
0.0
J I
Federal standard for solid fuel firing
1.2 1
j I
i.O 2.0 3.0
Percent Sulfur in Cool
4.0
5.0
FIGURE 33. S02 EMISSIONS VERSUS SULFUR IN COAL .
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119
would be required for most ooals before compliance with the Federal New
Source Performance Standard for solid fuel fired sources of 2.16 kg S09/10
g ^
kcal (1.2 Ib SO-XIO Btu) heat input could be met without some form of
desulfurization.
Figure 34 shows the expected emissions of sulfur dioxide from
combustion processes based on the heat and sulfur content in the fuel gas.
As can be seen, to meet the Federal standard for new sources based on solid
fuel firing, a sulfur level in the fuel gas of about 1000 ppm would be
allowable for low-energy gas with a heating value of 5.59 kJ/Nm (150 Btu/
scf). As the heating value of the gas increases, the allowable sulfur
content also increases.
Many states, however, have tighter standards for SCL emissions
and it appears that the trend is for tighter standards to be promulgated.
New Mexico has established one of the strictest standards for SCL emis-
6
sions from solid fuel-fired sources — 0.61 kg SCL/IO Kcal input (0.34
6
Ibs of SCL/10 Btu input). Meeting this standard would limit the sulfur
3
concentration in fuel gas with a heating value of 5.91 MJ/Nm (150 Btu/scf)
to 300 ppm or less. However, New Mexico has proposed a much stricter
c g
standard of 0.07 kg S02/10 Kcal (0.04 IbAO Btu) for gasification plants
involved in producing SNG. Whether this standard would also apply to
gasification plants producing lower heating value fuel gases is uncertain.
In addition to environmental limitations on sulfur content in
the fuel gas, there are also certain process considerations in an industrial
application. Hydrogen sulfide is known to have a high corrosion potential
in piping and distribution systems, especially when in the presence of water
vapor or oxygen. Also, when firing the gas directly in a furnace, sulfur
compounds in the fuel gas (such as hydrogen sulfide) can cause problems with
sulfidation of certain kinds of products, particularly high-grade steel
products. Determining the maximum limit of sulfur compounds in the gas to
prevent these problems from occurring will require further definition;
however, it is possible that these requirements may be more restrictive than
environmental requirements in some cases. A more complete discussion of the
potential deleterious effects of fuel gas contaminants on distribution systems
and products is given in Section V.
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120
Federal standard for solid,- xo>
fuel firinq, 1.2 Ib S02/10b A°
—Bt-a—
400
800 1200
S in Fuel Gas, ppm
ieoo
2000
FIGURE 34. S02 EMISSICMS VESSUS SULFUR IN FUEL GAS
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121
For this study a maximum sulfur concentration in the fuel gas
of 300 ppm was established. This limitation would allow meeting the
Federal standard for solid fuel firing of 2.16 kg SO-/10 Kcal (1.2 Ibs
c ^
S02/10 Btu) based on the fuel gas heating value for both cases described
in this study. Additionally, it is also a reasonable lower bound on what
can easily be achieved by atmospheric pressure, chemical-absorption type
sulfur removal systems, such as those analyzed in this study, without
unusually high operating cost or complex sulfur recovery processes.
The expected emissions of sulfur compounds for both hypothetical
industry plants studied are given in Table 30. Emissions are given as a
function of both the heat content of gas fired and the heat content of
coal gasified. In the case of the steel plant model, the disposition of
the Glaus plant tail gas must be considered. The tail gas, consisting
primarily of CO2 and H2S, could be handled in several different ways.
(1) The tail gas could be processed through a Stretford
or other type of liquid phase oxidation system to
remove the KLS and convert it to elemental sulfur.
(2) The tail gas could be combined with the clean gas
and burned in the plant processes.
(3) The tail gas could be incinerated or burned in a
boiler.
TABLE 30. EXPECTED EMISSIONS OF SULFUR DIOXIDE FROM
COMBUSTION PROCESSES IN MODEL PLANTS
Emissions, kg S02/I06 Kcal
(Ib S02/I06 Btu)
Based on Gas
kg S02/day Energy Burned Based on Coal
(Ib SC>2/day) in Processes Energy Gasified
Steel Plant
Model
1778
3869
(3925)
(8541 )
0
0
.316
.688
(0.
(0.
176)
383)
0.222
0.480
(0.
(0.
124)
267)
clean
clean
gas only
gas with
Glaus tai I gas
combi ned
Refinery Model 2020 (4460) 0.359 (0.200)(a) 0.417 (0.232)
(a) Low-energy gas plus refinery waste gas.
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122
Table 30 shows expected sulfur emissions for Cases (1) and (2)
above. Case (1) would be considered an expensive solution but would
minimize total atmospheric sulfur emissions. The complexity of the plant
would increase along with the amount of elemental sulfur that would have
to be handled. Case (2) represents the simplest solution but results in
nearly double the total atmospheric sulfur emissions. Case (3) would
result in the same total emissions as Case (2) if the tail gas were
incinerated with no sulfur controls. If the tail gas were burned in a
coal-fired boiler, which might be used for raising steam for operating
the gasification plant, SCu scrubbers could be used on the boiler to
reduce the overall sulfur emissions.
Emissions of Oxides of Nitrogen
This discussion is to evaluate the probable change in NO emis-
.X
sions that would result when changing from the combustion of natural gas to
the combustion of one of the moderate or low heating value fuels considered
in this study. The case in which there is no fuel-bound nitrogen will be
considered first. Then the effect of fuel-bound nitrogen, specifically in
the form of ammonia, will be considered.
Figure 35 shows the equilibrium nitric oxide concentration as a
function of the percent theoretical air for several different air preheats
of natural gas-air mixtures. The rapid increase of NO with air up to about
25 percent excess air, followed by a fall-off, is obvious from Figure 35.
Figure 36 shows, however, that for constant combustion temperatures, the NO
concentration tends to level off at a constant value as the percent theore-
tical air increases. It is clear, then, that the equilibrium NO concentra-
tion increases with increase in available oxygen and with combustion tempera-
ture. Gas composition has little effect on the curves of Figure 36 if these
two factors are used as basic values. The largest change is to adjust the
NO concentration linearly with the N~ concentration in the stoichiometric
mixture(42).
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123
5000
0)
e
3
"5
E
o.
CL
0
c
-------
124
Reducing
conditions-*
Oxidizing
10,000
£
Q.
O.
c
o
c
-------
125
Thus, in comparing natural gas with the other fuels of concern
in this study, and assuming a constant percent theoretical air, the adiabatic
flane temperature and amount of N~ in the stoichiometric mixture are the
primary considerations for the case with no fuel-bound nitrogen. This per-
mits the specific heating value of the fuel, the stoichiometric•fuel/air
ratio, and the air and/or fuel preheat to be neglected as considerations.
The next factor to consider is the effect of the available
reaction time. This is significant because the rate of production of thermal
NO is slow compared to the combustion times available or needed in most
furnaces. This is why a maximum value of 175 ppm of NO when burning natural
gas with 15 percent excess air is reasonable, whereas the equilibrium value
is about 3000 ppm (Figure 35). Figure 37 shows the effect of residence time
on curves comparable with Figure 36. These values can be compared with
current New Source Emission Standards for large boilers of 175 ppm, 230 ppm,
and 575 ppm of NO for 15 percent excess air burning gas, oil, and coal,
x g
respectively. These correspond to 0.36, 0.54, and 1.26 kg NO/10 kcal
(0.2, 0.3, and 0.7 pounds of NO per 10 Btu). It is seen from Figure 37
that at a combustion gas temperature of 1760 C (3200 F), the NO concentra-
tion only reaches 1/8 the equilibrium concentration shown in Figure 36 in
0.4 sec. (At only 3.05 m/sec, this would be a distance of 1.22 m.) For
2000 C (3600 F), the ratio is about 1/10. One may conclude then that for
flames at the same firing rate, same temperature, and same excess air,
there will be little difference in the actual concentration of thermal NO.
A computation can now be made of the relative NO values for dif-
ferent fuels operating under the same excess air conditions and same initial
temperature, providing no fuel-bound nitrogen (discussed below) is present.
Four fuels are considered, a natural gas (Table A-l), a Koppers-Totzek gas
considered as a replacement for natural gas in a secondary steel plant, and
a Wellman-Galusha gas mixed in proposed winter and summer proportions with a
refinery gas. The equilibrium NO at the adiabatic flame temperature with 10
percent excess air is computed for each of these gases from Figure 36, cor-
recting the concentration value by the ratio of N2 in the raw mixture to that
-------
126
Reducing conditions
10,000
Oxidizing conditions
1000
o
£
E
Q.
Q.
c"
O
c
0)
u
c
o
u
-------
127
for natural gas. The value is then further corrected for the heating value
of the raw mixture*. It is seen from Table 31 that the low temperature of the
refinery gas/Wellman-Galusha gas mixture reduces the NO production the most,
in spite of the high nitrogen content of the fuel. The high heating value of
the Koppers-Totzek gas per unit mass of products, plus the increased volume
ratio of fuel-to-air, more than compensates for the increased temperature of
the Koppers-Totzek gas and, thus, also results in lower NO production. As a
result, if essentially all fuel-bound nitrogen is stripped from the moderate
and low-heating value gases, these gases will give lower NO output than natural
gas under similar firing conditions.
TABLE 31. RELATIVE NO PRODUCTION FROM THERMAL FIXATION
OF VARIOUS FUELS AT 10 PERCENT EXCESS AIR
Relative
Fuel NOX Production
Natural gas 1.00
Koppers-Totzek 0.93
Wei I man-Galusha, winter mix with refinery gas 0.72
We IIman-GaIusha, summer mix with refinery gas 0.74
Nitrogen bound in various fuel constituents (primarily NH_ for gas
from coal) does not convert to NO by the same process as thermal fixation
^C
of elemental nitrogen. In the case of fuel-bound nitrogen, temperature and
time are of little importance. The two major factors are stoichiometry (or
percent excess air) which determines the amount of oxidant available, and the
concentration of nitrogen compounds in the fuel.
*As an example, the Koppers-Totzek gas may be compared with natural gas. The
adiabatic flame temperatures with 10 percent excess air are 2190 K and 2140 K.
From a cross-plot of Figure 36, the concentration of NO is 3400 and 3000 ppm,
respectively/ The raw mixtures have 63.0 and 75.3 percent N2, respectively?
using the ratio, the value of 3400 is corrected "to 2845. The heating value of
the raw mixtures are 1098 and 1074 Btu/lb, respectively; correcting to a
common heat input, 2845 ppm of NO becomes 2783 ppm of NO. The ratio of this
value to 3000, which is 0.928, is the NOx production of the Koppers-Totzek
mixture relative to natural gas.
-------
128
Ihe effect of stoichiometry on conversion of NEL to NO in a
•j X
methane flame is shown in Figure 38. These data are for a premixed flame
where fuel and oxidant are thoroughly mixed prior to burning. In nozzle
mix-type burners, which are more common in industry than premix burners, the
stoichiometry in the flame is primarily a function of the mixing rate be-
tween the fuel gas and combustion air. In these cases the amount of combustion
air would have only a minor effect on NO conversion.
X
Ihe major effect of fuel-bound nitrogen conversion to NO in nozzle
X (43)
mix-type burners is nitrogen concentration in the fuel. Turner, at al.,
have shown that the form in which the nitrogen is bound in the fuel has no
*
effect on nitrogen conversion. Figure 39 shows the conversion of fuel-bound
nitrogen to NO in a Rankine-cycle can-type combustor using a liquid fuel with
X
pyridine as the nitrogen carrying additive. The data for the curve in Figure
39 represent a wide range of excess airs of from 120 to 175 percent of theoretical
air and indicate that, within this range of excess air levels, excess air has
little or no effect on nitrogen conversion.
Figure 40 shows a compilation by Dykema and Hall of utility
boiler data over a wide range of nitrogen concentrations of the mass fraction
of fuel-bound nitrogen converted to NO . The curve of Figure 38 and correspondmg
X
data of Hazard (Figure 39) are added. While the scatter of the data is large,
it must be realized the there is an arbitraryness in accounting for the amount
of thermal nitrogen to be deducted from the total; the higher fraction mass
conversion calculation is particularly sensitive to this effect. Nevertheless,
the trend of the data is obvious.
Data on fuel-bound nitrogen, which predominantly consists of NH-,
in fuel gas from coal is limited. Table 32 illustrates some typical ammonia
concentrations in raw uncleaned gas from various types of coal gasification
processes. In cold gas desulfurization processes, much of this ammonia (at
least 90 percent) would be removed in the water scrubbing step preceding de-
sulfurization, as long as the scrubbing water is continuously stripped of
absorbed ammonia. Additional ammonia may be removed in the desulfurization step
depending on the sorbents used.
*
This analysis involved liquid fuels with eight different nitrogen containing
additives.
-------
1.0
x
O
z
o 0.8
ro
I
Z
>4—
O
c 0.6
129
OJ
>
c
o
O 0.4
"o
o
u
o
0.2
O.O1
0.7
0.8 0.9 1.0 I.I 1.2 13
Air/Fuel Ratio Relative to Stoichiometric
1.4
FIGURE 38. FRACTIONAL CONVERSION OF NH-. IN PRFMIXED METHANF-AIR
(44)
NH3 equivalent to 1200 ppm NO and air consisting of oxygen-
hefium mixture.
-------
130
V)
o
5
» 0.004
if
o>
>
jg
o>
o:
ox
c
u>
a
0.003
0.002
c
= 0.001
o
o
0.000
0.000
1
1
0.001 0.002 0.003 0.004
Mass Fraction of Nitrogen in Fuel
0.005
FIGURE 39. FUEL NITROGEN IN LIQUID FUEL-PIKED RANKINE-
CYCLE GQMBOSTOR CONVERTED TO NO *C44)
*Usina pyridine as the nitrogen source and using ASTM
Jet A combustor. Tests covered from 120 to 175 percent
theoretical air.
-------
X
O
TD
0>
c
O
O
c
-------
L32
TABLE 32. TYPICAL AMMONIA CONCENTRATIONS IN RAW
UNCLEANED FUEL GAS FROM COAL
Ammon i a
Gasif ier
Vo 1 ume
Percent
Ib/lb fuel
x I03
MJ/Nm3
(Btu/scf)
Reference
Koppers-Totzek
single stage 0.17 1.13
entrained slagging
(CL blown)
two-stage entrained 0.38 2.53
slagging (ai r blown)
Lurgi
pressurized 0.70 4.66
fixed-bed
11.3 (286)
4.9 (125)
12.7 (323)
46
47
48
(02 blown)
atmospheric
fixed bed
(air b-lown )
0.25 1.46 5.5 (139) 47
Table 33 shows expected emissions of NO (in lb/10 Btu of heat input)
for the ammonia concentrations shown in Table 32 using the curve of Dykema and
Hall from Figure 40. Values are given for both the raw gas and assuming 90
percent ammonia removal. In addition, Table 33 gives estimated emissions due
to thermal fixation of N_ assuming a thermal contribution of 100 ppm NO in the
flue gas on stoichiometric mixture. Total expected NO emissions from both
thermal fixation and oxidation of fuel-bound nitrogen assuming 90 percent NH-,
removal are also given.
-------
133
TABLE 33. ESTIMATED EMISSIONS FROM
RAW AND CLEANED FUEL GASES
NO Emissions, Kg/106 Kcal (Ib/IQ6 Btu)
Due to NH, in Gas
3] I I UOij -r-i , . ._
Thermal NO Assuming Total NO With
Assuming yu* 100 ppm NO in Stoi- 90 Percent NH,
Gasitier Raw Gas Removal of NH3 chiometric Mixture Removal
Koppers-Totzek
single-stage en- 0.79 (0.44) 0.08 (0.047) 0.15 (0.086) 0.24 (0.133)
trained slagging
two-stage en- 2.63 (1.46) 0.47 (0.259) 0.22 (0.120) 0.68 (0.379)
trained slagging
Lurgi pressurized |J3 (0.63) 0.3! (0.171) 0.16 (0.092) 0.47 (0.263)
fixed bed
Atmospheric 2.09 (1.16) 0.25 (0.141) 0.20 (0.112) 0.45 (0.253)
fixed bed
For the raw gas expected emissions of NO from oxidation of fuel-bound
nitrogen alone would exceed the Federal standard of 1.26 Kg NO/10 kcal (0.7
Ib NO/10 Btu) for coal-fired systems in two cases and would exceed the standard
for gas-fired systems of 0.36 Kg NO/106 kcal (0.2 Ib NO/106 Btu) in all cases.
With 90 percent removal of NH., the expected NO emissions including the assumed
contribution from thermal fixation would be less than the coal standard of
1.26 Kg NO/10 kcal (0.7 Ib NO/10 Btu) in all cases and would approach the gas
standard in most cases.
In both industry systems considered in this study, NH~ is assumed
to be entirely removed in the combination of water scrubbing and amine or
Stretford desulfurization. Emissions of NO would, therefore, consist primarily
of those from thermal fixation of elemental nitrogen. Under these circumstances
NO emissions overall would decrease relative to those with natural gas as was
shown in Table 31.
-------
134
Particulate Emissions
Particulate content in the final clean product gas from both of
the gasification plant models is negligible. Combustion of this gas, there-
fore, would be expected to result in negligible particulate emissions to the
atmosphere and no particulate control would be required. In both model plant
cases the low-energy gas would be replacing the firing of some heavy oil which
would result in an overall decrease in particulate emissions from these two
industries.
Emissions of Trace Constitutents
Emissions of trace organic constituents such as polycyclic organic
matter (POM) are a function of the number of long chain hydrocarbons or
ring-type-hydrocarbons in the fuel itself and of the combustion conditions.
Coal and oil both contain significant quantities of these compounds. However,
the product gas from gasification, should contain few, if any, long chain or
ring-type hydrocarbon components. Combustion conditions for firing the fuel
gas would be similar to those for firing natural gas. Thus, emissions of
these types of materials would be expected to be similar to that of natural
gas. They would be significantly less than if the coal were fired directly
or if oil were used directly as the fuel.
Other trace constituents, such as trace metals that may be vaporized
in the combustion process, are also potential pollutants. The more volatile
metals (mercury, etc.) would be vaporized in the gasification process but should
be condensed in the water scrubber and cooling sections of the gas-cleaning
processes. The ultimate fate of these constituents must still be determined
in order to assess the true environmental impact.
-------
135
VII. POTENTIAL IMPACT OF ADVANCED
HOT GAS CLEANING SYSTEMS
All fuel gas desulfurization systems that are applicable to
cleaning gas from coal and have been proven commercially successful are
at gas temperatures of less than 250 F. The two processes used in this
study, the MDEA and Stretford systems, operate at temperatures of ambient
or slightly above. The r<^« fuel gas from a gasifier, however, contains
significant amounts of sensible heat which could represent from 10 to 20
percent of the energy in the raw gas, depending on the process and the raw
gas temperature. There has been considerable emphasis on developing fuel
gas desulfurization processes capable of cleaning fuel gas at elevated
temperatures. This would allow the gas to be fired hot, thus, conserving
the sensible heat and increasing the overall thermal efficiency. This
concept has obvious merit, especially for power plant applications where
the hot gas needs only to be piped a short distance to the point of com-
bustion-. However, different considerations are necessary for industrial
plants. Therefore, an evaluation was made of the relative advantages and
disadvantages such systems might nave in an industrial situation.
Table 34 lists the leading hot-gas desulfurization systems under
development. These processes can generally be classed as those using fully
calcined dolomite of half-calcined dolomite (Consolidation Coal and Air
Products and Chemicals), those using iron oxide (Bureau of Mines and Babcock
& Wilcox), and those using molten salt baths (Battelle-Nbrthwest).
The dolomite processes operate at the highest temperatures [from
about 815 to 1100 C (1500 to 2000 F)] and regeneration yields an H2S-rich
gas suitable as a Claus feed. Regeneration of these processes is accomplished
with steam and C02 according to the following reaction:
CaS-MgO + H20 + C02 -»• CaCCyMgO + H2S.
This reaction is for the Consolidation Coal half-calcined dolomite process.
The Air Products and Chemicals full-calcined dolomite process has been
abandoned due to poor sorbent regenerability ^ 5 0 )^
-------
136
TABLE 34. ADVANCED HIGH-TEMPERATURE CLEANING
SYSTEMS UNDER DEVELOPMENT
Process Sorbent
Consolidation CaCO,'MgO
Coal* 3
Air Products CaO-MgO
and Chemicals
Bureau of Mines Fe~0, + fly ash
Babcock & Wi Icox ^e9^3
Battel le-Northwest NaCOj + CaC03
Temperature, C (F)
816-982 (
87I-I093C
423-816 (
371-649 (
593-923(1
1500-1800)
1600-2000)
800-1500)
700-1200)
100-1700)
Su 1 fur
Form Status
H2S Pilot
hLS Abandoned
S02 Pilot
SCU Experimental
H2S Pilot
*Conoco Coal Development Corporation
Processes using iron oxide as a sulfur sorbent operate at tempera-
tures of about 370 to 815 C (700 to 1500 F). The sorbent is regenerated with
air yielding an SC^-rich gas stream by the following reaction:
2FeS + 3-1/2
2S0
The SO- can then be reduced to elemental sulfur, converted to sulfuric acid,
or converted to CaSO, with lime or limestone scrubbing.
The molten salt process operates at temperatures of from 593 to
923 C (1100 to 1700 F) and absorb sulfur compounds in a molten solution of
NaCO., srcd CaCCs. The sorbent is regenerated with steam and CCu yielding an
H?S rich gas stream suitable for feed to a Claus sulfur recovery unit.
At the present time, none of the hot gas cleanup systems discussed
are commercially available. At present, all are in the pilot stage of
development with the exception of Babcock & Wilcox, which is experimental,
and Air Products, which has been abandoned. The time scale for commerciali-
zation of these systems is uncertain, but it would be unlikely that any would
be commercially available before 1980.
-------
137
In general, hot gas cleanup processes are not expected to be as
flexible as cold liquid scrubbing processes in achieving low-sulfur levels
(below 100 ppm) in the product gas^48). This could cause a problem in some
industrial situations where very low sulfur levels are necessary to minimize
corrosion in gas distribution systems and minimize effects on products in
direct-fired furnaces. In this study a sulfur level of 300 ppm was assumed
adequate for both environmental, piping, and product degradation purposes.
After actual trial or new standards, however, it may be determined that a
lower sulfur level would be desired. Under these circumstances, a cold
liquid scrubbing system would be more flexible in being able to achieve a
lower sulfur level.
None of the hot-gas cleaning systems discussed is capable of
removing armonia and only one, the Battelle-Northwest molten salt, is
capable of removing particulates; however, even this process would require
filtration of the molten salt, which is a difficult problem yet to be solved.
In cold gas liquid scrubbing processes, ammonia and particulates are reduced
to low levels in the gas by the water scrubbing steps preceding desulfuriza-
tion.
The anroonia compounds, if left in the gas, could lead to
unacceptably high NO emissions for some gasification processes due to
J^
oxidation of fuel bound nitrogen (see Table 33 in Section VI). Also, ammonia
compounds could lead to higher corrosion rates in piping (see Section V).
At present, no processes are available for removing aimionia compounds along
with sulfur from hot fuel gas.
Also, a hot fuel gas would result in a higher flame temperature
than would a cold fuel gas which would increase the production of thermally
produced NO . Figure 41 shows the effect of fuel temperature on flame
J^
temperature. Flame temperature could be reduced by dilution with excess
combustion air; however, this would reduce thermal efficiency by increasing
stack losses—defeating the purpose of a hot fuel gas.
Data on particulate loading in raw fuel gas are very limited, but,
depending on the process, particulate content can be high. Fixed-bed gasi-
fiers would tend to be lowest due to their large coal size and low flow
velocities. The Winkler fluidized-bed gasifier reportedly carries from
50 to 75 percent of the ash in the coal over with the raw gas (5 (I The
-------
138
Koppers-Totzek entrained slagging process results in about 50 percent of
the ash in the coal being carried over with the raw gas with the remaining
dropping out as slag. For one case, Hoppers indicates particulate loading
in the raw gas of 26 g/Kfcn3 (11.57 grain/scf )< 47>.
• Particulate removal devices capable of operating on hot-fuel gas
at temperatures similar to those of hot-gas desulfurization systems are not
well developed. Electrostatic precipitators have been used successfully at
temperatures of 255 to 590 C (500 to 1000 F) in the utility industry for
controlling fly-ash emissions. Laboratory tests have been conducted on hot
precipitators with gas temperatures up to 815 C (1500 F) with removal effici-
encies of 90 to 98 percent; however, long-term continuous operation was not
(52)
demonstrated .A novel granular bed filter has been developed with removal
efficiencies of greater than 90 percent on particles down to 2 micrometers '.
Other processes such as cyclones and ceramic filters have also been developed
for removing particulates from high temperature gases. Plugging and fouling
from tar compounds could be a problem in all high temperature particulate
removal systems when operating on raw fuel gas from coal. High temperature
corrosion from acid gases such as H-S is also a potential problem.
In cold gas liquid scrubbing desulfurization systems, particulates
are removed in the water scrubbing steps preceding desulfurization. These
liquid scrubbing systems can be highly efficient in removing particulates to
very low levels in the gas stream. Koppers reports that, for an inlet
3 3
grain loading of 26 g/ton (11.57 grain/scf), an outlet loading of 0.004 g/!S&n
(0.002 grain/scf) is achieved with a two-stage venturi scrubber^^ . This
represents a removal efficiency of greater than 99.9 percent. It is doubtful
that a high temperature particulate removal device could be as efficient as
cold gas scrubbing. In an industrial situation, where few furnaces would
have particulate control devices, the lower particulate removal efficiency
would be a drawback of hot desulfurization systems.
With cold gas cleaning systems, waste-heat boilers can be used to
recover heat in the raw gas by generating steam. This steam could be used
in the industrial plant, for driving pumps and turbines in the gasification
plant, or for sorbent regeneration in the cold-desulfurization system. Using
waste heat in this manner minimizes the differences in thermal efficiency
-------
139
REFERENCE FUEL HHV = 120 BTU/SCF
REFERENCE FUEL TEMPERATURE = 80F
STOICHIOMETRIC FUEL-AIR RATIO
INITIAL AIR TEMPERATURE = 82SF
4800
4600
01
tr
P 4400
cc
LU
0.
5
LU
I-
2
O
C 4200
CO
O
0
O
t-
<
co 4000
<
Q
3800
3600
INCREASE FUEL
TEMPERATURE
INCREASE FUELHHV
I
100
120 140 160 180
FUEL CHEMICAL PLUS SENSIBLE HEAT-BTU/SCF
200
FIGURE 41. EFFECT OF FUEL GAS CHEMICAL AND SENSIBLE HEAT ON
COMBUSTION TEMPERATURE
-------
140
between hot and cold gas processes. Three of the five hot gas desulfurization
processes shown in Table 34 (the two dolomite-based processes and the molten
salt process) also require steam for sorbent regeneration. The other two,
both iron oxide systems, use air and, as a result, yield sulfur as SCL which
is more difficult than H2S to convert to a usable or easily handled form.
Thus, differences in overall efficiency between hot and cold systems can be
minimized with waste heat recovery.
Probably the biggest drawback of hot gas cleaning systems for
industrial applications is the necessity for distributing the hot gas in
extensive and intricate gas distribution systems often necessary in an
industrial plant with a large number of furnaces. As can be seen from
Figure 42, a gas temperature of from 705 to 815 C (1300 to 1500 F) would
require distribution of three to four times the volume of gas that would
be required at 21 C (70 F). In addition, the higher temperatures would
increase piping degradation due to corrosion and high stress.
In summary, the availability of a hot gas desulfurization system
is not felt to be especially attractive in the industrial situations
reviewed here. The inability to remove ammonia combined with higher flame
temperatures would result in increased emissions of NO . Problems with
X
high temperature particulate removal would also result in increased
pollution potential of hot systems over cold systems and, combined with
an inability to achieve very low sulfur levels in the product gas, may
make hot systems inappropriate in some industrial situations. Also,
distribution of a hot gas would magnify corrosion and stress problems in
piping and would require larger diameter pipes with the addition of insula-
tion. With waste-heat recovery the difference in efficiency between hot
and cold gas systems is reduced (less than 5 percent overall difference in
most cases), which would minimize the potential advantage of a hot gas
system.
-------
Volume
Ratio,
500
1000
1500
Fuel Gas Tenperature, F
FIGURE 42. RELATIVE VOLUME OF FUEL GAS REQUIRED AT DIFFERENT
FUEL GAS TEMPERATURES FOR V-^70 F
-------
142
VIII. THE EFFECT OF AVAILABILITY OF ALTERNATE
CLEAN FUELS FROM COAL ON INDUSTRIAL DEMAND
FOR LOW- AND INTERMEDIATE-ENERGY GAS
A variety of advanced processes currently are under development
for manufacturing clean synthetic fuels from coal. These processes are
generally more sophisticated than existing commercial units and are intended
to operate more efficiently, economically, and on a larger scale. In
addition, many of these processes are capable of producing higher grade
fuels than low- or intermediate-energy gas.
Table 35 lists those processes currently under development by
ERDA for manufacturing substitute natural gas (SNG) from coal. SNG, which
has a heating value of about 39.4 MJ/Mn (1000 Btu/scf), is made by
methanating synthesis or intermediate-energy gas by reacting CO and EL, over
a nickel catalyst to yield CH.. The source of the intermediate-energy gas
can be most any oxygen-blown gasification process, but the advanced processes
under development and shown in Table 35 are intended to maximize the yield of
methane in the gasifier to minimize the amount of methanation required. None
of the processes shown in Table 35 are expected to be of commercial scale
before 1980. A variety of first generation commercial SNG plants are being
planned, however, based on current technology. Table 36 lists SNG projects
that are currently in advanced stages of planning or awaiting government
approvals.
Substitute natural gas from coal is expected to have properties
very similar to natural gas and from a combustion standpoint be directly
substitutable for natural gas with only minor burner adjustments. Table 37
shows compositions of several natural gases compared to several reported SNG
compositions from coal, one from oil, and a sample LNG (liquefied natural
gas).
Replacement of Natural Gas by Liquified
Natural Gas or Synthetic Natural Gas
It is seen that the normal range of natural gases (even a wider
range could be found) brackets the three synthetic gases produced fron coal in
-------
TABLE 35. HIGH-B1U GASIFICATION PROGRAM
(53)
Major Projects
Contract Value
$M (Cost Share)
Contractor
Location
Key Events
• CCL Acceptor
Process
26.8
(6.6)
Conoco Coal Dev. Rapid City, S.D.
Co.
Methanation plant con-
struction, complete
FY 75
• Hygas Process
18.5
(2.0)
Institute of Gas Chicago, III
Technology
Steam oxygen system
construction, complete
FY 75
Steam-Iron 18.2
Process (7.9)
Ash-Agglomerating 8.9
Process (1.7)
Institute of Gas Chicago, I
Technology
Complete pilot plant
construction FY 75
Battelle-Columbus West Jefferson, Complete pilot plant
Ohio construction FY 75
CO
• Bi Gas
66.0
( 10.0)
Bituminous Coal
Research
Homer City, Pa.
Complete pilot plant
construction FY 75
Synthane
19.0
Rust
Engineering/
Lumus Corp.
Perc
Bruceton, Pa.
Complete construction
FY 75
-------
144
TABLE 36. SNG PLANTS IN ADVANCED STAGES OF PLANNING
(54)
g
Developer Plant Capacity (10 Btu/day) Expected Starting Date
American Natura
Gas Company
Cities Service Gas
Co. and Northern
Natural Gas Company
E! Paso Natural Gas
Company
Natrual Gas Pi peline
Company
Panhandle Eastern
Pi peline Company
and Peabody Coal
Texas Eastern Trans-
mission Corp.
(WESCO)
Texas Gas Trans-
mission Company
1000 x I09 Btu/IO9 Btu/day
4-250 x I09 Btu/day trains
1000 x 10 Btu/day
4-250 x 10 Btu/day trains
785 x 10 Btu/day
1000 x 10 Btu/day
4-250 x I09 Btu/day trains
270 x I09 Btu/day
1000 x 10 Btu/day
4-250 x I09 Btu/day trains
250 x 10 Btu/day
First train-1981, sub-
sequent trains at 4-
year intervals
Currently under study
1980 - first 230 x 10
Btu/day plant pending
FPC approval
First train-1982, sub-
sequent trains at 3-year
intervaIs
1981
1980 - first 250 x 10'
Btu/day train pending
FPC approval
1983
-------
TABLE 37. COMPOSITION AND PROPERTIES OF SOME NATURAL GASES, LNG, AND SNG
Composition
or Property
CH4
C2H6
C3H8
Other HC
co2
CO
N2
H2
HHV, Btu/ft3
S.G.
Stoich. A/F
Wobbe No.
Natura 1
Gas
No. 1
94.9
3. 1
0.3
0. 1
1 .1
0.0
0.5
0.0
1029
0.588
9.70
1342
Natura 1
Gas
No. 2
90.2
3.7
0.6
0.2
0.8
0.0
4.5
0.0
1009
0.609
9.42
1281
Natura 1
Gas
No. 3
72.8
6.4
2.9
0.6
0.2
0.0
17. 1
0.0
945
0.695
8.90
1 133
LNG
86.3
9.0
3.2
1 .3
0.0
0.0
0.2
0.0
1 162
0.952
10.89
1440
SNG
( f rom o i 1
69.5
15.0
0.4
0.0
0.3
0.0
0.3
14.5
1027
0.541
9.52
1394
SNG
(COED)
88.9
0.0
0.0
0.0
2.9
0. 1
1 .6
6.5
921
0.558
8.63
1233
SNG
( Lurgi )
95.8
0.0
0.0
0.0
2.0
0. t
1 .4
0.7
872
0.577
9. 15
1280
SNG
(Biqas)
91 .8
0.0
0.0
0.0
1 . 1
0. 1
1.9
5. 1
946
0.549
8.87
1277
Cn
-------
146
respect to Wobbe number, and almost brackets them in respect to the heating
value. Thus, one would expect that only minor adjustments would be needed on
the control system (5 percent change in Wobbe number is usually assumed to
be tolerable without adjustment) to switch to one of these synthetic fuels.
In the case of LNG, an adjustment will certainly be required,
resulting from the high ethane content in the fuel. However, the stability
limits of the flame are not changed significantly.
A high hydrogen synthetic fuel made from oil is also shown. While
the Wobbe number is not as high as that of ING, the high hydrogen content
results in about a 40 percent increased value of the flashback velocity
gradient. Thus, there is a possibility with such a fuel as this that pre-
mixed burners might have to have their burner faces changed. In precision
heat treating, glass forming, and similar operations, the change in flame
shape may also result in a need for adjustment when switching to a high
hydrogen fuel such as indicated here.
Processes are also currently under development for producing clean
liquid fuels from coal by processes termed liquefaction. Unlike gasification,
which is an old basic technology, liquefaction is a relatively new technology.
Liquefaction of coal was accomplished by the Germans in the 1930's and 1940's
using gasification in combination with Fischer Tropsch synthesis, which combines
CO and ^ into higher hydrocarbons from about C2 through Cg. These lightweight
liquid fuels are currently being produced in a large gasification/liquefaction
plant in Sasolburg, South Africa, using this type of technology. This tech-
nology is generally considered too expensive and inefficient for use in the
U.S. today, and so ERDA is funding development of processes for directly
hydrogenating solid coal producing a heavy liquid fuel similar to a No. 6
residual oil. Table 38 lists the processes currently being developed to
accomplish this.
Another possibly attractive liquid fuel from coal is methanol
which is made through gasification in a process very similar to that used for
producing SNG (using a copper catalyst instead of a nickel catalyst). The
technology for producing methanol from coal is available; however, no
commercial plans are known at this time.
-------
TABLE 38. COAL LIQUEFACTION
(52)
Major Projects
• Coa 1 -Oi 1 Energy
Development (COED)
• Solvent Refined Coal
(SRC)
• H-coa 1
• Clean Coke
• Synthoi 1
Contract
$M (Cost
21 .
41 .
3.
(2.
1 I.
(2.
(1.
Value
Share) „ , ,
Contractor
0 FMC
0 PAMCO
0 HRI
7)
5 U.S. Steel
9)
1 ) Foster Wheeler
Location
Princeton, N.J.
Tacoma, Wash.
Trenton, N.J.
Cattelsburg, Ky.
Monroevi Me, Pa.
Perc
Key Events
Pi lot operations
comp 1 ete FY 75
Pi lot operations
started mid FY 75
PDU runs FY 75
pilot-plant decision
mid FY 75
PDU complete FY 77
pi lot p lant deci si on
FY 77
RFP for construction
June . 75
-------
143
Table 39 lists some pertinent properties of several grades of oil
along with liquified coal, methanol, and shale oil for comparison. When using
a liquid fuel as a replacement for natural gas, several considerations are
necessary.
Replacement of Natural Gas by Liquid Fuels
In industrial heating boilers and other types of heat exchangers,
and in many other industrial applications (note number of dual-fuel burners
under secondary steel industry discussed earlier), dual-fuel burners are com-
monly used which allow natural gas and various grades of oil to be burned
simultaneously. These typically burn No. 2 and/or No. 6 fuel oil; in the
latter case, provision must be made for heating the fuel slightly to be able
to pump and atomize it. It is clear that all the fuels listed in Table 6
except methanol have similar heating values. Thus, if their viscosity is
in the proper range (by preheating, if necessary), the fuel nozzle should
-perform properly at design capacity. The low heating value of methanol
indicates that a new nozzle would be required to obtain a higher flow rate.
The Bureau of Mines' hydrodesulfurized oil (Snythoil) and the shale oil could
be treated as No. 6 oil. It would require preheating by a sufficient amount
to be pumped. COED oil which is a product of pyrolysis or gasification falls
between No. 2 and No. 4 fuel oil in viscosity, and might require no preheating
or only mild preheating, depending on other circumstances. Methanol requires
no preheating, but its low viscosity may result in insufficient pump lubri-
cation; thus, a new pumping system might be required as well as new nozzles.
In regard to radiation, all the fuels except methanol would be
expected to be highly radiant; those derived from coal would probably be
more radiant and might require some dirtying of heat exchanger surfaces (say,
by adding magnesium oxide to the fuel) to obtain the proper radiation/convec-
tion balance. In the case of boilers, some change might be necessary in super-
heater controls. Methanol would perform similarly to a somewhat cooled
natural gas flame, with low radiant input.
-------
TABLE 39. PROPERTIES OF VARIOUS UOUID FUELS
No. 1 No. 2
Fuel Fuel Oi 1 Fuel Oi 1
HHV, Btu/lb 19,600 19,400
Kinematic viscosity,
mm2, at 100 F 1 .4-2.2 2.0-3.6
at 122 F
No. 6
Fuel Oi 1
18,300-
18,700
92-638
Bureau of
COED Mines(a) Shale Oi 1
19,000 17,700 18,000
5.5
300-500 30
Methanol
9,776
0.6
(a) Bureau of Mines' hydrodesulfurized oil (Synthoil).
-------
150
In furnaces where dual-fuel burners are not in use, the installa-
tion either of such units or of separate liquid fuel burners could be in
order. The considerations would be much the same as outlined above, except
that the fuel heating system, pumps, and burner could be designed specifi-
cally for the fuel. Since, in these instances, it would not be known,
a priori, that the change in radiation would have no detrimental effect,
this factor would have to be verified.
In some instances, the flame shape is important, and care would
have to be taken to ensure a similar shape. Difficulties could be expected
with tunnel burners or radiant tube burners; No. 6 fuel oil and similar
fuels would not be acceptable in these instances on the basis of presently
available burners. Premix burners cannot be replaced directly by fuel oil
burners, and alternative burner designs and furnace configurations might be
required.
The third alternative is to use a prevaporizer. Liquid fuel is
burned on the combustion side of a heat exchanger to heat the main air
stream to, say, 370 C (700 F). Liquid fuel is then sprayed into the hot
gas and vaporized, and the mixture can be substituted for premixed natural
gas and air with minor changes. Systems are commercially available for
vaporizing No. 1 and No. 2 fuel oils. It should be noted that methanol
will reach a stoichiometric mixture at only 18 C (67 F) mixture temperature,
and the fuel rich limit at 40 C (105 F). Air at about 205 C (400 F) would
vaporize the methanol to a stoichiometric mixture.
Liquid fuels for the industrial uses studied can be used to
completely replace natural gas, provided that at least some fuel with
vaporization properties similar to or better than No. 2 fuel oil is
available for situations where a gaseous fuel is essential. Also liquid
fuels can be stored indefinitely and used when needed, which is an at-
tractive characteristic in industries where fuel demand varies widely from
day to day. In all instances but those in which dual-fuel burners are now
used successfully, checks would have to be made on the radiation properties.
For methanol, because of low viscosity, it might be necessary to change
pumps and burner nozzles.
The gasified and liquefied products discussed in this section as
alternatives to low- and intermediate-energy gas have attractive features
-------
151
for industry. SMG could essentially be substituted directly for natural
gas in practically all industries with almost no foreseeable modifications.
Most industries would be willing to pay a somewhat higher price for this fuel
over low- or intermediate-energy gas depending on the degree of modification
that would be necessary in processing operations. Liquefied coal (No. 6 oil)
or methanol could also easily be used in many industries although modifications
such as addition or replacement of burners along with installation of heated
lines would be necessary. In many industries, however, equipment has already
been installed for using No. 6 oil and some operating experience has been
gained with its use. In these cases use of liquefied coal would be attractive.
However, the most important factors in determining the potential for
use of alternate clean fuels from coal instead of low- or intermediate-energy
gas are supply and cost. If all the SNG plants listed in Table 35 were con-
structed and operated at 100 percent load factor, they would supply about 2.0 x
12 15
10 MJ (1.9 x 10 Btu) per year of gaseous energy. In 1972 industry used
about 11 x 10 MJ (10.4 x 10 Btu) of natural gas and an additional 58 x 10
9 12
MJ (55 x 10 Btu) of oil in supplying its energy requirement of 24.4 x 10 MJ
(23.1 x 10 Btu) . The total U.S. demand for natural gas in 1972 was 24.4 x
1012 MJ (23.1 x 1015 Btu) and for oil 34.8 x 1012 MJ (33 x 1015 Btu)(2).
Construction plans and schedules for SNG plants have consistently fallen be-
hind, and today it seems certain that no commercial SNG plants will be in
operation by 1980 and only a few by 1985. A total of 176 sites have been
identified capable of supporting a 264 x 10 MJ (250 x 10 Btu) per day SMG
(54)
plant for 34 years . If all 176 sites were developed and operated at
12 15
full capacity, they would produce about 17 x 10 MJ (16 x 10 Btu) per
12
year of SNG. It would be highly unlikely that more than 5.3 x 10 MJ
(5 x 10 Btu) per year of SNG could be produced by the year 2000 which would
12
be less than half the 1972 industry demand and less than the 7.7 x 10 MJ
(7.3 x 10 Btu) used by the household and commercial sector in 1972
-------
152
It would be a good assumption, therefore, that SNG or any natural gas
equivalent will be reserved for high priority uses in the future and will
not be of any higher availability to industry than natural gas currently is.
At present, no commercial coal liquefaction plants have been
planned, and only one significant sized demonstration plant is scheduled for
construction (to be built in New Athens, Illinois, by Coalcon) producing
6.2 x 105 liters/day (3900 barrels/day) of oil (or approximately 24.3 x 10 MJ
per day [23 x 109 Btu/day]) and about 23.2 x 106 MJ/day (22 x 109 Btu/day)
of SNG. This plant is not scheduled for operation until the early 1980's.
ERDA's current plans call for the production of about 9.5 x
12 15
10 MJ/year (9 x 10 Btu/year) of SNG and liquefied coal products by the
(2)
year 2000 . This would be equivalent to about 16 percent of our 1972 use
of natural gas and oil of 59.2 x 1012 MJ (56.1 x 1015 Btu).
Even if the goal of 9.5 x 1012 MJ/year (9 x 1015 Btu/year) of
these fuels is attained, which would require a significantly accelerated
pace over that of today, it would be unlikely that these fuels would be
available to industry despite their relative ease of application. Rather,
they would be reserved for high priority uses such as home heating, trans-
portation, and chemical feedstocks.
Also, significant engineering and development efforts will be re-
quired to perfect the processes for manufacturing higher grade alternate fuels
from coal. This, combined with the greater complexity reouired in processina
operations, including the necessity for high pressure operation, in many cases
will probably result in significantly higher production costs for these fuels
compared to those of low- and intermediate-energy gas made with existing pro-
cesses .
Therefore, industry's pursuit of low- or intermediate-energy gas,
which is generated on site for their needs, seems entirely reasonable as a
means of securing both near- and long-range supplies of needed fuel.
-------
153
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(2) A National Plan for Energy Research. Development, and Demonstration;
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(3) Economics of Fuel Gas From Coal. Foster, J.F., and Lund, R.J., McGraw
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(4) Study of Potential Problems and Optimum Opportunities in Retrofitting
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(6) Energy Consumption in Manufacturing. Myers, J.G., et al., a report to
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(7) Special Survey on Gross and Net Consumption of Fuels and Energy; Com-
mittee on Taxation and Statistics, Energy Task Group, American Iron
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(8) A Cost Analysis of Air Pollution Controls in the Integrated Iron and
Steel Industry, Battelle report to NAPCA, Contract PH22-68-65, May, 1969.
(9) Potential for Energy Conservation in the Steel Industry, Lownie, H.W.,
et al., FEA, Contract CO-04-51874-00, May 30, 1975.
(10) Factors Affecting the Future of the Coal Industry in the United States,
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(11) Federal Findings on Energy for Industrial Chemicals, report from International
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(12) Challenge to U.S. Glass Manufacturers in These Energy-Critical Times,
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(13) The Reserve Base of Coal for Underground Mining in the Western United States,
Matson, T.K., and White, D.H., Information Circular 8678, Bureau of Mines,
p. 3, 1975.
(14) Cost Factors in Oxygen Production, Hugill, J.T., presented at Efficient
Use of Fuels Symposium, Institute of Gas Technology, Chicago, 111.,
December 9-13, 1974.
(15) What Does Tonnage Oxygen Cost, Katell, S., and Faber, J., Chemical Engineering.
June 29, 1959.
(16) Evaluation of Pollution Control in Fossil Fuel Conversion Processes Gasification,
Section 1; Koppers Totzek, Magees, E.M., Jahnig, C.E., Shaw, H., ESSO Research,
EPA-650/2-74-009a, January, 1974.
-------
154
(17) Oil and Gas Journal, April 7, 1975.
(18) Oil and Gas Journal. Nelson, W.L., April 14, 1958, April 21, 1958,
March 7, 1966, October 30, 1972.
(19) Oil and Gas Journal. Nelson, W.L., p. 132, March 17, 1975.
(20) U.S. Bureau of Mines Mineral Industry Surveys Crude Petroleum Petroleum Products
and Natural Gas Liquids; 1973 Final Summary, Bureau of Mines Energy
Breakdown, Table 3 reference; Table 4 reference, February 14, 1975.
(21) Oil and Gas Journal. April 2, 1973, and April 4, 1974.
(22) Mineral Industry Surveys; Crude Petroleum. Petroleum Products, and Natural
Gas Liquids, 1972 and 1973, U.S. Bureau of Mines.
(23) Oil and Gas Journal, January 24, 1972.
(24) Oil and Gas Journal. April 23, 1973.
(25) Oil and Gas Journal, Nelson, W.L., December 4, 1972.
(26) Bureau of Mines Technical Paper 560, Devine, J.M., Wilhelm, C.J., and
Schmidt, L., 1933.
(27) Materials Protection, J. Gutzeit, Vol. 7, 17, 1968.
(28) Oil and Gas Journal. Mottley, J.R., and Pfister, W.C., Vol. 61, 23, 177,
1963.
(29) Materials Performance, Tuttle, R.N., Vol. 13, 42, 1974.
(30) Corrosion, Treseder, R.S., and Swanson, T.M., Vol 24, 31, 1968.
(31) Materials Performance, Battle, J.L., et al., Vol. 9, 11, 1970.
(32) Materials Performance, Battle, J.L., et al., Vol. 14, 43, 1975.
(33) Proceedings 2nd International Congress on Metallic Corrosion, Obrecht, M0F.,
New York, 624, 1963.
(34) NKK Technical Report, Tanimura, M., Nishimura, T., and Nakazawa, T.,
Overseas, Tokyo, December, 1974.
(35) Proceedings of International Conference on SCC and Hydrogen Embrittlement
of Iron Base Alloys. Brown, A., Harrison, J.T., and Wilkins, R., Firmmey,
France, 1973.
(36) Corrosion. Samans, C.H., Vol. 20, 256, 1964.
(37) Corrosion. Ward, C.T., Mathis, D.L., and Staehle, R.W., Vol. 25, 394, 1969.
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155
(38) Stahl U. Eisen, Heischkeil, Werner, Vol. 68, 228, 1948.
(39) Proceedings 5th International Congress on Metallic Corrosion, Hewes, F.W.,
(40) Evaluation of Pollution Control in Fossil Fuel Conversion Processes
Gasification; Section 1: Lurgi Process, Shaw, H. and Magee, E.M.,
ESSO Research, EPA 650/2-74-009c (July, 1974).
(41) Industrial Boiler Design for Nitric Oxide Emissions Control. Brashears, D.F.,
Western Gas Processor and Oil Refiners Association, March 8, 1973.
(42) Analytical Studies on Kinetics of Formation of Nitrogen Oxide in Hydrocarbon-
Air Combustion, Martiney, P..I., Combustion Sci & Tech, Vol. 1, 461, 1970.
(43) Overall Reaction Rates of NO and No Formation from Fuel Nitrogen. DeSoete,
G.G., 15th International Symposium on Combustion, The Combustion Institute,
1093-1102, 1975.
(44) Influence of Combustion Modification and Fuel Nitrogen Content on Nitrogen
on Nitrogen Oxides Emission From Fuel Oil Combustion, Turner, D.W., Andrews,
R.L., Siegmund, C.W., Combustion. Vol. 44, 21-30, 1972.
(45) Conversion of Fuel Nitrogen to NO in a Compact Combustor. Hazard, H.R.,
Trans. ASME, J. Eng. Power. Vol. $6A, 185-188, 1974.
(46) Analysis of Gas, Oil, and Coal Fired Utility Boiler Test Data. Dykemh, O.W.,
and Hall, R.W., U.S. EPA, Symposium on Stationary Source Combustion, Sep-
tember 24-26, 1975.
(47) Koppers-Totzek; Take a Long Hard Look. Mitsak, D.M., and Kamody, J.E.,
Second Symposium, Coal Gasification, Liquefaction, and Utilization: Best
Prospects for Commercialization, Univ. of Pittsburgh, August, 1975.
(48) The Environmental Impact of Coal-Based Advanced Power Generating System.
Robson, F.L., Giramonti, A.J., Symposium Proceedings: Environmental Impact
of Fuel Conversion Technology, EPA-650/2-74-118, 237-257, October, 1974.
(49) Evaluation of Pollution Control in Fossil Fuel Conversion Processes; Gasi-
fication, Section 1, Lurgi Process. Shaw, H., and Magee, E.M., EPA 650/2-
74-069C, July, 1974.
(50) Low and Intermediate Btu Fuel Gas Cleanup, Colton, C.B., and Dandavati, M.S.,
EPA Symposium on Environmental Aspects of Fuel Conversion Technology II,
December 15-18, 1975.
(51) The Winkler Process. A Route to Clean Fuel From Coal. Banchik, I.N., EPA
Symposium, Environmental Aspects of Fuel Conversion Technology II, December,
1975.
(52) Progress in High Temperature Electrostatic Precipitation. Shale, C.C.,
APCA Journal. Vol. 17, 3, March, 1967.
(53)' ERDA'S Synthetic Fuels Plans. Knudsen, C.W., presented at the Industrial
Utilization of Gas From Ohio Coal Conference, Battelle Columbus Laboratories,
May 6, 1975.
-------
156
(54) Status of Synfuels Projects, September. 1975. Excerpt from Synthetic Fuels.
Vol. 12, 3, Cameron Engineers, September, 1975.
(55) Synthetic Pipeline Gas, Linden, H.R., presented to the Pacific Coast
Gas Association, San Francisco, California, September 8, 1971.
(56) United States Energy Through the Year 2000, Dupree, W.G., and West, J.A.,
U.S. Dept. of Interior, December, 1972.
-------
APPENDIX A
COMBUSTION OF LOW- AND INTERMEDIATE-ENERGY
GAS IN INDUSTRIAL PROCESSES
-------
APPENDIX A
COMBUSTION OF LOW- AND INTERMEDIATE-ENERGY
GAS IN INDUSTRIAL PROCESSES
INTRODUCTION
Moderate- and low-energy gas obtained from various gasification
processes have been suggested as substitutes for natural gas in many in-
dustries, including the two that are; the subject of this report, namely,
the secondary steel industry and the refinery industry. Problems to be
considered in making such a substitution are flame stability, fuel
cleanliness and pollution tendencies, flame heat transfer characteristics,
and overall flow rate (fan capacity). Three of these items are discussed
below; pollution problems are covered in Section VI.
Flame Stability
It should be noted that a change to moderate or low-energy gases
is the reverse direction to that made decades ago; as natural gas became
available, the use of various combustible mixtures from coal-gasification
processes were phased out. A similar more recent process occurred in
England with the development of the North Sea gas supplies. Generally
speaking, these fuel changes were accompanied by changes in types of
burners. For instance, in the residential area, the quiet, soft diffusion
flame burners in heating units were replaced by the noisier, harder, but
more compact premixed flame burners. Unfortunately, such changes have
reinforced a connotation that moderate- and low-energy gas implies large
combustor systems. Yet, the real reason is that the low burning velocity
of natural gas permits the use of premixed burners that lead to more com-
pact designs in the case of household heating applications. This example
clearly shows that each potential conversion must be analyzed in detail
in order to draw valid conclusions.
Basically, flames may be either of the premixed flame type,
wherein the fuel and air are uniformly mixed before entering the com-
bustion zone, or of the diffusion flame type, wherein the fuel and air
are separated until they reach the combustion zone. In the latter case,
however, the leading edge of the flame surface is premixed locally;
in fact, in many recent designs of burners, a small premixed region is
-------
A-2
purposely formed. Thus, the flame stability is related to premixed
flame characteristics. The flames may be either laminar, wherein
the rate of mixing (of mass, momentum, and energy) is controlled by
the molecular kinetic properties, or turbulent, wherein the rate of
mixing is controlled to a significant degree by the turbulence
characteristic of the flowing gases in the precombustion region.
Most industrial burners have turbulent flames; however, in consider-
ing the fine details of flame stability, the laminar flame character-
istics usually control the local phenomena.
Practical burners can combine features of both types of com-
bustion. For instance, many premixed burners use fuel-rich mixtures;
secondary air is added to the products of the premix flame to produce a
diffusion flame. Nozzle-mix burners (for example, a fuel jet surrounded
by multiple air jets firing into a burner tile) may show either a
diffusion flame or premixed flame, depending on where the flame is
stabilized. Thus, it is difficult to single out one feature of a com-
bustible mixture that can be considered to characterize the fuel for
comparison purposes, even if the burner is not changed in the process
of changing fuels.
If a comparative parameter must be chosen, however, the most
easily available pertinent parameter seems to be the flash-back velocity
gradient. Experimental values of this parameter are obtained by firing
a Bunsen-type burner in the open. The flow rate of the combustible mix-
ture to a laminar flame is slowly reduced until the flame flashes back.
It is found that the velocity gradient at flashback in laminar flow is
independent of duct sizes over a wide range of sizes and ambient atmos-
pheres. Values are available from one source (A-l) of information for
a wide variety of fuels, and some combination rules have been developed
for those fuel mixtures not listed (for instance, see Reference A-2).
-------
A-3
The great significance of the flash-back velocity gradient
in studies of industrial combustors is that it is related closely to
several other significant combustion parameters. For instance, the
flash-back velocity gradient is proportional to the blow-off limit in
an enclosed system, to the chemically controlled reaction rate per unit
volume, to the square of the burning velocity, and it is inversely pro-
portional to the ignition delay time mentioned by many investigators.
It also has been suggested that it is proportional to the peak frequency
(A-3)
of the combustion roar spectrum
Presentation of Flame-Stability Data.
Table A-l presents the information on the composition and higher
heating values of compositions that are considered characteristic of the
various fuels considered in this analysis. Table A-2 presents computed
values of the stability limits considered from three points of view:
(1) The usual critical flash-back velocity gradients
at stoichiometric and the maximum flash-back velocity
gradients are presented.
(2) The stoichiometric and maximum values of the heat
release rate (the product of the gradient and the
corresponding higher heating value per cubic foot
of fresh mixtures) are given.
(3) The stoichiometric and maximum value of the products
of the gradients and the corresponding higher heating
value of the fuel are tabulated.
Also included are the Wobbe Numbers (the high heating value
divided by the square root of the specific gravity) which comprise a
useful parameter in evaluating fuel changes in aspirating-type premix
burners or burners in which pressure sensitive controls are used to
regulate the relative rates of flow of fuel and air.
-------
TABLE A-l. FUEL COMPOSITION AND THERMAL PROPERTIES
Volume
Gasifier
Lurgi
Lurgi
Koppers-Totzek
Koppers-Totzek
Coke oven*-
Wellman-Galusha
Natural gas'c)
Propane'"^
Gasifying Medium
Oxygen- s t earn
Oxygen- s t eam-
stripped
Oxygen- steam
Oxy g en- steam-
stripped
Air-steam
N
1
2
2
1
4.6
50
0.6
0
co2
33
0
7
0
0.1
3
0.9
0
CO
13
20
56
61
10.6
29
0
0
Percent
H2
37
55
35
38
58.4
15
0
0
CH4
16
23
0
0
26.3
3
91.5
0
C3H8
0
0
0
0
0
0
1.3
98.6
HHV,
MJ/Nm3
12.7
18.7
11.6
12.6
19.3
6.8
42.0
99.3
Fuel
(Btu/scf)
(322)
(474)
(294)
(319)
(490)
(172)
(1066)
(2521)
Heat Release for
Stoichiometric
Mixture
MJ/Nm-;
3.4
3.8
3.7
3.7
3.7
2.9
3.8
4.0
1 (Btu/scf)
(87)
(96)
(93)
(95)
(95)
(73)
(97)
(102)
Adiabatic (a)
Flame
Temperature
K F
2104 (3328)
2320 (3717)
2041 (3214)
2232 (3358)
(a) Calculated with dissociation, at Stoichiometric ratio.
(b) Bureau Mines RI 5225, Fuel No. 43.
(c) Also contains 5.2 percent C«H,, 0.5 percent other hydrocarbons; Bureau Mines RI 5225, Fuel No. 1.
(d) Also contains 1.4 percent C0H,; Bureau Mines RI 5225, Fuel No. 3
J D
I
-t-
-------
TABLE A-2. FUEL STABILITY FACTORS
Flash-Back Velocity
Gasification Gradient, sec~l
Gasifier
Lurgi(c)
Lurgi(c)
(c)
Koppers-Totzekv '
Koppers-Totzek
Coke oven
(c)
Wellman-Galusha
Natural gas
(b)
Propane
Medium Stoichiometric
Oxygen- steam
Oxygen- steam- stripped
Oxygen- steam
Oxygen- steam- stripped
Air- steam
767
1930
2020
2660
2200
584
420
1:60
Max imum
775
1950
2640
4430
2290
650
420 .
600
Heat Release Rate,
103 MJ/Nm3-sec
(103 Btu/ft3-sec)
Gradient x HHV,
10^ MJ/Nm3-sec
(104 Btu/ft3-sec)
Stoichiometric Maximum Stoichiometric Maximum
2.6
7.2
7.4
10.0
8.0
1.7
1.6
2.1
(66)
(183)
(187)
(254)
(204)
(43)
(40)
(53)
2.6 (67)
7.4(187)
9.4( 40)
15.0(380)
8.5(2.5)
1.8 (46)
1.6 (41)
2.4 (61)
1
3
2
3
4
0
1
5
.0
.6
.5
.4
.1
.4
.7
.6
(25)
(91)
(63)
(86)
(105)
(9.7)
(44)
(142)
1.0 (25)
3.6 (92)
3.3 (84)
5.6(142)
4.3(110)
0.4 (11)
1.7 (44)
6.0(152)
Wobbe^
No.
368
769
353 '
i
404
847
187
1364
2019
(a) Higher heating value of the fuel divided by the square root of the fuel specific gravity.
(b) Flash-back velocity gradient obtained from Bureau Mines RI 5225.
(c) Flash-back velocity gradient computed using Reference A-2.
Ul
-------
A-6
The gradient values of Table A-2 are obtained from Figures A-l,
A-2, and A-3. Figure A-l presents the flash-back velocity gradients as a
function of the fuel gas concentration relative to the stoichiometric
*
value. These gradients were constructed using a modification, presented
in Reference A-2, of the techniques presented in Reference A-l and data
from the same source. Figure A-2 presents the critical value of the heat-
ing rate per unit volume, based on the fresh mixture properties. Figure
A-3 presents the curves of Figure A-l in an alternate form, each curve
being multiplied by the corresponding higher heating value for the fuel.
It is noted that the natural gas curve peaks close to stoichiometric, while
the remainder of the fuel-air mixtures peak on the fuel-rich side.
A consideration of Figures A-l and A-3 shows that natural gas
behaves much like the fuels that have the lower HHV. Other than natural
gas, the produced fuels (principally consisting of H , CO, and inerts)
line up roughly in order of the amount of inert present. Considering
Figure A-l, natural gas (with no appreciable inerts) has stability limits
lower than any of the listed fuels resulting from various coal gasification
processes.
In some uses of low- and medium-energy gas, the gas may be pre-
heated. Similarly, there are instances wherein the air is preheated. These
cases may be analyzed in a manner similar to that discussed below for the
nonpreheated cases. However, suitable stability curves similar to those
in Figures A-l, A-2, and A-3 must first be constructed.
Discussion of Flame Stability in Burners
Three general types of burners are considered in the discussion
of flame stability - pretnix burners, delayed-mixing burners, and nozzle-
mixing burners. While it is not difficult to distinguish premix burners
from the other two types, the distinction between delayed-mixing burners
and nozzle-mixing burners is sometimes rather vague. For the purpose of
this discussion, combustion in a nozzle-mixing burner will be more intense,
* Relation of fuel gas concentration relative to stoichiometric, F, to air
to fuel equivalance ration, or, is given in table of symbols, page A-32.
-------
A-7
August 26, 1975
5x10
4x10° '
3xlOJ -
Koppers-Totzek
(Stripped)
Lurgi (Stripped)
2x10
OT9~ 1.0 1.0 1.2
Gas Concentration, Fraction of Stoichiometric
FIGURE A-l. FLASH- BACK VELOCITY GRADIENT AS A FUNCTION
OF GAS CONCENTRATION IN MIXTURE
-------
August 26, 1975
A-8
o
0)
CO
CO
cd
u
4xl05
3x10
5
2x10
5
3
4J
I
i-<
o
C
S3
0)
4J
§• 4xl04
CO
105
8x10
6x12" -
3x10 &
2x10
10
Koppers-Totzek—|
(Stripped)
Lurgi (Stripped)
0.8
0.9 1.0 1.0 1.2
Gas Concentration, Fraction of Stoichiometric
FIGURE A-2.
CRITICAL HEAT RELEASE RATE PER- UNIT VOLUME
(FLASH-BACK VELOCITY GRADIENT TIMES HHV OF
MIXTURE) AS A FUNCTION OF GAS CONCENTRATION
IN MIXTURE
-------
en
4J
ffl
X
4-1
c
0)
•t-i
•o
rt
O
O
i-l
(0
O
ca
PQ
I
2x10
August 26, 1975
8x10
6x105 &
4x105 '"
3x105 •
> 2x10" -
10
8x10
6x10
4x10
,J MM^
KOPPERS-TOTZEK
(Stripped)
Lurgi (Strippea)
Koppers-Totzek
A-9
0.8 0.9 1.0 1.1 1.2
Gas Concentration, Fraction of Stoichiometric
FIGURE A-3.
FLASH-BACK VELOCITY GRADIENT TIMES GAS
HIGHER HEATING VALUE (HHV) AS A FUNCTION
OF GAS CONCENTRATION IN MIXTURE
-------
A-10
with at least a significant fraction of the combustion taking place within
or close to the burner tile. Delayed-mixing flames will generally extend a
considerable distance from the burner and often be characterized by a low
turbulence level and mixing rate. Significant amounts of furnace gases
might be recirculated into the base of their flames. To complicate the
problem further, some premixing is often used in delayed mixing and
nozzle-mixing burners to aid in producing a stable ignition region for
the flame.
jf
Premix Burners. Premixed flames are reasonably common in industry
and are the easiest to analyze. The premixed fuel and air are usually
supplied to the region from an inspirator or Venturi mixer, an aspirator
or suetion-type mixer, or a fan mixer. The burner may be a small port
or ported manifold type, a large port (or pressure type), a tunnel burner,
or a flame-retention type pressure burner. For high firing rates with
turbulent flow, the flame will not hold at the end of the duct. Therefore,
a variety of flame-holding systems are used. Figure A-4 is an example
of the flame-retention type burner, in which some of the combustible mix-
ture is slowed down and diverted into an annular combustion region. The
flame in the protected annular region acts as a pilot to maintain or hold
the main flame. In closed systems (such as tunnel burners), steps, recesses,
grids, and other obstacles are often used to hold the flame. These form
protected recirculation zones, which hold the flame and from which the
flame spreads.
In all of these cases, the key factor is a term proportional to
**
the velocity gradient at flashback. As a simple example, consider a closed
*
"Usually, a burner applied with gas and air which has previously been
mixed, but sometimes a burner within which the gas and air are mixed, ..
before they reach the nozzle (as opposed to nozzle-mixing burners)."
** Often, in the case of flame holding by obstacles, an explanation of
performance based on the concept of a delay time is advanced; this
delay time is proportional to the reciprocal of the flash-back
gradient.
-------
A-ll
M —
IS1
AIR &
GAS
FIGURE A-4.
PREMIX BURNER, FLAME
RETENIION TYPE
-------
A-12
system where the blow-off velocity gradient, G, , is, say B times the
*V*
flash-back velocity gradient, G .' For turbulent systems, the gradient
is usually given merely in the form of U/D--the average flow velocity, U,
divided by a characteristic diameter, D. Then, U, = B U^, ~ DG,., . Now,
if the critical velocity gradient is doubled by a change in fuel, then
both the blow-off and flash-back velocities will double. In many burners,
the equivalent of single or multiple steps are used, so that on premature
flash back the characteristic diameter is decreased as the flame moves
upstream; this decreases the critical flash-back velocity at the same
time as the flow velocity increases, thus stopping the flash back. For
such a design, increasing the critical value of G will increase the range
of flow rates for stable flames, but not necessarily the heating rate,
as will be shown.
A constant heating rate system will now be considered with a
change in fuel. Considering a single burner with a volume flow rate of
combustible mixtures, Q, and a heating value per unit volume of mixture,
H , the heat release rate will be QH . When the critical blow-off condi-
m m 23
tion is reached, the heat release rate is given by QH ~ UD H ~ D GH .
m m m
For a single size of burner, the key term for comparison is GH . The
relative values of this term are plotted on Figure A-2. It is seen that,
on the basis of the heat release rate at blow-off, natural gas and Wellman-
Galusha gas are about the same on the excess air side and all other gases
shown here are more stable against blow-off. On the other hand, these gases
are more prone to flash back, and their use could result in a significant
decrease in turn-down ratio.
**
If the fan power is limited, the change from, say, natural gas
to low energy gas may be complicated by this power limit. The air power
*3 /
is given by QAp, which varies with pQ /D . Assuming a constant heat release
rate, that is, if QH is constant, and that dynamic (rather than viscous)
/ o
pressure losses are controlling, the air power varies with p/D H . For
m
<
A list of symbols used in this section is presented on page A-32.
** Similar results are obtained if fan pressure is considered to be
controlling.
-------
A-13
a stoichiometric mixture in the air., p does not vary appreciably in cotn-
3
parison to H . Thus, the relative values of H are of great importance.
It is seen from Table A-l that the values vary from 102 for propane to 73
for gas from Wellman-Galusha gasifier. The stripped Lurgi, the unstripped,
and the stripped Koppers-Totzek, and the coke oven gas are directly
interchangeable with natural gas on this basis. We note that, if D is
increased to compensate for the lower value of H of the Wellman-Galusha
m
gas, flashback will be encouraged. (This is the reason that in shifting
to a medium- or low-energy gas from natural gas, there is a tendency to
shift to nozzle-mixing or delayed-mixing burners).
If the number of burners (or the number of elements in some
243
burner designs^ can be changed, then the constant term is p/N D H
(again assuming dynamic pressure losses^. Assuming that burner designs
for comparative fuels are to be limited by the critical velocity gradient,
4/3 2/3 5/3
then the constant term is PG /N H It is seen that the number of
burners (or number of ports') must be increased in changing to the'moderate
or low energy gas from natural gas to avoid flashback while at the same
2 -3/2
time the total area of the burners (ND ) must vary with (H ^ . Thus,
m
if N is about 1 for natural gas, then N would be about 25 to 30 for moderate
energy gases and abcmi- ^ t-n 6 for low-energy gases.
Although the volume of products is not exactly proportional to
the volume of fresh mixture, it is close enough that the term p/D H can
m
be considered also as a measure of flow power loss through a furnace and
stack. Thus, again, while several of the gases, as listed above, are
interchangeable with natural gas, Wellman-Galusha gas will require more
than twice the pressure compared to natural gas to move the products of
combustion through a furnace. In a boiler-type furnace, the higher
velocities associated with a change to low heating value gas would re-
sult in a higher heat fluxes initially and possibly excessive cooling
of the products of combustion in the latter part. In a furnace using
direct heat conduction to a material, this could be an advantage.
The Wobbe Number, which is the ratio of the higher heating
value of a fuel to the square root of the specific gravity of the fuel,
is the common measure of interchangeability in simple combustion units
with a fixed firing rate, where (a) fuel is used to aspirate air
-------
A-14
(inspirator or Venturi-type unit), (b) air is used to aspirate fuel
(aspirator or suction type), or (c) a pressure-type control is used to
control the ratio of the fuel gas and air. The reasoning that leads to
the Wobbe Number is as follows.
Consider a unit in which the fuel is used to aspirate the air.
In this combustion unit of fixed configuration, with, say, a constant
2
pressure drop on the fuel spuds, PfQf is a constant. For the heat re-
lease rate to be constant, QfH,- is also constant, and it follows that
2
H /p is a constant. Normalizing the fuel density to specific gravity
and taking the square root results in the Wobbe Number. Therefore, if
the Wobbe Number changes, the firing rate of this simple type of unit
changes with change in fuel unless spud size or supply pressure is
changed.
But this is not the entire story. In a combustion unit of
fixed configuration, with any of the types of interconnections between
fuel and air mentioned above, the ratio of momentum flux of the fuel to
2 2
air remains constant. Thus, P/}-: /P Q is a constant. If a denotes
I JL 3, cl
the air/fuel ratio relative to stoichiometric air/fuel ratio and H is
a
the heating value of air, Q H = Q..H /a. By substitution, it follows that
-L /2 a a t t
LH,/(p-/p ) ]/(aH ) is a constant. As the heating value of the air
£ r. a a
that is used in burning any hydrocarbon fuel does not vary greatly, a
change in Wobbe Number also results in a change of excess air in the com-
bustor if no other change is made. It is often assumed that a change in
Wobbe Number of more than 5 percent requires a change in spud size.
From Table A-2, it is clear that any change from natural gas
to one of the other fuels will necessitate a change in spuds or re-
adjustment of the control system in some manner.
-------
A-15
•i.
Delayed-Mixing Burners . Turbulent mixing is usually considered
as the rate controlling factor in turbulent diffusion flames of industrial
importance. The chemically limited reaction rate, which is far greater
than the gross reaction rate of the furnace, is not considered to be con-
trolling or even important, other than through its effect on flame stability.
However, the effect of turbulence itself is not well understood in complex
flow systems, and additional complications arise from the presence of a
flame that adds a random set of volume sources as the gases expand by heat
from random pockets of combustion.
Nonturbulent and turbulent diffusion flames have one feature in
common: the flames must be held at some point, line, or area. In a non-
turbulent flame, the adjacent fuel and air interdiffuse over the end of the
partition separating the two gases. At some distance downstream of the
partition, a combustible mixture of varying composition is reached over
a region greater than the laminar flame thickness. In this region, at
a distance equal to or greater than the quenching distance, a premixed
flame develops and holds (or "seats") the diffusion flame. In fact, the
diffusion flame may be pictured as a stepwise series of premixed flames,
each with hotter but more dilute initial composition.
In a turbulent flame, a firm seating of the flame often does
not occur (unless provision for a little local premixing has been properly
built into the burner). One notes that local cells of the fuel and air
are of different compositions, temperature, and velocities and have different
**
molecular and thermal dilutions as they approach the reaction zone. Thus,
there are only local regions where the maximum turbulent flame speed can
* Delayed-mixing burners are those "in which the fuel and air leave
the burner nozzle unmixed and thereafter mix relatively slowly*
largely through diffusion. This results in a long luminous flame
called a diffusion flame, luminous flame, or long flame." ^A~^
** This variation from the average of local time and space concentrations
is known as the unmixedness of the fluid.
-------
A-16
exceed the velocity of the oncoming fuel-air mixture. Therefore, the
flame-holding points shift about in space as the local low-velocity
regions shift about in the turbulent stream. Furthermore, all of the
leading edges of the flame must move at close to the maximum premixed
flame speed through the turbulent mixture, stretching and spreading the
#
flame. When the flame no longer contains enough local regions where it
can "buck" the oncoming stream and not be extinguished, it will blow off
unless held by some independent energy source.
It thus appears that the critical stability parameter in an
enclosed turbulent diffusion flame will be related to the maximum flash-
back velocity gradient rather than the velocity gradient specific to the
average mixture ratio.
Figure A-5 shows typical delayed mixing burners that will re-
sult in a long luminous flame. Figure A-5a is a version in which the
fuel and air velocities are similar and the flow streams are paralled.
Increase of the cross-flow gas at the Venturi throat results in a decrease
in flame length and luminosity. Natural gas and low Btu gases are inter-
changeable in this burner with change in gas pressure. We note that a
pilot flame is incorporated for ignition and/or piloting of the diffusion
flame. The pilot flames are usually premix or nozzle-mix flames. There-
fore, if the stability of the diffusion flame depends on the pilot flame,
then the stability conditions of the pilot flame are of prime importance.
However, even with a pilot flame, the diffusion flame may not be suffi-
ciently held so that a satisfactory flame results. Thus, the stability
characteristic of the diffusion flame must also be considered. On the
other hand, the pilot flame is not normally subject to a necessity for
a turn-down capacity. Current practice in design of burner, for safety
* (A-5)
Otsuka and Niioka suggest that, in cases where the flame is
being rapidly stretched as would be the case in a turbulent flame
front, the flame forms in the maximum temperature region rather
than the stoichiometric region often assumed in the literature.
-------
A-17
PILOT TIP
AIR
GAS
(b)
FIGURE A-5. DELAYED MIXING BURNERS
-------
A-18
reasons, is to insure satisfactory flame performance without a pilot flame.
It is noted that the protective effect of the short tile of this burner
helps insure satisfactory holding of the flame.
Figure A-5b shows a delayed mixing burner in which the fuel re-
mains in a high-velocity, coherent jet for a considerable distance, surrounded
by a low-velocity air mantle. The flame is piloted through the effect of
the recirculation and mixing annular region surrounding the fuel jet.
In neither of the burners is there any problem of flashback.
Thus, only the possibility of blowing off the flame need be considered
in comparing performance with various fuels. Considering the fuels in
Table A-l, it is seen from the values for the maximum flash-back velocity
gradient in Table A-2 that natural gas is the most unstable of the tabulated
fuels. For medium energy fuels, the combustion systems are much more stable.
However, this argument does not take into account the necessary change in
fuel flow rate with low energy fuels if the burner remains unchanged.
Figure A-5b may be considered as just a simple diffusion flame
of the Bunsen burner type, with only fuel in the central jet. With a
change in fuel, the maximum diameter of the flame increases as the stoichio-
*
metric air/fuel ratio increases. For turbulent flames at a constant heat
input rate, the length of flame changes little. For a constant shape of
burner and considering a constant heat input rate and a low velocity of the
air in relation to the fuel jet, the holding point of the flame will be
determined roughly by the product of the higher heating values and the
maximum flash-back velocity gradient. Figure A-3 (and Table A-2) present
the values of this point for the various fuels considered. It is seen
that the order of fuels has changed from those noted in the previous dis-
cussion. Propane, stripped Koppers-Totzek gas and coke-oven gas are the
most stable fuels, but natural gas is now above unstripped Lurgi and
Wellman-Galusha gases. When the fuel velocity is higher than the average
*
While the aspiration rate of the fuel jet cannot be significantly altered,
care is usually taken to eliminate as much swirl and turbulence from the
air flow as possible to keep from increasing the mixing rate unnecessarily.
-------
A-19
air velocity, the movement of the combustible interface outward with in-
creasing value of the stoichiometric air/fuel ratio also improves the
stability of natural gas relative to the remainder of the fuels.
This is not the entire story, however. For most delayed mixing
burners, such as shown in Figure A-5a, the fuel and air velocities are
*l.
about the same to inhibit premature mixing. Therefore, stability of the
flame, if the flame is held within the tile, is governed by whichever
velocity is controlling--the fuel velocity or the air velocity, or a
combination thereof—in the exact region of holding. Furthermore, if
changes in fuel are made without concomitant changes in burner dimensions,
the relative values of fuel and air velocity will change, and the significant
control point may change. The flame may find a stable region or attachment
around the annular air jet, rather than the fuel jet. In this case, the
flames stabilize closer to the air jet as the air/fuel volume ratio at
stoichiometric decreases. Furthermore, and more important, the air velocity
does not change much with fuel at a constant heat input rate. In this case,
the curves of Figure A-l should be considered for stability.
If the flame does not stabilize close to the inlets in either
position, then the slow mixing can result in other diffusion flames start-
ing beyond the tile in the region where recirculating gases will slow the
flow velocity and dilute the air annulus.
When these burners are used in radiant tubes, it is often desirable
to have the heat flux peak near the burner and hold at that value or fall
off gradually, rather than increase slowly to a peak value some distance
down the tube. To accomplish this, a small amount of air may be bled into
the fuel jet (or vice versa) so that the boundary of the fuel jet as it
emerges from the fuel tube is a combustible mixture. This portion of the
boundary burns as a premixed flame, both boosting the heat flux to the wall
near the inlet and serving as a pilot for the downstream diffusion flame.
However, because of the diffusion effects, there is still a composition
gradient, and the stability even in this case should probably be treated
as one would a diffusion flame stability problem.
*
These are sometimes called laminar flow burners, but this does not
denote viscous flow (Reynold's numbers are still high). Rather, it
denotes flow without high intensity turbulence in the interface.
-------
A-20
The pressure drops that are involved in supplying the fuel are
now considered briefly. As may be deduced from the discussion of the
Wobbe Number, in connection with premix flames for a pair of fuels in
which this number does not vary too much, the fuels are interchangeable
in diffusion-flame applications as well as premix-flame applications.
It is seen from Table A-2 that the medium energy gases are the closest to
natural gas, but are far from being within the 5 percent variation usually
allowed. Furthermore, a massive addition of propane, about 32 percent by
volume for the Koppers-Totzek unstrippable gas, would be required to boost
the values sufficiently to bring them within range. But it is noted that
the energy values of the stoichiometric mixtures are about the same for
these fuels as for natural gas, so that changes only in the burner or
control settings would be required to obtain satisfactory operation of
a burner system.
Interestingly, increasing the orifice sizes for the medium
energy gas sufficiently to maintain the same stoichiometry percent results
in a decrease in gas pressure while maintaining a constant heat release
rate. Changing the orifice size a lesser amount so as to maintain the back
pressure on the fuel, and maintaining a constant heat release rate results
in an increase in the excess air using fuel aspiration. This, of course,
may be handled by an additional adjustment.
One can conclude, therefore, that in replacing natural gas in a
diffusion flame with medium energy manufactured gas, no stability problems
will be encountered. In confirmation of this, one may note that burner
manufacturers often indicate these burners can be used with both natural
gas and coke-oven gas. However, there can be a stability problem with
lower energy fuels if some changes in burners are not made. For extreme
cases, the burner and type of flame may have to be changed.
-------
A-21
*
Nozzle-Mix Burners. Nozzle-mix burners combine the advantage
of the relatively short flame of the premix burner and the lack of flash-
back problems of the diffusion flame. The short flames are obtained by
three different methods. Figure A-6a shows the use of multiple high-
velocity air jets parallel with the fuel jet. The air jets aspirate the
fuel in around them and form short flames because of the small jet diameter
i-if
and potential core length. Figure A-6b shows the use of nonparallel jets.
These may impinge, may interlace (with multiple fuel jets as well as air
jets), or may be canted to produce a swirl flame and even a heavy recircu-
lation zone on the burner axis. If a disk is added to the end of the
fuel jet in Figure A-5b, a high velocity air flow and a recirculation zone
are formed which lead to an intense mixing. The burner in Figure A-5b then
becomes a nozzle-mix burner. Some of the fuel in this case may be diverted
radially to improve mixing further. In all these cases, the internally
recirculating hot gases plus the hot ceramic tile wall provides good flame
j^y*.^
stability.
If the flame is held as a diffusion flame in a nozzle mix burner,
then the flame might either be held around the central fuel jet or the
peripheral jets. The argument here is exactly the same as for the delayed
mixing burners. The main difference is that, when the flame is not attached
close to the inlet of either the fuel or air, rapid mixing may take place
before a stable region for the flame to seat is encountered. In this case,
the action of the flame is much like a premix burner.
Therefore, it is concluded that in changing from natural gas to
moderate or lower energy fuel in a nozzle mixing burner, the position of
the flame base may change from around the fuel jet to around air jets,
or vice versa, depending on relative flow velocities and change in laminar
flame speed. Therefore, an unqualified comparison of stability cannot be
made. As a result, it is not clear whether a flame might satisfactorily
contain itself within a nozzle-mixing burner tile with a specific change
in fuel. Again, as for the delayed-mixing burners, it should be noted that
several designs are specified by the manufacturers as operating with either
natural gas or coke oven gas.
* "A burner in which fuel and air are not mixed until just as they leave the
burner port, after which mixing is usually very rapid. The flame cannot
flash back to this type of burner". A-4.
** On occasion, the role of the fuels and air jets are reversed.
*** Care must be taken to prevent aspiration of cold furnace gases both into
the tile and the flame base.
-------
A-22
GAS
/-
AIR
GAS
AIR
(a)
(b)
FIGURE A-6. NOZZLE-MIXING BURNERS
-------
A-23
Flame Radiation
The effect of change in fuel on radiation output will now be
considered. It is obvious that heat is also transferred by convection
to work surfaces, and to boiler tubes. As a result, if less heat is trans-
ferred by radiation, more heat may be transferred by convection, with a
resulting decrease in the overall effect of the change. In furnaces where
large amounts of recirculating gas are present, the buffering effect is
increased further. Since much of the radiation will come from gases cooled
from their maximum temperature, differences in radiation will be reduced
by this effect as the gases loose heat. Particulate radiation is ignored
in this treatment, first, because there should be a little particulate in
the clean gases considered, and second, because no way of estimating an
expected concentration is available.
Figure A-7 is generated from Figures 6.9, 6.11, 6.12, and 6.13
of Reference A-6, using product composition and temperature for adiabatic
burning with 10 percent excess air of certain of the fuel gases listed in
Table A-l (unstripped). It is interesting to note the high radiating
ability of the natural gas flame, for flames more than about one foot
thick. Ultimately, of course, all the curves must flatten out at great
thickness as they cannot radiate in excess of the black-body temperature
of the particular composition. It is also noted that only the K-T gas
exceeds the natural gas in radiation, although the Lurgi gas is not too much
lower. Stripping of the CO, from the Lurgi gas would raise the products
temperature and probably bring all three curves close together. The product
gases of air-blown gas producers are highly diluted with nitrogen, and as
a result, the flame is cooled and the radiation is decreased, as seen from
comparing the Wellman-Galusha curve and the Winkler curve with the natural
gas curve .
A curve is also shown for the effect of air preheat on the radia-
tion output, for the Winkler gas. It is seen that the radiation output is
increased, but far less than enough to bring the gas up to that of natural
gas.
-------
A-24
200
100
CO
<
10
•H
W
W
Koppers Totzek Gas
Natural Gas
Lurgi (62 blown)
- Wellman Galusha (air blown)
Winkler (air blown)
Winkler(air blown)*
"O.I 0.2 0.4 0.6 Q8 I 2 4 6 8 10
Flame Thickness, ft
20 40
FIGURE A-7. RADIATION FROM ADIABATIC FLAMES
AT 10 PERCENT EXCESS AIR
-------
A-25
Some feel for the magnitude of the effects resulting from the
various changes in the fuel products can be obtained from a consideration
of Figures 6-14 of Reference A-6, which is a simplified emissivity chart
for CCL-lLjO mixtures in a restricted temperature range. A temperature-
emissivity product is plotted as a. narrow band of curves covering a range
of ratios of partial pressure of H.,,0 to CO-, against the flame thickness
times the sum of the CCL and ILO pressures. As an example, radiation from
the product gases from stoichiometric combustion of the natural gas and
Winkler gas are compared.
The slightly greater amount of (CC>2 + ikO) for the natural gas
leads to about 2 percent greater temperature-emissivity product for natural
gas, while the change in ILO/CCL ratio is from 1.90 to 0.41 leads to about
10 percent greater temperature-emissivity product for the natural gas flame
(actual amount increases with flame thickness). The absolute temperature
ratio of the natural gas to Winkler gas is about 1.14. Thus, even though
one temperature term is already in the temperature-emissivity product, there
is a further 50 percent increase of natural gas radiation compared to Winkler
gas. Thus, the gas temperature itself has the largest effect. As mentioned
before, convection heat transfer effects.gas cooling from heat losses, and
any soot radiation effects will reduce the significance of these differences,
but the differences will still be sufficiently large so that they must be
evaluated.
Another aspect of radiation is that associated with flame de-
tection and safety considerations. From the above discussion, it is clear
that the performance of any radiation activated controls on a furnace must
be considered, if the fuel is changed.
-------
A-26
Flow Considerations
There are three different comparisons that might be made relative
to flow rate when low or intermediate heating value gas is substituted for
natural gas. On the basis of equal heat inputs, the direct substitution of
one fuel for another in the fuel lines can be compared. Assuming stoichio-
metric mixture, the flows of premixed fuel and air can be compared and the
product flows can be compared. Table A-3 presents these comparisons, relative
to natural gas, for the three replacement gases of immediate interest to
the project. Both relative flow velocities, and more important, relative
pressure drops (assuming turbulent flow) are given.
If the same fuel lines are used, typical intermediate energy gas
from oxygen-blown producers must be delivered to the point of application
at 3 to 4 times the flow rate of natural gas to achieve the same heat input.
The low energy fuels from air-blown producers require anywhere from 6 to 9
(for Winkler gas, not listed) times the flow of natural gas. The differences
in the flow rates of the stoichiometric mixtures are less pronounced than
those for the fuel, since the "heating value" of air is about constant.
Because of the collapse effect of burning CO or H , as compared to hydro-
carbons, the product gases may have a lesser volume at standard conditions
than the raw mixture. As a result, the product flow rate for K-T gas
actually is lower than for natural gas. For the low energy gas from an
air-blown producer the increase is less than 20 percent. The corresponding
relative increase in pressure drop for the various fuels that would result
if the same fuel and flue gas equipment is used is also shown. For inter-
mediate energy fuels about 10 to 15 times the pressure drop would be in-
curred through existing distribution mains and burners; there is between
a negative 20 percent and positive 10 percent change in pressure drop through
heat exchangers and other gas passages downstream of the combustion zone.
For the low energy fuels, however, pressure drops of over 50 times that for
natural gas would be expected in existing mains and burners; corresponding
pressure drops in passages downstream of the combustion zone would show a
50 percent or more increase relative to natural gas.
-------
A-27
The increased flow rates and pressure drops in fuel supply systems,
burners, heat exchangers, and exhsiust flues that could be encountered in
retrofitting a process from the use of natural gas to low or intermediate
energy gas while maintaining the s:ame process heat input could pose a
serious problem. Supplying the necessary increased fuel supply rates to
various processes throughout an industrial plant will require either
pressurized distribution mains, larger distribution mains, or some com-
bination of the two. Pressurized mains would complicate the problem of
potential leakage of a toxic carbon monoxide-laden gas into working areas.
Increasing the size of distribution systems to handle the increased flow
at lower pressures could create problems for processes widely dispersed
throughout the plant or in the areas where space is at a premium. Only
one of the three gasification systems considered commercial in this study--
i.e., the Lurgi process—delivers the fuel gas under pressure (300 to 500
2
psig, 2070 to 3430/m ). Fuel gas from the other two processes would have
to be compressed, either before or after the gas cleanup stage ,for pressurized
distribution.
The increased flows and pressure drops occurring downstream of
the combustion zone with certain of the substitute gases, though less
than those in fuel supply systems, can potentially be a more serious problem.
Induced draft and forced draft fans would have to be boosted to higher
operating pressures to compensate for higher flow rates. In some cases
it may be possible to reduce the pressure drop through the process, such
as by removing tubes in boiler heat exchangers, to allow greater volumes
of flow at lower pressure drops without upsetting the heat transfer
characteristics of the process.
If changes in the process cannot be made to compensate for in-
creased flows and pressure drops, process derating may be necessary. This
problem could be more severe for handling the increased volumes of flue
gases than for handling of increased volumes of fuel. Analysis of Table
A-3 reveals that inability to handle additional flue gas volume could result
in a derating of up to 5 percent for intermediate energy (300 Btu/scf;
3
2664 Kcal/m ) gas or up to 25 percent for low energy gas (150 Btu/scf;
1332 Kcal/m3).
-------
TABLE A-3. COMPARISON OF VOLUMES OF FUEL GAS TO NATURAL GAS
Process
Lurgi
Kopp e r s -To t z ek
Wellman-Galusha
Natural Gas
HHV,
Fuel
Gasifying Medium Only
Oxygen-steam 12.7
(322)
Oxygen-steam 11.6
(294)
Air-steam 6.8
(172)
42.0
(1066)
Relative Flow Rates
MJ/Nm . (Btu/scf) Fuel Gas /Natural Gas
Stoichiometric Stoichiometric
Raw Mixture Fuel Raw Mixture Products
3.4 (87) 3.31 1.11 1.03
3.7 (93) 3.63 1.04 .885
2.9 (94) 6.20 1.31 1.18
3.8 (97) 1.0 i.o 1.0
Relative Pressure Drop
Fuel Gas/Natural Gas
Stoichiometric
Fuel Raw Mixture Products
13.5 1.19 1.11
14.9 1.01 .806
52.7 1.66 L49
1.0 i.o 1.0
r
ho
00
-------
A-29
Alterations necessary in burner designs are uncertain without
laboratory data on which to base the redesign. Burners that at one time
were used for low energy gas are not readily available today as production
items. Further, the old designs would no longer be acceptable in most
cases, as advances in burner and process technology have resulted in burners
with generally wider stability ranges, intermittent instead of continuous
piloting, and sophisticated combustion monitoring and control. This aspect
of the problem is discussed in a subsequent section.
It is generally felt that adequate industrial burners can be
developed for intermediate and most low energy gases. Generally, flow
areas in fuel supply lines and burner parts would have to be increased to
handle the increased fuel flows necessary to maintain the same energy input
as with natural gas or oil. Overall burner diameters or tile diameters
probably would not be increased in most cases, however, minimizing the
amount of modification necessary in the walls of the furnace.
Larger general-purpose burners should be easiest to retrofit to
low or intermediate energy gas. However, the performance of some specialty
types of burners may be difficult to duplicate. These include high-
intensity or high-velocity burners., burners where particular flame shapes
are necessary and applications requiring carefully controlled mixing and
combustion rates.
-------
A-30
REFERENCES
(A-l) Grumer, J., Harris, M. E., and Rowe, V. R., Fundamental Flashback,
Blowoff, and Yellow Tip Limits of Fuel Gas-Air Mixtures, U.S.
Bureau of Mines, RI 5225, 1956.
(A-2) Putnam, A. A., "Effect of Recirculated Products on Burning
Velocity and Critical Velocity Gradient", Combustion and Flame,
22, 277-279 (1974).
(A-3) Giammar, R. D., and Putnam, A. A., "Combustion Roar of Turbulent
Diffusion Flames", Trans. J. Engineering for Power, 92A,
157-165 (1970).
(A-4) North American Combustion Handbook, The North American Manu-
facturing Company, 1952
(A-5) Otsuka, Y., and Niioka, T., "The One-Dimensional Diffusion Flame
in a Two-Dimensional Counter Flow Burner. Combustion and Flame,
"21, 163-176, (1973).
(A-6) Hottel, H. C. , and Sarofim, A. F., Radiative Transfer, McGraw-Hill
Book Company, 1967, Figures 6-14.
-------
A-31
LIST OF SYMBOLS
D Characteristic burner diameter
F Gas concentration, fraction of stoichiometric
Gfb Critical flash back velocity gradient, calculated from data of
Reference A-l by Reference A-Z modification of Reference A-l
techniques
G, Blow off velocity gradient
bo
S Mole fraction of fuel in a stoichiometric mixture
U Average flow velocity through the burner
^fb Average flow velocity at flash back, proportion to EG^
Ufc0 Average flow velocity at blow off, proportional to DG^
Q Volume flow rate of combustible mixture
Qf Fuel flow rate
Q- Air flow rate
ci
HJJJ Heating value per unit volume of combustible mixture
H_ Heating value per unit volume of fuel
H Heating value per unit volume of air
N Number of burners
AP Pressure drop across burner
a Air/fuel ratio relative to stoichiometric air/fuel ratio; =
(1 - FS)/F(1-S)
0 Density of combustible mixture
p Fuel density
0 Air density
3
B Ratio of blow-off to flash-back velocity gradient
-------
APPENDIX B
MATERIAL AND ENERGY BALANCES
FOR MODEL PLANTS
-------
Oxygen
Air
Saturated
steam
To
pulverizer
Waste heat
recovery
water f\\
Raw
gas
cooler
MDEA sulfur
removal
CoaK Coal
storage pulverizer
Claus
plant
Cooling
tower
Clean gas
Vent
stream
Sulfur
a
i
Make up
FIGURE B-l. KOPPERS/MDEA GASIFICATION PLANT MATERIAL BALANCE FOR MODEL STEEL PLANT
-------
TABLE B-l. KOPPERS/MDEA GASIFICATION PLANT MATERIAL BALANCE FOR MODEL STEEL PLANT
(Metric and English Units)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2S
COS
H20
°2
so2
TOTAL
Coal
Metric
Kg/hr
34915.7
2356.9
352.0
898.1
7186.7
36.3
7079.7
--
-_
__
--
19045.4
--
--
1
as Received
Unit
wt7o
48.58
3.28
0.49
1.25
10.00
0.05
9.85
--
_ _
__
--
26.50
--
--
Kg/hr 71870.8
NM3/hr
Temperature
Pressure
Kl/hr
C
atm
--
__
--
English Unit
Ib/hr
76976
5196
776
1980
15844
80
15608
--
~ ~
__
--
41988
--
--
Ib/hr
SCFM
GPM
F
PSIG
wt%
48.58
3.28
0.49
1.25
10.00
0.05
9.85
--
— *™
__
__
26.50
--
--
158448
--
--
--
2
Coal to Gasifier
Metric
Kg/hr
34915.7
2356.9
352.0
898.1
7186.7
36.3
7079.7
—
_.
__
--
2200.8
--
--
Kg/hr
NM3/hr
Kl/hr
C
atm
Unit
wt7o
63.45
4.28
0.64
1.63
13.06
0.07
12.87
--
-_
__
--
4.00
--
--
55026.2
--
71
--
English
Ib/hr
76976
5196
776
1980
15844
80
15608
--
_ _
__
_-
4852
--
--
Ib/hr
SCFM
GPM
F
PSIG
Unit
wt7o
63.45
4.28
0.64
1.63
13.06
0.07
12.87
--
__
__
--
4.00
--
--
121312
--
160
--
3
Steam to Gasifier
Metric Unit English Unit
Kg/hr Mol.70 Ib/hr Mol.7»
_.
__
--
--
--
--
__
__
• •• •••• ^ ^ ^ ^
__ __ -_ __
--
11807.9 100.00 26032 100.00
--
-- — -- --
Kg/hr 11807.9 Ib/hr 26032
NM3/hr -- SCFM
Kl/hr -- GPM
C 121 F 250
atm 2 PSIG 15
-------
TABLE B-l. (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
H2S
COS
H2°
°2
so2
TOTAL
Temperature
Pressure
4
Oxygen to
Metric Unit
Kg/hr Mol.%
__
..
__
__
__
__
__
—
—
731.2 2.00
__
_-
40930.4 98.00
Kg/hr 41661.6
NM3/hr 30885
Kl/hr
C 110
atm 2
Gasifier
English Unit
Ib/hr Mol.%
__
__
__
--
__
--
--
—
__
1612 2.00
—
__
90236 98.00
Ib/hr 91848
SCFM 18176
GPM
F 230
PSIG 15
5
BFW to Gasifier Jackets
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
__
__
__
__
__
__
._
—
__
__ __ -- --
__
__
14908.7 100.00 32868 100.00
Kg/hr 14908.7 Ib/hr 32868
NM3/hr -- SCFM
Kl/hr 14.93 GPM 66
C 110 F 230
atm — PSIG
Steam
Metric
Kg/hr
--
—
--
--
--
--
--
—
--
__
__
--
14197.4
Kg/hr
NM3/hr
Kl/hr
C
atm
6
from Gasifier Jackets
Unit English
Unit
Mol.% Ib/hr Mol.%
--
--
__
__
__
__
__
__
__
__ __
__
_-
100.00 31300
14197.4 Ib/hr
SCFM
GPM
135 F
3 PSIG
--
--
--
--
--
--
--
--
--
—
--
--
100.00
31300
275
30
(j
-------
TABLE B-l.(Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
N2
COS
H20
°2
so2
TOTAL
Temperature
Pressure
7
Spray Cooling Water
Metric Unit
Kg/hr Mol.%
__
__
__
__
__
__
__
__
— — — -
_.
__
16456.3 100.0
Kg/hr 16456.3
NM3/hr
Kl/hr 16.48
C 29
atm
English Unit
Ib/hr Mol.%
__
__
__
__
«_
__
_-
— - --
__
--
36280 100.00
Ib/hr 36280
SCFM
GPM 72
F 85
PSIG
8
BFW to WH Boiler
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
__
--
--
--
__
—
--
--
_- __ __ __
—
_.
79855.8 100.00 176052 100.00
Kg/hr 79855.8 Ib/hr 176052
NM3/hr -- SCFM
Kl/hr 79.96 GPM 352
C 110 F 230
atm -- PSIG
9
Steam from WH Boiler
Metric Unit English Unit
Kg.hr Mol.% Ib/hr Mol.%
__
__
.
--
__
__
--
--
— — — ~ -— — —
--
__
76047.5 100.00 167668 100.00
Kg/hr 76052.9 Ib/hr 167668
NM3/hr -- SCFM
Kl/hr -- GPM
C 262 F 503
atm 47.6 PSIG 685
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
CO,
H2
N2
H2S
COS
H20
02
so2
TOTAL
Raw
Metric
Kg/hr
1745.4
..
--
--
--
--
3539.8
£. C. It O
U J / JLi.
18301.5
2643.5
1083.2
845.5
108.9
27397
.-
—
10
Gas to Scrubber
Unit
Mol.7o
--
--
--
--
--
--
--
41.44
7.35
23.17
0.68
0.46
0.034
26.86
--
--
Kg/hr 121377.6
NM3/hr 133951
Temperature
Pressure
Kl/hr
C
atm
--
177
1.47
English
Ib/hr
3848
--
--
--
—
--
7804
144872
40348
5828
2388
1864
240
60400
--
--
Ib/hr
SCFM
GPM
F
PSIG
Unit
Mol.7o
--
--
--
--
--
--
--
41.44
7.35
23.17
0.68
0.46
0.034
26.86
--
--
263052
78832
--
350
6.Q
11
Gas to Gas
Metric
Kg/hr
--
--
--
--
--
—
--
65712.8
18301.5
2643.5
1083.2
845.5
108.9
30622
--
--
Kg/hr
NM3/hr
Kl/hr
C
atm
Unit
Mol.7o
--
— '
--
--
--
--
--
40.18
7.12
22.47
0.65
0.44
0.032
29.1
--
—
119318.3
138140
--
77
1.40
Cooler
English
Ib/hr
--
--
--
--
--
--
--
1 /. 1. 0 TO
iH-H-O If.
40348
5828
2388
1864
240
67512
--
—
Ib/hr
SCFM
GPM
F
PSIG
Unit
Mol.7o
--
--
--
--
--
--
--
40.19
7.12
22.47
0.65
0.44
0.032
29.11
—
--
263052
81297
--
170
5.9
12
Scrubber Feed Water
Metric Unit English Unit
Kg/hr Mol.7c Ib/hr Mol.%
-_
--
--
--
--
--
-_
—
__
_-
--
--
--
126579.5 100.00 67512 29.11
--
-_
Kg/hr 126579.5 Ib/hr 279060
NM3/hr -- SCFM
Kl/hr 126.7 GPM 558
C 29 F 85
atm -- PSIG
td
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
H2S
COS
H20
°2
so2
TOTAL
Temperature
Pressure
13
Scrubbing Water Return
Metric Unit
Kg/hr Mo 1.7.
1745.4 1.36
—
_-
_.
_-
__
3539.8 2.75
_-
_.
_.
__
123353.5 95.89
_-
Kg/hr 128638.8
NM3/hr
Kl/hr 123.5
C 49
atm
English Unit
Ib/hr Mo 1.7.
3848 1.36
__
__
__
--
__
7804 2.75
__
-_
__
—
271948 95.89
__
Ib/hr 283600
SCFM
GPM 544
F 120
PSIG
Gas
Metric
Kg/hr
--
—
—
--
--
--
--
65712.8
18301.5
2643.5
1083.2
845.5
108.9
3173.3
--
14
to H?S Removal
Unit
Mol.7.
--
--
—
--
--
--
--
54.37
9.64
30.39
0.88
0.58
0.042
4.08
--
Kg/hr 91868.7
NM3/hr 102095
Kl/hr
C
atm
35
1.34
English Unit
Ib/hr
--
--
--
--
--
--
--
144872
40348
5828
2388
1864
240
6996
--
Ib/hr
SCFM
GPM
F
PSIG
Mol.7.
-- .
--
--
—
--
--
—
54.37
9.64
30.39
0.88
0.58
0.042
4.08
—
202536
60084
95
5
15
CW to Gas Cooler
Metric Unit English Unit
Kg/hr Mol.7. Ib/hr Mol.7.
—
__
—
—
__
--
__
- w
CO
__
_-
921231.6 100.00 2030968 100.00
--
Kg/hr 9121231.6 Ib/hr 2030968
NM3/hr — SCFM
Kl/hr 922.4 GPM 4062
C 29 F 85
atm -- PSIG
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
N2
H2S
COS
H20
°2
so2
TOTAL
Temperature
Pressure
Gas Cooler
Metric Unit
Kg/hr Mol.
__
__
—
__
--
__
—
__
—
__
948681.2 100.
—
Kg/hr 948681.2
NM3/hr
Kl/hr 949.9
C 49
atm
16
Effluent Water
English Unit
% Ib/hr Mol.%
—
—
—
—
—
__
—
__
__
—
00 2091484 100.00
—
Ib/hr 2091484
SCFM
GPM 4183
F 120
PSIG
Metric
Kg/hr
—
--
--
—
--
—
—
--
2075.6
865.6
--
--
--
Kg/hr
NM^/hr
Kl/hr
C
atm
17
Glaus Plant Feed
Unit English Unit
Mol.% Ib/hr Mol.%
_-
--
__
__
--
__
--
__
65.00 4576 65.00
35.00 1908 35.00
—
—
—
2941.1 Ib/hr 6484
1717 SCFM 1010
GPM
35 F 95
PSIG
Metric
Kg/hr
--
--
--
—
__
—
—
65712.8
16303.9
2643.5
1083.2
41.7
—
2062.9
—
Kg/hr
NM3/hr
Kl/hr
C
atm
Clean
Unit
Mol.%
--
--
--
--
--
--
--
56.10
8.86
31.35
0.92
0.03
—
2.74
--
87848
98961
27
1.24
18
Gas
English Unit
Ib/hr Mol.%
--
-_
—
-_
_-
__
__
144872 56.10
35944 8.86
5828 31.35
2388 0.92
92 0.03
_-
4548 2.74
—
Ib/hr 193672
SCFM 58240
GPM
F 80
PSIG 3.5
-------
TABLE B-l (Continued)
Stream No. 19
Dosr.ripUnn Sulfur By-Product
Metric Unit English Unit
Composition Kg/hr Mol.% Ib/hr Mol.%
C
H
N
S 772.9 100.00 772.9 100.00
0
Cl
Ash
CO
co2
H2
N2
H2S -
cos
H20 "
°2
so2
TOTAL
Kg/hr 772.9 Ib/hr 1704
NM3/hr -- SCFM
Kl/hr -- GPM
Temperature C — F
Pressure atm — PSIG
Clean Gas to
Metric Unit
Kg/hr Mol.%
__
—
—
__
--
—
__
3655.9 56.10
907.2 8.86
146.9 31.35
59.9 0.92
1.8 0.03
—
114.3 2.74
—
__ --
Kg/hr 4886
NM3/hr 5505
Kl/hr --
C 27
atm 1.24
20
Air Heater
English
Ib/hr
—
—
--
--
--
--
—
8060
2000
324
132
4
—
252
--
--
Ib/hr
SCFM
GPM
F
PSIG
Unit
Mol.%
—
--
--
—
—
--
—
56.10
8.86
31.35
0.92
0.03
—
2.74
—
--
10772
3240
__
80
35
21
Clean Gas to
Metric
Kg/hr
—
--
—
—
--
—
—
62056.9
15396.7
2496.6
1023.3
39.9
--
1948.6
—
--
Kg/hr
NM3/hr
Kl/hr
C
atm
Unit
Mol.%
--
--
--
--
--
—
--
56.10
8.86
31.35
0.92
0.03
--
2.74
--
__
82962
93456
—
27
1.24
Compressor
English
Ib/hr
--
--
--
--
--
--
—
136812
33944
5504
2256
88
—
4296
—
— —
Ib/hr
SCFM
GPM
F
PSIG
Unit
Mol.%
--
—
—
—
--
--
—
56.10
8.86
31.35
0.92
0.03
--
2.74
—
__
182900
5500
--
80
35
I
oo
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
C02
N2
COS
H20
°2
so2
TOTAL
Temperature
Pressure
22
Hot
Metric Unit
Kg/hr Mol.%
__
__
—
__
—
__
__
__
6651.5 2.12
154620.6 77.58
__
1429.7 1.12
43693.7 19.18
0.9 .0009
Kg/hr 206395.4
NM3/hr 168438
Kl/hr
C 260
atm
Air
English Unit
Ib/hr
--
--
—
--
—
--
—
—
14664
340880
—
3152
96328
2
Ib/hr
SCFM
GPM
F
PSIG
Mol.%
—
—
—
--
—
—
—
—
2.12
77.58
—
1.12
19.18
.0009
455024
99128
••—
500
— —
23
Air to Air
Metric Unit
Kg/hr Mol.%
__
—
__
_-
—
—
__
—
--
154558.9 79.00
—
__
46952.2 21.00
__ __
Kg/hr 201511.1
NM3/hr 165339
Kl/hr
C
atm
Heater
English Unit
Ib/hr Mol.%
__
—
__
__
__
—
—
—
__ __
340744 79.00
__
__
103512 21.00
_ _ — -
Ib/hr 4442 56
SCFM 97304
GPM
F "
PSIG
24
Effluent from Coal Preparation
Metric Unit
Kg/hr
—
—
--
—
—
—
—
—
6651.5
154670.6
—
18274.3
43693.6
— —
Kg/hr
NM3/hr
Kl/hr
C
atm
Mol.%
--
--
--
—
--
--
--
--
1.88
68.57
—
12.59
16.96
— —
223040
190555
. —
74
•" ~
English Unit
Ib/hr
--
--
—
—
--
—
--
—
14664
340880
--
40288
96328
— —
Ib/hr
SCFM
GPM
F
PSIG
Mol.%
—
--
—
—
--
--
—
—
1.88
68.57
--
12.59
16.96
— —
492160
112144
_ «•
165
•• ~
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
H2S
COS
H20
°2
so2
TOTAL
Temperature
Pressure
25
Slowdown Water
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
--
__
—
__
—
__
__
__
__
;; ; ;; ;;
—
__
709.4 100.00 1564 100.00
._
_« -> •• » -• -•
Kg/hr 709.4 Ib/hr 1564
NM3/hr — SCFM
Kl/hr 0.71 GPM 3
C F
atm -- PSIG
26
B lowdown
Metric Unit
Kg/hr Mol.%
__
—
__
__
—
__
—
—
—
--
3802.9 100.00
__
_ _ « •»
Kg/hr 3802.9
NM3/hr --
Kl/hr 3.81
C
atm
Water
English Unit
Ib/hr Mol.%
—
__
--
—
—
—
—
—
_-
—
__ __
8384 100.00
__
« •• « »
Ib/hr 8384
SCFM
GPM 17
F
PSIG
27
Slug to Filter
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
—
—
-- -- -- --
—
--
—
3539.8 50.00 7804 50.00
__
__
—
—— — -• —— ™~
3539.8 50.00 7804 50.00
—
Kg/hr 7079.6 lb/hr 15608
NM3/hr -- SCFM
Kl/hr -- GPM
C 49 F 120
atm ~~ PSIG
I
h-4
O
-------
TABLE B-l (Continued)
Stream No.
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
N2
H2S
COS
H20
°2
so2
TOTAL
Temperature
Pressure
28
Cooling Water
Metric Unit
Kg/hr Mol.%
__
—
__
__
__
__
--
—
__
— — — —
__ __
— — — —
_-
77571.5 100.00
—
"
Kg/hr 77571.5
NM3/hr
Kl/hr 77.67
C 29
atm
to Quench Tank
English Unit
Ib/hr Mol.%
__
__
__
__
__
--
-_
__
__
••— ——
->. — —
» w •• ••
-- --
171016 100.00
__ __
Ib/hr 171016
SCFM
GPM 342
F 85
PSIG
29
Water to Clarifier
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
__
-- -- -- --
•• •• — — ••-• •• —
--
__
__
— .
__. -- — --
— — — — — — — —
••« ^^ ~™ ^««
•• m* tm _ ^^ ^ "•
"
•••• M« •••• ^ tmt
74031.7 100.00 163212 100.00
—
Kg/hr 74031.7 ib/hr 163212
NM3/hr " SCFM
Kl/hr 74.12 GPM 326
C 49 F 120
atm -- PSIG
Slurry
Metric Unit
Kg/hr Mol.%
__
_•» _ «
™ ™ ~ *™
-- --
--
--
3539.8 20.09
-- --
•""• ™ *"
""
"
^ <• •• _
12332.3 70.00
__
Kg/hr 17617.5
NM3/hr
Kl/hr 12.4
C 29
atm
30
to Filter
English Unit
Ib/hr wt%
__
— •• « .
— — « ••
-- --
--
-_
7804 20.09
-- --
— — — —
"
""
-
— — ^ —
27188 70.00
-_
Ib/hr 38840
SCFM
GPM 54.4
F 85
PSIG
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
N2
COS
H20
°2
so2
TOTAL
Temperature
Pressure
31
Slag
Metric Unit English Unit
Kg/hr wt% Ib/hr wt%
1745.5 17.80 3848 17.80
--
__
_-
__
—
7079.6 72.20 15608 72.20
__
_.
—
979.8 10.00 2160 10.00
__
Kg/hr 9804.8 ib/hr 21616
NM-Vhr — SCFM
Kl/hr -- GPM
C F
atm — PSIG
32
Water from Filter
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
__
__
_-
—
._
__
—
—
—
__
14892.3 100.00 32832 100.00
—
Kg/hr 14892.3 ib/hr 32832
NM3/hr — SCFM
Kl/hr 14.9 GPM 66
C 29 F 85
atm -- PSIG
33
Water to Cooling Tower
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
_-
—
—
—
—
—
—
__
__
—
50122 100.00 110500 100.00
—
Kg/hr 50122 ib/hr 110500
NM3/hr *••<• SCFM
Kl/hr 50.2 GPM 221
C 29 F 85
atm -- PSIG
-------
TABLE B-l (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Cl
Ash
CO
co2
H2
H,>S
COS
H20
°2
so2
TOTAL
Temperature
Pressure
34
Make-Up Water
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
—
._
__
__
—
—
__
__
—
__
__
31751.5 100.00 70000 100.00
• *» —~ — — — ••
Kg/hr 31751.5 Ib/hr 70000
NM-Vhr — SCFM
Kl/hr 31.8 GPM 85
C F
atm -- PSIG
35
Clean Fuel Gas
Metric Unit
Kg/hr
--
--
—
—
—
—
—
62056.9
•15396.7
2496.6
1023.3
39.9
—
968.9
~ ••
Kg/hr
NM3/hr
Kl/hr
C
atm
Mol.%
--
—
--
—
—
--
—
56.88
8.98
31.79
0.94
0.03
--
1.38
*•••
81982.3
92171.4
16
6.44
English Unit
Ib/hr
—
—
—
--
—
«
—
136812
33944
5504
2256
88
—
2136
*™ "*
Ib/hr
SCFM
GPM
F
PSIG
Mol.%
—
--
—
--
--
__
—
56.88
8.98
31.79
0.94
0.03
--
1.38
"*™
180740
54244
60
80
w
I
-------
»-Clean gas
preparation
Scrubberv-s Cooler
*' (7) «
Coal storage
•—S.
l3)Cooling water
Tar oil
separator
Ammonia ,
stripping
15) Makeup water
to
Cooling pond
FIGURE B-2. WELLMAN-GALUSHA/STRETFORD GASIFICATION PLANT MATERIAL
BALANCE FOR MODEL REFINERY PLANT
-------
TABLE B-2. WELLMAN-GALUSHA/STRETFORD GASIFICATION PLANT MATERIAL BALANCE
FOR MODEL REFINERY PLANT
(Metric and English Units')
Stream No.
Description
Composition
C
H
N
S
0
Ash
CO
C02
CH4
H2S
Phenols
Tar
H20
°2
TOTAL
Temperature
Pressure
1
1
Coal as Received
Metric Unit
Kg/hr wt70
7711.1 68.0
544.3 4.8
238.1 2.1
442.3 3.9
771.1 6.8
952.5 8.4
—
— — __
: ::
__
—
—
680.4 6.0
__ __
Kg/hr 11339.8
NM3/hr
Kl/hr
C 25
atm
English
Ib/hr
17000
1200
525
975
1700
2100
—
— ~
;;
_-
—
—
1500
--
Unit
wt%
68.0
4.8
2.1
3.9
6.8
8.4
—
• —
—
--
--
--
6.0
--
Ib/hr 25000
SCFM
GPM
F
PSIG
77
—
Metric
Kg/hr
1233.8
87.1
38.1
70.8
123.4
152.4
--
-*•
—
--
—
—
108.9
--
Coal
Unit
Wt70
68.0
4.8
2.1
3.9
6.8
8.4
—
••••
V M
--
6.0
— —
Kg/hr 1814.4
NM-Vhr
Kl/hr
C
atm
25
--
2
Fines
English
Ib/hr
2720
192
84
975
272
336
—
•""
^ ^
--
—
—
240
— —
Unit
wt7o
68.0
4.8
2.1
3.9
6.8
8.4
--
•• ~
•• *•
--
—
—
6.0
— —
Ib/hr 4000
SCFM
GPM
F
PSIG
77
--
3
Coal Feed to
Metric Unit
Kg/hr
6477.
457.
200.
371.
647.
800.
--
™~
—
--
—
--
571.
— —
Kg/hr
NM3/hr
Kl/hr
C
atm
wt7o
3 68.0
2 4.8
0 2.1
5 3.9
7 6.8
1 8.4
--
~ ~
— —
--
—
--
5 6.0
--
9575.4
25
--
Gasifier
English
Ib/hr
14280
1008
441
156
1428
1764
—
~~
—
--
--
--
1260
--
Unit
wt7o
68.0
4.8
2.1
3.9
6.8
8.4
—
— -
;;
--
—
—
6.0
--
Ib/hr 21000
SCFM
GPM
F
PSIG
77
—
-------
TABLE B-2 (Continued)
Stream No.
Description
Composition
C
II
N
S
0
Ash
CO
co2
CH,
N2
NH3
Phenols
Tar
H20
02
TOTAL
Temperature
Pressure
4
Air and
Metric Unit
Kg/hr Mo 1.7.
—
—
—
-_
—
—
—
•••• ••••
_-
19186.0 59.01
—
—
5292.5 25.30
5828.7 15.69
Kg/hr 30307.2
NM3/hr 27474
Kl/hr
C 66
atm
Steam
English Unit
Ib/hr Mo 1.7.
_-
—
__
_..
—
—
_-
M •• • •
—
42298 59.01
—
—
11668 25.30
12850 15.69
Ib/hr 66816
SCFM 16169
GPM
F 150
PSIG
5
Hot Raw
Metric Unit
Kg/hr
9.1
—
--
—
—
79.8
11383.8
2126.0
421.9
615.5
19300.8
99.3
389.2
54.4
475.4
4075.5
•-r
Kg/hr
NM-Yhr
Kl/hr
C
atm
Mbli.7.
—
—
--
—
—
—
24.86
2.95
12.77
2.35
42.17
0.36
0.70
—
—
13.84
—
39030.7
38681
360
— —
Gas
English Unit
Ib/hr Mo 1.7.
20
—
—
—
—
176
25097 24.86
4687 2.95
930 12.77
1357 2.35
42551 42.17
219 0.36
858 0.70
120
1048
8985 13.84
—
Ib/hr 86048
SCFM 22764
GPM
F 680
PSIG
6
Ash
Metric Unit English Unit
Kg/hr wt7. Ib/hr wt70
81.7 10.18 180 10.18
—
—
—
—
720.3 89.82 1588 89.82
—
MM «— « •» M —
—
_-
__
Kg/hr 802.0 lb/hr 1768
NM3/hr — SCFM
Kl/hr " GPM
C F —
atm -- PSIG
-------
TABLE B-2 (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Ash
CO
CO-
CH4
N2
NH3
Phenols
Tar
H20
02
TOTAL
Temperature
Pressure
7
Gas to Gas
Metric Unit
Kg/hr Mol.7.
..
__
—
__
-_
—
11383.8 23.90
2126.0 2.84
421.9 12.30
615.5 2.26
19300.8 40.60
389.2 0.67
—
—
5320.6 17.39
—
Kg/hr 39557.8
NM-Vhr 40178
Kl/hr
C 57
atm
Cooler
English
Ib/hr
--
—
--
—
—
-_
25097
4687
930
1357
42551
858
—
--
11730
—
Ib/hr
SCFM
GPM
F
PSIG
Unit
Mol.7.
—
—
—
—
--
—
23.94
2.84
12.30
2.26
40.60
0.67
—
—
17.39
—
87210
23645
135
*••
8
Scrubbing Water
Metric Unit English Unit
Kg/hr Mol.7. Ib/hr Mol.7.
—
--
—
—
—
__
--
__ — — — — — —
__
__
—
—
69313.5 100.00 152810 100.00
--
Kg/hr 69313.5 Ib/hr 152810
NM^/hr ~ SCFM
Kl/hr 69.4 GPM 68.8
C 25 F 77
atm -- PSIG
9
Scrubbing Water Return
Metric Unit
Kg/hr wt7o •
9.1 0.01
-- --
__
--
—
79.8 0.12
—
__ __
—
99.3 0.14
54.4 0.08
475.4 0.69
68068.4 98.96
—
Kg/hr 68786.4
NM3/hr
Kl/hr 77
C 53
atm
English Unit
Ib/hr wt7.
20 0.
-_
_-
--
—
176 0.
—
-_
__
219 0.
120 0.
1048 0.
150065 98.
—
Ib/hr 151648
SCFM
GPM 127
F 127
PSIG
01
-
-
-
-
12
-
_
-
14
08
69
96
-
OS
I
-------
TABLE B-2 (Continued)
Stream No.
Description Gas
10
to Sulfur Removal
Metric Unit English Unit
Composition Kg/hr
C
H
N
S
0
Ash
CO 11383.8
C02 2126.0
H2 421.9
CH4 615.5
N2 19300.8
NH3
H2S 389.2
Phenols
Tar
H20 1499.6
°2
TOTAL Kg/hr 35736
NM3/hr 35160
Kl/hr
Temperature C 35
Pressure atm
Mol.T, Ib/hr Mol.70
—
__
—
_>
__
—
27.35 25097 27.35
3.25 4687 3.25
14.06 930 14.06
2.58 1357 2.58
46.39 42551 46.39
0.77 858 0.77
-_
__
5.60 3306 5.60
.7 Ib/hr 78786
SCFM 20692
GPM
F 95
PSIG —
11
Cooling Water
Metric Unit English Unit
Kg/hr Mol.7o Ib/hr Mol.7»
_-
—
—
__
—
—
—
__
—
MM «_ _» ••-•
125928.6 100.00 277625 100.00
Kg/hr 125928.6 Ib/hr 277625
NM3/hr -- SCFM
Kl/hr 126.1 GPM 555
C 25 F 77
atm — • PSIG
12
Cooling Water Return
Metric Unit English Unit
Kg/hr Mol.7o Ib/hr Mol.T,
—
—
—
__
__
—
—
—
—
__ __ — _ — —
_.
—
129749.6 100.00 286049 100.00
Kg/hr 129749.6 Ib/hr 286049
NM3/hr — SCFM
Kl/hr 129.9 GPM 572
C 53 F 127
atm -- PSIG
I
I-"
oo
-------
TABLE B-2 (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Ash
CO
co2
N2
NH3
Phenols
Tar
H20
02
TOTAL
Temperature
Pressure
13
Tar
Metric Unit
Kg/hr wt%
422.8 80.83
36.7 7.03
3.6 0.69
5.5 1.04
6.8 1.30
—
—
•"~ — ••
—
—
_.
47.6 9.11
—
Kg/hr 523
NM-Vhr
Kl/hr
C 25
atm
English Unit
Ib/hr wtT,
932 80.83
81 7.03
8 0.69
12 1.04
15 1.30
—
—
—
__
__
—
105 9.11
—
Ib/hr 1153
SCFM
GPM
F 77
PSIG
14
Ammonia
Metric Unit
Kg/hr wt7o
—
__
—
—
—
—
—
MM MM
99.3 20.00
—
__
397.4 80.00
—
Kg/hr 496.7
NM-Vhr
Kl/hr 0.42
C 25
atm
Solution
English Unit
Ib/hr wt70
__
__
—
—
—
—
__
M M •• M
219 20.00
—
—
876 80.00
__
Ib/hr 1095
SCFM
GPM 2
F 77
PSIG
15
Phenols
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mo 1.7.
—
—
-:_
—
—
--
--
—
-_
54.4 — 120
-_ __ __ __
--
"•• — •• — *• "• ••
Kg/hr 54.4 Ib/hr 120
NM3/hr — SCFM
Kl/hr -- GPM
C F
atm -- PSIG
tri
I
-------
TABLE B-2 (Continued)
Stream No.
Description
Composition
C
H
N
S
0
Ash
CO
co2
N24
NH3
H2S
Phenols
Tar
H20
02
TOTAL
Temperature
Pressure
16
Water to Gasifier Jacket
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
__
__
—
__
—
—
—
-- -- -- --
—
— — ~~ "•• •"•
--
-- -- -— --
__
64259.5 100.00 141668 100.00
>.
Kg/hr 64259.5 Ib/hr 141668
NMP/hr -- SCFM
Kl/hr 64.3 GPM 283
C 25 F 77
atm — PSIG
Water from
Metric Unit
Kg/hr Mol
—
__
—
__
—
—
—
•»•» ••»
—
__ __
--
-- --
—
58976 100
•_.
Kg/hr 58967
NM3/hr
Kl/hr 59.0
C 66
atm
17
Gasifier Jacket
English Unit
.% Ib/hr Mol.%
__
—
_-
__
—
__
—
W ~M
__
_— __
__
_-
.00 130000 100.00
—
Ib/hr 130000
SCFM
GPM 260
F 150
PSIG
18
Water Loss
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
__
—
—
__
__
—
—
w •• «« «••
^ ^
-------
TABLE B-2 (Continued)
Stream No.
Description
Composition
C
II
N
S
0
Ash
CO
co2
CHA
N2
NH3
H2S
Phenols
Tar
H20
02
TOTAL
Temperature
Pressure
19
Make-Up Water
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
—
__
__
._
__
—
__
MM M M M M MM
__
MM MM •»• MM*
—
__
16680.9 100.00 36775 100.00
—
Kg/hr 16680.9 Ib/hr 36775
NM3/hr — SCFM
Kl/hr 16.7 GPM 73.5
C 25 F 77
atm — PSIG
20
Sulfur
Metric Unit English Unit
Kg/hr Mol.% Ib/hr Mol.%
..
—
—
352.4 100.00 777 100.00
__
—
__
MM — — MM MM
—
__ __ __ ._
__
__
_.
.__
Kg/hr 352.4 Ib/hr 777
NM3/hr — SCFM
Kl/hr — GPM
C F
atm — PSIG
Metric
Kg/hr
—
._
—
__
—
—
.11383.8
2126.0
421.9
615.5
19300.8
14.5
--
—
444.1
—
Kg/hr
NM3/hr
Kl/hr
C
atm
21
Clean
Unit
Mol.%
--
—
—
--
—
—
28.70
3.41
14.74
2.71
48.67
0.03
—
—
1.74
--
34306.6
33513
16
™~
Gas
English
Ib/hr
—
—
—
--
—
—
25097
4687
930
1357
42551
32
—
—
979
—
Ib/hr
SCFM
GPM
F
PSIG
Unit
Mol.%
--
—
—
—
--
—
28.70
3.41
14.74
2.71
48.67
0.03
—
—
1.74
—
75633
19723
60
M -.
i
IS5
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TECHNICAL REPORT DATA
(Please read Inurucnons on the reverse before completing)
1. REPORT NO.
EPA-600/2-76-102
2.
3. RECIPIENT'S ACCsSSIOf»NO.
A. TITLE AND SUBTITLE
Environmental Aspects of Retrofitting Two Industries
to Low- and Intermediate-Energy Gas from Coal
5. REPORT DATE
April 1976
6. PERFORMING ORGANIZATION CODE
7-AUTHOR(S)D.A.Ball, A.A.Putnam, D.W. Hiss ong,
J.Varga, B.C.Hsieh, J.H. Payer, and. R. E. Barrent
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Battelle-Columbus Laboratories
505 King Avenue
Columbus, Ohio 43201
10. PROGRAM ELEMENT NO.
1AB013; ROAP 21BBZ-006
11. CONTRACT/GRANT NO.
68-02-1843
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
?..TYPE OF REPORT
inal; 9-11/74
AND PERIOD COVERED
14. SPONSORING AGENCY CODE
EPA-ORD
is. SUPPLEMENTARY NOTES Project officer for this report is W. J. Rhodes, Mail Drop 61,
Ext 2851.
16
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