-------
Figure No.
CTU3 3
» C O
LIST OF FIGURES vCent•\
13 Flow Diagram of Alternative Treatment Process for
Mixed Sludges from Electrolytic Copper Refining
(Waste Stream Number 16) 102
14 Schematic Diagram for Recovery and Recycle of Sludge
Solids from Primary Lead Smelter (Waste Stream
Number 17) 107
15 Schematic Diagram for Recovery and Recycle of Acid Plant
and Miscellaneous Sludges from Electrolytic Zinc
Production (Waste Stream Number 18) 112
16 Schematic Flow for Recycle of Sludges from Primary
Pyrometallurgical Zinc Acid Plant and Gas Cleaning
Sludges (Waste Stream Number 10) 116
17 Schematic Flow for Recycle of Sludge from Retort
Scrubber Bleed. Primary Pyrometallurgical Zinc
(Waste Stream Number 19) 118
18 Flow Diagram for Standard Grade Cyrolite Recovery from
Spcnl rullincia, ToL 3kiuu,.iii£3, ir.d rctlir.c Scrubber
Sludges ''W^stc Str°?!ns N1J!^°'*'C 2^ PTI^ 2^ ^ • t . • • - • 1 24
19 Schematic Flow Diagram of Alternative Process for
Primary Aluminum Shot Blast and Cast House Dust Disposal
(Waste Stream Number 22) 131
20 Diagram of Alternative Disposal for Blast Furnace
Slag from Pyrometallurgical Antimony Manufacture
(Waste Stream Number 23) 135
21 Flow Diagram Showing Chemical Landfill of Spent
Anolytc Sludge Solids (Waste Stream Number 24).... 139
22 Schematic Flow Diagram for Recovery of Rutile and
Carbon from Chlorinator Condenser Sludge (Waste
Stream Number 25) 142
23 Diagram of Alternative Disposal for Blast Furnace Slag
from Secondary Copper Refining (Waste Stream
Number 27) 147
xiv
§
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-------
LIST OF FIGURES (Cunt.)
Figure No. Page
24 Flow Diagram for Alternative Treatment of S02
Scrubwater Sludge from Secondary Lead Refining
(Waste Stream Number 281 151
25 Flow Diagram of Alternative System for Sludge
Treatment and Disposal from Secondary Aluminum Refining
(Waste Stream Number 29) 154
26 Flow Diagram for Salt Recovery from High Salt Furance
Slag in Secondary Aluminum Refining (Waste Stream
Number 30) 158
PART II
27 Chemical Landfill Costs 185
28 Sanitary Landfill Costs 193
APPENDIX
A-i Centrifuge Costs A-4
A-2 Holding Tank Costs A-5
A-3 Mixing-Tank Costs A-6
A-4 Cost of Slurry/Sludge Pumps A-7
A-5 Cost of Centrifugal Pumps A-8
xv
-
g:» 8}
3 r* =
o> =r 5
=i «D "
-------
p> «-f _ .
— ^* 9
'
EXECUTIVE SUMMARY
Several categories of metals smelting and refining industries, whose
wastes were classified as potentially hazardous were examined by EPA Contract
No. 68-01-2604, "Assessment of Industrial Hazardous Waste Practices in the
Metal Smelting and Refining Industry." Alternatives to landfill disposal
were evaluated.
1. Iron and steel coke production waste streams 1 and 2,
ammonia strll sludge and decanter tank tars, generally
were found to have no recovered material value.
2. Alternative treatment of iron and steel manufacturing
wastes were found to be in several general categories.
None of the alternative treatments offered definite
recovered material values in excess of the treatment
costs. The iron and steel air emission control dusts
and sludges, waste streams 3, 4, and 5 as well as
rolling mill sludge, waste stream 6, were wastes with
potential, but not definite, recovered material values
in excess of alternative treatment costs. The spent
pickle liquor, waste stream 8, alternative processes,
while recovering useful materials, did not provide
recovery values exceeding alternative treatment costs.
; Thp ff»Trn!<11ny industry ViaH nn»» wa«t<» stream, ferrochrome
e1->« fwactp «tr*»pm 17A1 with nntrnitinl rerovornrl material
- - -• t> r * * * *
value exceeding alternative treatment costs. The
remaining wastes contained recoverable materials
whose value did not exceed alternative treatment costs.
These were ferro and silicomanganese slags, waste
streams 13 and 14. Waste stream 11, ferrosilicon dusts,
did not have any recoverable materials.
4. Generally, only the primary nonferrous smelting and
refining industry, as opposed to the secondary, had
potentially hazardous wastes with definite recovery
value exceeding alternative treatment costs. The
major exception was the primary antimony, electrolytic
and pyrometallurgical, waste streams 23 and 24, which did
not have recovery value.
5. All of the secondary nonforrous smelting and refining
industries generated wastes without recovered material
values. Those were waste stream 27, copper refining
blast furnace slag; 28, lead refining SC>2 scrubwater
sludge; and 29, aluminum refining scrubber sludge.
The one exception was waste 30, secondary aluminum high
salt slag, which offered potential recovered material
value exceeding alternative treatment costs.
I
O
*
10
-------
Alternative Waste Treatment and Material Recovery Costs. Capital
and annual costs for alternative waste treatment and material recovery in the
metal manufacturing operations considered in this study are based on a
typical plant and are expressed in 1976 dollars.
The information concerning alternative waste treatment costs for
the industries considered are summarized in Table 1. Implementation of the
alternative processes results in net gains for six of the waste streams;
i.e., the value assigned to the recovered material exceeds the cost of
installing and operating the alternative waste treatment system. These
waste streams are:
1. Primary lead smelting sludge, waste stream 17.
2. Primary electrolytic zinc sludge, waste stream 18.
3. Primary pyrometallurgical zinc sludge, waste stream 19.
4. Primary aluminum scrubber sludges, spent pot liners
and skimmings, waste streams 20 and 21.
5. Primary titanium chlorinator condenser sludge, waste stream 25.
Twenty-one waste streams have alternative treatment costs (net costs
where applicable) that were less than $5 per metric ton ($4.50/short ton) of
product. (Alternative treatment costs in $ per metric ton of waste are also
shown in Table 1.) These are:
. Suiuric acid
pi«_klc liquor, wa3tc 3trca~. Z.\
2. Secondary aluminum scrubwater sludge, waste stream 29 - $4.15
3. Secondary lead scrubwater sludge, waste stream 28 - $3.84
4. Ferrochrome dust, waste stream 12 - $2.85
5. Copper smelting, acid plant blowdown sludge,
waste stream 15 - $2.85
6. Electrolytic copper mixed sludge, waste stream 16 - $2.48
7. Hydrochloric acid waste pickle liquor, waste stream 8B - $1.33
8. Primary aluminum shot blast and cast house dusts,
waste stream 22 - $0.54
9. Primary zinc pyrometallurgical dust, waste stream 19 - $0.31
10. Primary zinc electrolytic sludge, waste stream 18 - $0.29
-------
Table 1 Summary of /Utemative Waste Tr2atment Costs
Waste Stream
Iron and Steel Coke
Production - Ammonia
Still Lime Sludge
Iron and Steel Coke
Production - Decanter
Tank Tar from Coke
Production
Iron and Steel Prod. -
Basic Oxygen Furnace -
Wet Emission Control
Unit Sludge
Iron and Steel Prod.-
Open Hearth Furnace -
Emission Control Dust
Iron and Steel Prod.-
Electric Furnace - Wet
Emission Control Sludge
Iron and Steel Prod.-
Rolling Mill Sludge
Iron and Steel Pro
-------
CORRECT
N
« e-^.
The preceding document(s) has been refilmed
to assure legibility and its image appears
immediately hereafter.
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-------
Table 1 Summary of Alternative Waste Treatment Costs
S/Metric Ton of Waste
Wet
Haste Stream
Iron and Steel Coke
Production - Ammonia
Still Lime Sludge
Iron and Steel Coke
Production - Decanter
Tank Tar from Coke
Production
Iron and Steel Prod. -
Basic Oxygen Furnace -
Wet Emission Control
Unit Sludge
Iron and Steel Prod.-
Open Hearth Furnace -
Emission Control Dust
Iron and Steel Prod.-
Electric Furnace - Wet
Emission Control Sludge
Iron and Steel Prod.-
Rolling Mill Sludge
Iron and Steel Prod.-
Cold Polling Mill -
Acid Rinsewater Neu-
tralization Sludge
Pry
$/Metric Ton of
Product
Total
Net
Number Tctal Net Total Net
1 $ 7J.89 $ NRV $ 259.21 $ NRV $ 0.07 $ NRV
6'-. 58 NRV
12.66
12.66
6.16
6. 15
7.36
7.36
7.36
1.45
NRV
324.09
29.90
29.90
29.90
16.25
27.40
NRV
17.40
17.40
3.65
NR'.
0.71
17.-iO 0.48
0.48
0.4S
NRV
0.23
0.28
0.28
0.03 0.006
0.004 NKV
See page 7 for legend.
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Table 1 (Cent.) Summary of Alternative! Wiste Treatment Costs
$/Hotric Ton of .Vnstc
Waste Stream
Number ILJ2l:»L_ Net Total
Dry
Net
$/Mctric Ten of
I'roJuct
Total
Net
Iron and Steel Prod.
Cold Rolling Mill -
Acid Sinsewater Neu-
tralization Sludge
(IICU
Iron and Steel Prod.
Cold Rolling Mill -
Waste Pickle Liquor
Sulfuric Acid
7B $6.77 $ NRV $ 67.67 $ NRV $0.003 $ NRV
8A £.5.54 43.31 1,365.82 1,065.24 6.24 4.37
9A
Iron and Steel Prod.-
Cold Rolling Mill -
Waste Pickle Liquor -
Hydrochloric Acid CHC1)
Iron and Steel Prod.-
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (H2S04)
Iron and Steel Prod.- 9B
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (KC1)
8B 38.38
Ferroalloys - Ferro-
silicon Manufacture
Miscellaneous Dusts
11
0.99
3.74
24.80 449.78 290.63 2.06 1.33
NRV
NRV
N.A.
3.19 NRV 0.04 NRV
12.47 NRV 0.03 NRV
15.88 NRV
5.36 NRV
See page 7 for legend.
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Table 1 (Cont.) Summary of Alternative Waste Treatment Costs
$/Mctric Ton of K.istc $/;-'.,: ibr Ton of
"Not
Wet
Dry
Waste Stream
Number Total Net Total Nut Total
Farroalloys - Ferro-
silicon Manufacture -
Slag
Ferroalloys - Ferro-
sill con Manufacture -
Dust
Ferroalloys - Ferro-
silicon Manufacture -
Sludge
12A $ N.A. *, N.A. 5 3.91 $2.91 $6.85 $5.10
12B N.A. N.A. 18.82 NRV 2.85 NRV
12C 13.88 NRV 34.56 NRV 5.23 NRV
Ferroalloys - Silico- 13
manganese Manufacture -
Slag and Scrubber Sludge
Ferroalloys - Ferro- 14
manganese Manufacture -
Slag and Sludge
Copper Smelting - 15
Acid Plant Slowdown
Sludge
Electrolytic Copper
Refining - Mixed
Sludge
Lead Smelting - 17
Sludge
20.36 18.79 50.80 46.88 15.07 13.91
20.36 IS. 79 50. EC
15.07 13.!/1
379.27 NRV 884.97 NRV 2.65 NRV
16 350.40 NRV 991.13 NRV 2.48 NRV
6.80 1.01* 22.61 3.36* 1-34 0.20*
See page 7 for legend.
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-------
Table 1 CCont.) Summary of Alternative Waste Treatment Costs
$/Mctric Ton of Waste
Wet
Dry
Waste Stream
Number Tctal
Not Total
Net
S/Vn-tric Ton of
Product
Total Net
Electrolytic Zinc 18
Manufacture
Pyrometallurgical Zinc 19A
Manufacture - Sludges -
Primary Gas Cleaning and
Acid Plant Slowdown
Pyrorcetallurgical Zinc 19B
Manufacture - Sludges -
Retort Gas Scrubber
Bleed
Aluiiiinum Manufacture- 20
Scrubber Sludges
Aluminum Manufacture - 21
Spent Potliners and
Skimmings
Aluminum Manufacture - 22
Shot Blast and Cast
House Dusts
See page 7 for legend.
3.5
-------
T.ible 1 (Cont.) Summary of Alternative Waste Treatment Costs
$/Hctrlc Ton of Waste
IVe-:
Dry
:V;istg Stream
Pyrometallurgical
Antimony Manufacture-
Blast Furnace Slag
Electrolytic Antimony
Manufacture - Spent
Anolyte Sludge
Titanium Manufacture-
Chlorinator Condenser
Sludge
Number Tot^l Met 'total .\'Jt To- :.- ___._t.
$/:•!••; :•(': Von o:
!j-.;J £_ __
TO':P
23 $ N.A. $ N.A. $ 18.40 $ NRV $ 52.48 $ NRV
24 55.C5 NRV 165.15
NRV
25 12.53 14.85* 31.59 37.41'
36.70 NRV
10.39 12.31*
Copper Refining -
Blast Furnace Slag
Lead Refining - S02
Scrubwater Sludge
Aluminum 'le fining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
27 N.A. N.A. 37.86 NRV 13.25 NRV
28 25. fl NRV 85.36 NRV 3.84 NRV
29 16.59 NRV 55.29 NRV 4.15 NRV
30 N.A. N.A. 47.89 26.02 67.04 36.43
N.A. = Not applicable
* = Net gain, i.e., value of recovered material exceeds cost of alternative treatment
NRV » No recovery va lue
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11. Steel irill air emi ssion, wasty r.trcaras .*, A, and S - $0.28
12. Primary lead smelting sludge, waste stream 17 - $0.20
13. Galvanizing mill acid rinsewater neutralizing sludge,
waste stream 9A - 0.04
14. Galvanizing mill acid rinsewater neutralizing sludge,
waste stream 9B - $0.03
IS. Iron and steel rolling mill sludge, waste stream 6 - $0.006
16. Cold rolling mill acid rinsewater neutralization sludge,
waste stream 7A - $0.004
17. Cold rolling mill acid rinsewater neutralization sludge,
waste stream 7B - $0.003
18. Ammonia still sludge, waste stream 1
19. Decanter tank tar, waste stream 2
Nine waste streams show alternative treatment costs (net costs
where applicable) of more than $5 per metric ton ($4.50/short ton) of product.
These are:
1. Primary pyrometallurgical antimony slag, waste
stream Jj - $52.48
2. Primary electrolytic antimony sludge, waste
stream 24 - $36.70
3. Secondary aluminum refining high salt slag,
waste stream 30 - $36.43
4. Silico ant1 ferromanganese slag and sludge,
waste streams 13 and 14 - $13.91
S. Secondary copper refining slag, waste stream 27 - $13.25
6. Ferrosilicon dust, waste stream 11 - $5.36
7. Ferrochrome sludge, waste stream 12C - $5.23
8. Ferrochrome slag, waste stream 12A - $5.10
I
O
-------
cr.o a :
to e o
Value of Recovered Materials Versus Alternative Tr_e_atroent_Cost_s_
(Break-even Analysis).In summary, six alternative treatment processes
yield recovered materials whose value exceeds the alternative treatment costs
of operation; 18 processes do not provide Materials with discernible market
values. Of the remaining seven alternative processes, four can be expected
to reach a break-even point and three cannot.
Wastes with definite recovered material value exceeding alternative
treatment costs:
1. Primary lead smelting sludge, waste stream 17
2. Primary electrolytic zinc sludge, waste stream 18
3. Primary pyrometallurgical zinc sludge, waste stream 19A
4. Primary aluminum scrubber sludge, potlincrs and
skimmings, waste streams 20 and 21
5. Primary titanium chlorinator condenser sludge, waste stream 25
Wastes with potential recovered material value exceeding alternative
treatment costs:
1. Steel mill emission control sludge and dusts,
waste streams 3, 4, and S
2. Rolling mill sludge, waste stream 6
3. Slag from ferrochrome manufacture, waste stream 12A
4. Secondary aluminum high salt slag, waste stream 30
Wastes with recovered materials whose value does not exceed
alternative treatment costs:
1. Silico and ferromanganese slag and sludge, waste
streams 13 and 14
2. Spent sulfuric acid pickle liquor, waste stream 8A
3. Spent hydrochloric acid pickle liquor, waste stream SB
Wastes whose alternative treatments do not provide recovered
materials:
1. Ammonia still sludge, waste stream 1
2. Decanter tank tar, waste stream 2
3 n- •
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-------
-------
Table 2 (Cont.) Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value
Waste Stream
Iron and Steel Production -
Cold Rolling Mill - Acid
Rinsewater Neutralization
Sludge (H2SO4)
Iron and Steel Production -
Cold Rolling Mill - Acid
Rinsewater Neutralization
Sludge (HC1)
Iron and Steel Production -
Cold Rolling Mill - Waste
Pickle Liquor - Sulfuric
Acid
Iron and Steel Production -
Cold Rolling Mill - Waste
Pickle Liquor - Hydrochloric
Acid (HC1)
Iron and Steel Production -
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (H2S04)
Number
7A
7B
3A
SB
9A
Total
Annual
Cost
$ 2,740
2,740
4,370,620
1,439,280
4,470
\nnual Percent of
/alue of Market
"tecovered Price
'laterial Assigned
NRV
NRV
961,840
$ N.A.
N.A.
100L
Net Required
Annual . Percent Increase in
Cost Recovered Material Value
$ N.A. N.A.
N.A. N.A.
3,408,780 354
509,280 70C,100a 930,000
NRV
H.A.
183
N.A. N'.A.
See page 16 for legend.
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-------
Table 2 (Cont.) Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value
Waste Stream
Iron and Steel Production -
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (HC1)
Ferroalloys - Ferrosilicon
Manufacture - Miscellaneous
Dusts
Ferroalloys - Ferrosilicon
Manufacture - Slag
Ferroalloys - Farrosilicon
Manufacture - Dust
Ferroalloys - Ferrosilicon
Manufacture - Sludge
Number
9B
11
12A
12B
12C
Ferroalloys - Silicomanganese 13
Manufacture - Slag and
Scrubber Sludge
Annual Percent of
Total Value of Market Net
Annual Recovered Pricu Annual
Cost Material Assigned Cost
$ 3.740 $ NRV
214,400
239,690
99,750
183,150
452,090
NRV
NRV
N.A.
N.A.
61,300 100
NRV N.A.
N.A.
34,880 25
$ N.A.
N.A.
178,390
N.A.
N.A.
417,210
Required
. Percent Increase in
Recovered Material Value
N.A.
N.A.
291
N.A.
N.A.
1,196
See page 16 for legend.
i
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Table 2 (Cont.) Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value
Waste Stream
Ferroalloys - Ferromanganese
Manufacture - Slag and Sludge
Copper Smelting - Acid Plant
Slowdown Sludge
Electrolytic Copper Refining -
Mixed Sludge
Lead Smelting - Sludge
Electrolytic Zinc
Number
14
15
16
17
18
Total
Annual
Cost
$ 452,0<>P
265,4
-------
Table 2 (Cont.) Break-Even Analysis Between Alteriative Treatment Cost and Recoverable Resource Value
Waste Stream Number
Aluminum Manufacture - 20
Scrubber Sludges
Aluminum Manufacture - 21
Spent Potliners and
Skimmings
Aluminum Manufacture - 22
Shot Blast and Cast House
Dusts
Pyrometallurgical Antimony 23
Manufacture - Blast Furnace
Slag
Electrolytic Antimony 24
Manufacture - Spent Anolyte
Slodge
Titanium Manufacture - 25
Chlorinator Condenser Sludge
Copper Refining - Blast 27
Furnace Slag
Total
Annual
Cosi:
$2,099,140
2.099,140
82,360
141.70)
33,03-)
78,97(1
132,510
Value of
Recovered
Material
$3,180,000
3,180,000
NRV
NRV
NRV
172,500
NRV
Market
Price
Assigned
iooh
iooh
N.A.
N.A.
N.A.
1001
N.A.
Net
Annual
Cost
$1,091,860
1,091,860
N.A.
N.A.
N.A.
93,530*
N.A.
Required
. Percent Increase in
Recovered Material Value
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
N.A.
See page 16 for legend.
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-------
Table 2 (Cont.) Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value
Waste Stream
Lead Refining - S02
Scrubwater Sludge
Aluminum Refining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
Number
28
29
30
Totai
Annua".
Cost
38,-110
82,')3C
670,J90
Annual
Value of
Recovered
Material
$ NRV
NRV
306,050
Percent of
Market
Price
Assigned
N.A.
N.A.
Net Required
Annual . Percent Increase in
Cost Recovered Material Value
$ N.A. N.A.
N.A. N.A.
364,340 119
* = Net gain, i.e., value of recovered ra.it<:: ial exceeds cost of alternative waste treatment
N.A. = Not applicable
XRV = No recovery value
- for iron pellets
- for ferric chloride
- for hydrochloric acid
- for roadfill
- for zinc oxide
- for lead
- for zinc
- for cryolite
- for rutile
-1 - for potassium chloride
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unMiry Table of Ut« rnate Treatment Systems.
Benefits. Sta^t of Developmcni, and Costs
•If
Haste Stream Xuaoer
Iron and Steel Coke 1
Production - Annonia
Still tine Sludge
Iron and Steel Coke 2
Production - Decanter
Tank Tar fron Coke
Produdiea
Iron and Steel Prod. - 1
Basic Oxrgea Furnace -
Net EzUsioo Control
Unit Slodge
Iran and Steel Prod.- I
Open Heart* Furnace -
Enisxion Control Dust
Iron and Steel Prod.- S
Electric Furnace - Vet
Emission Control Sludge
Iron and Steel Prod.- 6
lolling Mil Sludge
~-> Ira* mat Sleel Prod.- 7A
Cold lolling toll -
Acid RinseMater Neu-
tralization Sludge
Iron and Steel Prod.- 71
Cold tolling Mill -
Acid lixsevater Neu-
tralization Sludge
(10)
Ira and Steel Prod.- IA
Cold lolling Mill -
Vast* Pickle Liouor -
SultVric Acid (MjSO^
Iron and Steel Prod.- 51
Cold tolling Mill -
Varta fickle Liouor -
Hrdncklorlc Acid (HC1)
Iron tod Steel Prod. - 9A
Calnnizing Mill - Acid
RinseKarer Neutralisation
Sludge (HjSO,)
Iron and Steel Prod.- 91
Cilvanizing Mill - Acid
Rinsevater Seutrali-ation
Sludge (HC!)
HHMUIHkMilk
mfSmmmSKm,
Alternative Trettnent S/vfc'.ric Ton
Process Developnent *'et
of kiste S/Hetric Ton of
Dry Product
Process Category State Keiefis Derived Tjtal Net Total Xct To:»l \;t ,
su.tab.e for cheaical
ladfill
S9.2I S SRV J 0.07 S \RV
Disposal P V De cxified. inert solids M.S8 SRV 324.09 NKV 0.71 SRV
au table for chenical
Uicfill
Reduction C V Fe'ric oxide recovery 12.66 7.36
Roasting far nc/cle. Lead and
zi ic < xide recovery for
sale.
Reduction C V Ferrii oxide recovery for I 12.66 S 7.36 S
Roasting reiyc'e. Lead and zinc
oxide recovery for sale.
Reduction C ¥ Tirrlt oxide recovery for 12.66 7.36
Roasting rtcyc e. Kead and zinc
o:ide xecovery for sale.
Sintering P V lion 'ecovery for recycle 6.46 1.45
Dissolution C V F>rri : oxi de recovery 6.13 NRV
Dissolution C V F;rri: chloride recovery 6.77 SRV
Precipitation C III 1 :rrlc chloride for sale. SS.S4 43.31 1
C ilciun sulfate (gypsun) for
cicnical landfill
Volatilization P IV lfti. chloric acid recovered 31.38 24.80
l ar recycle
Reduction C IV 1 err: c oxide recovered for
Roasting : tus<
Dissolution C V Fertic oxide recovered t 0.99 { NRV f
Dissolution C V Fer -ic chloride 3.74 NRV
mm m -,. _ __'
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29.90 17.40 0.48 C.28
29. 9J t 17.40 t 0,48 t 0.28
29.90 17.41} 0.48 0.24
16. JS 3.6S 0.03 O.OOt
27.40 NRV 0.004 NKV
67.67 SRV 0.003 NKV
36S.82 1,065.24 S.24 4.87
449.78 290.63 2.06 1.3J
3.19 S NRV t 0.04 S NRV
12.47 SRV 0.03 SRV
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Tib It J SiB-jar- Tablt. of Alternate Treaiarai Syste-a. tcnefitl. Stage of Development. and Costi (Cont.J
lute Streax S'uati-r
Ferroalloys,- Ferro- 11
silicon Manufacture -
Miscellaneous nuts
Ferroalloys - Ferro- 12A
silicon Manufacture -
Slag
Ferroalloys - Ferro- 128
silicon Manufacture -
Dust
Ferroalloys - ferro- I2C
silicon Manufacture -
Sludge
Ferroalloys - Silico- 11
•aagaaese Manufacture -
SUg and Scrubter Sludge
Ferroalloys - Terra- 14
aongafvesB Manufacture -
Slag lad Sludge
Copper Sstttting - 15
Acid Plant Slowdown
CO ilectrolytic Ccpper 16
Refining - Mixed
Sludge
Lead Sseltiag - 17
Electrolytic Zinc 18
Manufacture
Pyroawtaliurfical Zinc 19A
Manufacture - Sludges -
Priury Gas Cleaning and
Acid Plant Blxdwn
Pyroactallurjical Zinc 198
.Manufacture - Sludges -
Retort Cas ScrAier
deed
Aluaunuai Manufacture- 20 )
Scrubber Sludges I
Alu-anuti Manufacture - 21 j
Spent Potliners and
Sklamings
AluBinuti Manufacture - 22
Shot Ilast and Cast
House Dusts
Alternative Treatment
Process
Process Category
Disposal P
Precipitation C
Precipitation C
Precipitation C
Reduction C
(eduction C
Routing
Precipitation C
Precipitation C
Sintering P
Precipitation C
Sin:erin( P
Centrifuie P
?re:ipitbtion p g
Evaporation
Drying p ^
Oi spoil! '
Precipitation C
f/Matrlc TOT of tr«t«
Devclopr ;nt let Dry
Stun Bcnrfilr fl.. rived fotai M*t Total Htt
Cheucal landfill ':.A. S.A. 15.88 NRV
V Detoxification K.A. S.A. 1.91 2.91
V Detoxification K.\. N'.A. 18.12 NRV
V Oftoriflcation 13. SJ .VSV J'.ii XSV
IV Ferro and silicoaanganete 2(1.16 IS. 79 50.80 46. it
far recycle
IV Lead and :inc oxide M.Jo 16.79 SO. SO 46.81
for sale
V Detoxification *37".27 S SRV J 88". 97 J SRV
V Lead recycled for 5.80 1.01* 2J.61 5.J6*
reprocessing
V Zinc recycled for 15.81 3.50* 56.25 11.20*
reprocessing
V Zinc recycled for J.36 15.44- 11.78 51.08*
reuse
V Zinc recycled for 15.30 SRV M.59
-------
ry Table of Alternate Treatnei: Sy,te«s. Benefits, Stage of Developrent, and Costs (Cont.)
{/Metric Ton of Maste {/Metric Ton of
, ,-,.« vender Process Cite-orv Sti^ Ins: i:s Derived Total Htt Total Net Total Met
Pyroaetallurgical 21 Precipitaticn C V letoiifi cation $ N.A. J N.A. J 18.40 $ N3V S S2.48 t NRV
Antimony Muwfacture-
Blast furnace Slag.
Electrolytic Antimony It Disposal P - Wtc«ification 55.05 NRV 165.15 NRV 36.70 NRV
Manufacture - Spect
Anolyte Sludge
Titaaiaa Manufacture- 25 Centrifuge P III 'ita iium dioxide (rutile) 12.53 14.85- 31.59 57.41- 10.39 12.31-
Chloriaator Condenser Dewatering -tnd :arbon recovered for
Sludge Recycling -eus:
Copper Befining - 27 Precipitation C V wto.ification X.A. N.A. 37.56 NRV 13.25 NRV
(last furnace Slag
Uad lefining - SOj 28 Precipitaticn C V !*f.
-------
Cost Comparison of Alternative Treatment Processes and Landfills.
The costs for alternative treatment processes and landfill are shown in Table 4 .
The costs are relative and are expressed as ratios with the cost of sanitary
landfill without container!zation used as the denominator. The comparison is
made in terms of cost per metric ton of product. The lowest cost alternative
is designated for each waste.
As would be expected, the costs of sanitary landfill with container-
ization and chemical landfill are always higher than sanitary landfill without
containerization costs. In two cases, Waste Nos. 1 and 7, the sanitary landfill
cost with container!zatiou is the same as the chemical landfill cost. These
cases are characterized by large annual productions and relatively small
quantities of wastes. Containerization represents the dominant cost.
Sanitary landfill is the least cost alternative for 15 wastes when
liquids are not containerized.
Chemical landfilling because of the requirement to containerize
liquid wastes and its inherent higher costs does not provide any least cost
waste candidates.
Alternative treatment processes.excluding recovery values (total),
offer least costs for six of the wastes with one of these, pyrometallurgical
zinc retort gas scrubber bleed, waste stream 19, at par with sanitary land-
filling without containerization.
Alternative treatment processes, where recover/ valuus were included
(imi.1. mTur iuiisL cost possibilities for eicmt of the wastes.
CD C O ~
' S» Si —
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, ^ "* n
3 •-»• -
20
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[ii
-------
Table 4 Relative Costs for Landfill and Alternative Treatment Process (Per Unit of Product)
Waste Stream
Iron and Steel Coke Production -
Anmonia Still Lime Sludge
Iron and Steel Coke Production -
Decanter Tank Tar from Coke
Production
Iron and Steel Production -
Basic Oxygen Furnace - Wet
Enission Control Unit Sludge
Iron and Steel Production -
Open Hearth Furnace - Emission
Control Dust
Iron and Steel Production -
Electric Furnace - Wet Emission
Control Sludge
Sanitary
Landfill
Number W/0 Cent;in.
1
1
Sanitary
Landfill
With Contain.
3.50
5.75
3.83
3.83
3.83
Chemical
Landfill
3.50
5.92
4.35
4.35
4.35
Alternative Treatment
Process
Total
3.5
35.5
0.74
Net
NRV
NRV
0.43
0.74 0.43
0.74 0.43
Iron and Steel Production - 6 1
Rolling Mill Sludge
Iron and Steel Production - 7A 1
Cold Rolling Mill - Acid
Rinseuater Neutralization
Sludge (H2S04)
4.40 4.80 0.60 0.12
4.00 4.00 0.40 NRV
See page 25 for legend.
b 2 1- o- 1 Q
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-------
Table 4 Relative,Costs for Landfill and Alternative Treatment Process (Per Unit of Product) (Cont.)
Sanitary Sanitary Alternative Treatnx
landfill Landfill Chemical Process
Waste Stream Number W/0 Contain. With Contain. Landfill Total Net
78 1 4.00 4.00 0.30 NRV
Iron and Steel Production - Cold
Rolling Mill - Acid Rinsewater
Neutralization Sludge (HC1)
Iron and Steel Production -
Cold Rolling Mill - Waste
Pickle Liquor - Sulfuric Acid
8A
Iron and Steel Production - 8B
Cold Rolling Mill - Waste Pickle
Liquor - Hydrochloric Acid (HC1)
Iron and Steel Production - 9A
Galvanizing Mill - Acid Rinsewater
Neutralization Sludge
Iron and Steel Production - 9B
Galvanizing Mill - Acid Rinsewater
Neutralization Sludge (HC1)
Ferroalloys - Ferrosilicon 11
Manufacture • Miscellaneous Dusts
Ferroalloys - Ferrosilicon 12A
Manufacture - Slag
5.98
5.97
3.59
3.25
N.A.
N.A.
6.19
6.16
3.85
3.55
1.20
1.20
4.88
3.80
3.38 2.18
0.07 NRV
0.15 NRV
1.91 NRV
0.53 0.40
See page 25 for legend.
*•'
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-------
Table 4 Relative Costs for Landfill and Alternative Treatment Process (Per Unit of Product) (Cont.)
Sanitary Sanitary
landfill Landfill Chemical
Sludges - Primary Gas Cleaning and
Acid Plant Slowdown ••
Alternative Treatment
froccss
Waste Stream
Ferroalloys - Ferrosilicon
Manufacture - Dust
Ferroalloys - Ferrosilicon
Manufacture - Sludge
Ferroalloys - Silicomanganese
Manufacture - Slag and Scrubber
Sludge
Ferroalloys - Ferromanganess
Manufacture - Slag and Sludge
Copper Smelting - Acid Plant
Slowdown Sludge
Electrolytic Copper Refining -
Mixed Sludge
Lead Smelting - Sludge
Electrolytic Zinc Manufacture
Pyrometallurgical Zinc Manufacture
Number H/0 Contain.
12B J_
12C j_
13 1
14 1
IS 1^
16 1^
17 1
18 1
- 19A 1
With Contain.
K.A.
6.00
2.70
2.70
3.18
3.33
5.99
5.03
5.99
Landfill
1.20
6.20
3.45
3.45
3.47
3.58
6.19
5.22
6.19
Total
2.28
1.33
1.02
1.02
15.59
20.67
0.65
1.40
0.40
Ket
NRV
NRV
0.95
0.95
NRV
NRV
*
*
*
See page 25 for legend.
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Nl
*"
Table 4 Relative Costs for Landfill an.l Alternative Treatment Process (Per Unit of Product) (Cont.)
Alternative Treatment
Sanitary Sanitary
Lane fill Landfill Chemical Process
Waste Stream Number IV/0 Contain. With Contain. Landfill
Pyrometallurgical Zinc 19B ^ 3.26 3.55
Manufacture - Sludges - Retort
Gas Scrubber Bleed
Aluminum Manufacture - 20 1 5.20 5.54
Scrubber Sludges
Aluminum Manufacture - Spent 21 1 5.20 5.54
Potliners and Skimmings
Aluminum Manufacture - Shot 22 ^ N.A. 1.33
Blast and Cast House Ousts
Pyrometallurgical Antimony 23 1^ N.A. 1.25
Manufacture - Blast Furnace Slag
Electrolytic Antimony Manufacture- 24 l_ 3.23 3.52
Spent Anolyte Sludge
Titanium Manufacture - 25 1 4.29 4.53
Chlorinator Condenser Sludge
Copper Refining - Blast 27 j_ N.A. 1.26
Furnace Slag
Lead Refining - S02 = 28 j, 3.27 3.54
Scrubwater Sludge
Total Net
1.00 NRV
3.49 *
3.49 *
3.00 NRV
1.70 NRV
2.62 NRV
0.80 *
2.78 NRV
1.12 NRV
See page 25 for legend.
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to
I/I
Table 4 Relative Costs for Landfill and alternative Treatment Process (Per Unit of Product) (Cont.)
M&ste Stream
Aluadnifla Refining -
Scrubber Sludge
AliatinuB Refining -
High Salt Slag
29
30
Sanitary
Landfill
Sanitary
Landfill
Nun&er V/0 Contain. With Contain.
1
3.56
N.A.
Chemical
Landfill
3.84
1.20
Alternative Treatment
Process
Total
1.36
6.38
NRV
3.47
= is used to denote that the alternative" trsatment process results in a net gain.
= least cost alternative
.V.A.= Not applicable
NRV = No recovery value
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-------
INTRODUCTION
A study for the U.S. EPA under Contract No. 68-01-2604 has been
completed to assess the waste generation, treatment and disposal practices in the
primary and secondary metals smelting and refining industries. Potentially
hazardous wastes generated by these industries have been identified by that report.
This study assesses alternatives to sanitary landfill disposal of
these potentially hazardous wastes. The processes analyzed identify feasible
alternatives that enable materials or energy recovery, waste detoxification
or immobilization and volume, reduction for comparison with landfill
disposal,
The alternatives analyzed which have potential for treating hazardous
wastes are the physical, chemical, and biological processes which have been
identified under EPA Contract No. 68-01-2288.
were:
The potentially hazardous waste streams considered in this study
Waste
Stream
Number
Ferrous Metal Smelting and Refining Potentially Hazardous Wastes
A. iron and Steei Loke production
f?:
3 S,~:'
3 r+
to -3-
= a
1. Ammonia Still Lime Sludge
2. Decanter Tank Tar from Coke Production
B. Iron and Steel Production
1. Basic Oxygen Furnace - Wet Emission Control
Unit Sludge
2. Open Hearth Furnace - Emission Control Dust ...
3. Electric Furnace - Wet Emission Control Sludge
4. Rolling Mill Sludge
5. Cold Rolling Mill - Acid Pdnsewater
Neutralizat4 on Sludge
6. Cold Rolling Mill - Waste Pickle Liquor
7. Galvanizing Mill - Acid Rinsewater
Neutralization Sludge
3
4
S
6
7
8
26
I
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ro
-------
Waste
Stream
Number
C. Ferroalloys
1. Ferrosilicon Manufacture - Miscellaneous
Dusts 11
2. Ferrochrome Manufacture - Slag, Dust,
and S1 udge 12
3. Silicomanganese Manufacture - Slag and
Scrubber Sludge 13
-------
CO"
-5
Note:
Waste
Stream
Number
B. Lead Refining - S02 Scrubwater Sludge 28
C. Aluminum Refining
1. Scrubber Sludge 29
2. High Salt Slag 30
Waste stream number 10 was omitted from this study because
it is normally recycled. Waste stream number 26, smelter
slag from primary tin manufacture, was deleted from this
study because of insufficient information.
*> £
«= °
3 ,+
"
28
-------
DISCUSSION
The purpose of this study was to assess the alternatives to sanitary
landfill disposal (regardless of current practices) of potentially hazardous
industrial wastes generated by the metals smelting and refining industries.
Processes were identified that lead to materials or energy recovery, waste
detoxification, immobilization, and volume reduction. Costs were compared
with those for sanitary landfill disposal.
Types of watte processing involved in industrial waste reclamation
and recovery may be differentiated as follows:
Regeneration is a process which recovers the waste material in the
same form and composition as the original raw material. For example,
regeneration of hydrochloric acid from spent steel pickling liquor is accomplished
by spraying it into a high temperature chamber in which hydrochloric acid is
distilled and subsequently recovered, leaving a solid residue of ferric oxide
which is recycled for steel making.
Recovery and reclamation involves extracting ono or more components
from a waste material leaving the remainder for disposal. As an example, one
or more metals may be recovered from a waste material but at the end of the
process, remaining residues require treatment and/or disposal.
Recycling implies that the waste material is returned to an industrial
3 5."
2.55
o> e
3 ,
a :
=i o
is recycled tc the Smelting industry with nominal sorting operations but no
jiiajui prOCc5Si.u£ .
Reuse is similar to recycling except that the waste material is
utilized by a consumer different from the waste originator.
The feasibility to regenerate, recover, or reuse waste materials is
dependent on many factors, some of which are:
1. Value of recovered material.
2. Location of processing plant.
3. Concentration of recoverable component.
4. Quantity of waste.
5. Availability of a suitable treatment technique to
produce a recovered product of sufficient purity
for recycle.
6. Recovered material specifications.
29
-------
7. Where the costs for reclamation are economical by
comparison with the purchase of new raw materials
or to the costs of alternative treatment and disposal
procedures.
The major driving force for waste recovery and utilization has been
the profit motive. Unless a waste material can be treated to yield a product
of sufficient value to cover the costs to produce it, there is no profit
motivation and up to the present time the greatest inhibition to recovery has
been the economic factor.
The profit motive has persisted for many years and has dictated
the manner of industrial waste disposal and whether or not resource recovery
is practiced. These attitudes, however, are changing due to changing economic
conditions, resource depletion and most significantly to increasing awareness
of potentially hazardous waste disposal practices. These practices and the
need to conserve natural resources will inevitably increase waste disposal
costs.
The Resource Conservation and Recovery Act of 1976 expands the
Federal role in both the solid waste and resource recovery fields. Regulations
and other endeavors required by this act, will have a serious impact on solid
waste disposal techniques.
Waste disposal practices have affected the safety and availability
of water supplies as attested by numerous reported incidents. Surface water
supplies generally receive attention and are regulated by existing federal
and state pollution control proerams. Groundwat«r «!imnH««. or> the other
hand, ar* not a? Hosdy r^julatsd or protected as surface supplies even
though quality standards tor drinking and other purposes are the same for
surface and groundwater supplies. Approximately one half of the U.S.
population is served by groundwater and its use is increasing at the rate
of 25% per decade.
The wastes of concern in this project generally contain significant
leachable concentrations of toxic elements and are, therefore, considered
potentially hazardous if handled and disposed haphazardly on land. Disposal
methods, whereby waste materials axe exposed to rainwater, surface runoff or
groundwater, are environmentally unacceptable because toxic elements can be
leached into surface or groundwater supplies.
CTJ3
5-1.
e
3
Toxic materials of concern in this study are:
arsonic
cadmium
chromium
copper
nickel
lead
antimony
zinc
30
mercury
manganese
phenols
selenium
cyanides
I
o
•*>
10
-------
Consequently, disposal of wastes containing toxic materials in
unlined pits, ponds, and lagoons or in open dumps is a practice that bears
close study, examination, and scrutiny.
Since most of the potential toxic elements of concern are heavy
metals, the detoxification method used most commonly in this study relies
on reaction of the heavy metals with hydroxides. The detoxification reaction
forms precipitates of low solubility metal hydroxides which are not readily
leached from the waste material. In many instances, we have recommended
disposal of the metal hydroxide in a chemical or secure landfill to preclude
the mobility of residual soluble fractions remaining in the detoxified waste
material. The hydroxide chemicals most commonly used are lime, caustic, and
soda ash.
.ilfide precipitation of heavy metals has also been used to achieve
itrations, than fro~ hydroxide precipitation, in the soluble fraction
Sulfide
lower concent
of a waste. Sludge disposal of sulfide heavy metal precipitates, however,
may result in sulfide oxidation, generation of sulfuric acid and resolubilization
of the metals. SulfiHe nrncinitation has been used in conjunction with 1 i im» to
reduce cadmium levels in those wastes containing cadmium.
In those cases where the filtrates can be recycled, the final
concentration of contaminants is not critical, but when the effluents from
a treatment operation are discharged from the plant, then the system must be
designed to use all practical chemical and physical treatments to meet
effluent standards.
Costs were developed for alternative treatment of .v* potentix!'/
hazardous wastes generated frum jnelais smelling tuiu lexining inuustiics.
The alternative treatments were chosen for minimal impact on the environment,
for materials or energy recovery, waste detoxification or immobilization and
volume reduction. Each waste treatment scheme chosen and described in this
report was an alternative to a sanitary landfill as a minimum and to a secure
or chemical landfill to preserve and safeguard environmental conditions.
Cost comparisons were then made for the alternative treatment scheme,
and for sanitary and chemical landfilling the potentially hazardous wastes.
When material recovery was technically feasible, their value was included in
the treatment alternative costs. Further examination of these treatment and
disposal costs was made by a break-even analyses.
Waste stream number 10, Furnace Emission Sludge from Ferronickel
Manufacture, was deleted from the study because it is presently recycled to
process and is not disposed. Waste stream number 26, Smelter Slag from Primary
Tin Manufacture was also deleted from the study because insufficient information
was available on its characteristics.
Production levels, and the quantities and gross physical
characteristics of generated wastes are summarized in Tnhle S for
typical plants.
31
I
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.... ,,•,!•'.i
-------
Table 5 Summary Table of Waste Quantities, Production
Values and Gross Physical Characteristics
Tyoical
Plant
P reduction Physical
Hast* streaa No. Ml'/yr State
Ammonia Still Lime SludEe 1 2,503,000 Sludge
Decanter Tank Tar from Coke 2 2.500,000 Sludge
Production
Basic Oxygen Furnace - 'Vet 3 2,000,000 Sludge
Emission Control Unit
o, Sludge
K)
Open Hearth Furnace - Emission 4 500,000 Dust
Control Dust (4)
Electric Furnace - Wet 5 SCO, 000 Sludge
Emission Control Sludge
Rolling Mill Sludge 6 1,800,000 Sludge
Cold Rolling Mill - Acid 7A 7CO.OOO Sludge
Rinsewater Neutralization
Sludge (H2S04)
(HC1) 7B 700,000 Sludge
Cold Rolling Mill - Waste 8A 700,000 Liquid
Pickle Liquor - Sulfuric
Acid (H2S04)
F f i f • f •. f • r • • i ' i r i ' ) '
OBBMSff^ -»*.** . ~
"^"HBHlliik o 7 0 "" I- Q
Bulk From Typical Plant
Density Weight MT/yr Volume m3/yr
PciC^Ilt _
Solids MT/ra Dry Wet Dry Wet
30 1.2 700 2,300 - 1,900
15-30 1.2 5,500 27,600 - 23.000
40 2.0 34.600 86,500 - 43,300
1.5 6,900 - 4,600
40 2.0 4,400 10,900 - 5,400
40 1.6 3,100 7,300 - 4,900
30 1.2 100 400 - 300
10 1.1 30 300 - 300
20 1.1 3,200 78,700 - 71,500
} ; i ')•)'• ) i i ) . •
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-------
Table 5 (Cor.t.) Summary Table of Waste Quantities,
Pn-cltction Values and Gross Physical Characteristics
Typical
Waste Stream No.
Cold Rolling Mill - Waste SB
Pickle Liqu>r -
Hydrochloric Acid (HC1)
Galvanizing Mill - Acid 9A
Rinsewater Neutralization
Sludge (H2S04)
(HC1) 9B
Ferrosilicon Manufacture - 11
Miscellaneous Dusts
Quantity Generated
Bulk From Typical Plant
Production Physical Percent D3nsi^ Height MT/yr_Voluno m37yT
^^'/y^ State Solids .W/m Dry Wet _Dry Wet
700,000 Liquid
125,000 Sludge
125,000 Sludge
40,00: Dust
State Solids >fT/m'
20
1.1 3,200 37,500
30 1.6 1,400 4,500
30 1.1 300 1,000
1.5 13,500
34,000
2, BCD
9DO
Ferrochrome Manufacture - 12A 35,000 Slag
Slag
Ferrochroroe Manufacture - 12B 35,000 Dust
Dust
Fcrrochrome Manufacture - 12C 35,000 Sludge 40
Sludge
Silicomanganese Manufacture - 13 40,000 Slag
Slag and Scrubber Sludge
Ferromanganese Manufacture - 14 30,000 Sludge 40
Slag and Sludge
Copper Smelting - Acid Plant 15 100,000 Sludge 40
Slowdown Sludge
^•^^^•^•^•SV|e|jjjL w 7 O "" v* O
1.7 61,300
1.5 5,300
1.2 5,300 13,200
1.7 44,000
1.4' 8,900 22,200
1.2 300 700
;
9,000
36,000
3,500
11,000
25,500
15, 900
600
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-------
Table 5 (Cont.' Summary Table of Waste Quantities, Production
Values and Gross Physical Characteristics
Waste Stream
Electrolytic Copper Refining-
Mixed Sludge
Lead Smelting - Sludge
Electrolytic Zinc Manufacture
Sludge
Pyroaetallurgical Zinc
Manufacture - Sludges
Pyro. Zinc Mfg. - Retort
Gas Scrubber Bleed
Aluminum Manufacture -
No.
16
17
18
19A
19B
20
Typical
Plant
Product Ion
^f^/y•--
160, C. 10
110
100
107
107
153
,000
,100
,030
,000
,000
«
Physical
State
Sludge
Sludge
Sludge
Sludge
Sludge
Sludge
Percent
Solids
40
30
30
30
30
30
Bulk
^uantiiy ueneratea
From Typical Plant
Density Weight MT/yr
Mr/m3
1.
1.
1.
1.
1.
1.
3
2
3
3
8
4
400
6,500
2,600
13,000
1,100
17,900
1
21
8
43
2
59
Wet
,100
,600
,700
,000
,200
,500
Volume nryyr
Dry Wet
700
18,000
6;700
33,100
1,200
41.400
Scrubber Sludges
Aluminum Manufacture - 21
Spent Potliners and
Skimmings
Aluminum Manufacture - 22
Shot Blast and Cast
House Dusts
153,000 Solid
153,0"0 Dusts
2.4 9,000
1.2 1,100
3,700
1.000
Pyrometallurgical Antirony 23
Manufacture - Blast
Furnace Slag
Electrolytic Antimony 24
Manufacture - Spent Anolyte
Sludge
2,700 Slag
<>00 Sludge
2.0. 7,700
30 1.4
200 600
3.800
450
• •»
II
ui
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T. )
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-------
Table 5 (Cont.) Sjmmary Table of Waste Quantities, Production
Values and Gross Physical Characteristics
Waste Stream
Titanium Manufacture -
Chlorinator Condenser
Sludge
Copper Refining - Blast
Furnace Slag
Lead Refining - S02
Scrubwater Sludge
Aluminum Refining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
No.
25
27
28
29
30
TvDical
Quantity Generated
Bulk From Typical Plant
Production Physical Percent Densi^ Weight NfT/yr Volume
State Solids MF/m
7,600 Sludge 40
10,000 Slag
10,000 Sludge 30
20,000 Sludge 30
10,000 Slag
1.2
Drv
Wet
1.2 2,500 6,300
2.0 3,500
450 1.500
1.2 1.500 5,000
2.0 14.000
Drv
Wet
5,200
1,800
1.250
2,500
7,000
if '
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-------
PART I
ALTERNATIVE TREATMENT OF HAZARDOUS WASTES
FROM THE METALS SMELTING AND REFINING INDUSTRIES
NOTE:
The costs, cost factors, and methods used to calculate capital and annual
costs are presented in Appendix A, "Cost Data Base."
36
CD_ C O
{Q ™p O
• Q —•
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-------
-------
lime content is utilized to detoxify the hazardous constituents, such as
the heavy metals which are maintained as insoluble hydroxides. The
sludge is containerized for chemical landfilling.
Cost of Alternative Method of Waste Handling. A schematic diagram of
the flow scheme for the alternative method of disposal is shown in Figure 1.
A summary of capital and operating costs is shown in Table 6.
Treatment consists of sludge storage in an existing 7.6 m (2,000
gal.) tank from which the sludge is containerized and disposed in a chemical
landfill.
3 s;~
<• —
a. E* •
-------
AMMONIA
STILL ^.
SLUDGE
676 MT/year
7.6m3
TRUCK
SLUDGE
STORAGE
^_ CHEMICAL
w LANDFILL
Figure 1. SCHEMATIC DIAGRAM OF AMMONIA ST.'LL SLUDGE
ALTtftNAIIVfc IKtAIMfcNI (WASTE STREAM NUMBER 1)
39
I O
f>
,
3 ^.:
« =r;
3
-------
TABLE 6
Capital and Annual Operating Costs for Ammonia Still Lime Sludge
Alternative Treatment Method (Waste Stream Number 1)
700
.WETWCIGHT 2' 30°
ANN'.'AL f RODUCTION (METRIC TONSl: 2.500.000
ANNUAL WAiTE (METRIC TONS): DRY WEIGH!
CAP!'. A L COST
i-ACILITIES
EQUIPMENT
Transportation equipment costs are included in land disposal costs.
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
OPERATIONS AND niAiniTeNAraCE !O&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
or-o => ;
2. e °
->,*< * <
S. 5 •"!
«§•!
?• i
0 Jf :
i :
3 <-*• .
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
$181,450
$181.450
_ I
COS! /METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$78.89
259.21
0.07
SHORT TONS • 0.9 x METRIC TON
40
I
o
-------
A. Iron and Steci Coke Production
2. Decanter Tank Tar
(Waste Stream Number 2)
Waste Description. Coke oven gases are cooled with water sprays
which condense tars. The condensed tars are sent to a separation or decanter
tank where dense materials settle to the bottom and arc removed as decanter
tank tars. The lighter, loss dense materials such .as oils are decanted for
by-product recovery. ,\ typical steel mill producing 2,500,000 MT/yr will
generate 5,524 MT/yr of decanter tank tar.
These tars contain high concentrations of phenol, cyanide and heavy
metals and are therefore, considered potentially hazardous. Tar analyses and
solubility te«t- Ciltral-n analyses t\rc as follows:
Analysis of Tar (ppm)
1
Oil and Grease 15-30% Nickel <10
Phenol 0.2% Lead 30
Chromium 4
Copper 1
Manganese 44
Lead 30
Zinc 20
Cyanide 6
Water 70-85%
Thermal Content 2,700-5,400 Btu's/lb
Sni ii'ni i i t.y TKSL Filtrate Analyses
|!I
I ° 5
CO 3- JJ
3 • w
Manganese <0.01
Chromium < 0.01
Copper < 0.03
Load < 0.2
Nickel
N>
-------
Cost for Alternative Method of Waste Handling. A schematic
diagram of the alternative waste handling process is shown in Figure 2.
A summary of capital and operating costs is shown in Table 7 .
The waste tars are stored in an existing 19 m (5,000 gal.) holding
tank for containerization and disposal in a chemical or secure landfill.
»..• I
I
c o •"
5" 2. ~ =
§•- e
o »f -
a S
3 r* =
» =r r
«• «« °
-------
CO™
s» a: —
8
DECANTER
TANK TAR •
5524 MT/yetr
19m3
TRUCK
CHEMICAL
LANDFILL
TAR STORAGE
Figure 2. SCHEMATIC DIAGRAM OF DECANTER TANK TAR
ALTERNATIVE TREATMENT (WASTE STREAM
MIIMRFR ?)
o
I r+
CD :r
3 CD
5
W
43
I
O
^
ro
j
l^sSSffl
-------
TABLE 7
Capital and Annual Operating Costs For Decanter Tank Tar -
Alternative Treatment (Waste Stream Number 2)
2 JOCK 000
WET WEIGHT 27>600
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): OR V WEIGHT S>500
CAPITAL COST
FACILITIES
EQUIPMENT
Transportation equipment costs are included in land disposal costs.
_£.s i
3 ** :
2 2T <
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
*MnRTI7ATION
OHtHAIIUNS ANU MAINTENANCE \0&mi
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OP WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
$1,782,410
$1,782,410
TOTAL
$ 64.58
324.09
0.71
I
O
A
ro
SHORT TONS • 0.9 x METRIC TON
44
g
-------
*
,-S
B. Iron and Steel Production
1. 'Basic Oxygen Furnace - Wet Emission Control Unit Sludge
(Waste Stream Number 3)
2. Open Hearth Furnace - Emission Control Dust
(Waste Stream Number 4)
3. Electric Furnace - Wet Emission Control Sludge
(Waste Stream Number 5)
Waste Description. The sludges and dusts are generated in wet and/or
dry air cleaning systems, nnd may contain significant quantities of leachable
fluorides, lead, zinc and possibly copper and chromium as well. The latter
two heavy metals occur primarily in electric furnace wet emission control
sludge. The iron content of these dusts and sludges is very high and varies
from 29 to 55* of the total weight. Analyses and solubility test data which
indicate the potentially hazardous nature of these wastes are summarized as
follows:
Analyses of Dry Emission
Control Participates*
Iron %
Zinc °s
Manganese t
Lead °i
Cyanide ppm
Chromium ppm
Copper ppm
Nickel ppm
Fluorine ppm
Basic Oxygen
Furnace
Emission
Control
Sludge
54
3
1
0.4
500
120
210
65
Open Hearth
Furnace
Pmi 5 5 i OP
control
Dust
SS
5
0.5
0.8
600
1,000
240
Electric
Furnace
Fmi««i on
Control
Sludge
29
16
4
2
1.300
2,700
300
2,400
"=> '
3 rt- :
45
I
O
4*
10
-------
.o a =•
e o •
• P> r* _
Analyses of Filtrate from Solubility Tests
on Emission Control Particulatesl (mg/1)
Basic Oxygen
Furnace
Emission
Control
Sludge
Manganese
Chromium
Copper
Lead
Nickel
Zinc
Fluorine
PH
0.5
0.09
.09
.2
.5
.13
0.
0.
0.
0.
14
10.4
Open Hearth
Furnace
Emission
Control
Dust
12
0.03
0.06
0.4
0.4
0.1
19
8.9
S" »
2 ? =
Electric
Furnace
Emission
Control
Sludge
0.03
94
0.17
2.0
<0.05
0.06
11
11. S
Total amounts of waste generated from typical mills are summarized
as shown following:
Basic Oxygen
Furnace
Emission
Control
Sludge
Open Hearth
Furnace
Emission
Control
Sludge
Electric
Furnace
Emission
Control
Sludge
T'^ic^l P1 ?r»*
Production (KT
r**. . _ i / — -\
u> C W 1 1 J i J
Emission Control
Particulate
Generation
(kg/MT steel)
Total Generation
(Mf/year)
•? n
in6
17.3
34,600
13.7
6,350
0.5 x 106
8.7
4,350
Present Waste Disposal Methods. When these wastes are sufficiently
low in lead and zinc, they are recycled to the sintering plant. When the
contaminant concentrations arc too high and cannot be diluted with other low
lead and zinc waste materials such as rolling mill sludge, they arc disposed
in open dumps. Surface or groundwater may leach toxic elements from these
waste materials into tne environment.
46
-------
cr.o 3
» c o
~
-
8
Recommended Alternative Treatment Method. The proposed alternative
treatment process is one that removes the lead and zinc contaminants from the
hij;li iron content waste materials, in a central recovery facility. The
lead and zinc recovered as oxides may be sold to lead and zinc smelters. The
residue, high in iron oxide, is then recycled to the blast furnace.
The alternative treatment is known as the Kawasaki Process and was
developed by Kawasaki Steel Corporation (Japan). Figure 3 presents a schematic
flow diagram of the process. The process recovers most of the lead and 95%
of the zinc content of the feed in dust form and produces prereduced pellets
that can be fed to the blast furnace.
Iron oxide fines from emission control particulatcs arc dewatered
if necessary and analyzed. They arc mixed and the water and carbon content
is adjusted. The mixture is pcllotizcd on disc pclletizers without addition
of any beiiluuilf, as DCf dust ir- claimed to have a good binding effect. The
green pellets arc charged onto the grate prchcater. The hematite bonded
pellets enter the kiln where coke serves as a fuel and to generate a reducing
atmosphere, Lead and zinc are precipitntrvl from tho kiln's off-gases and sent
to zinc smelters. The prereduced pellets pass through a rotating
cooler prior to being discharged. The amount of zinc acceptable in
the charge is limited to roughly 5%.
The process was developed in the mid sixties. The first commercial
plant was put onstream at the Kawasaki Chiba Works in December 1968. A
240,000 tons per year plant was commissioned for the Kawasaki Mizushima Works
in in?'* A« nf rnHay. this is the most advanced and commercially proven
;.'i•_••;<.-5< f.ir r.'nr. rcr.tnir.ir.c dusts to nrrvln 7.inr-frpp prereduced iron pellets
for recycle to the blast furnace.
Cost of Alternative Treatment Method. Each steel mill combines the
open hearth dust or electric furnace sludge with the EOF sludge. This sludge
is then centrifugcd. Approximately 50,000 metric tons (55,000 s. tons) of
centrifuge discharge (dry weight) is produced annually. Eight man-hours per
day arc assigned to the operation. Costs are shown in Table 8 .
The centrifuge discharge is shipped to a centrally located processing
plant sized to accept wastes from eight or nine mills. The waste is combined
with coke breeze, pelletized and processed in a Kawasaki kiln.
Costs for a central Kawasaki process facility serving eight mills
arc presented in Table 9 . The costs shown are developed from cost estimates.
About 70,000 metric tons (77,000 s. tons) of coke breerc are required
each year. Fuel for the drier operation totais 138 x 109 kg cal (248 x 10* Btu's)
per year; average electrical energy consumption is equivalent to 1,000 hp. It is
assumed thnt each of the mills generates 70,000 me.tric tons (77,000 s. tons) of
centrifuge discharge (wet weight) which is transported 40 km (25 miles) to
47
§"•!
O r* -
I t
3 r+ •
a zr :
-------
IN-PLANT
(8 MILLS.*
Figure 3. SCHEMATIC DIAGRAM OF ALTERNATIVE PROCESS FOR MATERIAL
RECOVERY FROM STEEL MILL EMISSION CONTROL WASTES
(WASTE STREAMS 3, 4 AND 5)
48
IS. 3. ^ i.
CD o.
a. 9
I ?
3 "
CD =T
I 3 CD
I »*
I
O
^
10
-------
r.8g
TAELC 8
In-Plant Capital and Annual Operating Costs for Each of Eight Mills Using
a Central Processing Facility (Waste Streams Numbers 3, 4, and 5)
ANNUAL PRODUCTION (METRIC TONS): 2,500,000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 40,000
CAPITAL COST
FACILITIES
Sludge Sump
EQUIPMENT
Centrifuge $28,000
Sludge Conveyor 20,000
Pump 1,700
Piping 4.900
Installation 42,700
WET WEIGHT 94,500
$ 6,600
«*%• **••*»
e to the
ocjmen
97,300
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
UfhftATIONS AND MAINTENANCE (OE.M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
$47,250
4,990
4,990
TOTAL
$0.89
2.09
0.03
20,800
$124.700
20,300
57,230
6,120
83.680
I
o
-fit
to
SHORT TONS " 0.9 x METRIC TON
-------
TABLE 9
Capital and Annual Operating Costs for Central Treatment Facility
(Kawasaki Process) Serving Eight Mills (Waste Streams Numbers 3, 4, and 5)
ANNUAL PRODUCTION (METRIC TONS):
20.000.000 f ^8 plant-*]
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 350.000 vupTmc.»uT soo>000
CAPITAL COST
FACILITIES
EQUIPMENT
Installed Equipment
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL*
TAXES AND INSURANCE
ENERGY
.
569,000
3,500,000
569',280
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
$9.80
TOTAL
$17.80
13.99
25.42
0.24
0.44
*Waste Transport
SHORT TONS • 0.9 x METRIC TON
50
$5,930,000
5,930,000
2,372,000
11.4.23
2,319,820
5,827,160
751,200
t 8.898,^80
$ 4,000,000
4.898.180
5" Pi !±
<» ex.
3 rf
a zr
-------
cr-o s
c o
the central processing plant at a cost of $0.06/ton mile. Four men per
shift, are estimated to bo required for operating the process facility.
Tho major product generated in the process is iron pellets. About
200,000 metric tons (220,000 s. tons) of iron pellets are recovered annually.
A value of $20 per metric ton ($18 s. ton), the approximate price of iron
pellets, is assigned to the material. No value tfas assigned for the recovered
lead and zinc oxides.
Assuming eight mills share the costs of the centralized processing
plant, each mill has the following individual costs:
Capital Cost
In-plant $ 124,700
Process Plant (Pro-rated share) 1,779,000
TOTAL $1,903,700
Annual Cost
In-plant $ 83,680
Process Plant (Pro-rated share) 1,112,270
Recovered Material Value
«i ioc ocn
f -1 - - - i - ~^_
$ 500,000
3 r»
Net Annual Cost
Cost/Metric Ton of Waste
Wet Basis
Dry Basis
Cost/Metric Ton of Product
$ 695,950
:ict
$ 7.36
17.40
0.28
Total
$12.66
29.90
0.48
I
o
^
ro
SI
-------
~m V
if
B. Iron and Steel Production
4. Rolling Mill Sludge
(Waste Stream Number 6)
Waste Description. In the production of finished steel, the rough
billets, blooms and slabs from continuous casting mills and primary rolling
mills are sent to hot rolling mills where they are converted into a wide
variety of finished or semi-finished products including bars, rods, tubes,
rails, and plates. These hot rolling operations produce scale which is collected
in pits. The coarse scale is removed from the pits and recycled to the sinter
plant to reclaim iron value. The finer materials settling to the bottom of
the pit constitute the hot rolling mill sludge. The typical large integrated
steel plant processing 1,800,000 MT of steel through the hot rolling mill per
year produces 3,130 MT/yr of hot rolling mill sludge solids. The sludge
solids generation rate is 1.74 kg/MT of rolled steel.1
The principal component of mill scale is iron and iron oxide which
comprise 85-95% of the dry weight. Oil and grease content of the scale ranges
from 5-15% dry weight. The estimated trace metal composition of the hot rolling
mill sludge solids is shown as follows:1
Analysis of Solids in Sludge1 (%)
sj --
Chromium 0.03
Copper 0.025
Manganese 0.35
Oii-Grvasu 5-16
Nickel 0.025
Lead 0.05
Zinc 0.004
The oil and grease and perhaps trace metal content of this sludge
could present an environmental problem if leached into ground or surface
waters. An indication of the low magnitude of this possibility is shown
by the following data:
Solubility Test Filtrate Analyses (mg/1)1
Manganese < 0.01
Chromium 0.05
Copper 0.03
Lead <0.2
Nickel <0.05
Zinc 0.03
Oil $ Grease 0.5
pll 9.6
Present Waste Disposal Methods. At the present time, sludges
removed from hot rolling mills are open dumped on land. This practice could
produce- ground or surface water contamination from contained oil and grease
and possibly from heavy metals.
I
O
52
-------
or jo a :
e o '
Recommended Alternative Method for Waste Treatment. Because of
the very high iron and iron oxide content of hot rolling mill sludge solids
(85-95%) , it should be possible to recycle these solids to the sinter plant
for agglomeration and reclamation of iron values. A .system for processing and
reclamation of this sludge is shown in Figure 4. In this system, the scale
pit sludge amounting to 14 m5/day at 40°. solids is contrifuged to a solids
concentration of 80i>. These solids, amounting to 11 MT per day would be sent
to the sinter plant and processed for iron recovery. The filtrate from the
centrifuge amounting to 14 m3 would be sent to the mill wastewater treatment
plant where it would comprise less than 1% of total plant wastewater flow.
The above system will eliminate land disposal of hot rolling mill
sludge and thus obviate any associated ground or surface water pollution
potential. The oil and grease content of the sludge solids which are recycled
to the sJnter may result in increased hydrocarbon emissions from the sinter
operation. All of the iron values are recovered.
Alternative Waste Treatment Costs. The underflow frca the existing
scale pit is pumped to a 25 hp centrifuge. The centrifuge is operated 8 hours per
day. The centrifuge discharge is put in receiving bins and transported to a
sinter plant for recycling. The transport charge is estimated at Si/metric
ton ($0.90/s. ton). Four man-hours of labor per day are assigned to the
operation, excluding transport.
The centrifuge discharge is estimated to contain 1,953 metric tons
This yn'ue is bsseci or?
§"•
o «*
™3 -*- •
tun ($lu/s. ton) is assigned to thin waste.
the approximate value of iron pellets.
A block diagram of the recycle process is shown in Figure 4 and
the cost development for the process is summarized in Table 10.
53
I
O
£t
10
I
-------
-------
*
TABLE 10
Capital and Annual Operating Costs for Rolling Mill Sludge -
Alternative Treatment (Waste Stream Number 6)
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
Sump
EQUIPMENT
Centrifuge
Sludge Bin
Pump
Piping
Installation
1,?00,000
3,100
WETWCIGHT
$45,000
2,700
1,000
400
34,800
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
MMUHIIIAMUN
OPERATIONS .*.!».'!> !ulA.'NTENA*!Ct: 'P**»»
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
$18,900
4,180
3,920
4,180
NET
$1.45
3.65
TOTAL
$6.46
16.25
0.006
0.03
SHORT TONS - 0.9 x METRIC TON
55
_7.800
$ 3,100
83,900
17,400
104.400
31,180
2,170
$ 50,370
39,060
$ 11.310
3 .f :
5 g"L ,
r+ (|
I
I
o
to
-------
B. Iron and Steel Production
S. Cold Rolling Mill - Acid Rinsewater Neutralization Sludge
(Waste Stream Number 7A and 7B)
Waste Uescription. In cold rolling mills, previously hot rolled
steel is further processed to improve surface qualities and workability.
Before further treatment in the cold rolling mill, the steel products are
dipped in vats of hydrochloric or sulfuric acid (i.e. pickle liquor) to
clean surfaces. After removal from the pickling vats, the steel forms
(bars, plates, etc.) are rinsed with water. The rinscwatcr is neutralized
with lime resulting in lime sludge. When sulfuric acid is used for pickling,
the sludge solids generation rate is 0.16 kg/NTT of stocl. When hydrochloric
acid is used, the sludge solids generation rate is 0.04 kg/MT steel. A
typical plant which processes 700,000 MT of steel annually in the cold rolling
mill will produce 112 W of dry sludge solids f373 MT wet) if sulfuric acid
is used for pickling or 28 MT of dry solids (93 MT wet) if hydrochloric acid
is used. Cold rolling mill sludges will be composed principally of calcium
sulfate, iron, iron sulfatc, iron chloride, and iron oxides. They will also
contain oil and grease and hydroxides of heavy metals including chromium,
nickel, copper, and zinc. They arc considered potentially hazardous because
toxic heavy metals and oil and grease may solubilize and enter the environment.
A sample sludge analysis is as follows:
Sample Acid Rinscwatcr Sludge Analysis (ppm)1
5" 2. ^ —
^
5"" P» 2
2 3" = 3
5 *^*
I* ",2
<•
t .n riniu Lint I .612
Copper 403
Manganese 658
Nickel 2,035
Lead 191
2 5 r. c 9! 5
Cyanide 9.4
Oil and Grease 35,900
Phenol 1.8
Present Waste Disposal Methods. At the present time, sludges from
the cold rolling mill are open dumped on land. This practice could pose a
potential threat to groundwatcr and surface water quality if oil and grease
and solubilized metals in leachate cither percolate through permeable soils
to groundwater or are carried in runoff to surface waters.
Recommended Alternative Treatment Method. The disposal of acid rinse
neutralization sludges on land may be readily eliminated by combining them with
spent pickle liquor for recovery of iron and acid. The volume of clarifier
underflow sludges from neutralization of acid rinsewater will be less than one
cubic meter/day. This volume is insignificant compared to the daily volume of
spent picklo liquor amounting to 200 m^/day. The next section of this report
on waste stream number 8, describes processes for iron and acid recovery from
spent pickle liquor. The elimination of land disposal of acid rinse neutralization
sludges obviates any chance of ground or surface water contamination from their
disposal.
56
I
O
10
-------
There arc no known plants now using the proposed method of handling
acid rinse neutralization sludges.
Costs for Alternative Treatment Method of Waste. A diagram showing
the recycle of acid rinsewatcr neutralization sludge is shown in Figure 5.
The costs for the alternative disposal of sulfuric and hydrochloric acid
rinsewatcr neutralization sludge are summarized in Tables 11 and 12.
The sludge is pumped periodically to a storage tank where it is
mixed with spent pickle liquor. Either two or three man-hours per week are
assigned to the operation, depending on volume of acid neutralized sludge.
The sludge has no recovery value because of its relatively low volume but
will add to overall recovery of iron from spent pickle liquors.
?- e;
• §••*
Q.S r
=> n -
»* t
57
f M«HW Oik* M^T3
iE^tt^i
-------
0.32 MT/«Uy - SULFURIC ACID OR
0.08 MT/day - HYDROCHLORIC ACID
ACID RINSEWATER
NEUTRALIZATION SLUDGE
I
PUMP
T
EXISTING SPENT PICKLE LIQUOR
STORAGE TANK
Figure 5. SCHEMATIC DIAGRAM OF ACID RINSEWATER
NEUTRALIZATION SLUDGE RECYCLE.
(WASTE STREAM NUMBER 7A & B)
is
-------
TABLE
Capital and Annual Operating Costs for Alternative Treatment of Sulfuric
Acid Rinse Water Neutralization Sludge (Waste Stream Number 7A)
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Pump
Piping
Installation
700,000
100
WET WEIGHT 4QQ
$800
600
800
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
$2,110
100
100
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$ 6.85
27.40
0.004
SHORT TONS • 0.9 x METRIC TON
59
$2.200
400
$2.600
$ 420
2,310
10
.t J. 740
i"s
CD 3" ST
I
o
A
N>
-------
-»«< - »
TABLE 12
Capital and Annual Operating Costs for Alternative Treatment of Hydrochloric
Acid Rinse Water Neutralization Sludge (Waste Stream Number 7B)
§-5g
n «-f 3
ANNUAL PRODUCTION (METRIC TONS):
700.000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 30
CAPITAL COST
FACILITIES
WETWEIGHT
300
EQUIPMENT
Pump
Piping
Installation
$800
600
800
$2,200
CONTINGENCY
TOTAL CAPITAL INVESTMENT
A ktftll I A 1
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&MI
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
$1,400
100
100
$1,600
10
$2.030
I
o
£*
10
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$ 6.77
67.67
0.003
SHORT TONS » 0.3 x METRIC TON
60
-------
CD C O ~
* f° w "
=*c?.!
!3 °~;
12. ^ »' ?
P. Iron and Steel Production
6. Cold Rolling Mi 11 - Waste Pickle Liquor
a. Sulfuric Acid
(Waste Stream Number 8A)
Waste Description. Iron oxides, oil, Tease and dirt must be
removed from metal surfaces before subsequent steel finishing operations
such as cold rolling, annealing, galvanizing and tin plating. This is often
done by dipping the metal in 20°6 sulfuric acid followed by water rinsing to
remove the acid (hydrochloric acid is also used for pickling).
The quantity of waste acid generated from a typical plant which
pickles 700.000 MT of stoel per year is 79,000 MT. The pcr.eraticr. rate of
waste liuifuric acid pickle liquor is 115 kg/Ml of steel processed.
Waste sulfuric acid pickle liquor contains 13-15% iron principally
as iron snlfate from the reaction of sulfuric acid on iron oxide scale. In
addition, dissolved or particulate trace metals,including chromium, copper,
nickel, lead, zinc, oil, and grease will be present. The highly acid nature
of pickle liquor, toxic heavy metals, oil and grease make this waste a
potential environmental hazard. A sample analysis is as follows:
Sample Analysis of Waste
^1,1 TIM-;, A.-;.I PM-I.IM t.; >•! Cmu/ii
3 r* :
c» =r ;
^n^^^^e <,,|Vom l< ikH.
Free Sulfuric Acid
Chromium
Copper
Manganese
Nickel
Lead
Zinc
13
10
230
14
2.2
12
2-7%
Present Waste Disposal Methods. At the present time, waste sulfuric
acid pickle liquor is generally handled by contract disposal service companies
who neutralize it and leave residual solids in sludge lagoons. These solids
will be primarily calcium sulfate, iron sulfates, and heavy metals. Impoundment
in unlined lagoons with permeable soils could create ^roundwater pollution
problems if sulfite or other reduced forms of sulfur or toxic heavy metals
percolate to groundwater. Hence, these wastes are potentially hazardous.
I
O
K.
ro
61
-------
CD C O '
5" 2. =£ ;
-
Recommended Alternative Treatment Method. Figure 6 presents a
system for recovery of iron from spent sulfuric acid pickling liquor as
ferric chloride. The typical steel plant which pickles 2,000 MT/day of
steel produces 190 m3 of spent sulfuric acid pickle liquor. By the use
of the conceptual system shown, an estimated 63 WT of ferric chloride can
be recovered per day. This ferric chloride can find use in municipal
wastewater treatment as a primary coagulant and for phosphorus removal.
In the system, 190 mVday of spent sulfuric acid pickle liquor is
first blended with 77 m3 of 40% calcium chloride solution. The resulting
slurry is centrifuged for solids concentration. Approximately 36 m3 of
gypsum (i.e. CaS04) cake weighing 67 WT is produced per day. This cake would
be disposed in a chemical landfill.
Th? filtrate fron th? ci?ntr'£"g'* amounting to 240 m3/Hay is sent to
reduction tanks where scrap iron is added to increase conversion of iron to
ferrous chloride to deplete hydrochloric acid in the filtrate. The reduced
filtrate is then sent to chlorinators where ferrous chloride (Fed?) is
converted to ferric chloride solution (FcCls). Evaporators arc then used to
concentrate the ferric chloride to 110 m3 of 42-45% FeClj per day which would
be marketed. Evaporated water amounting to 127 m3/day can be recycled for
process use where high quality water is needed.
The environmental advantages associated with the ferric chloride
recovery process include substantial reduction of waste volume for disposal
(190 m3 reduced to 30 m3) as well as resource recovery. An effluent discharge
fiviii it-"' ' I°A*' r.r.t.l r,r, st picl'.ic liquor would bp <»1 i minaroH since « portion is
i'^COy^ I'*"1'.! P.? •? V2rlCIT"n^rtr' rnridrn~rit-r> pr.-l ,1 nrirtinn i <: rnrvrlorf n^ tho 4?-
-------
SOLIDS GYPSUM
TO CHEMICAL
LANDFILL
36m3/d»y
67 MT/diy
SCRAP IRON
9 MT/day
RECYCLE WATER ^
127m3/div "^
DUPLICATE
PUMPS
t
EVAPORATOR
TRIPLE
EFFECT VAC
FERRIC CHLORIDE
STORAGE TANKS
110m3/d»y
63 MT'day
Figure 6. SCHEMATIC DIAGRAM OF FERRIC CHLORIDE RECOVERY FROM SPENT
SULFURIC ACID PICKLE LIQUOP (WASTE STREAM NUMBER 8A)
63
-------
TABLE 13
Capital and Annual Operating Costs for Alternative Treatment of Waste
Sulfuric Acid Pickle Liquor (Waste Stream Number 8A)
ANNUAL PRODUCTION (METRIC TONS): 70° » °°°
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Storage Tanks
Reduction Tanks
Pipeline Mixer
Centrifuge
Chlorine Evaporator
Chlorinator
Evaporator
Pumps
Piping
Installation
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCb (O&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE NET
WET BASIS $ 43.31
DRY BASIS 1.065.24
COST/METRIC TON OF PRODUCT 4 • 87
3r200 WET WEIGHT
$ 875,000
240,000
5,500
120,000
12,400
18,000
280,000
7,400
29,400
1,450,700
$ 302,400
291,690
2,126,650
133,440
291,690
TOTAL
$ 55.54
1.365.82
6.24
78,700
$3,038,400
3,038,400
1,215,400
S 7.292,2^
$ 1,188,630
3,145,870
36,120
$ 4.370.fi^p
961,840
$ 3.408.7^
r-o a =•:
LH^
r* 5 «• '
,ve * • i
: 2. ~ 2.
- a
.?*«•»
SHORT TONS - 0.9 x METRIC TON
64
rc
-------
a c Q
5-SL?
The centrifuge filtrate flows to reduction tanks where nine metric
tons (10 s. tons) of scrap iron arc added daily. Chlorine, at a rate of 13.h
metric tons (15 s. tons) per day, is then added to the wastewater which is then
pumped to a multiple-effect evaporator. The condcnsatc flows to storage tanks
and the water is recycled. Sixty-four man-hours per day are assigned to the
operation.
The recovered material, 40% ferric chloride, is valued at $17.60 per
metric ton ($16/s. ton). A recovery value was not assigned to the gypsum
centrifuge cake.
•S"
B
a
I
O
-------
s- «
** - '
B. Iron and Steel Production
6. Cold Rolling - Waste Pickle Liquor
b. Hydrochloric Acid
(Waste Stream Number SB)
Waste Description. Inorganic acids are used to chemically remove
oxides and scale from metal surfaces before further metal processing. The
pickling process is used most widely in the manufacture of sheet and tin mill
products because of relatively low operating costs and ease of production.
The spent hydrochloric acid pickle liquor contains free hydrochloric
acid, metal chlorides, oil, inhibitors, and is potentially hazardous.1
Analyses of Spent Hydrochloric Acid
Pickle Liquor (Liquid Phase) (mg/l)l
Free Hydrochloric Acid 0.5-1.5»
Ferrous Chloride 20-30%
Chromium 7.S
6.4
213
11.8
0.75
Copper
Manganese
Nickel
Lead
Zinc
Oil and Grease
7.3
55
t* vrxi
•
.•.".-.t.~. hv.Hrn.-h ! .~. r- .- ~.~:
••• ....... '
Present Waste Disposal Methods. These wastes may be discharged to
a receiving stream after dilution with rinsewaters, ir.ay be discharged onto
open dumps, or may be neutralized with lime before disposal as above. These
practices are hazardous to the environment and are receiving the necessary
attention for improved disposal procedures.
Recommended Alternative Treatment Method. The trend in the industry
has been from sulfuric acid pickle solutions to hydrochloric acid solutions.
Hydrochloric acid offers several economic advantages over sulfuric-acid
pickle solutions. Spent hydrochloric acid is more suitable for regeneration
and recycling than is spent sulfuric acid because of its greater volatility.
In addition, regeneration and recycling spent hydrochloric offers a solution
to a difficult disposal problem, relating to the high solubility of its lime
neutralization salts. The regeneration process for spent hydrochloric acid
is generally used on continuous pickling lines.
66
I
o
A
ro
-------
The spent pickic liquor containing ferrous chloride is sprayed into
a reaction chamber that may be either a spray or fluidized bed roaster. Most
of the iron oxide formed in the roaster is recovered as pellets in the case
of the fluidized bed and as a powdery rouge- in the case of the spray roaster.
The recovered iron oxide rouges may be sold as a by-product or, if pellets,
returned to the steel manufacturing process. Ferric oxide in the roaster
off gases is removed in a cyclone. Hydrochloric acid is recovered from the
gases in an absorber and returned to the pickling line.
The spent hydrochloric acid regeneration process is being used
successfully in full-scale plants throughout the United States, Canada,
Europe, and Japan. These vary in size from as little as 3 GPM to 60 GPM.
The process offers many advantages and benefits in that it enables
the conversion of a hazardous waste to recycled hydrochloric acid and recovery
of iron oxide. The disadvantage of the process is its relatively high capital
and operating costs.
The process described in this report is the fluidized bed reactor
generating ferric oxide pellets. In the pickle bath, the scale is dissolved
with hydrochloric acid to form ferrous chloride and water. The hydrochloric
acid concentration decreases as the dissolved ferrous chloride increases.
The spent pickic liquor is pumped through a venturi scrubber where
it is concentrated by hot gases coming from the reactor. The concentrated
C the reactor OT f!n^lM*A^ ^t*A reactor Tn fV\A rnn«fpr
PTipOScH by "igh tPmnftrarnrrx; I^Anprnif imatply RTM^C
or 16008F) to ferric oxide and free hydrochloric acid gas. The ferric oxide
pellets, which also constitute the fluidized bed, are removed from the reactor
at the same rate as they are formed to maintain a constant bed level. The
reactor may be heated by gas or oil with air as the fluidizing agent.
The hot gases leaving the reactor contain hydrochloric acid gas,
water vapor, fuel combustion products and small amounts of ferric oxide dust.
The dust is separated from the off-gases in a cyclone and recycled to the
fluidized bed for pellet growth.
In the aforementioned venturi scrubber, the hot roaster gases are
cooled by exchanging heat to the waste pickle liquor as it is pumped into the
system. Ferric oxide particles present in the off-gases arc also washed out
in the venturi scrubber and returned to the reactor.
The cooled hydrochloric acid gases leaving the venturi scrubber are
passed into an absorber which is charged with fresh water or pickle rinscwater.
The feed rates to the absorber are controlled to yield 18 to 20% hydrochloric
acid for recycle to the pickle bath.
C then "U.~c
'-'iis '_•!'. loritk" iy
I
O
-------
Cost for Alternative Treatment Process. A schematic diagram of
the alternative waste treatment process is shown in Figure 7. A summary
of capital and operating costs are shown in Table 14.
The costs presented are for a Dravo-Lurgi HC1 Regeneration Plant.
Capital costs were provided by Dravo Corporation. Plant operations require
320 man-hours per week, 52 weeks per year. Annual material requirements
consist of 67,200 m^ (17.8 x 10& gallons) of process water and annual energy
requirements consist of 69 x 109 kg cal (124.3 x 109 Btu's) of fuel (natural
gas) and about 300 kw (400 hp) electricity.
The recovered material consists of 18% hydrochloric acid which is
priced at $15 per metric ton ($13.60/s. ton) which represents about 70% of
value. The other recovered material (Fe203 pellets)is valued at $20 per
metric ton ($18/s. ton) of contained iron.
er-o a
§•• E
r, j* -
I
o
^
10
68
- I
-------
STACK
I T 1
NEW WATER
1.900 LITERS
1
r
DUPLICATE
PUMPS
RECY
PICK
CLED TO
LEUNE
f
1 2 TANKS
75.000 LITERS
EACH
18% HO
DUPLICATE _ WATER | WET HI O"«'
PUMPS ^ — 1 S:UUBBER r~
1 l_ "—
j
4.8M.T./HR
2-TANKS.
75.000 L/EACH
WASTE
PICKLE-LIQUOR
4 M.T./HR
k ,,3.36m3/HR
WASTE
GASES
3JM.T./HR 1 A.,.or1n_ , HQ * GASES
»l A3.0J ^ 0.642 M.T.
1 HCI/HR
REGENERATED .
HCI
DUPLICATE
PUMPS
11 r~
SCRUBBER
&
SEPARATOR
r 1 '
PRODUCT I
STORAGE 1 DUPLICATE KOT. PICKLE
3200 L/HR 1
3.6 M.T./HR 1 4 M.T./HR
DUPLICATE
PUMPS
1
HOT
PICKLE
LIQUOR
" HOT
AIR BLOWER
14161/wc
j
NATURAL GAS
7.1m3/MIN
3.78x106kf«l/HR
FIUinl7FD ^
.. te- BED
._ , __ nnsT
CYCLONE
HOTGl
5504 I/*
RETURN •»'«•
1 i
CONVEYOR
F.j03 PELLETS
W 571 K»/HR
RECYCLE 3 TO
PROCESS
Figure?. SCHEMATIC DIAGRAM (IF HYDROCHLORIC ACID REGENERATION
PROCESS (WASTE ST1EAM NUMBER 8B)
o; anp
u 6u|aq
£;i|Bnl>
'eo|;ou
-------
TABLE 14
Capital and Annual Operating Costs for Waste Hydrochloric Acid Pickle Liquor
Regeneration (Waste Stream Number 8B)
ANNUAL PRODUCTION (METRIC TONS):
700,000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 3,200
CAPITAL COST
FACILITIES
Total
EQUIPMENT
.WET WEIGHT 37.500
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
$224,640
141,120
5,330
141,120
NET
S 24.80
290.63
TOTAL
$ 38.38
449.78
1.33
2.06
SHORT TONS • 0.9 x METRIC TON
70
$2,940,000
588,000
.t 3 f 528,909
a/a.uou
512,210
352,010
.439.280
509,280
930.000
§•"
Sff
3 r*
a sr
I
O
ro
-------
B. Iron and Steel Production
?. f!al v;»ni ?. ing Mill - Acid kinsewatcr Neutralization Sludge
(Waste Stream Number 9)
Waste Description. In the steel galvanizing process sheet steel
from rolling mills is cleaned, heated and dipped into molten zinc. Prior
to galvanizing, surfaces are cleaned with either sulfuric acid or hydrochloric
ncid. After removal of the metal from the acid pickling tanks, it is rinsed
with water and then galvanized. The acid rinsewater is neutralized with lime
resulting in dilute lime slurries which upon settling produce lime sludges.
The dry solids generated from neutralization of acid rinsewater
amounts to 10.8 kg/t>fT of steel when sulfuric acid is used for pickling or
2.7 kg/MT of steel when hydrochloric acid is used. The typical steel plant
riro'.li.ifinj; !2?,000 MT of galvanized steel per year generates 1,350 MT/yr of
sludge dry solids (4,500 MT wet) per year when sulfuric acid is used for
pickling or 338 MT/yr (1,125 NfT wet) when hydrochloric acid is used for
pickling.
Sludge from neutralization of acid rinsewater is composed principally
of Iron metal, iron sulfate, oxides or chlorides and calcium sulfate if
sulfuric acid is used. Other sludge constituents arc oil and grease and
trace amounts of heavy metals, chromium, nickel, copper and lead. Analytical
results arc similar to those of Waste Streams 7A and 7B.
Present Waste Disposal Method. At the present time, sludges from
tr.c neutralization of acid rinsewater are open dumped on land, in is practice
can pose a threat to ground or surtace water quality it oil and grease or
leached heavy metals percolate through permeable soils or are carried to
surface waters by runoff. Soil and runoff conditions at the individual plant
disposal sites would determine the degree of potential hazard to the environment.
Recommended Alternative Treatment Method. When hydrochloric acid
pickling is used, the volume of sludge produced is much smaller than when
sulfuric acid is used because the calcium chloride generated is water soluble,
whereas calcium sulfate from sulfuric acid rinsewater neutralization is
relatively insoluble. Each of the sludges will consist chiefly of iron
hydrates and may be mixed with the spent mother pickle liquor in which they
arc soluble. Oil and grease and trace metal content will be similar to that
of the mother pickle liquor.
The disposal of acid rinse neutralization sludges on land may be
readily eliminated by combining them with spent pickle liquor for recovery of
iron and acid. The volume of clarifier underflow sludges from neutralization
of acid rinsewater will be 11.5 m^/day for sulfuric acid rinsewater and 4.S
m-'/day for hydrochloric acid rinsewater. These volu.-.ies comprise only a small
3^3
» y a
3 <»
I
o
71
ro
-------
portion of the daily volume of total spent pickle liquor amounting to about
200 ir.Vday. The previous part of this report described processes for iron
and acid recovery from spent pickle liquors. Eliminating land disposal of
acid rinse neutralization sludges associated with galvanizing obviates any
chance of ground or surface water contamination.
Costs for Alternative Treatment Process. The sludge from sulfuric
acid rinsewater neutralization is pumped to a tank where it is mixed with
spent pickle liquor for treatment. The operation is estimated to require five
man-hours each week. The sludge has no recovery value. The flow scheme used
for cost development is shown in Figure 8 and -ts costs are summarized in
Table IS.
The sludge from hydrochloric acid rinsewater neutralization is
pumped to a tank where it is mixed with spent pickle liquor for treatment.
Four man-hours per week arc assigned to the operation. The sludge has no
recovery value. The flow scheme for cost development is the same as for
sulfuric acid rinsewater neutralization sludge and is shown in Figure 8.
The costs which reflect one less man-hour per week are summarized in Table 16.
I
o
^
to
72
-------
'2.2
. c
Q. 0
1.350 MT/y«.r SULFURIC ACID OR
338 MT/year HYDROCHLORIC ACID
ACID RINSEWATER
NEUTRALIZATION SLUDGE
I
PUMP
EXISTING SPENT PICKLE LIQUOR
STORAGE TANK
Figure 8. SO MATIC DIAGRAM OF ACID RINSEWATER NEUTRALIZATION
SLUDGE RECYCLE (WASTE STREAMS NUMBER 9A, 9B)
I
o
10
-------
<9 C O
TABLE 15
Capital and Annual Operating Costs for Alternative Treatment of Sulfuric Acid
Rinse Water Neutralization Sludge (Waste Stream Number 9 A)
ANNUAL PRODUCTION (METRIC TONS):
125,000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Pump
Piping
Installation
1,400
WET WEIGHT
4.500
$ 1,200
700
1,200
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPf HATSMrt PERSCNMEL
EOUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
S3.510
150
150
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$0.99
3.19
0.04
SHORT TONS • 0.9 x METRIC TON
74
$3,100
600
$3.700
$ 600
$3,810
60
$4.470
g-
8 g
«= °
3 r+
I
O
^
10
-------
TABLE 16
Capital and Annual Operating Costs for Alternative Treatment of Hydrochloric
Acid Rinse Water Neutralization Sludge (Waste Stream Number 9 B)
ANNUAL PRODUCTION (METRIC TONS): 125,0.00.
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Pump
Piping
Installation
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
UKtKAMNU HtHSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
SHORT TONS • 0.9 x METRIC TON
75
300
WET WEIGHT I.000
$1,200
700
1,200
150
150
TOTAL
$ 3.74
12.47
0.03
$3,100
600
$3.700
$ 600
$3,110
30
$3.740
3 *• Z
-
: I
I
O
-------
CD e o —
=•-
C. Ferroalloys
1. Ferrosilicon Manufacture - Miscellaneous Dusts
(Waste Stream Number 11)
Waste Description. Ferrosilicon is produced in electric submerged-
arc furnaces. Emissions are usually controlled by dry-type systems, primarily
baghouses. The captured dust is fine and of low density. The quantity of
dust generated depends, in part, on the type of alloy being produced. For
75% FeSi, the amount of furnace dust generated averages about 4SO kg per metric
ton of product, whereas, for 50% FeSi, dust generation averages about 225 kg
per metric ton. However, for any given facility, the amounts of dust
generated might vary from these average values by a factor of two or more.
An average dust generation factor of 338 kg/WT has been assumed for all
ferrosilicon production. A typical plant would accumulate about 13,500 MT of
furnace dust annually.
The dust i.s mainly .silica, iron oxide, ferrosilicon and lime, witli
chromium,'copper, zinc, manganese, nickel and cobalt combined amounting to
less than one percent. Some of these constituents, such as copper, nickel
and chromium are leachable but with very low concentrations of less than 0.5
mg/1. Dusts from ferrosilicon production should not be considered
potentially hazardous. Dust analyses are shown as follows:1
-
3 •* H:
"
« (
a
Chromium
Cupper
Zinc
Manganese
Nickel
Lead
Cobalt
ptl
Ferrosilicon
Dust Analysis (ppm)
160
21SO
1300
1500
32SO
82
Solubility Test
Filtrate Analysis Qng/1)
0.3
0.24
<0.01
0.06
0.10
<0.02
9.6
Present Disposal Methods. The furnace dusts generated in the
production of ferrosilicon are generally disposed of on land in open piles
or in landfill operations. Sometimes the dust is wetted for transport and
disposal to minimize dusting. Tests indicate that minimal concentrations of
metal constituents may leach into surface or groundwaters.
76
.......-,,Vi«yr
-------
l\c commended Altcmatix'e Treatment Method. One method of handling
the furnace dust from ferrosilicon production Lo minimize the potentially
adverse leaching effects, should this waste be considered hazardous, involves
mixing hydratcd lime with the dusts at a dose level of approximately S percent
by weight. The lime is stored and mixed with the furnace dust when the latter
is being transferred to trucks for subsequent disposal. A screw-type conveyor
would provide a convenient and efficient means for moving the dusts from a
storage bin to waiting trucks. A second screw conveyor could transfer stored
lime to the dust conveyor for mixing. A water spray would wet the mixture of
dust and lime as it leaves the first conveyor. The wetted mixture would be
trucked to a chemical landfill.
Equipment for carrying out liming operations such as those described
above is normally available and is used on a routine basis in similar applications
in many industries. The action of the lime and water will serve to detoxify
the potentially hazardous constituents of the dust.
Cost of Alternative Method of Waste Disposal. A schematic diagram
of the alternative method of disposal is shown in Figure 9 and a summary of
capital and operating costs is shown in Table 17 .
The dust is mixed with hydrated lime, sprayed with water and hauled
to a chemical landfill. The major treatment system equipment components
include a 52 m3 (13,700 <;al) dust storage tank, an 18 m3 (4,800 gal) lime
storage tank, a c cm (2 in.) screw conveyor for feeding the limo and a 3 m
(10 ft.) long, 23 cm (9 in.) diameter D section conveyor to load the dust/lime
-««-*f«r* t-ni-n a Hiimn truck.
About 1.9 metric tons (1.7 s. tons) of lime aie used daily. The
waste sent to the chemical landfill totals 10,160 m3 (13,200 yd3) annually.
The operation is conducted 3 hours per day and 3 man-hours of labor are
assigned. The waste transport cost is included as part of the chemical
landfill operation.
The waste has no recovery value.
I
3
O
77
-------
MISCELLANEOUS
DUST STORAGE
52m3
LIME STORAGE
18m3
38.6 MT/day
1.9MT/d»y
t
LIME FEEDER
CONVEYOR
3m LONG
-WATER SPRAY
TRUCK
10,160mJ
i
CHEMICAL LANDFILL
40.5 MT/day
Figure 9. SCHEMATIC DIAGRAM FOR ALTERNATIVE DISPOSAL OF MISCELLANEOUS DUSTS
FROM FERROSILICON MANUFACTURE (WASTE STREAM NUMBER 11)
78
o • S
5 ?
-------
-*ve *
TABLE 17
Capital and Annual Operating Costs for Alternative Disposal of Miscellaneous
Dusts from Ferrosilicon Manufacture (Waste Stream Number 11)
40,000
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Dust Storage Bin
Lime Storage Bin
Lime Feeder
D Section Conveyor
Piping
Installation
r
3 r* ar
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OKLKAI ICrJi ANU MAlNTC.'JA.'-iCC (Cam!
OPERATiNG rcnSGraiiicL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
SHORT TONS " 0.9 x METRIC TON
13.500
.WET WEIGHT
$11,800
3,200
2,100
900
300
18,000
1,740
37,180
152,400
1,740
TOTAL
$15.88
5.36
79
$36,300
7,300
$ 7,110
207,240
50
$214.400
-------
C. Ferroalloys
2. Ferrochromc Manufacture - Slag, Dust, and Sludge
(Waste Stream Number 12)
Waste Description. Ferrochrorae is produced in electric arc furnaces.
The major wastes are furnace slag and captured particulates from control of
furnace emissions. The particulates end up as cither dust or sludge depending
on whether a dry-type or wet-type collection system is used. In some cases
both wet and dry systems are used in series, producing both sludge and dust
as wastes.
The amount of slag generated in ferrochrome production varies from
l.S to 2.0 metric tons per metric ton of ferrochrome produced. Captured
particulate emissions average about 150 kg per metric ton of ferrochrome
production. A typical ferrochrome furnace slag contains about 4% free chromium,
3% chromic oxide (C^Oj), 22% silica (Si02), 30% alumina (A^Oj), 54i magnesium
oxide (MgOl. with the remainder consisting primarily of calcium oxide (CaO),
ferrous oxide (FeO), and carbon.'1
The particulate emissions from ferrochrome furnaces contain essentially
the same constituents found in the furnace slag, but in somewhat different
proportions. Chromic oxide content can exceed 20% with free chrome in the
range of 1 to 2%. Magnesium oxide is the most abundant single constituent
with concentrations of more than 30% possible. Annually, a typical plant
generates about 61,000 metric tons of slag and about 5,300 metric tons of
sludge and/or dust from control of furnace emissions.
Analytical data are summarized as follows:
«r.o 3 sr
§•§*£•
* •""" ** ^v
•« ••• o «.
»
Typical Analysis (ppnQ
1
Furnace Final
Slag Slag Scrubber E.P. Lagoon
Coarse Fine Sludge Dust_ Sludge
Chromium
Copp ei-
Lead
Zinc
Manganese
4540 3210
23 14
<10 20
25 70
500 300
1610 3300 1790
23 5-1 45
70 300 100
650 14,000 2500
800 7200 2000
Solubility Test Filtrate
Furnace
Slag Slag Scrubber E.P.
Coarse Fine Sludge .Dust
fmg/n
1
0.02
0.02
0.4
0.2
9.9
*
*
4
*
*
190
0.44
1.5
0.3
8.8
710
0.20
0.7
0.09
12.3
*Same as slag
-------
a c o »
5" £. — -
^^'.S s
Present Methods For Waste Disposal. It is common practice to
process fcrrochrome slag for recovery of metal values and to sell much of the
residual slag for use in road construction. The dusts derived from furnace
emission control .ire generally disposed of on land and covered, while the
sludges are accumulated in lagoons. In some cases, the chromium-rich sludge
from scrubbers is stored separately in anticipation of future technology that
would allow economical processing to recover the metal values. Solubility
tests suggest that leaching of chromium and lead from land-disposed furnace
emission wastes can pose a potential hazard. '
Recommended Alternative Treatment Method. In order to reduce the
possibility of leaching potentially hazardous constituents from the residuals
that remain after the ferrochrome slag is processed for metal recovery, it
is proposed that these residuals be blended with lime. Conveyors would
transfer the lime and the residual slag to a rotary blender. The mixture
would be loaded on trucks and hauled for use as read building material or
hauled to a suitable disposal site.
The dusts and sludge wastes recovered from furnace emission contain
significant concentrations of chromium and magnesium with potential for
recovery of these me Lai values. At the present time, the technology for
recovery of these metal values is not developed. If one were to detoxify the
chromium by conventional reduction precipitation techniques and then chemically
landfill the detoxified material, the recovery potential of the chromium would
be destroyed. Hence, the alternative disposal process suggested is a secure
chemical landfill for storage of the dusts and sludges until technology
permits recovery. The sludges will be dewatered in a filter before landfilling.
The proposed processes for treating the wastes generated in ferrochrome
yrciiiici. inn call in: expected Lu »reat.ly r?i.liirf! tho possibility ui icm-miiK
potentially hazardous constituents when the slag is mixed with lime and used in
road construction. The sludges and dusts will be stored in a chemical landfill
until technology is developed for recovery of the relatively high metal values.
Alternative Waste Treatment Costs. The slag is mixed with hydrated
lime in a 1.5 m-i (2 yd •>) mixer and transported to a 142 nt3 (5,000 ft3) loading
bin with a bucket elevator. About 8. 75 metric tons (9.6 s. tons) of lime are
used daily. A small amount of water is added in the process. The operation is
conducted 5 hours/day and 4 man-hours are assigned.
The slag can be used for road building.
$l/mettic ton ($0.90/s. ton).
It is valued nominally at
The slag disposal process is described schematically in Figure 10
and disposal costs are summarized in Table 18 .
The dust is sent directly to a chemical landfill. It has no
recovery value at present but may in the future with the development of
chromium extraction technology. Costs are summarized in Table 19 .
81
=
3 «f -
-------
«• c o
~
! 7 MTMry
FILTRiT
• FOR AIR EMISSION
SCDUMING
M% SO LI OS
CHCMICAL LANOriLL
Hn3/lliV
Fifluro 10. SCHEMATIC DIAGRAM OF ALTERNATIVE TREATMENT FOR DUST.
SLUDGE. AND SLAG FROM FERROCHROME MANUFACTURE.
(WASTE STREAMS NUMBERS 12A. 12B. 12C)
82
« g-r*
g-sf
o »* 3
s »*•
3 »* =r
-------
of c o •
S. a r* _
TABLE 18
Capital and Annual Operating Costs for Alternative Treatssent of Slag From
Ferrochrome Manufacture (Waste Stream Number 12A)
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
35,000
61.300 WET WEIGHT -
«£•«•*
3 H. sr
O> 3" JT
3 CO "
EQUIPMENT
Lime Storage Bin
Lime Feeder
Apron Conveyor
Mixer
Bucket Elevator
Loading Bin
Piping
Installation
$ 5,600
2,100
20,000
29,000
7,000
26,000
400
83,200
$173,300
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPEfJATfCNS Af.'C MAt.MTENANCE (O&M1
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
$ 18,900
8,320
168,440
8,320
34,700
$208.000
onn
203,980
1,810
$ 2,W_.
-------
TABLE 19
Capital and Annual Operating Costs for Alternative Disposal of Dusts
from Ferrochrome Manufacture (Waste Stream Number 12B)
OTJ3 =>
0 C O
" t» d
ANNUAL PRODUCTION (METRIC TONS):
35,000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
5.300
WET WEIGHT
Iff
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTPWAMCC fn*.Mt
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL (Chemical Landfill) $99,750
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
Nf-T ANNUAL COST
$99,750
$99.750
I
o
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$16.82
2.85
SHORT TONS - 0.9 x METRIC TON
84
-------
CO
The sludge is filtered and the filter cake is put in a chemical
landfill. The filtrate is recycled to air emission spmhhinj. The filter
is operated 12 hours/day. The sludge sump is sized to hold a 5-day supply
of sludge. Approximately 5,520 m3 (4,250 yd3) of sludge are landfilled each
year. Six man-hours/day are assigned to the operation.
The recovered material has no value at present but may in the
future with the development of chromium extraction technology.
The dust and sludge storage in a chemical landfill is also described
schematically in Figure 10. Costs are summarized in Table 20.
s ~
c o
3 r»
O 3"
85
-------
TABLE 20
Capital and Annual Operating Costs for Alternative Treatment
of Sludge from Ferrochrome Manufacture (Waste Stream Number 121
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): OR Y WEIGHT
CAPITAL COST
FACILITIES
Sump
Sludge pit
EQUIPMENT
Filter
Pump
Piping
Installation
35,000
5.300
WET WEIGHT
$ 4,200
7,900
50,000
1,000
1,000
38,500
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
EQUIPMENT REPAIR AND MAINTENANCE 4,920
MATERIALS
WASTE DISPOSAL (Chemical Landfill) 121,440
TAXES AND INSURANCE 4,920
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$13.88
34.56
5.23
SHORT TONS " 0.9 x METRIC TON
36
$ 12,100
90,500
20,500
$123,100
$ 20,070
$159,630
3,450
$183.150
=• e» EC;
-
3 :»;
-------
2-SSs-
=; e? •
C. Ferroalloys
3. Silicomanganese Manufacture - Slag and Scrubber Sludge
(Waste Stream Number 13)
Waste Description. Silicomanganese is produced in submerged-arc
electric furnaces. A greenish, glassy-textured slag is generated at the rate
of approximately 600 kg per metric ton of Silicomanganese produced. Control
of furnace fumes is accomplished by either wet or dry systems with collection
of particulates at the rote of 95 to 100 kg per metric ton of product. In
some cases, the dusts collected by the dry systems are slurried with water
for ease of handling and transport. A typical plant might generate 24,000 MT
of slag annually and collect 3,900 MT of particulates as dust or sludge from
control of furnace emission.
The major constituents of Silicomanganese slag are silica (SiO^) and
alumina (A^Oj), each at a concentration of about 30 percent by weight. Calcium
oxide (CaO}, magnesium oxide (MgO), manganese oxide (MnO) and manganese account
for most of the remaining 40 percent. Chromium, copper, lead and zinc are
found in approximately equal amounts varying from 20 to 30 ppm*.
Silicomanganese slag is essentially an aluminum silicate containing
about 5-7% manganese. Solubility tests on filtrates show almost complete
insolubility as follows:
'f1 3. ~ —
I 2
3
Solubility Tests on Filtrates (mg/1)
1
Chromium <0.01
CoppPT 0.17
Zinc u.Ub
Manganese u.i
Nickel <0.05
I.^arl and
82 ppm, respectively. These analyses are shown as follows:
Silicomanganese Sludge
Dry Basis (ppm)
Chromium
Copper
Lead
Zinc
Manganese
45
82
25,000
10,000
300,000
87
-------
«- -• o
The analyses of the filtrates from solubility tests on silicomanganese
sludge are shown following:
Solubility Test Filtrate Analyses
(mg/1)
if^i
iS~ « e
Chromium
Copper
Zinc
Manganese
Nickel
Lead
PH
Silicomanganese
Sludge
0.55
0.14
0.03
<0.02
<0.05
1.3
11.0
Present Waste Handling Methods. The furnace slag derived from
si iicumangancsc production i« frnniiently sold to local contractors for use
as fill. Slag that is not sold is stored or deposited in open piles. The
sludges resulting from the capture of furnace emissions are generally accumulated
in Ingoons or settling basins. The sludges are periodically removed from the
settling areas and dumped on land.
Solubility tests indicate that silicomanganese slag is virtually
insoluble. Therefore, leaching is not expected to present adverse environmental
effects. On the other hand, tests on dusts and sludges from furnace emission
control have shown that leaching of lead might present a problem and it is
suggested that alternative methods of disposing of these wastes might be
uixCu to prevent - pctcr.tially hszar^o'ie »nvirnntn(»ntnl condition.
Recommended AiLuraaLive 7ieai.iueut .'-'cthjc!. !r. the C2£0 of c' liromani
slag, the present methods for disposal are considered adequate. Much, if not
most, of the slag ends up as fill for road construction.
Resource recovery by reduction roasting is proposed for dusts and
sludges from furnace emission control. The treatment process is
based on the Waelz kiln, a process which was originally developed by Krupp
Grusonwerke in Germany in 1925. The same system is recommended for handling
scrubber sludges generated in the production of ferromanganese. Fcrronnngnncsc
and silicomanganese are commonly produced at the same plant since the slap from
ferromanganese production is used as raw material for silicomanganese production.
Thus, it is desirable to have a system that can handle sludges and dusts from
both types of ferroalloy furnaces.
A flowsheet for the system is shown in Figure 11. Thickened
sludges from the ferromnnganese and silicomanganese furnaces are filtered for
dewaterlng. The combined sludges arc then mixed with a rcductant, such as coke
breeze or a mixture of coke breeze and iron powder, and pelletizcd. The pellets
88
I
O
10
-------
erua 3
CD c o
IN-PLANT
(22 MILLS!
FERRO-MANGANESE
SLUDGE
5.000 MT/y«r
PUMP
SILICO-MANGANESE
SLUDGE
3.900 MT/ynr
PUMP
FILTER
PRESS
CENTRAL PLANT
STACK
BAGHOUSE
FAN
FLUE GAS
COOLER
LEAD - 6,300 MT/yiw
ZINC - 1,800 MT/vtir
OXIDE STORAGE
TRANSPORT TO
•LEAD AND ZINC
SMELTER
SILICO OR
FERRO-
MANGANESE
FURNACE
TRANSPORTATION
8.900 MT/ytw
(DRY BASIS)
COMBINED
SLUDGES
?00,000 MT/yror
COKE
BREEZE
1.600MT/year
CONVEYOR
CLOSED
MIXER
GRANULAR
PELLETIZER
1
f
CONVEYOR
WAELZ
KILN
CLINKER
STORAGE
185,000 MT/yiar
,«< -
Ig'S,-
!2.r* 5
a. a
o
3 -
O ^
i § «
Figure 11. SCHEMATIC DIAGRAM OF ALTERNATIVE TREATMENT FOR
SLUDGES FROM SILICO AND FERRO-MANGANESE MANUFACTURE.
(WASTE STREAM NUMBERS 13 AND 14)
89
-------
(D C= O
^~ »
.
arc then roasted in a Waelz kiln which is a rotating furnace that resembles a
cement kiln. The unit is fired by a burner at the lower end. The temperature
of the bed exceeds 1100°C. Fumes frcn; the hi In, which contain lead and zinc
oxides are collected in a baghouse. The clinker from the kiln is rich in
manganese and might be suitable for feed material for the ferromanganese or
silicomanganese furnace.
The first Waclz kiln was installed by Krupp Grusonwerke at Magdeburg
(Germany) in 1925 in order to distill zinc oxide from various zinc bearing
oxide ores and residues. A number of additional kilns have been installed
and are operated by zinc producers. It has been reported that New Jersey Zinc
Company has abandoned its use of a Waclz kiln for processing complex zinc-
manganese iron ore containing relatively high zinc concentrations.
3 H
IB =1
In 1974, Sotetsu Metal was founded in Japan as a joint venture of
Nisso Kinznku and 23 steel mills. Sotetsu has agreed to collect dusts
containing more than 20°; zinc and to treat them in a Waelz kiln having a
nominal capacity of 60,000 tons per year. The residual clinker may still
contain too much zinc to be recycled to the steel plant and this is one of
the reported operating difficulties.
In 1974 and 75, two industrial Waelz kilns with approximately
10,000 tons of zinc-ferrous in-plant fines were installed at the Waclz plant
of Berzelius Metallhutten GmbH, a sister company of Lurgi in the
Metallgesellschaft group. Lurgi claims 90°i Zn removal.
The alternative system for handling sludges would eliminate
tViB rfotontipi tUv»ot- nf jAachiTi" I1??.'.! ?.!>d ?inc IT.?, r.* th? rr.r~? tir.c woulJ c.11;1.
recovery of there marke^blA constit'.^ents. However, further investigation is
required to determine the feasibility of processing residues that contain zinc
and lead concentrations less than 5 percent. The process has usually been
applied to materials having zinc concentration greater than 20 percent. Also,
further study is necessary to evaluate the practicality of recycling the
manganese-rich residues to the silicomanganese furnace.
Cost of Alternative Method of Waste Disposal. These costs are
developed from Figure 11 on sludges from silico and ferromangane^e
manufacture plus wastes from other industries generating similar wastes that
can be processed in the Waelz kiln. The costs are summarized in Tables 21
and 22.
I
o
4*
10
Table 21 summarizes the costs for waste preparation at each
individual plant and Table 22 summarizes the costs for a central processing
plant serving 22 individual mills. Approximately seven of these mills arc
ferroalloy plants with the remainder being other industries having similar
wastes containing lead and/or zinc. The waste treatment/recovery operations
involves two operations at different locations.
90
-------
TABLE 21
Individual Plant Capital and Annual Operating Costs for Alternative Treatment
of Silico and Ferromaneancse Sludges fWaste Stream Numbers 13 and 14)
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): OR Y WEIGHT
CAPITAL COST
FACILITIES
Sludge Pits
EQUIPMENT
Filter
Pumps
Piping
Installation
30,000
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AN ; MAINTENANCE (O&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
SHORT TONS • 0.9 x METRIC TON
8,900
.WETWEIGHT
$79,000
1,800
1,300
61.100
$28,350
7,220
7,220
TOTAL
$3.44
8.57
2.54
91
$ 7,200
143,200
30,100
5 29,420
!!*-!
i~ =r _ "
S?5
I
O
4^
ro
-------
TABLE 22
Central Plant Capital and Annu.il Operating Costs for
Alternative Treatment (Waelz Kiln) of Silico and
Ferromanganese Sludges (Waste Stream Numbers 13 6 14)
660.000 f22 nlants)
ANMUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 198,0°0
CAPITAL COST
FACILITIES
WETWEIGHT
EQUIPMENT
Sludge Conveyors
Coke Breeze Conveyors
Mixer
Granular Pelletizer
Waelz Kiln
Bag House
Flue Gas Cooler
Air Fan
Installation
$ 40,000
10.200
27,200
100,000
2,750,000
560,000
35^300
4,896,500
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPF RATIONS
OPERATING PERSONNEL
FOIIIPMENT REPAIR AND MAINTENANCE
WASTE DISPOSAL *
TAXES AND INSURANCE
1,200,000
742,020
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
NET
$15.15
TOTAL
$16.70
DRY BASIS
COST/METRIC TON OF PRODUCT
37.88
41.76
1 1 • 36
12.53
_495_L000_
$8,432,100
8,432,100
1,686,400
$18,550,750
$ 3,023,750
5,137,640
106,290
.267.680
767,450
$7,500,230
iiSsr
' 3
co ?
a co
I
o
*Waste transport to processing facility
SHORT TONS • 0.9 x METRIC TON
92
-------
The first operation is conducted at each mill. It consists of
filtering the si.Uco- and ferromanganese sludges. The filter is operated
12 hours each day and is assigned 6 man-hour.6 per ('ny, Trxsts for this
operation are shown in Table 21 .
The filter cake discharge is then shipped to a centrally located
waste treatment/recovery plant. This plant is sized to accept the dewatercd
sludges from about 22 mills. The central plant has an annual capacity to
process about 200,000 metric tons (220,000 s. tons) (dry weight) of sludge.
The sludge is mixed with coke breeze in a mixer with a 3,400 kg (7,500 Ib)
capacity, pcllctizcd in a 2.4 n (8 ft) diameter granular pcllotizcr and then
roasted in a Waelz kiln. The contained coke breeze serves as fuel. The
operation is estimated to require 96 man-hours per day.
Costs for this operation are shown in Table 22 . Facility costs
for this operation are estimated to be equal to the installed equipment costs.
than an add-on to an existing plant.
The major metal recovered is zinc. It is assumed that the
silico- and ferromanganese sludges contain 3.5% and 1% zinc, respectively
and that the process results in 90% recovery. The recovered zinc oxide is
valued at $204 per metric ton ($185/s. ton) which is 25% of the metal value.
The plant also generates about 185,000 metric tons (203,500 s. tons)
of clinker each year. This material contains manganese and with the removal
of zinc and lead may be suitable for reprocessing. No value has been assigned
to this material nor ar? cost? included for its disnosal as landfill.
iia
IS.**
3
a
nie <.«ipj.Laj. ctuu annual coses ror eacrt of tne a mills, assuming a
pro-rated share of the centralized waste treatment/recovery plant are:
Capital Costs
In-plant $180,500
Processing Plant 843,200
(Pro-rated share)
TOTAL $lt023t700
Annual Costs
In-plant $375,800
Processing Plant 76,290
(Pro-rated share)
TOTAL $452,090
Recovered Material 34,880
Value
Net Annual Cost $417.210
-------
Cost/Metric Ton of Waste
Wet Basis
Dry Basis
Cost/Metric Ton of Product
Net
$18.79
46.88
13.91
Total
$20.56
50.80
15.07
3 r*
o sr
3 <»
I
O
94
-------
ill;
8
C. Ferroalloys
4. Ferromanganese Manufacture - Slag and Sludge
(Waste Stream Number 141
Waste Description. The production of ferromanganese generates slag
at the rate of about 600 kg per metric ton of alloy produced. The major
constituents of the slag are manganese (either as free metal or the oxide)
at greater than 50 percent concentration, and silica (Si02) anc* alumina
(A120-.), each at concentrations of 17 to 21 percent. Minor constituents
include copper at 310 ppm, chromium at 100 ppm, lead at 10 ppm, and zinc
at 20 ppm.i
Analyses of filtrates from solubility tests of ferromanganese
slag are as follows (mg/1)^:
Chromium 0.02
Copper 0.0-1
Zinc 0.03
Manganese 2.1
Nickel
Leas!
pH
<0.05
<0.02
5.9
Significant concentrations of toxic heavy metals did not leach and
this jslag is not considered hazardous at this time.
The control of furnace emissions with wet scrubber systems produces
a sludge which contains about 3.5 percent zinc, 0.5 percent lead, 2.0 percent
manganese, 50 ppm of copper, and 18 ppm of chromium.*
snowed relatively high values of copper, zinc, manganese and lead.
Solubility Test
Filtrate Analyses (mg/1)
Ferromanjjanese
Baghouse Dust
Cliromium
Copper
Zinc
Manganese
Nickel
Lead
pll
9S
0.2
4.5
110
7.5
0.53
SbO
9.7
-------
•
— M r+ •
3 2- — a
In some plants, the scrubber liquor is simply diverted to a lagoon
or settling basin where particulatc matter settles out in amounts corresponding
lo 150 kg/MT of ferromangancse produced. In other plants, lime is added to
the scrubber liquor and a clarifier is used to promote settling of solids.
The underflow from the clarifier is piped to lagoons where the sludge is
accumulated in amounts of about 165 kg/,\fT of product.
A plant producing 30,000 WT of ferromanganese per year would
generate about 18,000 NfT of slag and 5,000 MF of limed sludge annually.
Present Waste Disposal Methods. As noted under the discussion of
silicomanganese wastes, it is common practice to produce both silicomanganese
and ferromanganese at the same plant. Slag from the production of
ferromanganese is used as feed material for silicomanganese production or as
feedstock for electrolytic manganese. Thus, in general, ferromanganese slag
zs not considered a waste because of its high manganese content and is. in
fact, recycled. Tcbls indicate that leachate from slag storage piles would
probably be environmentally acceptable.
The sludge uorived from the control of furnace emissions in
ferromanganese production is accumulated in lagoons, sold as a fertilizer
additive,' or recycled. In some cases, the bottom deposits of the lagoons
are dredged occasionally and deposited in an open dump area. Solubility
tests performed on furnace emission particulates indicate a significant
potential for leaching of lead and zinc.1
Recommended Alternative Treatment Method. It is proposed that the
sludees resulHna fr™ tho control cf furnace emissions in siiicomanj-anese and
ferrc-nar.ganecc production plus similar wastes irom other indnstri<>« K» handled
by a single processing system as described in the previous section on
silicomanganese wastes. The sludges would be pelletized and reduction roasted
to vaporize lead and zinc for recovery as the oxides. This approach would
eliminate the problems of lead and zinc leaching and at the same time allow
recovery of these metals for reuse. As noted, however, further study is
required to establish the practicality of this system.
Cost for Alternative Method of Waste Disposal. The process scheme
for the alternative treatment shown in "Figure 11 is summarized for costs in
Tables 21 and 22 .
96
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A.
SECTION II
PRIMARY NON-FERROUS SMELTING AND REFINING HAZARDOUS WASTES
Copper Smclting-Acid Plant Blowdown Sludge
(Waste Stream Number 15)
\3 *•*
S.£t5'
i o
I °
I
Waste Description. Large amounts of sulfur dioxide (S02) gas are
generated from roasting sulfide copper ore concentrates. Most copper smelters
have a sulfuric acid by-product plant to recover S02 as sulfuric acid. The
sulfuric acid recovery process generates a waste blowdown slurry. The typical
smelter operation producing 285 MT of blister copper per day will generate
2270 m3/day of blowdown slurry from the sulfuric acid recovery plant. This
slurry will contain about 2% solids. The pH of the blowdown can be as low
as 3.0. The settleable solids generation rate is 3 kg/MT of blister copper
produced. The typical copper smelter producing 100,000 MT/yr of copper metal
will generate 270 MT/yr of blowdown settleable solids.
Blowdown sludges contain the following concentrations of elements:
Arsenic
Cadmium
Silicon
Copper
Mercury
Lead
Antimony
Selenium
Zinc
PH
Sludge Analyses
Dry Bases (ppm)
520
SOO
279,400
0.8
89
110
8,000
500
30
27,900
Solubility Test Filtrate
Analyses (mg/1)
0.80S
8.4
0.5
850
1.0
n.64
7.8
0.2
300
3.0
Major constituents of the slurry solids are metallic oxides, and
sulfates. Copper is present in high concentrations and may approach 25-30*
of the solids content. Zinc and lead are also present in appreci-ole
concentration. Other mccals present in trace amounts include cadmium, nickel,
antimony, and selenium.
Major metal components of dissolved solids include iron, copper,
and zinc. These will be present as sulfates and sulfitcs. The presence of
a number of toxic heavy metals in significant concentrations (i.e., copper,
line, cadmium, lead, and selenium), and soluble salts, impose a potential
hazard from land disposal of copper smelter acid plant blowdown.
97
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Present Methods for Waste Handling. Typically, smelter acid plant
blowdown effluent is sent to a thickener where thickened solids are recovered
and recycled to the smelter for copper values. Overflow from the thickener
containing suspended solids and dissolved solids is discharged to tailing
ponds associated with the mining and milling complex. Recycle of thickener
underflow is a desirable resource recovery operation, that is generally
carried out.
The thickener overflow contains appreciable concentrations of
dissolved solids and an estimated 0.77 MT/day of residual suspended solids.
These dissolved and suspended solids include the toxic heavy metals copper,
lead, cadmium, and arsenic, which pose potential ground and surface water
environmental hazards if these percolate through unlined tailings ponds
where they are being discharged.
Recommended Alternative Treatment Method. The present method for
wasto handling would be improved by further treatment and clarification of
thickener overflow to remove residual suspended solids leaving the existing
thickener and to precipitate the toxic components of the dissolved solids.
The alternative suggested is shown schematically in Figure 12.
The thickener overflow is treated with precipitating and flocculating
chemicals such as lime in a clari-flocculator. The clari-flocculator overflow
may be discharged to the tailings pond. The precipitated solids in the
clarifier underflow are centrifuged for a chemical landfill and the ccntrifugate
is recycled to the clarifier.
The proposed alternative process precludes potential environmental
horarHs K -rpmnvinn wsiHiial rnnnp-r hpprino «ii«n*»nH*»H «r>HH<: snrl
-
3 r* 2
el i « I vprl anliilc h»for tailings pond.
Cost of Alternative Treatment. The costs for the process scheme
described in Figure 12 are summarized in Table 23 and are based on the
following assumptions.
The major treatment system components are a 1.89 m (500 gal)
flocculant feed system, a 23 m3 (800 ft 3) lime silo and automatic feeder,
a 200 m3 (30* x 10') clarifier, a centrifuge, storage tanks and pumps.
Hydrated lime is added at the clarifier at a rate of 3.3 metric tons (3.6 s.
tons) per day. Flocculant addition to the wastewater flow is at a rate of
5 ppm.
The overflow from the clarifier is discharged. The underflow is
centrifuged and generates about 9.8 m3 (2,600 gal) of cake daily, which is
then sent to a chemical landfill. The filtrate is recycled to the clarifier.
Six man-hours are assigned to the operation per day. No material
value is recovered.
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3 Z.
2. ^1
AGIO PLANT
SLOWDOWN
2270m3/d»y
FLOCCULANT LIME STORAGE
SOLUTION 9 MT CAPACITY 800 FT3(23m3l
1.89m3 TANK 23m3
f
^UNDERFLOW SOLIDS THICKENER
RETURNED TO (EXISTING!
PROCESS
T t
FEEDER FEEDER
AUTOMATIC
82m/di" OVERFLOW
£200m3/div
0.77 M.T.
SUSPENDED SOLIDS
DRY LIME
3.3 MT/diy
I
CLARI-FLOCCULATOR OVERFLOW TO
1>m(>(A 'TAILINGS POND
RET RN
TOCLARIFIER
PUMP
''"'"' '"'"• I
UNDERFLOW 10.900 OAL/DAY
4) m3/DAY
1
STORAGE
TANK
18.9m3
i
PUMP
t
STORAGE
18m3 ^ 31.8m3/8 MRS
I
I FEED 41.3m3/8 MRS
CENTRIFUGE
TO OPERATE
8 HR/DAY
(
9.8m3/dty
r
STORAGE
BIN
»
CHEMICAL
LAND FILL
o
=
3
Figure 12. FLOW DIAGRAM FOR ALTERNATIVE TREATMENT OF PRIMARY COPPER
SMELTING • ACID PLANT SLOWDOWN (WASTE STREAM NUMBER 15)
-------
TABLE 23
Capital and Annual Operating Costs for Alternative Treatment of Acid Plant
Blowdown Sludge - Primary Copper Smelting (Waste Stream Number 15)
100 ,000
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
fACILlTIES
Sump
EQUIPMENT
Lime Precipitation System
Flocculant Feed System
, Clarificr
Tanks
Centrifuge
Pumps
Piping
Installation
a c o -
— aa r* ^
S|g2
is** • "
5" o pr o.
3 "• «
£« 5
» g-rt-
0.5 =r
*?S
<= » rt-
3 n- =r
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
Awn MAINTPNANrP IDAMl
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
SHORT TONS " 0.9 x METRIC TON
300
WET WEIGHT
$ 26,100
3,500
42,000
4,300
r o r\r\r\
•f U) WUU
1,900
10,300
121,300
$28,350
13,050
71,080
82,320
13,050
TOTAL
379.27
884.97
2.65
100
700
$ 5.300
267,400
53,500
326,200
* 53,170
207,850
4,470
265.490
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B. Electrolytic Copper Refining - Mixed Sludge
(Waste Stream Number 16)
Waste Description. In the electrolytic refining of copper, relatively
pure copper anodes(99.5% copper) are dissolved in sulfuric acid and copper is
clcctrolytically deposited to produce higher purity cathode copper (99.9%). A
number of dilute miscellaneous effluents are wasted in the electrolysis process.
These include contact cooling water from quenching hot anode or cathode copper,
spent anode washings, spent electrolyte and plant washdown. The flow of dilute
acid slurry from a typical electrolytic refinery producing 460 MT of refined
copper per day is 6,800 m?/day. Suspended solids content is 210 kg/day and
dissolved solids content 870 kg/day. Total dissolved and suspended solids in
the miscellaneous effluents amount to 2.4 kg/MT of copper produced or 384 MT/yr.
The settled sludge solids contain 2% copper, 1% lead, and significant
concentrations of cadmium, mercury, antimony, selenium and zinc. This waste
is considered potentially hazardous because of the possibility that these toxic
constituents may leach in concentrations sufficient to pose a threat to ground
water quality.1
Analysis of The Dredged Solids (ppm)
Cadmium 180 Nickel 10
Chromium 25 Lead 12,000
Copper 22,000 Antimony 800
Mercury 5 Selenium 550
Warinanpsp g Zinc 190
Present Method for Waste Handling. Wastewaters from electrolytic
copper refining are currently clarified in unlined lagoons or tailings ponds
and the settled solids are dredged and deposited on land. These practices
are environmentally inadequate because significant concentrations of toxic
heavy metals as described above may leach and percolate through permeable
soils or rock strata to ground water.
Recommended Alternative Treatment Method. The major portion of
potentially hazardous pollutants from electrolytic refining sludjas are contained
in the dissolved salts. Lime treatment of the wastcwaters will remove the
heavy metal pollutants from the water phase. It is uneconomical to recycle
the settled solids for the recovery of copper and/or lead value. The sludge
solids are then deposited in a secure chemical landfill.
Figure 13 presents a lime treatment process for removal of suspended
and dissolved solids from copper electrolytic refining wastewaters and
subsequent sludge disposal in a chemical landfill. Wastewaters arc limed and
clarified in a clari-floccular. The settled sludge amounting to 0.9 MT/day
(8,000 gal/day) is pumped to a centrifuge for dewatering. The filtrate from
the centrifuge amounting to approximately 22 mVday (5,800 gal/day) is recycled
to the clari-flocculator. After centrifuge dewatering, 9 MT/day of sludge
containing 0.9 MT/day solids will be put into metal drums and transported to a
101
I O J*
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AGITATOR
0.37 kW
LIME SLURRY
TANK
1.89m3
METERING
PUMP
1.18m3/d»y
1.18mJ/diy 5% Ct(OH)
590 k9/d>y
CLARIFLOCCULATOR
15.2m DIA x 3m DEEP
6m MIXING WELL
30.3m3/d»y
1.36m3/d*v
1% POLYMER
13.6 kg/day
CTJ3
o- <»
8 -
OVERFLOW TO
TAILINGS POND
6.813m3/day
UNDERFLOW
30 MT/d»y
3% SOLIDS
, C.9 MT/diy
RECEIVER
TANK
3.78m3
PUMP
I
O.MSm-'/mm
3.04 itm
TANK
3.78m3
PUMP
CENTRIFUGAL
3.04 .tm
i
, 30.3m3/8
0.06m3/mln
FILTRATE
21.8m3
CENTRIFUGE
8HRS
DISCHARGE
9 MT/djy
CHEMICAL
LANDFILL
Figure 13. FLOW DIAGRAM OF ALTERNATIVE TREATMENT PROCESS FOR MIXED
SLUDGES FROM ELECTROLYTIC COPPER REFINING (WASTE STREAM
NUMBER 16)
102
-------
~« s;
chemical landfill. It is estimated that forty-three SS-gallon drums would be
chemically landfilled each day.
Potential leaching of toxic metal constituents is precluded by
treating electrolytic sludge slurry with lime followed by disposal in a
chemical landfill. Neither of these practices is being used by the industry
at the present time.
Cost for Alternative Method of Waste Disposal. Waste treatment
costs are shown in Table 24. A relatively small amount of hydrated lime
590 kg (1,300 Ib) and floc-.ulant 13.6 kg (30 Ib) per day are added to the
wastewater. Following settling in a 560 m3 (SO1 x 10') clarifier, the
underflow is collected in a receiving tank and then punned to a centrifuge.
The daily centrifuge discharge amounts to about 8.5 m3 (2,244 gal) which is
containerized and sent to a chemical landfill. The centrifuge filtrate is
recycled to the clarifier.
Eight hours of labor are assigned to the operation daily.
recovered material has no value.
The
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TABLE 24
Capital and Annual Operating Costs for Alternative Treatment of Mixed Sludge
From Primary Electrolytic Copper Refining (Waste Stream Number 16)
^ j» **'
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$360.40
991.13
2.48
SHORT TONS - 0.9 x METRIC TON
104
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C. Lead Smelting - Siudgc-s
(Waste Stream Number 17)
Waste DCScrip tions.
1. Acid Plant Slowdown and Miscellaneous Slurries. Before lead ore
concentrates are reduction roasted to metal in a blast furnace, the fine particles
of the charge arc agglomerated in a sintering machine. The sinter machine fuses
the lead concentrates anc1 other lead bearing residues with lime and silica.
Sulfur contained in the lead ore concentrate is driven off as SO?
gas at the sinter machine. Since copious amounts of S02 are generated, acid
plants are built to recover SO. as sulfuric acid where possible. In the
production of the sulfuric acid, a blowdown slurry is wasted. This slurry is
railed ac<
-------
2. [-missions Control Sludges. Sinter gases laden with SO- are
partially scrubbed of particulates before entering the acid plant, liases from
other primary operations such as sinter crushing and blast furnacing are also
cleaned in dry or wet scrubbers. The bulk of the dry dusts or wet slurries
from gas cleaning operations arc recycled to the sinter for lead recovery but
a waste stream of 175 m /day containing 6 MT of solids is bled off. The solids
generation rate from the gas cleaning bleed-off is 19 kg/MT of lead metal.
Sfv*!
3 r* :
<» 3-;
rj n
Sludges resulting from scrubbing of emissions from sintering and
blast furnaces contain recoverable amounts of lead and zinc and significant
concentrations of cadmium, copper and mercury. This waste stream is considered
potentially hazardous.1
Present Individual Waste Handling Methods.
1. Acid Plant Blowdown and Miscellaneous Slurries. At the present
time, blowdown slurries from the acid plant are treated with lime and sent to
lagoons for settling. The miscellaneous slurries from plant washdown, the
cadmium plant and other sources are sent to the same lagoon as the lime treated
acid plant blowdown. The lagoon is dredged periodically and the sludge is
piled on the ground to dry. At some plants this sludge is eventually recycled
to the sinter while other plants may permanently dispose of the sludge on the
ground. Long term storage on the ground or permanent land disposal may produce
ground or surface water pollution either through percolation of leached toxic
metals through permeable soils to ground water, or transport of toxic metal
laden particulates by surface runoff. Soil and runoff conditions at individual
smelters would determine the degree of potential hazard.
2. Emission Control SluJees. Dilute slurries resaliiiiw from control
of emissions from sinters and blast furnaces are settled in unlined pits. The
pits are dredged penodically and the sludge stored on land generally for
months before recycle to the sinter plant for recovery. At some plants the
sludge may not be recycled and is, therefore,permanently disposed of on land.
usually in the slag dump. Long term on-land storage or permanent on-land
disposal of emission control sludges can present the same environmental threat
as the acid plant blowdown sludge.
Recommended Alternative Treatment Method for Combined Wastes. The
sludges resulting from the (1) acid plnnt blowdown and miscellaneous slurries and
(2) emission control sludges all contain recoverable amounts of lead and zinc.
It is estimated that a typical plant producing 315 OT of lead per day will
generate 3 NfT of lead and 1.5 MT of zinc that is available for recovery.
A system enabling recovery and recycle of solids from the various
sources is shown in Figure 14. Slurries from the acid plant and emission
control would be lime treated and clarified in lined or impermeable lagoons.
The settled solids would then be pumped to a storage tank. At this point, the solids
content of the sludge will be 30%. From the storage tank, the sludge will be
106
-------
1. ACID PLANT &
MISC. SLURRIES
460m3/dty
126 MT/day
y
LINED
LAGOON
1
FLOATING
SLUDGE
PUMP
t
LIME
1.13MT/day
\ r*
t
SLUDGE
STORAGE
TANK
53m3
Na2S
1.8 kg/day
T
2. E
LINED ^ S
LAGOON ^ 2
6
t
FLOATING
SLUDGE
PUMP
t
i
2. EMISSION CONTROL
SLUDGES
230m3/d.y
6MT/d«y
i
PUMP
22 MT
985% SOLIDS
RETURNED TO
PROCESS
I
\ 9
CENTRIFUGE
6 HRS/diy
FILTRATE
RETURNED TO
LAGOONS
Figure 14.
SCHEMATIC DIAGRAM FOR RECOVERY AND RECYCLE OF SLUDGE
SOLIDS FROM PRIMARY LEAD SMELTER (WASTE STREAM NUMBER 17)
107
-------
centrifuged to increase solids content to 854. The solids amounting to
22 MT per day are r^cycl^d to the sinter. Filtrate from the centrifuge amounting
to 53 rnVday is sent back to the lagoons.
In order to insure complete precipitation of the heavy metals from
the wastewaters, treatment with sodium sulfide in addition to the lime treatment
is recommended. It is estimated that only 4 to 5 pounds (1.8 kg) of sodium sulfide
per day would be sufficient to precipitate residual dissolved heavy metals as highly
insoluble metallic sulfides. With proper retention in lagoons or settling
basins, the combined lime-sodium sulfide treatment of acid plant blowdown,
primary emission scrubwater, and miscellaneous slurries should result in highly
purified effluent discharges to receiving waters.
The advantages to be derived from the proposed process are avoidance
of potential contamination of ground and surface water with toxic heavy metals.
In addition, resource recovery of up to 3 MT of lead and 1.5 MT of zinc per
day is possible at the typical plant.
Cost of Alternative Method for Waste Handling. The cost for the
flow scheme described in Figure 14 is summarized in Table 25.
A liner is installed in the acid plant blowdown lagoon. The lagoon
inflow is treated with hydrated lime and sodium sulfide. Daily material
usage consists of 1.13 metric tons (1.24 s. tons) of lime and 1.8 kg (4 Ibs.)
of sodium sulfide.
After settling, the sludge from the lagoon is pumped into a 53 m
Md^nnn 0*1.1 storage tank and then sent through a centrifuge. Twelve man-hours
per day are assigucu to the operation. Fi^^trical enerxy use is bsscd on sr:
average conci^ption of JS hp,
The centrifuge cake is returned to process; the filtrate flows to an
existing lagoon. The centrifuge cake contains several metals, i.e., lead,
cadmium, copper, antimony, and zinc. Its recovery value is based only on
lead, which is present in the largest quantity. The value used is $154/metric
ton ($140/s. ton) of contained lead. This cost represents about 25% of lead
value.
10.
! « =" 5
I 3
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<• e o
Table 25
Capital and Annual Operating Costs for Alternative Treatment of Primary Lead
Smelting Sludge (Waste Stream Number 17)
ANNUAL PRODUCTION (METRIC TONS):
110,000
ANNUAL WASTE (METRIC TONS):
CAPITAL COST
FACILITIES
Lagoon Liners
EQUIPMENT
DRY WEIGHT
6.5QQ
Lime Neutralization System $32,000
Sodium Sulfidc Feed System 2,000
Storage Tank 5,900
Centrifuge 56,000
Pumps 3,100
Piping 2,200
Installation 85,000
WET WEIGHT 21'600
$ 26,200
$186,200
'- ?:
• «_ «t <• £
• i*i
CD 3" J
Z) C9
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
' TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY OASIS
COST/METRIC TON OF PRODUCT
$56,700
10,200
21,940
10,200
NET
1.01*
3.36*
TOTAL
$ 6.80
22.61
0.20*
1.34
42,500
254.900
HOBOES!
$ 41,550
$ 99,040
6.380
$146.970
$lt>8,780
$21.810*
* = Net gain from alternative treatment
SHORT TONS - 0.9 x METRIC TON
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D. Electrolytic Zinc Manufacture - Sludge
(Waste Stream Number 18)
Haste Description. In the production of zinc by the electrolytic
process, zinc sulfide ore concentrates are first roasted to drive off sulfur
as S02 and then leached with sulfuric acid to solubilize zinc. Impurities
are precipitated from the zinc solution. The zinc is then plated electrolytically
from the purified solution onto a cathode as pure zinc.
1. Miscellaneous Slurries. There are a number of miscellaneous
acidic slurries associated with the electrolytic zinc purification process
including scrubber bleeds, acid leach bleeds, anode washings, and spent
electrolyte. A typical electrolytic zinc plant producing 28S NfT of zinc per
day will generate 1,500 mvday of miscellaneous wastewaters containing 2.6 MT
per day of solids. The solids generation rate from the miscellaneous wastewaters
is 9 kg/Mr of zinc product.
2. Acid Plant Blowdown. Because a large volume of S02 is driven
off by roasting the zinc sulfiUe ores, recovery of the SO) as sulfuric acid
is practiced. The sulfuric acid in turn, is used to leacn zinc from the
roasted ore. The by-product sulfuric acid plant itself generates an acid
blowdown slurry amounting to 1,380 m^/day for the typical plant. The solids
content of the blowdown slurry is 5 NfT/day. The solids generation rate in the
acid plant blowdown is 17 kg/MT of zinc metal produced.
The sludges which result from clarification of the (1) miscellaneous
slurries and (2) acid plant wastewaters contain zinc and significant concentrations
of cadmium, copper, and mercury. These sludges are considered potentially
hazardous due to possible leaching of toxic neavy metal constituents. Analyses
of the combined sludges are shown as follows :
Combined bludges Analyses (ppmj:
0> Ck. _.
c 3
§•• s
= ^ «
Cadmium 820
Chromium 44
Copper 2,510
Mercury 22
Manganese 8,740
Lead 15,300
Selenium 66
Zinc 220,000
Present Waste Handling Method. 1. The miscellaneous wa.-~.ewaters
discussed previously are presently discharged to unlined lagoons for solids
settling. Settled solids are dredged from the lagoon and dried on land
prior to shipment to a lead smelter for recovery of zinc and lead value. The
amount of wet sludge dredged per day amounts to 23 MT and contains 2.6 NfT
of solids.
2. Acid plant blowdown slurry is treated with lime for pH adjustment
and heavy metal precipitation and then routed to an tmlined lagoon for solids
settling. The wet sludge is dredged from the lagoons and dried on land prior
to shipment to a lead smelter for zinc and lead recovery. Approximately 5 MT
of solids arc contained in the wet sludges dredged each day.
110
-------
i <»
i a-
Because the combined sludges are acidic, the leachate will contain
soluble hazardous metals. The sludges are now settled in unlined lagoons.
The settled solids arc stored for some time before shipment to a lead smelter
for recovery.
The use of unlined lagoons for settling and unprotected storage areas
for these sludges present environmental pollution hazards if toxic heavy metal
constituents of these sludges leach to the groundwater or arc carried into
surface waters. Soil and runoff conditions at individual plants would determine
the degree of hazard.
Recommended Alternative Treatment Method. Recycle of acid plant
sludge and the other miscellaneous sludges for metal recovery is practiced
to a large extent by the industry. However, there are safeguards which can
be incorporated into existing procedures to eliminate the potential for ground
and surface v.-atcr contamination, so that existing recycle practice"; can become
environmentally sound. These include liming the entire wastewater discharge
to effect maximum metal precipitation; the use of lined lagoons; and substituting
a centrifuge for land storage to dewatcr slinlgos. These additional measures
will eliminate ground and surface water pollution.
Figure 15 Illustrates a modified electrolytic zinc plant sludge
handling and processing system for eliminating potential water pollution.
In this system, combined daily flow of 2,860 mVday from the acid plant blowdoun
and miscellaneous wastewaters are lime treated and clarified in a lined lagoon.
An estimated 3 m^/day of settled sludge will be pumped to a storage tank for
dewatering in a centrifuge. Twenty percent solids7sludgc will be centrifuged
ly CD"? -..'.'! L •-.':,. "!••.'-•. ••-•1'ivr •-. rr-uii. .•••! • v,-,-, jt nrvvify >.. ". m {>'•*?, Tin;
centrifuge cake containing O.i MI lead and i.5 nil zinc/day would bu stored in
lined pits prior to shipment for lead and zinc recovery. The filtrate from
the centrifuge amounting to 29 m'/day would be recycled to the lagoon.
Cost for Alternative Treatment. The costs for the process scheme
described in the block diagram of Figure 15 are summarized in Table 26 .
Plastic lagoon liners are installed in the two existing lagoons.
The lagoon inflow is treated with hydrated lime at the rate of 1.9 metric
tons (2.1 s. tons) per day. The settled sludge is pumped into an 18 m3 (5,000
gal.) sump and then centrifuged.
Ten man-hours per day are assigned to the operation. Electrical
energy use iu based on an average consumption of 25 hp.
The centrifuge cake is stored for reprocessing and the filtrate
returned to the existing lagoon. The centrifuge cake contains more zinc
than any other precipitated heavy metal. Its value of $204/mctric ton
($185/s. ton) of contained zinc represents 25% of zinc value.
Ill
3 "Z.
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1. MISC. FLOWS
1.480m3/day
RETURN
TO LAGOON
LIME SLURRY
TANK
1.9 MT LIME/day
L-L
MIX TANK
(EXISTING)
2880m3/day
LINED
SETTLING
LAGOON
FLOATING
SLUDGE
PUMP
31.3m3/day
STORAGE
SLUDGE
PUMP
FILTRATE
28.7m3/diy
CENTRIFUGE
2. ACID PLANT
SLOWDOWN
1,380m3/day
OVERFLOW TO
LAGOON DISCHARGE
8.8 MT
SOLIDS 085%
REPROCESSED
Figure 15. SCHEMATIC DIAGRAM FOR RECOVERY AND RECYCLE OF ACID PLANT AND
MISCELLANEOUS SLUDGES FROM ELECTROLYTIC ZINC PRODUCTION
(WASTE STREAM NUMBER 18)
112
» c o *
-£jr
s -
3 r* =r
"
-------
Table 26
Capital and Annual Operating Costs for Alternative Treatment of Sludge
From Primary Electrolytic Zinc Manufacture (Waste Stream Number 18)
ANNUAL PRODUCTION (METRIC TONS): 100.000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
2,600
WET WEIGHT 8.700
FACILITIES
Lagoon Liners
$ 31,300
3,100
Lime Neutralization System
Centrifuge
Pumps
Piping
Installation
$33,000
48,000
3,600
600
72,600
157,800
CONTINGENCY
TOTAL CAPITAL INVESTMENT
$ 38,400
230,600
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
$47,250
9,220
36,580
9,220
$102,270
6,380
fulfil
$117,100
29,140*
NET
$ 3.50 *
11.20 *
TOTAL
$16.81
56.25
"2. —S
0.29 *
1.46
* = Net gain from alternative treatment
SHORT TONS " 0.9 x METRIC TON
113
3 ^ ** 5
** iy ~ ~>
***„-.* •»«.«
-------
ff «•
>ve f v
t". Cyrometallurgical Zinc Manufacture - Sludges
(Waste Stream Number 19)
haste Description. In the production of zinc metal by the
pyrometallurgjca] process, zinc sulfide ore concentrates are roasted to drive
off sulfur as S02 gas and to volatilize metal impurities such as cadmium and
lead. The roasted material is then agglomerated in a sintering operation and
fed to heated retorts where the addition of coke reduces zinc oxides and
other zinc compounds to volatilized zinc metal. The volatilized zinc is then
condensed as zinc metal. The condensed zinc metal may be redistilled for
further purification or oxidized to produce zinc oxide by the French process.
Secondary operations include recovery of cadmium from sinter and
roasting fumes, production of lead oxide by the American process, and production
of sulfuric acid from the S02 contained in the roaster gases.
1. Slurries from Primary Cas Cleaning and Acid Plant Blowdown.
^articulates are removed from S07 laden gases in baghouses and wet or dry
«
g-
8
electrostatic precipitators before entering L'ne acid plant. Gases fro
other primary operations such as sintering and crushing are similarly cleaned.
Most of the dusts and slurries resulting from gas cleaning are recycled
immediately but a portion of the slurries amounting to 93 kg/MT zinc is hied
off, limed and thickened in conjunction with acid plant blowdown. For the
typical plant producing 310 MT of zinc per day, gas cleaning slurries may
total 1,090 m3/day and contain 29 MT of solids.
The typical plant generating sulfuric acid from S02 roaster gases,
generates 1,310 m3 of blowdown per day containing 9 MT of solids. The solids
generation rate is 90 kg/MT of zinc product. Both the acid plant blowdown
^T^d *Ko rrit; rlAtninrr c1 nt* 1*1 AC a •»•<» ^ rtmK i n/»^1 **n'^ W*»A/*OC C*»^ in n 1 j tii/» ^ T??*tT?^Tl t
[he sludee°resultiii!: iium liir CC.rr.binc.c1. trratmnnt nf ncid planr MnwHnurn
primary ^as scrubbing contain recoverable amounts of zinc and significant
concentrations of cadmium, copper, lead, and mercury which are considered
Potentially hazardous.1
2. Hetort Gas Scrubber Bleed ("Blue Powder"). A small portion of
the volatilized zinc laden gases produced in the retorting operations passes
through the zinc condensers and is recovered as "blue powder" from wet scrubber
Bleeds. The daily volume of wet scrubber bleed is 5 m^ and contains 3 OT of
solids. Solids generation rate of blue powder is 10 kg/KfT of iiuc product.1
Sludge analyses are shown as follows:
Analysis of Gas Cleaning and Acid Plant
Blowdown Sludges (ppm):
* i
Cadmium 822
Chromium 31
Copper 540
Lead 2,920
1J4
Selenium 46
Zinc 306,900
Mercury 9
»i
Hi
i-aca
-------
ff
Present Waste Handling Methods.
1. Primary Cas Cleaning and Acid Plant Blowdown Sludges. At the
present time, dilute slurries from the primary gas cleaning operations and
from the acid plant blowdown arc jointly treated in a lime treatment system
and sent to unlinec! lagoons for settling. The settled lime sludges containing
122 kg of dry solids per metric ton of zinc are periodically dredged from
lagoons and cither stored on land for several months before recycling or
permanently deposited on land.
The use of unlined lagoons for clarification and open dumps for
sludge storage or disposal may pose an environmental threat if potentially
hazardous metal constituents including cadmium, mercury, zinc, and lead
percolate through permeable soils to groundwater or are carried into surface
streams with runoff.
2. Retort Gas Scrubber Bleed ("Blue Powder"). At the present time,
scrubber bleed water from retort emissions control is clarified in a lagoon
which is periodically dredged. The dredged material (10 kg/MT zinc, dry
weight) is also often recycled after several months storage on land or may
be permanently disposed of on land.
Storage or permanent disposal of retort scrubber sludge poses a
threat to groundwater or surface water quality under the conditions described
for gas cleaning and blowdown sludges.
Recommended Alternative Treatment Method.
i. i j'AiiuU'jr' Gas Clcctuiiij- aiiU Ai_iu PlctitL Slowdown Siuugeb. The
31Uugo3 rcsultifnj Iroiii iiinc treatment ot gss cleaning scrubwulxr iiuu auiu
plant blowdown contain an estimated 30% zinc by dry weight and can be recycled
for zinc recovery. Approximately 11 MT of zinc per day is available for
recovery from these sludges.
Figure 16 depicts an environmentally sound system for effecting
immediate recycle of sludge solids to the process rather than short term or
permanent storage on the ground.
In this system, combined wastcwater flow from the acid plant blowdown
and emissions scrubber water totalling about 2.396 m^/day is sent to a thickener.
Underflow from the thickener amounting to 83 mVday is centrifuged for dewatering.
Overflow from the thickener amounting to 2,313 m-Vday is sent to a polishing
clarifier and its underflow amounting to 71 m3/day is also centrifuged.
Overflow from the clarifier and filtrate from the centrifuge amounting
to 2,360 m-Vday would be stored in a lagoon and should be suitable for reuse
in the emissions control systems for the roaster, sinter, and retort.
8
115
-------
1. ACID PLANT 4
GAS CLEANING
SLUDGES
\
2.39«Un3/
THICKENER
(EXISTING)
i
83m3/dsy
P
PUMP
(EXISTING)
rt»y
OVERFLOW
2313m3/d»y .
~> f
SUMP
75m3
1
PUMP
1
CLAR
24C
i
IFIER
m3
2242m3/d«v
71m3/«Uy
t
PUMP
IEXIS
riNG)
65% SOLIDS
CAKE RECYCLE
TO SINTER FOR
ZINC RECOVERY
30.7 MT/day
CENTRIFUGE
8 HRS/fky
;
118mJ/diy
2360m3/diy
RECYCLED TO EMISSION
CONTROL SCRUBBERS
Figure 16. SCHEMATIC FLOW FOR RECYCLE OF SLUDGES FROM PRIMARY
PYROMETALLURGICAL ZINC ACID PLANT AND GAS CLEANING
SLUDGES (WASTE STREAM NUMBER 19)
116
2. »* 2
3 r* =
""
10
-------
cr-O 3
-------
«r-o 3
c o
2. RETORT GAS SCRUBBER
BLEED SLUDGE
("BLUE POWDER"))
3 MT/diy
1
1
SLUDGE
STORAGE
(EXISTING)
5m"/d»y
SUMP
PUMP
CENTRIFUGE
\
0.5m°/dty
3 MT 95% SO LI OS
CAKE. RETURN TO *
PROCESS OR SOtO
4.5m3/d«v
P
FILTRATE
STORAGE
SUMP
RETURN TO
SCRUBBERS
4.5m3/day
3 .-.
Figure 17. SCHEMATIC FLOW FOR RECYCLE OF SLUDGE FROM RETORT
SCRUBBER BLEED. PRIMARY PYROMETALLURGICAL ZINC.
(WASTE STREAM NUMBER 19)
118
• t
M
-------
TABLE 27
Capital and Annual Operating Costs for Alternative Treatment of Sludge from
(1) Primary Gas Cleaning and Acid Plant Slowdown in Pyrometallurgical Zinc
Manufacture (Waste Stream Number 19)
J07.0QQ_
--S
I 3 ** =
2 2" o»
ANNUAL PRODUCTION (METRIC TONS): _
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 13,000 WET WEIGHT
CAPITAL COST
FACILITIES
Sump
EQUIPMENT
43.000
$ 7,700
Clarifier
Centrifuge
Sludge Bins
Pumps
Piping
Installation
(2)
$ 45,000
100,000
10,000
1.700
1,300
144,200
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O5.M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE TRANSPORT
TAXES AND INSURANCE
302,200
62,000
$37,800
14,880
20,:
14,!
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
$ 87,860
4.700
_.»53.180
, 817,220
$ 664,040
COST/METRIC TON OF WASTE
WET BASIS
DRY OASIS
COST/METRIC TON OF PRODUCT
NET
$ 15,44*
TOTAL
$ 3. 56
11.7R
1.43
* = Net gain from alternative treatment
SHORT TONS " 0.9 x METRIC TON
119
I
o
10
-------
TABLE 28
Capital and Annual Operating Costs for Alternative Treatment nf sinH
(2) Retort Gas Scrubber Bleed in Pyrometallurgical Zinc Manufacture
(Waste Stream Number 19)
107,000
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 1>10°
CAPITAL COST
FACILITIES
Sump
EQUIPMENT
WET WEIGHT ti
Centrifuge
Valves
Pumps
Piping
Installation
$25,000
100
1,400
400
20,300
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL
FnillPMFNTRPPAIR AND MAINTCNANCP
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON Of; WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$15.30
30.59
0.31
SHORT TONS - 0.9 x METRIC TON
120
$ 300
$47,200
$ 9,290
$23,460
900
$33.650
3 .
3
-------
IB C O
-
F. Aluminum Manufacture
1. Spent Potliners and Skimmings
(Waste Stream Number 21)
Waste Description. Metallic aluminum is produced by the electrolytic
dissociation of alumina (A^Oj) dissolved in a molten bath of cryolyte (Na3AlFg),
aluminum fluoride (A1F3), and calcium fluoride (CaF2). The bath, or electrolyte,
is contained in a carbon-lined shell which serves as the cathode. The free
molten metallic aluminum collects at the bottom of the cathode or pot and is
tapped off periodically as required. During operation of the cells, bath
materials gradually adhere onto the cathode liners and the weight of the
liners may nearly double before replacement. These "spent potliners" are a
major source of waste material in primary aluminum plants. Another source of
waste from cell operations is the "pot skimmings" derived from the removal of
crust buildup on the surface of the molten bath.
Since new potliners arc made of carbon, and since the weight of a
potliner approximately doubles over its lifetime resulting from accumulated
bath materials, the composition of the spent potliners is SO percent carbon
or more. The remainder is mostly aluminum, fluorine, and sodium. Traces of
cyanide are also present.
Typical analyses and solubility test filtrate analyses1'7 are
shown as follows:
Typical Analyses (%):
3 H
O 3
=>
-------
(a j*
r..7. icg/.'-f,11 f,-r sp.-5-.t pot liners. The average yer.eratior. factor for pot skim-nines
is about 5.5 kg/NTT of aluminum. A typical primary aluminum plant with an
annual production of 153,000 metric tons of aluminum would generate 7,344 Mr
of spent potliners and 842 MT of pot skimmings.
Present Methods for Handling Waste. Spent potliners anJ pot skimmings
contain valuable materials and, therefore, are either stored, sold or processed
for recovery of cryolite. Some of the larger primary aluminum plants have
cryolite recovery facilities that handle spent potliners and pot skimmings
from other plants as well as their own. Plants that do not have a reprocessing
operation store the wastes on site for periods ranging from weeks to years
depending, in part, on the proximity of a reprocessing plant. Different
cryolite recovery systems produce different grades of cryolite and not all
primary aluminum plants will accept the lower grades of cryolite. Some of the
cryolite recycle systems process scrubber water from potlinc emissions control
systems, in addition to spent potliners and pot skimmings.
Currently, the trend in the industry is toward dry systems for
controlling potline emissions. Sonic of these systems use alumina zf. a riediu.?.
for adsorbing fluorides contained in the cell emissions. The spent alumina,
along with the adsorbed fluorides is introduced into the cells as feed
material. Plants using dry emission controls require a higher ratio of
aluminum fluoride to cryolite cell feed than those using wet controls. The
"dry-plants" can use only 40 to 50 percent of the cryolite that can be
recovered from their own spent potliners. The technology for recovering
aluminum fluoride from spent potliners, when developed, would achieve a recovery
ratio of aluminum fluoride to cryolite more favorable to the material
requirements of these plants and would make reprocessing of all spent potliners
feasible. Thus, plants using dry potline emission control systems do not need
all of the recoverable cryolite and cannot process all the -~-«j
-------
«.e j> «
Reco»nondoJ Alternate Treatment Method.. 1" "j
" "
§-•5
° ""
process is described schematically in Figure 18.
The value of the materials contained in the spent potliners and pot
favorable' depending on the grade and type of recovered
and the size of the plant.
Of the more than 30 aluminum smelting P'"" -P ''e'Xn
States, probably no more than 20 percent have on-site essin
spent potliners for material recovery.
forproceng
for processing
a by-product of primary aluminum production. Two
Washington and Sheffield. Alabama, are »w,,Cu u^
two lants process speiu poLiincj? HUM. <>-»>
The benefits derived from processing spent
recovery systems during the roasting operation.
Cost for Cryolite Recovery System The costs for
recovery system as described by Figure" 18 summarized n Table
s to
be discussed in the following part of this report
123
I
O
£*
IO
-------
NO Jl WASTE
SCRUBBER
iioucm
SOIIOS TO lANOFItl
MSJM.T/VR.
|DBY BAJ|t)
CAKt
C«CO]TOLANOriLL
Mil* M T./YR.
IDRVIASISI
Figure 18. FLOW DIAGRAM FOR STANDARD GRADE CYROLITE RECOVERY FROM
SPENT POTLINERS, POT SKIMMINGS. AND POTLINE SCRUBBER SLUDGES
(WASTE STREAMS NUMBERS 20 AND 21)
« a
c a
3 r.
1
ro
-------
TABLE 29
Capital and Annual Operating Costs for Cryolite Recovery Alternative Treatment
of Potliners, Pot Skimmings and Potline Scrubber Sludges in Primary Aluminum
Manufacture ( Waste Stream Numbers 20 and 21)
ANNUAL PRODUCTION (METRIC TONS):
153,000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Installed Equipment
26,900
WET WEIGHT 59,500
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
QXic awn MAIMTrN&NCc iO&M)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
$453,600
171,840
173,780
171,840
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
$18.35*
$40.59*
TOTAL
$35.09
$77.63
7.14*
13.65
$1,790,000
1,790,000
716,000
$4,296,000
c=3o=«=tri=:
$ 700,250
$1,254,970
132,920
3,180,000
$ 1,091,860*
= Net gain from alternative treatment
SHORT TONS • 0.9 x METRIC TON
125
o
S <
I
o
10
-------
-------
H. Aluminum Manufacture
2. Scrubber Sludges
(Waste Stream Number 20)
Waste Description. Many primary aluminum plants use wet scrubber
systems for controlling emissions from the electrolytic cells. In a number
of plants the scrubber liquor is treated with lime and passed through a
clarrficr. The underflow from the clarifier is then discharged to a sludge
lagoon. In some instances, the clarifier is eliminated and the lime-treated
liquor is piped directly to a lagoon where the solids settle as a sludge.
The average amount of sludge accumulated on a dry-weight basis is 113 kg/MT
of aluminum produced. For a typical plant, this amounts to approximately
17,000 MT/yr. The scrubber water used to control emissions from anode bake
plants is usually trnntfirt together with the potline scrubber water. Thn
anode bake plant and potline scrubber system generates 3.7 kg of sludge per
metric ton of aluminum produced. The total weight of sludge generated
depends to a significant degree on the amount of lime added to the scrubber
water. The values given correspond to lime addition in amounts from 1 to 2
times the stoichiometric requirement; higher treatment ratios are sometimes used.
The sludge from the potline and bake plant scrubbers contains fluorine,
aluminum, carbon and sodium as major constituents, with fluorine accounting for
up to about 20 percent of the average sludge weight.
Typical analyses of scrubber sludges and solubility test filtrate
analyses are summarized as follows:
Typical Analyses (%)
2.!* 5'!
3 r+
-------
and the volume of the lagoon. The dredged material is commonly deposited on
open land near the lagoons. Alternatively, a new lagoon might be constructed
and the old lagonn phf«ed out a? the volume of accumulated sludge becomes
excessive. Successful methods have not been developed for recovering useful
materials from the sludges generated by lime treatment of potline emissions
scrubber water.
About half of the plants that have wet-type scrubbers for control of
potline emissions have some provision for recovering cryolite from the scrubber
liquor. In some cases, the recovery system is capable of processing spent
potliners, as well as scrubber liquor. A brief description of the method for
recovering cryolite from fluoride-bearing residues was given in the previous
section on spent potliners.
Recommended Alternative Treatment Method. Recovery of cryolite
from scrubber liquor, as an alternative to lime treatment and settling,
has the advantage of allowing roson-rc? recovery and reducing waste volumes.
However, cryolite recovery becomes advantageous, for appropriate production
capacities and the purity of aluminum being produced.
A system commonly used for processing potline scrubber liquor and
spent potliners for the recovery of standard grade cryolite is described in
the previous section covering spent potliners and is shown schematically in
Figure 18.
At least two plants operate systems for recovering standard grade
cryolite as noted in the discussion for spent potliner wastes. The two
plants, located at Longvicw, Washington and Sheffield, Alabama, are owned by
Reynolds Metals Company.
The advantage of processing potline scrubber water for recovery of
cryolite, as opposed to adding lime to precipitate solids in a clarificr and/or
lagoon is that it allows a valuable material to be recovered, thereby reducing
virgin raw material requirements, and at the same time reduces the amount of
fluoride-bearing waste material destined for land disposal.
Cryolite recovery from potline emission scrubber liquor reduces the
amounts of potentially hazardous wastes that must be land dispose^, thereby
reducing the probability of adverse environmental effects caused by Isaching.
In addition, because cryolite recovery reduces the amounts of virgin raw
materials required, the environmental impacts resulting from raw materials
acquisition, processing and transport are reduced accordingly and significantly.
...
3
a>
I
o
VI
128
*i I
*!
•1
-------
F. Aluminum Manufacture-
3. Shot Blast and Cast House Uusts
(fiaste Stream Number 22)
Waste Description. The prebaked carbon anodes used in aluminum
reduction cells must be replaced periodically. A metal rod extending from
the center of the carbon anodes serves to connect the anode electrically to
the anode bus. When the ..pent anodes are removed from service, the carbon
is broken off and the mctnl rods are saved for reuse. The rods which are
copper with steel ends arc cleaned by shot blasting and then reused. The
dust collected in the shot blast cleaning of the anode rods is a dust residue
that must be disposed of.
Molten aluminum tnpnprl from thp reduction cell? is transferred to
the cast house where it is alloyed with other metals and cast into ingots.
The skim removed from the molten metal amounts to about two percent of the
total metal poured and contain? about 50 percent aluminum and 50 percent
oxides. The skim is processed to recover 15 to 40 percent of the aluminum.
The residual material is frequently sold to secondary aluminum smelters for
further reclamation of aluminum values. One type of skim processing consists
of a rotating barrel which may be heated to prevent the skim from freezing.
The rotation causes the iretal to coagulate. Periodically, the rotation is
stopped and the metal is drained from the bottom through a tap hole. The
dust emitted in the skim processing operating is sometimes collected in a
cyclone-type system for land disposal.
The shot blast dusts which are mostly iron and carbon also contain
2-3% fluorine and 1-2% copper concentrations. The cast house dust is primarily
aluminum and oxides with small amounts of other metals such as copper and lead,
depending on the type of alloy cast. Analytical data arc shown as follows:
i r-
3 «-•• =
ta ar :
=> t»
Typical Analyses (ppm)
Shot Blast Dust
Fluorine
Copper
head
28,000
15,000
Cast House- Dust
6,200
4,600
Solubility Test Piltratc Analyses (mg/1)1
Shot Blast Dust
Copper 0.14
Zinc 0.2
Lead <0.02
Chromium <0.02
Manganese
Nickel
pli
20
0.13
7.4
129
-------
?•§§ =
» !± =
The dry dusts from shot blasting anode rods and the processing of
cast house skim total approximately 7.5 kg/SfT of aluminum produced. Shot
blast d'jst accounts for two-thirds of the total amount or 3 k»/Mr. A typical
plant prpducins .153,000 MT of aluminum annually would generate 76? NTT of shot
blast dust Q.
O
c
CD
=r
of recoverable materials arc relatively low and do not presently offer recovery
potential. In order to prevent leaching of potentially hazardous constituents
from shot blast and cast house dusts, an alternative to simple land dumping
or landfill is the treatment of these wastes with hydrated lime prior to
disposal in a chemical landfill. One means of providing such treatment is to
transfer the two waste materials to a storage bin and feed them at a fixed
rate to a screw conveyor. Just downstream of where the dusts are added,
hydrated lime and water would also be added. The wetted mixture leaving the
screw conveyor would then be transferred to a chemical landfill.
This method of handling shot blast dusts and cast house dusts is not
commonly prr.c^i ced ^'.i1- i« Hfsioneil to minimize the leachine and subsequent
movement of potentially hazardous constituents into ground water or nearby
watercourses.
Recommended Cost for Alternative Treatment Method. The dust is
mixed with hydrated lime, wetted with water and hauled Lo a chemical landfill.
The maior equipment components include a 17 m^ (600 ft 3) dust bin, a 2.3 nr
(80 ft-5) lime storage tank, a 5 cm (2 in) screw conveyor for feeding the lime
and a 5 m (IS ft) long D section conveyor to load the mixture into •-• dump
truck.
Two man-hours per day are assigned to the operation. Lime use for
a year is 64 metric tons (70 s. tons). The waste has no recovery value.
The cost for the proposed alternative method of waste disposal ns
shown in Figure 19 is summarized in Table 30 .
I
O
10
130
-------
SHOT BLAST DUST
CAST HOUSE OUST
3.28 MT/day
I
DUST
STORAGE
BIN
17m3
\
DHIVE
A
HYDRATED
LIME
STORAGE
>M).15 MT/cta
WATER
SPRAY
0.28 MT/day
1
D SECTION CONVEYOR
5.7m3
TO CHEMICAL
LANDFILL
3.71 MT/ctay
Figure 19. SCHEMATIC FLOW DIAGRAM OF ALTERNATIVE PROCESS FOR PRIMARY
ALUMINUM SHOT BLAST AND CAST KC'JSC DUST DISPOSAL (WASTE
STHEA-V- NUMBER 22}
131
O
=
3
O>
i .
.1
I
O
-------
TABLE 30
Capital and Annual Operating Costs for Alternative Disposal of Primary
Aluminum. Shot tilast and Cast House Dust (Waste Stream Number 22)
153.000
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Dust Storage Bin
Lime Storage Bin
Lime Feeder
D Section Conveyor
1>100
WET WEIGHT
Installation
$5,600
1,100
2,100
90°
ft ™n
9«700
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL
Fni.UPMFMT RFPAIR ANn MAINTFNANCF
• « » T»" « »4 A t /*
WASTEDISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
$9'
s A
'
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
J7S.33
0.54
SHORT TONS - 0.9 x METRIC TON
132
$19,700
3,900
$23.600
m^^BEB^^^E
$ 3,850
$78,980
30
i =l -» " a
"~ rf- 3"S
OL. <• =
is!
II
rl
• 4
H
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-------
G. Pyromctallurgical Antimony Manufacture - Blast Purnace Slag
(Waste Stream Number 23)
Waste Description. There are only two locations in the United States
producing blast furnace slag from primary antimony production. One location
is in Laredo. Texas and the other is in Montana. In 1974, 97% of the antimony
metal produced in the United States was from the Laredo, Texas smelter.1 Blast
furnace slag is produced as a waste product from the blast furnace smelting of
oxide and sulfide ores of antimony to recover pure antimony metal.
Blast furnace slag is produced at a rate of 2,800 kg/MT of antimony
metal. The slag is glassy and hard and produced in large chunks. The typical
plant producing 2,700 MT/yr of antimony metal generates 7,360 MT of blast
furnace slag. Principal constituents of slag are silicon dioxide, ferrous oxide,
calcium oxide, aluminum oxide, and antimony oxide. Other elements known to be
contained in slag in low concentrations include lead, copper, zinc, arsenic,
cadmium, chromium, nickel, and selenium. These are shown as follows:
_^
o j* -
a -
3 r+ 5
03-5
3 « °
Slag Analysis (ppm)
Lead 66
Copper 50
Zinc 500
Antimony 18,000
1
Arsenic
Cadmium
Chromium
Copper
3
0.09
< 0.01
5
Manganese 0.01
Nickel <0.05
Lead <0.2
Antimony 100
Zinc 1.7
Selenium <0.05
pH 9.2
Potentially hazardous constituents of blast furnace slag which may
leach into groundwaters include antimony, copper, zinc, and arsenic.
Present Methods for Waste Disposal. At the present time, blast
furnace slag is opeu Jumped on lend disposal areas. The permeability of the
soils at the land disposal areas is not known. There would be a danger of
ground or surface water contamination if potentially hazardous metal constituents
leached through permeable soils to groundwater or were carried in surface runoff.
Recommended Alternative Treatment Method. The antimony content of
discarded blast furnace slag is from 1 to 2% and processing this slag for further
recovery of antimony is not considered economical. Disposal of the lime treated
slag in a chemical landfill would be an alternative method for protection of
ground and/or surface water from heavy metal leaching. Maintenance of elevated
pll1* in the land disposal environment will detoxify the heavy metals as
insoluble hydroxide precipitates.
133
-------
The chemical landfill procedure alternates layers of slag with
hydrated lime. Thus, a one meter layer of slag underlain by 0.1 meter of
hydrated lime would be covered by 0.1 meter of hydrated lime. This layered
arrangement is used until the site is filled and then covered by 0.3 m of clay.
The volume occupied by 21.6 WT of blast furnace sJag generated in one
day is estimated as 14 m3 (500 ft3). The area occupied by one day generation
of slag piled to a depth of 1.2 m will be 11.1 m^. Approximately 490 m^ area
will be required to deposit a one year accumulation of alternating layers of
slag and lime to a 10 meter depth.
At the present time, producers of primary antimony metal are not
using the described alternative method. The benefits to be derived from use
of this method are the immobilization of any leachable toxic heavy metals as
the metal hydroxides in the lime layers thereby precluding possible movement
to ground or surface waters. There will be a 10% volume increase of waste
in the landfill due to the use of lime.
Cost for Alternative Method of Waste Disposal. The treatment process
is essentially a chemical landfill operation augmented by the addition of
hydrated lime between layers of slag. A lime storage shed is provided at the
disposal site. Approximately 223 metric tons (245 s. tons) of lime are used
each year. The incremental labor, beyond operation of the landfill is estimated
to be cwo hours daily. The waste has no recovery value.
The disposal system flow scheme is shown in Figure 20 and the associated
costs are summarized in Table 31.
<• e o
5" •• — =•
-^ —• ,* CD
£• S
3 »* =»
< i
134
I
O
10
—&
-------
OT.O 3
ANTIMONY
BLAST FURNACE
SLAG
21.6MT/day
\
HYDRATED
LIME
0.78 MT/cUy
> )
r
CHEMICAL LANDFILL
22.4 MT/day
Figure 20. DIAGRAM OF ALTERNATIVE DISPOSAL FOR BLAST FURNACE SLAG
FROM PYROMETALLURGICAL ANTIMONY MANUFACTURE.
(WASTE STREAM NUMBER 23)
135
I
o
10
-------
er.o 3 S
« e o w
— M rt- «
TABLE 31
Capital and Annual Operating Costs for Alternative Disposal of Blast Furnace
Slag from Primary Antimony Pyroraetallurgical Manufacture (Waste Stream Number 23)
ANNUAL PRODUCTION (METRIC TONS):
2,700
ANNUAL WASTE (METRIC TONS): OR Y WEIGHT 7,700
CAPITAL COST
FACILITIES
Lime Storage Shed
EQUIPMENT
.WET WEIGHT
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AMD MAinTcNANCE (CSiM)
OPERATING PERSONNEL
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
SHORT TONS • 0.9 x METRIC TON
$3,600
$ 9,450
170
12.270
118,940
'170
700
$4,300
1 i
700
141,000
$141,700
.-
TOTAL
$18.40
52.48
136
-------
M. Electrolytic Antimony Manufacture
(Waste Stream Number 24)
Spent Anolytc Sludge
Waste Description. Electrolytic antimony metal is produced by a
leaching-electrolysis process. In this process, a complex copper-antimony
sulfide ore concentrate is leached with sodium sulfide to dissolve the
antimony. The leach solution containing solubilized antimony as sodium
thioantimonate (Na^SbSj) is electrolyzed in diaphragm cells to yield antimony
metal. Although electrolyte is rccirculatcd, the gradual buildup of impurities
requires that spent anolyte solution be discharged. Approximately 13 nv* of
spent anolyte solution containing S40 kg of solids is discharged per day. The
solids generation rate is 210 kg/MT of antimony metal produced. For the typical
plant producing 900 MT/yr of antimony by the electrolytic process, 190 MT dry
weight of spent anolyte sludge is generated.
Spent anolyte sludge is composed primarily of metal sulfides. The
major metallic constituent is iron. Antimony will be present in the sludge
in the order of 2-3°i dry weight but is not present in sufficient concentration
for economical reprocessing. Other metals present in trace amounts include
arsenic, lead, copper, zinc, nickel and cadmium which can pose a hazard to
ground or surface water if leached from the sludge. These concentrations are
shown following:
Analysis of the Dried Anolyte Solids in ppm:
Arsenic 16
T - -. 4 r
uuppci
Zinc
JU
2
Nickel
A n «• <
-------
e»
. «•
Recommended Alternative Treatment Method. At 2°s antimony content
and 90% recovery efficiency, only 10 kg of antimony metal per day could be
extracted from the spent anolyte sludge. Thus resource recovery is not a
viable alternative for waste disposal.
Solids contained in the spent anolyte may be isolated from the
groundwater environment by a simple process as shown in Figure 21. In this
process, the 13 m-Vday of spent anolyte are clarified for solids removal.
Solids settled in the clarifier would accupy 1.<1 m , and clarifier overflow
amounting to 12 m-Yday would be discharged to the mine-mill tailings pond.
The clarifier sludge would be put into 55-gallon drums and trucked to a chemical
landfill. It is estimated that five 55-gallon drums would be required for
disposal of the sludge generated in one day.
By using the procedure previously described, it is possible to
isolate the settled anolyte solids for environmentally sound disposal in a
chemical landfill. The clarifier overflow, however, is not isolated from
the environment. This overflow will have high concentrations of iioiiloxic
dissolved solids such as sodium sulfate, sodium thiosulfate and sodium hydroxide.
Dissolved heavy metals will be present in the clarifier overflow at very low
concentrations. The 12 m-* clarifier overflow will be less than l°i of total
discharge to the tailings pond as previously discussed and the nontoxic
dissolved solids xvill be diluted to relatively low concentrations.
The proposed alternative method of sludge disposal is not commonly
practiced by the industry.
Cost for Alternative Method of Waste Disposal. The flow scheme for
Llie Disposal of thc:;c wastes by l!ic uescribi.-;] .i!Cer;>aliy? iwl'r.-J !;• >]!•.•>• r,
I., n;.,,,.^ ,'l anct the cor.t is su™.ro^ri:^-J i.:: Tttule 32.
A settling tank, sized for 24 hour retention (1.5 m-* - 400 gal) is
provided. The underflow is containerized and sent to a chemical landfill.
About 326 m3 (425 yd3) of waste are disposed annually. The waste has no value.
138
-------
.
a> c o "
"
SPENT ANOLYTE SLUDGE
13m3/diy
540 kg SOLIDS
CLARIFIER
1.5m3
T
OVERFLOW 12m3/dav
TO TAILINGS POND
SETTLED SOLIDS
TO CHEMICAL
LANDFILL 1m3/diy
Figure 21. FLOW DIAGRAM SHOWING CHEMICAL LANDFILL OF SPENT ANOLYTE SLUDGE
SOLIDS (WASTE STREAM NUMBER 24)
-8-
3 <*
139
-------
TABLE 32
Capital and Annual Operating Costs for Alternative Disposal of Spent Anolvtc
Slndge from Primary Antimony Electrolytic Manufacture (Waste Stream Number 24)
ANNUAL PRODUCTION (METRIC TONS):
900
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 200
CAPITAL COST
FACILITIES
WET WEIGHT.
600
EQUIPMENT
Clarifier
Valve and Piping
Installation
$1,500
100
1,600
$3,200
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL (Included in Waste Disposal Cost)
CGUiTMCNTrtCPAin A.'JC MAJNTEKANCC J ISO
MAItHIALi
WASTE DISPOSAL 32,110
TAXES AND INSURANCE 1 50
600
$3.800,
$620
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$55.05
165.15
36.70
SHORT TONS - 0.9 x METRIC TON
140
-
at e o "
* s- «J
0 tf
i-g
-------
I. Titanium Manufacture - Chlorinator Condenser Sludge
(Waste Stream Number 25)
Waste Description. In the production of titanium sponge metal, rutilo
(Ti02) concentrates are treated with chlorine gas to convert the rutile to TiCl4
gas which is then condensed, reduced, and purified to produce titanium sponge.
The chlorinator-condenser sludge contains impurities in the rutile plus some
carbon, chlorine, and titanium.
Chlorination sludge is generated at a rate of 330 kg/MT of titanium
metal product. The typi sal plant producing 7,600 MT/yr of titanium sponge
generates 2,500 MT/yr of sludge. The sludge contains approximately 23%
solids and 77% moisture.
Sludge from the chlorination and condensation processes has been
found to be about 40% water soluble.1 The water soluble portion contains
chloride and chloride-oxide complexes of chromium, titanium, vanadium and
other heavy metals. These are shown as follows:
Sludge Analyses (ppm)
<9 OL.
~g
1?
5 .*
Vanadium
Chromium
Zinc
Titanium
Chlorine
25,780
11,630
34,770
104,400
187,000
Because the high solubility of heavy metals in this sludge and the
danger of li/uroohlor;;: "-:•-; f'tw .•<:-!—:••••: -^ frvir ;•• •''• -:i-"--:\i -.«>.:.•„.>...-..i /
titanium ctxlorinator condenser siuugcs are considered potentially hazardous
if disposed on land.
Present Methods for Waste Disposal. At the present time, the two
plants producing titanium sponge metal employ contract disposal services for
sludge disposal. One of these firms uses a landfill while the second disposes
its sludge in lagoons constructed in highly impermeable glacial till and clay
underlain by shale. The type and permeability of soils at the ."andfill site
of a typical plant are not known. Since toxic heavy metal and chloride
constituents are easily solubilized from this sludge, contamination of
groundwater or surface water is a potential environmental hazard.
Recommended Alternative Treatment Method. On a dry basis, chlorination
sludge contains 52% carbon and 38% rutile (Ti02). The U.S. Bureau of Mines has
found in laboratory pilot studies that rutile and carbon can be recovered from
the sludge and recycled back to the process for recovery of titanium.' The
carbon is useful as a rcductant in the process.
Figure 22 illustrates the schematic flow for this full scale resource
recovery process. The sludge from the chlorinator and condenser totals
141
I
O
-------
—- fa f+ w
CHLORINATION SLUDGE
FROM PROCESS 27.5m3/d»y
i
_ OVERFLOW
14.3m3
SETTLING PIT
(EXISTING)
LIME
2.6 MT/diy
1
MIX
\
I 13MT/d»v
I 20% SLUDGE
TANK
-*•
30.3 MT/d»y
r
THICKENER
17.:
H
SETTLED
SOLIDS
1
r
PLASTIC
HOLDING
TANK
30m3
>
RUBBER LINED
SCREW
CONVEYOR
»m3 1
>
CENTRIFUGE
11
j UNDERFLOW
1 16 MT/day
Y 3.2 MT SOLIDS '
FILTRATE
10.7m3
CENTRIFUGE
11
5.3 MT
60% SO LI OS
TO CHEMICAL
LANDFILL
CAKE (MOIST)
r 70% SOLIDS
STEAM DRYER
-4—
I
7.2 M.T. DRY SOLIDS
RETURN TO PROCESS
c
3
ft
=>
• 3 MT/diy STEAM
Figure 22. SCHEMATIC FLOW DIAGRAM FOR RECOVERY OF RUTILE AND CARBON
FROM CHLORINATOR CONDENSER SLUDGE (WASTE STREAM NUMBER 25)
142
I
o
-------
cr-a =
(D C O
. Z
f S
o ,»
27.5 m /day, is settled in a pit and then transferred to a plastic holding
tank. From the holding tank, the sludge is transferred by a screw conveyor
to a centrifuge for dewatering. The sludge cake from the centrifuge containing
70% solids 15 then further dried in a steam dryer. l:rom the steam dryer, 7 MT
of dry solids per day can be recycled to the chlorinator for recovery of
titanium. The dry solids will contain 2.7 NfT of rutile (Ti02) or 1.7 WT of
elemental titanium. Approximately 3.7 Mr of carbon is recovered per day.
The waste filtrate from the centrifuge amounting to 17 m /day is
mixed with lime, thickened, and ccntrifuged. The precipitated solids are
chemically landfilled. The filtrates are recycled to the (existing) settling
pit.
The benefits attributable to rutile and carbon recovery from
chlorination sludge are resource recovery, waste volume reduction, and
elimination of potential ground and surface water contamination which
could result when the slii.W is deposited ir. landfills or lagooii.s.
Cost for Alternative Method of Waste Disposal. A summary of the costs
shown in Table 33 WHS developed based on the flow scheme outlined in
Figure 22.
The major system components include a 30 m3 (7,900 gal) holding tank,
a screw conveyor, centrifuge and steam dryer. The screw conveyor is mounted
under the holding tank and feeds the sludge to the centrifuge. The centrifuge
discharge is directed to c steam dryer and then recycled. The centrifuge
filtrate flows to a 19 m3 (5,000 gal) holding tank from which it is pumped
to an existing settling pit.
Operations are conducted 8 hours per day and assigned 4 man-hours
of labor. The steam dryer is estimated to use 12.7 x 109 joules (12 x 106 Btu's)
per day.
The recovered product contains 30% rutile. Rutile has a value of
about $230 per metric ton ($210/s. ton) which price is used to compute the
value of the recovered material.
3 r*
» =r
3 0>
143
I
O
£>
IS)
-------
TABLE 33
Capital and Annual Operating Costs for Alternative Treatment of Chlorinator
Condenser Sludge in Primary Titanium Manufacturing (Waste Stream Nurr.bcr 25)
7.600
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGHT _2JLQQ WET WEIGHT 6^30°
CAPITAL COST
FACILITIES
EQUIPMENT
Holding Tanks
Screw Conveyor
Centrifuge
Steam Dryer
Pump
Piping
Installation
$ 7,000
2,800
46,000
54,000
900
1,800
35,700
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSONNEL $18,900
cni MPMCNT RFPAIR AND MAINTENANCE 9 ,51 0
$198.200
39,600
$ 38,760
MA, I I- HI A* I. J»
WASTE DISPOSAL
TAXES AND INSURANCE
9,510
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
.f 14.85*
37.41*
12.31*
TOTAL
$12.53
31.59
10.39
* = Net gain from alternative treatment
SHORT TONS • 0.9 x METRIC TON
144
£f I-
3 S. — 0
=> 9
»1
J
J
I
o
10
-------
tr-o a
I ~ o ;
IS 2
A.
SUCTION III
SECONDARY NON-FERROUS REPINING HAZARDOUS W/VSTI-S
Copper Refining - Blast Furnace Slag
(Waste Stream Number 27)
Waste Description. Copper recovered from high grade scrap (i.e.
predominantly copper metal scrap) is refined in rcvcrbatory furnaces. Slag
from reverbatory furnace: containing recoverable amounts of copper along with
low grade scrap, drosses and skimmings arc smelted in blast furnaces. The
slag from the blast furnace is too low in copper content for further copper
extraction and is, therefore, discarded. Approximately 350 kg of discarded
slag is generated for every metric ton of copper metal produced. For a typical
plant producing 10,000 NfT/yr of secondary copper, 3,500 N(T of discarded slag
is generated per year. It is estimated that the typical »u<_oiiuary smelter
will operate its blast furnace about 100 days per year generating 35 NfT of
slag per day.
Although this material is dense and hard, solubility tests showed
significant concentrations of soluble zinc, cadmium, copper and lead and this
waste slag is, therefore, considered potentially hazardous.^
Solubility Tests Filtrate Data in mg/1
1
2inc
Chromium
Copper
Manganese
55
1.0
0.03
170
0.3
Lead 6
Antimony <0.2
T» • . n i
pll 9.4
Present Waste Disposal Methods. At the present time, blast furnace
slag is open dumped on land. This practice is environmentally unsound if
heavy metals including zinc, copper, lead, and cadmium) leach and percolate
through pormeable soils to contaminate groundwater. Soil conditions at individual
slag disposal sites would determine the degree of potential hai'-d.
Recommended Alternative Method Treatment. Since the industry
already recovers the maximum amount of copper from slags, further attempts at
copper recovery is not considered practical nor technically and economically
feasible. The concentrations of tin, lead, and zinc are also too low (1» or
less) for economical recovery. Other metals such as iron, silicon or aluminum
are not valuable enough to warrant recovery.
Detoxification with lime to precipitate soluble heavy metals as low
solubility metal hydroxides is a recommended alternative to prevent groundwater
contamination which could result from land disposal of blast furnace slag.
145
I
o
-------
A system for lime treatment of blast furnace slag is given in
Pigure 23. In this system, generated slag is layered with hydratcd lime
and wetted in a chemical landfill. The hydratcd lime requirement (f'a(OI|)2)
is estimated at 1UU kg (ilb Ibsj pc-r clay.
Cost for Alternative Method of Disposal. A schematic diagram of
the flow scheme for detoxification of secondary copper refining blast furnace
slag is shown in l-'igurc 23. The costs arc summarized in Table 34.
The treatment process is a chemical landfill operation augmented
by the addition of lime between layers of slag. The lime may be wetted following
its application. Approximately 100 kg of hydrated lime arc used daily.
A small storage shed is provided at the landfill. The incremental
labor beyond operation of the landfill is estimated to be 1 hour daily.
The waste has no recovery value.
• CO.
— m ++ _•
If.n
?-?
• g- H
«= ° rl
3 *• =>
I
o
A
10
.—^
146
II
-------
CO"
tf I* =
^— ;r* - =
I
o
*
10
147
-------
TABLE 31
Capital and Annual Operating Costs for Alternative Treatment of Blast
Furnace Slag from Secondary Copper Refining (Waste Stream Number 27)
10,000
ANNUAL PRODUCTION (METRIC TONS): _
ANNUAL WASTE (METRIC TONS): DRV WEIGHT
CAPITAL COST
FACILITIES
Lime storage shed
EQUIPMENT
3,500
WET WEIGHT
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
vS AMD MMiUTcn'ANCE (CSiMi
*
50
OPERATING PERSONNEL *
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS ,^F rfn
WASTE DISPOSAL 125,560
TAXES AND INSURANCE 50
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
TOTAL
$37.86
13.25
SHORT TONS - 0.9 x METRIC TON
148
$ 1,100
200
1.300
210
$132,300
210
$132.510
» er e
o.5
k*
• i
8
I
o
10
-------
:
B. Load Refining - S02 Scrubwatcr Sludge
(Waste Stream Number 28)
Waste Description. In the secondary lead smelting process, lead
scrap materials such as used lead batteries are smelted in blast or cupola
furnaces. Scrap iron is used as the reducing agent to convert lead compounds
to metallic lead. During the smelting process, sulfur compounds, such as lead
sulfate present in lead battery paste and residual sulfuric acid in scrap
batteries are reduced to sulfur dioxide (SO-.) and discharged in air emissions.
Scrubbing S02 from air emissions with lime solutions produces a predominantly
calcium sulfate-calcium sulfite sludge.
The solids content of the settled sludge amounts to 45 kg/MT of
lead metal recovered from scrap. A typical plant producing 10,000 MT/year
of load product generates dry sludge solids from SO, emission control
estimated at 450 metric tons. Daily sludge production totals 3.6 m3 containing
1.3 MT of solids and 3 MT of water.
The sludge solids resulting from settling of lime scrubwater contain
as much as 5% lead and trace concentrations of cadmium, antimony, and other
heavy metals in addition to CaS04 and CaSOs-l This sludge is considered
potentially hazardous because of the possible solubilization of toxic constituents
including lead and cadmium in a land disposal environment.
Analytical data on dried sludge and filtrates from solubility tests
are shown following:
» e
s-s
2 =T«
Analysis of uried Sludge (ppm)";
Cadmium
Chromium
Copper
Manganese
340
30
20
120
Nickel
Lead
Antimony
Zinc
5
53,000
1,000
25
Solubility Test Filtrate Analyses (mg/1)1
Zinc
Cadmi urn
Chromium
Copper
Manganese
1.3
5
0.05
0.5
0.21
Lead 2.5
Antimony < 0.2
Tin 1.6
pH 8.4
S02 emissions
Present Waste Handling Method. At the present time,
from secondary lead smelting arc scrubbed with lime at only one location. It
is expected that scrubbing SOi from secondary lead smelting at other locations
will become much more prevalent in the future. The lime scrubber solids are
149
-------
presently settled out in an unlined lagoon. Leaching toxic metal constituents
including lead and cadmium with subsequent percolation to groundwatcr could
pose a threat to groundwater quality it' soils are sufficiently permeable and
have low attenuation of metals from leachate. Soil conditions and permeability
at the one site are not known, and these would determine the degree of hazard.
Recommended Alternative Treatment Method. Figure 24 illustrates a
system for treatment of S02 scrubwater sludge which will eliminate the threat
of groundwater pollution. In this system, the settled solids from the SC>2
lime scrubber are detoxified with additional lime and sodium sulfide to
precipitate soluble toxic metals as insoluble hydroxides and sulfides. The
daily lime requirement beyond that which is presently used in the lime
scrubber is estimated as 4.5 kilograms (10 Ibs) for the typical plant producing
30 MT lead per day. The daily sodium sulfide requirement is estimated as 0.5
kilograms (0.1 Ib). A concrete sump should be used to hold sludge prior to
treatment.
3
-------
FILTRATE
RETURN TO
SLUDGE PON
2.84m3
CE
SLUDGE
POND
EXISTING)
4.5 kg Ca (OH), PFn
F^ £ rCr* ^^^
0.05 kg Ni,S day *
NTRIFUGE
DREDGE
(EXISTING)
i
4.286 MT/d»y (3.57 m3)
1.286 MT SOLIDS
3,000 MT WATER
MIX
TANK
3.8m3
\
3.72 kw AGITATOR
3.57 m3 (943 GALLONS)
PUMP
0.02m3/min
0.37 kW
1 1.43MT/diy 1 RUN
I SPGR1.90 4 MRS
Y 0.73m3
TO CHEM. LANDFILL
SLUDGE FROM SECONDARY LEAD REFINING (WASTE STREAM NUMBER 28)
151
cr-o s 5"
• c 2.
5" S. — S"
5
I
o
-------
TABLE 35
Capital and Annual Operating Costs for Alternative Treatment of
SO- Scrubwater Sludge - Secondary Lead Refining (Waste Stream Number 28)
10,000
ANNUAL PRODUCTION (METRIC TONS):
ANNUAL WASTE (METRIC TONS): DRY WEIGH1
CAPITAL COST
FACILITIES
Concrete Sump
EQUIPMENT
Mix Tank
Centrifuge
Pumps
Piping
Installation
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPCnATINC PCnSONNEl.
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
SHORT TONS - 0.9 x METRIC TON
450
WET WEIGHT 1.500
$ 5,000
25,000
1,500
1,100
23,300
$9.450
9,220
3,140
TOTAL
$25.61
85.36
3.84
152
$11,600
$53,900
13,100
$78.600
$12,810
$25,050
550
« •,*
I c o
3 r»
-------
C. Secondary Aluminum Refining
1. Scrubber Sludge
(Waste Stream Number 29)
Waste Description. High grade aluminum scrap is reclaimed by remelting
in pot or rotary furnaces. The smelting of low grade scraps and drosses is
performed in reverberator/ or rotary furnaces. Common salt and potash mixtures
are normally used as fluxing agents to separate impurities from the aluminum
metal.
One of the major contaminants in aluminum scrap which must be removed
is magnesium metal. In order to remove magnesium (demagging), chlorine gas or
aluminum fluoride is injected into the furnace. The chemical reaction which
ensues produces acidic gaseous emissions including MCI and MF. These emissions
must,be scrubbed with a lime slurry to neutralize acidity. Upon settling, the
lime slurry produces a sludge. The daily volume of lime sludge generated at
a typical secondary aluminum smelter producing 20,000 MT/yr of aluminum
(57 MT/day) is 30 m3. Tho solids content of the sludge is 4.3 Mr/day. Solids
generation rate from the lime scrubbing of demagging water is 73 kg/NTT of
aluminum metal produced.
The scrubber sludge contains a high concentration of fluoride,
chloride, and sodium. Trace metals present in significant concentration
include copper, lead, and zinc.1 This waste is considered potentially
hazardous because of the possible leaching of fluoride and heavy metals.
JL j* 5"!
o .
n r+
c **
3 r*
Dried Sludee Analyses (ppm)
1.
Chromium
Copper
Lead
Zinc
20
1,250
140
6,500
Present Waste Handling Methods. At the present time most secondary
aluminum smelters discharge scrubber sludge to unlined lagoons. A few smelters
use lined lagoons. The use of unlined lagoons in soils which arc permeable
could lead to contamination of groundwater by fluoride or heavy metals.
Recommended Alternative Treatment Method. An alternative method
for treating scrubber sludge which eliminates lagoons is presented in Figure 25.
In this system, dilute lime slurry from emissions scrubbing is first directed
to a thickener for initial solids concentration. Overflow from the thickener
amounting to 14 m5/
-------
SCRUBBER
PUMP
28.67 MT/day
26.11m3
PUMP
0.23m3/min
THICKENER
3.6m DIAM
2.4m DEEP
OVERFLOW
STORAGE
19m3
SLUDGE
14.28 MT
11.94m3
STORAGE
18.9m3
PLASTIC
rUiviP
0.06m3/mln
STEEL
CENTRIFUGE
4-8 HRS/d*y
FILTRATE
10m3
SOLIDS TO
CHEM LANDFILL
6MT
2.4m3
FILTRATE
STORAGE
11.4m3
PUMP
0.23m3/mln
Figure 25. FLOW DIAGRAM OF ALTERNATIVE SYSTEM FOR SLUDGE TREATMENT AND
DISPOSAL FROM SECONDARY ALUMINUM REFINING (WASTE STREAM
NUMBER 29)
154
• «•*•
3 rt-
5 3T
»•' •
»H
I
o
-------
0--0 3 =•
a> c o "
5- »!Z =
by using the above system, fluorides and heavy metals are not
leached from sludge solids in unlincd lagoons. A reduced volume of solids
would be safely deposited in a chemical landfill.
Cost for Alternative Method of Disposal. The costs for the flow
scheme described in Figure 25 are summarized in Table 36.
The scrubber wastewater flows into a 26 m3 (7,000 gal) thickener.
The overflow is returned to the scrubber. The underflow goes to a 19 m-*
(5,000, gal) storage tank and is then centrifuged. The filtrate discharge
from the centrifuge is temporarily stored in a 11.4 m' (3,000 gal) storage
tank and is pumped to the scrubber. The centrifuge solids arc sent to a
chemical landfill.
The system is operated 4 hours per day using 2 man-hours. The
yearly amount of v.'aste sent to landfill is 840 metric tons (925 s. tons). The
waste has no recovery value.
--B
gff-
3 ,->• =•
"«
15S
I
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-------
TABLfi .%
Capital anu Annual Operating Costs for Alternative Treatment of Scrubber
Sludge from Secondary Aluminum Refining (Waste Stream Number 29)
ANNUAL PRODUCTION (METRIC TONS):
20,000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT
CAPITAL COST
FACILITIES
EQUIPMENT
Storage Tanks
Filtrate Storage Tank
Centrifuge
Thickener
Pumps
Piping
Installation
1.500
.WET WEIGHT .'_
— c S-
-fsf
^ - w
=T S. ~" 2
C9 7" 44
3
-------
CT03 3
CD C O
•
C. Secondary Aluminum Refining
2. High Salt Slag
(Waste Stream Number 30)
Waste Description. The secondary aluminum refining industry processes
a wide range of aluminum-bearing wastes for metal recovery. About 10 to 15% of
the total secondary aluminum metal recovered is derived from aluminum dross.
The recovery of aluminum metal from highly oxidized dross generates large
quantities of salt slag which contains fluxing salts (50 to 65%), aluminum
metal (5 to 15%), and aluminum oxide (25 to 35%) as major constituents. Minor
constituents of interest include chromium (60 ppm), copper (310 ppm), manganese
(100 ppm), nickel (10 ppm), lead (300 ppm), and zinc (240 ppm),1
For each metric ton of aluminum metal recovered from dross, about
1,400 kg of salt slag is generated. Thus, about 14,000 MT of high salt slag
would be produced by a typical secondary aluminum smelter that recovers
10,000 MT of aluminum per year from dross.
Present Disposal Methods. At the present time, nearly all the high
salt slag residue from dross processing is disposed of in open dumps.
Potassium and sodium chlorides present at high concentrations in high salt
slag are relatively nontoxic when compared to heavy metals. However, the
high concentration of these constituents and their high solubility presents a
potential hazard to groundwater quality. Therefore, open dumping of high salt
slag in areas having permeable soils is environmentally unacceptable.
processing high salt slag to allow resource recovery is summarized in /-igure 26.
This system is based on a process investigated by the Bureau of Mines.3 The
slag is first crushed and then leached with water and a dilute brine. The
larger insoluble fractions containing metal are removed by a 16 mesh screen
and dried. The 16 mesh fractions and the soluble material .arc then vacuum
filtered. The oxide-containing solids removed in filtering are dried. The
filtrate, containing the dissolved salts, is evaporated and the residue is
centrifuged. The residual salts are then dried and mixed with .ryolite or
potassium aluminum fluoride to produce a saleable flux.
The metal-bearing fraction removed by the 16 mesh screen contains
about 70% motal and is generated at the rate of 70 kg/MT of slag processed.
The oxide fraction removed in vacuum filtering contains 10-12% metallics
and is produced at the rate of 330 kg/MT of slag processed. The salt fraction
amounts to about 600 kg/MT of slag processed.
|3 r*
1 2. 3 sr
e» a.
"2-
c o
3 ~
to =r
=> a>
157
-------
» c o -
—• ca r+ —
HIGH SALT
SLAG
f 56 MT/d«y
CRUSH
WATER
14 MT/day
•16 MESH
SOLIDS
IX WATER
SOLUBLE
CONTENT
20 MT
AI2O3 + H20
WA
t '
TER
t
STORAGE
TANKS
t
124MT/dty PUMPS
DILUTE BRINE |
f~ 16MT/diy
LEACH
^
FUEL
t
DE WATER
SCREEN
W 1
« 16 MESH SOLIDS _ „„„,„
-16 MESH 5.6MT/d.r|
. BifafilNC TO FURNACES
OR MILL FOR
VACUUM
FILTER
t
VACUUM
PUMP.
TRAP. ETC.
fl70MT
FUEL
v «
DRYER
EVAPORATOR
f
PUMP
T t
DUST " MT/diy
COLLECTOR "~ T
CENTRII
ATMOSPHERE * -16 MESH SOLIDS *
A 16.8 MT/diy
L— FAN AI203 FUEL-**
FOR SALE
SALT ,
DRYER '
J>
CONCENTRATING
DILUTE
BRINE TO
STORAGE
14 MT/diy
/day
unrucp
l l
PUMP
' ' PERIOD!
OISCHAI
DILUTE
c
*GE
AGE
BRINE
N> SCRUBBER &• PUMP — J
2 MT/d.y
I ADO CRYOLITE OR
MIXER M- POT. ALUM. FLUORIDE
I (5%)
t
FLUX 33.6 MT/d.v
RETURN TO PROCESS
Figure 26. FLOW DIAGRAM FOR SALT RECOVERY FROM HIGH SALT FURNACE SLAG
IN SECONDARY ALUMINUM REFINING (WASTE STREAM NUMBER 30)
158
3
«•
I
O
10
-------
cr.0 3
CD C O
The proposed system would greatly reduce the amount of waste
material requiring land disposal. Most of the by-products can be sold.
The only significant amount of waste might be the oxide-containing fraction
since local market conditions might not be favorable for this material.
Even so, it amounts to only one-third the total weight oi' the initial slag.
The Bureau of Mines is continuing its research on the process and
is presently working on 100 pound batches of high salt slag.
Cost for Alternative Treatment. The alternative process is described
in Figure 26 and the costs arc summarized in Table 37.
The capital costs and process factors from which the annual costs
are derived for this alternative process are based on the Bureau of Mines
estimates. The process is operated 8 hours per day with four workers.
Three materials are recovered in the process. Aluminum in the form
in which it comes out of the process contains about 70% metal. About 0.7
metric tons (0.8 s. tons) of this concentrate is produced per metric ton of
slag processed. A value of $264 per metric ton (J290/S. ton) contained
aluminum is assigned to this product.
Approximately 60% of the slag input is recovered as a salt-potash
mixture. The mixture is approximately a 1:1 ratio of sodium and potassium
chloride. The mixture is valued at $16 per metric ton ($17.60/s. ton),
based on 25% of the commercial value of potassium chloride.
'I'Krt v»/\w»o < *ii n ti I.IOC>«-A nKr*ti«- Z^5i f\f *K« c 1 n n inmtr r* r»n e i e 4-e of
*'" ~~...— — ..-... e ••—...._, ...•__. - -.—o r _. - , . „-- --
alumina which can be used in cement plants. Its value depends on the location
of the salt recovery plant in relation to cement plants and their need for
this material. The alumina is given a value of $12.50 per metric ton ($13.75/
s. ton) which is about 25% the value of alumina.
I
O
-------
TABLt 37
Capital and Annual Operating Costs for Alternative Treatment of High Salt
Slag from Secondary Aluminum Refining (Waste Stream Number 30)
ANNUAL PRODUCTION (METRIC TONS):
10.000
ANNUAL WASTE (METRIC TONS): DRY WEIGHT 14.000
CAPITAL COST
FACILITIES
EQUIPMENT
Installed Equipment
WET WEIGHT
CONTINGENCY
TOTAL CAPITAL INVESTMENT
ANNUAL COST
AMORTIZATION
OPERATIONS AND MAINTENANCE (O&M)
OPERATING PERSOr-"^:
EQUIPMENT REPAIR AND MAINTENANCE
MATERIALS
WASTE DISPOSAL
TAXES AND INSURANCE
ENERGY
TOTAL ANNUAL COST
RECOVERY VALUE
NET ANNUAL COST
COST/METRIC TON OF WASTE
WET BASIS
DRY BASIS
COST/METRIC TON OF PRODUCT
NET
$26.02
36.43
SHORT TONS - 0.9 x METRIC TON
3,220
59,090
TOTAL
$47.89
67.04
160
$ 150,000
$1,081,000
246,200
$1.477.200
240,780
$ 272,600
157,010
S 670,390
$ 306,050
.364.340
?P o
-»*< • °
3 <-t- :
-------
-s^ -_
3 S,^
rf 0
3 :t
-------
' Table 38 Summary of Alternative Waste Treatment Costs
t/Mctric Ton of Haste
Wet
Dry
Waste Stream
Iron and Steel Coke
Production - Ammonia
Still Lime Sludg.e
Iron and Steel Coke
Freduction - Decanter
Tank Tar from Coke
Production
Iron sr.cJ Steel Prod. -
3asic Oxy«cr. Furnace -
V.'ct lixission Cor.i;rol
Ur.it Sludge
Iron and Steel Prod.-
Open Hearth Furnace -
Emission Control Dust
Iron and Steel Prod.-
Elcctric Furnace - Wet
Emission Control Sludge
Iron and Steel Prod.-
Rolling Mill Sludge
Iron and Steel 'rod.-
Cold Rolling Mill -
Acid Rlnscwater Neu-
tralization Sludge
(H2S04)
See page 166 for legend.
Net
Total
Net
$/Mctric Ton of
Product
Total
Number Total
1 $ 78.89 $ NRV $ 259.21 $ NUV $ 0.07 $ MIV
6
7A
64.58 NRV
12.66
12.66
12.66
6.46
6.85
7.56
7.36
7.36
1.45
NRV
324.09
29.90
29.90
29.90
16.25
27.40
NRV
17.40
17.40
3.65
NR1.
0.71
17.-iO 0.48
0.48
0.43
1J..13
it.28
0.28
0.03 0.006
0.004 t'.KV
i : i : i ! i ..i i r i : r
?• i
SfrO-l-Q
i ». i
U 6u|aq
jo
«np
-------
Table 38 Summary of Alternative Waite Treatment Costs (Cont.)
$/Metric Ton of Wnstc
Waste Stream
Wet.
Number Total Met Total
Dry
Net
5/Metric Ton of
Product
Total
Net
Iron and Steel Prod.-
CoUl Rolling Mill -
Acid Rinscwatcr Neu-
tralization Sludge
(IIC1)
Iron and Steel Prod.-
Cold Rolling Mill -
Wr.ste Pickle Liquor -
Sulfuric Acid (H2S04)
Iron and Steel Prod.-
Cold Rolling Mill -
Waste Pickle Liquor -
Hydrochloric Acid CHC1)
7B $6.77 $ NRV $ 67.67 $ NRV $0.003 $ NRV
8A SS.54 43.31 1,365.82 1,065.24 6.24 4.37
8B 38.38 24.80 449.78 290.63 2.06 1.33
Iron and Steel Prod.- 9A
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge OI2S04)
Iron and Steel Prod.- 9B
Galvanizing Mill - Acid
Rinsevater Neutralizatio"
Sludge (HC1)
Ferroalloys - Ferro- 11
silicon Manufacture -
Miscellaneous D-ists
0.99 NRV 3.19 NRV 0.04 NRV
3-74 NRV 12.47 NRV 0.03 NRV
N.A. 15.88 NRV 5.36 NRV
See page 166 for legend.
-va
luuwnoop 9(\\ jo X)||Bnb
) anp 9| u
-------
Table 38 Summary of Alternative Waste Treatment Costs (Cont.)
I/Hetrie Ton of Waste $/Metric Ton of
Wet |)Ty Product
Waste Stream Number Total Not Total Not
Total Net
Ferroalloys - Ferro-
silicon Manufacture -
Slag
Ferroalloys - Ferro-
si licon Manufacture -
Dust
Ferroalloys - Ferro-
silicon Manufacture -
Sludge
Ferroalloys - Silico-
manganese Manufacture -
Slag and Scrubber Sludge
Ferroalloys - Ferro-
raanganese Mamifacture -
Slag and Sludge
Copper Srr.eltirsg -
Acid Plant Slowdown
Sludge
r.lcctrolytic Copper
Refining - Mixed
Sludge
Lead Srcelting -
Sludge
12A ;; N.A. $ N.A. $ 3.91 $2.91 $6.85 $5.10
12B
13
14
15
16
17
N.A. N.A.
12C 13.88 NRV
20.36 18.79
20.36 1C. 79
18.82 NRV
".4.56 NRV
6.80 1.01«
2.85 NRV
5.23 NRV
f.0.80 46.88 15.07 13.91
!i0.80 46.88 15.07 13.91
379.27 K'RV 881.97 NRV 2.65 NRV
360.40 NRV 991.13 NRV 2.48 NRV
22.61 3.36* 1.34 0.20*
See page 166 for legend.
F'rf'
t t i i
r i ?• i r i
7
6u|8q
luaujnoop om jo typnb
9U1 01 anp 8| J| '93|)OU
-------
Table 38 Summary of Alternative Waste Treatment Cos :s (Cont.)
$/Metric Ton of Waste
Wet
Dry
Waste Stream
Number Total
Net Total
Hot
$/Metric Ton of
Product
Total Net
Electrolytic Zinc 18
Manufacture
"yrowctaliiirgical Zinc 19A
Manufr-cture - SluJgcs -
?r;:;.ary <~,35 Clcauir.g ar.d
Acic: Plar.c Blowdowr.
P>-ro;r.ctallurgical Zinc 19B
Manufacture - Sludges -
Retort Gas Scrubber
Diced
Aluminum Manufacture- 20
Scrubber Sludges
Aluminum Manufacture - 21
Spent Pot liners and
Skimmings
Aluminum Manufacture - 22
Shot Blast and Cast
House Ousts
$16.81 $3.50* $56.25 $11.20'
3.56 15.44* 11.78 51.OS'
15.30 NRV
N.A. N.A.
30.59 NRV
35.09 18.35* 27.63 40.59*
35.09 18.35* 27.63 40.59*
75.33 NRV
$ 1.46 S 0.29*
t.45 6.21"
0.31 NRV
13.65 7.14*
13.65 7.14*
0.54 NRV
See page 166 for legend.
6u|«q
jo
o; anp
-------
Table 38 Summary of Alternative Waste Treatment Costs (Cont.)
o Stream
$/.'tetrj.c Ton of Waste
Wet
Dry
Number Total Net Total
$/Metric Ton of
Product
Total Net
Pyro:netal lurgical
Antimony Manufacture-
Blast Furnace Slag
Electrolytic Antimony
Manufacture - Spent
Anolyte Sludge
Titanium Manufacture-
Chlorinator Condenser
Sludge
23 $ N.A. $ N.A. $ 18.40 $ NRV $ 52.48 $
24 £5.05 NRV 165.15 NRV
25 12.53 14.85* 31.59 37.41'
NRV
36.70 NRV
10.39 12.31*
v-oppur Kenning -
Blast Furnace Slag
Lead Refining - SC>2
Scrubwater Sludge
Aluminum Refining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
*' N.A. N.A. 37.86 NRV 13.25 NRV
28 25.61 NRV 85.36 NRV 3.84 NRV
29 16.59 NRV 55.29 NRV 4. IS NRV
30 N.A. N.A. 47.89 26.02 67.04 36.43
* = Net gain, i.e., value of recovered material exceeds cost of alternative treatment
NRV = No recovery va lue
;uaujnoop aq
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jo
aim IIPIII .IROIA eeoi fli
-------
.«< .- o
13
Nineteen waste streams have alternative treatment costs (net costs
where npplicnMc) th.it were less than $5 per metric ton ($4.SO/s. ton) of
product. Those arc:
1. Sulfuric acid waste pickle liquor, waste stream 8A-54.87
2. Secondary aluminum ?crubwater sludge, waste stream 29 - $4.15
5. Secondary lead scrubwater sludge, waste stream 28 - $3.84
4. Ferrochrome dust, waste stream 12 - $2.85
5. Copper smelting, acid plant blowdown sludge,
waste stream 15 - $2.85
6. Electrolytic copper mi.xed sludge, waste stream 16 - $2.48
7. Hydrochloric acid waste pickle liquor, waste stream SB - $1.33
8. Ammonia still sludge, waste stream 1 - $0.07
g. Primary aluMiinum shot blast and cast house dusts,
waste «trcani 22 - SO.54
10. Primary zinc pyromcta!lurgical dust, waste stream 19 -• 30.31
11. Primary 7-inr cl or.t rol vt i c sludpc, waste stream 18 - $C.-N
12. Steel mill air emission, waste streams 3, 4, and 3 - SC.2S
13. Primary lead smelting sludge, waste stream 17 - $0.20
14. Decanter tank tar, waste stream 2 - $0.71
15. Galvanizing mill acid riujewate* neutralizing sludge,
waste stream 9A - 0.04
16. Galvanizing mill acid rinsewater neutralizing sludge,
waste stream 9B - SO.03
17. Iron and Steel rplling mill sludge, waste stream 6 - $0.006
18. Cold rolling mill acid rinsewater neutralization sludge,
waste stream 7A - $0.004
19. Cold rolling mill acid rinsewater neutralization sludge,
waste stream 7B - $0.003
167
| 3 r* :
I a> ^T I
=5 0» *
I
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>
ro
m-vaarm
-------
Eight waste streams show alternative treatment costs (net costs
where applicable) of more than $5 per metric ton (S4.50/S. ton) of product.
These are:
1. Primary pyrometallurgical antimony slag, waste
stream 23 - $52.48
2. Primary electrolytic antimony sludge, waste
stream 2<1 - $56.70
3. Secondary aluminum refining high salt slag,
waste stream 30 - $36.43
4. Silico and ferrcmanganese slag and sludge,
waste streams 13 and 14 - $13.91
5. Secondary copper refining slag, waste stream 27 - $13.25
6. Ferrosilicon dust, waste stream 11 - $5.36
7. Fcrrochromc sludge, waite stream 12 - $5.23
8. Fcrroclirome slag, waste stream 12 - $5.10
The determination of the significance of the above costs requires
consideration of the value of the product, the industry pricing structure and
the overall economic condition of the industries. Such analysis is beyond the
scope of this study.
B. Break-Even Analysis
The total annual costs resulting from the alternative treatment
processes are compared to the values assigned to the recovered materials in
Table 39.
The actual value of the recovered products is largely n function cf
demand. For the most part, the demand for the recovered product must be
geographically near its point of origin. In recognition of these factors, a
relatively low value, i.e. a fraction of the reported market value, was
assigned to the recovered material. In fact, higher prices than those assumed
may be obtainable in the market place. The product values assigned to each
of the affected industries and the likelihood of achieving a higher return
are breifly discussed below.
168
I
o
J^
ro
-------
Table 39 Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value
/Vnnual Percent of
Total
Annual
Cost
Waste Sticam
Number
1
Iron and Steel Coke Prod. -
Amnonia Still Line Sludge
Iron and Steel Coke Prod. -
Decanter Tank Tar from
Coke Production
Iron and Steel Production -
^ Basoc Oxygen Furnace - IVet
S Emission Control Unit Sludge
Iron and Steel Production -
Or-sr. Hearth Fum.ics - Emission
Control Dust
Iron and Steel Production - S
Electric Furnace - Wet Emission
Control Sludge
Iron and Steel Production - 6
Rolling Mill Sludge
1,882.410
1,195,950
1,195,950
1,195,950
50,370
Value of
Recovered
Material
$ NRV
NRV
500,000
500,000
500,000
39,060
Market
Price
Assigned
N.A.
N.A.
100a
iooa
100a
100a
Net Required
Annual Percent Inc
Cost Recovered Mali
$ N.A. N.A.
N.A. N.A.
695,950 139
695,950 159
695,950 139
11,310 29
in
See page 174 for legend.
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aui 31 eno si 11 '»ouou
-------
Table 39 Break-Even Analysis 8e~ween Alternative Treatment Cost and Recoverable Resource Value
Total
Annual
Waste Stream Number Cost
Iron and Steel Production - 7A $ 2,740
Cold Rolling Mill - Acid
Rinse-water Neutralization
Sludge (H2S04)
Iron and Steel Production - 7B 2,740
Cold Rolling Mill - Acid
Rinsewatev Neutralization
Sludge (HC1)
!-•
0 Iron and Steel Production - 8A 4,370,623
Cold Rolling Mill - Waste
Pickie Liquor - Sulfuric
Acid (H2S04)
Iron and Steel Production - SB 1,439,280
Cold Rolling Mill - Waste
Pickle Liquor - Hydrochloric
Acid (HC1)
Iron and Steel Production - 9A 4,470
Galvanizing Mill - Acid
Rinscwatcr Neutralization
Sludge (H2S04)
Annual Percent of
Value of Market Net Acquired
Recovered Price Annual Percent Increase in
Material Assigned Cost Recovered Material Val
NRV $ N.A. $ N.A. N.X.
NRV N.A. N.A. N.A.
961,840 100b 3,408,780 354
509,280 70C,100a 930,000 183
NRV N.A. N.A. N'.A.
See page 174 for legend.
i : f : t » r
1 ." 1 .' ! 1 I
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aq; o) onp B| )|
-------
Table 39 Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value (Cent.)
Waste Stream
Iron and Steel Production -
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (HC1)
Ferroalloys - Ferrosilicon
Manufacture - Miscellaneous
Ousts
Ferroalloys - Fevrosilicon
Manufacture - Sin^
Ferroalloys - Ferrosilicon
.•Manufacture - Dust
.-erroalloys - Ferrosilicon
Manufacture - Sludge
Number
9B
11
12B
12C
Ferroalloys - Silicoroanganese 13
Manufacture - Slag and
Scrubber Sludge
Annual Percent of
Total Value of Market Net
Annual Recovered Price Annual
Cost Material Assigned Cost
$ 3,740 $ NRV
214,^-03
239 ,,'9 3
99,753
183,153
452,093
NRV
NRV
NRV
N.A.
N.A.
61,200 100C
N.A.
N.A.
34,880 25
$ N.A.
N.A.
178.S90
N'.A.
N.A.
417,210
Required
Percent Increase in
Recovered Material
N.A.
N.A.
291
N.A.
N.A.
1,196
See page 174 for legend.
-,^_« ~
2*0-1- Q
\\ jo
o) enp «| }| '»0|;ou
-------
Table 39 Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value (Cent.)
Waste Scream
Number
Annual Percent of
Total Value of Market Net
Annual Recovered Price Annual
Cost Material Assigned Cost
Required
Percent Increase in
Recovered Material Value
-vl
to
Ferroalloys - Ferromanganese
Manufacture - Slag and Sludge
Copper Smelting - Acid Plant
Slowdown Sludge
Electrolytic Copper Refining -
Mixed Sludge
Lead Smelting - Sludge
Electrolytic Zinc
14
15
16
17
18
$ 452,090
265,490
396,450
146,970
146,240
$ 34,880
NRV
NRV
168,780
117,100
25
N.A.
N.A.
2Sf
2Sg
$ 417,210
N.A.
N.A.
21,810«
29,140*
1,196
N.A.
N.A.
N.A.
N.A.
Manufacture
?yrometallurgical Zinc 19A 153,180
Manufacture - Sludges -
Primary Gas Cleaning and
Acid Plant Slowdown
Pyrometallurgical Zinc 19B 33,650
Manufacture - Sludges -
Retort Gas Scrubber Bleed
817,220 100
NRV
g
N.A.
(664,040)
N.A.
N.A.
N.A.
See page 174 for legend.
c : f * r ! r i
f 1 • ! r i
ZVO-IQ
6u(«q
^i|Bnb
atn 01 ano «i 11 'aouou
-------
Table 39 Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value (Cont.)
Wastest^cam
Aluminum Manufacture -
Scrubber Sludges
Aluminum Manufacture -
Spent Potlir.ers and
Skimmings
Aluminum Manufacture -
Shot Blast and Cast House
Dusts
Pyrometallurgical Antimony
Manufacture - Blrst Furnace
Slag
Electrolytic Antimony
Manufacture - Spent Anolyte
Sludge
Number
Annual Percent of
Total Value of Market
Annual Recovered Price
Coi t Material As s i p.n cd
20 $2,C?<',140 $3,180,000 100
21 2,0$'--, 140 3.180.0CO IOC
22
23
24
{.2,860 NRV
10,700
;o,030
NRV
NRV
N.A.
N.A.
N.A.
Net Required
Ar.nu.-il Percent Increase in
Cost Recovered Material Value
$1,05 l.Si'O N.A.
i.osi.sec :;..\.
N.A. N.A.
N.A. N.A.
N.A. N.A.
Titanium Manufacture -
Chlorinator Condenser Sludge
Copper Refining - Blast
Furnace Slag
25
27
76,970
U-.2.S10
172,500
NRV
IOC
N.A.
93,530*
N.A.
N.A.
N.A.
See page 174 for legend.
am 0} enp t\ \\ 'io^ou
-------
Table 39 Break-Even Analysis Between Alternative Treatment Cost and Recoverable Resource Value CCont.)
Waste Stream
Annual ' Percent of
Total Value of Market Net
Annual Recovered Price Annual
Number Ccst Material Assigned Cost
Lead Refining - S02
Scrubwater Sludge
Aluminum Refining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
28 $ 58,410 $ NRV
29 82,930 NRV
30 6^0,390 306,050
25
N.A. $ N.A.
N.A. N.A.
364,340
Required
Percent Incre.T^c in
Recovered Material Value
N.A.
N.A.
* = Net gain, i.e., value of recovered material exceeds cost of alternative waste treatment
N.A. = Not applicable
NRV = No recovery value
- for iron pellets
- for ferric chloride
- for hydrochloric acid
- for roadfill
e - for zinc oxide
f - for lead
- for zinc
- for cryolite
1 - for rutile
^ - for potassium chloride
~ i .• t i t ; r-.i t v r t
ZPO-IQ
i
pau)||| 6u|aq
m u
filUl UVUl JB8IO 8801 81
-------
— c 8- _.
^s ?
Waste Streams No. 3, 4, 5, and 6 - Emission Control Sludge and Ousts
in Steel Manufacture. The initial value assigned to the contained iron was
based on the price of iron pellets, $20/per metric ton ($18/s. ton). This
represents about 20% of the value of steel scrap. If, in fact, the recovered
material is found to be similar to scrap, a valuation sufficient to achieve
the break-even point appears reasonable. The required price would be $48/
metric ton ($44/s. ton) which represents 80% of the price of low grade scrap.
Waste Stream No. 8A - Sulfuric Acid Waste Pickle Liquor. The
product recovered is ferriT chloride. Its assigned value is 50* of the
product price. Full value pricing would still leave a large gap between
alternative process costs and potential revenues generated.
Waste Stream No. 8B - Hydrochloric Acid Waste Pickle Liquor. The
recovered materials are hydrochloric acid and iron pellets.The value of the
former is computed at 70% of market value; the latter at 520/metric ton
($18/s. ton) contained iron is the fall market value. Most of the assigned
recovery value obtains from the hydrochloric acid. Break-even operation is
not achievable.
Waste Stream No. 12 - Slag from Ferrochrome Manufacture. The
recovered material can be used for road construction. Break-even operation
requires an increase in the assumed material price of $l/metric ton ($0.90/s.
ton) to $2.90/metric ton ($2.65/s. ton). A reasonable level of demand would
justify the higher value.
Waste Streams No. 13, 14 - Sludge from Silico and Fcrromanganese.
($lS5/n. tc~) which represents about 23* of markeL value. Assigning
full value to the recovered zinc and other metals would not result in a
break-even operation.
Waste Stream No. 30 - High Salt Slag from Secondary Aluminum
Refining. The recovered materials consist of aluminum, potassium chloride
and alumina. These materials were priced at 25% of their market values.
break-even operations require that they be priced at about 55% market value.
This appears achievable.
In summary, five alternative treatment processes yield recovered
materials whose value exceeds the alternative treatment costs of operation;
18 processes do not provide materials with discernible market values. Of the
remaining sevon alternative processes, four can be expected to reach a break-
even point and three cannot.
I
o
175
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Wastes with definite recovered material value exceeding alternative
treatment costs:
1. Prim.iry l^ad smelting sludge, waste stream 17
2. Primary electrolytic zinc sludge, waste stream 18
3. Primary pyrometallurgical zinc sludge, waste stream IDA
4. Primary aluminum scrubber sludge, potliners and
skimmings, waste streams 20 and 21
5. Primary titanium chlorinator condenser, waste stream 25
Wastes with potential recovered material value exceeding alternative
treatment costs:
1. Steel mill emission control sludge and dusts,
Waste alicctiiia 3, 4, clllu J
2. Rolling mill sludge, waste stream 6
3. Slag from ferrochrome manufacture, waste stream 12
4. Secondary aluminum high salt slag, waste stream 30
'.l.fr\°.tor v*
materials:
1. Silico and fcrromanganese slag and sludge, waste
streams 13 and 14
2. Spent sulfuric acid pickle liquor, waste stream 8A
3. Spent hydrochloric acid pickle liquor, waste stream SB
Wastes '.vhoic alternative treatments do not provide recovered
1. Ammonia ?tiil sludge, wast-.: stream 1
2. Decanter tar!: tar, waste stream 2
176
•: \
4 I
lis-i
111
o !
e °
3 r* :
» I
» <
S i
I
O
^
10
^ •
a
-------
5
3. Sulfuric acid rinsewater neutralization sludge,
waste stream 7A
4. Hydrochloric acid rinsewater neutralization sludge,
waste stream 7B
5. Sulfuric acid spent pickle liquor, waste stream 9
6. Hydrochloric, arid spent pickle liquor, waste stream 9
7. Fcrrociliccri - misc. Justs, waste stream 11
8. Dust from ferrochromc manufacturing, waste stream 12
9. Sludge from ferrochorme manufacturing, waste stream 12
10. Copper smelting acid plant blowdown, waste stream 15
11. Electrolyric copper refining - mixed sludge, waste stream 16
12. Pyrometallurgical zinc sludge (primary), waste stream 19B
'
-------
C. Summary of Alternative Treatment Systems and Benefits
The major processes used by the alternative treatment, systems, the
process category, stage of development and the benefits therefrom are
summarized in Table 40.
178
5: 5"
s
— . «•
o" §
° ;?
S ° »*
3 r+ 3-
0 3T =T
kJ
ri
-------
Table 40 Siamaary TajU of Alternate Treatment Systema.
leneflti. Star* of Development, and Cott>
Alternitlve Treatment
S/Hitrle Ton of Waste I/Metric Ton of
Process Develof »* it Vet Dry Product
um
fl
Waste Stream Number
Iron and Steel Cole 1
Production - Ammonia
Still Lime Sludge
Iron and Steel Cole 2
Production - Decanter
Tanl Tar fron Cole
Production
Iron and Steel Prod. - J
Basic Oiycrn Furnace -
Kct E-tision Coi.trol
Unit StuJie
Iron and Steel Prod.- 4
0{-?n llc_arth Furnace -
L&is>it>n Control Uusl
Iron :i'..! Stct-l Prod.- S
L!r*-lric Furnace - a'et
frassion Control Sludge
t— ' 1 rvr. 2'tins.-»a:er 'leii-
traliiatiui Sludic
C"'S04)
Iron and Steel Prod.- 7»
Cold Rollinc Kill -
Acid Hin*e*ater Neu-
tralization SluJjc
Iron anJ Stefl Prod.- 8A
ColJ Rollinf Kill -
•astc Pickle Llq-jor -
Sulfuric Acid (II,SO4)
Iron and Steel Prod.- II
Cold Roll int. Mil -
katte Pickle Liquor -
Hydrochloric Acid (IKl)
Iron and Steel Prod.- 9A
Calvanitinr. Mill - Acid
Rintrwjter Neutralization
SluJce (H^SOj)
Iron and Steel Prod.- 91
Oilvanilint. Hill - Acid
Rinscvater Neutra Illation
SluJfe (Kl)
EHi
Process Catefory Staf
Disposal f V
Disposal P V
Reduction C V
Roastinf
P.educ:ic,n C V
Roastinf;
Reouctior C V
Kqastinc
Smteriij P V
Dissolution C V
Dissolur ion C V
t Benefits Derived Tot il Net Total Net Tota:
Net
Detoxified, inert solids t 71.89 t NRV $ 2S9.21 J NRV S 0.07 t NRV
suitable for chemical
landfill
Detoxified, inert solids 61. SI NRV 124.09 NRV 0.1
suitable for chemical
landfill
1 NRV
Ferric oxide recovery li.66 7.36 23.90 . 17.40 0.<8 }.2S
for recycle. Lead and
zinc oxide recovery for
sale.
Ferric oxide recovery for S 12.66 S 7.56 S 29.90 i 17.40 t 0.4S { 0.21
recycle. Lead and zinc
Iron recovery fcr recycle 6.-!6 l.O 16. 2S 3.6S L
.05 9.C06
Ferric oxide recovery u. SS S'RV 27.40 VRV C.OCX NAV
Ferric chloride recovery 6.77 NRV 67.67 SRV O.OOJ NRV
Precipitation C III Ferric chloride for sale. Sf..S4 4J.31 !.JfcS.S2 1.06S.C4 6.24 4.»7
Calciur sJlfate (gypsum) for
chemical landfill
Volati litation P I
Reduction C I
Routing
Dissolution C
t Hydrochloric acid recovered 36.38 24.80 449.78 299.65 '
for recycle
' Ferric oxide recovered for
reuse
Dissolution C V Ferric chloride 1.74 NRV 12.47 NRV 0
recovery
ZPO-IQ
;uc
8^
8
2.06 1.)}
04 t NRV
.03 NRV
peui|jj 6u|«q
ujnoop 8q) ^o ^;i|Bnb
; oj. anp 8| ;| 'sonou
q; unqj JB8|o 8«8| 8{
-------
•r/ TftbU of Alttnuu Trt.itatnt SjrttMA. •owflts. Stag* «f Dmlepatit, a»4 Costs (Cant.)
Alternative Trc.itiaeni
X.mc Strtaa Huafcor
Ferroalloys - F«rro- 11
silicon Manufacture -
Miscellaneous Dusts
F*rroalloys • F«rro-
•* it icon Manufacture -
Slag
Ferroalloys * Ferro-
ktlicon Manufacture -
Uust
Ferroalloys - Ferio-
silicon Mfcnufact.ire -
Sludge
Ferroalloys - Silico-
ungjncse Manufacture -
Slag jnd Scn^ber Sludge
itrroj.loy* - Ferru-
•.ingjit-.^c Manufacture -
<|j- ...id Sludge
i_- LO|i;icr i«clting -
00 Acid PUnt Slowdown
Llcctrolytic Copper
Refining - Mixed
Sludge
LcaJ SMTIt ing -
Electrolytic Zinc
Manufacture
Pyruoctalluriical Zinc
Manufacture - Sludges -
Pritkjry Cat Cleaning and
Acid Plant
Pyrohrtallurgical Zinc
Manufacture - Sludges -
Hetort (^4 Scrubber .
UU-i-d
Aluainun Haaufactur*-
Scrubber Sludges
Sj'int Pot liners and
Proceit Cuetor
Oisposil
i:\ Precipitation C
\:» Precipitation C
i:<- Pncipltitton C
Reduction
toiitinj
Rtd.ictlort
Roa>tin<
IS Precipitation C
16 Precipitation C
17 Slnterirtf f
18 Precipitation C
19A Sintering P
191 Ctntrifjf* P
P«vcipil3tion pjC
Lvap< r«: ion
Ucwatcnng
'">"« P.C
elO|*aeflt
i»J6_
V
V
V
IV
IV
V
V
V
V
V
V
V
V
Benefit:. Derived
Oicaiul Imjfill
Detoxification
Detoxification
Detoxification
Ferro and silicomanfares*
for recycle
Lead and tine oxide
for sale
Detoxification
Detoxification
Lead recycled for
reprocessing
Zinc recycled for
reprocessing
Zinc recycled for
reuse
Zinc recycled for
reuse
( r>olitc recovery.
Cryolite recovered for
S/Mtric Ton of Vast*
Vet Dry
ToV.al Het Total Net
II. A. N.A. 1S.M NtV
II. A. N.A. 3.91 2.91
II. A. N.A. 11.12 NRV
lt.ll NRV 34. S6 NRV
2'). 36 IS. 79 SO.M 46.11
2). 36 11.79 SO. 80 46.11
J37-).27 $ NRV S SC.97 S SRV
360.40 NRV 99:. 13 KRV
•>.»0 1.01* 22.61 3.36*
1-i.Sl 3.50* S6.2S 11.20-
S.S6 IS. 44- 11.78 51. Of
li.JO NRV 5C.S9 NRV
3'.. 09 U.3S* 27.63 40.59*
31.09 l«.3S* 27.63 40. S9*
S/Hetric Von ot
Product
Total
S.S6
6. IS
2. IS
S.23
IS. 07
15.07
S 2.6S I
2.48
1.34
1.46
1.43
0.31
13.6S
13.6S
Net
NRV
S.10
NRV
NRV
13.91
13.91
KRV
KRV
0.20*
0.29*
6.21-
NRV
7.14-
7.14-
Alurinici Hiaufacture -
Shot BUu and Cast
lluu^e iKjsts
22 Precipitation C
Detoxification
N.A. N.A. 7S.33 NRV
O.S4 NRV
\ •
t ; c
( • ;
! •>
i :_i
jueuunoop ai|; jo
o; anp 8| ;| *90|;ou
-------
Table 40 Summary Table of Alternate TTeUsnt Systems. Benefits. Stare .of Development, amd Costs (Cont.)
Alternative Treatment
• Process Development
:...f Siren Chamber Process Category Stag*
Pyrometallurgical a Precipitation C V
Antimony Manufacture-
Blast Furnace Slag
Electrolytic Antimony 24 Disposal P
Manufacture • Spent
Anolyte Sludte
Titanium Minufacttirv— 2S Centrlfufe P III
CMorinator ConJenser Dewateriic
SluJt« Recycling
Copper Refining . 27 Precipitation C V
Bla»t Furnace Slag
UaJ Refining - SOj 21 Precipitation C V
Scrubwater SluJg*
Alu-.im=» Mefinin; - 29 Centrifui* P V
ScniSScr Sl-tlt* Uexatcritg
lluninjm Refinirr - JO Crushing IP IV
MirS Silt Slij Screen!r.{.
Dr'atcrit g £
Drying
Dissolution P.C IV
Evaporation
Devaterirg
Dryiat
Alternative Treatment Unit Process Categcry:
P. - Physical
C. - Chemical
Alternative Treatment Stage of Developmer.t :
I/Nitric Tom of Vast* 1/MtUtc Ton of
•et Dry Product
Benefits Derived Total Net Total Net Total Net
Detoxification J N.A. t N.A. $ 11.40 $ NRV I 52. <« t NIV
Detoxification SS.OS NRV 1SS.1S NRV J6.70 NIV
Titanium
-------
11
et al., U.S. Bureau of Mines Paper Presented in Proceedings of
the Fourth Mineral Waste Utilization Symposium. Chicago, 111.,
May 7, 8, 1974.
(4) Private Communication. Memorandum on Airco Plant Visit, by
R.C. Ziegler and M.A. Wilkinson. December 16, 1074.
(5) "Beneficiation of Aluminum Plant Residues," R.S. McClain and
G.V. Sullivan, Bureau of Mines, RI 6219, 1963.
(ft) "Air Polint ion Control in the Primary Aluminum Industry." Singaastcr
pnH RrpypT, July 23, 1973, KPA-45n/3-7'UiyWA .
(7) '"Recovering Aluminum and Fluorine Compounds from Aluminum Plant
Residues," Bureau of Mines RI 5777, 1961.
182
••< I
I
O
^
ro
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.
I 8 ~!
PART n
COST DF.V7.I,OPMENT FOR
SANITARY AND CHEMICAL LANDFILL DISPOSAL
OF HAZARDOUS WASTES
FROM THE METALS SMELTING AND REFINING INDUSTRIES
•s a>
183
-------
' P» !± •
SECTION I
cimrirc.Ai, (.ANPFTU, TOST r>r.VF,i,opw.trr
. ,
0.5
!
3 r¥ •
Disposal of hazardous wastes in chemical or secure landfills is an
appropriate disposal process for certain waste materials or for recovery of
process waste residues. The approach and method used to derive costs for
secure or chemical landfill disposal of wastes is described bcloiv. The cost
model incorporates major assumptions, costs and cost factors specified by
EPA. A chemical landfill cost curve (Figure 1) was developed from landfill
designs for 1,000 and 6,000 m3 of waste as shown following. This range of
waste volumes was used because a preliminary review of waste quantities gener-
ated by p number of typical plants fell within these values.
Landfill Design No. 1 (1,000 m of waste)
The initial trench excavated has a volume of 1,250 m . Covering for
the disposed material is estimated to occupy 25 percent of the disposed waste
volume. Thus, 1,000 m0 of waste can be placed in the trench.
The trench is formed with sloping sides (2:1). The dimensions of the
trench are:
Width:
Length:
Depth:
Bottom
Bottom
4 m
11 m
22 m
Top 15 m
Top 26 m
A icsuhato cuiiaecior. syst:.'.':i it installt--u i:i Lhu I.;-L:;II;!I. I'uivvinvl
chloride 10.2 cm (4") drain pipe is installed at 2 n intervals running the
length of the trench. These pipes arc connected to n transverse drain pipe at
one end of the trench.
-The trench is lined with bentonitc applied at a rate of 9.8 kg/m
(18 Ib/yd ). A 30 mil hypalon liner is installed over the bentonitc. The
lining is placed at the bottom and sides of the trench.
-t •>
The trench area lined is 700 m"" (840 yd"). Local on-site clay is
placed at one end and bottom of the trench to a depth of 0.6 m (2 ft) for
protection of the liner during vehicle operation. Local clay is also used
for cover of the disposed material. At completion, the surface of the crench
is sealed with a bentonite liner. The total area occupied by the trcuch is
600 m (0.15 acres).
I
o
A
ro
184
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co c o
M ** —
$60
3 4 S
VOLUME OF WASTE LANDFILLED ANNUALLY
(1,000 m3)
Figure 27. CHEMICAL LANDFILL COSTS
185
-------
Operations. It is assumed that the annual amount of waste disposed
is 1,000 m3 (1,300 yd^) and that the cover material equals 25 percent of the
waste, i.e. 250 m^ (325 yd3). Thus, one trench is filled each year.
The total space required for 20 years of operatic;;:; is 1.2 ha
(3 acres').
A concrete sump is installed at each trench operation for Icachate
collection. A pump is provided to remove rain water from the trench during
its operational life. The collected leachate is punped from the sump to a
trench currently in use.
Operations are conducted at the site 250 days per year. Three man-
hours/day are allocated for the purpose of covering the dumped wastes, inspec-
tion and related activities.
Costs.
Land - The land acquisition cost is $12,355/ha ($5,000/acre).
The cost of land needed for 20 years of operation is $15,000. It is assumed
that the lind is purchased on the basis of a 20 year, 10 percent mortgage with
no down payment. The annual payment then amounts to $1,755. A total of
$35,000 is paid over the 20 year period. It is assumed that the initial land
cost is recovered at the end of this period. The amount of interest paid is
$20,100. The average amount of interest paid per year is $1,005 which value
is used in the subsequent cost computations.
Trencti Construction - bince it is assumed L'nal one trench is
filleJ eacli year, its cost is considered as r.r. ar.r.ual cor.t. Ccr.Etr-ac
are computed as follows:
1.
2.
Excavation 1,250 m at $2.QO/m ,
Grading 700 m at $0.4/m ,
3. Survey, test boring, reports 20% of 1 5 2,
4.
5.
6.
7.
8.
9.
2 4 -
2 24*
llypalon liner 700 m at $4.40/m ,
Leachate collection drains 150 m at $5.75/m
Clay protective liner 360 m at $l/m ,
2 2
Finish bentonite liner 390 m at $1.80/m ,
Concrete sunp 1 x 1 x 1 m
Total
Contingency 20$
Total Construction Cost
'Escalated from $ 1974 to $ 2nd Qtr. 1976 using
M 6 S Equipment
Cost Index $1974 = 398.4; 2nd Qtr. 1976 « 178.5J
1S6
I ~s:
3 » *
I
o
^
10
-------
Facilities - A temporary, reusable fence, similar to a snow fence,
is erected around each active disposal site. The site perimeter is about
110 m. The fence cost is $7.20/lincal meter.
Equipment - A crawler dozer is used for spreading and compacting the
waste and cover material. Its estimated cost is $20,000.^ A 1 hp sump pump
is installed at an estimated cost of $1.600.2
Operations and Maintenance
Capital Recovery - Facilities and equipment are amortized over a
10 year period. A 10 percent interest rate is assumed.
Operating Personnel - Personnel costs, including supervision and
overhead are computed at $13.50/hr.
Maintenance - Maintenance costs of facilities and equipment are
computed as 4 percent of capital cost.
Waste Transport - The loading, transport and dumping of the waste
at the disposal site is estimated at $5/m-> of waste.
Taxes and Insurance - These costs are included as 4 percent of land,
facility and equipment costs.
Energy - The crawler dozer is operated on the average of two hours
per day and consumes IS liters (4 gal.) of dicsel fuel/hr. The cost of fuel
is calculated r,s $0.13/1 ^O.DO/sai. j. !:iectrical power cost for Rii^cullauouu^
lighting is assumed to be IS percent of the fuel cost.
Chemical Landfill Costs. Capital and annual costs for the operation,
based on the aforementioned factors, are as follows:
Capital Cost
Land
Facilities
Equipment
Dozer $20,000
Pump Installed 1 hp 1,600
Total
Contingency (Equipment
and Facilities)
Total Capital Investment
$15,000
800
$41.900
-------
Annual Cost
Land
Capital Recovery
Operations and Maintenance
Trench construction
Operating personnel
Maintenance
Waste Transport
Taxes and Insurance
Energy
Fuel
Electricity
$ 1,010
4,380
l,ouo
Total Annual Cost
29,760
1,150
$56,300
The annual cost ot $36,300 represents a unit cost of about $36/m
of waste disposed. The specific gravity of the waste is estimated to range
from 0.8 to 0.2. Disposal costs expressed in terms of unit weight are:
Specific Gravity
0.8
1.0
1.2
Landfill Design No. 2 (6,000 ro3 of wastej
Disposal Cost/Metric Ton
$45
36
30
3
This landfill is designed to accommodate 6,000 m' of waste. The
initial trench excavation totals 7,500 n^. Except where specifically noted,
the cost factors and methodology employed are the same as in the previous
computation.
188
tr-o 3 ;
3 n-
CD 3"
a CD
«-< I
-------
Pertinent parameters for this landfill are:
Width: Bottom 22.7 m Top 23.7 m
Length: Bottom 45.7 m Top 51.4 m
Depth: 6 m
Surface Area: 2,580 m
Area Occupied/trench: 2,000 m
Area required for 20 years: 4 ha (9.9 acres)
Trench Construction Cost
Excavation $15,000
Grading 1,000
Survey, test boring, reports 3,200
Bentonite liner 4,300
Hypalon liner 10,500
Leachate collection drain 3,100
Clay protective liner 1,200
Finish bentonite liner 2,660
Concrete sump 2 y 1 v 1 m 400
Total $41,360
Contingency 8,270
Total Construction Cost $49,630
Capital and annual cost factors which differ from the previous
calculations are as follows:
c. '-
» J
_ !
I
O
Dozer cost
Pump
Fencing
Dozer fuel consumption
Operating personnel
$30,000
2,400
190 m
19 1 (5 gal)/hr.
8 hr/day
189
-------
a c o ™
Off
Capital Cost
Land $49,500
Facilities 1,400
Equipment
Dozer $30,000
Pump Installed 2h hp 2,400 32,400
Total $83,300
Contingency (Equipment and 6,800
Facilities)
Total Capital Investment $90,100
Annual Cost
Land
Capital Recovery
Operations and Maintenance
Trench construction
Operating personnel
Maintenance
Waote transport
Tixcs and iiibusance
Energy
Fuel
Electricity
Total Annual Cost
» i
3 rf =r
e» 3- JS*
3 CD "
$3,320
6,600
, 3 OU
5.750
$127,250
This annual cost results in a cost/metric ton of waste of about $21.
Disposal costs as a function of weight arc:
Specific Gravity
0.8
1.0
1.2
Disposal Cost/Metric Ton
$26
21
18
190
-------
Disposal costs arc sensitive to the size of the operation and the
specific gravity of the material being landfilled. The chemical lanUfill
costs are based on the volume of waste landfilled as presented in Figure 27.
The disposal cost for plants with an annual volume of waste of less than
1,000 nP are based on a 1,000 m3 landfill operation; costs for plants generating
more than 8,000 m^ of waste annually are based on an 8,000 m-* landfill operation.
o _^ S
" ^
i:s
a 3- X
191
-------
SECTION II
SANITARY l.ANnFTf.r. COST DF.VELOPHENT
Costs are based on the same parameters, cost factors, and methodology
that are used for estimating the chemical or secure landfill costs except that
liner, leachate collection system, sump and pump costs arc deleted. A sani-
tary landfill cost curve (Figure 23) was developed from landfill designs for
1,000 and 6,000 ra^ of waste disposed annually as shown following.
Landfill Design No. 1 (1,000 m of waste)
waste.
The following costs are based on a landfill volume of 1,000 m of
Trench Construction Cost
1. Excavation 1,250 m at $2.00/m
1 , ">
2. Grading 700 a at $Q.
-------
VOLUME OF WASTE LANDFILLED ANNUALLY
(1,000m3)
Figure 28. SANITARY LANDFILL COSTS
193
3 •* :
CD =r i
3 CO
-------
Annual Cost
Land
Capital Recovery
Operations and Maintenance
Trench Construction
Operating Personnel
Maintenance
Waste Transport
Taxes and Insurance
Energy
Fuel
Electricity
$1,010
4,080
1,000
100
Total Annual Cost
21,660
1,100
$27,850
The annual cost of $27,850 represents a unit cost of about $28/m of
waste disposed. The specific gravity of the waste is estimated to range from
0.8 to 1.2. Disposal costs expressed in terms of unit weight a-e:
Specific Gravity
0.5
1.0
1.2
Disposal Cost/Metric Ton
*7C
28
23
Landfill Design No. 2 (6,000 m of waste)
These costs are based on a landfill volume of 6.00C m of waste.
Trench Construction Cost
1. Excavation $15,000
2. Grading 1,000
3. Survey, test boring, reports 3,200
Total $19,200
Contingency
Total Construction Cost
194
3,800
$23,000
II
2-g o •
™^ *
Q. '
3
n
-------
Capital and annual costs are as follows:
Capital Cost
Land
Facilities
Equipment
Total
Contingency
Total Capital Investment
Annual Cost
Land
Capital Recovery
Operations and Maintenance
Trench Construction
Operating Personnel
Maintenance
Waste Transport
Taxes and Insurance
Energy
Fuel
Electricity
a e o •
ft?I
•^ o ^T* ^
3 r+ :
-------
» c o •
5" £. — 5
if si
Disposal costs are sensitive to the size of the operation and the
specific gravity of the material being landfilled. The sanitary landfill
costs are based on the volume of waste deposited as presented in Figure 28.
The disposal cost for plants, with an annual volume of waste of less than
1,000 m3 are based on an 1,000 m3 landfill operation; cost? for plants
generating more than 8,000 m3 of waste annually are based on an 8,000 m
landfill operation.
Waste Containerization. Liquid and semi-liquid wastes are
containerized in 0.2 m-5 (55 gal.) drums for either chemical or sanitary
landfills. The added cost of containerization is estimated to be $12.50
per drum. This cost includes the container and the labor for filling the
container. Containerization costs are included in subsequent tables as
noted.
C, jj- -
i ••
3 »*• -
o> =• 5
3 ID q
196
-------
SECTION III
SANITARY AND CHEMICAL LANDFILL COSTS
Costs are presented for the sanitary and chemical landfill disposal
of wastes. The costs are shown for sanitary landfill without containerization
of liquid wastes in Table41; sanitary landfill with containerization of liquid
wastes in Table 42; and for chemical landfill with containerization of liquid
wastes in Table 43.
rV "
— S
C» 0>
^
?•-<
197
-------
Table 41
10
00
Waste Stream
Iron and Steel Coke
Production - Amnonia
Still Lime Sludge
Iron and Steel Coke
Production - Decanter
Tank Tar from Coke
Production
Iron and Steel Prod. -
Basic Oxygen Furnace -
Wet Emission Control
Unit Sludge
Iron and Steel Prod. -
Open Hearth Furnace -
Emission Control Dust
Iron and Steel Prod. -
Electric Furnace - Wet
Emission Control Sludge
Iron and Steel Prod. -
Rolling Mill Sludge
Iron and Steel Prod. -
Cold Rolling Mill -
Acid Rinsewater Neu-
tralization Sludge
7A
Summary of Costs for Sanitary Landfill
Disposal Without Sludge Containerization
Sanitary Landfill
Without Containerization
$/Metric Ton of Waste
Wet Basis
$ :.i.48
1.0.42
6.26
=-.17
12.25
:.i .00
Dry Basis
$ 70.57
52.27
15.64
13.33
22.70
30.82
84.00
$/Metric
Ton of
Product
$ 0.02
0.12
0.27
0.18
0.20
0.05
0.01
r T r
IT r i r ~i r i ?
ZPO-IQ
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eg.}. 01 »np *! \\ '«o|iou
888) 8|
-------
Table 41 Sugary of Costs for Sanitary Landfill Disposal Wi,hout Sludge Containerizatioa (Cant.)
Sanitary Landfill
Without Containerization
$/Metric Ton of Kaste I/Metric
Ton of
Wet Basis Dry Basis . Product
Kaste Stream
Iron and Steel Prod. -
Cold Rolling Mill -
Acid Rinsewater Neu-
tralization Sludge
(HC1)
Iron and Steel Prod. -
Cold Rolling Mill -
Waste Pickle Liquor -
Sulfuric Acid (H2S04)
Iron and Steel Prod. -
Cold Rolling Mill -
Waste Pickle Liquor -
Hydrochloric Acid (HC1)
Iron and Steel Prod. -
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (H2S04)
Iron and Steel Prod. -
Galvanizing Mill - Acid
Rinsewater Neutralization
Sludge (HC1)
Ferroalloys - Ferro-
silicon Manufacture -
Miscellaneous Dusts
Ferroalloys - Ferro-
silicon Manufacture -
Slag
8A
SB
9A
9B
11
12A
$ 28.00
$ 280.00
11.36
11.33
14.93
25.20
27S.30
132.81
48.00
(.4.00
8.33
7.34
$ 0.01
1.28
0.61
0.54
0.20
2.81
12.86
6u|»q
luawnoop
01 »np
t '»3|;ou
689| 8|
-------
Table 41 Summary of Costs for Sanitary Landfill Disposal Without Sludge Containerization (Cont.)
Sanitary Landfill
Without Container!zation $/Metri;
$/Metric Ton of Waste Ton of
Waste Stream Number
Ferroalloys - Ferro- 12B
silicon Manufacture -
Dust
Ferroalloys - Ferro- 12C
silicon Manufacture -
Sludge
Ferroalloys - Silico- 13
nanganese Manufacture -
Slag and Scrubber Sludge
K> Ferroalloys - Ferro- 14
o nanganese Manufacture -
Slag and Sludge
Copper Smelting - 15
Acid Plant Slowdown
Sludge
Electrolytic Copper 16
Refining - Mixed
Sludge
Lead Smelting - 17
Sludge
Electrolytic Zinc 18
Manufacture
Pyrometallurgical Zinc 19A
Manufacture - Sludges -
Primary Gas Cleaning and
Acid Plant Blowdown
Wet Basis
Dry Basis
$ --
10.42
8.95
24.00
17.82
10.42
11.94
9.62
$ 8.25
25.94
7.36
22.33
56.00
49.00
34.62
39.94
31.83
Product
$ 1.25
3.93
8.09
6.63
0.17
0.12
2.05
1.04
3.87
r i
ZVO-IQ
i r i t i - i
juaujnoop »m jo X;i|*nb
914; o
-------
Table 41 Summary of Costs for Sanitary Landfill Disposal Without Sludge Containerization (Cent.)
Sanitary Landfill
Without Containerization
$/Metric Ton of Waste I/Metric
Ton of
tosis Dry Basis
Waste Stream
Pyrometallurgical Zinc
Manufacture - Sludges -
Retort Gas Scrubber
Bleed
Aluminum Manufacture -
Scrubber Sludges
Aluminum Manufacture -
Spent Potliners and
Skimmings
M
° Aluminum Manufacture -
Shot Blast and Cast
House Dusts
Pyrometallurgical
Antimony Manufacture-
Blast Furnace Slag
Electrolytic Antimony
Manufacture - Spent
Anolyte Sludge
Titanium Manufacture-
Chlorinator Condenser
Sludge
Copper Refining
Blast Furnace Slag
Lead Refining - S02
Scrubwater Sludge
19B
20
21
23
24
25
27
28
$ 15-°°
8.70
21.00
15-68
22.92
$ 30.00
28.91
<».04
25.45
10.86
63.00
39.52
13.65
76.39
$ 0.31
3-38
0.13
30.96
14.00
13.00
4.77
3.44
6u|9q
)U9iunoop 9\(\ jo A)!|vnb
8ift o; 9np si )| *90|V>u
onn i mm main oaoi 01
-------
Table 41 Summary of Costs for Sanitary Landfill Disposal Without Sludge Container!zation (Cont.)
Sanitary Landfill
Without Containerization
$/Metric Ton of Haste S/Metric
Ton of
Wet Basis Dry Basis Product
Waste Stream
Aluminum Refining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
30
$ 12.25
$ 40.83
7.50
$ 3.06
10.50
N>
o
to
rr.i
ri
6u(»q
cnp B|
-------
Table 42 Su-mary of Costs fc:r Sanitary Landfill Disposal with Sludge Container!zation
Waste Stream
Iron and Steel Coke Production -
Ammonia Still Lime Sludge
Iron and Steel Coke Production -
Decanter Tank Tar from Coke Frod.
Iron and Steel Production -
Basic Oxygen Furnace - Wet
Emission Control Unit Sludge
Iron and Steel Production -
Open Hearth Furnace - Emission
Control Dust
Iron and Steel Production -
Electric Furnace - Wet
Emission Control Sludge
Iron and Steel Production -
Rolling Mill Sludge
Iron and Steel Production -
Cold Rolling Mill - Acid Rinse-
water Neutralization Sludge
(H2S04)
Sanitary Landfill
With Containerization
$/Metric Ton of Waste
Number Wet Basis Dry Basis
1 $ 73.11 $ 240.21
7A
62.50
57.54
40.13
51.51
67.88
313.64
93.85
13.33*
99.41
129.61
271.50
$/Metric
Ton of
Product
$ 0.07
0.69
1.62
0.18
0.37
0.22
0.04
•Same cost as without container!ration because waste is dry. (See Table 41)
6u|aq
luauunoop »i| i jo A)u*nb
am o; enp j| }| 'aojiou
8|tU Mill JB8|0 8«9| 8|
-------
Table 42 Summary of Costs f»r Sanitary Landfill Disposal with Sludge Containerization (Cont.)
Sanitai-y Landfill
With Containerization
$/Metric Ton of Waste
Waste Stream
Number
Iron and Steel Production - 7B
Cold Rolling Mill - Acid Ri'ise-
water Neutralization Sludge (HC1)
Iron and Steel Production - SA
Cold Rolling Mill - Waste Piikle
Liquor - Sulfuric Acid (H-.SO,)
Iron and Steel Production - 8B
Cold Rolling Mill - Waste Pickle
Liquor - Hydrochloric Acid (HClj
Iron and Steel Production - 9A
Galvanizing Mill - Acid Rin>«water
Neutralization Sludge (HjSO^.
Iron and Steel Production - 9B
Galvanizing Mill - Acid Rinuwater
Neutralization Sludge (HC1)
Ferroalloys - Ferrosilicon 11
Manufacture - Miscellaneous toists
Ferroalloys - Ferrosilicon 12A
Manufacture - Slag
Wet Basis
S 90.50
68.14
68.00
53.32
81.45
Dry Basis
S 905.00
1,675.76
796.88
173.00
271.50
8.33*
7.34*
$/Metric
Ton of
Product
$ 0.04
7.66
3.64
1.94
0.65
2.81
12.86
*Same cost as without contairerization because waste is dry"(See Table 41)
t - i - r - r
r .1 r.1
:" i : i
i : i
i
6uiaq
}U8Ujnoop am 1° £){|vnb
anp *\ \\ 'ao|)ou
-------
en czi rn irn ni
c: i r .> r.:
r.i (".;:•> i~.i
Table 42 Summary of Costs for Sanitary Landfill Disposal with Sludge Containerization (Cont.)
10
o
tn
Sanitary Landfill
Kith Containerization
$/Metric Ton of Waste
Waste Stream
Ferroalloys - Ferrosilicon
Manufacture - Dust
Ferroalloys - Ferrosilicon
Manufacture - Sludge
Ferroalloys - Siliconanganese
Manufacture - Slag and Scrubber
Sludge
Ferroalloys - Ferromanganese
Manufacture - Slag and Sludge
Copper Smelting - Acid Plant
Blowdown Sludge
Electrolytic Copper Refining -
Mixed Sludge
Lead Smelting - Sludge
Electrolytic Zinc Manufacture
Number Wet Basis
12B $
12C
13
14
IS
16
17
18
Pyronetallurgicc.1 Zinc Manufactxe - 19A
Sludges - Primary Gas Cleaning ard
Acid Plant Slowdown
62.50
53.72
77.57
57.59
62.50
60.07
57.73
Dry Basis
$ 8.25*
7.36*
181.00
158.38
207.69
201.00
190.96
$/Metric
Ton of
Product
$ 1.25
155.66 23.57
8.09
133.99 39.75
0.54
0.40
12.27
5.23
23.20
*Saine cost as without containeril ition because waste is dry. (See Table 41)
-ia
6u(aq
^nb
o; anp 01 \\ 'ao^ou
-------
Table 42 Summary of Costs for Sanitary Landfill Disposal with Sludge Container!zation (Cont.)
Sanitary Landfill
With Container!zation -aste is dry. (See Table 41)
c 3 f •"> 11 r 7 ! t : > : i r \ : i - y : u
8IU1 UVUtl J^»10 8891 81
-------
N>
o
Table 42 Summary of Costs for Sanitary Landfill Disposal with Sludge Containerization (
Waste Stream
Sanitary LmJfill
With Containerization
' $/Metric Ton of Waste
Number Wet Basis DTY Basis
Aluminum Refining - Scrubber
Sludge
Aluminum Refining - High
Salt Slag
29
30
43.50
$ 145.00
7.50*
$/Metric
Ton of
Product
$10.88
10.50
*Same cost as without containerir.ntion because waste is dry. (See Table 41)
o; «np oj ;| '
J89|0 «89|
-------
M
O
oo
Table 43 Summary of Costs for Chemical Landfill Disposal With Sludge Containerization
Chemical L;il(l1' l *'
, With Containcri ration* citric
$/Metric Ton of Waste 'r'o~ Qf
~. <-~ Number Wet Basis Ihv Has is Product
Iron and Steel Coke Production - 1
Ammonia Still Lime Sludge
Iron and Steel Coke Production - 2
Decanter Tank Tar from Coke Prod.
$78.89
64.58
38.79
$ 259.21
324.09
96.99
$ 0.07
0.71
1.68
Basic Oxygen Furnace - Wet
Emission Control Unit Sludge
Iron and Steel Production -
Open Hearth Furnace - Emission
Control Dust
Iron and Steel Production -
Electric Furnace - Wet
Emission Control Sludge
42.11
16.67
104.32
0.23
0.92
Iron ~.-'.d Stc<
R:lli".g Mil!
Coia RolltRg
writer '."OU'TP.
, CA T4
»1 Production - & ;>•»..>•.
Sludjrc-
. , -. f -- - 7A 73.88
M.li - Acid id use -
l;-£tl::i Sluci^e
136.73 0.24
295.00 0.04
r•-•>. r: •> r :• r t
1 i:.J r_iS ^4
; «np si ;|
110111 raait oooi 01
-------
Table 43 Summary of Costs for Chemical Lane Till Disposal with Sludge Containeriration (Cent.)
o
•o
Waste Stream
Iron and Steel Production - 7B
Cold Rolling Mill - Acid Rinse-
water Neutralization Sludge (HC1)
Iron and Steel Production - 8A
Cold Rolling Mill - Waste Pickle
Liquor - Sulfuric Acid (I^SO^)
Iron and Steel Production - 8B
Cold Rolling Mill - Waste Pickle
Liquor - Hydrochloric Acid (KC1)
Iron and Steel Production - 9A
Galvanizing Mill - Acid Rinsewater
Neutralization Sludge (H2S04)
Iron and Steel Production - 9B
Galvanizing Mill - Acid Rinscwatci
NeutriHzEtioii Sludge (HCi)
Chemical Landfill
With Containcrizntion*
J/Metric Ton if Waste
Number Wet Basis Dry Basis
$ 985.00
$98.50
70.41
70.27
57.87
88.65
1,731.64
823.44
186.00
295.50
$/Metric
Ton of
Product
$ 0.04
7.92
3.76
2.08
0.71
Ferroalloys
Manufacture
Ferroalloys
Manufacture
- Ferrosilicon
- Miscellaneous Dusts
- Fcrrosiliccr.
- Slag
11
12A
10.00
5.81
3.38
15.42
Only for liquid and semi-liquid wastes.
6u!8<1
luauinoop »m jo
-------
Table 43 Summary of Costs for Chemical Landfill Disposal with Sludge Containerization (Cont.)
N)
h-»
O
Naste Stream
Ferroalloys - Perrosilicon
Manufacture - Dust
Ferroalloys - Ferrosilicon
Manufacture - Sludge
Ferroalloys - Silicomanganesc
Manufacture - Slag and Scrubber
Sludge
Ferroalloys - Ferromanganese
Manufacture - Slag and Sludge
Copper Smelting - Acid Plant
81 ow do-.\T. S1 ud g e
Electrolytic Ccpper Refining -
Mixed Sludge
Number
12B
12C
13
14
15
16
Chemical Landfill
foith Container! zatioji*
$/Metric Ton of JVaste
Wet Basis Dry Basis
$ -- $ 9.91
64.58
55.51
84.43
62.68
160.85
8.83
138.46
197.00
172.38
$/Mutrii
Ton of
Product
$ 1.50
24.36
9.71
41.01
0.59
0.43
Lei., ^rrtltir..* - Slv.-Igi 17 64.58 214.62 12.68
Electrolytic Zinc Manufacture 18 62.38 208.73 5.43
Pyrortetallurgical'Zinc Manufacture - 19A 59.66 197.33 23.97
Sludges - Primary Gas Cleaning and
Acid Plant Slowdown
* Only
I -. r r i - f - 1 t
for liquid and semi-liquid wastes.
*:: r-i fT !r."i - t ii --< - J i-> -> --» --1
•KIBiik 2*0- 1. a ?:»r;
6uieq
Xv.|«nb
'80HOU
«88| 8|
-------
Table 4, Sununary of Costs for Chemical Uncflll Disposal with Sludge Containerization (Cant.)
„. • t i „. . I r; 1 1
Waste Stream
Pyrometallurgical Zinc Manufacture 19B $53.45
Sludges - Retort Gas Scrubber
Bleed
Chemical l.mnlfill
With Containcrization* $/MCtric
$/Metric Ton of Waste Ton of
Number Wet Basis Dry Basis .Product
$ 106.91 $ 1.10
Aluminum Manufacture - 20
Scrubber Sludges
Aluminum Manufacture - Spent 21
Potliners and Skimmings
Aluminum Manufacture - Shot Blast 22
and Cast House Dusts
Pyrometallurgical Antimony Mant- 23
facture - Blast Furnace Slag
Electrolytic Antimony Manufacture- 24
Spent Anolyte Sludge
Titanium Manufacture - Chlorinator 25
Condenser Sludge
Copper Rafining - Blast
Furnace Slag
Luid P.cfir-.ins - SO.. Scrub* a tor
Sludge
27
?S
53.93
* Only for liquid and semi-liquid wastes.
73 88
70 qa
81.25
179.25
11.51
32.73
13.57
221.63
178.88
17.23
270.83
20.97
0.68
0.24
38.70
49.25
58.84
6.03
12.19
6u|«q
luaiunoop am jo X);i«nb
am oi anp o| \\ 'eo^ou
aim u'Ml -reap see) *\
-------
Table 43 Sunraary
of Costs for Chemical Landfill Disposal with Sludge Containerization (Cont.)
Waste Stream
Chemical I-.ir.iin 11
With Containerizntion*
$/Metric Ton of Waste
Number Wet Basis Drv Basis
Aluminum Refining - Scrubber
Sludge
Aluminum Refining - High
Salt Slag
29
30
9.00
$/Mctric
Ton of
Product
$ 47.00 $ 156.67 $11.75
12.60
10
>-•
10
• Only for liquid and semi-liquid wastes.
peui|U 6u|aq
;uouinoop
-------
*•
" «• !± s
s
REFERENCES
PART II
.st» 2
I*!
I 3 ,«• =
« sr 5
1 3 » •
(I) Letter to Mr. E. Isenberg from Alexandra G. Tarnay, Hazardous
Waste Management Division (AW-465), 20 October 1976.
(2) "Building Construction Cost Data 1976," Robert Snow Moans Co., Inc.
(3) Calspan estimate
(4) "Liners for Land Disposal Sites, an Assessment," EPA/530/SW-137,
. March 1975
(5) Vendor Information
213
-------
J3 9 =•
# r
PART III
COMPARISON OF LANDFILL COSTS WITH
ALTERNATIVE TREATMENT COSTS
214
n
3 »
I
o
£t
10
-------
tr-o a
~ g
A. Comparison of Landfill and Alternative Treatment Costs
The costs for alternative treatment processes and landfill are
shown in Table 44. The costs are relative and are expressed as ratios with
the cost of sanitary landfill without containerization used as the denominator.
The comparison is made in terms of cost permetric ton of product. The lowest
cost alternative is designated for each waste.
As would be expected, the costs of sanitary landfill with container-
ization and chemical landfill are always higher than sanitary landfill without
containerization costs. In two cases, U'aste Nos. i and 7, the sanitary landfill
cost with containerization is the same as the chemical landfill cost. These
cases arc characterized by large annual productions and relatively snail
quantities of wastes. Containcrizaticn represents the dominant cost.
Sanitary landfiii i.s the least, cost alternative for 15 wastes '..-her.
liquids are not containerized.
Chemical landfilling because of the requirement to containerize
liquid wastes and its inherent higher costs does not provide any least cost
waste candidates.
Alternative treatment processes excluding recovery' values (total),
offer least costs for six of the wastes with one of these, pyrometallurgical
zinc retort gas scrubber bleed, waste stream 19, at par with sanitary land-
filling without containerization.
3 i-c
=•
Aiter:i..'!.t.iy's tre-.ttm-ut proecisui. •.-.•here recovery vnUic? •..•.-.re i:
(net) offer least cost possibilities for eight of the wastes.
Table 45 is a tabulation of the actual costs that were used to
calculate the relative costs shown in Table 44.
215
-------
Table 44 Relative Costs for Landfill and Alternative Treatment Process (Per Unit of Product)
Sanitary
Ur.dfill
iV/'O Contain.
to
1—*
a-
Iron r-nd Stcc? Coke Production -
/jzKor.ia Still :-::-•.- i-'l^.-»e
Iron and Steel Coke Production -
Decanter Tank Tar from Coke
Production
Iron and Steel Production -
Basic Oxygen Furnace - Wet
Emission Control Unit Sludge
Iron and Steel Production -
Open Hearth Furnace - Emission
Control Dust
Iron and Steel Production -
F.lectric Furnace - Wet Emission
Control Sludge
Iron and Steel Production -
Rolling Mill Sludge
Iron and Steel Production -
Cold Rolling Mill - Acid
Rinsewater Neutralization
Sludge (H-,S04)
7A
Sanitary
Landfill
With Cir.ti.in_.
5.50
5.75
3.83
3.83
3.83
4.40
4.00
Cher.ical
'..c.nr. f i 11
3.50
5.92
4.35
4.35
4.35
4.80
4.00
Alternative Treatment
Procoss
Tote!
3.5
35.5
0.74
0.74
0.74
0.60
Set
NRV
NRV
0.43
0.43
0.43
0.12
0.40 MRV
See page 220 for legend.
IB.
Liu
i : f
:: t
6ujoq
jueuinoop «m jo A*)i|*nb
aui oa one si v 'oouou
-------
Table 44 Relative Costs for Landfill i.nd Alternative Treatment Process (Per Unit of Product) (Omt.)
Haste Stream
Iron and Steel Production - Cold
Rolling Mill - Acid Rinsewater
Neutralization Sludge (HC1)
Iron and Steel Production -
Cold Rolling Mill - Waste
1'ickle Liquor - Sulfuric Acid
(H,SO.)
Iron and Steel Production -
Cold Rolling Mill - Waste Pickle
Liquor - Hydrochloric Acid (HC1)
Iron and Steel Production -
Galvanizing Mill - Acid Rinsewater
Neutralization Sludge (H2S04)
Iron and Steel Production -
Galvani-.ing Kill - Acid Rinsewater
Neutralization Sludge (HC1)
Number
7B
8A
SB
Sanitary
Landfill
W/0 Contain.
1
9A
9B
Sanitary
Landfill
With Contain.
4.00
5.9S
5.97
3.59
3.23
Chemical
Landfill
4.00
6.19
6.16
3.85
3.55
Alternative Treatment
Process
Total
0.30
4.88
3.33
0.07
0.15
Net
NRV
3.80
2.18
NRV
NRV
Ferroalloys
Manufacture
Ferroalloys
Manufacture
- Fcrrosiliccn 11 i
- Miscellaneous Dusts
- Ferrosiliccn 12A 1
- Slag
N.A. 1.20 1.91 NRV
K.A. 1-20 0.33 0.40
See page 220 for legend.
Zt-O-Kl
;u3Uinoop am jo
am o; anp «| 5! '
8IU1 UBUX JB8IO 9881 81
-------
Table 44 Relative Costs for Landfill and Alternative Treatment Process (Per Unit of Product) (Cent.)
Waste Stream
Ferroalloys - Ferrosilicon
Manufacture - Dust
Ferroalloys - Ferrosilicon
Manufacture - Sludge
Ferroalloys - Silicomanganese
Manufacture - Slag and Scrubber
Sludge
Ferroalloys - Ferroroanganese
Manufacture - Slag and Sludge
Copper Smelting - Acid Plant
Slowdown Sludge
Electrolytic Copper Refining -
Mixed Sludge
Lead Smelting - Sludge
Llectrolytic Zinc Manufacture
•'yro'-v.'l. i :.'~ :':'.''• '-'•'• i '•- ':;
SluJgcs - j*ri:rary Gas
Acid Plant BlowJo'. t.i :' i i i
6u|aq
;u8uinoop
aij} 0} an
$54; uvq:i J^ap ssa| t\
-------
Table 44 Relative Costs for Landfill and Alternative Treatment Process (Per Unit of Product) (Cont.)
Sanitary Sanitary
Landfill Landfill
Waste Stream Numbe:: W/0 Contain. With Contain..
Pyrometallurgical Zinc 19B 1_ 2.26
Manufacture - Sludges - Retort
Gas Scrubber Bl-ied
Aluminum Manufacture - 20 1 5-20
Scrubber Sludges
Aluminum Manufacture - Spent 21 1 5.20
Totliners and Skimmings
Aluminum Manufacture - Shot .22 ^ N-A-
Blast and Cast House Dusts
5 Pyrometallurgical Antimony 23 1_ N-A-
Manufacture - Blast Furnace Slag
Electrolytic Antimony Manufacture- 24 1. 3-23
Spent Anolyte Sludge
Titanium Manufacture - 25 1 4-29
Chlorinator Condenser Sludge
Copper Kcfining - Blast 27 l_ N'-A-
furr.-'icc Sing
->- ' 3 27
•C-T1 •^rio'il-l - 30-« . <•* '
Chemical
Landfill
3.55
5.54
5.54
1.33
1.25
3.52
4.53
1.26
3.54
Alternative Treatment
Process
Total
1.00
3.49
3.49
3.00
1.70
2.62
0.80
2.78
1.12
Met
NRV
*
NRV
NRV
NRV
•*•
NRV
x:iv
See page 220 for legend.
;ueiunoop uq; jo
; •0? 8J ^|
-------
Table 44 Relative Costs for Landfill and Alternative Treatment Process (Per Ur.it of Product) (Coat.)
Waste Stream
Alusninun Refining -
Scrubber Sludge
Aluminum Refining -
High Salt Slag
Sanitary Sanitary Alt-jniative Treatment
Landfill Landfill Chemical Process
Nuabtsr W/0 Contain. With Contain. Landfill
29
30
1
3.56
N.A.
3.84
1.20
Total
1.36
6.38
NRV
3.47
K>
KJ
O
N.A.
SRV
is used -.o denote that the alternative treatment process results in a net gain
least cost alternative
N'ot applicable
No recovery value
t-y ri-s rs rs 1-3 en tra rri t I ri :::i - > :i si =*__=-*. .-«. -*,
ZfrO-lQ
6u|«q
nit) jo
-------
t J
tj
Table 45
COST SUMMARY FOR LANDFILL AND ALTERNATIVE TREATMENT PROCESSES3
[S/METRIC TON)
WASTE STREAM
MOM AND mil COK*
PRODUCTION -AMMONIA
STILL LIME SLUDGE
IRON AND STEEL COKE
PRODUCTION DC
CANTER TANK TAR
ROMCOU
PRODUCTION
MON AND STEf I PRO-
DUCTION- BASK
OXVGE N FURNACE -
WET EMMSKJN CON-
TROL UNIT SLUDGE
MON AND STEIL PRO-
DUCTION -OPEN
HEARTH FURNACE -
EMISSION CONTROL
DUST
WON AND STtEL PRO-
DUCTION-ELECTRIC
FURNACE- WCT
EMISSION CONTROL
SLUDGE
WON AMD STtEL PRO-
DUCTION- ROt LINO
MH-LSLUOOS
WON AND STEEL PRO-
DUCTON-COIO
ROLLING MILL -ACID
RINSEWATER NEU-
TRALIZATION tt-UOGE
IRON AND STEIL PRO-
DUCTION -COLO
ROLLING MILL -ACID
RINSEWATER NEU-
TRALIZATION SLUDGE
WCII
MON AMD STEEL PRO-
DUCTION -COLD
ROLLING MILL • WASTE
FICKLE UOUOn • SUL-
FURIC AOO IM,«O4I
WASTE
NO.
t
2
1
4
I
,
7A
„
•A
SANITARY LANDFILL
WITHOUT
mkTAINCRIZATiflM
•USTE
DRY
•ASIS
1.4*
0.42
*2<
NRV
•-17
I1-2B
2140
2»J»
11JC
WET
•ASIS
7027
§227
11.C4
11JJ
22.7*
X*t
*4jOO
2*040
27*2*
NIODUCT
OJ02
0.12
027
0.1*
020
O.OS
0*1
001
12*
IRTM
DRV
IASIS
71.11
»
17 S4
RV
40.11
41 S1
67 J*
MM
•114
WET
IOJ1
11 3*4
I1M
M23
1*41
i:,..l
2.30
*BOO
10-57,
ODUCT
007
0. »
1.S2
0.1*
027
022
004
004
7J.
CHEMICAL LAUDFILL
WITHSLU3GE
CONTAINERI2ATION
WASTE
WET
•ASIS
7»M
MJ.
3».7»
MIV
42.11
*4J4
71 J*
M*>
7041
DRY
•ASIS
««21
124 M
KM
li«l
104^
11*7
ma
«5.
1731*
ODUCT
0.07
0.71
1 a
ALTERNATIVE TREATMENT
WASTE
frt
TOTAL
7*J*
Wit
12*
i
OJ3 12.H
OJ2 12JC
i
024
.4.
1
0.04
004
742
.«
1.7
Mi
[
NET
NRV
NRV
7J«
7J«
7.3*
1.4S
NRV
NRV
4JJ1
OTAU
25*21
»40,
2*M
2*£0
2*50
1.2S
27.40
6767
13KJ2
NET
NRV
NRV
17.40
17.40
1740
M*
NRV
NRV
10*124
PROOUC
OTALk
OO7
T
NET*
NRV
0.71 i NRV
t
j
1
OU j 02*
04*
0.4*
OO3
0004
OAOl
•24
021
'
021
OAC4
NRV
NRV
t*~>
• - FOR A TTFICAL MJUfT.
k - TOTAL DOES NOT INCLUDE RECOVERY VALUE.
c - NET INCLUDES RECOVERY VALUE.
N-A. - NOTAf»LK^BJ
- NET OAIN I HO < ALTERNATWI TREATMENT PR'XIESS
NRV - NO RECOVIIIV VALUE
) «np 6| ;| '9oi;ou
SIU1 UBUl JB910 8801 81
-------
Table 45
COST SUMMARY FOR LANDFILL AND ALTERNATIVE TREATMENT PROCESSES3
($/METRIC TON) (Cont.)
WASTE STREAM
IRON AND STtEL PRO
OUCTION -COLO
ROLLING MILL -WASTE
PICKLE LIOUOR •
HYDROCHLORIC ACIO
IMCII
IRON AND SiEELtRO
OUCTION - CALVANI
IMC MILL ACIO RINSE
HATER NEUTRALIZA
TIONSLUOG«H,S04>
IRON AND STEEL PRO
OUCTION CALVANI
ZINC MILL ACIO RINSE
MATER NEUTRALIZA
TKW SLUDGE IHCtl
FERROALLOYS-
FERROSILKON
MANUFACTURE
MISCELLANEOUS OUSTS
FERROALLOYS -
FERROSILKON
MANUFACTURE • SLAG
FERROALLOYS •
FERROSILKON
MANUFACTURE OUST
FERROALLOYS -
FERROSILKON
MANUFACTURE •
SLUDGE
FERROALLOYS-
SILKOMANGANESE
MANUFACTURE SLAG
AND SCRUBBER
SLUDGE
FERROALLOYS-
FERROMANCANESE
MANUFACTURE • SLAG
ANO SLUDGE
COPPER SMELTING •
ACIO PLANT
SLOWDOWN SLUDGE
ELECTROLYTIC
COPTER REFINING-
MIXED SLUDGE
HASTE
NO.
BB
fA
M
11
12A
124
12C
11
14
15
IB
. |
WITHOUT
CONTAINERIZATION
WASTE
DRY
BASIS
11.11
1441
2520
NRV
NRV
NRV
1042
NRV
145
24.00
1742
WET
BASIS
1211
4I.OO
B4.0O
• 11
J.J4
1.25
2544
7.J4
22 Jl
SB 00
44 OG
PRODUCT
Oil
WITH
; MTTAINERIZATION
WASTE
I1F>V
IIAiS
I.IOli
0.54
0.2O
241
1!M
1-25
141
• 09
1.B1
0.17
0.12
J.L.*
1 V-
«V
-illV
\illV
J SI
111V
,a 7>
>7
-------
tj
K)
Table 45
COST SUMMARY FOR LANDFILL AND ALTERNATIVE TREATMENT PROCESSES3
($/METRICTON)(Cont.)
1 «
WASTE STREAM
LEAD SMELTING •
SLUDGE
ELECTROLYTIC ZINC
MANUFACTURE tlUDT.E
PVROMETALLURGKAL
ZINC MANUFACTURE •
SLUDGES- PRIMARY
GAS CLEANING AND
ACB PLANT
SLOWDOWN
PYROMETAILURGKAL
ZINC MANUFACTURE •
SLUDGES -RETORT
CAS SCRUBBER BLIED
ALUMINUM MANUFAC-
TURE SCRUBBER
SLUDGES
ALUMINUM MANUFAC-
TURE -SPENT POT.
LINERS AND
SKIMMINGS
ALUMINUM MANUFAC-
TURE SHOT BLAST AND
CAST HOUSE DUSTS
PTROMETALLUR GKAL
AXTBMNV MANUFAC-
TURE • BLAST FURNACE
SLAG
ELECTROLYTIC
ANTIMONY MANUFAC-
TURE-SPENT
ANOLVTE SLUDGE
TITANIUM MANUFAC-
TURE • CMIORINATOR
CONDENSER SLUDGE
COPTER REFINtllG.
BLAST FURNACE SLAO
LEAD RE FINING- SO,
SCRUSMATER SLUDGE
ALUMINUM REFINING •
SCRUBBER SLUOGE
ALUMINUM RER NINO •
MICH SALT SLAG
WASTE
NO.
17
IS
(A
BB
JO
Zt
ZZ
ZJ
Z4
S
Z7
ZB
Z*
30
SANITARY LANDFILL
WITHOUT
OOMTAINE RIZATION
WASTE
DRV
BASIS
0.4Z
1*4
*.CZ
ISM
B.70
NRV
NRV
NRV
J1.00
15*1
NRV
ZZ*1
11JS
NRV
WET
ASIS
34.SZ
3B*4
31*3
30*0
Zi*1
404
ZS4S
10*4
SIM
31 il
11*3
7«JO
40*3
ISC
PRODUCT
CONTAIIIE IIZATION
WASTE
1 DRY
BASIS
ZJ>
1*4
3*7
OJI 1
11*0
•9*7
57.73
4BM
3JB
Oil
0.1S
30M
14M
13M
4.77
144
3M
10*0
SZ.1S
NRV
NRV
NRV
<7*B
S7.27
NRV
75.00
43JO
NRV
z: i co
1iO
NET
1*1*
3*0*
15.44-
NRV
1SJB*
I1JS'
NA.
NA.
NRV
14J6
NA.
NRV
NRV
NJL
l»ni
OTAL
22*1
54 JS
11.7B
xm
27.S3
27.*]
75_U
\»M
IBS. 15
)1*l
37 *t
BS3S
S»J»
47**
NET
3J4-
11JO*
51*B'
NRV
40i»'
40W
NRV
NRV
NRV
374
NRV
NRV
NRV
J»02
PROOU
OTALk
1J4
1.44
1V3
031
13.BS
11*S
0*4
52 4B
M7O
13.ZS
3*4
4.15
•7*4
CT
NET«
OJO-
021*
«J1-
NRV
B
7.14*
NRV
NRV
NRV
1131*
NRV
SRV
WV
M43
. ma A TYPICAL PtLAMT
. WAI OOESNOT INCLUDE RECOVERY VALUE
- NET INCLUDES RECOVERY VALUE.
- NOT ATTLICA I . C
- NET GAIN FR.», .LTERNATIVE TREATMENT FROCESS
- NO RECOVER < V»LUE
ZfrO-Kl
juaiunoop am jo
gi|; o; enp 8| )i
emi UBUI jvaio ssei si
-------
APPENDIX A
COST DATA BASE
3 .+
w ^~
=» »
A-l
-------
Cost Data Base. The costs, cost, factors and costing methodology
used to derive the capital and annual costs are documented in this section.
All costs are expressed in 1976 dollars.
The following categorization is used to present the costs:
Capital Cost
Facilities
Equipment
Installation
Contingency and Contractor's Fee
Annual Cost
Amortizaiion
Operations and Maintenance
Operating Personnel
Repair and Maintenance
'•In I r r i a 1 s
Waste Disposal
Taxes and Insurance
tnergy
Capital__Cosl_. The requirements for the alternative treatment
processes cover a broad range of facilities, equipment and activities. In
many instances, the alternative process entail the installation of a small
or moderate amount of equipment, which, it is assumed, can be incorporated
into existing plant operations. Some processes, however, require extensive
facilities and equipment equivalent to an entirely new plant.
The capital cost of a new plant is based on gross equipment or
total facility costs provided by A.D. Little and firms which have constructed
similar operating facilities in recent years. An example is the Dravo-Lurgi
HC1 Regeneration Plant, for which the capital cost and operating requirements
were provided by the Dravo Corporation. In the cases where only gross,
A-2
-------
installed equipment cost were available, the facility costs were estimated
to be equal to the cost of the installed equipment. Such costs c^n vary
considerably depending on the availability of suitable buildings, access
roads, railway sidings and utilities.
Itemized costs are presented for the small and moderate-size opera-
tions. Parametric costs were developed for items which are common to many
of the alternative processes; e.g. tanks, pumps and centrifuges. These and
other equipment costs are based on vendor quotations. The parametric and
other cost-estimating relationships employed are discussed below.
Sumps. Concrete pits sized to contain a 24-hour flow of wastewater
are included with some treatment processes. In addition, concrete sludge-
holding pits are provided, generally designed to hold a 7-day supply of sludge.
The pits are constructed ot ^0-centimet^r (8 inch) reinforced base
slabs and 40 centimeter (.16 inch) walls. A genernl cost-estimating relation-
ship was developed from a base slab cost of $20/square meter ($2/square foot)
and a wall cost of $300/cubic meter ($8/cubic foot) of concrete in place.
The costs include setup and layout, excavation, concrete, backfill and
cleanup.*
For example, the cost of a 6 cubic meter (212 square foot) pit,
measuring 3m x 2m x 1 m (9.8 ft x 6.6 ft x 3.3 ft) is computer as follows:
(3 x 2 x $20) + (2 x 3 x 1 x 0.4 x $300) + (2 x 2 x 1 x 0.4 x $300) = $1,320
Centri fuop«;.
~
Tnctc. q<; t> filTICtior of V.'Cl' fht rsf -.Tllf'r-* trrrirrnTOf!
'igure A-l. Power requirements for the size oh centri-
fuges shown range from 10 to 40.0 hp. The curve given in Figure A-l should
not be extended beyond the lowest point shown, since this point represents
the smallest sized centrifuge manufactured. Costs are based on equipment -
manufacturer quotations. Centrifuges are selected for operating 12 hours or
less per day.
Holding Tanks. Costs, based on vendor quotations, are shown in
Figure A-2, as a function of capacity for steel and fiberglass polyester
tanks.
Mixing Tanks. Mixing tank costs are shown in Figure A-3. The tanks
are of steel construction and include agitators and motors. Costs are based
on a vendor quotation.
Pumps . Pump costs, including motors, are shown in Figures A-4 and
A-5 as a function of capacity expressed in liters (0.264 gal) per minute.
The types and sires of pumps required for a particular activity cnn vary
widely, depending on the characteristics of the material being pumped and the
height and distance of transport. The curves in Figures A-4 and A-5 represent
costs for centrifugal and slurry pumps.
A-3
,s--s
I" 3,"=-
3
-------
100
10
4-
.-I-
- i
! o^>
\yiu ; i • ] j j ', J—j.—>—t"f"T"!
"i I ! ! i i I i ! I i i I I I I
i L..i-i-i--i44 r t H ilTn
i I I I!!!! MM |
! I ! I i I ' I I I i I ! '
i i i ! I
i j I i.|..p4 | ] L..i-j-;-j--H
""f"'T'^--^-^4-'---""""l"""-^ i-"4-4"i--r-ti
:r.r.:".]....i..-i.-t-- -1-1 ? '• !™t"t""h;l
j n.r.Li.i.. i- - -f""-tii
i :~..t~|-H-fi
i i—rT't-tTi i i i f I 11D
i i : j !.! : 'r \—+~+~r+-r\
_| l-Ll-i i ;j-
i
: r—r—;--',- \ f.— i i : i ! i
444iliii t Hiitiil
i i
! i i ! : : !:
i i! Mil
100
FLOW IN METRIC TONS OF SLUDGE/DAY
Figure A-1. CENTRIFUGE COSTS
A-4
'
II
s -
» -
r •
• ,
'
5 *" •" i
I 3* 2* *"*" ™"
* !**-<. 3* S
a o. _-
f>
'**
»•
L
» i
^
a
i
o
•P*
10
-------
100.0
10.0
o
g
.J....J—J-4—{--•-!
i i i J I I i
STEEL HOLDING TANKS j^JxMj j^x£? J 4..
i \ \""^i' j'Tt [ 5Zf\ \ \
i/| i : : ]jS/^*~~- OPEN TANKS
>^SEDJlx£K| i
i.o
i |
t" "~\ ! I 1 T T i j i i i
i i I j i j i i i \ ! i
t r i f""f"i"i": f
! I Mlill! j
100
VOLUME -W
Figure A-2. HOLDING TANK COSTS
A-5
» = IS
5" 2L — o
» ?»•• g «
_^<< - «
-------
10
i
-4—
§
5 1.0
i
..V-.
±;t:rn""-». i- -i t-i"
T/4/.r.n \ i t-~s"
I ' ' i ! i i_.
i i i i i j J....L
i \/\
44444 4 hH
g-S g
0 Jt
c " ^
3 r* =
» 3" O)
3 0>
-------
10.0
8
100
FLOW (LITERS/MINUTE)
1000
Figure A-4. COST OF SLURRY/SLUDGE PUMPS
A-7
to c o
= *- — *•
<° S-' 2 »
3 <-»• =:
o> =r 5T
3 o> w
-------
CB C O. __
f. '3
10.0
,40m HEAD
-'—'r-'.-'r /—T V-
j-trp^20m;HEADj
«5 1.0 -
1000
FLOW (LITERS/MINUTE)
10,000
Figure A-5. COST OF CENTRIFUGAL PUMPS
A-8
'•
C1
'
I
p
•
• '
»
I
S ;
t
s - =
C « H
5 !?2
** —' CO
=1 CD
-------
Piping. Instill leu costs of two types of pipes arc shown in Table
A-l. The basic costs are increased by 20* to account for ancillary fittings,
such as connectors, Ts, and valves.
Installation. Many factors can affect the cost of installing equip-
ment. These include wage rates, whether the job is performed by outside con-
tractors or regular employees, and site-dependent conditions (e.g. availability
of sufficient electrical service).
Varying installation cost factors are used, ranging from 75 to 200%
of equipment costs. For example, equipment which is delivered fully assembled,
such as centrifuges is assigned a 75% installation cost. A higher percentage
is applied for equipment which must be erected on-site, such as thickeners
and kilns.
CT03 3
O. C O
"* — «
~« f
« «-.
o-g •
0 _* •
o r •
= :
Type
Table A-l Install^ Pipe ('o«;ts
Diameter
(cm)
Plastic, Fiberglass Reinforced
Steel, Black, Schedule 40,
Threaded
5
7.5
10
i:
20
2.5
S
7.5
10
15
Cost/Meter
$24
32
38
66
110
13
21
36 •
48
98
Contingency and Contractor's Fee. This cost is computed as 20% of
the sum of the costs for facilities and equipment including installation.
A-9
-------
Annual Costs
Amortization
Annual depreciation and capital costs ar?
where
s
CA
B
r
n
BCr) (1 *r)"
Annual cost
Initial amount invested
Annual interest rate
Useful life in years
The computed cost is often referred to as the capital recovery factor. It
essentially represents the sum of the interest cost and depreciation.
An interest rate of 10'i is used. The expected useful life of
facilities and equipment is 10 years.'' No residual or salvage value is assumed.
Operations and Maintenance
General. Plant operations are based on an assumed 350 days
per year.
Upgrading I'prsnniiel. Fersonnei costs are based on an hourly
rate of $13.50. This includes fringe benefits, overhead and supervision.
Personnel are assigned for specific activities as required.
Repair and Maintenance. The cost of these activities is
calculated as 4% of capital costs.'*
Materials. The materials employed in the pretreatment
processes and their costs are shown below. The costs include the basic
material price plus estimated delivery costs.~
Coke breeze *
Calcium chloride
Chlorine
Scrap iron
Hydrated line
* Calspan estimate
$ 50/metric ton ($ 45/s. ton)
105/metric ton ( 95/s. ton)
ISO/metric ton ( 136/s. ton)
7G/mctric ton ( 68/s. ton)
55/metric ton ( 50/s. ton)
A-10
er-o 3 5
3 r* 3
» =r 5
= a
t*
X
• I
*'
I
o
ro
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Caustic soda
Pebble lime
Sodium Sulfide
Process water
Polyelectrolyte*
210/metric ton ( 191/s. ton)
50/metric Lou ( '15/s. ton)
300/metric ton ( 273/s. ton)
0.08/m-
$2/kg
(0.30/1,000 gal)
(0.90/lb)
The follcving material costs are used to compute the value
of recovered material. The costs exclude transportation costs.2*3
Potassium chloride
Scrap copper
Copper
Aluminum
Lead
Zinc
Iron Pellets**
Rutile**
$ 64/metric ton
1,120/metric ton
1,500/metric ton
1,056/metric ton
616/metric ton
814/raetric ton
20/metric ton
230/metric ton
($ 58/s. ton)
( 1,020/s. ton)
( 1,360/s. ton)
( 960/s. ton)
( 560/s. ton)
( 740/s. ton)
( 18/s. ton)
( 210/s. ton)
Waste Disposal. The sanitary and chemical landfill costs
described in Part II are used as applicable. A charge of Jl/metric ton
($0.90) is used for short-haul intra-plant transport of waste that is recycled.
capital cost.
Taxes and Insurance. These costs are included as $5 of the
Energy. Electrical-costs are based on the cost per horse-
power-year computed as follows:
Calspan estimate
*
Calspan estimate based on communications with operating plants.
A-ll
or.0 3
» er o
-
3 r*2
»
I
O
-------
, HP
(FTT
x0'7457
106 Btu's.4
Where C = Cost
HP = Total horsepower rating of motors (1 hp = 0.7457 kW)
E = Efficiency factor (0.9)
P =• Power factor (0.9)
II = Annual operating hours (as applicable)
CkW = Cost Per kilowatt-hour of electricity ($0.03)
1.1 - factor used for miscellaneous heating and lighting.
Steam cost is calculated at $4 per 10 Btu's: fuel cost at $/ per
*
i
f
4!
R •
tl,
ft
H
li
II
frl
o I B
o ff -
e o ,
3 r* :
A-12
-------
REFERENCES
APPENDIX A
(1) Building Construction Cost Data 1976, Robert Snow Moans
Company, Inc.
(2) Chemical Marketing Reporter, November 29, 1976.
(3) Wall Street Journal, January 27, 1977.
(4) Tarnay, A.G., EPA, (OSWMP) Letter Dated October 20, 1976
to Calsoan Corporation.
o jf
c o
B r*
A-13
-------
V-/EPA
Envifoonirnlol PfOli'Ctiotl
AUCMCV
Oilier ol Wntr- «
Waslf MiiruHit'nitfnt
tO" OC 7O4fiO
SW
Snlirt Wmtr
Alternatives for
;
Hazardous Waste
\
Management
in the Petroleum
Refining Industry
8 ?
= ° »f
3 rt- =r
to 3" ,-
w
o
^
ro
-------
Prepubliaation iaeu& for* EPA libraries
and State Solid Waste Management Agencies
O-J3
<• e o •
5" 2. ~S
ALTERNATIVES FOR HAZARDOUS WASTE MANAGEMENT
IN THE PETROLEUM REFINING INDUSTRY
This report (SW-l?2c) describee aork performed
for the Office of Solid Waste under contract no, 68-01-416?
and ie reproduced as received from the contractor.
The findings should be attributed to the contractor
and not to the Office of Solid Waete.
Copies will be available from the
National Technical Information Service
U.S. Department of Commerce
Springfield, VA 22161
U.S. ENVIRONMENTAL PROTECTION AGENCY
1979
-------
REFERENCES
APPENDIX A
(1) Building Construction Cost Data 1976, Robert Snow Means
Company, Inc.
(2) Chemical Marketing Reporter, November 29, 1976.
(3) Wall Street Journal, January 27, 1977.
(4) Tarnay, A.G., EPA, (OSWMP) Letter Dated October 20, 1976
to Calspan Corporation.
A-13
.
a c o
3*2. ~
«»if
-------