-------
REFERENCES
1. Mark, H. F., J. J. McKetta, D. F. Othmer, and A. Stamden. Kirk-Othmer
Encyclopedia of Chemical Technology. 2nd Ed. New York. Interscience
Publishers, John Wiley and Sons, 1966.
2. Arthur D. Little, Inc., Application of Physical, Chemical And Biological
Treatment Techniques to Hazardous Waste Management. Cambridge, Mass.
EPA Contract 68-01-3554, Composting Section, Page 1.
V - 96
-------
Filter Solids - Furfural Manufacture - Waste Stream No. 13
Waste Stream Description. In the production of furfural, the dehydrating
column bottom stream, which is the product stream, is filtered. From the
pressure filter, the product furfural is sent to storage and the waste stream,
consisting of fines and particulates from stripped hulls is, at present, sent
to land disposal at a rate of .005 kg/kg furfural produced. For details of
the manufacture of furfural see Waste Stream 12 - Still Bottoms from Stripping
Column - Furfural Manufacture.
Existing Treatment Methods. Present technology calls for landfilling of
the wastes from the pressure filter. The presence of furfural In the filter
solids classifies this as a potentially hazardous waste. Landfilling as a
disposal method is unacceptable due to the possibility of furfural leaching
Into the ground outside the disposal site.
Selected Alternative Treatment Process. Since the filter solids from
furfural manufacture contain furfural, estimated at 1 kg furfural to 1 kg
filter solid fines, the first step in the alternative treatment process is
vacuum distillation (or stripping as the case might be). A 90 percent recovery
of furfural will amount to about 158 metric tons per year with a value of about
$115,000. In this treatment step the accumulated fines and particulates with
the entrained furfural are fed Into a vacuum column. The pressure in the
column is reduced to about 100 mm Hg pressure and low pressure steam Injected
into the bottom of the column. The combination of vacuum and steam will strip
V - 97
-------
an estimated 90 to 95 percent of the furfural from the column feed. The
vapors from the still are condensed and recycled to the process decanter for
recovery of the furfural.
The next processing steps for treatment of the filter solids are hydrolysis
and composting of the hydrolyzed wastes. Since these wastes represent only a
small fraction compared to the still bottom waste from the stripping column
(Waste Stream 12), about 190 metric tons per year versus 18,500 tons per year,
they may be combined at this point for hydrolysis and composting. For further
details on the hydrolysis and composting treatment processes, and basis for
estimating composting, see Waste Stream 12.
Benefits and Environmental Advantages and Disadvantages. In addition to
the benefits, environmental advantages and disadvantages detailed under Waste
Stream 12, this process has also the advantage of recovering approximately
158 metric tons of furfural worth $115,000 per year.
Coat Analysis. Costs for treatment and disposal of the filter solids
from a 35,000 metric ton per year furfural plant, have been included In the
cost analysis of Waste Stream 12 - Still Bottoms - Furfural Manufacture.
V - 98
-------
REFERENCES
1. Mark, H. F., J. J. McKetta, D. F. Othmer, and A. Stamden. Kirk-Othmer
Encyclopedia of Chemical Technology. 2nd Ed. New York. Interscience
Publishers, John Wiley and Sons, 1966.
2. Arthur D. Little, Inc., Application of Physical, Chemical and Biological
Treatment Techniques to Hazardous Waste Management. Cambridge, Mass.
EPA Contract 68-01-3554, Composting Section, Page 1.
V - 99
-------
Spent Reactor Catalyst - Fluorocarbon Manufacture -
Waste Stream No. 14
Waste Stream Description. Twice a year the catalyst in plants producing
fluorocarbons is replaced and the spent catalyst sent to landfill. See Figure
i'\'
5-22. A typical analysis1*3 of the spent catalyst is as follows:
SbCl5 77 percent
CCl^ 10 percent'
CCl-jF 10 percent
Organics 3 percent
For a standard size plant, producing 80,000 metric tons per year of
fluorocarbons,! the semiannual purge amounts to about nine metric tons as
SbCl5, with a replacement cost4 of about $20,000.
The spent antimony pentachloride (SbCl,) reacts with water2 to produce
SbOCl with the evolution of chlorine (C1-). Further reaction with water
yields Sb^05Cl2 and more chlorine. The antimony oxyehloride (Sb^O^C^) is
slightly soluble in water. The antimony ion is potentially hazardous. The
provisional limits,3 as Sb, are 0.004 ppm in air and 0.05 ppm in water.
Existing Treatment Methods. The spent catalyst is placed in drums and
sent to land disposal. The waste is deemed potentially hazardous.
V - 100
-------
BASIS: 1 KG DIChLORODIFLUOROHETHANE
HYDROGEN CHLORIDE TO CONSUMERS OR_ 0.55
METHYL CHLORIDE PRODUCTION
REAQOR
I
>—
o
INITIAL CATALYST
• CHARGE
ANTIMONY TRICHLORIDE
CAR30N TETRACHLORIDE1.28
HTCROGEN FLUORIDE 0.33
DICHLORO-
DIFLUOROMETHANE
0.80
TRI CHLOROF-UORCMEThANE
*• 0.20
CARBOH TETRACHLORIDE
STRIPPER
HYDROFLUORIC ACIO
(TO RECOVERY)
IICL
DISTILLATION
SULFUR1C
ACID
BLEED TO BLEED TO
WASTE WATER HASTE MATER
HASHING AND DRYING
ANTIMONY PENTACHLORIDE 0.00022
SPENT CATALYST DISCHARGE,
TWICE PER YEAR
\
LAND DISPOSAL
SPENT REACTOR CATALYST , (J)
WASTE STREAM NO. 14
FIGURE 5-22 FLUOROCARBONS MANUFACTURE
-------
Selected Alternative Treatment Processes. Seven alternatives for
disposing of spent antimony pentachloride were considered, namely:
Treatment Remarks
1. Dechlorination, filtration
and rechlorination Catalyst recycled
2. Distillation Catalyst recycled
3. Calcination and rechlorination Catalyst recycled, but high
energy consumption
4. Iron precipitation
5. Hydrogenation > Toxic product
6. Hydrolysis
7. Sulfide precipitation
Since the first two treatments, dechlorination and distillation, meet
the criteria^ of resource and energy conservation best, these two treatments
designated Train 1 and Train 2 respectively, were studied in detail.
1. Train 1-Dechlorination. This treatment consists of dechlorinating
antimony pentachloride in the presence of ethylene trichloride, precipitating
antimony trichloride; SbCl5 + EtCLjH >- SbC^ + EtCljH
After filtering off the SbCl3, the antimony trichloride is chlorinated to
SbCl5; SbClj + C12 > SbCl^ and returned to fluorocarbon
manufacturing. The process is shown schematically in the flow diagram, Figure
5-23, and is discussed in further detail below.
V - 102
-------
STREAM NO.(I
FIG. NO. 5-2*2
3. FLOW SHEET)
SPENT CATALYS
SbCls - 18.0 KKg/YR
CC1. - 4.9 KKg/YR
ORGANICS - 0.8 KKg/YR
TETRACHLORIDE
.4KKg/YR TO PROCESS
ETHYLENE TRICHLORIDE 7.9KKg/YR
CARBON
PENTACHLORIDE
18.0 KKR/YR
TO
ETHYLENB
PENTACHLORIDE
12.1 KKg/YR
,TO STORAGE
TARS 3.1 KKg/YR
CHEMICAL LAND DISPOSAL
TRAIN I (DECHLORINATION)
SPENT REACTOR CATALYST FLUOROCARBON MANUFACTURE
WASTE STREAM NO. 14
FIGURE NO. 5-23
-------
On a dally basis,, about 80 kilograms of spent catalyst is reacted with
about 50 kilograms of ethylene trichloride at 120C and atmospheric pressure for
about 16 hours. The reactor mix is then filtered (1 hour). After washing
the residue with carbon tetrachloride, the residue is sluiced into a chlorinating
vessel with carbon tetrachloride, makeup antimony trichloride added and the
antimony trichloride chlorinated to the pentachloride. The antimony pentachlo-
rlde is then returned to fluorocarbon manufacturing.
The filtrate is pumped to a receiver and, over 4 hours, is separated by
distillation Into:
Carbon tetrachloride, CCl^
Ethylene trichloride, EtCl^H
Ethylene pentachloride, EtCleH
Still bottoms (chloride and fluoride tars)
The carbon tetrachloride is returned to the fluorocarbon process. The
ethylene trichloride is recycled to the dechlorinator. The ethylene pentachloride
is sold to the supplier of the ethylene trichloride. The still bottoms (about
two kilograms per batch) are drummed and sent to landfill chemical land disposal.
2. Train 2-Distillation. This treatment tentatively consists of taking
a side stream of the catalyst and, by distillation, separate it into these
components:
Lights (mostly freons)
Carbon tetrachloride, CC1,
Antimony pentachloride, SbCl-
Still bottoms (chloride and fluoride tars)
V - 104
-------
As shown in the flow diagram, figure No. 5-24, the lights are sent back
to the fluorocarbon manufacturing, along with the carbon tetrachloride. The
antimony pentachloride is returned to the hydrofluorinator. The still bottoms
are drummed and sent to chemical land disposal.
The distillation system would be automated and operated continuously.
Benefits and Environmental Advantages and Disadvantages. Both treatments,
dechlorination and distillation, require bench scale verification and procure-
ment of scale-up data. Since both treatment plants are relatively small, it
is recommended that the bench equipment be scaled-up to the full size plant,
without a pilot plant development step.
Environmentally, both treatments rate high for these reasons:
1. Recovery of a resource.
2. Low energy input.
3. Reduction of waste volume (1/25).
4. Detoxification of wastes.
Cost Analysis, The cost analysis is based on a plant producing 80,000
KKg per year of fluorocarbons operating 24 hours per day and 300 days per year.
A summary of capital cost, annual operating cost, and the cost Impact for
waste treatment follows.
V - 105
-------
I
s
FREONS
TO PROCESS
STREAM NO.U)
FIG. NO. 5-22
(PROC. FLOW SHEET)
SPENT CATALYST
18 METRIC TONS
YEAR
SbCl5 - 18.0 KKg/yr
CCl^ -4.9 KKg/YR
ORGANICS - 0.8 KKg/Y '.
TOTAL 23.7 KKg/YR
CARBON
DISTILLATION
COLUMNS
TETRACHLORIDE
4.9 KKg/YR
TO PROCESS
ANTIMONY
PENTACHLORIDB
18.0 KKg/YR
TO PROCESS
TARS 0.8 KKg/YR
TRAIN 2
(DISTILLATION)
CHEMICAL LAND DISPOSAL
SPENT REACTOR CATALYST FLUOROCARBON MANUFACTURE
WASTE STREAM NO. 14
FIGURE NO. 5-2j|
-------
WASTE STREAM NO. 14
TRAIN I
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 60 Kg/Day of Catalyst
Equipment Item
Dechlorinator
Dechlorinator Condenser
Antimony Trichloride Filter
Chlorinator
Carbon Tetrachloride Column
Carbon Tetrachloride Condenser
Carbon Tetrachloride Reboiler
Ethylene Trichloride Column
Ethylene Trichloride Condenser
Ethylene Trichloride Reboiler
Ethylene Pentachlorlde Column
Ethylene Fentachloride Condenser
Ethylene Pentachloride Reboiler
Ethylene Trichloride Stg. Tank
Distillation Feed Tank
Ethylene Pentachlorlde Tank
Nine Pumps
Ethylene Trichloride Pump
Size
100 t
1 Sq M
1.1 Sq M
100 t
Estimated Cost
$ 29,200
2,900
29,200
29,200
25 cm dla x 20 trays 32,100
1 Sq M 2,900
1 Sq M 2,900
25 cm dia x 20 trays 32,100
1 Sq M 2,900
1 Sq M 2,900
25 cm dia x 20 trays 32,100
1 Sq M
1 Sq M
19,000 I
380 I
19,000 I
10 A/Hr
190 i/min
2,900
2,900
29,200
2,900
29,200
7,900
7,300
V - 107
-------
WASTE STREAM NO. 14
TRAIN I
1. ESTIMATED INSTALLED CAPITAL COST (CONTINUED)
BASIS: 60 Kg/Day of Catalyst
Equipment Item Size Estimated Cost
Distillation Feed Pump 10 A/rain $ 900
Two Truck Stations 1,500
Subtotal $ 283,100
Engineering @ 10% 28,300
Contingency including freight @ 20% 56,600
Total $ 368,000
V - 108
-------
WASTE STREAM NO. 14
TRAIN I
2, ANNUAL FIXED CHARGES
Depreciation$368,000 @ 10%/year $ 36,800
Interest $368,000 @ 10%/year ' 36,800
Insurance and
Taxes $368,000 @ 4%/year 14.700
Total Annual Fixed Charges $ 88,300
3, DIRECT OPERATING COST
Raw Material
Ethylene Trichloride 7.9 KKg
-------
WASTE STREAM NO. 14
TRAIN II
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 60 Kg/Day of Catalyst
Equipment Item
Stripping Column
Associated Heat Exchangers
& Pumps
Carbon Tetrachlorlde Column
Associated Heat Exchangers
& Pumps
Antimony Pentachlorlde Column
Associated Heat Exchangers
& Pumps
Size
15 cm dla-20 trays
15 cm dla-20 trays
15 cm dla-20 trays
Estimated Cost
$ 19,000
21,900
21,900
Subtotal
Engineering @ 10%
Contingency Including freight @ 20%
Total
$ 62,800
6,300
12.600
$ 81,700
V - 110
-------
WASTE STREAM NO. 14
TRAIN II
2, ANNUAL FIXED CHARGES
Depreciation $81,700 @ 10%/year $ 8,170
Interest $81,700
-------
References and Bibliography
1. TRW Systems Group. Assessment of Industrial Hazardous Waste Practices,
Organic Chemicals, Pesticides and Explosives Industries, Redondo Beach,
Environmental Protection Publication, Report SW-118C, 1976.
2. Mark, H. F., J. J. McKetta, D. F. Othmer, and A. Stamden. Kirk-Othmer
Encyclopedia of Chemical Technology, 2nd Ed. New York Interscience
Publishers, John Wiley and Sons, 1965.
3. United States Patent Number 3,760,039, September 18, 1973, Washington,
D. C., Ertel Et Al.
4. Chemical Market Reporter, September 20, 1976, Volume 210, Number 12,
New York. Schnell Publishing Company, Inc.
5. Ottinger, R. S., J. L. Blumenthal, D. F. Dal Porto, G. I. Gruber, M. J.
Santy, and C. C. Smith. Recommended Methods of Reduction,
Neutralization, Recovery, or Disposal of Hazardous Waste. Volume II,
Toadcologic Summary. Redondo Beach, Environmental Protection
Publication 224-581, 1973.
6. Arthur D. Little, Inc. Application of Physical, Chemical and Biological
Treatment Techniques to Hazardous Waste Management. Cambridge. 2V.
Environmental Protection Contract 68-01-3554, 1976.
7. Incarus Corporation. Capital and Operating Costs of Pollution Control
Equipment Modules. Silver Spring. 2V. Environmental Protection
Publication EPA-R5-73-023a, 1973.
8. Personal Communication. E. P. Grumpier, Environmental Protection Agency,
to J. M. Genser, Processes Research, Inc., October 14, 1976.
V - 112
-------
Still Bottoms From Fractionating Column
Chlorotoluene (Benzyl Chloride) Manufacture - Waste Stream No. 15
Waste Stream Description. Benzyl chloride is commercially produced by
the following methods:
1. Boiling toluene is chlorinated in the absence of light and the reac-
tion mixture is then agitated with a mild alkali and distilled.1'3
2. Toluene and chlorine are mixed continuously in the vapor phase.1'2
The last step in either process is distillation where the benzyl
chloride as a product is taken from the overhead of the fractionating column.
The bottoms from the fractionating column is a waste product containing 0.0005
kg of benzyl chloride and 0.0005 kg of benzo-trichloride per kg of the product
benzyl chloride. This potentially hazardous waste is then discharged to
2
chemical land disposal. See Figure 5-25.
In 1972 production of alpha-chlorotoluene (benzyl chloride) in the
United States was 36,500 metric tons. The typical process facilities were
estimated to range in size from 10,000 to 15,000 metric tons per year.2
For the purposes of this study an annual plant capacity of 15,000
t
metric tons has been assumed and is based on operating 24 hours per day, 300
days per year.
The corresponding waste stream from the average fractionating column
is about 15 metric tons per year having the following approximate composition:
Component Metric Tons
Benzyl Chloride 7.5
Benzotrichloride 7.5
V - 113
-------
BASIS: 1 KG a - CHLOROTOLUENE (BENZYL CHLORIDE)
TOLUENE 0.730
CHLORINE 0.564
REACTOR
0.289
HCC-TO
BYPRODUCT
RECOVERY
REFLUX
CONDENSER
TOLUENE
(TO RECYCLE)
FRACTIONATIN"
COLUMN
FRACTIONATING
COLUMN
1.0 BENZYLChLORIDE
FRACTIONATING COLUMN BOTTOMS
BENZYLCHLORIOE 0.0005
BENZOTRICHLORIDE 0.0005
LAND
STILL BOTTOMS FROM FRACTIONATING COLUMN,
WASTE STREAM NO. 15
FIGURE 5-25 CHLOROTOLUENE MANUFACTURE
-------
Existing Treatment Method. The most prevalent method of disposal for
the fractionating column waste stream is landfill.
Alternative Treatment Methods. Although no proven methods of waste
recovery have been developed to date, it may be possible to use hydrogenation
and then recycle the streams back to the initial process. This system would
have to be developed in a pilot prior to installation in a commercial plant.
At present this would be hard to justify economically, because the recovered
costs for benzyl chloride and benzotrlchlorlde waste from a plant that pro-
duces 15,000 metric tons of chlorotoluene per year is only $12,400 per year,
•
Controlled incineration of this waste stream is possible but the costs
would be very difficult to justify.
Another method of disposing of the waste stream would be to collect
and transport it to a plant for chlorinolysis if one exists in the area.
On the basis of the analysis of the problem and review of the various
alternates, including incineration and chlorinolysis, it would seem that
chemical land disposal is still the most practical method of disposal of this
relatively small annual waste stream tonnage coming from the manufacture of
chlorotoluene.
I
V - 115
-------
REFERENCES
1. TRW Systems Group. Recommended Methods of Reduction, Neutralization, Recov-
ery, or Disposal of Hazardous Waste. Volume X, Profile Report. Environ-
mental Protection Agency Report No. EPA-670/2-73-053-J; August 1973.
2. TRW Systems Group. Assessment of Industrial Hazardous Waste Practices:
Organic Checmials, Pesticides and Explosives Industries: Environmental
Protection Publication, Report SW-118C, 1976.
3. The Condensed Chemical Dictionary, Eighth Edition, Revised by Gessner G.
Hawley, Van Nostrand Reinhold Company.
4. Chemical Marketing Reporter, September 20, 1976 Volume 210, Number 12 New
York Schnell Publishing Company, Inc.
5. Arthur D. Little, Inc. Analysis of Potential Application of Physical, Chem-
ical and Biological Treatment Techniques to Hazardous Waste Management.
Cambridge, Mass. Environmental Protection Agency Contract No. 68-01-3554,
1976 (chlorinolysis).
V - 116
-------
Distillation Residues From Batch Fractionating Towers
Chlorobenzene Manufacture - Waste Stream No. 16
Waste Stream Description. Chlorobenzene is commercially produced by
the following methods:
A, In batch process plants liquid phase dry benzene is pumped into a
glass-lined reactor to which iron filings acting as catalyst are added. Gaseous
chlorine is bubbled in at a rate to maintain 50C to produce crude Chloroben-
zene. The product is neutralized, allowed to settle and separate. Further
1 9
batch fractionating produces mono and dichlorobenzene. » The residues from
the fractionating tower are a waste product containing 0,004 kg of chloroben-
zene, 0.0001 kg of dichlorobenzene and 0.0399 kg of polychlorinated aromatic
resinous materials per kg of the product Chlorobenzene. This potentially hazard-
2
ous waste is then discharged to land disposal. See flow sheet Figure 5-26,
The purpose of this study is to evaluate potential alternative treatment methods
for disposing of these residues.
In 1973 production of Chlorobenzene in the United States was 180,000
A
metric tons. The typical process facilities are estimated at 32,000 metric
tons per year,^ operating 24 hours per day, 300 days per year.
The corresponding waste stream from the average size distillation
column is about 1,400 metric tons per year having the following approximate
i
composition:
V - 117
-------
CHLOROOEKZENES MANUFACTURE
BASIS: 1 M MONO CHLOROBENZENE
BENZENE 0.95
CHLORINE 0.875
00
CHLORINATOR
WATER
VENT
0.00135
BENZENE OR CHLOROBEHZENE
NEUTRALIZER
DICHLOR03ENZEME
SLUDGE TO RECOVERY'
SETTLER
BENZENE AND WATER 0.038
BENZENE AND CHLOROBENZENE 0.15
CHLOROGENZENE 1.0
CHLOROQENZE1IE AND
DICHLOROBENZENE 0.18
POLYCHLORINATEO AROMATIC
RESINOUS MATERIALS
AND LOSS 0.044
BATCH FRACTIONATING TOWERS
HC1 SCRUBBER VENT
HC1 0.0014
AIR
WASH STREAM DICHLOROBENZENE COLUMN
CHLOROBENZENE 0.00088
DICHLOROBENZENE 0.0037
I
WATER
ORTHO-DICHLOROBENZENE COLUH1 WASTE
CHLOROBENZENE 0.004
DICHLOROBENZENE 0.0001
I
LAND
DISTILLATION RESIDUES FROM BATCH FRACTIONATING TOWERS,
WASTE STREAM NO. 16
FIGURE 5-26 CHLOROBENZENE MANUFACTURE
-------
Component Metric Tons Per Year
Chlorobenzene 128
Dlchlorobenzene 3
Polychlorinated Aromatic Resinous Materials 1,280
Total 1,411
Existing Treatment Method. The most prevalent method of disposal for
the distillation column waste stream is landfill. Based on a production of
180,000 metric tons of chlorobenzene the total quantity of waste for landfill
would be 7,875 metric tons per year.
Alternative Treatment Methods. One possible method of handling the
waste stream from the manufacture of chlorobenzene would be to transport it to
a plant for chlorinolysis. One chlorinolysis plant producing carbon tetrachlo-
ride could handle the waste streams from several plants which would alleviate
the disposal problem in that particular area.
A more practical method is to dispose of the waste by controlled incin-
eration. This is discussed in the Incineration Section of this report.
V - 119
-------
REFERENCES
1. TRW Systems Group. Recommended Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste. Volume X, Profile Report.
Environmental Protection Agency Report No. EPA-670/2-73-053-J, August
1973.
2. TRW Systems Group. Assessment of Industrial Hazardous Waste Practices:
Organic Chemicals, Pesticides and Explosives Industries: Environmental
Protection Publication, Report SW-118C, 1976.
3. G. Hawley Gessner, The Condensed Chemical Dictionary, Eighth Edition,
Revised by Van Nostrand Reinhold Company.
4. John A. Riddick and William 8. Bunger, Organic Solvents, Techniques of
Chemistry, Volume II Physical Properties and Methods of Purification,
Third Edition, by Wiley - Interscience, A Division of John Wiley & Sons,
Inc.
5. Arthur D. Little, Inc. Analysis of Potential Application of Physical,
Chemical and Biological Treatment Techniques to Hazardous Waste Manage-
ment. Cambridge, Mass. Environmental Protection Agency Contract No.
68-01-3554, 1976 (Chlorinolysis).
V - 120
-------
Spent Alkali Scrubbing Solution - Cyanuric Chloride Manufacture
in Atrazine Production - Waste Stream No. 17
Waste Stream Description. The spent alkali scrubbing solution is a
waste stream from the manufacture of cyanuric chloride. See Figure 5-27.
Cyanuric chloride is one of the intermediate compounds necessary for the
production of atrazine. Atrazine, a selected herbicide, had a total production
rate in 1972 of 41,000 metric tons. A typical atrazine plant production
rate is 20,000 metric tons per year. In the cyanuric chloride unit,
hydrogen cyanide and chlorine undergo a catalytic polymerization to form
cyanogen chloride and then cyanuric choride.* The catalyst is usually
activated carbon when the reaction is carried out in the gas phase at
350 to 400C, or anhydrous aluminum chloride, boron fluoride, or HC1 for
a liquid phase reaction. The formation reaction 1st
Cl
A
3HCN + 3C1 Catalystv N N
U-j> | ||
Cl—C C—. Cl
\ /
N
Waste gases from the cyanuric chloride manufacturing unit pass through the
alkali scrubber to prevent the emission of hydrogen cyanide and cyanuric
chloride into the atmosphere. For a typical plant of 20,000 metric tons per
year, the total waste stream from the alkali scrubber is 224,600 metric tons
per year of which 90 percent is water. The remaining 10 percent of the
V - 121
-------
C12_
1.107
HC?I
0.405
N)
10
NaOH 0.646
(CM3)2 CHNH2
C,H,HH, „,„., 0.279
• 1 KG ATRAZINE 2 5 2 HaOH 1
-------
waste stream consists of sodium chloride (82 percent), insoluble residues
(14-1/2 percent), excess caustic (3 percent), and cyanuric acid (1/2 percent).
Fyj«ti"g Treatment Methods. The present method of disposal of the
alkali scrubbing wastes from cyanuric acid manufacture is deep well disposal.
This is subsequent to filtration (to remove the insoluble residues) and
neutralization. Deep well injection is not an acceptable means of disposal
for these scrubber wastes, because there is:
1. Possible infiltration of brine into water table.
2. Presence of residues such as sodium cyanide and cyamelide.
3. Nondetoxification of cyanuric acid component.
Selected Alternative Treatment 'Process. To successfully treat the
alkali scrubber wastes from cyanuric chloride manufacture it is necessary to
detoxify the cyanuric acid and insoluble residues, and then treat the
detoxified wastes which are contained within an 8.2 percent saline solution.
A process (see Figure 5-28) that meets these needs would comprise: pH
adjustment followed by ozonation, then biotreatment, plus evaporation and/or
sale.
It is essential, in order for the biotreatment step to be successful,
that the pH of the waste stream be adjusted to between pH 8 and pH 9. It is
doubtful that any significant addition of chemicals would be warranted since
the apparent pH would seem to be approximately 9.4. Adjustment would be
needed only if a process upset in the alkali scrubbing system occurs and
would involve the addition of either sodium hydroxide or hydrochloric acid.
V - 123
-------
<
I
M
10
18° HC1
IKKg/YR
SOX NaCl IKKg/YR
224,600_KKl
YEA!
STREAM N0.(l5
FIG. NO. 5^27
(PROC. FLOW SHEET)
SOLUTION
»^
CKg ^
iAR
» f*~ \
ii
3,25
202,140 KKg H,0
18,417 KKg NaCl
674 KKg NaOH
112 KKg Cyanuric
Acid
3,257 KKg Insolubles
P-
pH
ADJUSTMENT
OZONE
GENERATOR
BOILER FEED
WATER
COMPENSATE
STEAM COMPRESSOR . S~\_
I *Vx
Q
182,000
>£S_
YEAR
OZONATION
3.000 KKg/yr Sludge
} Landfill
MARINE BIOTREATMENT SYSTEM
SALINE
EVAPORATOR
50Z SALT SOLUTION
FOR SALE
38,200 KKi
KKg
YEAR
CYANURIC CHLORIDE MANUFACTURE - SPENT ALKALI SCRUBBING SOLUTION
WASTE STREAJ 17
FIGURE
-------
It has been determined2 that ozonation is effective in the destruction of
cyanuric acid and related cyanide wastes (the insoluble residues) by the
reaction: i
T
c ^\
s ~%. C • 0 + cyanates + other organics
HQ - C C - OH
N. ^ (urea)
H
The ozonation products are considered to be detoxified and suitable for
biotreatment. The only problem which exists in using normal biotreatment
methods is the presence of an 8 percent saline solution. Since the micro-
organisms normally associated with conventional aerobic and/or anaerobic
treatment systems will not exist in a salt solution, it would seem, there-
fore, that biotreatment of these detoxified wastes would be extremely
difficult. However, there is a novel method of biotreatment known as a
"marine" biopond. In a marine type biotreatment system, microorganisms,
'and possibly other forms of life such as algae, are taken from the sea and
'acclimated to the wastes in much the same manner as a conventional biological
treatment system. These organisms will feed on the ozonated products of
the residues and cyanuric acid and destroy them. As was previously stated, ;
the pH of the mixture should be maintained between pH 8 and pH 9, due to
the fact that this is the range of seawater and the microorganisms needed
for marine biotreatment will live best in this condition.
V - 125
-------
Once biotreatment has been accomplished, the brine stream must be
concentrated to aid in final disposal. This is necessary due to the magnitude
(approximately 850 liters per minute) of the stream. A "flat-plate vapor
compression" evaporator has been commercially demonstrated to have the
q
ability to desalt cooling water and treat certain industrial wastes.-*
In this evaporator (Figure No. 5-28) the salt stream is fed from the feed
pump through a heat exchanger, a deaerator and then into the body of the
evaporator. The stream in the evaporator body is circulated to the top
where it falls as a thin film over the internal heating elements and back
down into the bottom of the evaporator. Vapors generated from this enter
a compressor where they are further heated, due to the compression effect,
to a higher temperature. These hot vapors flow into the internal heating
elements of the evaporator and condense, evaporating more of the solution.
The condensate then flows through the heat exchanger where it preheats the
feed stream. This condensate, being essentially pure water, may then be
used as either boiler feedwater or cooling tower makeup water.
The ozonation and biological treatment steps are expected to eliminate
virtually all of the cyanuric acid and insoluble residues. The residues from
ozonation and biological treatment steps will exist as an inert sludge in
the biopond, and can be disposed of In a chemical land disposal. From the
evaporator there will be two streams. The first, the steam condensate, will
be returned for use as boiler feedwater at a rate of approximately 630 liters
per minute. The second stream, consisting of sodium chloride; sodium
V -126
-------
Feed
Otailliu
| Brine feed
K^.j Slum
I 1 Compressed »te«m
Oittillate
I Concentr»ted brine
VAPOR COMPRESSION EVAPORATOR
FIGURE 5-29
V - 127
-------
hydroxide, and water, contains almost 50 percent solids and is emitted at
a rate of 8,190 kg per hour. This represents a reduction of 82 percent in
the mass of the waste stream.
The salt stream from the evaporator, consisting of sodium chloride and
sodium hydroxide, may be disposed of through sale to a chemical user such as
a chlorine-caustic plant or pigments producer.
Benefits and Environmental Advantages and Disadvantages. The treatment
methods selected for the disposal of alkali scrubbing wastes from cyanuric
chloride offer the following benefits:
1. Ozonation will oxidize the cyanuric acid and other "cyanide" compounds
in the insoluble residues to cyanates (CNO~) and other less toxic
compounds. Hydrolysis will further degrade the cyanate complex to
nitrogen, ammonia, and carbon dioxide.
2. The technology of ozonation is well established. Many suppliers of
ozone systems exist within the United States.
3. A marine type biological treatment system could be expected to
provide a satisfactory method of disposing of waste organic matter
mixed in with saltwater streams.
4. After biological treatment, the use of the evaporator to concentrate
the salt stream will allow reuse of almost 182,000 metric tons per
year of water which can be used for boiler feed. This represents
a potential savings of $24,000 per year for the water and over
$250,000 per year additional if the sodium chloride-sodium hydroxide
stream is sold to a chlorine-caustic plant.
I
V - 128
-------
Environmentally, the treatment method proposed for the cyanuric chloride
scrubbing wastes has several advantages. These are:
1. Elimination of the need for deep well disposal.
2. Air emissions are negligible from the pH adjustment, ozonation,
biological treatment, and evaporation processes. These will consist
i
mainly of some ozone from the ozonation pond, and nitrogen and
CO2 mostly from the biological treatment section, and some as
products of oxidation from the ozonation process.
3. Since the condensate from the evaporator is recycled as cooling
tower makeup or boiler feedwater, and the concentrated salt stream
Is used as an industrial raw material, both water and land destined
wastes are eliminated.
The environmental disadvantages of the treatment processes are:
1. Sludge from the marine type biological treatment system (estimated
at approximately 3,000 metric tons per year) will have to be
disposed of in a chemical landfill. This disposal choice is due to
the salt content contained within the sludge.
2. Approximately 20 percent more ozone and air will have to be used in
the ozonation and biotreatment systems, respectively, than normally
would be expected.4 This is caused by the lower solubility of gases
in saltwater than in "fresh" water. The specific disadvantage occurs
at the ozonation system where this additional usage will result in
additional ozone discharges to the atmosphere.
V - 129
-------
Cost Analysis. The cost analysis is based on a plant producing
20,000 KKg per year of atrazine operating 24 hours per day and 300 days per
year. A summary of capital cost, annual operating cost, and the cost Impact
for waste treatment follows.
V - 130
-------
WASTE STREAM NO. 17
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 748.7 KKg/Day of Waste Scrubbing Solution
Equipment Item Estimated Cost
pH Adjustment 681,000 A/day $ 109,500
Ozonation Lagoon 681,000 i/day 262,800
Biological Treatment System 681,000 Jt/day 94,900
Evaporator 681,000 I/day 1,168,000
Ozone Generator 1,413,000
Subtotal $ 3,048,200
Engineering @ 10% 304,800
Contingency including freight @ 20% 609,600
Total $ 3,962,600
V - 131
-------
WATER STREAM NO. 17
2. ANNUAL FIXED CHARGES
Depreciation $ 3,962,600 @ 10%/year $ 396,300
Interest $ 3,962,000 9 10%/year 396,300
Insurance and
Taxes $ 3,962,000 <§ 4%/year 158.500
Total Annual Fixed Charges $ 951,100
3. DIRECT OPERATING COST
Raw Material $ 200
Utilities 46,700
Maintenance
-------
REFERENCES
1. TRW System Group. Assessment of Industrial Hazardous Waste Practices:
Organic Chemicals, Pesticides and Explosives Industries: Environmental
Protection Publication, Report SW-118C, 1976.
2. Private Communication, Farber, P. S. Processes Research with Emery
Industries, October, 13, 1976.
3. Prescott, James H. "New Evaporation - Step Entry". McGraw-Hill's 1972
Report on Business and the Environment, pp. 5-15
4. Babbit and Baumann. "Sewerage and Sewage Treatment," 8th Edition 1967,
John Wiley & Sons.
V - 133
-------
Spent Activated Carbon From Adsorption Treatment - Trifluralin Manufacturer
Waste Stream No. 18
Waste Stream Description. Trifluralin is an herbicide with a production rate
of about 10,000 metric tons per year in 1972. The compound is produced via the
mixed acid nitration of p - chlorobenzotrifluoride followed by a reaction with
dipropylamine. See Figure 5-30. These reactions are:
1.
+2H20
2.
+NaCl+NaHCO,
Cl
From the amination reactor the process stream is filtered and then decanted to
separate the trifluralin, which is in solution with chloroform (CHC13). The
wastewater stream from the decanter is sent to activated carbon adsorption and
then to biological treatment. The spent activated carbon, from a typical plant
producing 10,000 metric tons of trifluralin per year, amounts to a total of 1150
V - 134
-------
BASIS: 1 KG TRIFLURALIN
in
PCDT O.bl
H!i03 0.43-
I1AKE-UP
.* 1
* NO'lOMITRATOR -*-{'sTORAGEN} ^
1 1 1 \j^- ^X ofco
AC 10 SOLD
NH(C.H.). 0.34
ID 3 7 Z
'Z~ ••-2--3
- . 1 II
1
1 1 * *
STORAGE
»-n n, rilM ^ DlfiTTP/»Tnp *, Ftl TF» 1 » DIHITPO — .» AMIUATlOrj
2 4 1 — — 1 U— . 1 | W CHC1. 1 1 REACTO-R 1
(UOX, SOX. HF. ETC) V—
* 1
SCRU33ER 5PFHT FILTEp
1 '" ' CAKIRlUlit
(TO LAI1U FILL)
WASTE HATER (D
TO BIOLOGICAL
WASTE TREATMENT
•^ T(
-] >i ...^ Af
-^ FILTER B
1
DECANTER j o-SALT
WATER
COHDCNSER • -„,." —Old,
VAC EXHAUST j
TRIFLURALIH
1.0
TO ACTIVATED CARBON
ADSORPTION AND
BIOLOGICAL TREATMENT
Had 0.20
TRIFLURALIH 0.01
SOLVEilT •)
UNREACTEO >0.05
INTERMEDIATES]
SPENT ACTIVATED CARBON FROM ADSORPTION TREATMENT
WASTE STREAM NO. 18
FIGURE 5-30. TRIFLURALIN MANUFACTURE
-------
metric tons per year. Of the total spent carbon waste stream 600 metric tons
per year is spent carbon, 457 metric tons is unreacted intermediates and sol-
vent » and 93 metric tons is trifluralin and related compounds.1
Existing Treatment Methods. At present the existing treatment method for the
spent activated .carbon from trifluralin manufacture is storage in plastic-
lined steel drums. The plastic lining is necessary due to the fluoride content
of the components adsorbed within the carbon and their corrosiveness on bare
steel. This method of disposal is only a short term solution due to the accum-
ulation of drums over the years and the danger of leaks and/or spills from the
drums,
Selected Alternative Treatment Processes. To effectively treat the activated
carbon wastes from trifluralin manufacture it is necessary to first separate
the activated carbon from the wastes and then to treat the separated wastes.
Based on these criteria, the selected treatment scheme, (see Figure No. 5-31,)
for the trifluralin wastes require* the following unit processes:
1. Grinding
2. Solvent Extraction
3. Centrifuga tion
4. Vacuum Stripping, and* Distillation
5. Composting
6. Chemical Landfill
The first step in the alternative treatment processes is grinding the spent
activated carbon. There are several devices which can be utilized for this
V - 136
-------
Stream No. 1
Figure No. 5-30
(Process Flow Sheet)
SPENT CARBON ^.^^
1150 KKg ^^
YEAR
CARBON
STORAGE
tofc
9***
GRINDING
RECOVERED CHLOROFORh
SOLVENT EXTRACTION /
PROCESS RECT
^*
200 KK«»
YEAR
I FC
m>
CLE
)R
Y
SPENT ^^
SOLVENT
STORAGE -*!*
^Ntf^
-r^ W
CENTRIFUGAT
VACUUM
COLUMN
^ CHLOROFORM
' SOLVENT -*l^
EXTRACTION FROM
VACUUM
BTTpnVFUY
ON 1*.^ VACUUM
^*^ DRYER
1 CLEAN SPENT CARBON
600 KKn . .
YEAR
350 KKg/YR
CHEMICAL LANDFILL
COMPOSTING
SPENT ACTIVATED CARBON FROM ADSORPTION TREATMENT
TRIFLURALlN MANUFACTURE - WASTE STREAM NO. 18
FIGURE NO. 5-31
-------
purpose such as & pin mill or a ball mill. The purpose of grinding the spent
activated carbon Is to expose as much surface area as possible to the next
step In the process, solvent extraction.
Since trlfluralin, Its unreacted Intermediates, and the related fluoroaromatlc
compounds are all soluble In chloroform It should be possible to solvent extract
them from the ground-up, spent activated carbon. This extraction Is performed
continuously with extracted carbon and solvent drawn off In separate streams.
The extracted carbon Is next centrlfuged to remove more of the entrained sol-
vent. The recovered spent carbon from centrlfugatlon Is next sent to a vacuum
column where any remaining solvent Is stripped off and condensed. The spent
solvent from the solvent extraction step is combined with the spent solvent
recovered from the centrifuge and vacuum distilled to recover the chloroform
that had been originally trapped in the activated carbon. The chloroform thus
recovered is combined with the chloroform that had been vacuum stripped from the
carbon. It is estimated that 200 metric tons per year of chloroform would be
recovered from the original spent carbon with a worth of approximately $60,000
per year. The remainder of the chloroform would be returned to storage for reuse
in the extraction section of the treatment process.
The cleaned spent carbon (600 metric tons per year) would be sent to composting
for final disposal. At the composting area, the carbon is combined with lime and
buried in windrows for final decomposition by action of soil bacteria, air, and
sunlight. For details of basis for estimating composting, see Waste Stream 12.
The material remaining from the distillation process, after chloroform recovery,
V - 138
-------
consists of trifluralin and related fluroaromatic compounds (93 metric tons
per year), some chloroform and unreacted intermediates (about 260 metric tons
per year). Since nothing is known, at present, as to the nature of the related
fluroaromatic compounds, the only method which is appropriate for final disposal
is a chemical landfill, providing complete long-term protection of the surface
and subsurface waters from the wastes contained within the landfill. Any
leachates are contained, and subsurface flow into the disposal area is elim-
inated.2
Benefits. Environmental Advantages and Disadvantages. The economic benefits
of these treatment processes are:
1. Recovery of approximately 200 metric tons per year of chloroform valued
at about $60,000 per year.
2. Elimination of storage in plastic-lined drums as a means of disposal.
The environmental advantages of the treatment processes are:
1. Elimination of emissions to the air, water, and land.
2. Reduction in volume by over 50 percent of the material which is sent
to the chemical landfill.
i
3. Moderate energy utilization needed for the treatment processes.
The environmental disadvantage of this treatment process is that
chemical landfill is not the most desirable means of final disposal, even
with a volume reduction. It is almost certain that, if more detailed infor-
mation as to the phyBiochemical makeup of the related fluroaromatic compounds
were known, a better means of disposal and resource recovery could be determined.
V - 139
-------
Cost Analysis. The cost analysis is based on a plant producing 10,000 KKg per
year of trifluralin operating 24 hours per day and 300 days per year. A
summary of capital cost, annual operating cost, and the cost impact for waste
v
treatment follows.
V - 140
-------
WASTE STREAM NO. 18
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 3.84 KKg/Day of Spent Carbon
Equipment Item
Carbon Storage Tank
Carbon Conveyor
Grinder
Solvent Extractor 4
Solvent Pumps (3) @ 9,600
Spent Solvent Storage 5
Sludge Pump 1
Centrifuge 1
Solvent Pump
Carbon Conveyor
Vacuum Pump
Vacuum Dryer
Vacuum Column
Column BTMS Pump
Solvent Pump
Subtotal
Engineering @ 10%
Contingency including freight @ 20%
Total
32 M3
500 kg/hr
500 kg/hr
,000 £
20 4/min
,000 I
,000 kg/hr
,000 kg/hr
12 t/min
350 kg/hr
75 kw
350 kg/hr
3 */min
2 4/min
Estimated Cost
$ 148,000
22,000
29,000
74,500
28,800
23,400
21,000
159,000
8,500
44,000
36,500
53,000
177,000
11,300
7,800
$843,800
84,400
168,800
$1,097,000
V - 141
-------
2. ANNUAL FIXED CHARGES
Depreciation $1,097,000 @ 10%/year $ 109,700
Interest $1,097,000 @ lOZ/year 109,700
Insurance and Taxes $1,097,000 @ 4%/year 43,900
Total Annual Fixed Charges 263,300
3. DIRECT OPERATING COST
Raw Material
Utilities $ 19,500
Maintenance 0,04 x 1,097,000 43,900
Direct Labor 12,000 Hrs x 9,0 x 1,5 162.000
Annual Direct Operating Cost $ 225,400
Annual Disposal Cost
Composting 600 KKg @ $9,0/KKg - $5,400
Chemical Landfill $26,000 31,400
Total Annual Cost $ 520,100
Recovered Materials:
Chloroform - 200 KKg x $440 x .7 -61,600
Net Total Annual Cost $ 458,500
4. COST PER KKg PRODUCT $458.500 + 10.000 KKe $ 46.
5. COST PER KKg WASTE $458,500 * 1,150 $ 400.
6. IMPACT ON PRODUCT COST
0.37%
(Market value of 1 KKg product - $12,290)
Cost/KKg t Market value/KKg - $45.85 * $12,290 0.37Z
V - 142
-------
REFERENCES
1. Arthur D. Little, Inc., Assessment of Industrial Hazardous Waste Practices:
Organic Chemicals, Pesticides and Explosives Industries, Cambridge, Mass.
EPA Contract No. 68-01-2919, Pages 5-92.
2. Landfill Disposal of Hazardous Wastes - A Review of Literature and Known
Approaches. EPA/530/SW-165. Sept. 1975 Page 5.
V - 143
-------
Filter Cake Solids - Malathion Manufacture - Waste Stream No, 19
Waste Stream Description, In the manufacture of malathion, see Figure 5-32,
an intermediate compound dimethyl dithiophosphoric acid (DMDTPA), is for-
mulated by reaction of phosphorus pentasulfide and methanol in a toluene solu-
tion, the reaction being: P2S5 + 4(CH3OH) > H2S + 2(CH30)P-SH. Side
reactions which take place simultaneously with the formation of the dimethyl
dithiophosphoric acid produce insoluble reaction products. In order to separate
out these insolubles, the reaction solution is filtered. The discarded filter
i
cake for a typical malathion plant with an annual production rate of 14,000
tons per year totals 1,826 metric tons per year (0,13 Kg per Kg Malathion),
These wastes consist of 1,000 metric tons of filter aid, 756 metric tons of toluene
and insoluble reaction products and 70 metric tons of dimethyl dithiophosphoric
acid.1.2
Existing Treatment Methods. At present, this waste is detoxified with
2
sodium hydroxide and sent to landfill. In the detoxification with sodium
hydroxide it is hypothesized that the following reactions take place:
.P-OH + NaoS +
3NaOH + 2(CH30)2P-SH > NaSH + (CH30)2
I
This method of disposal can still be considered hazardous, because of the
possibility of leakage of materials into groundwater.
Selected Alternative Treatment Processes. The treatment sequences selected
(see Figure No. 5-33) for the spent filter cake from malathion manufacture
require the following steps:
V - 144
-------
BASIS: 1 KG HALATHION
<
I
M
Ol
'2*5 0.389—* OITHJJ
CH3OH 0.224— * "AMD"
TOLUENE 0.024 -r— J2II
KAKE-UP |
I 01
OIETHYLM
0.50!
COHCENSER j •• *£ «- TO CLAUS SULFUR
• RECOVERY PLANT
„__ r
— • " (CH30)ZP{S)SH
STILLATION
OVERHEADS'*
(U.EATE *
FJLTER \— •• F^J^R -. •» TO APPROVED LANDFILL
1
it
H 0 HaOH STEAM
THJON _ J 5TRIPPEP ... -tr» 4A5K I -*\ 5TRIPFERI—
HASTE KATER
OIKETHYL OITHIOPHOSPWRIC ACID 0.005
TOLUENE AND INSOLUBLE
REACTION PRODUCTS 0.054
I
TO APPROVED LANDFILL
TECHNICAL
'KALATHION 1.0
MALATHION MANUFACTURE
FILTER CAKE (^ AND LIQUID PROCESS WASTES (?
WASTE STREAMS NO. 19 AND 20
FIGURE NO. 5-32
NOATHUM 0.01
TOLUEtlE AND •»
tlALATHIOtl I 0.01S
IKPURITIES J
NaOH
I
BARGED TO SEA
-------
Stream No.- 1
Fig. No. 5-32
(Proc. Flow Sheet)
FILTER CAKE
Na OH
1826
1,000 KKg/Yr Filter Aid
756 KKg/Yr Toluene and
Insolubles
70 KKg/Yr Dimethyl Dithlo-
phosphorlc Acid
Y
30
YhAl
HYDROLYSIS
UNIT
<
I
TOLUENE TO RECYCLE,
STRIPPED
STEAM
STRIP?INC
COLUMN
FILTER .CAKE
WATER AND RESIDUAL
WASTES
555 KKg/YR (DRY BASIS)
STEAM
.AERATED LAGOON
ri.OOO KKg/YR (DRY BASIS)
* SLUDGE
COMPOSTING
FILTER CAKE - MALATHION MANUFACTURE
WASTE STREAM NO. 19
FIGURE NO. 5-33
-------
(1) Hydrolysis; (2) Steam stripping; (3) Decantation; (4) Composting;
t
(5) Biological treatment.
The first step in the treatment process is hydrolysis, In this step the
filter cake is combined with a sodium hydroxide solution in a stirred tank.
The chemical reaction is the same as was previously mentioned, that is, the
hydrolysis of dimethyl dithiophosphoric acid to dimethyl thiophsphate. This
results in a partial detoxification of the waste filter cake.
In the next step the partially detoxified filter cake Is steam stripped.
The steam stripping process will remove from the filter cake the entrained
toluene, the hydrolyzed dimethyl dithiophosphoric acid, and any other related
compounds which may have resulted from a reaction of the sodium hydroxide solu-
tion with the Insoluble reaction products. These steam stripped wastes are
sent to a decantation unit for the next step in the treatment process. In the
decantation unit toluene is recovered for reuse back in the original process.
It is estimated that the filter cake would retain about 0,3 Kg toluene per
kilogram of powdered carbon. This could result in a recovery of 300 metric tons
of toluene per year valued at approximately $35,000,
The decantation unit residues, after toluene recovery would be sent to
biological treatment (an aerated lagoon) for final treatment of any residual
wastes. The spent filter cake, which is now relatively clear of all hazardous
components can either be reused as filter aid or, which is more likely,
composted. This composting involves the mixing of the filter cake with lime
and/or limestone and progressively burying it in windrow piles. Powdered
V - 147
-------
carbon by itself will not degrade in a composting operation but will provide
the needed soil porosity. For details of basis for estimating composting, see
Waste Stream 12.
Benefits, Environmental Advantages and Disadvantages. The alternative
treatment method for disposal of spent filter cake from malathion manufacture
has several benefits. These are:
1. Replacement of landfill as a means of disposal with composting. This
is both a benefit and an environmental advantage, since landfill is generally
considered to be a "one time" land use, whereas composting allows the same
land to be used over again at intervals.
2, Recovery of about 1 metric ton per day of toluene with a worth of
$35,000 per year for reuse back into the process.
3. The biological treatment system will Insure that any hazardous materials
not detoxified in the hydrolysis step are reduced to harmless components.
Environmentally the treatment process has the advantage of eliminating any
emissions to the air or water plus the advantages mentioned under the preceding
benefits paragraph.
The environmental disadvantages of this treatment process are:
1. Land is still required to some extent for disposal (composting) even
though direct landfill Itself has been eliminated,
2. The biological treatment process will produce a sludge which must be
disposed of with the cleaned filter cake in the composting area.
Cost Analysis. The cost analysis is based on a plant producing 14,000 KKg
V - 148
-------
per year of malathion operating 24 hours per day and 300 days per year. A
summary of capital cost, annual operating cost, and the cost impact for waste
treatment follows.
V - 149
-------
WASTE STREAM NO. 19
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 6 KKg/Day of Filter Cake
Equipment Item
Sludge Pump
Hydrolysis System
Caustic Pump
Hydrolysis Pump
Stripping Column
Decanter
Toluene Pump
Waste Slurry Pump
Bottoms Pump
Aerated Lagoon
Size
15 */min
8,000 I
1 i/mln
15 A/mln
46 cm dla x 6 m
800 Jl
1 a/min
10 fc/min
10 A/min
1977 Dollars
$ 17,000
45,000
5,000
17,000
57,000
9,000
5,000
15,000
15,000
60,000
Subtotal $ 245,000
Engineering at 10% 24 500
Contingency including freight at 20% 49,000
Total Estimated Installed Capital Cost $ 318,500
V - 150
-------
2. ANNUAL FIXED CHARGES
Depreciation $318,500 @ 10% $ 31,900
Interest $318,500 <§ 10% 31,900
Insurance & Taxes $318,500 <§ 4%/year 12,700
Total Annual Fixed Charges 76,500
3. DIRECT OPERATING COST
Raw Material
50% NaOH - 30 KKg
-------
REFERENCES
1. Mark, H. F., J. J. McKetta, D. F. Othmer, and A. Standen. Kirk-Othtner
Encyclopedia of Chemical Technology, 2nd Ed., New York. Intersclence
Publishers, John Wiley and Sons, 1967.
2. TRW Systems Group, Assessment of Industrial Hazardous Waste Practices:
Organic Chemicals, Pesticides and Explosives Industries, Environmental
Protection Publication, Report SW-118C, 1976.
V - 152
-------
Liquid Process Wastes - Malathion Manufacture
Waste Stream No. 20
Waste Stream Description. In the final phases of the manufacture of
malathion, the crude product stream is purified. This purification consists
of first, a caustic (sodium hydroxide) wash, and second, a steam stripping
operation.* The combined wastes from the washing and stripping steps consti-
tute this waste stream, totaling approximately 14,350 metric tons per year
for a typical 14,000 MI malathion plant. The waste stream consists of 350 metric
tons per year (.025 Kg/Kg malathion) of malathion, toluene, and malathion impuri-
ties, and the remaining 14,000 metric tons per year (1 Kg/Kg malathion) of an
estimated 2 percent sodium hydroxide solution. See Figure 5-33.
Existing Treatment Methods. At present, the liquid process wastes from
malathion manufacture are disposed of by ocean dumping. This method of disposal
is unacceptable for several reasons; first U. S. laws and, in the near future,
international convention, will make this practice Illegal; second, this method
does not make any attempt to detoxify the waste, merely to dispose of it; and
third, no attempt is made to recover the 140 metric tons per year of malathion
(estimated value of $205,000 per year) and approximately 100 metric tons per
year of toluene (estimated value of $11,500 per year).
Selected Alternative Treatment Processes. In order to recover usable
products, reduce the volume of the waste stream and, detoxify the wastes, an
alternative treatment process has been selected based on sedimentation, resin
adsorption with solvent regeneration, vacuum distillation, hydrolysis and finally
biotreatment (composting). Sae Figure No. 5-34.
V - 153
-------
STREAM N0.(?»
FIG. NO. 5-32
(PROC. FLOW SHEETS)
MALATBION
LIQUID „
WASTES *^
14,350 KKg/yr
MALATBION 140 KKg/YR
TOLUENE i MALATHON
IMPURITIES 210 KKg/YR
2Z NaOH 14000 KKg/YR
SEDIMENTATION
TANK
-Jfe^
1
<
I
»-'
Ui
RESIN
COLUMNS
ACETONE
FOR REGENERATION
^MAKEUP ACETONE
0.15 KKg/YR
RECYCLE WATER
AS WASU WATER
12,600 KKg/YR
WATER, 1400 KKg/YR
HALATHION
•fIMPURITIES
225 METRIC TONS
YEAR
TO BE STRENGTHENED WITH
CAUSTIC AND USED FOR
HYDROLYSIS OF MALATHION
FILTER CAKE WASTES
TOLUENE TO RECYCLE
J__ 100 KKg/YR
TOLUENE
RECOVERY
COLUMN
4ALATHION + IMPURITIES
TO PRODUCT BLENDING
2TKKg/YR
ACETONE RECYCLE FOR
REGENERATION OF RESIN
COLUMNS
ACETONE
RECOVERY
COLUMN
MALATHION + IMPURITIES
TO PRODUCT BLENDING
225 KKg/YR
LIQUID WASTES - MALATHION MANUFACTURE
WASTE STREAM NO. 20
FIGURE NO. 5-34
-------
Since the organic waste constituents of the waste stream are a fraction
of the water carrier (about 2.4 percent), it is important to segregate these
from the water in order to reduce the volume of wastes to be treated. Toluene,
being insoluble in water, can be separated from the aqueous waste stream by
sedimentation (decantation). This process involves sending the aqueous waste
stream through a vertical tank with a large length to diameter ratio, and a
long retention time, to allow adequate time for phase separation between the
toluene (specific gravity 0.86) and the aqueous phase (specific gravity about 1).
The toluene recovered will, of course; contain some of the malathion and malathlon
impurities and constitute about 125 metric tons per year. The remainder of the
wastes (14,225 metric tons per year) are sent to resin adsorption.
Resin adsorption is a process for the removal of organic chemicals from
aqueous streams. "Haste treatment by resin adsorption involves 2 basic steps:
(1) contacting the liquid waste stream with the resins to adsorb the solutes
from the solution; and (2) subsequently, regenerating the resins by removing
the adsorbed chemicals...by washing with the proper solvent."^ The resin used
for adsorption is a polymeric adsorbent, generally a cross-linked type polymer
in the form of Insoluble beads. The adsorption of the organic compounds occurs
generally, through van der Waal's interactions which result in an adsorption
onto the surface of the resin. When the resin capability for adsorption is
,1
reached, the sorbate must be removed to allow repeated reuse of the adsorbent.
This is accomplished by backwashing with a solvent (acetone, in this case).
Resin adsorption will remove from the aqueous waste stream the remaining
225 metric tons per year of organ!cs, notably the remaining toluene, malathion,
and malathion Impurities.
V - 155
-------
The eluted wastes from the resin adsorption column and the toluene layer
from the sedimentation process are sent to separate vacuum distillation units.
In the toluene vacuum unit, toluene is distilled off and, about 100 metric tons
per year of toluene recovered for reuse as solvent back in the malathion pro-
cess. This toluene is worth approximately $11,500 per year. In the eluted
waste column, acetone is distilled off and stored for reuse as the elution
agent in the resin adsorption system. The bottoms from the toluene still and
the acetone recovery column are composed of 140 metric tons of malathion and
110 metric tons of malathion impurities. Technical grade malathion contains
3 percent impurities, or 420 metric tons per year from a 14,000 metric ton per
year plant. Addition of the recovered malathion would raise the impurity level
to 3.7 percent. Since malathion is applied as a direct spray onto a field,
a water base emulsion, or a petroleum base solution, it is not expected that
the slight increase in impurity level will have any effect on malathion effec-
tiveness as an Insecticide.
The liquid stream from the resin adsorption column consists of 14,000
metric tons per year of approximately 2 percent sodium hydroxide solution.
The water content of this stream is a combination of both the caustic wash
stream and the condensate from the steam stripping operation. Assuming that
10 percent of this stream is from the condensate, then this amount may be bled
off and the remainder (with a slight addition of sodium hydroxide) reused as
wash water. This recycling of the wash water will save some 250 metric tons
per year of sodium hydroxide and approximately 12,350 metric tons per year of
water. The reuse of this water is possible due to the removal of the organic
V - 156
-------
wastes by the sedimentation and resin adsorption. The bleed stream, 1,400
metric tons per year, contains 28 metric tons per year of sodium hydroxide as
a 2 percent solution. This can be used, with strengthening by additional
caustic, for the hydrolysis process to detoxify spent filter cake of waste
stream No. 19.
Benefits and Environmental Advantages and Disadvantages. The malathion
liquid wastes treatment processes have several benefits over the existing method,
these are: (1) elimination of ocean dumping as a means of disposal; (2) recovery
of toluene and malathion for reuse in the manufacturing process; (3) total
reuse of the water component of the waste stream, either as recycle back in
the malathion process or, as a detoxification aid for the spent malathion filter
cake, and (4) complete elimination of water and land destined wastes. The
environmental disadvantages of the processes are basically that they are energy
utilizers. This is due to the steam requirements for distillation and the elec-
trical pumping needs.
Cost Analysis. The cost analysis is based on a plant producing 14,000 KKg
per year of malathion operating 24 hours per day and 300 days per year. A summary
of capital cost, annual operating cost, and the cost impact for waste treatment
follows.
V - 157
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WASTE STREAM NO. 20
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 47.8 KKg/clay of Liquid Wastes
Equipment Item
Sedimentation System* including
Heated 40,000 I Vessel, Slurry
Pumps and Liquid Pumps
Adsorption System including
Pumps and Regeneration to handle
40 A/min
Distillation System for Acetone
Recovery including Pumps, Heat
Exchangers and a 30 cm dia x 6 m
Column
Distillation System for Toluene
Recovery including Pumps, Heat
Exchangers and a45cmdiax6m>
Column
Estimated Cost
$ 112,000
258,000
70,000
80,000
Subtotal
Engineering at 10%
Contingency including freight at 20%
Total Estimated Installed Capital Cost
$ 520,000
52,000
104,000
$ 676,000
V - 158
-------
WASTE STREAM NO. 20
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 47.8 KKg/day of Liquid Wastes
Equipment Item
Sedimentation System, including
Heated 40,000 I Vessel, Slurry
Pumps and Liquid Pumps
Adsorption System including
Pumps and Regeneration to handle
40 £/min
Distillation System for Acetone
Recovery including Pumps, Heat
Exchangers and a 30 cm dla x 6 m
Column
Distillation System for Toluene
Recovery including Pumps, Heat
Exchangers and a 45 cm dia x 6 m
Column
Estimated Cost
$ 112,000
258,000
70,000
80,000
Subtotal
Engineering at 10%
Contingency including freight at 20%
Total Estimated Installed Capital Cost
$ 520,000
52,000
104,000
$ 676,000
V - 158
-------
wastes by the sedimentation and resin adsorption. The bleed stream, 1,400
metric tons per year, contains 28 metric tons per year of sodium hydroxide as
a 2 percent solution. This can be used, with strengthening by additional
caustic, for the hydrolysis process to detoxify spent filter cake of waste
stream No. 19.
Benefits and Environmental Advantages and Disadvantages. The malathion
liquid wastes treatment processes have several benefits over the existing method,
these are: (1) elimination of ocean dumping as a means of disposal; (2) recovery
of toluene and malathion for reuse in the manufacturing process; (3) total
reuse of the water component of the waste stream, either as recycle back in
the malathion process or, as a detoxification aid for the spent malathion filter
cake, and (4) complete elimination of water and land destined wastes.. The
environmental disadvantages of the processes are basically that they are energy
utilizers. This is due to the steam requirements for distillation and the elec-
trical pumping needs.
Cost Analysis. The cost analysis is based on a plant producing 14,000 KKg
per year of malathion operating 24 hours per day and 300 days per year. A summary
of capital cost, annual operating cost, and the cost impact for waste treatment
follows.
V - 157
-------
Sulfur Sludge From Chlorination Unit - Parathion Manufacture
»
Waste Stream No. 21
Waste Stream Description. Parathion is an organophosphate insecticide
with a typical plant production rate of 20,000 metric tons per year. "The
synthesis of parathion, see Figure 5-35, involves (1) the reaction of phosphorus
pentosulfida with ethanol to produce diethyl dithiosphosphoric acid, (2) the
chlorlnation of the diethyl dithiophosphorlc acid to obtain the product diethyl
chlorothiophosphate...'
The first reaction is:
4(C2H5OH) + P2S5 > 2(C2H50)2 PSH + K^S
which is carried out at a temperature of 50-100C over a period of several
hours. The chlorlnation is generally carried out at a temperature of 10-40C
*•
over several hours and is:
(c2H5o)2 LSH + ci2 *- (c2H5o)2 "cl + HC1 + s
A careful control is kept on the temperature and chlorine ratio to prevent
undesirable side reactions. The elemental sulfur which is formed in the
chlorinator, is assumed, to appear in the form of "microspheres." These'
microspheres will tend to encapsulate both the starting material (diethyl
dlthlophosphoric acid), the chlorination product (diethyl chlorothiophosphate),
and other side reaction materials. For a plant producing 20,000 metric tons
per year of parathion the sulfur sludge from the chlorinator is 2,300 metric
tons per year.
V - 161
-------
to
MAKE
BASIS: 1 KG PARATHION ACET
S02 0.'109 ' SO, 0.210
t t
FLARE INCINERATOR' _J
t i SODIUM
'" CU 0.243 [ . „. P-KITROPHEHOLATE
H,S 0.058 2 . 5 0.115 j
i 1 j(AHD © 1
S5 0-378 COMPOUNDS)
... . ,,,. REACTOR » CHLORINATOR +• PARATHION UNIT
On 0.315 • — — . ——____ — "
-UP
ONE
ACETONE
RECOVERY
.
•- PARATHION 1.0
HC1 °-125 Had 0.188
. PARATHION 0.005
PARTIAL RECOVERY— P-NITROPHENOL .0.005
OTHER ORGANIC PHOSPflATES 0.005
1
* t BIOLOGICAL
«ASTE TREAT1CNT
OTHFR PI ANT »- n. .., .
HASTE SITES .-
{PARATHION <1 ppm)
APPROXIMATaY 80 PERCENT RECOVERY AS 32 PERCENT BY WEIGHT HC1 IN HATER
SULFUR StUDGE FROM CHLOR1HATION UNIT,
WASTE STREAM HO. 21
FIGURE 5-35 PARATHION KANTjFACTURE
-------
2
A sulfur balance Indicates that this sulfur sludge is composed of 93
percent (2,140 metric tons per year) elemental sulfur with the remaining 7 percent
(160 metric tons per year) being organophosphorus compounds. Because the
organophosphorus compounds are toxic, the sludge is classed a potentially
hazardous discharge.
Existing Treatment Methods. The present method of disposal of the waste
chlorinator sludge from parathion manufacture is incineration without controls
for abatement of 802 and phosphorus oxide emissions. This results in emissions
estimated at approximately 4,000 cfm (based on 300' days per year and 8 hours
per day) of which about 20 percent is SO . The magnitude of the emissions of
SO. and phosphorus oxides coupled with the extreme toxicity of the sludge if
not incinerated result in a totally unacceptable means of disposal.
Selected Alternative Treatment Processes. Goals established for an
alternative treatment were: (1) to separate the sulfur, for recovery purposes,
from the organophosphates and (2) to detoxify the organophosphorus compounds.
The following sequence of treatment processes (see Figure No. 5-36) can accom-
plish these purposes: (1) Heated sedimentation; (2) Ultrafiltration; (3) Fil-
tration; (4) Composting with lime and/or limestone.
V - 163
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STREAM NO. 1
FIGURE NO. 5-35
(PROC. FLOW SHEET)
SULFUR SLUDGE
2300 .KKG
YEAR
93Z SULFUR
7Z ORGANOPHOSPHORUS
COMPOUNDS
1
HEATED
SEDIMENTATION
TANK
ULTRAFILTRATION
SYSTEM
RECOVERED SULFUR
TO SALE
2140 KKG
YEAS
DECANTED
ORGANO-PHOS COMPOS
IMPURE
MOLTEN
SULFUR
ORGANO - PHOSPHOROUS
COMPOUNDS
ORGANO - PHOSPHOROUS
COMPOUNDS
+
SULFUR
(FILTER BACK-WASH)
CARTRIDGE FILTRATION
SYSTEM
ORGANO - PHOSPHOROUS COMPOUNDS
160 KKG
YEAR "
COMPOSTING
SULFUR SLUDGE FROM CHLORINATION UNIT
PARATHION MANUFACTURE - WASTE STREAM NO. 21
FIGURE NO. 5-36
-------
The sludge from the chlorinator is first sent to a steam heated sedimentation
tank. The tank operates at a temperature of about 125C, which is 12C over the
melting point of sulfur. The purpose of this tank is to melt the sulfur Component
of the waste stream and, if the organophosphorus components are insoluble in
liquid sulfur, to allow decantation of the insoluble organophosphorus compounds.
The liquid sulfur stream from the heated sedimentation tank is next sent to
ultrafiltratlon.
Ultrafiltratlon is a membrane separation system capable of segregating
dissolved or suspended species from a liquid stream on the basis of size.
In ultrafiltratlon, a porous membrane is sized to retain organic compounds of
molecular weight 150 and greater while allowing liquid sulfur to pass through
has a hydrostatic pressure of up to 10 atmospheres applied to the upstream side
of the supported membrane. A concentrated fluid of the large molecules
(organophosphates) is collected on the upstream side of the membrane while the
smaller molecule liquid sulfur, having passed through the membrane, is
collected on the downstream side of the membrane. It should be noted however
that almost all the work on ultrafiltratlon has been with aqueous solutions.
Extensive research and development work would be required to determine work-
ability of ultrafiltration with liquid sulfur.
The concentrated organophosphorus stream from ultrafiltration and sedimen-
tation is cooled down to ambient temperatures which will allow any retained
sulfur to resolidify. The cooled stream is next reflltered by use of a cart-
ridge type filter to remove the retained sulfur and "polish" the organophosphorus
V - 165
-------
stream. The cartridge filter is cleaned by backflushing with organophosphorus
solution, and this backflush stream is sent back to the heated sedimentation
tank. In this way it is assured that negligible amounts of sulfur exit with
the organophosphorus stream.
The concentrated molten sulfur stream exits onto a trough type conveyor
with cooling coils where it is "cast" into a solid and discharged in solid form
for sale.
\
The organophosphorus compounds (amounting to 160 metric tons per year)
would be sent to composting for final disposal. In the composting area, these
organophosphorus compounds are mixed with lime at the time of composting. This
lime causes a partial detoxification by the reaction:
S S
2(C2H50)2 PSH + Ca(OH)2 ^ Ca(SH)2 + 2(C2H50) P-OH
which (in this case) forms diethyl thiophosphoric acid. The remaining
detoxification occurs over a period of time due to exposure to air degradation
and bacterial action. For details Of basis for estimating composting, see
Waste Stream 12.
Benefits, Environmental Advantages and Disadvantages. The benefits of
the proposed alternative treatment processes are:
1. Recovery of over 2,000 metric tons per year of sulfur for sale.
2. Reduction of final treatment stream to 160 metric tons per year (a
93 percent weight reduction).
3. Exchange of a "final" form of treatment (incineration), which is also
energy intensive, with a "regenerative" form of treatment (composting).
- 166
-------
The environmental advantages of this alternative treatment process are the
elimination of incineration as a means of disposal. Besides requiring a great
deal of energy; incineration of this much sulfur would require extensive air
pollution control methods, most probably in the form of a lime/limestone
scrubbing system. Such a scrubber will produce extensive water pollution and
land disposal problems with regard to the scrubber water and the dewatered
scrubber sludge, respectively.
The environmental disadvantage of the alternative treatment processes is
that composting of organophosphorus compounds can be quite difficult. Additional
tin"* for the organophosphorus compounds to decompose in the composting area
may be necessary to ensure complete detoxification.
Cost Analysis. The cost analysis is based on a plant producing 20,000
KKg per year of parathion operating 24 hours per day and 300 days per year.
A summary of capital cost, annual operating cost, and the cost impact for waste
treatment follows.
V - 167
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WASTE STREAM NO. 21
1. ESTIMATED INSTALLED CAPITAL COST
BASIS? 7,67 KKg/Day of Sulfur Sludge
Equipment Item Estimated Cost
Sludge Pump 3 £/min $ 14,600
Sedimentation Tank 6,000 I 45,700
Sulfur Pump 9 Jl/min 8,900
Ultrafiltration System 10 Jl/min 4,400
Organophosphorus Pump 2 Jl/min 13,100
Sulfur Pump 8 Jl/min 8,900
•. Cartridge Filter 2 Jl/min , 13,100
Sulfur Conveyors 900 kg/hr 44,000
Organophosphorus Storage Tank 2500 I 14,600
Subtotal $167,000
Engineering <§ 10% 16,700
Contingency including freight @ 20% 33,400
Total $ 216,100
V - 168
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2. ANNUAL FIXED CHARGES
Depreciation $216,100 @ 10%/yr $ 21,600
Interest $216,100 @ 10%/yr 21,600
Insurance and Taxes $216,100 @ 4%/yr 8.600
Total Annual Fixed Charges 51,800
3. DIRECT OPERATING COST
Raw Material
Utilities $ 94,800
Maintenance 0,04 x 216,100 8,600
Direct Labor 7200 x 9.0 x 1.5 97.200
Annual Direct Operating Cost $ 200,600
Annual Composting and Leachate
160 KKg x 9.0 per KKg 1.500
Total Annual Cost $ 253,900
Recovered Materials
Sulfur <§ 58.00/KKg
58 x 0.7 - 40,60 x 2140 KKg -86.900
Net Total Annual Cost $ 167,000
4. COST PER KKg PRODUCT $167,000 t 20,000 KKg $ 8.35
5. COST PER KKft WASTE $167,000 + 2,300 KKg $ 73.
6. IMPACT ON PRODUCT COST
(Market value of 1 KKg product - $1,918)
Cost/KKg * Market value/KKg • $8.35 t $1,918 0.44X
V - 169
-------
REFERENCES
1. TRW Systems Group, Assessment of Industrial Hazardous Waste Practices.
Organic Chemicals, Pesticides and Explosives Industries, EPA
Contract 68-01-2919, Page 5-97.
2. TRW Systems Group, Assessment of Industrial Hazardous Waste Practices.
Organic Chemicals, Pesticides and Explosives Industries, EPA
Contract 68-01-2919, Page 5-99.
3. Arthur D. Little, Inc., Analysis of Potential Application of Physical,
Chemical, and Biological Treatment Techniques to Hazardous Waste
Management, Cambridge, Mass. EPA Contract 68-01-3554, Ultrafiltration
Section, Page 1.
V - 170
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Spent Activated Carbon - Explosives Manufacture
Waste Stream No. 22
Waste Stream Description. In the manufacture and handling of TNT and other
nitrated aromatic explosives, a variety of pollutants is generated, two general
classes of which are considered in this report. The first is "red water",
which is a 3 to 35 percent solids aqueous effluent produced by the purification
of TNT by the sellits process. Although the exact composition of red water is
not known, It is believed to contain sulfite salts, asymmetrical isomers of
6
TNT, and isomers of DNT (dinitrotoluene). Upon exposure to sunlight, the
0
initially colorless solution assumes a deep red appearance. Red water, when
Indiscriminately discharged into local streams would clearly present a serious
pollution problem.
"Pink water", a less concentrated form of "red water", is also photochemically
active and is primarily the result of the 2, 4, 6 isomer of TNT dissolved In
water. Pink water is generated principally from the washdown of equipment and
facilities at Load/Assembly/Pack (LAP) plants, and from the concentration of
red water In multiple effect evaporators (as practiced for example at the
Joliet Arnji Ammunition Plant) where the evaporator condensate is contaminated
with TNT waste products.
Adsorption onto activated carbon has been shown to be an effective means
i
by which the concentration of TNT in "pink" water from LAP plant washdown and
from evaporator condensate can be reduced from as high as 300 ppm to an acceptable
level of less than 1 ppm. Both the Joliet AAP and the Iowa AAP currently employ
V - 171
-------
carbon adsorption processes as integral parts of wastewater treatment facilities
o
on LAP production lines, and the Joliet AAP is in the process of installing an
activated carbon treatment system for their red water evaporator condensate.*
The projected future applications of activated carbon at each of the above-
mentioned plants may require the consumption of one ton or more of carbon per
day at each plant.
Existing Treatment Methods. At present, the spent TNT saturated carbon
at both the Joliet and Iowa AAP is being disposed of by open burning; a process
which, due to the nature of the material burned, results-in the-formation of
considerable amounts of NO and particulate emissions. The conversion of water-
X
borne to airborne pollutants is not an acceptable method of pollution abatement.
Open burning is also a costly process since no further utilization of the carbon,
either for adsorption or as an energy source, is made.''
There is, at this date, no industrial installation in operation for
regeneration of explosive saturated carbon.
Selected Alternative Treatment Processes. Alternative treatment processes
.for disposal of explosive saturated spent activated carbon must fulfill the
following criteria: (1) safety of operating personnel; (2) environmentally
acceptable emissions; (3) ease of disposal of final waste products. Based on
these criteria, two treatment systems have been selected for consideration and
analysis. The first is solvent regeneration, whereby the carbon is backwashed
with a suitable solvent, and the adsorbed nitrated aromatic explosive is stripped
off. The regenerated carbon would then be reused and the effluent solvent would
be distilled and also reused in subsequent regenerations. The still bottoms
V - 172
-------
would be either processed for recovery of any marketable values, or more
' t
probably incinerated under closely controlled conditions. The second alterna-
tive is thermal regeneration where the spent carbon would be removed from the
column to a furnace and heated in an oiqrgen-poor atmosphere. The adsorbed
material would be desorbed via its own thermal decomposition after which the
carbon would be quenched and returned to the adsorption column for reuse.
Laboratory studies have already been made using the above methods of treatment.
Among these are: (1) a bench scale study of the regeneration of TNT laden
activated carbon with toluene performed at the chemical laboratory, Edgewood
Arsenal; (2) a pilot plant scale study of the solvent regeneration performed
by Iowa AAP; (3) a study of the thermal regeneration of carbon by a fluidized
bed furnace performed jointly by Esso Research and Iowa AAP.
Thermal regeneration appears to be the more promising of the two spent i
carbon processing systems and is the system pursued in this report. A TNT
batch operation consisting of six lines and producing 308 KKg/d (92,400 KKg/yr)
is used as the standard plant size for this study. A flow diagram of the process
is given in Figure No. 5-37.
Benefits and Environmental Advantages and Disadvantages of Thermal
Regeneration Compared With Total Incineration
1. Advantages. The regenerated carbon recovers 50 percent of the
activity value of the reused carbon, and eliminates the disposal problem of
i
spent carbon. The only solid waste being 25 Kg of ash per day. Environ-
mentally, both the controlled incineration and carbon regeneration processes
will emit no pollution stream. (Processing of the scrubber wastes is not covered
in this report.)
V - 173
-------
141 KKg/YR WATER
141 KKg/YR SPENT CARBON
59 KKg/YR NITRO BODIES HOT COMBUSTION
WATER
SPRAY
WATER
<
l'' '
CENTRIFUGE
OVERBED
GAS OR OIL
OVERBED
COMBUSTION AIR
—^
t
QUENCH
UNIT
RECYCLE CARBON
1 -^»
COOLED *^
70.5 KKg/YR
GASES
< COMBUSTION GAS
OR FUEL OIL
COMBUSTION AIR
VENT
SPENT ACTIVATED CARBON EXPLOSIVES MANUFACTURE
WASTE STREAM NO. 22
FIGURE NO. 5-37
TREAT
70.5 KKg/YR
ACTIVATED CARBON
-------
2. Disadvantages
ja. The regenerated carbon Is only 50 percent as efficient as
the original activated carbon.
b_. The regeneration process causes an attrition loss of 50
percent of the spent carbon feed.
Cost Analysis. The cost analysis is based on a plant producing 93,000 KKg
per year of TNT operating 24 hours per day and 300 days per year. A summary of
capital cost, annual operating cost, and the cost impact for waste treatment
follows.
V - 175
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WASTE STREAM NO. 22
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 0.47 KKg/Day of Spent Carbon
Equipment Item Size Estimated Cost
Fluid Bed Incinerator 1.52 M dia $ 365,000
Packed Scrubber 45.7 cm dia 32.300
Blower 5.6 KW 8,900
Pump 38 Jl/min 6,700
Stack 25 cm dia x 30 M 6,700
Drum Storage 350-200 I Drums 8,800
Hopper 380 £ 24,400
Rotary Feeder 0,4 KW 1,800
Three Screw Conveyors 1.5 KW Each 96,300
Quench Tank 380 I 24,400
Storage Bin 3800 I 27,600
Subtotal $ 602,900
Engineering @ 10% 60,300
Contingency including freight @ 20% 120,600
Total . $ 783,800
V - 176
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WASTE STREAM NO. 22
2. ANNUAL FIXED CHARGES
Depreciation $783,800 @ 10%/year $ 78,400
Interest $783,800 @ 10%/year 78,400
Insurance and
Taxes $783,800 9 4%/year 31,400
Total Annual Fixed Charges $ 188,200
3. DIRECT OPERATING COST
Raw Material
Utilities $ 8,800
Maintenance 0.04 x 783,800 31,400
Direct Labor
1200 MH x 9.00 x 1.5 16,200
Annual Direct Operating Cost $ 56,400
Annual Disposal Cost 0
Total Annual Cost $ 244,600
Recovered Materials :
Activated Carbon 70.5 KKg x 1102/KKg x 0.7 -54.400
Net Total Annual Cost $ 190,200
4. COST PER KKg PRODUCT $ 190,200 t 93,000 $ 2.05
5. COST PER KKg WASTE (Wet Basis) $190,200 * 341
(Dry Basis) $190,200 * 200 $951.
6. IMPACT OH PRODUCT COST
(Market value of 1 KKg product - NA)
Cost/KKg * Market value/KKg • NA
V - 177
-------
REFERENCES
1. Draft Copy of Economic Evaluation of the Solvent and Thermal Regeneration
of TNT Laden Activated Carbon - 1st Lieutenant Donald F. Dustin, Edgewood
Arsenal, Aberdeen Proving Ground, Maryland - April 1975.
2. TNT Industrial Waste Treatment - WPC FY-73, MCA, Line Item 25 Joliet AAP,
Joliet, Illinois.
3. J.L. Rizzo - Manager Filtrasorb Department - Calgon Corporation - Telephone
Communication. September 1976.
4. Illinois Water Treatment Co. Project #1073 Report for A.M. Kinney, Inc.,
September 13, 1976.
5. Illinois Water Treatment Co. Project #1073 Report for A.M. Kinney, Inc.,
May 14, 1975.
6. Advanced Wastewater Treatment Seminar Manual, by Gulp. Wesner, Gulp, and
Benjes (pages 4-33) October 1975.
7. Telephone Conversation with Walker Process Division, Chicago Bridge and Iron
(Bruce Russard August 14, 1973).
V - 178
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Red Water - Explosives Manufacture
Waste Stream No. 23
Waste Stream Description. The purification of crude TNT by neutraliza-
tion with soda ash and washing with sellite (a solution of sodium sulfite)
results in the generation of an alkaline red colored aqueous waste containing
TNT impurities (sodium salts of dinitrotoluenesulfonic acids) and other organic
and inorganic salts. See Figure 5-38. The red water from batch TNT produc-
tion is considerably more dilute than that from the new continuous TNT;lines
(3 to 5 percent vs. 30 to 35 percent solids).!
Red water* is alkaline, with a pH of approximately 8.0, and is practi-
cally odorless. Red water from batch TNT production contains from 100,000 to
300,000 ppm of color bodies, whereas that from continuous TNT lines (Radford
AAP) contains up to 9 percent (90,000 ppm) of color producing nitrobodies.*
The color intensity in TNT waste streams increases with increase of pH, light
intensity, temperature, chemical dosages, and time of exposure to the above
variables. Essentially, the result is the color in red water.*
Existing Treatment Methods!. Currently the production rate of TNT is
low with a resultant relatively small quantity of red water produced. This
is now disposed of through sale to Kraft pulp mills. Because of the small
market, this method of disposal is viewed as only a temporary solution. Under
full production conditions, the red water generated is normally disposed of
by incineration.
*A nitrobody is any organic nitrated by-product from an explosives manufactur-
ing operation.
V - 179
-------
OUUM (CURRENTLY PURCHASED)
00
o
STRONG NITRIC
ANHYDROUS AMWNIA
TOLUENE
60S HN03
(FROM AOP)
-------
The batch TNT process red water is neutralized with sulfuric acid, concen-
trated by evaporation, and the concentrate incinerated in a rotary kiln. (See
Figure No. 5-39). Red water from continuous TNT process (Radford AAP) is fed
to a concentrator evaporator to increase the solids to 40 percent and then to
a rotary kiln for incineration.
Since the quantity of ash produced is significant (0.19. kilogram p
kilogram of TNT manufactured) large piles of ash have accumulated at some
TNT production sites. At one plant the ash has been disposed of by land
burial.1
Because of the environmental inadequacies of the disposal methods, a
considerable amount of effort is directed toward developing methods for the
utilization and recycle of red water ash.
Selected Alternate Treatment Process. Alternate treatment processes
for disposal of red water must fulfill the following criteria:
1. Safety of operating personnel; 2. Environmentally acceptable
emissions: 3. Ease of disposal of final waste products.
Based on the above criteria, several treatment systems were considered,
including a fluid bed reactor reduction process, the Tampella process, and a
red water acidification process.1
In fluidized bed reduction the ash resulting from red water incineration
is ground and reacted with carbon monoxide which also serves to fluidize the
solids. Carbon monoxide is generated by reacting coke with carbon dioxide.
The process produces sodium carbonate and I^S which can be used (after con-
version of H2S to 802) to produce sellite solution for recycling. The fluid-
ized bed reduction process ha<-, been evaluated in laboratory bench-scale tests.
V - 181
-------
STREAM NO. (T
FIG. KO. 5-38
PROC. FLOW SHEET
RED WATER
RESIDUAL H2S04
FINAL-
DISCHARGE STEAM'
FROM TNT
PROCESS AT
^52 SOLIDS
<
I
M
00
QUADRUPLE
EFFECT
EVAPORATOR
THICK LIQUOR.
|AT 40X SOLIDS
STACK
(CURRENT)
LOAD AND SHIP
TO PAPER HILLS
CONDENSATE. CONTAINING
NITRODODIES, TO DITCH
(CURROIT-UI FUTURE WILL
GO THROUGH ACTIVATED
CARBON ADSORPTION PRIOR
TO DISCHARGE)
(IN FUTURE, WILL
PROBABLY GO TO
SPRAY-TOWER SCRUBBERS)
STORAGE
TANKS
STORAGE PILE,
Ufl°ROTECTED
I
46m x 267m x 20m (100 K TONNES)
(LOAM SUBSURFACE)
ffUWKER C
(HO. 6 FUEL OIL)
ASH, AT 320-430'C
c
HOPPERS
LOAD AND
SHIP TO
PAPER MILLS
RED WATER WASTE DISPOSAL PROCESS ( JOLIET AAP )
WASTE STREAM NO. 23
FIGURE NO. 5-39
-------
In the Tampella process, pulverized coal is added to the concentrated
4
red water and the mixture is incinerated to produce a sodium carbonate smelt
plus gaseous hydrogen sulfide; these are used to produce sellite for recycl-
ing. This process has been tested in pilot-plant studies. (See Figure No. 5-
40)
In red water acidification, the wastewater pH is lowered by the addition
of acid. Steam is then added to convert the nitrotoluene sulfonates in the
red water to such useful^compounds as diaminotoluene and dinitrotoluene. The
red water acidification process is in the laboratory bench-scale evaluation
stage.
Of the three systems the Tampella process appears to be the most
promising and has been selected as the alternate treatment process.
Benefits and Environmental Advantages and Disadvantages. The Tampella
process is superior to the existing rotary kiln incineration process in the
following respects:
1. Recovery of Resource Material. Essentially all of the original sel-
lite in the TNT wash is dissociated in the incineration stage (possibly)
and recombined as follows:
(Eq 1) Na2so3+ Heat V Na20+S027'
(Eq 2) Na2o+C02(from coal combustion) ^ Na2C03
(Eq 3) Na2co3+S02 (from Eq 1) » Na2S03
Water
Sellite solution which is returned to
the TNT plant. The salvage value of the recovered sodium sulflte is about
V - 183
-------
STREAM SO.(T)
FIG. HO. 5-38
( PROC. FLOW SHEET)
00
*•
5250 KKg SOLIDS/YR
9730 KKg WATER/TR
15000 KKg/YR TOTAL
RED WATER DISPOSAL - TAMPELLA PROCESS
WASTE STREAM NO. 23
FIGURE NO. 5-40
STORAGE
5070 KKg/YR Na2S03
-------
$800,000. In existing incineration, the sodium sulfate crude salt cake is
\
sold for a low price or else must be deposited in a chemical landfill.
2. Waste gases will be scrubbed to eliminate possible NO pollution
of the atmosphere. This is also being done at the arsenals.
3. The total solid waste expected to be removed to landfill is approxi-
mately 220 kg of coal ash per day.
Cost Analysis. The cost analysis is based on a plant producing 30,000
KKg per year of TNT operating 24 hours per day and 300 days per year. A
summary of capital cost, annual operating cost, and the cost impact for waste
treatment follows.
V - 185
-------
WASTE STREAM NO, 23
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 50 KKg/Day of Red Water
Equipment Item Estimated Coat
Tanpella Process Installed $ 10,000,000
Subtotal $ 10,000,000
Engineering at 10% 1,000,000
Contingency including freight at 20% 2,000,000
Total Estimated Installed Capital Cost $13,000,000
V - 186
-------
WASTE STREAM NO. 23
2. ANNUAL FIXED CHARGES
Depreciation $ 13,000,000 @ 10%/year $ 1,300,000
Interest $ 13,000,000 @ 10%/year 1,300,000
Insurance and
Taxes $ 13,000,000 @ 4%/year 520,000
Total Annual Fixed Charges $ 3,120,000
3. DIRECT OPERATING COST
Raw Material
Utilities $ 110,200
Maintenance
0.04 x 13,000,000 520,000
Direct Labor
16,200 MH x 9.00 x 1.5 218,700
Annual Direct Operating Cost $ 848,900
Annual Disposal Cost, 66 KKg/year Insignificant
Total Annual Cost $3,968,900
Recovered Materials;
Sodium Sulflte 5070 KKg @ $220/KKg x 0.7 - 780,800
Net Total Annual Cost $3,188,100
4. COST PER KKg PRODUCT $ 3,188,100 * 30,000 $ 106.
5. COST PER KKg WASTE $ 3,188,100* 15,000 $ 213.
6. IMPACT OM PRODUCT COST
(market value of 1 KKg product - NA)
Cost/KKg * Market value/KKg • NA
V - 187
-------
REFERENCES
1. TRW Systems Group, Assessment of Industrial Hazardous Waste Practices:
Organic Chemicals, Pesticides and Explosive Industries. SW-118C report.
2. S. Schott, C. C. Ruchoft, and S. Migrigan TNT Wastes, Industrial & Engi-
neering Chemistry - October 1943.
3. Personal Conversation. A. H. Zipperstein, Processes Research, Inc., to
A. Carotti, Picatinny Arsenal, September 8, 1976.
4. Nay, Marshall W., Jr., C. W. Randall, and P. H. King. Factors Affecting
Color Development During Treatment of TNT Waste. Presented at 27th
Annual Purdue Industrial Waste Conference Purdue University, Lafayette,
Indiana May 2-4, 1972.
V - 188
-------
Waste Explosives - Waste Stream No. 24
Waste Stream Description. Explosives and propellants are manufactured
by the United States Government for the military in arsenals and ammunition
plants, and by private industry for commercial blasting purposes.
In 1973, waste explosives from GOCO (Government Owned-Contractor Operated)
plants amounted to 19,850 metric tons (MT) on a dry basis, and from all private
industry 5000 MT on a wet basis. This wet basis, the characteristic condition
of most private industry explosives wastes, relates to the dry basis on a 3.17
to 1 ratio. That is, wet basis/dry basis - 3.17. The waste explosives rate is
related to explosives production rate at a ratio of .003kg waste/kg product
for high explosives, and ,001 kg waste/kg product for blasting agents. These
ratios, on a dry basis, hold true for both GOCO and private industry manufac-
turing processes.
The wastes are, for the most part, obsolete or off specification items
and include;
Nitrocellulose. A mixture obtained by nitrating cellulose. The condi-
tions of acid concentration, temperature, and time of nitration vary depending
on the type of nitrocellulose desired.
Ammonium Picrate (Cgl^ONH^NO^). Produced by ammonia neutralization of
picric acid in water,
Diazodinltrophenal (DDNP), Results from the reaction of picramic acid
with sodium nitrite and hydrochloric acid,
Dinitrotoluene (DNT) and Trinitrotoluene (TNT). Both are manufactured .
V - 189
-------
by the stepwise nitration of toluene with mixed acids (nitric and sulfuric,
and nitric and oleum).
Pentaerythritol-Tetranitrate (PETN) and Dipentaerythritol-Hexanitrate
(DPEHN). Prepared by nitrating, without sulfuric acid, pentaerythritol and
di-pentaerythritol respectively.
Lead Azide. Obtained by reacting lead nitrate with sodium azide.
Nitroglycerin (NG). Manufactured in. a similar process to T.N.T., that is the
reaction of glycerin with mixed nitric and sulfuric acids.
?
Existing Treatment Methods. The Level I and Level II technologies for
disposal of waste explosives consist of open burning in a safe area. This
open burning, for the most part, consists of placing the waste high explosives
and detonators on either a noncombustible pad or in a burning pit. These
wastes are then covered with a flammable material such as fuel oil or straw
and remotely ignited with a squib or blasting cap. The practice is not environ-
mentally acceptable since the uncontrolled air emissions will contain particu-
lates, NO , and other compounds. In addition to this unburned explosives
A
remaining after combustion are a danger to personnel during cleanup operations.
Selected Alternative Treatment Processes. It is essential that the alter-
i
native treatment processes for disposal of waste explosives fulfill several
criteria. These are: (1) safety of operating personnel; (2) environmentally
acceptable emission; (3) ease of disposal of final waste products.
Based on these criteria, two treatment process trains have been selected
b,
for analysis. These are: (1) wet grinding, wet oxidation and sewage treatment
V - 190
-------
(aerobic and anaerobic); (2) wet grinding, chemical reduction, filtration and/or
evaporation and calcination.
Train 1, Wet Grinding, Wet Oxidation and Sewage Treatment, See Figure
i
5-41. Since most explosives are shock sensitive and come in cast or bulk form,
wet grinding is a necessary step which must be undergone in treating this hazard-
ous waste. In an automated or remote control wet grinding system, waste explo-
sives are passed through a metal detection and removal device where stray pieces of
metal are removed. The explosive is then conveyed into a blade type grinder where
it is simultaneously mixed with water and ground into small'partides. The ground
up wet explosive is then transferred to a mixing vessel (usually the grinder is
located directly on top of the mixing vessel) where additional water is added to
form a suspension of explosive particles in water.
From the mixing tank, the explosive slurry is sent to a wet oxidation unit
where air is injected into the slurry and, with the unit under pressure, the ex-
plosive slurry burns autogenically. A destruction of 80 to 90 percent on a COD/
2
TOC basis has been reported, and recovery of some portion of the heat generated
during wet oxidation should be quite possible, since high pressure steam is
being generated in the oxidation unit. This high pressure steam could power a
turbine for production of electricity. The bulk of the condensate could be
returned to the wet grinding operation with a bleed stream combined with the
2
oxidation reactor effluent and sent to a conventional sewage treatment plant.
The liquid effluent from the wet oxidation process, containing only 3 to
C j'
10 percent of the inlet organic concentration on a COD/TOG basis and 10 to 25
V - 191
-------
to
Ref. No. 1
WASTE EXPLOSIVES
250 KKg/Yr (Dry Has:
550 KKg/Yr Water
800 KKg/Yr (Wet Bas
WET GRINDING
WATER
WATER
WET OXIDATION UNIT
AIR COMPRESSOR
AEROBIC ANAEROBIC
BIOLOGICAL TREATMENT PROCESS
TRAIN 1
(WET GRTNDING-WET OXIDATION)
EXPLOSIVES MANUFACTURE - WASTE EXPLOSIVES
WASTE STREAM NO. 24
FIGURE NO. 5-41
-------
percent of the inlet nitrogen as either nitrates or ammonia, is also sent to
the sewage treatment process. Th6 latter involved aerobic treatment for con-
i
version of the organic carbon to CO2 followed by anaerobic treatment to convert
o
first the ammonia to nitrates and then the nitrates to N» k This three sludge
system, Figures 5-42 through 5-44 allows management of the separate biological
transformations which are necessary for successful denitrlfication. The high
rate system handles the bulk of the carbonaceous removal and, at this station,
the waste activated sludge is removed. Thus, the nitrification stage receives
a predominantly ammonia nitrogen feed and an enriched culture develops because
each system has its own sludge recycle. This process design also has other
desirable features. The high rate system protects subsequent nitrification
stages from any toxic chemicals which might escape the oxidation process.
Heavy metals, cyanides, thiocyanates, and toxic organic chemicals will either
be sorbed or biologically degraded before they reached the nitrification stage.
Since this is a staged system, there can be no direct short circuiting of
i t
materials from the influent to the effluent. Temperature effects on the enriched
culture of the nitrification stage are not as extreme as with a single sludge
system which contains only a marginal population of nitrifying organisms.
Once controlled nitrification has been established the biological denitri-
fication process can be optimized. The nitirifed effluent flows to a stirred
, ^s
anaerobic reactor where methyl alcohol is added in proportion to the nitrate
V - 193
-------
HIGH RATE
C—C02
PRIMARY
o
I
!-•
NO
SLUDGE
NITRIFICATION
NH3—N03
SLUDGE
DENITRIFICATION
N2
METHYL ALCOHOL
SLUDGE
THREE SLUDGE SYSTEM FOR NITROGEN REMOVAL
FIGURE HO. 5-42
-------
RAW
WASTE'
PRIMARY
SETTLER
OXYGEN
ACTIVATED SLUDGE
SETTLER
SETTLER
NITRIFICATION
DENITRIFICATION
FINAL
SETTLER
FINAL
"EFFLUENT
COMMON WALL CONSTRUCTION OF 3-SLUDGE SYSTEM
FIGURE NO. 5-43
-------
.MAJOR
PROCESS
FUNCTIONS
<
I
»-*
tf>
REMOVE
•SETTLEABLE SOLID'
AND PARTICULATE
COD
REMOVE BULK OF
SOLUBLE ORGANICS
AND PRECIPITATE
PHOSPHORUS
SODIUM ALUMINATE
AND
METHYL ALCOHOL
CHEMICAL
ADDITIVES
CONVERT
NH TO NO
T
CONVERT N03 TO
NITROGEN GAS AND C02
'AND FURTHER REDUCE
PHOSPHORUS
PROCESS FLOW DIAGRAM
FIGURE NO. 5-44
-------
nitrogen concentration. The organisms in this stage use the oxygen component of
the nitrate radical to oxidize the organic carbon of methyl alcohol. The end
products of this metabolism are elemental inert nitrogen gas and carbon dioxide,
which are liberated to the atmosphere.
Train 2, Wet Grinding, Reduction, Filtration/Evaporation and Calcination,
See Figure 5-45* Wet grinding is used to reduce the particle size of solid
waste explosives and when mixed with water a treatable slurry is produced. It
his been found that waste explosives may be chemically reduced by treatment with
solutions of sodium hydroxide and/or sodium sulfide. For example: Small quantities
of nitrocellulose are decomposed by adding it with agitation to five times its
weight of a 10 percent solution of sodium hydroxide that has been heated to 70C,
Agitation is continued for at least 15 minutes after all the nitrocellulose has
been added. The products of this decomposition process require additional treatment.
After pH adjustment and dilution, the cellulose can be handled by a sewage treat-
ment plant.
Lead azide may be destroyed chemically by mixing it with at least five times
its weight of a 10 percent sodium hydroxide solution. The mixture is allowed to
stand 16 hours and the supernatant solution containing sodium azide is decanted.
i
The sodium azide solution is disposed of by draining into the ground. The lead
is precipitated and can be recovered. This method is extensively used for waste
streams from lead azide manufacture. This procedure is not recommended unless
the effluent is treated.
V - 197
-------
REF. NO. 1
SO
0»
1000 METRIC TONS
YEAR
250 KKg/YR (DRY BASIS)
550 KKg/YR WATER
800 KKg/YR(WET BASIS)
250 KKg/YR NaOH
250 KKg/YR Na2S
FILTER OK
EVAPORATOR
WATER
CONDENSED OR
FILTERED WATER
TO RECYCLE
CHEMICAL REDUCTION CHIT
DOST CONTROL AND/OR
FUMB CONTROL UNIT
Cr—4
CALCINATION UHIT
TRACT 2
(WET GRIHDING-REDUCTION)
EXPLOSIVES MANUFACTURE - WASTE EXPLOSIVES
WASTE STREAM NO. 24
FIGURE NO. 5-
-------
I
Small quantities of PETN can be dissolved in acetone, and decomposed by
reaction with a concentrated aqueous solution of sodium sulfide. The technique
employed is to add a hot (80C) 33 percent solution of N32S-9H20 to an 11 percent
solution of PETN in acetone at such rate that the acetone does not boil. Seven
parts by weight of sulfide solution are used per part PETN, Stirring is continued
for 30 minutes after mixing is completed. The reaction products should be
burned in a spray injection type incinerator equipped with a caustic soda solution
scrubber.
TNT is decomposed by adding it slowly, while stirring to thirty times its
weight of a solution prepared by dissolving one part of sodium sulfide (Na2S»9H20)
in six parts of water. The reaction products should be burned in an incinerator
equipped with caustic soda solution scrubbers.
Picric acid in aqueous waste streams or excess picric acid is decomposed by
dissolving the material in 25 times its weight of water containing 1 part sodium
hydroxide and 21 parts hydrated sodium sulfide. The hydrogen sulfide and ammonia
liberated must be absorbed or scrubbed from the vent air. The solution from
the disposal process should be neutralized, and the phenolic material remaining
should be oxidized by chlorine or removed by adsorption on carbon. This disposal
technique is considered satisfactory where the quantity of picric acid is too low
to make recovery economically attractive, or when small quantities of the material
are contaminated.
Those primers and detonators which are charged with explosive materials
i
which can be decomposed by acids may be chemically "killed" by immersion in an
V - 199
-------
acid bath of sufficient strength to destroy the seals, This method permits recovery
of the metallic components as scrap, but is limited in application because the
Items must be segregated by explosive mixture prior to treatment,
Benefits and Environmental Advantages and Disadvantages,
Train 1, Wet Grinding, Wet Oxidation, Aerobic and Anaerobic Treatment,
The wet grinding, wet oxidation, biological treatment processes offer the follow-
ing benefits:
1, Wet oxidation has been shown to reduce, on a COD/TOG
basis, 80 to 97 percent of waste explosives,
2. In wet oxidation the water portion of the slurry provides
a heat sink for absorption of the enthalpy of combustion.
This shows up as a conversion of the water to high pressure
steam, This generation of steam, estimated at an elec-
trical equivalent of 500kw, based on a 1000 mt/year
waste treatment plant, represents a considerable energy
recovery. This energy can be recovered by utilization of
a steam turbine with an associated generation of electrical
energy,
3. No trace of unreacted propelIants or explosives remains
from the feed to the wet oxidation unit after reaction.
t
4, The "three sludge" system of aerobic and anaerobic
digestion, as shown in Figures 5-41 through 5-43 represents
a 90 percent or greater removal of total nitrogenous
materials from its inlet stream and a 98-99 percent
removal based on inlet nitrates content of material
to the wet grinding operation.
Environmentally, the wet grinding, wet oxidation, biological treatment
procedure for the treatment of waste explosives offers many advantages. These
are:
1. Emissions from the wet grinding system are minimal, consisting of
V - 200
-------
spills from the mix tank and occasional floor washdowns. These can be collected ,
V
with the water and any entrained explosives recycled for use in the wet grinding
operation.
i
2, Emissions from the wet oxidation process, following the grinding
operation, consist mainly of excess oxygen, nitrogen, CO2 and steam. This gas
stream, under high pressure, would be exhausted through a steam turbine, to
recover useful electrical energy, and to condense the steam. The noncondensibles
after the turbine can be exhausted to the atmosphere without any adverse effects.
The condensed steam from the turbine is recycled back to the wet grinding operation
eliminating this as an emission source.
3, The "3 sludge" biological treatment has air emissions consisting of
CO. and nitrogen and is therefore environmentally acceptable. The final sludge
from the biological treatment system is both biologically and chemically inert
This sludge may be dewatered with the water being returned to the wet grinding
and wet oxidation processes, and the dewatered inert sludge disposed of in a
landfill.
The environmental disadvantages of the wet grinding, wet oxidation processes
result in the main from the nature of certain of the explosives and/or propellents
being treated.
Existence of compounds containing halogen group species will require
A
special materials of construction in the wet grinding and wet oxidation processes.
In addition, these halogen compounds will evidence themselves in the vapor stream
i
from the wet oxidation unit necessitating special resistant metals for the energy
i
recovery turbine and a vapor scrubbing-neutralization system.
V - 201
-------
Heavy metals, from such compounds as lead azide and mercury fulminate,
will pass unchanged through the wet oxidation system and require the biological
treatment processes to include precipitation and sedimentation as well as
aerobic and anaerobic digestion.
These arernot environmental disadvantages per se, but do result in an
increase in capital and operating costs for the waste explosives process modules.
Train 2. Wet Grinding, Chemical Reduction, Filtration, Evaporation,
Calcination. Wet Grinding followed by chemical reduction offers a safe control-
lable means of disposal of waste explosives. The benefits are:
It The technologies of grinding chemical reduction, filtration, evapor-
ation, and calcination are well developed with the scale-up from pilot plant
processes easily defined.
2, All of the necessary equipment is commercially available and simple
to operate and control.
3, Energy requirements, excepting for the evaporation and calcination
processes, are not significant.
4, Chemical reduction and filtration will allow recovery of metals
from the waste explosives.
>
5. Wet grinding will safely reduce solid waste explosives into sizes
that are more reactive with chemical reduction (more surface area), easier to
convey, and since they are in a water slurry, safer to handle.
The environmental advantages of the wet grinding, chemical reduction
calcination disposal processes are;
V - 202
-------
1, Air emissions are not expected to be significant with proper fume
abatement equipment on the calcination process.
2. Water emissions will be negligible, if any, since the condensed
vapors from the evaporation process and some of the water from the filtration
process are recycled to the wet grinding, chemical reduction processes for reuse.
There are no liquid emissions from the calcination or wet grinding processes,
3, Solid wastes are generated only from the calcining process. Since
these have been "deactivated" in the chemical reduction process they may be
disposed of in a sanitary landfill.
The environmental disadvantages of these waste explosive disposal pro-
cesses are)
4. Air pollution control equipment, notably cyclones and wet scrubbers,
will be required to eliminate the air emissions from the calcining process.
5. The energy requirements of the evaporation and calcination process
are excessive. This will be only partially offset by the fuel valve of the
chemically reduced explosives,
6, If heavy metal explosives, such as lead azide or mercury fulminate
are disposed of by these processes this will complicate the solid waste disposal
problem. Either a heavy metal recovery system must be installed or the calcina-
tion solid wastes will have to be disposed of in a special chemical land disposal
site.
Cost Analysis, The cost analysis is based on a plant producing 125,000
KKg per year of explosives and propellents operating 24 hours per day and 300
days per year, A summary of capital cost, annual operating cost and the cost
impact for waste treatment follows,
V - 203
-------
WASTE STREAM NO, 24
TRAIN I
1. ESTIMATED INSTALLED CAPITAL COST
BASIS: 0.83 KKg/Day of Explosive Wastes (Dry Basis)
Equipment Item Estimated Cost
Grinder $ 10,200
Wet Oxidation Unit 307,700
Air Compressor 236,000
Slurry Pump 15,300
Aeration System 26,100
Steam Turbine 65,700
Biological Treatment System 60,000
Subtotal $ 721,000
Engineering at 10% 72,100
Contingency including freight at 20% 144,200
Total Estimated Installed Capital Cost $ 937,300
V - 204
-------
WASTE STREAM NO. 24
TRAIN I
2. ANNUAL FIXED CHARGES
Depreciation $937,300 @ 10%/year $ 94,000
Interest $937,300 @ 10%/year 94,000
Insurance and
Taxes $937,300 @ 4%/year 38,000
Total Annual Fixed Charges $ 226,000
3, DIRECT OPERATING COST
Raw Material
Utilities $ 1,400
Maintenance 0.04 x $940,000 38,000
Direct Labor
9600 MH x 9,00 x 1.5 129f600
Annual Direct Operating Cost $ 169,000
Annual Disposal Cost, Blosludge Insignificant
Total Annual Cost $
Recovered Materials:
None - Power Recovered is credited in Utility Cost
!
-------
WASTE STREAM NO. 24
TRAIN II
1. ESTIMATED INSTALLED CAPITAL COST
BASISj 0.83 KKg/Day of Explosive Wastes (Dry Basis)
Equipment Item Estimated Cost
Grinder $ 10.200
Slurry Pump 15,300
Chemical Mix Tank 106,700 •
Chemical Feed Tank 74,700
Pump 9,000
Filter 168,800
Evaporator 153,300
Calciner 87,600
Dust Collector 18,400
Subtotal $ 644,000
Engineering at 10% 64,400
Contingency including freight at 20% 128,800
Total Estimated Installed Capital $ 837,200
V - 206
-------
WASTE STREAM NO. 24
TRAIN II
2. ANNUAL FIXED CHARGES
Depreciation $ 837,200 @ lOZ/year $ 83,700
Interest $ 837,200 @ lOZ/year 83,700
Insurance and
Taxes $ 837,200 <§ 4Z/year 33,500
Total Annual Fixed Charges $200,900
3, DIRECT OPERATING COST
Raw Material
Caustic - 250 KKg/Year @ $155
Na2S - 250 KKg/Year
-------
REFERENCES
1. TRW Systems Group, Assessment of Industrial Hazardous Waste Practices:
Organic Chemicals, Pesticides and Explosives Industries, 1976.
2. Proceedings; National Conference on Management and Disposal of Residues
From The Treatment of Industrial Wastewaters, Washington, D. C.,
February 3-5, 1975. Page 87-97.
3. Earth, E. F. Nitrogen Removal by Biological Suspended Growth Reactors,
Advanced Waste Treatment and Water Reuse Symposium, Cleveland, Ohio,
March 30-31, 1971.
4. TRW Systems Group, Recommended Methods of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste, Volume VII, NTIS Publication
PB224-579-SET/AS.
V - 208
-------
SECTION VI - INCINERATION
Summary and Basis
Of the 24 waste streams included in this report, 19 were considered appli-
cable for incineration. Lead alkyls sludge, Waste Stream Wo. 10, and fluoro-
carbon manufacture spent reactor catalyst, Waste Stream No. 14, were eliminated
i
from consideration because of anticipated air and water pollution by the heavy
metals.
Nitrobenzene manufacture, crude nitrated aromatics Waste Stream No. 2 and
r
chlorotoluene manufacture benzylchloride and benzotrichloride Waste Stream
No. 15 were eliminated as being too small to consider; and cyanuric chloride
manufacture Waste Stream No. 17 was not deemed to be applicable for incinera-
tion because of its high water and low organic content. It was considered that
the 19 waste streams mentioned above could best be incinerated using four
distinct types of Incinerators (Table 6-1) as follows:
Five streams were processed in fluid bed units.
Eleven streams were processed In rotary kilns.
Two streams were processed,in liquid incinerators.
One stream was treated using the Tampella process.
i
Detailed calculations were made for sizing the processing equipment in
order to compute their costs. Basis data for preparation of the cost analysis
i
for this report were obtained from USEPA Report SW-118C, Assessment of
*
Industrial Hazardous Waste Practices: Organic Chemicals, Pesticides and
Explosives Industries; (1976).
VI - 1
-------
TABU HO. 6 • 1
WASTI STREAM CHARACTERISTICS AND IKCIHOATIOH SYSTEM SELECTIOH
Stream*
. Mi.
1
2
3
4
M
1 3
ISJ
6
7
8
f
11
Product and
Tryleel Plent Site
Perchloroachylene
39.000 KKs/yr
Hltrobentcne
20,000 EKc/yr
Chlorlnattd lolveati
50,000 KKs/yr
Color ome the pe
Eplchlorobydrln
75.000 KK|/yr
Toluene dlUocyaet*
27.500 KKs/yr
Vinyl chloride
monomer
136,000 KKs/yr
Methyl methacrylete
55.000 KXs/yr
Acrylooltrllo
80.000 KKt/yr
Malelc anhydride
11.000 KKs/yr
Ethanolamlne* mfr.
14,000 KKs/yr
Wa*t* Jcreem
Component*
Rexachlorobutadlcne (230)
Dlchlorobenxene (20)
Tetrachloroetbane (10)
1.2-Dlchlorobutadlene (10)
Tar* (20)
Crude nitrated aromatic*
(2.5)
Crude hexachlorobeniene end
Bexechlorobutedlene (6)
Ethyl, methyl, 1-chloro
ether (7.4)
BlenlorohydrlB (5.7)
Trlcbloropropane (37.1)
Eplchlorohydrla (1.06)
Polyuretbane* (19)
Iiocyanate* (0.58)
Ferric chloride (1.35)
Ethylene dlchlorlde (0.8)
Chloroethane* (37.0)
Tar* (0.05)
A*h (0.20)
Hydroqulnon* (1)
Varlou* polymeric
residue* (125)
Acrylonltrlle (2.5)
Higher nltrlle* (2.5)
Malelc anhydride (3.8)
Fumartc acid and tare
(26.5)
Trlethanolamloe (40)
Tar* (40)
Annual
Rate
"«
12,000
SO
300
4.000
558
1.400
4,730
160
333
1.120
Hourly *
Rate
«*/
1.700
7.0
42.0
560.0
78.0
660.0
660.0
55.0
47.0
155.0
Appro*.
Bt. Valve
KtCal/K« Incinerator Selection
2,200 Fluid bed reactor
6,000
1,800 Rotary kiln
2,700 Fluid bed reactor
7.200 Rotary kilo
4,100 Fluid bed reactor
7,200 Liquid* Incinerator
8,400 Liquid* Incinerator
4,800 Rotary kiln
• 7,300 Rotary kiln
Scrubber Selection
Pecked column
-
Packed column
Packed column
Packed column
Packed column
Packed column
Packed column
Pecked column
Packed column
Mote:
Stream Ho. 10 and 14 contain toxic Mtala
and are not to be loclnereted.
(1) Hourly rate fed to Incineration *y*tem.
•See Teble 2-1.
Auxiliary fuel required to
convert Clj to HC1
Insufficient amount of wi*te
to coniidcr «n Incineration
•yatcm. l'«« plant boiler (Ire
box.
Auxiliary fuel required to
convert C12 to RC1
Alb removal required
-------
TABLE NO. 6 - 1 (CONTINUED)
U>
Strei
—Ssi
12
13
1J
16
17
18
19
20
21
22
23
2*
*W«t
+Dr»
• Product and
Typical Plant Sis*
Furfural mil.
35.000 «g/yr
Furfural mfr.
35.000 «f/yr
ChlorotolucM »fr.
15.000 KX«/yr
Chlorobeuent mfr.
32,000 EKc/yr
Cyanurlc chloride
•fr. IB atramln*
production
20.000 KKs/yr
Trlflurallo mfr.
10.000 KKS/TT
Malatbloo mfr.
U.OOO RTs/yr
Halathlon mfr.
U.OOO nc»/yr
Perathlon mfr.
20.000 KXs/yr
Exploalvai mfr.
93.000 ttf/yr (TNT)
Exploalvee «fr.
30.000. KXs/yr TWT
Cxploalvee mfr.
125.000 KKt/yi
baala
basil
Haae* Stream
Coaponcnta
K*/nu
Sulfurlc acid (60)
Tara and polymcra (500)
riltar aellda (5)
Banaylchlorld* (.5)
Banaotrlchlorlda (.5)
PolychlorlMtad (.OU)
Armatlc raalnoua «at'l.
Sodium chlorlda (924)
Cyamirlc acid (6)
Sodium bydroxld* (31)
laaolubla realdue (161)
(Balanca watar)
Spant carbon (60)
Pluoroarotutlci (9.3)
Inttraedlataa (45.7)
and aolvcnta
DlBith/l dithlophotphorlc
acid (5)
Teluana & Inaol. reaction
prod. (54)
Carbon filter aid (71.5)
Nalathlon (10)
Tolutna & •alatbloo (15)
lapurltlta plua HaOH plua
vatar
Sulfur (105)
Dlathylthlophoiphorlc
acid (10)
Activated carbon (1.71)
NltrobodUa (0.72)
Water (1.71)
R«d water solid* (173)
Water (325)
Heat* axploalvea (2.0)
Annual
tat a
"«
19.600
350
15
1.400
224.600
1.150
1,826
350+
14,350*
2.300
350
13.000
150
Hourly Approx.
Rat* Ht. Value
KfVhr KKCal/K* Incinerator Selection Scrubber Selection
2.720.0 7,400 fluid bed Incinerator Packed column
49.0 3,300 Vie Stream; 12 Incinerator
2.1 3,600
195.0 2,500 Rotary kiln Packed column
31.200 . .
160.0 5.600 Rotary kiln Packed column
255.0 8,000 Rotary kiln Packed column
49.0+ 5,600+ Rotary kilo Pecked coluaa
2.000* 136*
320.0 2,600 Rotary kiln Packed column
42.0 3,300 Rotary kiln Packed column
71.0 acrubber
2.090 . Tampella proceae included
52.0 2,600 Rotary kilo Packed column
•crubber
•
W/HjSO^ recovery
-
Uaate atream too email to
conalder incineration
W/RC1 recovery
Incineration not practical.
Alooat all vater and inorsanice
in waate atreaa.
Aab removal reoulred
Aab removal required
Evaporation atep. then combine
and incinerate with Stream 19
W/S02 recovery
Aah removal required
(1) Hourly rate fed to Incineration ayateai.
-------
Cost data for most pollution control equipment modules were obtained from
A
Environmental Protection Cost Manual EPA-R5-73-023b July 1973. Costs for
treatment and disposal for the waste streams in this report are based on 300
operating days per year and 3 shifts per day unless otherwise stated. Unit
costs for utilities, maintenance, labor, taxes, insurance, land cost, and con-
tingency are per EPA letter.** For further detail of unit costs and bases see
Methodology Section. Incineration Cost Summary as shown in Table 6-2.
In the examination and review of the tabulated data on the summary sheets
it became apparent that savings could be realized by increasing the unit size
of the controlled incineration equipment while reducing the operation to
fewer shifts. For example, Waste Streams No. 3 and No. 8 were each recalculated
from 900 to 300 shifts per year and operation. In each case, an appreciable
cost saving per kkg of product was realized with 300 shifts per year operation.
For Waste Stream No. 3 the cost dropped from $3.00 to 1.70 per kkg of product
and for Waste Stream No. 8, the cost fell from $1.48 to $1.10 per kkg of pro-
duct. It is possible that by further reducing the number of operating shifts
and increasing the equipment size accordingly that additional cost savings might
be realized.
Although optimum cost determinations are beyond the scope of this report
and is usually not needed to generate order-of-magnitude cost data, the fore-
i
going cost analysis is presented for general interest. Cost optimization must
be considered once an incineration system has been studied and fully defined.
VI - 4
-------
TABU HO. • - *
VAST1 8TKIAN IHCIHEKATIOH COST SOOU1T
Straam*
»••
1
2
3
4
5
6
7
8
9
11
12
13
•*
13
Product and
Typical Plant Site
Inatallad
Coat
Parcnloroathylaa* *1.276.000
39.000 KKs/yr
Mltrobcniana
20,000 KKs/yr
ChloroMthana
50,000 KK(/yr
Cplchloiobydrln
75.000 KKg/yr
Tolutna dlliocyanta
27.500 KKs/yr
Vinyl chlorlda
awnoaar 136,000 KKf/yr
Mathyl awthacrylat*
55.000 KK|/yr
Acrylonltrlla
80.000 U«/yr
Malale anhydrUa
11.000 KKs/yr
14,000 KKs/yr
Furfural «£r. 1
33,000 KKg/yr
Furfural «fr.
35.000 KKg/yr
Ctiloretolaana mtr.
15.000 KKs/yr
Inaafflclant
184.000
938.000
173.000
946.000
371,000
153.000
160,000
198,000
,699,000
172.000
15 KKs/yr of
Annual
Find
$306.000
quantity of
48.000
225.000
42.000
228.000
89.200
37.000
38,600
47.500
408.000
41.200
vaat a la to
Utility
Coat/yt
$134,000
vaat* to cooaldar
6,400
25.000
7,000
8,000
11,300
5,000
3.000
5.000
110.000
2.000
Malnta-
oanca/rr
$52.000
Inclaarator
8.000
37.500
7.000
38,000
15,000
6.100
6,400
8,000
68.000
6.900
Labor/yr
$49.000
ayatcai
24.300
49.000
73.000
17.000
24.000
8,000
73.000
73.000
49.000
-
Total
Annual
Coat
$541.000
86,400
337.000
129,000
291,000
140,000
56,000
121,000
134,000
635.000
50,000
Coat par
Vaata
$ 45.
288. {l>
84.
231.
208.
30.
350.
363.
120.
32.
143.
Coat par
UCs
Product
$14.
l'7°(1>
4.50
4.70
2.10
2.50
O>
1.10
12.
9.60
18.
1.40
Reaource Recovery Poaalbllity
BC1 SOj Energy
Taa - Taa
.
Taa - Taa
Taa - Taa
Taa - Tea
Taa - Taa
Taa
Taa
Tea
Taa
Tea Taa
(Incinerate with StreM Ho. 12)
J
o avail to coaaldar loclnaration
<1) Ona Shift Pair Day.
•taa Tahla 2-1
•*>traaai K>. 10 and 14 coatalo toxic aMtala and ara not to b€ loetnaratad.
-------
TABU NO. 6 - 2 (CONTINUED)
WASTE STREAM INCINERATION COST SUMMARY
a*
Stres
_NO.
16
17
18
It
19 6
21
22
23
24
•Wet
•Wry
Installed Total
• Product and Capital Deprac. Utility Helnte- Annual
Typical Plant Sis* Coat Value/yr Cost/yr nance/ yr Ltbor/yr Cost
Chlorobanxeae «fr. 8 205.000 $ 49,200 $5,000 $ 8,200 $73.000 $135,000
32.000 KKs/yr
Cyanurlc chloride Water 1* 90 percent of waste strain, and Incineration la too coatly to consider.
20.000 KKs/yr at res toe
TrUluralln «fr. 225.000 54.100 5,000 9.000 73.000 141.000
10,000 KKc/yr
Malathloa 313.000 75.000 6.000 12.500 73.000 167.000
14.000 KKc/yr
20 Ns lath Ion 792,000 190,000 89,000 31,700 122,000 433,000
14,000 KKg/yr
ParathlOB 282,000 67.500 7,000 11.300 73.000 159.000
20,000 KKg/yr
Explosives »fr. 649,000 153,800 11,000 26.000 113,000' 306.000
93.000 KKg/yr
Explosives nil. 13,200.000 3,168,000 110,000 528,000 219,000 4.025.000
30,000 KKs/yr Stress 19
1240. +
69. 7.90 - Yes Yea
873. 3.30 ...
1530.
268. 134.
1105. 2.20
r
-------
Types of Incinerator Equipment
Many different types of incineration equipment are availabe for disposal of
gases, liquids and solid wastes. The type and form of waste will dictate the
i
type of combustion unit required.
L
1. Incinerators for waste gases are usually of the flare, direct com-
bustion, or catalytic oxidation type.
Of these three types, the flare is not environmentally suitable for
hazardous materials.
The direct flame type is suitable for waste gases with calorific value
less than 25 percent of the lower flammability limit.3
Catalytic oxidation is suitable for gases with low calorific values
(approximately 180 kg C/M3).3
2. Liquid injection incinerators are limited to pumpable liquids and
slurries which can be properly atomized (viscosity of 750 SSU or less) and are
commercially available in both vertical and horizontal design.3
3. Solid waste incinerators are available in many designs, among which
are rotary kiln, multiple hearth, multiple chamber, fluidized bed, and open pit.
*
Open pit incineration is not environmentally suitable for hazardous materials
i
as 1L cannot readily be adapted to secondary pollution abatement equipment,
hence is unacceptable under many air pollution codes.2
Equipment Selection and Benefits
The types of incinerator units having the greatest application in handling
the waste streams in this report are described below. The type of waste for
VI - 7
-------
which these and other units are best suited is shown (Ungrammatically in
Figure 6-1.
1. Liquid Waste Incinerator. See Figure 6-2.
a. Operating Principle.* Liquid waste is converted to the gaseous
state inside a combustion chamber, receiving heat transfer from the hot com-
bustion product gases to the injected liquid. Commonly, the amount of surface
exposed to heat is increased by atomizing the liquid to small droplets in the
liquid burner, directly at the point of fuel and air mixing.
A wide range of industrial liquid wastes may be incinerated pro-
vided the heating value is sufficient to maintain temperature for complete
combustion. When a low-heat-value liquid is incinerated, it must be blended
with a liquid of higher heat value or auxiliary fuel will be required.2
The ash, if any, will essentially be all gas borne particles and
will normally be removed by an appropriate air pollution control system. A
certain amount of particulate will drop out within the incinerator, occasional
shutdown and cleanout will be required. Depending on the quality of the liquid
waste and auxiliary fuel burned, cleanout may be required at about six month
intervals.^
b. Uses and Advantages.
(1) Capable of incinerating a wide range of liquid wastes.
(2) No continuous ash removal system is required other than for
air pollution control.2
VI - 8
-------
!|
0?£N PIT
I INCINERATORS
l
CFiN
I NtlNE RATION
MULTIPLE
CnAMfcJ
INClNcitATORt
MULTIPLE
HEARTH
INCINERATORS
ROTARY KILN
INCINEKATGH
FLLMOIZcD BED
INCINERATOR
IIQUIO
COMSUSTORS
CATALYTIC
COM&USTORS
GAS
COVijSTORS
RARES
TYPES OF INCINERATORS AND THEIR APPLICATIONS
FIGURE NO. 6-1
-------
LIQUID WASTES FXOM PLANT
SEPARATE TANKS FOR
H'OH AND LOW
MELTING-POINT LIQUIDS
STACK 100 FT. HIGH
* FT. 6 IN. I. 0.
4 FT. 4 IN. I. O. OUTLET
1INEO WITH ACH>-«EStSTINO
PLASTIC
VENTUII SCIUBtEt UNCO WITH
ACID. KSISTIMG PLASTIC
TEMPEIING
Alt HOWE*
10.000
OJ CU. FT./MIN.
FRESH WATEI
300 GPM.
(If CYCLED
WASTE
WATEI
I,X)OGPM.
COMiUSItON Al* tLOWEK
11,000 CU. FT./MIN.
7SHP.
TOTAL AM. 76 U./ll. WASTE
I klEMTESING
VO/AIRBIOWEH
^^ 10,000
CU. Ft MJN.
25 HP.
IECYCLEO
V/ASIE
WAI El
,000 GPM.
WAIEt
2,100 GPM.
pHI.O
INDUCED-DRAFT FAN
2,600 U./MIN.
43,000 CU. FT./MIN.
600 HP.
WATE*
240 GPM.
pH 1.0
WASTE TAI FEED: AVG. 10 GPM.
13,00 8TU. '18. '
TEMPERATMC BO-IODOC.
VISCOSITY ISO SSU.
I PSI FEED
4 tLMNEKS, COM»LIStK>N
GAS AND TAX NOZZUS
i/16 - IN.OMFICE
HORIZOHTALLY FIRED LIQUID WASTE INCINERATION$}
FIGURE 6-2
-------
c. Limitations and Disadvantages.
(1) Must be able to atomize tars or liquids through a burner
nozzle except for certain limited applications.
(2) Heat content of liquids must maintain adequate temperatures
or a supplemental fuel must be provided.
(3) Must provide for complete combustion and prevent flame impinge-
o
ment on refractory.
2. Rotary Kiln
a. Operating Principle. The rotary kiln2 provides the design flexi-
bility for incineration of a wide variety of liquid and solid industrial wastes.
Any burnable liquid capable of being atomized by steam or air through a burner
nozzle can be incinerated concurrently with a wide range of industrial solids.
Heavy tars may be fed as solid waste in packs or metal drums. The kiln can be
designed to receive 55 gallon drums, or a feed mechanism can be designed to
empty the drum and retain it. It is also capable of handling pallets, plastics,
filter cakes, and other solid chemicals passing through a liquid phase before
combustion.
The rotary kiln provides a maximum amount of turbulence, agitation
and surface air contact to achieve complete burnout. Complete combustion of
slow burning refuse is aided by a relatively long inventory time in the combustion
chamber. Ash discharge is continuous. Roll through a spherical or cylindrical
items would normally be prevented by the other solid refuse being incinerated.
Since the drive mechanism is outside the kiln, maintenance is low.
VI - 11
-------
There are no internal moving parts such as rabble arms, grates, or plows.
Care must be exercised in determining kiln size to provide for
adequate accommodation of solid wastes and maximize refractory life. As the
kiln size decreases, the unit becomes increasingly sensitive to excessive heat
release and temperature control becomes more difficult.
The rotary kiln is a high capital installation and would not be
considered practical for very low feed rates. Practical sizes are limited. At
a minimum, sufficient capacity must be provided to accommodate the feed packages
such at, drums or packs and prevent flame impingement on the refractory when
liquid wastes are incinerated. The maximum size is determined by turndown
problems, operating costs, maintenance of a proper combustion temperature, and
construction-fabrication costs. Turndown, the ratio of maximum to minimum ther-
mal capability, represents a problem due to leakage of air through the system.
Since the rotary motion of the kiln precludes the use of suspended
brick, the refractory is more susceptible to thermal shock damage. For this
reason, continuous operation should be maintained as much as possible. Rebrick-
ing of the hottest part of the kiln can be anticipated on roughly an annual
basis. Therefore, it is often advisable to maintain an inventory of kiln
refractory and refractory for multiple hearth furnaces in protected storage.
Airborne particles may be carried out of the kiln before complete
combustion. A high temperature secondary combustion chamber with intimate flame
contact is normally required for complete burnout. The fuel for the secondary
combustion chamber should be .dependable high quality waste liquid or commercial
fuel. The rotary kiln incinerator is shown in Figure No. 6-3.
VI - 12
-------
M
I
M
LO
t
1 WASTE TO INCINERATOR
2 AUTO-CYCLE FEEDING SYSTEM:
FEED HOPPER, PNEUMATIC FEEDER, SLIDE GATES
3 COMBUSTION AIR IN
4 REFRACTORY-LINED, ROTATING CYLINDER
5 TUMBLE-BURNING ACTION
6 INCOMBUSTIBLE ASH
7 ASH BIN
8
9 SELF-COMPENSATING INSTRUMENTATION-CONTROLS
10 WET-SCRUEBER PACKAGE-
STAINLESS STEEL, CORROSION-FREE WET SCRUBBER; GAS QUENCH
II EXHAUST FAN AND STACK
12 RECYCLE WATER, FLY-ASH SLUDGE COLLECTOR
13 SUPPORT FRAME
14 SUPPORT PIERS
15 AFTERBURNER CHAMBER
PROGRAMMED PILOT BURNER
PORTABLE ROTARY KILN INCINERATION UNITS
FIGURE NO. 6-3
1672
-------
b. Uses and Advantages
(1) Will incinerate a wide variety of liquid and solid wastes.
(2) Capable of receiving liquids and solids independently or in
combination.
(3) Not hampered by materials passing through a melt phase.
(4) Feed capability for drums and bulk containers.
(5) Wide flexibility in feed mechanism design.
(6) Provides high turbulence and air exposure of solid wastes.
(7) Long inventory time for slow burning refuse.
(8) Continuous ash discharge.
(9) No moving parts within the kiln.
(10) Adaptable for use with a wet gas scrubbing system.
c. Limitations and Disadvantages
(1) High capital cost installation for low feed rates.
(2) Cannot utilize suspended brick in kiln.
(3) Operating care necessary to prevent refractory damage.
(4) Airborne particles may be carried out of kiln before complete
combustion.
(5) Spherical or cylindrical items may roll through kiln before
complete combustion.
(6) Kiln incinerators frequently require excess air intake to
operate due to air leakage into the kiln via the kiln end seals and feed chute,
which lowers fuel efficiency.
VI - 14
-------
(7) Drying or ignition grates, if used prior to the rotary kiln,
n
can cause problems with plastics melt plugging grates and grate mechanisms.
3. Fluidized Bed Incinerator.
a. Operating Principle. Fluidized bed incinerators3 are quite versa-
tile, being usable for the disposal of solid, liquid, and gaseous combustible
wastes. The utilization of this process for waste disposal is relatively new,
having been in commercial use for only about the last dozen years. At present,
the most popular applications are in the petroleum and paper industries, in the
processing of nuclear wastes, and in sewage sludge disposal.
The basic fluidized bed combustor is shown in Figure No. 6-4. The
bed is essentially a vessel containing inert granular particles, such as sand,
Blower-driven air enters at the bottom and proceeds vertically through the bed,
agitating or "fluidizing" it and causing it to behave in a nature similar to
a dense liquid mass. Hastes are injected pneumatcially, mechanically, or by
gravity into the bed. Rapid and relatively uniform mixing of wastes and bed
material occurs.
.1
In the combustion process, heat transfer occurs between the bed
materials and the injected waste materials. Typical bed temperatures are in
the range of 760 to 870C (1400 to 1600F), Due to the high heat capacity of
the bed material, the heat content of the fluidized bed is approximately 142,000
*
kg-cal./m3 (16,000 Btu per foot3), which is about three times greater than the
^
heat capacity of flue gases in typical incinerators operating in the same
f
temperature range. Heat from combustion is transferred back to the bed
VI - 15
-------
FLUE GAS <==•
MAKEUP SAND
ACCESS
^
I r-v-JW- ~r Y ^ * k * t —— -* — * - ^~
AUXILIARY
BURNER (OIL OR GAS)
- - 'SAND BED
I' I' " Ti i*f 11 11
V
ASH REMOVAL
SCHEMATIC OF A FLUIDIZEJ) BED INCINERATOR1
FIGURE NO. 6-4
WASTE INJECTION'
FLU1DIZING AIR
VI - 16
-------
material. Solid materials remain in the bed until they have become small and
light enough to be carried off with the flue gas as a particulate. Collected
ash is generally land disposed.
>
Gas velocity, bed diameter, bed temperature, waste type, and
composition are important in designing a fluidized bed incinerator. Due to
waste particle size constraints, gas velocities are usually low, around 1.5
to 2.1 m (5-7 feet) per second. With present design technology, bed diameters
are limited to 15.3 meters (50 feet) or less. Bed depths range from 38 centi-
meters (15 inches) to a few meters. To avoid softening and agglomeration, bed
temperatures are restricted to below the material softening point. Certain
wastes have to be presized before feeding.
For adequate combustion, predrying of wastes may be necessary.
The use of recycled combustion gases in such a drying system can recover waste
heat, thus reducing auxiliary fuel input and costs. For start-up and for con-
ditioning of the bed, an auxiliary burner system is required.
As with most other incineration techniques, fluidized bed com-
bustion may generate particulate and/or gases which may require air pollution
controls prior to emission to the atmosphere. Wet scrubbers, dry collectors,
electrostatic precipitators, and fabric filters have proven to be effective in
reducing airstream partlculates. The method used to control gaseous pollu-
t
tants will depend upon the particular combustion products. Normally, no odors
and little nitrogen oxide is produced from fluidized bed combustion.
VI - 17
-------
b. Uses and Advantages
(1) General applicability for the disposal of combustible solids,
liquids, arid gaseous wastes.
i
(2) Simple design concept, requiring no moving parts in the com-
bustion zone.
t
(3) Compact design due to high heating rate per unit volume
(900,000-1,300,000 kg.-cal./hr. m3 (100,000-200,000 Btu per hour.-ft.3) which
results in relatively low capital costs.
(4) Relatively low gas temperatures and excess air requirements
which tend to minimize nitrogen oxide formation and contribute to smaller,
lower cost emission control systems.
c. Limitations and Disadvantages^'3
(1) Requires fluid bed preparation and maintenance.
(2) Feed selection must avoid bed damage.
(3) May require special operating procedures to avoid bed damage.
(4) Incineration temperatures limited to a maximum of about 1500F.
(5) With present design technology, unit capacity is limited by
a maximum bed diameter of about 15 m (50 feet).
(6) A potential problem in removing residual materials from the
bed.
4. Air Pollution Control Equipment. Following incineration of industrial
hazardous wastes the combustion gases will invariably require a secondary treat-
ment to render the waste stream quality acceptable to the atmosphere. A great
VI - 18
-------
variety of equipment is available for controlling air polluting emissions.
j»
Some wet scrubbers are: spray tower, packed bed, wet cyclone, orifice plate
bubbler, venturi, jet type. Among the dry type units are mechanical cyclones,
electrostatic precipitators, and fabric filters. In this report the packed
bed scrubber has been selected for all installations where secondary pollution
control equipment was required.
In the packed bed scrubber^- the effluent gas stream to be cleaned is
directed through a chamber or tower in which it makes contact with the scrub-
bing liquid. The high liquid surface area exposed to the gas stream is pro-
duced by interaction with the packed bed. The packed bed may be in the form
of a fixed packing or loose material which is supported by the action of the
gas stream passing through it. This latter type is called a floating bed
scrubber. Scrubbing liquid is generally passed through this type of scrubber
in a direction crosscurrent or countercurrent to the gas flow.
The fixed bed scrubber is not often used strictly for particulate
pollutant collection. Operating problems have been encountered when this
type of collector is utilized to clean a gas stream containing an excessively
high concentration of particulate material. Therefore, in conjunction with
}
this type of equipment, some form of dry collection equipment is used that
eliminates much of the particulate load on the wet scrubber and helps prevent
clogging.
The floating bed units, in which the packing is supported by the up-
ward motion of the exhaust gas stream, are reported to be more resistant to
VI - 19
-------
clogging caused by particulate collection than the fixed packed bed units.
This reported increased ability to handle particulate contaminant is
attributed to the relative motion between the materials which produce a self-
i
cleaning action and allows the collected particulate material to be removed
by the liquid flow. High particulate removal efficiencies (95 to 93 percent)
have been reported for floating bed scrubbing units.
Flooding occurs when the upward gas velocity in the packed tower
reaches a point at which there is a hold-up of liquid phase on the packing.
i
In this condition, the liquid held in the packing builds up and eventually
increases the pressure drop across the packed tower unit to the point where
liquid will be entrained and carried out with the exhaust stream. Care must
be taken in the design and operation of tower equipment to ensure that this
flooding condition is avoided and a reasonable pressure drop is maintained.
Properly designed packing materials allow a high liquid surface area to be
maintained within the scrubber. Operation at proper liquid-to-gas flow ratios
can achieve high gaseous pollutant removal at relatively low gas flow resist-
ances. Packing materials commonly used are plastic materials of various shapes,
L
including rings, spiral rings, berl saddles, and other shapes which allow a
high r_;_io of surface area to volume.
Utility consumption for the packed bed scrubber depends on the design
of the bed, the packing material used and the collection efficiency desired,
Typical water consumption for the packed bed scrubber ranges from 5 to 10 gpm
i
per 1,000 cfm. Normal packed scrubber design dictates a pressure drop of from
VI - 20
-------
1 to 10 inches of water with a total horsepower requirement of 0.3 to 2.8 for
fan and pumping costs. Efficiencies of 95 to 98 percent have been realized
for both particulate and gaseous control, although not necessarily concurrently.
The choice between crossflow and countercurrent scrubber design is
dependent on the particular application. Generally the crossflow scrubber
is applied to situations where the bed depth is less than 6 feet and counter-
current design is applied at bed depths of 6 feet or more. These applications
are based on the lowest combination of installed capital cost and operating
cost.
VI -.21
-------
REFERENCES
1. TRW Systems Group - -Recommended Metho-s of Reduction, Neutralization,
Recovery, or Disposal of Hazardous Waste - Volume III Disposal Process
Discriptions. August 1973. NTIS Publication PB-224-579-SET/AS
2. Manufacturing Chemists Association. A Guide for Incineration of Chemical
Plant Wastes SW-3, Adapted 197A.
3. Scurlock A. C., A. W. Lindsey, T. Fields Jr. and D, R. Huber, Office of
Solid Wastes Management Programs. Incineration in Hazardous Waste
Management EPA Report SW-141. 1975.
4. Personal Communications. Fluid Bed Reactor Sizing Data. Walker Process
Division, Chicago Bridge & Iron. August 14, 1973.
5. The 1975 Energy Management Guidebook.
6. Personal Communication. E. P. Grumpier, OSWMP to J. M. Genser, Processes
Research, Inc., October 14, 1976.
VI -. 22
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SECTION VII - LAND DISPOSAL
»
.Description.. The conventional sanitary landfill has been defined as "a
land disposal site employing an engineered method of disposing of solid wastes
on land in a manner that minimizes environmental hazards by spreading the solid
wastes in thin layers, compacting solids to the smallest practical volume, and
applying cover material at the end of each operating day."! A chemical waste
landfill is a modification of the conventional sanitary landfill to make it
acceptable for receipt of hazardous materials. In general, the landfill should
provide long-term protection for the quality of surface and subsurface waters
from hazardous deposits therein, and against hazards to public health and the
environment.!
It is assumed that the operation of a landfill is at the site of a typical
plant. Quantities of waste are based on the Individual waste stream only (not
accepting waste from other sources).
At best, a chemical land disposal is Level II technology, but in some
cases it may be the only alternative for waste disposal. Most of the criteria
used for design of a sanitary landfill for municipal wastes can also be applied
to a chemical land disposal. These criteria are well established in the liter-
ature, as well as documented in EPA publications.!"?
Cost Analysis (See Table 7-1). Costs have been developed for disposing of
hazardous wastes in a sanitary landfill which is really an unacceptable method
but was generated for comparison. The mode of operation was the same as for
*
municipal refuse.
VII - 1
-------
TABLE HO. 7 - 1
WASTE STREAM LANDFILL COST SUMMARY
Waste
Sanitary Landfill
Chemical Landfill
Products and
Streao No.* Typical Plant Size
1 Perchloroethylene
39,000 KKg/yr.
2 nitrobenzene
20.000 KKg/yr.
3 Chloromethane
50,000 KKg/yr.
4 Eplchlorohydrin
75,000 KKg/yr.
M
|_4
1 5 Toluene Diisocyantes
N 27,500 KKg/yr.
6 Vinyl Chloride
Mono. 136,000
KKg/yr.
7 Methyl Methacrylate
55,000 KKg/yr.
8 Acrylonitrile
80,000 KKg/yr.
9 Maleic Anhydride
11.000 KKg/yr.
10 Lead Alkyla
60,000 KKg/yr
Waste Streaa
Components
Hexachlorobutadlene
Chlorobenzenes
Chloroethanes
Chlorobutadiene Tars
Crude Nitrated
Aroma ties
Hexachlorobenzene
Hexachlorobutadlene Tara
Eplchlorohydrin
Dichlorohydrln
Chloroethers
Trichloropropane Tarn
Polyur ethane
Ferric Chloride
Isocyanates Tars
1,2 Dichloroe thane
1,1,2 Trichloroethan£
1,1,1,2 Tetrachloroethane
Tars
Hydroquinone Polymeric
residues
Acrylonitrile
Higher Nitriles
Maleic Anhydride
Fuoaric Acid
Chroaogenic Compounds
Tars
Lead
Generation
KKg/Year
12,000
50*
300*
4,000
558*
1,400
4.730
160*
333*
30,000
Cost $/
KKg Waste
10.00
98.00
97.00
17.00
97.00
17.00
17.00
98.00
98.00
7.00
Cost Impact $/
KKg Prod.
3.15
0.24
0.58
0.92
2.08
0.25
1.43
0.19
2.95
3.53
Cost $/
KKg Waste
48.00
157.00
128.00
55.00
156.00
67.00
76.00
158.00
166.00
61.00
Cost Impact $/
KKg Prod. ~
16.00
0.39
0.77
2.90
3.34
0.94
6.55
0.31
5.02
31.00
*Se« Table 2-1.
-------
TABLE NO. 7-1 (CONTINUED)
WASTE STREAM LANDFILL COST SUMMARY
Waste
Sanitary Landfill
Chemical Landfill
Products and
Stream No. Typical Plant Size
11 Ethanolamlnes 14,000
KKg/yr.
12 Furfural 35,000 KKg/yr.
13 Furfural 35,000 KKg/yr.
14 Fluorocarbon 80,000
KKg/yr.
£3 15 Chlorotoluene
15,000 KKg/yr.
U> 16 Chlorobenzene
32,000 KKg/yr.
17 Atracine 20,000 KKg/yr.
18 Trlfluralln
lO.OOO KKg/yr.
Waste Stream
Components
Triethanolamine Tars
Sulfuric Acid Tars and
Polymers
Fines and Participates
from Stripped Hulls
Antimony Pentachloride
Carbon Tetrachloride
Trichlorofluorome thane
Organics
Benzylchloride
Benzotrichloride
Polychlorinated Aromatic
Resinous Material
Water
Sodium Chloride
Insoluble Residues
Caustic
Cyanuric Acid
Spent Carbon Fluoro-
aromatlcs
Generation
KKg/Year
1,120
19,600
350*
18*
15*
1,400
224.600
Cost $/ Cost Impact $/
KKg Waste KKg Prod.
18.00
8.00
Combined
98.00
98.00
17.00
6.00
1.40
4.46
with Stream 12
0.02
0.10
0.77
71.00
Cost $/ Cost Impact $/
KKg Waste KKg Prod.
77.00 6.18
76.00 43.00
117.00 0.03
156.00 0.17
70.00 3.08
NA NA
(huge water volume makes
chemical landfill
Impractical.)
19
Malathlon 14,000
KKg/yr.
Intermediates and
Solvents 1,150 18.00 2.04
Filter Aid
Toluene
Insoluble Residues
Diaethyl Dithiopbospltoric
Acid 1,826 18.00 1.80
326.00
326.00
38.00
43.00
-------
TABLE NO. 7 - 1 (CONTINUED)
WASTE STREAM LANDFILL COST SUK'IARY
Waste Sanitary Landfill Chemical Landfill
Stream No.
20
21
22
23
24
Products and
Typical Plant Site
Malathlon 14,000
KKg/yr.
Parathlon 20,000
KKg/yr.
Explosives 93,000
KKg/yr.
Explosives 30,000
KKg/yr.
Explosives 125.000
KKg/yr.
Waste Stream
Components
Malathlon
Toluene
Impurities
Sodium Hydroxide
Dlethyl Thlophosphorlc
Acid
Activated Carbon
Nitrobodies
Kedvater Nitrobodies
of DNT
Waste Explosives
Generation
KKg/Year
14,350
2,300
350*
15,000
250*
Coat $/
KKg Waste
18.00
17.00
NA
NA
NA
Cost Impact $/
KKg Prod.
0.44
2.00
HA
NA
NA
Cost $/
KKg Waste
76.00
70.00
NA
NA
NA
Cost Impact $/
KKg Prod.
1.90
8.00
NA
NA
NA
NA - Not Applicable, see page 1-9.
*Druamed for Landfill
-------
The costs of chemical or secure landfills were developed using the sanitary
landfill techniques modified to insure the protection of subsurface water.
The following parameters were used: (See Figure No. 7-1).
1. Trench method of operation.
2. Landfill lined with compacted colloidal clay.
3. Synthetic liner over clay layer.
4. Primary leachate collection system (no leachate treatment).
5. Percolation barrier over each landfill.
6. Compacted cover material over the entire landfill.
7. Where applicable, encapsulation or chemical fixation was considered.
8. Land purchase was for one year's operation.
VII - 5
-------
X/XV >
Z
'IT>
'„-,
y' f^r sy rSw/>
MATRL.
f//////f//i/////i f//fs7/f/ 7/r / //.//fill
X:
\
\
_Q Q_ Q
.//. ,0,.;
/ /
<^LAY , , x
/ /////v> //////e//'(// / /////
MATUPAL-
WATER „ TABLE
TYPICAL £RQ55 SECTION
LAMPFILL
Ho.
YII - 6 .
-------
It was assumed that each liquid or semlliquid waste stream would require
•« . 3
either chemical fixation or encapsulation. A bench-scale pilot unit could be
used to determine the best technique. The cost for encapsulation or chemical
fixation was also assumed the same. This is a major portion of the overall
treatment cost for each waste stream; i.e., approximately 50-60 percent of
total treatment cost.
Drumming costs were added to those waste streams whose quantity amounted
to 20 drums or less per day. This cost is approximately $80 per metric ton of
waste generated. Waste streams whose quantities exceeded 20 drums per day
were assumed to be collected in tank trailers or tote bins for transport to
the landfill site depending on whether the waste is liquid or solid. The cost
for tank trailers or tote bins and the labor involved in transporting these
containers has little effect on the total costs.
It was assumed that there would be no significant difference in cost per
square meter for liner materials even though the materials of construction
would differ among waste streams.
Basis For Estimating
1. Land Cost equals $12,350 per hectare ($5,000 per acre).
2. Sanitary Landfill
a. Volume equals 1.25 R 1-P
D 100
V equals volume in cubic meters
R equals waste in MT
D equals density in cubic meters per MT
VII - 7
-------
P equals percent reduction from compaction
(Empirical formula from American Public Works)
e
b^. Disposal Cost. Curve developed from TRW report for cover
material, landfill equipment, and landfill labor.^
£. Leachate Cost. $1.32 per 1,000 liters or $1.30 per MT.6
3. Chemical Landfill
ja. Construction as shown in Figure No. 7-1.
1». Excavation and Haul. $5.25 per cubic meter (derived from ).
£. Compacted Backfill. $4.40 per cubic meter (derived from ).
d/ Liner Cost. $5.89 per square meter. Assumed 30 mil Hypalon
liner, or equivalent. (Derived from information from liner manufacturer).
£." Leachate Collection Sy s t em. $16,000 per hectare (derived from
EPA/530/SW-165, September 1975).
JL« Chemical Fixation or Encapsulation. $.05 per liter (derived
from EPA/530/SW-165, September 1975).
£. Operating Cost. $1.50 per MT or $1.50 per 1,000 liter (from
TRW curve for equipment and labor).
4. Quantity of land purchased was based on that needed for one year's
operation.
5. Densities and physical characteristics used to arrive at waste
stream volumes are approximate. Ranges used are: .23MT equivalent to municipal
m3
refuse to 1.6MT for heavy ends from perchloroethylene.
m3
VII - 8
-------
6. Cost Estimating Method for Sanitary Landfill.
£. Determine volume required in cubic meters.
t>. Assuming 2-3 meter cell layers are available for use, determine
surface area required:
Surface Area Required " V_ x W^ hectares
6
£. Multiply wrface area by cost of land ($12,3$0/ha).
ji. Use curve developed for cover material, landfill equipment,
and landfill labor. Escalate to 1977.
£. Add cost in A. to land cost.
jr.. If leachate treatment costs are to be included use $1.30 per
MT of wastes.
Example: Stream No. 5, Centrifuge Sludge - 588 Ml/year
Volume - 1.25 R x l^P - 1.25 x 588 x 1-50
D 100 1.23 100
- 735 m3.
Land Cost - 735 m3 x 10 ~4 x $12,350 - $150
6 m
Disposal Cost * $10/MT x 588 MT x Escalation
(From curve)
- 10 x 588 x 1.59 - $9,350
Leachate Cost - $1.30/MT x 588 MT • $ 765
Total $10,265
Cost for Drumming - $80/MT of waste
VII - 9
-------
Cost per MT of Waste » $10,265 + $80 - $97.
588
Cost per MT of Product = $10?265 + 588 x 80 - $2.08
27,500 27,500
7. Cost, Estimating Method for Chemical Landfill
£. Using density known or assumed kke, determine volume of waste.
m-*
_b. Using volume and assuming 1.5m depth of waste, determine area
required for 20 year life and multiply by land cost. ,
£. Using 3m for total excavation depth, determine excavation and
haul quantity and multiply times cost for excavation and haul.
jl. Using 1.5m, for total compacted clay and cover material,
determine quantity and multiply times cost for Imported clay plus compaction.
e_. Determine n»2 of liner material for 2 liners and multiply times
cost of liner.
f_. Determine leachate collection system cost, i.e., $16,000/ha.
£. Add cost for chemical fixation or encapsulation at $50/kkg or
$.05.
1
h. Determine operating cost at $1.50/kkg.
Example: Stream No. 5, Centrifuge Sludge - 588 kkg/year
(1) Using Density - 1 kkg. Volume - 588 m3
mj
(2) Land Cost - 588 m3x IP"4 ha x $12.350 - $484
1.5 m "m2" ha
(3) Excavation and Haul - $5.25 x 588m3 x 3m - $6,175
n? 1.5m
(4) Imported Clay Plus Compaction = $4.40 x 588m3 x 1.5m - $2,590
ta~ 1.5m
VII - 10
-------
(5) Liner Cost - 2 x 588m3 x $.55 x 10.7 feet2 - $4,615
1.5m feet7 m2
(6) Leachate Collection System Cost - 588m3 x 10"ftha x $16,000
1.5m m2ha
- $650
(7) Encapsulation or Chemical Fixation Cost »
588 kkg x 1000 x $.05 - $29,400
1.0 1
(8) Operating Cost - $1.50 x 588 - $885
MT
Total $44,800
Cost for Drumming - $80/lckg of waste
Cost per MT of wastes - $44,800 + $80 - $156
588
Cost per MT of product - $44,800 + 588 x 80 - $3.34
27,500 27,500
VII - 11
-------
References
1. Fields, Timothy, Jr. and LIndsey, Alfred H., Landfill Disposal of Hazardous
Wastes: A review of Literature and Known Approaches. Environmental
Protection Publication SW-165. U. S. Government Printing Office, 1975.
36 pp.
2. American Public Works Association. Municipal Refuse Disposal. 2nd
Edition, 1966.
3. Hanson, Robert J. and Merritt, Clifford A., Land Application of Liquid
Municipal Wastewater Sludges. Journal Water Pollution Control
Federation, 47,(1): 23, January 1975.
4. Office of Solid Waste Management Programs. SW-87d. Unpublished data.
' 5. Office of Solid Waste Management Programs. Assessment of Industrial
Hazardous Waste Practices: Organic Chemicals, Pesticides and Exploj
Industries. Environmental Protection Publication SW-118c. U. S.
Government Printing Office, 1976.
6. Office of Solid Waste Management Programs. Analysis of Potential
Application of Physical, Chemical and Biological Treatment Techniques
to Hazardous Waste Management. EPA Contract No. 68-01-3554.
7. Proceedings; Hazardous Waste Research Symposium, University of Arizona,
February 2-4, 1976. Environmental Protection Agency Publication
EPA-600/9-76-015, July 1976, 269 pp.
8. Personal Communication. E. P. Grumpier, OSWMP, to J. M. Censer,
Processes Research, Inc., 9 September 1976.
9. Personal Communication. E. P. Grumpier, OSWMP, to J. M. Genser,
Processes Research, Inc., 12 October 1976.
lO. Moselle, G., National Construction Estimator, 25th Edition. Solano
Beach, California, Craftsman Book Company of America, 1977. 242 pp.
yo!619
SW-lSlc
VII - 12
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