Waste Disposal at a Synthetic Rubber Plant
Author(s): L. D. Dougan and J. C. Bell
Source: Sewage and Industrial Wastes, Vol. 23, No. 2 (Feb., 1951), pp. 181-187
Published by: Wiley
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WASTE disposal at a synthetic rubber
PLANT *
By L. D. Dougan and J. 0. Bell
Assistant Manager and Process Chemist, respectively, Polymer Corporation Ltd., Sarnia,
The synthetic rubber industry series
and of continuous unit operations
its waste disposal problems are and
rela
unit processes subgrouped into the
tively new to this continent. process
The units. In addition to the proc
waste problems differ considerably ess
forunits there are control and research
different plant sites, depending on laboratories,
the two pilot plants, a main
raw materials used and the number of shop, an instrument shop, the
tenance
intermediates produced. This paper
storehouse, and the administration of
fices.
deals with waste disposal at the plant ofFollowing are brief descriptions
Polymer Corporation Limited, Sarnia,
of the basic unit operations and unit
Ont. processes, which are combined to make
The Polymer plant, located a few up the total process.
miles south of Sarnia on the St. Clair The steam and power plant, using
River, was built by the Dominion Gov pulverized coal as fuel, supplies process
ernment during World War II for the steam, electric power, and service wa
manufacture of synthetic rubbers. ter to the other units of the plant.
Construction and total operation were The boiler feedwater is lime-soda soft
accomplished between June, 1942, and ened and treated internally with phos
March, 1944. Since the war, produc phate. The wastes of the power plant
tion of rubber has been maintained, are softener and boiler blowdown, flue
with approximately 30 specialized rub gas, fly ash, and sluice ash.
ber types. In addition, the manufac Fractional distillation, carried out in
ture of chemicals, steam, electric power, towers similar to those of an oil re
and process water for other consumers finery, is the commonest unit operation
has been undertaken.
employed in the plant. It is used in
The Process and Its Wastes all the process units for separation of
hydrocarbon mixtures. Compression,
Using a mixture of light petroleum refrigeration, and heat exchange with
hydrocarbons, benzene, and isoprene cooling water are used as auxiliary op
as constituent raw materials, the Poly erations. Greatest use of fractional
mer plant integrates in a single project distillation is made in the light ends
the production of butadiene, styrene, recovery unit. The wastes associated
and isobutylene monomers and the var with fractional distillation, are hydro
ious types of general purpose, spe carbon blowdown and blowoff of safety
cialty, and butyl rubbers produced valves and small amounts of lubricat
from these monomers.
ing oils from pumps and compressors.
Table I is a list of the process units Countercurrent washing and extrac
showing their functions, raw and ac tion are other related and common unit
cessory materials, products, and wastes. operations used in the plant. In some
The total process is composed of a locations hydrocarbon gas streams are
* Presented at 1950 Annual Meeting, Cana
washed with water or dilute caustic
dian Institute on Sewage and Sanitation; solution to remove traces of soluble im
Lake of Bays, Ontario; Sept. 11-13, 1950. purities, the wash stream constituting
181
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182 SEWAGE AND INDUSTRIAL WASTES February, 1951
TABLE I.?Functions, Products, and Wastes of Synthetic Rubber Process Units
Process Unit Function Raw and Accessory Products Wastes
Materials
1. Steam and Provide service water, Coal, fuel oil, fuel gas, Service water, Sluice ash, fly ash, stack
power process steam, and water, lime, soda, phos steam, electrical gases, softener sludge,
electrical power. phate. power. boiler sludge.
2. Light ends Purify hydrocarbon Hydrocarbon mixture Fuel gas, ethylene, Hydrogen sulfides, mer
recovery feed, fractionate hy (methane to hexane plus propane-propylene captans, spent caustic,
drocarbon mixture, unsaturated homo cut, butane-buty light hydrocarbons, oils.
and crack ethane to logues) caustic soda, lene cut, pentane
ethylene. diethanolamine. and heavier cut.
3. Isobutylene Extract and purify Butane-butylene cut, Isobutylene, spent Sulfuric acid, C* hydro
extraction isobutylene. sulfuric acid, caustic C4. carbon, caustic soda.
soda.
4. Butyl?ne con Separate and purify Butane-butylene cut, n-butylene, butane. Acetone, oils, C* hydro
centration n-butylene. acetone, caustic soda. carbon, caustic soda.
5. Butyl?ne de Dehydrogenation of n-butylene, steam, fuel Butadiene-rich hy C< hydrocarbon, oils,
hydrogenation butyl?ne to butadiene. oil, fuel gas, quench oil. drocarbon mixture. stack gas.
6. Butadiene ex Extract and purify Butadiene-rich hydro Butadiene, spent C4 hydrocarbon, cuprous
traction butadiene. carbon mixture, cuprous C4. ammonium acetate solu
ammonium acetate solu tion, oils.
tion, flux oil.
7. Ethylbenzene Alkylation of benzene Ethylene, benzene, cata Ethylbenzene. Fuel oil, tar, hydro
and purification of lyst, caustic soda. chloric acid, caustic
ethylbenzene. soda.
8. Styrene Dehydrogenation of Ethylbenzene, catalyst. Crude styrene, fuel
cracking ethylbenzene to sty gas.
rene.
9. Styrene Purification of styrene.
Crude styrene, sulfur. Styrene. Heavy tar.
finishing
10. Butyl rubber Polymerization andMethyl chloride, cata Butyl rubber. Scrap butyl, oil, light
finishing of butyl lyst, ethylene, fuel gas. hydrocarbons.
rubber.
11. Copolymer Polymerization and Butadiene, styrene, General purpose and Butadiene, styrene
finishing of general brine, sulfuric acid. specialty rubbers. serum, softener sludge.
purpose and specialty
rubbers.
the waste. In the light ends recovery related unit processes used in the light
unit, both diethanolamine and caustic ends recovery unit for converting
soda are used to extract hydrogen sul ethane to ethylene, in the butadiene
fide and mercaptans from the hydro dehydrogenation units for converting
carbon feed to the plant. The solvents butyl?ne to butadiene, and in the sty
are regenerated by heating to drive r?ne cracking unit for converting
off hydrogen sulfide and mercaptans ethylbenzene to styrene. The process
as waste gases. The solvents become consists of exposing hydrocarbon mix
wastes only in cases of leaks or spills or tures to a high temperature with or
when the caustic soda cannot be re without the use of steam and/or a
generated due to build-up of sodium catalyst. The wastes associated with
hydrogen sulfide. In the isobutylene cracking and dehydrogenation are hy
extraction unit and the butadiene ex drocarbon blowdown and blowoff of
traction unit, strong sulfuric acid and safety valves, stable oil-in-water emul
cuprous ammonium acetate solution, sions, stack gases, and spent catalyst
respectively, are contacted with liquid or its breakdown products.
hydrocarbon streams for the extrac Polymerization is the chief unit
tions. These solvents are recycled and process used in the two rubber units.
become wastes only in cases of leaks or In the butyl rubber unit, isobutylene,
spills. Here again, hydrocarbon blow isoprene, and a catalyst are reacted in
down and blowoff of safety valves con liquid methyl choride solution at ? 150?
stitute the waste. F. to produce butyl rubber. The
Cracking and dehydrogenation are crumbs of rubber are first wet, then
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POLY
OU
WAS
FIGURE 1.?Schematic diagram of syn
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184 SEWAGE AND INDUSTEIAL WASTES February, 1951
screened, dried, milled into a sheet, elude boiler and softener blowdowns
and cut into lengths for packaging. In and sluice ash. Inorganic dissolved
the copolymer rubber unit, butadiene, wastes include caustic soda, sodium hy
styrene, and other monomers are re drogen sulfide, sulfuric acid, cuprous
acted as an emulsion in aqueous soap ammonium acetate, brine, hydrochloric
solution to form a rubber latex. The acid, and aluminum chloride.
latex is coagulated, then the coagulum The potential atmospheric contami
in turn is filtered from the serum, nants also have widely distributed ori
washed, dried, and compressed into gins and may be classified conveniently
blocks for packaging. The wastes as follows : odorous and corrosive gases,
from these two processes consist of highly inflammable gases, and fly ash.
The odorous and corrosive gases in
waste rubber in various forms, styrene
emulsion, and acidified brine-serum clude stack gases, hydrogen sulfide,
mixture. vaporized mercaptans, and hydrogen
Alkylation of benzene is carried out chloride. The highly inflammable gases
by contacting a mixture of ethylene include safety valve blowoffs of light
and benzene with a catalyst. The prod hydrocarbons plus periodic blowoffs
uct is a crude solution of ethylbenzene. due to upsets or shutdowns. Fly ash
Wastes from this process are hydro is found in the power plant stack gas.
chloric acid, caustic soda solution, tar, Another class of wastes are those
and safety valve blowoff. bulk quantities of materials which must
The Waste Problem be disposed of periodically. These
include scrap rubber, spent catalysts,
The waste problem has two aspects tars, sludge from brine softening, and
?the immediate one of installing and garbage.
operating facilities to prevent river
and atmospheric contamination and Original Design of Disposal System
the longer term one of continual effort Figure 1 is a schematic diagram of
to reduce losses, re-use, or to recover the waste disposal system, the original
and develop useful outlets for wastes. facilities being indicated with plain
In this latter aspect all wastes may be hatching.
considered temporary, as they repre Potential River Contaminants
sent either valuable intermediate and
accessory materials or potentially use The original design provided for a
ful materials. subdivision of used water disposal via
At Polymer, the potential river con an oily-water sewer, a trade waste
taminants are discharged to the waste sewer, and a cooling-water sewer.
disposal system in about 4 per cent The oily-water sewer was built to
(3.4 m.g.d.) of the total service water, carry oil-bearing waters. It was pro
the other 81.6 m.g.d. being used as cool vided with two separators: one, an al
ing water. As indicated in the previ ternate overpass-underpass type at the
ous section, the origins of the wastes copolymer unit for separation of rub
are widely distributed and the types ber wastes for disposal; the other, an
at the origins are fourfold; namely, A.P.I, oil separator near the outlet of
organic, suspended and dissolved, plus the sewer for removal and reclamation
inorganic, suspended and dissolved. of slop oil. The outlet of the oily-water
Organic suspended wastes include sewer was connected with one of the
emulsified and free oils and particles large cooling-water sewers for dilution
of rubber from colloid size to fairly of any wastes escaping the A.P.I, sepa
large chunks. Organic dissolved wastes rator. All manholes on the oily-water
include acetone and traces of dissolved sewers were vented through pipes ex
oils. Inorganic suspended wastes in tending 15 ft. above ground level to
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Vol. 23, No. 2 WASTE DISPOSAL AT SYNTHETIC EUBBEE PLANT 185
?56
DISTRIBUTION OF RUBBER POLLUTION ALONG ST. CLAIR RIVER BANK IN 1949-50
Survey of April 11/49 Total pounds of rubber to 25 miles below Polymer 650
Survey of June 15/4.9 Total pounds of rubber to 33 miles below Polymer - 264
Q - Survey of Nov. 10/49 Total pounds of rubber to 3 miles below Polymer s
(No rubber found between 3 and 34 miles below Polymer.)
? - Survey of May 11/50 Total pounds of rubber to 20 miles below Polymer s
I'll
Polymer
I
Corunna
I l Mooretown Courtrig
Miles Downstream from Polym
FIGURE 2.?Rubber pollution dist
provide for power plant.
the harmless
drain into reg
volatile hydrocarbons.
The trade waste sewer
overflows was
from
to carry soluble inorganic
ing-water w
sewer
as acids, alkalis, and brine
tor inPotential
fines the
recovery Atmo
buil
Two flare
copolymer unit was providestack
stalled
ration of rubber and to
prior conn
d
serum to the blowoffs
trade waste and
sewb
of them
Two cooling-water was a
sewers
hydrogen
stalled to carry the largesulfv
captans. These
used cooling water and stor
One of the cooling
vided withwater
pilo
ceives processends to assure
water from
Unit after it ofhas
thepassed
gases. F t
on top of the p
series of separating sumps, p
cooling water for the from
mixed emiss
benzene andheight
Styrene Unit
of 185 f
the effluent
of the oily wate
Bulk Wastes
low the
A.P.I, separator.
cooling-waterA dumping
sewer s
receive
flow from a thelarge bulk waste
pit, whi
stituents
stalled for the of an
settling w
of the sluice ash
periodically. from the
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186 SEWAGE AND INDUSTRIAL WASTES February, 1951
Improvements in Waste System at the butadiene dehydrogenati
Facilities added to the waste dis coalescer.
posal system since the original instal
7. Eeduction of styrene waste and
breaking of the styrene-in-water emul
lation are indicated in Figure 1 with
sion at the copolymer unit.
cross hatching.
The oily-water sewer was called upon The oil separator effluent is diluted
to handle considerable quantities of with 23 times its volume of cooling
rubber fines and styrene emulsion, as water several hundred yards before en
well as emulsified and free oil. During tering the river (where it enters the
the early period the separators were cooling-water sewer).
used to accumulate the rubber wastes. The trade waste sewer was receiving
The results were agglomeration and acids and alkalis in batch discharge.
further polymerization of the wastes, These have been largely put on a con
by-passing, poor separating efficiency, tinuous basis and the quantities of
and periodic major cleanouts requiring acids and alkalis are roughly equiva
several days and much labor. A coni lent so that the pH of the effluent at
cal bottom sludge separating tank was the river ranges from 6 to 8. The at
erected at the A.P.I, separator and mospheric acid concentrator at the
daily skimming of the oil-rubber-solids isobutylene purification unit was re
water sludge from the separator to the placed with a vacuum concentrator,
tank was instituted. Weekly skimming which decreased sulfuric acid dis
of the primary section of the copolymer charge by 63 per cent and lengthened
separator was adopted, using a pump the period between changing the acid
with a movable suction. A coalescer in the system from three months to
and separator was installed at the buta three years. The separator in the
diene dehydrogenation unit to break fines recovery system at the copolymer
the oil-in-water emulsion and recover unit is of the alternate overpass-under
quench oil. Facilities were installed at
pass type and was originally covered.
the copolymer unit to permit further The cover has been removed and it is
recovery of styrene from water and to now skimmed frequently enough to
coagulate styrene from water during keep the last two sections free of float
periods of unavoidable loss. The net ing solids. The result is that the aver
results of the changes outlined above age suspended content of the separator
were: effluent has decreased from 450 to 100
p.p.m. and only the finest material
1. Improved average condition of the
escapes.
A.P.I, oil separator effluent?namely,
Regular inspection and cleanout of
a reduction of total organic content
all separators, sumps, and septic tanks
from 465 p.p.m. to 300 p.p.m.
hasand oil
been instituted. In addition to the
content from 140 p.p.m. to 70 p.p.m.
dilution that various wastes receive
2. Reduction of 50 per cent in oil
loss to burning pit. within the cooling-water sewer, all ef
3. Reduction of 75 per cent fluent streams are brought together at
in clean
ing time and, therefore, down time ofpoint at the river bank so
a common
oil separator. that all waste-bearing streams get a
4. Reduction of 60 per cent dilution
in down of about 1:24 with used cool
time of copolymer separator. ing water. As a yardstick of the down
5. Reduction of sewer and manhole
stream rubber pollution and progress
fouling between the two separators.
of the waste disposal program, periodic
surveysand
6. Reduction of quench oil waste have been made of the rubber
breaking of the oil-in-water pollution
emulsion on the river bank to 20 miles
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Vol. 23, No. 2 WASTE DISPOSAL AT SYNTHETIC RUBBEE PLANT 187
downstream. The results of these sur large, but their points of origin are
veys are shown in Figure 2. widely scattered. In addition the
A fly ash removal system installed at methods of treatment required vary
the steam and power plant removes 85 and it is necessary, generally, to give
per cent of the ash from the stack gases individual attention at the source
and carries it in water slurry 2.5 miles rather than to use a common treating
to a disposal site. system. These facts were recognized
The disposal site for bulk wastes has in the original plant design. It has
been changed from a location near the been possible, therefore, to bring about
river to 2.5 miles inland near the fly the considerable improvements de
ash disposal site. scribed at a minimum cost. If a com
mon collecting system only had been
Conclusion
provided, much of the reduction of un
The amounts of contaminating mate desirable discharge would have been
rials in a plant of this type are not very difficult economically.
NUCLEAR REACTOR TECHNOLOGY SCHOOL
Industrial organizations interested nuclear engineering involve the same
in obtaining special training in nu fundamental engineering and manage
clear reactor technology for experi ment skills common to industry gen
enced engineers in their employ are erally. This school offers an unpar
invited by the U. S. Atomic Energy alleled opportunity for experienced
Commission to sponsor their enroll engineers to obtain a thorough under
ment in the 1951-52 session of the Oak standing of the specialized problems
Ridge School of Reactor Technology. the AEC deals with in its nuclear engi
Application deadline is April 1, 1951, neering program. Trainees remain on
and the school term begins September the payrolls of their home organiza
10, 1951. tions, and upon returning after com
Established in 1949 at the Oak Ridge pletion of the course, can be expected
National Laboratory, the school oper to help strengthen their companies '
ates a 12-month session open to two position to participate in the national
categories of engineering candidates. atomic energy program.
A limited number of recent college Further information and applica
graduates are accepted in category A tion forms may be obtained by writing
in the status of student employes. to the Director, Oak Ridge School of
Category B students are selected from Reactor Technology, P. 0. Box P, Oak
the applications sponsored by govern Ridge, Tennessee.
ment agencies and private industrial Because much of the material pre
firms interested in participating in sented in the curriculum of the Oak
the AEC national nuclear energy pro Ridge School of Reactor Technology
gram. Such firms need not be con will be classified, all enrollments are
nected with the AEC currently. contingent upon a personal security
Officials of the Oak Ridge Reactor investigation. Announcements of ap
School point out that the majority of pointments are expected to be made in
problems encountered in the field of April.
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