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CHAPTER 27
THE PLASTICS INDUSTRY
CHARACTERISTICS OF THE WASTE WATER
The main raw materials used for the production of plastics are
ethene, vinyl chloride, styrene, phenols, formaldehyde, urea,
acetylene and benzene.
The production of these monomeric compounds involves waste wa-
ter problems that have been mentioned in conjunction with the or-
ganic chemicals industry. The waste water problems o f the poly-
merization process will be treated in this chapter. The final
formation o f the polymers does not involve waste water problems
which cannot be solved by settling, since the polymers are gene-
rally insoluble in water.
The basic production processes for the polymers are condensa-
tion and polymerization in the presence of catalysts. Sometimes
intermediate stages are necessary.
The plastics industry discharges relatively small amounts of
polluted water. The greater portion of the effluent is cooling
water, but a small amount of polluted effluent contains certain
quantities of intermediate products, by-products and end-products
which are present in solution either as suspended solids or as
emulsions.
Resin, organic acids, tetrahydric alcohol, pentaerythritol,
formaldehyde, sodium formate, phenols, urea and, benzene might
be present, depending on the polymers being produced.
The concentration of the impurities varies over a fairly wide
range (Dickerson, 1 9 4 9 and 1950). The BOD value may be anything
from 200 to 10000 m g 02/1. The waste water is generally acidic.
Three types of waste water can be distinguished in the plastics
industry:
1. Waste water which contains biodegradable monomeric and poly-
meric compounds, such as the waste water from the manufacture
of polyacrylics.
2. Waste water which, in addition to non-refractory compounds con-
tains nutrients and suspended refractory compounds which are
often partially polymerized materials. This type of waste wa-
ter is produced i n the manufacture of polystyrene and poly
-ethylene.
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3 . Waste water which as well as non-refractory compounds contains
toxic materials such as cyanide. This type of waste water
comes from the manufacture of polyacrylonitrile, acrylo-ni-
trile-butadienestyrene copolymers and others.
Table 27.1 shows a characteristic analysis of the three types
of waste water.
TABLE 27.1
Waste water from the plastics industry
Type 1 Type 2 Type 3
PH 3-7 1-2 6-8
COD (g/l) 2-5 2-5 4-10
Dry matter (g/l) 1-6 2-8 4-10
Ignition residue (mg/l) 50-100 50-100 10-50
BOD;:, (mg/l) 1000-3000 200-500 200-500
Tur idity high opal high
Colour white white white
1-2 200-400 1-2
p (mg/l)
Acrylonitrile (mg/l ) - - 20-200
Biological treatment and chemical precipitation
Biological treatment is used to solve the problem of waste wa-
ter of type 1 (Harkness, 1964).
Waste water with the characteristics given in Table 27.1 can be
treated in an activated sludge plant. The LF value is 0.4 and
a COD reduction of 92% and a BOD reduction of 98% can easily be
achieved.
Chemical precipitation is often an attractive solution for waste
water of type 2. Calcium hydroxide is used as a coagulant, which
also precipitates the phosphate. Suspended materials as well as
emulsified materials will be removed by this treatment.
A waste water treatment plant can consist of the following
four stages:
1. Neutralization.
2. Flocculation and precipitation.
3 . Settling.
4. Centrifugation o f sludge.
Table 27.2 shows the analysis of waste water type 2 (see Table
27.1) after chemical precipitation. It can be seen that the COD,
BOD and phosphorous concentrations are considerably reduced.
5
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The result of this treatment is completely satisfactory. How-
ever, the temperature of the waste water might cause thermic pol-
lution, which of course must be taken into consideration (cooling
tower) before the waste water is discharged into the receiving
water.
TABLE 27.2
Analysis of waste water type 2 (Table 27.1) after chemical
precipitation
PH+ 10-11
COD (€?/I) 0.1-0.2
BOD5 (mg/l) 20-50
Dry matter (g/l) 0.2-0.5
Ignition residue (mg/l) 40-80
Colour none
p (mg/l) 2-10
+ ) Neutralization to pH <8 must be effected.
Other methods
Detoxification of cyanide can be carried out either by a strip-
ping process or by oxidation with chlorine.
Biological treatment is possible when cyanide is present in small
concentrations, but it will often be more costly than oxidation
with chlorine. The solution mentioned in chapter 13 can be used
for the chlorine oxidation.
Another possibility is treatment with hydrogen peroxide in alka-
line solution, The following process takes place:
RCN + 2H202 P RCONH 2 + H20 + O2 (27.1)
In Fig. 27.1 the efficiency of this process is given as a func-
tion of time with various ratios between H202 and RCN.
In accordance with equation 27.1 the stoichiometric ratio of
H202 and RCN is 2, but to obtain an acceptable efficiency a stoi-
chiometric ratio of 3 is recommended. Increasing the temperature
increases the efficiency as seen from Fig. 27.1.
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1 2 3 4 5 ho-;rs
Fig. 27.1. Detoxification as a function of time.
H2°2 = 10; ( 2 ) RCN
H2°2 = 3; (3) RCN
H2°2 = 2, all at 60°C.
(l) RCN
(4) is the mol relation 10, and (5) is 2, both at 25OC.
REFERENCES
Dickerson, B.W., 1949. How wastes are disposed of at a synthetic
resin plant. Chem. Ind., 65: 38.
Dickerson, B.W., 1949. A high-rate trickling pilot plant for cer-
tain chemical wastes. Sew. Works J., 21: 685.
Dickerson, B . W . , 1950. High-rate trickling filter operation o n
formaldehyde wastes. Sew. Ind. Wastes, 22: 636.
Harkness, N. and Jenkins, S . H . , 1964. Laboratory-scale treat-
ment o f effluent from synthetic resin manufacture. Treatment
after dephonolation. J. & Proc. Inst. Sew. Purif., Part 4:
337, 382.
Kohn, P.N., 1976. New process wins acidic acid from waste streams.
Chem. E n g . , : 58.
