Professional Documents
Culture Documents
ROLF NILSSON
Boliden Reymersholmsverken Research Laboratory, Helsingborg, Sweden
Abstract--The reduction of the metal content of waste water by chemical treatment with
aluminium sulfate or calcium hydroxide has been studied.
Pb(II), Cu(II), Cr(III), Hg(II), Cd(II) and As(V) are reduced to low levels by both precipi-
tants. Zn(II), Ni(lI) and Co(II) are precipitated only at pH-values _< 9.5. The precipitation of
Cu(II) and Pb(II) is greatly inhibited by the presence of nitrilotriacetate at pH _< 9.
INTRODUCTION
THE PRESENCEof metal ions in surface waters is a problem of increasing importance.
Mercury, for example, is causing great inconvenience. The mercury content of fish
in many places is so high that the fish are unsuitable for human consumption.
It is desirable to prevent the introduction of metals into waste water as much as
possible.
Even if it is necessary to avoid the introduction of metal ions into waste water, it
is of interest to know to what extent metals are removed when the water is chemically
purified.
In order to investigate this, the removal of metals by chemical treatment of the
water with aluminium sulfate or calcium hydroxide was studied.
EXPERIMENTS
The experiments were carried out with tap water and with municipal waste water.
In some cases orthophosphate was added to the tap water. A solution of a metal salt
was added. The water was then left for 3 h in order to allow the metal ions to be
chelated by organic substances in solution or to be absorbed by suspended particles.
During that time the samples were shaken from time to time. Then aluminium sulfate
of Boliden AVR quality or calcium hydroxide was added. The sample was slowly
stirred for 20 min and the floes were then allowed to settle. Some of the analyses were
performed at a simulated surface load of 0.5 m a (m 2. h) -1 by sedimentation. Most of
the analyses were, however, done after removing suspended particles by centrifuga-
tion. As the latter method gives a better reproducibility, it is of greater interest in this
connection.
In some cases sodium nitrilotriacetate (NTA) was added in order to study the
influence of chelating substances. In those experiments the NTA was added 30 min
before the metal salt. The metal concentrations were determined by atomic absorp-
tion.
Alumi- Alumi-
Metal Amount nium Ca(OH)2 nium Ca(OH)2 Aluminium sulfate Ca(OH)2
added (rag 1-1) sulfate sulfate
II II II II I II I I[
Landskrona Loudden
Aluminium Aluminium
sulfate Ca(OH)2 sulfate Ca(OH)2
Metal Amount Total Metal concentration after chemical treatment
(mg 1-1) (rag 1-x) (mg 1-x)
It can be seen from the tables that the degree of precipitation was about the same
in tap water, with or without orthophosphate added, as in mechanically treated
municipal waste water. The orthophosphate ion thus does not seem to have any
considerable influence upon the precipitation.
It can be seen from the tables that the concentrations of Pb(II), Cu(II), Cr(III) and
As(V) are reduced to low levels, in most cases to < 1 mg 1-1, by the chemical treat-
ment and that the results obtained are about the same with aluminium sulfate as with
calcium hydroxide. Cd(II) and Zn(II) are also reduced to a considerable extent,
especially with calcium hydroxide. Ni(II) and Co(II) are not influenced by aluminium
sulfate but can be precipitated by calcium hydroxide rather well. Mo(VI) and B(III)
cannot be precipitated by the two chemicals. Of special interest regarding mercury
are those results obtained from experiments made at the Eolsh~ill sewage treatment
plant in Stockholm in 1967 (WESTERMARK, 1968). The mercury content was reduced
from approx. 0.005 mg 1-1 to approx. 0.001 mg I -~ on simultaneous precipitation
with aluminium sulfate (Boliden AVR) and to < 0.001 mg 1-1 on subsequent precipi-
tation. The reason for the content of the residual liquid being so low after treatment
is that the mercury in the waste water is, to a large degree, bound to suspended
organic and inorganic matter, which is then flocculated out with the purification
chemicals.
Many metals are precipitated, as already shown, when chemical treatment takes
place, and one naturally wonders in which form these metals occur. It is possible that
many metals are precipitated as hydroxides.
The logarithm for the sum of the concentration of free metal ions and the concen-
tration of hydroxide complexes has been calculated (FIG. 1) as a function of pH
from values of the solubility products and complex constants of the hydroxides taken
from literature (SILL~.N, 1964). The lines showing those areas where the content is
greater than 1 mg 1-1 are marked with rougher lines. The slope of the lines increases
by one unit where the first hydroxide complex begins to dominate the contents of the
free metal ions and with a further unit where the second complex begins to dominate
the first etc.
pH
00 2 4 6 8 I0 12
I I I I I I
-2--
Crllll)
\ \\W'x\ / Zn(ll)
_~ -6 - ~'x'~-Cd(ZI)
~ "NiCID
x...~k,(zi)
-,o [.,°,]. [.] + oHIJ
FIG. 1. T h e solubility o f pure metal hydroxides as a f u n c t i o n o f p H .
54 ROLF NILSSON
If the rise in pH is brought about with NaOH, then the solubility of Cr(III) will
rise again, when the pH value rises above that of approx. 8 and of Zn(II) when it rises
above approx. 9. If the rise in pH is brought about by lime, then a rise in solubility
does not occur as the solubilities of calcium zincate and calcium chromite are relatively
low.
The actually precipitated metal hydroxides are not pure but nevertheless the
diagram gives a qualitative picture of the situation.
The curves show that Pb(II), Cu(II) and Cr(III) are precipitated to the con-
centration of < 1 mg l-X at a pH value of about 7. These correspond to the values
obtained by precipitation with aluminium sulfate. The experimental results con-
cerning Zn(II), Cd(II) and Ni(II) were, however, much better than those shown in
the diagram at pH 7 because the metals are co-precipitated with aluminium hydroxide.
As could be expected from the curves, lower values were obtained for Zn(II),
Cd(II) and Ni(II) on precipitation at pH 9.5 than at pH 7. However it is of interest
to note that the precipitation of those metals, which were already reduced to low levels
at pH 7, were not appreciably improved if the pH was increased to 9.5. Precipitation
does not, therefore, correspond to the precipitation lines at concentrations lower than
i mg 1- ~ because the precipitated hydroxides are not pure.
As(V) exists as arsenate ions in the waste water which are probably precipitated
together with the orthophosphate ions.
Cu[II)
~
X
X
8 0 02
o
Pb(II)
X
0
o
.I
I"
0.01 ,01
e- l Cr(IIl) •
l + .l Hg(II) +
0 I I I I I
O O,OI O.O2 0 05 0.04 0.05
NTA added mmoL/I
FIG. 2. Metal c o n c e n t r a t i o n in biologically treated waste water after flocculation with alumi-
n i u m sulfate (125 m g 1-1) as a f u n c t i o n o f a d d e d a m o u n t o f N T A .
Removal of Metals by Chemical Treatment of Municipal Waste Water 55
Before Before
floccu- After flocculation floccu- After flocculation
lation lation
(rag 1-1) (mmol 1-1) (rag 1-1) (mg 1-1) (mmol 1-1) (rag 1-1) (mg 1-1) (mmol 1-1)
0 0 0.4 < 0-01 < 0.0002 0-7 < 0.01 < 0-0002
3 0.012 1.0 0.9 0.014 1.4 1-3 0.016
6 0.023 1.0 1.1 0.017 1.4 1-4 0.022
12 0.047 1.6 1.6 0.025
TABLE 4. PRECIPITATIONOF Cu(II) WITH CALCIUMHYDROXIDEIN THE pH-RANGE 7-11 IN THE PRESENCE
OF NTA
(mg 1-1) pH 7.0 pH 8-5 pH 9.5 pH 11-0 pH 7.0 pH 8.5 pH 9.5 pH 11.0
Before Before
floccu- After flocculation floccu- After flocculation
lation lation
(mg 1-1) (mmol 1-1) (mg1-1 ) (mg1-1 ) ( m m o l l -x) (mg1-1 ) (rag1-1 ) (mmol1-1 )
Added amount o f Pb(II) = 0.021 mmol 1-1 : 4.3 mg 1-1; dosage of aluminium sulfate (Boliden
AVR): 125 mg 1-1.
56 ROLF NILSSON
TABLE 6. PRECIPITATION OF Pb(II) WITH CALCIUMHYDROXIDEIN THE pH-RANGE 7-11 IN THE PRESENCE
OF N T A
(nag 1-1) p H 7"0 p H 8"5 p H 9'5 pH I1.0 pH 7'0 pH 8"5 pH 9'5 pH 11"0
Before Before
floccu- After flocculation floccu- After flocculation
tion tion
(rag 1 - 0 (mmo 1-1) (mgl -l) (mg1-1) (mmoll -l) (mg1-1 ) (rag1 -I ) (mmol1-1 )
Added amount of Cr(III) = 0.023 mmol 1- i = 1.2 mg 1-' ; dosage of aluminium sulfate (Boliden
AVR): 125 mg 1-1.
Added amount of Hg(II) = 0-027 mmol I - I = 5-4 mg I-1; dosage of aluminium sulfate (Boliden
AVR): 125 mg 1-1.
Removal of Metals by Chemical Treatment of Municipal Waste Water 57
During the three hours that pass between the addition of the metal salt and the
addition of the precipitant a considerable amount of the metal content is absorbed
by the suspended particles. The absorbed amount was 50-90 per cent in mechanically
treated waste water and 40-60 per cent in biologically treated water to which no NTA
had been added. In solutions containing NTA the absorbed amount of metal was less
than in NTA-free solutions.
The amount of Cu(II) remaining in solution after flocculation with aluminium
sulfate is, roughly, 1 mol Cu for each mol of NTA added as long as the added amount
of the latter is less or equal to the added amount of copper ions (TABLE3).
Treatment of the waste water with calcium hydroxide in such amount that the pH-
value is raised to 9.5 or higher brings the Cu(II)-concentration down to < 0.2 mg 1-I
(TABLE 4).
The amount of Pb(II) remaining in solution after treatment with aluminium sulfate
is 0.60-0.85 mol per mol of NTA added as long as the added amount of the latter is
less or equal to the added amount of lead (TABLE5).
Treatment with calcium hydroxide to pH values 9.5 or higher brings the Pb(II)-
concentration down to <0-5 mg 1-1 (TABLE6).
The concentrations of Cr(III) (TABLE7) and of Hg(II) (TABLE8) are not influenced
by the NTA-concentration by treatment with aluminium sulfate in this investigation.
However it ought to be pointed out that if the mercury had been added to raw
sewage the degree of absorption could have been expected to be higher than in mecha-
nically or biologically treated waste water. At the sewage plant at Eolsh/ill the Hg-
concentration was considerably lower than in the experiments reported in TABLE 8.
Even at the low concentrations at Eolsh~ill it is essential to obtain a good reduction
of mercury (WEsTERMARK1968, TABLE2). The influence of NTA under those condi-
tions has not been covered in this investigation.
pH
0 2 4 6 B }0 ~2
0 I I I I l |
-2
CK(III)
_B'
-I0 -
The results reported above are in qualitative agreement with FIG. 3 in which the
solubility of pure metal hydroxides has been calculated as a function of pH for solu-
tions containing N T A and chloride ions. The concentration of NTA has been sup-
posed to be 5 mg NTA 1-1 = 10 -`*.7 mol 1-1) e.g. the concentration which can be
expected in municipal waste water if two-thirds of the tripolyphosphate content in
normal detergents are substituted by NTA. The chloride concentration has been sup-
posed to be 140 mg 1-1 ( = 10 -2.4 mol l-Z). The chloride complexes are of any
importance only in the case of mercury. It is assumed that the pH is raised by addition
of calcium hydroxide. The calcium ions added will compete with the metal ions over
the NTA molecules present. This has been taken into consideration. The following
equations are relevant for the metal concentration
where H3L denotes nitrilotriacetic acid. The concentration of metal ions in solutions
saturated with metal hydroxide is calculated according to equation (1). The values of
the equilibrium constants (solubility products and stability constants for the hydrox-
ide, chloride and NTA-complexes used in the calculations were taken from literature
(SILLfiN, 1964).
It can be seen from the figure that the curves tend to form a plateau at a concentra-
tion equal to the NTA-concentration (10 -4.7 tool 1-1) and this explains why copper
and lead were not precipitated with aluminium sulfate at pH 7. The calculated curves
descend with rising p H in agreement with the experimental findings. Curves have also
been calculated for calcium-free solutions, which are not given here. In absence of
competition from calcium most metals then form a marked plateau, over a wider pH-
range than in solutions containing calcium, at the concentration 10 -4"7 mol 1-2.
It is thus obvious that the presence of strongly chelating substances will influence
the precipitation of metals in waste water treatment plants. In the presence of NTA,
ions of many metals, among them copper and lead, will escape precipitation in the
chemical treatment plant at pH-values < 9.0. In biological treatment NTA is normally
degraded. If the biological step is overloaded the degradation is incomplete, how-
ever. The same is the case at low temperatures. GUDERNATSCH(1971) has found that
the C u - N T A complex is not biologically degradable even under favourable circum-
stances and that for example the N i - N T A complex is degradable only to an extent
of about 20 per cent. At least the metals copper and nickel can thus under unfavour-
able conditions pass a treatment plant equipped with both biological and chemical
treatment steps, a fact that has to be taken into consideration when a wider use of
NTA in detergents is being discussed.
TABLE 9. PROPOSED STANDARDS FOR MAXIMUM METAL CONCENTRATIONS (mg 1-1) IN WASTE WATERS
TO RECIPIENTS AND TREATMENT PLANTS
National Swedish
Board of
Environmental Royal Swedish Academy
Protection Switzerland of Engineering Sciences
Results obtained
Waters suitable by pre-
for fish Water to Water to precipitation
Mecha-
nically
or bio- Mecha- Biologi-
logically Receiv- Receiv- nically cally Calcium
treatment ing ing treatment treatment Aluminium hydro-
F1/F2 F3/F, plants waters* waters plants plants sulfate xide
AI 10 <0.2
As 0.1 1 1 1 <1.5 <1.5
Pb 0.1 1 1 <1 0'5
Cd 0.1 1 1 <1"5 0"2
Cr(III) }0.02 )0.1 2 2
Cr(VI) 0-1 0' 1 1-0 5-0 5.0
Cu 0'02 0-1 t 1 1.0 l'0 1-0 0.2 0.2
Ni 0.1 0'5 2 2 1 <6
Hg 0-1 0"1 0.002 <0'001t
Zn 0-1 0-5 2 2 5 <3 0-5
Sn 2
CN 0'01 0"1 0"5 0"1 1"0 0"5 0'1
REFERENCES
GUDERNATSCHH. (1971) Behaviour of nitrilotriacetic acid in the purification process and in waste
water. To be published.
SILLi~NL. G. (1964) Stability Constants of Metal-ion Complexes. Special publication No. 17, The
Chemical Society, London.
WESTERMARKT. (1968) Lecture given at a symposium on waste water treatment at Teknorama in
Stockholm, 27 March 1968.