AMMONIA REMOVAL FROM HIGH-STRENGTH WASTEWATERS

BY STEAM STRIPPING

lW3420

29.3p'.

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G. B. Wickramanayake, Ph.D., P.E.
Senior Engineer
ENVIRON Corporation
Princeton, New Jersey

INTRODUCTION, OBJECTIVES, AND SCOPE

Extracting metal values from some ores requires the use of hydrometallurgical
techniques that employ ammoniacal lixiviants. The metal values are recovered from the
pregnant liquors, leaving an aqueous wastewater which is high in dissolved solids and
ammonia. This wastewater requires treatment for removal of ammonia as well as dissolved
solids to meet the discharge standards. The purpose of this study was to evaluate the
effectiveness of steam stripping on removal and recovery of ammonia from metal smelting
and refining industry wastewaters.
The overall objective was pursued as two discrete tasks. Task 1 involved performing
theoretical and laboratory studies to determine the effects of wastewater composition on
(r

the equilibrium of ammonia (gas) and water and gas-liquid mass transfer rates, especially
within the temperature range of interest in actual plant operation. In Task 2, laboratory
tests were performed using a small pilot-scale steam stripping apparatus. Experiments were
conducted using two representative synthetic waste streams; pH adjustment was
accomplished using lime or caustic.
METHODS

One of the objectives of task 1 was to investigate how the distribution of inorganic
species and changes in temperature affect the equilibrium of ammonia (gas) and the
wastewater. Effects of different electrolytes such as Nat, Mg",

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Ca",

SO=,, and C1- on

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the Henrys Law constant (He) were evaluated. This theoretical study was based on
information given in the published literature and results obtained by data analyses using the
geochemical computer code EQ3/6.
The second part of Task 1 involved experiments to study the effect of varying SO,
concentration, molal strength, and the pH adjustment method [NaOH or Ca(OH),J on the
gas transfer rates for ammonia. Composition of the synthetic wastewaters evaluated in this
study is given in Table 1. Wastewater Stream A contained a high SO=, level than B,
whereas both A and C had the same SO=, level. The molal strength of Waste Streams B
and C were the same and were brought to such conditions by adjusting C1- concentrations.
The experiments were conducted in identical completely mixed batch reactors at
temperatures near 90C. The change in ammonia concentration with time was studied in
the solutions where pH was adjusted to 11.5 using NaOH or Ca(OH),.
During Task 2, a small pilot-scale steam stripping unit was designed and constructed
(Figure 1). Wastewater was released at the top of the packing materials in the column.
Steam was released from the bottom of the column to establish the counter-current
stripping effect. Experiments were conducted using two different synthetic waste streams
(Solutions B and C of Table 1). The pH of each waste stream was adjusted to 11.5 or
above using caustic or lime. Ammonia removal was studied under different pH adjustment
methods and different ratios of steam-to-wastewater flow. Steam and wastewater flow rates
were varied to determine the differences in ammonia removal efficiency.
RESULTS AND DISCUSSION

TASK 1:

Theoretical and Laboratom Studies on the Equilibrium and

Mass Transfer of Ammonia in Wastewater

The analyses of estimated Henrys Law constant and changes in solubilities of ammonia
indicated that adding caustic, compared with slaked lime, could result in higher Henrys
Law constants and lower solubilities for the three waste streams considered. These effects
may be attributed to the relatively high ionic strength found in wastewaters when pH was

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adjusted with NaOH. Between Solutions B and C, where the sulfate concentration was
varied without changing the solution strength (total number of moles), no significant
difference in Henry's Law constant or ammonia solubility could be seen for either of the
two pH adjustment methods. Highest Henry's Law constant and corresponding lowest

ammonia solubility were observed in Solution A which has the highest molal strength.
Experimental studies to determine the effects of dissolved species and pH adjustment
methods on the mass transfer rate coefficient (K) indicated that those effects were relatively
low and the maximum changes in mass transfer rate coefficient did not exceed 25 percent.

In two of the three different solutions tested, however, mass transfer rate coefficient was
higher for the waste stream where pH was adjusted using caustics. For solutions with
approximately the same SO', concentration but different molal strength, the mass transfer
rate coefficients were comparable when NaOH was used a s the pH adjustment method.
For Ca(OH), however, the K values were comparable for those where both the molal
strength and SO=, level were different. The overall analysis of data indicate that, when
compared with lime, addition of NaOH can promote ammonia removal for solutions with
relatively low SO', levels (5,OOOmg/L).
TASK 2

Ammonia Removal Studies Using Steam StriDpine Unit

The results of the steam stripping study are summarized in Table 2. Data show that
when the steam-to-wastewater flowrates are low (1.3 lb/gal), the ammonia removal
efficiency was as low as 93 percent. By increasing steam-to-wastewater flow rates to 3.8
Ih/gal, removals of more than 99.9 percent were observed. the removal efficiency in one
study was improved by 2 percentile points when the temperature of influent waste stream
was raised by ahout 20C. The addition of lime resulted in more than a 10C increase in
temperature because the hydration of lime is an exothermic process.
For wastewater with low initial SO', level (5,000 mg/L), ammonia removal was 3
percent higher when pH was adjusted with caustic rather than lime. These observations
agree with the trends predicted from the estimated Henry's Law constant and mass transfer
rate coefficient. In the experiments conducted with wastewaters using higher initial SO',

705

levels (20,000 mg/L), ammonia removal was slightly higher when pH was adjusted with lime
instead of caustic. These observations agree with the conclusions reached from the
corresponding mass transfer rate studies, which did not agree with the theoretical estimates
of solubilities based on Henrys Law constant.

In summary, more than 99.9 percent removal of ammonia can be achieved by

introducing high steam-to-wastewater flowrates such 3.8 Ib/gallon. Varying chemical
constituents such as SO=, and the molal strength has only a little effect on net NH,
removal. Higher removal efficiencies can be achieved by preheating wastewaters and
operating the stripping tower at high temperatures by increasing steam-to-wastewater
flowrates.
ACKNOWLEDGEMENT

This study was performed by Battelle Memorial Institute, Columbus, Ohio under
Contract No.68-03-3248 for US. Environmental Protection Agency, Cincinnati, Ohio. This
abstract has not been subjected to the review of the US EPA, and therefore does not
necessarily reflect the view of the Agency.

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TABLE 1. WASTEWATER CHARACTERISTICS FOR GAS

TRANSFER RATE EXPERIMENTS

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TABLE 2. SUMMARY RESULTS OF LABORATORY STUDY ON STFAM SIRWF"NG

Wastewater Temp, 'C

NHrN eone
Adjustment
Method

Wastewater

I,'

Column
Intlueut

Colunn
Effluent

Steam to
Wastewater Ratm

Average NH,
Influent

@W@W

26

101

1.9

5,200

32-102

26

101

1.3

5,200

255420

38

101

1.9

5,100

188-288

39

101

3.8

5,m

12-16

26

101

1.9

4,750

121-198

26

101

3.8

4,700

3.9-4.5

39

101

1.9

3,950

87-92

39

101

3.8

3,825

1.1-2.2

Cao

C (high SO=,) NaOH

99.91
99.96

Synthetic

100 gal. wastevrater

Tank

Pump

Thermocouple

P = Pressure Gauge
V = Valve

Figure 1 .

Experimental s e t u p f o r a m n i a removal by ste?m s t r i p p i n g

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