pH Neutralization and Total Suspended

Solids Removal at a Textile Dyeing and

Finishing Facility
by
Dudney Fox
Ken Pickle

Presented at the
76th Annual Conference of the North Carolina
American Water Works and Water Environment Associations

Pinehurst, NC
November 17-20,1996

ERM-Southeast, Inc.
7300 Cannel Executive Park
Suite 200
Charlotte, NC 28226
(704) 54l-8345

ERM
 pH Neutralization and Total Suspended Solids Removal
at a Textile Dyeing and Finishing Facility

BY
Dudney Fox
Ken Pickle
ERM-Southeast
Charlotte, NC

ERM-Southeast was retained by XYZ Textiles to design a wastewater pre-treatment system for
meeting effluent pH, temperature, and total suspended solids (TSS) limits. Wastewater flow
averaged approximately 1.6 MGD and in anticipation of production expansion, design flow for
this project was selected by the client as 3 MGD. Difficulties of the project included a widely
varying wastewater (pH and flow), a mystery source of TSS, no reliable pre-existing wastewater
characterization, and physical site constraints.

The first phase of this work involved characterization of the effluent pH. This characterization
showed that the effluent pH ranged from 1.8 to 12.6 (standard units) with the majority (>90%) of
flow being basic. Next we identified the chemical mechanisms responsible for buffering pH. It
was concluded that the carbonate system was the primary buffering species with additional
influences from the hydroxide system. Our objective behind understanding the controlling
mechanisms was to minimize the required volume for effective pH neutralization. Traditional
textile industry rule of thumb for neutralization basin design suggests a minimum 1 day retention
time. However, we felt a more site-specific solution was warranted. The carbonate and
hydroxide equilibrium equations were modeled to predict how a given volume of wastewater
would react to influent pH fluctuations. Iterations were performed and a volume of 375,000
gallons was selected for effective pH neutralization under design case acidic influent conditions.
Caustic wastewater neutralization is achieved through sulfuric acid addition using reconfigured
existing equipment.

The second phase of work involved addressing total suspended solids discharges. Our first step
was to identify the sources. The result of this effort was the identification of the facility’s water
treatment plant flocculation basin and the four rapid flow sand filters as the sources of TSS.
Both the floc basin drainage and sand filter backwash were incorporated with the wastewater
effluent. We felt that segregation of these streams would provide for an economical solution.
Our segregation approach was further supported because both streams could be recycled back to
the water plant after the solids had been removed. A 1,000,000 gallon earthen lagoon was
designed and constructed.
INTRODUCTION

In March 1994, ERM-Southeast was contracted by XYZ Textiles to provide engineering

assistance to assist the company in complying with effluent wastewater limits established by the
o
local POTW. These limits are pH (6-9 standard units), temperature (40 C), and total suspended
solids (TSS, 350 mg/L). Facility effluent measurements collected by the POTW indicated that
all three of these parameters were in violation of permit limits.

XYZ Textiles operates a textile batch dyeing and finishing facility consisting of two plants, Plant
A and Plant B, located adjacent to the POTW. The facility operates 24-hours per day for 50
weeks per year. The batch dyeing, Mercerizing, and finishing operations require approximately
1.6 million gallons of process water per day. The facility’s water treatment plant produces
process water via flocculation, clarification, and filtration. An acid addition pre-treatment
system previously treated process wastewater as well as plant sanitary flow prior to discharge to
the POTW via gravity sewer.

The existing pre-treatment system consisted of an in-the-pipe sulfuric acid addition system for
pH adjustment with no provision for retention, temperature reduction, or TSS removal. The
system configuration consisted of two feedback sulfuric acid addition systems installed in series.
Each acid addition system consisted of its own pH probe, controller, and dc-drive variable speed
metering pump.

The client’s objective was for ERM-Southeast to design a pre-treatment system capable of
meeting the pH, temperature, and TSS limits as well as to do so in a cost effective manner. The
design flow for this project was 3 million gallons per day (MGD). Additionally, the client
wanted to reuse as much of the existing system equipment as possible.

At the onset, the project did not seem to be a difficult one however, the difficulty increased
dramatically as ERM pushed away from the industry accepted approach to a more economical
technical-based approach. The more significant of these difficulties included: 1) Widely varying
wastewater - the pH and flow of the effluent varied significantly due to the batch nature of the
operation; 2) Mystery Source of TSS - XYZ Textiles could not initially identify any significant
source of TSS loading; 3) Ineffective pH control system - the old pH control system and layout
was inadequate; 4) Lack of characterization - there was no reliable pre-existing wastewater
characterization data; and 5,) Physical Site Constraints - a shallow groundwater table presented
difficulties with the design engineering phase.

APPROACH

Our approach to meeting the client’s objective involved a two phase approach. The first phase
involved meeting pH and temperature limits. The second phase involved addressing TSS
discharges.
pH and Temperature

Our first step of meeting effluent pH limits was to perform a review of the available literature
and consult with peers to establish the “tried-and-true” approaches to pH neutralization systems
for textile batch dyeing operations. As the first step evolved, we discovered that traditional
textile wastewater engineering suggests 24-hours of retention with acid and caustic addition as
necessary for effective pH neutralization. Additionally, the POTW recommended that a 24-hour
retention basin was needed. However, we felt that further investigation on the site specific nature
of the problem was warranted. This was due to economic constraints (construction costs) and
physical site limitations as well as our understanding of the chemistry involved with pH
neutralization and textile wastewater. This leads us to our next step.

Our second step was to characterize the wastewater. The characterization involved gathering pH,
temperature and flow information. Some data was gathered from historical facility records (pH
circular charts and flow totalizer readings) however, the existing data did not sufficiently
characterize the wastewater. Consequently, we conducted a field study to develop a more
detailed database for pH and temperature. Measurements were collected on two-minute intervals
over a five day period. The results of this effort indicated that the Plant A pH ranged from 1.8 to
12.6 and the Plant B pH ranged from 4.2 to 11.7. Presented in Figure 1 below is a graph of pH
measurements collected over a 14 day period on the Plant A and B effluent. Presented in Figure
2 below is a histogram of these pH measurements as well as other measurements collected in the
field.

Figure 1

Plant A and B pH
 Figure 2

pH Histogram for Plants A and B

As can be seen in the above figure, the majority of the measurements observed were in the
caustic range (>pH 7).

The flow averaged approximately 1.6 MGD with 85% of the total from Plant B and the
remaining 15% from Plant A. Additionally, the average temperature of the Plant A effluent was
o o
39 C and the Plant B effluent was 45 C. Approximately 90% and 98% of the pH
measurements from Plant A and B respectively were above pH 7. Approximately 28% and 41%
of the pH measurements from Plant A and B respectively were above pH 9. Table 1 below
summarizes the Plant A and B field pH measurements.

Table 1
Summary of pH Statistics from Plants A and B

Plant Mean pH Standard Minimum Maximum Number of

Deviation Measurements
Plant A 9.1 1.9 1.8 12.6 1526
Plant B 9.6 1.0 4.2 11.7 3456

Inspection of Figures 1 and 2, Table 1, and the flow and pH data provided insight as to how to
attack the problem in a more cost effective manner than simply providing 24-hours of retention.
Neutralization of the more frequent caustic wastewater flows and the subsequent basin pH could
be accomplished by modifying the existing sulfuric acid feed system. We believed that
neutralization of the occasional acidic wastewater flows could be accomplished through bulk
neutralization with the predominately caustic effluent, since the majority of the flow is caustic.
Sufficient volume would be required, however, so that the final effluent would not drop below
the lower discharge limit (pH 6). This leads to the third step of our approach.
The third step of our approach involved investigating and understanding the mechanisms that
control the pH of the wastewater such that a sufficient neutralization basin volume could be
provided to meet lower pH limits during acid dumps (low influent pH). We concluded that the
predominant buffering species controlling neutralization basin pH was the carbonate system with
additional influence from the hydroxide system. Carbonate species interactions are governed by
the following equations.

The total carbonate species concentration, CT,CO3, is defined by the following equation.

2
CT,CO3 = [H2CO3*] + [HCO3] + [CO3 ] (4)

[H+] and [OH-] interactions are governed by the following equation.

-14
[H+] + [OH-] = [H2O] KW= 10 (5)

For the next step we manipulated and modeled equations 2 through 5 using computer
programming code. The major assumption we made was that the neutralization basin could be
represented as a closed carbonate system. The following is a list of parameters that are model
inputs: Sample (basin) pH, Target (lower pH limit) pH, Acid (acidic wastewater) pH, and total
carbonate species concentration. The model output is a dilution ratio, or gallon acid (acidic
wastewater)/gallon sample (basin). The above model inputs: sample, target, and acid pH, are
known, however, total carbonate species concentration was derived. We used initial pH and total
alkalinity with a Deffeyes diagram (a plot of total carbonate species concentration versus pH and
total alkalinity) to calculate total carbonate species concentration. It is worth noting that at this
stage we understood that errors could occur in this approach for calculating total carbonate
species concentration from alkalinity. This is due to the assumption that alkalinity is solely due
to the carbonate species when using a Deffeyes diagram. However, we felt this would provide us
with a good starting point.

To test our hypothesis a second phase of data collection was required. For the second phase of
data collection we obtained one grab sample a day over a four day period. The samples were
analyzed for phenolphthalein and total alkalinity. Additionally, titrations were performed. Table
2 below summarizes the results of the alkalinity measurements.
 Table 2
Summary of Wastewater Alkalinity

Parameter Sample 1 Sample 2 Sample 3 Sample 4

6/2O/94 6/21/94 6/22/94 6/23/94
Alkalinity, 47 NA(1) 30 80
Phenolphthalein
(mg/l)
Alkalinity, 91 71 110 190
Total (mg/L)
Notes:
(1) - Initial Sample pH was lower than 8.3

Using the above total alkalinity measurements, initial sample pH, and a Deffeyes diagram, we
calculated a total carbonate species concentration for each sample. Next we input the four
parameters into our model and obtained the model’s prediction for acid addition at each titration
point. Upon comparison with the actual acid addition values, we found that the actual volumes
required for each titration point were 57% of the model prediction (average for all 4 samples).
Therefore, our next step was to calibrate the model by adjusting the calculated total carbonate
species concentration for each sample by 57% and re-running the model. Figures 3, 4, 5 and 6
below show the actual and model predicted titration curves for the four samples using the
adjusted total carbonate species concentration.
Figure 3

Titration Curve-Sample 1 (6/20/94)

Figure 4

Figure 5
 Figure 6

Considering the close correspondence of the curves in Figures 3, 4, 5 and 6 and the statistical
procedures utilized for calibrating the model, we concluded that our model was sufficiently
accurate in predicting the pH response of the neutralization basin to periodic acidic wastewater
influent.

Our fifth step was to input the parameters to determine the required basin volume. The following
parameters were used as inputs to our model: Basin pH: 8.3, Target pH: 6.5, Acidic Wastewater
pH 1.8, Total Carbonate Species Concentration: 2.5E-4 M (although the average of 57% of the
calculated concentration was 9.1E-4 M), Acidic Wastewater Volume: 2000 gallons. Using the
above inputs, the model predicted that approximately 320,000 gallons would be required to
maintain a basin pH of 6.5 under worst case acidic flow conditions. The client eventually
selected a basin size of 375,000 gallons, which provides a detention time of three hours at the
design flow of 3 MGD. Mixing and temperature reduction are provided by four 7.5 HP surface
aerators. Presented below in Figure 7 are some post construction influent and effluent pH
measurements taken on thirty-minute intervals over a six day period.
 Figure 7

As can be seen from Figure 7, the basin performs exceptionally well. Additionally,
measurements collected in the field indicate that the maximum effluent temperature over a six
o o
day period was 35.2 C, in compliance with the permit limitation of 40 C.

Total Suspended Solids

Our approach to addressing the TSS discharges was to first identify the sources. To identify the
sources we conducted a through review of all sources of effluent, consulted with facility
personnel, and discussed the nature of the problem with the POTW. As a result of this effort, the
plant team and ERM discovered that the facility’s water treatment plant has a five chamber
flocculation basin where alum is added which is followed by four rapid flow sand filters. Both
the floc basin drainage and sand filter backwash were periodically discharged into the wastewater
effluent and carried heavy TSS loads.

Our next step was to develop a solution to remove the TSS from the effluent. We felt that
segregation of these streams would provide for an economical solution. Our segregation
approach was further supported because both streams could be recycled back to the water plant
after the solids had been removed. Our solution is as follows:

l segregate the drainage and backwash from the dyehouse effluent;

l route the segregated flow to a lagoon for settling; and
l recycle the lagoon effluent to the head of the water treatment plant.
A 1,000,000 gallon earthen lagoon was selected based on plant engineering’s preferred basin
cleanout schedule. Based on similar operation at the city water treatment plant, we estimated
that solids removal from the lagoon would be required once every three to five years. As a result
of this effort, the facility is no longer experiencing TSS exceedences in the effluent to the
POTW.

COST EFFECTIVENESS OF APPROACH

XYZ Textiles required that a key element in ERM-Southeast’s design of the pH neutralization
basin must be to hold costs as low as possible while achieving pH control within the pretreatment
permit limits (6.0<pH<9.0). Our approach to cost reduction was to recognize that the selected
volume of the basin was the major determinant of the project costs. That is, the major cost
elements could be considered area costs proportional to the basin volume: clearing and
grubbing, grading, excavation, concrete liner, PVC underliner, floating aerators for mixing, and
electrical costs for the aerators. The client’s project team worked with us on a continuing basis
to assess the cost impacts of both the selected design bases and design details.

Total engineering and construction costs attributable to the 375,000 gallon, three hour detention,
pH neutralization basin were approximately $465,000, or approximately $1.24 per gallon. By
comparison, if we account for significant economies of scale and estimate that a 3,000,000
gallon, 24 hour detention basin might be designed and constructed for as little as $0.75 per
gallon, the resulting total cost would be $2,250,000. We believe that XYZ Textiles saved the
difference, approximately $1,785,000 or 80%, by going forward with a design based not on rule-
of-thumb, but on careful wastewater characterization and on application of well established
knowledge of the carbonate species buffering action.

The extra engineering costs required to develop a calibrated, predictive model of the carbonate
species buffering action for the wastewater amounted to approximately $12,000 and resulted in
the substantial total cost savings estimated above.

SUMMARY

The carbonate-hydroxide modeling approach to predicting a wastewater pH response has

potential for widespread application to the design of pH neutralization systems. Caution must be
used, however, and the need for a good wastewater characterization is extremely important.

REFERENCES

1. Snoeyink, Vernon L. and Jenkins, David, Water Chemistry, John Wiley and Sons, New
York, 1980.
 HISTOGRAM

l Over an extended period of time we had amassed >5000 pH measurements

l Next step was to analyze the data stastically
l Presented here is a histogram of the collected pH data
l As can be seen a majority of the pH observed >7 (90%), >9 (40%)

WHAT TO DO?

l What does all this mean?

l obvious choice --> design basin for bulk neutralization
l lit reviews, peer consult, industry consult, POTW consult --> 24 hours

THE BREAKTHROUGH

l How much is enough?

l At this point we thought a little bit of “better living through modern chemistry”
might provide much insight

: THE CARBONATE SYSTEM

l hypothesized that the carbonate system coupled with the hydroxide system
was the dominant buffering mechanism
l <<discuss equations>>

MODEL INPUTS
l We modeled these carbonate/hydroxide interactions through manipulation of
the equations to predict either 1) predicted amount of acid required to lower pH
between given set points or 2) predict amount of volume necessary to maintain
ph greater than some set point.
l relalized that errors could occur in this approach - however we felt that general
response would be accurately predicted - could then account for other
interactions through gross adjustment (calibration)
l not an itetarative modeling approach - computer just facilitated trial and error
and ease of number crunching
l First step was to calibrate the model against known titrations
l Next step was to model actual site flow conditions (design values are worst
case/conservative)