The Effect of Ozone Demand on Mass Transfer

Efficiency and It’s Importance to

In-Line Ozone Contactor Design

R. Michael Meyer, Angelo L. Mazzei

Mazzei Injector Corporation
Bakersfield, California, USA

Paul Overbeck
GDT Corporation
Phoenix, Arizona, USA

ABSTRACT

For disinfection purposes, the Dissolved Ozone concentration (mg/l) times

the Contact Time (minutes), also known as the CT Value, are critical. In
order to achieve a high CT Value, either high dissolved ozone concentrations
for short Contact Times, or low ozone concentrations for long Contact
Times can be employed. Long Contact Times can only be facilitated by large
volume contacting systems, which have large footprints and require large
capital investments. Therefore, high Dissolved Ozone concentrations are
advantageous. The new high concentration ozone generators are ideal for
achieving high dissolved ozone concentrations.

Mass Transfer Efficiency (MTE) and Ozone Demand are critical factors in
In-Line Contactor system design. The MTE is the percentage of the applied
Ozone that actually goes into solution under a given set of operating
conditions. Ozone Demand is the amount of ozone consumed by oxidizable
material in the water. Both the MTE and Ozone Demand must be taken into
account for prediction of Dissolved Ozone concentration, and hence CT
Value, during In-Line Contacting system design.

Presented in this paper is a computer program that facilitates the design of In-
Line Contactors which utilize side stream ozone injection via High
Efficiency Venturi's and Radial Mixing Nozzles. The predicted transfer
efficiencies are based on extensive empirical test results. The effect of Ozone
Demand on both the MTE and the resulting Dissolved Ozone concentration
are automatically calculated by the program.

The derivation of the mathematical equation utilized to predict the effect of

Ozone Demand on the Mass Transfer Efficiency is presented.

Introduction:

Side stream injection of ozone for purposes of in-line contacting affords

advantages of small footprint, and high mass transfer and energy efficiency.
For disinfection purposes, a CT Value (ozone concentration x contact time)
will be specified. In order to achieve the specified CT Value the dissolved
ozone residual must be known. The dissolved ozone residual is affected by
the Mass Transfer Efficiency and the Ozone Demand.

The Mass Transfer Efficiency of a side stream injection system that utilizes
high efficiency venturis and mixing nozzles has been studied in detail (2,3).
The data collected has been used to develop a spreadsheet that facilitates in-
line contactor design. The spreadsheet uses empirical Ozone Demand data,
contactor vessel volume and ozone generator output values to calculate the
dissolved ozone residual and CT Value. In addition, the proper venturi
injector(s) is specified, and based on operating cost data the overall cost of
operation is calculated. Table 1 is an example of this spreadsheet.

In-Line Contacting with Side Stream Injection:

The process of In-Line Contacting with Side Stream Injection is achieved by

taking a portion of the main flow and boosting it to a higher pressure to
operate a High Efficiency Venturi Injector(s). The High Efficiency Injector(s)
aspirates the ozone gas from the ozone generator and dynamically/violently
mixes it with the side stream flow.

The resulting, thoroughly mixed, ozone gas/water mixture is then discharged

at high velocity through specially designed nozzles back into the main flow.
The rate at which the maximum Mass Transfer Efficiency is achieved in the
main flow is a function of the mixing efficiency of the side stream ozone
gas/water mixture with the main flow. The high exit velocity of the nozzles
produces a mixing eductor effect and extremely rapid mixing of the side
stream with the main flow. The result is maximum Mass Transfer Efficiency
within a very short time.

Figures 1 & 2 depict the thorough mixing of the side stream and main flows in
the test apparatus used in the Mass Transfer Efficiency testing.

Figure 1
 Figure 2

Mass Transfer Efficiency:

Mass Transfer Efficiency is defined as the portion of applied ozone that goes
into solution in the water. The MTE is calculated from the mass of applied
ozone and the mass of ozone in the off gas as follows (2,3):

((O3 Conc. in x Gas Vol. in) - (O3 Conc. out x Gas Vol. out))
MTE = __________________________________________________ x 100
(O3 Con in x Gas Vol. in)

Operating parameters that affect MTE are water temperature, gas/liquid ratio
(Vg/Vl) and contactor pressure (1,2,3). Ozone is more soluble in cold water
than hot water. Low Vg/Vl’s promote high mass transfer efficiency, while high
Vg/Vl’s result in low mass transfer efficiency (2,3). High concentration ozone
generators facilitate low Vg/Vl’s even at high-applied ozone doses. Figure 3
demonstrates the affect of gas/liquid ratio on MTE.
 Figure 3

Side Stream Ozone Contacting Test Results

Transfer Efficiency vs. Gas/Liquid Ratio
100

95

90

85

80
Operating Conditions
120 GPM, 3 ft/s, 20 PSI
75
Applied Ozone Dose 2.26-7.04 mg/l
70
Ozone Conc. 27.9-134.2 g/m3
65
Contact Time 30 Seconds

60
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2

mazzei injector corp

High contactor operating pressures force more ozone into solution resulting in
increased MTE (1,2,3). Figure 4 demonstrates the affect of contactor pressure
on the MTE.
Figure 4

Side Stream Ozone Contacting Test Results

Transfer Efficiency vs. Operating Pressure
100
Exponential Line Fit
95

90

85

80
Vg/Vl 0.069-0.077
Ozone Dose 2.86-9.32 mg/l
75
80 GPM, 2 ft/s, 45 Second Contact Time
Ozone Conc. 39.6-131.0 g/m3
70
0 5 10 15 20 25 30 35 40

mazzei injector corp

Ozone Demand:

Ozone demand is the amount of ozone consumed by oxidizable material in the

water. Some factors that affect ozone demand are temperature, pH, alkalinity,
and organic content etc (1). The ozone demand for a water must be
determined empirically. For use in the system design spreadsheet, the ozone
demand determined by experimentation must be expressed a ratio of ozone
consumed to applied ozone. The units are:

Ozone Demand (mg/l)/Applied Ozone (mg/l).

Figure 5 demonstrates the ozone demand relative to applied dose for the well
water used in the mass transfer testing (3).

The slope of the ozone demand curve for the well water used in the Mass
Transfer testing was 0.36/1. This value was used in the system design
spreadsheet to correct the Observed MTE back to what the MTE would have
been if there were no demand in the test water.

It must be noted that this Observed MTE is not the same as the mass transfer
efficiency that would be calculated from the mass of dissolved ozone after the
demand has been met, divided by the mass of applied ozone.
Figure 5

Side Stream Ozone Contacting Test Results

Ozone Demand & Decomposition vs Applied Ozone Dose
10
9
Contact Time
4.2 Seconds 13.6 Seconds 30 Seconds 40 Seconds
8 80 GPM, 10-20 PSI
7
6
5
4
3
2
Power Regression Line Fit
1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

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Ozone Demand & Mass Transfer Efficiency:

The mathematical formula for correction of the No-demand MTE (ND MTE) to
the Observed MTE (Ob MTE) under a given set of operating conditions
follows:

Ob MTE = (1-(Applied Dose x (1-Demand Ratio) x (1-ND MTE))) x 100

______________________________________________
Applied Dose

The Applied Dose Factors Cancel Leaving:

Observed MTE =(1-((1-Demand Ratio) x (1-No Demand MTE))) x 100

The Observed MTE is used for calculation of ozone residual and CT Value
during system design.

Figure 4 shows that the ozone demand has a relatively greater effect on the
Observed MTE when the No-Demand MTE is low as compared to when it is
high. In addition, it makes sense that if the demand is 100% then all of the
applied ozone will have been consumed, and 100% of nothing will have to be
transferred.

Ozone Demand Effect on Observed

MTE
Figure 6
100

90
Observed Ozone MTE

No-Demand
MTE = 95%
80
No-Demand
MTE = 75%
70
No-Demand
60
MTE = 50%

50
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Ozone Demand Ratio

It must be noted that the Observed MTE is not the same as the mass transfer
efficiency that could be calculated from the mass of dissolved ozone (after the
demand has been met) divided by the mass of applied ozone. Mass transfer
efficiency calculated from the dissolved ozone residual will always be less due
to the ozone demand.

Contactor System Design Program:

Following are instructions on the use of the “In-line Ozone Contactor with
Side Stream Injection” spreadsheet. Table 1 is an example of the actual
spreadsheet, which can be referred to while working through the instructions.
Operating Parameters Section:

The following values must be entered.

Main Flow Volume:

The Main Flow Volume is the total volume of water with which the ozone is to
be contacted. Units are GPM.

Contactor Operating Pressure:

The Contactor Operating Pressure is the pressure in the main flow contactor
conduit. Units are PSI.

Applied Ozone Dose:

The Applied Ozone Dose is the dose of ozone required to meet the ozone
residual for the specified CT Value after the ozone demand and mass transfer
efficiency have been met. Units are mg/l. This value is typically determined
empirically by pilot testing.

Ozone Gas Concentration:

The Ozone Gas Concentration is the concentration of ozone in weight percent

in the feed from the ozone generator.

Expected Ozone Demand Ratio:

The Ozone Demand Ratio is the amount of ozone that will be consumed by
the ozone demand of the water. The value to be entered is the ratio of ozone
consumed relative to the applied ozone dose. This value is a ratio, not an
absolute mass of ozone consumed. For example, if 2.0 mg/l of ozone are
applied, and after the demand of the water has been met, the residual is 1.0
mg/l, the demand ratio is 1.0/2.0 or 0.5. This value must be determined
empirically by pilot testing.

Contactor Volume:

The Contactor Volume is the volume of the main flow-contacting conduit or

tank. This value is used to calculate the contact time and hence CT Value.

Calculations Section:

The spreadsheet calculates the following values from the values entered in the
Operating Parameters section.
Required Ozone Injection Rate:

The Required Ozone Injection Rate is the mass of ozone in units of

Pounds/hour that must be injected to achieve the specified Applied Ozone
Dose. This value along with the ozone demand must be determined
empirically.

Required Ozone Gas Flow:

The Required Ozone Gas Flow is the volume of ozone gas in units of SCFM
that must be injected. This value is calculated from the Required Ozone
Injection Rate and the Ozone Gas Concentration from the ozone generator.

Calculated Gas/Liquid Ratio:

The volumetric Gas/Liquid Ratio (Vg/Vl) calculated from the Required Ozone
Gas Flow and the Main Flow Volume (in units of CFM). The Vg/Vl value is
used along with the Contactor Operating Pressure to determine the Mass
Transfer Efficiency.

Mass Transfer Efficiency, MTE:

Mass Transfer Efficiency is calculated from the Contactor Operating Pressure,

Volumetric Gas/Liquid Ratio and the Ozone Demand Ratio. This is the ratio of
the mass of ozone in the off gas relative to the mass of ozone in the feed from
the ozone generator.

Calculated Ozone Residual:

The Calculated Ozone Residual is the calculated dissolved ozone residual

after the Ozone Demand has been met, minus the ozone in the off gas.

Contact Time:

The Contact Time (residence time) is based on the Main Flow Volume and the
Contactor Volume.

CT Value:

The CT Value is the Concentration x Contact Time used for prediction of

disinfection effectiveness calculated form the Contact Time and Calculated
Ozone Residual Values.
Injector Selection Section:

In the this section, an appropriate injector(s) will be suggested to meet the side
stream injection requirements dictated by the Required Ozone Gas Flow and
contactor operating pressure conditions. The injector(s) suggestion is for the
minimum required to inject the Required Ozone Gas Flow. The ozone mass
transfer testing documented that the percent side stream has relatively little
affect on the MTE (3). However, it is suggested that the minimum percent side
stream be about 10%.

Ozone Gas Pressure @ Injector:

The Ozone Gas Pressure is the pressure of the ozone gas from the ozone
generator that is available at the suction port of the injector(s). Head losses in
the conduit from the generator to the injector must be taken into account. Units
are gauge pressure, PSIG. Pressures less than one atmosphere absolute are
entered in units of negative gauge pressure. For example, if the Ozone Gas
Pressure were 0.5 atmospheres absolute (or 15” Hg vacuum), the value
entered would be –7.35 PSI ((14.7*0.5)-14.7).

Number of Injectors to be used:

The number of injector to be used in the side stream injection system is

specified. From this value and the Ozone Gas Pressure, the Required Suction
Capacity Per Injector is calculated. The Required Suction Capacity Per
Injector in units of actual CFM (ACFM). If a value > 10.5 CFM/Injector is
displayed, the injector specification is invalid and a greater number of injectors
must be specified.

Once a valid Required Suction Per Injector has been displayed, the injector(s)
Model is specified. The Boost Pressure Required (pressure added to the
Contactor Operating Pressure for injector operation), Total Side Stream
volume and Percent Side Stream are calculated.

Pump Requirement:

Pumping power requirements (Water Horsepower, WHP and Brake

Horsepower, BHP) are calculated for the Boost Pressure Required, Total Side
Stream Volume and Pump Efficiency Values.

Operating Costs:

The Total Operating Cost for the side stream injection system is estimated
from the costs for operating the ozone generator and the side stream pumping
requirements.
CONCLUSIONS:

The effects of operating parameters for in-line ozone contacting systems,

which use High Efficiency Venturi Injectors and Nozzles for side stream
injection, have been studied in detail (2,3). Calculation techniques that take
into account the key operating parameters that effect contactor design
(Operating Pressure, Gas/Liquid Ratio and Ozone Demand) have been used
to develop a useful computer program for contactor system design.

REFERENCES

1. Ozone In Water Treatment, Application and Engineering

AWWA Research Foundation, 1991, Lewis Publishers
Page 227

2. Angelo L. Mazzei, R. Michael Meyer, L. Joseph Bollyky, Ph.D.

Mass Transfer of High Concentration Ozone with High Efficiency
Injectors and Degassing Separators
IOA Pan American Group, Cambridge MA. Nov 13, 1995

3. R. Michael Meyer, Angelo L. Mazzei, L. Joseph Bollyky Ph.D.

Side Stream Injection with High Efficiency Venturi and Radial Mixing
Nozzle
IOA 14th World Congress, Dearborn Michigan USA 1999

Key Words

Ozone, In-Line Contacting, Side Stream Injection, Mass Transfer Efficiency,

MTE, Applied Ozone Dose, Gas/Liquid Ratio, Vg/Vl, System Pressure,
Ozone Demand, Contact Time, Gas/Liquid Interface, Flow Velocity,
 Mazzei Injector Corporation
Side Stream Ozone Injection For In-Line Contacting
Prepared For: Table 1
Project: Example Ozone Contactor System Design
Purpose For Ozonation:
Date: 5/31/00 Values In Shades Cells Must be Entered
Operating Parameter Units Value Comments
Main Flow Volume GPM 695 1 MGD
Contactor Operating Pressure PSIG 15 Pressure in the Main Flow Conduit
Applied Ozone Dose mg/l 8 Specified By pilot testing
Ozone Gas Concentration wt % 10
Expected Ozone Demand Ratio, mg/l/mg/l 0.36 mg/l Demand/mg/l applied: Determined Empirically
Contactor Volume Gal 1500 Volume of the main flow conduit or tank
Calculations
Required Ozone Injection Rate #/hour 2.78 From the Applied Dose & Main Flow values
Required Ozone Gas Flow SCFM 5.51 From O3 #/hr & wt% O3 Generator output
Calculated Gas/Liquid Ratio Vg/Vl 0.06 Gas Flow SCFM/Main Flow ft3/min
Mass Transfer Efficiency, MTE % 91.0 Ozone Off-Gas/Ozone Feed
Calculated Ozone Residual mg/l 4.40 Applied Dose - O3 Demand & off gas O3
Contact Time min 2.16 Contactor Volume/Main Flow Volume
CT Value, Conc. x Time, mg/l x min 9.50
Injector Selection
Ozone Gas Pressure @ Injector PSIG 12.00 Enter Sub-Atmospheric Pressures As -PSI
Number of Injectors to be used 1
Required Suction Per Injector CFM 1.67 Corrected for Pressure, Invalid if > 10.5 CFM
Specified Injector(s) Model 1583
Boost Pressure Required PSIG 45.0 Pressure added to the Main Flow Pressure
Side Stream Volume Per Injector GPM 33
Total Side Stream Volume GPM 33
Percent Side Stream % 4.8
Pump Requirement
Water Horsepower Required WHP 0.9
Pump Efficiency % 70
Brake Horsepower Required BHP 1.3
Operating Costs
Unit Ozone Generation Cost $/# 0.700 Dependent on O3 Generator & Operating Conditions
Cost For Ozone $/Day 46.7
Unit Electricity Cost $/kWh 0.08
Side Stream Pumping Cost $/Day 1.8
Total Operating Cost $/Day 48.5
Copyright Mazzei Injector Corporation, 500 Rooster Dr. Bakersfield California U.S.A.
Phone: 661-363-6500, FAX: 661-363-7500