8

WATER DISPOSAL SYSTEMS

T he disposal of produced water can be c1assified into two categories: surface disposal and subsur-
face, or deep-well, disposal. The vast majority of surface disposal of produced water occurs off-
shore, where the water is discharged into the ocean.

SUBSURFACE DISPOSAL
Pollution of surface water supplies or fresh water aquifers has become a serious concern in
recent years. This concern has focused attention on subsurface disposal as an economícally attractive
means of disposal of liquid wastes without polluting potable water supplies.

Subsurface disposal of liquid waste has been practiced by the petroleum industry since the early
1920's. Today it is common practice in many areas of the country, and several hundred thousand
barreIs of industrial wastes are being injected into subsurface formations each day. In addition to oH
field brines, plant waste solutions containing such diverse components as acids, caustics, inorganic
salts, and hydrocarbons are routinely injected into the ground in the oHfield.

The evolution of stringent requirements by several governmental agencies has added further in-
centive to consideration of subsurface disposal. As individuals, we are all vitally interested in main-
taining the quality of our waters. However, as members of industrial organizations concerned with
waste disposal at mínimum cost, meeting these water quality criteria represents a tremendous techno-
logical and economíc challenge. Since many waster streams can be successful1y injected into the
ground with a mínimum amount of pre-treatment, subsurface disposal is becomíng increasingly attrac-
tive from an economíc standpoint.

Produced Water Disposal

The composition and characteristics of brines and fresh waters used in water injection systems
have been previously discussed in detail. The same rules apply to the disposal of these waters. A brine
disposal system should be designed, constructed and monitored in exactIy the same manner as a water-
flood injection system.

The primary difference between injecting water into the ground to dispose of it rather than to
increase oH recovery, is that the water in disposal wells doesn't return to the surface is it does in
waterfloods following breatkthrough. The principal operational differences are twofold:

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 WATER DISPOSAL SYSTEMS

1. Incompatibility
Incompatibility between the injection water and the formation water is no longer a concem.
Mixing between the two waters is minimal, and the radial movement of the mixing zone
spreads any precipitate formed over a very large volume of reservoir rock. Hence, reser-
voir plugging as a result of mixing injection water and connate water is non-existent.
2. Reservoir Souring
Although often associated primarily with seawater floods, reservoir souring is a potential
problem in any sweet water-injection system. Additional corrosion problems, sulfide crack-
ing and hydrogen blistering in the production facilities are potentially catastrophic problems
brought about by reservoir· souring. In addition, the gradual souring of produced fluids
after the breakthrough of sour injection water may render the produced gas unsaleable
unless sweetening equipment is installed.
This is not an issue in water disposal wells.

Plant Water Disposal

The disposal of gas processing plant waters presents sorne slight1y different problems because the
composition of plant waste water is usually quite different from a waterflood injection water. However,
the same basic rules apply and cornmon sen se is still the rule of the day.
Gas plant waste waters are a mixture of many different streams.
1. Cooling Tower Blowdown
2. Boiler Water Blowdown
3. Ion Exchange Bed Regeneration Streams
4. Filter Backwash
5. Produced Water (Fresh or Brine)
6. Cleaning Solutions - Acids, Caustic, Detergents
7. Corros ion Inhibitors and Biocides
These streams are usually fed to a common holding pond or evaporation pit prior to treatment and
disposal. The holding pond should be lined to prevent soil pollution. It should be equipped with a
high-Ievel alarm to wam against overflow. An emergency overflow pit is also worthy of consideration.
One characteristic of plant waters is the cyc1ic nature of many of the streams. Blowdown, back-
wash and regeneration streams are all cyclic. Of course, the average composition of the pit water will
be constant, but there will be variations in the composition of the water entering the disposal system as
a function of time, depending on the frequency and amount of each stream and the size of the pondo
The composition of the pond water may change drastically during tum-around due to the di s-
charge of large amounts of acid and other c1eaning solutions.
The following guidelines are suggested in the examination of plant waters:
1. Determine the composition and amount of each stream entering the holding pondo
2. If it is a cyclic discharge, determine the discharge period and frequency.
3. Determine the corrosivity, suspended solids, and compatibility of the various streams.
These factors will enable you to select the proper materials, determine the needed pond capacity
and predict incompatibility problems. For example, if produced brine containing a large amount of

276 APPLIED WATER TECHNOLOGY

 SURFACE DISCHARGE

calcium is cornmingled with the regeneration backwash from a hydrogen zeolite hed, severe scaling
problems may occur in the disposal system. Sulfuric acid is cornmon1y used to regenerate hydrogen
zeolites, and the regeneration backwash contains a high sulfate concentration. Calcium sulfate scale
would be quite likely if these two streams were cornmingled. One solution would he to use hydroch1o-
ric acid to regenerate the bed rather than sulfuric acid and eliminate the sulfate ion. However, HCI is
more expensive than H2S04.
A second alternative would be to prevent cornmingling of the two streams by discharging them
into separate ponds. The ponds could than be pumped down on an alternate basis. It is often advisable
to look at the possibility of grouping the various streams into compatible groups and put them in
separate ponds. Each pond can then be injected sequentially with no mixing problems. This can pre-
vent or minimize scaling and decrease the filtration load.

Open or Closed System?

Although open systems are almost never used in water injection systems, they are sometimes the
most practical solution to the disposal of aerated waste waters. The primary challenge is to complete
the disposal well(s) in such a way that the tubular goods below the packer will be protected against
corrosion. Corros ion resistant alloys, non-metallic materials such as fiberglass, or plastic-coated steel
have all been used.

SURFACE DISCHARGE

Offshore Disposal
In most countries, water produced in offshore production operations must be processed to reduce
the oH and grease content to levels acceptable to local regulatory agencies. Although the toxicity of the
discharged water is of concern in sorne areas, removal of dispersed oH prior to discharge is often th~
sole process applied to this type of water.
There are four oH rernoval processes cornmonly used for this purpose:
1. Skirn tank
2. Corrugated plate interceptor
3. Induced gas flotation cell
4. Hydrocyc1one
These processes may be applied individually, or in combination to reach the desired result. Typi-
cal process designs are shown in Figures 8.1 and 8.2.

INCOMING
PRODUCTlON
SURGE
TANK !--1J-\.f\:.rl-'"'1

DEGASSING
TANK
WATER
OVERBOARD

Figure 8.1 Typical Offshore Produced Water Treatment

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 WATER DISPOSAL SYSTEMS

INCOMING 3-PHASE
PRODUCTlON SEPARATOR

GAS

HYDROCYCLONE DEGASSING
TANK

WATER
OVERBOARD

Figure 8.2 Offshore Produced Water Treatment with a Hydrocyclone

Each of these pieces of equipment is described in Chapter 6 under the heading of Dispersed OH
Removal.

Centrifuges have been used to a limited degree, but are very costly. Membrane filtration has been
tested, but presents significant operational challenges.

OIL-IN-WATER ANALYSIS

The oil content of a water depends on how it is measured. There is no absolute value.

Produced water contains both dispersed oH and "dissolved oH". The dissolved oH consists of
hydrocarbons, phenols, organic acids, and low molecular weight aromatic compounds such as benzene
and toluene.

Normal oH/water separation equipment cannot remove dissolved organic compounds. However,
values of "oH and grease" inelude both the dispersed oH and sorne of the dissolved organic compounds.
Hence, equipment performance cannot be accurately evaluated using "oil and grease" values.

A description of the various ways of measuring the oH content of a produced water are given in
Chapter 2.

TOXICITV ISSUES

The United States Environmental Protection Agency began requiring biomonitoring of aquatic
toxicity for produced water discharges in the Outer Continental Shelf of the Gulf of Mexico in Decem-
ber, 1993.

Aquatic toxicity is measured by comparing survival, growth and fecundity (egg production) of
living organisms in either synthetic water or natural seawater with that of the same type of organism
exposed to that same water containing varying percentages of produced water.

278 APPLlED WATER TECHNOLOGY

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 TOXICITY ISSUES

Toxicant Identiflcation
Toxic effects resulting from the discharge of produced water is the result of naturally occurring
toxic components originating from contact with the produced hydrocarbons an<J/or the formation rock
and/or treatment chemicals, which end up in the water phase.

The identity of the most likely toxicants has not been established with certainty. However, sorne
of the more likely culprits are surnmarized in the following section.

Treating Chemicals
It can be determined if treatment chemicals are the primary cause of toxicity by measuring the
toxicity of the produced water prior to chemical addition, and again after chemicals have been added.
If treatment chemicals prove to be the source of the problem, the identity of the specific chemical or
chemicals responsible can be established through a series of toxicity tests using the produced water and
different combinations of treatment chemicals.

Treating chemicals can be c1assified in three categories:

1. Production Treating Chemicals
• Emulsion Breakers • Paraffin Compounds • Water Treating Chemicals
• Detergents/Cleaners • Biocides Coagulants
• Corrosion Inhibitors • Scale Inhibitors Flocculants
• Oxygen Scavengers • Antifoamers Reverse Breakers
2. Gas Processing Chemicals
Typically methanol and/or glycol for hydrate inhibition, or glycol for gas dehydration.
3. Stimulation And Workover Chemicals
Production treating chemicals are the largest single source of concern, because these chemi-
cals come in contact with produced water.

The Most Toxic?

The following types of compounds appear to offer the greatest potential for toxicity based on
acute toxicity data using varying species and protocols:(8.2)
1. Quaternary Ammonium Compounds
"Quats" as they are often called, are cornmonly used as biocides, corrosion inhibitors, re-
verse breakers, and coagulants. They are quite soluble in water.
2. Amine Salts
Amines are commonly used as corrosion inhibitors and biocides.

Chemical Treatment lssues

1. System Application
Chemicals injected into pipelines or water injection systems will not be discharged over-
board, and so are not of concern. Glycol dehydration of gas is performed in a c10sed
system. Workover and stimulation chemicals can be caught and reused or treated prior to
discharge.

CHAPTER 8 279
 WATER DISPOSAL SYSTEMS

The primary concem is treating chemicals which are added to the produced fluids and end
up in the water phase.
2. Treatment Method: Batch or Continuous
Of particular interest are chemicals which are typically applied in high concentration
batches in normal production operations. These inelude scale inhibitors (squeezes), corro-
sion inhibitors and biocides. Low level continuous treatment obviously offers a lower po-
tential for toxicity.
3. Concentration
One must consider three concentrations: The actual treatment concentration, the concentra-
tion of the chemical in the water when it is discharged overboard, and the No Observable
Effect Concentration (NOEC).
Sorne fraction of the chemical injected into the system will be consumed or retained in the
system, which reduces the discharge concentration to a value les s than the treatment con-
centration. In addition, if batch treatments can be staggered, the concentration of a chemi-
cal in produced fluids from one well will be dHuted by production from other wells on the
platform.
4. Solubility
Biocides and scale inhibitors are the two elasses of chemicals which are highly soluble in
water, as are water treatment chemicals such as reverse breakers, coagulants and surfac-
tants. Corrosion inhibitors can be water soluble or oil soluble. Emulsion breakers typicalIy
have very liUle solubility in water, and most paraffin treating compounds tend to be more
soluble in oil than in waterJ8.2)
Many treating chemicals contain multiple components, and one or more of these may be
soluble in water, whHe others are not. There is also the question of how a particular com-
ponent partitions between oH and water.
5. Adsorption
Chemicals which are not very soluble in water can adsorb on the surface of solids, such as
corrosion products, which can end up in the water being discharged overboard.

Naturally Occurring Toxicants

If toxicity proves to be the result of chemical compounds which are naturally present in the
produced water, the cause of the toxicity is typically identified by subdividing the water into various
fractions and experimentalIy determining the toxicity of each fraction. A series of fractionation proce-
dures, each designed to remove a elass of compounds, is used to subdivide the mixture into a number
of samples that can be tested individually. This procedure makes it possible to identify the class of
compounds responsible for the toxicity.

The primary naturally occurring toxicants found in produced waters are:

• Dispersed OH • Radionuclides

• Soluble OH • Sulfides

• Heavy Metals: • Ammonia

Cd, Cr, Cu, Pb, Ni, Ag, Zn

280 APPLlED WATER TECHNOLOGY

 TOXICITY ISSUES

In addition, many produced waters have extremely high salinities, and all produced waters are
essentially free of dissolved oxygen.

While identification of most naturally occurring toxicants is reasonably straight forward, the defi-
nition of soluble oil is somewhat more elusive. The terro "soluble oH" is often used to describe the
organic materials which are dissolved in the water. Rabalais(8.3) categorized them in four groups in
descending order of abundance:
1. Organic Acids: The largest component.
Fatty Acids: Water produced with paraffinic oHs often has high concentrations of fatty
acids. However, the fatty acids in produced water are produced as sodium salts of the
acidJ8.4)

Aromatic Acids: Water produced with asphaltic oils contains notable amounts of naphthenic
acids.
2. Saturated Hydrocarbons
3. Volatile Aromatics and Phenols: Benzene and toluene comprise about 80% of these com-
pounds. They are typically more abundant in produced waters from gas condensate opera-
tions.
4. Polynuc1ear Aromatics: Smallest fraction; however, it is also the most toxico

Toxicity Reduction
If you wish to reduce the toxicity of a given discharge, it is necessary to first identify the cause(s)
of the toxicity.

Treatment Chemicals
If toxicity is due to treatment chemicals, there are several options which might result in reduced
toxicity:
1. Chemical Substitution
The first option would be to substitute a less toxic treatment chemical for the offending
product. For example, a glutaraldehyde might by substituted for a quatemary amine
biocide.
2. Change Treatment Method
The use of continuous treatment in place of batch treatment would substantially reduce
peak chemical concentrations in the produced fluids. This could significantIy reduce toxic-
ity.
3. Alter Chemical Composition
The use of a Iess toxic soIvent package, or alteration of the soIubility characteristics to
reduce the concentration in the water phase could reduce toxicity.

Natural Toxicity
Reduction of naturally occurring toxicity is somewhat more problematic due to the cost of addi-
tional equipment, increased operating costs, and space and weight limitations on offshore platforms.

Sorne of the more common water treatment equipment which could be considered for the purpose
of reducing naturally occurring toxicity are:

CHAPTER 8 281
 WATER DISPOSAL SYSTEMS

1. Gas Flotation
Dispersed gas flotation cells are cornmonly used offshore to reduce the oil and grease lev-
els in produced water to acceptable levels. A flotation cell can also tend to lower the
concentration of suspended solids.
2. Hydrocyclones
Hydrocyclones are commonly used to reduced the concentration of dispersed oil in pro-
duced water. This type of equipment typically has little effect on suspended solids.
3. pH Adjustment
Modest pH adjustment using phosphorous acid has been successfully employed in the Gulf
of Mexico as a means of precipitating "dissolved oil" so that it can be removed with dis-
persed gas flotation.
4. Filtration
Filtration equipment is primarily used to reduce the concentration of suspended solids in
produced water. However, it is also used to reduce the concentration of dispersed oil.
5. Air Stripping
Air stripping using a countercurrent stripping tower(s) could be used to reduce the concen-
tration of volatile fractions. Of course, the impact on air quality would have to be consid-
ered, and sorne sort of scrubber would probably be required.

REFERENCES
8.1 Place, M. c.: "Dissolved Organic Compounds in Produced Water." SPE Paper 22780, 1991.
8.2 Hudgins, C. M. Ir.: "Chemical Treatments and Usage in Offshore Oil and Gas Production Systems," J.
Peto Tech. (May 1992) 604.
8.3 Rabalais, N. N., et. al.: Fate and Effects oi Nearshore Discharges oi oes Produced Waters, OCS Study,
MMS 91-0004-0006 (1991)
8.4 Stephenson, M. T.: "Components of Produced Water: A Compilation of Industry Studies," J. Peto Tech.
(May 1992) 548.

282 APPLlED WATER TECHNOLOGY