Section 8 : Water Treatment

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8. Water Treatment
8.1 Introduction
Drilling processes generally create large volumes of waste fluids containing a variety of
wastewater pollutants, some of which are difficult and costly to treat or remove. In addition,
large fluctuations may occur in the wastewater's daily and hourly flow, temperature, and
composition. In some instances, several waste streams from different areas of the drilling process
may discharge at the same time. Generally, drilling fluids provide the greatest volume of waste,
with other major contributors are fluids associated with drilled cuttings, wash, rain and sewage
water from the rig and surrounding location. In some cases the fluids may be produced fluids
from the wellbore itself.
Traditionally, excess or waste fluids generated at a rig site were discharged into the environment.
However with increased environmental awareness and legislation, this practice has given way to
methods that either reduce or eliminate the amount of waste created, or treat the waste so that it is
environmentally acceptable to discharge.
Waste water at the rig site may include not only mud and recycled water, but also wash water
from the rig floor and decks, and storm runoff. In some cases it will include human waste, food
scraps, oils, soaps and other chemicals. The water treatment process should provide clean water
that is acceptable environmentally and conforms to environmental regulations. In cases where the
water may enter an aquifer or river system which will be used for public drinking water, more
stringent controls may be applied. Clean water is also critical to wildlife habitats and plants and
animals living nearby and in local rivers and ocean waters. If not properly cleaned, water can
carry disease, and harmful bacteria must be removed to make water safe. Water quality concerns
include solids and turbidity, nutrients (including nitrogen and phosphorus), organic carbon,
coliform bacteria, metals, oil, grease, sodium, toxic chemicals, algae and dissolved oxygen.
The water treatment required will therefore depend on the contaminants in the fluid to be
discharged, the location, and the local environmental regulations. In addition to the dewatering
already applied to the drilling fluid, the water treatments may include the following :
(a) Removal of remaining suspended fine solids
(b) Removal of color, metals, heavy metals and organic materials
(c) Removal of nutrients such as nitrates or phosphates
(d) Removal, destruction or inactivation of pathogenic (disease causing) organisms
(e) Reduction in total dissolved solids (TDS). This may be measured as conductivity.
(f) Reduction of specific contaminants to below the maximum contaminant level (MCL)
(g) Reduction in the biological oxygen demand (BOD) or chemical oxygen demand (COD).
Primary dewatering of mud and waste fluids from the rig location is one of the most important
steps in the overall water treatment process. In some cases, the effluent produced by dewatering
may be clear and safe to discharge to the environment, but most often will require further
treatment. At the rig location, the bulk of dewatering will be carried out on the drilling fluid waste
stream, with the primary function of enhanced solids removal, i.e. removing the bulk of the fine
solids entrained in the fluid through coagulation and flocculation mechanisms combined with
centrifugation of the flocked particles. The effluent produced by dewatering will often then be
discharged into a waste or containment pit, which will also be the discharge point for the other
liquid wastes from the rig site as described above.

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8.2 The Water Treatment Process
Water treatment can be defined as the polishing and final testing of dewatered fluid, rain water
and rig-wash water to ensure standards are met for release to the environment or compatibility for
re-use on rig. Water treatment services can also be used for several of the upstream remediation
services such as oil reclamation and sand/cuttings wash and are becoming increasingly important
as discharge parameters become more stringent.
There are three general treatment methods for wastewaters: These are physical, chemical and
biological treatment. Physical treatment methods consist of processes such as membrane
technologies, carbon adsorption, distillation, filtration, ion exchange, oil and grease skimming,
oil/water separation, sedimentation, steam stripping, and solvent extraction. Membrane
technologies, such as ultrafiltration and microfiltration are currently popular physical treatment
technologies. Chemical treatment methods include: Chemical oxidation, chemical precipitation,
chromium reduction, coagulation, cyanide destruction, dissolved air flotation electrochemical
oxidation, flocculation, hydrolysis, and neutralization (pH control). Biological treatment methods
include: biological nitrogen removal, bioaugmentation, activated sludge, extended aeration,
anaerobic processes, rotating biological contactors, sequencing batch reactors and trickling filters.
Water treatment is a multi-stage process to renovate wastewater before it is discharged to the
environment or a body of water and involves chemical treatment and circulation of the water. The
primary process involves precipitation and settling of various solids. In some cases pretreatment
is required to optimize their removal. The secondary process involves adjusting the properties of
the fluid prior to discharge. These adjustments include pH, elimination of pathogenic micro-
organisms) bacteria, protozoa, viruses and parasites) that may be present, and deodorizing the
fluid through aeration.

8.3 Flocculation and Chemical precipitation

This stage employs precipitation reactions and/or coagulants and flocculants to settle out not only
the remaining colloidal solids but also metals and other inorganics, fats, oils, greases, other
organic substances (including organophosphates). The use of coagulants and flocculants has been
discussed previously and will not be described in detail in this section.
Precipitation is a method of causing contaminants that are either dissolved or suspended in
solution to settle out of solution as a solid precipitate, which can then be filtered, centrifuged, or
otherwise separated from the liquid portion. A voluminous precipitate captures ions and particles
during formation and settling, in effect “sweeping” ions and particles from the wastewater. All
precipitation processes operate under the same principles. It is a physical-chemical process in
which soluble metals and inorganics are converted to relatively insoluble metal and inorganic
salts (precipitates) by the addition of a precipitating agent. Most often, an alkaline reagent is used
to raise the solution pH to lower the solubility of the metal constituent and cause it to precipitate.
Small amounts of oil or grease (1-5% by vol.) in the waste fluid act like solid particles and are
removed by coagulants and flocculants along with the other solids. Any free oil that is not
removed will float to the surface of the tank and can then be skimmed off. Any heavy or other
met also can also be removed at this stage through pH adjustment and hydroxide precipitation.

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8.3.1 Metals Removal
Precipitation of metals is the primary method of treating metal-laden wastewaters. In water
treatment applications, the metal precipitation process is often used as a pretreatment for other
treatment technologies (such as chemical oxidation or air stripping) where the presence of metals
would interfere with the other treatment processes. Metals precipitation from contaminated water
involves the conversion of soluble heavy metal salts to insoluble salts that will precipitate. The
precipitate can then be removed from the treated water by physical methods such as clarification
(settling) and/or filtration. The process usually involves pH adjustment, addition of a chemical
precipitant, and flocculation. Typically, metals precipitate from the solution as hydroxides,
sulfides, or carbonates. The solubilities of the specific metal contaminants and the required
cleanup standards will dictate the process used.
In the precipitation process, chemical precipitants, coagulants, and flocculants are used to
increase particle size through aggregation. The precipitation process can generate very fine
particles that are held in suspension by electrostatic surface charges. These charges cause clouds
of counter-ions to form around the particles, giving rise to repulsive forces that prevent
aggregation and reduce the effectiveness of subsequent solid-liquid separation processes.
Therefore, chemical coagulants are often added to overcome the repulsive forces of the particles.
The main types of coagulants are inorganic electrolytes (such as alum, lime, ferric chloride, and
ferrous sulfate), and synthetic low molecular weight cationic polymers and are described in detail
in Section 3. In some cases polymeric flocculants may be required for development of large flocs
that will settle out easily. These include medium to high molecular weight polymers (nonionic,
anionic and cationic) which are described in detail in section 4. The addition of coagulants
requires high energy turbulent mixing and is followed by low shear mixing of the flocculant low-
sheer mixing to promote contact between the particles.
Coagulants are added prior to polymeric flocculant addition. The coagulant addition is not critical
as long as it is added after pH adjustment and prior to polymer addition. The selection of the
proper coagulant is dependent upon water matrix, available products and sludge generation.
Sludge generation is important because of the cost of sludge disposal. Aluminum coagulants are
less sludge intensive than iron salts, but iron salts are typically less expensive.
Flocculating polymers accelerate the movement of solids and are the last products added. In batch
systems they are added into the batch tank; in a flow-through system they are typically added in a
flash mixer prior to the clarifier. Polymers used in heavy metal removal are usually high charge,
high molecular weight anionic polymers. However, there are some cases that may require a
cationic polymer or both. These streams usually contain some of the complexed metal
precipitants; for example, sulfide-based produces may need a cationic polymer because the sulfur
that is exposed is an anion.
Solids separation takes place in the batch tank or in a clarifier. There are several designs for
clarifiers, but in general they all force the water flow to slow down, therefore releasing the solids.

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Table 8.1 Effectiveness of Chemical Coagulation and Lime Softening Processes
Contaminant Method of Removal Removal %
Arsenic, As+3 Oxidation to As+5 required > 90
Arsenic, As+5 Ferric sulfate coagulation, pH 6 - 8 > 90
Alum Coagulation, pH 6 – 7 > 90
Lime Softening, pH 11 > 90
Barium Lime Softening, pH 10 - 11 > 80
Cadmium Ferric sulfate coagulation, pH > 8 > 90
Lime Softening, pH > 8.5 > 95
Chromium, Cr+3 Ferric sulfate coagulation, pH 6 - 9 > 95
Alum Coagulation, pH 7 - 9 > 90
Lime Softening, pH > 10.5 > 95
Chromium, Cr+6 Ferrous sulfate coagulation, pH 6.5 - 9 > 95
(adjust pH after coagulation for reduction to Cr+3)
Lead Ferric sulfate coagulation, pH 6 - 9 > 95
Alum Coagulation, pH 6 – 9 > 95
Lime Softening, pH 7 - 8.5 > 95
Mercury Ferric sulfate coagulation, pH 7 - 8 > 60
Selenium, Se+6 Ferric sulfate coagulation, pH 6 - 7 70 - 80
Silver Ferric sulfate coagulation, pH 7 - 9 70 - 80
Alum Coagulation, pH 6 – 8 70 - 80
Lime Softening, pH 7 - 9 70 - 80

a) Water Hardness
Water hardness is caused by the presence of any polyvalent metal cations, The principal
compounds causing hardness calcium and magnesium carbonate and bicarbonate compounds in
water, and to a lesser extent, by the sulfates, chlorides, and silicates of these metals.

Table 8.2 Principal Cations Causing Table 8.3 Hardness Classification Scale
Hardness and Associated Anions
Principal Cations Associated Anions Hardness (mg/L CaCO3) Hardness Description
Ca2+ HCO3- 0 - 50 Soft
Mg2+ SO42- 75 - 150 Moderately hard
Sr2+ Cl- 150 – 300 Hard
Fe2+ NO3- > 300 Very hard
Mn2+ SiO32-
Total hardness represents the sum of multivalent metallic cations and is normally considered to
be only calcium and magnesium. Generally, chemical analyses are performed to determine the
total hardness and calcium hardness in water. Magnesium hardness is then calculated as the
difference between total hardness and calcium harness.
Carbonate hardness is caused by cations from the dissolution of calcium and magnesium
carbonate and bicarbonate in water. Non carbonate hardness is caused by cations from the
dissolution of calcium and magnesium compounds of sulfate, chloride, nitrate, or silicate that are
dissolved in the water. Non carbonate hardness is equal to the total hardness minus the carbonate
hardness. Therefore when the total hardness exceeds the carbonate and bicarbonate alkalinity, the

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hardness equivalent to the alkalinity is carbonate hardness and the amount in excess to carbonate
hardness is non carbonate hardness.

b) Precipitation Softening
During precipitation softening, calcium is removed from water as CaCO3(s) precipitate and
magnesium as Mg(OH)2(s) precipitate. The concentrations of the various carbonate species and
the system pH play important roles in the precipitation of these two metals.
Carbonate hardness can be removed by elevating the pH above 10 with hydroxide ions provided
by lime, to convert the bicarbonate ions to carbonate ions. Before the solution pH can be
changed, any free carbon dioxide or carbonic acid must be neutralized. There no net change in
hardness in this reaction, however it does produce a lime demand.
H2CO3 + Ca(OH) 2 Æ CaCO3(s) + 2H2O
Further additions of lime and the increase in pH to 10 then cause the precipitation of calcium as
insoluble calcium carbonate.
Ca2+ + 2HCO3- + Ca(OH) 2 Æ 2CaCO3(s) + 2H2O
Non carbonate hardness cannot be removed simply by increasing the pH, but requires an external
source of carbonate, usually soda ash (sodium carbonate), to precipitate this calcium. This
process is called lime-soda ash softening.
Ca2+ + (SO42- or 2Cl-) + Na2CO 3 Æ CaCO3(s) + 2Na+ + (SO42- or 2Cl-)
Both carbonate and non carbonate magnesium hardness are removed by increasing the hydroxide
ion concentration .
Mg2+ + 2HCO3- + 2Ca(OH) 2 Æ 2CaCO3(s) + Mg(OH)2(s) + 2H2O
Mg2+ + (SO42- or 2Cl-) + Ca(OH) 2 Æ Mg(OH)2(s) + Ca+ + (SO42- or 2Cl-)

c) Use of Lime and Coagulants

To carry out softening precipitation with lime alone, a great deal of lime is typically needed to
work effectively; for this reason, the lime is often added in conjunction with ferrous sulfate,
producing insoluble ferric hydroxide. The combination of lime and ferrous sulfate is only
effective in the presence of dissolved oxygen, however. Alum, when added to water containing
calcium and magnesium bicarbonate alkalinity, reacts with the alkalinity to form an insoluble
aluminum hydroxide precipitate.

8.3.2 Heavy Metal Hydroxide Precipitation.

a) Precipitation Agents
In hydroxide precipitation, soluble heavy metal ions are converted to relatively insoluble metal
hydroxide precipitates by adding alkaline precipitating agents. The most common agents are,
• Hydrated Lime, Ca(OH)2
• Caustic Soda, NaOH.
• Magnesium Hydroxide, Mg(OH)2

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The first step in hydroxide precipitation is adding and thoroughly mixing the precipitating agent
with the waste stream. Precipitation reactions, which originate in a rapid-mix tank to form metal-
hydroxide precipitates, are given below, where M2+ is the soluble metal cation being removed.
• Hydrated Lime. M2+ + Ca(OH)2 Æ M (OH)2 (s) + 2Ca2+
• Caustic Soda. M2+ + 2NaOH Æ M (OH)2 (s) + 2Na+
• Magnesium Hydroxide M2+ + Mg(OH)2 Æ M (OH)2 (s) + 2Mg2+
Performance among the three hydroxide precipitation methods does not vary significantly. The
minimum metal hydroxide solubilities attained by each method are approximately the same,
however, sludge characteristics can vary tremendously.
Lime is the most commonly used hydroxide precipitating agent because it is pumpable, and is
low cost and effective. A disadvantage is that large amounts of sludge are formed.
Caustic is the second most commonly used hydroxide precipitating reagent. Its main advantage is
that it is highly soluble and rapidly dissociates into available hydroxyl ions, resulting in minimal
holdup time, and reducing feed system and storage requirements. Because caustic is a
monohydroxide, precipitating divalent metals requires two parts of hydroxide per part of divalent
metal precipitated. In contrast, lime, a dihydroxide, only requires one part hydroxide to do the
same job. Double the reagent requirements, combined with a higher cost/mole (roughly five times
that of hydrated lime), make caustic soda more expensive than lime. Although retention times
vary with the rate of reaction and mixing, 15–20 minutes is a common range for optimal,
complete precipitation. To maintain good process control, the dead time should be less than 5%
of the reactor residence time.
Magnesium Hydroxide’s main advantage is that a more dense precipitate forms because of
longer reaction times. The sludge volumes are much smaller (about 50% less) than those of lime
and caustic. This also improves sludge handling and dewatering characteristics. Increased
chemical costs will be offset by savings from easier sludge dewatering, compactness and greater
stability. Also, mixing magnesium hydroxide with caustic in a dual reagent system can reduce
sludge amounts by almost 50%. In areas with high sludge disposal costs, magnesium hydroxide
becomes a favorable choice. The cost of magnesium hydroxide is approximately three times as
much as hydrated lime. In addition, magnesium hydroxide precipitation systems are not as easy to
operate as lime or caustic. Because of the slow reaction times, equipment-sizing requirements
may prove to be costly owing to higher retention time requirements.

b) Solubility of Metal Hydroxide Precipitates

The solubilities of the metal-hydroxide precipitates vary, depending on the metal ion being
precipitated, the pH of the water, and, to a limited extent, the precipitating agent used. Typically,
the solubilities of most metal-hydroxide precipitates decrease with increasing pH to a minimum
value (termed the isoelectric point) beyond which the precipitates become more soluble, owing to
their amphoteric (soluble in both acidic and basic solutions) properties. Figure 8.1 shows the
solubility of various metal-hydroxide precipitates.

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 Figure 8.1. Solubility of Metal Hydroxides as a Function of pH

Pb(OH)2
Cr(OH)3

Zn(OH)2
Concentration (mg/L)

Ni(OH)2
AgOH

Cu(OH)2
Cd(OH)2

pH

The extent of precipitation depends on several variables,

• Maintenance of the proper pH throughout the precipitation reaction and subsequent settling
period. The pH of minimum solubility is different for each metal as shown above.
• A sufficient excess of precipitating agent to drive the precipitation reaction to completion.
• Effective removal of the precipitated solids.
Metal ions effectively removed via hydroxide precipitation include barium, cadmium, copper,
trivalent chromium, iron, manganese, nickel, lead, and zinc.
(i) Complex Formation. Reactions of the cations or anions with water to form hydroxide
complexes or protonated anion species are common. In addition, the cations or anions may form
complexes with other materials in solution, thus reducing their effective concentration. Soluble
molecules or ions, which can act to form complexes with metals, are called ligands. Common
ligands include OH-, CO32-, NH3, F-, CN-, S2O32-, as well as numerous other inorganic and organic
species. Introducing a strong oxidant (e.g., ozone) before the precipitation step may destroy some
of the metal complexes.
(ii) Chelating Agents. Metal hydroxide solubility is also increased by the presence of chelating
agents. A chelating agent forms multiple bonds with the metal ion that form a ring in which the
metal ion is held so that it is not free to form an insoluble salt. Common chelating agents are
EDTA and citrate. Methods to remove chelating/complexing agents include using starch xanthate,
ferrous sulfate, waste acids, sulfide ions, sodium hydrosulfite, and lime. A common water
practice is to use a combination of acid and lime to adjust the pH initially to around 2 with dilute
acid (sulfuric, nitric, or hydrochloric) which breaks the chelate. The pH is then raised to 9.5–11 to
form insoluble metal hydroxides. Chemical oxidation using potassium permanganate, ozone,
chlorine dioxide, or hydrogen peroxide has also been used to “break” metal-complexes and metal-
chelates to precipitate the metal ions.
(iii) Temperature. The solubilities of metal precipitates generally increase with increasing
solution temperatures.
(iv) Co-precipitation. The actual solubilities of metal precipitates are lower than the theoretical
solubilities if co-precipitation occurs. When the presence and precipitation of other metals in
solution aid in the removal of target metals through surface adsorption, it is called co-

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precipitation. The use of coagulants such as Alum or Ferric Chloride, and the production of
sweep flocs facilitates incorporation of the metal hydroxides directly into the sweep precipitation
matrix.
(v) Oxidation/Reduction. Certain metals may require oxidation (e.g., Fe2+ to Fe3+) or chemical
reduction (e.g., Cr6+ to Cr3+) to change the valence state so that a particular precipitation method
can be effective.
Hexavalent chromium must be reduced to the trivalent form prior to hydroxide precipitation. If
sulfide precipitation is used, this reduction, or pre-treatment, is not necessary. Reduction typically
occurs at pH 2.0 to 3.0 through adding acid and a reducing agent (e.g., sulfur dioxide, ferrous
sulfate, sodium metabisulfite, or sodium bisulfite). An oxidation-reduction potential (ORP) meter
can be used to monitor the reaction, notifying operators when it is complete. A color change
from yellow to green is typically evident.
Divalent iron or manganese ion can be oxidized to the trivalent form by aerating the water or by
dissolving oxygen into the water. Other techniques employed include the addition of hydrogen
peroxide, ozone, chlorine or permanganate. A combination of one or more process is sometimes
used to achieve high standards. When the oxygen or oxidation potential of the water is
increased, the metal ions will tend to loose electrons, and their oxidation level will be increased.
For example, soluble ferrous Fe2+ iron will be converted to insoluble Fe3+ ferric iron. The
ferric iron forms ferric oxide or rust which can be seen as a brown tide mark around tanks.

Advantages and Disadvantages of Hydroxide Precipitation

Removing heavy metals via hydroxide precipitation has several advantages. It is a well-
established, simple technology, is relatively inexpensive and has proven ability to achieve
regulatory effluent limits for several metals.. In addition to heavy metals, hydroxide precipitation
can also remove many non-metal pollutants, such as soaps and fluorides.
There are also several disadvantages. In practice the pH of minimum solubility, the isoelectric
point, may often differ (both higher and lower) considerably from the theoretical. In most cases,
actual solubilities will be greater than theoretical solubilities because of incomplete reactions,
poor separation of colloidal precipitates, and the formation of soluble metal-complexes (metal-
chelates). Conversely, they may be lower than theoretical solubilities because of co-precipitation.
Therefore it is essential to carry out jar tests to best simulate field conditions.
Table 8.4. Advantages and Disadvantages of Hydroxide Precipitation

Advantages Disadvantages
Well proven technology Precipitates tend to resolubilize if the pH changes
Simple pH adjustment Precipitation of mixed metal wastes may not be effective due
to different isoelectric points
Simple Operation Compexing agents adversely effect precipitation
Low Cost Precipitating Agents Some metals such as Cr6+ and Fe2+ require pretreatment
Little metal precipitation occurs below pH6

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8.3.3 Sulfide Precipitation
Sulfide precipitation converts soluble metal compounds into relatively insoluble sulfide
compounds, through the addition of precipitation agents. Commonly used agents are,
• Sodium sulfide, Na2S.
• Sodium hydrosulfide, NaHS.
• Ferrous Sulfide, FeS
• Calcium Sulfide, CaS
Sulfides are extremely reactive with heavy metals over a wide range of pH, and can be used to
remove lead, copper, chromium (6+), silver, cadmium, zinc, mercury, nickel, thallium, antimony
and vanadium. The precipitation reaction is usually carried out at near neutral conditions, pH 7 –
9. As for hydroxides, the metal sulfide precipitates must be physically removed from solution
through coagulation, flocculation, and clarification or filtration.
The initial step in the process is to prepare a sodium sulfite solution, which is then added in
excess to a reaction tank to precipitate the metal (M2+). Detention times vary, however 30
minutes is common.
M2+ + Na2S Æ MS (s) + 2Na+
Figure 8.2. Solubility of Metal Sulfides as a Function of pH

CdS
Concentration (mg/L)

ZnS

PbS
NiS

CuS Ag2S

pH

Two major sulfide precipitation processes exist depending on the way in which the sulfide is
introduced into the treatment process,
• Soluble sulfide precipitation (SSP) that uses soluble NaHS or Na2S
• Insoluble sulfide precipitation (ISP) that uses FeS or CaS which are only slightly water
soluble.
Soluble Sulfide Precipitation (SSP).
The SSP process uses two main precipitating agents, sodium sulfide and sodium hydrosulfide.
As both are highly soluble, there is no need for slaking and slurrying equipment. Liquid form
reagents are typically added from storage, whereas solid reagents are added from rapid-mix tanks.
As with all precipitating agents, jar testing should be used to determine optimal sulfide dosages.

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In high sulfide concentration there is usually a rapid precipitation of metal sulfides, which results
in small particulate fines and colloidal particles that have poor settling characteristics and poor
filterability. Through the effective use of coagulants and coagulant aids, separately or combined,
this problem may be solved by forming large, fast-settling floc.
The potential for excess sulfide is greatest when SSP is employed. Excess soluble sulfide in the
treated effluent may result in taste and odor problems, or present health or biotoxic hazards. The
rate of evolution of H2S from a sulfide solution per unit of water/air interface depends on solution
temperature (which determines the H2S solubility), the concentration of dissolved sulfide and pH.

Insoluble Sulfide Precipitation (ISP).

a) Ferrous Sulfide Precipitation
The ISP process, also know as the Sulfex process removes dissolved metals by mixing the
wastewater with an FeS slurry in a solid/liquid contact chamber. The FeS dissolves to maintain a
sulfide ion concentration of approximately 2 mg/L. Because of its instability, ferrous sulfide has
to be generated onsite from sodium sulfide and ferrous sulfate. When other metals are present that
are less soluble than FeS, the sulfide ion is released from the ferrous ion. The liberated ion will
form a hydroxide, as well as a precipitate, when the pH is maintained between 8.5 and 9. The
excess (unreacted) is then settled or filtered out of solution with the metal sulfide precipitate,
leaving the effluent practically sulfide free. Coagulants and coagulant aids may be used to aid in
the settling process. When FeS is added to a solution containing dissolved metals and metal
hydroxide, the following reactions occur.
FeS Æ Fe+3 + S-2
M+2 + S-2 Æ MS
M(OH)2 Æ M+2 + 2 (OH) -
Fe+2 + 2 (OH) - Æ Fe(OH)2
Typically, the ISP process requires 2 to 4 times the stoichiometric amount of FeS, i.e the actual
amount required chemically to react with the metals. Because of the very low solubility of FeS,
using excess FeS stops toxic H2S gas from forming. However, the use of an excess amount of FeS
adds significantly to the chemical cost of the process as well as sludge volumes. A considerably
larger (up to 3 times that of lime precipitation) quantity of sludge is produced from this process
because ferrous ions are added to the wastewater and they subsequently precipitate as ferrous
hydroxide.
The following factors are important to obtaining satisfactory results with the Sulfex process:
• Concentration of ferrous sulfide solids in the mixing zone.
• pH.
• Effective use of coagulants and coagulant aids.

a) Calcium Sulfide Precipitation

Calcium sulfide can be used as an alternative to ferrous sulfide as the precipitating agent. Calcium
sulfide minimizes some of the problems associated with soluble and insoluble sulfide
precipitation (i.e. H2S evolution and excess reagent requirements). Solid calcium sulfide is
typically slurried before it is added and it produces easily settable precipitates. Calcium particles
act as nuclei for producing metal sulfide precipitates and the dissolved calcium functions

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similarly to a coagulant. Calcium, added as CaS, is mostly dissolved after reaction and does not
significantly add to the sludge volume. For this same reason, the CaS dosage requirement, unlike
FeS, is near stoichiometric.
Calcium sulfide is stable only in the dry, solid form. In aqueous solutions, CaS reacts with water
to produce Ca (HS)2 and Ca (OH)2 as follows:
2CaS + 2H2O Æ Ca (HS) 2 + Ca(OH) 2
After CaS is added, the main reactions that precipitate metal sulfides are:
M2+ + HS- Æ MS + H+
–
H+ + OH Æ H2O
M2+ + S2 Æ MS

Treatment of Fluids with Multiple or High Heavy Metal Content

It may be more economically prudent to pre-treat wastes containing high concentrations (above
50 mg/L) of heavy metals using hydroxide precipitation before “polishing” with the Sulfex
process. In wastewater contaminated with more than one metal, selecting the optimal pH and
treatment chemical for a single stage precipitation process becomes more difficult and often
involves a trade off between optimal removal or two or more metals.
In general, for wastewater contaminated with multiple metals, the EPA states that a single stage
precipitation process does not provide for adequate treatment. Instead the EPA recommends a
series of chemical treatment steps using different pH values and/or different treatment chemicals.
Each of these treatment steps must be followed by a solids separation step in order to prevent the
resolubilization of the metal precipitates during the subsequent treatment step.

Advantages and Disadvantages of Sulfide Precipitation

Sulfide precipitation has several advantages over hydroxide precipitation.
a) The principle advantage is the very low solubilities that can be obtained as shown in Fig.
11.2. Good heavy metal removal is possible even with weak chelating agents present.
b) Strong chelating agents will hinder the process, but the metal will still be removed.
c) Precipitation can be achieved over a wide pH range (2 – 12). Metal sulfides are less
amphoteric than hydroxides, and therefore are less likely to resolubilize with changes in pH.
d) With the ISP orocess there is no need to pretreat hexavalent chromium (Cr6+), as the
reduction to the trivalent form (Cr3+) is catalyzed by the ferrous ions in FeS.
e) The sludge produced is easier to dewater with less leaching than metal hydroxides sludges.
Sulfide precipitation also has a few disadvantages.
a) Although sulfide precipitation processes do not produce significant air emissions, they must
be controlled (pH must be high enough) to prevent the release of toxic H2S.
b) Cr6+ may be reduced to Cr3+ by ISP; however, the process must be carried out under high pH
conditions to allow the hydroxide precipitate of chromium (+3) to form. T
c) The ISP process does not treat manganese, as manganese sulfide has a higher solubility than
ferrous sulfide.

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d) A major concern with sulfide precipitation is the generation of metal-sulfide sludge. This
sludge is considered toxic and hazardous.
e) ISP produces around three times more sludge than hydroxide precipitation.
Table 18.5. Advantages and Disadvantages of Metal Sulfide Precipitation
Advantages Disadvantages
High metal removal even at low pH (2 – 3) Potential hydrogen sulfide emissions
Low detention time due to high reaction rates Potential residual sulfide in effluent
Sulfide sludge exhibits better thickening and Soluble sulfide may cause an odor problem
dewatering than hydroxides
Sulfide precipitation is less influenced by The metal sulfide sludge is toxic
complex/chelating agents than hydroxides
Sulfide sludges exhibit less leaching than hydroxides Higher operating costs than fot hydroxides
SSP sludges have smaller volumes

8.3.4 Carbonate Precipitation

Heavy metals can also be removed by direct precipitation using a carbonate precipitating agent,
such as soda ash, sodium bicarbonate, or calcium carbonate. The solubilities of metal carbonates
depend on the specific metal ion precipitated and the pH of the wastewater. Generally, the
solubility of metal carbonates are intermediate between hydroxide and sulfide solubilities.
Carbonate precipitation is often preferred over hydroxide precipitation for removal of cadmium,
lead, and nickel, giving lower final residual concentrations than those of hydroxide. The process
produces metal carbonates and hydroxides, and the resulting sludge is classified as a hazardous
waste. Therefore, sludges from carbonate precipitation processes may need to be encapsulated or
fixed in some other way to stop the metals from leaching in an acidic environment.
Calcium Carbonate or Limestone is available in either high calcium (CaCO3) or dolomitic
(CaCO3MGCO3) form. Owing to its faster reaction rate and its more widespread availability, the
high calcium form is more often used. The powder form is desirable because both reactivity and
completeness of reaction increase proportionately to the available surface area.
The primary advantage of limestone is low cost and widespread availability. The main
disadvantage of calcium carbonate precipitation is that it is only effective for precipitating metal
ions in its operational pH range (5.0 to 7.0). Lime in combination with limestone as dual alkali.
The limestone is used as a pretreatment step to raise the pH to about 6.0, with lime completing the
precipitation process.
Sodium Carbonate (Na2CO3) or soda ash is an alternative to sodium hydroxide for acidic-metal
waste streams, which lack buffering capacity. Sodium carbonate is a weak alkali and imparts
some buffering capacity, allowing the pH to be controlled and precipitation to take place within
the neutral range. Buffering agents produce a smaller change in pH per unit addition than
comparable unbuffered reagents, such as lime and caustic.
Precipitation, using soda ash, occurs at much slower rates than with hydroxide methods, such as
lime or caustic and requires a minimum of 45 minutes retention time. Soda ash provides the
advantage of lower sludge generation rates (lower than using calcium carbonate) since sodium-
based end products are more soluble than calcium-based products. However, sodium-based
sludges do not filter as readily or attain as high a solids content as calcium-based sludges. In
addition, the supernatant may not be as low in metals content or total dissolved solids as when
lime is used as the precipitating agent.

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Advantages and Disadvantages of Carbonate Precipitation.
The main advantage of using carbonate precipitation is that it can operate at a lower pH range,
typically between 7 and 9. At this range, adjusting pH after precipitation wouldn’t normally be
required. Also, carbonate precipitation is competitively priced in relation to hydroxide
precipitation, and carbonates form easily filterable precipitates.
There are a few disadvantages of using carbonate precipitation. The treatment chemicals used for
this process tend to be abrasive and can damage feed equipment. In addition, the sludge produced
in this process is gelatinous and difficult to settle, and pre-treatment of chromium (+6) by
reduction is required.
Table 8.6. Advantages and Disadvantages of Carbonate Precipitation
Advantages Disadvantages
Carbonate precipitants are easy to handle and Retention times are longer due to slower reaction
can be purchased in bulk times
Forms easily filtered precipitates Carbonates mix easily and may emit carbon dioxide.
Unless aerated the reactions will be slowed
Sodium carbonate imparts buffering capacity Calcium carbonate particle have the potential to
and generates less sludge than lime precipitation become deactivated
Optimum treatment occurs at lower pH Sodium carbonate sludges do not filter as readily, or
to as high a solids content as calcium based sludges
Carbonate sludges have better dewatering Calcium Carbonate is only able to achieve a n
characteristics than hydroxide sludges. operational pH of 5 – 7
Cr6+ requires pretreatment by reduction, prior to
using carbonate precipitation

8.3.5 Metals Removal with Ferric Chloride

Ferric salts are very effective scavengers of heavy metals. In some cases ferric salts are the only
feasible method for removing a variety of heavy metals. This is due to several possible different
removal mechanisms, enabling ferric salts to remove heavy metals present in soluble, complexed,
chelated, colloidal, emulsified and particulate form.
At neutral to alkaline pH, ferric salts precipitate as amorphous hydrated oxide or oxy-hydroxide,
which has relatively stable and reproducible surface properties. Upon aging, the precipitate
transforms gradually into a crystalline iron oxide (goethite) form. However, its absorptive
properties remain quite similar. The ability of the ferric hydroxide precipitate to absorb ions with
heavy metals is characterized in single and multi-adsorbate systems. Heavy metals could be
absorbed both as cations (Cr3+, Pb+, Cu2+, Zn2+, Ni2+, Cd2+) in neutral to high pH, and as anions
(SeO42-, CrO42-, VO3(OH) 2-, AsO43-) in neutral to mildly acidic pH. For heavy metals present in
cationic form, the absorption efficiency increases with pH, while concentration of both sorbate
and ferric hydroxide play a secondary role.
The mechanism of heavy metals adsorption by the previously precipitated ferric hydroxide,
involves different related mechanisms. In practical applications, ferric hydroxide is precipitated
in situ, which facilitates incorporation of heavy metal cations directly into the precipitate matrix
in place of the similarly sized and charged ferric cations; mechanisms known as co-precipitation.
This accounts for only partial reversibility of the metal adsorption reaction upon reversal of pH.

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Advantages of Ferric Salts
The use of ferric salts overcomes a number of problems associated with the use of pH induced
hydroxide precipitation methods,
a) The formation of complexes or chelates causing higher than expected dose rates. The list of
potential complexing agents is extensive and may include for various heavy metals, such as
ammonia, chlorides, sulfates, cyanides, amines, thiourea, citric acid, EDTA and other organics.
Ferric salts can overcome the masking effect of complexing agents or chelating ligands, perhaps
by replacing trace heavy metal by the ferric cation.
b) An additional problem, which limits effectiveness of pH-induced precipitation of heavy metals,
is the presence of emulsions and colloids stabilized by surfactants commonly found in
wastewater. Metals could be encapsulated into colloidal particles or emulsion globules (including
in dissolved form), where they are relatively resistant to pH changes in the bulk liquid. Since
ferric salts are also coagulants, their practical effectiveness in heavy metal removal extends into
colloidal, emulsified and fine particulate forms of heavy metals.
Aluminum Salts can also be used to co-precipitate metals, however iron salts tend to work better
primarily because iron hydroxide is insoluble over a wider pH range and is less soluble than
aluminum hydroxide. Iron coagulants not only form a stronger and heavier floc, but co-
precipitation of iron-metal complexes is important and can reduce the solubility of metals
significantly.

8.4 Removal of Fats, Oils and Greases

Fats, oils, and greases are typically organic substances which tend to bead together or form
“slicks” on the surface of aqueous solutions. They behave in this way because these organic, non
polar substances are typically insoluble in water, which is inorganic and polar. Because they tend
to be less dense than water, they float to the surface rather than settling to the bottom. In
situations where the oily substance is free floating in slicks, skimming the surface of the solution
is often the best way to remove most of the material. However, oils, fats, and greases can become
emulsified in aqueous solution, meaning that small droplets of the oily product can become
suspended throughout the water. Often, other substances, such as soaps and detergents, in
solution can act as aids to making hydrophobic substances soluble in water. To remove
emulsified oils and greases, the emulsion must be broken up by destabilizing the electrical charge
attractions that keep the localized clusters of oily molecules stable in solution. This can be done
with the addition of a polymer designed for charge neutralization. In this way, the charge
attraction of the oily particles is disrupted, allowing them to separate from the aqueous solution.

8.5 Phosphorus Removal

Metal salts (most commonly ferric chloride or alum) or lime, are used for the removal of
phosphate compounds from water. When lime is used, a sufficient amount of lime must be added
to increase the pH of the solution to at least 10, creating an environment in which excess calcium
ions can react with the phosphate to produce an insoluble precipitate (hydroxylapatite). Lime is
an effective phosphate removal agent, but results in a large sludge volume. When ferric chloride
or alum is used, the iron or aluminum ions in solution will react with phosphate to produce
insoluble metal phosphates. The degree of insolubility for these compounds is pH dependent.
Moreover, many competing chemical reactions can take place alongside these, meaning that the

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amount of metal salt to add to the solution cannot simply be calculated on the basis of the
phosphate concentration, but must be determined in the laboratory for each case.

8.6 Nominal Organic Material Removal

Nominal organic material (NOM) includes color, total organic carbon (TOC) and disinfection by
products (DBPs), and are controlled by water treatment due to regulatory and/or aesthetic
constraints. Color, TOC and DBPs are partially removed by softening, and the amount removed
is dependent on the pH and the waste water. Iron and Aluminum salts may be used during lime
softening as settling aids and to increase color and TOC removal. The use of only coagulants
such as iron and aluminum salts will remove color, TOC is as effective.
a) Calcium carbonate precipitation removes from 10 – 30% of the color, TOC and DBPs.
b) Magnesium hydroxide precipitation removes from 30 – 60% of TOC and DBPs and 50 – 80%
of the color.
c) Iron and aluminum augmentation generally removes an additional 5 – 15% of the color, TOC
and DBPs in either calcium or magnesium precipitation.
d) Sequential treatment involving softening in series with coagulation will remove additional
color, TOC and DBPs.
e) Use of coagulants alone is as effective as using softening plus coagulants.

Color in water is classified as either true color or apparent color. True color is that partly due to
dissolved solids that remain after removal of suspended matter, whereas apparent color is due
suspended matter. True color is the most difficult to remove in water treatment. Color in
wastewater is not usually considered unsafe or unsanitary, but is an indicator along with odor, of
the condition or age of the wastewater. Black colored wastewater, usually accompanied by foul
odors, containing little or no dissolved oxygen, is said to be septic.

Organic chemicals in water primarily originate from synthetic compounds that contain carbon, or
naturally occurring organic matter such as decaying leaves, weeds and trees. The presence of
organic matter in wastewater is troublesome for the following reasons,

• Color formation
• Taste and odor problems
• Oxygen depletion in streams
• Interference with water treatment processes
• The formation of halogenated compounds when chlorine is added to disinfect water.
Many organic compounds are soluble on water, and can be divided into 2 groups, biodegradable
and non-biodegradable. Bio-degradable material consists of organics that can be used for
nutrients by naturally occurring micro-organisms within a reasonable length of time. These
material usually consist of alcohols, acids, starches and other mud products, fats, proteins, and
esters. They may result from wastewater discharges or may be end products of the initial
decomposition of plant or animal tissue. The principal problem associated with biodegradable
organics is the effect resulting from the action of micro-organisms, which may cause color and
odor problems. This is promoted under anaerobic or oxygen lacking conditions and can be
minimized by maintaining adequate levels of oxygen in the water through aeration.

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In oxygen present (aerobic) conditions, the end products of microbial decomposition of organic
compounds are stable and acceptable compounds. However, in oxygen absent (anaerobic)
conditions, decomposition results in unstable and septic end products.

8.6.1 Biological Oxygen Demand

Biochemical Oxygen Demand or biological oxygen demand (BOD) refers to the amount of
oxygen that would be consumed if all the organic material in one liter of water were oxidized by
bacteria and protozoa.
There are two main causes that drive up BOD in wastewater. The wastewater either contains too
much organic material or nutrients/fertilizers in the form of nitrates and phosphates which will
stimulate the overgrowth of plants and algae. However, once this organic matter (plants, algae,
human, food, and animal waste, biodegradable mud products) begin to decompose, it begins to
suck the oxygen out of the water.
The BOD water test is used to determine how much oxygen is being used by aerobic
microorganisms in the water to decompose organic matter. If these aerobic bacteria are using too
much of the dissolved oxygen in the water, then there will not be enough left over for the fish,
insects, and other organisms that rely on oxygen. The rich diversity of life on a healthy river is
then reduced to a low diversity (but sometimes high volume) of pollution tolerant organisms.
The BOD is measured as the amount of oxygen, divided by the volume of the system, taken up
through the respiratory activity of microorganisms growing on the organic compounds present in
the sample (e.g. water or sludge) when incubated at a specified temperature (usually 20 °C) for a
fixed period (usually 5 days, BOD5). It is a measure of that organic pollution of water which can
be degraded biologically. In practice, it is usually expressed in milligrams O2 per litre.
The first step in measuring BOD is to obtain equal volumes of water from the area to be tested
and dilute each specimen with a known volume of distilled water which has been thoroughly
shaken to insure oxygen saturation. After this, an oxygen meter is used to determine the
concentration of oxygen within one of the vials. The remaining vial is than sealed and placed in
darkness and tested five days later. BOD is then determined by subtracting the second meter
reading from the first.
The range of possible readings can vary considerably: water from an exceptionally clear lake
might show a BOD of less than 2 ml/L of water. Raw sewage may give readings in the hundreds
and food processing wastes may be in the thousands.

8.6.2 Chemical Oxygen Demand

The chemical oxygen demand (COD) is a direct measure of the amount of organic compounds
in water. Most applications of COD determine the amount of organic pollutants found in surface
water (e.g. lakes, rivers and strreams), making COD a useful measure of water quality. It is
expressed in mg/L which indicates the mass of oxygen consumed per liter of solution.
The COD measurement is based on the fact that nearly all organic compounds can be fully
oxidized to carbon dioxide with a strong oxidizing agent under acidic conditions. In contrast to
biochemical oxygen demand (BOD), the process of measuring COD causes the conversion of all
organic matter into carbon dioxide. For this reason, one limitation of COD is that it cannot
differentiate between levels of biologically active organic substances and those that are
biologically inactive. One major advantage of COD, however, is that it can be measured in a

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fraction of the time required by BOD. While BOD takes 5-7 days to determine, COD requires just
3 hours.
Some samples of water contain high levels of oxidizable inorganic materials which may interfere
with the determination of COD. Because of its high concentration in most wastewater, chloride is
often the most serious source of interference. Its reaction with potassium dichromate follows the
equation:
Prior to the addition of other reagents, mercuric sulfate can be added to the sample to eliminate
chloride interference. Table 11.7 lists a number of other inorganic substances that may cause
interference. The table also lists chemicals that may be used to eliminate such interference, and
the compounds formed when the inorganic molecule is eliminated.
Table 8.7 Inorganic Anions that Interfere with COD Measurement
Inorganic molecule Eliminated by Elimination forms
Chloride Mercuric sulfate Mercuric chloride complex
Nitrate Sulfamic acid N2 gas
Ferrous iron Sulfamic acid -
Sulfides Sulfamic acid -

Many governments impose strict regulations regarding the maximum chemical oxygen demand
allowed in wastewater before they can be returned to the environment.
8.7 Nutrients
Nutrients are essential foods for healthy aquatic organisms, but excess nutrients, especially
nitrogen and phosphorus compounds, over stimulate the growth of aquatic weeds and algae.
Excessive growth of these organisms can clog streams and navigable waters, interfere with
swimming and boating, and out compete native submerged aquatic vegetation, and, with
excessive decomposition, lead to oxygen depletion.

8.8 Water Treatment Systems

For reserve pits the fluid is circulated by using centrifugal pumps to pick up fluid at one end of
the pit and discharge it at the opposite end. Treatment chemicals are added to the pit directly or
injected into the fluid through the pump. Circulation continues after the proper amount of
chemical has been added to ensure adequate mixing. Proper pit design can greatly enhance this
process.
Once the pit is properly flocculated, circulation is stopped to allow solids to settle. Water samples
are drawn for analysis. When all discharge parameters are met, the proper regulatory agency is
contacted for discharge approval. All work is documented and submitted to the proper parties.
Upon approval, centrifugal pumps are used to discharge the water. The discharge is monitored to
ensure that only clean water is discharged.
For smaller processes, a separate secondary water treatment tank is used. Chemical additions are
made directly to the tank or injected through the pump. Frequently dissolved air flotation (DAF)
will be used to float the very fine solids rather than settling them.

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 Figure 8.3 Water Treatment in Open Pit System

Coagulants

Flocculants
Circulation
Pump Mist Aeration
System Pump

Chemical
Injection
Chemical Pump
Injection
Pump

Mud
TREATMENT IN PROGRESS

Clear
Water

Settled
AFTER Flocculated
Solids
TREATMENT

SW 9190 C

Water treatment can be carried out in earthen pits or open circular tanks. The advantage of using
tanks is the flexibility of moving the tanks from one location to another and the reduction on the
cost associated with the construction, impermeabilization, maintenance, cleaning and final
closing of earthen pits. The surface area is another relevant factor to be considered. The larger the
surface area, the larger the volume of rainwater received into the system for treatment.
Experience has also demonstrated that by restricting the volume available for collection and
treatment of wastewater during drilling operations, there is a reduction in the total volume of
water used for rig washing.
The site construction and environmental licenses/permits will determine the best acceptable
design for the water treatment system at the rig site. Figure 8.4 shows pit and tank treatment
systems.

Figure 8.4. Water treatment system on tanks and conventional three open pits.

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8.8.1 The Three Pits/Tanks System
a) Collection
Rainwater from the inner perimeter, wash water, and the effluent from the dewatering unit are
sent to the water treatment system for adjustment and recycling or treatment and final disposal.
Perimeter ditches are constructed to collect and carry rainwater or excess fluids on location. All
fluids must pass through a skimming system to separate any oil or grease before going to the
treatment system. This skimmer varies on size depending on the space restrictions, but it should
be designed to a minimum capacity of 75 bbl. The skimmer allows larger particles to settle and
enhances the separation of oil and grease. The design should have a first flush contingency gate
that allows diverting rainwater to dispose without any treatment while complying with quality
requirements. The skimmer must be inspected periodically inspected and maintained.
The pit/tank number one receives water from the skimming system and the dewatering unit. This
pit/tank is mainly used to homogenize and to characterize the water to be treated while at the
same time allowing suspended solids to settle.
b) Treatment
The treatment begins once enough volume is stored in the first pit/tank (around 70%). A sample
of the fluid is taken for treatability testing. The water treatment engineer runs this testing. Initial
characterization may perhaps include the parameters shown in Table 11.7.
Table 8.7 Initial Water Characterization
Control Parameter Units
pH Units
Color Pt, Co units
Turbidity NTU
Suspended solids mg/lt.
Sulfates mg/lt.

Pilot Tests are run to find the optimal concentration of coagulants, flocculants, pH adjustment
chemicals and chlorine required to treat the water prior to final disposal. The water treatment
engineer also determines the amount and the correct dosing time to inject the chemicals.
Homogenation and Aeration is then carried out prior to treatment with precipitation of
coagulation chemicals. The water transferred to pit/tank number two is homogenized by
circulating the water through the pumps and injecting coagulant and flocculant agents on the line.

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The second pit/tank should have a pipe connected around its perimeter. This pipe will be
perforated. As the fluid is pumped through the line the fluid will be discharged in a spray to the
center of the pit/tank. This will increase the aeration to maintain adequate levels of dissolved
oxygen.
Chemical treatment of the water takes place under the following stages. Organic or Inorganic
Coagulant is added to the fluid in a state of turbulent flow. This generates a physiochemical
instability of the colloids and the suspended solids. In this step the following processes take place:
• Hydrolysis of the used coagulant and destabilization of the suspended particles
• Formation of polymeric chemicals compounds
• Absorption of Polymeric chains by the colloids
• Mutual absorption of colloids
• Sweeping action
The next step is to use high or medium molecular weight flocculating polymers with varying
concentrations determined by Pilot Tests thus reaching the necessary size and weight to promote
separation and sedimentation of the solids. In this step the speed of the water mass is essential and
is regulated by the centrifugal pumps. Slower agitation is required to avoid breaking down the
extended polymer chains.
Sedimentation occurs when gravitational effects cause the particles to settle in the pit/tank. The
flocculated particles, change shape, size and resistance during this process. A clear effluent is
observed in contrast with the bottom sludge that has to be removed periodically to optimize space
for treatment. The clear effluent can be reused in the operation (washing, cooling, mud premix or
dilution), transferred to the third pit/tank for additional treatment or disposed if regulatory
requirements are met.
Clarification and final adjustment for disposal takes place in the third pit. After finalizing the
settling process, clarified effluent is pumped to the third pit for final adjustment, testing and
disposal. This stage consists of adjusting the pH, eliminating the possibility of pathogen micro-
organisms (bacteria, protozoa, virus and parasites) that may be present in the water and
deodorizing through aeration. Continuous aeration is also recommended to minimize the
biological and chemical oxygen demands (BOD and COD).
After final adjustment, water is tested again by the water treatment engineer to verify that it is
within the maximum permissible limits for discharge or reuse. Clear effluent can be transferred
to an irrigation system, or reused in the operation (washing, cooling, mud premix or dilution).

Figure 8.5. Three Tank System Treatment Process

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 Fresh water supply
Run-off water
1 3 Mud
Dewatering effluent
4 Treated water
6 2 Gray water & treated
Domestic water

10

7 2 2
9
8

1 Water Supply
2 Centrifugal Pump
Rig Tank 11
3
4 Camp
5 Domestic Water
Treatment Unit 2
13
6 Drilling Rig 12 Chemical Tank 12
15
Flocculation & Settling 12
7 Solids Control System 13
8 Dewatering Unit Tank No.2
9 Skimmer 14 Final Adjustment Tank No.3 16 14
2
Contingency Storage (Lab testing for quality control) 12
10
Tank 15 To Re-use
11 Initial Settling Tank No.1 16 To final disposal 2

8.8.2 The First Flush System

The First Flush System is a contingency set of gates that allows for direct disposal of water
during heavy rains. During normal conditions, rig runoff water is sent to the treatment pit/tank
system. However, high volumes of rainwater exceeding capacity might generate problems for
treatment and disposal. When this occurs, it is then recommended that a procedure allowing the
direct discharge of rainwater be put into practice. During the initial rainfall the rainwater will
wash most of the surface contaminants into the collection ditches and the contaminated fluid
stored within the collection tanks. The water treatment engineer will test the water regularly.
When the water parameters meet the local discharge regulations and no oil sheen is detected the
gate is opened and rainwater is diverted off location until rain stops and the drainage is closed
again. The water treatment engineer is responsible for monitoring this operation during periods
of rainfall.

Emergency Pit/Tank
It is recommended to have an additional emergency pit/tank for contingencies. The purpose of
this pit/tank is to collect excess water or mud in case of a water flow, excessive contaminated
rainwater from rig runoff stream, cement returns or any unplanned event. This pit/tank must be
kept empty and clean at all times.

8.8.3 Fluids Handling Recommendations

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• The ends of water hoses used on location for fluid transfer should be equipped with valves.
• Water used on the rig pump cooling systems should be recycled on a continuous basis.
• Fresh water tank overflows should be directed off location.
• Drilling fluid in mud tanks must be kept at minimum circulating volumes.
• Sand traps should be processed through a Desander with dumping of sand traps prohibited.
• Displacements: Prior to reaching casing point and in anticipation of cement displacement, the
active pit volume must be reduced. Facilities for storing displaced volumes should be
available and planning procedures put in place for better waste management results.
• Cement Returns: Coordination is imperative to detect and divert any cement returns to a
storage tank or to the emergency pit/tank
• Water Minimization: Rig washing should be controlled and minimized to reduce treatment
volume and associated costs. Use pressure washers for cleaning operations.

8.9 Laboratory Equipment and Testing Procedures

A fully equipped SWACO laboratory including HACH 2010 Spectrophotometer equip-ment will
be on location to assure that all discharged fluids are in compliance with all local environmental
regulations. Refer to Figure 4 for a typical water laboratory. All treated fluids will be checked for
turbidity, color, pH, conducti-vity, suspended solids, free oxygen, free chlorine, sulfates and any
other parameters required by local regulations. Daily records will be kept and maintained at the
rig site.
Laboratory Equipment Figure 8.6. Jar Test performed at site laboratory
a) HACH DR/2000 Spectrophotometer
b) Digital pH Meter HACH
c) Conductivity Meter HACH
d) Scale
e) Blender
f) Digital Reader/HACH
g) Digestor Reagent HACH
Materials
a) Graduated Beakers (200, 500, 1000 cm3 )
b) Graduated Cylinders (50, 100, 500, 1000 cm3)
c) Pipettes (0.5, 1, 2, 5, 10 cm3)
d) Separator Funnel (500 cm3)
e) Stands
f) Flask, Erlenmeyer (100, 250 cm3)
g) Filter Paper
h) Funnel
i) Distilled Water
j) Reagents for calibration usage in different methods
k) Calibrated Pipettes
l) Other Glass Material

8.10 Sampling Method

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The following guidelines are the main requirements in performing an adequate sampling and
monitoring program. These must be considered when additional testing by an external lab is
required. Samples must then be collected, preserved and sent to the outside source.
Custody Chain
The handling of the sample is controlled with a
“Custody Chain” form, from the delivery of
the containers to take the sample, until the
samples arrive at the lab for analysis. This
form must specify sampling site, sample code,
container, preservation analysis to be done, etc.
Sample Identification
All the samples must be identified with labels
indicating code, date hour, site of the sampling,
person responsible for taking the sample and
analysis to be done. Figure 11.7 Monitoring effluents
Guanare field- Morador 1X. Venezuela 1998
Sample Capture
Procedure, Materials, Equipment: The samples will be taken with any type of container (bailer,
jar, etc.) that allows the extraction of a representative sample maintaining the original
characteristics, according to local regulations. All procedures for capturing, preserving and
analyzing the samples will be carried out according to the guidelines described in the manual
“Standard Methods for the Examination of Water and Wastewater” published by the American
Health Association, American Water Works Association and Water Pollution Control Federation,
in their most recent edition.
Table 8.8 Personnel and Equipment
Quantity Description – Equipment
3 2 x 3 Centrifugal pump
4 20,000 gal. Cylindrical tanks (if tank system is the option)
1* 5 x 6 Centrifugal pump
1 4 x 3 Centrifugal pump
1 3” Diaphragm pump
2 1,000 lt. Chemical tank
1 Hatch 2010 portable field testing kit with reagents
1 Jar Testing unit or Pilot Testing unit
1 Digital pH Meter
1 Set of lab materials
1 Lab
1 PVC Aeration System
Quantity Description – Personnel
1 Water Treatment Engineer (per 24 hour shift)
4 Labor Hands (2 per 12 hour shift)
*An additional pump is needed if fluids need to be transferred from the skimmer to the
treatment tank.

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8.11 Alternative Systems

8.11.1 Water Treatment Plants

As an alternative to the conventional earthen pit or open tank systems, enclosed units can be used
for wastewater treatment. The design of the treatment is based upon the expected flow rates and
the physical and chemical characterization of the waste stream to determine the retention times
and additional features required such as filtrating or disinfecting.
The concept of using an enclosed unit provides a more efficient combination of primary and
secondary treatment methods, maintains better control over the quality of effluents and improves
the consumption of chemical products.
The application of water treatment plants in drilling operations employs the basic steps for
removal of total solids content in run off water and requires strict control on the changes of flow
rates. This provides a cost effective solution for water treatment reducing the risk of high volume
of storm contaminated water and the cost of constructing and closing earth pits.
The water treatment plant is especially recommended for use in minimal discharge locations or in
areas where water consumption and water disposal are considered relevant environmental
concerns. It requires minimization of waste generated from cleaning and location runoff water
and promotes recycling of fluid in order to maintain low volumes of final disposal and waste.

8.11.2 Purification (or Depuration) Plant

The Purification (or Depuration) Plant is a highly specialized
treatment unit composed of two 20ft. containers with a treatment
capacity of 15m3/hr (70 bbl/hr). It consists of a series of
flocculators, settling tank and filter modules that enable a
controlled and efficient removal of suspended and dissolved
solids.

Water from the equalizer tank or storage tank is pumped into the
pretreatment tank that has a capacity of 15 to 20m3. In this tank
coagulant agents are added to destabilize the particles in the
water. Continuous agitation is provided for an hour.

Water is then pumped to the flocculator where a slower agitation

is achieved to allow the formation of flocs big enough for
settling. The flocculator is designed to achieve a high settling
rate for any suspended solids. High molecular weight polymer
additions and pH control are needed to enhance polymer action
and limit the solubility of metal ions. Figure 8.8. Purification (or Depuration)
Plant

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1 Storage Pit
2 Water Treatment Module 4
3 Mixing Flocculation Tank 4
4
4 Chemical Dosage Tank
5 Settling Tanic Tank 4

6 Sludge
7 RL3charge
Dis
8 Sand Filter 3
1

9 Activated Charcoal
10 Filtration Unit
Filter
11 Return to Active
12 Treated
System Water
Storage Tank
13 Treated Water
Distribution 12

5
2

13
7

8 6

9 2

10

11
Figure 8.9. Purification (or Depuration) Plant

Dewatering Manual v 1.0 125

 Fig. 8.10 Mixing Flocculator tank
From the flocculator, water is pumped to the settling
tank, which is fitted with a series of inclined plates;
these provide an increased surface area due to the
projection on the horizontal plane of the plate’s
surface. This type of settling tank has an effective
surface area, which is derived from the sum of the
areas of each plate. This is greater than the
transversal area of the tank; consequently, it allows a
higher settling rate (proportional to the cross sectional
area).
The sludge, which accumulates in the bottom of the
settling tank, is removed and pumped back to the Figure 8.11 High Efficiency
dewatering system for final disposal. Settler (2.4m x 2.4m)
The purified water is discharged to a storage tank
prior to being filtered in the filtration modules.
In the first stage of filtration, water passes through a
sand bed to eliminate any suspended solids that might
remain in the effluent. This prevents any
deterioration of the activated charcoal bed through
which the water is passed in the second and final
stage of filtration.
The activated charcoal is used to absorb any organic
substances, phenols, oil droplets, odorous or noxious
substances that remain in the stream. At the end of
the filtration process, water is stored in a large
capacity tank ready for reuse in either the drilling Figure 8.12 Filtration units
fluid, waste mud treatment or is sent for final sand filter and charcoal filter
disposal. diam. 1.2m each

Unit Description
2 Containers 6.2m x 2.4m x 2.2m
Treatment capacity - 70 bbl/hr.
Settling tank – 24m x 2.4m
Filtration tank diameter – 1.2m
Power requirements : 10 kw – 380 volt – 50Hz or 440
volt 60 Hz

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8.11.3 Water Treatment Tank – Operation (Fig. 11.13)
A more conventional system consists of a single unit without
filtration tanks. The treatment plant consists of a transportable tank
with modules designed for flocculation and settling. Filter
cartridges can be incorporated in line at the end of the tank.
Wastewater is homogenized into an equalizer tank and then
transferred to the treatment plant by positive displacement pump.
Coagulants and flocculants are added in line and mixed by means
of a static agitator.
The flocculated stream enters the plant through a distribution
channel. This reduces the speed and allows the fluids to initiate the
slow agitation process in the first module.
The first module that receives fluid through a distribution channel is equipped with a variable
speed agitator that allows control of RPM to the desirable flocculation speed.
Overflow from the first module passes through a perforated wall that evenly distributes the flow
without destroying the formed flocs. The fluid initiates a settling process with a predetermined
retention time.
Sludge from the settling tank is transferred to the solids handling or dewatering systems.
Clarified effluent overflows to the third and final module. This compartment is used for final
adjustment of pH, disinfecting or any other chemical /physical parameter adjustment.

Unit Description
Treatment capacity - 100 bbl/hr.
Flocculation time - 20 min.
Settling time - 5 hr.
Dimensions: Tank mounted on a rectangular skid (12.2m
x 3.3m x 2.4m).
Refer to Figure 7.

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1Drilling Rig A Water for Treatment

2Skimmer B Sludge Discharge
3 Centrifugal Pump C Treated Effluent
D
4 Chemical Dosage Tank D To Final Storage or Disposal
5 Static Mixer
bbls)
6 Water Treatment Unit (480
7 Flocculation Tank C
8 Settling Tank 3
9 Final Adjustment Tank
1
10 SludgeCatchmentTank 9

8
10

6 B
7

4 3

3 2

Figure 8.13. Water Treatment Tank

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8.11.4 Enhanced Offshore Water Treatment System
This system is designed to meet water discharge
standards in offshore operations. It combines a chemical
treatment and a filtration module to efficiently treat oil-
contaminated fluids. It consists of dual set of tanks, and
a double filter vessel skid. The first vessel uses a 20-
micron solids filtration and the second uses hydrocarbon
filtration cartridges.
The system is designed with a dual configuration to
ensure continuous operation when cleaning or replacing
the filter media in the vessels. The operator is able to
switch the feeding to either one of the lines and performs
any repair or cleaning of the lines, vessels and filter media.
Refer to Figure 8.

Initial Design
An initial characterization of the effluent to determine oil and solids content as well as the
estimation of the maximum expected flow rate are required to determine size of the pit, size of the
vessels, filter cartridge requirements. Some of the essential factors for a successful wash water
treatment include:
• Minimum of two and a half times wash train volume in pit capacity
• Minimum one pit 75 to 100 cubic meters volume as the circulation tank
• Minimum one pit with 60 to 100 cubic meter volume as back up tank
• All oil base mud and oil waste must be transferred to a separated storage tank
• All transfer lines and storage pits need to be cleaned by flushing water prior to start the
treatment to avoid any oil sludge going into the water treatment system.

Flow Description
Wash water is stored in the tank for treatment of reuse if possible. The process initiates by
pumping the stored water through the first filtration vessel to remove suspended solids and
continues through the second vessel equipped with oil adsorption filters that removes residual
hydrocarbons volume from the water stream. Filtered water is then discharged overboard or re-
use in the rig or in the active system

Filtered water can be discharged overboard if it meets the maximum permissible limit of
hydrocarbon for discharge. An online hydrocarbon monitor can be installed at the end of the
filtration system to measure and final hydrocarbon content and re-route the flow if it does not
meet the expected value.

Wash pills will require a chemical pretreatment before entering the filtration unit. This might
include oxidation with hypochlorite and some addition of flocculating agents. Upon return and
storage of the pills, the water treatment engineer will determine the treatment requirements prior
to filtration and discharge of liquid effluents.

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A Flow Inlet A
B Disposal if Not Treatable
C Seawater Inlet
D Circulation Line
E Discharge Below 40 ppm
F Return Line Above 40 ppm 1

1 Pit for 2.5 times Wash Train Volume B

2 Back-up Pit
2
3 Circulation Pit 70 to 100 cbm
4 20 micron Solid Filter F
4
5 Oil Adsorbent Filter
6 Hydrocarbon Online Monitor 3
4
(Option)

C 5

D 5

Figure 11.14. Enhanced Offshore Water Treatment System

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