TPG 4510 Petroleum Production Specialization Project Department of Petroleum Engineering and Applied Geophysics

Supervisor: Jon Steinar Gudmundsson

METHODS TO CLEAN PRODUCED WATER

Carlos Arribas Miranda Trondheim, Norway June 2013

Abstract
Produced water is the largest oilfield waste; the total amount rounds 250 Mbbl/day. It is a mixture of inorganic and organic compounds, including oil, metals, chemicals, gases, microorganisms, etc. This report is an overview of different methods to treat the components and contaminants of produced water and the technologies applicable for this purpose reducing the environmental impact of oil and gas industry. Methods explained are physical, chemical and biological and the facilities where those technologies could be applied. There are several technologies described and compared according to the particles they separate, size, applications, advantages and disadvantages, etc. The limits of discharge and disposal are becoming more restrictive so water treatment companies have to keep on researching and developing new technologies in order to achieve those specifications.

Index
LIST OF TABLES ................................................................................. V LIST OF FIGURES ............................................................................... VI 1 INTRODUCTION ............................................................................ 1 2 DISPOSAL STANDARDS .................................................................. 2 3 CHARACTERISTICS OF PRODUCED WATER ....................................... 3 3.1 PRODUCTION AND SUSPENDED SOLIDS .................................................. 4 3.2 DISSOLVED SOLIDS .......................................................................... 5 3.3 DISSOLVED AND DISPERSED OIL .......................................................... 6 3.4 PRODUCTION CHEMICAL COMPOUNDS ................................................... 7 3.5 DISSOLVED GASES ........................................................................... 8 3.6 WATER IN OIL EMULSIONS .................................................................. 9 3.7 NATURALLY OCCURRING RADIOACTIVE MATERIALS (NORM) .................... 10 4 THEORY OF SEPARATION ............................................................. 11 4.1 PHYSICAL TREATMENT .................................................................... 12

4.1.1 Gravity Separation ............................................................... 12 4.1.2 Coalescence and Dispersion ................................................ 13 4.1.3 Flotation ............................................................................. 13 4.1.4 Membrane Treatment .......................................................... 14
4.2 EVAPORATION .............................................................................. 19 4.3 ADSORPTION ............................................................................... 20 4.4 CHEMICAL TREATMENT ................................................................... 21

4.4.1 Ion exchange process ......................................................... 21 4.4.2 Electrodialysis (ED) ............................................................. 23

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4.4.3 Chemical Oxidation and Ozonation ..................................... 24 4.4.4 Flocculants and Coagulants ................................................. 25
4.5 BIOLOGICAL TREATMENT ................................................................. 26 5 BEST AVAILABLE TECHNIQUES (BAT) ............................................. 27 5.1 SKIM TANKS ................................................................................ 27 5.2 CORRUGATED PLATE INTERCEPTOR (CPI) ............................................. 29 5.3 UF WITH CERAMIC MEMBRANES ......................................................... 30 5.4 DISK STACK CENTRIFUGES ............................................................... 32 5.5 HYDROCYCLONES ......................................................................... 34 5.6 IGF........................................................................................... 36 5.7 COMPACT FLOTATION UNIT (CFU) .................................................... 37 5.8 SAND CYCLONES ........................................................................... 39 5.9 C-TOUR .................................................................................... 40 5.10 MPPE ...................................................................................... 42 5.11 WALNUT SHELL FILTERS ................................................................. 43 5.12 MARES TAIL ............................................................................... 45 5.13 BAF ........................................................................................ 45 5.14 ACTIVATED SLUDGE ..................................................................... 46 5.15 MBR ....................................................................................... 47 6 FLOW DIAGRAM .......................................................................... 48 7 NEW CHALLENGES ....................................................................... 49 8 CONCLUSIONS ............................................................................ 52 FIGURES .......................................................................................... 61 TABLES ........................................................................................... 54

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REFERENCES .................................................................................... 61

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List of Tables
Table 1: Worldwide produce discharges (Steward, 2008) ............................ 54 Table 2: Worldwide produce discharges (Neff, 2011) ................................... 54 Table 3: Constituents summarize from gas fields (Ahmadun, 2009) ...... 55 Table 4: Constituents summarize from oil fields (Ahmadun, 2009) ........ 56 Table 5: Chemical compounds in gas-oil fields (Steward, 2008) .............. 55 Table 6: Ceramical membranes characteristics (USBR) ................................. 57 Table 7: Ekofisk C-Tour performance (Phillips) .............................................. 57 Table 8: BAT comparison........................................................................................ 58

List of Figures
Figure 1: Water/Oil production profile (Ebenezer, 2012) ............................ 61 Figure 2: Drag force, Stokes law (Fluids Mechanics UPM, 2010) ............. 61 Figure 3: Membrane sketch (Cheryan 1998) .................................................... 62 Figure 4: ED sketch (EET corporation) ................................................................ 62 Figure 5: Skim Tank configurations (Steward 2008)...................................... 63 Figure 6: Down-flow CPI (ESI) ............................................................................... 63 Figure 7: Up-flow CPI (ESI) ..................................................................................... 64 Figure 8: Oil coalescence and solids settling (ESI).......................................... 64 Figure 9: Disk Stack Centrifuge (Veolia) ............................................................ 65 Figure 10: Liner (Aker, Prosep) ............................................................................ 65 Figure 11: Hydrocyclone (NETL) ........................................................................... 66 Figure 12: Micron size separation Vs Oil viscosity (Cyclotech) .................. 66 Figure 13: Max and Min pressure drop operation Vs eff (Cyclotech) ....... 66 Figure 14: Micron separation Vs Droplet inlet size (Cyclotech) ................. 67 Figure 15: Hydraulical IGF (Unidro) ..................................................................... 67 Figure 16: Mechanical IGF (Unidro) ..................................................................... 68 Figure 17: CFU sketch (Statoil, 2010) ................................................................. 69 Figure 18: Sand Cyclone (Veolia) .......................................................................... 70 Figure 19: C-Tour flow diagram (Statoil, 2010) .............................................. 70 Figure 20: MPPE flow diagram (Veolia) ............................................................... 71 Figure 21: MPPE and flotation Comparison (Meijer 2010) ........................... 71 Figure 22: Walnut shell filter sketch (Siemens) ............................................... 71 Figure 23: Activated Sludge (Pipeline, vol 14, 2003) ..................................... 72

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Figure 24: ubsea Separation sketch, Marlim Project (FMC, Orlowski) ...... 72 Figure 25: Flow Diagram Example ....................................................................... 74

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1 Introduction

Oil and gas industry is one of the most important industries nowadays. Since 1850 when Edwin Drake drilled the first oil well, oil demand has been increasing thus, the oil and gas production. One of the problems of this production increase is the big amount of water it is produced with it, produced water is the largest byproduct stream associated with oil and gas production [Duhon, 2012]. So that, produced water can be defined, as the water that comes with oil and gas in the production facilities and it needs to be treated for different purposes such as reinjection or disposal.

Produced water is a complex mixture of inorganic and organic compounds, including oil, metals, chemicals, gases, microorganisms, etc [Neff, 2011]. The total amount of produced water is estimated in 250 Mbbl/d being the water oil ratio between 2 and 3 to 1 depending on where and when the water is being produced [Ferro and Smith]. The older the production field the bigger the WO ratio represented in figure 1 with an oil-water vs. time profile [Ebenezer, 2012]. The produced water can be classified in formation water and injected water. Formation water is the one trapped with the oil in the reservoir and since the well starts to produce oil so it does. Injected water is the artificial via to maintain reservoir pressure and lengthen the production of the field.

The motivation of the project is to explain different methods to treat the components and contaminants of produced water and the technologies applicable for this purpose reducing the environmental impact of oil and gas industry.

2 Disposal Standards
The environmental impacts of discharging water without the appropriate treatment are incalculable. That is why there are production water disposal standards for produced water, both offshore and onshore, according to the current water separation technology and the limits they can achieve. Several techniques are being developed and investigated in order to accomplish the zero content discharge. Both onshore and offshore can treat the water also for water reinjection to maintain pressure reservoir and lengthen the production of the field. The treatment of the water includes oil removal but also production chemicals, suspended solids, bacteria, etc.

Offshore regulations require total oil and grease content of the effluent below the regulations; they vary from one country to another. They range between 15 mg/l) in Argentina and Venezuela, up to 50 mg/l in the Guinean Gulf [Steward, 2008] (Table 1); from 29 mg/l in U.S. up to

40 mg/l [Neff, 2011] (Table 2). In the North Sea is regulated by OSPAR commission (Oslo-Paris) and it is 30 mg/l. Despite he existence of these standards, there are plenty of offshore facilities that do not achieve the regulations registered in the OSPAR commission.

Onshore facilities normally treat onshore production wells and offshore produced water that only has been treated superficially in order to be transported to the onshore facility. Onshore plants normally discharge by subsurface injection into rock formations, which has more restrictive limits than the onshore facilities. The limits are higher because of the risk of polluting fresh water in aquifers or soil pollution. Disposal in freshwater streams or aquifers is generally forbidden.

3 Characteristics of Produced Water

As it was explained, produced water is a mixture of organic and inorganic materials that depends on several factors, for instance, geographical location of the field, type of reservoir, lifetime of its reservoirAlso type of hydrocarbons produced affect the chemical and physical properties of the produced water [Veil, 2004]. Characteristics will vary form oilfields, gas fields or oil and gas fields; tables 3 and 4 show a summarize list of the possible compounds that exist in the different production fields. All parameters will be explained in this chapter. It is important that the total amount of produced water in gas 3

fields is much lower than in the oilfields, mainly because there is no water injection in gas fields for gas recovery increase.

3.1 Production and Suspended Solids

Production and suspended solids include clays, scales, waxes, bacteria, carbonates, sand, silt and asphaltenes [Veil, 2004]. Concentration of the solids varies from one field to another depending on the reservoir initial conditions. The general amount of suspended solids is small except in wells that produce in unconsolidated formation, where large volumes of sand and other suspended solids might be produced. In order to accomplish the water disposal requirements, the solids cannot affect oil measurement methods, and special equipment must be used. When suspended solids are present, it is necessary to apply different techniques in order to remove the solids. Chemical treatment is used to separate the oil droplets form the solid particles and the equipment must incorporate solids removal ports, jets and/or plates.

Precipitation solids or scales are the ions capable of reacting with temperature, pressure or composition changes. This phenomenon can occur in tubing, pipelines, vessels and water treatment equipment. The most common precipitating solids are carbonates and sulfates.

Carbonate scales can occur in all systems containing CO2 and ions, for instance Ca2+, which will precipitate as CaCO3. Carbonate scale

formation is mostly affected by changes in CO2 pressure and temperature, also by mixing different waters. Large pressure changes happen in chokes or flash tanks while temperature variations will take place in the heat exchangers [Sandengen, 2012].

Sulfates form in the same parameters variations but they are more dependent on concentration than pressure or temperature changes. They precipitate fast and cause big problems when they do it inside the production wells. It is possible to control its formation with the production temperature. For example, CaSO4 reaches its highest solubility at 38C (2150 mg/l), if the temperature is placed at 93C solubility decreases until 1600g/l.

3.2 Dissolved solids

Dissolved solids are inorganic constituents that are predominantly sodium (Na+) cations and chloride anions (Cl-). Other common cations are potassium (K+), magnesium (Mg2+), calcium (Ca2+), barium (Ba2+), Strontium (Sr+), iron (Fe2+), etc. There are also other anions such as carbonates (HCO3-, CO32-) and sulfates (SO42-) [Steward, 2008]. Tables 3 and 4 enumerate the metals dissolved in both gas fields and oil fields.

These ions affect produced water chemistry in salinity and scale potential principally [Hansen 1994]. The amount of solids dissolved in

the produced water can vary from less than 100 to over 300,000 mg/l [Steward, 2008; Roach, 1994]. It is important to pay special attention to dissolved solids in order to prevent scale formation in the piping, wellbore-bore formation, etc. It would carry big costs in cleaning and maintenance and the stop of the production in most cases.

3.3 Dissolved and Dispersed Oil

Dissolved and dispersed oil components are mixture of hydrocarbons including BTEX (benzene, toluene, ethylbenzene and xylene), PAHs (polyaromatic hydrocarbons) and phenols. Dissolved oil is composed by polar constituents distributed between low and medium carbon ranges, meanwhile the small droplets of oil suspended in the produced water are called dispersed oil. The size of the oil droplets is between 0,5 m and over 200 m [Steward, 2008].

The amount of dissolved oil depends on the type of oil, volume of produced water and age of production [Ahmadun, 2009]. The experience from the field tells that the temperature range where the water is treated (25-75C), does not affect the solubility of oil. Temperature only affects solubility above 75C. Phenols concentrations are low normally, in the North Sea for instance they have been never been detected over 20mg/l [Neff, 2010]. BTEX and phenols are the most soluble compounds in produced water, followed by aliphatic hydrocarbons, carboxylic acid and low molecular weight aromatic

compounds. Typical gravitational separation is not enough to separate dissolve oil from the produced water. Other technologies are needed such as adsorption, filtration, biological treatment or membranes.

PAHs and heavier alkyl phenols (C6-C9) are related to the dispersed oil because they are less soluble in produced water. They are considered the greatest environmental concern because of its toxicity and persistence in the environment. The total quantity of dispersed oil is determined by the source of the produced water. For example, produced water from gas/condensate fields exhibit higher levels of dissolved oil [Neff, 2011]. Oil droplets size distribution is the most important parameter, which affects oil and water separation treatments. It is experimentally demonstrated that the bigger the droplet diameter is, the better the equipment efficiency. The size distribution is influenced by system shearing (pumping, pressure drop in the piping system, etc.), oil-water interfacial tension, temperature, turbulence, density and other factors.

3.4 Production chemical compounds

Chemical components are added to treat operational problems. They are dissolved and used to prevent hydrate and scale formation, corrosion, wax deposition, bacterial growth, gas dehydration and emulsion. The totality of the chemicals varies from field to field and sometimes they appear in insignificant amounts. These low concentrations are explained

by the solubility of the chemicals in the oil phase, thus they are not treated in the cleaning water systems.

Production chemicals can be very injurious in low concentration, 0.1 ppm [Glickman 1998]. Besides the danger it represents, some chemicals like the corrosion inhibitor can reduce oil/water efficiency [Veil, 2004]. Table 5 shows the typical chemical production in oil and gas fields. The most common chemicals used in oil/gas production that affect the water facilities are the Scale inhibitors, scavengers, coagulants and flocculants and finally some gas treatment chemicals because they remain in water phase [Neff, 2011].

3.5 Dissolved Gases

The main gases, which are encountered in produced water, are natural gas (methane, ethane, propane and butane), hydrogen sulfide, carbon dioxide and oxygen. They are formed naturally, by chemical reactions or bacterial activities. Most of the gasses are saturated at reservoir conditions but as the well starts producing, most of the gases flash to vapor phase [Arthur, 2005]. These gases are removed in separators and stock tanks in most of the occasions.

The gas separation is influenced by the pressure and temperature in which the process occurs. The higher the separation pressure the higher the quantity of dissolved gasses will be. The opposite effect we get with

the separation temperature, the higher the temperature the lower the quantity of dissolved gasses.

Natural gas components are barely soluble in water at operation pressures. This solubility is based on pressure, temperature and specific gravity of the water. It is important to comment that these compounds are attracted to the dispersed oil droplets, that attraction is taken into account to design the flotation equipment for the water treatment [Steward 2008].

Looking at the other common gasses, hydrogen sulfide is corrosive and enables iron sulfide scaling, besides is extremely toxic if inhaled. It is necessary to be especially careful if the sulfide is present in the flotation cells when maintenance and adjustments are done. Carbon dioxide is also corrosive and may originate CaCO3 scaling. When the CO2 and the H2S are removed, pH increases so scale could also form.

It is relevant to comment the role of the oxygen. It is not found naturally in produced water but produced water may absorb it when it comes to surface. Water with dissolved oxygen causes corrosion and oil weathering that difficult the separation.

3.6 Water in oil Emulsions

Emulsion is a mixture of two immiscible liquids. In the normal emulsions, water is dispersed in small droplets from 100m to 400m in 9

diameter. If the emulsion is unstable, the oil droplets will coalesce into larger ones. This is a short time process. However a stable emulsion is a suspension of the two liquids with a stabilizer that maintains a film between the phases. This film may be removed so coalescence starts to act. In order to break it down chemicals or heat are used. In water in oil emulsions, the emulsion breakers must be oil soluble, so that, they have more time to act during the separation processes.

3.7 Naturally Occurring Radioactive Materials (NORM)

NORM originates in geological formations and can be brought to surface with produced water [Veil, 2004]. They can be found in production wastes, equipment and solids at the production facilities. The most abundant NORM compounds are
226Ra

and

228Ra,

the ambient

concentrations are ranged between 0,3 and 1,3 Bq/L and 16 to 21 Bq/L [Gafvert, 2006]. In the North Sea, Utvik confirms that the measure concentrations of NORM in produced water range from 0,23 to 14,7 Bq/L. Both compounds derive from uranium and thorium present in hydrocarbon bearing formations. As the produced water approaches to surface, temperature and pressure decrease so it may lead to a NORM scale production. [Veil 2004, Steward 2008]. The scales and sludge would accumulate in water separation facilities.

NORM regulations are more focused on the equipment accumulation rather than produced water limits. It has been proved than seafood

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consumption from produced water disposal does not affect human health. The specifications in NORM management are centered on identification, control and volume reduction of the wastes and solids, in order to diminish human exposure to radiation [Ebenezer, 2012].

4 Theory of Separation
The main goals for proper water treatment are nine [Arthur, 2005]. Deoiling (removal of free dispersed oil and grease); dissolved organics (bacteria and microorganisms) and gas elimination such as natural gas or carbon dioxide; suspended solids removal (mostly sand and other particles); desalination; sulfates and scaling agents clearance; disinfection and softening, in order to adjust water hardness and make it available for irrigation; and finally NORM removal. To meet this achievements different methods can be used, mostly physical and in less often chemical and biological procedures.

Physical procedures will separate contaminants and oil from water by the application of different forces. Chemical system bases its separation in the addition of components that will react with the contaminants wanted to remove. Finally biological will be focus in the use of several

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types of bacteria and microorganisms.

4.1 Physical Treatment 4.1.1 Gravity Separation

Gravity separation is the most usual process in water treatment. As it is known, oil is lighter than the volume of water they displace so, by Archimedes principal, oil droplets experiment a buoyant force. But the vertical movement of the particles through the water originates a drag force that withstands the flotation described by the Stokes law and sketched in figure 2. Droplets reach a constant velocity when the to forces are equal [Fluid Mechanic Notes, UPM, 2010].

vs= particles velocity g = gravity acceleration r = particles radius p= particle density f = fluid density = water viscosity
With the formula we can conclude that the bigger the droplet and the density difference the higher the vertical velocity. If temperature is increased, viscosity will reduce so a higher velocity is also obtained. Stokes law may be applied to droplets never below 10m, but field experience indicates that the lowest limit applicable is 30m [Devold, 2006].

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4.1.2 Coalescence and Dispersion

Coalescence is the process in which two or more droplets, bubbles or particles merge during contact to form a single daughter droplet, bubble or particle. If this occurs repeatedly, a continuous liquid phase forms [Schlumberger, 2013]. Coalescence is a time dependent process, the smaller de oil droplets diluted the greater the time to grow bigger droplets. Dispersion is the act of breaking up particles into smaller ones and distributing them throughout a liquid or gaseous medium. This process occurs when a large amount of energy is input in the system in a short period of time [Schlumberger, 2013]. This energy applied minimizes the surface area between the two fluids, which favors the separation between the droplets.

The coalescence and dispersion processes occur at the same time and they are totally opposed. If the kinetic energy of the particles in the system is larger than the difference in surface energy between the single droplet and the two smaller droplets formed from it, dispersion process is happening. In the other side, the motion of the smaller droplets causes coalescence [Ebenezer, 2012].

4.1.3 Flotation
Flotation consists in the injection and dissolution of air in the produced water. Then, the small air bubbles adhere to the oil droplets increasing its buoyancy, the specific gravity of the oil-gas bubbles combined is significantly lower that the oil droplet alone. When the oil has floated to

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the surface it is normally skimmed and removed. Flotation process is really effective, over 90% of the oil is removed in short periods of time and can remove very small oil droplets. The droplets separation size is lower if a chemical pretreatment is used to favor the flotation, coagulants and flocculants for example. This process can also be used to remove natural organic matter, volatiles, grease, etc.

The efficiency of the flotation process depends on specific gravity difference, droplet size and temperature. They usually work better with low temperatures, because at high temperature, dissolving air into the water requires more pressure. It also depends on the air bubbles size, the smaller the bubble size the more chances to adhere to the oil.

Flotation can operate as the principal separation force in two kinds of air flotation systems: Dissolved Air Flotation (DAF) and Induced Air Flotation (IAF), IAF will be explained later but DAF is barely used in offshore facilities for its size and weight, operation at high temperatures, etc [Unidro, Prosep]. It can function also as a secondary force to help other separation principles to perform.

4.1.4 Membrane Treatment

Membranes are thin films of synthetic organic or inorganic materials, which separate a certain fluid from its components. The separation is achieved by diffusion through the membrane under pressure difference. Several processes exist for this purpose, microfiltration (MF),

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ultrafiltration (UF), nanofiltration (NF), reverse osmosis (RO) and polymeric or ceramic membranes. Membrane treatment is more suitable for the stable oil water emulsions.

The process usually operates with a recycling water system that maintains a constant water flow. The same amount of water introduced in the tank at the same rate as it is withdrawn and clean. The process is stopped when the limit of particles displaced reaches a certain level concentration in the process tank. When the procedure stops, a clean in place is carried out (CIP), process is sketched in figure 3. It is important to mention that membranes normally need a pretreatment to remove free oil and bigger particles to lengthen the life of the membranes.

These types of procedures have some advantages over the traditional methods of flotation and separation. Using membranes for the treatment reduces the oil concentration from 1/40 to 1/200 initial feed and the total quantity of water used can be recycled [Madaeni, 2003]. They also have some disadvantages; it is very expensive to install membranes over a certain size. Most of the membrane processes include chemical pretreatments; to avoid scale formation (in NF and RO) and is common the addition of coagulants. They also suffer high degradation during their use so that they must be changed frequently in order to avoid membrane fouling [Madaeini 2003]. The flux varies with the time, the longer the time the more attached oil and solids stuck at the surface of the membrane the lower the flux [Jiang, 2008]. The space

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of installation needed is higher than the traditional methods and because of the chemicals used in the pretreatments several kinds of impacts into the environment may occur.

4.1.4.1 Filtration: MF, UF, NF and RO

MF has the largest pore size (0,05m to 2m) and operating pressure difference below 2 bars. MF is mainly used to remove suspended solids. UF ranges from 2nm to 0,05m and operating pressure between 1-20 bars; it is used for colloids and solids separation [Martinous, 2001, Judd 2003]. Both systems used as a pretreatment for other cleaning technologies NF, RO and electrodyalisis [Jurenka, 2010]. MF and UF can treat any type of produced water; they can operate with high TDS and salt concentrations.

NF is normally used for metals removal from produced water. It has membrane pore size between 0,5nm and 2nm, pressure difference of the process between 10 and 100 bars. It is used for multivalent ions and charged polar molecules [Martinous, 2001, Judd 2003]. NF membranes have negative charge at neutral pH; it is an important key for the separation properties of the membrane [Sutherland, 2009]. RO is capable of remove over 99% of the organic macromolecules and colloids, besides inorganic ions are also removed over 0,1nm [Bilstad 1994]. The most important problem of RO and NF is the complex pretreatment that needs to be done; NF and RO are mostly used for human consumption in desalination processes.

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Membranes can operate either cross flow separation or dead end filtration. Cross flow separation occurs in perpendicular direction with the flow, gravity and density difference makes the particles fall to the bottom of the flow and then be filtrated, only part of the feed water is treated. In dead end separation all water is treated and flow and filtration happen in the same direction.

The membranes applicable for oil separation purposes are polymeric or ceramic, being the second ones more expensive but capable of treating more water. Therefore a cost/benefit analysis must be done. Both membranes are explained below.

4.1.4.2 Polymeric/Ceramic Membranes

Ceramic (or inorganic) membranes have attracted interest due to their superior mechanical, thermal, and chemical stability. The primary advantage of using ceramic membranes is the ability to accomplish the current and pending regulatory treatment objectives with no chemical pre-treatment [Ebrahimi, 2010]. Ceramic membranes are made from alumina, titanium, silica and zirconium oxides and carbides. They are tubular and consist of a porous support material (-alumina), a separating layer and a decreasing pore diameter layer. Different materials applied for the different range of filtrations used by Ebrahimi..

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UF with ceramic membranes has been shown to be very effective in treating waste oil, grease and effluents and can compete against traditional separation techniques [Fabish, 2001].

Polymeric membranes are made from polyacrylonitrile (PAN) and polyvinylidene fluoride (PVDF). The main problem of the stable organic materials is the hydrophobicity of their basic materials. This results in a low water permeation rates. PAN membranes combine chemical stability and good aqueous filtration [Scharnagl, 2001]. The gravest problem of the polymeric membranes is their integrity. As a consequence to that, the integrity of the membrane must be tested to ensure the process. This test can be done with a pressure decay test. In this test, pressurized air is applied to the membranes at a pressure less than would cause the air to flow through the membrane, and the pressure decay is measured [Colorado School of Mines, 2009].

Current experiments mixed both types of membranes, a PVDF membrane with nano-sized aluminum particles improving antifouling performance of the membranes. In the UF experiment the removal efficiency of COD was 90% and in TOC 98%; oil residue was less than 1% [Lia, 2006]. This shows that UF process is the most competitive compared with the traditional systems of wastewater treatments. The main challenges of the membrane treatments to consolidate are the scale forming and the clogging. On their side, they have good efficiency

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and capacity; and also they are flexible and can accept well variations in flow and quality [Statoil, 2010].

4.2 Evaporation
The processes for produced water cleaning, which include steam formation in some way, are also called thermal technologies. Different evaporation systems has been tested and proposed for water treatment. They use few or none chemicals so waste sludge is cleaner. They also reduce equipment needed for the process, therefore O&M costs decreases substantially. The most applied thermal technologies used nowadays are multistage flash (MSF), multieffect distillation (MED), vapor compressor distillation (VCD), AltelaRainSM and freeze-thaw evaporation (FTE). The thermal technologies have being applied for water desalination and solids removal for human consumption sin the middle XX century. The application of these technologies has increased lately for produced water with the proliferation of shale gas in the United States. They have high O & M costs and energy consumption. In their advantage they do not need pretreatment and can handle over 100.000 of TDS [Dores, 2012].

Evaporation can also be used in traditionally in evaporation ponds where solar energy efficiently evaporates de water placed in artificial ponds. They have no mechanical systems, so low O&M costs. It is the cheapest facility for saline water disposal in the applicable areas. The main

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disadvantages of the ponds are that they need vast extensions and dry weather. These means they are only suitable in dry areas with high evaporation rates and availability of lands at low cost [Ahmed 2000].

4.3 Adsorption
Adsorption is the process where a special solid used for removing substances from the water. For oil and other non-polar substances presents in the oil, BTEX and PAHs the active carbon is the most used solid. It is made in order to achieve big internal surface, which improves the adsorption process. There are two kind of active carbon, Powder Activated Carbon (PAC) and Granular Activated Carbon (GAC). The one employed in the oil-water treatment is the GAC, it normally gas greater diameter than 0.1 mm [EPA, 2009].

GAC can be regenerated removing the adsorbed compounds through steam, thermal o physical/chemical procedures. The first two are common methods to recycle the active carbon. Steam regeneration is only suitable option when the carbon has only retain volatile products. Thermal regeneration is based in pyrolysis (burning the organic substances). It is a very effective regeneration process but it also has two big inconveniences, high carbon losses and cost [lennthec library, 2010]. Other adsorbents have been found in order to substitute the active carbon, specially the GAC. These materials are the organoclays, hydrophobic zeolite or polymer adsorbents. 20

Organoclays present several benefits in comparison with the GAC. They have higher adsorption capacity of hydrocarbons and they are very effective in removing soluble and dispersed hydrocarbons. Organoclays are used mainly in two purposes. The first one is as a pretreatment for membrane filtration systems UF / RO and also for ion exchange resins method. The second is a post treatment for oil and water separators [Islam, 2006]. Organoclays are manufactured by modifying bentonite with quaternary amine. Bentonite is basically montmorillonite; there are two types, sodium bentonite and calcium bentonite. Quarter amines used as oil-wetting agents, corrosion inhibitors and bactericides.

Zeolite is an alumina-silicate crystal with uniformly sized pores. It is naturally hydrophilic (affinity for polar molecules), after it is treated and the aluminum is removed, it becomes hydrophobic (affinity for nonpolar molecules). Polymers are manufactured with pore ranges from macro to almost micro pores. They worked in polymer beds and they are proved to adsorb faster than the active carbon.

4.4 Chemical treatment 4.4.1 Ion exchange process

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Ion exchange is the process where an ion replaces another one in an aqueous solution. The synthetic materials specially designed for these purpose are called ion exchangers or resins; resins developed for the water treatment purposes are IX resins [Colorado School of Mines, 2009]. These resins are capable of capturing the contaminant cationic ions dissolved in water, Calcium, Magnesium and be substituted by exchange cations from the resin.

Resins used in produced water treatment are known as Strong Acid Caution (SAC) where hydrogen and sodium cations highly dissociate and remain ready for the exchange (Equation 1) [Arthur, 2005].

( )

This process is only applied for hardness water removal and it can also be named as water softening. When the resin cannot exchange more ions it must be regenerated. The resin is backwashed with the typical cations that form the resins, Na cations, so that it is ready to begin the process again; there are regeneration looses, around 2% [Colorado School of Mines, 2009]. Ion exchange process is typically used for drinking water or discharge to environment and also is a usual process in nuclear power plants.

The major benefits of the process are low energy consumption; high efficiency in the resin regeneration process and TDS values manageable

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up to 7000mg/l. Important disadvantages are the needs of pretreatment and post- treatments that increase significantly the O&M costs and high sensitivity to fouling. Therefore, its main application is in the coal bed methane produced waters because they are free of the contaminants, which affect ion exchange performance.

4.4.2 Electrodialysis (ED)

ED and electrodialysis reverse (EDR) are processes where dissolve inorganic ions from salts are separated from the water through ion exchange membranes. The membranes are placed in between two electrodes and allow the ions to pass through. If the membrane is positively charged the negative ions will be separated and in reverse as shown in figure 4. That is why several membranes are positively or negatively charged alternately so every ion can be removed. EDR and ED are very similar processes; the difference lies in the electrodes. In EDR electrodes polarity is reversed in order to free accumulated ions in the membrane surface.

A pretreatment is needed for both ED and EDR, because suspended particles above 10 microns will block the membrane pores [lenntech treatment solutions], also potential scaling minerals must be removed. But they present some benefits, low-pressure requirements, no chemical addition and long membrane working life. ED process is able to

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eliminate from 59% to 94% of dissolved solids and up to 12.000 mg/L of TDS (normal operational conditions are 1.200 mg/l) [Jurenka, 2010].

4.4.3 Chemical Oxidation and Ozonation

The main objective of the chemical oxidation is to generate a powerful oxidizing hydroxyl (OH-), which reacts rapidly but non-selectively with nearly all organic compounds, formatting carbon dioxide and inorganic salts or less toxic products. Typical chemical oxidation processes are Advance Oxidation Processes (AOPs) and Ozonation.

AOPs present some advantages; the most important benefit is its capability of oxidation of organic compounds. Main disadvantage of the process is the addition of chemicals that increases the cost. AOPs have been tested in labs and in fields for produced water treatment but it is not applied commercially [Dores, 2012]. Its application for other wastewater treatment makes this process potentially valid for oilfieldproduced water when biological treatment cannot be used.

Ozone gas is created with electrical discharges in the ozone generator and then it is pumped into the tank. Inside the tank the ozone bubbles flows into a contactor where adsorption takes place. This process is called Ozonation. It is more effective than chlorine destroying bacteria and no harmful removal is needed (ozone decomposes rapidly). It is

24

complicated process that needs lots of technology to be applied. It is also corrosive, non-suitable with suspended solids, possibly toxic, etc.

Both processes provide high removal efficiency of toxic compounds, specially alkylated phenols but in the other hand some other toxics forms (Chlorinated and brominated phenols) in low concentrations [Grini, 2002]. Biological treatments are preferred over chemical oxidation because they are non-environmental friendly, complex and expensive to operate and maintain.

4.4.4 Flocculants and Coagulants

Coagulation is the process in which it is reduced the electric repulsion of particles (same electrical charge) with the addition of salts; then particles aggregate because of the remaining forces that attract the particles. Flocculation causes the aggregation with polymers aid. Coagulants and flocculants are the agents that cause respectively both processes. They normally remove efficiently heavy weight organic particles being incapable of removing low molecular weight and nonpolar particles. Those particles can be collected by biological systems.

Flocculants and coagulants miust be non-hazardous and biodegradable. They are designed to aid in the oil-water separation processes; typically they are ammonium and acrylamide. There are also several types of coagulants, which can be cationic (positively charged), anionic

25

(negatively charged) and nonionic (neutrally charged). Primary coagulants are made to neutralize the charges while secondary or coagulant aid mission is to maintain the flocs together so that they will not break during the process. Some primary coagulants are aluminum sulfate, ferrous sulfate or artificial polymers. Secondary coagulants can be sodium silicate or charged polymers [Minerallurgy notes, UPM 2010].

4.5 Biological treatment

Biological treatment is normally used for organic material removal with bacteria and other microorganisms; it is the latest process of produced water before discharge or reuse. It is very important to know the composition of the water in order to plan a specific treatment, for instance in oil industry there is a special high demand of oxygen from de bacteria to process the water [Schultz, 2005]. There are three basic biological treatment groups, aerobic (presence of oxygen), anoxic (oxygen deficient) and anaerobic (lack of oxygen). This oxygen quantity is directly linked with the type of bacteria involved in the degradation of the contaminants.

Aerobic treatments will take place in air presence with microorganisms, which use the oxygen molecules to assimilate the organics creating other compounds; they are also called aerobes. Anaerobic and anoxic microorganisms or anaerobes will process in air absence to assimilate the impurities. The compounds generated usually are carbon dioxide,

26

water and biomass for the aerobics processes and carbon dioxide, methane and biomass for the anaerobic [Mittal, 2011]. The main biological techniques are activated sludge, Sequenced Batch Reactors (SBRs) and Membrane Bioreactors (MBRs) and Biological Aerated Filters (BAFs). Because of its size and time of operation (days), they are impossible to install in offshore platforms with the usual flux of the production offshore facilities. They are also used in downstream oil treatment.

5 Best Available Techniques (BAT)

This chapter of the report is a description of the best available techniques for produced water in the oil & gas applications applying the principles explained in chapter 4. There are many different technologies to be able to cover all kind of diverse produced waters, varying its characteristics not only from one field to another but also the variation during the production time.

5.1 Skim Tanks

Skim tanks are the simplest and primary treatment of produced water. They are designed for long time residence (up to hours) where coalescence and gravity separation occur. They can have vertical or horizontal configuration and work at atmospheric pressure or under

27

pressure. These tanks can have several purposes, dispersed oil removal (Skim tanks), solids removal (Settling Tank) and when oil and water ratio is high, in order to make a bulk separation (Wash tanks).

In vertical skimmers oil droplets rise upward, meanwhile in the horizontal vessels, the droplets rise in a perpendicular direction with the water inlet flow. In both configurations, the air released during the water injection in the vessel helps the droplets to float. Figure 5 shows both configuration sketches. Vertical skimmers can include a spreader that helps the distribution of the flow. The oil is skimmed at the surface in both shapes. In order to control the oil level in the weir, a water leg could be used. Horizontal skimmers are proved to be more efficient than vertical skimmers. But vertical skimmers present useful features when sand and other particles must be handled because a sand drain can be added at the bottom. Also, vertical skimmers are less sensitive to flow variations.

Pressure vessels might be used when the water has to be pumped for any reason or there is a gas blow that creates difficulties in the water injection into the system. Otherwise, atmospheric tanks should be installed because of its lower cost.

Skimmers can remove droplet size above 150 m and a minimum time residence of 20 minutes [Steward, 2008]. The vessels are highly affected by temperature and they are not suitable for cold produced water.

28

Horizontal baffles can be installed to perform a better separation. They can treat high oil concentrations with solid contaminants.

5.2 Corrugated Plate Interceptor (CPI)

CPIs are coalescers, coalescers are devices that use gravity separation like the skimmers but they also induce coalescence to improve the separation. CPI is a basically certain number of parallel-corrugated plates with 2.5cm distance between them, where the oil water separation takes place called CPI pack (figure 6). Figure 7 shows a down-flow through the CPI pack, the process can happen the other way round call up-flow process (figure 8). It also exists crossed-flow devices that they work under pressure. It allows both horizontal and vertical configuration systems.

Process begins when the water enters into the nozzle (1), over there biggest solids will sink and settle for posterior collection (2). Water and oil will pass through a perforated distribution baffle plate (3). The CPI pack (4) receives the oily water, where the oil rises to the peaks of the corrugations (figure 8) and coalesces (5), it keeps moving upwards exiting the pack reaching the surface at the top of the chamber (6), where it flows over a weir (7) until the oil compartment (8). Water exits the pack (9) where the smaller solids settle and they are also removed (10). Water flows upward (11) into the clean water compartment (12). There is a secondary oil outlet adjacent to the water outlet (13) and

29

valve to ensure a gas blanket in the camber (14) [Energy Specialties International].

Down-flow and Up-flow processes have some differences. The inclination of the pack is usually 45and 60 respectively (see figures 7and 8) and the droplets size separation achieved is better in the downflow system, around 50m but solid removal is not important; meanwhile in the up-flow is always above 50m but the solids size removal cut off is up to 10m [Veolia, 2013]. Therefore, for oil and water separation, if solids content is insignificant down-flow might be used and in the opposite way. The inlet oil influent accepted can be as high as 3000mg/l within a flow rate variation from 20 m3/h to 200m3/h [Veolia, Paramount].

CPI exhibits many advantages, little operation and maintenance costs, it is simple and it has no moving parts, so that no energy requirements. It offers a continuous processing with high oil and solids efficiency (up to 150mg/l). The main disadvantage for oil wastewater is that this technology is inefficient with high amount of solids and sometimes it requires a post treatment if the disposal specifications are not reached.

5.3 UF with Ceramic membranes

Membrane process, as it explains chapter 4.1.4 of the report, basically consists in the filtration of the produced water through a membrane 30

with specific pore size because of a pressure drop between both sides of it. The application of the UF/MF water treatment for produced water has become a successful discovery, which can compete with traditional oil wastewater processes. It has been proved in various studies and field trails [Dores, 2010, Szp 2010]. MF is also a possible process but sometimes it does not reach the water disposal requirements; therefore UF is more popular. UF membranes are suitable for suspend solids oil and grease, organic carbons removal and metals; dissolved ions and organics will not be separated.

Ceramic membranes can have multiple pore sizes and configurations. Table 6 Summarizes filtration range, membranes materials and pore shapes for different manufacturers. The filtration size ranges from 5nm to 1.4m depending on the different technologies developed for the companies. All the membranes are built with alumina oxide and the filtration channel can have several shapes hexagonal, round, squared, etc [Benko]. The most important operating parameters for a ceramic membrane process are the volumetric flow rate of the water per filtration area, the trans-membrane pressure (average of feed and reject pressure minus filtrate pressure) and the back pulse of the water from the filtrate side to the feed side.

For instance, Veolias CerMem technology offers two different channel sizes 2mm and 5 mm with a dimension of 8.64m/1.42m. That makes a filtration area of 10.7m2 and 5 m2 respectively. And the pressure drop

31

is 1.3 bar in the first one and 0.5 bar in the second. Shows de approximated values of the water flow for the membranes described. Cross flow velocity should be between 3 to 4 m/s. Membrane component materials determine the pH range, 0 to 14 for silica membranes and 2 to 13 fro alumina and titania. The production rates depends of the number of modules installed, the biggest flow available is 170m3/h (30 or 52 modules installed, determined by the channel size) and it needs pump power up to 170 kW.

5.4 Disk Stack Centrifuges

Increasing the acceleration the droplets are subjected to can enhance the settling velocity of oil droplets achieving its separation from water, this can be realized in a centrifuge [Van den Broek, 1996]. For oil/water separation the centrifuges used are the Disk Stack Centrifuges. They consist in a frame, a motor with a transmission, separator bowl (double conical shape) and the inlet feed. The bowl has special inserts, the gravity discs with conical shape that establish the oil water interface. It is where the separation takes place; the distance in between the discs is less than 1 mm. The centrifugal force generated ranges from 5000 to 6000 gs.

The feed is introduced in the bowl and is accelerated to maximum rotational speed. The discs distribute the water due to the centrifugal force and separate oil, water and solids. The oil flows towards the center

32

of the bowl to the upper side of the discs; meanwhile the water and sediments flow in the opposite direction. The liquids are led to the neck of the bowl where they are removed. At the bottom of the bowl, in it widest point, some solids discharge ports are installed. A piston moves these ports, when the piston is at its lower position sediments are released [Faucher and Sellman, 1998].

An example of this system is the X20 developed by Alfa Laval. It is a special centrifuge system adapted to the oil and gas separation industry. It can process 170 m3/h and its energy consumption is 150kw/h. The small dimensions (3.15 m tall, 2.34 m long and 1.53 m wide) make it suitable for offshore purposes. Represented in figure 9 Disk stack centrifuges are capable of separate droplets with an approximately size of 5 to 15 microns and solids from 3 to 10 microns and above. In the solids removal, density is an important factor and it may be 1.4 g/ml or higher in order to have a proper separation [Miedek and Fislage].

Centrifuges system present some benefits, the most important ones are its efficient removal of smaller oil particles and solids and its application for heavy oil de-oiling (up to 11.5 API) [Alfa Laval]. Centrifuges do not need demulsifiers and also the rag layers found in traditional vessels are eliminated. But they have high maintenance and operational cost because of the rotation parts and also higher energy consumption. They are meant for small water streams [Statoil, 2010].

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5.5 Hydrocyclones
Hydrocyclone vessels are units formed with conical devices where centrifugal force and the specific gravity difference separate oil and water. Individual hydrocyclone conical devices are called liners (figure 10). The quantity of liners varies depending on the produced water characteristics and the water amount that needs to be treated. Figure 11 shows a hydrocyclone vessel with the liners inside.

Produced water is introduced under pressure into the hydrocyclone vessel, and makes its way to the water/oil inlet ports; placed at the larger diameter end of each liner. Pressure drop between the inlet ports and the outlet ports of the liner ensures the flow path. A swirl positioned axially in the liner induces a rotation flow throughout it. The conical shape of the liner increases de fluid speed rotation. As the diameter of the liner gets narrower the speed increases. Therefore the centrifugal forces also augment resulting in the separation of light oil and gas and heavy water and solids. The heavier materials move to the walls of the liner towards the outer port. Meanwhile, the oil moves in a closer vortex to the axis moving in the opposite direction towards the inlet port [FMC, Veolia brochures, 2012]. The functioning of a liner is sketched also in figure 10.

There are different factors that influence the separation performance, such as the operating temperature that affects the viscosity, usually the

34

higher the temperature the lower the viscosity. The decrease in water viscosity favors the droplet settling velocity and the coalescence activity. Figure 12 shows a comparison between different oil at constant efficiency, as the viscosity increases, the droplet size of the separation is also bigger. It can vary from 30 m to 10 m from heavy oil to light oil. The pressure drop in the liners is a very important factor. The higher the pressure drop the higher the tangential velocity is; and the hydrocyclone performance is better. But if the hydrocyclone operates at maximum flow rate, some turbulence may appear and it lows the efficiency of the process as it shows figure 13. Another important agent is the droplet inlet size. Cyclotech Technologies affirms that there is a critical droplet size around 10 m to 15 m where the efficiency drops notably (figure 14).

Several oil & gas companies have elaborated different designs, Siemens, Veolia, FMC because of the advantages they provide. They are compact modules with high efficiency and the can reduce oil concentration to 10 ppm. They do not need any pre treatment and energy consumption is very low, they only use energy to pump the water into the vessel. The main disadvantages of this system are that the solids can block the inlet and scale formation could happen increasing the maintenance cost. Besides they can treat any kind of produced water, a post-treatment may be needed in order to remove other dissolved components to achieve the disposal standards.

35

5.6 IGF
In the IGF units, the water is injected into the floatation tank but the bubbles are generated by physical procedures.it can be several gas injected such as nitrogen, natural gas, carbon dioxide or air (it is necessary to be extremely careful with the air ant its oxygen content for its explosion potential). There are two types of IGF, Hydraulic and Mechanical. In both of them a coagulant pretreatment could be use to favor the flocculation.

Hydraulic typical system is showed in Figure 15. It shows a flotation unit with three cells. The recycled water flows through the venture eductors, where the gas is sucked and the mixture is released into the chamber where flotation occurs. Then the oil is skimmed and removed and the water is pumped into the recycling system [Natco]. Normal manufacturers design each cell with around 50% efficiency that makes not cost-effective to install more three or four cells because more cells efficiency increase is too low [Steward, 2008].

Mechanical system includes a rotating impeller, driven by an electric motor that creates a vortex, which introduces de gas into the vessel. The gas mixes with the water and originates the bubbles. Figure 16 sketches the process. Hydraulic system is less expensive and involves less maintenance than the mechanical system because of the rotating

36

parts. In the other hand mechanical procedure allows to control bubble size and usually they are more efficient.

IGF can handle low oil concentrations from 15mg/l up to 500 mg/l, mechanical IGF are more efficient with lower concentrations (below 150mg/l) [Aker, Unidro]. It offers really high efficiency, over 98% in the separation sizes over 15m. They are not affected by flow rate variations and they can operate heavy oils with not big density difference achieving good separation results. They have high power consumption and a proper chemical pretreatment can increase their efficiency. They can operate onshore and offshore but in no floating facilities, as a consequence of skimming over a weir.

5.7 Compact Flotation Unit (CFU)

The CFU is a vertical separator vessel, which separates the three phases oil/water/gas by using centrifugal force and gas flotation. It has no moving parts and is capable of achieving high standards of oil removal. It has smaller volume and shorter retention than traditional flotation units (Statoil, 2010). That is why CFU suits ideally offshore applications, it reduces the size and weight of the oil/water separation facilities compared old systems [EPCON, Siemens]. CFU was developed by EPCON that nowadays is owned by MISwaco (Schlumberger), other companies have built similar systems such as Siemens with its Vorsep technology or OPUS. CFU systems are capable of reducing the oil content below 10

37

ppm [EPCON, Opus, VWS westgarth], and if two CFU systems work together, this content can be reduced to 5 ppm (EPCON).

Small oil droplets are made to coalesce, creating larger droplets, which are easier to remove. The droplets because of specific gravity difference form a continuous layer at the top of the vessel. Oil water separation is helped with a simultaneous flotation effect, caused by the release of residual gas from the produced water. In some occasions the gas flotation is increased with external gas injection and flocculants. As figure 17 sketches, the produced water enters the CFU tank horizontally, in a tangential direction. The distributor situated at the top chamber dispersed the water. The majority of any entrained gas is released at this point. Produced water makes its way under gravity trough the eductors towards the bottom chamber. The design of these eductors ensures that the gas from the upper chamber is drowning down into the eductors where it mixes with the water. One of the important features of the CFU is the perfect mix between gas and produced water. The shape of the eductors creates a vortex in the lower chamber, which favors the coalescence of the oil droplets, and a toroidal flow is created. The oil floats with the help of the gas and it moves to the top where it is removed with a skimmer. The water exits the vessel through the bottom [Veolia].

CFU system has many advantages; most of the companies confirm that it is a robust system with small footprint and low weight. Because they

38

have no rotating parts, it is easy to operate, no energy is required, and maintenance costs are also lower. It has a high flow capacity with low volume, for instance, an EPCON CFU system can operate a water flow up to 220 m3/h with a vessel volume of 2.4 m3.

5.8 Sand cyclones

The desander vessel is ideal for the inline desanding of produced water and is the most important element in the sand management system [Aker, 2012]. The vessel consists in two sections, the upper section where the separation occurs and the bottom section where the sand is removed. The principle of operation is the same as in every hydrocyclone. Separation happens due to the pressure drop in the liners inlet and outlet ports that creates two different vortexes. In the sand cyclones the solid particles move to the walls of the liner and the water flows in the smaller vortex. The sand will be accumulated in the catchment chamber at the bottom and discharged intermittently, meanwhile the desanded water discharge continuously.

The liners, very similar to de-oiling hydrocyclones are placed in the upper section between two support plates. They must be manufactured with special ceramic materials such as alumina ceramic (standard) or bonded silicon carbide [Cyclotech] in order to resist the erosion provoked by the solid particles [Aker, Veolia]. A sand cyclone sketch is

39

shown in figure 18; they can have different diameter size depending on the size of the particles that need to be removed. For instance, Aker suggest 1.5-inch diameter for 4 mm particles and a separation size ranged from 10 to 20 microns. For bigger particles, around 6 mm they put forward a 3-inch liner that can separate up to 40 microns.

5.9 C-Tour
C-tour system technology developed to extract dispersed and dissolved and dispersed oil, reducing the environmental impact in the North Sea. The participants were Statoil, Norsk Hydro, BP, Shell, etc. It was conducted at the Rogaland Research I Institute and Norsk Hydro research center. The name comes from the French scientist who discovered the phenomena of super critical fluids in XIX century, Cagniard de la Tour in 1822 [Voldum and Garpestad, 2008].

The principle of the process is to use natural gas liquid-condensate as a solvent to extract the hydrocarbons contaminants in produced water [Descousse, 2004]. The process includes several steps; the first is to collect the condensate from the production extreme. This can be done in the gas compression train scrubbers [Grini, 2002]. Then the collected condensate is injected at small rate into the produce water line (0,3-2% volume/volume). The second is the extraction of the hydrocarbons from the water into condensate phase; this process might take couple of seconds. And the last step is the separation of the condensate from the

40

water in a hydrocyclone system. Recycling of the rejected water must be done. Figure 19 is a diagram of the Ctour process.

The condensate should accomplish some features in order to achieve good results in the process. The condensate must remain in liquid phase during the injection and following extraction. Composition of the condensate is a very important factor [Voldum, 2008]. The condensate may contain some aromatic components, which, could be present in higher concentrations than in the produced water. It can end in an increase of the heavy aromatic compounds in the produced water. If the condensate does not reach the needed characteristics some pretreatments can be used. Some of them are increasing the processing pressure to match the liquid phase or flashing the condensate to reduce bubble point [Voldum and Garspetad, 2008]. Condensate injection and mixture is another key element for the process. The system must ensure a homogeneous dispersion throughout the produced water stream, providing the highest possible surface favoring coalescence process. Besides the dispersion, the higher the turbulence the better the mass transfer will be, which also helps the performance of the system.

Table 7 presents the results of the Ctour system in the Ekofisk, offshore oilfield in the North Sea. It is important to notice the low efficiency of the process in the C4-C5 phenols. Voldum explains this phenomenon affirming that those phenols are highly soluble in water with low bioaccumulation. The average of oil in water discharge ranges 1-2 ppm

41

and it is never higher than 2.2 ppm. Statoil confirms that the removal average of the Ctour system is: 95% for Dispersed oil, 92% in Naphthalene, 97% in PAH, 0% C0-C3 phenols (very important, it meets the zero content discharge), 50% C4-C5 phenols, 97% C6-C9 phenols and 10% to 80% BTEX.

5.10 MPPE
MPPE or macro porous polymer extraction is an Akzo Nobel technology elaborated in the 1990s. It is capable to withdraw dispersed and dissolved hydrocarbons to very low levels with flow rates from 200 m3 to 250m3. This technology is a liquid-liquid extraction performed by a macro porous polymer particle. MPPE system is commonly placed after the first separation processes, in gas/condensate fields after degasser/skimmer and in oil fields after hydrocyclones.

The MPPE usually consist in two columns that ensure a continuous operation, one is destined to extraction and the second for regeneration. The contaminated water passes through the first column packed with MPPE particles that contain specific extraction liquid. The particles have a diameter of 1m with pore size range 0,1 to 10 m. The hydrocarbons with high affinity for the liquid are removed. In order to clean the extraction liquid, low-pressure steam strips the hydrocarbons that are condensed and separated later in the second column (figure 20). It is a long process that takes usually one hour for each column

42

[Meijer, 2004]. Most of the oil/gas field components can be removed with a very high efficiency, BTEX and PAH`s, reach 99999% removal from 2000 to 3000ppm concentrations. It has been proved that chemicals such as scale corrosion inhibitors, demulsifiers or H2S scavenger have no negative effect on the performance. To improve the MPPE process it is necessary to optimize de steam consumption used in the regeneration tower and some solids pre-filter can be added to avoid blocks.

MPPE presents many advantages to become an even more important technology. It is a robust system with long life and flexible, it is capable of treating different kinds of water (oilfield/gas-field) with high efficiency removal, it presents 84% in EIF (Environmental Impact Factor) analysis [Meijer, 2004] (almost reaching the zero discharge goal). It has been demonstrated in Kvitebjrn that bioactivity in the field stopped during year 2005, when the MPPE system was installed; bioactivity of the field was restored in less than 3 months because of the high hydrocarbon elimination. Figure 21 presents a comparison between flotation and MPPE process. The worst disadvantage of this unit is its high price. Other disadvantages are the relatively high-energy consumption and the cost of the pre-treatment in the oilfield produced water.

5.11 Walnut shell filters

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Walnut shell filters consist in filtration and scrubbing processes in the same vessel. Filtration usually occurs down flow, as the liquid passes through the media, oil and solids are efficiently attached (coalesced) in bed. This process is based on time or pressure difference. Often, air or gas is added to create an airlift pump.

Then the scrubbing system starts, the scrub pump is opened and the media starts circulating in the scrubbing system. During this circulation the media is positively cleaned because of the turbulence of the backwash water and the air (if added) [Siemens, Cameron]. For the backwashing of the media, Cameron proposes a rotating media, which also allows a horizontal configuration process but it adds rotation parts to the system increasing O&M costs.

The addition of air into the vessel reduces considerably the backwash water required. Figure 22 sketches both processes by Siemens. The filtration needs the backwash cleaning approximately every 24 hours and it will take 15 to 20 to clean the media. The media is highly regenerated and only 5% per year will be lost.

Walnut filters can process maximum oil loading of 100ppm of oil and suspended solids with a high efficiency removal of 99% for insoluble hydrocarbons over 2 m and 90 to 99% for solids over 5 m. These filters are suitable for every oil gas production facility, either offshore or onshore. A typical flux rate would be 33m3/h. No pretreatment and low

44

energy needed for the process, only for the scrub pump and rotating part if existing.

5.12 Mares Tail

Mares Tail technology has been developed by Opus, it is basically an inline coalescer. Its purpose its to coalesce the very small droplets (smaller than 10m) of the produced water to improve the posterior performance of the hydrocylones or other separation technologies. Opus affirms the droplets size increase ranges 400to 500%. The unit contains a spool fibrous element fixed in the inlet. The dirty fluid enters the nozzle and flows along the spool in the same direction as the coalescence medium. As the fluid travels throughout the fibers, the small droplets are attracted to the surface and coalesce.

The main advantages are its high coalescing efficiency, tolerant to solids and unaffected by motion (available for floating offshore facilities). Compact and easy to operate and maintain. OPUS ensures it is its best cost effective technology. They do not need pretreatment but it is made as a pretreatment itself for a posterior more efficient removal.

5.13 BAF
It consists of a permeable media such as rocks, graves or plastic, which combines aeration and separation facilitating biochemical oxidation and

45

as a consequence the organic removal. BAF can remove oil, ammonia, suspended solids, nitrogen, heavy metals and hydrogen sulphide [Ebenezer, 2012]. The approximate removal capabilities are 60% to 90% of nitrification, 70% to 80% oil and 75% to 85% of suspended solids. They feed water of oil can never be over 60 mg/l [Colorado School of Mines, 2009]. Water recovery is 100% and it has low energy consumption. Cost is low as in most biological treatments and it is adaptable to wide range quality and quantity water flux.

5.14 Activated sludge

Conventional Activated Sludge Process (ASP) is the oldest and the most common biological wastewater treatment. In the ASP, as the microorganisms grow, they from particles that gather (flocs), settle to the bottom of the tank leaving a liquid free of organic material. An ASP is basically composed of an aeration tank where the biological reaction happens; an aeration source of oxygen; a clarifier where solids separate and settle and finally a tank to collect the solids and return them into the tank (called return activated sludge or RAS) or remove them form the process (waste activated sludge or WAS).

The process begins when the influent is injected into the aeration tank. Bacteria rise up as they move through it where the air is pumped in fine bubbles at the bottom, for the oxygen requirements of the process. Then the aerated mixed water, also called mixed liquor, overflows by

46

gravity to the clarifier tank where bacteria separate the organisms and settle to the bottom. The sludge is either pumped back to the tank with the new income of wastewater (RAS) or removed from the system (WAS); figure 23 sketches the process. According to Fakhrul Razi ASP can remove from 98% to 99% of total hydrocarbons with twenty days duration process. Mittal ensures that conventional ASP will meet specified discharge standards.

The evolution of the conventional ASP ended in the sequencing batch reactors in which all the treatment occurs in one singular tank. The process starts with the filling of the reactor with the influent, it can be aerated or anoxic. Afterwards, the react phase begins where aeration and mixing continue until the full biodegrading finishes. When biodegrading has ended, aeration and mixing are turned off and biomass settles down to the bottom of the tank. Then effluent is removed in the decant phase and then the sludge is also discharged. SBRs can operate 200.000 m3 a day ensuring denitrification and phosphorous removal, basic compounds needed to be discharge for human or agricultural consumption [Mittal, 2011]. SBEs are flexible and can vary and adjust shortly to the configuration of the process.

5.15 MBR
MBR process combines anoxic and aerobic treatment with an integrated immersed membrane. It is a similar process to the ASP with mixed liquor

47

in the aeration tank but they differ in the separation. In the MBR process the separation occurs because of the action of a polymeric membrane with MF/NF, meanwhile gravity settling occurs in the same system as in an ASP. Thus MBR provides an extra filter for the water that makes this process achieve better results in bio-solids removal (less than 1 mg/l) [Siemens]. It is small for being a biological process and it also shortens the performance time to 6 hours if the membrane is correctly clean with appropriate CIP. It also requires high maintenance of the membrane, which is the key to lengthen the life of it, such as dehydration besides the CIPs.

Table 7 shows a comparison of the BAT explained on the report, main characteristics and suitable operations.

6 Flow Diagram
Produced water facilities use various methods to treat the produced water. But every production facility despite its differences can be divided in several steps depending on the technologies applied and the limits they want to reach. Those steps are bulk removal or primary, secondary and tertiary or advanced treatment. Because of obvious issues offshore and onshore facilities are different in size and technology used, being the offshore more compact and lighter than the typical onshore plants.

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Onshore primary treatment normally uses separators and skimmers; it can also use hydrocyclones, CPI and ceramic membrane processes. Secondary is characterized by CFU and IGF and finally for tertiary treatment Walnut filter or MPPE for example. Also for advanced treatment all biological treatments and ion exchange for water softening. Offshore treatment needs to use the most compact and lighter systems necessary to reach the specifications for injection or disposal. They can use hydrocyclones, C-Tour, IGF, etc.

Figure 25 shows a possible flow diagram for a full line produced water treatment. The water could be used for reinjection for disposal or reservoir pressure maintenance and also for surface discharge. A hydrocyclone has been used as primary treatment after the 3 phase separators of the production train. The oil separated is redirected to the production train before the low-pressure separator. As a secondary treatment an IGF unit has been placed. The skimmed oil must be pumped into the production line. Another pump has been placed for the water recycling system in the IGFs units. Finally a walnut shell filter will cover the tertiary treatment for reinjection or disposal of the water.

7 New challenges
Produced water technologies has become an even more important cost issue in the oil and gas production industry since the new laws have

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lowered the disposal standards not only for dispersed oil but aromatic, production chemicals, etc. These new limits for discharge have increased the cost of produced water treatment and nowadays the oil and gas are lowering the price because of the global crisis since 2008. As a consequence of the increasing of the difficulties for disposal and the decreasing of the benefits, many efforts have been made for developing new BAT that can compete with traditional oil and water separators reaching the new standards at the lowest possible price.

Everyone must agree in the best via to save costs in produced water treatment is reducing the amount of produced water that has to be administered. But this is a difficult task, because water injection is a really common procedure for oil production and water is also need for water flooding. Other solution might be over treat the water achieving human consumption standards so freshwater would be obtained and many possibilities offer for freshwater utilizations.

One of the ways to reduce the cost is to separate the oil and the water in subsea facilities with simultaneous reinjection so the amount of water that needs to be treated at the surface is only the water in oil emulsions. [Ogunsina, 2005; Sheridan, 2013]. The first subsea hydrocyclone was installed by FMC; it is capable of separating heavy oil from water and reuses the water for reinjection to boost oil production of the field. It is called Marlim Project and it is built for PetroBras. It also includes other equipment for the sand treatment [FMC, 2011]. The systems consists

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basically in a sand remover, a set of vertical pipes (free gas removal), a pipe separator (60m long) and separation vessel (oil/water separators), another sand remover and an hydrocyclone (figure 24) [Orlowsky, 2012].

The other future goal of produced water companies is the final developing of the membrane RO and NF for oilfield wastewater. Many experiments have been carried out and ceramic membranes are being tested for RO and NF but they were not yet successful. Both systems will decrease considerably the chemicals, solids, metals, etc. The main objective of these technologies is to reduce the pretreatment that both of them need to perform and the integrity of the membrane. For such thin filters, there is a high risk of membrane fouling with oil and gas produced water. The possibility of application of RO for produced water means that produced water can be clarified to the limits of human consumption and agriculture irrigation. This capability will open produced water to a whole new market with new possibilities that could make produced water treatment profitable.

For instance, there is an emergent market of fresh water consumption in developing countries in desert areas where water supply is becoming a big problem. Countries such as Saudi Arabia or The Emirates, which are also oil producers. These countries, as a solution for the human fresh water consumption could treat oilfield, produced water with the new technologies, membranes generally, solving both problems, fresh water consumption and oilfield produced water.

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8 Conclusions
There are many different produced water techniques to optimize the treatment and make the process the best cost-effective. This is even more important in offshore platforms because of the additional difficulty of the weight, supplies issues, maintenancewhich makes only a few technologies available at a high price. In order to reach the zero disposal concentration, some tertiary technologies have to be developed and installed such as Ctour or MPPE so platforms become more environmental friendly and sustainable.

Another important via to reduce cost and to be more environmental friendly is reducing the amount of hard chemicals used to favor the separation and also used in pretreatments. Chemicals might change into water soluble or non-harmful to the environment, so that chemical developing cannot stop in order to reach those important goals.

The best via to save in produced water treatment is avoiding its production. Since this is very difficult to achieve, it is important to find any application for the treated water, which will reduce costs or make it profitable. The increase of water consumption in several areas of the world could be the solution for both problems, oilfield waste water and human fresh water consumption.

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53

Tables
Table 1

Worldwide produce discharges (Steward, 2008)

Table 2

Worldwide produce discharges (Neff, 2011)

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Table 3

Constituents summarize from gas fields (Ahmadun, 2009)

55

Table 4

Constituents summarize from oil fields (Ahmadun, 2009

56

Table 5

Chemical compounds in gas-oil fields (Steward, 2008)

Table 6

Ceramical membranes characteristics (USBR) Table 7

Ekofisk C-Tour performance (Phillips)

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Table 8 Technologies
Skim tank

Principle
-Coalescence -Gravity -Coalescence -Gravity -Filtration

Removal
-Dispersed oil -Solids -Dispersed oil -Solids -Suspended solids -Oil -Metals -Dispersed oil -Solids -Dispersed oil - Oil -Solids -Dispersed oil -Dispersed oil -PAH -Btex -Naphtalenes -Solids -Dissolved and dispersed oil

Size
>150m (oil) >50m (oil) >10m(solids) >5nm 1,4m >5 -15m (oil) >3-10m (solids) >10-15m >15m -Reduce 10 ppm -Reduce 1-2 ppm >10-20 m -Reduce 2 ppm

Advantages
-Treatment with high concentration and contaminants -Continuous process -Flexible -Suspended solids free

Disadvantages
-Affected by T -Probable addition of chemicals -Post-treatment may be needed - Membrane fouling -Membrane cleaning and maintenance -Chemicals -Rotating parts -Scales and solids block -Possible pretreatment with chemicals -High cost

Energy Consumption
-Low

Comments
-App offshore -Low O&M -Vertical/Horizontal - 200m3/h (WF)* -3000mg/l (C)** -170 m3/h (WF) -170kw/h -App offshore -High O&M -170 m3/h (WF) -150 kw/h -High O&M -33 m3/h (WF) -App Offshore -500mg/l (C) -Medium O&M -Low O&M -220 m3/h (WF) - App offshore -App offshore -Low O&M -Low o&M -App offshore - 3000ppm (C) -200m3/h (WF)

CPI

-Low

Ceramic Memb

-High

DSC

-Centrifugation

-Heavy oil app

-High

Hydrocyclones IGF CFU

-Centrifugation -Flotation -Coalescence -Gravity -Flotation -Extraction

- Compact and robust -Flexible -Very high efficiency -Compact and robust

-Low -Low -Low

C-Tour

-Very high efficiency

-High cost

-Medium

Sand cyclone MPPE

-Centrifuge -Adsorption

-Compact and robust -High efficiency -Zero discharge -Possible pre-treatment -High cost

-Low -High

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59

Walnut filter

-Coalescence

-Oil -Solids

>2 m (oil) >5 m (solids) <10 m (oil)

Mares tail

-Coalescence

-Dispersed oil -Organics -Ammonia -Metals -Organics -Solids -Ammonia -Organic -Solids -. -Inorganic ions -Metals -Inorganic ions -Solids -Dissolved comp

-Flexible -Compact -High filter regeneration -Cost /effective -Compact -Operate with solids -Flexible

-Long operation -Possible rotating parts -Post-treatment -Long time operation -Aeration -Big installation -Long time operation -Aeration -Big installation -CIP -Membrane maintenance -Pretreatment -Membrane fouling -Scale and solid blocks -Pretreatment -Contaminant -Post-treament

-Low (increases if rotating parts)

-33 m3/h (WF) -App Offshore -Low O&M -App offshore -Low O&M -60mg/l -Low O&M

-Low

BAF Activated Sludge MBR Ion Exchange Ed/EDR Thermal Tech

-Bacteria

-Low

-Bacteria -Filtration -Bacteria -Chemicals -Chemical -Filtration -Evaporation

-Flexible -Short for biological process

-Low

-Medium -Low -Medium -High

-Low O&M -High O&M -1200mg/l (solids C) -High O&M

-Pretreatment -High removal

*WF = Water flow (max) ** C = Oil concentration (max)

BAT comparison

60

Figures
Figure 1

Water/Oil production profile (Ebenezer, 2012)

Figure 2

Drag force, Stokes law (Fluids Mechanics UPM, 2010)

61

Figure 3

Membrane sketch (Cheryan 1998)

Figure 4

ED sketch (EET corporation)

62

Figure 5

Skim Tank configurations (Steward 2008)

Figure 6

Oil coalescence and solids settling (ESI)

63

Figure 7

Down-flow CPI (ESI)

Figure 8

Up-flow CPI (ESI)

64

Figure 9

Disk Stack Centrifuge (Veolia) Figure 10

Liner shape and performance (Aker)

65

Figure 11

Hydrocyclone (NETL) Figure 12

Micron size separation Vs Oil viscosity (Cyclotech) Figure 13

66

Max and Min pressure drop operation Vs eff (Cyclotech) Figure 14

Micron separation efficiency Vs Droplet inlet size (Cyclotech)

Figure 15

Hydraulical IGF (Unidro)

67

Figure 16

Mechanical IGF (Unidro)

68

Figure 17

CFU sketch (Statoil, 2010)

69

Figure 18

Sand Cyclone (Veolia)

Figure 19

C-Tour flow diagram (Statoil, 2010)

70

Figure 20

MPPE flow diagram (Veolia) Figure 21

MPPE and flotation Comparison (Meijer 2010) Figure 22

71

Walnut shell filter sketch (Siemens)

Figure 23

Activated Sludge (Pipeline, vol 14, 2003)

Figure 24

Subsea Separation sketch, Marlim Project (FMC, Orlowsky,2012)

72

73

Figure 25

Flow diagram example of a produced water facility

74

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