10 1016@j Chemosphere 2017 10 139

Accepted Manuscript
State of the Art of Produced Water Treatment
S. Jimnez, M.M. Mic, M. Arnaldos, F. Medina, S. Contreras
PII: S0045-6535(17)31724-1
DOI: 10.1016/j.chemosphere.2017.10.139
Reference: CHEM 20161
To appear in: Chemosphere
Received Date: 17 March 2017
Revised Date: 23 October 2017
Accepted Date: 25 October 2017
Please cite this article as: S. Jimnez, M.M. Mic, M. Arnaldos, F. Medina, S. Contreras, State of
the Art of Produced Water Treatment, Chemosphere (2017), doi: 10.1016/j.chemosphere.
2017.10.139
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ACCEPTED MANUSCRIPT
Oil and gas sector is one of the eight most water intensive industries.
PW is generated when water from reservoirs is brought to surface in oil extraction.
Composition and final use of PW determines its treatment train.
Combination of treatments are necessary when there is a wide variety of components.
Minimization, disposal and reuse are options for PW.

ACCEPTED MANUSCRIPT
1 State of the Art of Produced Water Treatment
2 S. Jimnez a,b, M. M. Mic a, M. Arnaldos a, F. Medina b, S. Contreras b,*
3 a R&D department of Acciona Agua S.A.U, Parc de Negocis Mas Blau II, Avda. de les Garrigues, 22,
4 08820 El Prat de Llobregat, Barcelona, Spain.
5 b Departament dEnginyeria Qumica, Universitat Rovira i Virgili, Av Pasos Catalans 26, 43007
6 Tarragona, Spain
7 * Corresponding author. E-mail address: sandra.contreras@urv.cat
9 Abstract
10 Produced water (PW) is the wastewater generated when water from underground reservoirs is
11 brought to the surface during oil or gas extraction. PW is generated in large amounts and has a
12 complex composition, containing various toxic organic and inorganic compounds. PW is currently
13 treated in conventional trains that include phase separators, decanters, cyclones and coarse filters
14 in order to comply with existing regulation for discharge. These treatment trains do not achieve more
15 restrictive limitations related to the reuse of the effluent (reinjection into extraction wells) or other
16 beneficial uses (e.g., irrigation). Therefore, and to prevent environmental pollution, further polishing
17 processes need to be carried out. Characterization of the PW to determine major constituents is the
18 first step to select the optimum treatment for PW, coupled with environmental factors, economic
19 considerations, and local regulatory framework. This review tries to provide an overview of different
20 treatments that are being applied to polish this type of effluents. These technologies include
21 membranes, physical, biological, thermal or chemical treatments, where special emphasis has been
22 made on advanced oxidation processes due to the advantages offered by these processes.
23 Commercial treatments, based on the combination, modification and improvement of simpler
24 treatments, were also discussed.
25
26 Keywords
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27 Produced water; oil and grease; oil and gas; advanced oxidation processes; industrial wastewater
28 treatments; reuse
29
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30
31 Content
32 Abstract..............................................................................................................................................1
33 Keywords ...........................................................................................................................................1
34 Content ..............................................................................................................................................3
35 1. Introduction..................................................................................................................................6
36 2. Sources of Produced Water ........................................................................................................7
37 3. Characteristics of Produced Water..............................................................................................8
38 3.1. Dissolved and dispersed oil compounds ...........................................................................13
39 3.1.1. Dissolved oil ...............................................................................................................13
40 3.1.2. Dispersed oil...............................................................................................................13
41 3.2. Dissolved formation minerals ............................................................................................14
42 3.2.1. Cations and anions.....................................................................................................14
43 3.2.2. Heavy metals and naturally occurring radioactive materials ......................................14
44 3.3. Production solids ...............................................................................................................15
45 3.4. Production chemical components......................................................................................15
46 3.5. Dissolved gases ................................................................................................................15
47 4. Regulatory requirements ...........................................................................................................15
48 4.1. Environmental Discharge ..................................................................................................16
49 4.2. Reuse on Extraction ..........................................................................................................18
50 4.3. Irrigation Reuse .................................................................................................................19
51 5. Produced Water management ..................................................................................................21
52 6. Conventional Treatments of PW ...............................................................................................23
53 7. Polishing Treatments of PW ......................................................................................................24
54 7.1. Physical Treatment............................................................................................................25
55 7.1.1. Adsorption ..................................................................................................................25
56 7.1.2. Cyclones.....................................................................................................................27
57 7.1.3. Enhanced flotation......................................................................................................28
58 7.2. Biological treatment ...........................................................................................................29
59 7.3. Membrane treatment .........................................................................................................32
60 7.3.1. Polymeric membranes................................................................................................33
61 7.3.2. Inorganic membranes.................................................................................................33
62 7.3.3. Microfiltration/ultrafiltration .........................................................................................33
63 7.3.4. Reverse osmosis and nanofiltration ...........................................................................34
64 7.4. Thermal Technologies .......................................................................................................35
65 7.4.1. Evaporation ................................................................................................................35
66 7.4.2. Multistage flash ..........................................................................................................36
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67 7.4.3. Multieffect distillation ..................................................................................................36

68 7.4.4. Vapour compression distillation (VCD).......................................................................37
69 7.4.5. Freeze-thaw/evaporation............................................................................................37
70 7.4.6. Hybrid Multieffect distillationvapour compression ....................................................37
71 7.5. Chemical Treatment ..........................................................................................................38
72 7.5.1. Chemical precipitation ................................................................................................38
73 7.5.2. Electrochemical processes.........................................................................................39
74 7.5.2.2. Other electrochemical technologies ...........................................................................40
75 7.5.3. Room temperature ionic liquids .....................................................................................40
76 7.5.4. Demulsifiers ...................................................................................................................41
77 7.5.5. Ion Exchange .................................................................................................................41
78 7.5.6. Macro-porous polymer extraction technology. ...........................................................42
79 7.5.7. Advanced Oxidation Processes (AOPs) ........................................................................42
80 7.6. Advanced Oxidation processes for PW treatment.............................................................44
81 7.6.1. H2O2 and H2O2/UV ......................................................................................................45
82 7.6.2. Fenton and Photo-Fenton processes .........................................................................46
83 7.6.3. Ozone (O3) .................................................................................................................49
84 7.6.4. Heterogeneous Photocatalysis...................................................................................49
85 7.6.5. Electrochemical Oxidation..........................................................................................50
86 7.6.6. Wet Air Oxidation and Supercritical Water Oxidation.................................................51
87 7.7. Combined Systems ...........................................................................................................52
88 7.8. Commercial Treatment Processes for Produced Water........................................................55
89 7.8.1. CDM technology.........................................................................................................55
90 7.8.2. Veolia: OPUSTM ..........................................................................................................55
91 7.8.3. Eco-sphere Inc.: OzonixTM ..........................................................................................55
92 7.8.4. EMIT: Higgins Loop....................................................................................................56
93 7.8.5. Drake: Continuous selective IX process.....................................................................56
94 7.8.6. Eco-Tech: Recoflo compressed-bed IX process .....................................................56
95 7.8.7. Altela Inc.: RainSM Dewvaporation............................................................................57
96 7.8.8. Aquasonic Corporation: RSE and RSD...............................................................57
97 7.8.9. EARTH Canada Corporation: TORRTM ......................................................................58
98 7.8.10. Frac Water Inc.: HEEDTM............................................................................................58
99 7.8.11. Crystal Solutions, LLC: FTE ...................................................................................59
100 7.8.12. BioPetroClean: ACT ...............................................................................................59
101 7.8.13. Prosep Inc.: C-TOUR..............................................................................................59
102 8. Conclusions ...............................................................................................................................60
103 9. Acknowledgements ...................................................................................................................62
104 10. References............................................................................................................................62
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106 1. Introduction
107 The Oil & Gas industry is characterized by the high-volume water consumption and
108 wastewater generation associated with extraction activities (the so-called produced
109 water) -upstream sector- and by the generation of complex wastewater associated with
110 refining activities -downstream sector-, as it is shown in Figure 1. In both cases,
111 wastewater has a high pollution potential and is complex, both regarding the chemical
112 composition and the technologies required for proper treatment. As a result, efficient
113 treatment and reuse of treated water is one of the main technological challenges with
114 regard to the management of the effluent.
115 a) b)
116 Figure 1. Process scheme for the
117 upstream (a) (which consist of several steps from which produced water is obtained)
118 and downstream (b) activities.
119 A certain amount of natural water is always found together with petroleum and gas in
120 reservoirs. It is also known as formation water. It is slightly acidic and sits below the
121 hydrocarbons in porous reservoir media. When oil and gas are extracted, the pressure
122 in the reservoir is reduced, and additional water is usually injected into the reservoir water
123 layer to maintain hydraulic pressure and enhance oil recovery [1]. Produced water (PW)
124 includes then the formation water (trapped underground) and injection water that are
125 extracted together with the fossil fuel during oil and gas production [2-5]. It contains also
126 hydrocarbons and chemicals added during the production and treatment processes [6].
127 PW is generally classified as oilfield PW, natural gas PW and coal bed methane (CBM)
128 PW depending on its origin [1].
129 Considering the global production of barrels of oil and related water, water to oil ratio
130 (WOR) is approximately 3:1 [7]. Global volume of PW generated is up to 39.5 Mm day , 3 -1
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131 although the WOR is increasing. However, by 2025, due to the ageing wells, the WOR
132 is expected to reach an average of 12 (v/v) for onshore crude oil resources. This will
133 reinforce the growth of the market of PW's management [7].
134 PW stream may contain various organic and inorganic compounds, harmless or toxic,
135 which come naturally from the extraction wells, and others that are related to chemicals
136 added for extraction purposes. PW quality varies appreciably according to the
137 geochemistry of the producing formation, the type of hydrocarbon produced, and the
138 characteristics of the producing well and the extracting method [8]. Therefore, this stream
139 properties and volume differ from one location to another, and even can vary over time,
140 as the well ages.
141 If PW meets appropriate water quality criteria, it could be reused again within the oil and
142 gas production process, or even for purposes such as irrigation, livestock watering,
143 aquifer storage, municipal and other industrial uses [8]. To this end, specific treatment of
144 PW is needed according to the requirements of each end-user and applications.
145
146 2. Sources of Produced Water
147
148 Oil and gas extraction from onshore and offshore wells entails the generation of PW,
149 either if the fuel production comes from conventional or unconventional sources such as
150 coal bed methane, tight sands, and gas shale:
151
152 Conventional Oil and Gas: When organic matter is buried under layers of sediments,
153 geothermal forces that exert high pressures and temperatures during millions of years,
154 cause hydrocarbon pyrolysis that convert that matter into petroleum, oil and gas. If this
155 process takes place in a confined layer of porous material, an oil and gas reservoir is
156 formed as the pores in the rock harbor the fuel. The reservoir keeps its pressure until the
157 well is drilled, when the high pressure is released and pushes oil and gas out to the
158 surface [8, 9].
159
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160 Unconventional Petroleum Resources: Recently, alternative oil and gas sources are
161 being exploited. The reduction of the conventional oil sources and recent technological
162 developments have made them profitable. Some of these unconventional sources are
163 shale oil and gas, tight sands, and coal bed methane. In shale, oil and gas are retained
164 within deep sedimentary formations which require high amounts of water, chemicals and
165 energy for their extraction [10].
166 United States have the biggest deposits of shale. The formation of the Green River in
167 Wyoming, Colorado, and Utah contains the largest of the United States oil shale deposit.
168 United States Federal Government manages the seventy per cent of the resource
169 commercially most important in the Green River [8, 9].
170 Shale gas is found trapped within shale formations. As the matrix permeability of shale
171 is low, for providing permeability, fracturing the rock is necessary for gas release.
172 Traditionally shale gas has been obtained from natural fractures; however, higher
173 demand has motivated the development of hydraulic fracturing technology (fracking).
174 Since the beginning of this century, it has become an increasingly important source of
175 natural gas in the United States, and this interest has expanded to potential gas shales
176 in the rest of the world [11].
177 Tight sands gas is also a resource of non-conventional natural gas produced from low
178 permeability compacted sediments. Like shale gas, advances in technology have
179 increased the development of compact sand into an economic resource.
180 Coal bed methane or natural gas is a non-conventional resource trapped in coal seams
181 underground. Because of the bacterial (biogenic) and chemical reactions that occur with
182 high temperature and pressure during the bituminization phase (thermogenic), methane
183 is produced in the coal seam. Higher rank coal methane is formed by thermogenic
184 production, and lower rank coal produced methane by biogenic production. In addition,
185 the volume of gas increases with coal, the depth and the reservoir pressure. The surface
186 area to volume of coal is high, so it may allocate large volumes of gas in comparison with
187 conventional gas deposits of comparable size [12].
188
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189 3. Characteristics of Produced Water
190 The complex composition of PW is variable. Its physical and chemical properties depend
191 on the geographic location of the field, the geological formation, the extraction method,
192 and the type of hydrocarbon product being produced. PW contains some of the chemical
193 characteristics of the hydrocarbon with which it has been in contact for centuries. Its
194 properties and volume can even vary throughout the lifetime of a reservoir [5].
195 PWs discharged from gas/condensate platforms are about 10 times more toxic than the
196 PWs discharged from oil wells, but, the volumes from gas production are much lower
197 [13].
198 The major groups of constituents of concern in PW are:
199 Salts (expressed as salinity, total dissolved solids (TDS), or electrical
200 conductivity).
201 Oil and Grease (O&G).
202 BTEX (benzene, toluene, ethylbenzene, and xylenes).
203 PAHs (polyaromatic hydrocarbons).
204 Organic acids.
205 Phenol.
206 Some natural inorganic and organic compounds (e.g., chemicals that cause
207 hardness and scaling such as calcium, magnesium, sulfates, and barium).
208 Chemical additives used in drilling, fracturing, and operating the well that may
209 have some toxic properties (e.g., biocides, corrosion inhibitors) [2].
210
211 In the oil and gas industry, most regulatory policies and technical requirements focus
212 their attention on O&G content, however salt content is also important in onshore
213 operations.
214 There is a controversy over O&G, since O&G content in PW is defined by the method
215 used for its measurement. The US EPA Method 1664 uses a direct measurement
216 method in which O&G is defined as a mixture of those components that are extractable
217 in hexane at pH 2 or lower, and remain after vaporization of the hexane. Therefore, this
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218 would include dispersed oil and water-soluble organics except low molecular weight
219 phenols, (which are highly soluble in water), low molecular weight acids, (which are
220 soluble in water and volatile) and BTEX (which are highly volatile).
221 With a wide range of typical pH 4.3-10 and a density around 1140 Kg m . Table 1
-3
222 summarizes the principal components in PW according to several references.
223
224 Table 1. Main components in produced water.
Component Concentration, Reference Concentration, Reference
mg L-1 mg L-1
Na 0-150000 [14] 132-97000 [15]
Cl 0-250000 [14] 80-200000 [15]
Ba 0-850 [16] 1.3-650 [15]
Sr 0-6250 [16] 0.02-1000 [15]
SO42- 0-15000 [14] 2-1650 [15]
HCO3- 0-15000 [14] 77-3990 [15]
Ca 0-74000 [14] 13-25800 [15]
K 24-4300 [15]
SO32- 10 [15]
Mg 8-6000 [15]
Fe 0.1-100 [15]
Al 310-410 [15]
B 5-95 [15]
Cr 0.02-1.1 [15]
Li 3-50 [15]
Mn 0.004-175 [15]
Ti 0.01-0.7 [15]
Zn 0.01-35 [15]
As 0.005-0.3 [3, 15]
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Pb 0.008-0.88 [3, 15]
Total Dissolved 100-400000 [14] 6554 [3]
Solids (TDS)
Chemical Oxygen 1220-2600 [3, 15]
Demand (COD)
Total Suspended 1.2-1000 [3, 15]
Solids (TSS)
Total Organic 0-1500 [3, 15] 0,1-11000 [4]
Carbon (TOC)
Total O&G 2-560 [3]
Saturated 17-30 [4]
hydrocarbons
Total BTEX 0.73-24.1 [17] 0.39-35 [15]
Benzene 0.032-14.97 [17]
Toluene 0.058-5.86 [17]
Ethylbenzene 0.086-0.57 [17]
m-Xylene 0.258-1.29 [17]
p-Xylene 0.074-0.34 [17]
o-Xylene 0.221-1.06 [17]
Total NPD 0.766-10.4 [17]
Naphthalene 0.194-0.841 [17]
C1-naphthalenes 0.309-2.9 [17]
Phenanthrene 0.009-0.11 [17]
C1-phenanthrenes 0.017-0.32 [17]
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Dibenzothiophene 0.001-0.023 [17]
C1- 0.006-0.103 [17]
dibenzothiophenes
C2- 0.004-0.12 [17]
dibenzothiophenes
C3- 0.003-0.089 [17]
dibenzothiophenes
Total 16 EPA PAH 0.0058-0.129 [17]
Fluorene 0.0041-0.067 [17]
Acenaphthene 0.0003-0.015 [17]
Chrysene 0.0006-0.015 [17]
Ammoniacal 10-300 [15]
nitrogen
Phenols 0.009-23 [15]
Total organic acids 0.001-10000 [4]
Formic acid 26-584 [18]
Acetic acid 8-5735 [18]
Propanoic acid 36-98 [18]
Butanoic acid ND-46 [18]
Pentanoic acid ND-33 [18]
Oxalic acid ND-495 [19]
Malonic acid ND-1540 [19]
Aliphatic acids 1.8-120 [20]
Benzoic acid 0.13-16 [20]
C1- Benzoic acid 0.089-16 [20]
C2-Benzoic acid 0.043-3.8 [20]
225
226
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227 3.1. Dissolved and dispersed oil compounds
228 Oil is composed of hydrocarbons as benzene, toluene, ethylbenzene, and xylenes
229 (BTEX), naphthalene, phenanthrene, dibenzothiophene (NPD), polyaromatic
230 hydrocarbons (PAHs) and phenols. The amounts of these compounds present in PW are
231 related to following factors:
232 Oil composition
233 pH, salinity, TDS, temperature
234 Oil/water ratio
235 Type and quantity of oilfield chemicals
236 Type and quantity of various stabilizing compounds (waxes, asphaltenes, fine
237 solids) [22]
238 The majority of the hydrocarbons do not dissolve in the water, so most of the oil is
239 dispersed in water as an emulsion, or clearly separated into two phases [21].
240 Therefore O&G in PW can be in the form of free, dispersed and emulsified oil.
241
242 3.1.1. Dissolved oil
243 It includes water soluble organic species: BTEX, phenols, aliphatic hydrocarbons,
244 carboxylic acid, and low molecular weight aromatic compounds [18]. The water-soluble
245 organic compounds in PW are usually polar constituents with a low number of carbons,
246 like organic acids such as formic and propionic. pH, temperature and pressure (in the
247 reservoir or during extraction) increase soluble organics in PW. Salinity does not
248 significantly affect the dissolved organics in PW [23]. Therefore, the amounts of soluble
249 oil in PW depend on type of oil, volume of water production, artificial technique, and age
250 of production [24].
251
252 3.1.2. Dispersed oil
253 It includes PAHs and some of the heavier alkyl phenols, like C6C9 alkylated phenols
254 that are less soluble in PW, and are found as dispersed oil [25]. Dispersed oil consists
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255 of small droplets of oil suspended in the PW. The amount of dispersed oil in PW depends
256 on the shear history of the droplet, the density of oil, the amount of precipitated oil and
257 interfacial tension between the water and oil [24].
258
259 3.2. Dissolved formation minerals
260 PW inorganic content is strongly related to the geochemical characteristics of the well.
261 They are present as dissolved salts, naturally occurring radioactive materials and heavy
262 metals.
263
264 3.2.1. Cations and anions
265 Cations such as Na+, K+, Ca2+, Mg2+, Ba2+, Sr2+, Fe2+ and anions such as Cl, SO42, CO3
266 2, HCO3 affect PW chemistry in terms of buffering capacity, salinity, and scale potential
267 [22]. Salinity, mainly due to dissolved sodium and chloride and in a lesser extent to
268 calcium, magnesium, and potassium, may vary from a few parts per million to about
269 300000 mg L-1 [26, 27].
270
271 3.2.2. Heavy metals and naturally occurring radioactive materials
272 PW contains trace quantities of various heavy metals such as cadmium, chromium,
273 copper, lead, mercury, nickel, silver, and zinc, mostly from natural origin [22]. Their
274 concentration can reach 102 to 105 times the one found on seawater [28].
275 Naturally occurring radioactive, materials, NORM, are originated in geological formations
276 and are brought to surface as dissolved solids in PW. NORM may precipitate into scale
277 or sludge when water temperature reduces as it reaches the surface. The most abundant
278 NORM compounds are 226Ra and 228Ra and barium [5]. According to Norwegian
279 Petroleum Industry handles produced water effluents with 226Ra and 228Ra
280 concentrations that range from detection limits, 0.31.3 Bq L-1 respectively, up to 16 and
281 21 Bq L-1 [29].
282
283 3.3. Production solids
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284 Production solids name a wide range of solid organic and inorganic materials that
285 accompany PW. They include formation solids, particles detached from the surrounding
286 materials, corrosion and anti-scale products from pipes and equipment, bacteria, waxes,
287 and asphaltenes [3]. Some other inorganic crystalline substances such as SiO2, Fe2O3,
288 Fe3O4, and BaSO4 can also be found [30].
289
290 3.4. Production chemical components
291 Besides its natural components, PW may include chemical additives dosed in drilling, to
292 treat or prevent operational problems and enhance oil/water separation afterwards [2,
293 24]. This group of substances is selected by the manufacturers attending to the
294 characteristics of the well and the fuel itself. They include gas hydrate inhibitors,
295 corrosion inhibitors, oxygen scavengers, scale inhibitors, biocides to mitigate bacterial
296 fouling, asphaltene dispersants, paraffin inhibitors, defoamers, emulsion breakers,
297 clarifiers, coagulants, flocculants, etc. [31].
298
299 3.5. Dissolved gases
300 Large quantities of dissolved gases are contained in oilfield brines. Most of them are
301 volatile hydrocarbons, but also CO2, O2, and H2S are commonly found in PW [22]. The
302 solubility of these gases in water decreases with water salinity and temperature, and
303 increases with pressure.
304
305 4. Regulatory requirements
306 Among all components, O&G are one of the groups of compounds that presents more
307 demanding restrictions for discharge and/or reuse according the legislation [2], therefore
308 it usually constitutes the main focus of the treatment.
309 Upstream PW contains originally on average approximately 500 mg L-1 of O&G.
310 Nevertheless, PW to disposal, usually treated by conventional means, can contain:
311 15 mg L-1 of O&G with an optimized treatment installation working properly
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312 35-40 mg L-1 with treatment facilities oriented to meet discharge limits according
313 to most seawater disposal international regulations
314 100 mg L-1 poorly treated effluents
315 For its discharge or its reuse, PW will be compelled to meet different quality requirements
316 depending on the after-use of the stream. Therefore, depending on the final use and the
317 efficacy of the conventional.
318
319 4.1. Environmental Discharge
320 In oil and gas industry, PW is conventionally treated through gravity-based separation
321 and discharged into the environment in offshore platforms or reinjected into the soil in
322 onshore ones. Despite the fact it should meet certain standards, this causes, soil, surface
323 water and underground water pollution [3]. For a long time, only non-polar oil in water or
324 O&G was regulated by government, while not much attention was payed to other
325 dissolved organics in PW. However, it is commonly known that organic components,
326 heavy metals and production chemicals have consequences on living organisms, since
327 metals and hydrocarbons from oil platforms are very toxic to the ecosystem, and alkyl
328 phenols strongly impact on fish populations [36, 37].
329 PW generated in offshore operations (platforms) is usually discharged into the sea. The
330 US offshore regulations govern the quality of the PW by the O&G concentration, toxicity
331 limitation, and prohibition of offshore discharges of produced sand. Regarding toxicity,
332 US regulations allow the toxicity criteria to be met through dilution.
333 Concerning suspended solids, there is no current regulation in US for PW ocean
334 discharge about them, however, SS tend to have oil layer adhered onto them, so they
335 should be also taken into account. This is why other countries like Russia are imposing
336 a limit of 10 mg L-1 [37].
337 A general limit set in the legislation for discharging PW to most offshore waters of North
338 Sea, the Mediterranean Sea, the Arabian Gulf, and Asia was 40 mg L-1 O&G, but an
339 increase in environmental concerns has forced many countries to implement more
340 stringent regulatory standards [37]. The Convention for the Protection of the Marine
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341 Environment of the NorthEast Atlantic sets that the maximum monthly discharge limit
342 to 30 mg L-1 O&G in the North-Est Atlantic area [38]. In the United States, Environmental
343 Protection Agency (US-EPA) stipulates a monthly average amount of oil in discharged
344 PW of 29 mg L-1, for the Outer Continental Shelf region, and a maximum of 42 mg L-1 for
345 daily discharge [39]. In Australia, permitted offshore discharge of O&G in PW is 30 mg
346 L-1 and the Peoples Republic of China now sets the monthly average limits of O&G and
347 chemical oxygen demand at 10 and 100 mg L-1, respectively [40].
348 In Spain, MAH/285/2007 is the Catalan regulation on sea discharge, on which the limits
349 are set for several parameters as 6-8 pH, 50 mg L-1 O&G, 700 mg L-1 COD, 300 mg L-1
350 BOD5, 300 mg L-1 TOC, among others.
351 Table 2 (a) and (b) shows worldwide limits of discharge [4, 41].
352 The EU Water Framework Directive adopted in 2000 (Directive 2000/60/EC) is
353 committed to zero discharge in response to the need for a more protective system
354 against the aquatic pollution. To achieve a zero-environmental harmful discharge, the
355 Norwegian Oil Industries Associations developed the Environmental impact factor (EIF),
356 which considers all the contaminants in PW. EIF evaluates the environmental risk and
357 assesses hazard of PW discharges, accounting for both composition and amount of the
358 discharge. The EIF is a proposed tool for PW impact reduction, management and
359 regulation. Its determination for a single platform allows the operator to rank the available
360 technologies for PW discharge reduction on a cost-benefit basis [37]. Similarly, OSPAR
361 Convention, the mechanism by which 15 Governments & the EU cooperate to protect
362 the marine environment of the North-East Atlantic, according to the resolutions taken on
363 Oslo and Paris Climate Change Conventions, has agreed on zero discharge of pollutants
364 into the sea.
365 Most oil and gas companies around the world are nowadays working towards the
366 implementation of zero-discharge of contaminants in PW [38]. Besides the legislation,
367 many water-stressed countries with oilfields are looking for ways of complementing his
368 limited resources of fresh water. They focus on efficient and economic methods to treat
369 the PW, so that they could be canalized to agricultural and industrial uses [5].
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370 Table 2. Worldwide produced water effluent oil concentration limitations according to a)
371 [41], b) [4]
372 a)
Country Oil concentration limitation
Ecuador, Colombia, Brazil 30 mg L-1 All facilities
Argentina and Venezuela 15 mg L-1 New facilities
Indonesia 25 mg L-1 Grandfathered facilities
Malaysia, Middle East 30 mg L-1 All facilities
Nigeria, Angola, Cameroon, Ivory Coast 50 mg L-1 All facilities
North Sea, Australia 30 mg L-1 All facilities
Thailand 50 mg L-1 All facilities
USA 29 mg L-1 OCS water
Zero discharge inland water
373
374 b)
Country Monthly average, mg L-1 Daily maximum, mg L-1
Canada 30 60
USA 29 42
OSPAR (NE Atlantic) 30 -
Mediterranean Sea 40 100
Western Australia 30 50
Nigeria 40 72
Brazil - 20
375
376
377 4.2. Reuse on Extraction
378 Oil and gas extraction causes a reduction of the pressure in the reservoir, therefore water
379 is usually injected to maintain hydraulic pressure and improve the recovery. The
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380 reinjection of PW is one of the best economic and environmental options for the PW
381 generated. In this way, PW that is usually considered a waste product, can be
382 transformed into a high valuable resource. The benefits of PW re-injection (PWRI) are:
383 It reduces PW disposal
384 It is an environmental friendly technique as it reduces fresh-water consumption
385 This lower fresh-water consumption implies economic advantages
386 It helps to meet new regulations regarding disposal
387 The general specifications for acceptable quality of oil-field PW for re-injection are less
388 than 10 mg L-1 of TSS and less than 42 mg L-1 of O&G [35]. It is especially crucial to
389 prevent the presence of sand and other solids in the re-injected stream, in order to avoid
390 plugging and pumps damage.
391
392 4.3. Irrigation Reuse
393 Finally, new trends in oil and gas industry are moving towards the reutilization of PW for
394 downstream beneficial uses such as irrigation, livestock watering, aquifer storage,
395 municipal and other industrial uses, in order to contribute to the sustainability of water
396 resources and to complement the actual demand.
397 Focusing on irrigation, despite the fact that in average about 21% of the total amount of
398 withdrawn water is used in agriculture in Europe, in its Southern countries, the share of
399 total water used by agricultural activities can be higher than 50% (e.g. in Spain is ca.
400 60% according to AQUASTAT reports) [32]. In the United States, irrigation also
401 represents the majority of fresh water use. Estimations made in 2000 accounted a 70%
402 of total water consumption in the Western US for irrigation. In this area, 64% of the water
403 used comes from surface water sources, while nationally is 59% [32].
404 Irrigation requires both large water volumes and high-water quality. Parameters such as
405 the sodium adsorption ratio (SAR) or the electrical conductivity (ECw, dS m-1) are
406 important criteria for ensuring that the water quality will not damage the crops. When the
407 source water has a high salinity, there is a greater potential for salt damage at lower SAR
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408 levels. Given the saline nature of PW with high sodium content, the SAR and ECw are
409 both important parameters to monitor before reuse.
410 In general, the following constituents and parameters are followed for crops health and
411 have to be kept within certain limits [32]:
412 pH normal range 6.58.4
413 Chloride < 70 mg L-1 generally safe for all plants
414 Nitrate < 10 mg L-1 nitrate nitrogen (NO3-N), 45 mg L-1 nitrate (NO3).
415 Boron is another important parameter to consider. The Food and Agriculture
416 Organization recommends different boron concentration for various types of crops [32].
417 According to the US-EPA guidelines for water reuse for irrigation (2012), the water quality
418 for irrigation for public areas and agricultural irrigation, for food crops that will not be
419 commercially processed, or any crop to be eaten raw is: pH 6-9, 10 mg L-1 biological
420 oxygen demand (BOD), 2 NTU turbidity, no detectable fecal coliforms/100 mL and at
421 least 1 mg L-1 residual chlorine. The water quality for irrigation of restricted access areas
422 and agricultural irrigation for food crops that will be commercially processed, or non-food
423 crops and pastures is: pH 6-9, 30 mg L-1 BOD, 30 mg L-1 TSS, 200 fecal
424 coliforms/100 mL and at least 1 mg L-1 residual chlorine [33].
425 In Europe, there is not yet a Directive defining requirements for water reuse. However,
426 some European countries have set limits for certain water reuse applications. E.g., in
427 Spain the normative that regulates water reuse is the Royal Decree 1620/2007. The
428 quality required varies according to the use, the highest quality is demanded for urban
429 residential use, aquifer recharge by direct injection, crop irrigation that are going to be
430 eaten raw, and cooling towers. Concerning reuse for irrigation, the following maximum
431 acceptable values have been set by this Decree: irrigation of crops that are going to be
432 eaten raw: intestinal nematodes 1egg/100 ml, Escherichia coli 100 CFU/100 ml, 20 mg
433 L-1 TSS, 10 NTU; irrigation of crops that are not going to be eaten raw: intestinal
434 nematodes 1egg/100 ml, Escherichia coli 1000 CFU/100 ml, 35 mg L-1 TSS, no limit on
435 turbidity; other irrigation uses: 1egg/100 ml, Escherichia coli 10000 CFU/100 ml, 35 mg
436 L-1 TSS, no limit on turbidity [34].
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437 According to these regulations, in the case of reusing polished PW, the main parameters
438 to be taken into account would be BOD, turbidity, pH and salinity content. However O&G
439 concentration, or the presence of harmful or toxic substances have also to be
440 considered.
441
442
443 5. Produced Water management
444 Among many different technology choices available, selection of a management option
445 for PW varies according to different factors such as chemical and physical properties of
446 the water, flow rate of water generated, end-use, regulations, technical and economic
447 feasibility, etc.
448 Water management technologies and pollution prevention strategies can be organized
449 into this hierarchy regarding environmental preferences:
450 (1) Minimization
451 (2) Recycle / Re-use
452 (3) Disposal (when water cannot be managed through minimization, re-use, or
453 recycle).
454 Examples of technologies and practices for each group are shown in Tables 3, 4 and 5.
455
456 Table 3. Water Minimization Technologies [2]
Approach Technology
Produced Water
Reduce the volume of water Mechanical blocking devices (e.g., packers, plugs,
entering the wells cement jobs).
Water shut-off chemicals (e.g., polymer gels).
Reduce the volume of water Dual completion wells (downhole water sink).
managed at the surface by Sea floor separation modules.
remote separation
Flowback Water*
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Use less water in frac fluids Substitute other materials, like CO2 or nitrogen in place
of water as main ingredient in frac fluids.
Use of gelled frac fluids instead of slickwater fluids.
457 * Mixture of fracking fluid and formation water
458
459 Table 4. Water Re-Use and Recycle Management Options [2]
Management option Use

Produced Water
Re-injection for enhanced Steam flood for oil sands.
recovery
Injection for future water use Aquifer storage and recovery
Injection for hydrological Subsidence control
purposes
Agricultural use Irrigation.
Livestock and wildlife watering.
Managed/ constructed wetlands.
Industrial use Oil and gas industry application.
Power plants.
Other (vehicle wash, fire-fighting, dust control on gravel
road).
Treat to drinking water quality Use for drinking water.
Other domestic uses.
Flowback Water
Use flowback water for future frac Use after settling, filtration, or other basic treatment
fluids step.
Use after more advanced treatment steps.
460
461 Table 5. Water Disposal Methods [2]
Practices
Discharge
Underground injection (other than for enhanced recovery)
Evaporation
Offsite commercial disposal
462
463
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464 6. Conventional Treatments of PW
465 Currently, the majority of PW generated worldwide at onshore facilities is reinjected into
466 the soil, either for disposal or for enhanced oil recovery processes. As the final
467 disposition of the water determines the type and extent of treatment [2], the treatment
468 facilities in onshore oil and gas production operations are mostly designed to remove
469 dispersed O&G and suspended solids, to avoid plugging and pumps damage. In offshore
470 operations, because the common practice is to discharge the treated PW to the sea, the
471 main treatment objective is to reduce O&G to acceptable levels and mitigate toxicity
472 impacts on aquatic fauna and flora. This normally implies to reduce O&G concentrations
473 in treated PW to 30-40 mg L-1, depending on the location [42, 5].
474 In the case of oil extraction, the raw oil stream is treated for its dewatering in a treatment
475 train as it is shown in Figure 2. The first stage of the separation system consists of two
476 (or three)-phase separators, like API separators (designed according to the standards
477 published by the American Petroleum Institute), coalescers, etc. In these devices, an oil
478 rich stream (that will go to the Oil Treatment System, which will be further dewatered and
479 purified), a water rich stream (that will go to the Water Treatment System), and a gas
480 stream are generated [39]. Water extracted from further Oil Treatment is also sent to the
481 Water Treatment System. The sum of those two streams is submitted to a primary
482 treatment (hydrocyclone, corrugated plate separator, API separator, or similar) followed
483 by a secondary treatment, usually a floater. The combination of these conventional
484 technologies are, in most cases, unable to produce an effluent that is compatible with
485 standards for beneficial reuse in irrigation or industrial processes, for example [42].
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486
487 Figure 2. Produced water treatment system, (modified from [39])
488
489 7. Polishing Treatments of PW
490 Considering the limit of 30 mg L-1 of O&G according to discharge legislation, and
491 especially if the PW is to be destined to reuse (irrigation, livestock watering, aquifer
492 storage, municipal and other industrial uses) the train of treatment shown in the previous
493 section is not sufficient, and in most cases it is necessary a tertiary water treatment or a
494 polishing treatment for the reduction of O&G content, and other concerning substances.
495 In 1995 the American Petroleum Institute made its recommendation on the Best
496 Available Technology for Produced Water Management on Offshore Gas and Oil
497 Installations [43] to treat this kind of effluents. According to that report, the factors that
498 contribute to the toxicity of PW, on which polishing treatment should be focused, are:
499 micro and nanoscale particles, salinity (9% or greater), volatile compounds, extractable
500 organics (acidic, basic, and neutral), ammonia and hydrogen sulfide.
501 The treatment methods assessed by API to reduce the pollutants in PW to almost
502 undetectable levels are based on combinations of different technologies: Carbon
503 Adsorption (modular granular activated carbon systems), Air stripping (packed tower with
504 air bubbling through the PW stream), Membrane Filtration (nanofiltration and reverse
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505 osmosis polymeric membranes), Ultra-violet light (irradiation by UV lamps), Chemical
506 Oxidation (ozone and/or hydrogen peroxide oxidation) and Biological Treatment (aerobic
507 system with fixed film biotower or suspended growth) [43].
508 Since 1995, PW treatments have been renewed and enhanced. In this section several
509 physical, chemical, biological methods and combined technologies, for PW, and other
510 Oil & Gas industries related effluents, polishing treatment, are being discussed. Among
511 chemical treatments, a special emphasis will be given to Advanced Oxidation
512 technologies due to the advantages offered by these processes (as it will be seen in
513 section 7.6). However, it should be noted that, once again, treatment processes depend
514 on the characteristics of PW and therefore, characterization studies PW are required for
515 the design of a treatment process, and to solely rely on literature is not recommended
516 [44].
517
518 7.1. Physical Treatment
519
520 7.1.1. Adsorption
521 According to Daigle (2012), adsorption is one of the treatments that can achieve higher
522 water qualities, since adsorption is able to retain pollutants to an extent of final effluents
523 with concentrations of ppb and lower [31]. The costs of installation and maintenance of
524 adsorption systems are the main drawbacks of this technology, and only restringing
525 and/or high added value situations justify their installation. However, there are also
526 economical adsorption media, such as walnut shell, that can be used to make adsorption
527 process more competitive.
528 The main limitations of these methods are that suspended particles that can plug
529 adsorbent media, that reduces removal efficiency, and the costs related to the
530 regeneration of the adsorbents and chemical wastes generated [45]. Another important
531 drawback is that pollution is just transferred from one phase to another, and would have
532 to be removed from the solid phase by another treatment as wet oxidation or incineration.
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533 Different adsorbent materials can retain both organic and inorganic compounds. They
534 have been used to remove manganese, iron, TOC, BTEX, oil and more than 80% of
535 heavy metals present in PW [46]. Activated carbon has been proven as capable of
536 removing soluble content, including BTEX. Insoluble free hydrocarbons can also be
537 retained by organoclay, which contribute to the removal of total petroleum hydrocarbons
538 (TPH) and O&G content [47]. Combination of both mentioned adsorbents also proved its
539 efficiency for the removal of TPH [48]. Copolymers can absorb up to oil 85% of oil content
540 of PW [49]. Zeolite pellets, used also as ion-exchange media, were used by Hansen and
541 colleagues (1994) [22] in a fixed bed system to adsorb dissolved organic compounds
542 from produced water. Acid backwash and solvents were used to regenerate zeolites.
543 Also neutralized amine tailored zeolites were used to remove between 70-85% of BTEX
544 from saline PW [50]. From oilfield-PW, an effluent that could be reused for water
545 reinjection, O&G< 2.4 mg L-1 and suspended solids< 2 mg L-1, was obtained by modifying
546 PET fibers from oleophilic to hydrophilic, that interacted with the substances containing
547 carboxylic, alcohol and amine groups [51].
548 Patented Crudersorb technology combined with polymeric resins treated offshore-PW
549 and depleted O&G concentration to less than 29 mg L-1. [52]. This patented media
550 retained suspended and dispersed oil droplets while the polymers adsorbed dissolved
551 hydrocarbons, aliphatic and aromatic carboxylic acids, and phenolic compounds.
552 Surface modification were performed over hydrophilic fiber ball that enabled the removal
553 of O&G of PW from alkaline/surfactant/polymer run-off [53].
554 In a proposed system consisting of two beds of strong acid ion exchange resin in series,
555 oil-free PW could be treated to remove calcium and magnesium. The chemical structure
556 of strong acid cation-exchange resin is sulfonated copolymer of styrene and
557 divinylbenzene. The system worked well with TDS of less than 50000 mg L-1. When the
558 TDS of PW is higher, sodium competes with calcium and magnesium for sites on the
559 resin [54].
560 The combination of bentonite with a certain modified polymer, organoclay and granular
561 activated carbon, was tested by Doyle and colleagues (2000) [48], as packed bed
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562 adsorption columns. Both system shown consistent hydrocarbons removal, together with
563 total petroleum hydrocarbon and O&G reduction to non-detectable levels. BTEX were
564 also reduced.
565 Li and coworkers (2008) [55] studied oil removal from PW in a fixed bed column. The
566 column contained hydrogen silicone oil modified porous ceramics filtration media.
567
568 7.1.2. Cyclones
569 A cyclone, uses centrifugal acceleration to mechanically reduce, or increase, depending
570 on the objectives of the process, the concentration of a dispersed phase (aggregates,
571 particles, droplets, etc.) within a dispersant media. The dispersed phase elements size
572 can range of 5 to 15 m, depending on the design of the cyclone. In the case of PW
573 treatment used cyclones are mainly those designed for liquid/liquid separation, since
574 both dispersate and dispersant are liquids.
575 A three-phase cyclone was designed by Seureau et al. (2013) to be applied on offshore
576 PW. Thanks to its three-phase design, it was able to de-sand and de-oil the treated
577 effluent [57].
578 A double cone air sparged hydrocyclone (DCASH) was designed for PW treatment. This
579 system used air bubbles to enhance removal efficiency of oil droplets [58].
580 Deng and colleagues (2002) [59] proposed crossflow a oilwater separator for polymer
581 flooding. The system consisted of different coalescence and separator sections. Sludge
582 was removed from the bottom and oil and gas was separated from the top. Oil
583 concentration in treated PW fell to less than 100 mg L-1.
584 Van den Broek and colleagues (2013), compared oil removal efficiencies of different de-
585 oiling systems [60]. Their rankings with respect to the performance of three physical
586 separators were: centrifuges, hydrocyclones, and plate separators. However, they also
587 concluded that these systems have a low removal efficiency and they could not remove
588 dissolved hazardous components.
589
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590 7.1.3. Enhanced flotation
591 Flotation process is used on conventional treatment trains. However, microbubbles-
592 enhanced flotation processes can be considered also suitable for PW polishing as it has
593 been able to remove small size droplets of oil, even emulsified [61]. These technologies
594 consist of four basic steps: (1) air bubble generation; (2) contact between gas bubble
595 and oil droplets; (3) attachment of gas bubbles to oil droplets; (4) ascent of air-oil
596 combination [65], given that this aggregate is significantly less dense than water itself.
597 These steps result into the formation of foam on the surface of the water which is
598 skimmed off [66], while the clarified water is collected at the bottom of the flotation zone.
599 In the case of Dissolved Air Flotation (DAF), air is dissolved into the influent stream at
600 high pressure inside a saturator. When saturated water is released within the flotation
601 chamber, microbubbles emerge due to the pressure gradient between the saturator and
602 the atmosphere. The bubbles tend to attach to the particles (solid or liquid), which
603 increase their buoyancy or diminish the density of the aggregate, and make them rise to
604 the surface [62]. A previous coagulationflocculation can be carried out in order to
605 increase efficiency [63]. PW usually contains natural and added surfactants, thus oils
606 become emulsified and tend to stay in the aqueous phase, which complicates the
607 treatment by flotation processes of this type of water. Another characteristic of PW that
608 can also negatively affect flotation is its high salinity, since density, dynamic viscosity
609 and surface tension are higher for high concentration of soluble species. An additional
610 fact that may hinder flotation is the lower solubility of air in this kind of matrix [64].
611 In dissolved gas flotation units (DGF), as the air in the case of DAF, mixtures of CO2/air
612 is introduced into the flotation chamber solubilized inside a recirculation stream, which is
613 injected through diffusers. The pressure difference between the solubilized stream and
614 the flotation chamber generates the quick desolubilization of the gas in the shape of tiny
615 microbubbles (size ranges from 50 down to 1 m or less). In the case of induced gas
616 flotation (IGF), the bubbles are generated by the direct injection of the gas inside the
617 flotation chamber. Bubble sizes tend to be bigger for IGF than in DAF, which could
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618 slightly decrease the efficiency of the process, given that flotation is more effective as
619 smaller the gas bubbles are compared to particle or droplet size.
620 O&G can be removed by mentioned flotation technologies, together with natural organic
621 matter, volatile organics and small particles from PW, without the use of any chemical
622 rather than coagulants in the cases when enhancement is required. However the
623 disposal of the sludge generated in this process has to be also considered as it could
624 imply a significant operation cost [66].
625 Gas flotation has been reported to remove particles as small as 25 mm and can even
626 remove contaminants up to 3 mm in size if coagulation is added as pre-treatment, but it
627 cannot remove soluble oil constituents from water [45].
628 Lab scale ferric chloride coagulation combined with organoclay adsorption was
629 investigated by Younker and Walsh (2014) as DAF pretreatment for the elimination of
630 naphthalene and dispersed oil from PW [47].
631 The EPCON compact floatation unit (CFU) (from Schlumberger Limited) is a commercial
632 three-phase separator based on a vertical vessel that combines centrifugal acceleration
633 and gas-flotation. Nevertheless, Epcon reports efficiencies for dispersed oil between 50
634 70% [56].
635 A novel process that used glass microspheres of low density instead of air microbubbles
636 has also been studied in simulated PW [67, 68]. Microspheres, that replace DAF of DGF
637 microbubbles, are added into the system during the rapid mix stage (coagulation phase),
638 and then are incorporated into the flotation chamber to drive the buoyance process. With
639 this process, high O&G removal percentages were achieved (up to 90% of elimination).
640 Furthermore, the use of microspheres entailed the advantage of saving the energy
641 required to operate a conventional DAF unit, related to air dissolution and injection [68].
642
643 7.2. Biological treatment
644 Microbial biodegradation is known to be an effective treatment to remove different kind
645 of compounds, including petroleum hydrocarbons, such as those present on PW.
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646 In biological oxidation, dissolved organics and ammonia are converted into water and
647 CO2, and nitrates/nitrites, respectively, by microorganisms such as bacteria, algae, fungi,
648 and protozoa. However their effect on TDS depletion is very limited [69]. The leading
649 mechanisms on biological oxidation of hydrocarbons are biodegradation and
650 bioflocculation. On biodegradation bacteria decompose hydrocarbon into smaller
651 molecules while using the released chemical energy for their metabolism. The
652 bioxidation of simple organic components, e.g., alkanes, is easier than that of complex
653 and large molecules [70]. Nevertheless, bacteria secrete natural surface-active
654 compounds that pseudo-enhance hydrocarbon solubility. This entails the improvement
655 of mass transfer within the media, which may accelerate biodegradation. Bioflocculation
656 takes place mainly in the presence of suspended sludge. Flocs adsorb and block soluble
657 and insoluble materials within its own matrix. This contributes to its removal by the
658 mechanical separation of those flocs.
659 According to Tellez and colleagues (2002), the efficiency of TPH removal of 98-99% can
660 be achieved by an activated sludge treatment unit with solids retention time (SRT) of 20
661 days [40].
662 Freires group (2001) studied the treatment of different mixtures of PW and sewage in a
663 sequence batch reactor, SBR, with acclimated sewage sludge. In 45% and 35% (v/v)
664 mixtures of PW and sewage, COD removal efficiencies varied from 30% to 50% [71].
665 Regarding salinity, this same work found that it did not have significant effect on COD
666 removal of mixed wastewater. Only the recalcitrant character of the PW seemed to hinder
667 the biodegradation [71]. Other sources corroborates the low effect of salinity. For
668 instance, TOC elimination removal was studied with 180 mg L-1 NaCl acclimated
669 microorganisms [72]. SBR, trickling filters and chemostat reactors treated PW. It was
670 observed that PW containing around 200 g L-1 TDS was still biodegradable. It also was
671 obtained despite that SBR long term operation was not stable, biomass was gradually
672 lost and TOC depletion worsened.
673 However, for higher salinity concentration, according to Tellez and colleagues (2002)
674 when salinity increased to 100000 mg L-1, the biodegradation rate fell dramatically [40].
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675 For hardly treatable influents, immobilization of microorganisms can increase treatment
676 efficiency. Li and colleagues (2005) experiments removed more than 90% COD from
677 oilfield PW with initial COD value of 2600 mg L-1. Bacillus sp. was immobilized on
678 polyvinyl alcohol (PVA) [76]. Also positive results were obtained for PVA immobilization
679 of B350M and B350 commercial microorganisms in the shape of a biological aerated
680 filter, BAF, with hydraulic retention time (HRT) of 4 hours and a volumetric load of 1.07
681 kg COD/ (m3 day-1) [77]. That biological aerated filter, BAF, removed 78% of TOC and
682 94% of oil.
683 BAF seemed to be able to remove organics, therefore COD, BOD, but also ammonia,
684 and other nitrogen compounds, iron, manganese, heavy metals, and hydrogen sulfide.
685 However as BAF retains solids, high concentrations of salts can decrease the biological
686 activity of the system due to salt toxicity effects caused by accumulation [45].
687 Also rotating biological disks were able to remove BOD and O&G up to 94% and 74%,
688 respectively [78].
689 Lagoons have been as well studied for PW treatment, like Beyer and colleagues (1979),
690 who studied a two-stage pilot lagoon [78]. They essayed a primary tank to oxidize the
691 suspended oil and dissolved organic compounds, and a second one to oxidize dissolved
692 ammonia compounds. A single-stage biological oxidation was used somewhere else for
693 removing ammonia and phenols from PW [69]. Free water surface (FWS) and
694 subsurface flow (SSF) pilot lagoons were tested for oilfield PW. COD elimination was
695 higher for SSF than for FWS wetlands. However, despite its cost-effectiveness the
696 temperature dependence of these systems can be detrimental. In addition, groundwater
697 contamination is a risk when lagoons are poorly lined and protected.
698 Also, reed beds has been tested for hydrocarbon and heavy metals removal. For
699 instance, 800 m2 of Phragmites Australis pond treated 20 m3 day-1 of PW, and depleted
700 more than 98% of hydrocarbons [81]. A 3000 m3 reed bed system reduced 96% of total
701 hydrocarbon content, while metal concentration decreased between 78% and 40%
702 depending on the particular specie [82]. These kind of systems are environmental
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703 friendly and can be considered cost-effective method, however the final effluents still
704 need certain polishing and they entail an important footprint.
705 Anaerobic degradation could be considered also a cost-effective alternative to biological
706 oxidation in those cases of organics concentrated PW [79]. Simulated PW based on
707 organic acids, especially naphthenic acid, was treated by anaerobic processes by
708 Gallagher and colleagues (2012) [80]. Results shown that certain organic acids were
709 depleted, nevertheless no degradation of naphthenic acids was obtained.
710
711 7.3. Membrane treatment
712 Microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO)
713 membrane can also be applied [83]. There are several advantages of applying
714 membrane separation to this field, such as the high quality of the obtained permeate,
715 their small footprint and its ease of operation. Also generates low quantities of sludge
716 and little chemicals and energy are required, both aspects contribute to the moderate
717 capital costs of this technology [84]. However, like in other areas, fouling is the main
718 disadvantage of this technology. It entails higher pressure requirements during operation
719 and chemical cleanings for its prevention. A fouled membrane has lower productivity,
720 lower selectivity, lower flux and even its lifetime can be drastically reduced. Furthermore,
721 once again, pollution is not really removed but transferred from one stream to another,
722 as organic content is concentrated in the rejection stream.
723 On PW treatment, different kind of membranes has been tested, from those made of
724 polymeric materials to the inorganic ones. Different pore sizes have also been used,
725 microfiltration (MF) membranes have the biggest pore, followed by the smaller
726 ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO) membranes. From lower
727 to higher effluent quality, membranes can be arranged as follows RO>NF>UF>MF,
728 however this order is also related to higher energy consumption, linked to operational
729 transmembrane pressures, 5200 kPa for MF and UF, up to 7500 kPa for RO. It is
730 commonly assumed that NF is the best option to balance quality and energy costs.
731
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732 7.3.1. Polymeric membranes
733 Polymeric membranes, mainly made of polyacrylonitrile (PAN) and Polyvinylidene
734 fluoride (PVDF), are able to retain particles, and emulsified and dispersed oil, with an
735 efficiency for dead-end and cross-flow operations between 85% and 100%, respectively.
736 Their life cycle is approximately 7 years, and they are cheaper than inorganic
737 membranes [45]. However, they are susceptible to thermal harms at temperatures above
738 50 C, and more sensitive to cleaning products [84].
739 A pretreatment process may be necessary prior to membrane separation due to the fact
740 that volatile and low molecular weight compounds cannot be separated by these
741 membranes. This pretreatment could also prevent the fouling due to oil, inorganic scaling
742 or bacteria, that otherwise may require daily cleaning [84].
743
744 7.3.2. Inorganic membranes
745 Thermal and chemical stability of inorganic membranes, usually based on ceramic
746 materials, are generally better than that of polymeric membranes. They have been also
747 investigated for PW separation, and has been especially useful for reducing total
748 suspended solids and suspended oil. For these fractions, ceramic membranes showed
749 higher yields than their counterparts [13].
750 The main drawbacks of this kind of membranes are its relative high capital cost, together
751 with the high energy required for the cross-flow recycle rates needed for fouling
752 management, which contribute to operating costs [13].
753
754 7.3.3. Microfiltration/ultrafiltration
755 While microfiltration membranes separate suspended solids, and reduce turbidity (pore
756 size 0.13 mm), ultrafiltration ones, with pore sizes between 0.01 and 0.1 mm, remove
757 color, odor, viruses and colloidal organic matter [44, 86], but also retain oil in a higher
758 extent that traditional separation methods [87]. Comparing both sizes, UF showed more
759 efficiency on hydrocarbons, suspended solids and dissolved constituent removals [88].
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760 Zhong and colleagues (2003) developed a generation of ceramic MF membrane
761 composed of zirconia (ZrO2) to treat PW that contained maximum oil concentrations of
762 200 mg L-1, that was first treated by flocculation and then passed through an MF
763 membrane at an applied pressure of 105 Pa [89]. The concentration of oil was reduced
764 to 8.7 mg L-1, and treated PW satisfied Chinese national discharge standards.
765 Using flocculation as a pre-treatment step for a MF membrane, less fouling occurs and
766 the removal efficiency for O&G is increased 95.6%. Also, by integrating UF with MF
767 membranes removal of suspended foulants is achieved and the flux recovery increases
768 61% [90].
769 Asatekin and Mayes modified UF membranes by incorporating an amphiphilic copolymer
770 additive, polyacrylonitrile-graft-poly (ethylene oxide) (PAN-g-PEO), for PW treatment
771 [91]. During their experiments, 96% of the dispersed and free oils were successfully
772 removed, which implied higher efficiency than PAN-UF commercial membranes, for
773 which the removal rate of COD is only 41-44%.
774
775 7.3.4. Reverse osmosis and nanofiltration
776 RO is able to remove smaller contaminants than the rest of membranes, and high-quality
777 influents are obtained. Their life expectancy is between 3 to 7 years. However membrane
778 fouling and scaling is especially critical in this process, together with high pressure
779 requirements, and capital costs [45, 92].
780 Despite the fact that early trials of treating PW with reverse osmosis were unsuccessful,
781 due mainly to the lack of pretreatment and integration [93], more recent experiments in
782 PW effluents from Bakersfield, California achieved better results [94]. Other authors
783 bench-scale studies indicated that successful RO membrane processes for oilfield PW
784 would require an appropriate pre-treatment for fouling prevention to not compromise the
785 integrity of the membrane [85, 95].
786 NF, with higher pore size than RO, is been used as a robust technology for water
787 softening and metals removal (pore size as small as 0.001 mm) [45]. In PW, this
788 membranes have been employed also on both bench and pilot scales [45, 94, 95].
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789 Mondal and Wickramasinghe studied the effectiveness of NF and RO membranes for
790 the treatment of oilfield PW [85]. Results showed a minimal improvement with RO when
791 compared to the effectiveness of NF treatment of the same feed water. This indicated
792 that these membranes, which require lower operating pressures (4105 to 2106 Pa),
793 could be a cheaper and a suitable alternative for PW treatment.
794 Ebrahimi and colleagues (2010) tested TiO2/TiO2 (1000 Da) and TiO2/Al2O3 (750 Da)
795 ceramic NF membranes to treat PW containing a TOC content of 292 mg L-1 and 2.6 mg
796 L-1 of oil, as a post-treatment in a combined system of membranes [90]. These tubular
797 NF membranes completely removed the oil and reduced the TOC content by 49.8% at a
798 low applied pressure (105 Pa). During these experiments, the permeate flux average for
799 the NF membranes was 123 L m-2 h-1 bar for 10 mg L-1 of oil at 60 C.
800
801 7.4. Thermal Technologies
802 These technologies are especially suited for regions where energy cost is relatively low,
803 and usually is related to oil extracting countries.
804 Main representatives of these technologies that can be applied to PW are evaporation,
805 multistage flash (MSF) distillation, vapour compression distillation (VCD) and multieffect
806 distillation (MED), which can be combined for higher efficiency [96]. Their main
807 advantage is their tolerance to PW high salinity concentration.
808
809 7.4.1. Evaporation
810 It has been proposed for treating saline wastewater containing oil components in different
811 distributions such as vertical tube, falling film, and vapor compression evaporation [97].
812 Its robustness enables the avoidance of physical and chemical pretreatment, and it
813 requires less maintenance than other technologies. Furthermore, this technology
814 reduces waste volumes.
815
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816 7.4.2. Multistage flash
817 Multistage flash (MSF) distillation process is a mature and robust technology for brackish
818 and sea water desalination. The evaporation of water is produced by a decrease in the
819 pressure instead of heating. The percentage of recovery of water is around 20%. The
820 remaining concentration of TDS (2-10 mg L-1) often makes necessary to include a post-
821 treatment [46]. An important drawback is also the formation of scale on surfaces, it
822 makes necessary the use of acid solutions or scale inhibitors [99]. Energy requirements
823 ranges from 21 to 25 Wh L-1, what makes it a relatively cost-effective process.
824 Nevertheless, the market has been limited due to the availability of membrane
825 technologies, less energy consuming and easier to operate [100].
826
827 7.4.3. Multieffect distillation
828 Multieffect distillation (MED) process can also be used for seawater desalination and PW
829 treatment. It is based on the application of multiple stages of evaporation of part of the
830 water load, minimizing the energy consumption by increasing the efficiency of the
831 process.
832 Depending on the design of the evaporator, the recovery of water ranges from 20 to 67%
833 [101]. Nevertheless, and as in the previous case, the scale formation in old designs has
834 prevented a more widespread use. This problem has tried to be overcome by the use of
835 falling film evaporators [96].
836 MED is considered a suitable technology for PW treatment with high TDS content [45,
837 96]. To avoid scaling, scale inhibitors and acid dosing may be required, as pH control is
838 essential to prevent corrosion. Energy consumption in MED processes ranges from 1.3
839 to 1.9 kWh bbl-1 (8 to 12 Wh L-1) [100].
840
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841 7.4.4. Vapour compression distillation (VCD)
842 In this case, vapour generated in the evaporation chamber is compressed thermally or
843 mechanically, which raises the temperature and pressure of the vapour. The heat of
844 condensation is returned to the evaporator and utilized as a heat source.
845 VCD is a reliable and efficient desalination process and can operate at temperatures
846 below 70 C, which reduces scale formation problems [102]. Energy consumption of a
847 VCD plant is significantly lower than that of MED and MSF. The overall cost of operation
848 depends on various factors, including water origin, zero liquid discharge (ZLD) target,
849 plant size, materials and site location. Cogeneration of low-pressure steam can
850 significantly reduce the overall cost [45]. The VCD process is used to treat PW and RO
851 concentrate (i.e., brine concentrator application) in a near-zero liquid discharge
852 application. To achieve it, the VCD system can work as a crystallizer [7].
853
854 7.4.5. Freeze-thaw/evaporation
855 This technology uses the principle of solubility dependence of temperature, and couples
856 evaporation with freezing. Constituents in the PW usually have lower freezing point than
857 pure water. When PW is cooled below 0C pure crystals of solvent are obtained and a
858 not frozen concentrated solutions (brine). The brines density is greater than that of the
859 ice, and the purified ice and brine are easily separated. Coupling the natural processes
860 of freezing and evaporation makes this technology an effective and economic method.
861 The process can remove 90% of total recoverable petroleum hydrocarbons, TSS, TDS,
862 volatile organic compounds, semi-volatile organic compounds and heavy metals present
863 in PW. But it has several limitations like the requirements of sub-zero ambient
864 temperatures and large footprint [98].
865
866 7.4.6. Hybrid Multieffect distillationvapour compression
867 Hybrid MEDVCD has been recently used to treat PW. This system increases production
868 and energy efficiency. This new technology would replace the older MSF plants [45]. It
869 has advantages over other conventional PW treatment methods, such as the reduction
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870 in chemical doses, overall cost, storage, fouling severity, handling, softer sludge and
871 other waste stream. More than 16 PW evaporators have been installed in Canada, and
872 more are expected to be installed in other regions of the world [103]. The life expectancy
873 of PW evaporators is 30 years [45].
874 ENTROPIE/SIDEM (Veolia) installs MEDVCD systems which ensure, they claim, the
875 high purity of treated PW (<2 mg L-1 TDS). This systems allow their direct use in industrial
876 applications, with or without minor polishing. These industrial applications include the
877 production of boiler feed water, process water and water for closed loop cooling systems
878 for many industries.
879
880 7.5. Chemical Treatment
881
882 7.5.1. Chemical precipitation
883 For the treatment of PW, different coagulants like modified hot lime, FMA (a mixed metal
884 polymer), Spillsorb, calcite and ferric ions have been used [63].
885 In the modified hot lime process, PW containing 2000 mg L-1 hardness, 500 mg L-1 SS,
886 10000 mg L-1 TDS, and 200 mg L-1 oil could be successfully converted to feed-water
887 quality for a steam generator [104]. In this process, alkali consumption and sludge
888 production could be reduced by 50% in comparison with conventional hot lime.
889 FMA is an inorganic mixed metal (Fe, Mg, and Al) polynuclear polymer. This compound
890 was useful in PW with high SS levels because of its properties of de-oiling, coagulation,
891 and scale inhibition. SS and oil were removed to levels between 92% and 97%,
892 respectively [105]. Houcine (2013) used Spillsorb, calcite, and lime to remove heavy
893 metals from PW. Results showed that lime removal efficiency is greater (>95%) than
894 other salts, and that it was an economical chemical [106]. In a study for the treatment of
895 oil and gas fields PW, ferric ion, as oxidant, and flocculants were used in the removal of
896 hydrocarbons, arsenic, and mercury [107].
897 Despite these results, coagulation and flocculation can be used to remove suspended
898 and colloidal particles, but seemed not to be effective for removing dissolved
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899 components. Furthermore, the increased concentration of metals, potentially toxic, in the
900 formed sludge, coming from the coagulant, can also be another drawback of chemical
901 precipitation technology.
902
903 7.5.2. Electrochemical processes
904 Based on the enhancement of chemical reactions that imply the generation or use of
905 electricity, electrochemistry is a relatively cheap green technology, compared to other
906 current treatments applied to PW. It does not generate secondary wastes, nor requires
907 the use of additional chemicals, and offers improved beneficial uses of PW.
908 For a high quality final effluent, a good option for PW treatment could be the integration
909 between even an electrochemical process unit and some of abovementioned chemical
910 processes, to achieve clean water production, storage of energy and recovery of
911 valuable metals from oilfield PW [1].
912
913 7.5.2.1. Electrodialysis (ED)
914 Most dissolved salts contained in PW are ionic. These ions are attracted to electrodes
915 with an opposite electric charge. In ED, membranes are arranged alternately and placed
916 between a pair of electrodes, allowing either cations or anions (but not both) to pass. A
917 spacer sheet is placed between each pair of membranes permitting feed water to flow
918 along the face of the membranes. Positively charged ions (e.g. Na+) migrate to the
919 cathode and negatively charged ions (e.g. Cl-) migrate to the anode. During migration,
920 the charged ions are rejected by similarly charged ion exchange membranes. Hence,
921 ions are concentrated in every second cell (concentrate), whereas the ions of the
922 neighboring cells are removed (dilute). By supplying and draining connections at the cell
923 frame, the dilute and concentrate flow can be pumped through the cells of the membrane
924 stack. ED was applied with positive results to the PW from a conventional well in Wind
925 River Basin of Wyoming, which contained H2S, oil, organic acids, BTEX, dissolved solids,
926 etc. [108].
927
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928 7.5.2.2. Other electrochemical technologies
929 The combination of electrochemistry with the effect of light or the presence of catalyzers
930 has also been proven as a suitable way of PW treatment [109].
931 Li and colleagues (2006) showed that COD removal efficiencies by photoelectrocatalysis
932 of synthetic PW were much higher than its removal by photocatalysis and
933 electrochemical oxidation separately [109]. In another study, again, Li and colleagues
934 (2007) reported that photoelectrocatalysis exhibited a superior capability to reduce
935 genotoxicity than photocatalysis [110].
936 Photoelectrolysis of PW generates hydrogen, which can be utilized in a fuel cell to
937 produce clean water, which upon further treatment can be converted into drinking water.
938 The future application of fuel cell technology in the treatment of PW commercially will be
939 possible after cost reductions, efficiency improvement and increased cells life span [111].
940 An electrochemical catalytic plant was applied at pilot scale by Ma and Wang (2006) to
941 eliminate organic substances in oilfield PW, using double anodes with active metal and
942 graphite, iron as the cathode and a noble metal catalyst. They achieved a reduction of
943 90% of COD and BOD in 6 minutes, suspended solids by 99%, Ca2+ content by 22%,
944 corrosion rate by 98% and bacteria (sulfate reducing bacteria and iron bacteria) by 99%
945 in 3 minutes [112].
946 Electrodeposition is a consolidated technology that is extensively used in various fields
947 of electrochemistry, where positively charged metal ions are deposited on the surface of
948 the object connected to the negatively charged electrode (cathode) by the passage of
949 electric current. This process can be used for recovery of metals from PW, Cu, for
950 example [113-115].
951
952 7.5.3. Room temperature ionic liquids
953 McFarlane and colleagues (2005) studied nine different hydrophobic ionic liquids (liquids
954 that contains only ions) in PW remediation by separating its organics [116]. Results
955 showed that certain hydrophobic ionic liquids are effective in the selective removal of
956 particular contaminants in PW, as toluene and 1-nonanol, and yet may be almost
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957 ineffective to other contaminants such as paraffinic organic compounds. However, the
958 low solubility of ionic liquids in aqueous phase limits an extended use of the ionic liquids
959 tested for the removal of water-soluble organic compounds from an aqueous waste
960 stream, as well as the difficulty in solvent regeneration.
961
962 7.5.4. Demulsifiers
963 The use of some surfactants used as production chemicals can induce the stabilization
964 of oil-water emulsions, by reducing the oil-water interfacial tension, and the zeta potential
965 on the surfaces of the oil droplets [117]. The skin surrounding the small droplets in the
966 oilwater emulsion avoids the water droplets from coalescing and the emulsion remains
967 stable. Demulsifiers are surface-active agents that would disrupt the effects of
968 surfactants. They can be used to separate emulsions present in PW. Almarouf and
969 colleagues (2015) developed an effective oilwater separator for the treatment of stable
970 emulsions in PW combining effects of chemical demulsification and oil droplet
971 coalescence, in order to promote the formation of two phases for further separation [118].
972 The presence of solids such as iron sulfides, silts, clay, drilling mud, paraffin, etc.
973 complicates the demulsification process [119].
974
975 7.5.5. Ion Exchange
976 The ion exchange process can remove arsenic, heavy metals, nitrates, radium, salts,
977 uranium, and other elements from the PW. Ion exchange resins can be made by either
978 naturally occurring inorganic zeolites or synthetically produced organic resins. Ion
979 exchangers exchange cations or anions present in the water by similarly charged ions
980 present within the resin [120]. Ion exchange has been applied in several industrial
981 applications, including the treatment of coal bed methane PW [121]. Resins can be
982 especially suitable in the elimination of monovalent and divalent ions and metals present
983 in PW [121]. According to Nadav (1999), ion exchange has the capacity to remove boron
984 from RO permeate of PW [122]. Ion exchange technology has a lifetime of approximately
985 8 years and requires pretreatment for solid removal, as well as the use of chemicals for
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986 resin regeneration and disinfection. The cost of operation represents more than 70% of
987 the total costs of this technology [45].
988
989 7.5.6. Macro-porous polymer extraction technology.
990 Macro-porous polymer extraction (MPPE) is deemed as one of the best available
991 technologies and best environmental practices for PW management [123]. It can reduce
992 the toxic content of PW. It consists on a liquidliquid extraction that uses macro-porous
993 polymer particles to immobilize the extractive phase. Dispersed and dissolved
994 hydrocarbons are removed by the immobilized extractive liquid. The processes work
995 generally with two columns working alternating extraction and regeneration [123].
996 Polymers were initially designed for absorbing oil from water but later were applied to
997 PW treatment in 1991 [124]. The first commercial MPPE unit offshore was installed in
998 the North Sea. MPPE achieved 99% removal of BTEX, and a removal efficiency of 95
999 99% for aliphatic compounds below C20, and total aliphatic removal efficiency of 91
1000 95% [125].
1001 Pretreatment through flotation processes or hydrocyclones, is required before the PW
1002 passes through the MPPE unit. Nevertheless, in gas/condensate PW streams pre-
1003 treatment is not necessary. From those streams MPPE can eliminate aliphatics, as well
1004 as BTEX and PAHs [126].
1005 Statoil ASA carried out a comparison between different treatments technologies and
1006 found that the MPPE technology had the highest Environmental Impact Factor reduction,
1007 approximately 84% [127]. The main drawback of this technology is its relatively high cost
1008 per unit.
1009
1010 7.5.7. Advanced Oxidation Processes (AOPs)
1011 These technologies include a number of different processes such as O3+H2O2, UV+H2O2,
1012 UV+O3, O3+UV+TiO2, UV+O3+H2O, Fenton reaction and Photo-Fenton reaction. In
1013 addition, there are also non-conventional AOPs such as wet air oxidation and humid
1014 oxidation with peroxide.
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1015 Chemical oxidation is a well-known and consistent technology for the removal of color,
1016 odor, COD, BOD, organics and some inorganic compounds from PW. In the case of
1017 AOPs, they all share a common objective: to generate powerful oxidizing radicals, mainly
1018 hydroxyl. This radical have a high reduction potential (E0 = 2.8 V), greater than ozone,
1019 hydrogen peroxide, chlorine or oxygen, and react rapidly and non-selectively with nearly
1020 all electron-rich organic compounds. Hydroxyl radicals crack down large molecular
1021 weight dissolved organic molecules to smaller ones, and they are even able to
1022 completely mineralize them [128-130]. When this extent is not achieved, shorter
1023 molecules can still be further removed easily by, for instance, a biological process or
1024 other processes such as activated carbon adsorption. Moreover, AOPs have been
1025 successfully used to reduce the concentrations of toxic organic compounds that inhibit
1026 biological treatment processes [42].
1027 The AOPs can be classified as homogeneous and heterogeneous processes according
1028 to Huang and colleagues (1993) [131], while Domnech and coworkers (2004)
1029 classified it according to the presence or absence of light [132]. Table 6 shows a
1030 classification of AOPs according to these authors.
1031 Table 6. Classification of AOPs [131, 132]
Non-photochemical Photochemical
Homogeneous processes
Ozonation in alkaline media (O3/HO) Photolysis of water under vacuum
Ozonation with hydrogen peroxide ultraviolet (VUV)
(O3/H2O2) UV
Fenton (Fe2+ or Fe3+/ H2O2) UV/ O3
Electro-oxidation UV/ O3/ H2O2
Electrohydraulic discharge - ultrasound Photo-Fenton (Fe2+ or Fe3+/ H2O2/UV)
Wet air oxidation (WAO)
Supercritical water oxidation (SCWO)
Heterogeneous processes
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Catalytic wet air oxidation (CWAO) Heterogeneous photocatalysis:
Catalytic wet hydrogen peroxide ZnO/UV, SnO2/UV, TiO2/UV,
oxidation (CWHPO) TiO2/H2O2/UV
Catalytic ozonation Photocatalytic ozonation
1032
1033
1034 Some advantages of the AOPs are the complete mineralization of recalcitrant
1035 compounds, in opposition to conventional water treatment methods such as flotation,
1036 filtration and adsorption with active coal, which are non-destructive physical separation
1037 processes that transfer pollutants to other phases, thus producing concentrated wastes
1038 [133]. Other advantage is that time required for treatment can be very short depending
1039 on water characteristics (i.e. minutes). Specifically, Catalytic Wet Air Oxidation, presents
1040 significant advantages over other technologies to remove organic compounds. It can
1041 treat high loaded inlet (>50000 mg L-1 COD) with different organic compounds with
1042 conversions >99%. Only air is required as a reactant, and no by-products are obtained,
1043 it operates at moderate pressure and temperature conditions, and the catalyst lifetime is
1044 >2 years [131].
1045 Generally, the application of these processes is recommended only to wastewaters with
1046 a content of COD below 5 g L-1, as a higher COD will need a high consumption of
1047 reagents [128]. Therefore, for the treatment of PW with high organic load, pretreatment
1048 operations, like dilution, coagulation and flocculation, etc., are needed to achieve a
1049 reduction of the initial load [134]. Optimization of reagents and energy consumption, and
1050 minimization of reaction time are critical aspects to be taken into account for PW
1051 applications.
1052
1053 7.6. Advanced Oxidation processes for PW treatment.
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1054 As these technologies are considered promising for this kind of effluents, and based on
1055 the references found on this regard [128-130, 133], it was considered necessary to
1056 create a separate section to describe its application on oil and gas industry waters.
1057
1058 7.6.1. H2O2 and H2O2/UV
1059 Hydrogen peroxide (H2O2) is a strong oxidant that can directly react with organic
1060 compounds. H2O2 becomes even more effective when it is used in combination with other
1061 energy or reagents, capable of dissociate peroxide into hydroxyl radical, which will act
1062 as oxidizing agents. For example, under UV irradiation shorter than 300 nm, H2O2 can
1063 decompose and generate radicals. The advantages of using this combination, H2O2/UV
1064 process, are the water solubility of H2O2, there is no mass transfer limitation, it is an
1065 effective source of HO, and there is no need for a separation process after treatment
1066 [136].
1067 Stepnowski and coworkers (2002) carried out the degradation of oil refinery wastewater
1068 after a pretreatment of flotation and coagulation, using H2O2 in the presence and in the
1069 absence of UV radiation, and was compared to PW treatment [137]. They analyzed TPH,
1070 dichloromethane (DCM), 1,2-dichloroethane (DCE) and methyl tert-butyl ether (MTBE).
1071 In total 83% DCM was removed with 11.76 mM of H2O2 using UV radiation, while the
1072 degradation of the TPH was slow, since it was removed a 69% of the total initial
1073 concentration in 8 days. The MTBE degradation was comparable to that of DCE and
1074 after 24 h there was total removal.
1075 Philippopoulos and Poulopoulos (2003) studied the application of the H2O2/UV process
1076 for the polishing of oily wastewater from a lubricant-producing plant. Using a high
1077 concentration of H2O2, most of the compounds identified in the wastewater were
1078 eliminated [138]. Nevertheless, the initial COD of the wastewater was reduced by only
1079 40% (resulting in 9000 mg L-1). The cause of this could be the formation of organic acids,
1080 generated from the decomposition of organic compounds present in the wastewater,
1081 which are more recalcitrant to photo-degradation with H2O2.
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1082 It was also observed that higher concentrations of H2O2 increase the degradation rate of
1083 contaminants, up to a maximum value, after which it begins for very high H2O2 levels.
1084 Lpez and coworkers (2000) attributed this decrease in the H2O2/UV process yield to
1085 hydroxyl radicals reacting with excess H2O2, i.e. scavenging, instead of reacting with the
1086 organic substrates [135].
1087
1088 7.6.2. Fenton and Photo-Fenton processes
1089 The classic Fenton reaction inferred by Haber and Weiss (1934) consists of an aqueous
1090 combination of hydrogen peroxide (H2O2) and ferrous ions (Fe2+), in acidic medium
1091 (optimum pH in Fentons reaction is ca. 3), which leads to the decomposition of H2O2 into
1092 a hydroxyl ion and a hydroxyl radical, and the oxidation of Fe2+ to Fe3+, as represented
1093 by Equation 1 [139]:
1094 2 + + 22 3 + + . + (1)
1095 As shown by Walling and Weill (1974), the Fe3+ produced in Equation 1 can react with
1096 H2O2 present in the medium, and be reduced back to Fe2+, also generating the
1097 hydroperoxyl radical, according to Equation 2 [140]. This reaction, known as Fenton-like
1098 reaction [137], occurs more slowly than reaction 1 [141]. The Fe3+ ions also react with
1099 the HO2 and are reduced to Fe2+, as shown in Equation 3
1100 3 + + 22 []2 + + + 2 + + 2. (2)
1101 3 + + 2. 2 + + 2 + + (3)
1102 The ratio between the concentration of ferrous and hydrogen peroxide ions is crucial for
1103 the development of the Fenton reaction. When a high concentration of Fe2+ ions with
1104 respect to H2O2 is used, the hydroxyl radicals generated in Equation 1 may react with
1105 excess Fe2+ (according to Equation 4), decreasing then the availability of hydroxyl
1106 radicals to react with the organic substrates [142].
1107 2 + + . 3 + + (4)
1108 When all the Fe2+ present in the medium is oxidized to Fe3+, the generation of hydroxyl
1109 radicals is interrupted and, consequently, the degradation of organic compounds. Fe3+
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1110 ions can form stable complexes with the degradation products (mainly the organic acids)
1111 present in the medium, which impairs the regeneration of Fe2+ [143, 144].
1112 According to Pignatello (1992), UV-Visible radiation strongly accelerates the degradation
1113 rate of organic pollutants by the Fenton process [130]. Under these conditions, the
1114 photolysis of Fe3+ complexes enables regeneration of Fe2+, and the occurrence of
1115 Fentons reaction, if H2O2 is available, as shown by Equation 5.
1116 ()2 + + h 2 + + . (5)
1117 Regenerated ferrous ions can react again with the H2O2 in solution to produce more
1118 hydroxyl radicals, promoting a photocatalytic cycle in the Fe2+/Fe3+ system. This reduces
1119 significantly the concentration of ferrous ions required, compared with the dark Fenton
1120 reaction [145].
1121 Main disadvantages of Fenton and related technologies could be the requirement of a
1122 low pH, and the necessity to remove iron as sludge after the reaction. Furthermore, some
1123 substances such as Cl, SO42, H2PO4/HPO42, which can be present in PW, may
1124 interfere with the reaction mechanism inhibiting the degradation process [146, 147].
1125 Safarzadeh-Amiri and coworkers (1997) investigated the UV-visible photolysis of
1126 ferrioxalate, an organic Fe (III) complex, with the addition of H2O2 to degrade BTEX, 1,4-
1127 dioxane, methyl tert-butyl ether, formaldehyde and formic acid, being some of them
1128 present in PW [148]. The results indicated that the UV-visible/ferrioxalate/H2O2 process
1129 has a higher energy efficiency than the UV-visible/Fe(II)/H2O2 process or the UV/H2O2
1130 process, resulting thus in lower treatment costs.
1131 The photo-Fenton process was also used by Moraes and coworkers (2004) for the
1132 degradation of the hydrocarbons contained in synthetic PW, simulated with gasoline in
1133 saline wastewater [149]. Results showed that in the presence of NaCl, total pollutant
1134 degradation did not occur. A possible reason could be the reaction of Fe3+ ions with Cl
1135 ions, forming FeCl2+ complexes, which, in the presence of UV radiation, may produce
1136 Cl2 radicals, with lower oxidation potential than the HO radicals, that decreases the
1137 efficacy of the process.
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1138 Mota and coworkers (2005) studied the photo-Fenton process in degrading phenol,
1139 present in PW, using black light lamps as UV-A radiation source [150]. Degradation
1140 achieved by the photo-Fenton was twice higher than by the Fenton process. The
1141 elimination of phenol increased with the intensity of the radiation source, due to the fact
1142 that the regeneration of Fe2+ ion rate grew, with the consequent increase in the
1143 generation of hydroxyl radicals.
1144 Tiburtius and coworkers (2005) investigated the degradation of a solution containing
1145 benzene, toluene and xylenes (BTX) and also water contaminated with gasoline
1146 (containing 25% ethanol), when applying Fenton and photo-Fenton processes [151].
1147 Total hydrocarbons present in gasoline-contaminated water were degraded in a 75%,
1148 the BTX were rapidly degraded, and intermediate phenolic compounds formed in the
1149 initial phase of the reaction were completely degraded after 30 min.
1150 Application of photo-Fenton process to water containing diesel oil to optimize the dose
1151 of reagents was also studied elsewhere. With Fe2+ ion concentrations of 0.1 mM (below
1152 the maximum discharge limit permitted by the Brazilian law, 0.27 mM), a 99%
1153 degradation of TOC was achieved [152].
1154 The performance of different AOPs for the degradation of acid water effluents from oil
1155 refineries was studied by Coelho and colleagues (2006). This effluent was composed by
1156 emulsified oil, slowly biodegradable compounds and toxic substances (such as phenols,
1157 sulfides, mercaptans, ammonias, cyanides). All processes, except Fenton and photo-
1158 Fenton, did not lead to satisfactory results. With Fenton process, only 27% of initial
1159 dissolved organic carbon DOC) was removed. However, the combination of these two
1160 techniques, operated in a continuous mode, reduced the initial DOC by 94%. The BTEX
1161 present were removed too to non-detectable levels. The disadvantages were the high
1162 concentrations of reagents used, therefore optimization is necessary [153].
1163 Fentons reagent yield was evaluated in the mineralization of organic compounds present
1164 in water contaminated by crude petroleum. Up to 75% TOC removal was achieved when
1165 high H2O2 (20%) and low Fe2+ (1mM) concentrations were used [154].
1166
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1167 7.6.3. Ozone (O3)
1168 In an ozonation process, both direct and indirect oxidation reactions take place; O3 can
1169 react slowly and directly with an organic substrate due its high reduction potential (2.07
1170 V) [156], but it can be also characterized as an AOP when it decomposes to generate
1171 hydroxyl radicals (indirect reaction) (Equation 6).
1172 23 + 22O 2. + 2 + 22. (6)
1173 The combination of ozone with H2O2, UV radiation or ultrasound improves degrading
1174 organic compounds efficiency [155].
1175 A main disadvantage of the use of O3 in the wastewater treatment is the cost; O3 is an
1176 expensive oxidant since requires energy to be generated [156, 157]. Furthermore, the
1177 efficiency of O3 depends on the gas-liquid mass transfer, which is hindered by the low
1178 solubility of O3 in aqueous solution [158], even lower in the case of PW due to salinity.
1179 Another drawback in the particular case of PW could be the possible foam formation by
1180 the bubbling of the gas inside the liquid effluent, which may contain natural and artificial
1181 surfactants.
1182 Morrow and colleagues (1999) proposed the use of ozonation to degrade water soluble
1183 organics in PW [159]. The process produced a water effluent with markedly reduced
1184 O&G content. The obtained effluent could be used as a drinking or irrigation water supply
1185 source and could be safely discharged into navigable waters. Several combinations for
1186 the treatment of soluble organics in synthetic and real PW were studied also elsewhere,
1187 using sonochemical oxidation and ozone [160]. While sonochemical oxidation could
1188 destroy some compounds such as BTEX, the combination of ozone and hydrogen
1189 peroxide over a pH range of 3-11 did not improve the oxidation of organics to CO2, but
1190 UV light, when used in combination with ozone, increased the destruction of BTEX.
1191
1192 7.6.4. Heterogeneous Photocatalysis
1193 Heterogeneous photocatalysis is a process in which two phases, solid and liquid, are
1194 present. The solid phase is a catalyst, usually a semiconductor (CdS, TiO2, ZnO, WO3,
1195 etc.). When the semiconductor is illuminated with light of greater energy than that of the
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1196 band gap, an electron e is promoted from the valence band (VB) to the conduction band
1197 (CB), leaving a positive hole, h+, in the VB and an electron in the CB. The hole itself has
1198 great potential to oxidize organic species directly when they are adsorbed to the surface
1199 of the catalyst, or indirectly via the generation of hydroxyl and superoxide radicals,
1200 promoted by the interaction of holes with water and oxygen in aqueous solution [161]. In
1201 the case of TiO2, a very commonly used photocatalyst, it absorbs radiation in the near
1202 UV light (<387 nm), which enables the use of sunlight to generate eh+ pairs [162].
1203 Bessa and coworkers (2001), studied the treatment of oilfield PW via a photocatalytic
1204 process using TiO2/UV, with the addition of H2O2. It was found a considerable reduction
1205 in the concentration of targeted components. The use of H2O2 in the photocatalytic
1206 process was dispensable, undesirable indeed, due to the corrosive effects of this
1207 substance to the catalysts [163].
1208 The degradation of MTBE (methyl tert-butyl ether, a gasoline additive) by photocatalysis
1209 was also studied elsewhere [164]. Higher degradation rate with Ag/TiO2/UV than with
1210 TiO2/UV was obtained. Maximum MTBE removal obtained was around 80%.
1211 Saien and Nejati (2007) degraded the aliphatic and aromatic fraction of a refinery
1212 wastewater using the TiO2/UV process [165]. TiO2 was added to the air saturated
1213 wastewater samples which were irradiated with an immersed mercury UV lamp (400 W,
1214 200-550 nm). Optimal values for catalyst concentration, fluid pH and temperature were
1215 obtained: 100 mg L-1, 3 and 318K, respectively. A maximum reduction in chemical
1216 oxygen demand of more than 90% was achieved after about 4 h irradiation and hence,
1217 73% after about only 90 min. The increase of TiO2 concentration decreased the rate of
1218 degradation, probably due to the increase in the turbidity of the solution, with the
1219 consequent reduction of light transmission.
1220
1221 7.6.5. Electrochemical Oxidation
1222 In these processes, the hydroxyl radicals can be produced by two pathways: anodic
1223 oxidation (direct form) and mediated electrooxidation (indirect form). The direct oxidation
1224 takes place at the anode itself (e.g. Pt, PbO2, doped with SnO2, etc.). In indirect oxidation,
49
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1225 strong oxidants, such as radicals, are produced at the anode, where chemical oxidation
1226 takes place. Meanwhile, chemical species, such as H2O2, are continuously formed in the
1227 cathode by the reduction of dissolved oxygen. This hydrogen peroxide can act as a
1228 reagent for Fentons system by adding iron to the system, therefore more hydroxyl
1229 radicals are formed. This Fenton process, by which the H2O2 is electrochemically
1230 generated, is called the electro-Fenton process [166]. The introduction of ultraviolet
1231 radiation helps reducing Fe3+ to Fe2+, increasing the oxidation efficiency of the system
1232 [167].
1233 Yavuz and Koparal (2006) investigated the degradation of a phenol-containing refinery
1234 wastewater (192.2 mg L-1 phenol, 590 mg L-1 of COD), via electrochemical oxidation,
1235 using a titanium electrode coated with titanium oxide and ruthenium oxide. They obtained
1236 a 94.5% removal of phenol and 70.1% of COD [168].
1237 Santos and coworkers (2006) employed dimensionally stable anodes in the electro-
1238 remediation of PW and refining wastewater. They claimed that removal of COD was
1239 favored by temperature. At a current density of 100 mA cm-2, the most efficient COD
1240 reduction was achieved at 50 C, which reached 40% after 12 h, and 57% after 70 h,
1241 removing up to 57% of initial COD from the wastewater. This reduction could be
1242 attributed to electrooxidation/electrodegradation and also to electrofloatation of oil
1243 droplets in suspension that aggregate on the surface thanks to the gas formed in the
1244 cathode (H2) and in the anode (O2 and Cl2) [169].
1245
1246 7.6.6. Wet Air Oxidation and Supercritical Water Oxidation
1247 Wet air oxidation causes the oxidation of pollutants under high pressure (106 2.2107
1248 Pa) and temperatures (150-370C) conditions. They lead to the generation of hydroxyl
1249 radicals through dissolved oxygen reactions [134]. The efficiency of this technique can
1250 be improved by the addition of homogeneous (such as Cu2+ salts) and heterogeneous
1251 (MnO2, CuO, Fe2O3 etc.) catalysts [133], which is known as catalytic wet air oxidation
1252 (CWAO).
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1253 Supercritical water oxidation (SCWO) involves the homogeneous oxidation above the
1254 critical point of water (374C and 22.12 MPa). Supercritical water is a very good solvent
1255 for organic substances and is completely miscible with gases like oxygen and carbon
1256 dioxide. Thus, oxidation of organic pollutants under supercritical water conditions occurs
1257 in a homogeneous single phase and takes place rapidly without interfacial mass transfer
1258 limitations. This technique obtains rapid results, but has high operational costs due to its
1259 high energy demand.
1260 Sun and coworkers (2008) studied a microwave (MW)-assisted CWAO (Catalytic Wet
1261 Air Oxidation) process at lower temperature (150C). Oxygen was supplied into the
1262 system at 0.8106 Pa pressure to treat a heavily contaminated petroleum wastewater
1263 from the oil refining industry. The MW-CWAO experiments were carried out with granular
1264 activated carbon (GAC) (5 wt. %) as catalyst. The results showed more than 90% of
1265 COD removal, and an increase in the biodegradability (measured as BOD5/COD ratio)
1266 from 0.04 to 0.47 within 30 min. This indicated a significant enhancement of the
1267 biodegradability of the solution, which would help in a further polishing biotreatment of
1268 petroleum wastewater [170].
1269
1270 7.7. Combined Systems
1271 The majority of the treatments described previously are suitable for certain groups of
1272 components, but other may be refractory or even inconvenient to them. This states that
1273 in many cases there is the need for a combination of different types of treatments for a
1274 major efficiency in the treatment of the PW. For example, if only membranes are used
1275 as treatment of PW, critical or irreversible fouling may occur because this wastewater
1276 contains oils, solids and bacteria. Thus, some pretreatments are required before the use
1277 of membranes [171]. An acidification pretreatment would serve to remove low molecular
1278 weight organic and inorganic substances such as boron before the use of a RO process.
1279 Also, some post treatment processes may also be needed after the RO process to meet
1280 the requirements [172], such as softening, etc.
51
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1281 Lee and Frankiewicz (2013) suggested the use of cyclones, before using hydrophilic UF
1282 membrane separation, as pretreatment process for reducing the content of oil and solids
1283 to less than 50 mg L-1 and 15 mg L-1; by this way, the membrane permeability could be
1284 extended for longer time. To reduce fouling potential, a hydrocyclone and a cyclone were
1285 used to remove fine oil-coated solids and to decrease O&G concentrations in the PW
1286 upstream [173].
1287 Some experiments were also carried out elsewhere to treat PW for irrigation quality
1288 standards [174]. Taking into account the oil and salt content sorption pellets made of a
1289 modified clay material (organoclay PS12385), and RO units for the separation of salts
1290 were proposed. It was obtained that sorption packed bed could separate more than 90%
1291 of the oil and the loading capacity of clay pellets was better than the activated carbon
1292 (more than 60%). TDS was separated in a 95% by the RO membrane, which allowed to
1293 recover up to 90% permeate. Two membranes used in series seemed to redeem the
1294 same results than in parallel disposition [174].
1295 A method of treating oilfield PW containing boron and solubilized hydrocarbon
1296 compounds was patented to reduce boron concentration bellow 2 mg L-1 [175]. It
1297 comprises water softening to remove substantially all divalent cations, raising the pH of
1298 the liquid above 9.5, and driving the liquid through a RO membrane.
1299 A pilot plant (see Figure 3), including flotation, sand filtration and UF membrane, was
1300 used to treat PW for discharge or injection into an oil-well. The content of suspended
1301 solid and oil was reduced to less than 1.0 mg L-1 and 0.5 mg L-1, respectively. Fe and
1302 bacteria concentrations also achieved the required standard for injection and discharging
1303 purposes [171].
1304
52
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1305 Figure 3. Proposed process for the treatment of the oilfield wastewater (PAC (polyaluminium
1306 chloride) and PAM (polyacrylamide)) [171]
1307
1308 akmakci and colleagues (2008) applied dissolved air flotation, acid cracking,
1309 coagulation and precipitation, cartridge filters, microfiltration and ultrafiltration as pre-
1310 treatment processes, and nanofiltration and RO to decrease the salt content [176].
1311 In a pilot study undertook to reuse oilfield PW for irrigation and potable purposes, a set
1312 of processes were proposed (see Figure 4). Silica level was reduced down to 3 mg L-1
1313 by adding 400 mg L-1 MgCl2. Hardness, TDS, boron and ammonia were removed up to
1314 96%, 95%, 90% and 80%, respectively [177].
1315
1316
1317 Figure 4. Pilot plant scheme for the treatment of oilfield PW [177]
1318
1319 Another configuration included wash tanks, dissolved gas flotation, walnut shell filtration,
1320 warm lime softening, membrane bioreactor and RO, to reach potable and irrigation water
1321 standards [178].
1322 Doran and coworkers (2013) combined warm precipitate softening at pH 9.7, cooling,
1323 fixed-film biological organics oxidation, pressure filtration, ion-exchange softening and
1324 RO to treat PW [179].
53
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1325 A pilot-scale hybrid RO process was intended to treat PW for irrigation or discharge to
1326 surface waters. After the treatment, the conductivity was decreased in a 98% and TDS
1327 by 96%, being therefore in compliance with the criteria for irrigation or discharge to
1328 surface waters [172].
1329
1330 7.8. Commercial Treatment Processes for Produced Water
1331 7.8.1. CDM technology
1332 CDM Smith Inc. commercializes a technology to treat high TDS coal bed methane PW
1333 through a combination of an ion exchange process, RO and evaporation. They have
1334 incorporated also a disinfection step with UV radiation to lessen the bacterial activity.
1335 The total cost of treatment of PW was found to be $ 0.30 per barrel. When pretreatment
1336 processes were included, membrane fouling was reduced and water recovery oscillated
1337 from 50% to 90% [8].
1338
1339 7.8.2. Veolia: OPUSTM
1340 This treatment is designed to remove soluble inorganic compounds, such as SiO2,
1341 CaSO4, and Mg(OH)2, organics, and boron [180]. The Optimized Pre-treatment and
1342 Separation Technology, OPUS, consists on the application of multiple treatment
1343 processes, involving degasification, chemical softening by Multiflo (a patented filtration
1344 system), media filtration, ion exchange softening, cartridge filtration and reverse osmosis
1345 technologies. The pretreatment processes after RO are designed to reduce hardness,
1346 metals content and suspended solids of the influent in order to reduce the scaling
1347 potential on the RO membranes.
1348
1349 7.8.3. Eco-sphere Inc.: OzonixTM
1350 OzonixTM consists of a patented AOP, which saturates contaminated water with ozone,
1351 using hydrodynamic and acoustic cavitation, and electrochemical oxidation. As water
1352 flows through the OzonixTM Reactor, bacteria cell walls are damaged and pollutants are
1353 oxidized, producing clean water that is ready for re-use, without generation of harmful
54
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1354 disinfection byproducts [181]. OzonixTM is primarily used for the treatment of fracking
1355 flow-back water, but it could also be used for PW treatment. The contaminated water is
1356 mixed with supersaturated ozonized water in a reaction vessel. Hydroxyl radicals
1357 generated from ozone decomposition oxidize metals, soluble and insoluble organic
1358 compounds and microorganisms. The whole process includes also electroprecipitation
1359 of hard salts, activated carbon cartridge filter and a RO membrane. Water recovery
1360 approaches 75% [45].
1361
1362 7.8.4. EMIT: Higgins Loop
1363 EMIT Higgins Loop technology is reported to be used for coal bed natural gas (CBNG)
1364 PW treatment. EMIT ensures that Higgins Loop CCIX technology, based on ion
1365 exchange resins, can economically and efficiently treat this type of effluent. It reduces
1366 sodium and bicarbonate content. They claim that the system removes sodium from the
1367 PW and concentrate it into a dense brine solution byproduct that may even be useful
1368 within the oil and gas industry. Sodium abstraction from the water drops its pH balance
1369 and decreases bicarbonate levels by removing carbon dioxide gas from the water.
1370 Product water recovery normally surpasses 99% [183].
1371
1372 7.8.5. Drake: Continuous selective IX process
1373 The Drake system is a three-phase, continuous fluidized bed system to remove
1374 monovalent cations by ion exchange (IX) with a strong acid resin. Energy requirements
1375 are slightly lower than those needed for the EMIT Higgins Loop system. The maximum
1376 product water recovery is described to be 97% [45].
1377
1378 7.8.6. Eco-Tech: Recoflo compressed-bed IX process
1379 The Eco-Tech compressed bed systems are presented as an evolution of conventional
1380 packed bed IX processes. They have different systems, containing e.g. two different
1381 compressed-bed columns for anion and cation removal, or three separate compressed-
1382 bed columns with a primary cation bed, an anion bed and a third polishing cation bed.
55
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1383 Recoflo systems are mainly used for recovering metals [8]. Recoflo ion exchange
1384 technology utilizes fine mesh resin beads, a fully packed resin bed, and counter-current
1385 regeneration. These distinctive characteristics are intended to help to improve exchange
1386 kinetics, diminish regenerate consumption, and rise the concentration of strip solutions.
1387 Eco-Tech claims to redeem results of a 40% salt reduction and 80% less regeneration
1388 wastes compared with conventional softeners treating an equivalent quality and quantity
1389 of water, as they do not need acid and caustic regeneration reagents. These systems
1390 are entitles to be easy to operate, modular and automatable [184].
1391
1392 7.8.7. Altela Inc.: RainSM Dewvaporation
1393 Dewvaporation is a desalination technology whose operation principle is based on the
1394 production of distilled water by countercurrent heat exchange [185]. Feed water is
1395 evaporated in one chamber and condensed on the opposite chamber of a heat transfer
1396 wall as distilled water. Approximately 100 bbl d-1 (15900 L d-1) of PW, with salt
1397 concentration as high as 60000 mg L-1 TDS, can be handled by this system. High removal
1398 rates of heavy metals, organics and radionuclides from PW have also been reported for
1399 this technology. In one plant, chloride concentration was reported to be reduced from
1400 25300 to 59 mg L-1, TDS from 41700 to 106 mg L-1 and benzene concentration from 450
1401 mg L-1 to non-detectable levels.
1402 According to Altela Inc., energy requirements of this system are low because it runs at
1403 ambient pressures and low temperatures.
1404
1405 7.8.8. Aquasonic Corporation: RSE and RSD
1406 Rapid Spray Evaporation (RSE) system is based on the ejection of contaminated water
1407 at high velocities through a specialized injector-nozzle. The rapid pressure changes
1408 causes the evaporation of the PW.
1409 Rapid Spray Distillation (RSD), is a recently patented process. Pressurized water is
1410 nebulized into a moving hot air stream. Because of the particularly high surface area of
1411 the water droplets, the water vaporizes instantaneously and efficiently.
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1412 This technology is mainly focused on the elimination of inorganic salts of the PW, as in
1413 both processes the water vaporizes within milliseconds, and therefore the solids in the
1414 solution flash and separate out. The water vapor is condensed and collected, while the
1415 precipitated solids form isolated crystalline particles, which are collected through a
1416 vacuum process and sold as a byproduct. AquaSonics claims to achieve nearly 100%
1417 conversion of salt water into fresh water [186].
1418
1419 7.8.9. EARTH Canada Corporation: TORRTM
1420 The Total Oil Remediation and Recovery (TORRTM) technology has been developed by
1421 EARTH Canada Corporation to remove and recover dispersed oil in water. The
1422 technology consists of a multi-stage adsorption step and a separation system. The
1423 Reusable Petroleum Adsorbent (RPA) media, a polyurethane-based material, removes
1424 large and small oil droplets (ranging from 2 m). In the adsorption process, the adsorbent
1425 media continuously adsorbs the oil emulsions, coalescing them, and desorbing them as
1426 larger oil droplets. In the separation chamber, the desorbed oil droplets lift to the top of
1427 the chamber and are recovered [187].
1428
1429 7.8.10. Frac Water Inc.: HEEDTM
1430 This technology has been developed to treat coal bed methane PW from fracturing
1431 treatment for its reuse. The High Efficient Electro-Dialysis, HEED, treatment units can
1432 treat PW with TDS ranging from 11400 to 27000 mg L-1 and sulfates from 4000 to 14000
1433 mg L-1 [188].
1434 Recovery of brackish water with this ED treatment is claimed to be 80-90%. The
1435 company assures that HEEDTM stack configuration required up to 40% less membrane
1436 area, resulting in more than 70% increase in energy efficiency. The product water quality
1437 is supposed to meet the requirements for the basic gel fracturing fluids.
1438 Some disadvantages of this system are the high treatment cost and membrane fouling.
1439 The membranes should be regularly washed or cleaned-in-place with dilute acid and
1440 alkali solutions for restoring performance when needed [45].
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1441
1442 7.8.11. Crystal Solutions, LLC: FTE
1443 Crystal Solutions, LLC, a joint venture of Gas Technology and BC Technologies, uses
1444 Freeze-Thaw/Evaporation, FTE for the treatment of PW. This technology is based in
1445 alternating freeze and melting steps, thus the dissolved solids become concentrated and
1446 fresh water is produced, suitable for various beneficial uses.
1447 By means of this technology, a PW containing 14000 mg L-1 of TDS was concentrated to
1448 a brine flow of approximately 64300 mg L-1 TDS and a fresh water flow of 924 mg L-1
1449 TDS. As for yields obtained, around 55% of the feed turned into melted water; roughly
1450 30% got lost by evaporation and/or sublimation; and only about 15% of the original feed
1451 remained as concentrated brine [98].
1452
1453 7.8.12. BioPetroClean: ACT
1454 Automated Chemostat Treatment (ACT) is a biological wastewater treatment solution.
1455 It is based on maintaining a pre-selected bacterial cocktail for a specified type of
1456 polluted water in a chemostat system. The process is maintained in a homeostatic state
1457 of bacterial growth and organic compound degradation.
1458 This technology uses low concentration of bacterial cells, therefore no aggregates are
1459 formed and each bacterium performs as a single cell. This feature increases the surface
1460 area available for biodegradation, improving the efficiency of the process.
1461 ACT operates as a continuous flow reactor without using activated sludge. The
1462 bioreactor can be used on-site (using the available infrastructure) due to its high flexibility
1463 in process modulation. This decreases the operational and maintenance costs,
1464 according to their marketers [189].
1465
1466 7.8.13. Prosep Inc.: C-TOUR
1467 C-TOUR is based on solvent extraction to remove both dispersed oil and water-soluble
1468 organics through condensate injection into PW streams.
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1469 During the condensate injection, hydrocarbon pollutants are extracted from the PW
1470 stream. Pollutants and injected condensate coalesce to form bigger and lighter oil
1471 droplets. These oil droplets are hydraulically or mechanically separated from the PW
1472 stream and reused in oil process streams.
1473 According to field trials performed with the C-TOUR process, removal efficiency of
1474 dispersed oil, 23 ring PAHs, and NPD was 70%, for C6 phenols it was approximately
1475 60%, and for C4C5 phenols 20% [56].
1476
1477 8. Conclusions
1478 The Oil & Gas industry is considered one of the eight most water-intensive industries
1479 due to the high volumes of water that are required for oil extraction and refining, and the
1480 subsequent amount of wastewater that is generated. Produced water is the aqueous
1481 effluent that is brought to the surface along with oil or gas in extraction operations. It
1482 includes formation water (trapped underground) and injection water that are extracted
1483 together with the fossil fuel during oil and gas production. The volume generated of PW
1484 is quantified up to 39.5 Mm3 day-1 and it contains a wide variety of compounds and a lot
1485 of them are toxic.
1486 Solutions to avoid the environmental impact of this type of wastewater are firstly its
1487 minimization, secondly its reutilization and finally and as a last option, its disposal. In the
1488 last two cases, a previous treatment is required to remove the large variety of toxic
1489 compounds that PW possess, though unfortunately, the legislation only pays attention to
1490 O&G, and not to the rest of present substances. However, lately more attention is being
1491 given to other PW hazardous parameters and components.
1492
1493 Characterization of the PW to determine its major components should be the first step in
1494 an attempt to select the best treatment options. Nevertheless, when measuring O&G on
1495 the effluents, its value depends not only on the chemical composition of the water itself,
1496 but also on the extraction procedure, so it should be a unification in this measure. The
1497 result of such characterization, with the rest of components, will determine if physical
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1498 pre-treatment is needed, if thermal treatment is advisable, if chemical dosing could be
1499 eluded, etc. Therefore, characteristics of the PW together with environmental factors,
1500 economic considerations, and local regulatory framework are needed to select the
1501 optimal option for treatment of PW.
1502 It is also important to consider the concept of zero liquid discharge, which in practice
1503 means the avoidance of additional pollutant stream generation and the minimization of
1504 waste. According to this, the best option after the treatment of PW is its reuse, but there
1505 is not enough legislation in this regard, despite the fact it seems critical to have more
1506 stringent controls and more parameters taken into account.
1507 Regarding PW treatments, there is a wide variety of them, so it is crucial to know what
1508 is required to be eliminated, as most of them are focused on just one kind of
1509 contaminants, and to choose the one which involved less energy and reagents
1510 consumption, and that generates less environmental impacts.
1511 Current thermal technologies are mature but may not be relevant in the future from the
1512 point of view of energy efficiency, unless reductions are made in energy costs.
1513 Membrane technology is another polishing treatment destined fundamentally for the
1514 elimination of salts; however, for future application, progress must be made in order to
1515 reduce membrane fouling, the waste generated and to optimize backwashing. MPPE
1516 technology may well compete also in the future processing of PW. Its potential to achieve
1517 a zero-pollutant discharge and a substantial reduction in energy consumption compared
1518 with thermal technologies is very promising, but further research is needed to reduce its
1519 relatively high cost. By the contrary, a cost-effective technology can be the
1520 electrochemical systems or its combination with other technologies.
1521 AOPs seem also efficient alternatives for the treatment of oil and gas wastewater, since
1522 the hydroxyl radicals can totally or partially degrade most organic compounds, by
1523 producing the complete mineralization of these components or their conversion to more
1524 biodegradable products, for a possible subsequent application of a biological treatment.
1525 Partial or complete mineralization is the main advantage of using AOPs in contrast to
1526 other processes that sometimes lead only to the transfer of contaminants from one phase
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1527 to another. Different AOPs have been studied for the treatment of oil and gas
1528 wastewater, such as photocatalysis, Fenton, photo-Fenton, ozonation, etc. It is important
1529 to imbalance benefits and drawbacks of these technologies, since for instance, Fenton
1530 process could require high doses of reagents, while ozonation or photo-treatments could
1531 imply high energy consumption. Moreover, most of the references in this matter are
1532 related to laboratory scale. Therefore, and in order to minimize costs, an optimization of
1533 the operating conditions with real wastewaters and bigger scales needs to be done.
1534 Currently, there are also in the market some packaged PW treatment technologies;
1535 however, most of these solutions are tailor-made to meet specific treatment needs for
1536 each individual exploitation site, and usually focus on just one group of PW hazardous
1537 components.
1538 Therefore, the solution for PW treatment could be the development of integrated
1539 processes that address the variety of concerning pollutants. These combined
1540 technologies will be studied in subsequent research by the authors. They would involve
1541 for instance a physical treatment aimed to remove the O&G content (e.g. DAF or settling)
1542 followed by membrane ultrafiltration, a chemical treatment (e.g. AOP) to eliminate the
1543 dissolved hazardous organic components and, finally, a reverse osmosis system for salts
1544 elimination.
1545
1546 9. Acknowledgements
1547 This review was carried out in the framework of the Industrial Doctorate Program co-
1548 funded by the Government of Catalonia (2013 DI 037).
1549
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Accepted Manuscript

State of the Art of Produced Water Treatment

S. Jimnez, M.M. Mic, M. Arnaldos, F. Medina, S. Contreras

Reference: CHEM 20161

To appear in: Chemosphere

Received Date: 17 March 2017

Revised Date: 23 October 2017

Accepted Date: 25 October 2017

PW is generated when water from reservoirs is brought to surface in oil extraction.

Composition and final use of PW determines its treatment train.

Combination of treatments are necessary when there is a wide variety of components.

Minimization, disposal and reuse are options for PW.

1 State of the Art of Produced Water Treatment

2 S. Jimnez a,b, M. M. Mic a, M. Arnaldos a, F. Medina b, S. Contreras b,*

4 08820 El Prat de Llobregat, Barcelona, Spain.

7 * Corresponding author. E-mail address: sandra.contreras@urv.cat

23 Commercial treatments, based on the combination, modification and improvement of simpler

24 treatments, were also discussed.

67 7.4.3. Multieffect distillation ..................................................................................................36

110 refining activities -downstream sector-, as it is shown in Figure 1. In both cases,

114 regard to the management of the effluent.

116 Figure 1. Process scheme for the

118 and downstream (b) activities.

128 PW depending on its origin [1].

133 reinforce the growth of the market of PW's management [7].

140 as the well ages.

144 PW is needed according to the requirements of each end-user and applications.

146 2. Sources of Produced Water

150 coal bed methane, tight sands, and gas shale:

158 surface [8, 9].

165 energy for their extraction [10].

169 commercially most important in the Green River [8, 9].

176 in the rest of the world [11].

179 increased the development of compact sand into an economic resource.

187 conventional gas deposits of comparable size [12].

198 The major groups of constituents of concern in PW are:

199 Salts (expressed as salinity, total dissolved solids (TDS), or electrical

201 Oil and Grease (O&G).

202 BTEX (benzene, toluene, ethylbenzene, and xylenes).

203 PAHs (polyaromatic hydrocarbons).

204 Organic acids.

222 summarizes the principal components in PW according to several references.

Component Concentration, Reference Concentration, Reference

Na 0-150000 [14] 132-97000 [15]

Cl 0-250000 [14] 80-200000 [15]

Ba 0-850 [16] 1.3-650 [15]

Sr 0-6250 [16] 0.02-1000 [15]

SO42- 0-15000 [14] 2-1650 [15]

HCO3- 0-15000 [14] 77-3990 [15]

Ca 0-74000 [14] 13-25800 [15]

As 0.005-0.3 [3, 15]

Total Dissolved 100-400000 [14] 6554 [3]

Chemical Oxygen 1220-2600 [3, 15]

Total Suspended 1.2-1000 [3, 15]

Total Organic 0-1500 [3, 15] 0,1-11000 [4]

Total O&G 2-560 [3]

Saturated 17-30 [4]

Total BTEX 0.73-24.1 [17] 0.39-35 [15]

Benzene 0.032-14.97 [17]

Toluene 0.058-5.86 [17]

Ethylbenzene 0.086-0.57 [17]

m-Xylene 0.258-1.29 [17]

p-Xylene 0.074-0.34 [17]