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Overview of Produced Water
(PW) Treatment and
Measurement
Dr. Ming Yang, NEL
NEL Slide 106/12/16
• Introduction
• Overview of PW
• Regulatory Requirements
• PW Treatment Technologies
• PW Composition Measurement
• Summary
Content
06/12/16NEL Slide 206/12/16
NEL – A Business of TÜV SÜD
NEL Slide 306/12/16
• Based in Glasgow, Scotland • 100 staff• National Engineering Laboratory
established 1947• Privatised in 1995
• HQ in Munich• 20000 staff• 800 locations• EUR 2.0 billion
NEL
TÜV SÜD
Energy,
Oil & Gas
Low Carbon
Technologies
Environment
Consultancy
Test & Calibration
Knowledge Transfer
& Training
Research & Development
What Do NEL Do?
16-12-06
Energy,
Oil & Gas
Low Carbon
Technologies
Environment
16-12-06
Facilities – Single Phase and Multiphase Flow
NEL’s PW & OIW Related Activities
NEL Slide 606/12/16
• Conferences and seminars– OIW Monitoring: 11
– PW Management: 17 (13 in Aberdeen, 3 in KL, 1 in Abu Dhabi)
• Clubs – PW Club: from 2003
– OiW Monitoring Club: from 2000
• Training course:– OiW Measurement / PW management
• Consultancy / JIPs
• Testing: PW / OIW / Separation
equipment
PW Club 2014. 20 companies in the Club
Club /
Event
SaltsJIP
Dissol
ved
GasesConsultancy
BTEX
Training Organi
c Acids
Alkyl
Phenol
s
Testing
Support
each other’s
activities
Core group
of people
Grow
overall
business
Grow
individual
business
06/12/16
NEL Slide 706/12/16
Facilities – Produced Water
• Introduction
• Overview of PW
• Regulatory Requirements
• PW Treatment Technologies
• PW Composition Measurement
• Summary
Content
06/12/16NEL Slide 806/12/16
1st Stage HP
Separator2nd Stage
SeparatorWell Fluids
Desalter
Degasser
C
F
U
Filter
EXPORT
OVERBOARD
P.W.R.I
Demulsifier
Deoiler
Wash water
Gas GasOil rich fluid
Produced water
Chemical
Gas
Produced Water / Typical North Sea Process Train
NEL Slide 906/12/16NEL Slide 906/12/16
Formation
Water
Saline formation brines in
the reservoir
Condensation
Water
Water vapour condensing
during production
Returned
injection water
Water injected to boost the
reservoir pressure
Water used for
de-salting
Washing the crude with
clean water and removing
What is PW?
Mill
ions B
bls
per
day
0
50
100
150
200
250
300
350
1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 2014
Total Water Production
Total Oil Production
For every 1 barrel of oil, 4 barrels of Water!
Global Oil and Water Production
NEL Slide 1006/12/16NEL Slide 1006/12/16
Source: OGP Report 2012e (Nov. 2013)
NEL Slide 1106/12/16
Percentage of PW Re-Injected
Potentially Harmful Substances Typically Analysed in the N.S.
NEL Slide 1206/12/16NEL Slide 1206/12/16
Hydrocarbon Chemistry – Common Organics in PW
06/12/16
Source of the table: John Walsh, SPE Webinar presentation, 2015
Aliphatic
Aromatic
Organic acid
Aromatic
Aromatic
Phenol
NEL Slide 1306/12/16
Aromatics Found in PW in the N.S.
Source: OGP Report 324, 2002
Aromatic hydrocarbon concentration range (mg/l) found
in PW from North Oil and Gas fields (1999-2001)
NEL Slide 1406/12/16
Washwater Discharge
Criteria
Phenols Found in PW in Indonesian and N.S.
Phenols in PW (mg/l) from 3 facilities in Indonesian and 5 facilities in the N.S.
Source: OGP Report 364, 2005
NEL Slide 1506/12/16
Organic Acids Found in PW in the N.S.
Source: Utvik, NEL PW Workshop, 2003
Organic acids found in PW from fields operated
by Norsk Hydro (now Statoil) 2002
NEL Slide 1606/12/16
Metal Seawater (µg/l)
Norsk Hydro 2002 (µg/l)
North Sea (µg/l)
Arsenic (As) 1 – 3 0.1 – 51 0.96 – 1.0 Barium (Ba) 3 – 34 400 – 214 000 107 000 – 228 000 Cadmium (Cd) 0.001 – 0.1 0.01 – 0.67 0.45 – 1.0 Chromium (Cr) 0.1 - 0.55 0.01 – 3.62 5 – 34 Copper (Cu) 0.03 - 0.35 0.67 – 8.0 12 - 60 Iron (Fe) 0.008 – 2.0 8 – 3715 4 200 – 11 300 Mercury (Hg) 0.00007 – 0.006 <0.013 – 0.06 0.017 – 2.74 Manganese (Mn) 0.03 - 1.0 1 – 1338 1 - 1338 Nickel (Ni) 0.1 - 1.0 0.02 – 4.46 22 - 176 Lead (Pb) 0.001 – 0.1 0.02 – 2.40 0.4 – 10.2 Zinc (Zn) 0.006 - 0.12 0.3 – 47.2 10 - 340
Metals found in produced water in the N.S.
• Introduction
• Overview of PW
• Regulatory Requirements
• PW Treatment Technologies
• PW Composition Measurement
• Summary
Content
06/12/16NEL Slide 1806/12/16
Discharge Limits (OIW) - Worldwide
NEL Slide 1906/12/16NEL Slide 1906/12/16
Country Discharge limits
Australia 30 average and 50 max
Brazil (Antonio Correa (2012) 29 mg/l monthly average; 42 mg/l daily maximum
Brunei 30 (Horiba single wavelength IR method)
Canada (OWTG 2010) 30 average (30 days rolling), 44 max for 24 hrs
Caspian Sea 20
China (GB4914-2008) Inner sea(<4 sea miles): average<20 mg/l or max<30 mg/l Inner sea(between 4< and 12 sea miles): average<30 mg/l or max<45 mg/l Outer sea: (>12 sea miles) Average<45mg/l or max<65mg/l
USA 29 mg/l monthly average; 42 mg/l daily maximum
Italy 40
Nigeria 20,10, 10 – 20
Trinidad and Tobago 40 Coastal and 80 offshore
Tunisia 10 max
Sultanate of Oman 5 (coastal) (UV/Visible spectroscopy)
OSPAR 30 mg/l (dispersed)
OSPAR - Current Legislative Safeguards
Current Performance Standards Guiding Principles
Dispersed oil: 30mg/l oil in water
Harmonised Mandatory Control
Scheme (HMCS) for use and
discharge of Production
Chemicals, requiring substance
level toxic pre-screening.
Approach to achieve the
Performance Standard involved
the application of :
BAT
BEP
BAT: -“means the latest stage of development (state of the art) of processes, of facilities or of
methods of operation which indicate the practical suitability of a particular measure for limiting
discharges, emissions and waste”.
BEP: -“the application of the most appropriate combination of environmental control measures and
strategies”
06/12/16NEL Slide 2006/12/16
OSPAR - Risk Based Approach (RBA)
Fig. 1 -Risk Based Approach
• OSPAR Recommendation 2012/5,
adopted in 2012
• Objective:
To reach a level of “zero harmful
discharge” from produced water
• The proposal combines:
A Whole Effluent Assessment (WEA)
A EIF: PEC/PNEC
Note: PEC/PNEC on all and every
substances identified in the produced
water.
PNEC
PEC
RBA is in addition to the 30 mg/l performance standard
06/12/16NEL Slide 2106/12/16
• Samples for WET analysis required at time of bi-annual sampling
• Installations should drop out if being decommissioned before 2018
• Installation should drop out of the assessment process if PEC/PNEC ≤ 1
• Dispersion modelling would be required at higher tiers of assessment
• Frequency of repeat testing will be determined once initial testing
completed
• Operators still required to meet 30mg/l and demonstrate BAT/BEP
OSPAR - Risk Based Approach (RBA) – UK Process
06/12/16NEL Slide 2206/12/16
• Introduction
• Overview of PW
• Regulatory Requirements
• PW Treatment Technologies
• PW Composition Measurement
• Summary
Content
06/12/16NEL Slide 2306/12/16
Overview of PW – Examples of PW Discharges in the N.S.
Avg. Flow Rate (m
3/h)
Avg. Flow Rate (m
3/d)
Avg. Flow Rate (bbl/d)
Small gas Platform 0.2 4.8 30.2
Large gas Platform 1.4 33.6 211.3
Oil platform 150 3600 22641.5 Source: OSPAR.Note: Based on 60 installations of which 53 were gas and 7 oil.
Onshore examples:
• PDO Nimr PW: >8333 m3/hr or 200,000 m3/d or (1.3 mmbpd) (Water to Oil Ratio: 7:1!)
• Daqing: 15.2 mmbpd with Water to Oil Ratio: 19:1!)
NEL Slide 2406/12/16
• Oil removal
– Mechanical (gravity, enhanced gravity - hydrocyclone / centrifuge
gas flotation, filtration, membrane, combination…)
– Physical / chemical: extraction, absorption, deoiler / surfactants
– Oxidation: Ozone, catalytic oxidation
– Biological: reed bed, biomass (bacteria eating oil!)
• Salt (dissolved solid - TDS) removal
– Reverse osmosis / electrodialysis
PW Treatment Technologies
06/12/16NEL Slide 2506/12/16
NEL Slide 2606/12/16
PW Treatment Technologies – Summary (Mechanical)
Technology Mini. size droplet removed (μm)
API gravity separator 150 CPI 40
IGF (no flocculant) 25 IGF (with flocculant) 3-5 Hydrocyclone 10-15 Mesh coalesce 5 Media filter 5 Centrifuge 2 Membrane Sub μm even 0.01
Source: Dan Arthur
NEL Slide 2706/12/16
Technology Examples on the Market
Adsorption Zeolite, GAC, MPPE, Osorb
Absorption OPS RM25, Mycelx, Cetco CrudSorb,
Enhydra PS-85
Extraction C-Tour
Chemical Deoiler
PW Treatment Technologies – Summary (Physical & Chemical)
NEL Slide 2806/12/16
PW Treatment Technologies – Summary (Physical & Chemical)
Supplier Cetco ET Ventures Symons CWSL Veolia Mycelx ABS Materials
Technology Abs. Abs.+Ads. Absorption Oxidation Abs. Abs. Abs
Model CruSorp ET#1 OPS RM25 Medium
AquaPurge MPPE Mycelx PW Unit 1
Capacity Up to 2x67 m
3/hr
2.3 m3/hr
(example not the max)
1.3 m3/hr
(example not the max)
Up to 100 m
3/hr
Up to 70 m
3/hr
66 m3/hr 14.3 m
3/hr
Weight 2 tonnes for 2x1.2 m
3/hr;
32.3 tonnes for 67 m
3/hr
n/a 3 tonnes for 2m
3/hr or 5
tonnes for 66 m
3/hr
1.5 tonnes for 1 m
3/hr
or 2 tonnes for 6m
3/hr)
770 kg for 66 m
3/hr
3.4 tonnes (only the treating equipment
Footprint 1.7x2x2.1 for 2x1.2 m
3/hr
or 6.6x3x4 (60 m
3/hr
capacity)
n/a 2x3x? 2x1.5x2 for 2 m
3/hr or
3x1x2 for 66 m
3/hr
capacity
1x1.5x1.7 for 1 m
3/hr
or 1x1.7x2 for 60 m
3/hr
capacity
2.6x0.8x2.4
12.2x6.1
Removal efficiency
90% (from 100 mg/l to 10 mg/l)
99% (from 150 ppm to 1.1 ppm)
94% (from 80-180mg/l to average 5 mg/l with a maximum outlet concentration of 11 ppm
50% - 60 % (from 50 ppm to 20 ppm)
50 to 99% 96% (from 121 to less than 5 ppm)
99.9% (277 ppm to 0.1 ppm)
Applications and field trial
Several offshore, see [58]
Only trial onshore [57]
Several offshore, see [59]
A few field trials offshore and onshroe
Several offshore and onshore, see [60]
Field trial on shore, see [43]
Onshore pilot trial. Lab trials
• More stringent regulations
– North Sea: 40 mg/l → 30 mg/l in 2007
– RBA in the North Sea (no longer just the dispersed oil!)
– Onshore: OiW < 10 mg/l
• Increasing water production (W/O ratio: 4:1 in general) / limitation in
space to add capacity, particularly offshore
• Increasingly more difficult PW due to:
– Chemical EOR such as polymer, ASP flooding etc
• Limitations in traditional technologies
Some of the Key Issues Facing PW Treatment Today
06/12/16NEL Slide 2906/12/16
• Introduction
• Overview of PW
• Regulatory Requirements
• PW Treatment Technologies
• PW Composition Measurement
• Summary
Content
06/12/16NEL Slide 3006/12/16
Total Oil
Dissolved Dispersed
Aromatics Acids AliphaticsAromatics Acids Phenols
BTEX
PAHs
Fatty acids
Naphthenic
Fatty acids
Naphthenic
Dispersed and Dissolved Oil
NPDs
PAHs
BTEX
NEL Slide 3106/12/16
Measurement of PW Compositions
NEL Slide 3206/12/16
Parameters Performance Standard
Measurement Methods Comments
Reference Other Lab Methods Online
OIW Y IR
GC-FID
Gravimetric
Colorimetric
IR
UV Absorbance
UV Fluoresence
Ultrasonic acoustic
Microscopy image analysis
Light scattering
UV Fluorescence / LIF
GC-FID as the reference method. Samples taken twice a day at an equal time interval
BTEX N GC/MS – ISO 11423-1 Detection limit specified
PAH N GC/MS/MS – ISO WD 14653-2 or USA EPA 610 16 PAHs + NPDs
Metals N Induced Coupled Plasma-Atomic Emission Spectrometry (ICP-AES), AAS; Dynamic Reaction Cell Inductively Coupled Plasma Mass Spectroscopy (DRC-ICP-MS), High Resolution Inductively Coupled Plasma Mass Spectroscopy (HR-ICP-MS), Hydride Generation Atomic Absorption Spectroscopy (HG-AAS), or Inductively Coupled Plasma Mass Spectroscopy (ICP-MS); voltammetry may also be used.
For Cd, PB, Zn, Ni, As, Cr and Cu. Detection limits specified
Mercury N ICP-AES or Cold Vapour Atom Absorption Spectroscopy (CV-AAS); voltammetry may also be used.
Detection limits specified
Phenols / Alkyl phenols
N GC/MS Detection limit specified
Organic acids
N GC/MS Formic, acetic, proprionic, butanoic, pentanoic and hexanoic organic acids
Source: https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/286015/Methodology_for_the_Sampling_and_Analysis_of_Produced_Water.docx
Note: Sampling frequency: for OIW - twice a day; all others - biannual
• Introduction
• Overview of PW
• Regulatory Requirements
• PW Treatment Technologies
• PW Composition Measurement
• Summary
Content
06/12/16NEL Slide 3306/12/16
Summary
• Water production is on the increase / discharge of PW is strictly
regulated
• Regulatory requirements tightening (lower OIW discharge limits and
moving towards Risk Based Approach)
• Many treatment technologies for the removal of dispersed and dissolved
• For the N.S., performance standard (discharge limit) is set only for OIW;
but analysis is required for other parameters with results being reported
NEL Slide 3406/12/16
Useful References
• OSPAR, BAT Document: Background Document Concerning
Techniques for the Management of Produced Water from Offshore
Installations. 124 pages, updated version published in 2013http://www.ospar.org/documents/dbase/publications/p00602/p00602_final%20version%20of%20bd%20on%20produced%20water_28-08-12.pdf
• OSPAR Agreement 2014-05: Establishment of a List of Predicted No
Effect Concentrations (PNECs) for Naturally Occurring Substances in
Produced Water. https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/361476/OSPAR_RBA_Predicted_No_Effect_Concentrations__PNECs__Background_Document.pdf
• OSPAR Agreement 2012-7: OSPAR Guidelines in Support of
Recommendation 2012/5 for a Risk-Based Approach to the
Management of Produced Water Discharge from Offshore Installations.
2012. www.ospar.org
• Practical Guidance Document on Whole Effluent Assessment, 2007 http://www.ospar.org/documents/dbase/publications/p00316/p00316_wea%20guidance%20document.pdf
NEL Slide 3506/12/16
Useful References
• OSPAR Agreement 2006-6: Oil in Produced Water Analysis – Guideline
on Criteria for Alternative Method Acceptance and General Guidelines
on Sampling Taking and Handling. www.ospar.org
• UK Government DECC, “Methodology for the Sampling and Analysis of
Produced Water and Other Hydrocarbon Discharges”, Feb 2014. https://www.gov.uk/government/uploads/system/uploads/attachment_data/file/286015/Methodology_for_the_Sampling_and_Analysis_of_Produc
ed_Water.docx
• “Norwegian Oil and Gas Recommended Guidelines for Sampling and
Analysis of Produced Water”, Revision No.: 1, Dec 2012. http://www.norskoljeoggass.no/Global/Retningslinjer/Milj%C3%B8/085%20Norwegian%20oil%20and%20gas%20recommen
ded%20guidelines%20for%20samling%20and%20analysis%20of%20produced%20water,%20rev%201,%2011.12.2012.pdf
• Ming Yang, “Measurement of Oil in Produced Water”, Chapter 2, K. Lee
and J. Neff (eds.), Produced Water, Springer, 2011 (available by google search!)
NEL Slide 3606/12/16
