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IWC 12-52
MPP No. 2012-132/DTM/mt/mk
“Toxic dissolved and dispersed hydrocarbons removal and reuse
in the oil & gas industry, gas/condensate, shale gas produced water,
refinery process water and groundwater with the Macro Porous Polymer Extraction
technology”
DICK TH. MEIJER, VWS MPP Systems / VWS Oil & Gas, Veolia Water Solutions & Technologies, Ede, the Netherlands,
KENNETH SEVERING, Whittier Filtration, Veolia Water Solutions & Technologies, Brea, CA, United States
This paper was presented at the International Water Conference, San Antonio (TX), USA on November 5, 2012
PAPER NUMBER IWC-12-52
KEYWORDS
MPPE, produced water reuse, wastewater reuse, groundwater reuse, dissolved and dispersed hydrocarbons, Zero Harmful Discharge (ZHD), Environmental Impact Factor (EIF), aromatic hydrocarbons, BTEX, Poly Aromatic Hydrocarbons (PAHs).
IWC 12-52
MPP No. 2012-132/DTM/mt/mk 2
ABSTRACT
Environmental legislation worldwide is aiming at a good balance between the extent of environmental protection and spending capital on water treatment systems with the associated carbon footprint. There is a clear trend to move from integral discharge parameters like BOD, COD, AOX etc. to more risk based approaches, like the Environmental Impact Factor introduced in Norway in the beginning of this decade. In risk based approaches a division is made between harmful and non-harmful constituents present in the water. Technologies specifically removing the harmful part are searched for to aim at an optimal balance between capital costs and environmental protection. A real life experience on the disastrous effect of unknown toxic content on the biotreatment confirming the Environmental Impact model will be presented. Macro Porous Polymer Extraction is such a technology that specifically removes the toxic non polar hydrocarbons from water. More than 35 units have been installed in the past years and applied in the various areas of the oil & gas industry. Examples are given of onshore shale gas produced water, refinery process/wastewater, groundwater and offshore gas/condensate produced water on platforms and future floating LNG plants. Constituents that are removed are among others, dissolved and dispersed oil (aliphatics), BTEX, Poly Aromatic Hydrocarbons (PAHs), MTBE, THT (Tetra Hydro Tiophene, an odorant used in natural gas for leak detection). Recently it has been discovered that > 80% of Mercury is removed from produced water raising the possibility to extend scope the technology. Finally the reduction of the Environmental Impact Factor with MPPE will be illustrated versus other technologies.
The Macro Porous Polymer Extraction (MPPE) technology from Veolia Water is able to remove dissolved and dispersed hydrocarbons with 99.9999% if needed. The MPPE technology is basically a liquid/liquid extraction process where the extraction liquid is immobilized in a macro porous polymer. In addition it allows the practically pure separated hydrocarbons to be completely used as a product. No other “waste“ stream is created.
IWC 12-52
MPP No. 2012-132/DTM/mt/mk 3
INTRODUCTION
The Macro Porous Polymer Extraction Technology (MPPE) has been proven in various applications to remove the non-polar generally toxic hydrocarbons from produced, waste and groundwater. This MPPE technology makes it possible to change the discharge regulation policy from generic BOD, COD requirements to one that is more focused on the toxic content of the water to be treated. This will lead to a discharge with constituents basically non harmful to the environment. In addition, where low BOD, COD levels are required, the MPPE technology can be applied to protect the biotreatment against toxic loads. In this paper an introduction to a risk based approach vs. total COD removal is given with subsequent examples validating this alternative approach. Cases are presented in the Oil and Gas industry on Zero Harmful Discharge and on combining the MPPE with biotreatment technologies to fulfill total COD requirements where significant toxic content is present.
REASONS FOR COD AND BOD
REQUIREMENTS FOR WATER DISCHARGE REGULATIONS
Most natural waters contain small quantities of
organic compounds. Aquatic microorganisms have evolved to use some of these compounds as food. Microorganisms living in oxygenated waters use dissolved oxygen to convert the organic compounds into energy for growth and reproduction. Populations of these microorganisms tend to increase in proportion to the amount of food available, when nutrient (N, P and some minerals) concentrations are not limiting. This microbial metabolism creates an oxygen demand proportional to the amount of organic compounds useful as food. Under some circumstances, microbial metabolism can consume dissolved oxygen faster than atmospheric oxygen can dissolve into the water. Fish and aquatic insects may die when oxygen is depleted by microbial metabolism. Especially discharge of (municipal) wastewaters into rivers or lakes may lead to depletion of oxygen as the feed of organic compounds and resulting oxygen demand is higher than the natural atmospheric oxygen input (related to the available surface area between water and air) and the dilution with fresh oxygenated water (related to the flow rate of fresh water).
As the amount of dilution with fresh water is often not controllable the environmental legislation
is aimed at the reduction of BOD and COD discharge to the environment.
REASONS FOR THE EMERGENCE OF RISK BASED APPROACHES TO WATER DISCHARGE
REGULATIONS
Discharge regulations based on BOD and COD for municipal wastewater have been proven effective in practice. For the offshore industry emerging in the seventies in the North Sea these requirements were not feasible and not meaningful. Not feasible as space limitations impede the use of biotreatment systems that are needed to lower BOD or COD levels. Not meaningful as the dilution prevents oxygen depletion.
From the very beginning the discharge regulations for the North Sea were only based on dispersed oil. The aim of this regulation was to reduce the formation of oil sheens on the surface water. The discharge limit was set at < 40 ppm dispersed oil. The discharge limit was mainly based on technical/practical limitations like space, weight and economics. Given these limitations no technologies were available to achieve lower limits.
By the end of the nineties extensive research was carried out by the Norwegian Oil & Gas industry on the toxic and non-toxic constituents of produced water and their effects on the environment. The investigations were probably driven by the Norwegian government dealing with the interests of the fishing industry. It has led to a change in approach of offshore produced water treatment resulting in a focus on the removal of toxic constituents.
THE ENVIRONMENTAL IMPACT FACTOR – A PRACTICAL APPLICATION OF A RISK BASED
APPROACH
The basis of this study consists of a detailed analysis to identify molecules and groups molecules that are toxic and nontoxic. The effect of the toxicity on their natural environment was assessed. This assessment was based on the accessibility of the toxic constituents to the natural organisms in the sea (alga, fish etc.), the biodegradability and the tendency of accumulation in the environment. Mathematical models of the spreading of toxic constituents in the sea were validated by the measurements of the constituents in mussels and other species located at different distances from platforms. For example at distances of 16 km downstream from platforms
MPP No.
higher powere me
Toxic/n
The e
constituefactor waproducedof that paEnvironmof each pconcept developepracticalproduced
GenericImpa
2012-132/DTM
oly aromatic easured in mu
nontoxic part
environmentaent was validas applied to d water to rearticular consmental Impacplatform in itsis a quantitaed to both foc measures od water strea
c chemical coact Factors o
M/mt/mk
hydrocarbonussels.
Table 1. t in offshore p
al impact of eated and a m its concentraflect the envistituent. In thct Factor cous own envirotive managecus the legis
on Zero Harmams (Buller e
Graph 1. omposition anof produced w
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his way the ld be determnment. The Ement tool lation and
mful Discharget al).
nd Environmwater streams
4
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Practicadisturbancesignificant dfollowing paoffshore gaonshore, baconstant cochemical pcompositio EFFECT OKOLLSNESreal life casKollsnes (N
Same TOCbioactivity sgas/condenwas tied-in Gassco in KThe gas trealready treaand C as wKvitebjørn at the site cJanuary 20This happeorganic car After MPPEwithin 3 moMPPE unit was restorewas discovinfluent incthe influentwater contawater from was 20–10Kvitebjørn)phenols (Cvariations iduring startbiomass waconcentratiBTEX conteto an unadaJacobssonand PAHs aet al, Kuala
CAL EXPERIETH THE PRENSTITUENTS
al real life expe of toxic loaddifferent situaaragraphs. Sas/condensatasically dealiomposition. Wroducer with n both qualita
OF TOXIC LOS WASTEWAse with StatoNO)
C (Total Orgastopped - In ansate producto the gas tr
Kollsnes, weeatment planating gas/con
well as Visundin October 20ceased to fun005 nearly allened without rbon content
E unit installaonths - After iin the beginn
ed within threvered that thereased signift did not increains more toxthe Troll and0 times highe, PAHs were2/C4) were 1n BTEX weret up. The conas poisoned ions of BTEXent greater thapted culture, Oslo 2006)at design lev
a Lumpur 200
ENCE ON HOESENCE OFS IN WASTE
periences of ds in wastewations are pr
Statoil in Kollste produced wing with a quWastewater fa constant catively and q
OAD IN THE ATER TREATil and Gassc
anic Carbon) autumn 2004
ction platformreatment planst of Bergen t at that momndensate fromd. Shortly aft004, the biotnction proper bioactivity hany increase(TOC).
ation bioactivinstallation oning of 2005ee months. Ae toxic fractioficantly, whileease. Kvitebjxic substanced Visund fielder (600 mg/l
e 10 times hig10–50 times e observed enclusion was due to the hi
X, PAHs and han 12 mg/l ce (Bergensen; MPPE remo
vels (98–99%06).
IWC 12-
OW TO DEA TOXIC
EWATER
the water in two resented in thsnes where water is treatalitatively
from a speciachanging quantitatively.
STATOIL TMENT – A
co in
levels, but 4 a new
m Kvitebjørn nt of Statoil ain Norway.
ment was m Troll A, B er the tie-in oreatment plarly and by
had stopped. e in total
vity restored of a mobile , bioactivity
Afterwards it on of the e the TOC oførn producedes than the ds. The BTEXfrom
gher and alkyhigher. Large
especially that the
igher alkyl phenolscould be toxin and oved BTEX
%) (Bergense
-52
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MPP No.
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TOXIC / REMOVAPRODUCcomplexspecialtycharacteflexibilitychemicatreatmenthat are every daGeneric chemicaadsorptioineffectivunit and applicatiotechnolo
2012-132/DTM
Photo 1. Stato
NON TOXICAL OF A SPCER – The u
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ay in composapproaches l oxidation anon appear to ve. A field pilomobile bioroon of the com
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Graph 2.
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otor has led tombination of tstrict control
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0500100015002000250030003500
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raph 3.
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IWC 12-
his combinatioa French
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Remaining COD
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-52
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MPP No.
The p
gas/condtreatmengas/condonshore and dowrefinery/glocationsproduceda short sconstitue THE ENVZERO HOIL ANDWATER of oil proproducedwater is By aiminof gas/coefficiencycan be aconstituehave prothan the after the technolo
The f
been meto levels Environmtool was the beginHarmful was set Norwegiaderivativ
2012-132/DTM
ZERO HARIN THE OIL A
presence of tdensate leadnt. This is upsdensate prodand shale ga
wnstream in regas locationss where oil and, refined ansurvey of expents in all the
VIRONMENTARMFUL DI
D GAS/COND– A compari
oduced waterd water showfar more toxi
ng the attentioondensate pry of the envir
achieved. Theents in gas/cooven to be in generic comapplications
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RMFUL DISCAND GAS IN
toxic constitus to challengstream in theduced water, as produced efinery wastes groundwatend gas basedd used. This
periences in rese areas.
TAL IMPACTSCHARGE IDENSATE PRson between
r and gas/conws that the gaic than the oion to lower throduced wateronmental ime concentrationdensate prpractice 10-2
mposition of os of standard
Table 3.
gas produced, vary from a er platform. Tct Factor (EIFby Norway incentury to imolicy. A challZero Harmful in 2007. Thiollowed by ot
CHARGE NDUSTRY
ents in the oges in water e oil and both offshorwater onsho
ewater and er. Basically d products archapter pres
removing tox
T FACTOR FN OFFSHORRODUCED n the composndensate as produced il produced whe toxic conter a high cos
mpact reductioions of the toroduced wate20 times high
oil produced wgravitational
d water that few m3 per h
The F) manageme the North Se
mplement a Zenging progrl Discharge fs approach other countrie
6
oil and
e and ore
in all re sents
xic
FOR RE
sition
water. tent st on
oxic er her water l
have hour
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(Chen et alAustralia (Ltested and Environme(Buller et aconstituentvarying betof ppm dissaromatic hyInhibitors (c(H2S), foamchemicals anot influenc
Offshore p
Graph 5.
produced w
) like The NeLowe) and Egproven to vental Impact Fl; Grini et al)s with more ttween a few hsolved and dydrocarbons corrosion, sc
mers, defoamare partially rce the separa
Grproduced wa
MPPE effecwater versus
etherlands (Ngypt. MPPE hery effectivelyFactor with 95. MPPE remothan 99% at hundred to aispersed BTEand aliphatic
cale, hydrate)mers, and othremoved (20ation perform
raph 4. ater toxic/non
ct on chemicas gravitationa
IWC 12-
NOGEPA; Dahas been y reduce the 5 to 99% oves toxic inlet level,
a few thousanEX and poly c constituents), scavengerser field -50%) and d
mance.
n toxic conten
al compositioal technologie
-52
ale)
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s. s
o
nt.
on es.
MPP No.
Graph Factor o
Table 4
SHELL MSHOWSThese oba study cB.V., Roable SoluPhilippinimpact owater strenvironmhydrocarthe BTEXenvironmphenols water enplatform.Norwegiaand showthe deterimpact o
2012-132/DTM
6. MPPE effof gas produc
te
4. MPPE remoil pr
MALAMPAYAS IMPACT SEbservations acarried out byb Phillips Coutions Servic
ne Governmeof a gas and gream (Shell Mment and conrbons, especX, have the h
ment. Remarkdo not have
nvironment ar. This is diffean studies. Tws that the mrminants affe
of the individu
M/mt/mk
fect on Enviroced water vechnologies.
moval effectiveroduced wate
A – CONFIREA WATER Eare supportey Shell Philip
onsulting Pty ces at the reqent. They studgas/condensMalampaya) ncluded that tcially the naphighest impakably they foa significant round the Shrent from the
This confirmsmarine enviroecting the envual produced
onmental Impersus gravitat
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MS EIF MODENVIRONMEd by the resu
ppines ExplorLtd and Sust
quest of the died the toxic
sate producedon the the polyaromhthalenes, act on the
ound that the impact on th
hell Malampae results of ths the EIF modonment is onevironmental water stream
7
pact tional
s and
DEL-ENT - ults of ration tain-
c d
matic nd
alkyl he aya he del e of
m. It
may be the(average teto the 7–10alkyl phenoimpact on talkyl pheno ONSHOREThe growinhas led to acombinatioHere the Mthe non-poaliphatics (dThe field teapprox. 4 meffectivenerequiremen Table 5. W
UNDERGRPRODUCEthe MPPE tapplied in uwater treatmHydro Thioto identify gto remove fbiodegradasoluble andkind of preccompound MPPE treasent to the discharge i
MPPE Gas
Compound
AliphaticsBTEX
Tetra HydroThiophene
e warm wateremperature o0˚C in the Nools to have a the environmols are suffici
E SHALE GAng importancea wastewatern of different
MPPE technollar hydrocarbdispersed oil
est has been months with ass of the tota
nts.
Water treatmeprodu
ROUND NATED WATER Ttechnology hunderground ment to remo
ophene). THTgas leaks. It ifrom wastewable, toxic, hid has a very cautions hadfrom the protment on loclocal municipn the local riv
Tas Storage pr
s
o (THT)
rs around theof 20˚C or higorth Sea) that
low to insignment. In these
ently biodeg
AS PRODUCEe of shale gar field trial wht technologielogy has provbons, BTEX, l) consistentlyrunning succ
a consistent ral COD to me
ent technologced water.
URAL GAS STREATMENThas been suc
gas storage ove BTEX anT is the odorais a challeng
water as it is nghly flammabunpleasant s to be taken
oduced wateration the treapal water treaver.
abel 6. roduced wat
Inlet mg/l 10 15
50
IWC 12-
e Philippines gher comparet cause the nificant harmfe conditions tradable.
ED WATER -as productionhere a es was applieven to removPAHs and y with 99%. cessfully for removal eet discharge
gies shale ga
STORAGE T - Since 200ccessfully
produced nd THT (Tetraant of the gasing compoun
non-ble, very watstrong odor. Ato remove th
r. After the ated water isatment prior
ter treatmen
Outlet mg/l < 0.5 < 0.3
< 0.5
-52
ed
ful the
- n
ed. ve
e
as
02
a s nd
ter All his
to
t.
MPP No.
PG
REFINERrequest aExtractioThe ope3 weekswithout cthe plantAPI sepasolids reDue to flcharacteconductethe overaverify its charactewas periand outlean indepof BTEXand EPHThe obtathe follow
2012-132/DTM
Photo 3. MPPGermigny so
RY WASTEWa MPPE (Maon) pilot unit wrational perio. The procescorrosion inht and treated arator, then amoval), followuctuations in
eristics, the Med over a threall performanability to trea
eristics. Durinodically samet were taken
pendent certifX, VPH (volatiH (extractableained analyticwing graphs.
M/mt/mk
PE unit Gaz dous Coulombs
WATER – FIEacro Porous Pwas operatedod of the piloss wastewateibitor) was ta in three (3) s
a pilot DGF uwed by the M
n the refinery MPPE pilot stee (3) week nce of the MPat fluctuationng the pilot plpled. Samplen. The samplfied laboratorile petroleume petroleum hcal results ar
de France, s, France.
ELD TEST -Polymer d at a refinert was around
er (both with aaken directly steps. First a
unit (for oil & MPPE pilot un
wastewater udy was period to chePPE unit andns in influent wlant trial, the es of both inlles were senry for the ana
m hydrocarbohydrocarbonsre presented
8
On
ry. d and from
an
nit.
eck d water unit let
nt to alysis ns) s). in
0,00
5,00
10,00
15,00
20,00
25,00
30,00
35,00
Sum of concentration (ppm)
Vola
0,00
5000,00
10000,00
15000,00
20000,00
25000,00
Sum of concentration (ppb)
VPH
0,00
10000,00
20000,00
30000,00
40000,00
50000,00
60000,00
70000,00
Sum of concentration (ppb)
VPH‐3
VPH-2
Gr
Gr
Gr
Gra
atile removal fromf
H‐1 removal fromf
3 Aliphatics remoMPP
Aromatics remov
raph 7.
raph 8.
raph 9.
aph 10.
m waste water dufieldtest
m wastewater durfieldtest
oval from waste wPE fieldtest
val from waste wfieldtest
IWC 12-
uring MPPE
o‐xylene
m.p‐xylene
ethylbenze
toluene
benzene
ring MPPE
dodecane
decane
octane
hexane
pentane
MTBE
water during
C8‐C10
C6‐C8
C5‐C6
water during MPPE
-52
e
ene
e
0
E
MPP No.
Conclusi• The MP
VPH 1,aliphat(Extracand aroremova
• The unweek, f
• The unwithout
GROUNREFINEprofiles orefinery asimilar. Swere medegreasilead freeMTBE (MEthyl verMTBE anwere intrto replacthe eightmolecule
0,0
2000,0
4000,0
6000,0
8000,0
10000,0
12000,0
14000,0
Sum of concentration (ppb)
EP
0
2000
4000
6000
8000
10000
12000
14000
Sum of concentration (ppb)
EP
2012-132/DTM
G
G
ion of MPPE PPE technolo,2,3 (Volatile ics and arom
ctable Petroleomatics) to aal efficiency wit was operatfully automatit was succet the necessi
DWATER RERY/GASOLINof the groundand gasolineSometimes aeasured probing solvents. e gasoline in Methyl Tertiarsion) are emnd ETBE areroduced in thce lead compties. It is a saes are creatin
00
00
00
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00
00
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00
PH‐1 Aliphatics reM
,00
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PH‐2 Aromatics reM
M/mt/mk
Graph 11.
Graph 12.
field pilot tesogy is able toPetroleum H
matics) and Eeum Hydrocaany level requwas measureted 24 hoursted. ssfully obserty of changin
EMEDIATIONNE LOCATIOdwater contame locations aralso chlorinatably due to tSince the inthe seventiery Butyl Ethe
merging in thee synthesizedhe gasoline apounds in thealient detail thng a new cha
emoval from wasMPPE fieldtest
emoval from wasMPPE fieldtest
st: o remove BTHydrocarbonsPH 1,2
arbons; aliphauired; > 99.9%ed. s a day, 7 day
rved remotelyng parameter
N OF ONS - The mination in re generally ved hydrocarbhe use of troduction ofs the presen
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e seventies ahat these allenge in wa
ste water during
C21‐C
C16‐C
C12‐C
C10‐
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ste water during
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9
EX, s,
atics %
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very bons
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ater
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treatment, ahave a strogroundwateremove froand field teO&G compbelow.
Tab
Table
0
2000
4000
6000
8000
10000
Concentration (µg/l)
M
as they are nong odor and er. In additionm groundwat
ests have beepanies of whic
ble 7. MTBE
8. MPPE perefinery / ga
Gra
Inlet
MPPE perforefinery/
non-biodegra are spread en they are difter. Successen carried ouch the results
/ ETBE infor
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aph 13.
rmance gr/gasoline lo
IWC 12-
adable, toxic,easily in the fficult to ful lab tests
ut with major s are given
rmation.
roundwater ons
Outlet
oundwateocations
-52
r
PAHs
DROs
GROs
BTEX
MTBE
MPP No.
GROUNAND COcountrieswas an imanufaclast centfor energLater coanatural glocationsTypical cdissolvedaromaticconcentrprohibitivthese soclean upand perfo
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5000
10000
15000
20000
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Concentration (µg/l)
MACR
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2012-132/DTM
DWATER REOAL GASIFICs behind the mportant sou
cturing of cheury, in the whgy, a source al has been mgas. This hass with major gconstituents id and disperscs, polyaromarations are sove for natura
o called hot spp these locatioormance is p
Groundwown coal / Co
G
0
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00
00
Inlet
MPPE perfbrown c
RO POROUS(MPPE)
dicated in theechnology is on technologysed in the maPE process h
mal use of thent.
M/mt/mk
EMEDIATIONCATION LOC
former iron curce for eneremicals. In thhole of Europfor city gas amainly replacs led to manygroundwater in these groused aliphaticatics and pheo high that thl attenuationpots is minimons. The MPpresented in
Table 9. water remedioal gasificatio
Graph 14.
O
formance goal/ coal galocations
S POLYMER) TECHNOLO
e previous pabasically a liy where the eacro porous has been speese MPPE pa
N BROWN CCATIONS – Incurtain brownrgy and e first half ofpe coal was and chemicalced by oil any former coal
contaminatioundwaters arcs (oil), dissolenols. Often they become . Remediatio
mally requiredPPE applicatiograph 14 bel
iation on locations.
Outlet
groundwateasification s
R EXTRACTIOOGY
aragraphs, thquid-liquid extraction liqupolymer part
ecifically desiarticles in wa
10
COAL n n coal
f the used ls. d
on. e lved these
on of d to on low.
er
PAHs
BTEX
Aliphatics
ON
he
uid is ticles. igned ter
MPPE PARmicroscopicpolymer pais 60–70%.developed applicationsstarted in 1was used foInitiated by emerged todissolved himmobilisinpolymer. Astechnology
Internal s
MPPE P
treatment pwater is paMPPE partbeads that immobilisedhydrocarboThe purifieddischarged
Periodicliquid is acchydrocarbostripped hyseparated falmost 100recovered, ready for re
RTICLES - A c (SEM) pho
articles is sho. These polymas controlleds. The applic991. Initially or absorbing the oil and g
o develop a mhydrocarbonsng an extractis a result this
y was develop
Phstructure of th
PROCESS - process, hydrssed throughicles. The pacontain a spd extraction lon componend water can e.
cal in-situ regcomplished bons using lowydrocarbons afrom the wate
0% pure hydrremoved fro
ecycling or di
scanning eleotograph of mown in photo mers were ind release mecation in watethe macro p dispersed o
gas industry, medium to res from water ion liquid in ts (patented) ped in the mi
hoto 4. he macro por
In the MPPErocarbon-conh a column particles are popecific extractliquid removents from the peither be reu
generation ofby stripping thw pressure stare then coner phase by rocarbon phaom the systemisposal.
IWC 12-
ectron macro porous
4. The porosnitially dia in medica
er treatment orous polym
oil from waterthe idea
emove by he pores of tMPPE id 1990s.
rous polymer
E water ntaminated acked with orous polymetion liquid. Thes the process watesed or
f the extractiohe eam. The densed and gravity. The
ase is m and left
-52
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MPP No.
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the systecontinuoand regeextractioshows a
2012-132/DTM
Photo 5. T
unit at LBC
condensed aem. The applous operationeneration. A ton and one ho
simplified flo
M/mt/mk
The MPPE p
Photo 6. Rotterdam, t
queous phaslication of two
n with simultatypical cycle our of regeneow-sheet of t
rocess.
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aneous extracis one hour oeration. Phothe MPPE
11
nds.
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The MPand dispersaromatics ((chlorinated(1,000,000
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CHEMICALMPPE - Aftdeveloped,actually on of Elf AquitTotal, then
The MP99% at 3,00beginning fthe results Petroleum 1998). At thspecific ste1997), but
d photo 6 is allation.
PPE technolosed hydrocar(BTEX), polyd) hydrocarbtimes reductechnology caoduced water and groundcluding the ocoatings and PPE technoloons in practicnot create a wcan withstandnts containinnhibitors, scas, demulsifierheavy) meta
Ta
L CONSTITUter the MPPE the first appa gas offshoaine in HarlinVermilion; p
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a photo of a
gy can reducrbons such aaromatic andons with 99.9tion), if requian be used foer, process wdwater in a wffshore gas apharmaceutgy separates
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ale inhibitors,rs, defoamerls.
ble 10.
UENTS REDUE technology plication in 19ore producedngen (which hoto 7). on performanent levels fro compounds
published in aonference (PAquitaine had(Kloppenburgned that tech
IWC 12-
full-scale
ce dissolved as aliphatics, d halogenate9999% remored. or treatment
water, ide variety ofand oil, ical industries the m for (re)use
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UCTION WITwas
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nce was abovom the very
(BTEX) anda Society of Pars and Meijd developed g and Venemnology for
-52
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2012-132/DTM
d water treatnal/maintena
o 7. MPPE u the
gislation at tha reduction inromatic hydrofore the MPPffshore indus
ments (NOGEd Petrusevki,nd the oil andnter) (ERT/Or1997), were ad aromatics ad water. The out by NAM (ands’ part of test with exceled at the 200nce (Meijer aore offshore densate prod and Shell (inssful offshorend beginning
mental pressustallation of t
M/mt/mk
ment due to ance reasons
unit at VermilNetherlands
hat time did nn dissolved aocarbons (PAPE technologstry (Dalen). NEPA study on, 1988), OSPd gas industryrkney Water addressing thand PAHs em first offshoreShell/Exxon)the North Sellent results, 1 Offshore T
and Kuijvenhofield tests we
duced water bn Malaysia). e field tests a
g of this centuure in the Nethe first comm
costs and s.
ion, Harlinges.
not formally romatics (BTAHs), it took gy was requeNevertheless
n 55 technoloPAR (OSPARy (Orkney WTechnology he issue of mission in e field test wa) on L2 in thea. It was a 4 which were
Technology oven, 2001).ere carried oby Statoil (in The combinaat the end of ury and therlands hasmercial MPPE
12
en,
TEX) a
ested s both ogies R,
Water
as e
out on
ation the
s led E
units offshoDutch part K15A and Koperation sseparation and aliphatconcentratistarted up iand Woodsare include(FPSO) offsDelta.
Due to fregarding tPAHs emisout on requNAM and Textensive oHydro on Ttests a conobserved fobelow C20 removal watotal alipha91–95% fo
REA
An examshown in greal life anaMPPE unit mono ethylThe design1,500 ppm BTEX (disp1,400–7,70dissolved oas a total to
Graph 15
ore, on the mof the North K15B). Thesesuccessfully sperformance
tics at 300–8ions. Statoil/Sin 2007 (Shoside Pluto in ed in Prelude shore Austra
further develohe issue of d
ssion, a formauest of OSPATotal (Meijer offshore field Troll B (Pollessistent reducor BTEX anda consistent
as measuredtics removal r Total and >
AL LIFE ROB
mple of the roraph 15 whealyses since treating gas ene glycol (M
n was to reduto < 1 ppm.
persed and d00 ppm and aoil) from 150–o 3–0.5 ppm
5. A real life actual MPP
most critical pSea (Total Fe units have since 2002 we of > 99% of00 ppm influShell Ormen otun; Salevik;2011. Recen(Floating LN
alia and in the
opments in Odissolved aroal investigatio
AR on oil prodet al, 2004). test was car
stad, 2005). Iction of > 99%d PAHs. For at reduction at in all field tethe picture w
> 95% for Tro
USTNESS O
obustness of re the design1994 are givproduced wa
MEG) regeneuce dissolvedIn practice inissolved arom
aliphatics (dis–1,437 ppm win the outlet.
example of dPE performan
IWC 12-
latforms in thF15A, NAM
been in with a f BTEX, PAHent Lange was
; Silverstone)ntly MPPE unNG), Ichthys e West Nile
OSPAR omatics and on was carrieduced water Later an
rried out by In these field% was aliphatics t 95–99% ests. For the was mixed: oll B.
OF MPPE
f MPPE is n values and ven for an ater and a eration streamd BTEX from nfluent levelsmatics) from spersed and were reduced.
design versusnce.
-52
he
Hs
) nits
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d
m.
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d
s
MPP No.
M
In recthat MPPgas/condphenomecases whfindings 1999 in tBelow ingiven. Thbetweenppb. Leadetectab
Gra
BOD,
parametewastewa
Induscontents
2012-132/DTM
MERCURY R
cent benchmPE also remodensate prodenon was cohere Mercuryconfirm the fthe NAM field graph 16 thehe observed 82 and 99%
ad, cadmium ble.
aph 16. Merc
CO
, COD, TOC ers are effec
aters. strial wastewas are present
M/mt/mk
REMOVAL W
ark studies itoves Mercuryduced water. onsistently oby was measufirst time this d test (Kuijvee results of sremoval effe
% at inlet leveand nickel w
cury removal
NCLUSIONS
and other “inctive in munic
aters where srisk based a
WITH MPPE
t was discovey from This
bserved in allured. These was measur
enhoven et alsuch a seriesectiveness vaels from 5 to 1were hardly
l with MPPE.
S
ntegral” dischcipal and non
significant toapproaches a
13
ered
red in l).
s are aries 120
.
harge ntoxic
oxic are
emerging. Ttoxic conte
Risk basthan dischaparameters
The conFactor as aoffshore prorecognition
Extractiotechnologieas has beeproduced w
The remissue to be are to be mfunction of biotreatmenloads.
MPPE hEnvironmewater.
The MPthe removaand ground
The % sMPPE unit concentratioperation.
MPPE ron various water bencplanned to so as to coremoval.
They focus ont to create ased approacarge policies s like COD. ncept of the Ea form of a risoduced wate worldwide. on technologes to implemeen proven in owater treatmemoval of toxic addressed w
met and toxic the biotreatmnt against hig
has proven antal Impact F
PPE technoloal of toxic condwater with leseparation peis independe
ion of the targ
removes Mergas/condens
chmark studiefurther substme to a “con
on selective ra Zero Harmfhes are morebased on int
Environmentask based apper goals is ga
gies like MPPent risk baseoffshore gas/ent. c hydrocarbowhen COD recontent thre
ment. MPPE gh and chang
95 to 99% reFactor in offs
gy has consintents in prodevels arounderformance oent of the inleget compoun
rcury with 81 sate Offshorees. Further sttantiate this p
ntrolled” and p
IWC 12-
removal of thful Dischargee cost efficientegral
al Impact proach to aining
PE are effectied approache/condensate
ns is a speciequirements atens the protects ging toxic
eduction of thore produce
istently showduced-, waste 99%.
of an installedet nds during
to 99% basee produced tudies are phenomenonpredictable
-52
e e. nt
ive es
fic
he ed
wn e-
d
ed
n
IWC 12-52
MPP No. 2012-132/DTM/mt/mk 14
Annexes
ACKNOWLEDGEMENTS
The basis of this paper is the series of field tests carried out on request of Oil and Gas companies and the data provided by them of running MPPE units since 1994. This has resulted in a wealth of information that has been used in this paper together with the publications mentioned in the reference list.
This paper would not have been possible without the help and support of Peter Nekeman, making the graphs based on the labtest and pilot test figures and Mrs Marijke Kuntzel for consuming the continuous stream of new drafts and her constructive comments. I would like to thank Jan Bart Kok for his contribution to the COD and BOD paragraphs of this paper.
REFERENCES
BERGERSEN, L. AND JACOBSSON, J. 2006—New Offshore Tie-ins and impact on Onshore Facilities, Field Case Kollsnes. Tekna Produced Water Management Conference, Stavanger, Norway.
BERGERSEN, L., JACOBSSON, J. AND MEIJER D.TH. 2006—Solving the Impact of High Toxic Loads in the Produced Water at the Kollsnes Gas Terminal by Applying the MPPE technology. NEL Produced Water—Best Management Practices, Kuala Lumpur, Malaysia, 29–30 November.
BULLER, A. T., JOHNSEN, S. AND FROST, K. 2003—Offshore produced water management—knowledge, tools and procedures for assessing environmental risk and selecting remedial measures. Memoir 3. Stavanger, Norway: Statoil Research and Technology Offshore.
CHEN, G.Z. AND EBENEZER T.I. 2012—Produced water treatment technologies. Faculty of Engineering, Department of Chemical and Environmental Engineering, and Energy and Sustainability Research Division, University of Nottingham, Nottingham NG7 2RD, United Kingdom. 4 July.
DALEN, A.V. 2004—Produced Water Regulations in the Netherlands. NEL Oil-in-Water Monitoring Workshop, Aberdeen, United Kingdom, 22–23 September.
ERT/ORKNEY WATER TECHNOLOGY CENTER, 1997— The removal of dissolved and dispersed organic components from produced water. ERT F92/178, requested by Exxon Mobil, Total, Amarada Hess.
GRINI, P.G., HJELSVOLD, M. AND JOHNSEN, S. 2002— Choosing produced water treatment technologies based on environmental impact reduction. HSE Conference, Kuala Lumpur, Malaysia, 20–22 March, SPE paper 74002.
ITHNIN, I.B. AND CHRISTOPHER, G. 2006—The discharge of produced water from oil and gas production: Legislation requirement in Malaysia. NEL Produced Water—Best Management Practices, Kuala Lumpur, Malaysia, 29–30 November.
KAA, C.C.R. VAN DER AND PETRUSEVKI, B. 1988— Inventarisation of removal techniques to reduce the benzene heavy metal emissions from offshore platforms. (In Dutch). NOGEPA (Netherlands Oil and Gas Exploration and Production Association) and Dutch Government, Report 61944-00-32-301-2.
KLOPPENBURG, M.F.C. AND VENEMA, W. 1997—De-oiling condensed glycol regenerator overhead vapours by steam stripping. 1997 SPE/UKOOA European Environmental Conference, Aberdeen, United Kingdom, 15–16 April, SPE paper no. 37846.
LOWE, I. 2006—Shaping a sustainable future—challenges for Australia’s oil and gas industry. APPEA Environment Conference, Coolum, Australia, 19–21 November.
IWC 12-52
MPP No. 2012-132/DTM/mt/mk 15
MEIJER D.TH. AND KUIJVENHOVEN COR A.T. 2001— Field-Proven Removal of Dissolved Hydrocarbons from Offshore Produced Water by the Macro Porous Polymer Extraction Technology. SPE Offshore Technology Conference, Houston, Texas, USA, 30 April–3 May, OTC 13217.
MEIJER D.TH., KUIJVENHOVEN COR A.T. AND KARUP, H. 2004—Results from the latest MPPE field trials at NAM and Total Installations. NEL Produced Water Workshop, Aberdeen, United Kingdom, 21–22 April.
MINISTRY OF ECONOMIC AFFAIRS, 1995—Declaration of Intent, Implementation of Environmental Policy for the Oil and Gas Industry. NOGEPA (Dutch Oil & Gas Exploration and Production Association), The Hague, the Netherlands, 2 June.
OSPAR DENMARK, 2004—Definition of a data collection strategy for aromatic hydrocarbons by OSPAR Contracting Parties in 2004, OSPAR Background Document concerning Best Available Techniques and Best Environmental Practice for the Management of Produced Water from Offshore Installations. OSPAR meeting of the Offshore Industry Committee (OIC), Dublin, Ireland, 15–19 March.
PARS, H.M. and MEIJER D.TH. 1998—Removal of dissolved hydrocarbons from production water by Macro Porous Polymer Extraction (MPPE). SPE International Conference on Health, Safety and Environment in Oil and Gas Exploration and Production, Caracas, Venezuela, June, SPE paper no. 46577.
PHILLIPS, R., RIOS, A. AND CAYMO, A. 2006—Assessing the Risk from Discharging Produced Water to the Marine Environment. NEL Produced Water—Best Management Practices, Kuala Lumpur, Malaysia, 29–30 November.
POLLESTAD, A. 2005—The Troll Oil Case—Practical Approach towards Zero Discharges, Troll Projects. Tekna Produced Water Management Conference, Stavanger, Norway, 18 January.
SALEVIK, P. 2009—Onshore Water Treatment, Experience from Ormen Lange, Nyhamna. Tekna Produced Water Management Conference, Stavanger, Norway.
SILVERSTONE, M. and Vik, E. 2012—Application of whole effluent assessment (WEA): evaluating the performance of the Ormen Lange produced water treatment plant. Tekna International Produced Water Management Conference, Stavanger, Norway, 24-25 January.
SJØTHUN, S., 2002—The Process of Developing a Total Effluent Water Handling System for Ormen Lange. Tekna Produced Water Management Conference, Stavanger, Norway.