II

SPE 36601
6i14i D

Sociaty of I%tdeutn En@’wB

Novel Filtration Process Eliminates System Upset FollowingAcid Stimulation Treatment

P.B. Hebwl, Shell Offshore Inc. and Z.1. Khatib, Sh;ll Develo~rnent Co.: W.D. N&man and A. Acock, Dowell
Schlumbe&K M. Johnson, Gulf States Environmental

Accompanying this practice comes the task of

processing well stimulation fluid returns without causin
2!I
severe upsets in the surface treating facilities. ‘
Recently, with the new EPA overboard discharge
requirements,’ processing the aqueous ghase ha!
proven to be much more difficult. Bansal, Durham,
Houchin,7 Picou,s and others evaluated the reduction or
elimination of acid additives and found that this kind of
optimization could be taken to only a minimum threshold
concentration before sacrificing the chances of
achieving successful acid stimulations. All of the
additives used in acid systems are, by design, water
Abstract
soluble or at least water dispersible. This characteri~lc
Recent changes in the environmental compliance rules
maximizes the efficiency of the acid. This same
and regulations regarding the overboard discharge of
characteristic causes the return fluid stream to have
produced water have altered the way well stimulation
unacceptable levels of these same chemicals, along
fluid returns are processed. The flow back of treatment
with their crude oil extractable counterparts. These
fluids, formetiy handled under exception rules, was
chemicals show up in the water phase of the separation
handled in a manner which normally minimized facility
system. Rather than attempting to reduce or eliminate
processing upsets. Wtih the introduction of the new
key mmponent additives in the #lmulation package and
regulations, processing stimulation returns caused
sacrificing the effectiveness of the treatment, some
system upsets and has even halted production until the
other methods of achieving appropriate water quatity
flow back treatment has been completely accomplished.
were investigated.
The application of a filtration process used to avoid
This paper discusses the necessity of treating the
these problems in several acid flow back situations is
stimulation flow back fluid through separate handling
presented. The filtration process equipment is
facilities. In this paper, (1) the impact of acid additives
described as well as operational considerations that may
on oil and grease content in overboattl water discharges
help eliminate facility upsets while maintaining
is quantified, (2) the causes of upsets in production
environmental compliance. Discussion of the additive
facilities are discussed, (3) the vahous options for
packages tested for pre-job oil emulsion and water oil
processing acid returns are summarized, and (4) a novel
and grease screening is inctuded. Fluid analysis of the
filtration process for removing both dispemed and
flow streams into and out of the filtration process and
soluble hydrocarbon in water is presented. The
cost for four case histories are summarized.
performance of this filtration process is demonstrated
Introduction through four field case histories and the cost for each is
The use of acid systems to stimulate or to improve oil summarized.
and gas production has been around since 1932.1 As
Returns Processing from AcidStimulated Wells
the understanding of the acidizing process has been
Acid stimulation to improve and maintain productivity of
better defined the acid systems have become more and
impaired wells is a profdable acthdty, thus a common
more chemically complicated. These chemical
practice for Shell Offshore Inc. However, reduction of
packages added to the live acid system improve not
well stimulation cycte time and minimization of
only the removal of damage but also the cfean-up and
associated production downtime are impofiant economic
flow back of spent acid, not to mention the
value driven. Historically, processing fluid from acid
enhancement of hydrocarbon production.
stimulated wells has caused production system upsets

279
2 P.B. HEBER~ 2..1. KHATIB; W.D. NORMAN; A. ACOCK
(i.e., emulsions) and often resulted in downtime for the
individual well as well as the entire production platform.
In addition, delays in returning the stimulated well to
produtilon have reduced the stimulation effectiveness.
Furthermore, environmental compliance on permitted
produced water overboati discha~e locations has been
difficult to attain.
Acid Stimulation. Acidizing sandstone formations
involves very complicated chemical mixtures to address
the different types of damage. These chemical
packages are necessafy to make sure that the live acid
can contact the damage it is injected to remove and to
assure the spent acid does not create emulsions or
precipitant that can hamper production. These acid
additive packages include surfactants, corrosion
inhibtiors, iron control agents, mutuai solvents, and
many other miscellaneous surfactant-based chemicals
for emulsion and sludge control, as well as dispming
agents.
Almost all of these additives are very water-soluble
hydrocarbon compounds. The effectiveness of any one
of these chemicals depends on temperature, substrate
surface area, and concentration in soluticm. The sutiac8
area and concentration relationship are often direct.
Higher surface area media mnsume higher
concentrations of the additives. Therefore many of the
additives are added in excess to assure adequate
concentration is present in the spent materials to impart
the properties for clean-up. Some of the most difficult
additives to quantify for acid treatments are those that
are multipurpose in function. These are additives that
can be consumed on the surface of the minerals and be
partitioned into the cmde or condensate. The problem
with these additives is that mnsumption in the formation
cannot be quantified accurately to assure threshold
additions, and without these threshold concentrations
being present these additives often do not work
effectively.
Production Processing Upsets. The causes of acid-
related facility upsets can be grouped into the following
broad categories:
Emulsions formed during pumping or while the fluids
are in the well. These emulsions are generally
prevented by proper Iaboratofy pre-screening of the
stimulation fluid packa e. Much work has been
9
performed in this area.5’6’ “8
Emulsions formed as produced fluids flow through
wellhead chokes. Injection of a properly selected
demulsifier into the well stream during flow back can
aid in breaking the emulsion.
Emulsions formed by commingling spent acid with
the buik production stream. These emulsions are
caused by the precipitation of solids and/or are due
to the incompatibility of the stimulation chemicals
(e.g., surfactants, foam diverter, etc.) with produced
280
M. JOHNSON SPE -1
fluids from other wells. These emuisions can
generally be prevented by processing the aqueous
phase from the stimulated well through separate
handling facilities.
● Stimulation chemicals in the returning fluid cause
produced water oil and grease quantiti& to increase.
In Janua~ 1993, the EPA not only lowered oil and
grease limits for produced water discha~es but aiso
required testing of almost all discha~es Inctuding
well treatment, completion, and workover fluids. The
new established oil and grease limits were lowered to
29 mg/i for a monthly average and 42 m@l daily
maximum’ using a gravimetric procedure.g
In anticipation of the new regulations and to
investigate the impact of well stimulation fluid on
produced water, oil and grease testing was petionned
on overboatd discharge water foliowing a well
stimulation job done in 1992. Returns from the well
were first pmessed through a test separator, followed
by a 100-barrel retention vessel. The aqueous phase
was then commingled with the existing produced water
stream pdor to entefing the gas flotation unit. The water
from the flotation unit was discharge overboard. Total
water produdion for the field was approximately
5,000 bbl/day. As shown in Table 1, the total oil and
grease results taken downstream of the flotation unit
were elevated above normal operating levels. Resutts
indicate that a significant amount of non-TPH or
“soluble” oil was present. Based upon today’s discha~e
standads, oil and grease limits would have been
exceeded. Removal of the total recoverable oil (i.e.,
dispemed and soiuble oil) is necessary to remain within
permitted timits.
Impact of Acid Additives on Oil and Grease
Measurements. A limited amount of pubtished
literature is available concerning the effects of
Simulation fluids on ~uced water oil and grease
testing results. Bansal investigated the effects of non-
producer fluids such as stimulation, compl&lon, and
workover fluids on produced water treatment equipment
efficiency. Bansal’s testing cieady demonstrated that
some chemical components incqmsted in an acid
stimulation package adversely affect oil and grease
separation efficiency using a flotation unit.
A similar approach was initiated et Sheli Offshore.
Oil and grease Iaboratofy te~ing was performed on
single additives blended with hydrochloric acid and on
typical well stimulation packages. The objective was to
identify which additives adversely affect the oil and
grease gravimetric and infrared procedures. Acid, acid
formulation, and additive samples were obtained from
two local stimulation companies and shipped to an
independent Iaboratoiy for testing. It is impottant to note
that all testing was done without the addition of crude
oil. Total recoverable and total petroleum hydrocarbon
procedures were measured and are repotied in Table 2.
SPE 36601 NOVEL FILTRATION PROCESS ELIMINATES SYSTEM UPSET FOLLOWING ACID STIMULATION TREATMENT
As shown in Table 2, several additives adversely
affect the oil and grease results. Some individual
components formed severe emulsions during the freon
extraction step, yielding erroneously lower oil and
grease values. The total acid package also has
detrimental effects on oil and grease. Note, that a lame
quantity of oil and grease measured was soluble oil.
Acid Flow Back Handling Options. Shell Offshore
Inc., which operates offshore fields only, evaluated the
various alternatives for processing returns associated
with well acid stimulation. The field options were
grouped into three broad oategofies for consideration:
● Disposal into an on-site subsurface injection well.
o Transport to another location for subsurface injetilon
or commercial disposal.
● Prooessed and treated on-site to reduca oil and
grease and then either (1) recombine with an existhg
produced water discharge stream, or (2) direct
discha~e.
Along with each of these options are advantages and
disadvantages. These are briefly summarized below.
On-site subsurface injection is a desirable option
since no environmental monitoring is required in
offshore OCSG (Outer Continental Shelf Gulf) waters.
However, this option is applicable only if a dispsal well
is available and permitted. First, the field must have a
permeable zone for inje~lon. In many fields this is a
show stopper. In addition, fluid injectivity rate and
pressures may vary depending on reseivoir zone
characteristics, ultimately causing Iong-term injectivity
problems. Secondly, the well must be mechanically set
up to inject into the desired zone. In many instances a
costly rig operation is require to accomplish the latter.
Additionally, the addition of costly facility equipment
such as pumps maybe necessary.
Subsurfam inje~lon of fluids at another offshore
OCSG location has similar advantages as the on-site
injection o~lon in that environmental monitoring is not
required, assuming another offshore location is
available. However, this wouid involve collecting
<Imulation returns in containers (i.e., tanks or barges)
and transporting to this other location. In addition to
transportation cast, along with this task comes increased
operational activities (e.g., lifting and loading of tanks
containing acid, etc.) and inherent risk (e.g., safety,
weather, etc.). The same concerns apply for onshore
subsurface disposal. For commercial disposal,
additional cost will be incurred. Exact charges may
depend on the fluid content.
The third option, on-site treatment, may be the
desired option for many field iocations. Generally,
enhanced water treating is necessmy to meet oil and
grease discharge limits. If this enhanced treatment
technique is economically feasible, recombining the
aqueous phase of the acid stimulation returns with the
existing produced water stream prior to overboard
281
3
discharge is the preferred method of disposal. Direct
discharge is mainly applicable for satellite facilities
without produced water treating facilities. in either case,
environmental monitoring is required. Because of the
possible high mncentration of water-soluble oil,
variabies like flow rate, dispersed oil content, produced
water treathg system effectiveness and other operating
conditions all affect discharge oil and grease. Additional
processing whioh extracts soluble oit/organic
components as well as dispersed oil is generally needed
to reduoe the oii and grease oontent to acceptable
discharge iimits.
Due to the many different acid stimulation chemicais,
stimulation methods, and faciiity-spectfic processing
o@lons, the most cost-effectNe method for processing
weli stimulation returns is weii or field specific. Sucoass
of the three aforementioned options fl.e., subsudace
injection, off-site disposal, on-site discha~e) is
associated with the capabilities of processing through
separate handling facilities. The returns are isoiated
from the normal produ~lon train for either prooassing or
disposai. If commingling occurs, the streams are
introduced at the farthest downstream point poasibie.
in the foliowing sections, an enhanced treatment
technique is discussed and qualified by fleid application.
Filtration - A Processing Alternative
Filtration Process. As cited cartier, stimulation
packages and the associated mtums oontain la~e
amounts of ‘solubie” oil when measuring oil and grease
quantities in water using the gravimetric extraction
laboratory procedure. Enhanced processing alternatives
must have the capability of removing these soiubie
hydrocarbons from the aqueous phase prior to
overboard discharge. A filtration process using
specialized media was successfully appiied for this
puqxms. The filtration media is a proprietary granular
material specifically designed for removing oil and
grease from extremeiy low-pH aqueous streams.
Suooess of the filtration prooess hinges on the
capabitiiy of initially isolating the stimulation returns
through separate handiing facilities, i.e., test separator
foiiowed by a iow-pressure or atmospheric retention
vessei. For three-phase test separator operations, the
gas and oil are processed through the normal production
dehydration facility and the aqueous phase is routed to
the retention vessel. If oil dehydration problems are
encountered, the oil stream from the test separator is
directed to enhancxed oil treating equipment or the test
separator is operated in a two-phase mode. in two-
phase operation, the entire liquid phase is routed to the
retention vessel. From the retention vessel, the oil is
either pumped into the system or processed with
additional enhanced separation techniques (such as a
centrifuge), while the aqueous fluid is fittered.
4 P.B. HEBERK 2..1. 10-L4T16 W.D. NORMAN; A. ACOCK
Although the specifics for each filtration job may be
slightly different, the following is an example of a
typioal fdttilon application. A sohematic is shown in
Figure 1. From the test separator, the fluid returns are
captured in a four-compartment 120 bbl tank with weim
to help ocmtrol and separate the tiiuid phases. The
cJean oil is flowed over a weir into the foudh
compartment and pumped to the oil processing facilities
of the platform. The add returns are transfemed from
the seoond and thiml wmparlments through the fitter
vessels. The filter vessels are sized for the anticipated
flow rates. The interfaoe between the oil and water is
monitored by use of sight glasses on the tankage.
The hydrocarbon-contaminated acid, completion
fluid, and waste water are pumped through a pm-filter
(usually a 25-mioron bag filter) to remove the
suspended solids, The effluent is then passed through
two vessets toaded with the filter media. This media
removes the water-soluble hydrocmbcms and additives
that are extracted in the oil and grease testing
procedure. The fluid is then passed through another
vessel containing GAC (granular adivated carbon), This
step is a precautionary stage to remove any component
that is not removed by the filtering media. The last
vessel of the prooess is a 175-gallon oontainer which
allows sampling and recyoting of the flow if neoessary.
Onoe the effluent limits are met, the stream is
discha@ into the flotation unit and/or ovedward. As
the oil and grease analysis readings begin to move out
of range, indicating the media is spent, the used media
is dumped Into cutting boxes and the vessels refilled
and put back online.
The processing rates for the return fluids range from
0.3 to 1.5 bamels per minute (450 to 2,150 bpd). Typical
equipment components and skid dimensions are (1) the
wmpartmentalized weir tank -18 ft length x 8 ft width x
8 ft height, (2) the filter skid -14 ft. length x 7 ft width x
8 R height, (3) the pump package - 7 fl length x
4 fl width x 6 ft height.
Field Application - Case Histories. Four separate
filtration applications are included as case histories. The
four oases are desoribed below.
●Case 1 was a single-well, ooiled-tubing acid
stimulation job on a horizontally completed well. The
well was located on an outlying jacket away from the
main processing facility. Returns were first routed to a
two-phase test separator. From the test separator, fluids
were sent to a 120-barrel atmospheric retention vessel
for oil and water separation. The aqueous filtration
effluent was discharged overboatd. Oil was pumped and
commingled into the bulk produtiion line for main faoility
processing.
●For Case 2, the filtration process was used to
handle the returns from a three-well stimulation job. The
wells were located on the platform with gas, oil, and
water processing capabilities. Flow from the wells was
282
M<JOHNSON SPE H
directed to a thre~phase test separator. The aqueous
phase flowed to a 12Marfel retention vessel prior to
filtration. The flttrate was commingled with the ptatform
produoed water stream prior to overboard disoharge.
●Case 3 was an identioal prooesa to Case 2
regarding the handting of returns. Case 3 was a new
sukea oil well completion that was treated with a
similar acid stimulation package immediately after
completion. Additional tankage was neoessafy to
provide retention time for initial oil and water separation.
●ln Case 4, the filtration process was utilized to aid in
the recovery of a facility processing upset that occumed
5 days a~er a single-well acid stimulation job. Total
field produdion was shut-in due to severe emulsion and
water treating problems. Initially, produoed fluids in the
vessels were prooessed via the retention vessel for
primary oil-water separation. The aqueous phase was
filtered and dkoharged overboard. Once vessel clea-
noutwas oomplete and field production was on-line,
separate handling facilities plus filtration were used to
unload the simulated well completely.
Several oil and grease measurements on the filter
influent and effluent streams were determined during
the operations of the four cases. Only the median
values are shown in Table 3. However, at times the filter
was slugged with up to 58% oil by volume. The
corresponding effluent oil and grease value was only
11 mgfl.
Cost summaries for the four case histories are listed
in Tabte 4. Larger volumes of fluid requhed tre~lng as
oompared to the amount of stimulation acid package
injeoted. The cost of treated fluid is evaluated in terms
of dollam per barrel. These cost ranged for $4.42 to
$17.38 per bamel. Disposal wst of the m~la was not
included. Generally, cost of disposal ranges from
$8-12/bbl of media depending on the hydmowtxm
content. For these four cases, these cost were less
expensive than the alternative options evaluated.
Conclusions
New oil and grease compliance limits for water
discharge have created the need for m-engineering the
flow back of well treatment, oomptetion, and workover
fluids. The following conclusions can be drawn:
1. Certain Wlmulation additives produoe high oil and
grease measurements using the gravimetric
extradion procedure even without the introduction
of produced hydrocarbons. These components are
non-TPH and defined as soluble oil.
2. Separate facilities for isolating flow back returns
from the normal dehydration train aids in minimizing
facitii processing upsets.
SPE 38801 NOVELFILTRATIONPROCESSELIMINATESSYSTEM UPSET FOLLOWINGACID STIMULATIONTREATMENT 5

3. Flow baok handlirm otilons for the aaueous tiase Wem~ VT

for offshore locati~ns can be grou~ into’ three T --.L.--I
r
❑ VN!l 1m-!
broad categories: (1) on-site subsurface injection,

‘L-
(2) off-site disposal, and (3) enhanoed treatment
prior to discharge. The most economical o~ion is

l–
owlb@d
well or field speoiflc.
4. Filtration of the produced fluid through specially
designed media has been proven in the field to be
technically and economically effective in removing
measurable oil and orease components. This has
allowed safe di~-arge of fluids within EPA
regulations and prevented system upset.
5. The filtration process has proven to be cost-
-m
competitive in comparison with alternative options
that were evaluated for the four cases presented. 120 bbl 4 chamber weir tank
CRUDESORB GM
Vssseu vassaL
References
Fig. QIow dlagmn of fittretionfwoc=a.
1. Acidizing Fundamentals, SPE Monograph Series,
Williams, Gidley, and Schechter
2. Coppel, C.P.: “Factors Causing Emulsion Upsets in
Surface Facilities Following Acid Stimulation,” JPT
(Sept. 1975) 1080-6S.
3. Durham, D,K., Ali, S.A,, Stone, P.J.: ‘Causes and
SolMlons to Surface Facilities Upsets Following Add
Stimulation in the Gulf of Mexlcq’ paper SPE 29528
presented at the Production Operation Symposium, held
in Oklahoma City, OK April 2+ 1995.
4. Federal Register, Volume 58, No. 41 (March 4, 1993)
pp. 12454.
5. Delorey, J.R. and Taylor, R. S.: “Recent Studies into Iron/
SudactanUSludge Interactions in Acidizing,’ paper
No. 8936-38 presented et the 38rn Annual Technical
Meeting of the Petroleum Society of CIM, held in
Edmonton, Canada (June 2-5, 1985) pp. 85-95.
6. Bansal, K.M.: ‘Effect of Nonproducer Fluids on
Produced Water Treatment Equipment Efficiency,’ paper
SPE 25199 presentad et the SPE International
Symposium on Oilfield Chemistry held in New Orleans,
Q March 2-5, 1993.
7. Houchin, L.R., Foxenburg, W. E., Usie, M.J., and Zhao,
J.: “A NW Technique for the Evaluation of Acid Additive
Packages,’ paper SPE 23817 presented at the SPE
International Formation Damage Control Symposium,
held in Lafayette, Q February 28-27, 1992.
8. Picou, R.A, Ricketts, K., Luquatte, M., and Hudson, L.M.:
“Successful Simulation of Acid-Sensitive Crude
Producers in the Gulf of Mexico,” paper SPE 23818
presented at the 1992 SPE Permian Basin Oil and Gas
Recovery Conference, held in Midland, TX, March 18-20,
1992.
9. National Pollutant Discharge Elimination System
[NPDES] Method 413.1: “Oil and Grease, Total,
Recoverable (Gravimetric, Separator Funnel
Extraction).’

283
6 P.B. HEBERn 2..1. KHATIB; WI). NORMAN: A. ACOCIQ M. JOHNSON

Table l-Overboard Discharge Oil Content During an Acid Flowback”

Acid Retention Vessei Outiet Flotation Unit Outiet
Flowback Gravimetric Gravimetric Infrared Infrared Grevimetric Grevimetri Infrared Infrared
Day TPHm TPHb c TPH@ TPH@
1 210 199 339 68 44 68 u
2 312 206 339 331 62 33 63 46
3 301 1s1 394 311 64 39 66 43
4 259 177 356 295 62 34 65 44
6 616 303 697 648 18 17 26 24
6 132 87 143 143 47 33 63 33
7 110 57 136 135 13 2 49 28
‘Prior to 1993
%PH - Totai Petroleum Hydrocarbons

Tabie 2-Laboratory Analysis of Oil Contents it Mirnulation FI ds

ontent (mg/1) f Lab Proce Um
Sample Gmvimetric Infmred Infmrwd
No. ~ TPHa TPH”
r 10 - 8
B <1 <1 <1
1-A 15* 90” 12*
1-B 18“ 861 ● 13*
2-A 2,841 8,400 728
2-B 298 3,891 87
3-A 28 600 114
3-B <1* 38* 8*
4-A 8 11 6
4-B Iron Control Aaent i <1 <1 <1 <1
5-A Non-Emulsifier Agent 183* 24* 217* 5“
5-B Non-Emulsifier Agent 593 13 782 43
6 Iron Reducing Agent ... , <1 <1 1 1
zr- Clay Contro!. .A~ftiti
.__..ive ! 1“3 11 14 5
7-B . .... ...-
Amm.Chlnri~@ I
1
<1 <1 <1 <1
8-A I 6.608 3,391 8,585 944
+0.5%NiS Preflush System
+0.5%NEA
+0.4% Ci+2%CCA
+50#icA I
8-B 15%Hci+o.5%Nls 2,182 236 2,124 95
+0.5%NEA Preflush System
+0.2%CI+1 Wim
+3~icA
9-A 30%Prefiush(8-B) 1,409 100 1*584 49
+30% Mud Add stage
+Ao%ovemush (7-B) I
Fiowback Mix I
I
m tai Petroieum Hydrocarbons
● Results are questionable due to severe emulsions in freon extract.

284
SPE -j NOVEL FILTRATION PROCESS ELIMINATES SYSTEM UPSET FOLLOWING ACID STIMULATION TREATMENT 7

Table 3-Application Case Histories

Case 1 Measurement I Influent ] Effluent
1 Horizontal Well I Gravimetric I 826 I <1
Stimulation
Gravimetric Silica 681 <1
Infrared 1,080 <1
Infrared Silioa 1,020 <1
2 Stimulation wells Gravimetric 626 5
Gravimetric Silica I 371 I 4 I
Infrared 665 6
Infrared Silioa 489 6
3 Subsea New Gravimetric 4,120 6
Completion
Gravimetric Silica 2,840 2.5
Infrared 6,000 89
4 Stimulation Gravimetric 1,860 3.5
Reoovery I I
Gravimetric Silica 787 2.9 I

Table Uost and Volume Case Histories

Tdd w Bad
Tdal per cost (* Labor)
case IdOr Equlprnwt Media sand Cosr
1 S8,000 SS,206 $4,766 $12.36 $7.00
Vdurne Treated 1,700 Ml
2 $8,8S0 I $6,963 1 $11,026 1 $16.S7 I $11.39
Vdurna Treated 1,ss0 bbl
3 sa,370 1 S6,796 I $13,026 I S4A2 I S3.11
Vdunm Treated 6,365 M
4 S7,3S0 I $7,020 I $9,727 $17.3s I $12.0s
Vdurna Treated 1,366 Ml
AVG. S8,166 I S72?46 I $9*SU I $s.00 I $s.18

285