ADSORPTION OF FOAM-FORMING SURFACTANTS IN BEREA

SANDSTONE

K. MANNHARDT J.J. NOVOSAD K.N. JHA

this article begins on the next page F

JCPT94-02-04 Adsorption of Foam-forming Surfactants in Berea Sandstone K. MANNHARDT, J.J. NOVOSAD Petroleum Recovery Institute K. N. JHA CANMET/Energy Research Laboratories Abstract Adsorption measurements carried out with representatives of four classes of surfactant suitable f(>r foam flo(>ding (alpha olefin sulphonate, internal olefin sulphonate, linear xyle,, sulphonate, and betaine) on Berea sandstone at different conditions of temperature and salinity are, described@ Adsorption of the anionic surfactants from a low salinity b e is low, but increases substantially at moderate
salinities. L' 'ted solubility of the anionic surfactants in aqueous media tends to drive these surfactants to the solid/liquid interface and can also lead to increased surfactant loss through precipitation. The taine is highly soluble, but adsorbs very strongly on sandstone. Adsorption of this surfactant can be reduced by mixing it with an anionic surfactant. Introduction EOR production in North America is dominated heavily by gas or vapour flooding. Out of a total of 371 EOR projects, '-)94 involve injection of steam, CO,, or hydrocarbon solvent(l). Because of the low
density and viscosity of the injected fluid, gas and vapour flooding processes tend to suffer from poor sweep efficiency. This problem may be alleviated through the use of mobility control foaMS (2,3). While the mechanisms of lamella generation and collapse are crucial to foam performance and propagation, the maximum dis- tance that a foam will travel is dictated by surfactant losses in the reservoir, caused by adsorption at the solid/liquid interface, pre- cipitation, chemical degradation. and partitioning into an immo- bile oil phase. This paper deals with the la,,,t, and frequently
inost important, of these mechanisms. Surfactant classes most commonly applied in laboratory studies of EOR-foams and in field applications include alkyl aromatic sulphonates and olefin sulphonates. Since niuch of the IEOR-foam literature deals with steam-foams, surfactant selection has often been determined by the requirement of chemical stability at steam flood temperatures. The fotlowin- rankin,, has been assigned to several surfactant classes in terms of their thermal stability(4): alkyl aryl sulphonates > olefin sulphonates > petroleum sulphonates > ethoxylated alcohols and
ethoxylated sulphates. The surfactants that have been found the most thermally stable are also the most likely to precipitate in the presence of inorganic electrolyte. Surfactant solubility has been found to decrease in the following order(41: ethoxylated alcohols or sulphates > olefin sulphonates > petroleum sulphonates = @ilkv] aryl sulphonates. A characteristic of the surfactants most comml)nly described in con- nection with EOR-foams is thus their Iiiiiited solubility in brines. 34 _ 0 2- - O@ The high molecular weight surfactant homologues suitable for steam-foanis have very limited
solubility in aqueous media and are expected to have a higher affinity for the solid/liquid interface than lower molecular weight homologues. Steam flood tempera- tures will I'avour low adsorption levels and increased solubility. During ste,,im flooding, a surfactant encounters salinity and tem- perature aradients, and a knowledge of the dependence of surfac- tatit hehaviour on both parameters is required. SLirfactaTits suitable for the extreme conditions of salinity and hardness encountered in many Alberta reservoirs have been iden- tified(51. Dt-,tailed measurements of the
adsorption properties of' these surfactants have been previously described(6-8). By contrast. reported adsorption data for surfactant classes commonly used for steain flocid applications are rather limited(9-15). This paper attempts to add to the knowledge of the adsorption properties of these surfa(@tants, and also demonstrates the potential of using sur- I'act@int mixtures to lower adsorption. Specifically, adsorption measurements were carried out at different salinities and tempera- tures with an atpha olefin sulphonate (AOS), an internal olefin sulphonate (IOS), @i linear xylene
sulphonate (LXS), a betaine, and a bet@iiiie/IOS mixture. Experimental Materials CO-, Berea sandstone cores [specific surface area by N2 adsorption: 0.91 tn2/g(-,)] were supplied by Cleveland Quarries (Amherst, Ohio). Core properties are listed in Table 1. Brities Three brines were used in core floods: 0.500% w/w (mass %) NaCl. 2.32(1% w/w NaCl, and 2.274% w/w TDS brine containing 2.192@,/( w/w NaC] and 0.082% w/w CaC'2. The latter two brines have the satne ionic strength. Surfactant solubilities were assessed in brines containing 0 to 5% w/w NaCl, or NaCl and CaCi, at dif-
ferent ratios and constant ionic strength (Table 5). One ai-nphoteric and six anionic surfactants listed in Table 2 were Llsed. Surfactant Solubility Measurements In ot-der [o ensure complete solubility of the surfactants to be used in core floods, the solubility of the surfactants listed in Table The Journal of Canadian Petroleum Technology
 • !ih.
---------------~J
Adsorption of Foam-forming
SlLlrfactants in Berea Sandstone
K. MANNHARDT, J.J. NOVOSAD
Petroleum Recovery Institute
K. N JHA
CANMET/Energy Research Laboratories
Abstract
Adsorption measurements carried ont with representatives of
four classes of surfactanl. suitable for foam flooding (alpha
olefin sulphonate. internal olefin sulphonate, linear xyLene
sulphonate, and betaine) on Berea sandstone at different
conditions of temperature and salinity are described. Adsorption
of (he anionic surfactants from a low salinity brine is low, but
increases substantially at moderate salinities. Limited solubility
of the anionic surfactant.<> in aqueous media tends to drive these
surfacranrs to the solid/liquid interface and can also lead to
increased surfactant loss through precipitation. The betaine is
highly soluble, but adsorbs very strongly on sandstone.
Adsorption of this surfactant can be reduced by mixing it with
an anionic surfacmnt.
Introduction
EOR production In North America i.~ duminated heavily by ga::;
or \apour tlaoding. Out 01" a loral of 371 EOR project.~. 294
involve injeclion of 'iteam, CO:!. or hydrocarbon solvelll(l).
Became of lIle low densiLy and viscosity of rhe injecred tluid. gas
and v'lpour nooding processe::; tend to suffer from poor sweep
efficiency. Tllis problem may be alleviated through the u ... e of
mobiliLY conLrol foams (~.ll.
While the mechanism ... of lamella gencnHion and collapse are
crucial LO foam performance and propagation. Lhe maximum dis-
Lance thar a foam will tmvel is dicLaLed by surfactaflt los!-les in the
rC!-Ien·oLr. c.Hlsed by adsorption [It the !-Iolid/liquid inLerface. (Jrc-
cipiraLiun. chemical degmdation. and parritLonin2: into an immo·
bile oil pha!-le. This paper d~als with thc la!-lt. and~fre4uenlly mOSl
inlponanl. of Lhese mechanisms.
Surfactant cla!-l ... e:-. IllO.o.l commonly applied in labotatory sludies
uf EOR-foams and in field application!:. include alkyl aromatic
'iulphonates and olefin suI phonates. Since much of Lhe EOR-foam
hLeraLure deals with steam·fOlllm, .'wrfacLam selection has often
hcen determincd by Lhe requirement of chemical stability aL .5.team
tloud temperarures. The following tanking ha~ been a ... "igncd tu
... c,'eral "urfacmnt cla~se.o. in Lerms of their therm:LI .~tabiliL\,'.Jt:
:L1kyl aryl suI phonates > olefin ... ulphonatc'i > petrol~um
sulphonalc" > ethoxylaLeu alcohol ... Llnd crhoxylated sulphaLes.
Tile surfactants dmt have been found Lhe most [herrnall\' stable are
also [he mosL likely to precipitate in the pte.~ence of Lllom:anic
e1eeltuIYle. Surfactant wlubiliLy hil~ been found to decrca~e ~l the
following OIJel,.JI: elhoxylaLed alcohoL~ or ~ulphales > olefin
.~ltlphonaLes > perrolc:ulTl slilphonates = alkyl aryl .mlphonates. A
characleristic of the surElctimLs mosL commonly de~cribed in con-
nectiun with EOR-foams i" thus theil lillILled ~olubLlit)' in brine~.
34
l',.
-1CPT91- o z- af
The hi!!h molecular wei!!ht surfact'LIlL homollll!l1CS SUitable ror
steam-foams have very limiLed solubilllY in aq7tCo'LL~ LIledia mnl
arc expected to have a higher aflinity fur Lhe ~oltd/liqllid intet facc
Lhan lower molecular weight hOlllologues. SLeam l1om1 LCLllPCnL'
ture~ will favour low adsorplion levcJ:.. and im:reased sollihility.
During steam nooding. a surfacliJllL encountcr....~aliniLy ami ICI;l'
perature gtatJienLs. and a knowledge of rlll: dependence of'illrrac·
Lant behaViour on hOlh parameLers i~ reqUIred.
Surfactants suitable fOi the e"lreme comJitLO[l!-. or :-.alinilY and
hardness encounLercu in many Albet1a reservoir'i have hecl! idctt·
rified l51 . Detailed measuremenls of the aJwrpLiutl propl.!rlic . . llr
thc.'ie .HlrfacLanls have been pre\'iomly t1e...,cribed(r,.HI. (3)' COtlttil.... l.
reported all'iorption data for .o.urfacLant clas!-lc'" comlllonlv LI~etl 1'01
steam fluod applicatLofHi are rather limLLed,·!·I'iI. Tllis paper
auempls to ndu to rhe knov.'ledge of the adsorplillll propCt lic!'. or
these surfacLants. and also ueLllons[ratt:~ the potenLial or lIsitl!!- Mtt-
factant mi"(tures to luwer adsorprion. Specifically. ad'iorptioll
mcasurements \verc caiTieu ouL aL tlLffcrenL salinities and tempe-t;t-
lUre'i with an alpha olefin sulphonate (AOSI. an inLernal oll.!rin
~ulphonale ([OS). a linl.!ar x:ylene ~ulphonate (LXS). a helainc. :lnd
a hetainellOS LIli"(lure.
Experimental
Materials
Core:)
Berca ~:Ltld:-.Lone cores [specilic MLrraCL.: iltt";L by N! ilt.l~otpril1n:
0.91 m~/g'/'l were supplicd by Cleveland Quarries tALIlIH:r:.1.
Ohto). Core propertie.~ are lisLed in Table I.
Brim's
Threc brine!-l were lt~ed Ln core tloou'i: O.500r:+ w/w (mil:." r:r)
NaCL 2.320% w/w Nae!. amI 2.:n·.J~c ,. . /w TDS bnnl.! conlaining:
2.192% w/w NaCI ;mJ 0.082% wlw CaCi,. Thl.! laIlcr LWO hritle~
have the ~atl1e LonlC 'itrength. SurracLanL soiubililies wetl.! il~.~l.!s:.ed
Ln brines containing: 0 LO St:;'}. w/w NaCI. Ot N:LCI ami cae!' al tlil·
fetCIl[ ratim and COnSlall( ionic strengLh (Table 51. -
SwfueJllIll.\
One amphOlenc anu !-lix anionic ~urlacLanL!-I li.~tl.!d itl Tallie 2
were ust!d.
Suriactant Solubility Measurements
In order ro ensure .:mnplete ~()llIbilily or the 'iLtrractatll:. III hI.!
used in cnrc tloous. rlle ~olubility or thl.! surfacL;um li:.ll!u ill Tahle
The Journal of Canadian Petroleum Technology
 TABLE 1: Core and displacement data.

Core ID 0<-2 0<-' Qi-12 0<-3 Qi-lO Qi-l1 0!-13 0<-. 0<-6 0<-7 Q{-14

Surfactant AOS AOS ADS lOS lOS lOS I.XS I.XS Step 60 Step 60 lOS 1518/
1416 1416 1416 1518 1518 1518 810 .'0 Step 60

BrIne O.S~ 2.J2~ 2.27Y. 0.57- Z.~2~ 2.27:': 0.51- O.SY. 0.5Y. O.S:<- O.SY.
NaCl NaCl IDS NaCl NaCl IDS NaCl NaC! NaCl NaCl NaCI
:,·..'.,.:.'.·.·i.·_ ~:~:-.. r-~
Temp. (oC) 23 23 23 23 23 23 23 75 23 75 23

.! Length (em) 9.86 10.12 9.34 9.72 9.75 9.67 51.44 9.65 9.510 9.65 10.17
Cross-sictlon 11.22 11.20 11.18 11.21 lL17 11.20 11.20 11.2J 11.21 11. 22 11. 21
(em)
Pore yolo (mU 24.9 25.9 24.4 26.5 23.6 23.6 24.2- 25.1 26.1 23.6 24.8
PorcEilty (frae.) 0.225 0.22.8 0.234 0.243 0.216 0.21B 0.229 0.232 0.235 0.218 0.218
Dry weight (gl 232.45 2.:39.02. 220.52 228.48 229.90 228.35 2.22..60 227.2.6 233.45 228.14 2.<10.38
Abs. perm. ("'"
aIr
brine

Injected surfac.
5 ••
220
'65
.
, 2<5
•••592
251
50.
237
•• 2
19. 183 ,
'7•
177.
••• 517
219
••• '67
190

cone. (gIl) 10.015 10.009 10.045 10.432 10.105 10.010 10.017 10.016 10.005 10.011 10.024-
Slug vol. (ml) 50.Z 49.4 48.5 52.4 49.8 45.6 47.9 50.0 49.8 47.6 49.5
(PV) ·Z.02 1.91 1.98 1.98 2.11 1.93 1.98 1. 99 1.91 2..0Z 1.99
Flow rate (c.l/h) 1.98 2.02 1.96 2.00 2.05 1.98 1-99 Z.Ol ].97 1.96 2.00

• 3,015 g/l Step 60, 7.009 gil lOS 1518

2 was measured as a function of salinity and surfactant concentra- TABLE 2: Surfactants.

tion by doing a salinity scan at consmnt surfactant concentration
and a surfactant concentration scan at constant salinity, ' ...
A=t!va canc~a' o

While it is realized that surfactants can exhibit complex phase

Trada N3J:IO o.c.lIl~l Cb.ss Hola=. vt.
(glaoU
plli '
solution)'"
behaviour and precipitation/dissolution properties(l6.lil). ,;irnple
'" to
Enordol MIS 141& C _ alpha ::19.0 :JZS ' 7.'
visual tests were taken as indicators of surfactant solubility in this 14 1EO
(Shdl Chaalca.l) ahrLn "'-Ilfanata
work. Surfactant solutions were prepared ill test tubes. and rhe sol-
ubility was detennined by visual inspection of the appearance of EIIord .. l MIS 1610 CLEO_Ie nLpha Z9.S ::156'0'

the sample. Samples showing any turbidity. a precipitate, or (Shall t:helllca.L) ahrLn sulCanate

phase-separation were denoted insoluble. These samples were

.3.Jy'a'
heated slowly to 85°C in a waterbath. The temperature at which EIlardet ICIS 151B CIS_IS Inlemal 25.2 '.0
(Shell 01=1 ..... 11 olefin ~lConate
the samples cleared was taken as the minimum solubility tempera-
ture, Some samples that were not soluble up to 85°C were heated EMrdet L'iS 1619 CI 6-18 lIne::r.r IS.Z 422.'·'
funher to 135°C in an oven. The calcium tolerance of two surfac- (Sh ... U t:he"lca.lI tolucna lOulfanate
tants (ADS 1416 and IDS 1518) was determined at 23°C by test-
ing rheir solubilities in brines of the same ionic strength as 2.32%
NaCl, but containing NaCl and CaCI:!. at different ratios (Table 5).
EIIarda 1 urs 910
(Shall 01",,10311
~-IO linear
lqrla]'\e sulConala
ZO.2 334'·' ,.. , l'~
~.. ,-: ,
EIIardat l.XS J.::I1G. C1::I_ 14 Ilnnr 19.5 .::197'·'
Core Floods (Sh,,11 Che!llicall :-oylana "ulf....... t ..
~:~.,' .'.
Adsorption was measured through single-phase displacement Shp:milo 60 AU::yl"",ldo- ::10.0 400'·' '.5
(Stc~"" ~pany) ""'talno of
tesrs in Berea sandstone. The core floods were modelled using a co""nul 011
one-dimensional convectton-dispersion equation '\'ith an adsorp- EIIard .. l 105 1519/ 5.5
tion term that uses the surface excess formalism, as described in Ste~arU'lo 60 ah:tura
(7,:] by J:III .. s)
detail in previous publications(6,1,'9). The model parameters allow
calculation of adsorption isotherms. (3.) S~cltlad bYa3.flufncturcr
(b) £'ilth,ated troll synlliatlc rout .. &uppU ..;I by aanufactw-cl'
Adsorption of four surfactants selected on the basis of the solu- (e) Average pI!. or solutions ~rapa.red tor core t!Gods

bility measurements (ADS 1416, [aS 1518, LXS 8lD, Stepan flo
60) and one surfacrant mixture (IDS 151S/Stepanflo 60) was mea-
sured in Berea sandstone 3t different conditions of temperature
and salinity (Table I). A new core was used for each adsorption
measurement. Cylindrical cores (3.SxlO cm) were cut to size and
dried at 110°C for several hours. They were mounted in a lead
sleeve inside a high pressure core holder at an overburden pres-
sure of 6.9 MPa (1000 psi). The pore volume was determined
using gas expansion, and the absolute permeability to air was
measured. The core was filled with CO:! and saturated with brine
by flooding with approximately 15 pore volumes (PV) of brine
against a back pressure of 0.2 MPa (30 psi). The absolute perme-
abiliry to brine was measured.
A measured volume of surfactant solution (2 PV, lO gil active
concentration) was injected into the brine-saturated core. followed
by brine of the same composition, all at a constant flow rate of
2 mUh (20 em/d). A non-adsorbing tracer (tritiated water) was
injected with the surfactant sohnion, and served as a check on rhe
material balance. The pH of the injected surfactant solutions is
included in Table 2: no buffering agents were used. The relative
February 1994, Volume 33, No.2
positions of the tracer and surfactant effluent profiles give a direct
visual indication of adsorption. The pressure drop across the core
was measured in all floods to detect core plugging by surfactant
precipitation. This allowed additional assessment whether the
measured surfactant los,; was adsorption or a combinarion of
adsorption and precipitation. All core floods were run at atmos-
pheric pressure and conditions specified in Table I.
Effluent fractions were analysed for surfacrant and tracer con-
centrations. The anionic surfactants were determined by two-
phase titration with Hyamine 1622 (BOH Chemica1)cZO), and the.
amphoteric surfactant by back titration with Hyamine 1622(21),
both in chloroform/water with mixed indicator at pH 2. Chemical
analysis of each component in the surfactant mixture
(anionic/amphoteric) involved titrating each sample twice, once at
pH 2 and once at pH 10, A[ pH 10, the anionic surfactant can be
titrated wirhout interference from the amphoteric. At pH 2. the
two surfactants form a complex. and the titration yields the excess
anionic or amphoteric not bound in the complex. The amount of
,;.
35