Note: Descriptions are shown in the official language in which they were submitted.
~:;L53272
1 B~CKG.~OUND OF TH~ INVENTION
__ ____ _
1. FIE~]) OF THE INVENTION: The invention'relates to the
use of a micellar so.lution of a thin film spreading agent,com-
prising polyepoxide condensates of resinous polyalkylene oxide
adducts and 'polyet~er polyols.for breaking or preventing petroleum
emulsions. More specifically, a'll or a substantial part:of the
organic solvents formérl.y required for preparation of liquid
solutions of this.interf'acially ~active compound.
. 2. DESCRIPTION OF THE PRIOR ART: One of the principal uses
~10 of the present composition is in the breaking of petroleum emulsions
` to permit the separation thereof into two bulk phases. Much of
the~crude petroleum~oil procluced throughout ~th~e world is accompan-
ied~by~some:wat,er or~brine which~originates in~or adjacent to the
geol;o~gical:formation from:~which' the oll is pro~dùced. The amount
l$,',~ o:~aqueous~phase accompany~ing~the oi~l:may.vary from a trace to a
very~;làrge~percentage~,of the total' fluid p:roduc:ed. Due to the :-
,n`,atur~al~occurrence in-most:petroleu.m of :oil-soluble~or dispers.ible
`' ~ idg~;~ag~ts~ much~o~f:the~aqueous~phase~ produced~with oil
~, ~ lèd~:the~r ~ ~ orming.stable~water-in-oil emulsions,~ .
~he L~iter~ture 'Gon~a~in.s~numerous~references to s~uch emulsions,
esul,:~ting~:~rom::~the:ir'~occùrrence~ ;and tXe methods
employ~ed~:~to~br~eak:them:and separate~salable ~etroleum. See, for
"exa~pl~e~ "The'~'rechnology~of. Re~olvin~ Pet~oleum Emulsions`' by L~
nso'n~and~:. W~ S'~ el, p. ~535 et seq~i ~Colloid ChemLs ry
9 ~ ~VoL-VI~, ~ by ~ o~è Ale~ander, R,hein~old Publishing Corp., New
"a ~ ~" ~ érf~acia~l Films~.,A~ff~ecting~the~Stability of
Em s~;~ ~ s",'~'¢~s,;~M.~.~ Blair, Jr.~in~Chemistry and
.,;InJus ~;y:(Lo~d,o,n),~ et~se :~( 60).
'y de ~ ~s' er;~' é:~to~` e
water-~soluble~'soa~ps,~Twit~chell~reagents~, and~sulonated glycerides.
'Thes~è~pr'oduc't's'~wer~e:~readily~co~pounded with~water to form easily
1::
' ~lS3~72
l pulnlable l;(lu;ds and w(fre c!~nvellifallt.ly applied by ~lmping into
flow linfes at t:he well head or by washillfg down the casing annulus
with ~a~er to commingle with well fluids prior to their'flow to
the surface. These products, however, were effective only at
relat1vely high concentrations and their use adf1ed subs~antially
to the cost of production.
Some ti.me ago, it ~as discovered that certain lightly sul-
fonated oils, acetylated caster oils and various polyesters, all
of which were ;nso~.uble in ~ater but soluble i.n alcohols and
aromatic hydrocarbons, were much more effective in breakin.g .
:~ emulsions. Accordingly,'essentially all commercial'demulsifier.
~ affevelop~ent has led to production of agents which are insoluble
f~ in ~oth water and petroleum oils-~lnd have other properties.to be
descr1bed below which cause~-tlem to~spr~ad aL oi1-water inter-
15~ ~aces to form~;very th1n,~mobile ~11ms which displace any emulsify-
ing agent pr.esent in~the~ o'il to:allow coalescence of dispersed
; wat~er droplets. '~Genera11y,~ such~interfacially:active compounds
are~hereafter~-refefrred':to a~s Thin~Film Spread'ing Agents', or '`T~SA's"
In.~:the~past, these:~have~.had' to~b~e compounded'w1th and dissolved
in~ al~ohol~s~or:~highly aromat1c hydrocarbon so~lvents in order to
roduc~e:re~adil;y~applied~:liquid~:f^ompcfsitions. A~wide variety of
su~ch c~ompo;sitions are required ~o trea~ the many di~erent emul-
~ s~icns~;enc~untered throu ~f~Ut the world..f~
Wh~i1e:pré~sent:~TFSA;compos~i~tions:are hi~,hly effective, bf~ing,
p.erhaps~ up~to.'fLfty~to-a~hun~dred~tLmes more eff~ctive per unit
vo1ume~ than ~he ;ori~lna~ water-:soluble demulsiflers, they suffer
.~ s~er`~ous:~pra~ct1~eal~de~1c~1encLes:~:because o~ their solubility.charac-
te~ist;i~cfi~ .FQ'r~é'xample,~alc~oho1s and the aromatic hydroc.arbons,
which~are required~-~for~pP'epara~tion:of~liquid, pumpable compositions,
3~0~ are~qulte~expen~si~e,~todqy~approaching in cost~that of the active
.demul:sifier 'in~edient its~elf~. Further, such:solvents are flam-
.:.~,.~: : :
,~, . . . - ., .
~f ~ ~ "
:. ,1 . .
' ~15327Z
1 m~ble ~nd ~ s clc~;~te s.~fet~l plo~le~ns ;~ en~ ol-e ex~-ense in '
shipping, s~or;ng and use. The low flash point fl~mmability can
- be improved by using high boiling aromatic solvents, but these
~re incrcasin~ly rare, e~pensive an~ dan~el-ous from the standpoint
of carcinogenicity and ~erm~to]ogical effects.
Still urther, present'demulsifiers cannot generally be used-
in a subterranean oil or gas well, in~ection we'll, or the'like,
since they cannot be washed down with either water ~or brine) or
a portiort of the produced oil, and, being viscous liquids which
are required in very small amounts, they cannot be reliably and
.
continuously delivered several thousand feet down at the fluid
level in a typical well withoùt use o~ elab~orate and expensive
delivery means.
' ; O~her appllcations;of l'FSA compositLons woul~ be acilita~ed
15~ ~ if they were readily soluble or dispersible in~water. For example,
much~heavy', vlscous~oil~ls~produced in the United State's by steam
inJe~ction~procedur~es.~Typically, wet' steam is inject`ed into the
ol~l produc~ing~;str~ata~for several~weeks in order to heat'the oil,
lower~ t~s vlsco~s~ity~and~increa~se~r~eservoir energy. Steam injec-
~ io~ is~then stopped~and~oil~i~s~fl~owed~or pumped from the bore-
hole which~was~used for~'~st~eam in~ection. Much of the water
resulting from~condensation of~the steam is also pioduced w~h
the~o~il in emulsi~fied form. ~Since emulsions are more viscou~
th'an~the~external~phase~at~the~same tempera~ure~, and thus create
increased~resistànce to~low~,~ productivity~of the steamed wells
c~an'be~impra~èd by ~nj`èc'tin~a~`~waL~or-soluble demulslfier into the
~''~ wet~st;eam during the~steam inject~ion period ~o`prevent emulsion
or~ ion,~S ,~ o~ex Ie,~ .S~.~Patent 3,39;6,~92, dated April
, 1966,~to~F.~;D.~ Mu~g;ee.; At~pres~est, the requirement o~ water
3~0~ solubilit~y~sériously limits~the~choice of d~emulsifiers for use in
ste~am or~water~injection to the~relatively;inefficient compositions
4-
~ " ~ . :- ` . .
~ j . . .
, ~ ~ ' , .
115327'2
As disclosed in my co-pending Canadian applications, Serial
Number 353,251, filed June 3/80 and entitled "Metho~ o~ Recovering
Petroleum From A Subterranean Reservoir Incorporating A Polyether
Polyol", Serial Number 353,232, filed June 3, 1980, and entitled
"Method of Recovering Petroleum From A Subterranean Reservoir
Incorporating Resinous Polyalkylene Oxide Adducts", Serial Number
353,258, filed June 3, 1980, and entitled "Method of Recovering
Petroleum From A Subterranean Reservoir Incorporting An Acylated
Polyether Polyol", and Serial Number 353,233, iled
June 3, 1980, and entitled "Method of Recovering Petroleum From A
Subterranean Reservoir Incorporating Polyepoxide Condensates Of
Resinous Polyalkylene Oxide Adducts And Polyether Polyols",
TFSA's are useful in processes.for enhanced recovery of petroleum.
U~sed in such pro~cess~es ~involving displacement of residual oil by
15 ~ ~ ;aqueous~solut~ions,:polymer solutlons and other a~ueous systems,
;these~agents~act to increase ~the amount of oil recovered. Such
act~on posslb~ly~arises from their ability to further water wetting
of reservolr~rock~ e~ssen ~the~vls~cosity of~the oil-water: inter-
'faciai ~l,ayèr~ ~and~promote' ~coalescence~of~dispersed droplets~ of
ér~ water~or~oil~in~the~other~phase~
By`use~o~the present~aq éous micellar~solutioDs~, the intro-
duc~tion~of~TFSA ~1nto~aqueous~disp1acement or flooding~ flUid5 iS
gr~e:atly f!acilî~ated. ~ In~ ad~d~ition, the present micellar solutions,
;.per:,~se, ~or in:~:cQmbinaticn with other components, can be used as
cbe ~l o d L~ gent ~ or~ as ~ pretreating ha~k or ~lue ahcad of
O~:her~ appli~Gati~ons~for-the~pr~e~sent:::TFSA~:micellar solutiQns in-
ude~heir u5e as~ loecùlatio~aids ~for~finely ground hematite and
:wag~e ~ ~orè~S durine;the~de$1 ~ ing~step~o~ore ~eneficiation, as
ao~ additiYes~fo~ ~impr~ovlne~the~ail;~re~-oval and detergent action: o~
cl~eaning~composit~ions~and~detergents designed~ for use :on polar
~ ~-
L5327Z
l ~ m.~terials, for ~lle im~rovc~n(l~t o~ solvcnt ext~-acLic~n processes
such'as tbose used in extraction of antib;otic pl-cd~lcts from
aqueoùs fermentation broths with'organic solvents, for the improve-
ment o~ efficiency and phase separation in the purification and
concentration of metals by solvcnt extraction with organic solu-
tions of metal colnplex-foL~ing agents, and as assistants to
improve the wetting and dying of natural and synthetic fibers and
for otller pL-occsses~normally involving the in.te~-f~ce'be~een
suraces of differing polarity or wetting characteristics.
10 - ` ` ' ' '
: SUMMARY OF THE INVENT~ON
. A primary object of'the present invent~.on is to provide
aqueous, li~uid compositlons of these TFSA's having new and` '.
' useful characLer'istic$ which sllow~production o: petroleum
emulslon ~reak:ers~and emulslon preventing,compositions free or
.rel~atively~free o~f~h:ighly flammable~-and env1ronmentally objection-
able:aromatic~hy'drocarbonsi compositions h'aving a comparatively
low c;ost; compos1ti~ons~which;'are soluble~or~dispersible`in wster
and~whi~ch,`~the'refore,~;can~often:be:`appli~ed by:more efec'tive
;me'tbod`s~than ~can exlsting~products; compositions which'can be
used in enhancsd~recover~ opera~ions SllCh as ste~m fl~odin~ ~nd
ag;ueous medium :flooding where`presqnt produc~s.cannot.be readily
app~ ed~;~and;co~position6 which~can be'compounded with water-
sD1ubl~e~reagent~s:of~o~ther ~yp:es~;, such`as corrosion inhibitors,
wstting:~a;gents~, s~cale~ hibitors,~biocides, acids,~etc., to
prov1dé~'multi~purpose~compoun:d's~for:~use:ln solvm~'many oil well:
coTnp1etLon,:pràduction~ transportation and refining problems.
.In~ac:cor~:ance~wi~h,the~pres~e-n~t ~invent1on, thes'e'a'ims are
ac~c~mplished by means~of amphipa~hic agent~s wh'i'ch'are''capable of
30~ orming mi~cellar~solut~ions~and wh'ich'by th~is mechanism or other
unde~ined actions,: coTnbined:with'~'thos'e`of a secon`d es'sential
6- ` :
.
~lS3272 ~
component which will be referred to as a hydrotropic agent, are
able to form homogeneous aqueous solutions containing a rela-
tively wide range of concentrations of TFSA.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The TFSA compositions of the present invention can be
broadly categorized by the following general characteristics:
1. Solubility in water and isooctane at about 25C
is less than about 1% by volume;
2. Solubility parameter at about 25C is in the range
: 10 of from between about 6.8 to about 8.5, with a
.majority in the range of from between 7.0 and about
7.9; and ~ ~
3. ~ Spread~at the~interface between white,~reflned
mineràl oil and~distil:led water to form films having
a calculated th1~cknoss no~'gréater than:about 20
Angs~tr~ms;~*~a~ preadlng~pressure of about 16:dynes
A'~co~posL~1On~h~ving~ the properties are gen~rally
po ~ ~:or~s ~ poly~ers~having~mo1ecular~ lghts ~
f~om: ~ ~,000~:to,,about~100~000 and having~str w tures ~`
ing~a`mul ~ lcity~;of~distr~ibutèd~hydrophilic and hydro-
pho'pic~moietle~.arranged~:ln lineàr or::planar array~which make
t~ m'~ùrfacè aat:~'ve and~lead~to~:thq;ir~àdsQxptlon at oil-water ~ :
ajcies,~:t,o~o ~ ~ve' ~: f lm9~
ke~moJY~c ~ nly~ ~ u~ntered~9u~rface-aati~ve~compounda,
~re~:ejnt~ ~ :,.~ pears~ to~be~:~incàpable of~forming a miaelle
:oil~Q~w4ter~ di9trib ~ d and;alte~rnating ~;
of~ r~,and~,nonpolar or~hydrophilicand hydrop~obic
oup~ in ~the. ~ ~ e~ ~ ~y~`p ~ ents the-kind of organiza-
'30::~ t:ion;~requlr~ed~f ~-~mi¢eLle~:~formatlon~'and thus impairs dispersion
,'' ~ : : : :
.,.. ,, . . . .,, ... . : . . .
~lS;3Z7Z
or so}ution in either water or low polarity organic solvents.
The TFSA's useful in the present invention have the :~
previously recited properties: .
~: ,
~ .
.
5~3;27Z
1 1. 'l`l~e ~so]ul~ y in ~ter .lnd in i~;~)oc~ e aL ,~l)o~t
25~C ~s less_than_.ll,)out 1% ~y_~olu~ne.
Solubility tests may be run by placing a 1 ml
sample (or the weight of solid product calculated to
have a volume of 1 ml) in a ~raduated cylinder of the
type which may,be closed with a ground glass stopper.
Tnerea~ter place 99 ml of wa~er in the-cylinder, close,
, place in a 25C water bath lmtil ~he~mal equili~rium is
reached, and remove from the bath and sllalce vigorously
~ , for one minute. Return the sample to the'bath for five
minutes and then repeat the shaking procedure. Finally,
retu~n~the sample to the~bath and,~allow it to stand
uietly for one~hour.,~-iThe'~cyli'nder contents should be
; carefully~examin~ed~a~d any~cloudine~ss or opacity of the
,5~ iqu~d~ph~ase or~the~appearance o'~any sediment or ~ :-
undissolved material~in~the cylind~er noted, thus
indlcating;that th~e~sampl~e satisf'ied~the requirement
~"~ for~Lnsol ~ lity~in~wa~er~
I oo' t nQ:~ sol~ b: it~ ~is~ deter~ined~ Si ilarly by
~substitutin~ this~hydrocarbon ~o~ the~wat,er u~sed '-
The-Sol~bilit:y~Parameter`(S.P.~) at~about 25C is fro~
` ;between~ ab~ut 6. g and~ about 8 . 5, . inclusive.
Me~hod8~0~ dete~ ination o ~s~ubLll y parame~er
are"d~sel~os ~in~Joel~`~H~ ;Hildebrand,;`'The Solubility o~
Nonel'~ ~ lyte5",~,Thi~d Edit~ion,~p~s. 425 et seq~ How-
,~ ever~, a ~ ified;~proc~edure, sufficiently accurate for
qualific-at :on~o~ a~u ~ f ~`:TFSA cQmposition may be
ut~iliz d..~ ~ pQne :t~ f~a
are~general1y~inso1uble i~ hy~drocarbon (non-hydrogen-
b~onding)~solvents~ having~a :lower solubi1ity parameter
,, ~, ~, - :
r f '~
llS3Z~7Z
than themselves. Therefore, the present composition
should be insoluble in a hydrocarbon solvent of a
solubility parameter of about 6.8. Since the solu-
bility parameter of mixtures of solvents is an
additive function of volume percentage of components
in the mixture, test solutions of the desired solu-
bility parameters may be easily prepared by blending,
for example, benzene (S.P. 9.15) and isooctane
(S.P. 6.85) or perfluoro-n-heptane (S.P~ 5.7).
A mixture of about 72 parts of benzene with
about 28 parts of isooctane will provide a solvent
having a solubility parameter of about 8.5 at room
temperature (about 25C). Perfluoro-n-heptane has
a solubiIity parameter of about 5.7 at 25C, so a.:. ..
mixture o:f 68 parts of this solvent with 32 parts of
benzene provides a solvent with a solubility parameter
of about 6.8, or isooctane.of a solubility parameter
6.85 may be~ used.
When 5~ ml of the TFSA are mixed with 95 ml of
2:0~ an 8.5 solu~ility parameter solvent at room tempera-
: ture,~a clear solution should result. When 5 ml of
: TFSA is mixed with a 6.85 solubility parameter
; solvent, a aloudy mixture or one showing phase
separation should result. Solvent mixtuxes have a
solubllity parameter between about 7.0 and about
7.9 may be prepared as described above and utilized
ln a ~imilar test procedure.
: : Ih interpreiing the solubility parameter and
, ~ ,
other tests, it:should be reaognized that the TFSA
30~ : ~ consists not of a single material or compound but
.~ a cogeneric mixture of products containing a range
of products of molecular weights distributed around
_ g _
~ . ~ ''" . ; '" ' ` ~
llS3Z~2
the average molecular weight and even containing
small amounts of the starting compounds employed in
the synthesis. As a result, in running solubility
and solubility parameter tests, very slight appear-
ances of cloudiness or lack of absolute clarity
should not be interpreted as a pass or a failure
to pass the criteria. The intent of the test is
to ensure that the bulk of the cogeneric mixture,
i.e., 75% or more, meets the requirement. When the
result is in doubt, the solubility tests may be run
in centrifuge tubes allowing subsequent rapid phase
separation by centrifugi.ng, after which the separat-
ed non-solvent phase can be removed, any solvent
contain`ed in it can be evaporated, and the actual
weight or volume of separated phase can be determined.
3. T~he T~SA should spread at the i*terface between
distilled water and refined mineral oil'to form films
with thickneJs no qreater than about 20 Anqstroms
(0.0020 micrometerj at a film Pressure of about 16
: Yne~s~per cm (0.0i6 Newton per meter).
Sult~ble methods of determining film pressure are
disclosed~in N. K. Adam, "Physics and Chemistry of
9urfaces", Third Edition, Oxford University Press,
' Lo~don, 1941, pgs. 20 et seq, and C. N. ~lair, Jr.,
"Interfacial Films Affecting ~he Stability of Petro-
leum~Emulsions", ChemistrY and Industry ~London),
1960, pgs.~538 et seq. Film thickness is calculated
on the assumption that all of the TFSA remains on
the area of interface between oil and water on which
the pr~duct or its solution in a volatile solvent has
been placed. Sinoe spreading pressure is numerically
equal to the change in interfacial tension resulting
- 1 0
:
-
~3L53272
from spreading of a film, it is conveniently
determined by making interfacial tension measurements
before and after adding a known amount of TFSA to an
interface of known area.
Alternatively, one may utilize an interfacial
fllm balance of the Langmuir type such as that
described by J. H. Brooks and B. A. Pethica, Trans-
actions of the Faraday Society (1964), p. 20 et seq,
or other methods which have been qualified for such
interfacial spreading pressure determinations.
In determining the interfacial spreading pres-
sure of the TFSA products, I prefer to use as the
oil phase a fairly available and reproducible oil
such as a clear, refined mineral oil. Such oils
are derived from petroleum and have been treated
with sulfuric acid and other agents to remove non-
hydrocarbon and aromatic constituents. Typical of
such oils is "Nujol'l,~distributed by Plough, Inc.
This oil;ranges in density from about 0.85 to 0.89
20~ ~ and usually has~ a solubility parameter between
, ~ ,
about 6.9~and about 7.5.. Numerous similar oils of
greater or smaller density and viscosity are
~ commonly available from chemical supply houses and'
}~ pharmacies.
Ji~ Other essentially aliphatic or naphthenic
~ hydrooàrbons of~low volatillty are equally usabie
3~ and will yield similar values of spreading pressure.
~ Suita~tle hydrocarbon oils appear in commercial
3~ tradè a3 refined "white oils", "textile lubricants",
"paraffin oil",~ and the like. Frequently, they
may aoi~tain very small quantities of alpha-tocopherol
: , : :
;. .
,
llS3Z72
(Vitamin E) or similar antioxidants which are
oil-soluble and do not interfere with the spreading
measurements.
::
, ~
~ :
`:~
,:
'
- lla -
~, .
, '
~lS3272
.
ile t:he exist:cnce of In;cellcs clnd o~ oily or aql-eous
nicellclr s~lu~:i.ons havc bcen known .ror some tirne (see, e.g.,
"Surface Activity", Moilliet, Collie and Bl.ack, D. Van Nostrand &
Co., New York (1961) ) Rnd are probably involved i.n many operations
involviIlg det:erj~,ency wh~rc cither oi.ly (nolll-ol~r) or e;~ hy
(highly polar) soil particles are to be relnoved, their utility in
cooperation' with hydrotropic agents for the present purpos~es is
- an une~pected and unpI-edictable ~iscovery.
In U.S. Patent No~ 2,356,205, issued August 22, 1944, to
, 10 Chas. M. Blair, Jr. ~ Sears ~ehman, Jr., a wide-variety of
'.: . . . :
::~ micellar solutions designed to dissolve'petroleum oils~ bitumen,
wax, and other relatively nonpolar compounas'are'described for
3~
3 ~ purposes of cleanin~g bii formation ~faces and for ef~ecti'ng en- .
,~.
' hanced recovery of petroleum:by solution thereof. At this early
~' 15 . date, however, the use of micellar~principles was not contem-
3~ plated for the~preparation.of solut:ions of t.he relatively hijgh
olecular weight~de~ulsifiers. : ~ ~ -
;However,~some~of~the prLncipIes disclosed in the'above
p~a:tent:,~omltting~the~:maln~ ob]ectLve~'therein of dissolvin~'rela-
: tively large amounts~of hydroc~arbons~, chlorinated hydrocarbons,
. and the~like,~ are applicable to;~preparation of the present com-
'~ posit~ions.
The four necessary component;s:of the micellar soluticns o~
3~ TFgA~are~
5~ : A micelle-~o~min~phip,s~ c ~ent, Such m~y be
: anionic,~ cationic~, or~nonîonic and, lf anio,nic or
7`' ~ cation:ic:,~mày~;be~either~ In~salt form or as the free
; 'acid.or fr;ee~base~or mixtures thereof,
2.~ d--_E~c ~ent ~T~is is a small to medium mole-
3~ cular;~welght~semi-polar compound containing oxygen. -
nitr~ogen or sulur and:capable o~ forming'hydrogen
- 1 2 - -
,., ~ ~ . . .
, 'i ~ .
llS3Z7Z
1 boncls. It is believed ~hat such a~nts cooperate in
SOllle ln~llller ~it h ~:h~ n~ atl)ic ~ nt to form clc,lr or
opalescent, stable compositions.
3 . W~ t. er.
4. 'rFSA, having the propertics' reclted aboYe.
In addition to t hese components, ~he micellar solutions may
contain, but are not required to contain, salts~ hydrocarbons, or
small amounts of other inorganic or organic material. Such'
~; constituents may be impurities, solvents, or by-products of
~10 syntheses used in fol~ing the hydrotropic a~ent, or may be addi-
io~s~found useful in iorming~ the composition o~f this invention.
As~an~example~of~the l~atter,'small~amounts of lnor~anic s~lts-;
such as~NaCl, Na2504~,;KN03;,~CaC1~2;~and the l~ikè~,' are~sometimes ~~
`hélp~ful~in promoting~homogeneity~with~a minimum~o amphipathic
~15~ and~'hydrotropic~agent;s~ They may`~also'yield-compositions of .
lower~freezlng~poin~t,~a pr~op~erty` seful~w n~'the eomposit on is~
'e~plo ~ ~in ~cold'~clim~ate`s~ Simila~rly,~et ~ le ~glycol,~met
, acetic~acid~ or~siinil~ar~org~anlo~compounds~ma~y be~incor~
p~ra~ed~into the composi~ o ,~ ~improve p~ysical~properti s
~ing~ ~o~in`t~ vls~os`ity~A~an'd~dens~i~ty,~or to i~prove ~stability.
" As~stated above,~;the~micel~le-forming amphipathic agents
ich`'may~b'e'used~in preparin~ the'aqueous solutlQns ~erein
cnt ~ ated~may be ~eithe~ ~cation-activej~ ~ni~on-active, or of the
rol~ytl'c type.~ p~athic~a~ents gen~erally have~pres~ent
a~ one~ra~d~i¢~a~'containing;about~10 or; more car~o atoms and
net-m~-re~``than a~out ~ cà ~ on~atom -p ~molecu q~.~ This
amphipa~hic~'e ts-` mpl yed~ the~pres ~ t~invention as a
gmpone~ of~ e~ve~icle~or~solv~nt~ or~dispersant employed in the
pres~ent~composi~ns~ T ~hydrophobic portions of these a ents
may~be~alipha~ic,~alicyclic~ ;alkylali~cyclie~, aromatic, arylalky~,
or~àlkylaromati~c. $he'pr~ef~rred~'type~of agents are those in
-` ~lS;3Z'~;~
which the molecule contains a long, uninterrupted carbon
chain containing from 10 to 22 carbon atoms in length. Examples
of suitable anion-active amphipathic agents include the common
soaps, as well as materials such as sodium cetyl sulfate,
ammonium lauryl sulfonate, ammonium di-isopropyl naphthalene
sulfonate, sodium oleyl glyceryl sulfate, mahogany and green
sulfonates from petroleum or petroleum fractions or extracts,
sodium stearamidoethyl sulfonate, dodecylbenzene sulfonate,
dioctyl sodium sulfosuccinate, sodium naphthenate, and the like.
!0 Other suitable sulfonates are disclosed and taught in U.S.
Patent No. 2,278,171, issued February 17, 1942, to De Groote
and Keiser.
Suitable cation-active compounds include cetyl pyridinium
chloride, stearamidoethyl pyridinium chloride, trimethyl-hepta-
decyl ammonium chloride, dimethyl-pentadecyl sulfonium bromide,
octadecylamine acetate, and 2-heptadecyl-3-diethylene diamino-
imidazoline diacetate.
Suitable nonelecfrolytic amphipathic agents include the
oleic acid estér of nonaethylene glycol, the steric acid ester
o polyglyceroli oxyethylated alkylphenols, and long chain
~; alcohol ethers of polyethylene glycols.
It is of course, well known that amphipathic compounds are
readily and commercially available, or can be readily prepared
to exhibit the oharacteristics of more than one of the above
mentioned types. Such compounds are disclosed in U.S. Patent
,~ ~
No. 2,262,743, dated November Il, 1941, to De Groote, Keiser
;~ and Blair. For convenience, in such instances where asurface-active ~iaterial may show the characteristics of more
than one of thè above described types, it is understood that it
~0 may be classifiéd under either or both types.
- 14 -
,................... . . . .
115~3Z7~
The mutual solvent or hydrotropic agents of the solution
utilized in the present invention are characterizable as
compounds
LO
': :
,
:` :
- 14a -
'' ~"7~
5~Z72
1 Of a hydl-ophobic l~y(:lroc~rboll.residue of colnparatively low molecular
weight combine~ with a hydrophilic ~roup of low molecular weight
and are free from surface-active properties. The'hydrophobic
resic~ue may'contain fr~m 2 to 12 carbon atoms and may be alkyl,
alicyclic, aromatic, or alkyl substituted alicyclic or aromatic,
or may be the'hydrocarbon portion of a heterocyclic or hydro-
carbon subst~ tèd heterocyclic group. The llydrocarbon residue
may have br~nched or normal chain structure, but no branch may
'" have a lèngth of.more than 7 car~o,n atoms from the point of .
attachment to the hydrophiiic residue, co~mting a'benzene or
cyclohexyl group as being equivalent in length`to an aliphatic
chain of three carbon~atoms.' Whére the hydrocarbon residue con-
sists of not more-than~4 carbon atoms, structures:of .the noEmal
pr~lmary alkyl~type~are pre~ferre'd.'. Where'the residue~is made up
~ 15 ~ ~of mo;re than fou'r carbon atoms,~ then~structures of secondary and
;~,~ ;,:; , :;~tertiary~types;~ar~e a~so~good~'wher~è~the~s'èc~nd~aDd~third~branches
may~b~e,~me~thyl or:-~eth ~;gr~up~s
~b `~ ` T~is~hy~drophobic~hydrocarbon residu~e'is~combined~either
d~rsctiy or~in~dir~ectly~with~:a~hy~drophi~lici~group~of one of the
following.groups~
a)~ A hyd~oxyl~group which may be alcoholic~ phenolic,
or carbo~ylic;;~
(b)~'~ An~aldehyde~group;~
",~ (:c)~,A~carboxy amide group;
(d)~ n~amine~sa~lt,group:; : ' '
(e) An~amine~rQup, and
(f~ n,~alkali~phenoLate~group~
h,,~ ~.,"indir~e~edly~c~ombined with one of these ~roups" is meant
that~:the',hydroc~arbon residue~is co~bined as,by etherification,
;:~ es~terification,~ar~amidiflc:at:ion, or ~he like~ with'another
;organic residue~whicb:~conta,ins~not ~ore than four carbon atoms
., - - . . ~ , .
,., ~ , : ;
~ 15327Z
and also one or more of the hydrophilic groups named above,
provided that after said combination, at least one of the hydro-
phile groups remains free. Specific examples illustrating this
class of compounds are: Ethyl alcohol, n~amyl alcohol, alpha-
terpineol, p-cresol, cyclohexanol, n-butyraldehyde, benzalde-
hyde, n-butyric acid, glycol mono-butyrate, propyl lactate,
mono n-butyl amine hydrochloride, n-propionamid, ethylene glycol
mono n-butyl amine hydrochloride, n-propionamide, ethylene
glycol mono n-butyl ether, pyridine, methylated pyridine,
piperidine, or methylated piperidines.
The solubilizer (mutual solvent ox hydrotropic compound
above described) is essentially a semi-polar liquid in the
sense that any liquid whose polar character is no greater than
that of ethyl alcohol and which shows at least some tendency
to dissolve in water, or have water dissolved in it, is proper-
ly designated as semi-polar.
The solubilizer or semi-polar liquid indicated may be
illustrated by the formula X - Z, in which X is a radical hav-
ing 2 to 12 carbon atoms and which may be alkyl, alicyclic,
aromatic, alkylalicyclic, alkylaryl, arylalkyl, or alicyclic-
alkyl in nature, and may, furthermore, include heterocyclic
compounds and substituted heterocyclic compounds. There is the
added limitation that the longest carbon atom chain must be
less than eight carbon atoms, and that, in such characteriza-
tion, cyclic carbon atoms must be counted as one-hal~. Z
represents:
H O U
- OH: - N / - C / : - CN / : - COOH or - O~e
where U and V are hydrogen or a hydrocarbon substituent and
Me is an alkalie metal;
- 16 -
~ .
llS~Z~7;~
N
if X is a cyclic tertiary amine nucleus;
~0
, .
~ -:
;:
'1; .
i.- . ..
. .
- 16a ~
" ,
NH ~3~S~Z7~ 1
if X is a cyclic secondary amine'nucleus.
' The scmi-polar liquid also'may be indica~ed by the following
for1nula: ~X -Y - R - (Z)n Here X and Z have their previous
significance, R is -C1~2 , ~ C2H4-, - C3Hs =; C3H6 or
--C2H4-- C2~4
and n is either one or two as t~e choice of R demands. Y is one
of the following: .
N, ;' - N - C-; - C- 0~;~ O- ~; ~0 - ; -S
In general, these hydrotropic agents are li.quids having di-
elec~tric constant values~ between about 6 and about 26, and have
at~1east~one polar:group contai.nlng Dne or Inore a~oms of oxygenr
5: : and/or n1trogen.~It is~si~gnifi:cant,.p~erhaps,-that all of the
so~1ub11iæ~ers are~of:types~kn~own~to be able to~form hydrogen
The choice:'of~so:lu~ilizer~:or:common~solvent and its:pro-
in;~the~m~ixture:~d'epends~somewhat-:upon~;~the amphipathic
agent:used,~:the:~amount~and:kind: of~TFSA used,~and the.pr~oportion
: ~ :water~"u.se~d,~and~is~best~.determined by preparing experimental
mixtu:res:~on a.small scale,
In 90~e'case:9,: it is~desirable to include in the-solution
;smal1~amoùnts;~of~a~cid,~'~alkali~ or inorganic sal'ts, as it has been
' , ~ d~-that~the~presen~ce~of~the~s`e electrolytes o:~ten gives solutions
n'g~gr:èate ~sta iIity~and;~a wider ~ange~
wa~er~and~orgàn c~mate l~.:.Exc~ess~a~cid,~:when used, will usually
q~n solu.t-'i~ons~con:~aining.~a~'cation~-ac~iv:e~or nonelectrolytic
7e:tting~:agen:t,~ but~; nat~exclusively sa. Excess alkali,: when used,
wnl~:usually~be~'in a~solutiDn oontaining~anion-active wetting
ag~ents,~ ~but;, again, ~not exclu:sively~
:, ~: : ~`,' ' ' ' . '
.
32t7Z
l - The polye~her polyol ol: IlSA utilized in this invention is
generally an organic polymer or semi-polymer wi`th an average
molecular weight above about 800 and below about 30,000 and has a
st.ructure which will allow orientation on polar surfaces with
much or most of the elements of the molecule in a thin p.lane. To
be effectively adsorbed at oil-water or oil-rock interfaces and
subsequently to be desorbed at water-rock interfaces, the TFSA
must ~enerally contain cons~ituents wllich givc'i~ a highly dis-
tributed hydrophi'le and hydrophobe character, and witho'ut such
concentrations of eithe`r hydrophilic or hydrophobic groups as to
produce water soIubility or oil solubility, in the ordinary
macroscopic sense. The TFSA also appears to differ from formerly
used surfactants'in that the effects on oil-water' interfacial
tensions as a function of concen'tration are limited. While .
spreading'efficiently at such interfaces to fo.rm thin.films with
spreading pressures up to about 3'5 to 40 dynes per cm, addition
or larger amounts of TFSA have relatively little''effect on inter-
facial tension.' Also,'the`'present TFSA constituent of the micellar
solution in contrast to formerly used surfactants, has relatively
'20 ~ ~:little or no tendency to stabilize;either oil-in-water or water-
in-oil emulsions when present in normal use amounts.
~`' UsuaIly the TFSA .constituents applicable to the practice of
~: the i~vention are or~anic molecules con~aining carbon', hy~ro~en
and oxygen, although in some instances they may also contain
'25~ sulfur, nitrogen, silicon, chlorine, phosphorous or other elements.
; - :Small:amounts of:inorganic materia'l such as alkalies, acids or
salts may appeàr in:the'compo5itions as'neutralizing agents-,
catalyst residues or otherwise,' The critical requiremen'ts ~or
: the TFSA compositions ~are'not s`o'much`compositional as structural
and physical. 'They must be'made'up of hydrophi'Ii'c '~polar~ moieties,
usually on'es' capable'of forming~hydrogen bon'ds, .s'uch'.'as hydroxyl, .
~ .
. -18- -
;
15327Z
1 carbonyl, ~ster, e~her, sul~l)ni.um, all~ino, alTITl)o~ Tn, phospho or
similar hydrogen bonding groups, connected by or to hydrophobic
groups, such as alkylene, al~yl, cycloaklyl, aryl, arylene,
aralkyl, polyalkylene, polyalkylyne, combinations of such groups
and such groups containing relatively non-polar substituents,'
such as hydrocarbon, chlorine, ~luorine and the like. Sometimes
the hydrophobic mOieTies are larger and contain more atoms than
the polar groups in the molecule, havi.ng a mi.nimum'or two ca~bon
. atoms in each group and up to as many as 36 carbon atoms, although
the actual ratio of sizes depends greatly on the'structure of the
hydrophilic moiety. .Most commonLy, the hydrop~lobic groups will
contain 14 to:22 carbon atoms and will have'linear or sheet-like
`~ conformations allowlng'for rela~tively flat orientation on surfaces.`
Polar moieties~other.~than~hydrogen bonding ones are not. .
: excluded from these'~compositions and, indeed, may.be del~iberately
included in some ;structur~es to improve adsorption and interfacial
s~preading~tendencies~ F~or example,' quaternary ammon'lum groups,
whi~le~ incapable~of~ forming~hydrogen bonds, can improve'spreading
and~Lnterfac'iaL~adsorption~in~some applications by way of their
2;0 ~ h;l~ly~ionized form~wh'ich:imparts cationic character to the mole-
~ cules in which they occur an~d, via coulombic repulsion effects,t`~ can improve spreading in a film.
Generally, the~TFSA~constitu~nts will contain at least two
each~of~the~required~hydrophilic (polar)~ and hydrophobic moieties
~5~ per moleculè~and~;commonly~will~contain~many~ more of~each. The
ef~fective produc~ts,; however, must have'the three'properties
described ~above. ~
Whi:le,'~as~point~ed out~above,' the effective TFSA may be'de-
;rived ~rom::a`wi~de~:var~iety~.of chemical.reactants and may contain
30~ numerous~diferent-~groups~or moiet;es, I have`found .that partic-
ularly effect~.products ar~e~'tho~se~'w.h`ic.h:`are`describe'd as a
~ ~ ~ -12-
~, -
, . .
~ I llS327Z
l polyepoxide con~ensate o~ at least one o~: (l) a.T)olyalkylene
oxide ~dduct of a fusible, water~-insoluble or~anic aromatic
. hydrocarbon solvent-soluble synthetic resin, wherein said resin
. has from betwcen about 4 to aho~1t lS phenolic~groups and is an
alkyl or cycloaliphatic substituted phenol-aldehyde condensate of
an ortho- or para-su~stituted phenol and an aldehyde, said con-
- densate resin being thereafter ~urther condensed with an alkyleneoxide containing less than about five carbon atoms in an amount
equal to at least one mol.e of alkylene oxide per phenolic moiety
.
~10 of said resin; and (2) a polyether~polyol having the formula:
[o(A)iN~n
":~ NRl L (.A) k~]~ m
wh:erein~
`~15 ~A~1s an~alkylene oxide~group5, -C,iH2iO~
~ is~oxygen;
i is ~a ~ po~sitive~ integer;no~greater~:than~about~la;
sitive~'integer nolgreater~: than~ about~LOQ
~int~eger~no~greater Lhan about~100j ~ :
is o~e~:of~ ~hydrog~en:, ~a monoualent~hydrocarbon ~roup containin~
1ess: than ~ aboùt ~::Cll , or [~ H].7 :
a positive~ integer~no gr ter~than~about~100; ~
a~h~n moié~y~:o~f~a~polyoL,~ a~pri~ary~or secondary
a ~ imar~y~or~ econ ~ y~po~1 a e,: a prima y or
5econd~:~y~-a~ino,~alcohoI;,~or~,hydr~ogen;~and ~
n~is~;`no-~g~eater~ ~ ~bout~: : is;~other t
d~one~Q-f~ ~ ~n~' -ze `~`-: d e othe`r-is~unity ~ en R
s~ ~ rQgen~ Th~se~:p:o~lyepQxlde~cQndensates must conform to
. ~: Xhe~p ~ icai~;p ~ erty~p-arameters set forth;above,`
The~polyal ~ lene~.oxide`a~dducts~are broadl~described in U.S.
:Pa;tént~2,499~,~365,~en~it1ed '~'Chem`ica~l Manufàcture", date~ March 7,
1~5327~
1950, to DeGroote, et al. These compositions also include
materials wherein less than one or two alkylene oxide units
may be reacted with each reactive structural group of the
starting resin.
The most common resin is an alkyl or cycloaliphatic sub-
stituted phenol-aldehyde resin prepared by condensing an ortho-
or para-substituted phenol with an aldehyde, most commonly with
formaldehyde or a formaldehyde progenitor such as paraformal-
dehyde or trioxane, under mildly alkaline or acidic conditions
to form a fusible and xylene-soluble polymer of low or moderate
molecular weight and which typically will contain from between
about 4 to about 12 phenolic groups. ~his resin is then conden-
sed, usually with an alkaline catalyst, with an alkylene oxide
or a mixture of alkylene oxides.
Alkylene oxides suitable for use in preparing the composi-
tions used in the present process include ethylene oxide,
propylene oxide, butylene oxide, 2-3-epoxy-2-methyl butane,
trimethylene oxide, tetrahydrofuran, glycidol, and similar
oxides containing less than about 10 carbon atoms. Because of
their reactivity and relatively low cost, the preferred alkyl-
ene oxides for preparing effective TFSAIs are the 1,2-alkylene
oxides (oxiranes) exemplified by ethylene oxide, propylene
oxide and butylene oxide. In tha preparation of many TFSAIs,
more than one alkylene oxide may be employed either as mixtures
of oxides or sequentially to form block additions of individual
alkylene oxide groups.
To be suitable for use in the present process, addition
.
and condensation of oxide must not be carried to the point of
producing water-soluble products. Where ethylene oxide alone
is condensed with the resin, the amount added preferably will
be between one and five moles per phenolic moiety in the
resin. The actual amount will vary with the size of the alkyl
- 21 -
~5~2.7Z
or cycloalkylene group attached to the phenol ring as well as,
apparently, with the composition and properties of the oil,
aqueous phase and rock formation encountered in the method.
Where propylene or butylene oxides or mixtures of one or
both of these with ethylene oxide are condensed with the pheno-
lic-resin intermediate, generally a greater amount of such
oxides may be reacted without leading to extremely polar,
water-insoluble products. In contract, the amount of epichloro-
hydrin or glycerol chlorohydrin which can be condensed without
producing agents not meeting the solubility and interfacial
spreading criteria defined above is usually somewhat lower.
On a solvent-free weight basis, the amount of alkylene
oxide or mixture of oxides condensed with the resin will fall
within the range of about one part oxides to about 10 parts of
resin and up to from between about l-to-5 and about 3-to-1.
The final product should contain at least about one mole of
alkylene oxides per phenolic moiety of the resin.
Compositions incorporated within the scope of the formula
set forth above for the polyether polyol contain an average of
about 1~ or more hydroxyl groups per molecule and are generally
composed of a cogeneric mixture of products obtained by con-
densing al~ylene oxides with smaller molecules containing two
or more reactive hydrogens as part of hydroxyl or amino groups.
Representative of these compositions is polypropylene
glycol, having an average molecular weight of about 1,200, to
which about 20~ by weight of ethylene oxide has been added.
Such a p~lyether glycol is theoretically abtainable by condens-
ing about 20 moles of propylene oxide with about one mole of
water, followed by addition of about six moles of ethylene
oxide. Alternatively, one may condense about 20 moles of
propylene oxide with a previously prepared polyethylene glycol
of about 240 average molecular weight.
- 22 -
X
l~S~27;~
.
1 Other suitable clihydric ~lcohols may be obtained by condens-
ing lkylene oxides or mixtures of oxides or in successive steps
(blocks) with diflmctional (with respect to oxide addition~ com-
p~unds, such as ethylene glycol, methyl amineJ propylene glycol,
hexamethylene glycol, ethyl ethanolamine, analine,' resorcinol,
hydroquinone and the like.
Trihydric ether alcohols may be prepared by condensation of
ethylene, propylene or butylene oxides with, for example, glycerin,
ammonia, triethanolamine, diethanolamine, ethyl ethylene diamine
or similar smaller molecules containing three hydrogens capable
of reacting with alkylene oxides. Similarly, polyether alcohols
with a multiplicity of hydroxyl groups may be'obtained by con-
de'nsing alkylene oxides with multireactive starting compbunds~
such as pentaerythritol, glycerol, N-monobutyl ethylene diamine,
trishydroxymethylaminomethane, ethylene diamine, dieth.ylenetri-
amine,' diglycerol,.hexamethylene'diam'ine, decylamine and cyclo-
hexylamine. DeGroote, in U.S. Patent No. 2,67~,511, describes a
number of amino derived polyols which he'subsequently esterfies.
Product 15-200., manufactured and sold by thè Dow Chemical Company,
~ and derived by oxyalkylation of glycerol with'a mixture of
ethylene and propylene oxides, is an example of a commercially
~ available'polyol of the kind contemplated herein.
:~ Generally, these compositions will have'average molecular
weights of 15,000 or less and will be'derived from reactive'
, ~ :
~ hydrogen compounds having 18 or fewer carbon atoms and lQ or
fewer reactive~hydrogens.
Other general descriptions of suitable polyether poly~ls
: coming within the scope'of the structure'detailed above,` along
'(~ with methods for carrying QUt the'actual manufacturing steps, are
~ , . . .
disclosed in "High Polymers, Vol X~II, Polyethers,".edited by
N. G. Gaylor'd, John Wiley & Sons, New York, 1~.63.' '
: . :
-23-
* Trademark
~L53272
Suitable polyepoxide for condensation with the compounds
set forth above include, particularly, the diglycidyl ether of
dihydroxyphenyl-methylmethane and the lower polymers thereof,
which may be formed as cogeneric mixtures and which have the
general formula:
/ \ I
H C - CH-CH - C_O_C6H4 - C(CH3)2 C6H4 2 2
o
-o-c6H4-c(cH3) ~ C6H4 CH2 2
wherein n is zero or a positive integer of less than about 6.
Other polyepoxides containing two or more oxirane or epoxy
groups, such as diisobutenyl dioxide, polyepoxypolyglycerols~
epoxidized linseed oil, epoxidized polybutadiene or the like,
may also be employed.
The compositions suitable for practicing the present
invention are prepared by reacting formaldehyde or a substance
which breaks down to formaldehyde under the reaction condi-
tions, e.g., paraformaldehyde and trioxane, and a difunctional,
with respect to reaction with formaldehyde, alkyl phenol, often
~ a~crude~mixture of alkyl phenols for economic reasons, by heat-
ing the reactantq between about 100 and about 125C in the
presence of a small amount of an acid catalyst 9uch as sulfamic
acid or muriatic acid or, alternativ@ly,in the presence o~ an
alkallne catalyst such as sQdium hydroxide or sodium methylate
and~,~ preferably, under substantially anhydrous conditions,
eXaepting the~water produced during the reaction. The aqueous
distillate which~begins~to form is collected and removed from
the reaction mixture. After several hours of heating at tem-
:
peratures slightly above the boiling point of water, the mass
becomes viscous and is permitted to cool to about 100 - 10SC.
At this point, an aromatic hydrocarbon fraction such as xylene
` may be added, and heating is resumed.
- 24 -
,`'`, ~ . .
1~5;~27Z
,
1 Furtlller aqueous distillate l,e~ins ~o form, an~ heating is continued
forlan ad~itional number of h~urs until at least about one mole
of aqueous distillate per mole of the.formaldehycle has been
distilled off. Xylene or other hydrocarbon w~ich may be'distilled
S with the water is ret-urned to the reaction mass. The temperature
at' the end of the reaction reaches about 180 - 250C. The
product is permitted to cooi to yield.the phenol-formaldehyde
. condensation product in ~he aroma~ic solvent.
: The molecular weight of these int~r~ediate concdensation
products cannot be ascertained wit~h certainty, but it is estimated
~ . ~ that the resins employed hereln'should contain from between about
; ~ ' 4 to about'15, pre~ferably from about 4 to about 6, phenolic '
'nuclei per resin:molecule.' The'solubility of the condensation
product in hydrocarbon solvent would indicate that the`resin.is a
~:15 linear or sheet-like poLymer,~ thu's distinguishing it from the
mor~e c:ommon phenol~-formaldehyde res'ins of the~insoluble:'cross-~
.linked~type.
Having: prepared~the~intermediate'phenol-formaldehyde pro~ucts,
'thè~'next~step i5 the QxyaLkylat~ion of the condensation`products
.:with~alkylene~oxi:de~.~;Th:i~s~ls a'chieved by mixing the`intermediate
phenol-ormaldehyde.condenæation product as is or contained in
he aromatic's~lvent with`a small amount o a suitable ca~alyst,
usually potassium~hydroxide:or sodium metllylate, in an autoclave.
The~con~ènsation product~is heated above~100C, and ethylene
S ~ ;oxide, propyl~ne;oxide, b~yl~e~e.~oxide`or mixtures of two or all
:three~o~f these~ox~ides,~::elther-.as a~mix'ture or by sequential addi-
tion~of:~fir~st eit,her~o~e~'or'another ~o the oxides is char~ed into
the Autoclave~un~t`il'~.ne~'press'ure'îs`in the vicinity o 75 - 100
30~ The:`reaction mixtur~e;is gràdually heated:until an exothermic: reactlon begins.~ The'exteroal heating is then re~oved, and
2 5--
, , ` : .. ~ . . . ..
~15 ~27Z
alkylene oxide or oxide mixture is added at such a rate that
the temperature is maintained between about 130 - 160C in a
pressure range of'30 - 100 psi. After all of the alkylene
oxide has been added, the temperature is maintained for an
additional 10 to 20 minutes to assure substantially complete
reaction of the alkylene oxide. The resulting product is the
alkylene oxide adduct of an alkyl phenol-formaldehyde condensa-
tion product, in which the weight ratio of the oxide to the
condensation product (on a solvent-free basis) is between about
~10 l-to-10 and about 10-to-1, preferably between about 1-to-5 and
about 3-to-1, and containing at least about one mole of alkyl-
ene oxide per phenolic moiety of the resin.
As to the limit~s of the various~constituents of the micel-
l~ar solutions containing TFSA, the following will serve as a
guide, the percéntages being by weight:
Percent
TFSA~;¢onstituents ~about 5 to about 75
HydrotropiG Agent ~ ~ about 2 to about 30
s~ Amphipathia~Agent ~ about 2 to about 30
~-20~ Water~ about lS to about 9Q
Although the~ex4ct~funation of the electrolytes previously
re~er~red~to is not~aompletely understood, the e~oct, ln part,
may~be~due~to the abillty~to blnd~water, i.e., to beaome
hydr4ted.~ his~uggests~;that certain other materials which are
h ~ ~ ~ rophi ~in charaater~and clearly differentiated ~from
t~hé'~class'es~f~non-polar solvents and semi-polar solubilizers
`may~be'the~functional~'equivaLent;~of an;electrolyte. Substances
of this~cla90~which 0rd~inarily~do not~dissociate include
3~ glyGero~ ethylen~e~glycol~diglycerol~sugar~ glucose, sorbitol,
~ 30~ mannitol,~and~the~lik~e~
: ~: :: ,
-~ - 26 -
X-
`:
,'s ~ .
.. . .
1153Z72
1 ~lso, a~ st~ted al~ove, t:hese solutions ~ay contair other
organic constit~lents such as hydl-ocarbons. These frequently are
used as thinning agents, aze~ropic distillation aids or reflux
temperature controllers in the manufacture of~the TFSA constituent
' and may be left therein when the present micellar solutlons are
prepared. To the extent that such compounds are prcs'ent they
appear to compete somewhat with the TFSA constit~lent for micel'le
space,' thus limiting, to isome extent, the maximum amount of TFSA
constituent which can be'brought into homogcneous solution.
' Selection of an effective TFSA composition for a given pet-
,
roleum emulsion and determi~ation of the amount required is
,
usually made'by so-called "bottle~tests", conducted', in a typical
situation, as follows: ' ' ' ' ' -
: , ~
A sample of fresh'emulsion is obtained and 100 mL portions
are poured into'each of several 180 ml screw top'prescription or
similar~graduated~'bottl'es~ Di~lute'solutions (1%'or 2%~ of'various
TFSA c~onstituents~are~'prepared~in lsopropyl~alcahol. By means of
a;~graduated pipett~e,~a small~volume of a TFSA solution is a'dded
~ t~o~a~bottle. A~sim;lar~volume~'of each"composition is added to
I ~ ~ other~bottles~con;tain~ing emulsion. The'bottles are'then closed
and~transferred to a'water bath held at the same temperature as
that empIoyed in the field trea~ing'plan~. iA~ter reac~ing ~
temperature,' the~bottles are'shaken briskly for several minutes.
~ After the~shakin~period, the'bottles are placed uprig~t in
g`~ the water bath~and al~lowed~to stand~quietly." Periodically, the
volume'of the;separat~ed;water layer is recorde~ alon~ with obser-
vations on the~ sharpness ~o;~the oil-water interface', appearance
of the oil and~clarity af the water phase.~
A~ter~the~standing~perLod, which may range from 30'minutes
~30~ to several hoùrs,~depending upon'~the'temperature,' the'~isco`sity
of the~emulsion~and;the~amount of~TFSA compositions-used, small
27-
. . . . . . .
, . . .
,J
~532~;Z
samples of the oil are removed by pipette or syringe andcentri-
fuged to determine the amount of free and emulsified water left
in the oil. The pipette or syringe used to remove the test
samples should be fitted through a stopper or other device
which acts as a position guide to insure that all bottles are
sampled at the same fluid level.
The combined information on residual water and emulsion,
speed of the water separation and interface appearance provides
the basis for selection of the generally most effective TFSA
L0 constituent. Where none of the results are satisfactory, the
tests should be repeated using higher concentrations of TFSA
constituents and, conversely, where all results are good and
similar, the tests should be repeated at lower concentrations
until good discrimination is possible.
In practicing the process for resolving petroleum emulsions
of the water-in-oil type with the present micellar solution,
such solution is brought into contact with or caused to act
upon the emulsion to be treated, in any of the various methods
or apparatus now generally used to resolve or break petroleum
emulsions with a chemical reagent, the above procedure being
used alone or in combination with other demulsifying procedure,
such as the electrical dehydration process.
One type of procedure is to accumulate a volume of emulsi-
fied oil in a tank and conduct a batch treatment type of
demulsification procedure to recover clean oil. In this pro-
cedure, the emulsion is admixed with the micellar TFSA solution,
for example, by agitating the tank of emulsion and slowly
dripping the micellar TFSA solution into the emulsion. In some
cases, mixing is achieved by heating the emulsion while drip-
ping in the micellar TFSA solution, depending upon the convec-
tion currents in the emulsion to produce satisfactory admixture.
In a third modification of this
- 28 -
532~
typ~ o~ Lre~ ent, a circul~.in~ UIllp ~iLh(lraws ~ sion from,
e.g., ~he bot~om of the tank and reint:rod~lccs it il-tO the top of
the tank, the micellar T~SA solution being added, for example, at
the suction side of said clrculating pump.
In a second type of treating procedure, the micellar TFSA
solution is in'troduced into tl-e well fluids at the wellhead, or
at some po;nt between the ~el;lllead al-d the final oil s~orage
tanlc, by mCatlS oE an ~djustal-lc pro~ort~:i.ollillg ll)ecll.lllislll ~r ~ or-
tioni.ng pump. Ordinarily, the flow of fluids through the subsequent
lines and fitti.ngs suffices to produce the desired degree of
mixlng of micell.ar TFSA solution and cmulsion, al~hough, in some
instances, additional mixing devices may be introduced into the
. .
flow system. In this`general procedure, the system may include
various mechani.cal devices--for withdrawing free water, separating
entrained water, or accomplishing quiescent settling of the
chemically treated emulsion. Ileating devices may like'wise be
incorporated in any of the treating procedures described herein.
A third type'of application (down-the-'hole?' of-micellar TFSA
solution to emulsion is to introduce the micel'lar solution either
,i , .
periodically or continuously 'in diluted form into the'well and to
allow it to come to the surface with the well f].ui(ls, and then to
flow the chc~ical'-containing emulsion through any desirable
~ ' surface equipment, such as employed in the other treating proced-
`~ ' ures. This particular t`ype o application is especially useful
,~ 25 when ~he micel'lar solution is used in connection with ac;dification
,
' : of calcareous oil-bearing s~rata, especially if dissolved in ~he
acid employed for acidification.
In all cases, it will be apparent from'the foregoing descrip-
tion,~the broad process consists simply in introducing a relatively
small proportion of micellar TFSA solution into a relatively
'' large proportion of emulsion, admi~ing the' chemical and emulsion
.
- 2 !~! -
1~5 ~Z~2
l e;~her L11ro~.1gh nat:1lral ~low, or ~11rough ~r~ci,~ r~ a~1s, ~ith
or'without the application of hea~, and allowing the' mixture'to
stand quiescent until the undesirable water content of the emulsion-
separates and settles from the mass.
5 . ' Besides their utîlity for'breaklng petroleum emulsions, the
present micellar TFSA solutions, as'mentioned earlier, may be
' used to prevent emulsion formation in steam flooding, in secondary
waterfl.ooding, in aci.dizing ~f oil-~-rod-1c;.llg ol111ati.o1ls, a1ld t:he
' like.
lO . Petroleum oils, even after demulsification, m~y contain
~: substantial amounts of inorgan'ic salts, either~in soIid form or
as small remaining brlne droplets.. For thLS reason, most petroleum
~ oils are'desalted prior to refining. The'des'alting step is
': effected by ad:dlng and mixing with the~'oil a few volume'pe.rcentages
~ of resh water to~: contact the~brine~'and salt. ~In the'absence of
demuls:ifier, su~ch~'added water~would also~become~emulsiied with-
out~effecting its~ w~shing~action. The pres:ent:micellar solutions
may~:be~added to the~fresh~'water~to prevent its~emulsification and
to~:ald~in phase~ se;paration~ and':removal of salt by~the'desalting
2p~ proce:s~s. 'Alternatively, if desired~,~they may be add.ed to the'oil
phase as.are present aromati.c solvent compositions,
Most petroleum oil, alon~.with its~accompanying brinès and
gases, is corposive~to:steel and other metallic structur:es with
wh:ic~h~:it~comes in:contact~; We:l'l.~tubing, casing, flow lines,
sepàrators and`lease;tanks~are often.seriously~attacked by well
1ui.d~s,~especially'where~acidic~ga~ses such as H2S'or C02 are
pro~duced:with the liquids,~bu~t~also ln systems free of such
gas~es, ~ ~
It has:b~een known~for~50me:time,' and as exemplified in U.S.
Patent.2,466,~517,'.issued April 5,~lg49, to Chas, M. Blair and Wm.
F.: Gross, that such'co'rrosive'at:tack of crude oil fluids can ~e
30-
~' ' . .
', ::~ ' '
~ S;~Z7~
l - m;.t:ig~ted or ~lrevcnted by ad~lition to the ~luids of small amoun~s
of organic inhibitors. Efectivè inhibitors compositions for
this use are usually semi-polar, surf~ce active compounds con- ''
taining a nonpolar hydrocarbon moiety attache~ to one or more
polar groups containing nitrogen, oxygen or sulfur or combinations
of such elements. Gener~lly thes'e';.nhi~itors or their salts are
soluble in oil and/or water (brlne~ and ~rcc1uent:ly a1pear ~o be
able to ~orm micelles in one or both of tlicse'phascs. Typical
inhibitors i.nclude'amines such as octyl amine, dodecyl amine,
dioctodecyl amine, butyl naphthyl amine, d1cyclohexyl arnine,'
~: benzyl dimethyldodecyl ammonium chloride, hexadecylaminopropyl
amine, decyloxypropyl amine, mixed amines prepared by hydrogenation
' . of nitrile' derivatives of tal1 oil fatty acids, soya acid este-rs'
of monoethanol amine,' 2-und'ecyl, l-amino.ethyl'imidazoline and a
::~15 wide variety of cationic nitrogen compounds of semi-polar char-
~ acter. ALso effect1ve~in some applications are nonyl succinic
:s~ acid,~d1ocylnaphthalene~:'sulfonic 'acid, trimeric'and dimeric fatty
acids, propargyl~alcohol, mercaptobenzothiozo~le:, 2, 4, 6-trimethyl-
~ 3j`~5-trithiaane,' hex~a~ecyldimethyl`benzimidazolium bromide, 2-
;~ ~2~0 .~ t~hiobutyl-N-tetrodec~ylpyridinium chl'orid'e, tetrahydronaph,thylthio-
: mbrpholine~ and the llke.
'~ : ' In contrast to the TFSA, corrosion inhibitors appear'~o
funct1on by orming on~the~metal surface strongly adherent,
hick,~closely~packed~fil~s which prevent;or lessen contact of
2~ corrosive~lui~ds~;snd gases with''the~:metal~and interfere with
ioniç~and electron t~ransfer react1ons:involved~ in the'corrosion
process.
3 - ~
Corrosion~inhibitors are'quite commonIy introduced down the
cas1ng ~annul-us o;f oil- wells wher~e'they commingle'with the well
30~ 1u;ds before~ their.trave1 up the'we`11 tubing and thus can ef~ec-
tively prevent corro'sion of wel'l equipm~nt. Where'corrosive'
,
i ~ .
~ - ' -31-
, , .
~15~27Z
1 a~ack occurs at the surface, th,e inhibitor may be introduced at
or near the well head, allowing ~t to adsorb on the flow lines
and surface equipment to insure protection.,
Addi~ion of inhibitor a,t either downhole~or surface locations
5 'm,ay be combined conveniently with demulsifier addition since the
latter is also frequently introduced in one of these locations.
` Inhibitors such as those ~entioned above, ~ay ~enerally be
incorporated illtO the TFSA micellar so1uti.o1ls, repl.acing a
:~ portion of or in addition to the TFSA~ constituent. Also, since
many of these inhibitors are themselves micelle-forming amphi-
: pathic:agents, they m:ay be included in the mi,cel'lar solution as
such, :replacing o~ther amphi.pathic~agents which might be`otherwise
' . utilized. vombining:the m1ceIlar solùtion~with corrosion inhibitor
, perm,its more~economic chemical treatment by reducing inventory to
15 ~ one;compound,~requ1ring~onl~y~one'chem~1ca1;injection~system ratherthan two~and~ess~ening~;~the~1abor and~supervis1on requir~ed'.
Still another~:impor.tant:effect of us~ing the'miceIlar solution
of-`TFSA~ànd~corrosion'~inh:ib~itor results from the prevention of
;emu1sification by th~e~.inhibit~or. 'Frequently,~:it has been found
20,~ ;that inhLb:itor~in the'amount`:r~eq~lired for eifective protectLon
causes~the for~ation of very rera~tive emulsions o wa~er and
;hydrocarbon, .especia11y~,in~:systems containln~ light, no~mally
nonému1sifying~hydrocarbons~such as~distil1ate, c~sing head
gaso1ine, kerosene,~diese1~fuel and~various refinery fractions.
5~ Inhibi.tor~s:~a~e~co~monly'~:used in~refiner~y systems where .emulsifica-
t~ion is hlgh1y~;object~i~nab~1e~and~where: the compositions ~ould be
designed~to:in;c1ùde~an ef~ect~ive:~'emu1siQn preventative miceIlar
,solution~o~ TF~A.~
Inhibitor use may range''from~a few to~se;veral hundred parts
30~ per:~mi11~1on';~based~on ~he Qil ~to~b~e~:~'treated, depending upon`thè
;',sev~erity of CQ~rrOSiO~. ~ For'a: given oil iel'd or` ~roup of wells,
,., ~:
~lS~272
1 t:~sts will normally be run to detelmi.ne ~he requirement for
micellar solution of TFSA and for inhibitor and a composition
incorporating these components in approximately the'desired ratio
will be prepared. In some'ins~ances, tXe req.uirement for micellar
splution of TFSA in ~he bes~ concentration may result in use of
corrosion inhibiLor, cmployed as micelle-former, in some excess
over that required for inhibition. This will not affect the
utility of the` micellar solution and will provide a comfortable
' excess of inhibition which can be helpful during the periods when
higher corrosivity may be encountered.
Examples of micellar solutions employing TFSA with inhibitor
in water disperslble,~ micel'lar solutions are given below.
Selection of the prdper' corrosion inhibitor for a given
: , . .
system or oii is usually made by conducting laboratory tests
under conditions simulating those encountered in the well or
flowline, Such ~t~es~t~s are exempliied by that described in Item
No.~lK155~, "Proposed~;S~andardized Laboratory Procedure for Screening
Corrosion Inhibi~tors for Oil and Gas Wells`', publ'ished by the
W~ational Associ~ation of Corroslon Engineers, Houston, Texas.
EXAMPLES OF THIN FILM SPREADING ~GaNTS
i ':~;
` EXAMPLE I~
RESINOUS~POLYALKYLENE~OXIDE ADDUCT'PRECURS`ER
25~ Referencé- is made to U~S~. Patent No~ 2,~99,365, to M. De
Groote, issued~March'7, 19SO,~whlch describes generally the manu- -
fac~ture of demu;lslfiers~by the ~xyalkylation o fusible, or~anic
: solvent~-solubl:e,~ alkylphenol ~resins. The'procedur'e of Example
'74a~of this pat~ent was ollowed to prepare'a fusible,' xylene'
30~ ' soluble'p-dodecylphenol resLn in xylene solution. The`aci'd
catalyst was neutralized, water~was removed by azetropic dis-
: -
--3 3--
` :
., ~ ~ .... . .
. . .
I ` ~153Z7Z
1 tillation of some zylene and 0.5% by weight of sodium methylate
catalyst was added. Using the procedure of Example'lb of the I
cited patent, 25% by weight of ethylene oxide, based on the final
batch weight, was added and reacted with the resin.
EXAMPLE IB . - '
FINAL PRODUCT PREPARATION
Reference is made to U.S. Patent No. 3,383,325 to V. L.
Seale, et al, dated May 14, 1968, which described demulsifiers
prepared by condensing polyet'her polyols and oxyalkylated alkyl-
phenol resins with'diglycidyl ethe`rs of bis-phenol'compounds.
One'hundred parts of~the:product of Example 1, in co-pending
S~erial No'.'''361~38'1~ fl1ed 'September'30, 1980, entitled
Micellar Solutions~Of~Thin Film~Sprea'ding:Agents~Comprising A
~ Po:lyethe'r~Polyol", was:~reacted~with'l5 parts of the diglycidyl
ethqr;:of~bis:-phenol:~A,~followed:by reacting:~with'80 parts of the
` d~:uct of~ ~ ~ e~IA,~-above?'~:~ l ln accordance with'the~procedure
of~the Se`al~e~ et;aL~ pat ~ t~,~ Example~D8~ Addition.:of the~final
ofi 5O2~extract was~omitted,~ Th~is~product meets the`
i~eria~fDr:~thin~il~sprcading~gent. ~ ~ :
The~'proc~d~re~employçd~in~Example~'4~a of U.S.' Pa~cnt ~,429,365.
,'~l~s:~sue~d~March.7,~ 19g0',~:~was~ followed~to produc~ an
ed ndet ~ _ 1 IA ~v 1~000
~ r~ ~ f ~ ~le:~ oxlde, ~S0 Ibs. of propyleDc`oxide
~LSt~ Z~
~ . .
.
l ' After coTnpl~tion of the oxide addition, the telnperature was
adjusted to 140C and 70 lbs. of diemthyl, diglycidyl hydantoin
dissolved in 250 lbs. of xylene was slowly introduced with rapid
stirring. A~er colnpletion o~ the cpoxy hyda~toin addition,
s,tirring and heating ~t 1`40C was continued until the batch
viscosity at 100C was between 1,500 and 2,000 centlpoises.
EX~LE III
Thè proced~re of Example I was followed except that conden-
sation with t.he oxylalkylated phenolic resin and final.addition
. .
of S2 extr'act` were both :de.l'eted. ~ . .
The product was an effectlve :demulslfier meeting the'criteria
described above, therefor. ~ h'is p~roduc~t wa~s~àlsa found to improve
the percentage of oil recovery when ùsed as an additive'to`water
:15 ~ us~ed in''experimental secondary~:waterflooding tests.
EXA~PLE IV :~
The~:proced~ure~'o~;Example'I is foll:owed,; except. that 12 parts
.o~ iba-Geigy:Resin~XB2818,:an~a~1k~1ated dihydantoin containin~
thr:ee~epoxi~de groups, was~ substituted for:the l~:.parts of diglycidyl
ether used~in Example I. ~Reaction was continued until ~he product
exhibited a visc~sity af'abou~ 1,50~ centipoises at l~oQc. The
f~nal:~product~met the~:'three~ cr~iteria for TFSA.
AU~L~ V
nto-~a~5~0D~g~al~ stainles~s:s.tee'l autoclave'equiljped with
st~rrer~j steam j~ackèt~,:cool;ing coils;and appropriate inlet and '.
-o~t:let;:linès wa:s~intro:duce~d~l,:OO.O~lbs. af co~mercial polypropylene
: glyeol~with~a*erage molec~ular~weigh~t of 4,.000.~ Sixteen pounds of
.~ 30~ a~50%~:aqueQus~solution~of~potass;ium hy'droxide'was then added to
the'g~lycol. St'eam:was:admitted to the'jacket ànd the` contents
wer'e'stirred whi'le't~e~'t:emperature'was'br:ought to about 125C~
35-
,
,, ~, .. .
~15~27Z
1 A slow stream of nitr~gen was bl~wn through the vessel
c~ntents during the heating period to effect removal of water.
Mitrogen sparging was stopped when a sample of the glyol showed a
water content below 0.1%.
At this point, commercial,epox;dized soyabean oil containing
an average of three epoxy groups per glyceride molecule was added
at a slow continuous rate while the temperature was increased to
145C. Addition was stopped after 90 lbs. of epoxidized soyabean
oil had been introduced. Stirring and heating at 145C was
continued until the reaction mixture had a viscosity within the
range of 1,200 to 1,400 centipoises when measured at 100C.
EXAMPLES 'OF MICELLAR SOLUYIONS INCORPORATING TFSA''s
EXAMPLE A
Wt. %
Product of Example II 38
Isopropanol 16
Dodecylbenzene sulfonic acid 16
20 ~ Diethylene triamine 4
Water 26
Thig product is an effective'e~ulsion breakex for e~ulsions
~i' produced in the Glendive fiel'd of Montana and is particularly
useful as a synergistic component when combined with'other aqueous
Z5~ ~ TFSA compositions such as described in my co-pending application
Serial No~'' 361,788' , filed October 8, 1980 , entitled
"Micellar Solutions Of Thin Film Spreàding Agents Comprising
i: :
Polyepoxide'Condensates Of Resinous Polyalkylene Oxide'Adducts
And Polyether Polyols".
-36-
~1~3;~7~
,
1 - F,X~MPLE B
__ ................. . .
Wt. %
Pr~duct of Ex'ample III 25
Xylene - 8
Sodium salt of p-nonylphenoxy- j
pentaethoxy sulfuric acid 15
Isopropallol ' 31
Methanol , 6
' Water 15
This is a solùtion of very low pour point which is suitable
- for use as a demulsifier in oil fiel'ds where ambient temperatures
are wel'l below freezing.
.
l~ EXAMPLE C
wt. %
`, 15
, Product o Example'III 31.3
'i~ Isoprop,anol 3I.2
l .
hmmonium, nonylp~enox-yethoxy~sul~ate 15.6
Sodium- acetPte O . 2
Water ~ , 21.7
' ~ '
Among procedures which'have'been found useul in selecting
e~fective micellar TFSA solutions for this use, one involves a
determination of oil displacement eficiency from prepared oil-
containing rock cores-in e~uipment described below. A tube of
2 ~ glass or transparent poiymethacrylate ester, having an inside
diamcter of ab~out 3,5 cm (l~ in.~ and a len~th of about 45 cm (18
,), lS fitted~with i~nl'et connectlons and appropriate'valves at
each~end. The tube is mounted vertically on a rack in an'air
bath equlpped with a'fan, heater and thermostat which allows
selection and maintenance'of te'mperatures in th'e range of between
,~ 30 ~ : ~
~' ~ about 25 - 1309,C. ' ~ '
,, ~ :: .
. "
',,'` ' -37-
.~,, . . ' .
`, .
,.:, . . .
, .... . .
`" 1153;~7Z '
l To ~elec~ n erfectivc ~nicellar '1`1'SA sollltiol- ror ~Ise in a
given oil foL~ation, samples of the oil, of the producing rock
formation and of the water ~o be used in the flooding operation
were obtained. The formation rock is extracted with toluene to
remove oil, is drled and is then ground in a ball mill to the
point where a large percentage passes a 40 mesh sieve. The
fraction between 60 and l00 mesh in size is ret'ained. The tube
described above is removed from the alr bat1l, opene~ and, after
insert'ion of a glass wool retainer at the lower end, is packed
' with the ~round formation rock. The tube is tapped gently from
time-'to-time during filling to ensure close packing and is`visuaIly
inspected to assure absence of voids.
The.tube'is then returned to the air bath,~connected to the
inlet tubing, the temperature is adjusted to the oil formation
temperature and water representative of that produced from the
formation is admitted slowly through the bottom line from a
callbrated reservo1r in an amount just sufficient to fill'the
packed~rock~plug~in the''tube.~ ~This volume'is determined from the
calibratlons~and is~ referred~to as the'"pore vol~me", being that
~2~ vo~lume o~f water j~ust sufficient'to'flll the por`es or interstices
of~the paclced plug~rock.
The upper lin~ to ~he reservoir is then connected to a
: :
cal~brated reservQir contalning the oil representing that ~rom
the~f~ormation~to be f1Ooded~ By proper manipulation of valves,
5~ the line~is~fil1ed~with oll which is then slow~y pumped into the
core from the~reservoir~ a~ter th'e lower valve'is opened to allow
displacement of the ~ormation~water'.
As breakthrough~of oil at the'bottom is noted, pumping is
stopped and the`~vgluune of oll introduced into~the' sand is deter-
- 30 ~mined from the~'reservoir readings. ~This'is referred to as the
' volume'of'oil in place.'~ ~he'tube'o~ sand containing oil is then
, ~ .
- -38-
'
.
1~3;~72
1 left in the air bath at the ~emperature of the formation for a
period of three days to allow establishment of equilibrium between
the ground fonnation rock and the oil with respect to adsorption
of oil constituents on the rock and lowering of interfacial
tension. The tlme allowed for,,equilibrium may be varied widely.
At higher temperatures, the time required ~o reach equilibrium is
probably reduced. Usually, for comparative tests, three days are
allowed'to age.'the oil-rock plug.. Results with 'this procedure
closely simulate`work with actual cores of oil-bearing rock.
'~10 The:oil and wat'er samples used for test:purposes are prefer-
ably taken under an inert gas such as h;gh purity-nitrogen, and
, ' are maintained out of contact with'air during all miniuplat-ions .'
: . . . .
in o.rder to prevent oxidation o the oi~ a~d concomitant intro-~
duction of spurlous polar, surrace-active constituents in the
5: oil. At this point, ,the;rock-oil: system simulates the original
, oil~formatio~ before~ prLmary:~producti~on oil has.com enced-ànd
well before~any~se~condary~waterflood o~peration.
The~'up'p~er:~inl'et~line~:'to~the~;'tube is now'connected to the
s~ample~of:watèr:used~in~the floàding of the oil formation and, by
~, ~ means~,o~ a~:syringe pump or similar very small vblume positive
di'splacement pump~,'the'water is~pumped into t~e sand body from
: . the`t~ap~to.displace luids out of the~bottom tubin~:connection
::in~to~a~calibrated receivsr, ~The'pumping rate is-adjùsted to one
, 9 mulsting~the~ratè~of~fl'ood~water advance in an actual operation,
which~'is u~sually in:~a~r~ange of~1~to 50 c~ psr day. ' Pumping is
,ma~in:t:aine-di~st'~his r,ate~:until two pore volumes of`water have been
pumpsd~thr~ough:,~'the~;`sand.~
The volumes~of~fluids colleeted in the'receiver are measured
aDd~the~relative~amount of'~oil:and water displaced from the rock
30~ sàmple~'are~'det'ermined and:recorded. Of special interest is.the -
volume'o'f~oil`di~splac~ed as~:a fraction of the original pore`volume.
"~ , _3~_ ,
. . -
,. .
, .
~ 27 Z
l Tllis inforlllat:ion may be vie~!;?d as an indication of the approximateperc~nt,~e of oil originally in pla~e which is pro(l~lced by natural
water drive following drilling of a well into the rock formation
iollowed,by the primary phase of field production carried to the
approximate economic limit.
Following this step, one to thrce additional pore volumes of
water containing the TFSA micellar solution to'be tested are
pumped s.lowly th.rough the plug and the volumes of a~ditional oil
and water displaced are de'termined. Typically, where such an
initial "slug" o micel~lar TFSA solution is in~roduced, it may be
.~ ` . .
. contained in a volume of fluid rangi.ng from 1% to 100% of the
pore volume,' bùt mos~t frequently it will be'in a slug volume-'of
10% to 50% of pore volume.'
After this flnal~displacement step, the~produced.oil and
5~ . water are agaln~measured. By~comparlng the amount of:oil produced
by~this additlonal~injection~of water~containing:, or preceded.by
a~solutLon,~of~micellar~TFSA~sollltion:wlth~'the`'amount produced
when~thé`~`same~vol ~ e~'of:water'~containLng~no TFSA solution is . ~:
ècted,~ one:~can:~e~aluate'the~effectiveness of~the partic~lar
..micellar:TFSA~so~lution;~us~ed~for enha'nclng~the recovery of additional
oil:~over 'and above`~hat obtained:by~`ordinary waterfloodin~
Ge~erally, six or~more sand columns of the kind d~ac~ib~d
: above:~are'mo~nted;in.the~hea~ed.air bath. Test~of a given miceIlar
''TFSA~solut~ion~ls~then~run in~t~riplicate, using.identical conditiQns
conc~entrations,~s~imwltane;ously- with`~hrqe blank tests run
similarly~but vithout -d~dition Oe mfcellar~TFSA solution to the
The~:compo~si~ion~of Example'C~was~t~st~d by this.procedure
; with;~'t~e~'followi~g~conditions~
30~ :Oil ~ East Tex'as Fîel'd
. API Gravity approximatel'y`40.'4'
4'0s'
:"
.7 Z
ter -- ~lixed w~L~r u~d in rlc)od o~erations
Ai~ th T~mperature -- 150F (Same as fo~m~ltioll temperature~
Oil was, displaced by p~nping two pore volumes of water into
the sand. After measuring the'volumes of oil and water produced
through the bottom'line,, a further 0-.2 pore volumes of water!
containing 3,500 ppm of the composition of Example C was injlcted
followed by 2.8 ~olumes of water containing 200 ppm of the com-
position of Example ,C. Measurement of ~.he vol~lmcs of oil and '
water produced were read after each 0.2 po,re vol~mes of water was
: 10 injected. . '-
.
~ , Results of this tes~ at the' points:'of 2,3 and 5 pore'volumes
.: -
of injected water are given in the table:bel~ow wh'erein averag~es
o~f three duplicate'd:et'erminations are'pres'ented.
Oil:Recovery as %~of
5~ Oi'l''in Pl'ace' '~
Composition of Ratio of Increment
: Example,C : of Oil Production
: -Added to:Water After:Initial 2
Po:re Volumes ~P.V.) :No;¢hemical after Initial- P.V. Chemical/
of,Water'~Injected~ 'Addi't'ion:~' 2 P.~.' of Water No Chemical
3~ `43.2~ '46.2 2.0
: 5 ~ 46 . 0~ 50. 0: . L~ 68
.Use of~ the compo~sLtion of Example C in the amounts given
::: above resulted in the productlo~ of loa% more oil ~ram l~jection
o~ one~,incremental~pore~,volume of water than~was~ produced by
in~;ection~a~lone~:;a'nd`~ave~ 68% more~oll after three'inc,re-
mental~;~pore.volumes:of~t~reat;èd:water inj~:ection~ .~
' Although the invention:~has been described in terms,of
specified~embodi~ents.which~are'set forth in deta'il, it should be
un.dèrq~tood:t~:at~sthis~is by illu~stration on.ly and that thè'inven-
t~ion~.is~not~n:ec';e~ssar~ily ~limited~thereto, since'alternative
~ ;.emb~'dimen:ts~and oper~ating~teehniques wi'll become'apparent to
3:~ t~ho~e'skilled in:'the~'art in~view o'f the discl'osure.' 'Accordingly,
modlf~ication .~are~ ontemplated whi'ch'can be made'without.departing
~: rom.~he spirit of the described inv~n~ion.
-41-
. J
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