SOCIETY OF’PETROLEI.

JM
ENGINEERS OF AIME
6200 North Central Expressway T~’RSPE 4351
Dallas, Texas 75206

THIS IS A PREPRINT --- SUBJECT TO CORPtECTION

Structural Relations of Organic Corrosion

Inhibitors and Scale Preventives as
Applied to Oil Field Chemistry

By
Gerald D. Hansen and Charles C. Nathan, Betz Laboratories Inc. and.
Ber.Sloat, Member AJ.!4E, Betz Laboratories Inc.

@ Copyright 1973
American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc.

This paper was prepared for the Oilfield Chemistry Symposium of the Society of Petroleum
Engineers of AIME, to be held in Denver, Colo., May 24-25, 197’3. permission to coPY is re-
stricted to an abstract of not more than 300 words. Illustrations may not be copied. The
abstract should contain conspicuous acknowledgment of where and by whom the paper is presented.
Publication elsewhere after publication in the JOURNAL OF PETROLEUIV1TECHNOLOGY or the SOCIETY OF
PETROLEUM E1’JGINEERS
JOURNAL is usually granted upon request to the Editor of the appropriate
journal provided agreement to give proper credit is made.

Discussion of this paper is invited. Three copies of any discussion should be sent to the
Society of Petroleum Engineers office. Such discussion may be presented at the above meeting and,
with the paper, may be considered for publication in one of the two SPE magazines.

l\iK’rl/Ac’r
-...---..
%mipolar molecules sLIcllas surfactants
arc extensively en!lloyedin the production of
petroleum for the solution of problem of
corrosion, scalin~, emulsion fon~tation:etc.
‘1’l\is
paper describes some f~indamentalrelations
whicl}have been developed between ti)estrllcturo
of sltrfactantmolecules and t!leiraction as
corrosion inhibitors and as scale preventives.
,\lso~ivcn arc laboratory met’~odsfor predictin
when scaling, etc., may be expected due to
incompatibility of oil-field brines with onc
another or with additives sllchas cnploved in
polymer and micellar floodin:.
Correlation of puhlishe<ldata cn certain
polar materials based on sulfur, oxy?cn and
nitrogen have shown that in a given hcmolo~ous
series, corrosion inhibition effectiveness
increases with increasing rnmbcr of carbon
atoms in the alkyl chain(s) attacheclto the
polar ::roupwhich aclsorhsonto the metal. The
Lanqnuir /\&OrptiOn Constant inCrCaSeS b!~a
factor of ten for cnch additional four cnrbon
atom ad(lcdto the nolcculc, ‘whct!lert’:cchnil]:
are strai:;htor brancllcd,for sulfilricaciJ
used in the picklinq of steel. There is no
sinnific~nt CIi?fcrcnccin corrosion jnhil)itor
cfficiencv in this systcm ar:on~t!lehm’lolomolls
scri.esof oxy:cn and nitrcycn coy.poun(ls
such a!
amines, ketones, and aldchydcs reported; how-
ever, sulfur compounds of a ?,ivencar!>on
numhcr apnear to bc about two orders of maqni-
t~de more cffectivc than nitrozcn en-.
oxv:cn
compounds of the snnc cnrlmn rnmber.
Studies carricclout on polar mtcrinls
use{las corrosion inllihitorsand/or 0s scale
preventives in other svstcm sllc!~as si-ullatc(l
oil field bri.ncs,cooling waters, hoilcr fced-
watcrs, have indicated that alt!]ou+ t7e
adsorption concepts Jeveloncd for acid
corrosion inhibitors are of imnortancc, other
factors arc of equal or ~reater imrmrtance. ‘h
concept of rate control of a precinitatinz sal
such as calcium carbonate is develoncd and dat
presented indicatin~ t}~atthe effectiveness
of rate control additives such as phosnhonates
and polymers is determined by the maflnitudeof
the formation constant of the compound formccl
by the cation and the additive as comnarcd to
that of the cation and the precipitating anion
 . ● 9
“STRUCTURAL RELATIONS OF ORGANIC;CORROSI014INllIllI”l’ORS
50 AND scALE PREVENTIVES AS APpLIED m OIJ.FIELIIclm[ww” SPE 4351

m2 interaction of rate control a:ents organic corrosion inhil]itorsarc ~enerall:

such as polymers with and without addition of considered to obey a lian:muirty!>cadsorption
other additives and in tllcpresence and absence isotherm in which the fraction of monolayer
of precipitating cations, as well as other salts covcra~e,@,and the fraction corrosion inhibi-
such as sodium chloride, has been investi~ated, tion,~, arc assumed to hc eqlml and related to
and the importance of such interactions on the concentration of active adsorbinq inhibitor
viscosity of polyncr solutions and their scaling c~by the relation ~iven in Equation (l). llere
tcncicncicsis illustrated. the parameter ~-is a constant for the species
bein~ considerclland hns ~lnitswhich arc
determined by those of c, Frol!l the practical
ecohomic stand!mint of ‘i-nhihitor Ilsaqe,other
Numerous stuclicsdurin!:the pnst 20-25 conditions hei.n:cq~lal,the most desira!>le
years have discussed the importance of senipolar inhibitor is that onc whic!l:ives a hi~ll
or::anicmolcclllcsin the solution of various effectiveness fita low Vnltlcof c_,or in other
moblens of oil findgas production. .knonfl these words, onc whicilhas hi~llvalues of n in
are the application of high molecular weiqht cqllation(l). Thlls,various in!libit~rsnay I)c
nitro:en compounds used as corrosion in!~illitnrs readily con~>arcdon the basis of J,anvrnuir a
in oil well acidizinq and in ?)roducinqoil and values, which are generally determined fro;-
~:as~jclls. Another important use of surfact.ants cxperinental data on corrosion inhibitor effect
is in the breakinz of oil field emulsions. A iveness at various concentrations.
laryc number of materials have been patented or
Dtlicmvisedescribc[lfor use as corrosion inhibit
ors or dcmu].sifiers,and some of t!lemore
important factors Jctermininq t!lciractivity,
such as chain len:th, nature of the polar zroup Eldridgc (1) tohulatc,l150 orqanic mines
and hy(lro!lhilicversus h~drophobic nature of t!lc aldcl]ydes,ketones mcrcaptans, etc., either
!L)rlcculc,
nave been clucldated, used or pro!)oscdas inhibitors in slllfuricacid
(4.9%, 25”C, 4S hr. exposure) of corrosion of
Coltl?(lS’t[W
----- I;JIIIBITORS
---.-----.----— Ii{Sllt(]:{(:
------. ACI1)S
..--.--. - 101!3Steel. ‘~hcmaterials are listed in
decrcasin: order of effectiveness basc(lon in-
!)rqfiniccorrosion inhibitors, :;cnerally crcasinficoncentration rcqlliredfor (a) 90%
~olwllatc(lfrom nitro~en bascsj nave 10J1YIlccn inhibition, (b) 50$ inhibition or (c) rmtcrials
used in nctal ?>icklino.an(iclcanin!{,and a which ~ive less than 50% inhil)itionat any
considcrnblc amount of infor]llation is reported concentration tested. Concentrations arc :.ivcn
i.ntilecorrosion literature on such systems. In in wcicht percent in tllcranqc of 0.003 to 2.5°;
recent years, oil field acidizin~ operations In the present discussion, we have chano.ed
have also become a major application of corrosio weiflhtpercent to moles of inhibitor per 100 r.
inhibitors in strong wineral acid systc~s, how- of solution by clividinfl by the formal molecular
ever, tllcliterature in this field is not as weiflhtof tllcinhibitor. This allows for
extensive as in metal pickling, etc., appli- comparison of an homologous series, such as
cations. Ilntilrecent years, the ?~rincipalaci(l aliphatic amines, on the basis of equal concen-
u.sc[l
in picklin.qwas sulfuric, bht this hns Ix-en tration of functional inhibitin~ Croup(s).
ra!li(lly
replaced I)yhy(lrochloricfor reasons of
econony, PolllItioncontrol, etc. 1![:1 !):{s
alvfnys l)A’I’A
ANI)C/\LCULATIO}!S
... --...-------..-
..--
hcen the favore~lac+.dfor well stimulation,
either alone or with adtlcxl IiF for dissolution In order to use Eldrid:e’s data for
of silicious materials. calculation of Lanqnuir a values, we note from
Equation (1) that the l,an-qmuir value of a has
AlthouRllthe conditions of the two the numerical value of the reciprocal of–the
applications differ, the oil Sielflconditions conccntra:iond~ich effects 50°6inhibition.
xenerally using hi@mr strenqth aci(?sand at It can also be shown that the concentt’ationre-
incrcasin:lyhi:hcr tcnncraturcs as well clepths quired for 90% inhibition should be nine tines
increase, wc ]Iavc attcmpte[lto corrclatc some that required for SO% inhibition, so that the
of the extensive data reported on pickling value of the Langmuir a can be also calculated
inhibitors. It was hopeclthat any correlations as nine times the recij-rocalof the concentra-
found in these systems would bc useful, pcw SC, tion required for 90% Inhibition.
for applications to systems such as picklinq ant
oil well acidizing, but more generally, that Such calculations were carried out for
such correlations might he useful in other all of the 112 materials for which Eldrid~e
applications of semi-polar, or~anic, adsorption- ,qaveeitl~erthc90% and/or the SO’%concentratic
type materials used as surfactants in other values. Table 1 gives. as an example, data for
systems, c.:., oil ficlclwaters, as corrosion all of the straiqht chain, primary, secondary,
inhibitors, scale preventives, etc. and tertiary mnincs reported by Eldrid~c.
SPE 4351 GERALD D. IIA??SEN
, CIIARLESC . NATIIASl ,VJD DEN SLOAT 51

Lannrnuira values were calculated from the equilibria between adsorption and desorption.
concentra~ion(s) listed for 50 and/or 90% Then tilefree cnersy diffcrcnce,AF, between
inhibition. Also, the ratio between the SO and two molecules havin!;J.anqmuirconstants
90% inliibitorvalues (theoreticalvalue 9.0) different by factor of tcn s]louldIIC!;ivcnby
was calculated. ‘l%eamincs arc tabulated Equation 2.
accordin!~to the total number of carbon atoms
in the molecule. Fi5urc 1 is a plot of the -~’ = IW fn k2/kl (2)
losarithm of the value vs. the nllmherof carbon
atoms in the molecule. ‘rhestrai~]ltline, ~~]lic]l = (2.3 (298) (1.937j loq 10/1
is drawn by visual cstination, lies C1OSC to
all of the points with the exception of = 1362 cal
diinethyl.amine.Data for primary, secondary and
tertiary amincs apnarcntly all fall on the Since Langmuir a increases by one log-
same line; only the number of cari>onatoms is arithmic unit for an i-ncreaseof four carbon
important in determining the value of a, an atoms in chain lencthj the chnnne in free
increase of four carbon atom resultini-in a cner~y pcr carl)onatom or C117cqllals_l_3:J-2- =
ten-fold increase in the value of .-
a. 4
340 cal. This value a~rccs well with t!lc
Stldies of this type on corrosion inhibi- al>nroximtion of 0.3-0.4 K cal . jllstcited.
tion and other sllrfactant-adsorptionprocesses
and have been reported extensively. i;cil;lVC Calcul:ltc(lI,:lnflnuir a valllcsfor
;;: :H:72) reported data for corrosion of otllcrseries 01”l~orlolo,,.o~ls cO.7~)0~lniiS ~ivcn in
mil(lsteel in onc normal IIC1at 77°F with 4S- !~l[{ri~l,:c}s t~~>]c. I’!lc$cseries inclll(!c
hours ex!]osuretime. Inhil)itorcontent was slll)stitutcd anilines to]llj,!incsxi,li~!illcs.
constant at 1000 p!xIL
expressed as Imsic nitroqen pvri, !illcs qlli]lol
incs, IIltif!inc+nl(lr!lvlle$ .
corres!>ondinqto 0,0072 moles/h:uuhed yrans }~ctoncs,ncrcaptnns, Sill Cil’CS itn(l (Ii%lll fidcs.
sollltion. For the series of nrima-rymines, “1’])c
SO;,:I: I:c1lcI.21t].cn(l~
are SIIOWTI ;)sfor
Llct:)yl
to (Iccyl,inl]ibitorcf}iciencv incrcmscd alin!)atjcilHillC3S, i.e., increasinfl il)llil)itot-

with chain lcnqth: llowcvcr,branchinq of the efficiency witl~clmin.len:~. th or al)ollt onc

nolecules was found to be deleterious, and (Iccadcincrcasc in t!lca k’allmfor follrcarl~on
pril:lary
amines cf a !:ivencarbon number were ate!’ts as Shown. E’llrthernnrc, all OF the
hctter inhibitors than were secondary or nltro~cn and oxy!I,cn .i)asc[l inllil~itors c311 I)c

tertiary wnincs with t!~csame numhcr of carbon re!~rcscntcd!Jyt:lcSn!.lc li:lc:1sis flivonin

atoms in the nolccllle. l:i~:urc 1.

The increase in inhibitor efficicncv with “1’llr

slllt”~lr
cm.lpount!s
arc qllitci~t.crostin
increasing chain lcn~th is generally nttr’ihl~ted 1. It will l~c
an(larc also shown in I:i:nlre
to Trauhe’s ll~lle,which states that a(lsorption seen that the a Value at a qivcn chnin lrn~.til
in n (livenhomolo~ollsseries is proportional to is ~nllc]}
l~i,,!l~r--for
tileslllfl~r
cmnmln[ls t!~~ll
fraction of saturation solllbility.or inversely t“orthe various alin!laticamincs. ~.11of-t!lc
proportional to act~lalsolllhility,which slllf~lr
couIpmlnlls
can l~crc!)rcscntc(!
by one line
.qcncrallyfalls off with increasin~,chnin lcnvtll w!licll
!lascsscntiallv tllcS:l:tw
slollcas t!lilt
in t!lcho~oloflousseries. for t~lcalipllatic:unincs(actllallvnll of tile
nitroqcn nnd oxvfcn cmnounds) . Note, however
.l~lsornticm
of inn::-c.h,ain
polar natcrinls that the Iinc for t!lcslllfllr
crmmlnds is nt
from solution onto nctals and other !>olarSoli(l least two orders of :Jaolnitlhlc
al~ovctl~eotllcrs,
surfaces may bc Consi(lercdas bei,ng(Ietcrnined indicating:the vcrv lli~!ll
c“ficicncv of t!:e
by two factors: (a) strcn;th of tileprivary slllf~lr
cn!l?wm~nds
as corrosion inl]ihitorsFnr
bon(ihctwccn the soli{land t!leattracted nolar fllricaci(!. Tt is ZISO of
~il(lsteel in sill
[;roun,and (h) the Van dcr Haals’ forces hctwecn interest tilntall of t!lcslllphllr
cnmnolmls -
methylene nroups in adjacent adsorbed molecules wl]cthcrmcrcalltans.sulfides or dislllfidcsfall
comprisin~ the adsorbed filonolaycr.‘Ilcn\lsorp- on the sane line.
tion encr!!yis contrihutetlrouflhlyabout half
and half bctwccn the primary adsorption and An additional poi[ltof interest is shown
Van dcr \laals’forces. ‘rhcproportional con- I>yconi]:lrison
of tllcrcportcclrfltiosof conccn-
tribution by the Van (ier?;aals’forces will, of trations for !N)3an(l50°ti
in!lil)ition
with t!le
course, increase with incrcasin(!chain Ic]lflth, ratio of nine as predicted I)yI;qllation
(l).
and has been reported to he shout 0.3-0.4 K cal. ‘1’here
are tilirtv-onccntri.csin llldridqc’s
per C112sroup. titblcfor which the ratios can hc calclllatcd.
“1’hc
ratio rnnccs from 2.7 to 23, with the
t!ccan calculate the ma:nitutleof the :comctric avcrnpc of 7.1 wul a standar(ldevia-
Van dcr l!aals’forces from the data shown in tion of 0.30 Iwarit:mic [Inits,or a factor
Fi2ure 1 by assumin!:that t?lcLanTnuir a values of two (that is bctwccn ratios of 3.5 - 14).
ax-cessentially equilibrium constants r;lati.n: The distri.huti.on
of ratios is not normal;

‘{STRUCTURALRELATIONS OF ORGANIC CORROSION IN1lIBITORS
52 AND SCALE PREVENTIVES AS APFLIED TO OIL FIELD CHEtfISTRY”
however, two-thirds of them are clustered around
a value of 7.9 (5.0-12.6). Considering the
extreme ranges of concentration in Eldridgets
table and that some of these concentrations are
given to but one significant figure (which at
the very low concentrations may be only an order
of magnitude) the agreement with the calculated
9:1 ratio is satisfactory.
CORROSION INHIBITORS, SCALE PREVENTIVES, ETC.,
IN BRINES
.——.— AND OTHER
——.— —- ..AQUEOUS SYSTEMS
... --..—-- —----- ..-.—
An additional problem important in the
production of oil by secondary recovery methods
such as water flooding is that of scale
formation by commingling of incompatible waters,
or by changes in temperature, pressure and/or
chemi;al composition of the waters, such changes
resulting in reduction of volubility of carbon-
ates and sulfates of calcium, strontium and
barium.
Among the various methods employed to
prevent the precipitation and deposition of
these materials are the use of inorganic (and
more recently organic) additives added in less
than stoichiometric amounts. These materials
are known to change the volubility of scale-
forming materials OT to alter the rates of
precipitation, mode f deposition, etc., in
some manner that re((.ce scaling problems are
effected. Previous investigators have postulated
that their action is primarily clueto adsorp-
tion of the additives on the ~rowing crystal
nuclei so as to change the crystal form, etc.,
as shown by Smith and Alexander (3) and by
others. In the present work are described
experiments indicating that there are other
factors equally important or more important in
prevention of calcium carbonate and sulfate
scales by additives such as phosphonates.
Indication is that the volubility, itself, is
increased by formation of particles of very
small dimensions, which were predicted by
Kelvin’s classical work to have solubilities in
excess of lar~er particles. The mechanism by
which particle size is maintained in the range
of ion pairs is dependent on the formation
energies of the precipitating species and of
the controlling species.
These problems of scale formation are by
no means unique to oil production, water
floodin~,etc., but are found in most industrial
systems employing cooling water, in boiler feed
systems and in steam production, etc. In
general, these other systems involve waters
which are relatively “fresh” as compared to
many oil field waters which are brines of high
salinity or dissolved solids content. The
presence of these dissolved solids, in particu-
lar calcium, magnesium and other alkaline earths
in fairly large concentrations as compared to
normal cooling waters, boiler feeds, etc.,
,.
SPE 43S1
intensifies and complicates the investigation
and application of surfactants.
The more promising recently-developed
methods for increasing the efficiency of
oil-field flooding operations include the use
of micellar solution as described by Cogarty
et al (4) and the use of solutions of high
molecular weight polymers as described by
Sloat(5) Current articles by Carpenter and
by l[olmand Josendahl(7) discuss the effect of
the brines on the efficacy of both micellar and
polymer flooding. In particular, calcium and
magnesium in a brine may precipitate out the
polymer, thus destroying its effectiveness.
Furthermore, they may cause instability of’the
micellar solutions, resulting in highly viscous
emulsion formation, and other undesirable
effects. Our work has shown that reaction
between polymers and calcium ion actually gives
a decrease in viscosity for acrylamide systems,
and that precipitates formed are filtrable
through rather large membranes, thus indicating
that actual plupgin~ of the porous structures
rather than modification of viscosity is a
cause of reduced efficiency of flooding
operations brouxht about by interaction of poly
mers and the brines containing them. It is
accordingly seen that knowledge of the compcsi-
tion of the brine and the effect on the sur-
factants, as well as steps to mitiqate any
harmful effects,can be of utmost importance in
assuring a successful flood.
I- This work as described below has been
divided into three sections:
(A) Adsorption of a certain class of scmi-
polar or polar organic molecules that have beer
applied as corrosion inhibitors in systems
other than stron~ acids, e.g., fresh waters
and brines.
(B) Use of such afientsas scale preventives,
and the mechanism(s) ,hat may account for thei]
effectiveness.
(c) The effects of these molecules when used
in conjunction with certain polymers for the
control of scalin~ in brines caused by divalenl
cations, and the effect cf the ions on these
polymers used as water flood additives.
A. CORROSION
._ -.-.-.— IN11IBITION
----——— --——.IN——BRINES
—
One role of inhibitors has been to reducf
the dissolution of base metal under brine
conditions. The most effective mechanism
appears to be adsorption on metal surfaces of
a film which reduces normal electrochemical
activity. The effectiveness of such a film is
dependent upon its ability to cover the metal
completely, as explained above.
 ,-
sPl?43s1
------- GERALD D. HANSEN.
, CILARLESC. NATHAN AND BEN SLOAT
Adsorption and polarization studies
indicate that adsorption of a particular
rmlecule is effective in reducing corrosion orJly phosphonates, have the capability of inhibi(~2~g
if there is a complete and continuous film which
~an be maintained under the conditions of the
?xperiment. Simple site-site adsorption is not
z sufficient criterion for inhibition.
Figure 2 shows adsorption isotherms for a series
of phosphonates which are frequently used as
najor constituents in inhibitor treatments. As
can be seen, the data appear to follow classical
adsorption concepts; however, this does not
prove that inhibition is necessarily a function
of adsorption of the inhibiting molecules. On
the contrary, at electrolyte concentrations
lower than those in ordinary oil field brines,
and in the presence of air, adsorption alone
does not give acceptable corrosion inhibition.
Nor should specific site-site interaction
without lateral interaction be expected to give
a continuous film. Under certain conditions,
the use of such materials alone has been shown
to permit localized attack or pitting. It has
also been shown that, in conjunction with other
agents (phosphate in the presence of such
divalent metal ions as calcium), adequate
protection can be maintained at hi@ler pllvalues .
Corrosion inhibition by phosphonates has
been described by hatch and Ralston(81 In high
carbonate or hard, brackish waters, the poly-
phosphates arc known to be rather ineffective
as inhibitors; however, they show that a
combination of zinc ion and ANTP (amino methyl
triphosphonate ) can be used effectively in
such systems. As a part of the present work,
we have found that certain combinations of
phosphate and phosphonates are effective in
controllin~ corrosion at pliof 7 and above.(9)
The polarization data shown in Figure 3
indicate the type of current control exhibited
in differential aeration cells under conditions
of pretreatment and no pretreatment. Once a
protective film is laid clown,the phosphonate
inhibitors are very effective corrosion control
materials. The effectiveness in such systems
usually increases with increasing calcium
concentration. The advantage of the phosphonate
systems and, more especially the compounded
systems, is the control of calcium sulfate
scaling as well as of corrosion.
B. SCALE PREVENTION BY P1[OSP1-lATE,
PHOSP1K3NATES,
POLYMERS, ETC. — -— -...--.—-.--——-...-.—-
— .-——.-..—— ------- — both the thermodynamics and the kinetics of the
The action of certain phosphates in
inhibiting calcium carbonate precipitation was
probably first recognized by Rosenstein(lO~and
subsequently by Hatch et al. Hatch and Rice(l1)
coined the term “threshold effect” for the
action of these metaphosphates. It was also
noted that other phosphates exhibited this
53
effect under certain conditions. Our work
showed that other materials, including the
calcium salts formation and precipitation.
The initial investigationswere primarily
in cooling water studies, but considerable
effort was expended in boiler water treatment
studies under t?~eguidance of Ilalland
Partridge.
J.[anyworkers have subsequently studied
tl~eeffect of additives on modification of
crystal structure of scale-forming materials.
Alexander and coworkers as well as ;Iichaels
et al (lS) indicated that under the proper
conditions, precipitation rate could be
controlled, by additives throufihcrystal modi-
fication. llleirwork was preceded much earlier
by-that of Kelvin, who proposed that
volubility is a function of the surface free
energy of the precipitating material, and there
fore of its particle size; however, subsequent
efforts were not successful in demonstrating
any substantial increase of volubility with
reduction in particle radius.
Because of the effects of certain phos-
phates on the rheology of many systems, and
also because of the historical relationship of
boiler deposition to the properties of the
specific system (the prcci.pitatinqscale and
the additive employed to control the precip-
itation), it has been postulated that the effec
of additives, such as phosphates, on volubility
of a scale, such as calcium carhonatc, is of an
adsorptive nature; however, our work has
indicated that the adsorption mechanisn may be
but one of several factors important in control
ling deposition.
Specifically, a relationship has been
observed between the ability of an additive
molecule to affect the formation of a series of
calcium salts and the dissociation constant of
the additive molecule. I:ora modifying addit!v
to be effective, the formation constant as
*
defined below, of the additive with calclum,
must be greater than the formation constant of
the ion pair of calcium, e.g., CaC03, in the
precipitating system. Additional work by us
has shown that the relation is qeneral for
calcium precipitating in other systems, not
only those in which CaC03 is the precipitate
formed. Because of the need for information or
system, the general class of materials
exhibiting such behav”~~lhas been called “Rate
i
Control Agents” by us.
For the reaction A+ B = AB (3)
Then formation constant
(AB) .
-—— - (4)
(A) (B) P
 “STRUCTURAL RELATIONS OF ORGANIC CORROSION INHIBITORS .,
54 ANl)SCALE PREVENTIVES AS APPLIED TO OIL FIELD CHEMISTRY’) SPE 4351

Where (A) = concentration of cation, copolymers is difficult. Analysis of calcium

~a++
e.g.$
(B) = concentration of anion,
e.g., S04, C03, phosphonate,
polymer anion
(AB) = concentration of complex
contents in controlled experiments and observa-
tion of precipitating tendencies give only
approximate values of formation constants and
the effect of temperature. Copolymers with low
content of acrylic acid groups reflect the
character of low WV homopolymei’s. They appear
to be exothermic with but low values of forma-
tion constants.

In Figure 4 are shown the formation c. EFFECT OF

-——.. BRINES
...-
—- ON POLYIERS,
——- —-— ETC.
constants for CaS04. The values are deter-
mined by potentiometric techniques in dilute The use of polymers as viscositv modifier
solutions of the reactants. The data are seen in brines emphasizes the importance of any
to be in essential agreement within limits of interaction of multivalent cations in the brine
experimental error with those of Bell and with the polvmers, as recently pointed out by
George(18) which are included for comparison Carpenter.(6~ Accordingly, we have investigate
on the figure. In Figure S are given formation the characteristics of several members of a
constants for materials shown to be effective series of linear polyacrylates in order to gain
in preventing the precipitation of CaS04, and an understanding of their possible reactions
it can be seen that all of the materials have with calcium. There is an important limitation
formation constants greater than that of CaS04. to obtaining direct measurement by the poten-
tiomctric technique used for determination of
We have further found that the most effect- formation constants of high M’:moIecuIes by
ive control agents are those which have form- precipitation of their salts. This limitation
ation constants greater than but somewhat close is the poisoning of specific ion electrodes by
to that of CaS04. Since CaS04 nuclei and adsorption of the polymer on the membrane.
aggregates from solution can grow and approach
the limiting volubility of CaS04, it iS logical It was observed that materials for which
from thermodynamic concepts that control of the formation constant, $, is close to but
precipitation should prevent growth as much as slightly less than that of the precipitating
possible. Further work in other systems such system, will actually accelerate precipitation
as CaC03, etc., has led to similar results from of the system. Accordingly, solutions of
which it is inferred that at a given tempera- polymer and a number of other rate control
ture, the formaticn constant of the rate contro: agents with known ~ values were nixed in dilute
agent and the cation should be greater than solutions with calcium. Observations were made
but close to that of the precipitating species. at several temperatures to determine the condi-
tions under which the a~ent(s) act as precipi-
In studying the effects of polymers and tation accelerators rather than rate control
their interaction with cations contained in agents.
oil field brines, etc., the polymer should be
considered in the same manner that any reactive Data are shown in Fi.Wre 7 to illustrate
anion would be considered. Formation constants the effect of addition of salt to a system
for a number of polymers have been determined, containing the highest MIVpolymer in the series
but the potentiometric method employed is of polyacrylates described above. At any Siven
limited to lower molecular weight materials. temperature, the value of ~ is lowered by the
In Figure 6 are shown data for a series of addition of the salt. The relationship between
linear acrylic polymers of molecular weight log ~and l/T indicates that the fo~ation of
varying from less than 5000 to about 100,000. the complex is endothermic in both instances.
The value of the logarithm of the formation
constant is shown as a function of temperature. A particular polymer which has been used
Low molecular weight acrylic polymers of this successfully in some water flooding operations
type have rather low formation constants with is a proprietary formulation, a copolymer of
calcium, the value of ~ increasing with acrylamide and sodium acrylate, with the ratio
increased molecular weight. The slope of log p of amide to acrylic function being about 60:40.
versus l/T shows that the lower W materials The molecular weight of the material is believe
are exothermic but the higher MW polymers are to be between one and ten million. Polymers
endothermic. This is to be expected in view of this type are unique in that their calcium
of the increased entropy of the high MW salts are quite soluble. Accordingly, observ-
materials. ation of precipitation cannot be used for
determination of this t~e of material. Also,
Determination of the formation constants since the polymer salt particles do not have th
for very high molecular weight homopolymers or tendency to grow, rate control agents do not
SPE 43.51 GERALD D. HANSEN, Ci-iARLES
C. NATHAN AND BEN SLOAT
limit their salt formation. Analyses of
solutions of this polymer were carried out by
a titration method in which known quantities
of calcium were added to the system, and the
amount in solution was thea determined by
analysis. Figure 8 shows typical data of this
sort.
It can be seen that the addition of NTA
(nitrilotriaceticacid) gives an increase in
the amount of calcium which can be titrated;
but the effect of HEDP (hydroxy ethyldiphos-
phonic acid) is a decrease in available calcium
indicating the growth acceleration capability
of the lIEI)P.
Figure 9 shows the formation constant data
for the same rate control agents used in
Figure 8. It is readily seen that the growth
accelerators have formation constants well
below that of the polymer at room temperature
(1/T = 0.0033°K), while those formateriaIs
which increase calcium polymer soluhility lie
near or above it.
An additional finding from this work,
important in water flooding operations, is
that certain agents which act as precipitation
accelerators may alter the viscosity of the
polymer system. Viscosity measurements were
carried out by use of a Brookfield rotational
“infinite cup” viscometer. Figure 11 shows
the effect of addition of 2% salt to a solution
of 500 ppm polymer at relatively low shearing
rates. Figure 12 shows the viscosity data for
a calcium polymer soIution with no salt ad{ied
55
and for comparison the same system with 15 ppm
added HEDP.
There is no apparent effect of the lWllP.
In Figure 13 are given the data for the calcium
polymer in the 2% salt solution, and the same
system with a further addition of 10 ppm llECP.
The addition of the HEI>Pdoes
.-—a.have an effect in
this case, as shown by lowerlng of viscosity.
The above data indicate that in usinE
this type of polymer system, the possible
effect of corrosion or scale control additives
on the system must be considered rather than
adverse effect of the divalent ions alone. It
is also concluded that the nature of the
specific polymer employed in water floodin~ may
be a major factor in determining reactions
between the various constituents normally found
in the oil field brines and the polymer and
other additives.
Further studies are bein~ carried out in
systems of varying ionic strength, hardness
content, and additive composition in order to
extend the utility of the concepts which have
been illustrated above.
ACKNOIVLEDGE!,lEW
— — ——-- .---
‘l’he
authors express their appreciation
to the management of Betz Laboratories, Inc.
for permission to publish this work and to
?lrs.E.G.Varney and Dr. P.Davis for their help
in the gathering and interpretin~ the data.

REFERENCES

(1) G.G.EldridEe and J,C.Karner, “Inhibitors and Passivators’”,p, 910,

from “Corrosion handbook” edited by H.11.lJhliC-.John
l’lilcy
3 Sons. Ncw York, 194S

(2) C,C.Nathan, ‘Stud.icson the Inhibition by Anines of the Corrosion of

Iron by Solutions of !IighAcidity”, ---
Corrosion
--— ,5_,
-+.. 199 (1953)

(3) 13.P.Smithand A.E.Alexander, “The Effect of Additives on the Process of

Crystallization”, J.CO1l.
----- Sci LJ 34
--—-— --} #l, September 1970

(4) W.B.Gogarty and lt.C.Tosch,J1!!iscj,ble-T~e llaterf100ding: Oil Recovery

with Nicellar Solutions”, J.Pet.
--.--.--.-—-- Tech. 19, 1407 (1’368)
-- ---

(5) li.Sloat,‘How Six Polymer Floods are Faring”, Oil

— — and
.-—-Gas Jour.
--------
p. 101-103, Dec. 11, 1972

(6) 1).!l.Carpenter,l,~[icellar
Flood Te~ed prmnisinq Oil !~ecovervTOol’i>
Oil and .Gas
-—— Jour., p. 65-68, Dec. 4, 1972
. --——

(7) L.W.l{olmand V.A.Josendahl, !IllesemoirBrines Influence Soluble-oil

Oil
Flooding Process” .- and Gas
—----- Jour., 158-168, Nov. 13, 1972
—....----
(3) Ralston, “A~lP-Zincfor Control of Oxy[:enCorrosion’,
C,B.llatchand P,ll.
SYnposillmon oil Field Chemistry, Div. of Petroleum Chemistry, .ICS,
Ilouston,Texas, Feho22, 1970.

(j-)) W.L.llarpeland J.!!.!hmohuc,‘EffectivePhos!i~ate/P!u3sphonatcl’reatmcnts

, Annual :.leeting
Replace Chromate-Based l]ro~rams’: of CoolinR Tower
Institute, Ilouston,Texas. Jan. 29-31, 1973

(10) L.Rosenstcin, U.S,Patent iteissue#2fl,754 (1933)

(11) C,ll.llatch
ant]O.Rice, S~lrfacc-Active Properties of llcxametapl~osnl~atcs
‘,
I-~(\.-~_ny2.-
Chem. 31
----------~ 51 (1939)

(12) ~;,i).llanscn (;ontrolof t!le‘;atcof Precinitatc

and E,A,Cut!~ri.e,
Growth and the I)reci?>itation
in .lqllcous
Systems ‘,U.S.l’atent~~3,513,204

(13) R.1:.llall,
“!lakin~Calcillmin t!atcrBehave Paper !Iilland ?:ood}:CWS
.Lusust1939 and E.P.Partridqc, ‘Thrcsholcl -L--—--’–---’------T--31
Trcatmcntj In(l.l;n,7.Chcn
.--— -i$—---
--. ...-~
58 (1939)

(14) A.E..4lexanclcr
et al, “’lIIc
Effect of’.L(lditives
on the Process of
Crystallization J.COI.1.Sci. .—$ 3s3 (1953)
..—--.-.--..-- 13

(15) A.S.;lichaelsand F.W.l’ausch,,Jr,, ;IITBulletin 6h (1970)

(16) L’.lllornson
[J.ordKelvin), I’hil.’lau.~~, ~~~ (1871)
.—-------
L-

(17) G,i;.llanscn
and E.A.Clltllric,
‘In!lihition
of Scale Formation”, 11.S.Patent
# 3,s47,317

(18) R.P.Jlelland J.J!.B.Georce, “The Incomplete Dissolution of Some ..

“rhallousand Calci~[mSalts at l)iffcrentTe~!~erat{lrcs”,
Trans. Far.— Sot.
.-—. ----- —
 N
.
I-I I I 1 I I I I

..”
c):
C.$”
I
ml ‘%’%”$cv%cwmm?
rl-l-t-cF-l-cr --
* e
C2C?L’
co
c-
Fxxxt- l-r-xl-l-r-
XCer-xxxxcxx x
*cmeeL.:mNm C.=fcw
. . . . . . . . . . . .
ml-t- r-cnmJml-Nm me I I

t-c c=
er l-cc
Y“e c IJ9*.
C’c-c?c
U)UJ

.. KY ret- vY -
Xxl-xxc-x xxx
CTci-icm-wmmm
. . . ..X . . . .

,-.
u. ,

cl Ill

m
F
IOll:ltlll

cob
* Nl%m N (--.1
<.0 ehel-c’cr
. . . . . . .
o11111 Imcoeec?c

!=,

“E;
=-c,

.-v!
 ,, .

NO PRETREATMENT Pt?ETREAThfEAfT

700 ‘% 700
‘.
-- ..
*.
‘.
650 ‘>
~~nf,~~ \
/’ \
\
>600 ..’ 600 ‘,
E ~“ Formulahon A %
F \
\
.
$ 550 \
e z
w ‘>
0 ,/
+
o
0.500 . 500 .“’
t
.“
.
● p: \
450
●

/ — Formulation B
#
0 400 400

L , ! , 1 I 1 t 1 [

0.1 02 03 0.4 0.1 02 0.3 0.

CURRENT - mA

Fig. j - Influence of pt.osp!>onaw ?,rwla+.:on~ on tt.e Corro:; on of ,r!il’d

:Leel as a fum%’.m Or pretreat:.ent; 2L-k.our exposure to p}! 3
●
A.MWA TIC AIUINES
fresh wt.er at a-ci eni. te-qxmt.ui-v.
0
● From 900/. = 6
.
0 From 50 % ; C

I ,!
10:
234567891011 121314
CARBON NUMBER

~ig. 1 - Lmumir adsorption constant of P.omlogous series.

m
w
Cj

DADP
7

I , 1 I r

6 3.5 3.4 3,3 3.2

(1/T)Xio3 “K
N
Fig. h - Variation cf formLiOn constant, fl , w:th te~cra%urc az a
fonctim o? te.werature - (A) celciu-., carbonaL?, (1,) CrA:tU-.
suifate and (C) Calc:u-, :u.l%te.17

ATMP

HMP
9 m
A
/

.HEDP
~:=;.iz’:;:::;
,
~.-----
------
---
0
●

,’
,’

BI-IMP

/7 . .------
.
------
----
.-E 1 , , I & 1 , 1

5 10 15 20 25 30 3.5 3.4 3.3 32 3. I 3.0 2.9 2.8 2.7

CONCENTRATION, ppm (’/T)X 103‘K
Fig. 5 - Rate control effect of various agents on Ca204 precipitation:
Fig, 2 . Adsorption isotherms.
(A) C}lC bLP, (B) CMC 12M8, (C) CMC 12M31, (D) CMC 7Mt and (E) ‘k~b.
... *

A A

.//’

I I I I I I I 1 t [ 1 I I I -1

35 3.4 3.2 3. I 3.0 3.5 3.4 3.3 3.2 3.1 3.0

(&;x103 “K (’/T)
X103 ‘K
Fig. 6 - Varietion of forcation cOn~t~t, % , with teqerature as a f~ctlon Fig. 7 - “iari ation of forcm.tiofi constant, B , with temperature as a
o? molecular weight: (A) IW.WIOIJ, OOO, (B, C) !W+,000 and (D) !.?4<5,003. function o< ionic strength: (A) polymer in deioni Zed water and
(B) wlymer in 2 percent NaC1.

iO

4 ==-

1 I I I I I

--- )
3,5 3.4 3.2 3. I 3.0
ppm co” SUPPLIED TO 500 Ppm ‘OLYMER
(I;;;x 103‘K
Fig. 9 - Comparison of calcium formation constmts of various rate control
agents in the range of that for a calcium acrylate pOIYmer:
FiE. 8 - Effect of rate control agents on the volubility of 8
calcium polymer salt: (A) nitrilotriacetic acid, (A) etbylenediaminetriacetic acid, (B) hydroxyethylethylene-
diaminetetraacetic acid, (C) nitriolotriacetic acid,
(B) hydroxyethylethylene-di aminetriacetic acid, (C) entreated
polymer, (D) Hydroxyethyldiphowhonic aclc’ and (D) hydroxyethyl hosphonic acid, (E) sodium phosphate aod
(E) sodium phosphate. ‘/,) p.alyme: (approximate),
 1000
A

/“’” B A

/“”

10
.B

1 1 t [ I I I 1 1 t

10 20 30 40 10 20 30 40 50 60
TEMPERATURE “C RPM
Fi~. 10 - Effect of termerature and ionic ZtrcnEth on tk.e sol~bilits of a
calcium polyrer silt; 500 PPII polymer and-203 pp-n Ca++ supplied
(A) ~n dr?icmi.ed writer and (i?) in 2 percent iklC1.

,
1000

\
M
x
,. \

‘n\: x
●

I I I 1 t I I J I 1 , I , 1

10 20 30 40 50 60 10 20 30 40 50 60
RPM RPM
Fig. 12 . Effect of rate control agent on calcium polymer viscosity; Fig, 13 - Effect of rate control agent on calcium polymer viscositY
500ppm polymer, bOO ppm CaU, X untreated, ● treated with 15 ppm in 2 percent NaCl, 500 ppm polymer, 1+00 ppm Ca++, X untreated,
h~droxyethyldiphospkonic acid. t treated with 10ppm hydroxyethyldiphosphonic acid.