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SOCIETY OF’PETROLEI.

JM
ENGINEERS OF AIME
6200 North Central Expressway T~’RSPE 4351
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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
-...---.. atom ad(lcdto the nolcculc, ‘whct!lert’:cchnil]:
are strai:;htor brancllcd,for sulfilricaciJ
%mipolar molecules sLIcllas surfactants used in the picklinq of steel. There is no
arc extensively en!lloyedin the production of sinnific~nt CIi?fcrcnccin corrosion jnhil)itor
petroleum for the solution of problem of cfficiencv in this systcm ar:on~t!lehm’lolomolls
corrosion, scalin~, emulsion fon~tation:etc. scri.esof oxy:cn and nitrcycn coy.poun(ls
such a!
‘1’l\is
paper describes some f~indamentalrelations amines, ketones, and aldchydcs reported; how-
whicl}have been developed between ti)estrllcturo ever, sulfur compounds of a ?,ivencar!>on
of sltrfactantmolecules and t!leiraction as numhcr apnear to bc about two orders of maqni-
corrosion inhibitors and as scale preventives. t~de more cffectivc than nitrozcn en-.
oxv:cn
,\lso~ivcn arc laboratory met’~odsfor predictin compounds of the snnc cnrlmn rnmber.
when scaling, etc., may be expected due to
incompatibility of oil-field brines with onc Studies carricclout on polar mtcrinls
another or with additives sllchas cnploved in use{las corrosion inllihitorsand/or 0s scale
polymer and micellar floodin:. preventives in other svstcm sllc!~as si-ullatc(l
oil field bri.ncs,cooling waters, hoilcr fced-
Correlation of puhlishe<ldata cn certain watcrs, have indicated that alt!]ou+ t7e
polar materials based on sulfur, oxy?cn and adsorption concepts Jeveloncd for acid
nitrogen have shown that in a given hcmolo~ous corrosion inhibitors are of imnortancc, other
series, corrosion inhibition effectiveness factors arc of equal or ~reater imrmrtance. ‘h
increases with increasing rnmbcr of carbon concept of rate control of a precinitatinz sal
atoms in the alkyl chain(s) attacheclto the such as calcium carbonate is develoncd and dat
polar ::roupwhich aclsorhsonto the metal. The presented indicatin~ t}~atthe effectiveness
Lanqnuir /\&OrptiOn Constant inCrCaSeS b!~a of rate control additives such as phosnhonates
factor of ten for cnch additional four cnrbon 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” SPE 43S1

however, two-thirds of them are clustered around intensifies and complicates the investigation
a value of 7.9 (5.0-12.6). Considering the and application of surfactants.
extreme ranges of concentration in Eldridgets
table and that some of these concentrations are The more promising recently-developed
given to but one significant figure (which at methods for increasing the efficiency of
the very low concentrations may be only an order oil-field flooding operations include the use
of magnitude) the agreement with the calculated of micellar solution as described by Cogarty
9:1 ratio is satisfactory. et al (4) and the use of solutions of high
molecular weight polymers as described by
CORROSION INHIBITORS, SCALE PREVENTIVES, ETC., Sloat(5) Current articles by Carpenter and
IN BRINES
.——.— AND OTHER
——.— —- ..AQUEOUS SYSTEMS
... --..—-- —----- ..-.— by l[olmand Josendahl(7) discuss the effect of
the brines on the efficacy of both micellar and
An additional problem important in the polymer flooding. In particular, calcium and
production of oil by secondary recovery methods magnesium in a brine may precipitate out the
such as water flooding is that of scale polymer, thus destroying its effectiveness.
formation by commingling of incompatible waters, Furthermore, they may cause instability of’the
or by changes in temperature, pressure and/or micellar solutions, resulting in highly viscous
chemi;al composition of the waters, such changes emulsion formation, and other undesirable
resulting in reduction of volubility of carbon- effects. Our work has shown that reaction
ates and sulfates of calcium, strontium and between polymers and calcium ion actually gives
barium. a decrease in viscosity for acrylamide systems,
and that precipitates formed are filtrable
Among the various methods employed to through rather large membranes, thus indicating
prevent the precipitation and deposition of that actual plupgin~ of the porous structures
these materials are the use of inorganic (and rather than modification of viscosity is a
more recently organic) additives added in less cause of reduced efficiency of flooding
than stoichiometric amounts. These materials operations brouxht about by interaction of poly
are known to change the volubility of scale- mers and the brines containing them. It is
forming materials OT to alter the rates of accordingly seen that knowledge of the compcsi-
precipitation, mode f deposition, etc., in tion of the brine and the effect on the sur-
some manner that re((.ce scaling problems are factants, as well as steps to mitiqate any
effected. Previous investigators have postulated harmful effects,can be of utmost importance in
that their action is primarily clueto adsorp- assuring a successful flood.
tion of the additives on the ~rowing crystal
nuclei so as to change the crystal form, etc., I- This work as described below has been
as shown by Smith and Alexander (3) and by divided into three sections:
others. In the present work are described
experiments indicating that there are other (A) Adsorption of a certain class of scmi-
factors equally important or more important in polar or polar organic molecules that have beer
prevention of calcium carbonate and sulfate applied as corrosion inhibitors in systems
scales by additives such as phosphonates. other than stron~ acids, e.g., fresh waters
Indication is that the volubility, itself, is and brines.
increased by formation of particles of very
small dimensions, which were predicted by (B) Use of such afientsas scale preventives,
Kelvin’s classical work to have solubilities in and the mechanism(s) ,hat may account for thei]
excess of lar~er particles. The mechanism by effectiveness.
which particle size is maintained in the range
of ion pairs is dependent on the formation (c) The effects of these molecules when used
energies of the precipitating species and of in conjunction with certain polymers for the
the controlling species. control of scalin~ in brines caused by divalenl
cations, and the effect cf the ions on these
These problems of scale formation are by polymers used as water flood additives.
no means unique to oil production, water
floodin~,etc., but are found in most industrial
systems employing cooling water, in boiler feed A. CORROSION
._ -.-.-.— IN11IBITION
----——— --——.IN——BRINES

systems and in steam production, etc. In
general, these other systems involve waters One role of inhibitors has been to reducf
which are relatively “fresh” as compared to the dissolution of base metal under brine
many oil field waters which are brines of high conditions. The most effective mechanism
salinity or dissolved solids content. The appears to be adsorption on metal surfaces of
presence of these dissolved solids, in particu- a film which reduces normal electrochemical
lar calcium, magnesium and other alkaline earths activity. The effectiveness of such a film is
in fairly large concentrations as compared to dependent upon its ability to cover the metal
normal cooling waters, boiler feeds, etc., completely, as explained above.
,-
sPl?43s1
------- GERALD D. HANSEN.
, CILARLESC. NATHAN AND BEN SLOAT 53

Adsorption and polarization studies effect under certain conditions. Our work
indicate that adsorption of a particular showed that other materials, including the
rmlecule is effective in reducing corrosion orJly phosphonates, have the capability of inhibi(~2~g
if there is a complete and continuous film which calcium salts formation and precipitation.
~an be maintained under the conditions of the
?xperiment. Simple site-site adsorption is not The initial investigationswere primarily
z sufficient criterion for inhibition. in cooling water studies, but considerable
effort was expended in boiler water treatment
Figure 2 shows adsorption isotherms for a series studies under t?~eguidance of Ilalland
of phosphonates which are frequently used as Partridge.
najor constituents in inhibitor treatments. As
can be seen, the data appear to follow classical J.[anyworkers have subsequently studied
adsorption concepts; however, this does not tl~eeffect of additives on modification of
prove that inhibition is necessarily a function crystal structure of scale-forming materials.
of adsorption of the inhibiting molecules. On Alexander and coworkers as well as ;Iichaels
the contrary, at electrolyte concentrations et al (lS) indicated that under the proper
lower than those in ordinary oil field brines, conditions, precipitation rate could be
and in the presence of air, adsorption alone controlled, by additives throufihcrystal modi-
does not give acceptable corrosion inhibition. fication. llleirwork was preceded much earlier
Nor should specific site-site interaction by-that of Kelvin, who proposed that
without lateral interaction be expected to give volubility is a function of the surface free
a continuous film. Under certain conditions, energy of the precipitating material, and there
the use of such materials alone has been shown fore of its particle size; however, subsequent
to permit localized attack or pitting. It has efforts were not successful in demonstrating
also been shown that, in conjunction with other any substantial increase of volubility with
agents (phosphate in the presence of such reduction in particle radius.
divalent metal ions as calcium), adequate
protection can be maintained at hi@ler pllvalues . Because of the effects of certain phos-
phates on the rheology of many systems, and
Corrosion inhibition by phosphonates has also because of the historical relationship of
been described by hatch and Ralston(81 In high boiler deposition to the properties of the
carbonate or hard, brackish waters, the poly- specific system (the prcci.pitatinqscale and
phosphates arc known to be rather ineffective the additive employed to control the precip-
as inhibitors; however, they show that a itation), it has been postulated that the effec
combination of zinc ion and ANTP (amino methyl of additives, such as phosphates, on volubility
triphosphonate ) can be used effectively in of a scale, such as calcium carhonatc, is of an
such systems. As a part of the present work, adsorptive nature; however, our work has
we have found that certain combinations of indicated that the adsorption mechanisn may be
phosphate and phosphonates are effective in but one of several factors important in control
controllin~ corrosion at pliof 7 and above.(9) ling deposition.

The polarization data shown in Figure 3 Specifically, a relationship has been


indicate the type of current control exhibited observed between the ability of an additive
in differential aeration cells under conditions molecule to affect the formation of a series of
of pretreatment and no pretreatment. Once a calcium salts and the dissociation constant of
protective film is laid clown,the phosphonate the additive molecule. I:ora modifying addit!v
inhibitors are very effective corrosion control to be effective, the formation constant as
*
materials. The effectiveness in such systems defined below, of the additive with calclum,
usually increases with increasing calcium must be greater than the formation constant of
concentration. The advantage of the phosphonate the ion pair of calcium, e.g., CaC03, in the
systems and, more especially the compounded precipitating system. Additional work by us
systems, is the control of calcium sulfate has shown that the relation is qeneral for
scaling as well as of corrosion. calcium precipitating in other systems, not
only those in which CaC03 is the precipitate
B. SCALE PREVENTION BY P1[OSP1-lATE,
PHOSP1K3NATES, formed. Because of the need for information or
POLYMERS, ETC. — -— -...--.—-.--——-...-.—-
— .-——.-..—— ------- — both the thermodynamics and the kinetics of the
system, the general class of materials
The action of certain phosphates in exhibiting such behav”~~lhas been called “Rate
inhibiting calcium carbonate precipitation was i
Control Agents” by us.
probably first recognized by Rosenstein(lO~and
subsequently by Hatch et al. Hatch and Rice(l1) For the reaction A+ B = AB (3)
coined the term “threshold effect” for the
action of these metaphosphates. It was also Then formation constant
noted that other phosphates exhibited this (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++ contents in controlled experiments and observa-
e.g.$
tion of precipitating tendencies give only
(B) = concentration of anion, approximate values of formation constants and
e.g., S04, C03, phosphonate, the effect of temperature. Copolymers with low
polymer anion content of acrylic acid groups reflect the
character of low WV homopolymei’s. They appear
(AB) = concentration of complex 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 55
limit their salt formation. Analyses of and for comparison the same system with 15 ppm
solutions of this polymer were carried out by added HEDP.
a titration method in which known quantities
of calcium were added to the system, and the There is no apparent effect of the lWllP.
amount in solution was thea determined by In Figure 13 are given the data for the calcium
analysis. Figure 8 shows typical data of this polymer in the 2% salt solution, and the same
sort. system with a further addition of 10 ppm llECP.
The addition of the HEI>Pdoes
.-—a.have an effect in
It can be seen that the addition of NTA this case, as shown by lowerlng of viscosity.
(nitrilotriaceticacid) gives an increase in
the amount of calcium which can be titrated; The above data indicate that in usinE
but the effect of HEDP (hydroxy ethyldiphos- this type of polymer system, the possible
phonic acid) is a decrease in available calcium effect of corrosion or scale control additives
indicating the growth acceleration capability on the system must be considered rather than
of the lIEI)P. adverse effect of the divalent ions alone. It
is also concluded that the nature of the
Figure 9 shows the formation constant data specific polymer employed in water floodin~ may
for the same rate control agents used in be a major factor in determining reactions
Figure 8. It is readily seen that the growth between the various constituents normally found
accelerators have formation constants well in the oil field brines and the polymer and
below that of the polymer at room temperature other additives.
(1/T = 0.0033°K), while those formateriaIs
which increase calcium polymer soluhility lie Further studies are bein~ carried out in
near or above it. systems of varying ionic strength, hardness
content, and additive composition in order to
An additional finding from this work, extend the utility of the concepts which have
important in water flooding operations, is been illustrated above.
that certain agents which act as precipitation
accelerators may alter the viscosity of the ACKNOIVLEDGE!,lEW
— — ——-- .---
polymer system. Viscosity measurements were
carried out by use of a Brookfield rotational ‘l’he
authors express their appreciation
“infinite cup” viscometer. Figure 11 shows to the management of Betz Laboratories, Inc.
the effect of addition of 2% salt to a solution for permission to publish this work and to
of 500 ppm polymer at relatively low shearing ?lrs.E.G.Varney and Dr. P.Davis for their help
rates. Figure 12 shows the viscosity data for in the gathering and interpretin~ the data.
a calcium polymer soIution with no salt ad{ied

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.
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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.
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CARBON NUMBER

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m
w
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(1/T)Xio3 “K
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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

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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.