SPE
Society of Pet.roIllun Engineers
SPE 22580
A New Method for the Quantitative Determination of the PHPA
Polymer Content of Drilling Fluids and Other Aqueous Systems
L.Z. McCulley, Amoco Production Co., and E. Malachosky, * ARCO Oil & Gas CO.
'SPE Member
Copyright 1991, Society of Petroleum En9ineers Inc.
This paper was prepared for presentation at the 66th Annual Technical Conference and Exhibition of the Society of Petroleum Engineers held in Dallas, TX, October 6-9, 1991.
This paper was selected lor presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper,
as presented, have not been reviewed by the Society of Petroleum Engineers and are sUbject to correction by the author(s). The material, as presented, does not necessarily reflect
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of where and by whom the paper is presented. Write Publications Manager, SPE, P.O. Box 833836, Richardson, TX 75083-3636 U.S.A. Telex, 730989 SPEDAL.
Abstract
The need for a reliable, quant.it.at.ive analyt.ical
method for the det.erminat.ion of the partially hydrolyzed
polyacrylamide (PHPA) polymer content. of drilling mud
and ot.her wat.er-base fluids has been evident. for some
t.ime. Previous methods have been based on eit.her t.he
predpitat.ion of the anionic PHPA molecule or alkaline
hydmlysis of t.he amide nit.rogen to form ammonia. All
these met.hods are semiquant.it.at.ive det.erminations and
are subject to a wide variety of int.erferences. Anot.her
severe limit.ation, in t.he case of drilling fluids, is that a
port.ion of the mud filtrat.e is used for analysis, The free
polymer cont.ent of t.he filt.rat.e is rarely, if ever, the same
as t.he unfilt.ered liquid phase of t.he whole mud.
The method described in t.his paper is truly quanti-
t.ative and is an absolute rather t.hen an empirical
met hod. It is based on the t.ot.al oxidation of all organic
material in a sample of t.he liquid phase of a wat.er-base
dJ"illing fluid. The amide nit.rogen in t.he polymer mole-
cule forms ammonium ions during the digest.ion and oxi-
dat.ion process. These ammonium ions are then
measured with an ammonia gas·sensing elect.rode afler
conversion to ammonia by means of a simple pH adjust-
ment.
In addition, a sampling technique has been devel-
oped which enables the analyst t.o obt.ain a solidl'·free
port.ion of the liquid phase of a drilling mud sample
without. filtering the liquid t.hrough t.he mud filter cake.
Thus, t.he met.hod assures measurement. of t.he available
free polymer cont.ent of the fluid phase of t.he whole mud.
The met.hod described is ideally suit.ed t.o t.he det.er-
mination of t.he PHPA cont.ent. of any aqueous solutions
including t.hose encountered in wastewater treatment.
and sludge dewat.ering operat.ions. The results of both
laborat.ory and field evaluations of t.he method are pre-
sent.ed.
References and illust.rat.ions at. end of paper.
415
Introduction
Bot.h Amoco Product.ion Company and ARCO Oil
and Gas Company have been using mud syst.ems based
on part.ially hydrolyzed polyacrylamide polymer (PHPA)
extensively in bot.h domestic and int.ernat.ional oper-
at.ions for some time. The advantages of low-solids
polymer mud syst.ems are well known, and t.he PHPA
syst.ems in general have been receiving increased at.t.en·
t.ion in t.he last. few years. The t.echnology of t.hese sys-
t.ems is cont.inually developing as more field experience
is obt.ained, and mud engineering practices and guide-
lines are being continually updated as our knowledge
and underst.anding of t.hese syst.ems increases. The paper
by Kadast.er, Guild, Hanni, and Schmidt.! provides a good
hist.oJ"ical background of t.he development. of PHPA mud
syst.ems, and also present.s a comprehensive set. of
guidelines for the field applicat.ion of t.hese syst.ems.
One of the major considerat.ions in eit.her field or
laborat.ory evaluat.ion of a mud syst.em is the ability t.o
monit.or and cont.rol t.he mat.erial concent.rat.ions. Being
able t.o det.ermine t.he PHPA polymer content. in t.his t.ype
of syst.em is crit.ical. The test. met.hods currently being
used, while providing information as t.o t.he presence or
absence of PHPA polymcr, arc unable t.o prOVide reliable,
quant.it.at.ive informat.ion as t.o the concentration of
available polymer in t.he liquid phasc of the whole mud.
This paper will describe t.he development. of an analytical
procedure which overcomes most. of t.hc objections t.o
existing met.hods. The complet.e procedur'c can be found
in t.he Appendix.
Discussion
Existing Methods
Thcre are a number of procedures described in t.he
Iit.e,'at.ure for the det.erminat.ion of the polyacrylamidl'
cont.ent of aqueous solutions, but. few oC t.hem arc appli-
cable t.o t.he usually complex samples encount.ered in
whole mud or mud filt.rate analysis. Most. of these
met.hods are int.ended for the analysis of t.he dilut.e
polymer solut.ions of t.he type encollllt.erl'd in wat.er
t.reat.ment. or EOR operations.
 A NEW METHOD rOR QUANTITATIVE DETERMINATION or TIlE PHPA POLYMER
2 CONTENT or DRILLING rLums AND OTIIER AQUEOUS SYSTEMS
Beazley 2 used a size-exclusion chromatographic
technique to measure PHPA in the 1-100 mg/L range in
oilfield waters. Scoggins and MillerS described an
iodometric method, and Foshee, Jennings, and West 4 used
a turbidimetric procedure based on an insoluble chlo-
rami de reaction product formed when the polyacrylamide
is treat.ed wit.h sodium hypochlorite. Kuehne and Shaw 6
also describe bot.h manual and automat.ed turbidimet.ric
methods.
One of t.he earliest met.hods used for the det.ermi-
nation of t.he PHPA content. in t.he more complex drilling
fluid samples is the "floc" method. In this method, the
polymer is precipit.at.ed from an acidified filtrate sample
with a solut.ion of a polyvalent cat.ion such as aluminum
or tin, and t.he volume of precipit.ate is measured aft.er
cent.rifuging. This floc volume is then related to PHPA
concent.ration by reference t.o a previously prepared cal-
ibration curve. This calibration curve is prepared by
testing a number of solutions of known polymer cont.ent.
and plot.ting floc volume as function of polymer concen-
tration.
This met.hod, while relat.ively easr and requiring
few reagent.s, is subject, to a number of mterferences. It.
is not specific for the polyacrylamides and many other
anionic polymers can also be precipitated. This includes
t.he majority of t.he polymeric materials commonly used
in drilling fluids - filtration control additives, thinners,
dispersants, deflocculants, and many of the polymer vis-
cosifiers. In addition, t.he volume of the floc is also
influenced by the tot.al ionic strengt.h, the pH of t.he test.
solut.ion and the speed and duration of centrifuging.
From an analyt.ical perspective, t.he amide group in
t.he PHPA molecule is the most likely functional group
on which to base an analytical technique. This amide
group can be hydrolY7.Cd in either acidic or alkaline
menia, with the formation of either ammonium com-
pounds or ammonia gas. Measurement of the ammonia
produced by acid digestion, followed by alkaline hydl'O-
lysis, of polyacrylamide flocculants used in treat.in~
potable water WilS reported by Crummett. and Hummel
JI1 1963. The procedure provided encouraging results,
but the authors acknowledged t.hat the less-than-desira-
ble accuracy and precision was relat.ed to uncertainty
as to the completeness of the digestion process.
Two methods for det.ermining the PHPA content. of
drilling fluids which are also bilsed on the hydrolysis of
the amide group are described by Fraser 7 and Clapper,
Norfleet, and Alford. A Both these methods are based on
direct alkaline hydrolysis of a silmple of either whole
mud or mud filt,l·ate. The method described by Fraser
involves the distillation of the ammonia generat.ed in t.he
hydrolysis reaction int.o a boric acid absorbing solut.ion,
with subsequent tit.ration with a standard acid solution.
Clapper, Norfleet, and Alford purged the react.ion mix-
ture during hydrolysis with a stream of air and passed
the gases through a Drager tube. The tube is packed
with an absorbent impregnated with an indicat.or that
changes color when contact.ed by ammonia gas. The
t.ime required for the t.ube t.o change color complet!'ly is
measured, and t.he PHPA content. of t.he sample is est.i-
mated by comparing this t.ime t.o t.he times recorded for
polymer solut.ions of known concent.rat.ion. Fraser also
uses polymer solutions of known concent.ration for cali-
bration, but att.pmpts to carry the hydrolysis reaction to
completion by extending the boiling period to the point
where no additional ammonia is produced.
Both t.hese methods have serious shortcomings from
an analyt.ical perspective. There is no way to determine
if the hydrolysis reilcl iOIl is t.ruly quanti tal ive, alld both
methods acknowledge that control of the tesl conditions
is critical, since smilll variat.ions in anyone of iI number
of procedurill parameters (time, temperilture, air flow,
sample size, amount of caustic pl'eselll.) can affect t.he
416
SPE 22580
resuUs. The most. serious objection, however, relat.es to
the use of filt.rat.e for t.he analysis.
It. is recognized that. filt.ration of a PHPA-containing
fluid t.hrough a filt.er cake will result in removal of a
port.ion of the polymer. The ext.ent of the polymer
removed is influenced by a number of fact.ors: eleet.ro-
Iyt.e cont.ent. of t.he fluid, amount. and types of solids in
the mud, nat.ure of the filt.er cake, molecular weight of
the polymer, and type and quant.it.y of ot.her polymeric
materials present.. The use of a liIt.rat.e sample from t.he
API fluid loss t.est. was t.herefore considered t.o be
unsuit.able for any t.ruly quantitative procedure for t.he
determination of the PHPA concent.rat.ion in drilling
fluids.
Aft.er a careful consideration of fact.ors discussed
above, it. was decided t.hat. an attempt would be made to
develop a procedure which would eit.her eliminat.e or
minimize t.he objections t.o t.he existing met.hods. The
init.ial effort.s were directed toward the development of
a suit.able digestion procedure, since the work relat.ed to
developing a sampling technique would require digestion
and analysis of PHPA solutions. In addit.ion, for reasons
which will be discussed lat.er, a decision was made t.o use
the ammonia ion-selective elect.rode ((SE) t.echnique for
the actual nit.rogen determinat.ion.
Digestion Procedure
Since the method in general was directed toward
the det.ermination of the nitrogen in the amide group,
and since the intent was t.o ult.imately measure the
nit.rogen in t.he form of ammonia, t.he pdmary object.ive
of a suit.able digest.ion procedure was to provide a quan·
tit.at.ive conversion of the amide nitrogen t.o either
ammonium ions or ammonia gas. Direct. hydrolysis in
alkaline media at room t.emperature would have been an
ideal solution, but. it. was known t.his t.echnique provided
much less t.han quant.it.at.ive conversion. Even the vig-
orous reaction condit.ions ut.i1ized by Fnlser 7 were not
adequate to effect. complet.e conversion even aOer 60
minut.es of boiling,. probably due to t.he shielding or
"hiding" of t.he amide groups in t.he long, high moleculilr
weight. polymer chain. This "shielding" effect, can also
explain why an acid hydrolysis t.echnique, followed by
adjust.ment. of t.he pH t.o 11 or higher to convert the
ammonium ions t.o ammonia gas, also result.s in less than
quantit.ative conversion of t.he amide nitTogen to ammo-
nium ions.
AO.er ext.ensive laborat.ory evaluation, a digestion
t.echnique which is essent.ially a modificat.ion of t.he
classical Kjeldahl digestion process was selected. This
t.echnique result.s in the tot.al oxidation of all organic
mat.erial present in the sample, wit h conversion of all
organic mt.rogen t.o ammonium ions. The digestion con-
sist.s of heating a portion of the aqueous sample in the
presence of sulfuric acid unt.i1 all wat.er has been
expelled and t.he sulfuric acid has j!-'st reached t.he tem-
perature where sulfur t.rioxide fumes are being gener-
at.ed. At. this point. a "charring" of the organic matter
in the sample will commence, as evidenced by a discol·
orat.ion of t.he sample solution, I'ilnging from a st.raw
color to black, depending on t.he amount. of organic
matter present. A small amount. of hydrogen peroxide is
now added and t.he solut.ion is again heat.ed until the
dense, white snlfur t.rioxide fumes are produced. The
solut.ion should be wat.er·clear ilt. t.his point., indicating
complet.e oxidat.ion of all organic millt.er. This sample
now contains ammonium ions from the quant it.iltive con-
version of all or'gilnic nit.rogen present in the original
sample. All t.hat. remains is to diltrt!' t.he sample t.o a
known volnme and proceed wit.h till' nit.rogen dell'rmi-
nat.ion st.ep of t.he procedlll'e. This is quite similar 10 a
t.echnique used by Thompson ilml Morrison" for the
digest.ion of nit.rogen-cont.ilining organic silmples pdor to
SPE 22580 LOYAL Z. MCCULLEY AND ED MALACIIOSKY
colorimetric det.ermination of ammonia by use of
Nessler's Reagent..
Since this digestion process involves heat.ing sul-
furic acid t.o t.he point of the actual evolul.ion of sulfuric
trioxide fumes, some provision must be made for the
removal of t.hese fumes. If the digest.ion is done in a
laborat.ory, heating the samples in an Erlenmeyer flask
on a hot plate inside a conventional fume hood is sat.is-
factory. When the test is being conducted where no
fume hood is available, which is normally the case when
t.he t.est. is being run at. t.he rig site, the use of a special
digestion apparat.us and fume scrubber syst.em such as
the one described in t.he Appendix is strongly recom-
mended.
One very import.ant benefit of a digestion process
which is truly quantitative is the abilit.y t.o use primary
st.andards for the calibration of the measuring syst.em,
rat.her than relying on empirical calibration techniques
such as t.hose employed by Fraser7 and Clapper, Norfleet.,
and Alford. s In order for this to be valid, however, there
must be a known, predictable relat.ionship between the
amount. of nit.rogen measured and t.he original polymer
cont.ent..
It. is generally accepted t.hat. most. PHPA polymer
products supplied for use in drilling fluids have molecu-
lar weight.s ranging from 10 t.o 15 million, and are about
30% hydrolyzed - that is, for every 70 amide groups
along t.he polymer chain there are 30 carboxylic acid
groups (these cal'boxylic acid groups have usually been
neutralized with sodium hydroxide). One can then cal-
culate that the theoretica nitrogen content of a pure,
30% hydrolyzed polyacrylamide polymer is 12.58% by
weight.. Ar.tual analysis of samples of solid PHPA pro-
ducts supplied by t.he vendor companies gave values for
nitrogen content. which average about 11.4% by weight.
This value is in agreement with st.atement.s from bot.h
vendors and manufacturers t.hat. most. dry products con-
t.ain about 10% impurit.ies, consisting primarily of
adsorbed water with small amounts of organic com-
pounds and inorganic salts.
The result.s of t.he analysis of some t.ypical solid
PHPA products are shown in Table I, along with t.he
theoretical values. The analysis of t.he polymers was
conducted by conventional elemental analysis techniques
using a Carlo Erba CHON Analyzer.
Sampling
It. is widely recognized that the filtrat.ion of a sol-
ution containing PHPA polymer through a filter cake
will result. in removal of a portion of the polymer. In t.he
early stages of the development of this overall proce-
dure, it was observed that in the analysis of API filtrat.e
from laborat.ory muds which had ident.ical whole-mud
PHPA content. but. varying amount.s of filt.rat.ion-cont.rol
addit.ives (hence varying API fluid loss values), the mea-
sured PHPA content decreased with decreasing fluid
loss. Since it was accept.ed that at. some point a filt.ra-
tion st.ep would almost. cert.ainly be required in any
sampling procedure, a series of test.s were designed to
provide information on acceptable filtration techniques.
Convent.ional theories regarding behavior of PHPA
polymers in aqueous solutions state t.hat t.he largest.
effective size of a I;iven polymer occurs when the
polymer is dissolved III fresh water, with t.he polymer
chains contracting in t.he presencf' of electrolytes such
as sodium chloride. Thus, if a filfflr with a particular
pore size would permit the passage of a given polymer
in fresh watel', it would also be expected to permil the
filtrat.ion of the same polymer in a salt solution. In
order t.o determine an acceptable fil1ration media, a sol-
ution cont.aining 1.00 lb/bbl of a solid PHPA product in
417
3
deionized water was prepared. A port.ion of this
1.00 Iblbbl solut.ion was then used to prepare another
solution which was formulated to contain 0.67 Iblbbl
PHPA and 10% by weight sodium chloride. Separate
10 mL port.ions of each solution were then filtered
through disposable, 25 millimeter diameter syringe fil-
ters with pore sizes of 0.20 micron, 0.45 micron, and
0.8 micron. Five replicate 1.00 mL portions of each fil-
trat.e and each stock solut.ion were then digest.ed, oxi-
dized and analyzed for nitrogen according to the
procedure described in this paper (see Appendix). The
calculat.ed PHPA concentrations for the deIOnized wat.er
solut.ion and the 10% sodium chloride are shown in
Tables 2 and 3, respectively. A summary of t.he
reduction in PHPA content as a function of pore size is
shown in Table 4. Based on these results, the
0.80 micron pore size filt.er was selected as the smallest
permissible pore size for filtration of samples prior to
analysis. Even t.hough there was a reduction in PHPA
content of over 7% in the deionized water matrix, PHPA
reduction in actual drilling fluid samples can be expected
t.o be ne~ligible. If t.he total ionic strengt.h of a polymer
solution IS relatively low, use of a filt.er with a pore size
of 1.2 microns would provide an added margin of safet.y.
In order to avoid filt.ering a polymer-cont.aining sol-
ution through a filt.er cake, t.he fluid phase of a whole
mud sample must. be separat.ed from the solids. Fraser 7
suggested simply cent.rifuging t.he sample to achieve this,
but. many mud samples do not respond well to this sepa-
ration technique, and quit.e ollen a satisfactory centri-
fuge is not. available. The t.echnique finally selected
utilizes a combination of st.eps - dilution wit.h a sodium
chloride solut.ion, flocculat.ion of solids with a chemical
Oocculant., cent.rifuging if necessary, and finally filtering
a portion of t.he supernat.ant. t.hrough a 0.8 micron dis-
posable membrane filter.
Tbe dilution of a whole mud sample with 10%
sodium chloride solut.ion not only facilitates the sepa-
ration of t.he solids by the chemical Oocculant., but also
provides t.he high ionic st.rength environment necessary
to minimize t.he effective size of t.he polymel' chains.
This size reduction has the effect of reducing or elimi-
nat.ing loss of polymer during the filtration step.
The flocculant. used is a high molecular weight
(approximat.ely 5 million) poly(ethylene oxide) resin
which is widely used in t.he mining indust.ry 1.0 flocculate
t.he solids in colloidal suspensions. It is added to the
dilut.ed whole mud sample as a 0.5% by weight solution
in water. Flocculat.ion and coagulat.ion of t.he solids in
t.he sample will commence after addition of t.he floccu-
lant.. Some mud samples will settle sufficiently in 5 to
10 minut.es t.o permit the removal of a few milliliters of
essent.ially solids-free supernatant. fluid. If not, t.he solids
can be separated by cent.rifuginl; for 2-3 minutes at.
speeds as low as 1800-2000 revolutions per minute (these
speeds can be easily attained wit.h a hand-crank cent.ri-
fuge). Finally, a few millilit.ers (2-3) are filtered through
a disposable, 25 millimeter diamet.er membrane syringe
filt.er wit.h a pore size of 0.8 micron or 1.2 micron.
This final filt.rat.ion st.ep is necessary to remove any
remaining colloidal part.icles in t.he fluid phase. It should
not be neglect.ed, even if the supernat.ant appears clear.
If t.he amount. of colloidal material is higb enough to
begin t.o blind t.he filter and produce a not.iceable back-
pressure, remove and discard the syringe filter and
replace wit.h a fresh unit..
The sampling proc£!dure discuss£!d ahove (and
described in det.ail in the Appendix) meds t.h£! criteria
of providing a means for obtaining a solids-fre£! sampl£!
of the liquid phase of til£! whol!' lIlud without filfNing
t.he fluid t.hwugh a filter cake.
 A NEW METHOD FOR QUANTITATIVE DETERMINATION OF THE PHPA POLYMER
4 CONTENT OF DRILLING FLUIDS AND OTHER AQUEOUS SYSTEMS
Nitrogen Determination
The nitrogen in the digested and oxidized sample is
determined by use of an ammonia ion-selective electrode.
This device is actually a gas-Rensing electrode. The
nit.rogen in t.he acidic solut.ion result.ing from the
digestion and oxidation ~rocess is actually in t.he form
of ammonium ions, NB 4 • These anunonium ions are
convert.ed to dissolved ammonia gas, NBs, by adjust.ing
the pH of t.he solut.ion t.o 11 or higher with a st.rong base
such as sodium hydroxide. The electrode has a semi-
permeable membrane which separat.es t.he sample sol-
ut.ion from the internal filling solution and the sensing
element. of the electrode. The dissolved ammonia gas in
t.he sample solut.ion diffuses through the semi-permeable
membrane and reacts with the int.ernal filling solution.
This reaction creates an electrical potential which is
measured by the electrode. This potential, which is
propol-tional to the amount of ammonia present in the
solution, is then displayed as either an analog or digital
signal on a pH meter wit.h an expanded millivolt scale.
There are many suitable meters available, many of them
with features which permit the measured potent.ials to
be displayed directly in t.he concent.rat.ion unit.s selected
by t.he analyst..
The ISE t.echnique for t.he final det.erminat.ion of the
nitrogen was chosen because of t.he relat.ive simplicit.y
of operat.ion and because of r.-eedom from int.erferences.
Sample color and turbidit.y have no effect on measure-
ments. Most anions and cat.ions will not. int.erfere. The
only really major direct int('rferences are relatively low
molecular weight volatile aminI'S, and t.he probabilit.y of
t.hese materials being present in a sample after the
digestion and oxidat.ion process is extremely remot.e.
The measurement is arrected by variat.ions in t.he
level of total dissolved ionic species (total ionic strength)
in t.he sample solulion, but this is compensat.ed for by
simply adjust.ing the t.otal ionic strength in all standards
and samples t.o t.he Mme level by t.he addit.ion of an ionic
stnmgth adjusting burrel' (lSA).
One very import.ant feature of this overall met.hod
is t.hat standardization and calibrat.ion can be performed
through use of materials other t.han nit.rogen-cont.aining
polymers. Since t.he nitrogen in t.he samples being ana-
lyzed is ultimately converted 1.0 ammonium ions prior t.o
the measurement st.ep, standards cont.aining ammonium
ions derived from any mat.erial may be used. This per-
mits t.he usc of high-purit.y mat.erials such as reagent.
grade ammonium chloride for the preparat.ion of primary
standards for usc in st.andardizat.ion and calibrat.ion of
t he electrode syst.em. This does not, however, eliminate
the need t.o periodically evaluat.e t.he overall efficiency
of t.he procedure. It is recommended t.hat. t.his verifica-
t.ion be performed by preparing a reference solution
containing a known concentration, normally 1.0 Iblbbl,
of t.he part.icular product used in t.he mud syst.em being
analyzed. Samples of this reference solution should then
be periodically carried through the entire samplmg,
digestion, and analysis process.
Fluid Loss and PUPA Content
As menl ioncd in the "Sampling" section, it was
observed that, in a given nuid, as t.he API nuid loss
decreased there was a corresponding decrease in the
PHPA content in t.he filtnlte. Our conclusion was t.hat
as t.he nuid loss decreasp.d, t.hp. erredive pore size
thl'ough t.he filt.p.r cake was also decreHsillg, thus per-
mitt.ing t.he passage of less polymer. This is admilf.p.dly
a very simplistic moricI, but the nHturc of IIIP. filler cake
appcHred 1.0 have a dcfinite~ e rre ct. on the pHssHge of the
PHPA.
418
SPE 22580
In order to furt.her study this effect, a series of four
samples were prepared. Four lab barrels of If stock
PHPA solut.ion containing 1.00 Iblbbl PHPA in deionized
wat.er were prepared and t.ransferred to mixing cups. To
one sample, 1.0 g of a finely ground composit.e shale was
added, 5.0 g to the next., and 10.0 g t.o the next. One
sample was carried through t.he process as a control,
wit.h no solid material added. The four samples were
mixed for 20 minut.es on a laborat.ory mixer. The API
filtration test. was run and the filtrate samples were
analyzed for PHPA using the digestion and nit.rogen
det.ermination processes described in t.his paper. Sam-
ples of each of t.he unfilt.ered whole fluids were then
processed through the entire procedure, including the
sampling, digestion and nit.rogen measurement. The data
on the sample formulation and API fluid loss is summa-
rized in Table 5, and the result.s of the PHPA analysis
is in Table 6. Each analysis was performed in duplicat.e.
These result.s clearly show t.hat a significant amount
of the PHPA is being removed by the filt.er cake. There
is some reduction in the free polymer in the fluid phase
of the whole mud, probably due to adsorption of the
polymer by t.he solids. However, t.hese t.est.s clearly show
t.hat the majorit.y of t.he polymer removed is a conse-
quence of t.he filtration process and not. due to adsorp-
tion.
Accuracy and Precision
During the development. of t.his procedure over the
past. 2-1/2 years, lit.erally hundreds of samples of various
t.ypes have been analyzed. Precision amI accuracy st.u-
dies on a variet.y of sample types have been conducted.
The present status of the met.hod can best. be demon-
st.rated by t.he data in Table 2 and Table 3. The values
in "RSD" columns are t.he relat.ive st.andard deviations,
or t.he st.andard deviat.ion expressed as a percent.age of
the mean. Wit.h t.he exception of one set. of measure-
ment.s, t.his value ranges from 1.24 t.o 5.20.
The only means of evaluating t.he accuracy of the
met.hod was t.o compare t.he results t.o the known con-
centration of test. solutions prepared in the laboratory
under carefully controlled condit ions. In t.hese t.wo
series of t.ests only t.he unfiltered samples could qualify
as "known" mat.erials, and in both cases the values
obt.ained by the new procedure indicat.e t.he met hod is
capable of a very high accuracy.
The conclusions regarding precision are that under
laboratory condit.ions, t.he st.andard deviation can be
expect..ed t.o be 5% of the amount pl'esent or less, and
10% of t.he amount. present., or less, undC'r field or rig-site
conditions.
Field Tests
Field Mud System - Amoco Catoosa Lease
The met.hod was used t.o monit.or t.he PHPA content.
of t.wo wells drilled by Amoco Product.ion, Research,
Tulsa, at. t.he Amoco rig t.est facility in Catoosa in ,Janu-
ary and February, 1990.
Testing conduct.ed during t.he drilling of t.he first
well, DM-15A, provided the opportunit.y to evaluate t.he
suitabilit.y of t.he method for field usc. The port.able
digest.ion and fume removal syst.ems werp. used and per-
mitted t.he digest.ion and oxidation of samples in an
enclosed area wit.h completp. safC'ly. The t.est. results
were in good agrep.ment wit.h the calculalpd PHPA con-
tenL
Thp. second well where the m{'thod was used to
monitor Ill(' PHPA provided milch lIlore information on
the performHnce of HIP mcl.hod. No other met hod was
SPE 225'80 LOYAL Z. MCCULLEY AND ED MALACBOSKY
used for the purpose of comparison, but. a careful mat.e-
rial balance syst.em was used t.o calculate the expected
PHPA cont.ent. Fluid volumes were carefully monit.ored,
and fluid and product losses on t.he cuttings and at. the
solids cont.rol equipment. were taken into account.
Wat.er usage was measured, and an est.imat.ed loss of
product by adsorpt.ion on the solids was also t.aken int.o
account.
The mud used was a simple PHPA system with a
low-viscosit.y PAC for fluid loss cont.rol and sufficient.
sodium chloride t.o maint.ain chlorides at
3,000-5,000 mg/L. Small amount.s of xant.han polymer
were added as required to maintain rheology in t.he
desired range. Typical mud propert.ies are shown in
Table 7, and the measured and calculat.ed values for the
PHPA concentrat.ion for a total of 16 days are summa-
rized in Table 8. This dat.a is also shown graphically in
Figure 1.
Bot.h test. wells were drilled t.o dept.hs of approxi-
mat.ely 1250 ft wit.h 8·3/4 in. diamet.er bit.s. The total
mud volume was maint.ained at. about. 250 barrels.
Field Mud System - ARCO Alaska Well
A part.ially hydrolyzed polyacrylamide (PHPA)
polymer mud syst.em was used t.o drill an explorat.ory
well for ARCO Alaska, Inc., on the Kenai Peninsula.
Ant.icipat.ed hole problems required a potassium based
mud syst.em and environment.al considerations suggested
that pot.assium chloride would not be a suit.able pot.as-
sium source. Consequent.ly, an ARCO mud formulat.ion,
using pot.assium nit.rate as t.he t.he potassium source, was
selected t.o drill t.he well. The mud system contained
2,000-4,000 mg/L pot.assium during t.he phase of the well
discussed below. A minimum PHPA cont.ent. of 0.5 Ib/bbl
in the suction pit was considered necessary to produce
the required rheological and shale st.abilizing properties
in t.he mud syst.em. Table 9 shows typical mud proper-
ties upon conversion t.o t.he new system and at the end
of Ihe t.est. period.
The PHPA conlent. of the whole mud was contin-
uously monitored in t.he field using the technique
described by Fraser.' Samples of t.he mud were taken
and sent t.o t.he ARCO labs in Plano, TX, for PHPA
analysis using the new t.echnique. A split. portion of
t.hese samples was also t.ested at. the Amoco laborat.ories
in Tulsa, OK. Table 10 summarizes and compares the
dala from the t.hree determinations.
It is interesting to not.e t.hat. t.he field results (run
on samples of the whole mud) arc consist.ently lower
than t.he results from the new procedure. This is t.rue
even after adjustment. of the whole mud values for the
report.ed solids content of the mud system.
Wit.h the except.ion of the samples from 5/3 and 5/5
the agreement bet.ween the two laborat.ories is excp.llent..
Since the precision of the dat.a on these two sampleI' is
also relatively poor in comparison to the ot.her samples,
there appears t.o be a possibilit.y that. the two samples
may not have becn tl1oroughly mixed before splitting.
Conclusions
A new analytical procedure has been developed
which permits the det.ermination of the free polymer
conlent. of the fluid phase of wat.er base drilling nuids.
It. is t.ruly quant.itative, and is not. dependent. upon
empirical calibrat.ion. The accuracy and precision of the
method is very good. This met.hod overcomes most. of I.he
objections t.o existing met.hods, and is expect.ed t.o pro-
vide reliable, quant.it.ative informat.ion t.o drilling person-
nel.
419
5
The design, engineering and maintenance of PHPA
mud systems should be improved and enhanced t.hrough
use of the informat.ion and dat.a which t.his met.hod can
provide.
Acknowledgement
The authors would like t.o thank the entire st.affs of
the Drilling Fluid Research groups at. Amoco and ARCO
for their assistance and support during the development.
of this procedure. We also thank Amoco Producl.ion
Company and ARCO Oil and Gas Company for permis-
sion to publish this paper.
References
1. Kadaster, A. G., Guild, G. J., Hanni, G. L., and
Schmidt, D. D.: "Field Application of PHPA
Muds," paper SPE 19531 present.ed at. the 64th
Annual Technical Conference of the SPE, San
Antonio, October 8-11, 1989.
2. Beazley, P. M.: "Quant.itat.ive Det.ermination of
Partially Hydrolyzed Polyacrylamide Polymers in
Oil Field Production Waters," Anal. Chem. (1985)
57, 2098-2101.
3. Scoggins, M. W. and Miller, J. W.: "Det.ermination
of Wat.er Soluble Polymers Cont.aining Primary
Amide Groups Using the Starch-Triiodide
Met.hod," SPE Journal (1979), 151-154.
4. Foshee, W. C., Jenninp, R. R., and West., T. J.:
"Preparation and Teshng of Part.ially Hydrolyzed
Polyacrylamide Solut.ions," ~aper SPE 6202, pre-
sented at. t.he 51st Annual Technical Conference
of t.he SPE, New Orleans, October 3·6, 1976.
5. Kuehne, D. L. and Shaw, D. W.: "Manual and
Aut.omat.ed Turbidimet.ric Met.hods for the Det.er-
mination of Polyacrylamides in the Presence of
Sulfonat.es," paper SPE 11784, present.ed at t.he
Int.ernat.ional Symposium on Oil Field and Geot.h-
ermal Chemist.ry, Denver, June 1-3, 1983.
6. Crummett, W. B. and Hummel, R. A.: "The Deter-
mination of Traces of Polyacrylamides in Wat.er,"
Jour. A WWA <February, 1963), 209-219.
7. Fraser, L. J.: "New Met.hod Accurat.ely Analyzes
PHPAs in Muds," Oil and Gas J. (.July 6, 1987),
39-42.
8. Clapper, D. K., Norfleet, J., and Alford, S. E.:
"Analyzing PHPA in Mud Filt.rat.es," World Oil
(April, 1989) 77-82.
9. Thompson, J. F. and Morrison, G. R.: "Det.ermi·
nation of Organic Nit.rogen: Conlrol of Variables
in the Use of Nessler's Reagent.," Anal. Chl'm.
(1951) 23, 1153-1157.
Appendix - Experimental Section
Equipment, Reagents, and Supplies
The PHPA product.s used in t.his st.udy were com-
mercial products obt.ained from t.he various sel'vice com-
panies. The flocculant. used was POLYOX WSR
Coagulant., obt.ained from Union Carbide Corporation,
Specialt.y Chemicals Division, South Charleslon, WV.
The DIGESDAHL digestion apparat.us and th(' fum('
scrubber syst.em were obt.ained from Ih(' Harh Company,
Loveland, CO. The ammonia glls-sensing electrode
syst.em and ISE-pH inst.rument.ation were obtained from
Orion Research Incorrorat.ed, Laboralory Producl.s
Group, Bost.on, MA. AI laborat.ory l'ea~el1ls w('r(' ACS

A NEW METIIOD FOR QUANTITATIVE DETERMINATION OF TIlE PHPA POLYMER
CONTENT OF DRILLING FUJIDS AND OTHER AQUEOUS SYSTEMS
reagent. grade mat.erials unless ot.herwise specified. All
the ot.her apparatus and supplies were obtained from
various laborat.ory supply firms. All wat.er used was
dist.iIIed or deionized.
When t.his t.est. is perfOl'med in t.he field, the use of
syringes and micro- and macro-pipett.ing syst.ems wit.h
disposable t.ips is recommended for the measurement. of
small volumes « 10 mL) and PMP plast.ic graduat.ed
cylinders are suggest.ed for measurement. of larger vol-
umes. Conventional volumetric glassware and plast.ic
ware is used in nonnal laborat.ory environment.s. Not.e
that t.he 5N sulfuric acid and 3% hydrogen peroxide
specified for t.he digest.ion and oxidat.ion are t.he same as
reagent.s used for t.he MIBT t.est..
Any t.ime t.he test. is conduct.ed where a conven-
tional laborat.ory fume hood is not. available, the Hach
digestion apparatus wit.h fume removal system (or equiv-
alent.) must be used. The fumes generat.ed during the
digest.ion are very irrit.at.ing and any exposure t.o them
should be avoided. The use of the digestion and fume
removal syst.ems permit.s t.he test. t.o be performed safely
in any area.
Procedure - Drilling Fluids
1. Obt.ain a 10.0 mL sample of t.he whole mud and
t.ransfer t.o a 25 x 200mm t.est. t.ube fitted wit.h a
screw cap or rubber st.opper. Add 30 mL of 10%
NaCI solut.ion and mix t.horoughly_
2. Add 1 mL of 0.5% POLYOX solut.ion and mix by
gently invert.ing t.ube several times (do not shake
vigorously after addit.ion of POLYOX). Allow
t.ube to sit in upright. posit.ion for 5-10 minut.es.
3. Using a disposable syringe, wit.hdraw about. 3-5 mL
of supernat.ant. fluid. If solids have not. seWed
si~nificantly, cent.rifuge a port.ion of t.he t.est. sol-
utIOn using a 15 mL cent.rifuge t.ube, then wit.h-
draw supernat.ant..
4. At.t.ach a disposable 0.8 01' 1.2 micron syringe filter
unit and filt,er t.he fluid int.o a clean, dry glass or
plast.ic vial.
5. Transfer a 1.0 mL sample of the fluid t.o either a
125 mL Erlenmeyer flask (Iaborat.ory) or the
100 mL digest.ion flask (field). Add 10 mL 5N
H2S0 4 ,
6. Heat. unt.il the water has been expelled and the
evolution of dense, whit.e fumes begins. There
should be a charring or discolorat.ion of t.he small
amount of liquid in flask. Cont.inue heating for
1-2 minut.es. Do not. heat to dryness. (If using
digest.ion unit, set. temperature at. 425°C.)
7. Add 10 mL of 3% hydrogen peroxide. If using an
Erlenmeyer flask remove from heat. and cool
before addit.ion. If using digest.ion apparat.us, add
t.o capillary funnel while st.ill heating.
8. Boil unt.il all wat.er has been expelled and dense
whit.e fumes are again visible. Conl.inue heat.ing
for 1-2 minutes.
9. Remove flask from heat., cool, and add about
60-70 mL of water. Add 3-4 drops of t.hymol-
phthalein indicator and 7.0 mL 5N NaOH sol-
ution, t.hen mix thoroughly. Solut.ion should be
colorless. If solution is blue, add 5N H 2S0 4 drop-
wise until blue color disappears. Transfer t.o
100 mL volumet.ric flask (if digesl.ion was per-
formed in Erlenmeyer flask) and dilut.e to volume.
420
sPE 22;80
SPE 22580
10. Prepal'e ammonia electrode according to manufac-
turer's inst.ructions. Calibrat.e and st.andardize
the ISE system wit.h 1.0 mg/L and 10.0 mf/L
nitrogen standards, prepared by dilution 0 a
1000 mg/L stock solution (prepare st.ock solution
by dissolving 3.819 g reagent. ammonium chloride
in wat.er and diluting to 1 liter). Use 3.0 mL of
t.he pH-adjusting ISA, rat.her than the 2.0 mL
suggest.ed in the electrode inst.ructions. Use
150 mL beakers and stir on magnetic stirrer while
taking readings.
11. If using a met.er which reads directly in concen-
tration, adjust. instrument. t.o read the proper
value when a st.able reading is obtained in each
standard. (If the inst.rument. being used does not.
have this feat.ure, record readings while operat.ing
in millivolt. mode. Obt.ain a reading on a
100 mg/L st.andard in addit.ion to the 1.0 mg/L
and 10.0 mg/L. Plot millivolt. readings on linear
axis of 3-cycle semi-log paper and concent.rat.ion
on logarithmic axis.)
12. Transfer sample to 150 mL beaker, place on mag-
net.ic stirrer, immerse electrode and add 3.0 mL
of pH-adjust.ing ISA. St.ir at. a moderat.e rat.e and
record concent.ration or millivolt. reading when
stable. If operating in millivolt mode, refer to
calibrat.ion curve prepared in St.ep 11 above.
NOTE: Some values may fall below t.he 1-10 or
1-100 mg/L range of t.he calibration, but. elect.rode
response should be linear t.o at. least one decade
above and below calibration range, so values in
range of 0.1-1.0 mg/L are reliable.
13. The PHPA cont.ent. of t.he liquid phase of t he whole
mud is calculat.ed as follows:
PUPA, Iblbbl Nitrogen Content, mg/L,)(O 308)
( from Step 12 .
(I)
x [ (10 x W.F.) -I 30 ]
(10 x W.F.)
whel'e: W.F. Water fract.ion of whole mud as
obt.ained from ret.ort t.est,
expressed as a decimal
Not.e: The theoretical nit.rogen cont.ent of a pure
polyacrylamide polymer, with exactly 30% of t.he
amide groups hydrolyzed, is 12.58% by weight..
We have analyzed replicate samples of t.he com-
mercial dry polymer products suppled by t.he
drilling fluid service companies and have found
that the average nit.rogen cont.ent of these dry
polymer pr?ducts approximat.es 11.4% by weight.
The precedmg calculations are therefore based on
a dry powder product wit.h a total nit.rogen con-
t.ent of 11.4% by weight..
If it. is det.ermined t.hat. the nit.rogen cont.ent. of the
product being used in a given syst.em is substan-
tially different from 11.4%, t.he resu\t.s obtained
with Equat.ion (l) above can be corrected as fol-
lows:
Corrected PIIPA)
( Content, lblbbl = Vallie from (I) above
llA )
(2)
x ( Actual Nitrogrn Con!.rnt
of Product, in wt.%
A correction will also be necessary if at any step
ill the procedure, a sample volume which dirTers
from t.he specified amount is used.
 SPE 22Cj80

SPE 22580 LOYAL Z. MCCULLEY AND ED MALACIJOSKY 7

Procedure • Water Samples
The processing of samples from wast.ewater t.reat.-
ment. or EOR operations can be performed in much t.he
same way as the drilling Ouid samples. The Oocculat.ion
st.ep may be omil.t.ed if t.he solids cont.ent. is low enough
t.o permit. filt.ration of a sample t.hrough the membrane
filter. Also, in cases where t.he polymer cont.ent. is quit.e
low, a larger sample size may be processed in order t.o
provide a nit.rogen cont.ent. in t.he opt.imum range for
measurement. (1-10 mg/L in the final t.est. solut.ion).
Interferences
Since t.his met.hod is based on t.he total oxidation of
all organic material in t.he sample, t.he most common
source of int.erferences are ot.her nit.rogen-cont.aining
polymers. The most frequently encount.ered mat.erials of
t.his type are the vinyl amide-vinyl sulfonate copolymer
products which are used as high t.emperat.ure filt.rat.e
reducers, and the polyacrylamide-cont.aining bent.onit.e
ext.enders. These mat.erials must be absent for the
described t.est t.o be reliable. The majority of t.he
common products used in wat.er base mud systems do not
interfere.

Table 1
Composition of Commercial Products*

% by Weight
Product Carbon Hydrogen Oxygen Nitrogen Total
PHPA Product A 40.26 6.30 31.63 12.05 90.25
PHPA Product B 36.38 5.47 26.20 9.18 77.22
PHPA Product C 36.69 5.33 31.05 9.61 82.67
PHPA Product D 38.70 5.87 30.37 10.00 84.95
PHPA Product E 39.79 5.91 30.74 11.36 87.79
Theoretical + 46.21 5.65 26.70 12.58 91.14

* Pro~ucts are commercially available solid PHPA, obtained from drilling fluid service com-
pames.
+ For 30% .hydrolyzed PHPA

Table 2
Filtration Studies
1.0 lb/bbl PHPA in Deionized Water

Filtration PHPA Content

Media lb/bbl Mean, X RSD
None 1.02, 1.02, 1.02, 0.992 4.12
0.97, 0.93
0.8 micron 0.90, 0.93, 0.92, 0.916 1.24
0.92, 0.91
0.45 micron 0.83, 0.90, 0.90 0.872 3.92
0.89, 0.84
0.20 micron 0.28, 0.17, 0.20, 0.216 18.7
0.22, 0.21

421
 SEE 22580

Table 3 Table 4
Filtration Studies
Filtration Studies
0.67 lb/bbl PHPA in 10% NaCI
Summary
Filtration PHPA Content
Media lb/bbl Mean, x: RSD Reduction of PHPA Content, %

None 0.70, 0.67, 0.68, 0.678 1.92 Filtration Media Deionized Water Salt Water
0.67, 0.67
0.8 micron 0.64, 0.63, 0.71, 0.672 5.20 None o o
0.69, 0.69 7.66 < 1.00
0.80 micron
0.45 micron 0.62, 0.61, 0.61 0.61 2.01
0.62, 0.59 0.45 micron 12.10 10.03
0.20 micron 0.34, 0.33, 0.34, 0.336 1.63 0.20 micron 78.23 50.44
0.33, 0.34

Table 6
Filtration Studies
Table 5 Comparison of PHPA Content of Filtrate
and Whole Muds·
Filtration Studies
Effect of Solids on API Filtration PHPA Content, lb/bbl
Sample API Fluid
~ Loss, mL Whole Mud API Filtrate
Sample No. 1 No control 0.94, 0.99 1.02, 0.99
1 2 3 4 0.81, 0.80
2 98 1.00, 1.04
1.0 lb/bbl PHPA 350 350 350 350
Solution, mL 3 25 0.95,0.93 0.44, 0.43
Composite Shale, g 0 1 5 10 4 14 0.92,0.89 0.29, 0.29
Mixing Time, min 20 20 20 20
API Fluid Loss, mL N/C 98 25 14 * The filtrate samples were digested and analyzed without
further treatment. Whole mud samples were flocculated,
filtered, digested, and analyzed.

Table 7
Typical Drilling Fluid Properties
Catoosa Test Wells

2/21/90 2/27/90
Mud weight, lb/gal 8.85 8.70
Plastic viscosity, cP 14 12
Yield point, Ib/100 sq ft 6 11
10 second Gel Strength, Ib/100 sq ft 1 2
10 minute Gel Strength, Ib/100 sq ft 1 2
API Fluid Loss, mL/30 min 6.8 10.2
Total Solids, % by volume 4 3
MBT, lb/bbl Bentonite equivalent 5 2.5
pH 8.1 9.5
Chloride, mg/L 4000 2900

422
 Table 8
PHPA Field Test - Catoosa Lease
Comparison of Analytical Results to
Table 9
Material Balance Calculations Typical Drilling Fluid Properties
ARCO Alaska Well
PHPA, lb/bbl
Sample Data Analysis Material Balance 5/8/91 5/12/91
2/2/90 1.64 1.64 Mud weight, lb/gal 9.0 9.6
2/5/90 2.30 1.97 Plastic viscosity, cP 13 10
2/6/90 1.90 1.97 Yield point, Ib/100 sq ft 4 15
2/7/90 1.92 2.13 10 second Gel Strength, Ib/100 sq ft 1 5
2/12/90 1.34 1.34 10 minute Gel Strength, Ib/100 sq ft 6 15
2/13/90 1.41 1.38 API Fluid Loss, mL/30 min 6.5 6.8
2/14/90 1.37 1.38 Total Solids, % by volume 3 9
2/15/90 1.39 1.38 MBT, lb/bbl Bentonite equivalent 9 16
2/16/90 1.82 1.79 pH 8.6 9
2/17/90 2.11 1.96 Potassium, mg/L 2300 3700
2/20/90 2.00 1.96
2/21/90 1.87 1.96
2/26/90 1.08 1.08
2/27/90 0.79 0.89
2/28/90 0.97 1.09
3/1/90 0.90 1.30

Table 10
Comparison of Laboratory To Field Data
ARCO Alaska Well

Sample Laboratory Data

Date Time Solids, vol % Field Field** Amoco* ARCO* Avg STD DEV
5/3/91 12:00 PM 3 0.60 0.62 0.74 0.57 0.66 0.1004
5/4/91 2:00 PM 5 0.55 0.58 0.76 0.72 0.74 0.0741
5/5/91 2:00 PM 5 0.65 0.68 0.78 0.65 0.72 0.0911
5/6/91 2:00 PM 6 0.70 0.74 0.84 0.77 0.81 0.0656
5/7/91 2:00 PM 6 0.70 0.74 0.89 0.84 0.87 0.0597
5/8/91 1:00 PM 6 0.65 0.69 0.83 0.75 0.81 0.0479
5/9/91 3:00 PM 7 0.65 0.70 0.90 0.82 0.86 0.0753
5/10/91 6:00 PM 8 0.68 0.73 0.80 0.82 0.82 0.0191
5/11/91 2:00 PM 9 0.55 0.60 0.65 0.79 0.81 0.0434
5/12/91 3:00 PM 9 0.68 0.74 0.92 0.98 0.95 0.0299

Field results obtained by use of method described by Fraser

* Results from both Amoco and ARCO laboratories obtained by use of new method as
described in Appendix. Replicate determinations performed in each lab.
** Adjusted for reported solids content of the mud system.

423
 Figure 1
PHPA Field Test - Catoosa Lease
Comparison of Analytical Results to Material Balance Calculations
3 -.--------------------.,

--t-'
C
-
.............
---- ...~.
. .

(])
--t-'
C
o
u
ct
I
1- .- : - - : .

0.... Legend
• Muterial
Balunce

o Anulysis
o- t - - - - - - - - r - - - - - - " " " " I - - - - - - - - I
15 20 25 30
Test Number

424