~CPTbh-OI-03
Methods of Sludge Control
During ~~cid Stimu lation Treatments
By C. W. CROWE,'" A, R. HENDRICKSON" and R F. DaBBER THIEN"
(l6th l-lnJnrul Technical Jlleeting, The Peh'ole1l1lL Society of C.l.M., Calgal'Y, lUay, 1965)
ABSTRACT
The formation of asphaltic sludge during acid stimula-
tion has been a serious problem in man:r areas for sel'era)
,rears_ Such sludge:;; han· had ad,"erse effects on the re-
suUs of treatments in se\"eral Canadian resenoirs_
Recent studies ha"e shown that sludl-:"e rna}' also affect
results in many are,lS where its effects ha"e not l'et been
recog-nized.
These studies indicate that:
L-Sludge is a precipitate of colloidal materials pres-
ent in crude oils.
2.-The preeipitates occur due to changes in the en-
vironmental conditions of the crude b}' the addition
of materIals such as acid.
3.-0nce formed. sludl:!:e is insoluble in most treatin::r
chemicals.
.J.-Sludge can be preH"nted or contrOlled by the use of
stabilizinJ,! agents in treating flUId or by the use of
certain soh'ents as the outer phase of ac.id-in~oil
emulsions.
The purpose of this paper will be to show how and why
slud~e is formed and how it can be pre\'ented or con-
trolled. Simple laboratorJ- tests t(] determine the probabil-
ity of sludge formation prior to treatment are discussed.
Aetnal field results point out some of the problem areas
in Canada and show that slud~e control durin~ acidizing
treatments can increase producth'ity in these areas_
INTRODUCTION
T HE formation of sludge b.r crude oil on c.ontact
with acid has been recognized as a serious problem
in isolated areas for some time. The problem was ap-
parently first observed in certain California wells.
In these well.:5. it was noted that following acidizing
treatments the wells wel-e very slow to clean up, and
often a great deal of asphalt-like material was re-
turned with the treating fluids. In some cases, com-
plete or partial plugging of the well resulted from the
treatment. A Rtudy of this problem revealed that the
crude oils produced from these wells actually formed
solid precipitates upon contact with acid, An analysis
of these sludge-like precipitates shc)\l.:ed them to be
made up mainly of asphaltenes, resins, paraffin waxe,<>
and other high-molecular-'.. · eight hydrocarbons. These
material~ were apparently precipitated from the crude
by the reduction in pH as a result of acid contact.
Recently. it was found that the formation of crude
oil sludge during acidizing is also a seriom; problem
in certain formations in Canada. It has been ob-
served that wells in a number of fields ha"e experi-
enced the same problern:i as those in California. Ex-
amination of crudes from the~e ,veils also shows the
same sludge-forming tendenc.ies.
:;·Dowell Division of file Dow Chemical Company,
Tulsa, Oklahoma.
" :;:·Dowell of Canada Ltd.• Calgary, AlbeTta.
14
A comprehensive study recentl}' undertaken by the
Duwell Research Laboratory in Tulsa, Oklahoma, in-
dic<ltes that these slLldge~ rna." also he a problem in
many <lreas where its effects have not previously been
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recognized. In a survey of crude oils ft-om many fields
and formations in all the oil-producing areas of the
United States and Canada, it was found that a sub-
~tantial percentage (28-35 pel' cent) of all naturally
occurring oils tested produced precipitateg upon cun-
tact ,'vith acid.
i\fECHANIS:\I OF SLUDGJ...: FORMATWN
Nearly all crudes contain a considerable amount of
asphaltic and related material. These materials arc
generally present (1. 2) in the form of ~olloidal pal'-
ticle,5:, Due to theil' complex chemical nature, they are
classified chiefly on the basis of their physical prop-
erties_ The most common classification system is Wi
follows:
N entral Resins - These material~ are high-mole-
cular-weight aromatic hydrocarbons, which are insolu·
ble in alkalies and acid:) and completely miscible with
petroleum oil~, including light fractions (C~, fraction).
A..spllaltenes - These 5ubsbnces are similar to the
neutral resins, but insoluble in light gasoline::; and
petroleum ether. In contrast hi the neutral resins, i:he
asphaltenes <lre precipitated in the pre~ence of an ex-
cess of petroleum ether. Both aSllhaltene~ and neutral
resins are completely soluble in benzene, chloroform
and carbon disulphide.
AS1Jhaltogenic Acids - ThE'~e materials are soluble
in alkaline solutions and in :-;uch sol\'ent~ as benzene.
and are present in petroleum in rather insignificant
quantities.
The neutral resins and asphaltenes are therefore
the most important asphaltic. eompoullds of petroleum.
Detailed analytical ultracentrifuge studies (2) of
several crllde~ have shown that colloidal parti~le::;
present in crude oil range fr'lm :15 to 45 A in cliam-
eter- The colloidal range is generally considered to be
from 10 to 5,000 A. Other studies 13, 4) have incli-
cated that colloidal particles in crude oil are composed
of asphaltic material surrounded by adsorbed peptiz-
ing materials. These studies have led to the concepl
that asphaltenes form the center uf t.he micelles, with
neutral resins adsorbed on the surface of the asphalt-
ene particles, It has been prop used that the :;ubstances
with the greategt molecular weight and most pro-
nounced aromatic nature form the nucleus. Around
this nucleus are arranged lighter and less aromatic.
constituents and there is a gradual transition to pre-
ponderantly aliphatic compounds. In other words.
there is no distinct interface either within the mi-
The Journal of Canadian Petroleum
 -----
celle or'Pbetween it "and the surrounding environment.
It "is these adsorbed materials which stabiliz~ the col-
loidal materiat
Although the. stability of colloidal asphaltene. par-
tichis is primarily attributed to adsorbed peptlzmg
agents, other stabilizing factors have also been noted.
It has been shown (5, 6) that the colloidal material
in crude oil is electricaU~~ charged. The imposition of
a potential across a· small bod:r of oil results in elec-
trodeposition of asphaltic material at the positive elec-
trode. This shows that negatively cha!'ged particles
exist and that the neutralization ·of this· charge can
result in precipitation of the material., Our labora-
tory tests have also 'shown that the colloidal material
present in the crude is attracted to the positive elec-
trode. It was, however, noted that if the oil was first
treated with acid and then electrolized, there 'was 3-
tendency for the colloidal material pr.esent to migrate
to the negative electrode_ This seems to indicate that
contact with acid tends to disrupt the normal electri-
.' cal charges present on the colloid particles. This may
be, in part, responsible for the precipitation of '~he
asphaltic colloidal particles to form crude oil sludge.
This, however, appears to be only part of the stant,
as not all crudes form precipitates upon contact with
acid. Apparently, the naturalll' present stabilizing
agents are usually capable of maintaining the sta-
bility of the asphaltic colloidal material even in ·'he
presence of strong acids. It would appear that the
formation of crude oil sludge may be related to a de-
ficiency in the quantity of the natural stabilizers
present in some crudes. It is interesting to note that
highly asphaltic crudes, which normally contain large
quantities of naturally surface-active agents, seldom
form sludges upon contact with acid. Due to the sur-
face-active material present, however, the:r do tend
to form bad emulsions_
It has been observed (7) that some crude oils form
solid films at the interface of the crude with an aque-
ous medium having a pH below 8_ In these studies,
droplets of crude oil were pendent up from the end of
a capillary in distilled water or brine. After a shod
period, the droplet was partially retracted. In the re-
traction process, a point was soon reached where the
Acid on N on-Sludge.-Forming C1~lCle..
Techn~logy, January-March, 1966, Montreal
------
droplets of ·oil ·appeal'ed to. be encased in a me~brRn­
ous structure_ As the reti:.:action process contmued,
the membl'ane showed pronounced wrinkling and fold-
ing_ The occurrence of these rigid membranes at the
oil-water interface suggested that a f.Hm of material
was irrevel-sibly produced upon compression of .the
interface. Residues from these membranes were ob-
served to be stable in solution for several days. Simi-
lar residues have been concentrated (8) by means of
water-spray extraction techniques. These concentrates
were found to be quite rich in resins, waxes and as-
phaltic materiaL The physical appearance of this ex:
tract, as described, prompted a stud}' of the possible
l'elationship of these films to the crude oil sludge
formation problem_
MICROSCOPIC STUDIES
The crude oil sludge formation process has been .- ..
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observed and photographed using a microscope with a
~ ~.-
photographic attachment. The technique employed con-
sisted of applying a small quantity of crude oil to a
glass microscope slide and placing a droplet of acid :.
in the oil. The surface of the acid droplet. was then
observed for evidence of hgid film formation_ In
order to make the film more visible, the surface of
the droplet was scratched with a fine wire_ This
caused wrinkling and folding of the film and made it
more visible and easier to photograph. It was ob-
served that all crude oils which exhibited acid-sludge-
forming tendencies produced permanent rigid .films
at the oil-acid interface. With those oils which. did
not form sludges, no such films were observed. Fig-
woe 1 is a photomicrograph of two crudes to which
have been added a droplet of acid. The oil on the
left, a crude which does not form sludge, has not been
affected. The environment of the crude on the right,
however, has been changed to the extent that a preci~
pitate is beginning to form. In this photomicrograph
it appears to be a "skin" around the droplet of acid.
In Figure 2, in the left-hand photo, the "skin" is be-
ginning to flake off of the acid droplet and the small
flakes may be s.een drifting in the crude oil phase. In
the right photo, the flakes are beginning to coalesce
into the mass known as crude oil sludge_
..
Acid Droplet on Sl'l£dge-Fo1'1ning Crude.
Figu1·e 1.
~'. " .
15
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PUTtides Coagulating into Mass. "Skill" Flakij/g off ... lcicl Droplet.
Figztre .2.

r I.-The oil-acid mixtm·e is strained through ~l fine

IOO-mesh screen and th(~ screen examined for
chunks of asphaltic material. Crudes which pre-
sent severe acid sludge problems produce. solid
lumps of asphaltic mab~rial.
2.-The oil, itself, i.5 examined under the micro-
scope for ~igns of asphaltic precipitate. Some-
times precipitates are formed which are finely
divided and may pass through the lOO-mesh
screen.

RATE OF CRUD~ OIL SLlJDG~ FORMATION

A stud.y was made to determine the rate at which

Sludge j-'rom Sludge Dried to Show sludge forms upon contact of a sludge-forming crude
Pl·oduciug W dl. that Material is a Solid
Precipitate and not alL oil with hydrochloric acid. In this study, samples of
E'lImlsion. crude from the Swan Hill formation were mixed with
15 per cent hydrochloric acid for varying lengths of
Figure ~l.
time. The exposure period was terminated by neutral-
izing the acid with ammonium hydroxide. After neu-
Tn FiYUT€ 3, on the left, the sludge appears as it tralizing the acid, the mixture was transferred to a
might occur in the formation. On the right is shown centrifuge tube and the sludge centrifuged to a mini-
the same sludge after being dried. This dried material mum volume. The quantity of sludge formed wus l'e-
slwws that the sludge is actually a solid residue, corded on a volume basis and expressed as a per cent
rather than an emulsion, which it Inay sometimes re- of the original crude.
semble. As a result of these tests, it was shown that !;Iudge
formation begins almost ImmediatelJ,' upon contact of
the oil and acid. The following quantities of sludge
TESTlNG FOR CRUDE: OIL SLUDGE were produced in the acid contact times indicated .

.A crude oil can be tested for sludge-forming tend- Time % Sludge

encies by means of a simple test. This test consists
of pladng, in a 4-oz. bottle, 50 ml. of acid containing I min. 0.4%
5 min. 0.8%
any desired additive~. and then adding 50 rol. of '~he 10 inin. L2 l !c,
crude being tested. The bottle is then shaken for one 4 hrs. 2.8~'~
minute and placed in a water bath adjusted to the
bottom-hole temperature of the well from which the Tests were also run on various crudes to determine
sample was taken. At the end of 4 hours, the bottle is the total amount of sludge which each WQuld form
removed and the oil examined. The examination is upon l'ontaet with acid for 4 hours. The results of
done b.y two methods: these tests are shown in Table L

16 The Journol of Canadian Petroleum


-'!
PREVENTION OF CRIJDE OIL SL'!DGE
A number of methods have been devised for pre-
venting the formation of crude oil sludge. These in-
elude: .
1.-Acid-oil emulsions made with aromatic solvents.
2.-Additives for use in tre~ting acid.
The selection of the proper sludge-prevention tech-
nique is largely dictat~d by individual well character-
istics. In some areas, wells respond better to the acid-
aromatic oil emulsion system; in others the use of
add,itives has proved nlOre effective_
The use of the acid-aromatic oil emulsion acidizing
technique was developed largely as a result of experi-
ence gained in stimulating wells in the Virginia Hill
D-3 "eef oil pool. In 1960, a problem developed in
this pool which first led us to consider the possible
use of this technique. When these wells were acidized,
. several began producing what appeared to be a very
thick emulsion. Laboratory tests proved that, although
there was no emulsion behveen the spent acid and
crude oil, there was a heavy black precipitate sus-
pended at the interface between the oil and acid. This
was tested and was found to contain a high percent-
age of asphaltic material.
A number of tests were made to determine which
solvents would dissolve this asphaltic material. These
tests showed both carbon disulphide and aromatic
solvents to be effecth'e. As carbon disulphide could
not be pumped safely, it was decided to develop a
method of using aromatic solvents in combination
with acid to prevent sludge formation. In order to in-
sure uniform mixing of the solvent and acid, it was
decided to combine the two components ill the form
of an oil-outer-phase emulsion. Laboratory tests
showed that an emulsion with a ratio of 30 :70 oil to
acid 'would prevent or greatly reduce the amount of
sludge formed. It was also found that this formula-
tion tended to dissolve or disperse any sludge already
- TABLE I dispersed in treating acid. Outstanding results have
QUANTITY OF SLUDGE FORMED BY VARIOUS
CRUDE OILS UPON CONTACT WITH ACID
.,,
Contact time - 4 hours
Contact temp. - 150°F
.' % Sludge
Crude Oil I dentijical£oll (by t'o[ume)
Goose River Pool, Beaverhill Lake
Formation, Canada. __ .. ___ .' .. _. .. 1.3%
Swan Hills Fonnation, Canada. __ . _. __ . 2.8%
Snipe Lake Pool, Beaverhill Lake For-
mation, Canada. _......... ______ .. 2.6%
Red Fork Formation, Oklahoma _. _.. _. 0.1%
Mississippi Lime Formation, Oklahoma_ 2.0%
Abo Formation, New lvlexico ..... _. _.. 0.1%
Beaver Creek Field. Madison Fomla-
tioD, Wyoming _.... --.-------. ---. 1.5%
Rozet Field, Minnelusa FonnatioD,
Wyoming.. ... - --._--- .. - . . . - . . . .
_ 0.1%
Santos and Brandna Fonnations,
California .... _. ___ ... __ " ____ . ___ 3.8%
TechnDlogy. January-March. 1966. Montreal
- - : - - - ..
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r J
Figure 4.-Acid Containing Anti-Sludge Additive. There
is no Tendency 101' Sludge to Fonn.
present. Treatments using this technique have been
carried out in the Virginia Hills, Swan Hills, Snipe
Lake and Kal.Tbob fields with great Sllccess_ In -chese ,.
treatments, all wells cleaned up rapidly with no in- "....
~
dication of returned sludge.
Anti-sludge agents for acid have been used for some
time for the prevention of crude oil sludge. The ma-
terials which are generally used for this purpose are
alkyl phenols, fatty acids and certain oil-soluble sur-
,.
face-active agents. These additives apparently act as
synthetic stabilizing agents for the colIoidal asphaltic
material- pl·esent in the crude. Bl.T adding additional
stability to the colloidal material present) the forma-
tion of sludge is prevented_
A new additive has recently been developed for the
pre,'ention of crude oil sludge. This material is a blend .. '
of surface-active agents and stabilizers, and is easily
been obtained in many wells where this material has
been used. In Figure 4, we see a droplet of acid in
contact 'with a sludge-forming crude oil. In this case, ---~--
howe,'er. a small quantity of the new anti-sludge ad-
ditive has been added to the acid. As can be seen, the
formation of the usual insoluble "skin" has been pre-
vented. Because these "skins" are not able to form,
sludge formation is prevented.
Formed
Once fo;rmed in the formation, crude oil sludge is
vel')' difficult to remove. WelIs which have been dam-
aged b}' sludge are sometimes impossible to clean up ~~~ .~::­
so t.hat a profitable rate of production can be restored. ::-~ - .
Successful stimulation treatments in sludge areas, '. ::;
then, must depend on preventative chemicals which
will not allow sludge to form.
SUMMARY
In summary, nearly all crude oils contain compon-
ents which can precipitate as sludge when the natural
environment is changed by the addition of acid. The
formation of crude oil sludge is often confused with
emulsion problems due to the similarity in appear-
ance and effect. Sludge is an extremely difficult ma-
terial to clean up and qUite often leads to permanent
permeability damage. Properly designed treatments
can prevent the formation of sludge and cut down on
costs in a short period of time_
17
 BIBLIOGRAPHY

(1 ) Ray, B. R., l-FithersPoQn, P. iL, and Gl'im, R. E.,

"A Stud" of the Colloidal Characteristics of Petro-
leum Using the UltI-acentrifuge," J. Phys. Chern.
(1957), 61, 1296.
(2) lFitTIC1'SPOIJH, P. A.. , and Munil·, Z. A., HSize and
Shape of Asphaltic Particles in Petroleum," PTodllC-
('I'S Monthly, Aug. 1960, pp. 20-31.
(3) Kelltmsteyn: SC.i'DWC of Pctl"o[r.u?n, IV, 2700, Oxford
Univ. Press, H138.
( 4) Pfeiffer and Saal: ./. Pilys. Chem. (1940) I 44, 139,
(5) Pl"eckslwt, G. lV. Del..• isle, N. G., CQttn:-ll, C. E., and DOBBERTHIEN
Katz, D. L.. "A~phaltic Substances in Crude Oil," A. R. Hendrickson is a group leadE.!r In the Applied Research
Tm"s. A.TME (1943). 151, 18B. and Development Section of Dowell's Research Laboratory in
(uj Ka.tz. D. L., and BCll, K. E., "Nature of Asphaltic Tulsa This group deals With stimulation services, auxiliary
Substance:;," Iud. Ell!!. Chcm. (1945) J 37, 195. services and products. Mr, Hendrick.son Joined Dowell as a
t'i) Reisbcl"g, J., and D()Sc!Wl', T. M., "Interfacial Phe- chemist In 1950 after receiving his M.S. in orgamc chemistry
nenwna ill Crudc Oil-1Nater Systems," Producen.· from the University of New Hampshire. He advanced to re-
MOltth11/, Nov. 1856, I'. -13. search chemist in 1952, and has been In his present position
(8) Dodd. C. G., M001'C, ./. lJ'., and DC1lekas, ill. 0., "ule- since 1956. He has authored many popers on acidlzing, and,
talliferous Substance5 Adsorbed at Crude Petroleum- together with Dr. D. R. Wieland and R E. Hurst, developed
Water InterfaC'e'3," II/d. Ellg. ChrnlL, 45.1759, (195:3). the data ond baSiC colcula~lons for Dowell's Acid Guide."

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Curtis W. Crowe is a chemist in the Applied Research and
Development Section of Dowefl's Research Laboratory in Tulsa,
Oklahoma. He Joined Dowell in 1960 after receiving his M.S.
degree in chemistry from Oklahoma State Universi tv. Prior to
jOining Dowell, he worked as a ch~mist for the American
Smelting and Refining Co,
R. F. Dcbberthien is the distrlcl engine~r for Dowell of
Canada in Calgary, Alberto. He joined Dowell In 1952 after
graduating from St, Francis Xavier Universltv in Antigonish,
N.S. He worked in the field in on ~ngineerlng capacity until
1957, when he was sent to the Research ond Development
Group in Tulsa, Oklohoma. He ossumed his. present position
With Dowell of Canada on his return from Tulsa In 1958, Mr.
Dobberthien has been the co-author of man\' papers on
fracturing ond acidizing.

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18 The Journal of Canadian Petroleum