211

The iron protoporphyrin group of cytochromec is covalently linked to the

protein via thioether bridges between the porhyrin ring and two cysteine
residues in peptide chain, presumably formed b y addition of the -SH
group across the double bond of the 2- and 4-vinyl groups of the proto-
porphyrin.
Asphaltenes Deposits
Asphaltenes are among the least understood deposits occurring in the
oil field. They arethought tobethebyproduct of complex hetero-atomic aro-
matic macro-cyclic structures polymerized through sulfide linkages (see
Figure 11-1).
Porphyrins are common in nature and are part of a larger class of
chemicals called cytochromes (colored bodies), which are iron-containing
electron-transferring proteins. These proteins sequentially transfer electrons
fromflavoproteins to molecular oxygen, and they all contain iron-porphyrin
prosthetic groups. The porphyrin ring ispresent inseveral biological systems
and includes chlorophylls of green plant cells. Although many cytochromes
have been highly purified, with one exception they are usually very tightly
bound tothemitochondrial membrane and difficult toobtain insoluble and
homogenous form. The exception is cytochrome c, which is very easily
extracted frommitochondria bystrong salt solutions.
According toAlbert Lehninger,
}.
11
Asphaltenes and Crude Oil
Fig. 11-1 Possibleasphalteneorigins
Hemin
CH2=CH H CH3
H~C,,(C) ~~-CH=CH2
\ ( i - N ~ _ /
H :: Fe+: : c t \'tH ~ Reducedproductscondensed
C==N N___./ withsulfur toformhighmolecular
/ -1 I~HCH weight andviscous polymers.
t ~?~/t ~ 3
HOOCCH~H2 h H2-CH;zCOOH
Porphyrin nucleus
y
213
Polymeric Forms
Derived from Protoporphyrin
Giventheinformation provided intheprevious twoparagraphs, andin
particular thequote fromLehninger about thethioester formation of apoly-
mer called cytochrome c, protoporphyrin provides asuitablestructural ana-
logtoasphaltene. Thefact that sulfur isinvolvedinthepolymerization isnot
altogether surprising, since sulfur radicals (single unpaired electrons) are
very common in this element's chemistry. Sulfhydryl radicals are often
formed fromtheheterolytic cleavageof hydrogen sulfide (agascommon to
crude oils).
These sulfhydryl radicals areenergetic enough to react with activated
double bonds likethosefound ontheprotoporphyrin molecule. Thedouble
Coplaner Orbital Overlap or Pi Bonding
In theearlier sections of thisbook wetalked about theroles of hydro-
gen bonding, London dispersion forces, and ionic interactions in aggrega-
tion phenomena related to complex hierarchical structures. An additional
type of interaction is found to be operative for systems exhibiting high
degrees of unsaturation, and thisinteraction iscalledpi bonding. Themech-
anismof this interaction involvesthe overlap of partially filled electronic
orbitals between two conjugated (alternating double and single bonded
atoms) molecular species.
The interchange of electrons between orbitals of separate molecules
leads toaforceof attraction between thetwomolecules. The electron inter-
actions arequantum mechanical innature, and adetailed description of the
magnitude of these interactions requires quantum calculations be applied.
However, ashasbeen thepractice sofar, theintuitivelyunderstandable con-
cept of blending orbitalswill best suit our treatment of thisphenomena.
Configurations of the molecules undergoing pi bonding must allowa
sufficientlycloseapproach for theelectron clouds of themolecules toshare
electrons. Theplaner configuration of theporphyrin and certain other con-
jugated molecules allowsthese molecules tobestacked (seeFig. 11-2). If a
comparison of relative strength ismade between London dispersiveattrac-
tion forces, hydrogen bonding, and pi bonding forces, the pi bonding
strength would fall somewhere between them as in the following order:
hydrogen bonding> pi bonding> inductiveforces.
Thus condensation withother electrophiles (e.g., hydrogen sulfide) is
possible and the product will consist of several repeating porphyrin units
exhibiting veryhighmolecular weights. Thehigh degree of unsaturated ring
carbons (double bonds between carbons) and the conjugated nature is
responsible for extremely intense coloration of these species. An additional
property of theporphyrin ringisitshighdegree of planarity derivedfromthe
fusedunsaturated structure.
Asphaltenes and Crude Oil ---:
'01J
C
'6
c
0
..0
" 0 .
()
" . ; : : : ;
CO
E
e
CO
>,
(5
0.
Q j
C
CO
0: : :
('II
: " /
~
'l"'I
'O i l
u : : :
214
- - - - ~ - - - - - - - - - - - - -
= = = =
>- Section III, Chapter 11
215
Solvation Sheaths
Solvationsheaths for complex molecules suchasthepolysulfide-linked
protoporphyrins, whichwill hereafter becalledasphaltenes, canbeviewedin
much the samewayasthe bipolar stabilization of emulsions weredescribed
inPart I of thisbook. The asphaltenes represen t ahigh degree of unsatura-
tion and possess high aromatic character, while the surrounding crude is
more aliphatic incharacter. Thus thesolvationsheath presumably consistsof
molecules that exhibit both aromatic and aliphatic character. The useof the
word "presumably" in the preceding sentence isintended to convey to the
reader the fact that these structures havenot been unequivocally identified.
Anillustration of thepresumed solvatedasphaltene isfound inFigure 11-5.
It should berealized that thesolvatingspecies could consist of alarge
number of alkyl-substitutedaromatic or hetero-aromatic molecules, aslongas
thepossibilityof pi bonding exists. Figure 11-5represents asolvationsheath
that consists of alkyl-substituted anthracene, phenanthrene, dibenzoan-
thracene, substituted benzopyrrole, and ahost of different alkyl-substituted
derivatives, whichcanbeand often arepresent in thesheath. Thus acriteri-
umfor successful solvationisestablished, whichrequires thepresence of both
aromatic and aliphatic character inthesolvatingmolecule.
Over the years, petroleum chemists and engineers have developed a
nomenclature for the polysulfide-linked protoporphyrins and the group of
solvating chemicals suspending them: they are asphaltenes, resins, and
maltenes, respectively. These names arecommonly used torefer toblack, vis-
bond isactivatedbytheelectron-donating capabilities of theconjugated dou-
blebond of themacrocyclic protoporphyrin. Thefree-radical reaction isself-
propagating, sincethe sulfhydryl radical decomposes toformasulfur-termi-
nated macroradical. The molecular weight isdetermined byseveral factors
that include radical-radical termination, hydrogen abstraction from laibile
molecules, and chain transfer reactions through abstraction of hydrogen to
formalessreactiveradical. A representative example of the perceived reac-
tionand end product expected isillustrated inFigure 11-3.
The sulfide-linked protoporphyrin (pp-S-pp) is highly branched or
cross-linkedintheaboveexample, but because of thepossibilityof ringreso-
nance structures asecondary mechanism canbeinvoked toexplain asignifi-
cantly high degree of linearity. This mechanism involves the attack on the
protoporphyrin byhydrogen sulfideatoneof thevinyl carbons (ethylene sub-
stituent), ahydride shift fromthe sulfhydryl substituent, and radical forma-
tion of the cross-ringethylene group. The resultant product of thisreaction
mechanism isalinear polysulfide-linked protoporphyrin of significantlyhigh
molecular weight. A proposed example of this reaction mechanism isillus-
trated inFigure 11-4.
The significance of the linear form of polysulfide-linked protopor-
phyrinisthat it canbeextended within solvationsheaths that result insignif-
icantlyhigh crude oil viscosity.
Asphaltenes and Crude Oil ...:
y
Fig. 11-3 Sulfide-linked protoporphyrins
1
Fig. 11-4 Possiblereactionmechanism
Linear Segment Of Polysulfide
H
's ----+
I i _ _ }
solvated asphaltene Fig. 11-5 Presumed
d n) Region Aliphatic (Lon 0
d ) Region Aliphatic (Lon on
?,g
19
?' 1~
' : ' l J
' I I . : >
' J I.)
::8
' II.)
' II.J
' II: )
' ' 0
"0
' n,
18
' 1J .J
""
' I I ;,)
"0
' II,")
'Ii,)
"0
'II,,)
'II:J
y
219
Asphaltene Destabilization
As mentionedearlier,asphaltenesaresensitivetoshearingforcesand
electrostaticinteractions.Inthissectionwewilltrytogainanunderstanding
of whythesemoleculesare sensitiveto electrostaticand shearingeffects.
Manynaturallyoccurringand syntheticpolymersaresensitivetoshearing
forces, andoneof themainreasonstheyareinvolvestheextendedchain
lengthof thesepolymers.Althoughthebonds producedbythereactionof
vinylmonomers arecovalent,theextendedlengthof thesepolymersplaces
significantstressontheinternal bonds.
Insymmetricmoleculeslikelinear polyethylene,thecenter of massis
equallydividedoneithersideof thecentral carbon-carbonbond. Thelength
of eitherof thetwosegmentsisequal,andwhenstressisappliedatapointin
thepolymerchain, themomentumimpartedtoeachof thesegmentsispro-
portional tothemassandshearvelocityacquiredfromtheshearingforce.If
themagnitudeoftheshearingforceisstrongerthanthecarbon-carbonbond
Electrostatic Behavior of Asphaltenes
The high degree of electron delocalization associated with the
asphaltenes, maltenes, andresinsaccountsfor arelativelyhighchargedis-
persal effectthatisdistributedoverthelargelyplanermacrocyclicgroup.The
overall signof thedispersedchargeispartiallynegative, and similarelec-
tronegativemacrocyclesarerepelled; however,intermolecular blendingof
thebonding1T orbitalsdoesoccuriftheintermoleculardistanceissmalland
proximityisof sufficientlylongduration.
This behavior is analogous to that of London forces of interaction
between non-dipole containing molecules, with the exception that the
resultingaggregatemaintainsitsnet electronegativecharacter.Thestrength
of theintermolecularassociationof thesemacrocyclic-conjugatedsystemsis,
as wasmentioned, betweenthat of the hydrogen bonding and London
forcesof induction. Thustheseaggregatesareshearsensitive,andoncedis-
turbedfromtheir effectivebonddistancestheyacceleraterapidlyfromtheir
solvationsheath.
Becausetheystillpossessanoverallnegativity,theycanalsobedisrupt-
edbyelectronicforcesderivedfrommagneticallyinducedfrictional charges
thatarisefromtheir motionwithrespecttoanelectron-richsink(e.g.,pipe
wallor another asphaltene). Theseelectrostaticinteractionsandshearsensi-
tivityoftenresult instrippingthesolventsheathing (resinsandmaltenes)
fromtheasphaltene. As aresult of thelossof thestabilizingmaltenesand
resins, theasphaltenespresent adiscontinuoussurfacetothesurrounding
crudeoil andprecipitateasinsoluble,amorphousmassesfromthebulkfluid.
cous (lowAPI gravity)petroleumcrudeoils. Later operational definitions
will beusedtodescribesomeof thephysical behavior exhibitedbythese
materials.
Asphalienes and Crude Oil ...:
220
Metallocenes
Thusfar asphalteneshavebeen describedaspolysulfide-linkedproto-
porphyrinpolymers,andlittlementionhasbeenmadeof theirpowerful coor-
dinationabilities.Heminandchlorophyll complexesarenotableexamplesof
thestrengthof thesecomplexes,whereironandmagnesiumareboundtothe
central porphyrinnucleusof theprotoporphyrin. Thesecomplexesarevery
commoninbiologicalsystemsandservecriticalfunctionssuchascarryingoxy-
gentothebloodinthecaseof hemoglobin, andelectrontransport for pho-
tosynthesisinplants. HemoglobincontainsanFe2~coordinated to thepor-
phyrinnucleus, andfunctionsasaligandsitefor oxygentransport. Theoxy-
genisreversiblycoordinatedwiththeFe2+ andno oxidationor reductionof
theironoccurs.
Theanaerobic conditionsunder whichbiodegradationof thesecom-
poundsoccursaresufficientlyseveretocausereductiontotheprotoporphyrin.
Althoughcompletereductiontothepureprotoporphyrinisnot expected, a
significantpercentageisthought tobereduced inthepresenceof lesselec-
tronegativeions.Thusamoreaccuratepictureof thepeptized(resinandmal-
tenesheathed) asphalteneisgraphicallydepictedinFigure11-6.
Unsheathed Asphaltene Cores
Asecondaryfunctionof theresinsandmaltenesistheprotectionof the
inner asphaltene core fromexternal electrostatic influences and solvent
incompatibility.Thefattyalkylsubstituentsof thearomaticor polyaromatic
resins and maltenes providebuoyancyand insulation for the asphaltene.
Whenthesestabilizingspeciesareremoved, thebareasphaltenepresentsan
electronegativeandsolvent-incompatiblesurfacetothebulkfluid,andbegins
toseparatefromthesystemasasolid.Thisgenerallyoccursbecausethebare
asphaltenecoreof onepolymerchaincaninteract withthat of another and
formpi complexesof enormous sizerelativeto theoriginal parent. Other
interactionsarenowpossiblewithother surfacesthat attract theelectronega-
tivecore. Electropositivesitesonpipewalls(or mineral deposits) canalsoact
ascollectionpointsfor theaccumulationof thesegrowingaggregates.
strength, the bond will break and the polymer molecular weight will be
reduced. Thusthelonger thesegmentsoneither sideofthe appliedshearing
stress,themorelikelythebondistobreak.
Pi-bondorbital overlapandbondingisnot nearlyasstrongascovalent
bonding forces. Consequentlybond shearingbyrelativelysmall forcescan
easilycausedisruption. As London forcesof attraction betweenfattyalkyl
chainscanbeeasilyovercomebymoderatelysmallshearingforces,sotoocan
pi bonding forces. Thefirst pi bonding moleculesto beremovedarethe
resinsand maltenes, andoncethesearestrippedfromtheasphaltene, the
corepolymerbecomesunstablebecauseit isnolonger surrounded byalkyl
tailscompatiblewiththebulkcrude.
:--- Section III, Chapter 11
}.
;:..
-s
;:,-
t
~
~
~
2
slnclusion of FE'+in the porphyrin nucleus
....
Fig.11-6
Hemin Nuclei
Aliphatic (London) Region
~
~
~
~
~
~
\
~
/
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
~
--------~- -;--;. -------,;; -~---.- ------;:; --,- --."----.s.-.-r - - - - - -- ~- -. - -.- - - - - -- --
rr-: tr-, r--: r-=tr ""' r"-' ' :r7 "," r --------
=.: <-; {""Cz'_J , ' ,,~C()I, '~"vZ,_fl,
' '. '.., '" '. " .. ..
( 0 Cllr <II II ~II, -<:11,.-<II II CII, +-CII,-<:II II )jH, ....('11,.-<:11 H CII,
"'- ;..c',~,,:t-\ ,____J f-(II''''; I:~' / '>~CII'7S /., "'" '/ L'lI-CH,,.,; 1l-z~t' ' >~CII' 7 S _
H\ ~--J , I.=cF lit: r= H\ J - = "~ ,r . e ion
' ,," " " ,,' P' BondingR g
nc, ..... ",
l_~~'~" ,) ..~, ~ ncu, 'po"
C) R.~_, c I~~,~.. , ~~", ~~.. coon
'~'".;!''' ~".;r , uooc u, ..ooccn " ,
-("; ). .~,,;, '). .; , \ .~?, \ ,.-"--- "---"'),
----':~y:---~~J ;6~: --~--,:J ;'~:_-_'~"J & J : __~-:9~c J _
(If,
~ ~ ~
I
~
-
-
-
~
~
~
-
~
~
~
-
~ ~
-
~
Aliphatic (London) Region

~
~
~
-
~
-
~
-
-
~
~
-
~
~
~
-
~
-
~
~
t-o
to
'-
222
Ext er nal ~egat e
Asphaltene Destabilization
In the foregoing treatment of asphalteries, maltenes and resins have
been mentioned frequently, and ageneral aliphatic aromatic structure has
been proposed to describe them. Although these structures arereasonable,
Magnetic Susceptibility
and Streaming Potential
If the structural composition of asphaltenes is comprised of metal-
locene complexes of Fe" or hemin nuclei copolymerized with protopor-
phyrins through sulfidelinkages, arequirement of the Helmholtz theory of
the double layer demands that charges be neutralized. Thus counterions
must bepresent either intheporphyrin nuclei or at theinterface between the
stabilizing micelles (resins and maltenes). This precondition then suggests
that fattyacid anions, amines containing unshared electron pairs, or oxides
will bepresent at or near the interface between the asphaltene and the sur-
rounding crude oil solvent.
Sincemoving charges and magnetic fields are known toinduce mag-
netic andelectric fieldsrespectively, itisnot surprising that themobile hemin
nuclei produce electronic effects in nearby susceptible surfaces. These
induced fieldsnot onlyaffect thesurfacesexternal totheasphaltene, but they
alsointroduce adrag effect ontheasphaltenes. The induced fieldsand drag-
produced effectsaredescribed asstreaming potential, and haveformal math-
ematical descriptions that will not nowbediscussed. Aninteresting manifes-
tation of streaming potential inlow-conductivitysystemsistheproduction of
staticelectrical discharges.
Theinclusion of Fe" intheporphyrin nucleus isimportant, both inbio-
logical systemsand inasphaltenes. Inbiological systemsFe2+inhemoglobin
isrequired for respiration, and hemoglobin and asphaltene structures arein
a group of compounds known as metallocenes. The metallocenes involve
bonding and antibonding p orbitals of aromatic nuclei with unfilled d-
orbitals or hybrid orbitals of acentral metal ion. This situation isdepicted in
Figure 11-7.
The arrangement of the hemin and protoporphyrin rings depicted in
Figure 11-7alsoapplies tothepolysulfide-linked asphaltene structures; how-
ever, itisquestionable ifthe sheathed (peptized) asphaltenes conformtothis
bi-porphyrin metallocene structure. An interesting phenomenon associated
withthesemetallocene structures isthat many exhibit high magnetic suscep-
tibility. The complexes [Fe(CN)63-andFeF63- ...] in aqueous solutions yield a
magnetic moment of 2.3Bohr magnetons for theformer and 6.0for thelater.
This magnetic susceptibility isverymuch responsible for the interactions of
asphaltenes withmetal surfaces and other unsheathed asphaltenes.
>- - Section III, Chapter 11
}.
~
; : . . .
0{;
;::,.
'"
W
[J :
'"
;;
."
~
. "
"
Fig. 11-7 Metallocene arrangement of hemin and protoporphyrin rings
Hemin
: ?~~~~ /~~3 _
I [-<'C-CH=CH2
-N~_ ,-'N
,'H'" ~
HC_'-''; : ~ cu
c\\~ . _. <~; : ~--N " N-<
\\ ; : ~c\\ -: -C\\~,-,Fe=*'" ~~)~ /b~HCH3
c\\ - C .> , <, v
c\\~-::::- ~'-../ \\ ~" " ,:" " HooccH;GH2 h H2---CH[200H
\\C~ \" -,~,~' ~\\'
" ,_~, ,I
"C- " . ' .rc
I I ~.:--" ~c\\}
\\c ~ f / coo\\- Protoporphyrin
~-::::- \ -::::::::.c . . -C\\~
/ c~ t\\-~
c~/ {\
_. . . C\\-l
cc\\~
\\00
~
224
Summary
This chapter attempts to explain some of the chemistry involvedwith
high aromatic, hetero-aromatic, and hetero-atomic macrocyles. Itproposes
plausible but hypothetical structures for components comprising aclassof
chemicals calledasphaltenes, maltenes, andresins. Anattempt wasalsomade
to explain the stabilization forces of the solvating intermediary resins and
maltenes, andthenature of pi orbital intermolecular overlap. Ascaleof inter-
activestrengths wasdeveloped to givean insight into the macro-aggregates
association. Finally, ashort discussion of the types of forces acting on the
asphaltene aggregates suggested that shearing forces and electrostatic inter-
actions could destabilize these aggregates.
they need refinement tofurther elucidate the mechanisms of their interac-
tionswiththeasphaltene core, Muchof theliterature onasphaltenes suggests
that the resins and maltenes (peptizing agents) are precursor molecules to
the asphaltene. This possibility is quite likely, and reasonable candidates
couldbederivedfromthelactams of gamma amino acidsor thepyrroles and
pyrrolidines. Thus a fatty-alkyl-substituted pyrrole or fused pyrrole would
serveverywell asabi-layersheath. Figure 11-8showstwopossiblecandidates.
Although Figure 11-8describes thefused pyrrole and proline aspor-
phyrin precursors, theycouldalsobebreakdown products of aporphyrin par-
ent. Thus thereports in theliterature regarding thecomposition of the sta-
bilizing or peptizing rnaltenes and resins would appear tobe quite reason-
able. Thephysical chemical properties of thepyrroles and fusedpyrroles are
quiteinteresting and exert strong interactive forcesover theporphyrin nucle-
us. There isconsiderable transfer of negative charge tothe carbon atoms in
thepyrrole ring, whichgiveit ahigh dipole moment =1.8Debyes.
Becauseof thehighnuclear pelectron density, pyrroleisoxidizedbyair
evenmore rapidly than aniline or phenol, leading todark-colored resinous
polymers. It islikelythat thisstrong dipole actstostabilizethehemin fraction
of theasphaltene, whilethealiphatic tail disperses itinthecrude oil.
Figure 11-9shows the polysulfide protoporphyrin surrounded byan
alkyl substituted fusedpyrrole, whichisthestructure wepropose for thenon-
iron asphaltene. The inclusion of iron would favor this arrangement even
more strongly because of the dipole moment present in the pyrrole. An
important feature of the above-proposed arrangement isthe positioning of
the aliphatic tailsof the sheath. This spinelike arrangement then allowsthe
interaction of other aliphatic species such asparaffins, alkyl-substituted fatty
acids, and alkyl tailsof awidevarietyof chemicals present incrude oil.
The interaction of these spinelike alkyl projections with similar alkyl
groups resultsfromLondon inductiveforces. The more massivetheinteract-
ingalkyl substituent, themore shear-sensitivethesheath becomes. When sol-
vent molecules likepropanes, butanes, pentanes, andhexanes arevolatilized,
theresulting agitation isoftensufficient todisrupt theprotective sheath (strip
themaltenes and resins).
:--- Section III, Chapter 11
Fig. 11-8 Alkyl-substituted porphyrin precursor

""
~
~
~
'--
).
~
;:,-
.,
f
R =CH3CH2 CH2CH1CH2CH1CH1CH1CH2CH1CH1CH2CH1CH2CH1CH3
~
~
Hc--cR CH2-H2C
I I I I I I
HCy(L'~V2C
1 1 H A
r-
Pyrrole
}.
--
Alkyl Substituted Porphyrin Precursor
--
Hc--cR CH2-H2C
I I I I I I
HVC", /V2C
~ ,C). ..
Proline
CH2--H2C
H - J I
COOR..-/CV2C
~
~
+
c~R
I I I I
CVH
~
to
tc
v,
y
W t : r : w l ' w " ' l m I W W : \ I ' U w u u " i j j U ' . , ! ! U ! ! l ! ! I I i l i _ U U l I ! l i U _ I U l l i l i l i l l l l U i l l l l i t i i i i i l i i i illllii,IIIIIIIIIII,IIIIII"III,IIIIIIIIIII',II:I:II.1
Fig. 11-9 Polysulfide protoporphyrin surrounded byan allkyl-substituted fused pyrrole
227
Barrow, Gordon M. Physical Chemistry. 2d. ed. NewYork:McGraw-Hill
Book Co., 1966.
Handbook of Chemistry and Physics. 56thed. Cleveland: CRCPress, 1975-1976.
Lehninger L. Albert. Biochemistry: The Molecular Basis of Cell Structure and
Function. NewYork:WorthPublishers, Inc., 1970.
References
Problems
11-1. What type of interactions account for the strong protective forces
found inasphaltenesheathing structures?
11-2. Rank therelativestrengths of London forces, hydrogen bonding, ionic
bonding, and pi bonding inorder of increasing strength.
11-3. Explain howstreaming potential affectsthe stabilityof the asphaltene
aggregate.
11-4. Essayquestion: Propose an alternate structure for asphaltene aggre-
gates, andjustify the proposed structure on the basisof the behaviors
exhibited by these aggregates. (Note, the structure described in this
book isonlyaproposed structure.)
The preceding chapter also discussed the disruptive forces acting on
thealkyl-pyrrole-sheathed polysulfide-linked protoporphyrin hemin structure
(peptized asphaltene). Three main disruptive force typeswere implicated:
shear stress, electrostatic, and London alkyl sensitization. The shear-stress
forces imparted to the peptized asphaltene are small, but their very high
aggregate weight make themsusceptible todisruption bysmall shear forces.
Streaming potentials exert drag effects on the core as the internal metal-
locene complexes induce charge innearby surfaces, and the resultant core
shiftsact tostrip the protective sheathing. Finally, the London attraction of
external phase alkyl groups with the alkyl groups of the protective sheath
increase sheath masssufficiently toallowevenminor agitation caused bythe
volatilization of light crude fractions todisrupt thesheath.
Asphaltenes and Crude Oil ..:
229
Operational Definitions
Versus Chemical Composition
It isinstructivetonote that thetruestructures of asphaltenes arenot as
unequivocal as the preceding chapter would lead one to believe. The oil
industry hasdefined thesematerials onanoperational basis, and thisopera-
tional definition ismore adescription of physical behavior than actual chem-
ical structure. Oil companies haveknownfor yearsthat asphaltenes aredesta-
bilizedand precipitate fromcrude oil samples when added tomultiple vol-
umes of pentane. This observation hasbecome entrenched intheliterature
and isaccepted as the definition of asphaltene. Although this definition is
unsatisfactory tochemists, it isvalidinmany respects toother professionals,
suchaspetroleum engineers.
Thus screening processes aimed at determining asphaltene contents
areconducted byaprocedure that involvesthe dilution of the crude oil in
multiple volumes of normal pentane. Thejob of the physical chemist isto
rationalize thisoperational definition withchemical structures that wouldbe
expected to exhibit the observed behavior. Additionally, once a rational
chemical structure isarrived at, it isthe chemist's job toperform analytical
Bulk Behavior of
Asphaltenes
}.
12
Field Problems with Asphaltenes
Asphaltenes are responsible for many of the field problems experi-
enced byproduction companies. Thediscussion ontheproposed structure of
asphaltenes and the associated peptizing agents has explained much about
230
Indirect Evidence
for Asphaltene Composition
Manytimesthebehavior of chemical systemswhen acted upon byexter-
nal influences can be invoked asdeductive mechanisms for understanding
the chemistry of components within the system. Such deductions are often
retrievable fromtheprocessing of crude oilsafter their production. Onesuch
process istheextraction of heavyvacuumtower bottoms intherefinery. This
process involvesthe N-methyl pyrrolidone extraction of these heavybottoms
products to remove the polar species fromthe nonpolar in preparation for
further refining processes.
The N-methyl pyrrolidone combines with the black tar bottoms and
allowsphase separation of the nonpolar paraffins. The paraffin bottoms are
sent to the dewaxing process, and the pyrolidone fractions are sent to the
asphalt distillation unit for retrieval of solvent and preparation of asphalt.
Giventhis information, what typeof chemical structures would be expected
to partition soreadily into the polar N-methyl pyrrolidone phase? Or more
importantly, would the proposed structures developed in chapter 11 be
expected toyieldtothis solvent treatment?
In order toanswer these questions, it isimportant tounderstand some
of the properties of the solvent. N-methyl pyrrolidone is a high-dielectric
aprotic solvent, which solvates by dipole-dipole interaction with the solute.
Aprotic solvents are held less strongly than protic solvent molecules, and
sincethey areheld lessstrongly, the solvation activation energy isless.
An example of this is the rate of displacement of an iodide ion bya
chloride ion in methanol (protic solvent) versus dimethylformamide (DMF,
aprotic solvent) where therateintheDMFismore than 1,000,000timesfaster
than inthemethanol. For agivenaprotic solvent, the attraction between sol-
vent molecules and nucleophile increases withthepolarizability of thenucle-
ophile, and hence withitssize. Thus theproposed structures arecompatible
withthe solute solvent behavior described above. Figure 12-1showssomeof
the solvent features ofN-methyl pyrrolidone.
tests that further characterize the composition of the operationally derived
sample (pentane insoluble fractions).
Becauseof thecomplex character of themacro-aggregates and thesen-
sitivitytochemical alterations that arepossible, these characterizations canbe
extremely complex. Thus, the actual structure or structures comprising
asphaltenes will require the complete and unambiguous synthesis of these
materials before complete characterization isaccepted.
>- - Section III, Chapter 12
231
Fig. 12-1 N-methyl pyrrolidone
thephysical chemical behavior of thesesystems,but littleinformationhas
been givenabout their behavior inactual fieldsystems.Thedepositionof
asphalteneshasbeenobservedinalargenumber of locationsinproducing
wellsandassociatedtransferandstoragefacilities.Someof thesedepositions
occur at locationsof particular interest, whichincludewell chokes, casing
perforations, formationrock, thevacuumsideof pumps, storagetanks,and
well tubing. Withtheexceptionof storagetanks, eachof theselocationshas
somethingincommon, andthat somethingisshearanddrag.
In thediscussiononthesensitivityof theasphalteneaggregatesinchap-
ter 11,thestrippingof thepeptizingagentsfromthecoreasphaltenewaspro-
posedasareasonfor precipitation. Butwhatabout thestoragetank?Again,
thediscussionof Londonalkylaggregationandconsequent sheathdestabi-
lizationhelpstoanswerthequestion. Thequiescentconditionsprevailingin
storagetanksfavoraccumulationandaggregationof alkylfractionswiththe
alkylexteriorof thepeptizedasphaltene. Overaperiodof timetheaggrega-
tionshavebecomesomassivethatthemildagitationaccompanyinglight-end
lossbecomessufficientlystrongtodesheaththepeptizingshell.
In additiontodeposition, other problemsaretheresultof asphaltene
content incrudeoils.Asignificantproblemisthat of viscosity,andtheasso-
ciateddifficultiesof productionrate, pumpingenergies, andtransfer rates.
Highasphaltenecrudeoilsaregenerallyhighinviscosityanddifficulttohan-
N-methyl pyrrolidone
1. Dipole Moment
2. High Dielectric
3. Polar Aprotic
4. 11.2H Solubility
Parameter
Solvent Features
Bulk Behavior of Asphaltenes ...:
I
I
232
Acid Effects on Asphaltene
Field personnel often conduct acidjobs on wellsthat havescaled up
withinorganic salts. These acidjobs areusually conducted byback flushing
thewellswithhydrochloric acidsolutions. Veryoften theacidtreatment of an
asphaltene-containing well will result in coagulation of the asphaltenes and
anevenmore serious production impediment will result.
Over theyearsthewell-servicecompanies that conduct theseacidclean-
ups havedeveloped chemical additives that areintended to ameliorate the
problem of sludge formation. A great deal of proprietary chemistry is
involved, and alistingof specificchemicals wouldbeout of thescopeof this
book. The success these companies havehad with additives for asphaltene
sludge control has been lessthan spectacular. The typesof chemistries are
extremely varied, and theconcepts of howtheadditives act toprevent sludge
are not fully rationalized. However, many of the additives are complexing
agents with multiple ligand sites such as EDTA, citric acid, tartaric acid,
biuret, and glycols.
Theaddition of thesecomplexing agents doesappear tohaveapositive
effect on thereduction of sludgewhen added to theacidizingpackage. This
effect isattributed tothesequestration of acidsolubleironsaltsthat arefound
inhigh concentration in the spent acidwash. However, giventhe proposed
structure for asphaltene described previously, it isnot surprising that seques-
tration of iron saltswouldreduce sludgearisingfromtheacidization process.
One additional factor isoperative inthe destabilization of asphaltenes
bystrong acidsolutions, and thisfactor arisesfromthefact that pyrroles are
dle, Themolecular weight of theasphaltene anditshigh dispersion through-
out thecrude mixdetermine theviscosityof thecrude oil.
Although wehavejust begun toelucidate thestructural composition of
the asphaltenes, wehavenot yet determined the extent towhich it ispoly-
merized. Thus, viscosityeffectsassociated withthismolecular weight remain
somewhat of amystery. However, some intelligent guesses are possible. At
least twothingsmust beknowninorder todetermine theeffect of asphaltene
molecular weight on crude oil viscosity:asphaltene concentration and aver-
agechainlength of thepolysulfide-linked constituents. Wecandetermine the
quantity of asphaltene bythepentane insoluble method, but determining the
polysulfide constituents ismore difficult.
Assume that the protoporphyrins and hemin constituents arisefrom
decomposed plant and animal systems.Assumingalsothat theproportion of
these substituents issmall compared toparaffins, fattyacids, and other bio-
molecules, then it isasafebet that these molecules will have amolecular
weight that isinverselyproportional tothat ratio. Andasaresult of thishypo-
thetical experiment, molecular weights of approximately 500,000 to
1,000,000 grams per mole are expected (hemin and chlorophyll ratios in
micrograms per gram). These molecular weightswould most certainly pose
viscosityproblems evenat lowconcentrations.
:---- Section III, Chapter 12
233
Asphaltenedepositionsarecommoninaverylargenumber of produc-
ingwellsthroughout theworld,andtheir costtotheproducersissignificant.
Mostcrudeoil productioncompaniesusexylenewashesfor theremoval of
asphaltene depositsfromwells, transfer lines, and storagefacilities.This
remedial procedurerequiresconsiderableinvestmentsintime, solvent,and
lostproduction. Oftenthedepositionsaresoseverethatthewell'sproduction
ratefallsfromthousandsof barrelsper daytozero.
Oil Field Treatment Methods
Artificial Causes
of Asphaltene Deposition
Asmentioned earlier, certain techniques intended to enhance the
recoveryof petroleumresult inexacerbationof theproblemof asphaltene
deposition.Aparticularlystrikingexampleof thisistrueisinthewidespread
usageof C02 flooding. This technique results in significant amounts of
asphaltene deposition when the formation being treated contains heaw
crudeoils.Althoughlesscommon, theuseof nitrogenforenhancedproduc-
tionalsoproducesasphaltenedeposits.Thenitrogenfloodmethod, however,
produceslesssludgethanthecarbondioxideinjectionmethod.
Whatfactor inthesetwomethods couldaccount for thequantirative
differencesintheamount of sludgeformed?Theconditionsunder which
injectionof thefloodgastakesplaceandtheconditionsthegasencounters
duringitstorturousjourney tothefluidmatrixdeterminetheconditionand
compositionof thegaswhenitarrives.Nitrogenisquitestableathighpres-
sureand significantlyhightemperatures, whereascarbondioxidecanand
doesundergo chemical alterationunder similarconditions. Thus, theper-
centageof carbonmonoxide(CO)reachingthereservoircanbesignificant.
Asmentioned above,theheminfunctioninrespirationistransporta-
tionof oxygentothetissues.Itisalsocommonlyknownthat carbonmonox-
ideismorestronglybound to hemoglobinthan oxygen, and that carbon
monoxideisastrongcomplexwithhemoglobin, of whichheminisamajor-
component. Thiscarbon monoxidethus produced cancomplexwith the
heminintheasphaltenecore.Thiscomplexprobablydoesnotdestabilizethe
polysulfide-linkedheminprotoporphyrin core. It ismorelikelythat thebe-
products of carbondioxidebreak downtocarbonmonoxideandcarbonic
acidthatcausethedestabilization.Thisisbecausethepeptizingagents(alJ ;;rl..
substitutedpyrroles)areacidsensitive,andwater-coordinatedcarbonicacid
affectsthedestabilization.
slightlyacidicwithapKa=15comparedtophenol, pKa=9.9.Thisisonefac-
tor for thedestablizationof thepeptizingsheath. (Aninterestingsidenote
aboutthebehaviorof protoporphyrinsisthatwhentheyarereactedwithalka-
linesolutionsof ferricchloride, heminisformed.)
Bulk Behavior of Asphaltenes ---!
234
Production Factors Affecting
Asphaltene Deposition
The production engineering staffsof many oil companies have been
responsible for the major progress inthe prevention of asphaltene deposits.
The success has been due to production procedures, systemequipment
design, and remediation procedures implemented by field engineers.
Production procedures areextremely important for optimization of produc-
tionfromcrude oil reservoirs. Production rates, wellhead pressure, fluidand
gasturbulence control, perforation depths, fracturing control, tubing design,
and transfer-line design are all areas inwhich engineers havesucceeded in
controlling thedeposition rates of asphaltene deposits.
Although physical designs havebeen the most successful methods for
thecontrol of asphaltene deposition, there isapractical limit totheextent to
which design modifications canbeimplemented. For example, producing a
well belowthe bubble point pressure (e.g., the pressure at which the most
volatilecrude fractions begin toescape fromtheliquid) isknown toreduce
asphaltene deposition, but in some cases this pressure is below what is
required tolift thecrude.
Obviouslythissituation isunacceptable fromanypoint of view,sopro-
duction must occur abovethe bubble point. An interesting sidenote to this
situation involvesthe natural tendency of asphaltenes toformconstrictions
The rate of decrease inproduction depends on therate of deposition,
but inseverecasesproduction rates can drop toonlyafraction of theunob-
structed ratewithin days. Thus methods toprevent these depositions arean
important part of aproduction company's strategy. Manyservicecompanies
havebeen activelyinvolvedin the research and development of products to
address the problem of asphaltene deposition, but these efforts havebeen
hampered bytheextreme complexity of theproblem. Much of thedifficulty
encountered by these research efforts involves the lack of a clear under-
standing of thechemical nature of the deposits, and thespecificchemistries
needed to effectively treat the problem. Therefore, production companies
havehad torelyonsolventwashprocedures and theingenuity of production
engineers toaddress theseproblems.
Over theyears, manyattempts havebeen made toactivelyinterfere with
the deposition of asphaltenes, and only avery limited progress has been
made. Three of theverylimited number of chemicals that havebeen intro-
duced into theproblem crudes withpartial successinclude aromatic fattysul-
fates, fattyaminearomatic fattysulfatesalts, andaromatic amines. Thedegree
to which this classof chemistry issuccessful inpreventing deposits can be
described asextremely limited at best, and evenharmful atworst. Therefore,
continuous treatment programs have not been applied in many cases.
However, the addition of these chemicals to solvent wash systems has
enhanced removal effectiveness.
:--- Section III, Chapter 12
r
235
Fluid Transport Equipment
The high sensitivity to shear destablization exhibited by asphaltene
aggregates requires that turbulence be minimized inthe production and
transport of crudes containing asphaltenes. Thus theuseof low-shear pumps
isadvisablein transporting asphaltene containing crude oils. Sudden expan-
sions inlineconstruction and large numbers of valvesand other fluid-divert-
ing methods should beavoided, sincethey add turbulence tothefluid. Most
of theserecommendations arecommonly practiced byoil producers andhave
evolvedtoahighlevel of efficiencyover theyearsbymethods of trial anderror.
One factor that affects the deposition of asphaltenes may not seem
important on the surface, but it ismore important than commonly recog-
nized: corrosion. Giventhe proposed structure for asphaltene aggregates, it
should berecognized that thepresence of oxidized metals canposeaserious
threat tothestabilityof theasphaltene aggregates. The transition metal com-
plexes of protoporphyrin can formwithgreat facility, and the stabilityof the
Asphaltene Deposition Control
by Treatment of other Problems
Inthepreceding chapter about theproposed composition of asphaltenes,
maltenes, andresins (andtheir interaction withsurfacesandsurrounding chem-
icals)fattyalkylinteractions wereseentoplaya roleinthestabilityof theasphal-
teneaggregates. Theseinteractions includetheassociationoflong chainparaffin
waxeswiththealiphatic tailsof theprotectivesheath of theasphaltenes.
The association of the paraffin waxes with the asphaltenes has long
been known toreduce the tendency of crude oilstoexhibit waxnetworking
phenomena. Thus crude oilswithhigh percentages of waxaccompanied by
asphaltenes exhibit lower pour points, but higher viscositiesdue tothe high
molecular weight of the asphaltenes. Additionally when asphaltene deposits
areexamined, they arefound to beincloseassociation withwax. Veryoften
the percentages of each component, wax and asphaltene, are found to be
nearly equally divided. Thus confusion arisesastowhich component actually
causesthedeposition problem, andtreatments directed at themisunderstood
problem sometime result infavorable results.
The introduction of waxcrystal modifiers often inadvertently affects a
solution to an asphaltene problem byreducing the instability introduced in
thepeptizing sheath of the asphaltene bywaxinteraction withthe externally
directed alkyl tailsof the sheath. Conversely, the introduction of one of the
limited number of effectiveasphaltene dispersants alsoinadvertently effectsa
solution tosomewaxproblems.
within production conduits that act aschokes to maintain flowrates, which
are below the bubble point of the fluids. This effect is driven by the
asphaltenes' natural tendency to seek an equilibrium point of effective dis-
persion inthe crude oil matrix.
Bulk Behavior oj Asphaltenes ---:
236
Acheson,R.M.An Introduction to the Chemistry of Heterocyclic Compounds. 3d.
ed. NewYork:JohnWiley& Sons, 1976.
Barrow,GordonM.Physical Chemistry. 2d. ed. NewYork:McGraw-HillBook
Co., 1966.Rodriguez,Ferdinand. Principles of Polymer Systems. NewYork:
McGraw-HillBookCompany,1970.
Seymour,RaymondB.Introduction to Polymer Chemistry. NewYork:McGraw-
Hill BookCompany,1971.
References
I
i
t
I
i
~
f
I
i
Summary
Theprecedingchapter discussedtheoperational definitionof asphal-
teneversusthe proposed chemical structure. The operational definitionis
basedonthedispersibilityof themacro-aggregatesinapurehydrocarbonsol-
vent (typicallypentane). Thechemical compositionwasderivedfromdirect
andindirectmethods, andseekstoexplainphysicalbehaviorthatisconsistent
withtheoperational definition. Theprocessof deductionisheavilyemployed
andinvolvestheextrapolationofknownphysicalbehaviorinprocessessuchas
solventwashingofvacuumtowerbottomswithpolar aproticsolvents.
Further deductionsaremadefromthebehaviorof asphaltene-contain-
ing oils when subjected to mineral acid treatments of producing wells.
Inferenceswerealsodrawnfromtheeffectivenessofsequesteringagentsused
for sludgepreventionduringtheacidtreatment of wells.Finally,arational-
izationof thebehaviorof asphaltenesinthepresenceof artificial drivestim-
ulantswaspresented, whichappearstobeconsistentwiththeproposedstruc-
ture. Thustheentirechapter isdevotedtothejustificationof theproposed
structurefor asphaltenes.
Intheprecedingchapter wealsodiscussedthefieldtreatment methods
for thepreventionandremoval of asphaltenedepositsoccurringinoil wells
and surfaceequipment. It wasnoted that the majorityof successful tech-
niques for asphaltene deposition control are the production techniques
developedbyfieldengineers. Itshouldalsohavebecomeevidenttotheread-
er that thechemical methods of deposit preventionareoftentheresult of
misapplicationof treatment chemistries. Additionallythe methods for the
removal of depositedasphaltenesisstill approached through theuseof sol-
ventsandchemical dispersants.Thustheareaof asphaltenedepositpreven-
tionshouldbeconsideredanareaof continuedemphasisandafruitful area
for specialtychemical companyresearchanddevelopment.
aggregatesislargelydetermined bythenature and extent of theresulting
complex. Thus, corrosion control canalsobeuseful in the prevention of
asphaltenedepositions.Sinceitisnot practical toconstructwelltubing, trans-
fer lines,fittings,or storagefacilitiesfromcorrosion-resistantmetals, chemi-
cal additivesthat acttoprevent corrosionof mildsteel canbehelpful inthe
preventionof asphalteneproblems.
:--. Section III, Chapter 12
237
Solvent Testing
Testingfor asphaltenes isaproblem inmanyrespects, sinceasphaltenes
areoperationally defined bysolubilityinmultiplevolumes of normal pentane.
Becauseof thispoorly characterized andinadequate physical chemical defini-
tion, test methodologies canvaryconsiderably fromlaboratory tolaboratory.
Several questions arisewhen solvent testsareperformed on crude oil
samples. Should the crude sample be filtered to remove extraneous solids
before being introduced into the pentane? If the sample isprefiltered, will
someof theasphaltenes beremoved? Should aneffort bemade toremovethe
waxfraction prior to solvent testing? Should the filtration beconducted on
heated samples? Should the samplefirst besolvent tested, theprecipitate fil-
tered, and ashed inamufflefurnace todetermine inorganics? Will prefiltra-
tiondestabilize the asphaltene aggregates byshear effects?Andsoon.
Theend result of all thesequestions ismore questions, and theanswers
areoften assubjectiveasthe operational definition. Thus standardization of
all testingisrequired; however, thestandard methods arejust asillusionary as
theoperational definition. Herein liesaproblem for those seeking afunda-
mentally supportable testing procedure. Italso leads to the confusion sur-
rounding the structural elucidation of the offending materials, and compli-
catesthe design of chemistries that could haveapplication indeposit reduc-
tion. Considering this state of confusion, it is quite reasonable to make
assumptions based on the indirect evidence of asphaltene structure and
extend theseassumptions totesting procedures.
}.
13
Asphaltene Testing Methods
238
Thin Layer Photometry
One technique that has been reported involvestheuseof ahigh-pres-
sure dual windowquartz cell through which the liveoil (sample retrieved
under reservoir conditions) iscirculated. The pressure isgradually reduced
fromreservoir conditions whilealight source passesthrough thecirculating
sample to aphotodetector. When precipitation begins, the light isscattered
bytheparticles of forming organic solids, and thedegree of scatter isamea-
sure of the precipitate. This method allowsacombination of visual observa-
tion, photometry, andvideo recording during thetest. The useof liveoil isa
veryimportant part of thistest methodology. Byusingliveoil, the test proce-
dure avoidstheproblem of aprevious deposition history and more accurate-
lyrepresents thebehavior of fluidsasenvironmental conditions change.
There arealsosomedrawbacks tothis testing procedure, not theleast
of whichistheprovision ofliveoil. Sinceliveoil must beretrieved under con-
ditions existing in the reservoir, complicated procedures for collecting the
fluidareinvolved. Theproducing oil company must stopproduction, remove
tubing obstructions, and lower apressure container into the well to collect
Core Testing Procedures
Core test methods canbeveryeffectiveindetermining the deposition
tendencies of organic materials, and if they are conducted with the appro-
priate precautions, they can help answer somequestions about thebehavior
ofasphaltenes (seeFig. 13-1).
Theextent towhichthistestmethodology isemployedisnot known, but
it doesnot appear tobewidespread. The concept issimple, however, and the
testingresultsarelookedupon favorablybyoil company personnel. Whenever
possiblecoresamplesareobtained fromtheproducing formation, andall test-
ingisperformed onthesesamples. In addition tothecoresample, samplesof
theasphaltene deposits fromthesameformation aretested onthecore.
Since xylene is the solvent most often employed for well cleanup of
asphaltene deposits, thesampleissuspended inxyleneandpumped through
thecore. Thepressure required toforcethedispersed asphaltene xylenemix
canbequite high (100psi or higher) soitisnecessary touseanHPLC pump
(high pressure liquid chromatography pump). After several core volumes
havebeen displaced, the xylene mixture isreplaced bypentane, and circu-
lated whilemonitoring pressure and absorbance. The addition of pentane is
intended tocauseprecipitation of asphaltenes inthecoreand thereby cause
apressure increase. The spectrometer isstandardized on the initial xylene
mixture and compared to a Beer's law plot of concentration versus
absorbance. Once the core isfouled with asphaltene, xylene or xylene plus
chemical isadded totest theremoval efficiencyof the chemistry. Other test-
ing can be performed, such as adding a chemical to the original xylene
asphaltene mix, or to the pentane to determine the effectiveness of deposi-
tion inhibitors.
> - - Section III, Chapter 13
: : . .
~
it
W
"
5'
o Z
~
~
t;-
}.
Fig.13-1Core-testing procedure
Sample
Reservo ir
Pressurized Co re Ho lder
Pressure
Transducer
Duel Channel Reco rder
High Pressure Liquid
Pump
t;
10
240
Proposed Microwave Tests
Microwavesradiateenergiesthat occur at levelsthat areof thesame
magnitudeas therotational energies exhibitedbymoleculespossessinga
dipolemoment. Giventheproposedstructureforasphalteneaggregatesfrom
previoussections,absorptionof microwaveswouldbeexpected. Theunfor-
tunatefactthat largemoleculespossesssomanyinternuclear distancesthat
Size Exclusion Gel
Permeation Chromatography
The idea of separations based on sizeseems to be a reasonable
approachtothecharacterizationof asphalteneaggregates,sincethemolecu-
larweightof theasphaltenecorecanbeveryhigh.Theconceptof sizeexclu-
sion isbasedon the ideathat higher molecular weight materialswill be
excludedfromhighsurfacearearesinbeadsthathavewell-definedchannels
of known sizethat accommodate small molecules. These resins can be
obtainedwithavarietyof porechannelsandplacedinacolumninlayersof
increasingporesize.
Thesampleisplacedonthecolumn,andamixtureofsolventsarethen
added to drivethe samplethrough the column. As the sampleproceeds
through thecolumn, thesmallermoleculesareincorporated intothepore
spacesof thelayeredresins,whilethehigher weightmaterialscontinueto
progressthroughthecolumn.Thisprocedureisusuallyassistedbytheuseof
ahighpressurepumpthat providesforareasonableflowrate. Althoughthe
pressuresusedtendtobehigh, theflowratesarelow;consequently,theshear
forcesalsotendtobelow.Thus, theappropriatechoiceof solvent/solvents
usedaseluentsisextremelyimportant for thesuccessof thismethod.
Thistechniquehasmanyadvantages,oneofwhichistheisolationofrea-
sonablylargesamplesthat canbeusedfor further characterization.Onedis-
advantageofthismethodisthatitwillalmostcertainlyremovethesheathfrom
theasphalteneaggregate,makingitdifficultcharacterizethesematerials.
thesample. Thesecollectionprocedures areexpensiveanddifficult,sothe
producersarereluctant toprovidesamples.Howeverwhenthistestmethod
isused, the resultsappear to beveryreliableasameans of determining
deposittendencies.
Figure 13-2 showsthe arrangement of the asphaltene deposition
device.Itisalsointerestingtonotethat thisdeviceisthesameasthecloud-
pointdeviceshowninthesectiononwaxes.Thedifferenceintestingmethod-
ologybetweencloud-pointtestsand asphaltenedepositiondetermines the
resultsobtained. Thecloud-pointtestobservesthebehaviorof thecirculating
fluidsunder conditions of decreasingtemperature and constant pressure,
whiletheasphaltenetest observesthebehavior of fluidsunder decreasing
pressureatconstanttemperature.
>-Section III, Chapter 13
~
{;
~
~
"
~
'"
~.
~
~
}.
Graphical
Information
Fig. 13-2 Light-beamasphaltenedetermination
Focal
Lens
rSampleOut
Heated
Cooled
Chamber
tv
....
. . . . .
242
Designing Asphaltene
Deposit Control Chemicals
Muchof thechemistrydevelopedtoaddresssurfacephenomena has,
inmanycases,evolvedasaprocessof trial anderror rather thanastheresult
of profound insight into theinteractions producing thesurfaces. However
once effectivetreatment chemistrieshavebeen developed, rational argu-
mentsbasedonfundamental conceptscanbeusedto explaintheinterac-
tions. Infact,whatincremental progressismadeisgenerallyduetoamore
thoroughunderstandingof thechemical andphysicalprocessestakingplace
Proposed Ligand Replacement Method
Selectiveextractionof theFe2' bytheadditionof phthalonitrileispos-
sible,sincethecomplexformedunder temperaturesof approximatelySW O C
givesaphthalocyaninestructure. Thisphthalocyaninestructureisanalogous
to the hemin structure but contains four additional nitrogen molecules
replacing the methylidynegroups. Figure13-3showsthe structure of the
phthalocyanineandtheperceivedinteractionwiththeheminfractionof the
asphalteneaggregate.
AftertheselectiveextractionofFe2+isaccomplished,thesamplecanbe
washedwithacetonitriletoremovethesolublephthalonitrile, andtitratedto
apotentiometric endpoint usingstandardcopper sulfatesolution.
thethree-dimensional momentsofinertiacannotbesortedfromthemmakes
indirectmeasurement necessary.Additionallytheinteractionsofmoleculesin
liquidor solidphasesconfusespectral interpretations, andmicrowavestudies
aregenerallyconductedongasphasesamples.
Althoughtheforegoinglimitationswouldappear toprevent anyappli-
cation of microwaveanalysisto samplesof asphaltenes, someinteresting
behavior of theseaggregatesmakemicrowavestudiespossible.Asphaltene
canbeatomized(carriedbysufficientlyenergetic gassesintohead spaces).
Thisbehaviorisobservedingasprocessingplants,whereasphaltenedeposits
occur abovetheliquidlevel incompressor overheads. Becauseof thisphe-
nomena, the intentional atomizationof asphalteneaggregatescanbesub-
jectedtomicrowaveradiationstudies.If thegasusedfor atomizationpossess-
esnodipolemoment, themicrowavespectraof theatomizedasphaltenewill
betheabsorbingspecies.
Theproblemof high-molecular-weightmaterial possessingamultiplic-
ityof internuclear distancesstill needstobeaddressed. Byaddinggasphase
moleculespossessingvaryingdipolemomentstotheatomizationstream,indi-
rect spectral measurements couldbemade. Thus the atomizedasphaltene
aggregateabsorbingmicrowavesin aparticular frequency rangewouldbe
selectivelymaskedby the addition of knownwavelengthabsorbingpolar
molecules.
:--- Section III, Chapter 13
s .
~
~
;,.
"
~
~
0 1
~
s .
'" [;-
L_
-
Fig. 1 3-3 Phthalocyanine structure and interaction with hemin fraction of asphaltene aggregate
Hemin
Polys ulfideProtoporphyrin
~ S--CH2 --CH H CH,
ccc
HC~ "'-c~ "'-c-: ~
\
I I I ;C--CH -CH2
C-N 'N-c
1 / . . Fe+ Tf ~
H~' .. _ 'CH
"'-c-N N--CI
( - ~ ~ "'-tHCH,
~c/"~c/ ~c/
HOOCCH2-CH2 H CH2-CH2 COOH
~------------Iron Phthalocyanine Complex
- . ' +
+
:I :
Z :r:::r:: , =: =: n=n
v~= i =-<U =n~r:~) -:I :
~ , ~ I ~=
: = \\_. _
z:=i ~ N: /u Z.' '.
N~ ; : ; : ; : : : : ++ ~
~I (~ i ~y-z" Fe "z~ =:
<, ~ H' =: II I ' \
1 H i =4rr-u~ I L /~::r:
9~ i ~uy-u~ ~ ~ ("J=i
H 20 0 <1 C =:-=: N :I :::x ::
: . .
H
H I )
H) 1
N;::::::----u=Z
/_
==~
~u~
:r:: == Z
Phthalonitrile
to
it
244
J
I
Chemical Handles
The design of chemistries capable of affecting the behavior of macro-
aggregate structures isoften approached bydrawing fromanalogous behav-
ior inother systems. An example of this kind of inferential reasoning isillus-
trated bytheuseof quasi oil-soluble/ water-solublematerials inthetreatment
of emulsions. Emulsions arecomposed of bipolar molecules that exhibit this
biphase solubility, and because they do, areasonable approach totheir reso-
lution consistsof theuseof materials that exhibit thesamequalities. Thus the
property of hi-phasesolubilitycanbeconsidered achemical handle that pro-
videsameans bywhich theemulsion mayberesolved.
Approaching thedevelopment of chemicals that possessproperties sim-
ilar tothoseof theproposed asphaltene aggregate involvesthesameinferen-
tial reasoning. What chemicals will interact with the sheath molecules or the
coremolecules toimpart additional stabilitytotheaggregate? What chemicals
could alter thecoreand enhance itsdispersion? What typeof chemical could
causethe asphaltene aggregate tobecoiled instead of extended inthe crude
oil?Cantypical parts per million dosagelevelsof chemicals accomplish stabi-
lization, or coilingof theasphaltene core, toproduce alower systemviscosity?
Examination of the proposed asphaltene structure reveals that alkyl-
substituted pyrroles surround the asphaltene core. I fthese pyrroles are dis-
placed byapolymeric analog, will thepolymeric analog hold theasphaltene
core more strongly than the individual alkyl substituted pyrroles? Further,
since the alkylated pyrroles areweaklyacidic, will asomewhat stronger acid
analog bind more completely with the asphaltene core? At this point, it
should be obvious that the process of asking the last twoquestions has pro-
vided ajumping off point for asynthetic approach. Figure 13-4 showsacan-
didate that cameinto focus bytheposing of the twoquestions above.
The possibilityof thepolymer formed inFigure 13-4 being arranged as
aprotective sheath around the asphaltene core isdetermined bythe confir-
mation of thepolymer backbone of thepolyvinyl octadecyl pyrrolidone. If the
inthesystemsbeing studied. Thus, approaching aphysical chemical problem
withonlyrudimentary understanding of it canbeaverylargeimpediment to
arriving at adequate chemical treatment methods.
This has been the case with respect to the behavior of asphaltenes.
Often approaching the solution to a problem requires that the chemist
ignore the commonly accepted descriptions of the systemand work froma
framework built fromhisor her ownexperience withthe problem. Because
the asphaltene literature is confusing, and contradicts many of the experi-
ences of this chemist, itwasnecessary to rebuild amodel that wasconsistent
with my own experiences. As aresult the proposed structures developed in
chapters 11and 12are themodels that will beused todesign somepossible
synthetic products to address the problem of preventing asphaltene deposi-
tion. This will begin by the examination of the structures and elucidating
reactivesitesthat can beused.
:--- Section III, Chapter 13
Fig. 13-4 Possiblepolymericasphaltene stabilizer
s .
Polysulfide Hemin Protoporphyrin Core
H U H
"
H I I H H H H II
en, CHI CHI en, en, CHz CH). CI I I CI I I ca, ca, CHz CEI l CHz CH2 en,
CI I I en, CHI CHz en, CHI en, CI I ). en, CI I I CHl CHI en, cu, CHz CHI
HCI --1'12I -1CI --rlzHCI --l'lzI -lCli'llz HCI --rI 1HCliHlHCliH2I 1CliHl HClilI lHCliHl11CliHzHCliB2 HCliH).I I CI --YlzHCli"lHClilll
"\ / '''' I I 'Y"'" "\ ( "'" H'Y"'" Hey"" "y"'"Hy"'"U\("" Uy"'"Hy"'"Hy"'"11\ ( "" 11\ ( "", I"V"'"11"'-14 ""'-'" "\ ( ""
I I I I I I I I I I I I I I I I
-- C~ c ---Lllr-- C----CIlr- c -Cllr--c ---Lllr-- e----CIlr- c ----Cl1r- c ~ c ~ c---LUr-- C-CUr-c ------CU:- c ~ e----CIlr- c ----Olr- c----cu,.
;,.
{l.
;:,-
'"
~
~
~.
~
~
~
'i:
v,
en,
cu,
Cllz
en,
CA,
CHz
en,
en,
CHI
en,
CHz
CHI
CI I I
CHz
CHz
CHz
CHz
CH,
en,
CI -I z
CHz
CHI
CH,
en,
err,
CH,
en,
en,
CHz
CHz
CHz
CHI
en,
CHI
en,
CHz
CHI
CH,
CHl
ell).
ell).
CI-l).
en,
ell).
ell).
ell).
CUI
CH1
ell.
CHz
CHI
en,
CI I ]
elll
en,
CH,
CHI
ca,
ClI ]
' E l i z
CH1
en,
CH,
CH,
CI I z
C",
en,
CHI
ClI ]
en,
en,
en,
CHl
cu,
Oil
CI I 2
CHl
en,
CHl
CI I .
ca,
cu,
en,
en,
CH,
01).
en,
CHz
ClI ).
e1I1
C111
en,
en,
011
en,
en,
CHl
CHI
CH1
01).
ell).
CHz
CUI .
C",
CHl
or,
CH,
CHl
err,
CHl
en,
CH).
en,
CHI
CI I I
CI I 2
en,
eHz
CHz
CI I 2
ell).
en,
cu,
en,
cu,
en,
en,
en,
en,
cu,
ca,
cu,
en,
en,
en,
en,
CI I ).
ell).
en,
en,
CII).
CI I ).
ell).
eH1
CHI
en).
ca,
CH).
CH,
Cll).
CHz
cu,
CH).
eH}
CH).
ell).
ell).
en,
CI I I
en,
CI f).
en,
en,
CUl
CI I ).
Cllz
CU).
CI I I
CIi:
CHz
CH).
CI I ).
CI I ).
CI I ).
cu,
en,
CH,
eH1
en,
CHl
cu,
CH).
en,
CU,
CHl
en,
en,
en,
CHl
cn,
CI I l
Cll:
en,
ClI :
en,
CH,
en,
Oil
CH,
CH).
Oil
en,
CH,
en,
en,
CHI
CHI
CHz
Clil
CI I ).
en,
en,
CH).
CI I ).
CHz
en,
Gil
CHz
en,
L
C---CH2-
~ ~" en ..
n
..
n
R
R '1iHZ
Hy~o
I
R '1iH2
Hy<zO
I
HC=CHz
1-Vinyl-4 -0ctadecyl 2- Pyrrolidone
- r-r-
-----~"" ..-"~""
tilii.l.ttWjj!!H!!t\ll!lh'''I"''W= 'eyMUm!!! MWlWW",WM'I I W"WW'I W,uweu'!MWWI '!!lUWtWWWI I UI lI tfWttt'ttt"rMtlltllttwwtf!I 'I WttiW''MI t,,!tfiU!!I I Hfvl;W#W'I t!"t:'W'ltIttt"'tt:I'" 'tl tttltfWrI !! UiMtlWU't II t j t t tee t I '
246
Chemical Treatment Versus Reaction
Averyimportant aspect of chemical treatment involvesthealteration of
the physical behavior of asystembythe addition of very small quantities of
chemical under conditions of temperature and pressure that prevail in the
field. Chemical reactions, ontheother hand, require specificconditions that
areseldomavailableinactual fieldsituations. Therefore, anyattempt toalter
the physical state of asystemisconstrained bythe prevailing conditions. In
addition tothese constraints, the complex components present in crude oil
must alsobeconsidered, and theproduct must zeroinontheproblem. Thus
thechemistry developed must havethepower toaffect achange inthephys-
ical systembyinteracting withtheoffending material atlowlevels, andunder
less-than-ideal conditions.
In chapter 12wesawthat complexes of phthalocyanine could beused
toselectivelyextract theFe" fromthehemin fraction of theasphaltene core.
Becauseof thestrength of thiscomplex, itseemsthat theprecursor molecule
phthalonitrile could be useful in addressing some of the physical problems
associatedwiththeasphaltene aggregates. The useof complex formation for
altering theasphaltene aggregatewassuggested inchapter 12incombination
with well acidizing programs. Thus the processes of development benefits
fromaknowledge of practices and procedures that havebeen effectivein
seemingly unrelated areas.
The question of whether or not the extraction of the iron fromthe
hemin group of the asphaltene corewill act tostabilizethe aggregate isstill
not answered, but a plausible argument for potential stabilization has
emerged. Byremoving theFe2+ fromtheasphaltene core, streaming potential
forces associated withthe iron complex or hemin havebeen reduced. The
reduction of streaming potentials resulting fromtheinclusion of iron inthe
coreshould enhance thestabilityof theaggregate. Figure 13-5indicates why
removal of ironfromthehemin couldpossiblyleadtolower streaming poten-
tial forces.
Figure 13-5illustrates the possible extraction of iron fromthe hemin
group of the asphaltene core bythe formation of the phthalocyanine com-
plexformation fromtheaddition of phthalonitrile. The resultant polysulfide
protoporphyrin core loses its surface charge, and the phthalocyanine iron
complex isreadily dispersed inthecrude oil matrix.
The polysulfide protoporphyrin core still presents aproblem because
of its high molecular weight and matrix extensibility, which isexhibited as
high viscosity. Thus, some method of cleaving the polysulfide links under
mild production conditions would appear tobeanapproach.
intended protective polymer cantakeaspiral form, and theunshared pair of
electrons of thenitrogen caninteract withthe core, then aprotective sheath
couldbeformed. Thisprotectivesheathwouldbeconsiderably lesssensitiveto
stripping forces, because of itsincreased molecular weight and largenumber
of delocalized electrons onthenitrogen of thepyrrolidone ring.
:--- Section III, Chapter 13
s .
>-
~
;:,-
' "
~
~
~'
~
~
Charge Neutral Surface
Iron
Phthalocyanine
Extraction
" Phthalonitrile
J). ."
::) i Uo-,\>-.
"I., 1 1 1 <;
_[ N' ~
N r i ? '
t=ZI\1 1 " ' "
r=. " (' l"
"~~ 1 j" Core Iron
"Z+ ,,
H J
" ,0 )' :t' ;' \~f )::
< / J /
I I,
t=N, ,N' \
/ ' ~'
Z "j I
~
,;" ,.,----,
' l s . r-:
" ti v [ . ~
)1-,\ H . U,y
"
H
Partially Positive Surface
Fig. 13-5 Removalofironfrom hemin
&
' C"'.1 ---' ,-.;1 ' "~'''' , -<;1 " <" ,
~-<!I:;1' :)E ' ~1 l,-5_';!lr-I!~ ).,?-""'_CII, -1 5, ( ": ,...c.... ' .7 .1 t-C1 I,-s......( : 1 I,._...J: .,,.~r..- ~ll, -1 S-
") 'i " :1' -, /i=c" " " " : ' - " ' " i:: -N...,_1 .'1 I '~I 1 \ ,l:.-f..... l1 '1 1 1 \[: \ ' 1\
I" . . 'lC1 I, 1 1 . : '1 \1 .: 1 1 , II. ,Ct\, 1 \) ~. ""IICll,
t'P ):?:;<" p" " 'n)2}.,;<' " OO" ~;<" " ' ' ' ' ' ' ,~, " ,~" ,,,,,,,
" " " ::::;' 1' \" :' ;:~ll" ,~_;;;:;~" ,,~~~~:" " ~~~),,
___' ~~bA<:" " ' 1I J 1~.)....' cA~~" ,,~,....~A, __""'n II~A -.....,,....t~;: v.},, 1i~,....l' cA(" " " ,"
~" , ,,-" " - -- - -0 1,- -.,- - .. - _- - -( 1 1 ',- otI_ -)1-- - - - -crf! _.u _ ..!' ..., ... _'!,. _.!!_
~ - - - -
, , , , ,
, ~ , I
~HJ m~ ;I~ ' Il;)
~ ~ ~ ~
~ ~ ~ ~ ~
-----: C: cS: j: : - --: : ciX J~: --: : ( : : ( : ( 5,: : --: : cr~tj,: --: : CX X j(
" " " II ~ U " " " II" " I' " ' '
j~
,:~
I I I I I
~ ~ ~ ~ ~
~ ~ ~ . ~
F,., ' I' " ' " " ' II;, ' ,U
' It,- -U- - 1-;- - - - - -'m- ,,- -,,- - - - - -',....- 11 - i,----_~"l.. -!I' " -...,. .:u , , _ _ , ... _ tI __ ' _
~:C ' X :lJ I:: ~:C ' t.>:(J .:' ,::(X X )I,' : ,~: CX JX ),J: ::C X ' X ):,'
" Il" II" 11 " I( II " II II )I 11 "
t" -' ::r;i!..1.:. )c ~ 6 = < .. ' .r,,,,,,,~:~" )I' At5=.' ' ' ' . " " 1' -r' : : & . I:.~~)=. ,rc".....~::;J :\" .~;)=. ' ' ' ' 1' -
' " ' ,,, <;;:.:K ." O" "c ':, , " ,2-" ,,,
u[. H .In~ lit) . #I: ~ " K II, II : . ' \<..:U, II' , " ueli,
~'- ~ ,u,-!: U,cOOII 'h, ..'~1 ,-ct1 f: 0I1 \1 ~q.I' 1 \;-<: 1 1 ,( : 001 1 ~1 1 1 ,"': ;l1 rOIlIl
\l( )( l( '.C~;;~~;: -n, II( )I.)CC~~' ]\( )( lCUI, n, lI( J( I( ;CII, II,
"~~~~l'" "r--';Y1 i" "~"f--!l'" "~--;: ~1 1 " "";--';--!1 1 "
___' ~:~;A,," " " " It 1l~..J ..::::-..:AC " " " " " 1 \I' ~....... ~:A," " " ' I\ IJ ..::::-c.)~..J .::: .. p."": " II).::::-.:A:A" ....... II
i: : : -,r -1 1 ' - - - - - ~: : - ..,,- - II- - - - - -~~: - -" - _11_ - - - - ~-:: _ !.!. _ .2' ~t_'!. _ ~ _
, ' l' I
'"
-<..
-,
" oiii_IIIIY " IIINIIII*ln' *IIIII' llllilliHlllliM iI NM IIM IM lllilIl_1ill1illl1liIlIiiiIliiHlllrilillilllllilliltllllllllmlllllllk llmll" IIIIIIIIIII.m ............ ' ." " ...... ," " ," " " " " " " " " " .. " " " " " ." " " " , ..,,,,,,,,,,.,,.,,,,
248
Combination Product
for Treatment of Asphaltene
Atthispoint inthediscussionwehaveproposed possibleanswerstothe
questions posed at the beginning of this chapter. All of these proposed
answers are only suspected to be valid, since they have not to date been
Radical Reactions with Sulfur
Radical reactions with sulfur, and substituted alkyl sulfur compounds,
areverycommon inpolymer technology. Mercaptans (CnH2n+lSH)havelong
been known for their chain transfer capability and are commonly employed
asmolecular weight modifiers inpolymerization reactions of vinyl monomers.
The hydrogen of the mercaptan isreadily abstracted byterminal radicals of
the growing vinyl polymer chain. This abstraction process terminates the
growth of thepolymer withhydrogen provided bythemercaptan.
The resulting alkyl sulfideradical canthen goon toinitiate polymeriza-
tion of anewvinyl polymer chain, formadi-sulfidebyradical-radical reaction
with another mercaptan radical, or abstract aproton from another proton
laibilesource. Sulfur andmercaptan behavior, asdescribed above, arealsocon-
sistent withthe asphaltene corecomposition. The problem, however, remains
unsolved. What typeof radical reaction cantakeplacetocleavethesulfidelinks
without being spent on themetalspresent at conditions present inthefield?
The radical used to attack the polysulfide links of the core asphaltene
must beenergetic enough topenetrate theprotective sheath, causeheterolyt-
ic cleavage of the R-S-R,and produce ahydrogen-terminated R-SH. Itmust
alsobeinsensitivetometal radical interaction and capable of producing arad-
ical that continuously propagates thedesired cleavage (betrulycatalytic).
This excludes peroxides, because they are reducible by the iron, and
produce variousforms explosiveethers. Azonitriles arerelativelyinsensitiveto
metals, and decompose onheating toformreasonably energetic radicals, and
therefore could be considered. They are verysensitive to decomposition by
heat, and prolonged periods of storage at moderate temperatures. One addi-
tional possibilityinvolvestheuseof anasymmetrically substituted di-alkyl sul-
fide. Figure 13-6illustrates theformation (and self-propagation potential) of
vinyl benzyl tertiary mercaptan.
What type of catalytic reaction can be used to cleave the polysulfide
linkswithout being too costlyor too drastic? Di-alkyl sulfides aresusceptible
tooxidation reactions, free radical reactions, and acidic reactions. However,
oxidation reactions aredangerous and require considerable amounts ofreac-
tant toaffect achemical reaction. Much of theoxidizing agent would alsobe
spent on the iron complex and other reactive compounds present in the
crude. Reducing agents and conditions are also considerably more drastic
than those typicallyencountered in production operations. This leaves the
radical reaction procedure astheonlyrealistic possibility.
:--- Section Ill, Chapter 13
}.
~
~
;:,..
~
~
"'
~
~.
~
; : ; : .
~
Fig. 13-6 Formation and self-propagation of vinyl benzyl tertiary mercaptan
Self Propagating Mechanism
ProtonAbstraction
~
~
,
,
- - - - - - - - - - - - - - - - - - ~
I I +i S+
/
/
Vinyl benzyl tertiary
butyl mercaptan
~
/
s+
/
,
------. . R-S + R-SlI +
R-S-R +
s+
Styrene
tertiary butyl
sulfhydride
~
+
H S+
/
/
t-o
.....
'-D
~i.ij lu lij ~I ~~W I I I I .~~i~iij illliillllll' ij lllll! li~ij ij mlliI lilllllllllllliI O O W liij llllll' ll~I I .I I I I I I I I I I iI i." ' I I I I I I I I I I I I _ I I lIn. 1I'111I11' 11111111111111 , lIlIlIIlIllIlllilllllil 1II1111T ; lU Ilillilllllnllm, I. flll i11111111 II . II lIilil I 1II11111111! II I I I : M". I' I iI MI I I I I I .I ' II" H........ '
250
~.
Barrow,GordonM.Physical Chemistry. 2d. ed. NewYork:McGraw-HillBook
Co., 1966.
Lehninger,L. Albert.Biochemistry: The Molecular Basis of Cell Structure and
Function. NewYork:WorthPublishers,Inc., 1970.
Rodriguez,Ferdinand. Principles of Polymer Systems. NewYork:McGraw-Hill
BookCo., 1970.
Seymour,RaymondB.Introduction to Polymer Chemistry. NewYork:McGraw-
Hill BookCo., 1971.
References
Summary
Thepreceding chapter discussedsomeof themethods usedfor the
characterizationof asphaltenes.Themainemphasisinthesetestmethodolo-
giesisthedeterminationof thephysicalbehaviorof thesesystemsunder dif-
ferent conditionsof pressure, temperature, and shear.Additional methods
weresuggestedfor thedetermination of molecularweight,microwavetech-
niques, and complexformationanalysis.Thischapter alsoemphasizedthe
relativelypoor understandingof thechemical natureof asphaltenesthathas
resultedintheverylimitedmethodsof analysis.
Theprecedingchapter wasalsointendedtoillustratethethought pro-
cessinvolvedindevelopingchemistriesaimedat thesolutionof aspecific
problem. Thestartingpointforthisprocessistheformulationof appropriate
questionsandarational approachtoansweringthequestionsposed.Another
aspect of this approach involvesthevalidityof the proposed structureof
asphaltenes.Theentireschemecouldfalllikeahouseof cardsifthestructure
isvastlydifferentthantheoneproposed. Nevertheless,researchinvolvesthe
takingof risks,but earlypreparationandthoughtful approachesreducethe
risksinvolved.
appliedinreal asphaltenesystems.Thevalidityof our proposedstructurefor
asphalteneaggregates,thereactivityof theproposedadditives,andtheend
productsof thesereactionsserveonlyasamodel for themethods usedto
developchemistriesfor thetreatment of complexsurfaces.
However,if theapproachtakenprovestohavemerit, itcanbeextend-
edtoincludeother possibleapproachestosolutions.Thus, fromtheabove
discussiona systemof products including analogous chemistries to the
polyvinylpyrrolidone, phthalonitrile, andvinylbenzyl tertiarybutyl mercap-
tancouldbecombinedandusedtotreatproblemsof asphaltenedeposition.
:--- Section III, Chapter 13
251
Some Physical and Chemical Testing
Oneof themost difficult problems tosolveprior tothefieldapplication
of anytreating chemical dealswiththeformulation of chemistries that effec-
tivelytreat problems withintheconstraints of thesystem. Satisfactoryphysical
characteristics of the treating chemical are included as apart of the con-
straints thesystemdemands. If achemical freezes at 50F, itsapplication in
areas where the average ambient temperature isbelow 30 F isill-advised,
sinceit wouldbefrozen most of the time. Most chemicals that areadded to
wells, transfer lines, or storagefacilitiesarepumped, andfrozen materials will
not lend themselves to pumping. Therefore, blending of the activeingredi-
ent isnecessary tofacilitates itsinjection bypumps.
The process of blending canbeveryinvolvedand requires agreat deal
of expertise and physical testing methods to assure acompatible product is
provided tothe usagepoint. Manyof the test procedures can beapplied to
the entire product lineof aspecialtychemical company, and specific chemi-
calsrequire some special tests. In this chapter an effort will bemade to list
someof themethods used byspecialtytreating chemical companies todeter-
mine if theproduct/products aresuitablefor shipment. Generally thisfunc-
tion isperformed byaquality control group for thepurpose of assuring that
the product to be shipped fallswithin certain guidelines of chemical and
physical behavior.
}.
14
Physical Properties of
Treating Chemicals
I
I
~
252
Gel permeation chromatography
Molecularweightsof waterinoil de-emulsifiershavebeencorrelatedto
their efficiencyintheresolutionof extremelysmall (stable) emulsions,thusa
measureof themolecularweightof certainproductshasbecomeanimportant
Nuclear magnetic resonance spectroscopy
Another method that hasbeenemployedfor control of oxideadditions
involvestheuseof nuclear magneticresonancespectroscopy(NMR).Thistech-
niqueisparticularlyvaluablewhenparent moleculessuchasphenolicresinsare
employedasthenucleusfor epoxidationreactions.Thearomaticprotonshifts
aresufficientlyremovedfromthemethylene,methine, andmethyl protonsthat
aratiocanbedeterminedbyintegratingthepeaksateachabsorptionfrequen-
cy.Figure14--1showsarepresentationof thistechnique.
Therearelimitationstothismethod, andoneof themostsignificantaris-
eswhentheparent moleculeisthesameasthe subunitsadded through the
propoxylation.Agoodexampleofthisisfoundwhendi-propyleneglycolisused
astheparent, whichisoftenthecasewhenhighmolecularweightpolypropy-
leneoxideproductsaremade. However,theNMRanalysisprovesvaluablewhen
mixedpropylene/ ethyleneoxidereactionsareperformed, sincethemethylpro-
tonsof thepropylenecanbecomparedtothemethineandmethyleneprotons
adjacenttotheoxygen.
Chemical Tests
Hydroxyl numbers
Duringthemanufacturingof propyleneandethyleneoxideproducts, it
isnecessarytodetermineif thereactionhasproceededtothesyntheticspecifi-
cations of the product development chemist, When a parent molecule is
propoxylatedtoformthesecondstepproduct inamultiphaseoxideproduct,
itisnecessarytomonitor theextent towhichthereactionhasproceeded. Just
after themanufacturingprocedurehasreachedatheoretical chargeof oxide,
andthepressurehasreceded, asampleistakentothelaboratoryfor analysis.
Onetypeof ananalysisthat isperformed employsaceticanhydrideto
acylatethe terminal hydroxyl unitspresent in themolecule. Thisreactionis
performedbytheadditionof apyridineaceticanhydridemixturetoaweighed
amount of product. Thepyridine/acetic anhydrideisaddedsuchthat thereis
anexcessof aceticanhydridetothehydroxylfunctional of theoxideadduct.
Theproduct/acetic anhydridepyridinemixisheated torefluxtoassurethe
reactioniscomplete. Oncethereactioniscomplete, water isadded, and the
aceticacidformedfromthehydrolysisistitratatedagainstablank (asampleof
refluxedaceticanhydride/pyridineminussample)withastandardnormalityof
sodiumhydroxide.
Theacetateester of thehydroxylfunctionof thesampleisnot available
for titration, andthedifferencebetweentheblankandthesampleistakento
represent thedegreetowhichtheepoxidationreactionhasproceeded. This
testiscommonlyreferredtoashydroxylnumber testing.
:--- Section 111, Chapter 14
Fig. 14-1 NMRanalysis of phenolic resin
}.
.._ ,
:0<'
~
~.
9
~,
1 ::
1:;'
~
'1l
~
~,
1!l
~
""
i:l,
~
PPM (Megaherz)
Propoxylated Tertiary Butyl Phenoxy Resin
to
'.I,
",
:'I I I !lI I ~lI i MI I !lI I Nlij _ .I .I .I Mllllm I NI I I I N'I I I U I .I I I I ""ij li.lliI I MllI I I MI .1I I MllI I iiI Nliillillu NlI I I U U liI I llllllliI I I NllflI NI H I tI I I I I K I liU lilllllll.I !I "I I MI I MI lI lI I I I I I I I I I I llhlllllll"I I MI lI llI iNI I I lI I lI I I iI I I I I !I I I I ""I I I tI NlllllllliI tliiI I M"Nlln, "1I I 1"lI lI I lftllllllll"I I I I I I "lq l.I I I I ~I I I ~""I I I ~I "I H 'ij "I _ ""I !I , "11 1 1 1 .""'"'1 '., , "" 'iii' 1 '" .. "".,,,,,,.,,_ ... ,
254
Viscosity measurements
When chemical treatments areapplied infieldapplications, theyareusu-
allyapplied through theuseof pumps. Therheology of theproduct isanimpor-
tant factor inthe abilityof thepump tomovetheproduct. Iftheviscosityistoo
Sedimentation stability
Polymer molecules remain suspended under ordinary conditions because
the kinetic energy of the solvent molecules (Brownian motion) isvery much
greater than the sedimentation of the force of gravity.However, aggregations
can form between polymer molecules and settling can occur. Thus the tech-
nique of ultracentrifugation isusedtoforcetheseaggregations tooccur, andthe
resultant increase inaggregate massincreases the likelihood of sedimentation.
This technique isusually performed on capillary tubes of sample, and after a
period of several minutes at high speed, the sample isvisuallyinspected for
phase separations.
Physical Testing
Freeze-thaw stability
The stability of field treating chemicals under widely variable condi-
tions of moisture level, environmental temperature, and applied pump shear-
ing forces plays avery important role in determining whether the chemical
will besuitable for sale. Because of this, physical tests are conducted that are
exaggerated approximations of the conditions towhich the chemicals will be
subjected. Freeze-thaw testing isone such test, and it consists of exposing the
chemical tocyclesof temperature that areextremes of those expected infield
applications. The sample isplaced in an oven at 140F and held there for a
minimum of 1day. After the sample has been exposed to 1400 F for 1day it
isplaced inafreezer at -40F,held for 1day, and the cycleisrepeated at least
4times. The sample must not separate into phases or change in appearance
over this period, or it will berejected.
part of quality controL Gel permeation chromatography (GPC) iswidelyused
for this determination. Naturally occurring macromolecules have been frac-
tionated for yearsbyuseof columns packed withaqueous dextran gels. Thissep-
aration isbasedontheselectiveseparation of thepolymer molecules, whichpen-
etrate therigidgel structure constituting thestationary phase inthesecolumns.
Crosslinkedpolystyreneresinsareswollenbyappropriate solventsinorder
to utilizethis technique for the separation of many synthetic polymers. Bythe
use of appropriate liquid-solid elution columns, it ispossible to characterize
molecules assmall ashelium and aslarge asmacromolecules with an average
molecular weight of 100million. Commercial GPCunits employ the change in
the index of refraction with concentration for specificpolymers indilute solu-
tion. Sigmoidal curves areobtained when the elution volume isplotted against
thelogarithm of molecular weight.
:--- Section III, Chapter 11
255
Barrow,GordonM.Physical Chemistry. 2d.ed.NewYork:McGraw-Hill BookCo.,1966.
Lehninger, L.Albert. Biochemistry: The Molecular Basis of Cell Structure and
Functum: NewYork:WorthPublishers,Inc., 1970.
References
Summary
Thepreceding chapter discussedaverylimitednumber of teststhat are
routinelyperformed byqualitycontrol laboratoriesof specialtychemical com-
panies. Theintent of thechapter wastoillustratetheextent towhichcontrol of
thechemistryismonitored, but not asanexhaustivelistingof thetestingper-
formed bytheselaboratories. Obviously,procedures for theanalysisof amines,
quatemary ammoniumsalts, phenolic resin molecular weight, aldehydecon-
tent, acidcontent, basecontent, conductivity,andahost of other chemical and
physicalproperties areperformed.
Specificmention wasmade of the hydroxyl,NMR, and GPCmethods,
becauseof thehighproportion of productstheepoxidechemistryrepresentsto
the specialtychemical companies. Representativephysical test alsoweremen-
tionedtoemphasizetheprecautions necessaryfor theprovisionof chemistries
withhighresistancetophysicalchangestotheenduser.
Specialized testing procedures
Veryoftenspecializedtestsareconducted on theproducts todetermine
their performance effectivenessin the applications for which they were
designed. Water in oil emulsion breakers are routinely screened for perfor-
manceonwell characterizedemulsionsystems,whichareobtainedonaregular
basisfromnearby production areas. The testingisperformed asdescribedin
chapter 5,wherethecrudesampleisinjectedwitharangeof chemical from10
ppmto100ppm, shakenvigorouslyfor 5minutes, placedinawaterbathat 1400
F,andvisuallyobservedfor rateof waterdrop, smoothnessof theinterface, and
completenessof treatment.
Oil inwaterde-emulsifiertestingislessfrequentlyperformed, but canbe
valuableingauging the effectivenessof theseproducts. Syntheticoil inwater
emulsionscanbeproduced byaddingasampleof crudeoil toabrinesolution,
andagitatingitwithahighshear device(e.g.,ablender). Oncetheemulsionis
formed, thechemical/chemicals areadded indosagelevelsfrom1ppmto20
ppmandvisuallyobservedfor phaseseparation. Theclarityof thewaterisusu-
allythe determinant of the chemical'sjudged effectiveness.However,solvent
extractionmethods describedinchapter 5arealsoused.
high, thepumpwill cavitate,stop, shear thintheproduct ifitisthixotropic, or
shear thickentheproduct ifitisdilatant. Thusviscosityprofilesaretakenonthe
product under varyingconditionsof shear stressandtemperature todetermine
ifadversephysicalbehaviorwillresultupon pumpingthe chemical.
Asphaltenes and Crude Oil ...:
I
I
I
I
t
1 .: . . ...
,
,I: .'
r .
,,~