CHARACTERISTICS OF HEAVY RESIDUE

PYROLYSIS: A SYSTEMATIC APPROACH TO THE

DESIGN OF FOULING MITIGATION STRATEGIES
USING CHEMICAL ADDITIVES
Christopher Russell1* and Ron Sharpe2
1

Nalco Energy Services Research and Development, Refinery

Process, 7705 Highway 90-A, Sugar Land, Texas, 77478, USA;
2
Nalco Energy Services, Downstream Technical Consulting, Block
102, Cadland Road, Hardley, Hythe, Southampton, SO45 3NP, UK
* crussell@nalco.com
Introduction
Over the last decade, there has been a marked shift in the
provenance of refinery crude slates due to diminishing reserves of so
called conventional petroleum. The trend toward relatively heavier
and sour crudes includes an increase in the occurrence of opportunity
crude blends, which present distinct problems to refiners, such as
increased occurrences of fouling and corrosion. Acquisition of
feedstock blends is usually accompanied by bulk compositional
analysis, for example, asphaltene, sulfur, and metals content, so
operators may attempt to plan refining strategy and infer potential
processing issues. Unfortunately, such analysis is not always
indicative or conclusive, and refinery processes may often suffer,
resulting in lower conversion and in serious cases, unforeseen shutdown and an outright ban on certain crude blend constituents. The
bottom of the barrel upgrading facilities are often amongst the most
effected, especially those reliant on thermal conversion, such as
visbreaking and coking, where rampant fouling and deposition may
occur. The work presented here concerns such thermal conversion
processes, with particular emphasis on fired heater process side
performance. Here, we describe a pyrolysis technique for examining
the potential fouling issues for various feeds, both those considered
conventional and opportunity, and introduce a novel method for
providing a relative ranking system, or index, which considers the
rates of surface and bulk coke formation together with intrinsic
stability parameter changes with process severity. The data provides a
unique insight into cracking behavior and has permitted the
development of a systematic approach to the selection of antifoulant
additives to assist unit engineers achieve operational targets, such as
extended run-length and increased conversion, and, more efficient
decoking procedures, both on-line and off-line.
Experimental
Residual Stability Analysis (RSA) Small aliquots of feed and
pyrolysis residue samples were made up into two toluene dilutions
(75 % vol and 25 % vol) before being titrated with i-octane. The
optically detected flocculation point (decrease in transmittance) was
then used to calculate stability values for the sample. In essence, the
method is a modification to ASTM D 7157-05, as only two dilutions
are required for determination of stability values, which results in
faster sample turn-around time.
Laser Particle Size Analysis A determination of bulk liquid
toluene insolubles was obtained using a standard particle counter.
Samples of feed and pyrolysis residue were first diluted in toluene to
0.1 % vol prior to flow through the counter. The machine provides a
numbered distribution over a set particle size range. With further
manipulation, an approximate particle volume was calculated by
assuming a spherical particle shape.
Pyrolysis Apparatus and Procedure The pyrolysis apparatus
used in this study is a modified high temperature high pressure

batch autoclave reactor. The main features include constant pressure

operation, distillation of cracked products, additive injection into
reactor during pyrolysis, and quantification of surface deposit via
stainless steel micro-reactor inserts. A detailed description of the
technique is described by Russell et al. (2010)1.
Results and Discussion
Feedstock Characterisation Instances of process fouling
excursions in the furnace tubes of thermal conversion units such as
visbreakers and cokers have been linked to certain characteristics of
feed blends, such as sodium content and other inorganic constituents.
However, evidence from the field is somewhat anecdotal, and bulk
analytical results are sometimes misleading. Furthermore, laboratory
data on fouling tendency that includes a measure of surface and bulk
coke formation is notoriously hard to find. The lack of a suitable feed
characterisation method that indicates fouling tendency has led unit
operators and service providers alike to be occasionally caught off
guard when processing opportunity crude blends, and even
misdiagnose problems and prescribe ineffective treatment programs.
A characterisation method was therefore developed by Nalco that
permits full examination of stability parameter changes and foulant
evolution with increasing severity, and thus some relative ranking of
feed fouling tendency. Although the reasons behind the variation in
fouling tendency are in the early stages of proprietary development,
the ranking system allows for a systematic design of antifoulant
additive mitigation strategies. The characterisation provides data over
a full profile covering a wide range of thermal severities, represented
by a single data point i.e. each data point represents a single batch
pyrolysis experiment. The method of course has drawbacks, such as
lack of dynamic flow, however, this is more than compensated for by
high sheer stirring, and the generation of representative tar product at
each severity that is of a quantity that allows a full range of test work.
The novel aspect of the apparatus is the inclusion of a convenient
method for the accurate and precise measurement of surface
deposition during pyrolysis.
Nalcos service package for visbreaker management includes the
installation and operation of vistar stability and solids monitoring
equipment. Nalco has developed the equipment within the research
and development department, and it consists of a laser particle
counter for the assessment of toluene insoluble particulates, and a
Residual Stability Analyzer (RSA). The RSA is based on the concept
outlined in ASTM D 7157-05, and provides a measure of intrinsic
stability (S), oil solvency power (So) and asphaltene solubility (Sa).
The S value is primarily used for unit monitoring, and may be
directly correlated to other stability monitoring methods such as the P
value. The other stability parameters, So and Sa, may be examined in
tandem to provide some indication of the formation of insoluble
asphaltene or coke precursor like material. The concept is outlined by
Wiehe (2008)2. Essentially, when the solvency power of the oil
surrounding the asphaltenes becomes less than the asphaltene
insolubility, there is the potential for insoluble foulant formation,
especially on hot surfaces. The severity at which this occurs is
different for every feed blend, two examples of which are displayed
in figures 1 and 2. Here feed blend A reveals the potential for
destabilized foulant formation at a thermal severity of 27 thermal
severity minutes (TSM), whereas feed B reveals this threshold to be
at 35.7 TSM. The data alone indicates feed A to have relatively more
fouling potential than feed B. However, as mentioned above, there is
some evidence that the concentration of certain feed constituents,
(e.g. inorganic particulates), can have a dramatic effect on fouling
potential at process temperatures. It is important, therefore, to
emphasize that the stability testing here is performed at ambient
temperature, whereas under process conditions, the point of

Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels Chem. 2012, 57(2), 1017
Proceedings Published 2012 by the American Chemical Society

instaability may welll be at a relativ

vely lower seveerity. Furthermorre,
anallytical detection limits may also play a part in caalculating stabiliity
paraameters. The primary y-axis in figures
f
1 and 2 represents coke in
mg / g pyrolysis product,
p
with fillled squares den
noting bulk liqu
uid
cokee (toluene insollubles), and filleed diamonds rep
presenting surfaace
depoosit (also toluen
ne insolubles). The
T duration of the
t coke induction
period in this study is denoted by an
nalytical detectio
on limits.

film beecomes thicker. IInstead, radical formation is thoought to play a

key rolle in increasingg surface foulannt thickness annd hardness. A
similar depositional reggime maybe appplied to the cokke generated in
many parameterrs that may be
the bullk liquid. Theree are therefore m
used too describe or chharacterize a feeeds coke generaation potential.
Initiallyy, however, the iinduction periodd duration will be compared for
each evvent described in figure 1. IIn this case, suurface coke is
depositeed after 5 TSM, followed by buulk liquid coke att 13 TSM, then
the preedicted occurrennce of insoluble asphaltenes at 27 TSM. The
order oof these characteeristics is not unnusual, but the rrelative timings
feed. For instance, in figure 2,, the induction
are uniique for each fe
period for surface depposit is very shoort, at 0.5 TSM,, whereas bulk
coke aappears at 20.5 TSM, relativeely longer thann for the feed
examplle in figure 1. T
Therefore, despiite the predictioon of insoluble
asphalteene formation ooccurring at a rellatively lower seeverity for feed
A, the ssurface fouling ttendency is actuually greater for feed B. This is
a signifficant observatioon, which is not discernable from
m conventional
analysiss. Coke formatioon rate is also a significant chaaracteristic of a
feed. Suuch informationn, including the sseverity of formaation described
above, hhave been includded in a relative fouling index:
Nalco Resid Foouling Index = {(ST)(BC ip; k))(SC ip; k)}
where: ST = stability threshold; BC = Bulk Coke; SC = Surface
Coke; ipp = Induction Peeriod; k = Rate

ure 1. Full charracterisation of feed

fe blend A.
Figu

Thhe fouling index is highly weighhted to the duration of the coke

inductioon period, as onnce this is breacched, fouling caan quite rapidly
and cattastrophically deevelop. The fouuling index is pplotted together
with a bbulk H / C measuurement of the ffeeds in figure 3..

Figu
ure 2. Full charracterisation of feed
fe blend B.
In ffigure 1, the ap
ppearance of deetectable surfacce coke occurs at
arouund 5 TSM, whiich is followed by
b an initial perriod of depositio
on,
thenn by a rapid, cataastrophic, period
d of deposition at
a around 14 TSM
M.
The three stages of surface
s
coke forrmation is a com
mmon characteristic
for every feed, with durations and
d rates at each stage
s
different for
f
eachh feed: The Indu
uction Period iss thought to represent a period of
foullant precursor transformationss (e.g. decreasse in asphalteene
soluubility via side-cchain cleavage, condensation
c
and
d dehydrogenation
of rresins, and chan
nges in maltenee solvency) initially resulting in
neglligible generation and deposiit. The point at
a which surfaace
depoosition first beco
omes significantt though must alsso be dependent to
som
me extent on both
h the chemical and
a physical natture of the surfaace
and its relative attraaction to foulantt or foulant preccursors. The Inittial
d by a gradual rate
r of deposition
n. The rate is allso
Stagge is represented
uniqque for each feeed. Over this staage, catalytic gro
owth is thought to
be thhe prevailing coke formation meechanism. The Significant
S
Stagee is
alsoo characterized by rate and on
nset severity. At
A these severitiies
how
wever, catalytic growth
g
plays an
n ever-diminishin
ng role, as foulaant

Figure 3. Nalco Foulinng Index with H / C ratio.

Ass expected, sam
mples with a relaatively low H / C ratio exhibit
relativeely higher foulinng tendency thann those with relattively higher H
/ C, ass there may bee relatively morre polynuclear aaromatic cores
amenabble for insolubiliity and coke forrmation. Feed A resides in this
set of ffeeds, and mayy therefore be cclassed as a rellatively normal
fouling feed of moderaate fouling. Feedd B, on the other hand, does not
reside w
with the convenntional feed set.. In fact, Feed B belongs to a
group oof feed blend ttypes whose prrovenance is Brrazil and West
Africa. These feeds haave a distinctlyy short surface ccoke induction
period, and thereforee a strong tenndency toward surface coke
depositiion over bulk liqquid coke formattion.
An
ntifoulant Add
ditive Program Design The data presented
above ccombines stabiliity parameters ttogether with suurface and bulk
liquid ccoke formation tendencies for tthe first time too describe feed

Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels Chem. 2012, 57(2), 1018
Proceedings Published 2012 by the American Chemical Society

foulling tendency. This

T
novel and unique
u
approach
h also permits the
t
deveelopment and recommendattion of speciifically design
ned
antiffoulant additive treatment progrrams. For exam
mple, a feed with
ha
foulling index that resides
r
in the pro
oblematic Braziil and West Afriica
zonee requires a sllightly differentt approach to feeds
f
that exhib
bit
relattively normal fouling tenden
ncies. In these cases, surfaace
passsivation is a keey step in delaaying the onsett of surface co
oke
form
mation. Howeveer, it has been discovered thatt these passivattor
addiitive chemistriees are feed specific with regard to theeir
perfformance, i.e. a particular passsivator chemisstry may perforrm
betteer with one feeed blend over another.
a
An exaample of this feeed
speccificity is display
yed in figure 4.

temperaature coke supppressant relatiive to alternattive passivator

technollogy with the saame high tempeerature coke supppressant. It is
importaant to note that,, although not rreported here, thhe activity and
perform
mance of high ttemperature cokke suppressants are also feed
specificc, and Nalco uuses the same test procedure for screening
purposees.
Ann indication of the performancce of the antifooulant program
may bee revealed by application oveer a full severiity profile. An
examplle of such a stuudy is displayedd in figure 6, whhere two stage
passivaation was usedd in synergisstic combinatioon with high
temperaature coke supprressant.

Figure 5. The perform

mance synergy of two stage paassivation with
high tem
mperature coke ssuppressant relaative to other techhnology.

Figu
ure 4. The perfo
ormance of passivator additives appears to be feeed
speccific, and is meeasured by the intensity of passsivator chemisttry
signnature under X-R
Ray microscopy.
The feed under ex
xamination in figure 4 revealls that passivattor
b performance. Also displayeed on figure 4 are
a
techhnology D has best
phottomicrographs of
o the reactor in
nserts under vissible light (abov
ve)
and focused X-Ray
ys (below). The performance iss measured by the
t
intennsity of the passivator
p
chem
mical signaturee. For passivattor
techhnology D, thee signature is most intense and widespreead
sugggesting that even
n after pyrolysiss at relatively hiigh severity, mu
uch
of thhe insert surfacee is visibly clear of coke deposit. In summary, itt is
important for the passivation
p
step
p to be perform
med on as clean
n a
ults in maximu
um surface co
oke
surfface as possiblle, which resu
inhibition, and faciliitates ease of rem
moval.
In an attemp
pt to narrow the performancce variability of
passsivators, Nalco has
h developed a passivation tecchnology that may
m
be aapplied to most feed
f
type conditiions. The techniq
que is described in
a reecent patent3. The
T process of passivation
p
is unique,
u
and rath
her
com
mplex, as it is comprised of two stages, orr two passivation
chem
mistries, which have to be app
plied separately and in sequencce.
The process is someewhat versatile, as it may be adaapted for most un
nit
t technology iss a
startt up programs. A further advantage offered by the
uniqque performancee synergy with continuous
c
dosee high temperatu
ure
cokee suppressant chemistry, which is not obseerved with oth
her
addiitive combinatio
ons. The synergy
y is significant, as
a it also perform
ms
overr a wide range of
o feed types, inccluding the problematic Brazil and
a
Wesst Africa blend
ds. Laboratory data depicting the performan
nce
syneergy is displayed in figure 5, where a dram
matic increase in
perfformance is observed for the neew two stage prrocedure and high

Figure 6. Application of two stage paassivation and high temperature

coke suuppressant over ffull severity proffile.
Here, ppyrolysis severityy is displayed ass intrinsic stabiliity degradation,
as this iis not affected bby the antifoulannt program. This is a significant
observaation in itself, as the technoloogy applied to the furnace is
differennt to that whicch may be appplied further ddownstream to
alleviatte deposition pproblems in fr
fractionator tow
wers and heat
exchanggers. In these innstances, a dispeersant type additiive is used that
may moodify intrinsic sstability, S. Thee untreated profiile is displayed
on figurre 6 in black, annd it appears thatt surface deposittion begins at a
relativeely low severity , and acceleratees into the signiificant stage as
the stabbility of the pyroolysis product appproaches 1.3 1.2. However,
when thhe laboratory deesigned additive program is appplied (two stage
passivaation and high temperature ccoke suppressannt) the profile
changess dramatically. It appears that the induction pperiod prior to

Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels Chem. 2012, 57(2), 1019
Proceedings Published 2012 by the American Chemical Society

signnificant surface coke

c
generation
n is markedly increased to a staage
betw
ween 1.4 and 1.3
3, where generaation and deposiition proceeds att a
relattively fast rate. At
A these severities, the generatio
on of coke materrial
is unncontrollable. The
T data suggests that surface co
oke formation and
a
depoosition is controlled, or inhibited
d, up to a point or
o severity, beyond
whicch there is catastrophic deposittion. Perhaps thee system becom
mes
supeersaturated, and reaches a thresh
hold beyond whiich coke formation
is unncontrollable. Fo
or a visbreaking
g unit, the laboraatory data suggests
that run length may
m
be extend
ded with stablee conversion, or
convversion may be increased with little change to run length. Forr a
cokiing unit, which operates at a significantly high
her severity, mo
ost
cokee formation cou
uld potentially bee shifted into the coke drum itseelf
and away from the furnace.
f
Depending on the objectives off unit engineers,, the application of
m
the specifically designed furnace heater antifoullant package may
r length or con
nversion, or an acceptable
a
ratio of
resuult in increased run
the two. An example of such a casse history is disp
played in figure 7,
u
where folllowing good results
r
with theeir
for a visbreaker unit,
prevvious feed blend
d, experienced seevere fouling witth the introduction
of uup to 35% of a particularly
p
prob
blematic opportu
unity crude. Herre,
the leading furnace skin tube temp
perature is displaayed for untreatted
gns.
and treated campaig

Figu
ure 7. Field data depicting the performan
nce of laborato
ory
desiigned antifoulantt additive packag
ge to visbreaker furnace.
In tthe initial untreeated run (denoted by data in red), heater tu
ube
cokiing is so rapid that
t
conversion is reduced after only 60 days and
a
the uunit shut down for
f decoking aftter 100 days. Succh interruptions in
proccessing can lead to significant lo
oss of revenue.
his
An investigattion into the fouling characcteristics of th
oppoortunity feed using the techniqu
ues described ab
bove revealed it to
exhiibit Feed Type B behavior i.e. sh
howing a high teendency to surfaace
depoosition over fo
ormation of insolubles in the bulk phase. The
T
folloowing run was started
s
using thee two stage passivation procedurre,
withh continuous high temperatture coke sup
ppressant dosaage
throoughout. In this treated
t
run the feed
fe composition
n was similar, wiith
up tto 35% opportun
nity crude, and conversion
c
target remained simillar
to thhe untreated run
n, therefore theree was not an ag
ggressive approaach
to conversion increaase. In fact, the target was to maintain
m
run leng
gth
for a prescheduled
d, larger scale, turn around. The
T treated run is
denooted by the bluee data points in figure
f
7. Over th
he initial days aft
fter
startt up, there is a dramatic diffference between
n the treated and
a
untrreated run. Simiilar to the laborratory studies, an
a increase to the
t
period of time thatt coke surface deposition is reelatively inhibitted
und 60 days or so,
s the tube metal
appeears to be apparrent. After arou
tempperature (TMT)) begins to rise, but at a signifficantly lower raate

than unnder untreated cconditions. At a run length off 170 days, the
converssion is reduced slightly to facillitate operation to the targeted
shut doown date. Howeever, over the peeriod when the vvisbreaker was
operatinng comparablyy to untreatedd conditions, tthe laboratory
designeed antifoulant trreatment packagge succeeded in increasing run
length bby 70 days, or 70 %. This is a significant inncrease that the
refineryy operators are vvery satisfied witth.
Thhe data presennted here dem
monstrates how a systematic
approacch to the designn of antifoulantt additive treatm
ment programs
involvinng precise and uunique laboratorry work can havve a significant
impact on fired heaterr performance bby effectively reeducing surface
coke foormation and depposition.
usions
Conclu
A laboratory pyyrolysis apparattus and proceddure has been
developped by Nalco too characterize aand relatively raank the fouling
tendenccy of heavy resiidue feeds by coombining stability parameters,
and a measure of buulk liquid and surface coke fformation. The
techniqque offers a meethod to distingguish between nnormal fouling
feeds aand those feeds that exhibit a relatively greatter affinity for
surface fouling over buulk liquid phase ccoke formation. The reason for
the obs erved differencees is currently uunder investigatioon. Antifoulant
treatmeent programs have been sppecially designed using the
informaation on fouling tendency, and w
whether or not thhe feed exhibits
a high affinity for ssurface fouling. In such insttances, surface
passivaation is a key tacctic, although sccreening in the rrig is necessary
as theree is some feed ttype specificity.. The variation was somewhat
negatedd by the deveelopment of a new two stagge passivation
proceduure, which also eexhibits a usefull synergistic relaationship with a
particullar high tempperature coke suppressant material. Under
laboratoory conditions, the treatment prrogram effectiveely inhibits the
onset oof significant suurface coke form
mation, and sugggests that unit
operatoors may be able to extend run length or increaase conversion.
Indeed,, the program ddescribed above was applied to a real furnace
heater oon a visbreaker, where the leadinng skin tube meetal temperature
indicateed that the treattment package eextended visbreaaker run length
by at leeast 70 %.
Referen
nces
(1) Ruussell, C. A., Croozier, S., Sharpee, R. Energy andd Fuels, 2010,
244, 5483.
(2) W
Wiehe, I. A. Proceess chemistry off petroleum macrromolecules,
RC Press, Taylorr and Francis Grroup: Florida, 20008
CR
(3) Shharpe, R., Russelll, C. A., Crozierr, S. (Nalco Co., USA).
Suurface passivatioon technique for reduction of fouuling. US
Paatent 8,092,618 B
B2, January 10, 22012

Prepr. Pap.-Am. Chem. Soc., Div. Energy Fuels Chem. 2012, 57(2), 1020
Proceedings Published 2012 by the American Chemical Society