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CORROSION
Paper No.

218
The NACE International Annual Conference
96
and Exposition

NAPHTHENIC ACID CORROSION AND ITS CONTROL

Mich~cl
J,.Zetlmeisl
I’etrolite Corporation
369 Marshall Ave.
St. Louis MO 63119

ABSTRACT

This paper first presents a brief description of naphthcnic acid corrosion and the main factors which influence
its onset and severity. After a brief discussion of traditional control methods, it proceeds to a discussion of chemical
inhibition, which is a relatively new control technique. Chemical inhibitors can bc divided into two broad
classifications: phosphorus-based and non-phosphorus-based. Three types of phosphorus-based inhibitors have been
reported: amine-neutralized phosphate esters, alkaline earth phosphonate phcnatc sulfide plus trial!iyl pbosphatc, and
thiazolines plus di- and tri-alkyl phosphates. Non-phosphorus based inhibitors include: t}liazolincs, organic
polysulfides, and sulfonated akyl phenols. A description of each inhibitor and its ct’festiveness in the laboratory
and field is prcscntcd.

Keywords: naphthenic acid, corrosive liquids, high tempcralurc corros]on, inhibitors, phosphates, phosphitcs,
phosphonate phenate sulfides, thiazolincs, organic polysuifidcs. sulfonatcxl alk!l phenols

iNTRODUCTION

Although the focus of this paper tvill be on chemical inhibition of naphthenic acid corrosion, bccausc of its
unusual nature a description of the phenomenon irnd the main factors which iniluencc it will first bc prcscntcd.
Control methods, other than chemical inhibition, will also bc discuwd.

In 1956 I)erungs assembled a summary of the tcchno]ogy dealing \vith naphtheniu acid corrosion LIp to that
time. ] He described the appearance of the corrosion as “. highly characteristic, varying with incrcasc in stream
velocity from sharp-edged, crater-like holes to sharp-edged streamlined grool’cs. ”’ I;ur(lle]morc, it was observed that
there ;as no scale lcf( behind because of the volubility of the iron naphthmmtc corrosion product More rcccntly,
Piehl has published a summary of corrclatiorrs and obscrvatiorrs (mm years of l-icld experience lvith naphthcnic acid
corrosion. z

Initial observation of naphtbcnic acid corrosion dates back to the 1930’s. Its occurrence in these early years
was confined primarily to processing crudcs from California, Venezuela, Russia and Romaniil. In recent years,
however, that list has been expanded to include crudcs from the North Sea, West Africa, China, India.

SOURCE OF THE PROBLEM

Although it is obvious that the source ol’the prohlcnl is naphtbcnlc acids in the crude, charactc]izat]on ot’those
acids is not a trivial matter. In the pLII-CSt sense naphlhcnic acid is a fi~c-mcmbcrcd aliphatic ring \\ith an attached
alkyl group terminating in a carboxy]lc acid group. as dcpic(ect in F]gurc 1. 10 p]-ac[lce. holvcver: it is an cxtrcmcly
complicated mixture of high bol]lng po]nt carhox!lic acids Very sophist] catccl anal! >tical methods such as ~:lit
Copyright
01996 by NACE International, Requests for permission to publish this manuscnpt in any form, In part or in whole must be made m writing to NACE
International, Conferences Division, P.O. BOX 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Assoclatlon. Printed in the U.S.A.
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Atom Bombardment Mass Spectroscopy (FABMS) arc necessary to distinguish the type of molecular structures in
a given naphthenic acid mix for a particular crude. ~That method showed that five and six-membered saturated ring
structures, including fused rings, predominate. ‘fhese acids occur in the crudcs at relatively Io\v concentrations (up
to a few pcrccnt by weight). Depending on the boiling points of the ocids they hecomc sclcctivcly enriched into the
heavier cuts during the distillation process and form corrosive non-aqueous clcctrolytcs at blghcr temperatures. In
short, the problcm ccntcrs on the higher molecular weight acids, rather than the smaller molecules which \vill go
overhead and aggravate aqueous corrosion in those systems

INFLUENTIAL FACTORS

The main factors which govern the onset and severity of the corrosion are: acid number, temperature, vclouity,
metallurgy, and sulfur content.1’*’4’5
’s’7 Typical locations of the corrosion will also be discussed in this section.

Acid number. The most common method of indexing crudcs according to acid content is a titration method to
determine total acid number (TAN) which is a measure of the numhcr 0[ mg KOH required to neutralize one gram
of oil. The exact amount of acid needed to CLLUSC a problcm is still in question. Neverthc]ess, some useful guidc]incs
have been reported. For instance, I)crungs puts the threshold TAN below which there is no problcm at 0.5 mg
KOH/gm oil.’ Piehl prefers to look at the specific cut where the corrosion is occurring and places the threshold acid
number in the cuts at 1,5 to 2.2 These threshold values are helpful, but should not be taken as abso]utcs. Some
authors find little correlation between corrosivity and ‘[’AN. Since the naphthcnic acids arc a mixture in any
particular crude and vary considcrab]y from crude to crude, two different crudcs ~vith the same TAN will not
necessarily have the same corrosivity. Even with the sophisticated characterization method discussed above,~
however, the reason for diffcrcnccs “in corrosivity remains unclear. One co[ljecturc is that some structures arc
stcrically hindered from approaching [he rnc[al sur[ace.

In discussing acid content and corrosivity, Craig has reported data shelving that typically only about 5’+4of
the naphthenic acids present in a crude iire corrosive.8 IIc de[ines a corrosi~c acid number (CAN) which is
ca]culatcd by converting the equivalent weight of iron lost in the corrosion process to an equi]’alcnt number of
milligrams of KOI-I pcr gram of oilx

Tcmpcrnturc. Onset of the corrosion is at a tcmpcraturc of about 420”l; (2 16“C). ‘1’hccorrosion mtc peaks at about
500-550°F (260 -288”C), and diminishes in the 700-750”F (370 -400”C) range, probably bccausc at this temperature
the acids are unstable. Obviously, the occurrence is mLICh ahovc the aqueous dc\\Jpoint: i.e. the corrosion occurs
in a non-aqueous elcctrolytc,

Metallurgy. Carbon steel is the most susceptible metal. On the other hand, the most cffcctivc rnctallurgical remedy
is 317 stainless steel. This material is very similar to 316, but has a molybdenum (Me) content of s-~’??o, compared
to z-s~. for 316. Pichl cites a critical Mo threshold of z.f~. for adequate protection from naphthcnic acid attack.

Observations that 316 is adequate arc probably owing to Mo content in the high cnd of the specification range as
was common in older castings of 316. Aluminum has also been useful, both as an alloying clcmcnt and in
aluminized coatings .t’59’i0 Its use has been Iimi(ed by its mechanical properties.

SULFUR. Sulfidic corrosion is another type of high tmnperaturc attack Its temperature range overlaps ntiphthcnic
acid corrosion, starting at about 500[’F (260”C) uod increasing l-rum there.’.’” Since virtually all crudcs have some
sulfur, the effects of sulfidic and naphthcnic acid corrosion can bc confounded. Several people have observed that
higher sulfur content tvill mitigate naphthcnic acid corrosion, prcsumahly because of stabilization of iron sLllfide
scale which the naphthcnic acids tend to dissol~c.z

Location. Naphthcnic acid corrosion is ohscrvcd in transfer Iincs, totver internals, and side-cut piping. Enrichment
ofthc acids into the gas oils makes these cuts particularly corrosive. The characteristic localized attack is frequently
observed in locations of high shear stress, sL]ch as clhoivs and do}vnstrcam of thcrmowclls In general, the corrosion
problcm is more severe whcr-c the physical state oi’ the acids is changtng. c.g J’aporizing, as in a transfer Ilnc, or
condensing, as in a vacuum tower.’”5

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CONTROL METHODS

The primrrry trrrditional control methods arc hlcnding, ncutra]iztition and metallurgy 1>Z45C
Thcuscofchcmical
inhibition is a fairly recent Lkvclopmcnt.

Blending. This method involves blcndingthe acidic crucles ivitb a low acid cruck inordcrto get the TAN below
the critical threshold value. The method is not always prac[icahlc bccausc oflilmited availability of crudcs for
blending. Also, the concept ofa safe, critical Iowcr threshold might not be valid, as discussed previously.

Neutralization. This method involves conversion ofthc :icids to naphtbcnatcs by the addition of caustic. The
disadvantage oftllis mcthodis tl]atthe naphthcntltes c:inf[)rnl \erystablcc nlulsions. Also, anexcess ofcaustic can
cause deposition, fouling, and caustic cmbrittlcmcnt. Sodium contamination of resid is also ii problcm in some
cases.

Mctdlurgical. As discussed above, upgrading the metallurgy to 317 ss is the surest method of control, Oldcr
literature indicates 316 ss, but the additional molybdenum content of 317 ss has been found to be critical

CHEMICAL INHIBITION

Traditional filming amine corrosion inhibitors areincll’cctive inthisapp]ication.’] This incffcctivcncss sterns
from inadequate thermal stability and the absence of a sulfide scale t~hich many filming amines require to 1X
effective. Inhibitors which have been found successful can bc divided into ttvo broad categories, i.e. phosphorus-
containing and non-phosphorus. Thep]lc)sl~llt) rLls-co]ltt]iniIlg for]nLl]ations are gcncra]ly more effective than the non-
phosphorus, but bring with them the concern about poisoning dowmstrcam catalysts

The phosphorus-based inhibitors lvhich have been reported in the corrosion Iitcraturc and/or disclosed as
patents use either phosplurtc esters, phosphitc esters, or l>ll(~sl~ll(~llti[
c-[~lle]l:ttc sulfides as the phosphorus source
‘rhcsc formulations miry also lMVCothcrc[>ll~I~<>l~ctl[s

Phosphate cxtcr plus amirsc. ]~A gcnclic structure nfa phosphate cstcris given in l:igure 2 l; ffcctivcncss of the
inhibitor was demonstrated in both laboratory and I-icld tcs[s The lahorator! test lvas run under the follo!ving
conditions: oil with TAN=5, tcmpcraturc of 500”1; (260”C), test duration u!’ 48 hours, qrstcsccnt I1OJVcond]t]ons,
nitrogen atmosphere.

The proposed mechanism for inhibition is formation of a phosphate complex with iron ions at the metal
surface. Such complexes arc very stable bccausc of the strength ofthc F’c-P bond.

Two successful field applications arc discussed. In the first application, corrosion rates went from an average
of 500 mpy (1 2.7 mm/y), based on inspection data, in the furnace header to nil \vith inhibitor treatment. Inhibitor
treatment consisted of high initial doses (80-90 ppm), follolvcd by maintenance dosages of 20 to 40 ppm. Treatment
also reduced transfer iinc ~1/ probe activity I’rom 50-] 0() mpy ( 1.27-2 54 nlnI/y) do]i’rl to nil.

The second field application addressed vacuum tower damage in the hea~y vacLIunl gas oil (HVGO) section,
specifically the draw tray and the packing above the dl-a~v. Inhibitor i!as added at a rate of 15 gi>d to the llVGO
return to control this corrosion. Ano[ber 15 g]~d ]vas addcci to the spray oil return to protccl the tower pac!ilng and
trays below the draw tray. About 13000 bpd I-IVGO and 4000 hpd vac bot[oms am produced. An 17R probe in the
rundown line and metal counts in tbc HVGO indicate succcss

t~en:ttc” sulildc.13 The backbone of the structure and a general

Triill&lI)h~sl)h:lt~ /~lIlfillinc eattb metal l)hosl)llon:~te-I)
approach for this type of chemistry is given in Figure 3. ‘rhc tria]kyl portion of the trial kylI>llosi>llatc can bc C1-CtO,
but trihutylphosphatc is prcfcrrcd because of i[s commercial a\’ai]ability. About 2040% of the phenol hydrosy
groups are pbosphonatcd Calcium is the prcl’c]rcd alka]inc cartb.

Typical composition contains the f’ollol~ing % conlpoLinds Ca- 1.65. 1’-1.03, S-3.2.

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It is recommended to start the inhibitor concentration high at 2000-3000 ppm for a short period of time to
build up a protective coating on the metal surface. Maintenance dosages range from 150-1500 ppm, depending on
severity of conditions.

The presence of the alkaline earth phcna(es eliminates formation of solids which can cause do~vnstream
problems.

The following conditions were used for the \vcight loss immersion coupon lab test: temperature of 500°F
(260”C), Kodak naphthcnic acid in paraffinic hydrocarbon oil (’IAN not specified), nitrogen sparge, 18-20 hours
duration, carbon steel coupons. The calcium phosphonatc-phcnak sulfide (CaPPS) and the tributylphosphate (TBP)
brought the corrosion rates from about 103 mpy (2.62 mm/y) (o 47.6 (1.2 1) and 47.8 (1.2 I mmly) respectively.
About 2000 ppm inhibitor were used. Ca phosphonatc phenatc sulfide :ilonc did not form solids, whereas TBP alone
did form solids. Combinations of the two at 500 113P + 1500 CaPPS, then 1000 + 1000, and finally 1500 + 500
gave corrosion rates of 30.6 (0.78), 33.2 (0.84) and 46.4 mpy (1.18 mnl/y) rcspcctivcly, solids not being formed
except with the last mixture.

In another set of experiments with 1V. H~S spargc a blank corrosion rate of 204 mpy (0.52 mm/y) \\’as
measured. Using only 750 ppm of the CaPPS compound there ~vas no reduction in corrosion. Using a total of 750
ppm of this compound and TBP, corrosion rates \vcrc Io\vcrcd to 2-5 mpy (0.05-0.1 mm/y) and solids formed when
the amount of TBP was greater than the CaPPS. ((]nc might co~ljccturc from the lower blank and the better inhibitor
protection that enhanced sulfide scales were being formed,)

Di- or Tri-alkyl phosphitm plus thiw.olincs. i41’

Generic chcmica] structures for these components arc given in Figure 4. lhc patent covers mixtures of
thiazolines plus varying amounts of phosphates.14 The laboratory test used the follofving conditions: high flash
solvent plus commercial grade naphthenic acid to a “IAN of ubout 16, tcmpcraturc 600”1: (3 15“C), I“AJH,S spargc,
and carbon steel tvcight loss coLIpons. Using thiazoline alone, corrosion rates were cut by greater than 50 “/o, i.e
from 141 mpy (3.58 mm/y) to 60 to 70 mpy ( 1.52-1 78 mndy). lJsing dicthy] phosphik alone corrosion rates \vcrc
Iowcrcd to about 5 mpy (013 mnl/y’). (Jsiog comhioa[ions ivitb die(hyl pbosphltc Corrosion rtitcs were clroppcd to
lCSSthan 10 mpy (0.254 mnl/y) typically. ‘1’hccombinations have the advantage of introducing lCSSphosphorus to
the system. Similar results )verc obtained using dimcthyl phosphite and dihu(y] phosphitc Trimcthy I and tributyl
phosphates also lowered corrosion rates considerably OVCI-the blank, but Ivcrc not quite as cl’fectivc as the climcthyl
and dibutyl compounds.

More detail on the use of an optimum mixture of thiazolincs and phosphates was published later.)j Both
laboratory and field data were prcscntcd, These data emphasize the need to establish a protective coating on metal
surface by treating with a high passivation dosage, ~ollo~vcd by a lower maintenance dosage.

The mechanism of inhibition by the phosphorus-based formulations involves reaction with the metal surface
to form a protective iron/phosphorus compound lvhich prevents further attack. T\vo of the authors present c~rldcncc
to support this mechanism. The ct’feet of the inhibitor on other alloys is not spcci(ical]y addressed Nc\crthclcss,
it would be a fair conlccturc that there Jvould 1X some effect, at Icast on the Iowcr alloys.

NON PHOSPHORUS BASED INHIBITORS

Thiazoiincs. As mentioned above, these compounds alone at about 1300 ppm ga~e about 50% protection, compared
to a blank, in a laboratory test.’”

Organic polysulfidcs. ” A generic chemical structure is given in Figure 5. The preferred molecular weight is in the
300-600 range. The lahoratow test lvas as follo!~rs: [cmpcraturc contmllcd autoc]avc, 18 hour weight loss of mild
steel cylindrical coupons, rotating coupons at lluid velocity >10 ll>S, ‘~AN=l 1, N2 in vapor space.

At 400”F (2040C)in the ahsencc OF lI~S 67% protcctiou \v]th 1000 ppm of an allcycllc polysull’idc lvas
demonstrated, and 3 l% pro(cction at half the dosage With 4[!4 1[2S 5S[!4-X()%,pro[ec(lon ivas ach]cvcd with 500-

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1000 ppm of an aliphatic or alicyclic polysulfidc. At 5000 F and 500-1000 ppm of organic polysufide 30-70%
protection was achieved.

Sulfcsnatcd alkyl phenols.’7 This structure is given in Figure 6. This patent discloses use of alkyl phenol sulfonic
acids as inhibitors in crude oils and gas oil with a TAN of 3.5 to 5.5. As high as 76°/0 protection was observed with
10,000 ppm inhibitor(nonylphenol su]fonic acid in this example) in a laboratory test at 500”F (260 “C), At lower
doses the following was observed: 500 ppm-40% protection; 200 ppnl-50%; 100 ppm- 21°/0. In the same
laboratory test dodeclybmu.ene sulfouic acid aggravated the corrosion, and diiilkyln:]phtlla lenc su]l’onic acid,
neutralized with cyclohexylarnine, gave about 12“/0 protection

One other application of chemical to alleviate naphthcnic acid corrosion is the usc ofamines to malw amides, )l
Since this process involves a stoichiomc(ric rcac(ion between the carboxylic acid group and the amine functionality,
it is not strictly speaking inhibition, but rather more like ncutra]ization. The same paper that discusses the usc of
amines also mentions successful application of an inhibitor at 1000 ppm to reduce naphthenic acid attack, The
authors did not discuss the chemical nature of the inhibitor.

CONCLUSIONS

1. Both phosphorus-based and ncm-phosphorus-based chemicals ha\)c cffcc[cd significant ICVCISof naphthcnic acid
corrosion inhibition.

2. Phosphorus-based inhibitors arc gcneral]y more el’fcctivc. but cause concern about potential poisoning of
downstream catalysts.

3. The three phosphorus based inhibitors, lvhich have hccn rcpor(cd and/or patented, involve treating first at high
dosage to establish a protective coating on the metal surface and then trimming to a lo\ver maintenance dosage.

4. Non-phosphorus based inhibitors, based on thiazo]incs, organic polysulfides, and alk~l phenol sulfonic acids,
have been reported.

5. More is yet to come

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REFERENCES

1, Derungs, W. A., “Naphthenic Acid Corrosion-An Old Enemy of the Petroleum Industry,” Corrosion, 12
(1956): p.41.

2. R.L. Piehl, “Naphthenic Acid Corrosion in Crude Distillation Units,” CORROSIONR7, paper no, ]96,
(Houston, TX:NACE International, 1987).

3, T,P. Fan, “Characterization of Napthenic Acids in Pctroleurn by Fast Atom Bombardment Mass
Spectrometry,” Shell Development Company, Elcllaire Research Center, Houston, 1991 p[>. 371-375

4. J, Gutzeit, “Naphthenic Acid Corrosion in Oil Fkfincrics,” Materials Performance, 10(1 977): pp. 24-35

5. E.F. Blanco, B. IHopkinson, “Experience With Naphthenic Acid Corrosionin Refinery Distillation Process
Units,” CORROSION/83, paper no. 99, (Houston, TX:NACE International, 1983).

6. Jayaraman, A,, Singh, H,, Lcfcb\’re, Y,, “Naphthcnic Acid Corrosion in Petroleum Refineries-A Review,”
Revue De Institut Francais Du Petrolc, Vol. 41, No, 2, 1986, pp. 265-274

7. American Petroleum Institute, “High Temperature Crude Oil Corrosivity Studies, ” API Publication 943,
September 1974.

8. H.L. Craig Jr., “Naphthenic Acid Corrosion in the Refinery,” CORROSION/95, paper no. 333, (Houston,
TX:NACE International, 1995),

9. C.A. Robertson, H.L. Myers, “Application and Use of Aluminum Coatings in Oil Refinery Processes,”
Materials Protection, September, 1967.

10. E.N. Skinner, J.F. Mason, J.J. Moran, “High Temperature Corrosion in Refinery And Petrochemical
Service,” prcscntcd at the 16th Annual Con fcrcncc, National Association of Corrosion Engineers, Dallas, TX,
1960.

11. G.L. Scattergood, R.C. Strong, W.A. I.indley, “Naphthenic Acid Corrosion, an Update of Control Methods,”
CORROSION/87, paper no. 197, (Houston, TX:NACE International, 1987).

12. E. Babaian-Kibala, H.L Craig Jr., G.L. Rusk, K.V. Blanchard, T.J. Rose, B.L. Uehlein, R.C. Quinter, M.A.
Summers, “Naphthenic Acid Corrosion in a Refinery Setting,” CORROS1ONI93, paper no. 631, (Houston,
TX:NACE International, 1993).

13. J.G. Edmondson, S.B. Pruett, “High Temperature Corrosion Inhibitor,” (JS Pat. No. 5,314,643 (1994)

14, M,J. Zetlmeisl, B.T. Outlaw, “Corrosion Inhibitors for Use in Hot I-Hydrocarbons,” U S. Pat. No. 4,941,994
(1990).

15. M.J. Zetlmeisl, “A Laboratory and Field Investigation of Naphthenic Acid Corrosion Inhibition,”
CORROSION/95, paper no. 334, (1-Iouston, TX:NACE International, 1995).

16. P.R. Peterson, F.P. Robbins, W.G. Winston, “Naphthcnic Acid Corrosion Inhibitors,” U.S. Pat. No.
5,182,013 (1993).

17. E. Babaian-Kibala, “Naphthcnic Acid Corrosion [nhibitor,” LJ.S, Pat No. 5,252,254 (1993)

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(CH2)X COOH

\ I
FIGURE 1- NAPHTHENIC ACID

o
I
HO P OH

OR
FIGURE 2- PHOSPHATE ESTER
R-ALKYL

OH OH OH

10
‘R)2Ra’@
S)(

o
(R),

H, PO 4
+

Ca O
FIGURE 3- ALKYL PHENOL SULFIDE PHOSPHORIC ACID CALCIUM OXIDE,
R-C5 TO C24, X=l TO 4, Y= O TO 9, Z = 1 TO 5

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RIO —
OR

P—OR~
0
N
$s
(R, )X

(R, )Y

I
OR2
G

PHOSPHATES THIAZOLINES

FIGURE 4- PHOSPHITESAND THIAZOLINES

RI, R2, R3, R4, R5- Cl TO C,.

R-S)( -R

FIGURE 5- ORGANIC POLYSULFIDE

R, R’- ALKY WITH C6 - C30 OR CYCLOALKYL WITH 1 TO 4 RINGS X -2 TO 6

OH

FIGURE 6- SULFONATED ALKY PHENOL R - C4 TO C20, PREFERABLY C9

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