AD-751 249

CORROSIVE NATURE OF CERTAIN MEDIA IN THE

PRODUCTION OF PETROLEUM ADDITIVES

JG. A. Aiiakhverdiev, et a!Foreign Technology DivisionWright-Patterson Air Force Base, Ohio

11 September 1972

!2

DISTRIBUTED BY:

National Technical Information ScrviceU. S. DEPARTMENT OF COMMERCE5285 Port Royal Road, Sp~ingtield Va. 22151

/I

FTD -HT-23-897-72

FOREIGN TECHNOLOGY DIVISION

CORROS LVh!' NATURE OF CERTAIN MEDIA IN THE PRODUCTIONOF PETROLEUM ADDITIVES

by

C. A. All•ikhveodiyev, A. M. Kyazlmov, et al.

ii E

Approved for public rplease; '

Reproduced by listribution unlimitea.

NATIONAL TECHNICALINFORMATION SERVICE

U S Oepartmen4 of CommerceSrl l VA 22151

P--,U C- - -L,':TA--R - A-~-

616 ho&iU, ofc aafleatca __indxinggtWIsClast.OrNIGmAT)3S ACTIVITY (Cnwi author)T; 'lt

-Fr nTedhnlology Division 341S-q IED" -ArFreSystems Command ýL GRO- -- _

S..S A irOR TFTLrc e

CORROSIVE NATURE OF CERTAIN4 MEDIA- IN -TH-E. 'f!JT0 - -'OF 'PETROLEUIK 0DDITIVES

4. 06SCRIPTIVIC NVIEBt (2yp. Of iw!. and bmclzgivo dati)

G. A. Allakhverdiyev, A. M. Kyozirnov. et al..

11 EOT DATE 78. TOTAL NO. OF PAGES 17b. NO. OF REFS-

12Ko>71 6&.COPKTRACT OR GRANT NO. 08. O;tAIGAR* REPORT NUMSKRtS)

b.POEN.73543 FTD-HTL25 -0897-72

f C. sh. wrml[R REPORT NO(S) (Any' o~ef mnbenr dmt a"y too &dal~iIC.~IT~IUTONSTATCMEs"T

Approved for public release; distribution unlbuited.

11 SUPPLEMENTARY KOTES 12. SPONSORING MILITARY ACTIVITY

Foreign Technology DivisionWright-Patterson AFB, Ohio

-A 37% aq. HCBO samn. was the most corrouiive m-ediwn for an. oiladditive (INIhP-21) prepd. by condensing an alkylphenol with11CHOO and NHi5 at 96 to 980. The corr(,ivenes.; was increasedby the presence of HCO2fl (ph 2-7). Carbon and stainless steelwere corroded at 5 mn/ye~ar arid 0.01 g/m, , re"p. in 1% HCOýHsoln. JhH40H inhibited corrosicon during additLve prod~ction.Carbon 3teels were~ corroded at 0.1 and 0.4 to 0.5 S/m .in the1l1q, and vapor phase, resp., of the condensation products dur-i~ng drying, due to the presence of water, HC02 1i, and otherevapn. products at- 1200.. [AP113861220]

.44

P~ 13/ IJ1CLA3STFIEDSecurity Classification

514. 4

16;W ZA INL -Lubricaýnt -:AdditiveJ Ir J:>ijnoIFormaldehydeCarbon SteelStainless SteelSteel CorrosionAmmonia

-- 7

ASC-TRSecriy lasffcaVo

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FTD-HT-23-897-72f

CORROSIVE NATURE OF CERTAIN M4EDIA IN THEPRODUCTION OF PETROLEUM AD.01TIVES

By:- G. A. Allakhverd~yev., A. M. Kyaziriov, et al..

English pages: 6

Source: Az-eobaydzhanskoye Neftyanoye Khozyaystvo,

No. 1, 1971, -pp. 36-38.

Requester: ASD

Translated by: AIO Paul J. Reiffi, Jr.

Approved for public release;distribution unlimited.

1'dIS TRANSLATION IS A RENDITION OF THE ORIGI-EDITORIAL COMMENT. STATEMENTS OR THEORIES PREPARED BY:ADVOCATED OR IMPLIED ARE 1ReSE OF 7HE SOURCEA1.DDG NOT NECESSARILY REFLECT THE POSITION TRANSLATION DIVISIONOR OPINION OF THE FOREIGN TECI*-OLOCY DI- FOREIGN TECHNOLOGY DIVISIONVISION. WP-AF8* OHIO.

tiifAT~r,~Ž877 Date 11 Sep~t19.72

-- A .- 4q

U. S. BOARD ON GEOGRAPHIC NAMES TRA.NSLITERA1TION S7YST~EM

Block Italic Transliteration Block Italic TransliterationA a A a A, a ? P p R, rE 6 Is Bs b C c C C S, sB a Be V, v T mT T, tr r r. G, g Y y Y y U, uAi D, d 0 F, f

Es E Ye. ye; E,e X X X X Kh, khXI~ X Z Zh$ zh UL U LIZ Ts, ts

s 3* Z' z 4 R IV Ch, chHx X u IH U 19 1W Aflu Sh, sh

RR R J Y.,y III l IU q Shch, shchKx X Kx K, k -~ biJ1 a 17A L,l 1~ ~ bNUal Y, y .M X M At -Mm M- hZ bXxH N N n 3* 3 -ip E,.e0o 0 0o 0, 0 1O0 10 Yu, yu

fi n 17 n P, p 3iR 2* Ya, ya

ye~ initially, after vowels, and after , ;e elsewhr-re.When writter as 1ý in Russian, transliterate ags y~s or V-.The use of diacritical marks is preferred, but such marks -Amay be omitted when expediency dictates.

FTD-HT-23-897-72iv

CORROSIVE NATURE OF CERTAIN MEDIAIN THE PRODUCTION OF PETROLEUMADDITIVES

G. A. Allakhverdiyev, A. M. Kyazimov,V. G. Yusifov, S. M. Efendizade,

A. F. Agalarova, and R. G. Gadzhiyev

'The production of petroleum, additives is of great importance

to the improvement of the working properties of lubricating oils.

However, the use and separation. during the individual stages

of synthesis, of a number of substances which display a highly

corrosive nature, causes the destruction of the equipment and

distribution 'Lines of commercial facilities.

Corrosion in the production of an additive which possibly is Z

Snot so great as to cause destruction of the equipment can, however,

facilitate the contamination of the synthesized additive with the"-.corrosion products which, considering modern-day demands for high- -

. qua~lity additives and lubricating oils, is intolerable.

Corrosion in additive produccion processes has not been

studied thoroughly nor has it been sufficiently discussed in th%-fS~literature. Investigations have been conducted only into the

behavior of certain steels during the pro.duction of alkylphenol.

,[I], and also the corrosive condition of equipment and distribi,,1.-Io

Sline~s of commercial facilities in certain Soviet petroleum addi[ ".• e:plants.VE

S--=FTD-HT-23,-897-72

G.A laherieA 4.Kainv

"A-quaintihng ourselvez. with the -corrosive condition of theeq.e~ipment in both experimental and. Id' trý al facilities has once

:'again affirmed the necessity. of studying corrosl.on in the productlon-

"of additives for the purpose of devising effective anti-orrosion

measures and e:Lectn-. the -o star-ind -economicaiiy feasible.

-materials for equipment and pipeline construction.

-- 1---- Th is'paper presents the results of experiments on the *v tJ--I corrosion resistance of certain structural materials durin6

condensation of alkylphenol with forralin and ammonia with the

subsequent settling and drying of the condensation productsiwhichar tchnological processes for INMP-21 additive; the snh•1

method and production techmiques for this additive are given s 1[2, 31. A"

Condensation takes place at 96-980 C at atmospheric pressureand mixing for two hours. Then, the condensation product settles -- !9!

out of the aquious layer in the same reaction vessel and is fed to A

the drying tower (p = 60 mm Hg, cm, t = 120 0 C). --V

The condensation process occurs in a rather complex medium:

owing to the chemical condensation reaction taking place, the

content in the system of certain of the components decreases and

the concentration of the others increase.s to a certain degree

which naturally complicates the possibility of correctly estimating jthe corrosive nature of individual components during the process.

Therefore, for the purpose of establishing the causes which have -

an effect on corrosion, it is advisable also to study the effect

of the individual components and sample mixtures of these 7 •

components on the durability of steels.

Corrosion experiments were conducted usihg laboratory

apparatus (Fig. 1) modeled after that used in industry. I -:Steel samples, prior to testing, were subject to grinding,

having been carefully degreased with ethyl alcohol, then held -in

FTD-HT-23-897--72 2

- - - - ,

44

.79

Fig. 1. 1, 2, 3 -alkyiphenol, formalin,aquious ammonia vessels; 34 - Pumps; 5-mixer; 6 - heat exchanger; 7 - condensationreactor; 8 -refliux condensor.; 9 - dryingcoL-mn.KEY: (a) To vacuum ejection; (b) To flotation.'

a desiccator for 24I h cver freshly-roasted calcium chloride,. and

weighed on spevial scales during the vapor-gas and liquid phasesof' condensation.

A comparison of' the .esults (Tables 1, 2) showed that, of' allcomponents of' the condensation process the mo~st aggressive wasAtechnical f'ormaiine (37% aquious formaldehyde solution).

Rate of corrosion invarious media g/h12 -h

Steel Forma- Aquious Alky 1.-

St.3 I.W1 ,910 00 %.%065 .C 015St. 20 e2. G1 M 214 0.102 0.100 1 0.130 0.1160

16GS 1;.623 1720 OO3() 0.035 O .C.S5 0.900Ih) O21021 0.000 Orpa 0.018 005OKhl3 '0.2131 0.171 0.0(00 OOD 0.000 0.2Khl3 1p.27, 0-252 0.000 0.0DO0 .0 21 OKh17 0.210.103 0.00 0.000 0.015 am02

p vapor gas phase; 2zh -l'iquid. phase -_

FTD-JIT-23-897-72 3

--hze n~

ji 3 41-W6. -01 AM -121-, /OO- M4

] i QD'.t 0o-cr.001---i -va ,015a AW OAW -'m54 OiOB0.1 .0.1 1, AAZIU OAIa .

1 S. - o.oiPl &ooi 0. 01,5 210 23 050 o5 0.400.9&~.1j , K2 .12 :A11 ,.02 001 1.01 ,5042483 O.4 0.42D-is ~ -iSt.20 -OM12 0.1 iO.O2 A.00 2.03 0 .21.0- 004950- 52 0.10S.V6,1.o 0011 2- - ' .00. 013 0 - .00Z 0-1 15110M-.26

3 0. 096..OJ~hl3 0.000 IM0 M00 0.000 0.165 0.140 0W0O.l0 .16005

ihl7 0.000 AM, 0( P 0,00 .00G. AM0i- 0329" 0.07- O00:i` -,~)

"- '- - 2e rat- o'~ corrosion for various brandz of carbon-st-eel-s i-n-_I torinalir .-a~ll as -in the liquid and vapor-jgas, phases..)- was -i

-.- In this medium, brand OKhl3 lKhi3, 2Kh13, and K1117 stainless

steels were the most durab~le. ..

Kh18N1OT, OKh22N5T, Khi7Nl3M2T :3teels in formalin (and also~~. in other media) did not luse even so imuch as i.Lheir metallic luster,

while OKhl3, lKhl3, 2Khl3, and Khl7 steels tarnished and were coated1.1' with notCiceable corrosion spots mairJ-y on the sample faces. Carbon Ksteel samples were coated with-a loose and easily removed layer ofdark-grey condensation products in the-liquid phase (b) and brown

~ Irust spots in the vapor-gas phase (a) (Fig. 2).

Following removal of the corrosion product, corrusive damai,:e

of a uniform nature was dietected or, thee surf~ace ofC carbon steel

samples.

~p

FTD-HT-23-897--724

to -hi in- -~mln a n'sgiiat -- t ---- 15-

-"-4~ - -1 a aquou -aifoi su-lto d-- -not '

The rateeve of corrosiony for carbon steels- in aiypeolrealtive

- -apparcrtly, is explained by the presence of acids (HCOOH) [4I] in

:1the formalin whit.-ij in turn can be explained by the rather low pH

of the solution (pH =2.7).

The presence of formic acid in the solution gives the later

a rather noticeable aggressive nature in relationship to certain

structural steels [5]. Thus, for example, it has been shown that

in a 1% solution of formic acid, carbon steels are subjected to

corrosion at a rate of 3 mm/year. For OKh37T, OKh22N5T, and

Khl8NlOT steels this indicator of corrosion is on the order of

0.01 g/m,

it was discovered that the medium of the condensation process

itself becomes less aggressive than the formalin solution.

In order to explain the reasons for the slow down in

corrosion under Jthese conditons3 we conducted tests in sample

* mixtures by pairing the individual condensation reagents.

-~ As a result, we established that the basic factor c-ausing

the slow down of the corrosion process is the aquious solution of

ainmcnia since the mixture of alkylphenol and formalin with

aquious ammonia solutions do not exhibit aggressive properties in

relationship to either stainless or carbon steels.

Carbon steIE-ls in an alkylphenol formalin mixture are subjez--r

to corrosion at almost the same rate as when in formalin alone.

FTD-IiT-23-897-72 5

-I•- , ',• ". .. . ,• .. _ - . .. - _.

Stainless steels Khl7, OKdl3, iKhl3, and 2Khl3 both in formalin

and during the condensation process undergo corrosion-at at

L noticeably slower rate. M1 •~I1

The rate of corrosion for carbon, st6ls in the liquid phase-2L

- of condensation products during drying did not exceed 0.1 g/m

although in the vapor-gas phase these steels corroded at a rate2of 0.4-0.5 g/m which, it is clear, is explained by the presence

of water vapor, HCOOH, and other products which evaporized during

drying, and also by the relatively high temperature (120 0 C).

BIBLIOGRAPHY

I. Ty c anon A. r. Knpposai••a• cTeOrtcccn, repr'reo-19hz =a-fI . HA-zo MciAAxprms', 1969.

2. Ky AISO A. Id. flpca,-Mcau X MCCAM1~ "13A-1:0 XHU;M-

a flpnca"xu X•mcAam. Tp. 11 Bcemosr.oro Teat.itqeatoroIt .C3Cfl.~a~N-. iz-vo .Xx= , 1966.4. Y o xop A~ ~oVauAbt ru.A. 1epean, C anri. MA, ISS?.5. I An.-a Ii, 1 Ka-.pe na A. H-. *StEmHTa xeTaA-

.o,1" X 5. T. 51. ,0.

FTD-HT-23-897-72 6