PETROLEUM AND GAS PROCESSING

PRETREATMENT OF CRUDE OIL BEFORE REFINING

D. N. Levchenko UDC 665.622

At the 25th Congress of the CPSU (Communist Party of the Soviet Union), in a review pa-
per of the Central Committee of the CPSU, Comrade L. I. Brezhnev named the tenth Five-Year
Plan for growth of the national economy of the USSR as "the Five-Year Plan of efficiency and
quality."
As is well known, increases in production efficiency and in the level of commercial
product quality are highly dependent on the degree of pretreatment or preparation of the raw
material being used. In petroleum refineries, this raw material is crude oil, with minimal
contents of chloride salts and water.
The basic aim in pretreating crude oil before refining is the production of high-quality
petroleum products from this crude oil. Crude oil pretreatment is a large factor in obtain-
ing higher levels of economic efficiency in petroleum refining processes and in petrochemical
production. Even a slight reduction in the costs for crude oil pretreatment, expressed in
mere kopecks per metric ton of crude oil, will give savings of several million rubles per
year, not even considering the consequences that cannot always be represented in monetary
terms (e.g., decreases in the amount of environmental pollution, etc.).
When well-pretreated crude oil is being processed, the operating runs of atmospheric
and atmospheric-vacuum pipestill units for crude oil distillation may be two or three times
as long; other effects that may be observed are significant increases in the quantity of the
petroleum products, particularly residual stocks, and increases in the operating life of cat-
alysts in secondary refining processes.
According to data reported in [1-3], in the refining of crude oil with salt contents
below 5 mg/liter, the savings amount to $0.75 to $1.50 per cubic meter of crude oil processed,
and crude oil distillation unit operating runs are extended to 3-5 years.
When processing crude oil with a salt content of 5 mg/liter instead of 20 mg/liter, the
savings amount to about 40 kopecks per metric ton of crude oil.
In the Soviet Union, very serious attention began to be given to the matter of increas-
ing the quality of crude oil pretreatment only in the 1960's, when there was a sharp increase
in the quantity of crude oil processed, even though it had long been known that the presence
of chloride salts in crude oil causes hydrochloric acid corrosion of crude oil distillation
equipment, particularly when hydrogen sulfide is present (combination corrosion).
As is well known, chloride salts get into crude oil during the production process, as
a part of the emulsified brine water from the reservoir. The removal of these salts from the
oil involves breaking the water--oil emulsion in the dewatering process and subsequently wash-
ing out the salts in the desalting process.
Complete removal of the brine-water salts from crude oil should be carried out in the
oil fields when the crude oil is dewatered. However, some refineries are still receiving
crude that is poorly dewatered in the fields, with water contents of 1-2% and salt contents
of 300-3600 mg/liter, several times greater than the limits specified in GOST 9965-62.
The damage to the national economy from admitting such crude oils to the refineries has
been pointed out convincingly in an article by Ya. G. Sorkin [4].
The stability of a water-oil emulsion depends on its dispersity and on the crude's con-
tent of natural emulsifiers that stabilize the emulsion.

All-Union Scientific-Research Institute for Petroleum Processing (VNII NP). Translated

from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 3-6, June, 1976.

J This material is protected b y copyright registered in the name o f Plenum Publishing Corporation, 227 West 1 7th Street, N e w York, N. 1,.
. 10011. N o part o f this publication may be reprodueed, stored in a retrieval system, or transmitted, in any f o r m or by any means, electronic,
mechanical, photocopying, microfilming, recording or otherwise, w i t h o u t written permission o f the publisher. A c o p y o f this article is
available f r o m the publisher f o r $ 7. 50.

411
 Many investigators have shown that the emulsifiers stabilizing these emulsions consist
of asphaltenes, resinous substances, high-melting paraffin waxes, and ceresins [microcrys-
talline waxes] present in the crude [5-9].
However, the content of emulsifiers is still not a sufficient characteristic of crude
oil emulsifiability. It is also necessary to know the state in which these emulsifiers ex-
ist. Formation of stable water--oil emulsions is promoted only by those emulsifiers that are
in the crude oil in a disperse state (dispersions or colloidal solutions). Studies performed
at VNII NP have shown that, when the dispersed substances are removed from the crude oil,
the oil loses its ability to form stable emulsions [8]. Emulsifiers that are present in a
disperse state (asphaltenes) are adsorbed at the interface between the water droplets and
the oil, forming a gelatinous hydrophobic film that prevents coalescence of the water drop-
lets when they collide.
Rapid coagulation and the formation of a gel of colloidal asphaltene particles at the
interface is promoted by salts, i.e., by electrolytes present in the brine water.
The stability of a water-oil emulsion increases with time; i.e., the emulsion "ages."
Breaking such emulsions and washing out the salts involves great difficulties [i0]. H e n c e ,
the demulsification of freshly formed emulsions must be carried out in the oil fields, striv-
ing for maximum "removal of the brine water from the oil. The recovered brine water should
be used in the fields for injection into the formation to maintain pressure. When oil with
high contents of brine water is supplied to refineries, it may be necessary to dispose of
the brine Water by discharge into rivers, with a consequent increase in the salinity of the
fresh water.
In breaking water-oil emulsions, special-purpose surfactants known as demulsifiers are
widely used today.
The primary action of a demulsifier consists of peptization of the hydrophobic gelatin-
ous film surrounding the water droplets in the emulsion, i.e., converting the structurized
gel of asphaltic-resinous substances and wax crystals into a dispersion of oleosol, colloi-
dally dissolved in the oil.
Widely used as effective demulsifiers of water-oil emulsions are various modifications
of nonionic surfactants; these are block copolymers of alkylene oxides obtained from various
compounds, containing a mobile hydrogen atom in the molecule [10-13]. The addition of these
surfactants to water-oil emulsions in amounts from I0 to 50 ppm by weight (depending on the
emulsion stability) will lead to rapid breaking of the emulsion and separation of the water.
In the USSR, effective nonionic demulsifiers were first used in crude oil pretreatment
in 1960; previously, the most widely used material was the rather ineffective NChK ["neutral
black contact" (crude sulfonates)] [14-18].
During this time, a number of domestic nonionic demulsifiers were developed and the pro-
duction technology was w o r k e d o u t at VNII NP; these demulsifiers include OZhK, Diproksamin
157, Proksanols, Proksamins, and others [I0, 13, 17, 19, 20].
The OZhK demulsifier is used by many refineries in desalting crude oil; Diproksamin 157
is thus far used only as a demulsifying additive for turbine oils; the other additives are
still in the stage of commercialization. Hence, pretreatment of crudes in the oil fields,
and frequently in the refineries as well, is performed with imported nonionic demulsifiers
(Dissolvan 4411, Separols, etc.).
All refineries must discharge wastewaters from the ELOU's [electric desalting units],
after biological treatment, to watercourses or bodies of water, since these wastewaters are
too saline to mix with the recirculating water; hence the biodegradability of the substances
getting into the wastewaters is of great importance. All the demulsifiers thus far used are
classed as nonbiodegradable, with the exception of the OZhK demulsifier, which is 50-65%
biodegradable. Recently VNII NP has developed the biodegradable nonionic demulsifiers OMK
and ODP, currently in the stage of first commercial production [21, 22].
Demulsifiers that are completely soluble in the oil, so that they will not ge~ into the
wastewater, may also be used in refineries, provided they do not affect the quality of the
resulting petroleum products.
The degree of crude oil desalting in ELOU's has been upgraded recently through the use
of more modern process technology, efficient demulsifiers, and more modern electrodehydrator

412
 TABLE I. Crude Oil Desalting in Refineries

1971 1972 1973 1974

raw crude O raw crude O raw crude ~ raw crude ~ v

Refinery

water, salts, salm, water, salt>, ;alts, water, salt}, /Z~]

-
water, salts,
m~ / satts,
% rag/ mg/ rag/ % mg/ '"~" ~" ling/
liter liter i% mgz
liter [iter liter liter % liter /liter
Volgograd
Kirishi
K remenchug
1,8
0,84
1148
1306
18 0~6
0,7
- 859
905
9
9
0,2--0,6 15~176176
270 7
0,4
0,9
180--4175
720 6
Moscow 0,35 238 0,63 417 7 0,25 <7l~ 7 160--553710 56
1,2 1625 22 1,2 1180 16 1,4 1135 7
Novokuibv- I
shevsk "
No vo-Pototsk
0,2--1,4 29011924~
0,4
0,2--0,7
1,2
50 003 116 0,1--0,5 112--150018
0,5 390 3
< 0,9
0,16
50--2270 ~5
57 2
Novo-Ufa
Omsk 17; N4 4
0,4--1,1
1,2
20~80700 93 0,4--0,86 200--2748
1,5 206 2
0,24
0,88
100--2785
126 3

designs [17]. Another important factor is the entrance of West Siberian crudes into the pic-
ture, as these crudes are considerably lower in content of brine water.
In such refineries, such as the Omsk Petroleum Refinery, desalting gives a residual salt
content of 3 mg/liter; contents of i0 mg/liter are obtained in many refineries.
However, by no means all refineries have achieved the required degree of desalting.
There are still refineries processing crudes with salt contents of 15-20 or even 30-40 mg/li-
ter. This can be explained mainly by poor pretreatment in the oil fields and by the differ-
ing contents of water and salts in the oil received by the refineries. Of the shortcomings
in ELOU operation, we should mention inadequate operation of the second-stage desalting in
many refineries, as a result of poor mixing of the wash water with the oil.
The saline water discharged from the ELOU's, even after treatment, cannot be used in
the refinery as recirculating water; hence there is an incentive to reduce the quantity of
such wastewater.
By recycling the wash water, i.e., by using the water after the second (third) stage
for washing the crude oil in the first stage of electrodesalting, the total discharge of
wastewater from the ~LOU's can be reduced by a factor of 2 or more.
Great attention must be given to the purity of the water used in the final stage of de-
salting. By doing this, higher degrees of desalting can be achieved with small consumptions
of water [23, 24].
Any zero-discharge water system requires large of amounts of heat to be used in vapor-
ization of the water [from brine wastes] and hence can be used only in exceptional cases,
either when the need is extreme or when low-cost energy is available and the dry salts can
be utilized rationally.
In connection with the increase in capacity of crude oil distillation units, electro-
dehydrators with higher capacities are required. Commercial e!ectrodehydrators currently
used in refineries have hourly crude-oil throughput rates equivalent to 1-2 times the vol-
ume of the electrodehydrator. The development of designs for high-capacity electrodehydra-
tors and the commercialization of these designs are important tasks. In this respect, the
most promising design approach is toward the use of electrodehydrators with nonuniform elec-
tric fields.
Recently introduced in the petroleum refining industry were Model IEG-160 and 2~G-160
horizontal electrodehydrators of VNIINEFTEMASh [All-Union Scientific-Research Institute of
Petroleum Machinery Construction]. These are an improvement over vertical or spherical
electrodehydrators, but even they no longer satisfy the demands of industry. The designs
of horizontal electrodehydrators have been improved (three electrodes, dual liquid feed) in
the interest of higher capacity.
Also important is process control in crude oil pretreatment. At VNII NP, we have de-
veloped procedures for determining the salt content of crude oil (GOST 2401-62 and GOST
21534-76) and for the emulsifiability of crude oil and the content of demulsifier [25-27].

413
 It has been established that, for certain types of crude oil, the removal of water-
soluble salts does not eliminate hydrogen chloride corrosion in the distillation process
[28-30]. Such crudes probably contain water-insoluble organic chlorine compounds (or, more
precisely, organic halogen compounds) that are decomposed upon heating the oil to evolve
hydrogen chloride. It has been demonstrated experimentally that, when crude oils with high
contents of nitrogen compounds are distilled, considerable amounts of hydrogen chloride are
evolved.
This suggests that the source of hydrogen chloride evolution is the thermal decomposi-
tion of organic chlorine complexes of the type of Ni(CsHsN)~CI2, Ni(CsHsN)2[(NH2)2CS]CI2,
et c.
This view is further supported by the decomposition of these complexes when heated in
alkaline medium.
Thus a n e w problem arises in removing organic chlorine compounds in crude oil pretreat-
ment. In all probability this will require caustic treatment of crude oils containing or-
ganic chlorine complexes in significant amounts.
In Table I we present material on crude oil desalting in a number of refineries during
the period 1971~1974~

LITERATURE CITED
i. W. A. Roberts, Oil Gas J., "66, No 15, 63 (1968).
21 L. C. Waterman, Hydrocarbon Proc. Pet. Ref., 44, No. 2 (1965).
3. G. I. Kaz'min, Long-Term Continuous Runs of Process Units between Maintenance Operations
in Canadian Refineries -- Conditions for Obtaining Such Runs, and Technoeconomic Effi-
ciency (Review)[in Russian], TsNllTEneftekhim, Moscow (1969).
4. Ya. G. Sorkin, Khim. Tekhnol. Topl. Masel, No. 12, 2-4 (1975).
5. D. N. Levchenko, A. D. Khudyakova, and L. I. Ratich, Khim. Tekhnol. Topl. Masel, No.
i0, 21-25 (1970).
6. G. N. Pozdnyshev, A. A. Petrov, and A. M. Makarova, Khim. Tekhnol. Topl. Masel, No. l,
18-22 (1969).
7. A. A. Petrov, G. N. Pozdnyshev, and M. M. Borisov, Khim. Tekhnol. Topl. Masel, No. 3,
11-14 (1969).
8. L. N. Orlov and D. N. Levchenko, Khim. Tekhnol. Topliv Masel, No. 4, 19 (1971).
9. M. V. Mavlyutova, R. N. Lipovich, and L. S. Alekseeva, Nefteprom. Delo, No. 5 (1967).
I0. D. N. Levchenko, N. V. Bergshtein, A. D. Khudyakova, et al., Crude Oil Emulsions with
Water and Methods of Breaking These Emulsions [in Russian], Khimiya, Moscow (1967).
ii. D. N. Levchenko, A. D. Khudyakova, A. L. Kalitaeva, et al., Khim. Tekhnol. Topl. Masel,
No. 4, 24-29 (1960).
12. D. N. Levchenko, N. M. Nikolaeva, and A. D. Khudyakova, Khim. Tekhnol. Topl. Masel, No.
3, 20 (1963).
13. N. M. Nikolaeva and D. N. Levchenko, Khim. Tekhnol. Topl. Masel, No. 9, 26 (1964).
14. Z. A. Bernadyuk, D. N. Levchenko, A. F. Korzh, et al., Khim. Tekhnol. Topl. Masel, No.
9, 34 (1960).
15. D. Ya. Muchinskii, D. N. Levchenko, N. V. Bergshtein, et al., Khim. Tekhnol. Topl.
Masel, No. 6, 37 (1965).
16. D. N. Levchenko and N. M. Nikolaeva, Khim. Tekhnol. Topl. Masel, No. 8, 28 (1968).
17. D. N. Levchenko, N. V. Bergshtein, and Ya. I. Pinkovskii, Crude-Oil Desalting in Re-
fineries (Review) [in Russian], TsNIITEneftekhim, Moscow (1973).
18. D. N. Levehenko, N. V. Bergshtein, B. Z. Abrosimov, and Ya. I. Pinkovskii, Khim.
Tekhnol. Topl. Masel, No. 8, 5 (1972).
19. S. A. Feigin, L. I. Buchina, and D. N. Levchenko, Khim. Tekhnol. Topl. Masel, No. 12,
27 (1961).
20. N. M. Nikolaeva, A. T. Sereda, and D. N. Levchenko, Neftepererab. Neftekhim. (Moscow),
No. 4 (1965).
21. V. V. Bulatnikov, D. N. Levchenko, and A. T. Sereda, Neftepererab. Neftekhim. (Moscow),
No. 6, 3 (1975).
22. V. V. Bulatnikov, D. N. Levchenko, and A. D. Khudyakova, Neftepererab. Neftekhim.
(Moscow), No. 5, 48 (1973).
23. James A. Hart, Oil Gas J., No. ii, 93 (1973).
24. Gary E. Congram, Oil Gas J., No. 52, 153 (1972).

414
25. A. A. Khudyakova, D. N. Levchenko, and L. I. Rashich, Khim. Tekhnol. Topl. Masel, No.
i, 62 (1973).
26. D. N. Levchenko and N. I. Lavrova, Khim. Tekhnol. Topl. Masel, No. Ii, 45 (1975).
27. D. N. Levchenko and E. N. Makaevskaya, Neftepererab. Neftekhim. (Moscow), No. ii, 1
(1975).
28. V. M. Germash, V. A. Lyalin, A. V. Shreider, et al., Neftepererab. Neftekhim. (Moscow),
No. 8 (1974).
29. M. D. Shapiro, A. E. Stromenko, et al., Neft. Gaz. Prom., No. 6 (1973).
30. M. D. Shapiro, A. E. Stromenko, et al., Neft. Gaz. Prom., No. 5, 43 (1975).

HYDROCARBON GROUP COMPOSITION OF TS-I AND RT [JET] FUELS FROM

WEST SIBERIAN CRUDES

M. V. Khokhlacheva, L. O. Kogan, UDC 553.9821571.i]

A. A. Polyakova, E. D. Radchenko,
I. V. Rozhkov, and M. D. Khaikin

The feasibility of producing jet fuels from any given crude oil will be determined by
the hydrocarbon group composition of the fractions corresponding to these fuels in distil-
lation range. The hydrocarbon composition of jet fuel cuts produced from Baku crudes and
sour eastern crudes has been investigated previously [1-6].
Mass spectrometric methods [7, 8] have been used in studying the composition of jet
fuels obtained from West Siberian crudes.
These crudes were distilled in an ARN-2 apparatus with a column separating capability
equivalent to 20-22 theoretical plates; TS-I fuels were obtained, with the characteristics
listed in Table I.

TABLE I. Characteristics of TS-I Type Fuels Obtained from West Siberian and
Romashkino Crudes

GOST 10227- TS-I type fuel obtained from indicated crude

62 standard GOST 16564- IS
71 standard

Density. at 20~
g/em a
for TS-1
fuel

0.775 Min.
for RT
fuel

0.775 Min.
haim IBalyk
l
~ ~
~ ~e
~ ~
g ~5~:~
~ =o g
"S '~

I
I~
o

Distillation,
0,783 0,776 0,778 0,785i 0,789 0,789 I 0,786 0,779
~
BP 150 Max. 135 Max. 148
I
98% 141
232 143 137
249 135
230 137 {I 139 136
250 Max. 280 Max. 230 228 236 I 240 242
Initial crystallization
temp., *C - 60 Max. - 60 Max. -60,8 --60,I --60,7 -60,3
Content, % --60,8 --60 t-60, 7 --60,5
Aromatic hydro-
carbons 22 Max. 18.g Max. ,,8
I
14,2 20,4
Total sulfur 0.25 Max. 0.10 Max. ,,035 14,0
0,082 0,09 20,0
0,05 i 0,065
21,3 0'05 [I 0'10
20,1 It 0'17
15,6
Mercaptan
sulfur
Thermal stability,
GOST I1802-66,
0.005 Max. 0.001 Max. ',0003 None ,ooo31o,ooo]o,oo
quagtityof sed.in
mgll0Oml
Yield on crude, wt.~o
18 Max. * 6.0 Max. t,2
%1
13,6
13,6
14,5
14,2
17,2
19,1 23,6
174 j14
23,4 t 24,2 I 19,2
*Standard based on sequence of qualification test methods.

All-Union Scientific-Research Institute for Petroleum Processing (VNII NP). Translated

from Khimiya i Tekhnologiya Topliv i Masel, No. 6, pp. 7-8, June, 1976.

This material is protected b y copyright registered in the name o f Plenum Publishing Corporation, 227 West 1 7th Street, N e w York, N. Y.
10011. No part o f this publication may be reproduced, stored in a retrieval system, or transm itted, in any f o r m or by any means, electronic,
mechanical, photocopying, microfilming, recording or otherwise, without written permission o f the publisher. A copy o f this article is
available from the publisher f o r $ Z 5 0 .

415