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Development of an efficient and economical process for the removal of inorganic salts from crude petroleum
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Development of an efficient and economical process for the removal of inorganic salts from crude petroleum
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Content
DEVELOPMENT
OF AN EFFICIENT AND ECONOMICAL PROCESS FOR THE
REMOVAL OF INORGANIC SALTS FROM CRUDE PETROLEUM
A Thesis
Presented to
The Faculty of The Department of Chemistry
University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Master of Science in Chemistry
by
Reagan Evans McChristy
August, 194-0
t ft 17- +
C/
This thesis, written by
REAaAH...EIAMS..MCCER,B..T.I.
under the direction of h.Xs Faculty Committee,
and approved by a ll its members, has been
presented to and accepted by the Council on
Graduate Study and Research in partial fu lfill
ment of the requirements fo r the degree of
MASTER OF SCIENCE
Deary
Secretary
Date 8~ 3! 40-
Faculty Committee
Chairman
•McCHRISTY— CRUDE DESALTING
ii
TABLE OF CONTENTS
Page
LIST OF TABLES . . . . . . . . . . ........... iii
LIST OF PLANTES. . ........... iv
PREFACE. ........... ... . . . . .. ..... ... .... v
Chapter . ' " '
I. INTRODUCTION ... ............ 2
Occurrence of Salts. ..........
Corrosion Problems . . ................
Salt Depositions ......... . . .
General Discussion of Crude Desalting. .
II. DESCRIPTION OF DESALTING METHODS’ .............. 9
Simple Washing and Settling. •••• .......... ..... 9
Heat and Pressure. . . i ........ ............ 9
Solid Contact. ......................... 10
Electrical Dehydration ....................... 10
Chemical Treatment . ................. 11
Centrifuging . . . . . .. . .. . . .. . . ............ 12
III. EXPERIMENTAL WORK.......... 13
Introductory Summary .... ............ ........ 13
Procedure. • .............. ....... .............. 15
Apparatus. . .......... ..... ......... 15
First experimental runs. .................. 18
Excelsior Contactor. ........ ............. 20
Addition of solvent .................. .... 20
Sodium hydroxide ............... 22
Glass Contactor............... 22
Improving the apparatus. ....,•......... 22
' Final Experimental Unit......... 24-
Varying amounts of alkali. .............. 27
Eliminating the solvent............ . . 31
Hard water ................. * * * V •■'33
Excelsior contactor......................... . . 3U \
IV. SUMMARY AND CONCLUSIONS. ..............................3&
2
3
6
7
BIBLIOGRAPHY
iii
LIST OF TABLES
Table Page
1. Analysis of an Oil Well Brine* .......... 4.
2. First Experimental Runs • . * ........... 19
3* Effect of Excelsior Column .............................. 21
4-. Glass Contactors. . • . • • ............................. 23
5. Varying Strength of Alkali .............................. 28
6. Elimination of Solvent.............. 32
7. Excelsior Contactors ......................... ..... 35
iv
LIST OF PLATES
Plate Page
I. Experimental Apparatus No • 1 • • ...... 16
II. Picture of Final Experimental Apparatus. ........ 25
III. Diagram of Final Experimental Apparatus. ........ 26
IV. Emulsion Stability Curve for Crude B .......... 30
V
' PREFACE.
General, methods-of crude desalting now in use are described.
An efficient and economical continuous process for salt removal
has been developed in the laboratory. It involves forming a secondary
emulsion by agitating the crude with a weak alkali solution, resolving
this emulsion, and separating the water by heating and passing
through excelsior-packed columns. A removal of 85 to 95$ of the salt
is accomplished.
The data compiled indicate that the success of the laboratory
experiments could be approximately duplicated on a commercial scale.
Desalting experiments were made on tv/o heavy California
asphaltic base-crudes with satisfactory results. Further investiga-.
tions v/ill be necessary to determine whether the described process
will be applicable to other types of crude.
A comprehensive bibliography is included.
The author v/ishes to express his appreciation, for the assis
tance of R.E. Vivian, Ph. D., Professor of Chemical Engineering at
the .University of Southern California, who directed the work.
2
CHAPTER I
INTRODUCTION
Occurrence of Salts
Crude petroleum, as it is delivered to the refiner, almost
invariably contains a small amount of inorganic salts. Usually these
salts are dissolved in the water which is emulsified with the crude
oil, but frequently they also occur in the crystalline form. These
solid particles are of microscopic size and are dispersed uniformly
in the oil. They are often associated with wax crystals or are sur
rounded by a thin layer of amorphous wax (13, IB, 37).* Roberts and
Stenzel (45) state:
In the most frequently occurring case, the salts in crude oils
consist principally of water-soluble mineral salts, originally
present in the oil as residues of the brine-in-oil emulsions
formed as a consequence of field production conditions. As receiv
ed at the refinery, these salts may be present wholly in the form
of brine-in-oil emulsions, wholly in the form of suspensions of
crystalline salts, or partly in each form. Which of these condi
tions obtains will depend upon the conditions of agitation, expo
sure, heating, and evaporation to which the oil has been subjected
in the field, in transit, and in storage. Mineral acids, for
example, hydrochloric acid, may be present in solution in either
the brine or oil; while insoluble solids, for example, "dirt",
volcanic ash, or silica, may be dispersed in either phase. What
ever their physical condition, the salts in suspension in the oil
will consist, in general, of extremely fine particles, usually
10~4 cm. or less in diameter. In general, these suspended mater
ials will be stabilized due to the presence at the interface of
concentrations of the naturally occurring emulsifying agents in
the oil.
The presence of these salts has been known for many years, but
■^References are listed at the end of the paper.
3
only recently has their deleterious effect upon refinery equipment
and upon the quality of the finished products been fully appreciated.
The percentage of chloride salts of calcium, magnesium, and
sodium in crude petroleum has increased to such an extent in recent
years that their reduction has become imperative to many refiners (5).
The exact reason for this increase is not definitely knov/n, but it
is probable that a combination of fhctors contributes to the condition.
The acid treatment of wells is becoming quite common in fields
which produce from limestone formations. This results in the produc
tion of calcium and magnesium salts by the chemical action between
the acid and the limestone or dolomite (18, 29, 3&, 37). New oil
fields are being developed which produce crude of higher salt content,
and old fields are being depleted with an attending increase in the
amount of emulsified brine from edgewater.
It is difficult to describe a truly typical example of oil well
brines for they vary greatly in composition. An illustration of the
type of inorganic salts usually present can be seen in Table 1 which
shows an analysis of an oil well brine. Sodium salts are ordinarily,
though not necessarily the most prominent, and similarly, chlorides
usually predominate, but occasionally the sulphates and carbonates
reach rather high percentages. The chlorides, however, are the most
troublesome•
Corrosion Problems
Salts in petroleum are responsible for many of the problems
4
TABLE 1
ANALYSIS OF AN OIL WELL BRINE
Radical Parts Per Million Percent of Total Salt
Sodium 11,203.0
44*39
Calcium 618.5 2.81
Magnesium
374*4
2.80 50
Sulphate
5*4
.01
Chloride 19,2.19*0 49.36
Carbonate 0.0 0.00
Bicarbonate 419.7 .63 50
Total 31,840.0 100.00
Groups Percent
Alkalies............ 44*39
Earths............. 5*61
Strong Acids........ 49*37
Weak Acids ..... .63
experienced by the producer, the carrier, and the refiner. Equip
ment, pipe lines and tanks all suffer the consequence of their corro
sive effects. When these salts enter the distillation equipment,
associated as they are with crude oil and water, the conditions are
such that they hydrolize to yield free hydrogen chloride. This acid
is especially active in the condensing sections where it dissolves in
the liquid water which is present.
It is generally accepted that some chloride compounds decompose
or hydrolize to form corrosive products in the condensing sections
of the refinery system, and that sulphur compounds are the principal
cause of corrosion at high temperatures. Puckett (4-2), from analysis
of products of corrosion, attributes the major portion at high temper
atures to the chloride salts and free acid in petroleum. He states
that the chlorides of calcium and magnesium hydrolize to produce free
hydrogen chloride that establishes an oxidation-reduction cell with
hydrogen sulphide and iron. Davis, Jones and Neilson (8) state that
in the cyclic reaction of the oxidation-reduction cell, ferrous
chloride is produced by the reaction of hydrogen chloride with the
iron; the ferrous chloride is acted upon, in turn, by the hydrogen
sulphide to form iron sulphide and liberate hydrogen chloride, which
again attacks more iron. Hanson (26) states that the corrosion cycle
is occasioned by the fact that the hydrogen sulphide present reacts
with the iron to form iron sulphide; the iron sulphide then reacts
with the hydrogen chloride to form ferrous chloride and to reliberate
hydrogen sulphide.
6
Most refiners use ammonia in combating this type of corrosion.
It serves to combine with the hydrogen chloride and thus prevent its
corrosive action. However, difficulties may be experienced from this
procedure through the deposition of solid ammonium chloride in con
densers in such amounts that the tubes become clogged.
Salt Depositions
Salt presents problems to the refiner other than those of cor
rosion. It is deposited in heat exchangers, still tubes, fractiona
ting columns, and other sections where there is a rapid heat input.
These depositions cause clogging, hot spots, and tube blistering with
their consequent loss of "on-stream" time. Frequently plants must be
shut down to have tubes cleaned with steam, water, or mechanical
devices. Even though tubes are not entirely stopped, the crystalline
deposit soon reduces the coefficient of heat transfer to such an
extent that it is no longer economically possible to continue opera
tion.
The presence of salts in charging stocks also materially affects
the deposition of coke in cracking stills ( 26, 37). This is probably
due to the fact that the salt crystals act as nuclei around which the
carbon particles deposit at high temperatures. In this manner it not
only acts somewhat in the nature of a catalyst but also serves to fuse
the coke to the tube or shell. Coking of tubes not only decreases
the length of time a still can remain in operation, but it materially
increases fuel requirements.
7
Inorganic salts which are not crystallized out in distillation
equipment are carried through the system and are retained in the resi
dual products, making it difficult for some refiners to meet solubil
ity specifications on their asphalts and road oils*
All the foregoing conditions have led to the development of
methods for lowering the salt content of crude petroleum* The most
important of these are simple washing and settling, heat and pressure,
contact with a solid, electrical precipitation, chemical treatment,
and centrifuging*
General Discussion of Crude Desalting
Crude oil almost always is associated with a certain amount of
moisture* Most of the salt contained in the crude is dissolved in
this water which usually occurs in the form of a water-in-oil emulsion.
If it can be separated from the oil and drawn off, a lowering of the
salt content will be accomplished* Since the complete removal of the
water is impractical, it is better to put in additional water to
dilute the brine so that what is left after dehydration will be fairly
free from salt. This is the procedure which is ordinarily followed.
A second emulsion is formed v/ith this added water so that both the
small droplets of brine and the tiny salt crystals can be contacted.
Fine dispersions give better removal of salt, provided they can
subsequently be coagulated and drawn off. Care must be exercised in
controlling the degree of dispersion since the particles tend to
8
become colloidal in size so that electrical effects and Brownian Move
ment (6) prevent’ settling-. ■ .
Dowrs investigations. (13) upon crude oil emulsions indicate that
asphalt is present as a hydrophobic colloid which stabilizes water-in-
oil emulsions. It has been demonstrated by analysis that more asphalt
is present at the interfaces than in dry oil. Petroleum emulsions have
been found to become more stable with age ‘ due to the adsorption of
these protective colloids at the oil-water interfaces (3> 6). For
this reason they should be resolved as soon as possible after forma
tion.
Variations of these principles are utilized in desalting pro
cesses which have been developed. These methods can be divided into
six general groups which will be described briefly.
CHAPTER II
9
DESCRIPTION OF DESALTING METHODS
Simple Washing and Settling
Very light crude which does not form a stable emulsion with
water can be desalted to a certain extent by simply washing the oil
with water at atmospheric temperature and pressure, and allowing the
two liquids to separate due to natural gravitation. This process
is slow, and large storage space is necessary for settling. Hawthorne
and Bedell (29), using mid-continent crude, found that washing the
oil through water is preferable to washing the water through oil. The
quantity of water used is dependent upon factors such as the nature
of the crude, and the type and amount of agitation. A concentrated
brine favors separation by increasing the specific gravity difference
between the oil and water phases. A weak brine leaves less salt in
the water which remains in the crude. A balance between these
extremes must be reached in order to give optimum results.
Heat and Pressure
Heat greatly decreases both the viscosity and the specific
gravity of oil thus aiding materially the separation of the oil and
water. Pressure has little, if any, effect upon the separation, but
it is necessary, when working with high temperatures, to prevent boil
ing and the loss of light petroleum fractions.
Heat also tends to expand the water droplets thus lowering the
10
surface energy of the surrounding oil film to such an extent that it
may break and allow the water to coalesce. Temperatures of 130°F.
to 3Q0°F. are commonly used with pressures ranging from atmospheric
to 175 pounds per square inch. Three to fifteen percent water is
added to the crude.
Solid Contact
Few commercial plants desalt crude petroleum by contact with a
solid, but laboratory experiments indicate the feasibility of the
process. Some of the solids which have been used with success are
cloth ( 14.), sand ( 38), excelsior (29, 30, 61), diatomaceous earth ( 15),
and other porous substances. These solid materials may be contacted
with the emulsion by stirring directly into the oil, or by acting as
a filtering medium through which the oil passes. The resolving
action is due to two physico-chemical principles. The solid is
ordinarily wetted preferentially by the water which is in the inter
nal phase, and the small openings in the filtering medium tend to
distort the tiny globules of water to such an extent that the surround
ing oil film is broken, allowing the dispersed phase to coagulate.
Electrical Dehydration
The electrical dehydration of crude petroleum is best suited
to parts of the country where power is cheap. Electric fields of
high potentials ( 16,000 to 33,000 volts) are used for breaking
emulsions, thus desalting the crude. Both direct and alternating
current are used, but the latter is more popular. Electrodes are
11
ordinarily placed about twelve inches apart and the crude is intro
duced directly between them.
Eddy and Eddy (17) studied Cottrell1s process (7) with the aid
of photomicrographic motion picture film. They says
When an emulsion is subjected to the influence of a high
potential alternating field, the minute water particles,
electrically charged by the field, rupture the enveloping oil
films and coalesce, forming larger water droplets. This action
of stress and strain, attraction and repulsion, on the conduct-
ting water particles continues until all the microscopic drops
of water in the original emulsion have broken the bonds of the
entrapping oil films, the larger droplets serving as nuclei
until the entire water content is freed into large drops, which
settle out.
Chemical Treatment
This treatment for the desalting of crude oil involves the use of
certain chemicals called demulsifiers. These chemicals are added to
the water and help prevent the formation of a stable emulsion. A
large number of compounds have been used for this purpose with appar
ent success, the most common being sodium carbonate. No one reagent
has been found which will resolve the emulsions of all types of crude.
Dow (13) has divided these demulsifiers into six classes accord
ing to their action upon the oil film surrounding the dispersed water
globules. The first group consists of chemicals like calcium chloride
which have a strong tendency to take up water. Other chemicals such
as sodium chloride in group two, cause flocculation by combining with
the emulsifying agent. Group three consists of compounds like sodium
carbonate which react with the organic acids that may be present (6).
Compounds like the sodium soaps are listed in group four and break
12
water-in-oil emulsions by their tendency to invert the phases
(3, 6, 12, 13)• Group five is composed of substances like ferric
chloride that tend to neutralize the charge on the surface of the
emulsified water, and the last group is made up of solvents such as
gasoline which dissolve the material in the protective film.
Centrifuging
Gravity separations can be speeded up tremendously by the use
of centrifugal force. Continuous centrifuges capable of handling
crude oil emulsions have been developed.
The addition of heat provides two advantages. It lowers both
the specific gravity and the viscosity of the oil, thus allowing
easier and quicker separation. Ayres (3) points out that while sub
sidence of the dispersed phase is proportional to the force applied,
centrifugal force has only a slight coagulating action, and some
reagent should be used to cause coalescence.
CHAPTER III
13
EXPERIMENTAL WORK
Introductory Summary
The complete study of crude desalting using all possible combin
ations of variables and methods would be an enormous task for one
individual. In the first place each type of crude presents a, separate
problem. A combination of factors which will work well on one crude
may be a complete failure on another. In any one of the several
general methods which may be attempted there are many variables such
as' the amount of water added, degree of agitation, type of agitation,
strength of alkali, type of alkali, temperature of mixing, temperature
and pressure of the resolving apparatus, rate of flow through the
apparatus, type and amount of chemical demulsifier, kind of solid
contactor, and time of contact.
An attempt was made to keep the present work simplified as much
as possible. For this reason alterations in equipment and procedure were
planned so that "only one variable was ‘ changed at any one time.
A complete study vra.s made of the literature. The best author
ities upon crude desalting made four general recommendations for the
most efficient removal of salt from crude oil. They.are, first, the
use of sodium carbonate as a demulsifying agent; second, the use of
a brine tank through which the emulsified crude is percolated; third,
the use of a solid contact column packed with excelsior; and finally,
the use of a settling tank of sufficient size to allow one hour or
u
more for the coalesced water particles to settle out.
These recommendations were incorporated into the experimental
desalting unit. Use of the first and third proved to be essential
while the second and fourth appeared to be of little value in the
present work. Sodium carbonate was found to be the most satisfactory
alkali, but it was used as an emulsifying agent instead of a demulsi-
fier, for the two California heavy crudes experimented upon did not
form stable emulsions when agitated with pure water. Excelsior exhi
bited a much stronger coagulating action than ground glass and gave
very favorable results when used in conjunction with the proper amount
of sodium carbonate. The brine tank and settling tank, as applied
to the present conditions, were found to have little effect upon
desalting and were eliminated.
For the sake of brevity approximately one half of the total
number of experimental runs will not be described in this paper.
Duplications will be eliminated and merely runs which lead to definite
conclusions will be discussed. It was possible to duplicate results
to a surprising degree of accuracy , which indicates that uniform
desalting can be expected on a commercial scale.
All of the experimental runs followed one general plan. A
secondary emulsion was prepared by the addition of an alkali solution
to the crude oil and this emulsion was subsequently resolved and the
water separated. Sodium carbonate was found to be the most satis
factory alkali, and it was used in a majority of the runs. Various
15.
strengths from 0.125 to 2.0$ were used, with the percentage of solu-
, . ' - ' ■ ■ ' ' ^ ■ - ' . ' ’ ’
tion ranging from 5 to 20$ by'volume *of the'crude oil charged.
Many changes were made in the equipment in the earlier portion
of the work, while the later experiments were designed to find the
best possible manner in which to use this equipment.
Procedure
A series of experiments was conducted upon two crudes to deter
mine the stability of. the emulsion formed between the oil and water. ■
It was found that when pure water was agitated with the oil the two
layers separated upon standing a few hours. However, very little salt
was removed by this simple washing due to insufficient contact with
the water. When a small amount of alkali was added a stable emulsion
was formed. This emulsion furnished the intimate contact necessary to
remove the salt. Further experiments indicated that' emulsions formed
with sodium carbonate could be resolved most easily. It.should be
noted that the sodium carbonate is used as an emulsifying agent not
as ,a demulsifier.
The major problem, that of breaking the emulsion and separating
the salty water from the oil constitutes the larger portion of the
present work.
Apparatus
Plate I shows a diagram of the small scale apparatus designed
for desalting experiments. Number (1) is the crude supply tank, a
thirty gallon drum with the top cut out. Heat is provided with a
c S s = j f J C
17
steam coil of 1/4. inch copper tubing. Number (2) Is an iron funnel
through which the sodium carbonate solution is added. The brine tank,
number (3) is constructed from 8 inch standard pipe and is 34- inches
tall. It is filled to a height of 25 inches with 2.5$ sodium chloride
solution. This level is maintained by draining through valve
number (9) • Number ( 4. ) is the solid contactor. It is constructed
from 6 inch standard pipe, is 34- inches tall, and is completely filled
with broken glass. The settling tank number (5)* is 4-0 inches of 4-
inch standard pipe placed at an angle of 30 degrees from horizontal.
Numbers (3), (4-)* and (5) are steam-jacketed.
The charge of crude is placed in the drum (1) and heated to
150°F. The sodium carbonate solution enters the system through the
funnel (2) on the suction side of the pump. Its rate is controlled
by means of a needle valve. The. gear pump (8) picks up this mixture
of crude oil and carbonate solution and forces it through the system
at a positive pressure. A by-pass arrangement (11) provides a means
of recirculation through the pump and consequently controls the amount
of agitation. The emulsified crude enters the bottom of the brine
tank (3), rises through the sodium chloride solution, and passes into
the top of the contacting tank ( 4.). It flows out the bottom and into
the lower end of the settling tank where the water is allowed to
settle and is drawn off at (6) while the dry oil is continuously
removed at (7). A temperature of 200°F., and a pressure of 50 pounds
3 ?er square inch is maintained. The rate of flow of the oil is two
18
gallons per hour and four hours are required for one complete passage.
No. 1 are summarized in Table 2. Approximately 38% of the water was
removed in the first run. A pump speed of 144-0 R.P.M. gave too
much recirculation and accordingly, too much agitation. It was evi
dent that very good contact was obtained for the salt was lowered
in direct proportion to the amount of water removed. In order to
reduce the amount of mixing, the pump speed was cut to 38 revolutions
per minute and no recirculation was employed in runs No. 2 and No. 3*
This allowed a much better water drop, but the salt was left in the
oil indicating that insufficient contact was supplied. In run No. 4
the rate was raised to 20 gallons per hour with a pump speed of 130
revolutions per minute. The poor results again indicated lack of
proper contact. Therefore, recirculation was again utilized.
No brine was used in runs No. 7 and No. 8, and although the
salt reduction was as good as in any of the previous runs, no free
water could be drawn off; only a black water-rich emulsion settled
out. Consequently, the brine was replaced.
A different type of oil (Crude B) was tried in the next few runs.
This oil is somewhat lighter than Crude A and usually carries about
twice as much salt. The amount of alkali was changed for the first
time in run No. 12. Adding 20$ of the solution gave a slight increase
in salt removal but left the water content too high for the crude to be
processed properly.
runs.--The data obtained with apparatus
TABLE 2
FIRST EXPERIMENTAL RUNS
I Run No.
! " '
Crude
CO ^
g ^
NaCl
(#/l000 Bbls
Pump Speed
(R.P.M.)
Rate
(Gal./Hr.)
Gallons
Run
Temperature
(°F.) ■
Pressure
(#/Sq.In.)
Na2C03 .
Solu
tion
Dehydrated
Crude
% Salt
Reduction
(Amt.%
of
Oil)
Conc.M&BS NaCl*
(%) (%) (#/ioo0
Rblsi^
1 A 1.5 103 1440 12 20 220 50 5 0.5 4.0
63 39
2 A 1.7 92 38
4 20 200 50 5 0.5 1.5 53 42
3 A 1.0 83 38
4
12 200 50 5 0.5 0.7 55 34
4
A 1.2 83 130 20 20 200 50
5 0.5 2.5
6l 27
5 A 0.9 83
130
4
20 200 50 5 0.5 2.0 70 16
6 A 1*2 90 130 2 20 200 65 5 0> 5 1.5
66 27
7 A . 1.2 90 130 2 20 180 50 5 0.5 1.2 56
39
8 A 0.4
76 130 2 11 190 50 5 0.5 2.0 43 43
9 B 2.2
174
130 2 20 190 50
5 0.5 4.0
143
18
10 B 2.2 174 130 2 12 190 40 5 °»5 3.4
128 26
H B 2.2
174 1440 2 12 190 50
5 0.5 3.6 126 27
12 B ,1.6 112 1440 2 12 190 50
, 5 0.5
6.8
114 35
*A11 salt figures given in this paper are calculated on the basis of NaCl.
20
Excelsior Contactor
The poor results of this first series of experiments necessitated
some change in the method, Hawthorne and Bedell (3&), in their
experiments upon desalting crude oil, found that excelsior gave better
results than other solids used in the contact method for resolving
water-in-oil emulsions. Therefore, it was decided to replace the
glass with excelsior.
Table 3 shows the results of this procedure. The excelsior was
first saturated with a brine solution in order to eliminate any possi
bility of its taking up water from the crude and thus giving false re
sults on the first test run. A slight improvement was noted.
Numbers 13 and 14 were batch runs. The system was filled and
the samples were taken after standing for four hours. That the extra
settling time greatly improved results is evident when No. 15 is
compared with No, 13* Slowing down the pump again showed a beneficial
effect in No. 16.
Addition of solvent.— An attempt was made to aid separation of
the water and oil phases by adding gas oil to the crude. This lowered
the viscosity and raised the A.P.I. gravity. Solvents of this kind
are said to have a beneficial effect other than the two mentioned
above. It is thought that they tend to dissolve the oil film surround
ing the water particles which allows the water to coalesce (13)•
Experiments indicated that the water drop was improved only slightly,
but that the salt removal was helped .considerably as is shown by
TO
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TZ
EFFECT O F EXCELSIOR COLUMN
22
comparing No. 17 with No. 16.
Sodium Hydroxide. — The result of using sodium hydroxide as the
emulsifying agent is illustrated in numbers IS to 25. Larger per
centages of alkali were added, and in two instances, No. 20 and No. 21,
the brine was replaced with calcium chloride. These experiments
indicated that sodium hydroxide could be used but has no definite
advantage. Further experimentation upon its use was dropped in view
of the fact that its cost is approximately three times that of sodium
carbonate•
Glass Contactor
Results were still far from satisfactory and it was decided to
refill the contactor with glass. A perforated metal plate was placed
six inches from the bottom to hold the glass and allow a settling
space for water. Oil was removed directly under the plate and water
was withdrawn from the bottom of the contactor.
Improving the apparatus. — The next series of runs designed
particularly to improve the apparatus, was tabulated in Table 4-. The
crude, solvent and alkali solution were mixed for five minutes at
atmospheric temperature with an electric beater. The emulsion was
then heated to 150°F. in the crude tank before it went to the pump.
It was given no recirculation in the line.
Numbers 26 and 27 were alike except for the pressure which was
raised to 75 pounds in the latter experiment. Gasoline was added in
place of gas oil in No. 28 and there was a slight improvement in salt
VjJ
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Run No.
Crude
M&BS
(»
NaCl
(#/!000 Bblstl
Pump Speed
(R.P.M.)
H
00
H
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TO TO TO TO TO TO
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ON
o
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♦
4^
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4^
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00
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Rate
(Gal./Hr.)
Gallons
Run
Temperature
O M
Pressure
(#/Sq.In.)
o>
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H* C+
HO.
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Reduction
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24
removal.
t K
A second contactor was put in the system, and Run No. 29 illus
trates its beneficial effect. Water and sediment were reduced to
0.8$ and the salt was lowered'from 123 td 4.8 pounds per thousand bar-,
rels.
Very little water was withdrawn; from the settling .tank with this
apparatus so in Run No. 30 it was eliminated. The brine tank was
also by-passed so that the oil passed through only the two contactors.
Results equaled those in previous experiments. Therefore, it was
decided to fill the brine tank with glass and have three solid con
tactors. This gave the best salt removal and water drop of any of
the runs thus far. As can be seen in Run No. 31j 87$ of the salt was
taken out of the crude.
The object of Run No. 32 and No. 33 was to see how the rate of
flow effected desalting. The rate was raised from 2 to 11 and then
to 18 gallons per hour with very little loss of efficiency. Gutting’
the added gasoline from 15 to 5$ in No. 34 bad a detrimental effect,
but as will be shown later, this was probably caused by the type of
mixing received rather than by the elimination of the solvent.
Final Experimental Unit
The first contactor was replaced by one tv/ice as tall but having
the same volume, and the remainder of the experiments utilized this
70 inch cylinder. All three contactors wT ere constructed with a free
space in the bottom and provision was made to draw ?/ater from each.
o
27
Thereafter, approximately 90% of the water was recovered in the first
contactor, A pre-heater was also put in the line to allow the oil to
be raised to any desired temperature before entering the contactors.
Plate II is a picture of the experimental unit after these
changes were made. Plate III shows the same unit diagrainatically.
The crude oil charge is placed in number (1). The pump, number (12),
forces the oil through the system under a positive pressure. This
pressure is held at about 30 pounds per square inch and is shown on
the gauges, numbers (10) and (11). The crude oil charge is heated to
the desired temperature while passing through the pre-heater,
number (2). The crude flows in series through the contactors, numbers
(3), (A), and (5). It goes in at the top and is withdrawn six inches
from the bottom. The final product is removed at number (6). Water
is continuously drawn off at numbers (7), (8), and (9). The by-pass,
number (13) can be used to regulate the flow, but is ordinarily kept
closed. The vents, numbers (14-) > (15), (16), aucl (17), are opened
while the system fills to let the air escape. They are also used to
exhaust gases and prevent vapor locks.
Doubling the velocity through the first contactor, as was
accomplished by using, the taller pot, apparently had no effect, for the
same amount of water was removed before and after its installation.
Varying amounts of alkali.— The next eighteen experiments shown
in Table 5 were designed to illustrate the effect of the strength of
alkali upon different types of crude. Ten percent of a 0,25% sodium
TABLE 5
VARYING STRENGTH OF ALKALI
Run No.
I
i
Crude j
C O
___—
O i
1 — I
,a
o
H O
oo
c ti H
Pump Speed
(R.P.M.)
i
i
•
u
tc
-P •
a i aj
O Gallons
Run
Temperature
( * * • )
< D *— v
^ S 3
W*H
Ui *
0) a*
t-i C O
Alkali
Solution
Dehydrated
Crude
i
% Salt
Reduction
Amt.(%
of Oil)
Cone.
( % >
M&BS
( «
NaCl
:t e y
36 B 1.2 187 138 13 65 200 50 10 0.25
2.6
39 79
37 B 1.2 187 138 13 100 200
65 10 0.25
1.8 A6 75
38 B
1.6
175
138
13 65 200 70 10 0.25
2.8
A3 75
39 B 1.6
175 138
13 65 190 65 10 0.25 2.A A1
77
AO B 0.8 171 138 13 65 200
65
10 0.2.5 2.A AO 77
41
A 0.8 158 138 13 65 200
65
10 0.25 A.O
5A
66
A2 A 0.6 158 138
15 50 200
65
10 0.25 A* A
56 65
A3
A 1.3
158 138 15 32 200
65
10
0.125
2.0
31
80
AA
A 1.2 158 138 15 65 200 30 10 0.125
0.8 28 82
A5 B 0.8
1A7 138 15 100 200 30 10
0.125 0.A A3 71
A6 B
0.6
1A6
138
15 32 200 30 10 0.125 0.2 36 75
A7 B l.A 1A2 138 15 50 200 30 5 0.5 0.A 2A 83
A8 B 1.0 150 138 15 25
200 30
5 1.0
l.A
32
79
A9 B 0.9 135
138 15 A0
200 30 10 0.5 l.A 29 79
50 B 1.0 135
138 15 A0 200 30 20 0.5 A.O 20 85
51 B 1«A 139 138 15 A0 200 30 5
2.0 A.O
85 39
52 B l.A 1A8 138
15 A0 200 30 5 0.75 0.7 19 87
53 B l.A 1A8 138 15 A0 200 30 5 0.25
0.2
6A
57
oa
29
carbonate solution was added in Runs No. 37 to 42. The first four runs
were made on Type B crude and the next two, on Type A. It should be
noted that in running the two crudes in exactly the same manner,
almost twice as much water was left in Crude A as in Crude B, and
that salt removal was approximately 10$ higher in the latter. Note
also that in the next four experiments where the alkali was cut to a
strength of 0.125$, the efficiency of salt removal was exactly reversed.
That is, Crude A gave better results than Crude B. It is evident that
10$ of 0.125$ sodium carbonate solution is not enough to give proper
contact when using Crude B, for although the water drop was excellent,
salt removal was poor. Other variations were made in the amount of
solution added, as well as the strength of alkali in the runs which
follow.
Plate IV shows in graphic form the results of Runs No. 47, 4^,
51, 52 and 53. These runs were made upon Crude B and all variables
were held constant except the strength of alkali which is plotted
against percentage of salt removed (Curve A) and the percentage of
water removed (Curve B).
These experiments indicate very definitely that there is an
optimum condition to be reached using a strength of alkali which will
give a good water drop and at the same time, give an intimate contact
which will remove the largest percentage of salt.
On the left hand side of the curve the water drop is excellent
but the salt removal is low because of insufficient contact. The
two curves cross at approximately 0.7$ sodium carbonate which is the
G H J WS 2 . W S S £
% ' “ " i M
31
most efficient point for this crude. Moving toward the right, con
tact becomes better and desalting efficiency would continue to rise
to 100% provided the water could be removed. However, the resolving
action of the apparatus is limited which causes the curve to drop
off as the emulsion becomes more stable. On this side of the curve
the percentage of salt removed runs higher than the water drop.
There are at least two reasons for this. Salty water settles faster
than pure water so that the heavier brine drops out first. Then too,
brine tends to cause coalescence so that water particles containing
the most salt separate first. These effects become less pronounced
as stability increases and the two curves become almost identical.
The same relations hold for each type of crude. The curves are
merely shifted either to the right or the left.
It- can be seen by comparing Hun No. 44 to No. 45 that dropping
the pressure from 65 to 30 pounds per square inch allowed a much
better water drop and also lowered the salt content. This is probably
due to the fact that the reduced pressure causes a slight amount of
agitation which helps break the oil film surrounding the water parti
cles.
Eliminating the solvent.— With these facts established the next
step was to eliminate the solvent. The results of this procedure were
recorded in Table 6. Number 34 was run with the regular 15% of gaso
line. Reducing the solvent to 10 and 5% in No. 55 and No. 56
respectively had no effect upon the removal of salt.
In these three experiments, as in the ones to follow, the mixing
TABLE 6
ELIMINATION OF SOLVENT
Run No.
0
* 3
u
o
CO
S'-"
to
I —1
&
CQ
O
H O
O O
O H
Pump Speed 1
(R.P.M.) j
1
Rate
Gal./Hr.
Gallons
Run
Temperature
{*•)
< D •
1 0 •
to a*
0 t o
4fS
Alkali
Solution
Dehydrated
Crude
% Salt
Reduction
Amt.
(% of
0.1)
Done.
{%)
M&BS
(»
NaCl
#/iooo
Bbls»
54
B 0,8
ia
138
15 32 200 30 10
0.125 0.4 41
72
55 B 0.8
144
138 15 32 200 30 10
0.125 0.8 39 73
56 B 0.8
144
138 15 32 200 30 10
0.125 0.6
41
72
57 B 0.8
144
138 15
26 200 30
5 0.5 1.0 28 81
58 A 0.8.
99 138 15
26 200 40 5 0.25 0.4 23 77
59 A 0.8
99
138
15
26 200 40 5 0,25 0.4 23 77
60 B
1.4
190 138
15 40 240 30 10
0.5 1.2 27 86
61 B 1,6
176 138
15 40 240 30 10
0.75 1.4
21 88
33
was done at l65°F. This reduced the viscosity of the oil to such an
extent that eliminating the gasoline had little effect upon the degree
of dispersion and allowed a true evaluation of the benefit derived
from the solvent.
No solvent was used in the remaining experiments. Five percent
of 0.5$ sodium carbonate solution was emulsified with the crude in
Run No. 57 and since 81$ of the salt was removed, it seems evident
that 5$ of added water is enough for efficient desalting provided the.
proper strength of alkali is utilized.
Hard water.— In all experiments to this point, soft water was
used. Runs No. 58 and 59 illustrate the effect of replacing the soft
water with ordinary tap water. The results were exactly the same in
each case which indicates that substantial savings could be realized
in commercial operation by using untreated water. The sodium carbonate
could be added to hard water in a storage tank. Most of the calcium
and magnesium carbonate which precipitates would settle to the bottom
of the tank, and a filter placed in the line would remove the remain
ing portion. This procedure would eliminate the possibility of
carrying calcium and magnesium into the crude.
Runs No. 60 and 61 illustrated the added benefit derived from
increasing the temperature. They were run at 24-0°F. and appear to
substantiate the point mentioned before that the agitation caused by
the added heat and low pressure tends to break the oil film surround
ing the water particles.
3U
Excelsior Contactor— To this point a large number of trials
have been made to ascertain the best possible method and apparatus
for desalting crude petroleum. Many of the ideas tried have not
. t' '
proved successful. On the other hand, each has contributed something
toward the final success of the project. A great many conclusions
can be. drawn from the work thus far, and it now remains to show just
what results can be expected from the process which has been develop
ed. With this in mind the last four runs were made.
The glass was taken from the contactors and it was replaced
with excelsior. The proper strength of alkali was calculated from
previous runs, and the percentage of solution added was that which
would be a reasonable amount in actual plant operation. Two runs
were made on Crude A and two were made on Crude B. Each .of these
last four was longer than previous runs. They are tabulated in
Table 7. The results are exceptionally good, the salt reduction
being from 90 to 95%• From 1.0 to 1.4$ water was carried by the
original crude, and 5% to 1% was added. The dehydrated crude
showed only a trace of water in each case.
TABLE 7
EXCELSIOR CONTACTORS
*
o
£3
Crude
CO
2§
----6 9 --
H
rQ
PQ
O
O
rH O
O H
« j \
1 2 5
Pump Speed
(R.P.M.)
Rate
(Gal./Hr.)
Gallons Run
Temgerature
C D •
Alkali
Solution
Dehydrated
Crude
% Salt
Reduction
c q t r
0 C O
cw=te
Amt.
{ % o f
Oil)
^ o
^ o
o
•
M&BS NaCl
( % ) ( # / 1 0 0 0
Bbls.)
6 2 A 1 . 2 1 5 0 1 3 8
15 300 2 0 0 30 7 .2 .2 Trace 8
95
63 A 1 . 0 158 138
15 3 0 0 2 0 0 30
5 .25 Trace 1 2
93
64
B
1.4
2 0 0 138
15 3 0 0 2 0 0 30
5 .75 Trace 2 1 90
65 B 1.2 199 1 3 8
15 3 0 0 2 0 0 30
5 .70 Trace 18
91
U!
CHAPTER IV
36
SUMMARY AND CONCLUSIONS
I* An efficient and economical removal of salt from heavy.California
asphaltic base crude can be accomplished, by emulsifying the oil
with a dilute sodium carbonate solution and then resolving the
emulsion and separating the water, by heating and running it
through excelsior-packed columns.
2. Excelsior was found to be the most efficient packing for the solid
contactor.
3. No brine tank is necessary to aid in breaking the emulsion provided
the proper amount of alkali is used.
U* No settling tank is necessary in the apparatus described.
5. The stability of the emulsion is controlled principally by the
amount of alkali added.
6. The degree of agitation also controls stability but to a lesser
extent.
7. A small amount of alkali leads to emulsions which are easily
resolved, but the water is not contacted sufficiently with the
. salt to achieve proper removal.
8. A large amount of alkali gives the necessary intimate contact,
but leads to emulsions which are hard to break.
9* An optimum condition for desalting can be reached by balancing
the amount of alkali so that sufficient contact is realized and
yet the water can be separated.
10. A slight amount of agitation in the contactors due to a high
temperature and low pressure aids coalescence by tending to break
the oil film surrounding the water particles.
11. The rate of flow through the contactors has little effect upon
desalting efficiency provided the oil remains in viscous flow.
12. Each crude presents a separate problem, but each can be desalted
easily by proper adjustment of the alkali.
13. Sodium carbonate was found to be the most satisfactory alkali for
desalting.
14* Five percent of added water is sufficient for proper desalting
if the right strength of alkali is used.
15. Hard water may be utilized provided arrangement is made to remove
the calcium and magnesium carbonate which precipitates.
16. Adding a solvent to lower the specific gravity of the oil has
little effect upon the water drop.
17. Results are easily duplicated, v/hich indicates that uniform desalt
ing can be expected on commercial units.
38
Bibliography
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39
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4-0
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UMI Number: EP41529
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Creator
McChristy, Reagan Evans
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Core Title
Development of an efficient and economical process for the removal of inorganic salts from crude petroleum
School
Department of Chemistry
Degree
Master of Science
Degree Program
Chemistry
Degree Conferral Date
1940-08
Publisher
University of Southern California
(original),
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engineering, petroleum,OAI-PMH Harvest
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McChristy, R. E.
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engineering, petroleum