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March15, 1938’
‘
V
'
1
L. v. CHANEY ETAL
_
2,111,487
PROCESS FOR SWEETENING HYDROCARBON OILS
'
Filed July 25, 1936
>7 2 Sheets-Sheet 1
INVENTOR.
LOVELL
Y
M CHANEK
ALBERT E. BUELL
IRWIWM
' ATTORN
S. .
'
March ‘15, 1938.
4
2,111,487
L. v. CHANEY ET AL’
PROCESS FOR SWEETENING HYDROCARBON ‘0114s
2 Sheets-Sheet 2
Filed-Julyl25, 1956
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BY
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I
Patented Mar. 15, 1938
2,111,487
UNITED ‘STATES PATENT OFFICE
2,111,487
’ PROCESS FOR SWEETENING HYDE-OCAR
-
‘
BON OILS
Lovell V. Chaney and Albert E. Buell, Bartles
ville, 0kla., assignors to Phillips Petroleum
Company, a corporation of Delaware
Application July 25, 1936, Serial No. 92,630
7 Claims. (Cl. 196_—29)
This invention relates to the re?ning of hydro, - leum product through a bed of moist treating
carbon ?uids. More particularly, it relates to agent comprising cupric chloride carried on
improvements in the sweetening of “sour” petro
fuller’s earth, or other porous and adsorbent car
leum hydrocarbon products by means of a moist
5 solid reagent comprising copper chloride adsorbed
on carriers.
-
The improved method of re?ning petroleum
.hydrocarbon products herein set ‘forth is of spe
cial value and application in the treatment of
10 light petroleum distillates such as natural gaso
rier, and the treating agent maintained in an
active or sweetening state by means of air added 5
to the petroleum hydrocarbon oil being sweet
ened.
The petroleum products to be sweetened,'and
to which air or other gas containing'free oxygen
has been added, are passed through beds of this 10
treating agent, the petroleum products ?owing
kerosenes, petroleum solvent naphthas, lique?ed‘ either upward or downward through the beds.
line, re?nery straight run and cracked gasolines,
- petroleum‘ gases; and the like.
Such unre?ned ' On emerging from the treating agent bed, the
‘petroleum products contain mercaptans which
15 give the products undesirable odors and render
gasoline or other petroleum hydrocarbon ?uid, is
sweet to the well known “doctor” test, has an 15
them corrosive and unstable. Petroleum hydro
excellent odor and does not contain any of the
carbon products containing mercaptans are com; undesirable constituents, ,many of which are un
monly termed “sour”. Conversion of these mer _ stable to light or heat, usually introduced into
captans partially or entirely to disul?des, or
zocompletely removing them, is ‘usually termed
sweetening. customarily, these‘ “sour” com
pounds are' altered, or removed, by chemical
treatment of‘ the '“sour” hydrocarbon ?uid with
2 alkali plumbite and sulfur. In some instances,
the‘ sweetened product by the aforementioned
customary sweetening methods.
20
As disclosed further in co-pending application
Serial No. ‘725,405, the principal chemical re
actions in sweetening sourpetroleum hydrocar
bon oils with cupric chloride carried on an ad- ' -
particularly with natural gasoline, sweetening is sorbent material are believed to be as shown in 25
the following equations:
accomplished with alkaline hypochlorite solu
- tions but, like the alkali plumbite method; this
(1) 2GuClz-l- 4RSH —)2R——S——Cu +R—~S—-S—R+
Cupric
method has proved to be not only unecondmical
and cumbersome but also has been found to
O.
Alkyl
Hydrochloric
disuliide
acid
1
introduce undesirable constituents’ into the prod
ucts being sweetened, such constituents in many
instances of ‘high mercaptan content products
beingsas detrimental to the petroleum products
the mercaptan is converted to the alkyl disul?de
and the rest is left as cuprous mercaptide. ’The 35
The object of this invention is to provide an
economical and easily operated method for re~
?ning sour petroleum hydrocarbon oils.‘
A further and more speci?c object is to pro
vide improvements in the method of sweetening
sour petroleum hydrocarbon oils by means of a
moist re?ning agent consisting of carrying agents
impregnated with cupric chloride, said re?ning
5
4HCl
Cuprous
mercaptide
(2)
35 treated as those present originally. Still other
methods have been suggested for the removal or
conversion of mercaptans but in nearly every in
stance these methods involve numerous treating
steps, requiring close control, so that the increase
40 in operating costs renders them uneconomical.
'
Mercaptan
chloride
agent being retained in a constantly active state
by air dissolved in the sour hydrocarbon oils.
In co-pending application Serial No. 725,405,
a novel method of sweetening petroleum hydro
carbon products was described, whereby sweet
55 ening is accomplished by passing a sour petro
2R—S—Cu+2CuClr->R—S—S—R+4Cu0l
Cuprous
Cupric
mercaptide chloride
Alkyl
disul?de
30
Cuprous
chloride
In the ?rst step of the reaction, one-half of
latter then reacts (as shown in Equation 2) with
additional cupric chloride to give alkyl disul?de
and cuprous chloride. . On .combining the two
equations into one, the ultimate .reaction is:
(3) 4CuCIz-I- 4RSH -—)2R—S—S—R+ 4Cu0l + 41101‘
Oupric Mercaptan
Alkyl
cuprous Hydrochloric
chloride
disulfide
chloride
40
acid
Since cuprous chloride and hydrochloric acid
are formed in the reaction at the expense of the
cupric chloride, the. reagent, when treating pe- 45
troleum oil without the addition of air, will grad
ually lose its activity, and ?nally become spent,
as the amount of mercaptan sulfur in the oil
passed through the reagent becomes more nearly
equivalent to the cupric chloride used on the 50
reagent. When the, petroleum oil contains only
a very small quantity of mercaptan sulfur the.
'life of the reagent is comparatively ‘long, but
when the mercaptan content is high the life of
the reagent is quite short.
'
_'
55
2
2,111,487
Spending of the reagent is prevented and its
activity maintained over long periods by dissolv
ing air in the petroleum oil previous to its pas
sage through the reagent bed. In this manner
the cuprous chloride and hydrochloric acid,
formed as shown above in the sweetening step,
react with the oxygen in the air to give cupric
chloride and water.
10
(4)
4CuCl‘+
41301 I +
Cuprous Hydrochloric
chloride
acid
O:
—)4CllClg+2HaO
Oxygen
Cupric Water
(from air) chloride
The treating agent contains a substantial
quantity of water and. the hydrogen chloride
formed as shown in Equation 1 is dissolved in the
15 water or, rather, in the solution of the copper
salt. The cuprous chloride likewise remains in
solution at the same point in the bed. The oxy
gen needed to convert the cuprous chlorid and
hydrochloric acid back to cupric chloride is fur
20 ni'shed by the oxygen in solution in the oil and
the reagent is immediately and continuously re
generated. If insu?icient water is present, the
‘hydrogen chloride passes oif as a gas dissolved in
the oil and the cuprous chloride is precipitated
25 in the solid form. -When the hydrogen chloride
due to channelling can be prevented by passing
the oil at a relatively high rate upward through
the bed of sweetening agent for periods of short
duration at relatively frequent intervals.
This .
serves to lift the reagent bed slightly and to dis VI
turb the granules thereof sui?ciently to break up
incipient channels in the bed.
Where the treating agent has failed to sweeten
the petroleum oil, due to the formation of these
" channels, we have obtained a large increase in 10
volume of oil sweetened, per volume of treating
agent, by passing the oil up through the treating
agent bed at rates between 0.7 and 2.5 ft. per
minute. When the ?ow rate of the oil up through
the bed is less than about 0.7 it. per minute, the 15
velocity is not high enough to disturb the gran
ules of treating agent sufliciently to break up the
channels, and rates in excess of about 2.5 ft. per
minute cause so much lifting that particles of
the treating agent are carried out of the con 20
tainer by the oil stream. We prefer to carry out
this step in the process by passing the petroleum
oil up through the treating agent bed at rates be
tween 1.0 and 1.8 ft. per minute, although the .
preferred rate in individual cases is in?uenced 25
is carried away from the cuprous chloride the‘ somewhat by the size and shape of the treating
regeneration does not take place and the reagent
therefore soon becomes spent. In this petroleum
oil treating process su?icient moisture is main
30 tained in the treating agent such that it has a
agent granules, by the depth of the treating
water content substantially greater. than that of
agent bed and by the density of the petroleum oil.
We prefer to treat at rates such that the linear
velocity of the petroleum' oil through the sweet 30
ening agent is less than 0.5 ft. per minute where
an adsorbent mixture of cupric chloride hydrate
the oil contains only a moderate concentration of
crystals and substantially dry adsorbent material.
Continuous regeneration of the cupric chloride is
35 obtained and the treating agent remains in a
highly active state over long periods of time dur
ing which many equivalents of mercaptan sulfur
are sweetened by one equivalent of cupric chlo
ride.
Spending of the treating agent, due to insuf
?cient water, has been observed in the commer
cial application of this process where the De
troleum oil was ' exceptionally free from .dis
solved water and it was, therefore, necessary to
45 add water to the oil being processed or to the
solid treating agent.
'
In the commercial practice of the process as
mercaptans and less than 0.2 ft. per minute
where the oil is very sour, or contains a relatively
high concentration of mercaptans.
35
As an example of the utility of this step in the
refining of petroleum hydrocarbon products with
a re?ning agentconsisting of cupric chloride car
ried on fuller’s earth, a treating plant processing
a very sour (0.05 per cent, by weight, mercaptan 40
sulfur) West Texas natural gasoline at an aver
age rate of 14,000 gallons per day through a bed
of this re?ning agent 4 ft. deep and 4 ft. in diam
eter consistently sweetened approximately 200,000
gallons of gasoline after each ?lling of the treat 45
ing tank with cupric chloride re?ning agent be
fore failing to completely sweeten the gasoline.
described in said co-pending application the vol
In this normal treating the gasoline was passed
ume of petroleum oil which can be treated per
through the re?ning agent bed at rates approxi
50 volume of the cupric chloride sweetening agent
varies widely in different instances where the oil
and sweetening agent are identical. This varia
tion is due to variations in the rate at which the
petroleum oil is passed through the sweetening
55 agent bed. For example, when treating a very
mating a linear velocity of 0.13 ft. per minute. A
pump was then installed and gasoline passed up
through the re?ning agent bed for \20 to 30
‘minutes every 3 or 4 days, or after approximately
every 50,000 gallons of gasoline had been sweet-,
ened, at a rate of 150 gallons per minute, or at 55
sour petroleum oil a greater volume can be treat
approximately 1.6 ft. per minute. Other than
ed per volume of sweetening agent when the oil ' this periodical short cessation of normal sweet
is treated at relatively low rates, such as a linear ening operation, the cupric chloride treater op
velocity of 0.4 ft. per minute through the sweet
60 ening agent bed, than at higher rates such as 4.0
ft. per minute. This is due to less complete re
generation of the sweetening agent at the higher
rates, the regeneration apparently not being as
rapid as the sweetening.
65
where channelling had occurred.
75
»
On the other hand, we have found that when
the sweetening agent failed to sweeten after hav
ing been used consistently at very low rates, an
average sample of the sweetening material has
practically the same potential sweetening power
as it had originally, indicating that small chan-_
nels had formed in the bed of sweetening material
and set up a condition equivalent to sweetening
at high rates through the local areas in the bed
'
.
We have found that this failure in sweetening
erated continuously for over 8 months and sweet
ened over 3,500,000 gallons of this very sour 60
natural gasoline without once opening up the
‘treater or otherwise disturbing the re?ning agent
.bed. In normal sweetening operation the
gasoline ?ows continuously from the fractionator
kettle through an alkaline sodium polysul?de 65
treater. to remove elementary sulfur, and down
through this cupric chloride re?ning agent bed.
In the drawings:
'
Fig. 1 illustrates, diagrammatically, a system for
carrying out the present invention;
70
Fig. 2 is'a view, partially in section, of an ap
paratus for introducing air or oxygen into the
hydrocarbon stream;
Fig. 3 isa sectional view of a treater.
It is to be understood that the speci?c system 75
3
2,111,487
and apparatus shown in the accompanying draw-
that the total normal petroleum oil sweetening
_‘ ings are for the purpose of ‘illustration only, and
indicate one manner in which applicants’ inven
tion ‘can be carried out, and that other systems
and apparatus suitable for carrying out the in
vention as described and claimed may be sub
requirement can be sweetened in the remaining
treating tanks while any one is out of service"
for the short period of reverse flow.
Flow of air into the petroleum oil is also con
trolled and recorded by means of a needle valve,
not shown, in the air line to the oil and air con
stituted.
'
‘
Fig. 1 illustrates the operation of our improved
method of sweetening petroleum hydrocarbon
10 oils with cupric chloride solution on a solid car
rier. In normal sweetening operation, sour
petroleum oil .enters the oil and ‘air contacting
chamber 3 through pipe, I. A controlled amount
of air enters contacting chamber 3 through pres
.15 sure reducing regulator 4, valve 5 and check valve
8. Automatic proportioning of air into the hy
drocarbon oil is accomplished by proportional,
control 9 working in conjunction with diaphragm
valve 1 motivation for which is furnished by dif
20 ferentials across vhydrocarbon oil ‘ori?ce 2 and
air ori?ce 6,,co-acting through an' air block or
pilot valve actuated by an external source of
air at constantmoderate pressure, so that every
. change in the ?ow rate of hydrocarbon oil‘v causes
25 a proportional change in air rate. The desired
proportion of air to petroleum hydrocarbon oil
tacting chamber 3, Fig. 1, ori?ce 5 and a'record
ing ?owmeter or a manometer, also not shown in
Fig. 1.
10>
Automatically proportioning the air into the
gasoline is essential where the quantity of mer
captans in the gasoline is of such magnitude that
the air required to maintain the cupric chloride
treating agent in a continuously regenerated state 15
is approaching the solubility of air in the hydro
carbon oil being processed. Without an auto
matic proportioner, the tendency in this critical
range would be either to add too much air to
the oil, and raise the vapor pressure of the oil, 20
or to add too little, with the possible chance, of
permitting the treating agent to become spent.
Automatically proportioning the air into the
hydrocarbon oil is preferred where the mercapr
tan content of the oil is of the order of 0.04 per 25
cent by weight. Where the mercaptan content is
is established by drilling the ori?ces in the ori?ce . around 0.002 per cent, air is satisfactorily added
plates'in the air and petroleum oil lines to. the to the oil by manual control.
'
proper sizes for the desired proportions. ,
Sometimes ‘sweetening is also carried out by
so
bedof moist sweetening agent- consisting of cupric
admitting the sour petroleum oil into the bottom
of treating tank I4, Fig. 1, and passing the oil up
through the sweetening agent bed at a relatively
low rate, removing the sweetened oil from the
top of the tank. Fig. 1 is not complicated with
35 chloride solution on a carrier material. Petroleum
the extra lines and valves -to show treating in
oil passes down through the bed of_re?ning agent
this manner. After normally treating up-?ow at
3,5
and emerges, sweetened, from treating tank l4
through line l5, valve l6 and through line I‘! to
upward ?ow of petroleum oil is increased period
30
Sour petroleum oil containing the air passes
then from contacting chamber 3 through line I 0,
through valves .H and I2 (and through line l3
into the top of tank l4 in which is contained a
sweet oil storage. Valves l8,’ I9, 20, 2|, 23 and
40 24 are closed.
*.
After a predetermined volume of petroleum oil
has been sweetened through treating tank It, for
example, valve I2 is closed and valves I8, 32, 34,
36 and H are opened so that oil through line l0,
45 line 31, tank 33, centrifugal pump 35 and line
38 will completely ?ll tank l4 when air and vapors
are-vented from tank‘ I! by opening valve 30.'
When tank I4 is liquid full, valves H and 30 are
closed, valve I2 is opened and pump 35 is started.
50 Circulation of oil is then in the reverse direction
to that in normal sweetening, oil being drawn
from the top of tank [4 through lines I3 and 31
into surge tank 33. Pump 35, taking suction from
the bottom of surge tank 33, discharges oil
55 through line 38 and line l5 into the bottom of
treating tank l4 below the sweetening agent bed.
Flow rate of 011 up through the tank is determined
by ori?ce 26 and manometer, or recording ?ow
meter, 21 and the ‘?ow rate regulated by valve
60 36 so that“ the velocity of 011 up through the treat
a relatively low rate for a predetermined time,
ically to the desired high rate by means of a
pump, or other means for obtaining this high 40
rate, for a relatively short time, after which nor-'
mal treating is resumed.
‘
.
Where theisour hydrocarbon oil can be supplied
to the treating agent, inthis reverse ?ow step, in
su?icient quantity to maintain the required up
45
ward'?ow rate for the desired length of time, '
the oil is passed up through the cupric chloride
treating agent bed but once and then passed on to
sweet storage, rather than recycled, for even 'at
the higher rates required for the slight disturb 50
ance of the treating agent bed the oil is com
'pletely. sweetened. In this manner of maintain
ing the high flow rate up through the treating
agent bed, air is added to the gasoline in the re
quired proportion to maintain the treating agent 55
in a regenerated state, whereas in, the recycling
method no regenerating air is necessary.
In sweetening through two or more treaters
in parallel, valves 20, 22 and 23, controlling the
?ow of petroleum oil into and out of treating‘ tank 60
ing tank ' is approximately 1.5 ft. per minute.
25, are open as are correspondingly placed valves .
Ori?ces 26 and 28 are square-edged so that the
?ow of -oil in either direction can be measured
on other treating tanks if more are in the sys
tem. Square-edged ori?ces 26 and 28, with cor
' with them in conjunction with a manometer or
65 with a ‘specially arranged recording ?owmeter. -
After passing petroleum oil at the prescribed
rate up through the cupric chloride re?ning agent
in treating tank I 4 for 20 to 30 minutes, pump
35 is stopped, valves l8 and I9 are closed and
70 normal sweetening resumed by opening valves‘ I I
and it. During the short period of reverse ?ow
in treating "tank l4, sour petroleum oil is sweet
ened by passage through cupric chloride re?ning
agent in treating tank 25. Sizes of treating tanks
75 and quantities of sweetening agent are used such
responding m'anometers or ?owmeters 21 and, ‘
29», are conveniently placed in the lines into the 65
top of the treating tanks in order to determine
that the desired amount of petroleum oil is pass
ing through each of the treating tanks arranged
in ‘parallel and to regulate the periodical rela
tively high rate of upward ?ow of oil through 70
the sweetening agent for the prevention of chan
nelling.
Fig. 2 illustrates in detail a typical device for
mixing air, or other oxygen-containing gas, with
the petroleum oil to be sweetened with the cupric
15
4
chloride treating agent.
2,111,487
Petroleum oil enters
through conduit i into chamber 3 where it is in
timately commingled with air entering the cham
ber through conduit 40 and porous plate 4|, the
Cl porous plate serving to subdivide the air stream
many times to greatly increase the contact sur
face between air and petroleum oil. Porous plate
4| is composed of Alundum, or other similar ma
terial, and is maintained in a swedge nipple with
10 babbitt 42. The petroleum oil and air mixture
leaves chamber 3 through conduit Ill.
Fig. 3 shows the construction of a typical treat
ing tank containing cupric chloride sweetening
agent. During sweetening operation sour petro
leum oil, partially saturated with air, enters tank
l4 through conduit l3, impingingagainst ba?le
43 to prevent disruption of the granular treat
ing agent bed by the flow of oil. The sour pe
troleum oil is sweetened in passing through sweet
ening agent 44, and the sweetened oil passes
through perforated wooden plates 45, hair-felt 46
and leaves tank !4 through conduit l5. Sweeten
ing agent 44 is supported by two perforated wood
en plates 45, consisting of perforated boards ar
ranged to form a floor, the two plates being held
apart by spaced boards 41, and the whole sup
ported by steel beams 48 resting on an angle iron
ring 49. Hair-felt 46, or the like, packed tightly
between the perforated plates prevents the granu
30 lar sweetening agent from passing through the
plate perforations.
During the step of periodically passing petro
oxygen-containing gas with said impregnated ad
sorbent material.
'
2. A cyclic process for sweetening mercaptan
bearing petroleum oil with a solid adsorbent car
rier material impregnated with a sweetening 5
agent consisting of a solution of a copper salt
and a chloride adapted to react to form cupric
chloride, said impregnated adsorbent material
being maintained in a moist condition and hav
ing a water content substantially greater than 10
that of an adsorbent mixture of cupric chloride
' hydrate crystals and substantially dry solid ad
sorbent material, comprising admixing a free
oxygen-containing gas with said mercaptan
bearing petroleum oil, contacting said oil and
free oxygen-containing gas with said impreg
nated adsorbent material, thereby converting the
mercaptans in said oil to disul?des and simul
taneously maintaining said sweetening agent ac
tive, and continuously collecting the sweetened
petroleum oil, discontinuing contacting said mer
captan-bearing petroleum oil and admixture‘ of
free oxygen-containing gas with said impreg
nated adsorbent material, subsequently passing
a petroleum oil up through said impregnated ad 25
sorbent material at a relatively high velocity for
a relatively short duration of time, discontinuing
said relatively high velocity of upward passage
of petroleum oil through said impregnated ad
sorbent material, and repeating the process.
30
3. A process forv sweetening mercaptan-bear
ing petroleum oil, comprising impregnating
leum oil up through the sweetening agent bed at fuller’s earth with a solution of copper sulfate
a relatively high rate to break up incipient chan ' and a soluble alkaline chloride, maintaining the
35/ nels in the bed, oil enters through conduit ‘l5,
water content of said impregnated fuller’s earth 35
Fig, 3, impinging upon batlle plate 50, passes up substantially above that of a mixture of cupric
through sweetening agent 44 and leaves treating chloride hydrate crystals and substantially dry
tank l4 through conduit l3. Oil partially satu
fuller’s earth, mixing air with said petroleum oil,
rated with air, is also passed up through the ?ltering said petroleum oil and air downward
40 sweetening agent bed at lower rates during the through said impregnated fuller’s earth at a rate
normal sweetening operation.
in the range of 0.05 to 0.4 ft. per minute, where
Manholes 5|, Fig. 3, are provided for admitting by the mercaptans‘ in said oil are converted to
sweetening agent to treating tank l4 through the disul?des, and collecting the sweetened oil, dis
top and for removing it therefrom at the side. continuing contacting of said admixture of pe
45 Drain 52 is provided for completely emptying
troleum oil and air with said impregnated fuller’s 45
vtank I4 of liquid.
earth, passing said petroleum oil up through said
Having described our invention what we claim
and desire to secure by Letters Patent is:
1. A process for sweetening mercaptan-bear
50
ing petroleum oil, comprising impregnating a
solid adsorbent carrier material with a sweeten
ing agent consisting of a solution of a copper salt
and a chloride adapted to react to form cupric
chloride, said impregnated adsorbent material
being maintained in a moist condition and hav
ing a water content substantially greater than
that of- an adsorbent mixture of cupric chloride
- hydrate crystals and substantially dry solid ad
sorbent material, admixing a free oxygen-con
60
taining gas with said mercaptan-bearing petroi
leum oil, contacting said oil and free oxygen
containing gas with said impregnated adsorbent
material, thereby converting the mercaptans in
said oil to disul?des and simultaneously main
taining the sweetening agent active, and col
lecting the sweetened petroleum oil, discontinu
ing contacting said petroleum oil and admixture
of free oxygen-containing gas with said impreg
nated adsorbent material, subsequently passing
' said petroleum oil up through said impregnated
adsorbent material at arelatively high velocity
for a relatively short duration of time, discon
tinuing said relatively high velocity of upward
passage of petroleum oil through said impreg
nated adsorbent material and resumingcontact
7.5 ing of said admixture of petroleum oil and‘free
impregnated fuller’s earth at a rate in the range
of 0.7 to 2.5 ft. per minute for approximately
one-half hour, discontinuing said upward pas
sage of petroleum oil and resuming downward 50
passage of said admixture of oil and air through
said impregnated fuller’s earth, and collecting
the sweetened oil.
.
4. A cyclic process for'sweetening mercaptan
bearing petroleum oil with a solid‘ adsorbent 55
carrier material impregnated with a sweetening
agent consisting of a solution of a copper salt
and a chloride adapted to react to form cupric
chloride, said impregnated adsorbent material
being maintained in a moist condition and hav
ing a water content substantially greater than
that of an adsorbent mixture‘ of cupric chloride
hydrate crystals and substantially dry solid ad
sorbent material, comprising admixing air with
said mercaptan-bearing petroleum oil, contact 65
ing said oil and air with said impregnated ad
sorbent material, thereby converting the mer-V
captans in said oil to disul?des-and simultaneous
ly maintaining'said sweetening agent active, and
collecting the sweetened petroleum oil, discon
tinuing contacting said petroleum oil and ad
mixture of’ air with said impregnated adsorbent
material, subsequently'passing said petroleum oil
up through said impregnated adsorbent material
at a‘ relatively high velocity for a relatively short
>
5
2,111,487
duration of time, discontinuing said relatively ~ air to said oil, ?ltering said oil and air down
Y high velocity of upward passage of petroleum oil ward through said impregnated fuller’s earth at
through said impregnated adsorbent material, a rate less than approximately 0.4 ft. per minute,
and repeating the process.
5. In a process -for sweetening mercaptan
bearing petroleum oil with asolid adsorbent car
rier material impregnated with a sweetening
agent consisting of a solution of a copper ‘salt
and a chloride adapted to react to form cupric
10
earth, and subsequently passing a light petroleum
oil up through said impregnated fuller’s earth '
at a rate in the range of 0.7- to 2.5 ft. per minute 10
being maintained in a moist condition and hav
ing a water content substantially greater than
that of an adsorbent mixture of cupric chloride
for approximately one-half hour, thereby pre
venting'permanent channelling of said impreg
nated fuller’s earth.
7. In a process for sweetening‘ mercaptan- ‘
said mercaptan-bearing petroleum oil, passing
bearing petroleum oil‘ partially saturated with 15
air, the steps which comprise passing said oil at
said oil and air downward through said impreg
nated adsorbent material at a relatively low rate,
thereby converting the mercaptans in said oil to
disulfides‘ and ‘simultaneously maintaining said
a rate less than approximately 0.4 it. per minute
up through a sweetening agent consisting of a
solid Tadsorbent material impregnated» with a
solution oi a copper salt and a chloride adapted .20
sweetening agent active, and ‘continuously col
lecting the sweetened petroleum oil, the step of
discontinuing the normal relatively low rate‘ of
passage of petroleum oil downward through the
25 impregnated adsorbent material and passing said
petroleum oil upward through the impregnated
adsorbent material at a predetermined relatively‘
high rate, thereby preventing the formation of
- channels in said impregnated adsorbent material.
30
said oil and air through said impregnated fuller’s
chloride, said impregnated adsorbent material
hydrate crystals and substantially dry solid ad
15 sorbent material, comprising admixing air with
v20
thereby converting the mercaptans to disul?des,
and continuously collecting the sweetened oil,
the step of periodically discontinuing ?ltering
6. In va process for sweetening mercaptan
bearing lightpe'troleum oil, comprising impreg
nating fuller’s earth with a solution of cupric . '
vchloride, maintaining the water content of said
impregnated fuller’s earth, substantially above
35 that of a mixture of cupric chloride hydrate crys
tals and substantially dry iuller’s earth, adding
to react to form cupric chloride, said impreg
nated adsorbent material being maintained in a
moist condition and having a water content sub
stantially greater than that of an adsorbent mix
ture of cupric chloride hydrate crystals and sub 25
stantially dry adsorbent material, periodically
increasing the rate/of passing said oil, partially
saturated with air, up through said sweetening
agent to a rate in the range of 0.7 to 2.5 ft. per
minute for approximately one-half hour, decreas 80
ing said rate of upward passage of said oil
through said sweetening agent to a rate less than
approximately 0.4 ft.‘ per minute, and repeating
the steps.
‘
LOVEIL V. CHANEY.
ALBERT E. BUELL.
35
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