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Патент USA US2108438

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Patented Feb. 15, 1938
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t
; UNITED STATES PATENT‘ OFFICE v
raooEss 0F‘ TREATING HYDRO‘CARBON'
-
vnrons WITH zmo omloamn
Franklin E. Kimball, Los Angeles, Calif.
‘ No Drawing. Application July 21, 1936,
Serial ’ No. 91,788.
9 Claims.‘ (01. 196-36)
This invention relates to processes ofrtreating carbon liquid and by withdrawing the condensed
hydrocarbon vapors with’ zinc chloride and has gum-containing hydrocarbon liquid.
for its object to render more expeditious. and
I Willhereinbelow describea preferred embodi
cheaper ‘the application of said processes by ‘em‘-_ ' ment of my improvements in processes of treat
5 lploying the use of- a fused maintained treating- ing hydrocarbon vapors. with fused’ zinc chlo- 5‘
mixture containing su?icient'zinc chloride to prevent separation of ammoniumqchloride and su?lcient ammonium chloride to prevent separation of
zinc chloride atatemperature between 355- degrees
10‘ Fahrenheit andzinc chloride melting-temperature.
'
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‘
ride.’ The description is an example of an illus
tration portraying my improvements. It is to
be‘ understood that my invention is not limited
nor ‘restricted to the employment of the use of
theE precise mixtures, concentrations, quantities, l0,
proportions, pressures nor temperatures whose use
Considerably above 355 degrees Fahrenheit ap-
‘proximately ‘the'same degree‘ of heat melts zinc
chlorideas decomposes ammonium chloride. Am-
l5,‘ monium. chloride does notfmelt with heat but it
are employed in the operation of such an illus
trative process as is thus hereinbelow described
as being a practical example of an application
whichv portrays my improvements.
15
decomposes with heat. 7 Solid ammonium chloride
Inc’the application of such an illustrative proc-
exists only in the form, of needle-like’ crystals
ess', mineral oil may be continuously supplied to
which pack down and form the interstices‘ too‘
a suiab-le heater and’ continuously cracked under
small to conduct the hydrocarbon vapors through
pressure by processes well-known to those skilled
2Q; the ammonium chloride with a practical velocity‘
At a temperature of 355 degrees Fahrenheit a.
mixture of three parts of zinc chloride and, one
' part of ammonium chloride lique?‘es. ‘
.
.-
I ‘pass hydrocarbon vapors containing hydro;
25 gen sulphide and gum-forming vapors at a tem‘—
intheart of manufacturing gasoline. From sul- 20
phur bearing oils,_hyd1'ooarbon vapors containing
hydrogensulphide may be Continuously formed
Theijvapors may then be continuously separated '
fromlrunvaporized residue- The vapors may then
be .cohtinuously ‘ partially dephlegmated.
At a 25
perature between355 and 487 degrees Fahrenheit
pressure between 50 and 100 pounds per square
beneath the surface'of a fused‘ maintained treat-
inch gage pressure, the vapors may then be con
ing-mixture containing approximately three parts
tinuously further partially Cooled and Partially
of zinc chloride to prevent, separation, of ' am-
oondensed‘to such a degree that the Vapors may
30; Vm‘onium‘ chloride and one part of ammonium
chloride to prevent se’parationof zinc chloride,‘
be continuously Withdrawn from the dephlegma- 30
tionyessel at a» temperature between 355 and 487
'
supply to the treating-mixture a fused mixture
degrees Fahrenheit. '_
of chlorides ofzinc and'ammonimn, separate and
withdraw‘the vaporsfrom the?treatii'ig-mixture,
“The pressures of the application Ofthe treat
ment'of the hydrocarbon Vapors may be 00H
V 35 withdraw from the ‘treating-mixture a fused mix-
>
trolled by employing the use of suitable pressure 35
tul‘e of chlorides of zinc and ammonium, ‘contain-
regulators such as Howell-known to those skilled
ing products of reaction, supply ammonia. tothe
withdrawn ‘vapors, pass the ammonical vapors
in the ‘art of treating hydrocarbon vapors. Prior
tothe' entry of the vapors into the primary bub
beneath the Surface of a, maintained’ aqueous
4:0 solutionof calcium chlorida'fsupplyfto the ‘aquem
ous solution of calcium chloride Water and'calcium chloride, separate and withdraw the vapors
from the'aqueous solution of calcium ‘chloride and
withdraw from the aqueoussol'ution of calcium
45 chloride’ water and calcium chloride admixed
.th
W1 _
,Ond
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S d
en 6
gu
m_c" minim ' h dr 0 rb
on _
g
y
0 a‘
on
ble-tower‘, the pressure may he stepped down from
the pressure betw‘jaen, 50 to 100 pounds per Square 40
inch‘gagopressure, for ihemaliing of a subjec?fm
of the ‘(apqrs to 3‘ polymenza'tlqn, treatment whue
theynexlst in" superheated condltlon at {l pressure
bet-Ween 10 and 15 pounds per.squa‘re Inch gage
pressure.’ Therqupon’ polymenzed products may 45
be readily held in the vapor phase because the
temperature is still yet above the temperature of
hqmd' I remove gum'f°rm_mg Vapors ?pm hy'
their condensation under‘the pressure whose use
dr°9arbPn Vapors by effectntg 9‘ catalytic poly‘
50 menza'tlon of the gum'ffJrmmg Vapor? to form
is being employed in making the application of
gums, by. Partlany coohng and partlally Con"
of the vapors from the primary bubble-tower, the
densing the ‘hyrocarbon Vapors
a con-
pressvure may be stepped down to a pressure he...
densed gum-containing hydrocarbon liquid, by
separating and Withdrawingthe hydrocarbon var‘
tween 5'and 10 pounds per square inch gage
pressure’for' the making of a subjection of the
55 pors from'th'e condensed gum-containing hydro-
the treatment. Again, subsequently to the exit 50
vapors
a‘ subsequent treatment for removing 55
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2,108,438
2
reaction products from the vapors with a sec
ondary bubble-tower.
At the temperature between 355 and 487 degrees
Fahrenheit and the pressure between 10 and 15
pounds per square inch gage pressure, the with
drawn hydrocarbon vapors may then be contin
uously passed into the bottom of a suitable pri
mary bubble-tower and may be continuously
withdrawn from it at the top thereof. A fused
10 mixture of one part of ammonium chloride and
three parts of zinc chloride may then be con
tinuously passed into the top of the primary bub
ble-tower and may be continuously withdrawn
from it at the bottom thereof. Within the pri
15 mary bubble-tower the vapors are brought into
contact with the primary treating-mixture by
bubbling therethrough in a series of superimposed
pans such as are well-known to those skilled in
the art of treating hydrocarbon vapors. The va
20 pors, from off of the top of each pan below, pass
into the pan above at a point beneath the sur
face of the liquid therein. The treating-mix
ture, from off of the top of each pan above, passes
into the pan below at a point beneath the surface
25 of the liquid therein. Thereupon the vapors be
come desiccated by the lower pans.
The treating of the hydrocarbon vapors in the
primary bubble-tower may be controlled by ma
nipulations of the amounts of ammonium chlo
30 ride and of zinc chloride being passed into the
top. It is aimed to supply one pound of am
monium chloride and three pounds of zinc chlo
ride for each barrel of gasoline being supplied for
treatment. By manipulations of the amounts of
35 the two ingredients of the fused treating-mixture
being supplied to the top of the primary bubble
tower, the resulting composition of the treating
mixture which is being withdrawn from the bot
tom of the primary bubble-tower is thereby care
40 fully maintained at a proportion of approximate
ly 25% of ammonium chloride to 75% of zinc
chloride. The temperature of the treating of
the vapors in the primary bubble-tower may be
controlled by manipulations of the amounts and
45 temperatures of the vapors and treating-mixtures
thereby forming hydrocarbon liquid containing
gums. The vapors generate steam from the aque
ous calcium chloride solution thereby facilitating
the maintaining of the gasoline hydrocarbons in
the vapor phase. The calcium chloride solution 10
also extracts ammonium chloride from the va
pors. The condensed hydrocarbon liquid also ex
tracts from the vapors gums that are resultant
of zinc chloride catalysis in the primary treat
ment. Both liquids may be continuously with 15
drawn from the bottom of the secondary bubble
tower.
The treating of the hydrocarbon vapors in the
secondary bubble-tower may be controlled by
manipulations of the amounts of the ingredients 20
of the solutions that are being supplied to the
top of the secondary bubble-tower. It is aimed
to supply approximately twenty pounds of cal
cium chloride in aqueous solution for each barrel
of gasoline that is being supplied for treatment.
This is in order to flush away adequately the
condensing
hydrocarbon
liquid.
Additional
amounts of water may also be supplied in the
calcium chloride solution in such quantities as
are su?icient to o?set such amounts of water 30
as may be vaporized in the application of the
treatment. By the manipulations of the amounts
of both ingredients of the solutions being sup
plied to the top of the secondary bubble-tower,
the resulting composition of the aqueous calcium 35
chloride solution which is being withdrawn from
the bottom of the secondary bubble-tower may
be carefully maintained within the proportions of
35 to 45 per cent of water and 50 to 60 per cent
of calcium chloride.
The temperature of this 40
exit ?ow of calcium chloride solution may also
be carefully maintained at a temperature be
tween 275 and 325 degrees Fahrenheit by means
of manipulations of the temperatures and pres
sures of the vapors which may be supplied for 45
being supplied. Thereby, the temperature of the
a subjection to an aqueous calcium chloride
treating-mixture being withdrawn from the bot
tom of the primary bubble-tower may be care
fully maintained at a temperature between 355
treatment.
The withdrawn hydrocarbon vapors from off
of the top of the secondary bubble-tower may
then be continuously cooled and condensed there 50
and 487 degrees Fahrenheit.
‘
The primary bubble-tower may be constructed
of acid-proof materials such as are well-known
to those skilled in the art of treating hydrocarbon
55
in. The calcium chloride solution, from off of
the top of each pan above, passes into the pan
below at a point beneath the surface of the liq
uid therein. The calcium chloride solution par
tially cools and partially condenses the vapors
vapors with zinc chloride.
Gaseous ammonia may then be supplied to the
hydrocarbon vapors which have been withdrawn
from the primary bubble-tower. Sui?cient quan
tities may be supplied to render the vapors slight
ly ammoniacal.
The ammoniacal hydrocarbon vapors may then
be continuously supplied to the bottom of the
secondary bubble-tower and continuously with
drawn from it at the top thereof. Aqueous solu
tions of calcium chloride may then be continu
65 ously passed into the top of the said secondary
bubble-tower and may be continuously with
drawn from it at the bottom thereof. Within the
secondary bubble-tower the vapors may be
brought into contact with the aqueous calcium
70 chloride solution by bubbling therethrough in a
60
series of superimposed pans such as are well
known to those skilled in the art of treating hy
drocarbon vapors. The vapors, from off of the
top of each pan below, pass into the pan above
75 at a point beneath the surface of the liquid there
by forming gasoline.
The condensed gasoline may then be further
treated with ?fty degree Baumé sulphuric acid,
an aqueous solution of caustic soda and an aque
ous solution of sodium plumbite by processes well
known to those skilled in the art of manufac
55
turing gasoline from sulphur bearing mineral oil.
Although I have hereinabove shown and de
scribed only one process of re?ning gasoline em
60
bodying my invention, it is to be understood that
various changes and modi?cations may be made
in making the application of my improvements
in processes of treating hydrocarbon vapors with
out departing from the spirit of the invention and 65
the spirit and scope of the appended claims.
I claim:
1. In the re?ning of hydrocarbon oils, at a
temperature below zinc chloride fusion-temper
ature the step which comprises treating the oil 70
in the vapor phase, at a temperature above 355
degrees Fahrenheit, with a fused maintained
treating-mixture containing approximately one
part of ammonium chloride to prevent separa
tion of zinc chloride and three parts of zinc
3
2,108,438
chloride to prevent separation of ammonium
chloride.
7»
‘
2. In the re?ning of hydrocarbon oils, at a
temperature'below zinc chloride fusion-tempera
ture, the step which comprises treating, the, oil
in the vapor phase, at a temperature above 355
degrees Fahrenheit, with a fused maintained
,
»
20,
containing hydrocarbon liquid and withdrawing
the cOndensedgum-cOntaining hydrocarbon liq
uid.
7. A process comprising passing hydrocarbon
vapors at a temperature between 355 and 487 degrees Fahrenheit beneath the surface of a fused
treatingemixture‘ containing su?icient' ammoni
maintained treating-mixture containing approxi
um chloride to prevent separation of zinc chlo
mately three parts of zinc chloride to prevent sep
10 ride and suf?cient zinc chloride to prevent sep
15
partially cooled vapors from the condensed gum~
aration of ammonium chloride and one part of 10
‘ ammonium chloride to prevent separation of zinc
aration of ammonium chloride.
3. In the re?ning of hydrocarbon vapors, at a chloride, supplying to the treating-mixture a fused
temperature between v355 degrees Fahrenheit and mixture of chlorides of zinc and ammonium, sep
zinc chloride fusion-temperature, the step which arating and Withdrawing the vapors from the
comprises passing the vapors beneath the surface treating-mixture, withdrawing from the treating 15
of a fused maintained treating-mixture contain
mixture a fused mixture of chlorides of zinc and
ammonium containing products of reaction, pass
ing sufficient ammonium chloride to prevent S61)?
aration of 'zinc chloride and suflicient-zinc chlo
ing the withdrawn vapors beneath the surface of
a maintained aqueous solution of calcium chloride,
ride to prevent separation‘of ammonium ch10
ride.
~
supplying to the aqueous solution of calcium chlo 20
4. A process comprising passing hydrocarbon ride Water ‘and calcium chloride, separating and
withdrawing the vapors from the aqueous solution
vapors at a temperature between 355 and 487 de
grees Fahrenheit beneath the surface of a fused
of calcium chloride and withdrawing from the
maintained treating-mixture containing approxi
aqueous solution of calcium chloride water and
mately three parts of zinc chloride to prevent sep—
calcium chloride admixed with condensed hydro
aration of ammonium chloride'and one part of
carbon liquid.
ammonium chloride to prevent separation of zinc
chloride, supplying to the treating-mixture a
fused mixture of chlorides of zinc and ammonium,
30 separating and withdrawing the vapors from the
treating-mixture, withdrawing from the treating
25
7
8. A process comprising passing hydrocarbon
vapors containing gum-forming vapors at a tem
perature between 355 and 487 degrees Fahrenheit
beneath the surface of a fused maintained treat-. 30
ing-mixture containing approximately three parts
mixture a fused mixture of chlorides of zinc and - of zinc chloride to prevent separation of ammo"
ammonium containing products of reaction, par
tially cooling and partially-condensing the with
35 drawn vapors, separating and withdrawing the
partially cooled vapors from the condensed hydro
carbon liquid and withdrawing the condensed hy
drocarbon liquid.
'
5. A process comprising passing hydrocarbon
40 vapors containing gum-forming vapors at a tem'
nium chloride and one part of ammonium chloride
to prevent separation of zinc chloride, supplying
to the treating-mixture a fused mixture of chlo 35
rides of zinc and ammonium, separating and with~
drawing the vapors from the treating-mixture,
withdrawing from the treating-mixture a fused
mixture of chlorides of zinc and ammonium con
taining products of reaction, passing the with
40
perature between 355 and 487 degrees Fahrenheit
drawn vapors beneath the surface of a maintained
' aqueous solution of calcium chloride, supplying to
beneath the surface of a fused maintained treat
ing-mixture containing approximately three parts. the aqueous solution ‘of calcium chloride water
of zinc chloride to prevent separation of ammo
and calcium chloride, separating and withdrawing
the vapors from the aqueous solution of calcium 45
45 nium chloride and one part of ammonium chloride
to prevent separation of zinc chloride, supplying
to the treating-mixture a fused mixture of chlo
rides of zinc and ammonium, separating and with
, drawing the vapors from the treating-mixture,
50 withdrawing from the treating-mixture a fused
chloride and withdrawing from the aqueous solu
tion ofv calcium chloride water and calcium chlo
ride admixed with condensed gum-containing
hydrocarbon liquid.
‘
‘
v 9. A process comprising passing hydrocarbon 50
mixture of chlorides of zinc'and ammonium con
vapors containing hydrogen sulphide and gum
taining products of reaction, partially cooling and
gum-containing hydrocarbon liquid.
forming vapors at a temperature between 355 and
487 degrees Fahrenheit beneath the surface of a
fused maintained treating-mixture containing ap
proximately three parts of zinc chloride to prevent 55
separation of ammonium chloride and one part of
ammonium chloride to prevent separation of zinc
6. A process comprising passing hydrocarbon
vapors containing hydrogen sulphide and gum
mixture of chlorides of zinc and ammonium, sep
partially condensing the withdrawn vapors, sepa
rating and withdrawing the partially cooled va
55 pors from the condensed gum-containing hydro
carbon liquid and withdrawing the condensed
chloride, supplying to the treating-mixture fused
forming vapors at a temperature between 355 and 7 arating and withdrav‘ring the vapors from the 60
487 degrees Fahrenheit beneath the surface of a treating-mixture, withdrawing from the treating
mixture fused mixture of’ chlorides of zinc and
fused maintained treating-mixture containing ap
proximately three parts of zinc chloride to prevent
separation of ammonium chloride and one part of
65 ammonium chloride to prevent separation of zinc
chloride, supplying to the treating-mixture a fused
mixture of chlorides of zinc and ammonium, sep
arating and withdrawing the vapors from the
treating-mixture, withdrawing from the treating
70 mixture a fused mixture of chlorides of zinc and
ammonium containing products of reaction, sup
plying ammonia to the withdrawn vapors, par
tially cooling and partially condensing the ammo
niacal vapors, separating and withdrawing the V
ammonium containing products of reaction, sup~
plying ammonia to the withdrawn vapors, passing
the ammoniacal vapors beneath the surface of a 65
maintained aqueous solution of calcium chloride,
supplying to the aqueous solution of calcium chlo
ride water and calcium chloride, separating and
withdrawing the vapors from the aqueous solu
tion of calcium chloride and withdrawing from 70
the aqueous solution of calcium chloride water
and calcium chloride admixed with condensed
gum-containing hydrocarbon liquid.
FRANKLIN E. KIMBALL.
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