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Патент USA US2403735

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July 9, 1946.
R. B.IMAS_ON ETAL
' 2,403,735
HYDROGEN CHLORIDE MANUFACTURE‘
Filed Nov. 26, 1942
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2,403,735
Patented July 9, 1946
‘UNITED STATES PATENT OFFICE
2,403,735
HYDROGEN CHLORIDE MANUFACTURE
Ralph Burgess Mason and Jerry A. Pierce, Baton
Rouge, La., assignors to Standard Oil Develop
ment Company, a corporation of Delaware
Application November 26, 1942, Serial No. 467,054
(01. 23-156)
s 4 Claims.
1
2
It is an object, therefore, of the present in
This invention concerns a continuous method
vention to prepare hydrogen chloride in a high
for the preparation of hydrogen chloride. The '
invention relates in particular to the preparation
degree of purity fromvchlorine and gaseous hy
drocarbons in the absence of air. and thus to pre
oi! hydrogen chloride by the intercombustion of
pare hydrogen chloride suitable for immediate
use in reactions requiring this compound in the
chlorine and the readily available gaseous hydro
°carbons such as are present in oil ?eld and pe
anhydrous condition
troleum refinery locations.
The preparation of hydrogen chloride by the
'
Another object of the invention is to prepare I
hydrogen chloride in a high degreeof purity and
reaction of chlorine and methane in the pres
free from contamination with organic halides by
. ence of air has been known for some time. .When 10p the intercombustion of chlorine and easily avail
air is used to assist or support the combustion
of chlorine and methane the product is diluted
with a large amount of inert gases. These dilu
ents have to be removed for the more important
commercial uses of hydrogen chloride. Absorp
tion of the reaction product in water toremove
the diluents is disadvantageous since the scrub
bing system has to be constructed of relatively
costly materials in order’ to be resistant to cor;
able normally gaseous hydrocarbons.’
A further object of the invention is to prepare
hydrogen chloride in a high degree of concen
15 tration without employing water to effect con
centration of the hydrogen chloride.
Other objects will be apparent from the, fol
lowing description and illustrations of the inven
tion:
According to. the invention, chlorine and any
rosion; Furthermore, absorption of hydrogen 20 one, or a mixture, of the normally gaseous hy
chloride in water is particularly undesirable when
drocarbons are separately heated to a tempera
the anhydrous compound has to be prepared, such
ture between 1200° F. and 2000“ F., and then
as is necessary in the preparation of organic hal
brought together in a con?ning space or chamber.
ides .by the reaction of hydrogen chloride with
The gases ignite spontaneously and a continuous
unsaturated compounds; and when hydrogen 25 flame is established at the point of physical un
>
chloride is employed as a catalyst promoter with
ion, giving as the products of combustion essen
aluminum chloride in reactions, such as isomer
tially hydrogen chloride and carbon. The re
ization, alkylation, polymerization, and the like.
action products are held for a short period of
To effect the intercombustion of chloride and 30 time within a con?ning space or chamber at
gaseous hydrocarbons burners modeled after
about the reaction temperature. During this pe
those commonly employed to prepare hydrogen
riod any small amounts of chloro-hydrocarbons
chloride by the combustion of hydrogen and chlo
formed in the combustion are decomposed to hy
rine were found to be unsatisfactory. With such
drogen chloride, carbon, and hydrogen. ‘ The hy
burners substantial quantities of chloro-hydro
drogen chloride is then conducted from the com
35
carbons and other by-products were formed and
bustion chamber and collected as conveniently
Im- in general intercombustion was incomplete.
suitable. The carbon formed in the reaction is
proved, but still unsatisfactory, functioning was
partly deposited on the burner and such parts of
obtained with a burner in which the reactants
the preheating equipment as occur in the reac
were mixed by impingement. Satisfactory inter
tiorr chamber. Anotherportion of the carbon is
combustion was found to occur only when the
entrained in the product gases and removed from
reactants were preheated ‘and then brought to-5
gether at the burner preferably, by impingement,
the reactor.
and then the combustion products held at tem
peratures between 1200° F. and 2000° F. for a short
period of time. Under these conditions it was
conditions, especially when e?ected at substan
tially atmospheric pressure, proceeded smoothly
iv
'
.
apparatus to preheat the reactants to the desired
temperature. The chlorine and hydrocarbon gas,
found that the normally gaseous hydrocarbons
and chlorine reacted to form hydrogen chloride
and carbon almost quantitatively. Furthermore,
it was found that the intercombustion under such
"
In the preferred form of the invention the heat
of reaction of the chlorine and hydrocarbon gas
is utilized by means of suitable heat exchange
for example, natural gas comprising essentially‘
methane,’ are heated
50
and without hazard provided feed rates and 're- 1
action conditions were adjusted to prevent sub
separately’ by
passing "
through tubular (Fcoil type heat exchangers dis.
posed in the space where the intercombustion
occurs.
The tubes or coils terminate at a com
mon point where the reaction occurs with evolu
tion of large amounts of heat. Since carbon is
stantial quantities of unreacted chlorine being
55 formed as a product of the reaction and is de
present in the exit gases.
2,408,785
Q
3
V
,
posited to some extent within the reactor and
on the elements or the heat exchanger, it be
4
be heated to the same or difierent temperatures,
should be in the approximate range or
comes necessary at regular intervals to discon- - v but
1200*’ F. to 2000s F. The chlorine and the gaseous
tinue processing and to remove the deposited
hydrocarbon react to form hydrogen chloride and
carbon. Consequently, it is desirable to operate
carbon. The reaction products pass upward in
the reactor l, and are withdrawn through line 25
and cooler 21 to the carbon recovery system 29.
pairs 01’ reactors so that one may be in operation
while the other is being cleaned of carbon, and
continuous production or hydrogen chloride thus
maintained. A common recovery system for the
While part of the carbon is withdrawn in susa
hydrogen chloride may be used for each pair of 10 pended form along with the gaseous hydrogen
chloride, another portion of the carbon is de
reactors.
posited on the walls of the reactor i and on the
The method commonly employed for collecting
coils ‘I and I1, and may be eventually removed as
the hydrogen chloride is to pass the reactant
will be described hereinafter. A suitable carbon
gases through a series of ?lters or a Cottrell pre
system comprises several bag filters in
cipitator for removing the entrained carbon and 15 recovery
series followed by a Cottrell precipitator. How
then to a compression system for liquefying the
ever, other known types 01’ recovery equipment
hydrogen chloride. The carbon collected in the
may be used.
reaction zone, in addition to that entrained in
The ?ltered reactionproducts are compressed
the hydrogen chloride, may be recovered from
the reaction system by the use of scrapers, and 20 in compressor 3! to a su?icient pressure to
liquefy the hydrogen chloride which is passed to
collection 01' the carbon black made in a hopper
a storage drum or pressure cylinder 33 from
below the burner equipment after the reaction
which
non-condensible gases ‘ are vented
through
has been terminated and the equipment cooled.
line
5.
.
Carbon still adhering onto the burner equipment
As mentioned previously,‘ some of the carbon
can be removed by subsequently burning in air 25 produced
in the reaction deposits within the re
and utilized as an auxiliary source of heat ior
actor.
When
this carbon deposit is sumcient to
preheating reactants or for other purposes, if so
interfere with the reaction in any way, such as
desired. However, the reaction of-chlorine with
by causing an excessive pressure drop through
hydrocarbon gases is so highly exothermic that
the reactor. or retarding the rate of heat ex
more than sumcient heat is ordinarily available 30 change
between products and reactants, ?ow oi’ in the combustion zone for preheating the re
reactants is terminated in the system described
actants. In fact, in some cases coolers may be
while a. ?ow of reactants is started in a similar
required to prevent overheating of the reactor.
parallel reactor system. The same product re
An important feature‘ of the invention is the
particular manner in which the chlorine and the 85 covery system may be used for both reactors.
Part of the carbon may be removed from tE-Je
gaseous hydrocarbons are brought into contact
oil-stream reactor by tapping the equipment with
a hammer 31, thus dislodging most oi.’ the carbon
adhering to the sides 01' the reactor and from
50 as to effect their mutual combustion at the
point of physical union in a con?ned space in
the absence of other gaseous materials. Many
types of apparatus may be devised as embodi 40
ments of the inventio .
some portions of the coils ‘I and IT. This carbon
is allowed to drop into a hopper 39 at the bottom
of- the reactor from which it may be recovered.
Scrapers may also be used to remove carbon from
the reactor and heat exchangers. In case the
'
As an illustration of the invention and em
bodiment thereof the following description and
attached drawing are presented:
, carbon is to be recovered by scrapers, it will be
most convenient to construct the heat ex
In the drawing, numeral I indicates a con
fining chamber such as. a tower or elongated
changers of straight tubes rather than coil~type
vessel in which the reaction takes ‘place. The
hydrocarbon gas enters through line 3 contain
elements. Some carbon will remain in the re
actor system, and must be removed by combus
ing valve 5 and passes into coil ‘I disposed in
reactor I wherein the gases are preheated to the 50 tion with air which is admitted through line 4|.
Torch gas may be admitted with the air if nec
desired temperature. If it is desired to heat the
essary
to reach combustion temperatures. Prod
hydrocarbon to a lower temperature than results
ucts
of
combustion may be removed through line
from passing it through the entire length oi.’ coil 1,
43, and valve 45 by closing valve 41 in line 25.
valve 5 may be closed and the hydrocarbon
passed through line 9 and valve II, and thus
through only a part of coil 1'. By adjusting valves
5 and II, part of the hydrocarbon can be passed
through the entire length of the coil, and part
through only a fraction of the length of the coil
so that temperatures of varying degrees can be
obtained. The chlorine is fed through line l3
and valve I 5, and passes into coil l1 disposed
similarly in reactor I, to coil 1. As in the case
of the hydrocarbon gas, the temperature to which
the chlorine is preheated may be regulated by
passing all or part of it through line I! and valve
2!. The materials of which coils 1 and I‘! are
constructed must be capable oi’ withstanding cor
rosive atmospheres at high temperatures, for ex
ample, in the range of 1200" F. to 2000° F..
Quartz is a suitable material for these tubes.
The coils 1 and I1 terminate in a burner 23 in
- which the nozzles are arranged in such a manner
as to impinge the two gas streams on to each
With the equipment of the type thus described
55 the following results were obtained:
Approx. reactor temp., "F _____ _., ............ ._ 1,450
Hours of run ___________ _ .
l 700
2,000
1
l
92
92
106
Chlorine feed, parts/min ______________________ _ .
800
850
900
60 Wt. percent excess chlorine (above theoretical)__
Wt. percent excess methane (above theoretical).
2
0
0
4
5
0
Chlorine in exist gas, parts/min _______________ __
Theoretical H01 prod, parts/min_ ._
0
825
4. 4
840
0
925
Actual HCl prod, parts/min __ ._.
798
823
882
98
0. 5
95
0
Methane feed, parts/min. .
_______ ..
Percent hydrogen chloride produced (based on
chlorine feed) _________________ __' ____________ __
Percent chlorine unreacted ___________________ __
1
'
97
O
65
These data indicate that at elevated tempera
tures methane and chlorine react to' form hydro
gen chloride and carbon almost quantitatively.
The extent of the reaction is shown to be ap
proximately the same in the temperature range
70
1450° F'. to 2000° F. The carbon black recovered
from the reactor, as well as from the ?lters and
pfrecipitator,
is of a suitable grade for a variety
11888.
0
other. ‘The chlorine and the hydrocarbon may 75 It should be obvious that the disclosure is cap~
able of some variation within the scope of the
5
.
inventive concept as set iorth in the previous de
scription, and that the invention should‘not be
considered limited by the foregoing speci?c em
bodiments described for purposes merely of illus- _
tration. The invention on the other hand is to
be determined by the following claims.
What is claimed is:
_
l. A process for preparing hydrogen chloride by
the reaction of chlorine with a normally gaseous
hydrocarbon which consists in heating sepa
- rately chlorine and a normally gaseous hydro
carbon by the heat generated by their reaction,
bringing said heated gases in separate conduits
together to a common point. burning the two
6
gases at the point 01 contact. one supporting the
combustion of the other. and recovering the hy
drogen chloride thus formed.
2. A process for preparing hydrogen chloride
according to claim 1, in which the normally
gaseous hydrocarbon is a petroleum ?eld gas. a
3. A process for preparing hydrogen chloride
according to claim 1, in which the normally gas
eous hydrocarbon ‘is a petroleum re?nery gas.
4. A process for preparing hydrogenchloride
according to claim 1, in which the normally gas
eous hydrocarbon is methane.
‘
‘
RALPH BURGESS MASON.
JERRY A. PIERCE.
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