close

Вход

Забыли?

вход по аккаунту

?

Патент USA US2102863

код для вставки
Dec. 21, ‘1937.
2,102,863
a. w. TALBERT ET AL
MANUFACTURE OF PAVI‘RTIAL OXIDATION PRODUCTDS
Filed Nov. 6. 1935
._i
.. i
.F9LY.;:
I
-
m
//
Patented Dec. 21, 1937
- I
‘ 2,102,863
‘UNITED STATES‘
PATENT OFFICE .
2,102,863
MANUFACTURE - 0F PARTIAL OXIDATION
PRODUCTS
'
4
Guy W. Talbert, Summit, N. J., and John D.
Kerr, Forest Hills, N. Y., assignors to National
Aniline & Chemical Company, Inc., New York,
N.-Y,, a corporation of New York
Application November s, 1933, Serial No. 696,802 '
8 Claims.
(01. 260-123)
This invention relates to ‘improvements in the
manufacture of partial oxidation products of
organic chemical substances, and especially of
normally solid organic chemical substances, by
5 a. process which involves passing a 'vaporous re
action mixture containing the organic chemical
substance in the vapor phase and an oxidizing.
, gas in contact with an oxidation catalyst main
tained at-a suitable reaction temperature.
H.
It
O relates generally to an improved process and ap
paratus for forming the vaporous'r'eaction mix
ture, and more especially to an improved process
and apparatus for forming a mixture of va
porized naphthalene and air for use in the cat
15 alytic formation of phthalic anhydride;
» "The present invention has for an object im
provements in the manufacture of ‘partial oxi
dation products of organic chemical substances
by catalytic processes of the type hereinbefore
the material employed‘ and the sensitivity of the
reaction to changes in the composition of the
reaction mixture and in the reaction conditions.
Thus, mixtures of naphthalene and air within
certain ranges of proportions are likely to ex- 5
plode; it is therefore desirable for e?icient and
safe operation that the concentration of naph
thalene in the air-naphthalene mixture supplied
to the catalyst be known and/or controlled sub
stantially at all‘ times. To avoid operating with- 10
in the explosive range of naphthalene-air mix
times while securing ef?cient utilization of the ' -
naphthalene, it is generally the practice to em
ploy a relatively high ratio of air to naphthalene,
as for'example 25 parts to 30 parts by weight of 15
airper part by weight of naphthalene. The re
action between naphthalene and air is more-'
over, highly exothermic, and is preferably car- _
ried out at a relatively high temperature (for ex
ample, in the neighborhood of 350° C. to 550° 0.). 20
20 referred to, whereby uniform mixtures of nor
mally solid vaporizable organic chemical sub-» In view of the relatively small size of the pas
stances and oxidizing gases may be obtained and sages through which the vaporous reaction mix
consequently high yields and uniformity of the
desired product may be secured.
25 A further object of the-present invention is
to provide a satisfactory and efficient apparatus
for carrying out such improved processes.
Other objects of the invention will in part be
obvious and will in part appear hereinafter.
30 The invention will be describedas applied to
the vapor phase catalytic oxidation of naphtha
lene with air for the production of phthalic an
hydride. It is to be understood, however, that
the invention is not limited thereto and that
35 changes may be made in the details'of the
process and apparatus as well as in the mate
' rials treated, proportions of ingredients, order
of steps, etc. within the scope of the appended
, patent claims.
40
'
'
ture travels in contact with the catalyst and the
consequent high speed ,of passage, and further
owing to the relatively high reaction tempera- 25
ture employed and the relatively small amount
of naphthalene present at any instant, changes
in the composition of the vaporous reaction mix
ture produce far reaching effects upon the cata
lytic reaction and consequently upon the quality 30 '
and yield of the product _(phthalic anhydride)
obtained.
'
It has heretofore been proposed to provide a
naphthalene vapor-air mixture, for use in the cat.
alytic formation of phthalic anhydride, by provid- 35
ing a relatively large, shallow body of molten
naphthalene and passing a stream of air over the
surface thereof, whereby naphthalene vapors are
sublimed and mixed with the air.
This pro
In the vapor phase catalytic oxidation of cedure has the disadvantage that,_uniformity of 40
naphthalene with air‘ for the production of “operation is di?icult to'secure. Unless a very
phthalic anhydride in accordance with one well pure naphthalene is employed, the composition
of the vapor changes as the vaporization pro
known method, a mixture of air. and naphtha
lene vapors is passed in contact with a catalyst
45 maintained at a suitable reaction temperature;
as for example, vanadium oxide‘associated with
a suitable carrier and contained in tubes of ' small
cross sectional area which are in indirect heat
contact with a temperature controlling bath
50 that is adapted to boil at a temperature suitable.
for maintaining the desired reaction tempera
ture.
'
‘
'
The proper formation of the vaporous reac
tion mixture employed in the oxidation entails
55 considerable diiliculty, owing to the nature of
gresses, due to initialv sublimation of the more
volatile fractions of the body of molten material, 45 l
with consequent change in the composition of ‘
the air-vapor mixture. The passage,; further
more, of such large quantities of air as are re
quired for the production of vaporous-mixtures
of the desired concentration over a large surface 50
of molten naphthalene renders exceedingly vdif
?cult maintenance of a uniform concentration
'of the air-vapor mixture.
It has also heretofore been proposed to form
the naphthalene vapor mixture by passing a 65
2,102,863
2 .
stream of heated air through a body of molten
naphthalene under such conditions, that the air
is substantially saturated with naphthalene va
por at a known temperature, forming a primary
varying with and regulated by the pressure in
said high pressure zone.
In accordance with a
jfurther feature of the present invention, the
stream of air is passed through a conduit under
air-naphthalene mixture, and then diluting the‘ suitable pressure to provide the desired ?ow
through the system (which will be referred to
saturated air-naphthalene mixture with addi
tional air. While this procedure is much su
perior to the above-mentioned procedure, in that
only a part of the large quantity of air employed
10 in the oxidation reaction is passed in contact
herein as the “normal” gas pressure), a reduc
tion in pressure of said air stream is produced
ina zone of said conduit by the ?ow of said air
stream therethrough, and liquid naphthalene‘ is 10
with the molten naphthalene, so that more ac
drawn into the air stream by the reduction in
curate control is obtainable, it has the disad
pressure thereby produced.
vantage of requiring regulation and/or control -
In the practice of the present invention in ac
cordance with a preferred method of procedure,
a stream of air, heated to a temperature above
of the temperature of the molten naphthalene,
15 of the concentration of the primary air-naphtha
lene mixture, and of the amount of auxiliary air
employed for producing the ?nal vaporous re
action mixture. In addition, variations in the
pressure in the system, as for example changes
20 in the resistance of the catalyst mass to the
flow of gas mixture therethrough, which vari
ations are not transmitted to the primary air
the melting point of naphthalene, is passed
through ‘a conduit leading to a catalytic convert
er containing a catalyst adapted to bring about
the oxidation of naphthalene to phthalic anhy
dride, which conduit contains a‘ Venturi con— 20
striction or other suitable means for producing,
a reduction in pressure by the ?ow of the air
vapor mixture and the auxiliary air stream in
stream through said conduit, and naphthalene
the proper ratio, cause variation in the concen
in molten condition is drawn into said air stream
through ‘a calibrated ori?ce by the reduction in 25
25 tration of the air-vapor mixture and consequent
pressure resulting from the ?ow of said air stream '
ly in the quality and yield of the. product. '
According to the present invention, regulation
of the concentration of naphthalene in the naph
thalene-air mixture is obtained by utilizing the
30 ?ow of the air stream through the apparatus to
control the introduction of the naphthalene into
the mixture. ’ We have found, according to the
present invention, that many of the objections
to the prior methods of forming the vaporous
35 reaction mixture may be overcome and other
through said Venturi constriction. It will ac
cordingly be understood that where a conduit
having a Venturi pipe therein is referred to in
the appended claims it is intended to include 30
any conduit having a restricted cross-section in
a zone thereof whereby on passing a stream of
gas through the conduit a Venturi effect in the
gas stream is produced. In order to renderthe
highly desirable advantages may be secured by
supply of naphthalene substantially independent
of external conditions, the naphthalene is main
employing the so-called “Venturi” or similar ef
tained under a pressure substantially the same
35
fect, for example that which results from the ,as that prevailing in the conduit leading from
flow of a ?uid through a graduated constriction of
the Venturi to the catalytic converter inlet; as
the “Venturi” type in a conduit, to supply the
naphthalene to the air stream. Inasmuch as
the reduction in pressure which ,occurs at the
throat of a Venturi pipe varies in, accordance
with variations in the speed of ?ow of the air
stream through said pipe, it is possible, in ac
cordance with the present invention, to main
tain a substantially uniform ratio of naphthalene
to air in the vaporous reaction mixture, notwith
standing variations in the rate of ?ow of the
for example, by maintaining a body of molten 40.
naphthalene in a closed vessel at a relatively
constant surface level and controlling the pres
sure on the surface of said body of naphthalene
so as to have it correspond substantially with
the pressure prevailing in the conduit between
45
the‘ Venturi and the catalytic converter inlet
(herein referred to as the pressure of the result
ing gaseous reaction mixture). The surface
level of the body of molten naphthalene is pref
erably maintained at a point below that at which 50
50 air stream through the system.
The invention accordingly comprises the steps ‘ the naphthalene is introduced into the-Venturi,
and their relation, and the apparatus, having the
so that the naphthalene is drawn into the air
features of construction and combination and
arrangement of parts adapted to carry out said
55 steps, which will be illustrated in the process and
apparatus hereinafter disclosed. The scope of
‘the invention will be indicated in the appended
stream substantially solely by the reduction in
pressure produced by‘ the ?ow of, the air stream
patent
claims.
.
.
.
.
> In the conversion of naphthalene to phthalic
anhydride by catalytic oxidation in the vapor
phase with air, in accordance with one feature
of thepresent invention, the vaporous or gaseous
reaction mixture is produced by passing a stream
through the Venturi zone of the conduit.
'
. The invention will be further described in con
5a
nection with the accompanying drawing in which ,
Fig. 1_ diagrammatically represents one form
of apparatus for carrying out'the invention;
Fig-2 illustrates a somewhat different appara 60
tus for carrying out the invention; and
Fig. 3 is a vertical section of a Venturi tube
employed in the practice of the'invention, show
of air through a zone of high velocity in such a ing details of its construction.
_ The apparatus illustrated in Fig. 1 comprise a 65
65 manner as to create a suction in said zone, which
suction is sensitive to pressure variations in said jpreheater I, a Venturi tube 2, a supply tank 3,
air stream, ‘and liquid naphthalene is introduced
into said zone in a quantity proportionate to the
a separator l, and a catalytic converter 5.
The preheater l shown in the drawing is pro
quantity of gas passing through said zone. In vided with a suitable gas inlet 6 and vis'aglapted to
70 accordance with another feature of the present Y effect the heating of thej_=gas by indirect heat 70
invention, the stream of air is passed. ?rst ; exchange with steam, .is'uitable means such as,
through a zone of high velocityand low pressure,
and second through a zone of low velocity and
high pressure, and liquid naphthalene is intro
75 duced into the low pressure zone under a pressure
steam inlet 1 being provided for the introduction’
of steam; A dr'awo?' 8 is shown for'withdraw
ing steam and/or condensate.
A gas conduit 9 75
'
leads from the preheater l to the Venturi tube 2.
2,192,883
This conduit may be lagged or jacketed, if
desired.
,
,
‘
The Venturi tube 2 is provided with a gas pas
3
.
The Venturi tube 22 is provided with a gas
passage therethrough from the conduit 30 to a
conduit 3| leading to the inlet of‘ the separator
sage therethrough from the inlet conduit 9 to a "24, and has intermediate of these conduits a
vconduit [0 leading to the separator 4, and has
throat 32. Conduits 33 and 33' are adapted to
intermediate of these conduits a throat ||. Con
conduct liquid from the supply tank 23 to suit- .
duits I2 and I2’ provide communication from the
able inlets or ori?ces in the venturi at or near
the throat 32 thereof.
liquid supply tank 3 to the interior of the Ven
The liquid supply tank 23 is provided with a
turi tube‘ at a point at or near the throat || I
liquid inlet 34 as well as outlet conduits 33 10'
thereof.
The liquid supply tank 3 is shown as a closed and 33'. Suitable devices, such as test cocks
35a, 35b and 350 permit the determination of the
vessel provided with a suitable inlet M for supply
liquid level in the supply tank. A valved vent 39
ing liquid naphthalene. The inlet I4 may be con
nected with any suitable source of liquid and the may also be provided to open the tank to the
level of liquid in the tank may be regulated in atmosphere if desired. A steam jacket 237' may
any suitable manner, as by manual control of the be employed for maintaining the liquid in the
'
valve i412. The inlet i4 -is preferably connected supply tank in a heated condition. ‘
The separator 24 may be of any suitable con- "
with a suitably heated constant-level liquid‘feed
of the well-known type adapted to maintain the
20 liquid in the tank 3 at a substantially constant
surface level. If desired, an auxiliary liquid sup
ply l3 may be provided. A steam jacket 37' or
other-suitable heating or insulating means may
. be supplied for maintaining'the liquid in the supN? in ply tank in a heated condition where such‘is de
sirable. A valved vent l8 to the atmosphere may
also be provided for opening the tank '3 to the at
mosphere if desired.
gases or gas and vapor enter through conduit 3|
and leave through a conduit 31. A steam'jacket
247‘ having a suitable steam inlet and a drawoff is
provided for avoiding a temperature drop in the 25
separator.
‘
or gas and ‘vapors enter through conduit l0 and
leave through a conduit It. A steam jacket 47'_
vails in conduit 31 and variations of pressure in .
struction for removing suspended matter from
the gases or gas and vapor passingtherethrough.
A centrifugal separator or electrical precipitator,
for‘ example, may be used for this purpose. In
the separator illustrated in the drawing the gases
having a suitable steam inlet and a drawoff is
provided for avoiding heat losses or a‘ tempera
ture drop in this unit of equipment.
40
In the separator illustrated in the drawing, the
Conduit 31 leads to the settling chamber or
‘separator 25 wherein further removal of "sus
pended matter .may be e?ected. This separator
is likewise provided with a suitable steam jacket. 30
257'. The conduit 31 is connected by means of an
equalizer pipe 36 to the supply tank 23 at a point
above the liquid level in said tank. In this way
the liquid in the supply tank may be maintained
under substantially the same pressure that pre 35
. The separator 4 may be of any suitable con
'30
structionfor removing suspended matter from
the gases or gas and vapor passing therethrough. 20
Conduit i6, which leads from the separator 4
to the catalytic converter 5, ,is connected by
means of an equalizer pipe I5 to the supply tank
3 at a point above the‘liquid level in said tank.
By this means the liquid in the supply tank may
be maintained at substantially the same pres~
sure as prevails in conduit l6, and variations in
pressure in the latter immediately‘ transmitted
td the liquid in the supply tank. Both the equal
izer pipe l5 and the conduit l6 have been illus—
trated as being suitably lagged with insulation
I52‘ and I62‘. If desired, these pipes may be jack
eted or, where maintenance of high temperatures
either is not necessary or'may be obtained in
another manner the lagging may be dispensed
‘ with.
-
Converter 5, of well known construction, is
adapted to contain a suitable catalyst for carry
ing' out ‘the. oxidation process and is provided
with a valved outlet |9_ for the withdrawal of
60 reaction products while maintaining desired pres
sure conditions in the catalytic converter.
. The apparatus illustrated in Fig. 2 comprises
a preheater 2|,_a Venturi tube 22, a supply tank
v23, separators 24 and 25, and converter 26.
'
,The preheater 2| is provided with a gas inlet
21. As illustrated the preheater may employ
steam as a heating medium, suitable means being ‘
provided for'bringing the steam into-heat‘ex
change relation with the gas in its passage
through the preheater. For this purpose a steam
' inlet 28 and drawoi‘l 29 are shown for introducing
steam ‘and for withdrawing steam and/or con
densate. Agasv conduit 30 leads from the pre
heater 2| to the Venturi tube 22. This conduit
may be lagged or jacketed, if desired.
this conduit immediately transmitted to the liquid
in the supply tank.
‘
A condut 38 connected with the separator 25 by
an annular passage 38' leads to the converter 26.
The conduits 31 and 38 as well as the equalizer
pipe 36 have been shown as being provided with
suitable steam jackets 317', 337', and 367.. It will
be understood, of course, that under certain con
ditions these may be dispensed with if so desired 45
or suitable lagging may be substituted.
The converter 26 is-of well-known construction
and contains a suitable oxidation catalyst. . It is
provided with suitable valved-outlet means 40 for '
withdrawal of the reaction products of the cata
lytic conversion.
'
-
Fig. 3 illustrates a preferred type of Venturi
tube, for use in the preferred process of this in-‘
vention, having a tapered inlet portion 4| and a
tapered outlet portion 42 which are provided with
?anges 43 and 44 cooperating to form a union
between these two portions of the Venturi tube. '
The ?anges may be suitably drilled and secured
by stud bolts 45 or other suitable securing means.
Internally of the tubesyat the intersection of the 60
tapered walls, a portion is cut away to admit an
annular sleeve 46. , The sleeve 46 is designed to ?t
smoothly into the Venturi so that no appreciable
roughness of the walls occurs. This sleeve 46 also
serves to properly alignv the two tapered mem~
bers 4| and 42.
l
’
Adjacent the constricted portion of the Ven
turi tube, the member 42 is providedwith two
wells or chambers 41 and 48. The wells are pro
vided with pipes 49 and '53 adapted tqconnectv
them with the supply tank‘. The wells‘ are also;
provided with ori?ce plates 5| ‘and 52 having ori--[-_-v
?ces 5|’ and 52' communicating with the interior
of the Venturi passage at a point slightly toward
the outlet side thereof from the maximum con
2,102,868
4
passed in contact with the catalyst which is suit
striction of the throat. The or?ce plates‘ are ad
vantageously separate members which may be ably heated to cause the oxidation of naphtha
screwed into the walls of the Venturi tube and lene and its conversion to phthalic anhydride.
constitute replaceable units. The wells 41 and - The reaction product is withdrawn at outlet I9.
The quantity of naphthalene drawn in and
48 are provided with plugs 53 and 54 ‘to provide
access to the ori?ce plates 5| and 52', for cleaning, mixed with-the air will vary, of course, depend
ing on the design of the apparatus, the pres
replacement, etc. The pipes 49 and 50 are provid
sure conditions existing" in the system, etc. As
ed with screens 49s and 50s to remove solid mate
rial which might plug the ori?ces. The screens an example, we may consider a Venturi tube
10 may be of any suitable type, as for example,v
standard removable suction and pressure strain
ers of about 100 mesh, such as are ordinarily used
let and outlet portions being 25 inches and 55%
in pipes to remove sediment.
A needle valve 55 threaded into the plug 54 and
15 having an adjusting knob 56 is provided to control
the ?ow of liquid through the ori?ce 52’. The
valve stem 51 of the needle valve is suitably
packed by the gland 58 to prevent leakage during
operation. The ori?ce 52' is preferably some
20 what larger in diameter than the ori?ce 5|’ so
that the ?ow of liquid into the venturi is con-'
trollable within wide limits.
having‘ a diameter of Bile-inches at the ends, a 10
diameter at the throat of 131; inches, a length
of 801/4 inches (the lengths of the tapered in- .
-
The venturi is preferably constructed of brass,
while the sleeve 46 and the ori?ce plates 5| and 52
may avantageously be stainless steel. The in
terior walls of the venturi may be ?nished smooth
after assembly so that no roughness occurs at
the points where these ?ttings are inserted.
' In the operation of the apparatus shown in Fig.
1, as applied to the catalytic oxidation of naph
thalene to phthalic anhydride in accordance with
inches respectively)‘ and provided with a naph
thalene inlet ori?ce 5|’ of 1*; inch diameter at
a distance of 1%}, inches below the-maximum
constriction. Under the conditions above set
forth (that is an air supply at about 30 pounds
gauge pressure and a catalytic converter op
erating at a gauge pressure of about 22 pounds 20
at the exit thereof) about 3,000 pounds of air '
may be- passed through the system per hour.
Under these conditions, the gauge pressure on
the discharge side of the venturi, or in conduit
IE, will be about 28 to 28.5 pounds. Thus there 25
willbe a pressure differential of about 1.5 to
about 2 pounds between the intake side and the
discharge side of the venturi. Such an appa
ratus operating under the speci?ed conditions
will maintain a supply of 100 pounds of mol- '
ten naphthalene through the ori?ce 5|’ solely
one method of operation, air under suitable pres- . by the suction created by the air in passing
sure for passing the vaporous reaction mixture through the venturi, giving a weight ratio of
through the system, including the catalytic con
30 to 1 of air to naphthalene.
By maintaining the surface level of molten
35 verter (for example, air at a gauge pressure ofv
about 30 pounds per square inch for use in con
naphthalene in supply tank 3 at a substantially
nection with a converter operating at a gauge
constant level not substantially above the ori?ce
5|’, a substantially constant ratio of naphtha
lene togair is secured; notwithstanding the ?uc~
tuations in the operation, temperature, speed
pressure at the exit thereof of about 22 pounds)
‘is admitted from a suitable source to the inlet of
40 preheater I in which it is heated to “a suitable
temperature adapted to provide vaporization of
naphthalene, as for example, about 150° to about
160°‘ C. Naphthalene in a molten condition is
supplied to the tank 3 in such quantities as to
45 maintain a. substantially constant level of liquid
in said tank.
.
of gas ?ow, pressure and the like which ordi
narily occur in the manufacture of phthalic
anyhydride by. vapor phase catalytic oxidation
of naphthalene.
The equalizer l5 automatically and rapidly
maintains the naphthalene in supply tank ‘3 at
substantially the pressure prevailing in conduit
.|6, so that the effect of ordinary pressure varia
tions occurring in the system on the naphtha
lene supply is substantially eliminated; and by
The preheated air enters the Venturi tube and,
‘passing through the throat || thereof, creates a
suction which draws naphthalene through the
50 conduits l2 and I2’ from the supply tank 3. The
turbulence resulting from the ?ow of the air . maintaining a constant surface level of naphtha
stream through the Venturi throat results in lene in the tank 3 at or below the level of the
rapid and efficient mixing of the naphthalene ori?ce 5|’, the naphthalene is drawn into the
and heated air as well as assisting in rapid venturi 2 solely by the venturi effect produced
by the ?ow of air through it. If desired, the
55 vaporization of the naphthalene.
In the usual operation, the flow of naphthalene naphthalene in the tank 3 may be maintained
through tube I2’ is regulated by a suitable valve, at a constant level at or above the ori?ce 5|’;
such as needle valve 55. Ordinarily this valve but in that event the hydrostatic head of liquid
is closed except at the beginning of the process naphthalene becomes a factor in its supply, and
naphthalene may be introduced into the system
60 when a. reaction mixture‘ rich in naphthalene is
desired in order to get the temperature in the , even if no air is‘?owing through the venturi 2.
converter 5 up to the desired point. After the To avoid such a result, which may lead to dan
process is well started, the naphthalene is ordi-‘ gerous operating conditions, the naphthalene is
narily fed to the'Venturi tube solely through preferably maintained in tank 3 at a surface
supply pipe l2, the quantity being regulated by -‘ level about 2 inches below the level of ori?ce 5|’. 65
65
' the ori?ce 5|’. Preferably the level of naphtha
For delivery of the same weight of air per
lene. in tank 3 is maintained substantially con
hour through the venturi, it is evident that the
stant- at a point about 2 to about 8 inches below converter may be operated at other‘i pressures
the ori?ces 5|’ and 52'.
'
-
70 ' The air-naphthalene'mixture passes from the
Venturi tube into the separator or tar extractor
l where suspended matter is removed. It then
passes throughthezconduitJli to'the converter '
5, preferably without substantial reduction 'in‘
temperature. In- the converter 5 the mixture is
within the- limits‘ of the air supply.~pressure; ,
since a lowering of the pressure in the converter,
merely eifectsa reduction of the pressure on'.
the discharge side of the venturi and a conse
quent reduction of pressure on the intake side
of the venturi, which change is transmitted to’
the naphthalene in the tank 3 by the equalizer 75
5
2,102,863
ii. If the converter 5 is operatedat such a low
pressure that the pressure on the discharge
side of‘ the venturi is say 12 to ‘14 pounds per ‘
square inch (or about atmospheric pressure), the
equalizer I 5 may be eliminated and the vent l3
may be opened to the atmosphere. Even un
der the latter conditions, naphthalene will be
drawn into the air stream by the suction pro-'
duced in the venturi, although of course not
10 necessarily at the same ratio of air to naphtha
lene as in the above example. However, in the
catalytic conversion of naphthalene to phthalic
anhydride, operation at such relatively low pres
sure is not ordinarily desirable since it diminishes.
the output of theconverter and otherwise affects »
formity in the quality and yield of phthalic an
hydride are obtained.
While the invention has been speci?cally de
scribed in connection with the production of
phthalic anhydride by the catalytic oxidation of
naphthalene in the vapor phase, as has been
noted, the invention is not limited thereto but
may be generally applied to other processes for '
the manufacture of partial oxidation products
of organic chemical substances by catalytic oxi 10
dation in the vapor phase. Thus, the. process
and apparatus of the present invention may be
employed for the production of partial oxidation
products by employing molten anthracene, phe
nanthrene, acenaphthene, acenaphthalene, ?uo-v
the process.v Discharge pressures in the venturi -rene or other vaporizable normally solid organic
greater than about 12 to about 14 pounds per chemical substances instead of naphthalene.
Other oxygen-containing and/or oxidizing gases
square inch generally require the use ‘of the equal
izer l5,.or other suitable means for maintain , may be employed instead of air.
Suitable temperature and pressure gauges
20 ing pressure on the naphthalene supply during may, of course, be provided for the apparatus of 20
,the operation of the apparatus shown, and pref
erably at substantially the pressure prevailingv our invention in order to ascertain the conditions
in various portions of the apparatus. We have
in the conduit IS.
The operation of the apparatus shown in Fig. found it desirable, for example, to provide pres
sure gauges 59 and 60 at the inlet and near the
2 is carried out in a similar manner. Thus, pre
heated air is passed from the preheater 2|, at outlet of the Venturi ~tube in order to assure
a temperature .for example, of about 150° to proper regulation of the pressure conditions in
about 160° C., through the Venturi pipe 22.’ The
reduction in pressure cause by the passage of
30
the preheated air through t 'e Venturi pipe 22_
serves to draw molten naphthalene from the sup
ply tank 23 into the preheated air through the
conduit 33 or conduits 33 and 33'.
The result
ing vaporous reaction mixture is, passed through
separator 24 and then through conduit 31 tov
settling chamber 25, wherein more complete re
moval of tar and other suspended matter is ef-v
fected.
The resulting cleaned vaporous- reac
tion mixture containing naphthalene vapor and
40 air then passes into catalytic converter 26 where
it is contacted with a suitable catalyst (as for,
example vanadium oxide associated with a car
this unit'of the apparatus.
-
In the above description of one method of
operating the process and apparatus of our in
vention, the prevailing pressures have been set
forth in terms-oi gauge pressure. However, the
pressures existing in the various zones or" the
system need not always be maintained at a posi
tive gauge pressure to come within the purview
of our invention. Reference to pressures as high
pressures and low pressures is purely relative and
pressure as used in the appended claims refers
not to gauge pressure but to absolute pressure.
As is. well known the pressure and velocity head 40
of a ?uid undergoes wide variation in passing
from the inlet to the throat of a Venturi and
rier) under reaction conditions adapted for the - from the throat to the outlet thereof. The fluid
in the zones in proximity to the inlet and outlet
‘ production of phthalic anhydride ‘and the result
is ‘at comparatively high pressure and corre
ing
reaction
mixture
is
withdrawn
from
the
con
45
spondingly
low velocity while in the restricted
verter through the outlet 40. As in the case of
the apparatus shown- in Fig. 1, the pressure on area at or near the throat there is created a low
the naphthalene contained in supply tank 23 is prmsure zone in which the ?uid travels at high
maintained at substantially the same pressure velocity.v In the claims these zones have ac
cordingly been referred to for convenience as 50
50 as prevails in the conduit 31 by the equalizer 36. zones
of low velocity and high pressure, and a
The process and apparatus of the‘ present in
vention possess manifold advantages as com- » zone of high velocity and low pressure, respec
pared with those heretofore employed.
Inas
much as the introduction of naphthalene in the
preferred practice of the invention depends sole
ly upon the quantity of air passing through the
system a de?nite ratio of naphthalene to air may
tively.
'
4
We claim:
1. In the conversion of a normally solid or
55
ganic vaporizable substance to partialoxidation
products by catalytic oxidation in the vapor phase
with an oxygen-containing gas, the method of
forming a vaporous reaction mixture of the oxy
gen-containing gas and vapors of said substance
60 Since the quantity of liquid naphthalene intro
duced into the gas stream depends on the pres‘ which comprises passing a'stream of the oxygen
sure at the point of introduction and the pres containing gas through a Venturi pipe, maintain
sure applied to the liquid, variations in pressure ing a.‘ body of said substance in molten condi
of the gas stream result in a corresponding vari~ tion, drawing said substance from said body into 65
said stream of oxygen-containing gas by the suc-
be maintained notwithstanding. fluctuations in
the operation and conditions of the process.
ation in they rate of introductionof the naph
thalen'e. Consequently the adverse e?ect, of such
variations is in large part' compensated and a
tion created by said stream in passing through
said Venturi pipe and forming a vaporous reac
tion mixture, maintaining the surface level of
greater uniformity of composition of ,the result- ‘ said body substantially constant, and maintain
ant gas mixture is obtainable than byprevious ing a substantially constant pressure on said body 70
70 methods of operation. vThe process and appa
of said substance.
ratus, moreover, are simpler to control, less trou
blesome to operate, and are more certain in their
maintenance of the desired ratio than those
75 heretofore. employed. As a result, greater uni
~
\
2. In the conversion of anormally solid or
ganic vaporizable substance to partial oxidation
products by catalytic oxidation in the vapor phase
with an oxygen-containing gas, the method of 75.
6
2,102,863
forming a vaporous reaction mixture of the oxy
gen-containing gas and vapors of said substance
which comprises passing a stream of the oxygen
containing gas through a Venturi pipe, maintain
ing body of said substance in molten condition,
dra ‘ ng said substance from said body into said
stream of oxygen-containing gas by the suction
created by said stream in passing'through said
Venturi pipe and forming a, vaporous reaction
10 mixture, maintaining the surface level of said
body substantially constant at a point not sub
stantially above the point at which said sub
stance is introduced into said stream of oxygen
containing gas and maintaining a substantially
15 constant pressure on said body of said substance.
3. In the conversion of a normally solid or
ganic vaporizable substance to partial oxidation
products by catalytic oxidation in the vapor phase
‘with an oxygen-containing gas, the method of
tion mixture, maintaining the surface level of
said body substantially constant at a point not
substantially above the point at which said naph
thalene is introduced into said stream of oxygen
containing gas, and maintaining a pressure on
said body of naphthalene substantially corre
sponding with the pressure of the resulting va
porous reaction mixture.
6. In the conversion of a normally solid organic
vaporizable substance ‘to partial oxidation prod 10
ucts by catalytic oxidation in the vapor phase
with air, the method of forming a vaporous re
action mixture of air and vapors ofsaid substance
which comprises passing 'a stream of air through
a Venturi pipe, maintaining a body of said sub
stance- in molten condition, drawing said sub
15
stance from said body into said stream of airby
the suction created by said stream in passing
through said Venturi pipe and supplying heat to
the resulting mixture, thereby forming a vaporous 20
20 forming a vaporous reaction mixture of the oxy
gen-containing gas and vapors of said substance ‘ reaction mixture, maintaining the surface level
which comprises passing a stream of the oxygen
of said body substantially constant at a "point
containing gas through a Venturi pipe, maintain
ing a body of said substance in molten condition,
drawing said substance from said body into said
stream of oxygen-containing gas by the suction
created by said stream in passing through said
Venturi pipe and forming a vaporous reaction
not substantially above the point at which said
material is introduced into said stream of air,
and maintaining said substance at substantially
the pressure of the resulting vaporous reaction
mixture.
'
.
7. In the conversion of naphthalene to phthalic
mixture, maintaining the surface level of said ‘anhydride by catalytic oxidation with air, the
not substantially above the point at method of forming a.vaporous reaction mixture
which said substance is introduced into said of naphthalene vapor and air which comprises
stream of oxygen-containing-gas, and maintain
passing a stream of heated air through a Ven
80 body
turi pipe, drawing molten naphthalene “from a
stantially corresponding with the pressure of the ' body thereof into said air stream by the suction
85 resulting vaporous reaction mixture.
created by said air stream in passing through said
4. In the conversion of naphthalene to phthalic Venturi pipe, thereby forming a vaporous reaction
anhydride by catalytic oxidation in the vapor mixture, maintaining the surface level of said
phase with an oxygen-containing gas, the method body of molten naphthalene substantially conof forming a vaporous reaction mixture of ‘the stant at a point not substantially above the point
oxygen-containing gas and vapors of naphtha
at which said naphthalene is introduced into said
lene which comprises'passing a streamof the air ‘stream, and maintaining a pressure on said
oxygen-containing gas through a Venturi pipe, body of naphthalene substantially corresponding
maintaining a body of naphthalene in molten with the pressure of the resulting vaporous reac
ing a pressure on said body of said substance sub
condition, drawing naphthalene from said body
45 into said stream of oxygen-containing gas by the
tion mixture.
35
'
'
40
'
suction created by said stream in passing through
8. In the conversion of naphthalene to phthalic
anhydride by catalytic oxidation with air, the
said Venturi pipe and forming a vaporous reac-'
method of forming a vaporous reaction mixture '
tion mixture, maintaining the surface level of
of naphthalene vapor and air which comprises
said body substantially constant, and maintaining
passing a stream of air at a temperature of about
a pressure on said body of naphthalene substan
tially corresponding with the pressure of the re
viding a body of molten naphthalene at a tem
sulting vaporous reaction mixture..
'
,
'
5. In the conversion of naphthalene to phthalic
anhydride by catalytic oxidation in the vapor
55 phase with an oxygen-containing gas, the method
of forming a vaporous reaction mixture of/ the
oxygen-containing gas and vapors of naphthalene
which comprises passing a stream of the oxygen
containing gas through a Venturi pipe, main
taining a body of naphthalene in molten condi
tion, drawing- naphthalene from said body into
said stream of oxygen-containing gas by the suc
tion created by said stream in passing through
said Venturi pipe and forming a vaporous reac
150° to about 160° 0. through a Venturi pipe, pro v50
perature of about 130° C., introducing naphtha
lene from said body into the throat of said Ven
turi pipe, thereby forming a vaporous reaction
mixture, maintaining the surface level, of said
body of naphthalene at substantially the level of
said point of- introduction of naphthalene'into
said Venturi pipe, and maintaining a pressure on
vthe surface'of said body of naphthalene substan- ,
tially corresponding with the pressure of the re 60
sulting vaporous reaction mixture.
. GUY w. TAIIBER'I‘.
JOHN D. KERR.
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 105 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа