United States Patent (19) 11) 4,203,906

Takada et al. 45) May 20, 1980

54 PROCESS FORCATALYTIC VAPOR PHASE 3,180,877 4/1965 Benichou et al.................. 260/346.4

OX DATION 3,353,923 11/1967 Pelers ............................ 260/346.4X
75) Inventors: Masahiro Takada; Hiroyuki Uhara, Primary Examiner-Richard Raymond
both of Tatsuno; Takahisa Sato, Attorney, Agent, or Firm-Omri M. Behr
Himeji, all of Japan 57 ABSTRACT
73) Assignee: Nippon Shokubai Kagaku Kogyo Co., A process for catalytic vapor phase oxidation which
Ltd., Osaka, Japan comprises using a fixed-bed shell and tube heat ex
21 Appl. No.: 922,791 change type reactor in which a bundle of a multiplicity
22 Filed: Jul. 7, 1978 of tubes filled with at least one type of oxidizing catalyst
are disposed in a shell and these tubes are passed
30) Foreign Application Priority Data through the apertures formed in at least one perforated
Jul. 13, 1977 (JP) Japan .................................. 52-83.036 shield plate to partition the inside of the shell into at
Jul. 14, 1977 (JP) Japan ................................. 52-83.609 least two heat transfer medium feed zones and in such a
Jul. 20, 1977 (JP) Japan .................................. 52-86010 manner that each of the tubes passing through the per
51) Int. C.’............................................ CO7D 307/89 forated shield plate is not in direct contaction with the
52 U.S. C. ................................. 260/3464; 260/385; shield plate but the outer surface of the tube and the
260/396 R; 260/346.75; 260/465 C; 260/465.3; inner surface of the aperture are spaced apart by a dis
260/687 R; 562/545; 562/546; 562/547; tance of between 0.2-5 mm, supplying feed gas to the
422/201; 568/479;568/480; 568/476 tubes of the reactor, and conducting exothermic cata
58) Field of Search ................ 260/385, 396 R, 346.4, lytic vapor phase oxidation while controlling the tem
260/346.75, 465 C, 465.3, 604 R; 562/545-547 peratures for the heat transfer medium in each of the
56) References Cited
zones so that the temperature difference between each
of the zones can be maintained between 0-100 C.
U.S. PATENT DOCUMENTS
3,129,230 4/1964 Hughes ............................. 260/346.4 13 Claims, 5 Drawing Figures
U.S. Patent May 20, 1980 Sheet 2 of 2 4,203,906

FI C. 2 FIG 3

FIG 4 FG 5

~ ,…? )
º,)
 4,203,906 2
1.
activity of the catalyst from the inlet to the outlet in the
PROCESS FOR CATALYTICWAPORPHASE reaction tube. This method, however, requires at least
OXIDATION two types of catalysts of different catalytic activities,
and no optimum reaction temperatures can be selected
This invention relates to a process for catalytic vapor 5 for respective catalysts charged in each of the layers.
phase oxidation and a reactor used therefor and, in Moreover, if these catalysts show different degrees of
particular, to a process for catalytically oxidizing hy aging changes in their catalytic activities, control and
drocarbons in vapor phase using a fixed bed multi-tubu keeping of the optimum reaction temperatures are fur
lar heat exchange type reactor. More specifically, it ther difficult to inevitably lower the over all yield for
concerns a structure of a multi-tubular heat exchange 10 the desired products.
type reactor which can keep a catalyst used therein at A still further effective method is proposed as dis
optimum reaction conditions and restrict the generation closed in U.S. Pat. No. 3,147,084 and in German Laid
of hot spots (abnormal local heating in catalyst layers), Open Patent Publication No. 2,513,405 wherein a shell
upon exothermic catalytic vapor phase oxidation of of a multi-tubular heat exchange type reactor is entirely
hydrocarbons, and a method of using such a reactor. 15 partitioned with a shield plate into two heat transfer
Catalytic vapor phase oxidations are generally highly medium feed zones and reaction is carried out while
exothermic and it is thus very important to control the circulating heat transfer medium at different tempera
reaction temperature within a certain range and restrict tures in each of the zones. It is, however, very difficult
the generation of hot spots in the reaction zones, which to this method to insert as many as several thousands of
imposes great efforts on those skilled in the art. No 20 reaction tubes into a perforated plate used as the shield
satisfactory control of the catalytic reaction tempera plate in the reactor, and those portions between the
ture with the catalysts can be attained only with the perforated plate and the reaction tubes that are con
uniform circulation of heat transfer medium in a reactor tacted by the heat expansion of the tubes are abrased by
and hot spots appear frequently to result in excess oxi the pulsation of the heat transfer medium to cause cor
dation locally in the reactor, particularly where the 25 rosion and destruction unless the reaction tubes and the
oxidation reaction has to be proceeded sequentially to perforated plate are secured to each other by welding
convert starting materials into end products such as in or expanding the diameter of the reaction tubes. The
the oxidation of naphthalene or o-xylene into phthalic above securing fabrication however requires trouble
anhydride, oxidation of benzene, butylene or butadiene some works such as accurate perforation, welding and
into maleic anhydride, oxidation of propylene into acro 30 diameter expansion over several thousands of portions.
lein or acrylic acid, oxidation of ethylene into ethylene It is, accordingly, an object of this invention to pro
oxide, ammoxidation of propylene into acrylonitrile, vide an improved process of catalytic vapor phase oxi
ammoxidation of aromatic hydrocarbons such as tolu dation and a reactor used therefor.
ene and xylene into aromatic nitriles such as benzoni It is another object of this invention to provide a
trile, phthalonitrile and the like. As the result undesired 35 process of catalytic vapor phase oxidation in which
combustion reaction is increased to lower the yield of catalyst is kept at its optimum reaction conditions and
the aimed products. In addition, since the catalysts are an apparatus used therefor.
always exposed locally to high temperature by the pres It is a further object of this invention to provide a
ence of the hot spots, the life of the catalysts is de structure of a multi-tubular heat exchange type reactor
creased in that portion to result in disadvantages. capable of restricting the generation of hot spots and a
Various counter measures have been employed in method of using such a reactor.
order to overcome the foregoing disadvantages in the These objects of this invention can be attained by the
vapor phase oxidation. As one of the most popular catalytic vapor phase oxidation process which com
methods, the diameter of catalyst filled tube is de prises using a fixed-bed shell and tube heat exchange
creased in order to increase the heat transfer rate per 45 type reactor in which a bundle of multiplicity of tubes
unit volume of the catalyst. This method is, however, filled with at least one type of oxidation catalyst is dis
defective in that the number of the filled tube is in posed in a shell and these tubes are passed through the
creased and it increases the fabrication cost of the reac apertures perforation in at least one perforated shield
tor, as well as takes much time for the charging and plate to partition the shell into at least two heat transfer
discharging of the catalyst. 50 medium feed zones in such a way that each of the tubes
In other effective methods proposed so far, catalyst passed through the perforated sheild plate is not in
layer is diluted with an inert substance or, as disclosed direct contaction with the shield plate but the outer
in Japanese Published Unexamined Patent Application surface of the tubes and the inner surface of the aper
No. 85485/1973, generation of hot spots is restricted by tures are spaced apart with a distance between 0.2-5
the insertion of cylindrical material containing closed 55 mm, feeding feed gas to the tubes of the reactor, and
cavity in the center at the cross section of a reaction conducting the exothermic catalytic vapor phase oxida
tube filled with the catalyst entirely or partially in the tion while controlling the temperatures of the heat
axial direction of it thereby providing a space in which transfer medium in each of the zones partitioned by the
no catalyst is present and no reaction mixture passes shield plate so that the temperature difference therebe
through. This method is, however, defective in that the 60 tween is kept within the range between 0-100° C.
cost is inevitably increased by so much as the substan In order to obtain high yield an improved reactor for
tially inert material is contained. It has a further defect varying reaction temperatures corresponding to reac
that recovery of useful metal components from the tion stages has hitherto been proposed (Japanese Pub
catalyst removed from the reactor after the degradation lished Unexamined Patent Application No.
of the catalytic activity is very laborious to lower the 65 80473/1973.) However, settlement of the temperature
recovery efficiency. described in the Patent Application No. 80473/1973 is
A further effective method suppresses the tempera to carry out the reaction smoothly by providing a con
ture rise in the hot spots by gradually increasing the troller in a circulation mechanism of the heat transfer
 4,203,906
3 4.
medium, so it is difficult to obtain almost shielded reac the shell 2 is divided into at least two heat transfer
tion temperature zones as in the present invention. In medium zones A and B by the disposition of at least one
the above process it is rather proposed to provide reac perforated plate 10 at a desired position, to the apertures
tion zones wherein the heat transfer mediums are com 11 of which are passed through the reaction tubes 3. As
pletely separated each other as a means for obtaining shown in FIG. 1 and FIG. 2, the perforated shield plate
such shielded reaction temperature zones. Therefore, it 10 is not in direct contaction with each of the reaction
is clear that the present invention relates to a simple and tubes 3 passing therethrough but the outer surface of the
economical reactor having a novel constitution in stead reaction tube 3 and the inner surface of the apertures 11
of a conventional case. are spaced apart at a distance between 0.2-5 mm. The
The reactor specified as foregoings in the process of 10 presence of the distance is important. If the reaction
the present invention has an advantage in that the struc tubes 3 and the shield plate 10 are arranged closed or
ture is simple to make the fabrication process simplified secured to each other with no gaps, the reaction tubes 3
and reduce the fabrication cost and, in addition, it has a and the shield plate 10 are undesirably contacted to
further feature as detailed hereinafter, that no substan each other and abrased due to the heat distortion re
tial heat distortion is generated. The use of this reactor 15 sulted in the reaction tubes 3 or the shield plate 10 be
in catalytic vapor phase oxidation enables to control the cause of the temperature difference between the zones
temperature of the heat transfer medium in the catalyst A and B, or frequent heating or cooling effected in the
layer region where exotherm is most significant to a reactor. Moreover, the fabrication of the reactor is
lower level than the temperature for the heat transfer laborious and costly. On the contrary, too wide gap
medium in other region to restrict the exotherm in the 20 makes the temperature control more difficult as the
hot spots. This enables to increase the conversion rate amount of heat medium moving between the zones A
of the feed gas to be oxidized in the succeeding zone and B is increased. It is required, based on our experi
substantially to 100% and thus permits most effective ence, that the distance between the outer surface of the
utilization of the catalyst. Particularly, the use of the reaction tube 3 and the inner surface of the apertures 11
above reactor according to this invention in the cata 25 in the shield plate 10 is between 0.2-5 mm and, prefera
lytic vapor phase reaction where the reaction is pro bly, 0.3-1 mm for performing satisfactory temperature
ceeded sequentially, restricts useless combustion caused control with no substantial movement of the heat trans
by the over oxidation in the hot spots to ensure im fer medium between the zones A and B.
proved yield in the desired products and enables to Heat transfer medium for heat exchange is supplied to
increase the concentration of the starting material as 30 the outer side 12 of the reaction tube bundle (shell side)
compared with that in the conventional catalytic vapor in the reactor 1 for keeping the reaction temperature
phase reaction. The reaction where catalysts and reac constant in the reaction tubes and it is introduced for
tion temperatures are different in each of the reaction heat exchange by way of a volute pump or an axial flow
steps and, hence, two or more reactors have been re pump 13 and 14 from inlets 15 and 16 and through
quired so far can be conducted with only one reactor by 35 annular conduits 17 and 18 into the zones A and B re
the process according to this invention. Moreover, this spectively. Then, it is discharged through annular con
invention provides a further merit that the catalyst life is duits 19 and 20 and from exits 21 and 22 respectively
prolonged astonishingly. and sent to heat exchangers (or heating devices) 25 and
This invention will be understood best in connection 26 for cooling (or heating) and then further circulated.
with the accompanying drawings, wherein: The method of circulating the heat transfer medium is
FIG. 1 is a vertical cross sectional view of a reactor noway limited only to the foregoing method. If the
for carrying out the process of this invention; temperature difference is very great between the zones
FIG. 2 is a cross sectional view of a part taken along A and B, keeping and control of the reaction tempera
line II-II in FIG. 1; ture can be facilitated by making lateral flow directions
FIG. 3 is a cross sectional view of a part of the shield 45 of the heat transfer medium at the shield plate 10 identi
plate mounting portion in another embodiment of this cal by introducing the heat medium from the outlet 22
invention; in the zone B where the heat medium is introduced from
FIG. 4 is a cross sectional view of a part of the shield the inlet 15 in the zone A. It is also possible to provide
plate mounting portion in still another embodiment of a flow control mechanism to each of the circulating
this invention; and 50 mechanisms for facilitating the temperature control in
FIG. 5 is a cross sectional view of a part of the shield each of the temperature zones, and either one of the
plate mounting portion in a still further embodiment of heat transfer medium cooling (or heating) means 25 and
this invention. 26 can be saved where exotherm (or endotherm) in the
FIG. 1 shows one example of a fixed-bed type shell zones A and B, the moving amount of the heat transfer
and tube heat exchange type reactor 1, whose shell 2 55 medium between the zones A and B and the circulating
contains in its inside a lot of (for example several hun amount of the heat transfer medium by way of the cir
dreds to several thousands or more) reaction tubes in a culating devices of the pumps 13 and 14 are known
diameter, for example, of 5-50 mm loaded in parallel previously.
with the axis of the shell 2. Each of the reaction tubes 3 Number of the shield plates 10 may be increased to
is fitted at its upper and the lower end respectively to 60 more than one where more strict temperature control is
each of the apertures in tube plates 4 and 5 respectively required for both of the zones A and B. It is recom
and secured thereto by means of diameter expansion mended, where the reactor has a great diameter and
and welding. At the lower portion of the reaction tubes, thus a lot of reaction tubes, to change the direction of
are secured a wire mesh screen 6 for the prevention of flow direction of the heat transfer medium by buffle
catalyst falling and a perforated plate 7 to the shell 2 by 65 plates 27 to thereby increase the heat exchange effi
means of welding and the like. The shell 2 is secured at ciency.
its upper and the lower ends with a front cap 8 and a At least one type of catalyst in the form of granule
rear cap 9 by means of welding or the like. The inside of such as in spherical, pellet and irregular form is charged
 4,203,906 6
5
in the reaction tube 3 and the feed gas is supplied The heat transfer medium used in this invention in
through the conduit 28 to the reactor 1 and the gas clude, in addition to the above medium, hot oil, naph
contacts the catalyst in the reaction tube 3 to conduct thalene derivatives (S.K. oil), mercury and the like.
the oxidation reaction. The reaction heat generated in While the process of this invention can be applied to
the course of the reaction is heat exchanged with the 5 any exothermic catalytic vapor phase oxidation, it is
heat transfer medium to keep the catalyst layer at a particularly advantageous for the catalytic vapor phase
predetermined temperature. The reaction mixture con oxidation of hydrocarbons including various produc
taining the desired products is sent through the conduit tion processes such as oxidation of naphthalene or o
29 to collection, recovery and purification steps. In the Xylene into phthalic anhydride, oxidation of benzene,
above reaction steps, the starting reaction material may 10 butylene or butadiene into maleic anhydride oxidation
be adversely introduced from the conduit 29, passed of propylene into acrolein or acrylic acid, oxidation of
through the reaction tube 3 and then discharged out of ethylene into ethylene oxide, ammoxidation of propy
the conduit 28. lene into acrylonitrile, oxidation of isobutylene into
FIG. 3 shows another embodiment of this invention methacrolein or methacrylic acid, ammoxidation of
and it shows a vertical section of a part of a shield plate
5 isobutylene into methacrylonitrile, ammoxidation of
3C in which no substantial movement of the heat trans aromatic hydrocarbons such as toluene and xylene into
fermedium is taken place between the zones A and B by aromatic nitriles such as benzonitrile and phthalonitrile,
annular fins 34 secured to reaction tubes 33. It is so oxidation of naphthalene into naphthoquinone, and
device that the heat transfer medium can be moved by 20
oxidation of anthracene into anthraquinone. In these
keeping the distance between the outer surface of the reactions, hydrocarbons and molecular oxygen are in
reaction tube 33 and the inner surface of the apertures troduced at the co-existence of an inert gas if required
35 in the shield plate 30 to between 0.2-5 mm. The into the reactor and oxidized into a desired product.
presence of the distance is important and, if the reaction The catalytic vapor phase oxidation can thus be ef
tube 33 and the shield plate 30 are closed too nearly or 25 fected with an extreme ease by using the reactor speci
secured to each other, the reaction tube and the shield fied in this invention. As stated above, while the reactor
plate are undesirably contacted and abrased where tem defined by the present invention is best suited to the
perature difference between the zones A and B is great conduction of the sequential oxidation, it has been
or frequent heating or cooling is taken place in the found based on our experience that the temperature
reactor. Moreover, fabrication of the reactor is labori 30 difference as great as 100 C. at the maximum can be set
between the heat transfer medium in each of the zones.
ous. On the contrary, it is not necessary and disadvanta The temperature difference between the heat transfer
geous to make the gap excessively wide. Since the dis medium in each of the zones is therefore between
tance between the reaction tube and another is selected
between 6-30 mm in a usual multi-tubular reactor, the 0-100° C. and, preferably, 0-80 C. As for the reason
distance between the shield plate and the reaction tube 35 of necessity of the temperature difference of 0° C. speci
is naturally restricted thereby. fied in above, there is a case that two or more sequential
The fin is secured to the reaction tube in such a man reactions having highly different heats of reaction from
ner as it covers the distance described above as shown each other can be advantageously carried out at nearly
in FIG. 3. The distance between the fin and the shield
the same temperature only by controlling the flow rates
of the heat transfer medium in each zone in the reactor
plate is controlled to between 0.2-5mm and, preferably, of this invention. Further, it means that at the beginning
0.3-1 mm, whereby no substantial movement of the heat of the reaction, even if several tens degree centigrade of
transfer medium between zones A and B is effected in temperature difference is required, activities of the cata
its circulation and the temperature for each of the reac lyst varies gradually with the lapse of time and the
tion temperature zones can be controlled with satisfac 45 temperature difference between each zone decreases,
tlOn. , -
and finally the temperature difference is sometimes
The fin may be disposed in parallel with the shield reversed.
plate or it may be secured to the reaction tube 43 in such More specifically, in the production of phthalic anhy
a manner that the top end of the fin 44 comes nearest to dride from o-xylene or naphthalene using two reaction
the shield plate as shown in FIG. 4. The fin 44 may be 50 temperature zones A and B, temperature between
attached either above or below the shield plate 40, or as 300-400' C. is employed in the preceeding stage and
shown in FIG. 5 fins 54 may be attached to a shield the temperature between 350-450° C. is employed in
plate 53 so that they alternately comes above and below the subsequent stage and the temperature difference has
the shield plate 50. to be kept between 30°-60° C. if the catalyst of a same
The distance above described as between 0.2-5mm, 55 composition is employed. Such a condition can be satis
preferably, 0.3-1 mm is somewhat influenced by the fied with ease. In the oxidation of benzene, butylene or
type of the heat transfer medium used. When highly butadiene into maleic anhydride using two reaction
viscous medium, for example, molten salt (mainly com temperature zones A and B, the temperature for the
posed of a mixture of potassium nitrate and sodium preceeding stage is at 320-400° C. and the temperature
nitrite) is used, the reaction temperature is high and the 60 for the subsequent stage is at 350-450° C. and it is
amount of the heat transfer medium passing through the required to maintain the temperature difference be
gap can be small even if the distance is somewhat wide. tween 20-50 C. The above condition can also be satis
in using other heat transfer medium such as phenyl fied with ease.
ether medium (for example "Dowtherm') and poly Satisfactory results can also be obtained in carrying
phenyl medium (for example "Therm S''), it is, how 65 out the process of this invention using catalysts of two
ever, desired to make the distance somewhat narrower or more different compositions, because the reaction
even in a lower temperature reaction as compared with can be proceeded at reaction temperatures more suited
the use of the molten salts. to the performance of the respective catalysts.
 4,203,906
7.
It has been found, more characteristically to this Table 2
invention, that the process according to this invention is Reaction Phthalic
also applicable to such catalytic upon phase oxidation as temperature S.W. G.C. anhydride
comprising a preceeding oxidation of propylene into Time elapsed (°C) (hr) (1/g) yield (wt.%)
acrolein and a suceeding oxidation of the acrolein into Initial 370 4,000 20 12.8
acrylic acid where the reaction temperature in each of 3 month 375 4,000 20 2.1
the reaction zones is different as much as by 50-100° C. 6 month 381 4,000 20 10.4
12 month 390 4,000 20 105.9
EXAMPLE
O-xylene was catalytically oxidized by air in vapor 10
EXAMPLE 2
phase into phthalic anhydride using a vertical type mul
ti-tubular reactor as shown in FIG. I having 24 steel Reaction was conducted for 12 months using the
tubes 4 m in length, 25.0 mm in inside diameter and 29.0 same catalyst and the same reactor as those in Example
mm in outside diameter, in which a shield plate is situ 1, increasing the gas concentration to 16 (1) air/o-xylene
15 (g) and under the reaction conditions as shown in Table
ated at the half height of the reactor and the distance 3. The results are shown in Table 3.
between the reaction tubes passing through the shield
plate and the shield plate was adjusted to about 0.6 mm. Table 3
The catalyst employed in this oxidation reaction was Reaction
prepared in accordance with the description of Exam 20 temperature Phthalic
ple 1 in U.S. Pat. No. 3,926,846 and had a catalyst com (C) S.V. G.C. anhydride
position: V2O5:TiO2=2.1:97.9 on the weight basis and, Time elapsed A. B (hr) (1/g) yield (wt.%)
based on the total weight of V2O5 and TiO2, 0.49% by Initial 360 380 4,000 16 114.5
weight of P2O5, 0.146% by weight of K2O and 0.25% 3 month 363 380 4,000 16 113.9
6 month 365 383 4,000 16 113.5
by weight of Nb2O5. The porosity of the catalyst was 25 2 month 368 389 4,000 16 113.0
measured by mercury porosimeter, and the pore vol
ume of pore diameters of 0.10-0.45 micron amounted to
86% of the total volume of pores of diameters of less COMPARATIVE EXAMPLE 2
than 10 microns.
The catalyst thus prepared was charged by 1,500 cc 30 gasReaction was continued for 3 months increasing the
concentration in Comparative Example 1 to 16 (1)
per one reaction tube so as to give a 3 m catalyst layer air/o-xylene (g) and under the reaction conditions
length, 1 m of the total layer length situating a tempera shown in Table 4. The results are shown in Table 4.
ture Zone in the preceeding Stage (A) and remaining 2
m situating in the temperature zone in the subsequent Table 4
stage (B). 35 Reaction Phthalic
In the initial stage of the reaction, the temperature of temperature S.V. G.C. anhydride
the molten salt on the shell side of the reactor was main Time elapsed (C.) (hr) (l/g) yield (wt.%)
tained at 355° C. in the temperature zone A and at 375 Initial 380 4,000 6 04.1
3 month 407 4,000 16 97.7
C. in the temperature zone B, and the reaction was
started at a concentration of 20 (l) air/o-xylene (g) and 40
at a space velocity (S.V.) of 4,000 hr. The reaction EXAMPLE 3
was continued thereafter for one year while controlling
the temperature in both of the temperature zones A and Phthalic anhydride was prepared according to the
B so that the optimum yield was obtained for phthalic process in Example 1 and using two types of catalysts.
anhydride. The result are shown in Table 1. In the 45 The catalysts were prepared according to the descrip
Table 1, the yield for phthalic anhydride is expressed by tions of Example 1 in U.S. Pat. No. 4,046,780. A catalyst
weight % based on o-xylene supplied. The gas concen having a catalytically active substance of a composition:
tration (G.C.) is for the concentration air (1)/o-xylene V2O5:TiO2:Nb2O5:P2O5:K2O:-
(g). Na2O=2:98:0.25:1.02:0.15:0.1 (weight base) was pre
50 pared as the catalyst for the preceeding stage. The po
Table 1 rosity distribution of the catalyst was measured by a
Reaction mercury porosimeter. The pore volume of pore diame
temperature Phthalic ters of 0.15-0.45 micron amounted to 88% of the total
(C) S.V. G.C. anhydride pore volume of pores of diameters of less than 10 mi
Time elapsed A. B (hr) (1/g) yield (wt.%) 55 crons, which is to be referred to as 88% pore volume of
Initial 355 375 4,000 2O 15.3 0.15-0.45 micron hereinafter. The catalyst was used as
3 month
6 month
355
357
375
375
4,000
4,000
2O
20
115.0
114.5
the preceeding stage catalyst.
i2 month 359 375 4,000 2O 114.1 Then, another catalyst having a catalytically active
substance of a composition: V2O5:TiO2:Nb2O5:P2O5:-
60 K2O:Na2O=2:98:0.25:1.3:0.15:0.1 (weight basis) and
COMPARATIVE EXAMPLE 1. having 87% pore volume of 0.15-0.45 micron was pre
pared as the subsequent stage catalyst.
Reaction was continued for 12 months while using The catalysts thus prepared were charged in the reac
the same catalyst as in Example 1, using a same scale of tion tubes in the same reactor as employed in Example
a reactor as in Example 1 where no shield plate is pro 65 1 in which the subsequent stage catalyst was filled to a
vided so as to form a single temperature zone and under length of 1.5 m in the temperature zone B and then the
the reaction conditions shown in Table 2. The results precedding zone catalyst was filled to a length of 1.5 m
are also shown in Table 2. in the temperature zone A and the reaction was ef
 4,203,906
10
fected. The reaction conditions and the results of the lyst for oxidizing the acrolein into acrylic acid was
reaction are shown in Table 5. prepared according to the descriptions of Example 1 in
Table 5 U.S. Pat. No. 3,833,649. The preceeding stage catalyst
Reaction 5
was an oxidizing catalyst having a composition, except
temperature Phthalic for oxygen, of Co4Fe1BiW2Mo10Si1.35Ko06 in atomic
(C.) S.V. G.C. anhydride ratio, and the subsequent stage catalyst was an oxidizing
Time elapsed A B (hr-l) (/g) yield (wt.%) catalyst supported on a support and having a metal
Initial 360 375 3,500 16.6 117.2 composition of Mo12.V4.6Cu2.2Cro.6W24.
3 month
6 month
365
370
375
375
3,500
3,500
16.6
16.6
17.0
16.9 10
The subsequent stage catalyst was at first charged
each by 1,250 cc per one reaction tube in the tempera
ture zone B to form a layer height of 2.5 m. Then, 250
EXAMPLE 4 cc of 5 mm of diameter of spheric alundum was filled
thereover for cooling reaction gas in such a manner that
Maleic anhydride was obtained from benzene in the its upper end levelled with the plane of the shield plate.
same reactor as in Example 1. The catalyst used in this Then, the preceeding stage catalyst was charged further
oxidation was prepared according to the descriptions of thereover so as to form a 2.4 m charged layer length. A
Example 1 in U.S. Pat. No. 4,036,780. The completed gas mixture having a reaction gas composition of 7.0%
catalyst prepared had a catalytically active substances by volume of propylene, 12.6% by volume of oxygen,
Of a composition: V2O5:MoO3:P2O5:- 10.0% by volume of steam and balance of inert gas
Na2O= 1:0.40:0.015:006 (molar ratio). mainly containing nitrogen was supplied to the preceed
The catalyst thus prepared was charged by 1,500 cc ing stage catalyst at a space velocity (S.V.) of 1,350
per one reaction tube so as to give a 3 m catalyst layer hr (NTP) and the reaction was started while main
length. taining the temperature of 320 C. for the temperature
In the initial stage of the reaction, temperature was zone A and at 255 C. for the temperature zone B at the
maintained at 345 C. for the temperature zone A and at 25
370° C. for the temperature zone B, and the reaction initial stage of the reaction. The reaction was continued
was started at a gas concentration of 22 () air/benzene
thereafter for 12 months while controlling the tempera
(g) and at a space velocity of 2500 hr 1 (NTP). The ture in both of the temperature zones A and B so as to
reaction was continued thereafter for 12 months while obtain the optimum yield for acrylic acid. The results
controlling the temperatures for both of the zones A 30 are shown in Table 8.
and B so that the best yield was obtained for the yield of Table 8
inaleic anhydride. The results are shown in Table 6. Reaction S.V. to Acrylic acid
Table 6 temperature preceeding single
Time (C) catalyst G.C. pass yield
Reaction 35 elapsed A B (hr) (mol%) (mol%)
temperature Maleic
(°C) S.V. G.C. anhydride Initial 320 255 1,350 7 86.5
Time elapsed A B (hr) (l/g) Yield (wt.%) 3 month 320 260 i,350 7 86.9
6 month 320 266 1,350 7 87.5
Initia 345 370 2,500 22 94.2 12 320 270 1,350 7 88.0
3 month 347 370 2,500 22 92.8 month
6 month 350 372 2,500 22 93.0 40
12 month 355 375 2,500 22 92.7
What is claimed is:
1. A process for catalytic vapor phase oxidation
COMPARATIVE EXAMPLE 3 which comprises using a fixed-bed shell and tube heat
Reaction was continued using the same catalyst as 45 exchange type reactor in which abundle of a multiplic
employed in Example 4 and employing a same scale of ity of tubes filled with at least one type of oxidizing
a reactor as used in Example 4, in which no shield plate catalyst are disposed in a shell and these tubes are
was provided so as to form a single temperature zone passed through the apertures formed in at least one
and under the reaction conditions shown in Table 7. perforated shield plate to partition the inside of the shell
The results are shown in Table 7. 50 into at least two heat transfer medium-feed zones and in
Table 7 such a manner that each of the tubes passing through
Reaction Maieic
the perforated shield plate is not in direct contaction
temperature S.W. G.C. anhydride with the shield plate but the outer surface of the tube
Time elapsed (C.) (hr) (1/g) yield (wt.%) and the inner surface of the aperture are spaced apart by
Initial 370 2,500 22 93.2 55 a distance of between 0.2-5 mm, supplying feed gas to
3 month 378 2,500 22 90.0 the tubes of the reactor, and conducting exothermic
6 month 385 2,500 22 85.3 catalytic vapor phase oxidation while controlling the
2 nonth 390 2,500 22 8.7 temperatures for the heat transfer medium in each of the
zones so that the temperature difference between each
60 of the zones can be maintained between 0-100 C.
EXAMPLES 2. A process according to claim 1, wherein each of
Acrylic acid was obtained by the oxidation of propy the heat transfer medium feed zones is respectively
lene in a similar reactor to that in Example 1 excepting provided with means for circulating the heat transfer
that the length of a reaction tube was 6 m. As the cata medium.
lysts used in this oxidation, a preceeding stage catalyst 65 3. A process according to claim 1, wherein the perfo
for mainly preparing acrolein from propylene was pre rated shield plate is provided by one and the inside of
pared according to the descriptions of Example 1 in the shell is partitioned into two heat transfer medium
U.S. Pat. No. 3,825,600 and the subsequent stage cata feed zones.
 4,203,906 12
1.
4. A process according to claim 1, wherein the dis 8. A process according to claim 6, wherein the annu
tance between the outer surface of the tube and the lar fins are provided only on one side of the shield plate.
inner surface of the aperture in the perforated shield 9. A process according to claim 6, wherein the annu
lar fins are provided alternately on both sides of the
plate is between 0.3-1 mm. 5 shield plate.
5. A process according to claim 1, wherein the tem 0. A process according to claim 6, wherein the annu
perature difference between the heat transfer medium in lar fins are provided so as to outwardly open toward the
each of the zones partitioned by the shield plate is be gap between the tube and the shield plate.
tween 0-80 C. 11. A process according to claim 1, wherein one type
6. A process according to claim 1, wherein annular 10 of an oxidizing catalyst is filled in the reaction tubes.
fins having an outer diameter of a size capable of cover 12. A process according to claim 1, wherein two
ing the gap between the outer surface of the tube and types of oxidizing catalysts are filled in the reaction
tubes.
the inner surface of the aperture in the perforated shield 13. A process according to claim 12, wherein two
plate is secured to the tubes in the vicinity of the shield 15 types of the oxidizing catalysts are filled in the reaction
plate. tubes corresponding to each of the zones partitioned by
7. A process according to claim 6, wherein the annu the shield plate respectively.
As :
lar fins are made flat.
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