United States Patent (19) 11 4,256,783

Takada et al. 45) Mar. 17, 1981

54 CATALYTIC VAPOR PHASE OXIDATION 3,147,084 9/1964 Franzen et al. ...................... 422/197
REACTOR APPARATUS 3,353,923 1 1/1967 Peters.................................... 422/197
3,547,188 2/1970 Kuhnlein ......................... 165/159 X
75 Inventors: Masahiro Takada; Hiroyuki Uhara, 3,566,961 3/1971 Lorenz et al. . ... 165/160 X
both of Tatsuno; Takahisa Sato, 3,811,498 5/1974 Ferraro et al. ....................... 165/16
Himeji, all of Japan FOREIGN PATENT DOCUMENTS
73 Assignee: Nippon Skokubei Kagaku Kogyo Co., 2307685 8/1974 Fed. Rep. of Germany ........... 165/159
Ltd., Koraibashi, Japan
Primary Examiner-Joseph Scovronek
21 Appl. No.: 37,930 Attorney, Agent, or Firm-Omri M. Behr
22 Filed: May 9, 1979 57 ABSTRACT
Related U.S. Application Data - A catalytic vapor phase oxidation reactor which com
62) Division of Ser. No. 922,791, Jul. 7, 1978, Pat. No.
prises a fixed-bed shell and tube heat exchange appara
4,203,906. tus in which a bundle of a multiplicity of tubes filled
with at least one type of oxidizing catalyst are disposed
30 Foreign Application Priority Data in a shell and these tubes are passed through the aper
Jul. 13, 1977 JP Japan .................................. 52-83O36 tures formed in at least one perforated shield plate to
Jul. 14, 1977 JP Japan .................................. 52-83.609 partition the inside of the shell into at least two heat
Jul. 20, 1977 (JP) Japan .................................... 52-86010 transfer medium feed zones and in such a manner that
51 Int. Cl. .......................... B01J 8/06; F28D 7/00; each of the tubes passing through the perforated shield
F28F 9/00 plate is not in direct contaction with the shield plate but
the outer surface of the tube and the inner surface of the
52 U.S. Cl. ...................................... 422/197; 165/81; aperture are spaced apart by a distance of between 0.2-5
165/140; 165/161; 165/162; 422/201; 422/202; mm, supplying feed gas to the tubes of the reactor, and
422/205; 422/211
58 Field of Search ............... 422/197, 202, 205, 201, conducting exothermic catalytic vapor phase oxidation
422/198 US, 211 US; 165/81, 140, 159, 160, while controlling the temperatures for the heat transfer
161, 162; 260/346.4 medium in each of the zones so that the temperature
difference between each of the zones can be maintained
56 References Cited between 0-100° C.
U.S. PATENT DOCUMENTS
2,986,454 5/1961 Jewett .................................. 422/197 9 Claims, 5 Drawing Figures

9
U.S. Patent Mar. 17, 1981 Sheet of 2 4,256,783

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Sirfrary stratric instr
U.S. Patent Mar. 17, 1981 Sheet 2 of 2 4,256,783

No.<
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 4,256,783 2
1.
catalyst removed from the reactor after the degradation
CATALYTIC VAPORPHASE OXIDATION of the catalytic activity is very laborious to lower the
REACTOR APPARATUS recovery efficiency.
This is a division of application Ser. No. 922,791, filed A further effective method suppresses the tempera
7-7-78, now U.S. Pat. No. 4,203,906, issued May 20, 5 ture rise in the hot spots by gradually increasing the
1980. activity of the catalyst from the inlet to the outlet in the
BACKGROUND OF THE INVENTION reaction tube. This method, however, requires at least
1. Field of the Invention - two types of catalysts of different catalytic activities,
This invention relates to a process for catalytic vapor 10 and no optimum reaction temperatures can be selected
phase oxidation and a reactor used therefor and, in for respective catalysts charged in each of the layers.
particular, to a process for catalytically oxidizing hy Moreover, if these catalysts show different degrees of
drocarbons in vapor phase using a fixed bed multi-tubu aging changes in their catalytic activities, control and
lar heat exchange type reactor. More specifically, it keeping of the optimum reaction temperatures are fur
concerns a structure of a multi-tubular heat exchange ther difficult to inevitably lower the over all yield for
type reactor which can keep a catalyst used therein at the desired products.
optimum reaction conditions and restrict the generation A still further effective method is proposed as dis
of hot spots (abnormal local heating in catalyst layers), closed in U.S. Pat. No. 3,147,084 and in German Laid
upon exothermic catalytic vapor phase oxidation of Open Pat. Publication No. 2,513,405 wherein a shell of
hydrocarbons, and a method of using such a reactor. a multi-tubular heat exchange type reactor is entirely
2. Discussion of the Relevant Art 20 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 in this method to insert as many as several thousands of
imposes great efforts on those skilled in the art. No 25 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 abraded 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 30 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- 35 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 sch as benzonitrile, It is another object of this invention to provide a
phthalonitrile and the like. As the result undesired com- 40 process
bustion reaction is increased to lower the yield of the catalyst isofkept catalytic vapor phase oxidation in which
at its optimum reaction conditions and
aimed products. In addition, since the catalysts are al
ways exposed locally to high temperature by the pres an apparatus used therefor.
ence of the hot spots, the life of the catalysts is de It is a further object of this invention to provide a
creased in that portion to result in disadvantages. 45 structure of a multi-tubular heat exchange type reactor
Various counter measures have been employed in capable of restricting the generation of hot spots and a
order to overcome the foregoing disadvantages in the method of using such a reactor.
vapor phase oxidation. As one of the most popular These objects of this invention can be attained by the
methods, the diameter of catalyst filled tube is de catalytic vapor phase oxidation process which con
creased in order to increase the heat transfer rate per 50 prises using a fixed-bed shell and tube heat exchange
unit volume of the catalyst. This method is, however, type reactor in which a bundle of multiplicity of tubes
defective in that the number of the filled tube is in filled with at least one type of oxidation catalyst is dis
creased and it increases the fabrication cost of the reac posed in a shell and these tubes are passed through the
tor, as well as takes much time for the charging and apertures perforation in at least one perforated shield
discharging of the catalyst. 55 plate to partition the shell into at least two heat transfer
In other effective methods proposed so far, catalyst medium feed zones in such a way that each of the tubes
layer is diluted with an inert substance or, as disclosed passed through the perforated shield plate is not in
in Japanese Published Unexamined patent application direct contaction with the shield plate but the outer
No. 85485/1973, generation of hot spots is restricted by surface of the tubes and the inner surface of the aper
the insertion of cylindrical material containing closed 60 tures are spaced apart with a distance between 0.2-5
cavity in the center at the cross section of a reaction mm, feeding feed gas to the tubes of the reactor, and
tube filled with the catalyst entirely or partially in the conducting the exothermic catalytic vapor phase oxida
axial direction of it thereby providing a space in which tion while controlling the temperatures of the heat
no catalyst is present and no reaction mixture passes transfer medium in each of the zones partitioned by the
through. This method is, however, defective in that the 65 shield plate so that the temperature difference therebe
cost is inevitably increased by so much as the substan tween is kept within the range between 0-100° C.
tially inert material is contained. It has a further defect In order to obtain high yield an improved reactor for
that recovery of useful metal components from the varying reaction temperatures corresponding to reac
 4,256,783
3 4.
tion stages has hitherto been proposed (Japanese Pub and welding. At the lower portion of the reaction tubes,
lished Unexamined patent application No. 80473/1973.) are secured a wire mesh screen 6 for the prevention of
However, settlement of the temperature described in catalyst failing and a perforated plate 7 to the shell 2 by
the patent application No. 80473/1973 is to carry out means of welding and the like. The shell 2 is secured at
the reaction smoothly by providing a controller in a 5 its upper and the lower ends with a front cap 8 and a
circulation mechanism of the heat transfer medium, So it rear cap 9 by means of welding or the like. The inside of
is difficult to obtain relatively isolated reaction tempera the shell 2 is divided into at least two heat transfer
ture zones as in the present invention. In the above medium zones A and B by the disposition of at least one
process it is rather proposed to provide reaction zones perforated plate 10 at a desired position. Plate 10 is
wherein the heat transfer mediums are completely sepa 10 provided with apertures 11 through which are passed
rated from each other as a means for obtaining such the reaction tubes 3. As shown in FIG. 1 and FIG. 2, the
shielded reaction temperature zones. Therefore, it is perforated shield plate 10 is not in direct contaction
clear that the present invention relates to a simple and with each of the reaction tubes 3 passing therethrough
economical reactor having a novel construction. but the outer surface of the reaction tube 3 and the inner
The reactor specified hereinbefore for use in the pro 15 surface of the apertures 11 are spaced apart at a distance
cess of the present invention has an advantage in that between 0.2-5 mm. The provision of the distance is
the structure is simple to make, has reduced cost and, in important. If the reaction tubes 3 and the shield plate 10
addition, as detailed hereinafter, it is not distorted by are arranged closed or secured to each other with no
heat. The use of this reactor in catalytic vapor phase gaps, the reaction tubes 3 and the shield plate 10 are
oxidation enables one to control the temperature of the 20 undesirably contacted to each other and abrased due to
heat transfer medium in the catalyst layer region where the heat distortion resulted in the reaction tubes 3 or the
the exotherm is most significant to a lower level than shield plate 10 because of the temperature difference
the temperature for the heat transfer medium in the between the zones A and B, or frequent heating or
other region thereby restricting the exotherm in the hot cooling effected in the reactor. Moreover, the fabrica
spots. This enables one to increase the conversion rate 25 tion of the reactor is laborious and costly. On the con
of the feed gas to be oxidized in the succeeding zone trary, too wide gap makes the temperature control more
substantially to 100% and thus permits most effective difficult as the amount of heat medium moving between
utilization of the catalyst. Particularly, the use of the the zones A and B is increased. It is required, based on
above reactor according to this invention in the cata our experience, that the distance between the outer
lytic vapor phase reaction where the reaction is pro 30 surface of the reaction tube 3 and the inner surface of
ceeded sequentially, restricts useless combustion caused the apertures 11 in the shield plate 10 is between 0.2-5
by the over oxidation in the hot spots to ensure im mm and, preferably, 0.3-1 mm for performing satisfac
proved yield in the desired products and enables to tory temperature control with no substantial movement
increase the concentration of the starting material as of the heat transfer medium between the zones A and B.
compared with that in the conventional catalytic vapor 35 Heat transfer medium for heat exchange is supplied to
phase reaction. The reaction where catalysts and reac the outer side 12 of the reaction tube bundle (shell side)
tion temperatures are different in each of the reaction in the reactor 1 for keeping the reaction temperature
steps and, hence, two or more reactors have been re constant in the reaction tubes and it is introduced for
quired so far can be conducted with only one reactor by heat exchange by way of a volute pump or an exial flow
the process according to this invention. Moreover, this 40 pump 13 and 14 from inlets 15 and 16 and through
invention provides a further merit that the catalyst life is annular conduits 17 and 18 into the zones A and B re
prolonged astonishingly. spectively. Then, it is discharged through annular con
BRIEF DESCRIPTION OF DRAWINGS
duits 19 and 20 and from exits 21 and 22 respectively
and sent to heat exchangers (or heating devices) 25 and
This invention will be understood best in connection 45 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; 50 ture can be facilitated by making lateral flow directions
FIG. 3 is a cross sectional view of a part of the shield 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 into the outlet 22 in
invention; the zone B where the heat medium is introduced into
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 55 a flow control mechanism to each of the circulating
this invention; and 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 60 zones A and B, the moving amount of the heat transfer
and tube heat exchange type reactor 1, whose shell 2 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 65 The number of the shield plates 10 may be increased
is fitted at its upper and the lower end respectively to to more than one where more strict temperature control
each of the apertures in tube plates 4 and 5 respectively is 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
 4,256,783
5 6
thus a lot of reaction tubes, to change the direction of phenyl medium (for example "Therm S"), it is, how
flow of the heat transfer medium by baffle plates 27 to ever, desired to make the distance somewhat narrower
thereby increase the heat exchange efficiency. even in a lower temperature reaction as compared with
At least one type of catalyst in the form of granule the use of the molten salts.
such as in spherical, pellet and irregular form is charged 5 The heat transfer medium used in this invention in
in the reaction tube 3 and the feed gas is supplied clude, in addition to the above medium, hot oil, naph
through the conduit 28 to the reactor 1 and the gas thalene derivatives (S.K. oil), mercury and the like.
contacts the catalyst in the reaction tube 3 to conduct While the process of this invention can be applied to
the oxidation reaction. The reaction heat generated in any exothermic catalytic vapor phase oxidation, it is
the course of the reaction is heat exchanged with the 10 particularly advantageous for the catalytic vapor phase
heat transfer medium to keep the catalyst layer at a oxidation of hydrocarbons including various produc
predetermined temperature. The reaction mixture con tion processes such as oxidation of naphthalene or o
taining the desired products is sent through the conduit xylene into phthalic anhydride, oxidation of benzene,
29 to collection, recovery and purification steps. In the butylene or butadiene into maleic anhydride oxidation
above reaction steps, the starting reaction material may 5 of propylene into acrolein or acrylic acid, oxidation of
be alternatively introduced from the conduit 29, passed ethylene into ethylene oxide, ammoxidation of propy
through the reaction tube 3 and then discharged out of lene into acrylonitrile, oxidation of isobutylene into
the conduit 28. methacrolein or methacrylic acid, ammoxidation of
FIG. 3 shows another embodiment of this invention isobutylene into methacrylonitrile, ammoxidation of
and it shows a section in elevation of a part of a shield 20
aromatic hydrocarbons such as toluene and xylene into
plate 30 in which no substantial movement of the heat aromatic nitriles such as benzonitrile and phthalonitrile,
transfer medium takes place between the zones A and B oxidation of naphthalene into naphthoquinone, and
because of annular fins 34 secured to reaction tubes 33. oxidation of anthracene into anthraquinone. In these
This prevents the heat transfer medium from moving by reactions, hydrocarbons and molecular oxygen are in
keeping the distance between the outer surface of the 25
troduced with the co-existence of an inert gas if re
reaction tube 33 and the inner surface of the apertures quired into the reactor and oxidized into a desired prod
31 in the shield plate 30 to between 0.2-5 mm. The uct.
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 too closely spaced or fected with an extreme ease by using the reactor speci
secured to each other, the reaction tube and the shield 30
fied in this invention. As stated above, while the reactor
plate are undesirably contacted and abraded where defined by the present invention is best suited to the
temperature difference between the zones A and B is conduction of the sequential oxidation, it has been
great or frequent heating or cooling takes place in the found based on our experience that the temperature
reactor. Moreover, fabrication of the reactor is labori
ous. On the contrary, it is not necessary and disadvanta 35 difference as great as 100° C. at the maximum can be set
geous to make the gap excessively wide. Since the dis between the heat transfer medium in each of the zones.
tance between the reaction tube and another is selected The temperature difference between the heat transfer
between 6-30 mm in a usual multi-tubular reactor, the medium in each of the zones is therefore between
distance between the shield plate and the reaction tube 0-100° C. and, preferably, 0-80 C. As for the reason
is naturally restricted thereby. 40 of necessity of the temperature difference of 0° C. speci
The fin is secured to the reaction tube in such a man fied in above, there is a case that two or more sequential
ner as it covers the distance described above as shown reactions having highly different heats of reaction from
in FIG. 3. The distance between the fin and the shield each other can be advantageously carried out at nearly
plate is controlled to between 0.2-5 mm and, preferably, the same temperature only by controlling the flow rates
0.3-1 mm, whereby no substantial movement of the heat 45 of the heat transfer medium in each zone in the reactor
transfer medium between zones A and B is effected in of this invention. Further, it means that at the beginning
its circulation and the temperature for each of the reac of the reaction, even if several tens degree centigrade of
tion temperature zones can be controlled with satisfac temperature difference is required, activities of the cata
tion. lyst varies gradually with the lapse of time and the
The fin may be disposed in parallel with the shield 50 temperature difference between each zone decreases,
plate or it may be connically-shaped and secured to the and finally the temperature difference is sometimes
reaction tube 43 in such a manner that the top end of the reversed.
fin 44 comes nearest to the tube and extends outwardly More specifically, in the production of phthalic anhy
towards the shield plate as shown in FIG. 4. The fin 44 dride from o-xylene or naphthalene using two reaction
may be attached either above or below the shield plate 55 temperature zones A and B, temperature between
40, or as shown in FIG. 5 fins 54 may be attached to the 300-400° C. is employed in the preceeding stage and
tubes 53 so that they alternately are disposed above and the temperature between 350-450° C. is employed in
below the shield plate 50. the subsequent stage and the temperature difference has
The distance above described as between 0.2-5 mm, to be kept between 30°-60° C. if the catalyst of a same
preferably, 0.3-1 mm is somewhat influenced by the 60 composition is employed. Such a condition can be satis
type of the heat transfer medium used. When highly fied with ease. In the oxidation of benzene, butylene or
viscous medium, for example, molten salt (mainly com butadiene into maleic anhydride using two reaction
posed of a mixture of potassium nitrate and sodium temperature zones A and B, the temperature for the
nitrite) is used, the reaction temperature is high and the preceeding stage is at 320-400° C. and the temperature
amount of the heat transfer medium passing through the 65 for the subsequent stage is at 350-450° C. and it is
gap can be small even if the distance is somewhat wide. required to maintain the temperature difference be
in using other heat transfer medium such as phenyl tween 20-50° C. The above condition can also be satis
ether medium (for example "Dowtherm') and poly fied with ease.
 4,256,783
7 8
Satisfactory results can also be obtained in carrying vided so as to form a single temperature zone and under
out the process of this invention using catalysts of two the reaction conditions shown in Table 2. The results
or more different compositions, because the reaction are also shown in Table 2.
can be proceeded at reaction temperatures more suited TABLE 2
to the performance of the respective catalysts.
It has been found, more characteristically to this Reaction S.W. G.C.
Phthalic
anhydride
invention, that the process according to this invention is Time elapsed temperature (C) (hr) (1/g) yield (wt.%)
also applicable to a catalytic two phase oxidation pro Initial 370 4,000 2O 12.8
cess as comprising a preceeding oxidation of propylene 3 month 375 4,000 20 2.
into acrolein and a succeeding oxidation of propylene 10 6 month 38 4,000 20 10.4
into acrolein and a succeeding oxidation of the acrolein 12 month 390 4,000 20 105.9
into acrylic acid where the reaction temperature in each
of the reaction zones is different as much as by 50-100'
C. EXAMPLE 2
EXAMPLE 1. 5
O-xylene was catalytically oxidized by air in vapor Reaction was conducted for 12 months using the
phase into phthalic anhydride using a vertical type mul same catalyst and the same reactor as those in Example
ti-tubular reactor as shown in FIG. 1 having 24 steel 1, increasing the gas concentration to 16 (l) air/o-xylene
tubes 4 m in length, 25.0 mm in inside diameter and 29.0 (g) and under the reaction conditions as shown in Table
mm in outside diameter, in which a shield plate is situ 20 3. The results are shown in Table 3.
ated at the half height of the reactor and the distance TABLE 3
between the reaction tubes passing through the shield Reaction Phthalic
plate and the shield plate was adjusted to about 0.6 mm. temperature (C) S.W. G.C. anhydride
The catalyst employed in this oxidation reaction was Time elapsed A. B (hr) (1/g) yield (wt.%)
prepared in accordance with the description of Exam 25 Initial 360 380 4,000 16 14.5
ple 1 in U.S. Pat. No. 3,926,846 and had a catalyst com 3 month 363 380 4,000 6 113.9
position: V2O5:TiO2=2. 1:97.9 on the weight basis and, 6 month 365 383 4,000 6 113.5
based on the total weight of V2O5 and TiO2, 0.49% by 2 month 368 389 4,000 6 13.0
weight of P2O5, 0.146% by weight of K2O and 0.25%
by weight of Nb2O5. The porosity of the catalyst was 30
measured by mercury porosimeter, and the pore vol COMPARATIVE EXAMPLE 2
ume of pore diameters of 0.10-0.45 micron amounted to Reaction was continued for 3 months increasing the
86% of the total volume of pores of diameters of less gas concentration in Comparative Example 1 to 16 (1)
than 10 microns.
The catalyst thus prepared was charged by 1,500 cc 35 air/o-xylene (g) and under the reaction conditions
shown in Table 4. The results are shown in Table 4.
per one reaction tube so as to give a 3 m catalyst layer
length, 1 m of the total layer length situating a tempera TABLE 4
ture zone in the preceding Stage (A) and remaining 2 m Phthalic
situating in the temperature zone in the subsequent stage Reaction S.V. G.C. anhydride
(B). Time elapsed temperature (C.) (hr 1) (I/g) yield (wt.%)
40
In the initial stage of the reaction, the temperature of Initial 380 4,000 6 104.1
the molten salt on the shell side of the reactor was main 3 month 407 4,000 16 97.7
tained at 355C. in the temperature zone A and at
375C. in the temperature zone B, and the reaction was
started at a concentration of 2001) air/o-xylene(g) and at EXAMPLE 3
45
a space velocity (S.V.) of 4,000 hr 1. The reaction was Phthalic anhydride was prepared according to the
continued thereafter for one year while controlling the process in Example 1 and using two types of catalysts.
temperature in both of the temperature zones A and B The catalysts were prepared according to the descrip
So that the optimum yield was obtained for phthalic tions of Example 1 in U.S. Pat. No. 4,046,780. A catalyst
anhydride. The result are shown in Table 1. In the 50 having a catalytically active substance of a composition:
Table 1, the yield for phthalic anhydride is expressed by V2O5:TiO2:Nb2O5:P2O5:K2O:Na2O
weight % basis on o-xylene supplied. The gas concen =2:98:0.25:1.02:0.15:0.1 (weight base) was prepared as
tration (G.C.) is for the concentration air (1)/o-xylene the catalyst for the preceding stage. The porosity distri
(g). bution of the catalyst was measured by a mercury poro
TABLE 55 simeter. The pore volume of pore diameters of
Reaction Phthalic 0.15-0.45 micron amounted to 88% of the total pore
temperature ("C.) S.W. G.C. anhydride volume of pores of diameters of less than 10 microns,
Time elapsed A. B (hr) (1/g) yield (wt.%) 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 355 375 4,000 20 1 S.O 60 the preceding stage catalyst.
6 month
12 month
357
359
375
375
4,000
4,000
20
20
14.5
114.
Then, another catalyst having a catalytically active
substance of a composition:
V2O5:TiO2:Nb2O5:P2O5:K2O:Na2O
COMPARATIVE EXAMPLE 1. =2:98:0.25:1.3:0.15:0.1 (weight basis) and having 87%
65 pore volume of 0.15-0.45 micron was prepared as the
Reaction was continued for 12 months while using Subsequent stage catalyst.
the same catalyst as in Example i, using a same scale of The catalysts thus prepared were charged in the reac
a reactor as in Example 1 where no shield plate is pro tion tubes in the same reactor as employed in Example
 9 4,256,783 10
1 in which the subsequent stage catalyst was filled to a lysts used in this oxidation, a preceding stage catalyst
length of 1.5 m in the temperature zone B and then the for mainly preparing acrolein from propylene was pre
preceding zone catalyst was filled to a length of 1.5 m in pared according to the descriptions of Example 1 in
the temperature zone A and the reaction was effected. U.S. Pat. No. 3,825,600 and the subsequent stage cata
The reaction conditions and the results of the reaction 5 lyst for oxidizing the acrolein into acrylic acid was
are shown in Table 5. prepared according to the descriptions of Example 1 in
TABLE 5, U.S. Pat. No. 3,833,649. The preceding stage catalyst
Reaction 1. Phthalic was an oxidizing catalyst having a composition, except
temperature (C.) S.V. G.C. anhydride for oxygen, of Co4Fe1BiW2Mo10Si1.35KO06 in atomic
Time elapsed A. B (hr) (1/g) yield (wt.%) ratio, and the subsequent stage catalyst was an oxidizing
Initial 360 . . . . 375 3,500 16.6 17.2 catalyst supported on a support and having a metal
3 month
6 month
365
370
375
375
3,500
3,500
16.6
16.6
117.0
; 16.9
composition of : Mo12.V4.6Cu2.2Cro.6W24.
The subsequent stage catalyst was at first charged
15 each by 1,250 cc per one reaction tube in the tempera
EXAMPLE 4 ture zone B to form a layer height of 2.5 m. Then, 250
cc of 5 mm of diameter of spheric alundum was filled
Maleic anhydride was obtained from benzene in the thereover for cooling reaction gas in such a manner that
same reactor as in Example 1. The catalyst used in this its upper end levelled with the plane of the shield plate.
oxidation was prepared according to the descriptions of Then, the preceding stage catalyst was charged further
Example 1 in U.S. Pat. No. 4,036,780. The completed '' thereover so as to form a 2.4 m charged layer length. A
catalyst prepared had a catalytically active substance gas mixture having a reaction gas composition of 7.0%
of a composition : by volume of propylene, 12.6% by volume of oxygen,
V2O5:MoO3:P2O5:Na2O = 1:0.40 : 0.015: 0.06 (molar 10.0% by volume of steam and balance of inert gas
ratio). 25 mainly containing nitrogen was supplied to the preced
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-1 (NTP) and the reaction was started while main
length. taining the temperature at 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 30 initial stage of the reaction. The reaction was continued
370° C. for the temperature zone B, and the reaction thereafter for 12 months while controlling the tempera
was started at a gas concentration of 22 (l) air/benzene ture in both of the temperature zones A and B so as to
(g) and at a space velocity of 2500 hr 1 (NTP). The obtain the optimum yield for acrylic acid. The results
reaction was continued thereafter for 12 months while
controlling the temperatures for both of the zones A are shown in Table 8.
and B so that the best yield was obtained for the yield of 35 TABLE 8
maleic anhydride. The results are shown in Table 6. Reaction S.W. to Acrylic acid
TABLE 6 temperature preceeding single
Tine (C.) catalyst G.C. pass yield
Reaction Maleic elapsed A B (hr) (mol%) (mol%)
temperature (C) S.V. G.C. anhydride 40
Time elapsed A. B (hr) (1/g) Yield (wt.%) Initial 320 255 1,350 7 86.5
3 month 320 260 1,350 7 86.9
Initial 345. 370 2,500 22 94.2 6 month 320 266 1,350 7 87.5
3 month 347 370 2,500 22 92.8 12 month 320 270 1,350 7 88.0
6 month 350 372 2,500 22 93.0
2 month 355 375 2,500 22 92.7 45
Having thus set forth the nature of the invention,
what is claimed is:
COMPARATIVE EXAMPLE 3 1. A fixed-bed shell and tube heat exchange type
Reaction was continued using the same catalyst as reactor for use in exothermic catalytic vapor phase
employed in Example 4 and employing a same scale of 50 oxidation, comprising: a bundle of a multiplicity of
a reactor as used in Example 4, in which no shield plate tubes filled with at least one type of oxidizing catalyst
was provided so as to form a single temperature zone disposed in said shell, said tubes being passed through
and under the reaction conditions shown in Table 7. apertures provided in at least one perforated shield plate
The results are shown in Table 7. to partition the inside of said shell into at least two heat
TABLE 7 55 transfer medium feed zones in such a manner that each
Maleic
of said tubes passing through said perforated shield
Reaction S.V. G.C. anhydride plate is not in direct contact with said shield plate, the
Time elapsed temperature (°C) (hr) (1/g) yield (wt.%) outer surface of said tube and the inner surface of the
Initial 370 2,500 22 93.2 apertures provided in said shield plate are spaced apart
3 month 378 2,500 22 90.0 60 by a distance of between 0.2-5 mm.
6 month
2 month
385
390
2,500
2,500
22
22
85.3
81.7
2. A reactor according to claim 1, wherein each of
said heat transfer medium feed zones is respectively
provided with means for circulating the heat transfer
medium. s
EXAMPLE 5 65 3. A reactor according to claim 2, wherein only one
Acrylic acid was obtained by the oxidation of propy shield plate is provided on the inside of said shell parti
lene in a similar reactor to that in Example 1 excepting tioning said shell into two heat transfer medium feed
that the length of a reaction tube was 6 m. As the cata ZOS
 4,256,783 12
11
4. A reactor according to claim 2, wherein the gap 6. A reactor according to claim 5, wherein the annu
lar fins are flat and are generally parallel to said shield
between the outer surface of said tubes and the inner plate.
surface of the aperture in the perforated shield plate is 7. A reactor according to claim 5, wherein said annu
between 0.3-1 mm.
lar fins are provided only on one side of said shield
plate.
5. A reactor according to claim 2, wherein said tubes 8. A reactor according to claim 5, wherein said annu
include fins having an outer diameter of a size capable lar fins are provided alternately on both sides of said
shield plate.
of covering the gap between the outer surface of said O 9. A reactor according to claim 5, wherein said annu
tube and the inner surface of said aperture in said perfo lar fins are generally conically-shaped and disposed so
rated shield plate, said fins being individually secured to as to outwardly open toward the gap between said tube
and said shield late,
k
said tubes in the vicinity of said shield plate.
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