JPS58157748A - Gas-phase nitration of benzene - Google Patents

Abstract

PURPOSE:A novel crystalline aluminosilicate zeolite with a specific molar ratio and a control index is used as a catalyst to react benzene with a nitrating reagent, thus producing the titled compound used as a raw material for aniline with no formation of by-products in high catalyst activity. CONSTITUTION:In the vapor-phase nitration of benzene with a nitrating agent such as NO2, N2O3 or N2O4, a crystalline aluminosilicate zeolite in which the molar ratio of silica/alumina is at least 12 and the control number is 1-12 is used as a catalyst. The catalyst is a novel ZSM zeolite and, for example, ZSM-5 (control index is 8.3), ZSM-48 (control index is 3.4) are cited, which are made by Mobile Oil Company. The catalysts have higher activity compared with conventional ones and form substantially no by-products such as dinitrobenzenes, resulting in good reaction selectivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for nitrating benzene in a gas phase, and more specifically, in a method for nitrating benzene in a gas phase using a nitrating agent such as NO2. Alumina molar ratio is at least /,,2 and control index is /~7.
This invention relates to a gas phase synthesis method for nitrobenzene, which is characterized by using crystalline aluminosilicate zeolite as a catalyst.

Nitrobenzene is used in large quantities as a raw material for aniline and as an intermediate for organic industrial chemicals, and is an important key industrial chemical. The manufacturing method of nitrobenzene is 3 years F and M.
The principle has not changed since the nitration of benzene was first carried out by John K. Itsscherlich to this day.

In other words, it is a method of nitration in the liquid phase using a mixed acid, which is a mixture of nitric acid and concentrated sulfuric acid.Although the production method has progressed from the initial batch method to the current continuous method, it is still difficult to process waste sulfuric acid and waste water. Since it is a mutual law, the problems remain unresolved.

On the other hand, the gas-phase nitrification method has been studied because it is expected to have advantages such as the simplicity of the process, no waste sulfuric acid, and the use of cheaper nitrogen oxides instead of sulfuric acid. Unfortunately, it is not as good as the liquid phase method in terms of reaction yield (3) and catalytic activity, and so far it has not been industrialized. Until now, there are only the following three publications regarding the gas phase nitration method of benzene.

/) USA'FLFF No. 73 and 1 Industry and Engineering Chemistry J
une, /93 Otsu Otsuko page parable describes that phase nitration of benzene with NO2 is carried out using silica gel as a catalyst. According to the description, silica gel with a particularly high surface area is highly active, but even in that case, the reaction temperature is ~1 temperature of 3/θ°C and the NO2/benzene molar ratio is 2. , gI sardine, space velocity)=θ, θJmu~6. /A5 KP/mold catalyst/hr At an extremely slow feed rate, space-time recovery ¥ = θ, θ/daj~θ, θ3/3/nitrobenzene/
To! They have reached low grades of P-PBl medium/hr.

According to the description in the same document, only silica gel has catalytic activity, and bauxite, viscous alumina, T1O2-pumice, etc. are said to be ineffective for the gas phase ni(g) conversion of benzene. It is also estimated that the reaction follows the following equation.

c) British Patent No. Sg B, No. 733 describes the HNO of benzene.
There is a description that gas phase nitration with 3 or NO2 is carried out using a phosphate or a calcined product of phosphoric acid supported on a solid absorbent as a catalyst. According to the example, nitrobenzene was obtained by nitration of benzene with I(NO3) using calcium metaphosphate as a catalyst, but nitrobenzene was obtained by nitration of benzene with 1(NO3/benzene
Molar ratio = θ, 36'7, temperature = /7J''C,:
, WH8V = θ, /76 given/Nitrobenzene space-time yield = 0.07 cre/2 under conditions of swamp/catalyst/hr&
・Results in catalyst and hr remain low.

On the other hand, gas phase nitration has been studied for the purpose of controlling the isomer ratio (bara/ortho ratio) of nitrochlorobenzene produced during nitration of chlorobenzene. JP-A No. 2003-120002 discloses that when chlorobenzene is nitrated in the gas phase with NO2 in the presence of a molecular sieve catalyst (zeolite catalyst) having a pore size ranging from about JA to about /θA, a wide range of nitrations can be achieved. There is a description that nitrochlorobenzene with a controlled rose/ortho ratio can be obtained using the following method. In this case, examples of specific zeolite catalysts include "zeolonta θθH",
rAW-3θθ Sieve”, “Zeoron 3θθ”, “/3
"X Mole Killer Sieve" is listed.

As for the reaction results, for example, when "Zeolonso θθ-H" is used as a catalyst, under the condition that the reaction flow #koθθ°CNo, /chlorobenzeneΦ molar ratio = 237, wI of chlorobenzene (S■ = θ, At a feed rate of 2g9Ky11・catalyst・hr (however, diluted with 3θ times as much nitrogen gas), the space-time yield (STY) = 0. (19g/2・catalyst・hr)
However, the activity is still insufficient. Incidentally, % Qu Zhao, 5; 4t-963;, No. 27 does not mention that the gas phase nitration of benzene is carried out using the zeolite catalyst.

The present inventors, in view of the possibility that gas phase nitration of benzene can bring about the above-mentioned divine advantages in the process, have arrived at the present invention as a result of diligently searching for a catalyst active in gas phase nitration. It is.

That is, the present invention provides a method for nitrating benzene in a gas phase using a nitrating agent such as NO2, in which a crystalline aluminosilicate having a silica/alumina molar ratio of at least /- and a control index of /~/co is used. This paper relates to a gas phase nitration method for benzene that uses zeolite as a catalyst.

According to the method of the present invention, extremely high catalytic activity can be obtained compared to the silica gel catalyst or phosphoric acid group catalyst used in the conventional gas phase nitration method of benzene, and by-products such as dinitrobenzene are almost eliminated. Good reaction selectivity can be obtained without much effort. Furthermore, compared to the conventional zeolite catalysts used for the gas phase nitration of chlorobenzene, such as mordenite-type zeolite ("Zeolon-2θθH") and X-type zeolite (r/3x molecular sieve), the method of the present invention The new zeolite used in (Silica/Alumina 9
At a molar ratio of 7.2 (7), this novel zeolite developed by Il Corporation exhibited surprisingly high catalytic activity when used in the gas phase nitration of benzene.

This high catalytic activity is thought to be due to the composition and structure of the new zeolite (rZsM zeolite) used in the method of the present invention, but it is currently difficult to provide a sufficient chemical explanation. By the way, liquid phase nitration using a mixed acid of nitric acid and oxidizing acid is explained by the ionic mechanism shown by the following equations (Kirk -Ot).
hmer ” Encyclopedia of Che
mical Technology', 2nd,
Ed, Vol,) Dan7za, 5-7g8 pages) HNO3+ 1(2SO4=====:H2NO3
+ H8O4・Q・・−(, aH2No3 □ N
o2 + 1 (zo a11@work@6111
16111111811 (,y) @ii5 for gas phase nitration? , the position has not yet been determined.

(8) In other words, according to the cited document 7, pages 0 to 725, HNO is explained by a free radical mechanism (such as (7))
3・OH+ -No2 Fist・・・・・・(J
-)RH+ -No2
R・ +HNO2・Fist 0・・・・ (6)R” +
”NO2HNO2*11@* Fist+1*@ (
7) According to Jack Fi, R4ckmann et al. (' Journal of the American
Chemical 5ociety'/? J'／
(lθ3) reduction e~7) Aromatic cation radical and No.
, formula (a) ~ which estimates the reaction mechanism of ll'l
(9) etc.), 06H,e + 06H6;shi (C6
H6) 2 + Φ ...Fist (♂) + + + (06H6) 2
e1NO2-ChiC! 6H, No+2+c6H6...
Φ... (9) On the other hand, according to Au5loos, P et al. (#InternationalJournal of
ChemiOal Kinetic' /97
F (/θ) Otsu! 7-tt7) The cation mechanism is estimated. The search for a catalyst that is active in gas phase nitration under these circumstances was extremely difficult as it was difficult to set a working hypothesis. If we extrapolate the reason for the lack of activity, it seems to be as follows.

1) Since the silica/alumina molar ratio was 272 or higher, which was higher than conventionally known zeolites, the so-called acid strength increased and was effective in activating No or benzene.

N) The unique crystalline pore structure with a control index of /~7.2 promotes electrostatic polarization of NO2 near the active site and activates it.

Setting aside the above speculations, the method of the present invention will now be specifically explained. The crystalline alumina silicate zeolite catalyst (hereinafter referred to as zeolite catalyst) used in the method of the present invention is a novel catalyst having a silica/alumina molar ratio of 27.2 or more and a control index (described later) -/~/, 2. It is a zeolite that was developed relatively recently by the Mobil Oil Company and is collectively known as the "ZEIM series zeolite"21. Although these zeolites have a very low alumina content and therefore a high silica/alumina molar ratio, they are very active even when the silica/alumina molar ratio exceeds 30. These zeolites remain active in the presence of steam at such high temperatures that they irreversibly disintegrate the frameworks of other zeolites, such as type X, type A and type zeolites. Furthermore, if carbonaceous precipitates are formed (usually called a coking phenomenon), they can be removed (decoking) by burning at a higher temperature than usual to restore activity.

ZSM zeolite has a high silica/alumina molar ratio of 4
? As a characteristic, the silica/alumina molar ratio is determined by conventional analytical methods such as atomic absorption spectroscopy. This ratio represents as close as possible to the ratio in the hard anionic framework of the zeolite crystals, excluding aluminum in cations or other forms in the binder or in the channels. Zeolites with a silica/alumina molar ratio of at least /2 are effective, but in some cases zeolites with a very high silica/alumina molar ratio of /J or more are also effective. Furthermore, in some cases, it may contain substantially aluminum;
It is also possible to use zeolite with a nearly infinite silica/alumina molar ratio. In this way, zeolites that are "highly siliceous" and "highly siliceous" are also included in the definition of the present invention.

After activation, the ZSM-based zeolite of the present invention exhibits "hydrophobic" properties with greater intracrystalline adsorption capacity for n-hexane than for water.

Next, the control index will be explained. This index, originally devised by Mobil Oil researchers, indicates the extent to which the pore structure of zeolite crystals controls the approach of molecules with a cross-sectional area larger than n-parafraction. . A specific measuring method described in Japanese Patent Application Laid-Open No. 1/33.223 will be described below. A sample of the zeolite, either pelleted or extruded, is ground to approximately the size of coarse sand particles and placed in a glass tube.

The zeolite is treated with a stream of air at +4 to C for at least 75 minutes before testing. After this zeolite is 7 lashed with helium, a current is applied to 29θ~j
/θ°C, and the overall conversion rate is adjusted to /θ~. A mixture of hydrocarbons consisting of n-hexane and 3-methylpentane is diluted with helium such that the molar ratio of helium/total hydrocarbon is y//, LH8V = / hr -] Pass it over zeolite. After -0 minutes of flow, a sample of the effluent is taken 1 and analyzed to determine the fraction remaining unchanged for each of the two hydrocarbons. Although the above experimental procedure represents favorable conditions and can bring the overall conversion to the desired /θ~gO range for most zeolite samples, in the case of very low activity San-jL, e.g. If the silica/alumina molar ratio is particularly high, it may be necessary to use a slightly more severe φ condition.

In these cases, in order to achieve a minimum overall conversion of about /θ, the evaporation should be at about 500°C and the eV should be less than /, eg, less than /θ.

The control index is calculated like manure.

The value of this control index is close to the ratio of the cracking rates of the two hydrocarbons.

The zeolite suitable for the present invention has a control index of / to /3. The control index of some representative substances is shown below.

Control index ZSM-g θ, S ZSM-zu ni, 3 ZSM-7,/ ni, 7ZSM-/,!
7! ZSM-, 23?・7 26M-3! ; Daj ZSM-J to Ko28M-& 3φgH-Zeolon (Mordenite) θψgRKY
θ·y Amorphous Silica-Alumina θ,6 The value of the control index described above is an important critical definition of the zeolite useful in the present invention. However, the above-mentioned measurement method includes a certain range, and depending on the measurement conditions, it may show a slightly different value.

Therefore, measurements should be made under several conditions and the average value should be adopted.0 Above, the new zeolite used in the method of the present invention was defined by one value of the silica/alumina molar ratio and the control index, A specific example of these is ZSM zeolite developed by Mobil 0 Oil Company. Those are ZSM
-3; SZSM -//, 28M-/, 2, ZSM
-23,28M-3'l SZSM-3g, ZSM-1
13 and ZSM → Za (both are trademark names).

ZSM-3 is disclosed in detail in Japanese Patent Publication No. 117-/θθ6, and its preparation method and ZSM-! The X-ray diffraction pattern is also cited as a reference in the method of the present invention.

ZSM -/ / is a special public service issued in 1963. 232 in detail in Publication No. 0, and its preparation method and ZSM-/
The X-ray diffraction pattern of / is cited as a reference in the method of the present invention.

Is ZSM-/a2 special public show 5.2-/6θ7? The preparation method and ZSM-/, 2 are disclosed in detail in the publication No.
The X-ray diffraction pattern of is also used as a reference in the method of the present invention (/S
).

28M-23 is Tokukai Sho, 5'/-/&? ? It is disclosed in detail in the θθ publication, and its preparation method and ZSM-2
The X-ray diffraction pattern of No. 3 is also cited as a reference in the method of the present invention.

ZSM-341 is JP-A-63-! The preparation method and the X-ray diffraction pattern of ZSM-3& are disclosed in detail in the Datata publication, and are cited as reference in the method of the present invention.

ZSM-45 is disclosed in detail in Japanese Unexamined Patent Publication No. ShojJ-/Gugu Sθθ, and its preparation method and X
The line diffraction pattern is also cited as a reference in the method of the present invention.

What is ZBM-3? U.S. Patent No.
It is disclosed in detail in No. y, its preparation method and ZSM
The X-ray diffraction pattern of -4t3 is also cited as a reference in the method of the present invention.

ZSM-113 is disclosed in detail in Japanese Unexamined Patent Publication No. 500 in 1983, and its preparation method and ZSM-4t3
The X-ray diffraction pattern is also used as a reference in the method of the present invention (/
(B).

ZSM-'Ig is described in JP-A-36-133223, pages 7.23 to 7.2, its preparation method and ZS
Although the X-ray diffraction pattern of M-41 is disclosed in detail, they are also cited as a reference in the method of the present invention.

By reference to the aforementioned patents which disclose in detail examples of novel ZSM-based zeolites that can be used in the present invention, these ZSM-based zeolites will be identified by their respective X-ray diffraction patterns.

Although these ZSM-based zeolites are generally prepared in the presence of organic cations, they exhibit virtually no catalytic activity in their original form. These are carried out in an inert atmosphere, for example sl
It is heated at Iθ°C for 7 hours, then ion-exchanged with an ammonium salt, and then fired in air at 5fθ°C to be activated, resulting in a so-called H-type ZEIM zeolite.

Yet another activation method involves ion-exchanging the above-mentioned ammonium ion-exchange type ZSM-based zeolite with polyvalent cations such as alkaline earth metal ions or rare earth metal ions.
There are methods such as firing in air.

Even when ZSM-based zeolite is synthesized in the form of alkali metal ions, it does not substantially exhibit catalytic activity as it is. In this case, as mentioned above, after ion exchange with ammonium salt, it is calcined to obtain H-type zsM zeolite, or alkaline earth metal ions, rare earth metal ions, or alkali metals other than group 1 of the periodic table (■) are used. Polyvalent metal cation type ZS is obtained by ion exchange with appropriate polyvalent metal cations and then firing in air.
Activated as M-type zeolite.

Alternatively, there is a method of treating and modifying ZSM-based zeolite with a compound of the following elements to use it as a catalyst.

/) Tlla group elements Sc, Y, rare earths and actinides u) Vla group elements Or, MO and W3)
Vla group elements and Rθ 1I) nb group elements lJg, Ca, Sr and E
a, t) lTIb group elements b and Ga B) Vb group elements sb and B1 7) Vll) group elements Te Compounds containing the above elements are mixed with ZSM zeolite in the form of a solution, concentrated and calcined. Through the process, the ZSM-based zeolite catalyst is essentially modified as oxides of those elements.

Examples of suitable solvents in this case include water, aromatic and aliphatic hydrocarbons, alcohols, organic acids (such as formic acid, acetic acid, propionic acid, etc.) and inorganic acids (such as hydrochloric acid, nitric acid and sulfuric acid). Also useful are halogenated hydrocarbons, ketones, ethers, and the like. Of these, water is the most commonly used.

After ZSM zeolite is impregnated with these solutions, it is concentrated and dried, but in some cases, it is filtered and dried after impregnation. Drying is usually carried out at a temperature of θ°C to /Sθ°C. After drying, baking is performed in an air stream at a temperature of 3θθ℃ or higher, preferably 3Sθ to OtsuS.
It is cured for several hours at a temperature of θ°C, more preferably between θθ°C and jjθ°C.

(/ta) The amount of each element that modifies the ZSM zeolite as its oxide through this firing process is /vrt% ~ sowt, ts
chosen between. By doing so, the ZSM-based zeolite becomes substantially modified with the oxide of the above-mentioned element, which is useful for improving reaction selectivity such as preventing coking on the catalyst surface.

Although ZSM-based zeolites can be used alone after being pressure-molded and packed into a reaction tower, they are usually mixed with a diluent to supplement the strength of the catalyst and avoid local heat generation during the reaction. (These diluents (or binders) are preferably inert substances that have sufficient durability under the gas phase nitration reaction conditions and do not induce side reactions. Examples of these inert diluents include, for example, Examples include alumina.

As the nitrating agent in the method of the present invention, there are nitrogen oxides of N0 or higher, specifically, No. 2, No.

The gas phase nitration in the present invention is carried out at a reaction temperature of about /Sθ°C ~
ZSM system (,! θ
) It is carried out by continuously feeding a gas phase mixture of benzene and a nitrating agent onto a zeolite catalyst bed and separating the formed nitrobenzene from said gas phase mixture. Preferably, the gas phase nitration reaction is carried out in the presence of nitrogen as a diluent. A specific example of how the reaction occurs in this case is as follows. Benzene is preheated and vaporized, fed into the reactor after mixing with a constant flow rate of diluent nitrogen gas, and then mixed with a gas phase stream of nitrating agent (such as No□) before contacting the heated catalyst bed. Post-heated catalyst bed (
Yet another feeding method is as follows.

A mixture of benzene and N2O4 at a predetermined molar ratio is fed into a vaporizer using a feed pump under water cooling, where it is vaporized, mixed with nitrogen gas for dilution at a constant flow rate, and then introduced as a uniform gas phase flow to a heated catalyst bed for catalytic reaction.

The nitrating agent preferably used in the present invention is No□, but the molar ratio of No□ to benzene is generally θ, j ~
3.0, more preferably a molar ratio of /, θ to 2.5.

Each reaction component and diluting nitrogen gas can be fed into the reactor at an arbitrary space velocity while maintaining a predetermined composition ratio.

In order to explain the present invention in more detail, specific examples are provided below, in which the activity of catalysts is compared and studied using one method. Seven of the methods are atmospheric fixed bed flow reactions, which are commonly used in catalyst activity tests, and the other seven are micropulse reactions. The atmospheric pressure fixed bed flow reaction data, which is the first method, shows so-called stationarity and is often used as a means of proving catalyst activity in patents, literature, etc., and there is no problem.

The second method we used, the micropulse reaction, is a reactor in which a microreactor and a gas chromatograph are directly connected, and the catalytic activity can be measured very easily, but the measured value is based on the so-called unsteady activity. It is said to indicate. Regarding the micropulse reaction, Murakami et al.
'Catalyst vol. ．． 2J (Otsu) gu 3~'Ig7 page (79
g/year)) 7θ, 2) describes its usefulness in catalyst activity testing and precautions for use. According to this, as mentioned above, the micropulse reaction is an unsteady reaction, and the flow reaction is a steady reaction, so the results of the two may or may not match. Aside from detailed comparisons, it is important to make general activity comparisons such as whether the activity of a certain catalyst is zero or whether there is a large difference in activity between two types of catalysts. Sufficient for use.

In fact, there are some examples of using micropulse reactions for comparative studies of catalytic activity in various literature (for example, '1
Proceedings of the 1st Annual Catalysis Conference (A) (1979 and 1977) 797 pages, -10 pages 1.23 O pages 1, 27, 2 pages 1.27 pages, etc.).

We also used the micropulse reaction method because of its simplicity, but we also collected data for comparison with the normal pressure flow method.

As a result, when the reaction is limited (in the case of the present invention, gas (23) phase nitration of benzene with No2), the trends in the magnitude of the catalyst activity obtained in the micropulse reaction are consistent with the trends in the normal pressure flow reaction. We have confirmed that.

The following examples are some specific embodiments of the invention,
The present invention is not limited thereto.

Example/Part/(Synthesis of ZSM-J) British Patent No. 1. Based on '102,9g1, ZSM-,S was synthesized as follows.

Distilled water 3.2651', aluminum sulfate 6JP, salt 7.29, tetra-n-propyl bromide, 21/
l'y1 sulfuric acid/Otog were mixed in this order to obtain liquid A. water,
l! 3?7. No. 3 sodium silicate 79/g (.2 g) was mixed to obtain liquid B. Next, both solutions A and B were added and mixed in a /l stainless steel autoclave. A white gel forms immediately, but continue stirring. The autoclave was sealed, the temperature was raised to 760°C, and stirring was continued at that temperature to carry out hydrothermal synthesis. Gauge pressure showed 3; -A KfAd. ! /
It's been a long time since I took out the anti-support contents. After repeating washing and filtration 5 times with distilled water of 90°C, dry at -θ°C for 75 hours, and then blow air with /θ11L/! The Si was fired at 20° C. for an hour while flowing at a rate of 1/2 min. The white crystals obtained were glono, yield = , r, 2. /, corresponds to %. As a result of X-ray diffraction measurement, this white crystal was ZSM-! It matched the diffraction pattern of ;

Next, the Na type 26M-3 obtained above was ion-exchanged three times with 5'% ammonium chloride water 3θθ1 each for A, 5'CX, 2 hours, and then srs ammonium chloride water, 20θ1 at 5°C. After repeating ion exchange and filtration for ×-night, the mixture was dried at 726°C for 70 hours to obtain 371 NH4 type 28M crystals. (Equivalent to recovery rate = g/%) This NH, type ZSM-3; was heated to j & θ℃ while flowing air.
Bake for a long time and make H type ZSM-3.Te3AJ'! Obtained. The X-ray diffraction pattern of this product is also Tokuko Sho 6-7096.
ZSM-,! described in Publication No. 11! It matched the diffraction pattern of ;

Results of analysis of HmZSM-j by atomic absorption method S10□
/Aa203 molar ratio=j,! Met.

Part 2 (Catalytic activity test using micropulse reaction) First, the micropulse reaction method will be explained. The reactor is described in the previously cited literature by Murakami et al. ('Catalyst vol. 1)
4) Described in detail in 171r3-II, page 7<m/))K. A quartz glass micro-reaction tube with an inner diameter of 4 t w and a length of θ- is placed in an electric furnace and attached to the front stage of the injection section of a gas chromatograph.

After filling this micro-reaction tube with quartz wool to form a vaporization section, the lower layer is filled with a catalyst of approximately jθ■ to approximately -〇〇■, and nitrogen or helium as a carrier gas is continuously supplied at a constant flow rate to a predetermined temperature. First, preheat the catalyst. Next, a mixture of benzene and N2O4 is collected with a microsyringe at a concentration of about θ, S~/μ under water cooling, and quickly injected from the top of the microreaction tube. A mixture of benzene and N2O4 is passed through a quartz wool vaporizer along with a carrier gas (nitrogen or helium) to react with benzene vapor and No, A, and catalyst beds, respectively. This reaction mixture is directly introduced into a gas chromatograph and analyzed.

Experiments were carried out as follows using the micropulse reactor.

The ■-type ZSM-3 synthesized in Example 1 was filled into a SO■ (pressure-molded, pulverized, 2/I-'Ig mesh) micro reaction tube, and helium was flowed at a flow rate close to that of the ion pipe. ◇Benzene and N were preheated at θθ°C for 0.5 hours.
gO, mixture (No21/benzene molar ratio -,2,l
Microcycle under ice cooling (27) θ with phosphorus 9, jp! It was collected and quickly injected from the top of the micro reaction tube. The temperature of the catalyst bed (reaction temperature) is θθ
It is °C.

The analysis conditions for the gas chromatograph were as follows.

Glass column 3φx, 2m.

Column packing material = j% PKG, 2θM/Unipor
t, HP Aθ ~ go mesh, injection part temperature =,
2Sθ°C1 The obtained result is benzene conversion rate = A'
The lΣ ratio was 5, and the nitrobenzene selectivity was 9.

Example/Example except that the reaction temperature was 2jθ°C and 300°C.
The reaction was carried out in exactly the same way. The obtained results are also shown in Table 1 along with Examples.

(-g) Example J NO2/benzene molar ratio is /, 3. /, θ and H θ, j
The reaction was carried out exactly once as in Example 1, except for 0. The results obtained are shown in Table 1, together with Example 2 and Thickness.

Table-Jll-ZSM-(Catalyst (change of molar ratio) Example 1 Its/(Synthesis of Ts02 modified ZSM-3) Distilled water/θ
Telluric acid in d: Hg'l'e04・jH20/-/jy
+ NH, -28M-!, synthesized in Example/, is added to the denatured solution in which +NH, -28M-! ; /y dispersed at 0℃ to 70~7
Stir for hours. Concentrate this on a hot water bath at 113°C
It was dried for 6 hours and fired for 3 hours at jθθ°C in an air stream to obtain T602 modified ZBM-! ; got /, lf. Te
The loading rate in terms of O2 was 4 twtqb.

Part 2 (Catalytic activity test) TeO2-proactive ZSM- synthesized as above as a catalyst
The reaction was carried out according to Example 6 using jθ town. However, the reaction temperature is /jθ°C.

θθ”C, 2jθ°C and 3jθ°C.

The obtained results are shown in Table 30 Table J TeO2 modified 28M-3 catalyst example j Its/(Synthesis of La ion exchange ZBM-3) Distilled water/θrnl and lanthanum nitrate La(NO3)3 HA H
9HH, type zSM-j/f synthesized in Example / was dispersed in an ion exchange solution containing 20/1, and the mixture was ion-exchanged at 0°C for 2 hours, filtered with water, and then washed with water at /B°C. Dry for 76 hours, then bake at 500°C for 3 hours in a stream of air.
Ion Exchange ZSM-j Part 2 (Catalytic Activity Test) Six La-23M was synthesized as a catalyst as described above! ;
The reaction was carried out according to Example/ using sohy.

However, the temperature of the reaction water is 2 to 0°C.The obtained result is the benzene conversion ratio = JJ, / %.

The nitrobenzene selectivity was 91/%.

Example 1/(Synthesis of oxide-modified ZSM-3) In place of telluric acid in Example 1, various oxide-modified compounds shown in Table 4 were used in designated children according to Example 1. ZEIM-j
f was synthesized. The obtained results are shown in Table ◇ Part 2 (Catalytic activity test) Various oxide-modified 28M-5fso synthesized as described above
The reaction was carried out according to Example 1 using Misaki.

However, L Hog/benzene molar ratio;
, 2Sθ°C, O obtained resultant JJ: ￥ 1 - 0 shown in Table 5 Table 3 Comparative results -;
Le! / jJ :') ”' le(ty, s, p −
2p109 *n3) was used in SO■, and the reaction was carried out according to Example/, except that the R temperature shown in Table 6 was constant.The obtained results are shown in Table 0 Table B - Comparative Experiment A phosphoric acid-based catalyst (Br1t, P.

The reaction was carried out in the same manner as in Example 1, except that 50 μm of As2.73.2) was used. The results obtained are shown in Table-7.

Table 7 -4 Comparison experiment 3 Mordenite (Incorporated) type zeolite and Y type zeolite (Shokaishojter'B; No. 3.27), which are known catalysts for gas phase nitration from chlorobenzene/NO2 Publications) are each s
The reaction was carried out according to Example 1, except that otng was used and the predetermined reaction temperature shown in Table-g was used. The results obtained are shown in Table-2.

Table-g Example 7 (Catalytic activity test using fixed bed flow reaction) An experiment was conducted as follows using a normal atmospheric pressure fixed bed flow reaction apparatus. Length 3.2 cm, inner diameter θ. In a 1 cm quartz glass reaction tube, H-ZSM-J (
,24'-4' I METS, SH) /P(,2J
! cc) was filled and preheated for 7 hours at θθ°C using a N2 gas stream. Meanwhile, a N2O4/benzene mixture (NO□/benzene mol) was mixed with an ice-cooled microfeeder.
e ratio = 2.31I) is fed to a vaporizer filled with molten alumina at a rate of 7 y/hr to vaporize it, and at the outlet of the vaporizer, N2 carrier for dilution (3'B;
*//min) after mixing, feed into the reaction tube,
The catalytic reaction was carried out on a catalyst bed maintained at /jθ°C. At this time, S■')=/θ, /7θhr"".

After leaving the reaction tube, the reaction mixture gas was trapped in water cooling, and the exhaust gas was neutralized with alkaline water and then purged. The trapped material was analyzed by gas chromatography. The average values for 7 hours from /S(3j) minutes to /hours/j minutes after the start of the reaction were as follows.

Benzene conversion rate = Sg, 7tinitrobenzene selectivity = 27. nitrobenzene STY') = θ,
a t * h r Note) /) SV: Gas hourly velocity, 2) STY: Space-time yield In the example, the catalyst was synthesized in Example DA. The reaction was carried out in accordance with Example 7 except for the following. SV=/g, 773br-”
. The average values for 7 hours from 1S minutes to 7 hours/j minutes after the start of the reaction were as follows.

Conversion rate of benzene = 3 U9% Selectivity of nitrobenzene = 9 O7 STY of nitrobenzene = 0.78 h/-emct
t*hr comparison: In a comparison using a pulse reaction of a known gas phase nitration catalyst,
M-type Zeolone (3O), which had relatively high activity Zeolon-SoθθH, which is an olide (see Comparative Experiment 3)
The reaction was carried out in the same manner as in Example 7 except that /P was used as a catalyst. SV-/Otsu, 27θhr O lj minutes after the start of the reaction ~/
When the trap was analyzed for 7 hours up to hours/j minutes, only traces of nitrobenzene could be detected at a benzene conversion rate of θ.

Procedural amendment (spontaneous) August r, 1988 1, Indication of case 1989 Patent application No. 89189 2, Title of invention Process for vapor phase nitration of benzene 3, Person making the amendment Relationship with the case Patent application Address 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Takeshi Hijikata 4 Agent address Sumitomo Chemical Co., Ltd. 5-15 Kitahama, Higashi-ku, Osaka Name Patent attorney (61,46) Katsuya Kimura TEI, +061220-3404 5. Amendment Column 6 for Detailed Description of the Invention in the Target Specification Contents of the Amendment [+] The fifth line from the bottom of page 10 of the specification is corrected to read "Difficult to set. 1 - Difficult to even set."

(2) In the same article, on page 11, line 9, the phrase "aluminosilicate zeolite catalyst" is corrected to "aluminosilicate zeolite catalyst."

(3) Same, page 21, lines 4-5 from the bottom &ir N 0
(4) In the same article, page 30, line 2 says that the molar ratio is 1.5°10 and 0.5J.
55,” he corrected.

that's all

Claims (1)

[Claims] (1) Crystalline alumina having a silica/alumina molar ratio of at least /2 and a control index of /~7.2 in a method for gas phase nitration of benzene using a nitration agent. A patented gas phase nitration method for benzene that uses silicate zeolite as a catalyst. Axis method. (3) The 7+ method of Patent No. 1, the nitration agent is NO2. (W, Th quality aluminosilicate zeolite is Z
SM-';, ZSM-//, ZSM-/, 2, zsbh
, z, g, ZS11')-311, ZSM-35, ZS
The method according to claim 1, Q or 3, which is M-3δ, zSdo3 or ZSM-11g. (5) Claim 1, wherein the crystalline aluminosilicate zeolite is H-type or cation-exchanged with alkaline earth metal ions or rare earth metal ions.
1.2.3 Still the method described in section q. (B) Crystalline aluminosilicate zeolite/)l
itai elements Sc, Y, rare earths and 7 cutinoids, 2) Vla group elements C, r, Mo and W3
)■ Mn and Re of group a elements 47) Mg, Cm, Sr of II b# elements
At least/
A method according to claim 11.2.3.17 or 3, which is modified by a compound of the element. C'7) The method according to claim 6, wherein the modification step includes a calcination step, and the calcination substantially converts the compound of the catalyst modifying element into an oxide form to modify the crystalline zeolite. (a) Gas phase nitration reaction 'J/, ffθ°C ~ 3θ
Claim 1, carried out at a temperature in the range θ°C, λ
,3,g1.5. g3''%t or the method according to claim 7. (5') Claim 1.3.3, t, in which 0.8 to 3 mol of nitrating agent is used per mol of benzene;
g. The method described in Section 7. (10) Claims 1, 3 and 3, wherein the gas phase nitration reaction is carried out using an inert gas such as nitrogen as a diluent.
The method described in S1 Otsu, 7, and g Kashiwa 9-cho. (//) The product obtained by gas phase nitration is nitrobenzene.Claim No. 7, Co, 3, Da, S1
The method described in item B, 7, 9 or 70.