JPH01301658A - Production of pyrrole - Google Patents

Abstract

PURPOSE:To obtain the subject compound useful for polymer material in high selectivity and high productivity, by contact catalytically reacting furan and ammonia using specific pentasil-type crystalline aluminosilicate as a catalyst in the presence of steam. CONSTITUTION:In a catalytic reaction of furan and ammonia to obtain pyrrole in the presence of steam, a pentasil-type crystalline aluminosilicate having molar ratio of silica to alumina (Si/Al) is 20-1000, preferably <=200 is used as a catalyst. The reaction is carried out with 2-15 times mol, preferably 4-10 times mol molar ratio of ammonia/furan. The reaction temperature is 375-550 deg.C, preferably 400-500 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing pyrrole by catalytically reacting furan and ammonia in the presence of steam.

Pyrrole can be induced into conductive polymers and is attracting attention as a new polymer material, and there are great expectations for its future development.

(Prior Art) The synthesis reaction of pyrrole using furan and ammonia as raw materials is said to be based on a substitution reaction of oxygen atoms, as shown in the following reaction formula.

Representative references regarding this reaction are shown in Table 1.

Alumina, silica/alumina is used as a catalyst,
Furthermore, catalysts in which MoO2, CaO, BO2, etc. are supported on these catalysts have been introduced. Hatada et al. also use HY type zeolite.

Margins below (Problems to be Solved by the Invention) In improving the virol production technology, there is a need for the development of catalysts that exhibit high selectivity and high productivity.

In Table 1, it is broadly classified into cases in which I(20) coexists and cases in which H2C does not coexist. When the reaction is carried out without H2C coexisting, as described in U.S. Pat. No. 2,478,452, carbon is precipitated,
There is a problem that it cannot withstand long-term use. Actually Yu,
In the experiment of K. Yurev et al., the regeneration process was performed for 150 minutes after the reaction for 100 minutes.
In the pulse experiment by Tada et al., the activity rapidly decreased as the number of pulses increased.

In US Pat. No. 2,600,289, the problem is solved by coexisting I-I 20, and its significance is highly evaluated.

In order to produce virol at a lower cost, it is important to increase the selectivity from furan to virol. Furan is a relatively expensive raw material, the boiling points of furan and virol are significantly different from each other at 31°C and 1130°C, and it is easy to separate unreacted furan and product virol;
In addition, it is necessary to collect and reuse excess ammonia, and the same system can be used to collect and reuse unreacted furan.Furthermore, according to the conventional technology, the furan selectivity is 80 to 95% (see Table 1). However, there is a need for a catalyst that provides even higher selectivity.

(Means for Solving the Problems) From this perspective, the present inventors conducted intensive studies on the development of a catalyst that provides high selectivity, and found that a pentasil-type catalyst with a silica to alumina molar ratio (Si/A E ) of 20 or more was developed. The present inventors have discovered that when crystalline aluminosilicate is used as a catalyst, the reaction results are superior to those of conventional techniques, leading to the creation of the present invention.

That is, the present invention uses a pentasil-type crystalline aluminosilicate having a silica to alumina molar ratio (Si/AA) of 20 or more as a catalyst when producing virol by catalytically reacting furan and ammonia in the presence of water vapor. The present invention relates to a method for producing pyrrole, characterized in that it is used as -5=.

The pentasil type crystalline aluminosilicate used in the present invention is described, for example, in the Journal of Physical Chemistry.
Chemistry, Vol. 85. P22
38), S i Oa and Aj
It constitutes a three-dimensional network structure consisting of Oi, and the trihedrons in the structure are cross-linked by bridges of oxygen atoms, and the ratio of all atoms of aluminum and silicon to oxygen is 1.
:2. In addition, 10 formed by 10 5R rings
It is said to have ring-membered pores.

Pentasil type crystalline aluminosilicate can be prepared by a known production method. For example, a reaction mixture containing a silica feed material, an alumina feed material, an alkali metal ion feed material, water and a cationic organic nitrogen compound is heated at 100-250°C.
It is obtained by heating to a temperature of C and reacting for a sufficient time to form crystals. For details, see ZSM-5 (U.S. Patent No. 3702886) and ZSM-11 (U.S. Patent No. 3) developed by Mobil Oil Corporation.
709979) etc. can be used.

The silica to alumina molar ratio (Si/AI) of the pentasil-type crystalline aluminosilicate used in the present invention is preferably 20 or more in terms of selectivity, and the upper limit is not particularly specified, but it is 1000 or less, preferably 20.
00 or less. When it exceeds 1000, the activity of the catalyst decreases and the productivity per unit amount of catalyst deteriorates, which is not preferable.

In pentasil-type crystalline aluminosilicate, it is said that the electron valence of the aluminum-containing tetrahedron is balanced by the inclusion of cations within the crystal, and these cations can be exchanged with cations using known ion exchange technology. Can be exchanged. In providing the present invention, protons, M
Alkaline earth metals such as g, Ca, Sr, La, C
Those ion-exchanged with rare earth metals such as e or noble metals such as Pd can be used.

When carrying out the present invention, the ammonia/furan (molar ratio) can be selected from 2 to 15 mol, preferably from 4 to 10 mol.

Further, the H2O7 furan (mole ratio) can also be selected from 2 to 15 moles, preferably from 4 to 10 moles.

Furthermore, the reaction temperature can be selected from 375 to 550°C. More preferably, a temperature of 400 to 500°C can be selected.

Furthermore, the reaction pressure is not particularly limited, and either reduced pressure or increased pressure can be selected.

The amount of catalyst to be used can be determined by a conventional method by measuring the activity of the prepared catalyst.

W/F CW-catalyst weight (g), F: Furan flow rate (
moj2/Hr)) can be selected from 100 to 600, but is not particularly limited.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Catalyst Preparation I Q brand sodium silicate aqueous solution (SiOz-29
, 9% by weight) was added with 180 g of a 10% tetrapropylammonium hydroxide aqueous solution, and further aluminum sulfate CAI. (504)3・18H20) 25g and water 4
00g was added and stirred for 10 minutes.

Thereafter, while stirring the solution strongly, 10% sulfuric acid was added dropwise to adjust the pH to 0 to 10.5 to obtain a homogeneous gel. Place this gel in a 1P autoclave equipped with a stirrer,
The mixture was vigorously stirred at 0°C for 30 hours. After cooling to room temperature, the obtained product was washed with sufficient ion-exchanged water, and then 1
Filtration by immersion in an aqueous N nitric acid solution at room temperature for 4 hours was repeated four times to obtain a proton type. After drying at 120"C, it was compression molded and further crushed into 8 to 14 mesh pieces and used as a catalyst.

The obtained catalyst was identified as SM-5 by X-ray diffraction. Further, the molar ratio of silica to alumina (Si/A) determined by X-ray fluorescence analysis was 27.

Catalyst Preparation 2 By cation-exchanging the catalyst prepared in Catalyst Preparation 1, Mg-Mg-11Zs, Ce-Ce-11ZS
, Pd-IIZSM-5 was J-sized.

Cation exchange is performed for each metal salt of IN [MgC1□, Ce(N
O:l) 3, PdC]□] Using an aqueous solution 10 times the amount of the catalyst, cation exchange was performed at 80°C for 3 to 4 hours.

After repeating the exchange reaction 4 times, washing with water and drying was performed.
Calcined at 0'C for 3 hours. Grind and press the Geeri.
After molding, it was crushed into 8 to 14 mesh pieces and used as a catalyst.

Catalyst Preparation 3 511! Solution A and solution B having the following compositions were prepared by stirring in a beaker at room temperature.

Solution A Q brand sodium silicate 1000 g water
1400 g Solution B Aluminum sulfate 1, 32 g Thorium chloride 320 g Tetrap D pylammonium bromide 135 g Concentrated sulfuric acid 92 g Water 1900
A reaction mixture (gel) was prepared by mixing solution A and solution B at room temperature in a high-speed stirring homogenizer with an internal volume of 10β.

”Pour the mixture mentioned above into an autoclave with an internal volume of 7β,
After replacing the gas phase with nitrogen gas, close the autoclave and
The mixture was heated with stirring at a rotational speed of 8 Qrpm until the reaction temperature reached 140°C. Next, increase the rotation speed to 600 rpm.
The mixture was reacted for 36 hours at a reaction temperature of 140°C. The product obtained by cooling to room temperature was treated in the same manner as in Catalyst Preparation 1 and used as a catalyst.

The obtained catalyst was identified as ZSM-5 by X-ray diffraction. Furthermore, the molar ratio of silica to alumina (Si/Aβ) determined by X-ray fluorescence analysis was 47.

Catalyst Preparation 4 A catalyst was prepared in the same manner as Catalyst Preparation 1. However, the reaction solution to be charged into the autoclave in step 1 was arranged as follows.

5 g of aluminum sulfate and 400 g of water were added to 150 g of Q brand sodium silicate aqueous solution, and further 50 g of triethylammonium chloride was added. After stirring for 10-10 = minutes, the pH was adjusted to 11 to 11.5 with 10% sulfuric acid.

It was made into a proton form in the same manner as in Catalyst Preparation 1 and used as a catalyst.

The obtained catalyst was identified as ZSM-5 by X-ray diffraction. Furthermore, the molar ratio of silica to alumina (Si/A j!) determined by X-ray fluorescence analysis was 90.

Catalyst Preparation 5 10 g of aluminum sulfate and 400 g of water were added to 150 g of Q brand sodium silicate aqueous solution, and further 30 g of octamethylene diamine was added, followed by stirring for 10 minutes. Then, while stirring the solution strongly, 10% sulfuric acid was added dropwise to p
A homogeneous gel was maintained by adjusting H11 to 11.5. This gel was placed in a 1β autoclave equipped with a stirrer and heated to 180°C.
The mixture was stirred for 100 hours. After cooling to room temperature, the obtained product was washed with sufficient ion-exchanged water, and a crushed proton type catalyst was obtained in the same manner as in Catalyst Preparation 1.

The obtained catalyst was identified as ZSM-11 by X-ray diffraction. Furthermore, the molar ratio of silica to alumina (Si/Aβ) determined by X-ray fluorescence analysis was 50.

Example 1 10 g of the catalyst prepared in Catalyst Preparation 1 (hereinafter referred to as 023M-5) was filled into a quartz reaction tube with an inner diameter of 20φ, and an experiment was conducted using a normal pressure flow method. The temperature of the catalyst layer is raised in an external heating furnace under a nitrogen stream, and after reaching a predetermined temperature (400'c), a predetermined amount of ammonia and water are poured into the catalyst layer, and after processing for 30 minutes, raw material furan is introduced. The reaction was started. Ammonia was measured at 75 Nml/min using a mass fluorometer.
1.7% each of furan and water using a metering pump.
g/Hr, 3.4 g/Hr.

At the outlet of the reaction tube, a L lamp cooled with dry ice-ethanol and an absorption layer containing water were passed in series to collect the reaction product. The reaction product was quantified using a capillary column using OV-1 as a column.

The reaction results were measured at 20% after 3 hours had passed since the start of the reaction.
The reaction product was collected and determined from the weight of the collected product. The reaction results are calculated using the following formula. The results are shown in Table 2.

Productivity - pyrrole produced (g/Hr)/catalyst amount (χ)
Examples 2-3 Reactions were carried out in the same manner as in Example 1. However, the reaction temperature was 425°C (Example 2) and 450°C (Example 3).
And so. The results are shown in Table 2.

Examples 4 to 6 The cation exchange catalyst prepared in Catalyst Preparation 2 was used as a catalyst.
Except for charging 0g and carrying out the reaction at a reaction temperature of 400°C,
The reaction was carried out in the same manner as in Example 1. The results are shown in Table 2.

Examples 7 to 8 The reaction was carried out in the same manner as in Example 4, except that the catalysts prepared in Catalyst Preparations 3 and 4 with silica to alumina molar ratios of 47 and 90 were used as catalysts.

The results are shown in Table 2.

Example 9 A reaction was carried out in the same manner as in Example 4, except that H2SM-11 prepared in Catalyst Preparation 5 was used as a catalyst.

The results are shown in Table 2.

Margin below

Claims (1)

[Claims] A pyrrole characterized in that a pentasil-type crystalline aluminosilicate having a silica to alumina molar ratio (Si/Al) of 20 or more is used as a catalyst when producing pyrrole by catalytically reacting furan and ammonia in the presence of water vapor. manufacturing method