SU1766500A1 - Method for preparation of catalyst for methanol amination - Google Patents

Description

one

(21) 4865401/04 (22) 11.09.90. (46) 10/07/92. Bul №37

(71) Leningrad Scientific and Production Association for the development and implementation of petrochemical processes

(72) M.I. Yakushin, S.V. Vodolazhsky, E.A. Lyubimova, A.F. Babikov, Yu.N. Zelentsov and V.P. Yaskin

(56) GDR Patent No. 149213,

cl. C 07 C 87/08, published 1982

USSR Author's Certificate No. 151676, cl. 01J 37/04, 1962. (54) METHOD OF PREPARING THE CATALYST FOR AMINATION OF METHANOL

(57) Use: organic synthesis. The essence of the invention: mixed powdered powders of aluminum hydroxide, kaolin and 10-15% by weight of aluminum hydroxide, waste catalyst of the same composition are mixed. Add one. Then formic acid is added to the mixture in the amount of 15-20 hours per 100 hours. catalyst. The catalyst mass is formed into granules. Dry the granules in air flow at 90-100 ° C for 3-4 hours, calcined. Characterization of the catalyst: methanol conversion 89-91%, methylamine yield 74-78%, mechanical strength 2.24 kg / mm, BET specific surface area 233 m2 / g. 2 tab.

The invention relates to the field of producing heterogeneous catalysts for the amination of methanol, namely, containing aluminum oxide and natural aluminosilicate (kaolin) as components.

A known method for the preparation of a catalyst for the amination of methanol is 1. The composition of the catalyst: SI02 is 12-18 wt.%, The rest, and SI02 is introduced into the catalyst in the form of cabel. The catalyst is prepared as follows: 100 hours of pseudoboehmite (AIOOH) is mixed with 50 parts of kaolin, the mixture is treated with 10 parts of 5% HNOZ and 60 hours of distilled water to obtain a plastic mass, which is further subjected to molding into granules, dried in for 3 h at 120 ° C and then calcined at 600 ° C for 6 h.

&

Yo

The prepared catalyst has the following characteristics:

Content,% Bulk weight, kg / l Total pore volume, cm3 / g, pores with a diameter

12-18 0.6

0.55-0.75

4nm 30% 15nm 10% Synthesis of methylamines on this catalyst is characterized by the following indicators:

Conversion SNZON,% 99.1

The output of methylamines,% 55,4

Volumetric speed

on liquid SNZON, 1,1

Temperature

synthesis, ° С310-450

Vj

About About SL About About

The disadvantages of this method of catalyst preparation are a significant consumption of a relatively expensive component, kaolin, a high energy consumption at the stage of catalyst drying and calcination, the use of an environmentally harmful component, peatation of a catalyst, of nitric acid, which at the stage of calcination decomposes into toxic NOa, load 1u 1Cg & atmospheric air.

Closest to the invention is a method, which is known to the catalyst for low molecular weight alcohol: 10% kaolin, the rest is prepared as follows.

The washed H20 precipitate obtained from aluminum sulphate is dried, crushed and mixed with kaolin powder in a 9: 1 ratio. Pre-manufactured crushed, calcined material of identical composition (retur) in the amount of 30-60% by weight of fresh active oxide is added to this mixture. aluminum. Then, in order to peptize the mass, 55-60% nitric acid is added at the rate of 3-3.5 kg per 10 kg. Water supply in the batch regulate the moisture content of the mass, which in granules with a diameter of 8-12 mm. They are dried by blowing with hot air at 120-180 ° C, then calcined in reflux gases at 500 ° C until the oxides of nitrogen are removed.

The disadvantages of the prototype method are the following: the need to use for peptizing a mass of large quantities of concentrated nitric acid, which, decomposing during the subsequent calcination of the catalyst, releases large amounts of environmentally harmful nitrous gases; the need to introduce large amounts of retur in the catalyst, which increases the cost of the catalyst; high drying temperature leads to cracking of the granules and impairs the mechanical strength, porous structure and catalyst activity.

The purpose of the invention is to improve the ecology, simplify the method, improve the physicomechanical characteristics and increase the catalyst activity.

The goal is achieved by the proposed method of producing a catalyst by mixing powdered powders of 90 parts of dry aluminum hydroxide calculated on 100%, Uch kaolin and 10-15 hours of calcined previously prepared catalyst, which is used as crushed catalyst production (retur). 45 parts of distilled or chemically purified water are added to the mixture, then a mass of 15–20 parts of 90% formic acid is peptized.

acid. The mixture is stirred to a state of uniform plastic mass, molded on a screw press, the resulting granules are dried in a current heated to 90-110 ° C

5 air for 3-4 hours and calcined in a stream of hot air at 470-500 ° C for 5-6 hours.

The catalyst prepared by this method is tested in the process of aminating methanol under the following conditions: synthesis temperature 380 ° С, liquid methanol loading volume 1.2 h, molar ratio NHS / CH3 5.

The difference of the proposed method is in the use of formic acid in the amount of 15–20 h per 100 h of the finished catalyst as a peptizing agent, in the amount of 10–15% by weight of aluminum hydroxide used as a retour of waste from the sieving of the finished catalyst. drying the finished catalyst is carried out at 90-110 ° C for 3-4 hours.

The invention is illustrated by the following examples.

PRI me R 1. Powdered powders (sieve N 0.15) 100 parts of aluminum hydroxide A) 20z H20 (PPPb50 ° with 20%), 10 hours, kaolin and 12 parts of catalyst waste identical

Compositions (retur) are mixed, 45 parts of water are added to the mixture with continuous stirring, then 18 parts of 90% formic acid are added. The duration of peptization 0.5 hours. The catalyst mass is molded.

5 on a screw press into granules with a diameter of 3.5 mm, which are dried in a stream of air at 90-110 ° C for 3.5 mm, which are dried in a stream of air at 90-110 ° C for 3.5 hours and calcined at 480 ° C for 5.5 h. Pol0 is taken as 100 h, the catalyst whose mechanical strength is determined by the knife method (OST 38.01267.8-82). The total specific surface area is determined by the VET method, the pore distribution over radii is determined by

5 mercury porometry.

The relative activity of the catalyst samples is determined by conducting catalytic experiments in a laboratory setup at atmospheric pressure.

0 Experimental conditions: T 380 ° С, volumetric rate for liquid methanol 1.1, volume of catalyst in the reactor 10 cm, molar ratio Mn3 / CH3OH 4.

Product analysis is carried out by

5 GLC on the stream. The relative unit of activity is the yield of the sum of mono-, di-, and trimethylamines (in%) from the prototype catalyst under these conditions.

Example2 and 3. The catalysts are prepared according to Example 1, except for the content

retour and drying mode of the catalyst (listed in Tables 1 and 2).

PRI me R 4 (prototype). 100 parts of aluminum hydroxide of composition Н20 are dried and mixed with 10 parts of kaolin powder. Pre-manufactured crushed, calcined material of identical composition (retur) in the amount of 45 hours is added to this mixture. Into the mixed dry mixture is introduced 30 hours. 56% nitric acid for peptization and 20 parts of water. The catalyst mass is formed on a screw press into granules with a diameter of 3.5 mm, which are dried in a stream of hot air when heated from 120 to 180 ° C for 3 hours at a rate of temperature rise of 20 ° C / h. Get 100 hours of the catalyst, which test for strength and catalytic activity is carried out as in example 1.

The technical and economic efficiency of the proposed method for the preparation of a catalyst for the methylation of methanol consists in a higher mechanical strength, a decrease in the fraction of micropores difficult to reach for reactants with 1.5 nm in the total specific surface area of the catalyst, and an increase in environmental safety.

0

five

0

five

process by eliminating the use of nitric acid as a peptizing agent and replacing it with formic acid. In addition, the catalyst preparation technology is simplified due to the abandonment of a separate stage of preliminary preparation of the retur and a decrease in the catalyst drying temperature, and the relative activity of the catalyst increases by about 6 times.

Claims (1)

The invention The method of preparation of the catalyst for the amination of methanol by mixing aluminum hydroxide with kaolin, adding filler - crushed waste catalyst, peptization acid, molding, drying and calcination, characterized in that, with the aim of improving the ecology, simplifying the process and obtaining a catalyst with increased activity , peptization is carried out with formic acid in the amount of 15-20 hours per 100 hours of catalyst, the filler is added in the amount of 10-15% by weight of aluminum hydroxide and drying is dried stvl dissolved in a stream of hot air at 90-110 ° C for 3-4 hours. Table I