RU2333193C1 - Method for obtaining benzol - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention concerns method for obtaining benzol from acetylene in the presence of solid phase, where benzol is obtained by polymerisation in mechanical and chemical reactor with grinding spheres at the fluid coolant temperature of 15-20°C for 20-40 minutes in the presence of crystal quartz.

EFFECT: increased degree of acetylene to benzol transformation at lower process temperature.

2 cl, 8 ex, 1 tbl

Description

The invention relates to the chemical industry, in particular to methods for producing benzene.

A known method of producing benzene by converting non-aromatic organic compounds by contacting them at 200-1500 ° C with a carbon material of the diamond type [Murata Kazuhisa, Ushijima Hirobumi. Aromatization process. Pat. 55337022 United States, IPC ⁶ 13/00 S07S, S07S 3/367. Agency of Industrial Science And Technology. No. 323810; Claim 9/9/96; Prior. 12/7/93, No. 3-340174 (Japan); NPK 383/407].

A known method of producing benzene from methane or natural gas. Process conditions: 630-700 ° C, atmospheric pressure, volumetric feed rate of 1200-1600 h ^-1 , composition catalyst, wt.%: Nickel 0.3-1.0; rhenium 0.15-0.5; aluminum oxide the rest. The catalyst is pre-treated with air at 700 ° C for 3 hours, then it is purged with air for 0.25 hours and methane or natural gas is passed through after drying [USSR Author's Certificate No. 1811153, cl. C07C 15/04, C07C 2/00, 1996]. The disadvantage of this method is the complexity of the technology, the high temperature of the process.

A known method of processing hydrocarbon gases and liquid hydrocarbons in the reactor-activator in the presence of solid particles. The process is conducted for 5-30 minutes, followed by exposure to 60 minutes of reaction products in the reactor after the cessation of machining and shutdown of the reactor-activator. The solid phase is added in an amount up to a third of the volume of the reactor-activator, while particles of non-porous mineral material (quartz, quartz glass), or silica gel, or aluminum oxide, or iron chips are used as the solid phase [RF Patent, No. 2256690, cl. 7 C10G 15/00, C10L 3/10, 2005].

Closest to the proposed method is a method for producing benzene by heating acetylene to ~ 900 ° C over activated carbon [Brief Chemical Encyclopedia, T.1, p. 412, Moscow, 1961].

The disadvantage of this method is the low conversion of acetylene to benzene and the high temperature of the process.

The objective of the proposed method is to increase the degree of conversion of acetylene to benzene and lower the process temperature.

The technical result is that benzene is obtained from acetylene by polymerization in a mechanochemical reactor with grinding balls at a coolant temperature of 15-20 ° C for 20-40 minutes in the presence of crystalline quartz.

Grinding steel balls, crystalline quartz (particle size 2-4 mm) are placed in a hermetically sealed planetary mill reactor, acetylene is pumped (after removing air) and the mixture is treated for 5-40 minutes. The process proceeds at a coolant temperature of 15-20 ° C, the temperature is maintained by external cooling and is accompanied by the conversion of acetylene to benzene. Benzene selectivity reaches 80%.

The process of polymerization of acetylene is carried out in a mechanochemical reactor of a laboratory centrifugal planetary ball mill type AGO-2. Acetylene is introduced into a sealed, pre-evacuated, water-cooled reactor. The internal volume of the reactor (80 cm ³⁾ filled with grinding balls of 8 mm in diameter (the total mass of the balls 120 grams) and particles of crystalline quartz (2-4 mm particle size). The mass of quartz is 10-20 grams. The reactor vessel and grinding balls are made of hardened steel. The pressure in the reactor after filling with acetylene was 0.1 MPa. The rotational speed of the reactor in a portable motion 1290 rpm The mechanical activation of the system was carried out for 5, 10, 15, 20, 30, or 40 min at room temperature.

Acetylene and hydrocarbons were analyzed by gas chromatographic methods using a thermal conductivity detector. C ₁ -C ₆ hydrocarbons were separated by gas chromatography in a column filled with a spherochrome; stationary liquid phase - triethylene glycol butyrate. Non-hydrocarbon gas components were determined by the gas adsorption method in a column filled with CaA zeolite as an adsorbent. The carrier gas in all cases was argon. Benzene was determined on a Crystal-2000M gas-liquid chromatograph with a flame ionization detector on a capillary quartz column (25 m) with an SE-54 phase, and the carrier gas was helium.

Examples of specific performance.

Example 1. Acetylene is machined in an activator reactor of an AGO-2 mill for 5 minutes under the conditions described above. The amount of quartz is 10 grams.

In addition to acetylene and benzene, gas after mechanical treatment contains hydrogen, methane, ethane and carbon oxides in an amount of 15% vol.

The resulting gas mixture contains: acetylene - 84% vol., Benzene 1% vol.

Example 2. Acetylene is machined in an activator reactor of an AGO-2 mill for 10 minutes under the conditions described above. The amount of quartz is 10 grams.

The resulting gas mixture contains: acetylene - 71% vol., Benzene 5% vol.

Example 3. Acetylene is subjected to mechanical treatment in an activator reactor of an AGO-2 mill for 15 minutes under the conditions described above. The amount of quartz is 10 grams.

The resulting gas mixture contains: acetylene - 52% vol., Benzene 15% vol.

Example 4. Acetylene is machined in an activator reactor of an AGO-2 mill for 20 minutes under the conditions described above. The amount of quartz is 10 grams.

The resulting gas mixture contains: acetylene - 25% vol., Benzene 62% vol.

Example 5. Acetylene is subjected to mechanical treatment in an activator reactor of an AGO-2 mill for 30 minutes under the conditions described above. The amount of quartz is 10 grams.

The resulting gas mixture contains: acetylene - 16% vol., Benzene 80%.

Example 6. Acetylene was machined as in example 5, but 20 grams of quartz was introduced into the reactor.

The resulting gas mixture contains: acetylene - 0% vol., Benzene 84%.

Example 7. Acetylene was machined as in Example 6, but 20 grams of quartz was introduced into the reactor. Processing time 40 min.

The resulting gas mixture contains: acetylene - 0% vol., Benzene 82%.

An example of a prototype.

Acetylene is passed over activated carbon at a temperature of 20 ° C. Benzene does not form under these conditions.

The results obtained in comparison with the prototype are shown in the table.

Thus, the proposed method allows to obtain benzene from acetylene in mild conditions with a large yield.

Table. Process parameters According to the proposed method According to the prototype Temperature ° C twenty twenty twenty fifteen twenty fifteen twenty twenty Processing time, min 5 10 fifteen twenty thirty thirty 40 The amount of quartz, g 10 10 10 10 10 twenty twenty Residual acetylene,% vol. 84 71 52 25 16 0 0 one hundred The yield of benzene,% vol. one 5 fifteen 62 80 84 82 0

Claims (2)

1. A method of producing benzene from acetylene in the presence of a solid phase, characterized in that benzene is obtained by polymerization in a mechanochemical reactor with grinding balls at a coolant temperature of 15-20 ° C for 20-40 minutes in the presence of crystalline quartz. 2. The method according to claim 1, characterized in that the use of quartz with a particle size of 2-4 mm