The method of liquid-phase oxidation of hydrocarbons

 

A method of liquid-phase oxidation of hydrocarbons at elevated temperature and pressure in a multi-zone reactor with a total for all zones contacting steam space. The method includes the filing of the original hydrocarbons in the first zone of contact, the output oxidate from the last zone, the flow of oxygen-containing gas in the zone of contact, recycling of secondary steam oxidation through the zones of contact at a temperature below the reaction temperature oxidation with subsequent dispersion in each zone contact, recycling under the pressure of the reaction mixture in the zones of contact, the heat of oxidation reaction, the stirring secondary vapours from all areas of contact. Moreover, according to the invention the source of the hydrocarbons is heated and saturated with oxygen prior to being fed into the first zone of contact by mixing with the recirculating flow of secondary vapor oxidation, oxygen-containing gas is heated reaction mixture and mixed with secondary steam oxidation. Preferably recirculating secondary pairs oxidation to mix with the recirculating part of the reaction mixture. When this mass ratio of the flow of recirculating secondary productivity and selectivity for the target products of the oxidation process, increasing the conversion rate of oxygen, increasing the security of the process, the decrease of metal and simplify the design process of oxidation. 2 C.p. f-crystals, 1 Il.

The invention relates to the chemical and petrochemical technology and can be used to implement processes such as liquid-phase oxidation of isobutane to tert-butylhydroperoxide, isopentane in tert-AMYLPEROXY, toluene into benzoic acid, ethylbenzene and cumene in the relevant gidroperekisi, isobutylene to methyl methacrylate, isoamylenes into the corresponding oxide, etc. in the presence of catalysts, with or without them.

There is a method of liquid-phase oxidation of mixtures of paraxylene and paratoluidine at high temperature and pressure in a multiphase reactor (French patent 2416725, CL 01 J 2/04, 1979), including the filing of the original hydrocarbons in the first zone of contact, the output oxidate from the last zone, the flow of oxygen-containing gas in the zone of contact, the heat of oxidation reaction on heat transfer surfaces located directly in the zones of contact.

This method is characterized by low removal rates of production per unit of reaction volume in units is e close of the present invention is a method of liquid-phase oxidation of hydrocarbons at elevated temperature and pressure in a multi-zone reactor with a total for all zones contacting steam space, including the filing of the original hydrocarbons in the first zone of contact, the output oxidate from the last zone, the flow of oxygen-containing gas in the zone of contact, recycling of secondary steam oxidation through the zones of contact, recycling under the pressure of the reaction mixture in the zones of contact, the heat of the oxidation reaction, with stirring secondary vapours from all areas of contact, and feeding separate streams mixing with recirculated in each zone of contact with the threads of the reaction mixture at a temperature below the reaction temperature oxidation and subsequent dispersion of the resultant gas-liquid flow in each zone contact (RF patent 2106342, class C 07 C 407/00, 409/00, 1996).

The known method has the following disadvantages: - lack of preparation of the feedstock prior to entry into the reaction zone leads to performance degradation and wasteful expenditure of heat; - the high energy intensity of the oxidation process due to the need to maintain a given rate of oxidation due to the large number of injection wells; - low productivity of the reactor and a low selectivity for the target products due to insufficient pochacco reactor; - the complexity of the system of automatic control and regulation of the oxidation process; - not reliably solved the security issues of the implementation process of oxidation.

The task of the invention is to improve the productivity and selectivity of the target product of the oxidation process, increasing the conversion rate of oxygen, increasing the security of the process, reducing the total metal consumption and simplify the design process of oxidation.

This task is solved in that the liquid-phase oxidation of hydrocarbons at elevated temperature and pressure in a multi-zone reactor with a total for all zones contacting steam space, including the filing of the original hydrocarbons in the first zone of contact, the output oxidate from the last zone, the flow of oxygen-containing gas in the zone of contact, recycling of secondary steam oxidation through the zones of contact at a temperature below the reaction temperature oxidation with subsequent dispergirovannom in each zone contact, recycling under the pressure of the reaction mixture in the zones of contact, the heat of oxidation reaction, the stirring secondary vapours from all areas of contact, and € mixing with the stream of recirculating vapor oxidation, oxygen-containing gas is heated reaction mixture and mixed with secondary steam oxidation, recirculating secondary pairs oxidation is mixed with recirculating part of the reaction mixture, and the mass ratio of the recirculating flow of secondary vapor and recirculating the reaction mixture is from 1: 0.2 to 1:1.

The differences of the proposed method against known include; preparation of initial hydrocarbons, consisting in their heating and oxygen saturation before feeding into the reaction zone of the reactor by mixing with secondary steam oxidation. At the same time cools the secondary vapor oxidation and efficient use of the heat of oxidation reaction, regardless of oxygen-containing gas (air, oxygen-enriched air, oxygen); - heated oxygen-containing source gas to the reaction mixture and mixing with secondary steam oxidation. The oxygen-containing gas is fed into the reactor through an injector into the circulation reservoir, located in the liquid reaction medium. Circulating reservoir source of oxygen-containing gas is diluted in the secondary injector pairs oxidation and heated liquid reaction sidenote process as the oxygen-containing gas, on the one hand, is heated in a circulating reservoir, and on the other, will be cooled at possible violations of the technological regime and the ingress of liquid hydrocarbons return stroke in the coolant reservoir when the pressure in it, which is especially dangerous when working with oxygen; mixing the secondary recirculating vapor oxidation prior to entering into the distribution device with a part of the recirculating pump of the reaction mixture enables a very fine atomization gas and significantly more efficient mass transfer between gas and liquid. The number of injection of cells can be reduced and thereby reduced energy consumption on the one hand, and simplified system of automatic control and regulation of the oxidation process and a simplified structural design. Reducing the number of injection of cells, and thus reduce the amount of circulating fluid has a positive effect on the selectivity of the oxidation process. This is because when a large circulation of the liquid reaction mass dramatically increases the contact time with the metal surfaces of the equipment that adversely skazyvaet the gidroperekisi.

The possibility of effective mass transfer at all points of the reactor high power even with a small amount of injection of the cells contributes to a more effective use of reaction volume, i.e., the productivity of the reactor. The composition of the secondary vapor oxidation reactor becomes more homogeneous in the reaction zones.

Effective mass transfer allows you to maintain a lower concentration of oxygen in the gas phase, and therefore, can improve the selectivity of the oxidation process and to reduce the consumption of oxygen due to the smaller output with inertly, which is especially noticeable when working with oxygen, when the output of the gas phase is almost there.

The drawing shows an example implementation of the proposed method of liquid-phase oxidation of hydrocarbons.

The source of the hydrocarbons fed into the reactor 1 through mass transfer cell 2 in the layer of the reaction mixture in the first zone of contact. In massoobmenu cell, made for example in the form of tubes or columns filled with nozzle or separated / tube sheet or other plates, is heated source of hydrocarbon and oxygen saturation before entering into the reactor. While at the same time, kionna mixture by gravity passes sequentially through the zones of contact, shimmering through the partition separating the zone of contact.

Oxidate derived from the last zone of contact. Oxygen-containing gas is fed into the reactor through an injector located in the water reservoir 3, where it is rapidly diluted secondary steam oxidation and heated liquid reaction mixture. This provides directional circulation and mixing of the secondary vapours from all areas of contact, in a common vapor space of the reactor and circulating reservoir 3. The liquid reaction mixture, re-circulated under pressure by means of pump 4, achladies in heat exchangers 5, is fed to the nozzle 6 and the vertical pipes 7 together with streams injected from the steam space 8 of the secondary vapor is directed into the reaction volume chambers. Flows discharged from the vertical pipe, with high speed dispersed on the support 9 in the volume of the reaction mixture in each zone of contact. The heat exchangers 5 provide additional heat of the oxidation reaction in the zones of contact by cooling the recirculating flow of the reaction mixture. Secondary pairs oxidation containing inert, oxygen and hydrocarbons are washed with water source is major pairs oxidation optionally partially condensed in heat exchanger 10. The condensate is returned to mass transfer in the cell 2, and neskondensirovannyh secondary pairs oxidation partially derived from the system (when using as the oxygen-containing gas is air enriched with oxygen, or pure oxygen output of the secondary vapor oxidation of the reactor is not required), and partly with the help of blowers 11 enter the reactor through a distribution device 12. Part of the recirculating secondary vapor oxidation with discharge gas 11 can napravljaetsja in the pipe feeding the oxygen-containing gas, which is especially effective when working with oxygen or air enriched with oxygen.

Part of the re-circulating pump 4, the liquid reaction mixture is fed into the recirculation line of the secondary vapor oxidation from the blowers 11 before entering into the distribution device 12. The distribution device can be configured, for example, in the form of a vertical pipe, with symmetrically arranged on the opposite side of the horizontal pipes. Horizontal pipes can be joined to the pipe ring. On a tangent to the ring and transverse pipes in a horizontal plane mounted nozzle with a certain diameter holes. The upper part of the distribution is l, provides the rotation of the upper part of the distribution device 12 with simultaneous fine dispersion of gas throughout the cross section of the reaction zone, including in remote locations (regardless of the form of the cross section of the reaction zone).

The output oxidate may be regulated by valves 14 level in the discharge chamber 13.

Below are examples of oxidation of isopentane and isobutane in the pilot horizontal reactor of stainless steel, having three of the same volume of the zone of contact, through which passed through the reaction mixture. The capacity of the reactor is 40 liters

Example 1.

In the reactor 1, the mass transfer through the cell 2 serves 41 kg/h isopentane at a temperature of 30oC. circulating Through the collector 3 serves air in an amount of 8.4 kg/h at a temperature of 40oC.

The reaction temperature oxidation 155oC. Pressure in the reactor 45 ATA.

From the reactor output secondary pair of oxidation in the amount of 7.1 kg/h at a temperature, of the following composition, wt.%: Oxygen - 1,67
Nitrogen - 93,15
The carbon dioxide - 1,37
Hydrocarbons With2-C4- 1,11
The isopentane - 2,70
Total - 100%
Get oxidat in the number of 42.3 kg/h, of the following composition, wt.%:
Oxygen - 0,01Acetone - 0,69
Methanol - 0.02
Oxide 2-methylbutan-2 - 0,13
Oxide 2-methylbutane-1 - 0,01
Methyl - 0,06
Isopropanol - 0,08
Ethanol - 0,27
Methylisobutylketone - 0,18
Tertiary amyl alcohol was 1.04
Secondary isoamyl alcohol - 0,07
2-methylbutan-1-ol-3 - 0,01
Primary isoamyl alcohol - 0,06
Gidropress ethyl - 0,20
Gidropress of isopropyl - 0,25
Gidropress tert.amyl - 6,79
Gidropress Deut.amyl - 0,34
Acid - 0,82
Water - 0,30
Total - 100%
Example 2.

In the reactor 1 serves 10 kg/HR of isobutane at a temperature of 30oC. circulating Through the collector 3 serves a source of oxygen-containing gas, containing 85% oxygen, in the amount of 2.7 kg/h at a temperature of 40oC.

The temperature of the oxidation reaction 140oC. Pressure in the reactor 51 ATA.

From the reactor are selected oxidat in the amount of 12.7 kg/h, of the following composition, wt.%:
Nitrogen - 3,20
Oxygen - 0,23
CO2- 1,22
Propane - 0,39
Isobutane - 37,34
N-butane - 0,79
The isobutylene - 0,08
Methyl tertiary butyl ether - 0,24
Acetone is 2.01
Methanol - 0,51
The isobutylene oxide - 0,25
Somelady aldehyde - 0,05
Methyl - 0,07
Isopropanol - 0,03
Tertbutanol - 27,14
Torbutrol + n-butanol + Isobutanol - r /> Acid (C1-C4- 0,79
Water - 1,09
Total - 100%
The output of the secondary vapor oxidation of the reactor 1 is missing.


Claims

1. The method of liquid-phase oxidation of hydrocarbons at elevated temperature and pressure in a multi-zone reactor with a total for all zones contacting steam space, including the filing of the original hydrocarbons in the first zone of contact, the output oxidate from the last zone, the flow of oxygen-containing gas in the zone of contact, recycling of secondary steam oxidation through the zones of contact at a temperature below the reaction temperature oxidation with subsequent dispersion in each zone contact, recycling under the pressure of the reaction mixture in the zones of contact, the heat of oxidation reaction, the stirring secondary vapours from all areas of contact, characterized in that the source of the hydrocarbons is heated and saturated with oxygen prior to being fed into the first zone of contact, due to mixing with the recirculating flow of secondary vapor oxidation, oxygen-containing gas is heated reaction mixture and mixed with secondary steam oxidation.

2. The method according to p. 1, wherein those of the Sabbath. the Method according to p. 2, wherein the mass ratio of the recirculating flow of secondary vapor and recirculating the reaction mixture is from 1:0.2 to 1:1.

 

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