RU2332353C2 - Method of obtaining chlorine and device for its realisation - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention can be used when obtaining chlorine from hydrogen chloride. Method of obtaining chlorine includes continuous supply of preliminary prepared gas mixture, containing hydrogen chloride and oxygen in stehiometric ratio, oxidation of hydrogen chloride with oxygen with formation of target product - chlorine and reaction water with their further separation. Gas mixture is supplied in flow reaction section of plasma-chemical reactor, where it is activated simultaneously directly both under action of electromagnetic radiation from streamer discharge region mainly in ultraviolet range, and under action of radiation with flow of accelerated electrons. In order to create streamer discharges in gaseous medium, generator of high-voltage pulses of nanosecond duration with voltage not less than 100 kV and frequency not less than 50Hz is used, as source of electromagnetic radiation molecules and atoms of reaction medium itself are used. The device for obtaining chlorine is also claimed. It consistes of chamber for preparation of hydrogen chloride and oxygen gaseous mixture, plasma-chemical reactor for obtaining chlorine in mixture with water, generator of high-voltage pulses, device for separation mixture into chlorine and water, accumulative reservoir for reaction water.

EFFECT: increase of degree of hydrogen chloride conversion with reduction of material and energy expenditure.

5 cl, 2 ex, 6 dwg

Description

The invention relates to chemical technology, specifically with respect to processes for the production of chlorine from hydrogen chloride by oxidation of the latter with oxygen, and devices for carrying out the process.

A known method of producing chlorine by supplying a gas mixture containing hydrogen chloride and oxygen in a stoichiometric ratio to the reaction zone of a plasma chemical reactor, oxidizing hydrogen chloride, producing chlorine and water, followed by their separation (see RF patent No. 1801943, С01В 7/04, 19.03 .1991.)

The disadvantage of this method is the low conversion of chlorine, leading to a large amount of residual hydrogen chloride, the utilization of which leads to material costs and difficulties in its disposal.

A device is known for producing chlorine from hydrogen chloride by supplying a reaction mixture of air and hydrogen chloride to a flow-type reactor with the formation of an activation zone in which the process of oxidizing hydrogen chloride is carried out (see RF patent No. 2253607, С01В 7/01, 02/19/2004) .

A disadvantage of the known device is the low efficiency of its work to ensure the implementation of the known method for producing chlorine.

The task is to obtain a high degree of conversion of hydrogen chloride, reducing material and energy costs for the process.

The problem is solved due to the fact that the gas mixture containing hydrogen chloride and oxygen in a stoichiometric ratio is pre-prepared and fed to the flow reaction zone of the plasma chemical reactor with oxidation of hydrogen chloride in it with oxygen with the formation of chlorine and reaction water, followed by their separation, while in the reaction zone, the gas mixture is activated directly as under the influence of electromagnetic radiation from the streamer discharge zone, mainly in the ultraviolet range, t and under the influence of irradiation with a stream of accelerated electrons, in order to create streamer discharges in a gaseous medium, a nanosecond high-voltage pulse generator with a voltage of at least 100 kV and a frequency of at least 50 Hz is used, and the molecules and atoms of the reaction medium itself are used as a source of electromagnetic radiation .

The implementation of this method of producing chlorine from hydrogen chloride is provided by a device containing a chamber for preparing a mixture of hydrogen chloride and oxygen, a plasma-chemical reactor, a high-voltage pulse generator, a device for separating the resulting chlorine with water, a storage tank for reaction water, the reactor is made in the form of a metal cylinder, inside of which a metal rod is coaxially mounted between the upper and lower insulators, the upper insulator is rigidly fixed between the two flanges, and along its axis and the axis of the rod there is a terminal for supplying a positive charge to the rod, and the lower part of the rod is fixed through a centering sleeve on the lower insulator with the possibility of free movement of the end of the rod, together with the insulator, in the axial direction, the lower insulator is perforated with holes for the passage of the activated gas mixture and at the exit from the plasma-chemical reactor, a perforated lattice made of graphitofluoroplast is installed. In this case, the device for preparing the gas mixture is made in the form of an ejector with cavities for supplying active gas — oxygen and cavities for supplying passive gas — hydrogen chloride, a nozzle nozzle, a mixing chamber with a diffuser, connected to the manifold by the manifold and covering the upper part of the reactor, and the collector cavity is connected to the cavity reactor holes. The phase separator of the reaction products consists of two stages, one of which is located at the outlet of the reactor, and the second at the outlet of the storage tank. The first stage of the separator consists of four coaxially mounted shells with annular spaces between them, in which the wire spirals spacing them are placed, forming channels for the passage of water and reaction products, while the wire spiral placed in the channel for passing reaction products is dressed in a fluoroplastic tube with an end fixed in a conical fairing covering two inner shells and connected to a third shell, the lower end of which is connected to the lower flange of the shell block and with it the upper perforated disk is connected to which the inner shell and the central pipe are connected with the lower end mounted in the bore of the protrusion of the lower flange, and the protrusion is equipped with a lower disk with the inner shell connected to it with the possibility of moving them along the axis, the outer shell is connected by the lower end to the collector water supply and has in the upper part of the hole with a water drain pipe. A spacer with channels for the passage of reaction products and a diametrical rib, in which channels with water inlet and outlet pipes are placed, is fixed on the lower flange of the block. The second stage of phase separation is made in the form of a container filled with material with a developed surface of fluoroplastic chips.

The method of producing chlorine and a device for its implementation are illustrated by drawings, where:

figure 1 is a schematic illustration of a device;

figure 2 - plasmachemical reactor;

figure 3 - ejector chamber for preparing a gas mixture;

figure 4 - phase separator of the reaction products, the first stage;

figure 5 - section "GG" on the phase separator of the first stage;

figure 6 - phase separator of the second stage with cumulative capacity.

A device for producing chlorine from hydrogen chloride by oxidizing it with oxygen (Fig. 1) consists of a chamber 1 for preparing a gas mixture of hydrogen chloride and oxygen, a plasma-chemical reactor 2, a high-voltage pulse generator 3, a device 4 for separating reaction products into chlorine and water - the first stage , storage tank 5 for reaction water. In this case, the reactor 2 (Fig. 2) is made in the form of a metal cylinder 6, inside of which is coaxially mounted, between the upper 7 and lower 8 insulators, a metal rod 9, and the upper insulator 7 is rigidly fixed between two flanges 10 and 11, in the upper insulator 7 fixed terminal 12 for supplying a positive charge to the rod 9. The lower part of the rod 9 is fixed through the sleeve 13 in the lower insulator 8 with the possibility of free movement of its end together with the insulator 8 in the axial direction, while the lower insulator 8 is perforated with holes 14. At the outlet of the reactor 2 there is a lattice 15 made of graphite fluoroplastic and perforated with holes 16.

The chamber 1 (figure 3) for preparing the gas mixture is made in the form of an ejector with cavities 17 of active gas — oxygen and 18 passive gas — hydrogen chloride, with a cavity 19 in which the nozzle nozzles 20 are placed, with a mixing chamber with a diffuser 21, the outlet of which connected to the flange 22 of the collector 23 (figure 2) mounted on the outer side of the upper part of the reactor 2 and connected to the reactor cavity by several rows of holes 24. The phase separator 4 of the first stage (figures 4, 5) consists of four coaxially located shells 25, 26, 27, 28 with channels 29, 30, 31 in them, in which the wire spirals 32, 33, 34, spacing them, are placed, forming channels for the passage of water and reaction products. The wire spiral 34, located in the channel 30, for the passage of reaction products, is dressed in a fluoroplastic tube to protect the spiral from exposure to aggressive reaction products. The spiral 34 (together with the tube) is fixed in a conical fairing 35 that covers two inner shells 27 and 28 and is connected to the shell 27, the lower end of which is connected to the lower flange 36 and the upper perforated disk 37 is connected to it, to which the shell 28 is connected and a central pipe 38, and with a lower end mounted in the bore of the protrusion 39 of the flange 36. On the protrusion 39 is dressed the lower disk 40, connected to the shell 28 and together with its end having freedom of movement along the axis. The shell 25 is connected to the upper flange 41, and the lower end to the collector 42 with a pipe 43 for supplying water to it. In the upper part of the shell 25 there is an opening with a pipe for draining water from the cavity 29. A spacer 44 (FIGS. 4 and 5) with channels 45 and 46 for the passage of reaction products and a diametrical rib 47, in which channels with pipes 48 are placed, is fixed to the lower flange 36 and 49 water inlet and outlet. Between the turns of the spiral 34 there are several pieces of plates 50 spacing the distance between the turns. The spirals 32 and 33 are fixed to the shells, for example, by welding.

The vessel 5 (FIG. 6) for accommodating the reaction water is provided with a water discharge pipe 51 and a neck 52 for connecting a phase separator of the first stage and a mouth 53 for connecting a phase separator of the second stage, consisting of a vessel 54 filled with material 55 with a developed surface of fluoroplastic shavings.

The implementation of the method of producing chlorine using the device described above is carried out by continuously supplying a pre-prepared gas mixture in a chamber 1 containing hydrogen chloride and oxygen in a stoichiometric ratio to the flow zone of a plasma chemical reactor 2 and oxidizing hydrogen chloride with oxygen to form the target product - chlorine and reaction water with their subsequent separation in the phase separator of the reaction products of the first stage and the phase separator of the second stage, chlorine from the separator of the second stage 54, 55 sent to the consumer, and the reaction water into the reservoir 5 through the necks 52 and 53.

In the chamber 1 (Fig. 3), the mixture is prepared under pressure by pressure pipe 18, is ejected into the cavity 19 and the mixing chamber 21, from which through the pipe 22 (Fig. 2) the mixture enters the manifold 23, from which it is evenly distributed through the openings 24 around the entire circumference of the reactor 2 and is fed into the flowing reaction zone of the plasma chemical reactor. In the reaction zone, the gas mixture is activated simultaneously both under the influence of electromagnetic radiation from the streamer discharge zone mainly in the ultraviolet range, and under the influence of irradiation with a stream of accelerated electrons, while a generator (Fig. 1) of high voltage pulses is used to create streamer discharges in the gas medium ( GVI) of nanosecond duration with a voltage of at least 100 kB and a frequency of at least 50 Hz, and the molecules and atoms of the reaction medium itself are used as electromagnetic radiation fusion of hydrogen chloride with oxygen and the formation of the target product - chlorine and reaction water. The reaction products through the holes 14 in the insulator 8 and then through the hole 16 in the lattice 15 enter the input to the separator 4, where when moving through the channel 30 they are cooled on both sides by water pumped through the channels 29 and 31 and are separated into gaseous chlorine and water. From channel 30, the reaction products through channels 45 and 46 (FIG. 5) enter tank 5 (FIG. 6), from where water is discharged through line 51, and chlorine is directed to the consumer through separation packing 55.

A prototype of the device was manufactured and the method for producing chlorine was tested on it, the fulfillment of the task was confirmed. The manufacture of the device and the tests carried out confirmed the possibility of industrial use of the device and method for producing chlorine.

Installation was tested in the following modes.

Example 1

Gases were supplied to the mixing zone with the costs:

- hydrogen chloride - 24 kg / h;

- oxygen - 5.8 kg / h.

The gas mixture was passed through the zone of streamer discharges of the GVI-150 generator.

The temperature in the reactor chamber was 20.2 ° C.

The outlet temperature is 19.2 ° C.

The pressure in the reactor under these conditions is 0.49 kgf / cm ² .

The reaction products were sent directly to the neutralization system.

At 800 s from the moment the generator was started, a gas sample was taken with a standard volume of 1 liter.

The combined content of chlorine and hydrogen chloride was determined by titration after passing the entire sample through a 10% KI solution.

The degree of conversion was 97 wt.%.

Example 2

Gases were supplied to the mixing zone with the costs:

- hydrogen chloride - 33 kg / h;

- oxygen - 7.2 kg / hour.

The gas mixture was passed through the zone of streamer discharges of the GVI-150 generator.

The temperature in the chamber is 22.1 ° C. The outlet temperature is 21.1 ° C.

The pressure in the reactor under these conditions is 0.402 kgf / cm ² .

The reaction products were sent directly to the neutralization system.

For 380 s from the start of the GVI-150 generator, a gas sample was taken with a standard volume of 1 liter.

The combined content of chlorine and hydrogen chloride was determined by titration after passing the entire sample through a 10% KI solution.

The degree of conversion was 96 wt.%.

Claims (5)

1. The method of producing chlorine by continuously supplying a pre-prepared gas mixture containing hydrogen chloride and oxygen in a stoichiometric ratio, and oxidizing hydrogen chloride with oxygen to form the target product - chlorine and reaction water, followed by their separation, characterized in that the gas mixture is fed into flow-through reaction zone of a plasma chemical reactor; in the reaction zone, the gas mixture is activated simultaneously directly as under the influence of electromagnetic radiation from streamer discharge mainly in the ultraviolet range, and under the influence of irradiation with a stream of accelerated electrons, while to create streamer discharges in a gaseous medium, a nanosecond high-voltage pulse generator with a voltage of at least 100 kV and a frequency of at least 50 Hz is used, and as a source Electromagnetic radiation use molecules and atoms of the reaction medium itself. 2. The device for implementing the method according to claim 1, consisting of a chamber for preparing a gas mixture of hydrogen chloride and oxygen, a plasma-chemical reactor for producing chlorine in a mixture with water, a high-voltage pulse generator, a device for separating the mixture into chlorine and water, a storage tank for reaction water wherein the reactor is made in the form of a metal cylinder, inside of which a metal rod is coaxially mounted between the upper and lower insulators, the upper insulator is rigidly fixed between the two flanges, in the upper a terminal for supplying a positive charge to the rod is fixed, the lower part of the rod is fixed through the centering sleeve on the lower insulator with the possibility of free movement of the rod together with the insulator in the axial direction, the lower insulator is perforated with holes for the passage of the activated gas mixture, and perforated is installed at the outlet of the plasma chemical reactor holes a lattice made of graphitofluoroplast. 3. The device according to claim 2, characterized in that the gas mixture preparation chamber is made in the form of an ejector with cavities of active gas — oxygen and passive gas — hydrogen chloride, a mixing chamber and a diffuser, the outlet of which is connected to a collector mounted on the upper side parts of the reactor, while the reservoir cavity is connected to the reactor cavity by several rows of holes located around the circumference of the reactor cylinder. 4. The device according to claim 2, characterized in that the phase separator of the reaction products consists of two stages, one of which is located at the outlet of the reactor, and the second at the outlet of the storage tank, while the first stage consists of four coaxially mounted shells with ring gaps between them, in which the wire spirals spacing them are placed, forming channels for the passage of water and reaction products, while the wire spiral in the channel for passing reaction products is dressed in a fluoroplastic tube with an end insulated in a conical fairing covering the two inner shells and connected to the third shell, the lower end of which is connected to the lower flange of the shell block and the upper perforated disk is connected to it, to which the inner shell and the central pipe are connected with the lower end mounted in the bore the protrusion of the lower flange, and on the protrusion a lower disk is dressed with an inner shell connected to it with the possibility of moving them along the axis, and the outer shell is connected by the lower end to the water supply manifold and s an opening in the upper part with a drainage pipe, the lower flange is fixed spacer block shells with channels for passage of the reaction products and the diametral edge with the channels and the water inlet and outlet pipes. 5. The device according to claim 2, characterized in that the second stage of the phase separator is made in the form of a container filled with a material with a developed surface - fluoroplastic shavings.

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