DE1467136B2 - PROCESS FOR THE PRODUCTION OF CHLORINE - Google Patents

Description

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The invention relates to a method for producing a negligible amount of water. If of chlorine from hydrogen chloride and / or ammonium but chlorine from hydrogen chloride and / or ammochloride, wants to produce granulated masses again with active niumchlorid, the amount present must Components are loaded and steadily under the water as low as possible, otherwise in Effect of gravity in a moving layer 5 Presence of iron chloride-impregnated graph tiles, nulate the side reaction

These granulated masses, which in a circle by ρ η ^ λ u <-i

circulate one reaction zone to another, ^{l te {} ~ ^ls + ^H 2 ^U ~ * ^te z ° * + ^{6 HU}

can take the form of platelets, globules, cylinder runs. This results in a large one in the form of HCl dem, tablets or, in particular, an irregular io proportion of the chlorine previously bound to iron own. They generally consist of a lorry. If, on the other hand, one works according to the invention, porous, with one or more active constituents- d. H. with the introduction of the active elements in fine particles impregnated carrier. part solid form, one avoids this disadvantage.

In the course of the reaction cycles which they under- The condition of the surface layers of the granu-

are thrown, the granulated masses become poor in the active ingredients. These in general and those in the zone in which they are located mean the prevailing circumstances on the surface of the grains. If this zone of substances can be lost through evaporation, especially at an elevated temperature, or if the compounds which are not negligible in view of the not negligible impregnating compounds are in a slightly vaporous tension of certain salts at the elevated 20 fusible form, the active temperatures of the reaction zones or by erosion Components of the granulated masses in dough-like sion from the surface layer of the grains. Be state. It is then appropriate to s? In this zone.

As a result, the performance of the apparatus decreases the active ingredients in the state of fine distribution V gradually, and after a few weeks they can be introduced because they unite immediately Masses become completely inactive. 25 with the active ingredients of the grains.

It is therefore necessary, continuously or intermittently, to separate the When working according to the invention

To replenish masses of the active ingredients - practically no subtle loading stemming from the introduction. This recharging can be brought about by subjecting the granulated masses to sieving by re-impregnating the carrier, a particularly sensitive and cumbersome way of working, which 30 The analysis of the masses clearly shows that the following steps are required: emptying of the reactors, guided components have been fixed.
Cooling of the masses, re-impregnation, drying This process makes it possible to

nen of the re-impregnated masses, rewarming composition of the granulated masses constantly increases men and reintroduction into the reactors. get the reactions of chemical transformation

It has now been found that it is possible to carry out the 35 under always the same conditions and Recharge of the granulated masses within the composition of the reaction products is important Carry out reactors yourself, without having to keep the process constant, every time the emergency The chemical reaction agility taking place in it becomes noticeable, the active components interfere, with the active ingredients, the content of which has been reduced, introduces in an expedient manner. Components are fixed on the grains. 40 If you mind looking for another from the

The process according to the invention for the preparation of the invention works different process and thereby introduces the active constituents of chlorine from hydrogen chloride and / or ammonium at a point where chloride, in which granulated material, which the surface layers of the masses hard and solid from precipitated on a carrier active If one or more of the masses at the outlet of the or several substances are at elevated temperature, one finds that the totality of the ((constituents) is always found in a state of fine distribution of gravity in a moving layer through one under the action of the substances introduced The recharging of the masses reaction chambers flows, whereby it is gradually on is therefore impossible in this way,
active constituents is depleted, is characterized by the method on which the invention is based

draws that the known production of chlorine by alternating without interrupting the process the active constituents are returned to the system by chlorinating and oxidizing polyvalent ones by converting these active ingredients into fine metal oxides. These procedures include in the first partial state in their active form or in a stage the passage of hydrogen chloride and / or Form, which can give the active form, in or chlorammonium vapors in bulk, which metal introduces immediately in front of a zone in which the oxides are contained in order to the corresponding chlorides active forming impregnating the granular masses, and then in a second stage the oxidation ingredients are in a doughy state. these chlorides with oxygen or air to release

The German patent specification 1113 929, which put the chlorine.

Production of chlorine according to the DEACON method

driving, the reintroduction into a basic reaction equations looks like this:
Fluidized bed of catalyst particles of subliming 2 Fe O +12 HCl -> 4 FeCl 4- 6 HO

system by the gaseous reaction products with ^{2 3} <■> _c r » ? <: n \ *

made copper chloride. To this end, 4 ^ eU ₃ + JU ₂ - »2 ^ e ₂ U ₃ + 6 U _{2 condenses}

one partially the reaction products and leads to one works advantageously with reaction

Reactor either an aqueous or hydrochloric acid solution, which in addition to ferric chloride also contains potassium from Copper chloride back. This regeneration chloride to reduce the volatility of the ferric chloride requires an additional partial condensation to add a beneficiary, e.g. B. cadmium or step. In addition, a non-copper chloride and an inert carrier are introduced into the reactor.

3 4

Increased yields are obtained by putting the rids, carbonates or hydroxyds, iron and copper in

successive phases of chlorination and metallic form, e.g. B. from filings or in different

Carries out oxidation in a moving layer. bound state as chloride, carbonate or oxide

The reacting masses run from the top after being introduced.

below in superimposed chlorination and 5 In all of these cases it is important that the solid Oxidation chambers around, where they are in a finely divided state in countercurrent to the substance to be introduced Hydrogen chloride or a gas containing oxygen is located so that it is uniform throughout meet. Since the masses are constantly distributed around the introduction zone and carry the maximum amount of body it follows that good yields are obtained when it comes into contact with it. To the dispersion can be, even if the degree of conversion io of the imported material will favor one per pass is relatively low. Preferably deploy where Using air as the oxidizing gas was thanks to it the speed of the grains is greatest the method possible, gas mixtures with one for example in the narrowed, the two reaction portion of chlorine above 20 percent by volume. zoning space, or at the top of one

The content of the reacting masses of active reactor under sprinkling of the cone of the grains. According to a particularly interesting embodiment yield of the chlorination and oxy-form reactions of the invention, potassium and dation are carried out on the one hand. A reduction in the total content of copper and iron, on the other hand, is a separate one.
The introduction of potassium, preferably in the tradable gas, while a change in the form of potassium chloride, can in the narrow channel, relative contents of the various salts and 'which overlooks the chlorination chamber, causes the oxides to reduce the active ingredients Composition of the reaction gases'. The grains there have great fluctuations in speed and, in particular, their concentration, which favors the dispersion of the salt,
reduced in chlorine. Iron and possibly copper are demonstrated

During the reaction cycles, which the reactive 25 preferably in the form of filament at the summit of the

are subject to the masses, impoverish this all-oxidation chamber, i. H. at the exit of the chlorinator

gradually of active ingredients. This impoverishment zone, a. One can so easily the finely divided

can be caused by evaporation of certain metal dispersing by making the cone, which

Salts, especially of ferric chloride, which one by the flow of the grains in the narrow, the two

A not negligible vapor tension is formed in the channel separating the 3 ° chambers, in which

elevated temperatures of the reaction zone have sprinkled a large part of the oxidation chamber. Man

or by erosion of the surface layer of the grains, the concentration of the filament in it is avoided

ner, a layer which is richest in the active axial part of the chamber, what would occur if

Components is. the filing light is placed directly in the narrow part

As a result, the performance of the apparatuses 35 leads would decrease. The contact between the introduced for the production of chlorine gradually from, and after iron and that unite in the oxidation chamber Weeks of the reacting masses of gases letting the chlorine present excessively can be become inactive. guiding the iron in ferric chloride, which is un-

The state of the inorganic, the granulated is fixed indirectly by the grains.

The mass of impregnating ingredients fluctuates strongly 4 ° The introduction of solid substances can be carried out by means of a

with their chemical composition. If any establishment can be effected, but one

Most of these compounds are present as chlorides, pneumatic injectors are particularly suitable

make them a relatively fusible mixture.

and under the conditions under which the examples

Reactions are carried out, they are in 45 The following are the results of some experiments,

doughy state. In contrast to this, if what is designed in a system according to the invention

a large proportion of these compounds were carried out in the form of. The system is shown schematically in the

. Significantly less fusible oxides are present, drawing shown. However, this is not intended to result in any

the masses are perfectly hard and firm. Limitation of the invention.

The chemical composition of the masses changes 5 ° This plant, which is used for the production of chlorine constantly during the reaction cycle to which they are subjected while running out of hydrogen chloride and / or ammo are. The active constituents of the bulk nium chloride used consists of two overalls in the state of chlorides when they are in contact with one another in reaction chambers, which afterwards the chlorination gas, which is hydrogen chloride, each other from the granulated, with active constituents and ammonium chloride, are or have been, when 55 parts of impregnated contact material flowed through they will be in the chlorination zone or at the exit.

these are located. This zone is there or immediately before The system has a chlorination chamber 1, the entrance to this zone, in which in accordance with provided with a passage 2 for the supply of the the invention is the introduction of the active grains, with line 3 for the introduction of chlorine components accomplished in a finely divided state. 60 hydrogen and / or sodium chloride, with outlet 4 The active components of the masses are there in the for water vapor and optionally ammonia and Mainly in the form of chlorides and consequently with channel 5 for the forwarding of the grains into the oxyder elevated temperature in a doughy state. dation chamber 6. This latter chamber is

One can see the necessary active ingredients in with line 7 for the introduction of air, with exhaust

the form of chlorides or in any other form 65 let 8 for the mixture of nitrogen and chlorine and

introduce which turns into chlorides on contact with an outlet channel 9 for the grains. These will

the gases located in the introduction zone then through a device 10, not shown,

can implement. Potassium can be obtained in the form of ChIo- z. B. an elevator for air or something else

Elevator, lifted in the bins from where they are in the Channel 2.

A container 12, which contains powdered potassium chloride, is via a pneumatic injection system 13 with the feed channel 2 for the grains tied together. A similar device 15 allows iron filings to be introduced into the upper empty part the oxidation chamber to sprinkle the grains.

Under the operating conditions of the plant, the chlorination chamber is kept at a temperature between 450 and 500 ^° C. and the oxidation chamber between 530 and 560 ^° C. The grains are in a doughy state in the chlorination chamber and in the upper part of the oxidation chamber.

The grains circulating in this system are cylindrical with a diameter of 5 mm and a length of 4 to 8 mm. They consist of an inert carrier (aluminum silicate) on which various active components are fixed: FeCl ₃ , KCl and CuCl ₂ .

As they circulate through the plant, these grains constantly lose their active ingredients. The one in the The examples given in the following table show the rapid depletion of the masses during the tests and the easy recharge of these masses by injecting the active ingredients within of the system by the described and drawn facilities.

The table includes test pairs, under the same operating conditions with and without introduction of the active ingredients carried out.

Salary of the masses
before trying
Gram atom

Fe / kg

Gram atom

K / kg

Test duration,

Days

Introduced

Components

Salary of the masses
after trying
Gram atom

Fe / kg

Gamma atom

K / kg

Loss%: Fe ...
K ...

la

2.44
1.42
12th

2.01

1.29
20th
9

Ib 2a 1.96 1.15 1.35 12th 3 Fe + KCl - 1.87 0.75 1.42
4.5
Profit 5 35

2 B

1.05

- Fe

1.0

35

40

45

⁵⁰

The above results in the table clearly show that the introduction of iron filings and Potassium chloride makes it possible to avoid the depletion of active ingredients, and even these masses to enrich if necessary.

With regard to the technical progress achieved by the invention, the following is also stated:

In fact, it all depends on the initial set chosen. According to the example it can be seen that this Amount varies from 1.05 to 2.44 gram atom Fe / kg of mass. To get the iron content again produce, one introduces iron according to the invention in such amounts that one established the Offsets losses. In practice, therefore, one can regulate the amount of refreshment by using consecutive Performs analyzes of the re-loaded granules.

In the art, it is expedient to use masses with a content of about 1.1 gram atoms Fe / kg (these are essentially the initial compositions of Examples 2 a and 2 b), and below these Conditions one must employ 241 granular masses to 11 chlorine starting from the equivalent To obtain mass of necessary hydrogen chloride. When there is no refresher and if the same amount of hydrogen chloride is fed to the reactor inlet, it will decrease the effectiveness of the masses by 35% after the lapse of 3 days. Then only 650 kg ■ of chlorine generated even though the same amount of mass (24 t) is kept in circulation.

In contrast, it can be seen in Example 2 b that according to the invention one is able to reduce the Limit the yield of chlorine to only 5%. It would certainly be possible, even this humiliation of 5% if the refreshment was continued until the masses had theirs recovered the initial active ingredient content. To be in the plant with a use To get from 241 masses to 11 generated chlorine would then have to be at least

0.40 χ 56 ΙΟ- ³ χ 24 10 ³ = 538 kg Fe / t

need to refresh generated Cl _2.

Thus, the technical progress achieved by the invention is undeniable because it has been shown that for an equal amount of HCl introduced, the final production of chlorine immediately corresponds to the claimed Freshening up the crowds is bound.

Claims (3)

Patent claims: 1. Process for the production of chlorine from hydrogen chloride and / or ammonium chloride, at which granulated material, which consists of active ingredients deposited on a carrier consists and under the action of gravity in a moving layer one or more elevated temperature reaction chambers flows through it characterized in that the active ingredients are used without interrupting the process returns to the system by keeping these active ingredients in a finely divided solid state in its active form or in a form which the active form can give, in or directly in front of a zone in which the active ingredients impregnating the granular masses are introduced are in a doughy state. 2. The method according to claim 1, characterized in that the active ingredients in finely divided solid state together or separately through a pneumatic delivery system. 3. The method according to claim 1, characterized in that the active ingredients in Introduces as perfect a dispersion as possible. 1 sheet of drawings