DE1667216C3 - Process for the production of ammonia and chlorine from ammonium chloride - Google Patents

Description

Oxygen-containing gas, treated and thereby First the mass is through e.nen btrom e.nes

reducing gas, such as carbon monoxide, hydrogen or luminous gas, at a temperature of between SOO and 55O ° C activated, wherein the reducible band parts of the catalytic mass, d. H. essentially some of the iron oxides contained therein are reduced.

With the mass previously reduced in this way, ammonium chloride is brought into contact at a temperature between 350 and 500 ° C., preferably in the vicinity of 420 ^{° C.} , is discharged.

As soon as the ammonia has been released, the chlorinated mass is released through a Sauerv.off containing gas stream is oxidized. As a result of the oxidation of the metal chlorides and of the non-chlorinated reduced oxides an increase in temperature. The passage of the oxygen-containing gas is carried out while maintaining an ao Temperature continued between 480 and 550 ° C and at the same time the chlorine was released in a gaseous state made and won. The mass is then reactivated by a reducing gas in the Circuit for a later work process of the same as Kind of used.

The solid, reactive mass described above can be used in various ways. For example the mass can be in the form of a static, moving or fluidized bed be used.

The scope of the invention is not departed from, if the solid, reactive mass with dissociation products of ammonium chloride, such as a mixture of Hydrochloric acid and ammonia.

It is also within the scope of the invention if a newly prepared solid, reactive mass in a appropriate stage of the process described above is used. So can the first Use of a newly produced reactive mass in which the iron as iron (!!!) oxide is present, the use begin with the phase of activation and reduction by means of a reducing gas flow.

In another case, in which the main effective Components are present in the state of chlorides, can with the use of the mass in the oxidation and chlorination phase are started.

In the following examples the procedure is followed of the invention with reference to the four preferred embodiments explained in detail.

example 1

The solid, reactive mass was produced by mixing 80 g of iron oxide Fe ₂ O ₃ in a finely divided state, 10 g of LiCl, 18 g of KCl, 7 g of Mn ₃ O ₁ and 20 g of finely precipitated silica.

The mass was placed in a reaction vessel through which a stream of luminous gas with a temperature of between 500 and 53O'C was passed through. After the mass under a weak The stream of a reducing or inert gas was cooled with 25 g of ammonium chloride brought in contact. Then the mass was heated to 400 to 420 ° C to liberate the ammonia, which was removed by a stream of nitrogen. At the end of the ammonia evolution the mass became the Subjected to the action of a stream of oxygen, whereby the iron chlorides and iron oxides of lower valences were oxidized.

As a result of the exothermic course of the reaction, the temperature rose, which then rose to about 500 to 530 ° C was held. During this hold time, oxygen continued to be passed through to free the chlorine close. After the reaction vessel was purged with a nitrogen gas, the mass became the action of a reducing gallium, for example of coal gas, subject. Some of the chlorine remained during this first stage of the process fixed to the manganese oxide.

The mass produced in this way was brought into contact with 23 g of ammonium chloride, the whole to 400 Heated to 420 ° C and the released ammonia is removed by a stream of nitrogen.

Then the chlorinated catalytic mass was treated with a stream of oxygen and the exposed Chlorine obtained.

Components used and weight of the same

Recovered

ammonia

in ° / o

Time I NH ₃

Sound of the gases

after 1 hour

Dechlorination

length of time

Remarks

about the condition

the one in dechlorination

arising gases

1. 80g Fe ₂ O, ·! - 18g KCl + 20g SiO ₂

2.80g Fe ₂ O ₃ - 10g LiCI - 20g SiO,

3. 80g Fe ₂ O ₁ r 18g KCl - + - 10g LiC! - 20g

SiO ₂

4. 80g Fe ₄ O, + 18g KCl-I-7g Mn ₃ O ₄ + 2Og

SiO ₂

5. 80g Fe ₂ O ₃ - 18g KCI + 10g LiCI + 7g

Mn ₃ O ₄ r 20 g SiO ₂

1 hour

30 minutes 1 hour

1 hour

10 mins

1 hour 30 minutes

1 hour 10 minutes 99

98.7

98.7

98.85

29
73.8

55.9
71.7
78.0

During the first phase of this process, niaks were obtained. During the course of I hour and 10 minutes 98.85% of the employed in the course of 1 hour 79 ° / ₀ in the form of ammonium chloride, ammonium form of gases, which 78 ° / "

Pure gas

The gas contains
carried away
FeCl ₃

Pure gas

Pure gas

Pure gas

second phase were the fixed chlorine in chlorine and 2 ° / ₀ chlorine

containing hydrogen acid. In the following 30Miiutes was another 9.1% of the used chlorine recovered. This gas ; Part contains 26 "" Chlorine. So overall are in the course of 1 hour, 30 minutes SK.i% of the chlorine free 5 cleared; been.

During the process, 65% of that contained in the mass is reduced to the Fe state Eiseir. saturated.

I into the use of lithium in the solid, reactive To make mass landland a series of four further attempts were made with masses, whose compositions were similar to those of Example 1, but in which one or two effective Filed elements. The results of these attempts are compiled in sections 1 to 4 in the table above. Section 5 repeats the results of example 1.

Il

B e i s ρ i e 1 2

The solid, reactive mass was obtained by mixing KOg Fe ₂ O;,. 10 g LiCl, ISg KCl. 9 g of CuCl and 20 g of finely precipitated silica are produced. The mass was placed in a reaction container through which a stream of luminous gas at a temperature of between 500 and 530 ° C. was passed. The mass was then treated under the same conditions as in Example I.

In the course of this experiment, H) O "" of the individual ammonia and during the dechlorination in the course of 1 hour 69.8 "ι, of the fixed chlorine with a content of gases obtained in chlorine of 72.2% and 1.9% NCI.

B e i s ρ i e 1 3.

The solid, reactive mass was obtained by mixing 150 g of bauxite (with an iron content of 59.8 g) which had previously been calcined at 900.degree. made with 10 g LiCl, IK g KCl and 7 g Mb ₃ O ₁ . This mass was placed in a reaction vessel and reduced by passing a Leuchlgasirom at a temperature of between 500 and 530.degree.

The mass was then treated in the same manner as described in Example 1 above.

In this experiment, 99% of the _{ammonia used in the form of NH 1} Cl and, in the course of 1 hour, 70.1% of the fixed chlorine with a chlorine content of the gases in chlorine of 71.5% were removed in the course of 1 hour % and obtained HCl from 0.85 ⁰ Z ₀ .

By continuing the desloration, a total of 100% was achieved over the course of 2 hours, 45 minutes. of the fixed chlorine recovered.

Comparison example 4

A solid, reactive mass was made from the same basic ingredients as in the case of Example 3, however omitting the LiCI, made from the following components:

150 g bauxite (59.8% iron) annealed at 900 C.
18 g KCI,
7 g Mn ₃ O ₁ .

This mass was treated under the same conditions as in the previous example.

_{In this experiment, 97.9% of the NH 3} used was obtained in the course of 1 hour, 30 minutes and 65% of the fixed chlorine with a chlorine content of 67.3% and of HCl in the gases in the course of 1 hour 2.1% gained.

Further dechlorination until the fixed chlorine was exhausted was carried out in the course of 3 hours, 100% of the chlorine recovered for 30 minutes.

In the following table are the results of the example 3 and Comparative Example 4 are summarized.

Nl-! , Extraction
Jos in I orni from NH ₁ CI
cingcNCl / .lcn ammonia Duration of proceedings NH ₃
O ' Dechlorination
After 1 hour Salary of Gases lintchlorination
At the end of the procedure Duration of proceedings /O "in
of the fixed ° / o Cl. V ₀ HCl "U
recovered 1 hour 99.2 Chlorine* 71.5 0.85 fixed Cl ₃ 2 hours example 3 15 minutes 70.1 100 45 minutes I sin 97.9 67.3 2.1 3 hours Example 4 30 minutes 65 100 30 minutes

The table shows that both the production of ammonia gas and the production of chlorine gas in the process according to the invention described in Example 3 due to the addition of the Lithium chloride is significantly improved and also the duration of the dechlorination is significantly shortened will. With a 100 percent recovery of chlorine, the process time will be 3 hours and 30 minutes reduced to 2 hours and 45 minutes. Extends over longer periods of time This results in excellent economic efficiency through the process according to the invention.

Claims (2)

1 The chlorine in elemental form is freed and gained 1. A process for the preparation of ammonia table ^we * ^e "^ _{to Herste} |. Lung of ammonia and and chlorine of ammonium chloride to give be used to, / * _on j _UMC hlorid case of release of ammonia a solid, reactive 5 Cnlor ausιαμ ^ Process in the industrial mass of iron (III) -CAid and potassium chloride with ^ er Lurcn " ^nr k continuously working plant a reducing gas at 500 to 55O = C be scale in a come ^ ^^^ _enumerated , _t « _n acts and then With the ammonium, it is ^e ™ ""' _hne consecutively through chloride to temperatures between 350 and SOO'C Ar «, svo ^ f ⁵ ^ f ^ _{here in every} r stage that is heated and whereupon the release of the chlorine to ge ^ ¹ ™ ^e ™ J ⁿ * ° _{n "de} reaction generated gas so volldie previously obtained, chlorinated mass with a by""* _{f *";. makes we} d so far it has oxygen-containing gas stream at temperatures suitable as ^ ogiicn β difficult proven , ren between 480 to 550 ° C, thereby Ä ^ nd arjjs ^ ^. characterized in that the solid, reactive from the chlorine erte ^ Mass ^^ ^ ^^ ^^ mass additionally contains a lithium compound. 15 factions irei to. ' is used. 2. The method as claimed in claim 1, characterized in that- '«^ £ ^" 1? en A process for the preparation is characterized in that a solid, reactive ^The Lithiumchlond / _"n"! V ^g ° chloro _nd of ammonium chloride, containing EisendID-oxide / potassium chloride mass of ammonia and ".ni.d _{ks ejn £} is used, in which the atomic ratio of where ^ma " _n ^z "^; f _E ^e Sfii) - _O xide and potassium chloride Potassium to iron between 0.2 and 0.7 and the mol- *> ^^ Sci at 500 to 550C loading ratio of lithium chloride to potassium chloride with a ^redu ^ ^en ^^ ^ _the ammonium chloride between 0.3 and 1.2, preferably 0.5 and 1.0, lies «. J ^^^ Ä ™ »and heated to 500 ° C and J ^^^ Ä »u whereupon to release the chlorine the previously _a5 containing, chlorinated mass containing an oxygen • sustaining gas flow at temperatures between 480 and 55O ° C, which is characterized by treated. The invention relates to a process for preparing the solid, reactive mass in addition a Lithiumvon ammonia and chlorine from ammonium chloride, ^{verb 'nd} ^ / ~ _ugten Ausfübrungsform of Verwobei to the release of ammonia a solid, 30 In a revorzufct ^c ".. * * _ft reactive reactive mass of ferrous oxide and potassium chloride driving according to the invention w ^ rdenefes ^ reactive, with a reducing gas at 500 to 550 ° C to- ^L 'j ^ta "^ _a S _d SSzTta defd AtoS Ss and then used with the Ammoniumchlor.d chlond mass, ιη ^ α ^ ^ ^ ^ ^ to temperatures between 350 and 500 ⁰ C and heated from potassium to m «.. ™ 'JT] T""KaTiumchlorid whereupon, to release the chlorine, the chlorinated mass previously obtained with a Oxygen contains between 0.3 and U unu, preferably between u.5 5 ^e 5o'c ⁿ SS ^{at temperatures BETWEEN 48} ° ^TO ""Da's EiSnD oxide can preferably be in the form of a ⁵⁵ Solid, reactive masses are known which contain minerals, such as a ferrous B. «x, t. ^^^ make it possible.Ammonia and chlorine from ammonium 40 den. As ^ ^hlumw . ^b ™ ^you _E ⁿ * i ^^ Chloride or from one of its dissociation erth.umch ond used It is a giving mixtures of hydrochloric acid and other lithium compounds such as To produce ammonia. These masses are made of lithium carbonate, ™ Bäumeneed ^ ΖΖ% ££ essentially from one or more iron oxides, their use to L> th, umchlo ^ ^msetz « ⁿ · which are preferably bound to potassium chloride. 45 Optionally, the solid wTe silica From Belgian patents 632 265 and a solid inert ^Ve f ^ S ^, ^ 660 509 are already processes for the production of and e.nes or more Akt'vierungmittel, such as eme NH ₃ and Cl _{2 are known} from NH ₄ Cl, according to which NH ₄ Cl is combined with copper, manganese or MrtaHen a reactive mass, which consists of a with a reduced- from the group of the rare ^E ^ "^ ¹ ,, * / ™haben · Generating gas at 500 to 55O ⁰ C activated mixture of 50 ^{Bringing together d} "« ^ ^h « ^the ^ ° '™: an iron and a potassium compound, with reactive mass-forming elements: can be in any Be Temperatures between 350 and 500 ⁰ C, preferably arbitrary and known manner are carried out as for example ^ d "ch brought into contact near 420 "C, the chlo- simple mixing of the constituents ^{J" ^^ "1} ^ J. ured mass then by means of an oxygen-containing divided state. It is also be «P ¹ ? ^ * J ^uch _n ™ ⁸ _n Gas stream is oxidized and the chlorine is at a temperature of 55 Hch, the solid, reactive mass du ^ P "^« ™ ^ " doors from 480 to 550 ^ C is cleared. inert, solid ^v ^ unnungsm.ttelii '™ t «" « ^Losun ß It turns out to be advantageous to salt before using meta, then drying and ^ e such a solid, reactive mass with the aim of adding the ^ "^^^ J ^ Activation of the mass of the iron oxide at least partially wise to reduce. During the subsequent work 60 in the French Pa, snow 1 393 417 In the course of chlorination, the ammonium-chlorine process is the catalytic and fixing mass in id and / or its dissociation products with the reacting aqueous bath by * ^^ ££ * $ * £ tive mass brought into contact, which the chlorine ^ "E-senox.daufTragerstoffte.lchenund ^ of ammonium chloride is fixed in chloride form, and the addition of the other components is made the released ammonia is recovered. In the 6 _S den,. “Active masses