DE1210005B - Process for the production of sulfur and hydrogen by thermal dissociation of hydrogen sulfide - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

210 005 Int. α .:

COIb

German class: 12 i- 17/04

Number: 1210005

File number: S 70001IV a / 12 i

Filing date: August 19, 1960

Opening day: February 3, 1966

The invention relates to a method for the production of sulfur and hydrogen by thermal dissociation of hydrogen sulfide.

It is known that hydrogen sulfide breaks down into its elements when passed through a hot porcelain tube. Also, it is henceforth known to use an electric arc for the dissociation of hydrogen sulphide into its elements, even it is known to suspend the hydrogen sulfide exposure to oxygen to allow decompose it into its elements ¹ ^. However, these known processes have the disadvantage that, although the sulfur can be completely recovered, the hydrogen is lost in the process.

The invention is based on the object not in an industrial process from hydrogen sulfide to extract only the sulfur, but also the hydrogen. - The solution to this problem is according to the invention in that the hydrogen sulfide in a combustion chamber with the addition of so much oxygen or oxygen-containing gases that are burned for the dissociation of the unburned Hydrogen sulfide in sulfur and hydrogen sufficient temperature is achieved, with a possible heat deficit by additional Heating is applied to the gases entering the chamber that are formed during the reaction Gases are rapidly cooled, sulfur and water vapor are condensed from them, the sulfur is extracted and the hydrogen sulfide-hydrogen mixture obtained after the condensation be treated by processes known per se in order to remove the hydrogen sulfide, which is recycled, from the Separate hydrogen.

In a special embodiment of the invention, the dissociation in the presence of a granular, refractory Material such as alumina, bauxite, refractory earths, oxides, magnesia, preferably magnesia-thorium mixtures, which are activated by cerium oxide, made existing contact mass.

One particularly active catalyst is obtained if one starts enriched with a greater proportion ThO ₂ Magnesia (about 40 to 80 ° / ₀ ThO _2), wherein the ThO ₂ is itself activated by incorporation of a small proportion of cerium.

The practical implementation of the method according to the invention takes place as follows:

_{H 2} S and O ₂ are introduced separately into the combustion chamber, the latter being advantageously preheated to the highest possible temperature. The _{amount of O 2} is adjusted so that the temperature, which should generally preferably be between 1400 to 1500 ° C., processes for the production of sulfur

and hydrogen by thermal dissociation

of hydrogen sulfide

Applicant:

Societe Chimique de la Grande Paroisse

(Azote et Produits Chimiques), Paris

Representative:

Dipl.-Ing. G. Kalep, patent attorney,

Berlin 38, Altvaterstr. 31

Named as inventor:

Marcel Jean, Paris;

Jean Housset, Rouen, Seine, Maritime

(France)

Claimed priority:

France of August 21, 1959 (803 257)

is held. The emerging mixture only contains small amounts of H ₂ S.

Immediately at the exit of the furnace, the gas mixture is abruptly quenched, e.g. B. by introducing into a Low pressure boiler, the water pipes of which are kept below 159 ° C, a temperature below or at which the condensed liquid sulfur is thin. By injecting cold water into the kettle leaving gas precipitates sulfur powder, which does not adhere to the walls and due to the condensation of the water vapor formed is easily recoverable.

After the condensation and separation of the sulfur and then the water vapor, a gas mixture of H ₂ S and H ₂ remains, from which the H ₂ S can be separated either by liquefaction or by dissolving in a selective solvent or by using both processes at the same time.

If necessary, after the condensation of the sulfur and the water vapor, the invention can work towards an enrichment of the gas in H ₂ and its depletion in H ₂ S by a new partial combustion with O _{2 taking place in a second furnace} New dissociation of the H ₂ S caused in such a way that after renewed condensation of the sulfur and water vapor formed in the course of the second oxidation

609 503/3 «

Claims (1)

3 4. an H ₂ -rich mixture, with a low content of causing what in general and especially with regard to H ₂ S is formed and so the separation of the latter is of no interest to the conversion yield, is facilitated. as long as the reaction is carried out without pressure. For these burns, instead of pure O _2, for reasons of easier condensation, or air or O ₂ -enriched air, 5 separation of the constituents of the mixture obtained can be used, the air preferably being strongly preheated. an economic advantage can nevertheless arise, "After the H _{2 S has been separated off, an H 2} : Njj mixture is obtained if a moderate pressure of about 5 to 20 atm is used a reactions a higher H ₂ S yield dissociation illustrative example cited. to obtain io, it may be necessary, maximum of the reaction indicate the temperature, _the x _ERÜ p _era ture may be about 100 be this increase example to 200 ° C and 1000 m ³ / h H ₂ S are ^{preheated to 500 °} C. and only brings about a slight increase in the O ₂ consumption passed the upper part of a cylindrical furnace, and with a slight decrease in the H ₂ content obtained its metal jacket with a layer of refractory and 15. insulating stones is protected. The furnace is with The process according to the invention is well suited for conversion reactions running regularly under pressure, granular fragments of 20 to 30 mm, made of magnesia (35%) ¹ ^ d thorium oxide (65%), the ThO _{2 used} itself being 0.95 % C claims:
sends, whereby the ThO _{2 used} itself with 20
0.95% Ce is activated. 1. Process for the extraction of sulfur and By a tube coaxial with the inlet of the H ₂ S by thermal dissociation of hydrogen line is pressed in _{O 2.} The feed line of the hydrogen sulfide, thereby marked ' O ₂ drains into a chilled mouthpiece that draws or that the hydrogen sulfide in one contains several side rows of holes through the 25 combustion chamber with the addition of so much oxygen 116m ³ / h O ₂ is regularly distributed in the H ₂ S flow or gases containing oxygen are burned, will. that one for the dissociation of the unburned Upon contact with the previously heated catalyst, hydrogen sulfide turns into sulfur and hydrogen Satorstoff burns the H ₂ S, and the temperature sufficient temperature is achieved, whereby a is increased to 1400 to 1500 ⁰ C by throttling the 30 possible heat deficit due to additional O ₂ supply regulated. In this way there is heating of the gases entering the chamber an equilibrium is reached extremely quickly, and the mixture is applied, which is formed in the reaction takes the following, the thermochemical co-gases rapidly cooled, from it sulfur and water weight corresponding composition: steam condenses out, the sulfur recovered 35 and the sulfur obtained after the condensation ^ 2 430 m ³ hydrogen-hydrogen mixture according to H2O 232 m known procedures are treated to the H ₂ S 347 m ³ hydrogen sulfide, which is returned to the Sulfur vapor 925 kg is led to separate from the hydrogen. 40 2. The method according to claim 1, characterized The abrupt cooling of this mixture shows that the dissociation in the presence of a low-pressure boiler delivers about 1200 kg of steam with granular, refractory material, such as alumina, 12 atm and about 900 kg of liquid sulfur, the last bauxite, refractory earth, oxides, Magnesia, before traces of sulfur, are caught in a cold water, preferably magnesia-thorium mixtures, which washer. After cooling, the remaining gas mixture (767 m ³ ) that has been activated by cerium oxide contains about 55% H ₂ . This clock mass is made.
H ₂ is separated from the _{unconverted H 2} S with the aid of 3. The method according to claim 2, characterized by a known measure, which is characterized in that H ₂ S, which is treated as a contact mass magnesia, can then be returned to the furnace a larger proportion, apply. 50 or about 40 to 80% thorium dioxide As already mentioned above, can be determined by the inventions ^J is enriched, the Thoriumdioxyd itself generation through partial combustion with O ₂ also through the incorporation of a small amount of cerium obtained high temperature, the mixtures with very activated.
considerable amounts of sulfur vapors, H ₂ and H ₂ S supplies. 55 Considered publications: It should be emphasized that some in the implementation Gmelin, Handbuch der Inorganic Chemistry, occurring reactions an increase in volume 8th edition, Volume 5, Part B, 1953, pp 7/8. 609 503/341 1.66 © Bundesdruckerei Berlin