The method of gas purification from hydrogen chloride

 

(57) Abstract:

The invention relates to a method of cleaning gases and can be used for separation of hydrogen chloride (HCl) from various gas mixtures and for removal of HCl gas emissions, such as exhaust gases of the processes of thermal treatment (incineration, pyrolysis) of industrial and household waste. Essence: in the method of cleaning gas from the Hcl adsorption of hydrogen chloride from the gas phase provide a solid adsorbent, and then carry out the regeneration of the adsorbent. As the adsorbent of hydrogen chloride using natural zeolites, the adsorption is carried out at from 20 to 100oC, regenerate the adsorbent by heating to 250-300C. as adsorbent use natural high-silica zeolites (clinoptilolite, mordenite), dehydrated and neobespechenie, and pre-dictionaraoke and dealuminated also dehydrated and neobespechenie. The technical result of the proposed method of gas purification from hydrogen chloride is to simplify purification technology gas from the Hcl through the use of adsorption of the solid adsorbent and eliminating additional process steps, such as distillation technical hydrochloric acid, and exception obrazovaniya gas purification and can be used for separation of hydrogen chloride (HCl) from various gas mixtures and for removal of HCl gas emissions, for example, flue gas processes thermal treatment (incineration, pyrolysis) of industrial and household waste. The gas mixture and emissions may contain 1-10% (by weight) of hydrogen chloride.

To absorb the HCl from the gas mixtures typically use methods adsorption or binding of alkaline reagents. Cleaning gas emissions when recycling is also an introduction to the mixture of different additives, linking the released hydrogen chloride.

The known method according to which the furnace for combustion or pyrolysis of chlorinated wastes injected specially synthesized granules on the basis of calcium hydroxide or sodium hydrogen carbonate with the addition of other substances (sodium hydroxide, oxides of magnesium or aluminum). Granular additives absorb the hydrogen chloride and other acid gases emitted at temperatures up to 800oC [1]. The method is not applicable in the processes of high-temperature (>800oC) pyrolysis for gas separation processes, excluding additives in the original environment, for example, in the processes of organic synthesis or distillation of volatile chlorides.

Also known methods of gas purification from hydrogen chloride, in which the absorption of HCl by INIA, or water [2, 3, 4]. The absorption of hydrogen chloride is produced by passing a stream of hot gas through the nozzle of calcium carbonate or calcium carbonate-magnesium (dolomite), by bubbling gas through a suspension of calcium hydroxide or calcium hydroxide with additives of calcium carbonate, irrigation flow of gas with a slurry of lime milk or water. The disadvantage of these methods is the formation of unusable waste (sludge, wet pastes or wastewater) containing the chlorides of calcium, magnesium, and other substances and are not subject to discharge into the environment. The disadvantage of the methods is also a multi-stage process to produce a marketable product: for disposal of hydrochloric acid is necessary, in addition to the adsorption process of hydrogen chloride, to the purification and distillation received contaminated HCl solution.

The closest the merits of the claimed invention is a method consisting in the adsorption of hydrogen chloride gases from the solid adsorbent and subsequent regeneration of the adsorbent [5]. Prototype method allows you to clean gases from the hydrogen chloride without the formation of unusable waste. The disadvantage of this method is the low selectivity of the solid adsorbent.

The technical result is achieved by adsorption of hydrogen chloride from the gas phase solid adsorbent and regenerate the adsorbent. As the adsorbent of hydrogen chloride using natural zeolites, the adsorption is carried out at from 20 to 100oC, regenerate the adsorbent by heating to 250-300oC. as an adsorbent use natural high-silica zeolites (clinoptilolite, mordenite): natural, dehydrated and neobespechenie, and pre-dictionaraoke and dealuminated also dehydrated and neobespechenie.

The essence of the proposed method of gas purification from hydrogen chloride is that the absorption of HCl carry out solid adsorbent, which is used as natural zeolite, clinoptilolite or mordenite. For this purpose, the gas is cooled to 20 to 100oC when the regeneration of the adsorbent is passed through the nozzle of the natural zeolite, which is the adsorbent of hydrogen chloride. Regeneration of the adsorbent is conducted by heating up to 250oC and above. For h is t for adsorption and absorption of hydrogen chloride. Released during regeneration of the adsorbent HCl is used to produce hydrochloric acid or used for other purposes. The regenerated adsorbent is used repeatedly (PL. 1).

Pre-cooling gas is required in order to increase the adsorption capacity of the zeolite. In Fig. 1 shows the adsorption isotherms HCl high-silica zeolite - clinoptilolite - and low-silicon zeolite - phillipsite at different temperatures. From this figure it follows that the adsorption capacity of highly siliceous zeolites 4-5 times more than the low-silicon zeolites. In addition, the increase in temperature of the adsorption interaction above the 100oC leads to a decrease of adsorption capacity of 3 and more times. The temperature is raised to 250oC leads to the translation of HCl in the gas phase (table. 1, line 5) that is used for the regeneration of the zeolite adsorbent.

To increase the absorption capacity of natural zeolite in the hydrogen chloride regenerated adsorbent can be optionally humidified air containing water vapor, or water directly. An even greater increase in the adsorption capacity of the solid adsorbent for hydrogen chloride is achieved in the case of application of PR is of the adsorption capacity of natural, dehydrated and decationizing of clinoptilolite, which show a significant (2-fold) increase in capacity of the zeolite HCl for samples pre-decationizing and delaminating and saturated with water.

Example

Through the nozzle, consisting of 1 kg of natural clinoptilolite or pre decationizing and delaminating of clinoptilolite, crushed to a fraction of 0.5 - 3.0 mm, pass gas, consisting of N2, CO2, CO, NH3H2O, containing 6.0 wt.% HCl. Gas through the nozzle miss up to saturation of the sample. After completion of the adsorption process, the zeolite is heated for 10-15 minutes without air to 250-300oC evolved hydrogen chloride is collected. The regenerated and cooled adsorbent used again. Hydration of the adsorbent is achieved directly by passing through the nozzle wet the source gas, or air containing water vapor, or spray water into the layer of the adsorbent.

Methods of preparation of the zeolite and the results are shown in table. 3.

Technical efficiency of the proposed method of gas purification from hydrogen chloride in comparison with the prototype is to simplify technology clear for example, distillation technical hydrochloric acid, and the exclusion of education unusable waste in the cleaning process.

Literature

1. Akira Deguchi. Gasification of wastes generated during the reprocessing of old cars, and the use of gas for electricity generation. - KAGAKU kogaku. in 1991, 55, N 1, S. 37 and 38.

2. Patent Of Russia No. 2019275, B 01 D 53/34, 15.09.94.

3. Patent Of Russia No. 2095130, 01 D 53/68, 10.11.97.

4. Aufarbeitung von Abfallsalzsaure. - Techn. Rdsch. Sulzer. in 1991, 73, N 4, p. 35-38.

5. Patent Of Russia No. 2015158, 01 D 53/34, 1994.

1. The method of gas purification from hydrogen chloride, comprising the adsorption of hydrogen chloride from the gas phase solid adsorbent and regeneration of the adsorbent, characterized in that the adsorbent of hydrogen chloride using natural zeolites, the adsorption is carried out at 20 - 100oWith the regenerate the adsorbent by heating to 250 - 300oC.

2. The method according to p. 1, characterized in that the adsorbent of the hydrogen chloride used drive high-silicon zeolites, clinoptilolite and mordenite.

3. The method according to PP.1 and 2, characterized in that the adsorbent using natural zeolites, dehydrated and neobespechenie.

4. The method according to p. 1, wherein eolit, dehydrated and diabetogenic.

 

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