The method of decomposition of hydrogen sulfide

 

(57) Abstract:

The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide gas mixtures. The described method of decomposition of hydrogen sulfide to produce hydrogen and sulfur comprising contacting sulfurous gas through the layer of solid material capable of decomposing hydrogen sulfide with hydrogen gas and the formation of sulfur-containing compounds on the surface of the material at this stage of the decomposition is carried out in hemosorption-catalytic mode at a temperature below the melting point of sulfur to produce hydrogen and surface chemisorbing sulfur-containing compounds. The reactivation is carried out at a temperature below the melting point of sulfur, and the regeneration is carried out at a temperature above the melting point of sulfur. The technical result - the process of decomposition of hydrogen sulfide is carried out at a low temperature such as a room, there is no need for frequent regeneration of the catalyst after each stage chemisorption.

The invention apply is taken for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide gas mixtures.

Hydrogen sulfide is the main byproduct of oil refining, and hydrometallurgy, in large quantities (up to 50%) is contained in the gas-condensate deposits of natural gas is the main product of decomposition of many mineral and organic substances. Simultaneously, the hydrogen sulfide is a strong toxic poison, causing poisoning of living organisms. Therefore, the exhaust gases of industrial plants must be thoroughly cleaned from hydrogen sulfide. At the same time, the hydrogen sulfide can be the feedstock for production of valuable chemical product hydrogen.

Direct thermal decomposition of hydrogen sulfide into hydrogen and sulfur by reaction

H2SH2+S-Q (1)

is a highly endothermic process and can be very noticeable speed to occur only at high temperatures.

The known method of thermal decomposition of hydrogen sulfide into hydrogen and sulfur, including the transmission of sulfurous gas through the reaction zone at a temperature 850-1600°C, where the decomposition of hydrogen sulfide (H2S to hydrogen and sulfur, and the subsequent cooling of the specified gas to temperautre: high temperature, required to achieve a high degree of decomposition of hydrogen sulfide; high energy consumption on the implementation of the reaction and the possible compensation of heat losses; the possibility of reducing the degree of decomposition of hydrogen sulfide due to the reverse reaction between hydrogen and sulfur cooling gas; the impossibility of application of the method for processing of gases containing hydrocarbons and other impurities, which can be subjected to pyrolysis at high temperature; low efficiency of the process by reducing the concentration of hydrogen sulfide in the hydrogen sulfide-containing source gas; the need to use special expensive structural materials with high temperature resistance for the design of high-temperature reaction zone. Besides, the decomposition reaction of hydrogen sulfide at high temperature leads to the formation of gaseous sulfur consisting of saturated molecules S2. The latter circumstance adversely affect thermodynamics of the whole process, because it is known that obtaining less energy efficient products in the condensed liquid or solid state conducive to shift the equilibrium of the reaction towards formation of reaction products.

One of the known methods demonstrates how the catalytic decomposition of hydrogen sulfide into hydrogen and sulfur, including circulation sulfurous gas through the catalyst bed at a temperature of 450-800°With removal of the formed sulfur from the circulating gas (US 3962409, 01 17/04, 08.06.76). The advantage of this method is the relatively low temperature of the implementation of the decomposition reaction of hydrogen sulfide. The disadvantage of this method is the low equilibrium degree of decomposition of hydrogen sulfide in the specified temperature range (no more than 15%).

The closest is a method of decomposition of hydrogen sulfide into hydrogen and sulfur, including periodic transmission of sulfurous gas through the bed of sorbent, containing sulfides of iron, cobalt or Nickel, at a temperature 258-536°C, which alternated with periodic heating the sorbent to a temperature of about 700°C for regeneration (US 2979384, 423/573, 01.04.61). During the transmission of sulfurous gas specified components of the sorbent interact with the hydrogen sulfide with the formation of gaseous hydrogen and solid polysulfides of these metals. During regeneration of the sorbent is thermal decomposition of these policy which raised the possibility of achieving a high degree of decomposition of hydrogen sulfide.

The disadvantage of this method is the relatively high temperature decomposition of hydrogen sulfide, a further reduction which is limited by low flow velocity, these chemical reactions at low temperature and high temperature regeneration of the sorbent.

The invention solves the problem of optimization of the process by reducing the temperature of decomposition of hydrogen sulfide and reducing the temperature of the regeneration of the sorbent.

The problem is solved by the method of decomposition of hydrogen sulfide to produce hydrogen and sulfur, which includes the transmission of sulfurous gas through the layer of solid material capable of decomposing hydrogen sulfide with hydrogen gas and the formation of sulfur-containing compounds on the surface of the material, periodic regeneration of the material by decomposition of these sulfur-containing compounds and sulphur separation, the stage of decomposition is carried out in hemosorption-catalytic mode at a temperature below the melting point of sulfur to produce hydrogen and surface chemisorbing sulfur-containing compounds, the reactivation is carried out at a temperature below the melting point of sulfur, and the regeneration is carried out at a temperature of Viseu route that can significantly lower the temperature of reaction (1). It is this feature incorporated in this invention. The essence of the developed method consists in the combination of the paired hemosorption-catalytic decomposition of hydrogen sulfide on the catalyst surface at a temperature below the melting point of sulfur, followed by periodic removal of sulfur from the catalyst surface at a temperature above its melting temperature. The developed method allows to reduce the temperature hemosorption-catalytic stage below the melting point of sulfur (110-120°C), and the decrease in temperature favors the increase in the degree of surface coating dissociatively hammarbyhamnen hydrogen sulfide, and, consequently, increases the capacity of the catalyst with respect to adsorbed hydrogen sulphide. In addition, thermodynamic effect is achieved by the sulfur in the condensed state, thus substantially lowering the temperature of the catalyst regeneration (above 110°C, but below 350°C) and condensation of solid sulfur. This allows you to simplify the process and reduce the cost of equipment for implementing the method, significantly reduce the energy costs of implementing the Finance H2S and without the removal of hydrocarbons and other impurities.

The method is as follows.

Hydrogen sulfide-containing gas with an initial temperature below the melting point of sulfur is passed through the layer of the solid catalyst with the ability to dissociatively chemosensitivity hydrogen sulfide in this temperature region. When this is coupled chemisorption of hydrogen sulfide with the formation of gaseous hydrogen and solid sulfur-containing products chemisorption on the surface of the solid catalyst. Leaving a layer of solid catalyst hydrogen-rich gas directed to the selection of product hydrogen or used in any other way. As you fill the chemisorption capacity of the catalyst and the appearance of hydrogen sulfide in the gas phase at the outlet of the layer of the solid catalyst transmittance sulfurous gas through the layer of solid catalyst cease and begin to pass through the layer reactivating gas not containing hydrogen sulfide or its containing at a concentration of not greater than its concentration in the original hydrogen sulfide-containing gas. The temperature of the reactivating gas should be below the melting point of sulfur 110-120° is bogda catalytically active centers. Thus, there is a reactivation of the catalyst. Then again serves the original hydrogen sulfide-containing gas, after filling the surface of the catalyst hammarbyhamnen hydrogen sulfide begin again to skip reactivating gas at a temperature below the melting point of sulfur, thus there is an accumulation of solid sulfur on the catalyst surface. This cycle chemisorption - reactivation of the catalyst is continued repeatedly without changing the chemisorption capacity of the catalyst, with solid sulfur accumulates on the catalyst surface in the amount of 50-100% by weight of the catalyst. After solid sulfur will block the active centers of the catalyst, the temperature of regeneration is increased to a temperature above the melting point of sulfur, liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly behind the layer of catalyst. Thus the regeneration of the catalyst. Cycle processes chemisorption - reactivation - regeneration is carried out repeatedly without changing the chemisorption capacity and the activity of the catalyst. This final product is hydrogen and solid sulfur. To ensure continuity method are parallel to at least the th sulfurous gas, revitalizing and regenerating gas.

One of the options for the implementation of the developed method is a reactivation of the catalyst in a confined space with a circulation of gas through the layer of chemical sorbent - catalyst, or without it. Similarly, the stage of regeneration of the catalyst can also be in a confined space with a circulation of gas through the layer of chemical sorbent - catalyst, or without it.

The main advantage of the proposed method is the possibility of decomposition of hydrogen sulfide at low temperature, for example room temperature and below, with the resulting sulfur accumulates on the catalyst surface, but not by disabling the active component of the catalyst. As the surface coverage of the catalyst solid gray to such a level, when it comes to blocking of the active component of solid sulfur, the catalyst is heated in the atmosphere of the regenerating gas to a temperature above the melting point of sulfur. Liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly behind the catalytic zone. Thus, freed the surface of the catalyst and the regeneration of the active component.

Example 2.

Processing is subjected to a gas containing 5 vol.% of hydrogen sulfide, and nitrogen, oxygen and a mixture of light hydrocarbons. The gas is passed at a temperature of 0°With through the layer of molybdenum disulfide S2. Leaving a layer of the specified material gas contains hydrogen in an amount of 5 vol.%, as well as nitrogen, oxygen and a mixture of light hydrocarbons, hydrogen sulfide is absent. After 40 min after the start of the transmission of sulfurous gas at the outlet of the layer of this material appears sulfide, therefore, the supply of the source gas stop and start to submit your initial sulfide, containing gas at 0°C. Cycles chemisorption - reactivation repeat repeatedly to fill the surface of the molybdenum disulfide solid grey. Then through a layer of specified material serves regenerating gas is nitrogen at a temperature of 175°C, liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly after the catalytic layer and cooled to 0°C. the Regeneration is carried out for 15 min, then through a layer of specified material of molybdenum disulfide S2when 0°resumed the supply of the source gas mixture containing hydrogen sulfide. This cycle hemosorption-catalytic decomposition of hydrogen sulfide - reactivation of the solid catalyst - regeneration of the catalyst with sulfur condensation in the condenser, located directly behind the catalytic zone, perform repeatedly with a 100% conversion of hydrogen sulfide and without loss of quality gas emerging from the layer of solid material.

Example 3.

Processing is subjected to natural gas containing 40% hydrogen sulfide. The gas is passed through the layer hemosorption-catalytic material is a sulfide of cobalt COxSyat a temperature of - 5°C. Exiting sulfide italicizing gas at the outlet of the layer of sulfide catalyst begins to decrease the concentration of hydrogen and appears sulfide, therefore, the transmission source gas stop and isolate the reaction volume by known methods. After that begin to circulate the gas phase through the catalyst bed at a temperature of 45°C. After 40 min reactivation finish and begin again to submit the original hydrogen sulfide containing gas at -5°C. Cycles chemisorption - reactivation repeat repeatedly to fill the surface of the catalyst solid grey. Then through a layer of the specified catalyst serves regenerating gas is nitrogen at a temperature of 190°C, liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly after the catalytic layer and cooled to 0°C. After 10 min after the start of regeneration of the catalyst, the flow of regenerating gas stop and re serves the original hydrogen sulfide containing gas. The process is carried out in periodic mode repeatedly without reducing the 100% conversion of hydrogen sulfide and without reducing the chemisorption capacity of the catalyst.

Example 4.

Processing is subjected to gas consisting of a mixture of synthesis gas (CO+H2) and 0.1% of hydrogen sulfide. The specified gas is passed through a layer of sulfide catalyst composition of CoxMOySz, ohlajdat missing. After 45 min after the start of transmission in the outgoing gas appears sulfide, therefore, the supply of the source gas stop and start feeding reactivating gas is nitrogen at a temperature of 60°C. After 20 min reactivation finish and begin again to submit the original gas mixture at a temperature of -10°C. Cycles chemisorption - reactivation repeat repeatedly to fill the surface of the catalyst solid grey. Then a layer of the specified catalyst is isolated and heated at a temperature of 120°C, liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly after the catalytic layer and cooled to 0°C. After 50 min after the start of regeneration of the catalyst is recycled to the original hydrogen sulfide containing gas. The process is carried out in periodic mode repeatedly without reducing the 100% conversion of hydrogen sulfide and without reducing the chemisorption capacity of the catalyst.

Example 5.

Processing is subjected to gas consisting of a mixture of 90% nitrogen and 10% hydrogen sulfide. The gas is passed through the layer hemosorption-catalytic material is porous Nickel metal, cooled to -20°C. At the outlet of the layer of the specified material processed gas aetsa hydrogen sulfide, therefore, supply of the source gas stop and begin to apply revitalizing the hydrogen gas at a temperature of 60°C. After 20 min reactivation finish and begin again to submit the original gas mixture at a temperature of -20°C. Cycles chemisorption - reactivation repeat repeatedly to fill the surface of the catalyst solid grey. Then through a layer of the specified catalyst serves regenerating gas is nitrogen at a temperature of 300°C, liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly after the catalytic layer and cooled to 0°C. After 50 min after the start of regeneration of the catalyst, the flow of regenerating gas stop and re serves the original hydrogen sulfide containing gas at a temperature of -20°C. the Process is carried out in periodic mode repeatedly without reducing the 100% conversion of hydrogen sulfide and without reducing the chemisorption capacity of the catalyst.

Example 6.

Processing is subjected to gas consisting of a mixture of oxygen and 0.01% hydrogen sulfide. The gas is passed through the layer hemosorption-catalytic material is porous bored Nickel, cooled to 20°C. At the outlet of the layer of the specified material processed gas with who is hydrogen, therefore, supply of the source gas stop and start feeding reactivating gas is nitrogen at a temperature of 60°C. After 20 min reactivation finish and begin again to submit the original gas mixture at a temperature of 20°C. Cycles chemisorption - reactivation repeat repeatedly to fill the surface of the catalyst solid grey. Then through a layer of the specified catalyst serves regenerating gas is nitrogen at a temperature of 140°C, liquid sulfur flows from the catalyst surface and condenses in the condenser, located directly after the catalytic layer and cooled to 0°C. After 20 min after the start of regeneration of the catalyst, the flow of regenerating gas stop and re serves the original hydrogen sulfide containing gas. The process is carried out in periodic mode repeatedly without reducing the 100% conversion of hydrogen sulfide and without reducing the chemisorption capacity of the catalyst.

Thus, as seen from the above examples, the proposed method allows for the decomposition of hydrogen sulfide at low temperature such as a room, there is no need for frequent regeneration of the catalyst after each stage chemisorption.

The method of decomposition of cerovo the Dogo material, capable of decomposing hydrogen sulfide with hydrogen gas and the formation of sulfur-containing compounds on the surface of the material, periodic regeneration of the material by decomposition of these sulfur-containing compounds and sulphur separation, characterized in that the stage of decomposition is carried out in hemosorption-catalytic mode at a temperature below the melting point of sulfur to produce hydrogen and surface chemisorbing sulfur-containing compounds, the reactivation is carried out at a temperature below the melting point of sulfur, and the regeneration is carried out at a temperature above the melting point of sulfur.



 

Same patents:
The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide and/or mercaptans, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide and mercaptans gas mixtures
The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide and/or mercaptans, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide and mercaptans gas mixtures

The invention relates to medicine and can be used in any microbiological laboratories carrying out work with anaerobic microorganisms

The invention relates to a method for preparing CdS photocatalyst for hydrogen production and to a method of obtaining hydrogen from water by photochemical reaction with its application

The invention relates to energy, chemical, petrochemical, automotive, food industry, medicine, agriculture and, in particular, can be used:

- when creating hydrogen generators;

- when generating power plants to heat buildings, industrial objects;

in chemistry in the production of various organic and inorganic compounds;

in ecology to neutralize the harmful impurities in the wastewater;

- in the automotive industry for the production of hydrogen generators, replacement of hydrocarbon fuel;

in the oil and gas industry for the regeneration of spent oil wells to increase production of oil and gas;

in the pharmaceutical industry for the production of pharmaceuticals;

in the field of medicine to create a wide range of medical devices;

in the field of medicine to create new methods of rapid treatment of patients;

- in the food industry for the production of activated water and a variety of beverages;

in the food industry in the production of beer, wine, vodka and other alcoholic beverages;

The invention relates to processes of reforming of natural gas for ammonia production

The invention relates to power equipment and can be used to produce hydrogen as in stationary and transport
The invention relates to the field of gas and oil, and in particular to methods of decomposition and recycling of hydrogen sulfide and/or mercaptans, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide and mercaptans gas mixtures

The invention relates to a method of catalytic reduction of sulfur dioxide from a gas mixture containing at least 10 vol.% water, whereby the gas mixture is passed over the surface resistant to sulfur hydrogenation catalyst in sulfide form with a bulk velocity component at least 2000 h-1in the presence of a reducing component, preferably at least partially consisting of hydrogen, with the molar ratio of the reducing component and sulfur dioxide, comprising more than 10 and up to 100 at a temperature of from 125 to 300With, the gas mixture is passed after the specified recovery through dry oxidizing layer for oxidation of sulfur compounds, more specifically hydrogen sulfide, to produce elementary sulfur

The invention relates to the field of chemical technology and can be used for purification of exhaust gases from sulfur compounds, carbon monoxide and organic compounds in the gas, oil refining, chemical and other industries

The invention relates to a process for recovering sulfur from a gas containing hydrogen sulfide, which includes: i) oxidation of part of the hydrogen sulfide in the gas stream of oxygen or oxygen-containing gas phase oxidation to sulfur dioxide; (ii) the interaction of the gas obtained at the stage of oxidation of at least two catalytic stages, in accordance with the Claus reaction; (iii) catalytic reduction of SO2in Gaza, leaving the latter at least two catalytic stages, and catalytic reduction takes place in the catalyst bed, located after the last catalytic stage of the Claus process

The invention relates to the production of elemental sulfur from gases of non-ferrous metallurgy, containing mainly nitrogen and sulfur dioxide, and can be used at the enterprises of chemical, petrochemical, gas processing and metallurgical industry

The invention relates to the field of chemistry, and in particular to methods of decomposition of hydrogen sulfide, and can be used for the production of hydrogen and sulfur from hydrogen sulfide, and also for purification from hydrogen sulfide industrial gas emissions
The invention relates to chemical technology, in particular the acidic hydrogen sulfide gas coking, and can be used in coke, oil and gas industry, ferrous and nonferrous metallurgy

The invention relates to a device for producing sulfur from gases containing sulfur dioxide or hydrogen sulfide, and can be used for gas processing nonferrous metallurgy, oil and gas industries, and also in the construction of gas-phase reactors in the chemical industry

The invention relates to the oil and gas industry and can be used, in particular for gas purification from hydrogen sulfide by liquid media followed by obtaining sulfur method Claus
The invention relates to the utilization of sulfur dioxide and can be used in metallurgical and chemical industries for the processing of gases containing sulfur dioxide to 1%

FIELD: gas and petroleum processing.

SUBSTANCE: invention relates to methods for decomposing and utilizing hydrogen sulfide and/or mercaptans, which methods can be used for production of hydrogen and sulfur from hydrogen sulfide as well as for purification of gas mixtures polluted by hydrogen sulfide and/or mercaptans. Method comprises passing hydrogen sulfide and/or mercaptan-containing gas at temperature below 200°C through solid catalyst bed placed in liquid capable of dissolving reaction intermediates and/or sulfur arising on catalyst surface to release hydrogen and/or hydrocarbons.

EFFECT: lowered reaction temperature and eliminated need of frequent solid catalyst regeneration.

7 ex

Up!