The method of producing hydrogen and sulfur from hydrogen sulfide

 

(57) Abstract:

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 method of producing hydrogen and sulfur from hydrogen sulfide includes the transmission source sulfurous gas through the layer of solid material capable of adsorbing the hydrogen sulfide with hydrogen gas and formation of solid sulfur-containing compounds on the surface of the material, periodic regeneration layer by decomposition of these sulfur-containing compounds and vapor emissions of elemental sulfur. The transmission source sulfurous gas through the layer of solid material capable of activating hydrogen, is carried out at a temperature below 200oAnd the regeneration of the particulate material is produced by passing a regenerating gas containing no hydrogen sulfide or its containing at a concentration lower than in the original hydrogen sulfide-containing gas. In addition, the transmission of the regenerating gas is performed with the temperature not exceeding 350oC. the Invention allows p is SS="ptx2">

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 gas emissions.

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 850-1600oWith, where the decomposition of H2S to hydrogen and sulfur, and the subsequent cooling of the specified gas to a temperature of 110-150oFor condensation of the formed sulfur (U.S. patent 4302434, CL 01 In 17/04, etc. from 11.04.80, publ. 24.11.81).

The disadvantages of this method are the 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 while reducing apostasy structural materials with high temperature resistance for the design of high-temperature reaction zone.

Lowering the temperature required for decomposition of hydrogen sulfide, possibly due to the use of catalysts. The known method for the catalytic decomposition of hydrogen sulfide into hydrogen and sulfur, including the transmission of sulfurous gas through the catalyst bed at a temperature of 450-800o(U.S. patent 3962409, class C 01 B 17/04, etc. 24.10.74, publ. 8.06.76). 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%).

There 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 258-536oWith that alternated with periodic heating the sorbent to a temperature of about 700oWith his regeneration (U.S. patent 2979384, CL 423/573, etc. from 23.12.58, publ. 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. adnych sulfides and elemental sulfur vapor. The advantage of this method is 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 authors sought to develop a method of decomposition of hydrogen sulfide into hydrogen and sulfur, providing a high degree of decomposition of hydrogen sulfide (up to 100%) at low temperatures (not higher than 250oC) reduction of energy costs for the method, the rejection of the use of special heat-resistant materials for the manufacture of equipment, the opportunity to engage in the processing of hydrogen sulfide-containing gases of complex composition without prior purification and concentration of hydrogen sulfide.

The problem is solved in that in the method of producing hydrogen and sulfur from hydrogen sulfide, which includes the transmission source sulfurous gas through the layer of solid material capable of adsorbing the hydrogen sulfide with hydrogen evolution and obrazovaniya these sulfur-containing compounds and vapor emissions of sulfur, the transmission source sulfurous gas through the layer of solid material is carried out at a temperature below 200oWith, as specified solid material select the material having the ability to activate the hydrogen sulfide at a temperature below 200oAnd regeneration is produced by passing a regenerating gas containing no hydrogen sulfide or its containing at a concentration lower than in the original hydrogen sulfide-containing gas with a temperature not exceeding 350oC.

The technical effect of the proposed method is to achieve a high degree of decomposition of H2S, with a considerable reduction of the temperature of the implementation of the decomposition reaction of hydrogen sulfide (below 200oInstead 258-536oC), which allows to simplify and reduce the cost of equipment for implementing the method, significantly reduce energy costs for its implementation (1.5-2.5 times), and also enables processing of hydrogen sulfide-containing gases without prior concentration of H2S, the removal of hydrocarbons and other impurities.

The method is as follows.

Hydrogen sulfide-containing gas with an initial temperature below 200oWith miss camposanto to activate the hydrogen sulfide in this temperature region. When this happens, the adsorption of hydrogen sulfide with the formation of gaseous hydrogen and solid sulfur-containing products of adsorption on the solid surface. Leaving a layer of solid hydrogen-rich gas directed to the selection of product hydrogen or used in any other way. As the appearance of hydrogen sulfide in the gas at the outlet of the layer of solid material passing sulfurous gas through the layer of solid material stop and pass through the layer regenerating gas not containing hydrogen sulfide, or containing, in a concentration not exceeding its concentration in the original hydrogen sulfide-containing gas, with a temperature that provides a vapor of elemental sulfur from the specified layer, but not higher than 350oC. When the decomposition of sulfur-containing products of adsorption from the vapor of elemental sulfur. Leaving a layer of solid material regenerating gas is cooled to the required temperature for condensation of sulfur vapor. As the termination of allocation of sulfur vapor from the layer of solid material, again passed through the layer of solid material source hydrogen sulfide-containing gas with a temperature below 200oWith and so on. m of which are alternately interleaved modes of transmission source sulfurous gas and regenerating gas.

The main advantage of the proposed method is the possibility of adsorption of hydrogen sulfide with hydrogen gas at a low temperature (e.g. room temperature), which in turn allows to convert hydrogen sulfide-containing gas without pre-heating, providing lower energy costs for the implementation of the method and minimizing the use of expensive and bulky heat-exchange equipment. In addition, in this case, the processing involved only the hydrogen sulfide, and exclude the unwanted side effects of other components and impurities sulfurous gas (hydrocarbons, organic compounds etc) that allows to process source gases with low concentrations of hydrogen sulfide and complex composition without pre-concentration and purification of hydrogen sulfide. This separation in time stages of adsorption of hydrogen sulfide with hydrogen evolution and regeneration of solid material emitting sulfur allows you to shift the equilibrium of the decomposition reaction of hydrogen sulfide in the direction of formation of hydrogen and sulfur and to achieve the degree of conversion of hydrogen sulfide substantially higher than theoretical equilibrium level for the implementation of the reaction in the one with the volumetric heating layer, in the result, the temperature of regeneration is significantly reduced in comparison with the prototype. It also helps reduce energy consumption and minimize heat transfer equipment. In addition, the implementation of the method given the generally low temperatures allows the use to create an installation of conventional structural materials instead of special heat-resistant steels, which significantly reduces its cost. An additional advantage of the method at low temperatures is the formation of sulfur in the form of molecules of S6and S8instead of S2(typical for high temperatures), which significantly improves the heat balance of the decomposition reaction of hydrogen sulfide and contributes to a further reduction of energy consumption, the total reduction in comparison with the prototype can be 1.5-2.5 times.

Example 1.

Processed gas containing 3% vol. of hydrogen sulfide, and nitrogen, carbon dioxide, methane and water vapor. The specified gas is passed at a temperature of 25oWith through a layer of granular graphite-like carbon material constituting the three-dimensional carbon matrix with the pore volume of 0.2-1.7 cm3/g formed tape St, x-ray density 2,112-2,236 g/cm3and porous structure with a pore distribution with a maximum in the range 200-2000 (U.S. patent 4978649, CL From 01 To 31/10, etc. from 19.04.89, publ. 18.12.90), while leaving a layer of the specified material gas contains hydrogen at a concentration of up to 3%, as well as nitrogen, carbon dioxide, methane and water vapor. 15 minutes after the start of transmission of sulfurous gas when leaving a layer of the specified material gas begins to decrease the concentration of hydrogen, and unreacted hydrogen sulfide, cease transmission of sulfurous gas and start passing a regenerating gas containing nitrogen, methane and carbon dioxide with a temperature of 150oC. Leaving the layer of material regenerating gas is cooled for condensation of the contained sulfur vapor. Passing a regenerating gas is carried out for 30 minutes, after which it re-produce the transmission of sulfurous gas and so on.

Example 2.

Processed gas containing 5 vol.% of hydrogen sulfide, and nitrogen, oxygen and a mixture of light hydrocarbons. The specified gas is passed at a temperature of 0oWith through a layer of molybdenum disulfide (MoS2released is the number 5 vol.%, as well as nitrogen, oxygen and a mixture of light hydrocarbons, hydrogen sulfide is absent. After 40 minutes after the start of transmission of sulfurous gas at the outlet of the layer of this material appears sulfide, therefore, the supply of the source gas stop and begin to apply regenerating gas CO2at a temperature of 175oC. the Regeneration is carried out for 15 minutes, then through a layer of specified material of molybdenum disulfide (MoS2again the supply of the source gas mixture containing hydrogen sulfide at 0oC. This cycle decomposition of hydrogen sulfide - regeneration of the particulate material is carried out several times without loss of quality gas emerging from the layer of solid material.

Example 3.

Processed gas composition, similar to that specified in example 1. The specified gas is passed at a temperature of 30oWith through a layer of material containing sulfides of transition metals (e.g. Nickel, cobalt or iron), deposited on a porous carrier. The hydrogen sulfide at the output of the layer is not present within 20 minutes, while there has been release of hydrogen. After appearing in the output gases of hydrogen sulfide stop the transmission of sulfurous gas and start p is the second layer of material regenerating gas is cooled for condensation of the contained sulfur vapor. Passing a regenerating gas is carried out for 15 minutes, after which it re-produce the transmission of sulfurous gas and so on.

The method of producing hydrogen and sulfur from hydrogen sulfide, which includes the transmission source sulfurous gas through the layer of solid material capable of adsorbing the hydrogen sulfide with hydrogen gas and formation of solid sulfur-containing compounds on the surface of the material, periodic regeneration layer by decomposition of these sulfur-containing compounds and vapor emissions of sulfur, characterized in that the transmission source sulfurous gas through the layer of solid material is carried out at a temperature below 200oWith, as specified solid material select the material having the ability to activate the hydrogen sulfide at a temperature below 200oAnd regeneration is produced by passing a regenerating gas containing no hydrogen sulfide or its containing at a concentration lower than in the original hydrogen sulfide-containing gas with a temperature no higher than 350oC.

 

Same patents:

The invention relates to a catalytic method implementing the reaction of steam reforming of ethanol in order to obtain a synthesis gas or enriched hydrogen gas mixture, which can be used in various industries, including hydrogen energy, for example, as fuel for fuel cells

The invention relates to the petrochemical industry, in particular to obtain a distillate fractions

The invention relates to methods of producing synthesis gas for ammonia production

The invention relates to a process for the catalytic purification of hydrogen-containing gas mixtures of carbon monoxide and can be used in various fields of chemical industry, for example in the production of ammonia, and hydrogen energy, in particular, as a fuel for fuel cells

The invention relates to chemical technology, namely reactors for processing hydrocarbon gases and can be used in devices for production of synthesis gas for further use in methanol synthesis, Fischer-Tropsch, fuel cells, heating and hot water systems for generating heat

The invention relates to a system and a method for converting hydrocarbon gas in the reformed gas containing hydrogen and carbon monoxide

The invention relates to the technology of complex processing of hydrocarbon fuel gases, such as methane and other natural gases, to obtain a synthesized substances

The invention relates to a method of manufacturing a synthesis gas, intended for use in the synthesis of gasoline, methanol or dimethyl ether

The invention relates to the process of obtaining mixtures of hydrogen and carbon monoxide by catalytic conversion of hydrocarbons in the presence of oxygen-containing gases and/or water vapor
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%

The invention relates to catalysts for sulfur by the Claus process and its preparation

The invention relates to the design of the reactor thermal stage of the Claus process, consisting of a cylindrical chamber and tangentially installed burner which consists of two concentric pipes to enter the sour gas, located in the center of the gas burner, which is additionally equipped with a divider, made in the form of a cone (powellites, hemisphere, etc.,), which provides the intensification of the combustion process by pre-mixing air and gas, and also provides a uniform movement of products of combustion in the reaction chamber

The invention relates to the field of petrochemicals and can be used in the processing of oils with different sulfur content

The invention relates to a method of direct oxidation of sulfur compounds to sulfur using a catalyst based on copper at temperatures below 200C

The invention relates to a method for desulfurization of gas containing H2S

The invention relates to the petrochemical industry, such as the Claus process for sulfur from hydrogen sulfide

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!