The method of purification and dehydration of natural gas and associated petroleum gas with a high content of hydrogen sulfide

 

(57) Abstract:

The invention relates to oil and gas industry, in particular to methods of gas purification from sulfur compounds. Cleaning and drying of natural gas and associated petroleum gas with high hydrogen sulfide content includes obtaining sulfur dioxide by burning sulfur and sulfur-containing compounds in the furnace, its mixing with the solvent, the washing solution or the source gas from the hydrogen sulfide to produce elementary sulfur and water, the removal of the suspension of sulfur and separating the sulfur from the solvent, and returning the solvent and part of the sulfur in the cleaning process and the drying gas by absorbing water from the gas in two stages. First source gas is washed with an aqueous solution of sulphurous, sulphuric acid and sulphur dioxide, is obtained by purification of flue gases formed during the combustion regeneration gases and partly sulphur in the furnace of the boiler, and then do the final cleaning and drying of gas on a solid adsorbent and disposed of heat from the combustion regeneration gases and sulfur. The method improves the depth cleaning and drying gas from hydrogen sulphide and moisture while simplifying the process. 1 Il.

The present invention relates to gazouli.

A known method of cleaning and drying gases from hydrogen sulphide chemical regeneration of the adsorbent, including the absorption of hydrogen sulfide from gases and moisture adsorbent (zeolite) with subsequent regeneration of the sulphur dioxide, which is produced by burning sulfur in the furnace. In the process of chemical regeneration of the adsorbent by the sulfur dioxide absorbed by the adsorbent hydrogen sulfide is reduced to elemental sulfur and water, which make the air stream and separated in the separator [1] . /N.In.Calcev "Fundamentals of adsorption technique", M., "Chemistry", 1976.

The main disadvantage of this method and device is that in the process of chemical regeneration of the adsorbent on its surface is allocated and deposited elemental sulfur, which fills the micropores of the adsorbent, reduces its adsorption capacity and lifetime of solid absorber.

The closest in technical essence and the achieved effect to the developed method is a method of cleaning and dehydration of natural gas and associated petroleum gas, including the production of sulfur dioxide from the combustion of sulphur in the furnace, the mixture of sulfur dioxide with the solvent (glycol), flushing of the source gas this solution for recovering elemental sulfur from cerovski process [2]. /A. P. Klimenko "Liquefied petroleum gases", M, "Nedra", 1974/.

The main disadvantage of the above method and device is that in the process of cleaning and drying cannot be achieved with a high degree of purification and drying gas, and to hammarbya of hydrogen sulfide used a three-component mixture consisting of glycol, water and sulfur dioxide, for regeneration and reuse of which require large energy inputs and complex hardware design. In addition, the use as solvent sulfur dioxide glycol or ethylene glycol leads to the appreciation of the cleaning process and the drying gas because of the large ash with purified gas.

Task - increasing the depth cleaning and drying gas from hydrogen sulphide and moisture while simplifying the process.

The solution of this problem is that the method of purification and dehydration of natural gas and associated petroleum gas with high hydrogen sulphide content, including the production of sulfur dioxide by burning sulfur and sulfur-containing compounds in the furnace, its mixing with the solvent, the washing solution or the source gas from hydrogen sulphide and obtaining elemental sulfur and water, the removal of the suspension of sulfur absorber Isdu gas is carried out in two stages. First, the original pre-cleaned gas from the hydrogen sulfide in the absorber catalytic nozzles by washing with an aqueous solution of sulphurous, sulphuric acid and sulphur dioxide, obtained by burning regeneration gases and flue gas cleaning water in the scrubber with a catalytic nozzles in the second phase, carried out deep cleaning and drying of gas on solid adsorbents such as molecular sieves, which are periodically regenerate and cooled purified and dried gas, and a regeneration gases after the adsorber is directed to the combustion in the furnace.

The analysis of the level of technology has allowed to establish that the applicant is not detected similar, characterized by signs, identical to all the essential features of the claimed invention, therefore, it meets the criterion of "novelty."

The invention is illustrated in the drawing, which presents a schematic diagram of the cleaning unit and the drying of natural gas and associated petroleum gas from hydrogen sulphide. The unit contains a filter 1 for gas purification from mechanical impurities and liquids, mounted in front of the entrance of the gas in the absorber 2, which produce a preliminary treatment of the source gas hydrogen sulfide from the tank 3 to drain vodenicharski sieves. The cleaning unit is also equipped with regenerative heat exchanger 7 for heat regeneration gases, reboiler 8 for heating the gas supplied to the regeneration of the adsorbent, water refrigerator 9 for cooling the gas before it is fed into the separator 10 and separation of condensate water and heavy hydrocarbons.

The regeneration gas after the separator 10 is directed into the furnace of the boiler 11 for combustion. The resulting flue gases by the exhaust fan 12 is served in the scrubber 13, the nozzle of which is irrigated with water from the tank 14 by a pump 15. The resulting weak solution of sulfurous and sulfuric acid is poured into the tank 14 and thence pump 16 serves for irrigation nozzles absorber 2. A water suspension of sulfur is separated in a centrifugal separator 17, the water returns to the tank 14, and sulfur - into the sump 18.

The principle of operation of the cleaning unit and the drying gas is as follows. The source gas with a high content of hydrogen sulfide is first cleaned of solid particles and liquid phase in the filter 1, and then submit it to the absorber 2, the filled rings process, is made from bauxite, which accelerate chemical reaction hammarbya. The nozzle absorber 2 is irrigated with a weak solution of sulphurous and sulphuric acids, which are served by the pump 16 from the tank 14. In Procera and water. The chemical reaction proceeds in the following way: 2H2S + H2SO3= 3H2O + 3S.

Aqueous suspension of sulfur is poured into the tank 3 for preliminary sedimentation separation, and then share sulfur and water in a centrifugal separator 17. The water return to the tank 14, and sulfur - into the sump 18. The degree of purification of the source gas from the hydrogen sulfide in the absorber 2 is 0,65 - 0,95. Final deep cleaning and drying gas is carried out in one of the adsorbers 4, 5 and 6 are filled with the adsorbent, in particular a zeolite NaX. After the adsorber cleared and drained the gas is fed to the next process operation, such as liquefaction. When the adsorber 4 operates in the mode of adsorption of the gas adsorber 5 is in the cooling mode, and the adsorber 6 is in a regeneration mode. On saturation of the zeolite adsorption periodically produce switching adsorbers from one mode to another. For regeneration of the adsorbent used part of the purified gas (8 - 10%), which is initially heated in the regenerative heat exchanger 7, and then reboiler 8 to a temperature of 350oC and purge the adsorbent within a certain time. The regeneration gas with high content of hydrogen sulfide after the adsorber is cooled in rivers is t from the gas separator 10 and the gas is burned in the furnace of the boiler 11 in the air stream. Flue gases containing sulfur dioxide (a product of combustion of hydrogen sulphide: 2H2S + 3O2= 2SO2+ 2H2O), oxides of nitrogen and oxygen is supplied by fan 12 in the scrubber 13, having semi-coke heads, which is irrigated with water from the tank 14 by pump 15. In the result of the interaction of sulfur dioxide and water on the surface of char having catalytic properties, it forms sulphurous acid: SO2+ H2O = H2SO3and also, due to the presence in the flue gas oxygen, it forms sulfuric acid: 2SO2+ O2+ 2H2O = 2H2SO4. In addition, the sulfur dioxide is highly soluble in water (40 volumes of SO2in the same volume of water). The formed sulfur and sulfuric acid are served by the pump 16 to the nozzle of the absorber 2, where the contact of the hydrogen sulfide from the acid and the formation of elemental sulfur. Purification of flue gases from sulfur dioxide can reach 0,99.

An example of performing the method of cleaning and drying of natural gas from hydrogen sulphide and moisture.

The source of natural gas with a flow rate of 2000 m3/h containing 8.6 g/m3of hydrogen sulfide, served in the cleaning unit and the drying gas. In the filter 1 produces separation from gas solids and a liquid phase, and then p is SUP> served in the adsorber 4, filled with zeolite NaX, which produces deep cleaning gas to a residual content of hydrogen sulfide 5-10 mg/m3and it dried to a dew point of minus 60 - 70oC. Cleaned and drained the gas is fed, for example, on liquefaction. After saturation of the zeolite adsorber 4 hydrogen sulphide it is switched to the regeneration mode, and the mode of adsorption is connected adsorber 5. For regeneration of the adsorbent and restore it to its absorptive properties select 100 - 150 m3/h purified gas is cooled by this gas adsorbent of the adsorber 6, then heat the gas in the regenerative heat exchanger 7 to a temperature of 150 - 160oC and the firing reboiler 8 - to a temperature of 350oC and fed into the adsorber 4. The regeneration gas after the adsorber 4 with hydrogen sulfide content of 11,5 17,2 g/m3and temperature 250oC initially cooled in the regenerative heat exchanger 7, and then in water refrigerator 9 to a temperature of 25 - 30oC and separate the condensate water in the separator 10. After the separator 10, the gas is fed into the furnace of the boiler 11, which burn in air flow. In the process of regenerative combustion gases in the boiler furnace is formed of 1500 - 2000 m3/h of flue gases with an average content of sulphur dioxide 2.0 g/m3. Flue gases , astorias and combines with water, it forms sulphurous acid and sulphuric acid, which serves for irrigation nozzles absorber 2 by a pump 16. As a result of interaction of sulfur, sulfuric acid, and an aqueous solution of sulfur dioxide with hydrogen sulfide on the surface of the catalytic nozzles Raschig rings, made of activated bauxite and treated hydrophobic material is formed elemental sulfur, which wash away irrigated with a solution in tank sump 3. Then concentrate sulfur is separated from the liquid in the centrifuge 17 and dried in the sump 18. For maintaining or increasing the content of sulfur dioxide in flue gases and, accordingly, increasing the concentration of the acid fed to the absorber 2, the furnace 11 may be additionally burn a portion of elemental sulfur. This uses the calorific value of hydrogen sulfide and sulfur. The heat received in the boiler 11, can be used for industrial and domestic use.

Reboiler 8 and the boiler 11 may be combined in one unit that will reduce the amount of equipment used.

Thus, the developed technology for purification of natural gas allows deep cleaning from hydrogen sulfide is th environment cleaning products, as the product gas cleaning is used to obtain a cheap reagent used to hammarbya of hydrogen sulfide. Deep cleaning and drying of natural gas from hydrogen sulphide and moisture to the desired condition is only possible adsorption method, but this would adsorbent ten times more than in the proposed method, and, accordingly, a larger gas flow to the regeneration of the adsorbent and heat energy for heating it, and the problem of disposal of the product gas cleaning without damage to the environment would remain very complex, requiring additional equipment and cost.

Comparison of the essential features of the proposed and known solutions gives reason to believe that the proposed solution meets the criteria of "inventive step" and "industrial applicability".

The method of cleaning and drying of natural and associated gases with high hydrogen sulphide content, including the production of sulfur dioxide by burning sulfur and sulfur-containing compounds in the furnace, its mixing with the solvent, the washing solution or the source gas from hydrogen sulphide and obtaining elemental sulfur and water, the removal of the suspension of sulfur absorber and the separation of sulfur from rococco gas produced in two stages, first, the original pre-cleaned gas from the hydrogen sulfide in the absorber catalytic nozzles by washing with a solution of sulphurous, sulphuric acid and sulphur dioxide, obtained by burning regeneration gas, and flue gas cleaning water in the scrubber with a catalytic nozzles in the second phase, carried out deep cleaning and drying gas adsorbents, molecular sieves, which are periodically regenerate and cooled purified and dried gas, and a regeneration gases after the adsorber is directed to the combustion in the furnace.

 

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