System and method for hydrogen sulfide removal and co-production of sulfur with activated coke containing calcium oxide

Abstract

The application discloses a system and method for removing hydrogen sulfide and co-producing sulfur with active coke containing calcium oxide, and the system comprises a coke oven, a high-temperature separator, a heat exchanger and a Claus reactor, wherein the coke oven is provided with a material inlet, a reducing gas inlet and a product outlet; the high-temperature separator is provided with a product inlet, a product gas outlet and a solid outlet, and the product inlet is communicated with the product outlet; the heat exchanger is communicated with the product gas outlet at the heat release side inlet of the heat release channel; and the Claus reactor is provided with a product gas inlet, an H2S gas inlet, a tail gas outlet and a sulfur outlet, and the product gas inlet is communicated with the heat release side outlet. According to the system and method, the gypsum and the coal powder are uniformly mixed, and then are sent into the coke oven to be reduced and coked in the H2S gas atmosphere, so that the active coke containing calcium oxide is efficiently prepared; the sulfur dioxide gas generated in the coking process is reacted with the hydrogen sulfide in the Claus reactor to generate the sulfur, and the industrial solid waste gypsum and the H2S tail gas are recycled.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of activated coke preparation, in particular, the present application relates to a system and method for removing hydrogen sulfide and co-producing sulfur from activated coke containing calcium oxide. BACKGROUND

[0002] Activated coke, as a cheap and easy-to-produce, reusable adsorbent material, is widely used in pollutant treatment, air purification, water treatment, etc. However, fresh activated coke has poor adsorption and catalytic oxidation capacity for hydrogen sulfide, and usually needs to be modified by alkali metal oxide. At present, the commonly used modification method in industry is calcium oxide modification, which uses calcium carbonate to load calcium oxide on activated coke. It mainly impregnates activated coke with calcium carbonate solution and calcines to produce activated coke containing calcium oxide. Carbon dioxide pollution gas is generated in the production process.

[0003] The production of industrial by-product gypsum in China is about 118 million tons, and the comprehensive utilization rate is only 38%. Among them, about 43 million tons of desulfurization gypsum, the comprehensive utilization rate is about 56%; about 50 million tons of phosphogypsum, the comprehensive utilization rate is about 20%; about 25 million tons of other by-product gypsum, the comprehensive utilization rate is about 40%. The cumulative stockpile of industrial by-product gypsum has exceeded 300 million tons, of which more than 50 million tons of desulfurization gypsum and more than 200 million tons of phosphogypsum. The large stockpiling of industrial by-product gypsum not only occupies land, but also wastes resources. The acid and other harmful substances contained therein are easy to pollute the surrounding environment, which has become an important factor restricting the sustainable development of coal-fired unit flue gas desulfurization and phosphate fertilizer enterprises in China.

[0004] Hydrogen sulfide (H2S) is a toxic and foul-smelling acid gas, which not only causes corrosion of metals and other materials, but also easily leads to catalyst poisoning and deactivation in chemical production. H2S also harms human health and causes environmental pollution. With the increase of high-sulfur crude oil processing capacity in China, the amount of H2S-containing acid tail gas produced in oil refining and hydrogenation refining units is increasing year by year. Since the concentration of H2S in most acid tail gas is low, there is no good treatment method at present. Therefore, harmless treatment technology for large amounts of H2S gas generated in the fields of petroleum, natural gas, coal and mineral processing industries has become a hot spot of attention.

[0005] Therefore, it is of great significance to efficiently and low-cost prepare activated coke containing calcium oxide and to resourcefully utilize industrial by-product gypsum and H2S-containing industrial tail gas. SUMMARY

[0006] The present application is based on the discovery and realization of the inventors of the following facts and problems: The modification method commonly used in industry is calcium oxide modification, which mainly impregnates active coke with calcium carbonate solution, calcines at high temperature to produce active coke containing calcium oxide, and produces a large amount of carbon dioxide gas. The industrial by-product gypsum is stored in large quantities, which not only occupies land but also wastes resources, and the contained acid and other harmful substances are easy to pollute the surrounding environment. A large amount of H2S gas is generated in the fields of petroleum, natural gas, coal and mineral processing industries, which needs harmless treatment technology.

[0007] The present application aims to at least solve one of the technical problems in the related art. To this end, embodiments of the present application propose a system and method for removing hydrogen sulfide and co-producing sulfur from active coke containing calcium oxide, which uniformly mixes gypsum and coal powder, and then sends them into a coke oven for reduction and coke making in an H2S gas atmosphere, realizes efficient preparation of active coke containing calcium oxide, and realizes resource utilization of industrial solid waste gypsum and H2S tail gas by reacting sulfur dioxide gas generated during coke making with hydrogen sulfide in a Claus reactor to generate sulfur.

[0008] The system for removing hydrogen sulfide and co-producing sulfur from active coke containing calcium oxide according to an embodiment of the present application comprises:

[0009] A coke oven, which is provided with a material inlet, a reducing gas inlet and a product outlet, the material inlet is used to send in coal powder and gypsum, and the reducing gas inlet is used to introduce H2S and / or CO;

[0010] A high-temperature separator for gas-solid separation of the mixed product after reaction in the coke oven, the high-temperature separator is provided with a product inlet, a product gas outlet and a solid outlet, and the product inlet is in communication with the product outlet;

[0011] A heat exchanger, which has a heat release channel and a heat absorption channel, the heat release channel is provided with a heat release side inlet and a heat release side outlet, the heat release side inlet is in communication with the product gas outlet, and the heat absorption channel is provided with a heat absorption side inlet and a heat absorption side outlet;

[0012] A Claus reactor, which is provided with a product gas inlet, an H2S gas inlet, a tail gas outlet and a sulfur outlet, and the product gas inlet is in communication with the heat release side outlet.

[0013] The system for removing hydrogen sulfide and co-producing sulfur containing calcium oxide active coke according to the embodiment of the present application has the following advantages and technical effects: the coal powder and the gypsum are sent into a coke making furnace to react with the reducing gas H2S and / or CO, so that the active coke containing calcium oxide can be obtained, and the industrial solid waste gypsum and the hydrogen sulfide tail gas can be treated. The mixed product generated is subjected to gas-solid separation by a high-temperature separator to obtain the active coke containing calcium oxide and the gas containing SO2. The gas containing SO2 needs to be cooled by a heat exchanger due to the high temperature, and then is introduced into a Claus reactor to react with the external H2S gas to produce sulfur.

[0014] In the embodiment of the present application, the calcium sulfate is used as the raw material, the calcium sulfide is reduced by the coal powder to prepare the active coke containing calcium oxide, and no carbon dioxide is discharged in the preparation process. Meanwhile, the sulfur dioxide generated in the decomposition process of the calcium sulfate reacts with the industrial tail gas containing H2S to co-produce sulfur, so that the resource utilization of the hydrogen sulfide is realized. The calcium oxide is a low-carbon product, and the calcium oxide is added into the active coke to strengthen the activation process and improve the performance of the active coke in the preparation process.

[0015] In some embodiments, a desulfurization tower is further included, which has an active coke inlet, a tail gas inlet and a desulfurized active coke outlet, the active coke inlet is in communication with the solid outlet, the tail gas inlet is in communication with the tail gas outlet, and the desulfurized active coke outlet is in communication with the heat absorption side inlet.

[0016] In some embodiments, a sulfur storage tank is further included, which is provided with a sulfur inlet, and the sulfur inlet is in communication with the sulfur outlet.

[0017] And / or, an active coke storage bin is further included, which is provided with a solid inlet, and the solid inlet is in communication with the solid outlet.

[0018] In some embodiments, a coal powder storage bin, a gypsum storage bin and a stirrer are further included, the coal powder storage bin and the gypsum storage bin are respectively in communication with the stirrer through a feeder, and the stirrer is in communication with the material inlet of the coke making furnace through a feeder.

[0019] The method for removing hydrogen sulfide and co-producing sulfur containing calcium oxide active coke according to the embodiment of the present application adopts the system according to the embodiment of the present application, and includes the following steps:

[0020] (1) mixing the coal powder and the gypsum to obtain a mixture, and reducing and coke making the mixture and the H2S gas in a coke making furnace to obtain a mixed product;

[0021] (2) subjecting the mixed product to gas-solid separation, so that the solid obtained by the separation is the active coke containing calcium oxide, and the gas obtained by the separation is the gas containing SO2;

[0022] (3) the SO2-containing gas and H2S gas are subjected to a Claus reaction in a Claus reactor to produce sulfur.

[0023] The method for producing active coke containing calcium oxide and co-producing sulfur by removing hydrogen sulfide according to the embodiment of the present application has the advantages and technical effects that: after the gypsum and the coal powder are uniformly mixed, they are sent into a coke oven to perform reduction and coke-making reactions in an H2S gas atmosphere to produce active coke containing calcium oxide, and the pyrogenic sulfur dioxide gas reacts with the hydrogen sulfide in a Claus reactor to produce sulfur.

[0024] In the embodiment of the present application, the use of hydrogen sulfide gas for reduction can reduce the decomposition temperature of calcium sulfate. With calcium sulfate as the raw material, the carbon in the coal has a reducing property, and the calcium sulfide is reduced by the coal powder to produce active coke containing calcium oxide, and sulfur dioxide is simultaneously generated, and no carbon dioxide is discharged during the production process. In the embodiment of the present application, the reduction of the gypsum is realized to obtain calcium oxide, the coal powder is pyrolyzed and activated, and the calcium oxide is added into the active coke, and the calcium oxide strengthens the pore-forming process during the production of the active coke to form active coke with a rich pore structure, thereby improving the performance of the active coke. The active coke containing calcium oxide has physical and chemical adsorption properties and can be used for treating multi-source pollution gas.

[0025] In the embodiment of the present application, compared with other sulfur recovery processes, the process adopts the Claus sulfur recovery process, and the system has high stability. The high-concentration H2S gas entering the Claus reactor directly reacts with the SO2 gas generated by the coke oven, and the first stage of the Claus process can be omitted, that is, the process of producing sulfur dioxide by reacting hydrogen sulfide with oxygen is omitted, thereby improving the efficiency of the reaction. In the embodiment of the present application, the difficult-to-treat industrial by-product gypsum and the H2S-containing industrial tail gas are synergistically utilized to produce high-value sulfur, which provides a sustainable and pollution-free treatment method for the currently difficult-to-treat industrial by-product gypsum and low-concentration H2S tail gas, realizes the resource utilization of the industrial solid waste gypsum and H2S tail gas, and can treat H2S tail gas of any concentration.

[0026] In some embodiments, in the step (1), the coal powder and the gypsum are ground respectively before being mixed; preferably, the coal powder and the gypsum are ground to 200 mesh or less respectively;

[0027] And / or, the coal powder comprises at least one of lignite, bituminous coal, and anthracite;

[0028] And / or, the gypsum comprises at least one of desulfurization gypsum, phosphogypsum, and fluorogypsum.

[0029] In some embodiments, in the step (1), the temperature of the reduction and coke-making reaction is 800-1200℃;

[0030] And / or, the time of the reduction and coke-making reaction is 1-3h.

[0031] In some embodiments, in step (1), the H2S gas is replaced by a mixed gas of H2S and CO.

[0032] In some embodiments, in step (1), the mass ratio of the coal powder to the gypsum is 10-100:1.

[0033] In some embodiments, in step (1), the molar ratio of the H2S gas to the gypsum is 2:1.

[0034] In some embodiments, in step (3), the temperature of the Claus reaction is lower than 425℃.

[0035] In some embodiments, in step (3), the molar ratio of SO2 to H2S in the gas containing SO2 is 1:2.

[0036] And / or, the Claus reaction is catalyzed by a catalyst, preferably, the catalyst is vanadium pentoxide.

[0037] In some embodiments, in step (2), the separated gas containing SO2 is cooled by a heat exchanger; the temperature of the separated gas containing SO2 is 800-1200℃, and the temperature after cooling is 300-425℃.

[0038] And / or, in step (3), tail gas is produced after the Claus reaction, and the tail gas is desulfurized by the desulfurization active coke containing calcium oxide obtained in step (2) to obtain desulfurization active coke.

[0039] And / or, in step (3), the desulfurization active coke is regenerated by heating with a heat exchanger. BRIEF DESCRIPTION OF DRAWINGS

[0040] Figure 1 It is a schematic diagram of a method for removing hydrogen sulfide and co-producing sulfur by using active coke containing calcium oxide.

[0041] REFERENCE NUMERALS:

[0042] Coal powder storage 1; gypsum storage 2; stirrer 3; coke oven 4; high-temperature separator 5; heat exchanger 6; Claus reactor 7; desulfurization tower 8; active coke storage 9; sulfur storage tank 10. DETAILED DESCRIPTION

[0043] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to explain the present application, and cannot be understood as a limitation of the present application.

[0044] As Figure 1As shown, the system for removing hydrogen sulfide and co-producing sulfur with active coke containing calcium oxide according to the embodiment of the application comprises:

[0045] A coke oven 4 is provided with a material inlet for feeding in coal powder and gypsum, a reducing gas inlet for feeding in H2S and / or CO, and a product outlet.

[0046] A high-temperature separator 5 is used for separating the mixed products after reaction in the coke oven 4, and is provided with a product inlet in communication with the product outlet, a product gas outlet, and a solid outlet.

[0047] A heat exchanger 6 is provided with an exothermic channel having an exothermic side inlet in communication with the product gas outlet and an exothermic side outlet, and an endothermic channel having an endothermic side inlet and an endothermic side outlet.

[0048] A Claus reactor 7 is provided with a product gas inlet in communication with the exothermic side outlet, an H2S gas inlet, a tail gas outlet, and a sulfur outlet.

[0049] In the system for removing hydrogen sulfide and co-producing sulfur with active coke containing calcium oxide according to the embodiment of the application, the coal powder and gypsum are fed into the coke oven to react with the reducing gas H2S and / or CO, so that not only the active coke containing calcium oxide can be obtained, but also the industrial solid waste gypsum and hydrogen sulfide tail gas can be treated. The mixed products generated are subjected to gas-solid separation by the high-temperature separator to obtain the active coke containing calcium oxide and the gas containing SO2. The gas containing SO2 has a too high temperature and needs to be cooled by the heat exchanger, and then fed into the Claus reactor to react with the exogenous H2S gas to produce sulfur.

[0050] In the embodiment of the application, the calcium sulfate is used as the raw material, the calcium sulfide is reduced by the coal powder to prepare the active coke containing calcium oxide, and no carbon dioxide is discharged during the preparation process. Meanwhile, the sulfur dioxide is generated during the decomposition of the calcium sulfate and reacts with the industrial tail gas containing H2S to co-produce sulfur, so that the hydrogen sulfide is recycled. The calcium oxide is a low-carbon product, and the calcium oxide is added into the active coke to strengthen the activation process during the preparation process and improve the performance of the active coke.

[0051] In some embodiments, a desulfurization tower 8 is further included, which has an active coke inlet, a tail gas inlet and a desulfurized active coke outlet, the active coke inlet is communicated with the solid outlet, the tail gas inlet is communicated with the tail gas outlet, and the desulfurized active coke outlet is communicated with the endothermic side inlet. In the embodiments of the present application, by arranging the desulfurization tower, the unreacted hydrogen sulfide gas in the Claus reactor can be removed. The active coke passes through the desulfurization tower to obtain desulfurized active coke, and the high-temperature gas separated from the gas-solid separation passes through the heat exchanger to regenerate the desulfurized active coke, so that the active coke is heated to 300-500 DEG C, the adsorbed hydrogen sulfide is desorbed, and the regenerated active coke can be recycled; the desorbed hydrogen sulfide enters the Claus reactor again for reaction.

[0052] In some embodiments, a sulfur storage tank 10 is further included, which is provided with a sulfur inlet, and the sulfur inlet is communicated with the sulfur outlet.

[0053] In some embodiments, an active coke storage bin 9 is further included, which is provided with a solid inlet, and the solid inlet is communicated with the solid outlet. In the embodiments of the present application, the active coke carried by the SO2-containing gas first enters the high-temperature separator for gas-solid separation, and part of the separated solid active coke is stored in the active coke storage bin, and the other part is used for desulfurization in the desulfurization tower.

[0054] In some embodiments, the active coke storage bin 9 is further provided with an active coke outlet, and the active coke outlet is communicated with the active coke inlet.

[0055] In some embodiments, a pulverized coal storage bin 1 and a gypsum storage bin 2 are further included, which are respectively communicated with the stirrer 3 through the feeder, and the stirrer 3 is communicated with the material inlet of the coke oven 4 through the feeder.

[0056] In some embodiments, the reducing gas inlet is arranged at the bottom of the coke oven 4.

[0057] In some embodiments, the coke oven 4 includes a burner for heating the coke oven 4.

[0058] The method for removing hydrogen sulfide and co-producing sulfur by using the active coke containing calcium oxide according to the embodiments of the present application adopts the system according to the embodiments of the present application, and includes the following steps:

[0059] (1) mixing the pulverized coal and the gypsum to obtain a mixture, and performing reduction and coking reaction on the mixture and the H2S gas in the coke oven 4 to obtain a mixed product;

[0060] (2) performing gas-solid separation on the mixed product, and separating the solid to obtain the active coke containing calcium oxide, and separating the gas to obtain the SO2-containing gas;

[0061] (3) The SO2-containing gas and the H2S gas are subjected to a Claus reaction in the Claus reactor 7 to produce sulfur.

[0062] The method for producing sulfur by removing hydrogen sulfide with the active coke containing calcium oxide according to the embodiment of the application mixes the gypsum and the coal powder uniformly, and then sends them into a coke oven to perform reduction and coke-making reactions in a H2S gas atmosphere, so as to prepare the active coke containing calcium oxide. The pyrogenic sulfur dioxide gas and the hydrogen sulfide are reacted in a Claus reactor to produce sulfur.

[0063] In the embodiment of the application, the reduction with the hydrogen sulfide gas can reduce the decomposition temperature of calcium sulfate. With calcium sulfate as the raw material, the carbon in the coal has a reducing property. The calcium sulfide is reduced with the coal powder to prepare the active coke containing calcium oxide, and the sulfur dioxide is generated at the same time. No carbon dioxide is discharged in the preparation process. In the embodiment of the application, the reduction of the gypsum is realized to obtain calcium oxide. The coal powder is pyrolyzed and activated. The calcium oxide is added into the active coke. The calcium oxide strengthens the pore-forming process in the preparation process of the active coke, so that the active coke with a rich pore structure is formed, and the performance of the active coke is improved. The prepared active coke containing calcium oxide has physical and chemical adsorption properties, and can be used for treating multi-source pollution gas.

[0064] In the embodiment of the application, compared with other sulfur recovery processes, the process adopts the Claus sulfur recovery process, and the system has high stability. The high-concentration H2S gas entering the Claus reactor and the SO2 gas generated by the coke oven are directly reacted, so that the first stage of the Claus process, i.e., the process of preparing sulfur dioxide by reacting hydrogen sulfide and oxygen, can be omitted, and the efficiency of the reaction is improved. In the embodiment of the application, the industrial by-product gypsum which is difficult to treat and the H2S-containing industrial tail gas are resourceized and synergistically utilized to produce high-value sulfur, which provides a sustainable and pollution-free treatment method for the industrial by-product gypsum which is difficult to treat and the low-concentration H2S tail gas, realizes the resource utilization of the industrial solid waste gypsum and the H2S tail gas, and can treat H2S tail gas with any concentration.

[0065] In the embodiment of the application, the H2S, the coal powder and the gypsum are reacted to generate calcium oxide. Meanwhile, the coal is pyrolyzed and carbonized under a reducing atmosphere to generate the active coke containing calcium oxide and the SO2 gas with a high concentration. The gypsum and the coal are subjected to a reduction reaction as follows:

[0066] 2CaSO4+C→2CaO+2SO2+CO2

[0067] C+CO2→2CO

[0068] CaSO4+CO→CaO+SO2+CO2

[0069] The gypsum and the hydrogen sulfide are subjected to a reaction as follows:

[0070] H2S→H2+S

[0071] CaSO4 + H2→ CaO + H2O + SO2.

[0072] In the embodiment of the present application, the gas containing SO2 contains not only SO2, but also part of H2 and S2. The S2 enters the sulfur storage tank together with the S2 produced by the Claus reaction to recover sulfur, and the obtained sulfur is stored in the sulfur storage tank.

[0073] In some embodiments, in the step (1), the coal powder and the gypsum are ground separately before mixing; preferably, each is ground to 200 mesh or less;

[0074] And / or, the coal powder comprises at least one of lignite, bituminous coal, and anthracite;

[0075] And / or, the gypsum comprises at least one of desulfurization gypsum, phosphogypsum, and fluorogypsum.

[0076] In some embodiments, in the step (1), the temperature of the reduction and coking reaction is 800-1200℃, and specifically, for example, 800℃, 900℃, 1000℃, 1100℃, or 1200℃; and / or, the time of the reduction and coking reaction is 1-3h, and specifically, for example, 1h, 2h, or 3h. In the embodiment of the present application, by optimizing the temperature and time of the reduction and coking reaction, the decomposition reaction of the gypsum and the coking reaction are fully and efficiently carried out. When the reaction temperature is too high, the calcium oxide obtained by the decomposition of the gypsum sinters, the active coke becomes coke, the pore structure collapses, and the adsorption performance decreases; when the reaction temperature is too low, the decomposition reaction of the gypsum and the coking reaction are not conducive to occur. When the reaction time is too long, the yield of the active coke is low; when the reaction time is too short, the decomposition of the gypsum is not complete, and the pore structure of the active coke is not developed.

[0077] In some embodiments, in the step (1), the H2S gas is replaced by a mixed gas of H2S and CO.

[0078] In some embodiments, in the step (1), the mass ratio of the coal powder to the gypsum is 10-100:1, and specifically, for example, 10:1, 30:1, 50:1, 80:1, or 100:1. In the embodiment of the present application, by optimizing the mass ratio of the coal powder to the gypsum, the active coke containing calcium oxide with excellent adsorption performance is obtained. When the proportion of the gypsum is too high, the proportion of calcium oxide in the prepared active coke is high, the content of the active coke as the adsorption main body is low, and the adsorption performance is poor; when the proportion of the gypsum is too low, the pore-forming effect of calcium oxide in the coking process is weak, the pore structure of the active coke is poor, and the active coke with developed pore structure cannot be formed.

[0079] In some embodiments, in the step (1), the molar ratio of the H2S gas to the gypsum is 2:1. By optimizing the ratio of the H2S gas to the gypsum, the preparation of the calcium oxide-containing active coke and the yield of the conversion of the hydrogen sulfide into the sulfur are facilitated in the embodiments of the present application. If the ratio of the H2S gas is too high, the content of the sulfur dioxide required for the Claus reaction in the product gas is reduced, and the yield of the sulfur is decreased. If the ratio of the H2S gas is too low, the content of the generated sulfur dioxide is reduced, and the yield of the sulfur is decreased.

[0080] In some embodiments, in the step (3), the temperature of the Claus reaction is lower than 425℃. By optimizing the temperature of the Claus reaction, the occurrence of the Claus reaction is facilitated in the embodiments of the present application. If the temperature is too high or too low, the rate of the Claus reaction is low.

[0081] In some embodiments, in the step (3), the molar ratio of the SO2 to the H2S in the gas containing the SO2 is 1:2.

[0082] In some embodiments, the Claus reaction is catalyzed by a catalyst, and preferably, the catalyst is vanadium pentoxide.

[0083] In some embodiments, in the step (2), the separated gas containing the SO2 is cooled by the heat exchanger 6; the temperature of the separated gas containing the SO2 is 800-1200℃, and specifically, for example, 800℃, 900℃, 1000℃, 1100℃, 1200℃, and the temperature after the cooling is 300-425℃, and specifically, for example, 300℃, 350℃, 400℃, 425℃.

[0084] In some embodiments, in the step (3), tail gas is generated after the Claus reaction, and the tail gas is desulfurized by the active coke containing the calcium oxide obtained by the gas-solid separation in the step (2) to obtain desulfurized active coke.

[0085] In some embodiments, in the step (3), the desulfurized active coke is regenerated by heating by the heat exchanger 6; the temperature of the regeneration is 300-500℃; the regenerated active coke is recycled; the regeneration desorbs the hydrogen sulfide adsorbed by the desulfurized active coke, and the desorbed hydrogen sulfide enters the Claus reactor for the reaction; the regeneration is performed in a nitrogen atmosphere, and the nitrogen is introduced from the heat absorption side inlet of the heat exchanger 6.

[0086] In the embodiment of the present application, the tail gas generated after the Claus reaction is desulfurized by using active coke containing calcium oxide, which can remove the unreacted hydrogen sulfide in the tail gas. The desulfurization active coke containing calcium oxide is heated by the heat exchanger for regeneration, so that the hydrogen sulfide adsorbed by the active coke is desorbed, the waste heat of the product gas of the coke oven is fully utilized, and the energy utilization efficiency is improved. The gas containing SO2 is cooled to 300-425℃, and then the Claus reaction is carried out in the Claus reactor with H2S gas, which is beneficial to improve the sulfur yield and reduce the emission of hydrogen sulfide-containing tail gas. The desulfurization active coke is regenerated in a nitrogen atmosphere, and the nitrogen can come from a nitrogen generator or a nitrogen cylinder. Nitrogen is an inert gas, which carries the regenerated hydrogen sulfide out as a carrier gas.

[0087] The present application will be described below with reference to specific embodiments, which should be merely illustrative in nature and not limit the present application in any way.

[0088] Embodiment 1

[0089] A method for removing hydrogen sulfide and co-producing sulfur by using active coke containing calcium oxide:

[0090] A system for removing hydrogen sulfide and co-producing sulfur by using active coke containing calcium oxide, comprising: a coke oven 4, a high-temperature separator 5, a heat exchanger 6, a Claus reactor 7,

[0091] The coke oven 4 is provided with a material inlet, a reducing gas inlet and a product outlet, the material inlet is used to send in coal powder and gypsum, and the reducing gas inlet is used to introduce H2S and / or CO; the reducing gas inlet is arranged at the bottom of the coke oven 4;

[0092] The high-temperature separator 5 is used to separate the mixed products after the reaction in the coke oven 4, and the high-temperature separator 5 is provided with a product inlet, a product gas outlet and a solid outlet, and the product inlet is in communication with the product outlet;

[0093] The heat exchanger 6 has a heat release channel and a heat absorption channel, the heat release channel is provided with a heat release side inlet and a heat release side outlet, the heat release side inlet is in communication with the product gas outlet, and the heat absorption channel is provided with a heat absorption side inlet and a heat absorption side outlet;

[0094] The Claus reactor 7 is provided with a product gas inlet, an H2S gas inlet, a tail gas outlet and a sulfur outlet, and the product gas inlet is in communication with the heat release side outlet.

[0095] Further comprising a desulfurization tower 8, the desulfurization tower 8 has an active coke inlet, a tail gas inlet and a desulfurization active coke outlet, the active coke inlet is in communication with the solid outlet, the tail gas inlet is in communication with the tail gas outlet, and the desulfurization active coke outlet is in communication with the heat absorption side inlet.

[0096] Also included is a sulfur storage tank 10, which is provided with a sulfur inlet, which is in communication with the sulfur outlet.

[0097] Also included is an active coke storage bin 9, which is provided with a solid inlet and an active coke outlet, which are in communication with each other.

[0098] Also included are a pulverized coal storage bin 1 and a gypsum storage bin 2, which are in communication with the mixer 3 through a feeder, and the mixer 3 is in communication with the material inlet of the coke oven 4 through a feeder.

[0099] The method comprises the following steps:

[0100] (1) The lignite and desulfurized gypsum are ground to 200 mesh or less, and the feeder sends the lignite and desulfurized gypsum into the mixer 3 at a ratio of 10:1 (total amount of 100 kg), and then the mixture is sent into the coke oven 4 by the feeder, and reacts with hydrogen sulfide at 900°C for 2h to obtain a mixture. The hydrogen sulfide enters the furnace body from the bottom of the coke oven 4. The molar ratio of H2S gas to gypsum is 2:1.

[0101] (2) The mixture is subjected to gas-solid separation, and the separated solid is active coke containing calcium oxide, and the separated gas is a gas containing SO2; the gas containing SO2 is cooled by the heat exchanger 6; the temperature after cooling is 350°C;

[0102] (3) The gas containing SO2 is subjected to a Claus reaction with H2S gas in the Claus reactor 7 to produce sulfur, wherein the molar ratio of SO2 to H2S in the gas containing SO2 is 1:2.

[0103] (4) The tail gas produced in the Claus reactor 7 is introduced into the desulfurization tower 8, and part of the active coke containing calcium oxide obtained by gas-solid separation in step (2) is used for desulfurization to obtain desulfurized active coke; the desulfurized active coke is regenerated by heating in the heat exchanger 6; the regenerated active coke is recycled; the regeneration desorbs the hydrogen sulfide adsorbed by the desulfurized active coke, and the desorbed hydrogen sulfide enters the Claus reactor for reaction.

[0104] Example 2

[0105] A method for removing hydrogen sulfide and co-producing sulfur using active coke containing calcium oxide:

[0106] The system for removing hydrogen sulfide and co-producing sulfur using active coke containing calcium oxide used is exactly the same as in Example 1.

[0107] The method comprises the following steps:

[0108] (1) The anthracite and desulfurization gypsum are ground to 200 mesh or less, and the feeder sends the anthracite and desulfurization gypsum into the stirrer 3 at a ratio of 50:1 (total amount is 100 kg), and then the mixture is sent into the coke oven 4 by the feeder, and reacts with hydrogen sulfide at 1100℃ for 1h to obtain a mixture. The hydrogen sulfide enters the oven body from the bottom of the coke oven 4. The molar ratio of the H2S gas to the gypsum is 2:1.

[0109] (2) The mixture is subjected to gas-solid separation, and the separated solid is active coke containing calcium oxide, and the separated gas is a gas containing SO2; the gas containing SO2 is cooled by the heat exchanger 6; the temperature after cooling is 400℃;

[0110] (3) The gas containing SO2 is subjected to a Claus reaction with H2S gas in the Claus reactor 7 to produce sulfur, wherein the molar ratio of SO2 in the gas containing SO2 to H2S is 1:2.

[0111] (4) The tail gas produced in the Claus reactor 7 is introduced into the desulfurization tower 8, and part of the active coke containing calcium oxide obtained by gas-solid separation in step (2) is used for desulfurization to obtain desulfurization active coke; the desulfurization active coke is regenerated by heating in the heat exchanger 6; the regenerated active coke is recycled; the hydrogen sulfide adsorbed by the desulfurization active coke is desorbed, and the desorbed hydrogen sulfide is introduced into the Claus reactor for reaction.

[0112] Example 3

[0113] A method for removing hydrogen sulfide and co-producing sulfur using active coke containing calcium oxide:

[0114] The system for removing hydrogen sulfide and co-producing sulfur using active coke containing calcium oxide is exactly the same as in Example 1.

[0115] Comprising the following steps:

[0116] (1) The bituminous coal and desulfurization gypsum are ground to 200 mesh or less, and the feeder sends the bituminous coal and desulfurization gypsum into the stirrer 3 at a ratio of 100:1 (total amount is 100 kg), and then the mixture is sent into the coke oven 4 by the feeder, and reacts with a mixed gas of hydrogen sulfide and carbon monoxide at 1000℃ for 3h to obtain a mixture. The hydrogen sulfide enters the oven body from the bottom of the coke oven 4. The molar ratio of the H2S gas to the gypsum is 2:1.

[0117] (2) The mixture is subjected to gas-solid separation, and the separated solid is active coke containing calcium oxide, and the separated gas is a gas containing SO2; the gas containing SO2 is cooled by the heat exchanger 6; the temperature after cooling is 425℃;

[0118] (3) the SO2-containing gas and H2S gas are subjected to a Claus reaction in the Claus reactor 7 to produce sulfur, wherein the molar ratio of SO2 to H2S in the SO2-containing gas is 1:2.

[0119] (4) the tail gas produced in the Claus reactor 7 is introduced into the desulfurization tower 8, and is subjected to desulfurization using part of the active coke containing calcium oxide obtained in the step (2) to obtain desulfurization active coke; the desulfurization active coke is regenerated by heating in the heat exchanger 6; the regenerated active coke is recycled; the regeneration desorbs the hydrogen sulfide adsorbed by the desulfurization active coke, and the desorbed hydrogen sulfide is introduced into the Claus reactor for reaction.

[0120] In the present application, unless otherwise explicitly specified and limited, the terms "mounting", "connection", "linking", "fixing" and the like should be understood in a broad sense, for example, can be fixed connection, can be detachable connection, or can be integrated; can be mechanical connection, or can be electrical connection or communication with each other; can be directly connected, or can be indirectly connected through an intermediate medium; can be the internal communication of two elements or the interaction relationship between two elements, unless otherwise explicitly limited. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0121] In the present application, the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate manner in any one or more embodiments or examples. In addition, the skilled in the art can combine and combine the different embodiments or examples described in the specification and the features of the different embodiments or examples without contradiction.

[0122] Although the above embodiments have been shown and described, it can be understood that the above embodiments are exemplary and cannot be understood as limiting the present application, and the changes, modifications, replacements and variations of the above embodiments made by those skilled in the art are within the protection scope of the present application.

Claims

1. A system for the removal of hydrogen sulfide co-producing sulfur with activated coke containing calcium oxide, characterized in that, The system comprises: a coke oven, which is provided with a material inlet for feeding in coal powder and gypsum, a reducing gas inlet for feeding in H2S or a mixed gas of H2S and CO, and a product outlet; a high-temperature separator for separating the mixed product after reaction in the coke oven, which is provided with a product inlet, a product gas outlet and a solid outlet, and the product inlet is in communication with the product outlet; a heat exchanger, which is provided with an exothermic channel and an endothermic channel, the exothermic channel is provided with an exothermic side inlet and an exothermic side outlet, the exothermic side inlet is in communication with the product gas outlet, and the endothermic channel is provided with an endothermic side inlet and an endothermic side outlet; a Claus reactor, which is provided with a product gas inlet, an H2S gas inlet, a tail gas outlet and a sulfur outlet, and the product gas inlet is in communication with the exothermic side outlet.

2. The calcium oxide-containing active coke system for the removal of hydrogen sulfide coproduced with sulfur according to claim 1, characterized in that, The system further comprises a desulfurization tower, which is provided with an active coke inlet, a tail gas inlet and a desulfurized active coke outlet, the active coke inlet is in communication with the solid outlet, the tail gas inlet is in communication with the tail gas outlet, and the desulfurized active coke outlet is in communication with the endothermic side inlet.

3. The calcium oxide-containing active coke system for the removal of hydrogen sulfide coproduced with sulfur according to claim 1, characterized in that, The system further comprises a sulfur storage tank, which is provided with a sulfur inlet, and the sulfur inlet is in communication with the sulfur outlet. The system further comprises an active coke storage bin, which is provided with a solid inlet, and the solid inlet is in communication with the solid outlet.

4. The calcium oxide-containing active coke system for the removal of hydrogen sulfide coproduced with sulfur according to claim 1, characterized in that, The system further comprises a coal powder storage bin, a gypsum storage bin and a stirrer, the coal powder storage bin and the gypsum storage bin are respectively in communication with the stirrer through a feeder, and the stirrer is in communication with the material inlet of the coke oven through a feeder.

5. A process for the removal of hydrogen sulfide co-producing sulfur from activated coke containing calcium oxide, characterized in that, The system of any one of claims 1-4 comprises the following steps: (1) mixing coal powder and gypsum to obtain a mixture, and carrying out reduction and coking reactions of the mixture and H2S gas in a coke oven to obtain a mixed product; (2) carrying out gas-solid separation of the mixed product, and the separated solid is active coke containing calcium oxide, and the separated gas is a gas containing SO2; (3) carrying out a Claus reaction of the gas containing SO2 and H2S gas in a Claus reactor to produce sulfur.

6. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 5, characterized in that, In step (1), the coal powder and gypsum are ground respectively before mixing; and / or, the coal powder comprises at least one of lignite, bituminous coal and anthracite; and / or, the gypsum comprises at least one of desulfurization gypsum, phosphogypsum and fluorogypsum; and / or, the temperature of the reduction and coking reaction is 800-1200 ℃; and / or, the time of the reduction and coking reaction is 1-3 h; and / or, the H2S gas is replaced by a mixed gas of H2S and CO.

7. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 6, characterized in that, In step (1), the coal powder and gypsum are ground to 200 mesh or less.

8. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 5, characterized in that, In step (1), the mass ratio of the coal powder to the gypsum is 10-100:

1.

9. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 5, characterized in that, In step (1), the molar ratio of the H2S gas to the gypsum is 2:

1.

10. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 5, characterized in that, In step (3), the temperature of the Claus reaction is lower than 425 ℃; and / or, the molar ratio of SO2 to H2S in the gas containing SO2 is 1:

2. And / or, the Claus reaction is carried out under catalysis of a catalyst.

11. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 10, characterized in that, In the step (3), the catalyst is vanadic anhydride.

12. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 5, characterized in that, In the step (2), the separated SO2-containing gas is cooled by a heat exchanger; the temperature of the separated SO2-containing gas is 800-1200 ℃, and the temperature after cooling is 300-425 ℃. And / or, in the step (3), tail gas is generated after the Claus reaction, and the tail gas is desulfurized by the active coke containing calcium oxide obtained by gas-solid separation in the step (2) to obtain desulfurized active coke.

13. The process for co-production of hydrogen sulfide removal and sulfur from activated coke containing calcium oxide according to claim 12, characterized in that, In the step (3), the desulfurized active coke is heated and regenerated by a heat exchanger.

Images