CN108557774B - Device and method for analyzing and reducing sulfur by active coke sulfur dioxide - Google Patents

Device and method for analyzing and reducing sulfur by active coke sulfur dioxide Download PDF

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CN108557774B
CN108557774B CN201810677069.6A CN201810677069A CN108557774B CN 108557774 B CN108557774 B CN 108557774B CN 201810677069 A CN201810677069 A CN 201810677069A CN 108557774 B CN108557774 B CN 108557774B
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sulfur
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reduction
tower
active coke
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CN108557774A (en
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马春元
李军
赵希强
冯太
夏霄
张世珍
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Shandong University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0473Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
    • C01B17/0482Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon or solid carbonaceous materials
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0473Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
    • C01B17/0486Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with carbon monoxide or carbon monoxide containing mixtures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/02Preparation of sulfur; Purification
    • C01B17/04Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • C01B17/0473Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide
    • C01B17/0491Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by reaction of sulfur dioxide or sulfur trioxide containing gases with reducing agents other than hydrogen sulfide with hydrogen or hydrogen-containing mixtures, e.g. synthesis gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00Waste heat recuperation
    • F23G2206/20Waste heat recuperation using the heat in association with another installation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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Abstract

The invention relates to an integrated device and method for analyzing and reducing sulfur by active coke sulfur dioxide, belonging to the field of air pollutant treatment and resource utilization. The device comprises a desorption reduction tower and a cooling tower connected with a gas outlet of the desorption reduction tower, wherein the top of the desorption reduction tower is a material inlet, and the bottom of the desorption reduction tower is a material outlet; the inside of the analytic reduction tower is sequentially provided with a preheating section, an analytic section, a carbothermic reduction section and a cooling section from top to bottom; a gas guiding and homogenizing device is arranged above the preheating section, the analysis section, the carbothermic reduction section and the cooling section; the cooling tower is sequentially provided with a high-temperature separator, a reheater, a condenser and a liquid sulfur collector from top to bottom; the gas outlet of the analytic reduction tower is connected with the top of the high-temperature separator; the exhaust gas outlet of the liquid sulfur collector is sequentially connected with a catalytic reducer and a post-processor; a sulfur storage tank is arranged below a liquid outlet of the liquid sulfur collector; and heat exchange medium pipe boxes are arranged on the outer wall of the analytic reduction tower and correspond to the preheating section, the analytic section, the carbothermic reduction section and the cooling section.

Description

Device and method for analyzing and reducing sulfur by active coke sulfur dioxide
Technical Field
The invention belongs to the field of air pollutant treatment and resource utilization, and particularly relates to an integrated device and method for analyzing, reducing and sulfur by active coke sulfur dioxide.
Background
In view of the severity of the current environmental protection situation, the realization of clean and efficient energy utilization is the main research direction of many researchers. The three currently accepted pollutants are SO respectively 2 Most of the sources of release are from coal-fired power plants and the steel industry, of which the most important is the SO in the flue gas 2 Is provided. At present, limestone-gypsum wet desulfurization technology is mostly adopted in power plants to remove SO in flue gas 2 The technology has the advantages of high desulfurization efficiency, simple process, and the like, but also has the advantages of huge water consumption, and the formation of a large amount of inferior desulfurized gypsum (CaSO) 4 .2H 2 O) is easy to cause secondary environmental pollution and the like. Active coke dry desulfurization technology using coal as raw material, comprisingThe active coke desulfurizing agent can be repeatedly used, has no water consumption, has no secondary pollutant generation and the like, and is widely researched and utilized. Wherein SO is 2 In the complex pore structure of active coke, the active coke exists in the form of sulfuric acid, SO is resolved from the active coke with saturated adsorption 2 And realize SO 2 Is particularly important for clean treatment or resource utilization. In the prior art, activated carbon or activated coke is used for adsorbing SO 2 Then the activated carbon or activated coke is resolved and SO is carried out 2 React with reducing agent and coal to make SO 2 Reduction to sulfur vapour, i.e. the prior art has all been to separate the activated carbon/coke from SO 2 The separation treatment is to synthesize sulfur, and the integrated treatment of analyzing and recovering sulfur is not realized.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an integrated device for analyzing and reducing sulfur by active coke sulfur dioxide.
In order to solve the technical problems, the technical scheme of the invention is as follows:
an integrated device for resolving and reducing sulfur by active coke sulfur dioxide comprises a resolving and reducing tower and a cooling tower connected with a gas outlet of the resolving and reducing tower, wherein the top of the resolving and reducing tower is provided with a material inlet, and the bottom of the resolving and reducing tower is provided with a material outlet; the inside of the analytic reduction tower is sequentially provided with a preheating section, an analytic section, a carbothermic reduction section and a cooling section from top to bottom; the cooling tower consists of a high-temperature separator, a reheater, a condenser and a liquid sulfur collector from top to bottom in sequence; the gas outlet of the resolving section of the resolving reduction tower is connected with the top of the high-temperature separator; the exhaust gas outlet of the liquid sulfur collector is sequentially connected with a catalytic reducer and a post-processor; a sulfur storage tank is arranged below the side of the liquid outlet of the liquid sulfur collector; and heat exchange medium pipe boxes are arranged on the outer wall of the analytic reduction tower and correspond to the preheating section, the analytic section, the carbothermic reduction section and the cooling section.
The analytic reduction tower is divided into a preheating section, an analytic section, a carbothermic reduction section and a cooling section, and heat exchange medium pipe boxes are arranged at positions corresponding to the preheating section, the analytic section, the carbothermic reduction section and the cooling section on the outer wall of the analytic reduction tower; firstResolving and then re-mixing with SO 2 The sulfur vapor is generated by the reaction, and finally, the residual active coke is cooled and recovered, SO that SO is adsorbed by a sectional heating mode 2 Is characterized by that it utilizes the separation of active coke and the integrated treatment of recovering sulfur, and separately sets reaction equipment to make SO 2 Compared with reduction, the treatment mode of the method is simpler and more effective, and the efficient removal and recycling of pollutants are realized.
Preferably, a gas guiding and homogenizing device is arranged above the preheating section, the analysis section, the carbothermic reduction section and the cooling section; the inlet of the analytic reduction tower is provided with a diversion cone.
Further preferably, the gas guiding and homogenizing device is formed by combining a supporting plate, a conveying funnel, a porous mesh plate and an exhaust pipe; the material conveying funnel penetrates through the porous mesh plate, the opening part of the material conveying funnel is positioned above the porous mesh plate, the closing part of the material conveying funnel is positioned at the lower side of the porous mesh plate, and the supporting plate is used for fixing the material conveying funnel and bearing the weight of part of materials; and a gas space is formed above the porous reticular plate, below the supporting plate and between the adjacent delivery funnels.
The material conveying hopper is used for collecting and distributing materials, the porous net plate is used for inertial separation of powdery adsorption materials, and the cleanliness of collected gas is improved; the lower material pipe of the material conveying funnel is positioned below the material layer and is used for preventing the precipitated gas from reversely flowing to form a gas plug, and a gas space is formed between adjacent material conveying funnels and is connected with the exhaust pipe so as to discharge the precipitated gas.
Preferably, a pipeline for connecting the catalytic reducer with the postprocessor is provided with a spent gas pipeline, and the spent gas pipeline is sequentially connected with a spent gas inlet pipeline and a spent gas outlet pipeline of the reheater; the exhaust gas branch pipeline is connected with an exhaust gas inlet pipeline of the reheater to form a first connecting port, and the exhaust gas branch pipeline is connected with an exhaust gas outlet pipeline of the reheater to form a second connecting port; a valve is arranged between the first connecting port and the second connecting port; the outlet of the exhaust gas pipeline is connected with the bottom of the carbothermic reduction section material layer.
The heat exchange medium pipe box is a channel for heat exchange medium to flow.
As one embodiment of the application, the gas outlet of the analysis section and the gas outlet of the cooling section are connected with the bottom of the carbothermic reduction section; the heat exchange medium enters the cooling section from the opening at the lower part of the cooling section of the heat exchange medium pipe box, the heated air moves upwards, and the opening at the upper part of the cooling section of the heat exchange medium pipe box is connected with the burner; the flue gas of the burner enters a heat exchange medium pipe box of the carbothermic reduction section; finally, the heat exchange medium is discharged from the opening of the preheating section of the heat exchange medium pipe box, and the heat exchange medium and the adsorption material exchange heat reversely.
SO of analysis section and cooling section 2 The gas enters a carbothermic reduction section; the exhaust gas is recycled and reused, the exhaust gas enters a carbothermic reduction section to be in countercurrent contact with materials after being heated by a reheater, and high-temperature gas of a combustor enters a carbothermic reduction section heat exchange tube box.
As another embodiment of the application, the gas outlet of the analysis section and the gas outlet of the cooling section are connected with a burner, and the outlet of the burner is connected with the bottom of the carbothermic reduction section; the heat exchange medium enters the cooling section from the opening at the lower part of the cooling section of the heat exchange medium pipe box, heated air moves upwards, and flows out from the opening at the upper part of the cooling section of the heat exchange medium pipe box; the heat exchange medium enters from the opening of the carbothermic reduction section of the heat exchange medium pipe box and flows out from the opening of the preheating section of the heat exchange medium pipe box.
Realizes the recovery and reutilization of the exhaust gas, and the heat and SO after the gas of the analysis section and the gas of the cooling section are combusted by the burner 2 The gas enters the carbothermic reduction section to be utilized, SO of the analysis section and the cooling section is burnt out by a burner 2 Organic gas in the gas to improve the purity of sulfur. The high-temperature gas of the burner enters the bottom of the carbothermic reduction section, and the high-temperature gas moves upwards to contact with the activity Jiao Ni to heat the active coke and SO 2 Gas, SO 2 The gas reacts with the activated coke.
In the two embodiments, the recovery and reuse of the exhaust gas refers to: residual sulfur-containing byproducts (H) in the exhaust gas 2 S、COS、CS 2 Etc.) has the effect of inhibiting the formation of new sulfur-containing byproducts in the carbothermic reduction stage of the analytical reduction column.
Preferably, the inner spaces of the preheating section, the analysis section, the carbothermic reduction section and the cooling section are provided with heat exchange pipes which are horizontally or vertically staggered.
The spacing and the position of the heat exchange tubes are determined according to the shape of the active coke, wherein the active coke is powdery, and the active coke is columnar, and the active coke is vertical. The heat exchange tube realizes uniform heating of active coke.
Preferably, the high-temperature separator is an axial-flow guide vane type cyclone, and the cyclone components are made of high-temperature-resistant and wear-resistant materials.
Further preferably, the material of the cyclone component is 310s alloy steel or a ceramic material.
And the high-temperature separator is used for recovering active coke adsorbent particles carried in the sulfur-containing mixed gas and improving the cleanliness of sulfur steam.
Preferably, the reheater and the condenser are internally provided with heat exchange pipes which are vertically staggered.
The reheater recovers heat in the sulfur-containing mixed gas, the heat exchange medium is system exhaust gas, the sulfur-containing mixed gas is arranged in a pipe, and the system exhaust gas is arranged outside the pipe.
The sulfur-containing mixed gas in the condenser is conveyed to the inside of the pipe, and the heat exchange medium is conveyed to the outside of the pipe.
Preferably, the liquid sulfur collection device directs the liquid sulfur to a sulfur storage tank and delivers a portion of the remaining exhaust gas to the reheater and a portion to the post-processor.
Preferably, the post-processor deacidifies the exhaust gas, and the clean exhaust gas obtained by dust removal and purification is discharged.
An integrated method for analyzing and reducing sulfur by active coke sulfur dioxide comprises the following specific steps:
1) The sulfur-carrying active coke adsorbent is heated in a preheating section of the analytic reduction tower to separate out water in the adsorbent, and separated out water vapor is led out by a gas leading-out and homogenizing device positioned at the upper part of the preheating section, so that the pressure in the tower is ensured to be in a normal range; the sulfur dioxide absorbed in the desorption section adsorbent is desorbed and leaves the desorption section to be sent to a carbothermic reduction section; desorption of SO 2 Active coke adsorbent in carbothermic reduction stage and resolved SO 2 The gas undergoes carbothermal reduction reaction to generate elemental sulfur, and the elemental sulfur leaves the analytical reduction tower in a gas phase form and enters a cooling tower; analysis of SO 2 The active coke adsorbent is regenerated active coke, and is cooledResidual SO of the cooling section 2 The gas is released and led out and enters a carbothermic reduction section to be reduced into sulfur, and the regenerated active coke leaves the desorption reduction tower and returns to the desulfurization tower to continuously adsorb SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The heating and cooling processes of the adsorbent are both indirectly heated by a heat exchanger, and the adsorbent and a heat exchange medium are subjected to reverse heat exchange;
the carbothermic reduction section mainly reacts to C+SO 2 =CO 2 +S;
Other side reactions are also involved:
C+CO 2 =2CO;
C+H 2 O=CO+H 2
2CO+SO 2 =2CO 2 +S;
2H 2 +SO 2 =2H 2 O+S;
2) The sulfur-containing mixed gas generated by the analytic reduction tower is sent into a cooling tower, active coke adsorbent, sulfur-containing mixed gas heat and sulfur in sulfur steam are recovered through a high-temperature separator, a reheater, a condenser and a liquid sulfur collecting device in sequence, and finally the sulfur is stored in a liquid sulfur storage tank in a liquid form; recovering active coke adsorbent particles entrained in the sulfur-containing mixed gas by a high-temperature separator; the reheater recovers heat in the sulfur-containing mixed gas, and the exhaust gas is heated; condensing the sulfur vapor by a condenser; the condensed liquid sulfur flows into a liquid sulfur collecting device along the wall of a condenser tube, the liquid sulfur collecting device guides the liquid sulfur into a sulfur storage tank, the exhaust gas is sent into a catalytic reduction device, part of the liquid sulfur in the exhaust gas is recovered again by the catalytic reduction device, and then part of the exhaust gas is heated by a reheater and then sent back into active coke in a carbothermic reduction section of a analysis reduction tower, and residual sulfur-containing byproducts (H 2 S、COS、CS 2 Etc.) inhibit the generation of new sulfur-containing byproducts in the tower, and the other part of the exhaust gas enters a post-treatment device for deacidification, dust removal and purification to clean exhaust gas and is discharged.
Preferably, the activated coke is heated to 105-150 ℃ in a preheating section.
Preferably, the activated coke is heated to 300-500 ℃ in the resolving section.
Preferably, the activated coke is heated to 600-1000 ℃ in the carbothermic reduction stage.
Preferably, the temperature of the active coke after being cooled in the cooling section is 50-90 ℃.
Preferably, the temperature of the sulfur-containing mixture at the outlet of the reheater is 400-700 ℃.
Preferably, the temperature of the exhaust gas at the outlet of the reheater is 300-600 ℃.
Preferably, the exhaust gas temperature at the condenser outlet is 120-160 ℃.
The invention has the beneficial effects that:
the invention provides a sulfur analysis and reduction integrated device and method for active coke sulfur dioxide, which control the temperature distribution of an internal interval of a reactor according to the analysis and carbon thermal reduction reaction process requirement conditions of a sulfur-carrying active coke adsorbent, so that the analysis and carbon thermal reduction process is completed in the same reactor, the complexity of a system is reduced, the system structure is more compact, high-purity sulfur is recovered, and two burner arrangement modes are provided according to different heat feeding modes of a carbon thermal reduction section. Can realize SO in the coal-fired flue gas 2 Has wide application prospect in the removal of sulfur and the recycling of sulfur.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application.
FIG. 1 is a process and apparatus (arrangement 1) for the analytical reduction of sulfur dioxide in activated coke;
FIG. 2 is a process and apparatus (arrangement 2) for the sulfur resolution reduction of active coke sulfur dioxide;
FIG. 3 is a bottom view of a gas-derived equalization device;
FIG. 4 is a schematic diagram of a gas-guiding-out and homogenizing device;
wherein: 1. a reduction tower is analyzed; 2. a preheating section; 3. analyzing the section; 4. a carbothermic reduction stage; 5. a burner; 6. a cooling section; 7. a high temperature separator; 8. a reheater; 9. a condenser; 10. a liquid sulfur collecting device; 11. a liquid sulfur storage tank; 12. a catalytic reducer; 13. a post-processor; 14. a diversion cone; 15. the gas is led out of the material homogenizing device; 16. a heat exchange medium pipe box; 17. A blower; 18. a support plate; 19. a material conveying funnel; 20. a porous mesh plate; 21. and an exhaust pipe.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The structure of the active coke sulfur dioxide resolving and reducing sulfur integrated device comprises a resolving and reducing tower 1 and a cooling tower connected with a gas outlet of the resolving and reducing tower 1; the top of the analytic reduction tower 1 is a material inlet, and the bottom is a material outlet; the inside of the analytic reduction tower 1 is sequentially provided with a preheating section 2, an analytic section 3, a carbothermic reduction section 4 and a cooling section 5 from top to bottom; the cooling tower is sequentially provided with a high-temperature separator 7, a reheater 8, a condenser 9 and a liquid sulfur collector 10 from top to bottom; the gas outlet of the analytic reduction tower 1 is connected with the top of the high-temperature separator 7; the exhaust gas outlet of the liquid sulfur collector 10 is sequentially connected with a catalytic reducer 12 and a post-processor 13; a sulfur storage tank 11 is arranged below the liquid outlet of the liquid sulfur collector 10; the outer wall of the analytic reduction tower 1 is provided with a heat exchange medium pipe box 16 at the positions corresponding to the preheating section 2, the analytic section 3, the carbothermic reduction section 4 and the cooling section 6.
The preheating section 2, the analysis section 3, the carbothermic reduction section 4 and the cooling section 6 are provided with a gas leading-out and material homogenizing device 15 above.
The inlet of the analytical reduction tower 1 is provided with a diversion cone.
A gas outlet 16 is arranged at a gas leading-out and homogenizing device 15 of the preheating section 2, the analysis section 3, the carbothermic reduction section 4 and the cooling section 6; the gas outlet of the carbothermic reduction section 4 of the analytical reduction tower 1 is connected with a cooling tower through a gas pipeline.
A fan 17 is arranged in front of a exhaust gas separation pipeline on a pipeline connected with the catalytic reducer 12 and the postprocessor 13.
The structure and process of the present application are further described below with reference to the accompanying drawings:
as shown in fig. 1, the analytic reduction tower 1 is vertically arranged, the inside of the tower is sequentially divided into a preheating section 2, an analytic section 3, a carbothermic reduction section 4 and a cooling section 6 from top to bottom, each section is respectively provided with a replacement heat pipe for exchanging heat with sulfur-carrying active coke and regenerated active coke, and different heat exchange pipe arrangement modes can be used according to the shape of the active coke. For powdery active coke (the diameter is 50 mu m-1 mm), the heat exchange tubes are horizontally staggered, and the powdery active coke is arranged outside the heat exchange tubes and the heat exchange medium is arranged inside the heat exchange tubes; for columnar active coke (the diameter of the cylinder is 1-9 mm), the heat exchange tubes are vertically arranged, and the columnar active coke is arranged in the heat exchange tubes and the heat exchange medium is arranged outside the heat exchange tubes. The sulfur-carrying active coke sent from the desulfurizing tower enters the analysis reducing tower 1 from the upper part, and sequentially enters the preheating section 2, the analysis section 3, the carbothermic reduction section 4 and the cooling section 6 to participate in heat exchange. Firstly, sulfur-carrying active coke enters the preheating section 2 through the guide cone 14, is heated to 105 ℃ to separate out water absorbed in the adsorption process, and is discharged from a gas outlet of the preheating section in the form of water vapor. The sulfur-carrying active coke from which the vapor is discharged enters a resolving section 3 and is heated to 400 ℃ to separate out SO 2 The gas is used for simultaneously desorbing and converting sulfur-carrying active coke into regenerated active coke, and the separated SO 2 The regenerated active coke is led out from the gas outlet of the analysis section to enter the carbothermic reduction section, the regenerated active coke enters the carbothermic reduction section 4 to be heated to 800 ℃, and the hot active coke and SO led out from the analysis section 3 and the cooling section 6 at the temperature 2 The gas undergoes carbothermal reduction reaction to generate sulfur, and is led out of the analytical reduction tower 1 in a gas phase form; the active coke enters a cooling section 6 for cooling after the reaction of the carbothermic reduction section 4, and the residual SO is remained at the same time 2 The gas precipitation is sent to the carbothermic reduction section 4 through a gas outlet of the cooling section to participate in carbothermic reduction reaction, and then the regenerated active coke is sent to a desulfurizing tower to be desulfurized, and the active coke adsorbent is recycled.The method comprises the steps that heat exchange medium air enters into the lower opening of a cooling section 6 of a heat exchange medium pipe box 17 in an analytic reduction tower 1, is heated to 300 ℃ at the upper opening of the cooling section 6 of a heat exchange medium pipe box 16, enters a combustor 5 for supporting combustion, obtains high-temperature flue gas of 800 ℃ from the combustor 5, heats a carbothermic reduction section 4, is discharged from the carbothermic reduction section 4, sequentially enters an analysis section 3 and a preheating section 2, heats active coke adsorbent in reverse heat exchange with the active coke adsorbent, and finally flows out from the opening of the preheating section of the heat exchange medium pipe box 16;
the carbothermic reduction section mainly reacts to C+SO 2 =CO 2 +S;
Other side reactions are also involved:
C+CO 2 =2CO;
C+H 2 O=CO+H 2
2CO+SO 2 =2CO 2 +S;
2H 2 +SO 2 =2H 2 O+S;
the temperature of the high-temperature flue gas from the outlet of the burner is 800-1200 ℃.
Another embodiment of the present application, shown in fig. 2, differs from fig. 1 as follows:
the difference from the embodiment shown in fig. 1 is the SO parsed from the parsing stage 3 and the cooling stage 6 2 The gas is sent into a burner 5 to process and analyze combustible substances in the gas, and SO is directly processed 2 The gas is heated to 800 ℃, and simultaneously organic gas byproducts generated in the resolving process are burned out, and then carbon thermal reduction reaction is carried out with the active coke adsorbent to generate sulfur, so that the purity of the sulfur is improved; the lower opening of the cooling section 6 of the heat exchange medium pipe box 16 in the desorption reduction tower 1 is filled with heat exchange medium air, the heat exchange medium is discharged from the upper opening of the cooling section 6 of the heat exchange medium pipe box 16, the heat exchange medium enters from the opening of the carbothermic reduction section 4 of the heat exchange medium pipe box 16, and flows out from the opening of the preheating section 2 of the heat exchange medium pipe box 16.
As shown in fig. 1 and 2, the sulfur-containing mixed gas generated in the desorption reduction tower 1 is sent into a cooling tower and is sequentially subjected to a high-temperature separator 7, a reheater 8, a condenser 9 and a liquid sulfur collecting device 10 to recover active coke absorption in sulfur steamThe additive, the heat of the sulfur-containing mixed gas and the sulfur are stored in a liquid state in a liquid sulfur storage tank 11. The high-temperature separator 7 is an axial-flow guide vane type cyclone, the cyclone components are made of high-temperature-resistant and wear-resistant materials, 310s alloy steel or ceramic materials can be considered, and outlet gas mainly recovers entrained active coke adsorbent particles through the high-temperature separator 7, so that the cleanliness of sulfur steam is improved; the inner pipes of the reheater 8 are vertically staggered, heat in the outlet gas is mainly recovered, a heat exchange medium is system exhaust gas, the outlet gas is arranged in an outlet gas pipe, the temperature of the outlet gas at the outlet of the reheater 8 is 400 ℃ outside the system exhaust gas pipe, and the exhaust gas is heated to 300 ℃; the inner pipes of the condensers 9 are vertically staggered, sulfur steam flows through the inner pipes, heat exchange medium flows through the outer pipes, and the temperature of gas at the outlet of the condensers 9 is 120 ℃; the condensed liquid sulfur flows into the sulfur storage tank 11 along the wall of the condenser tube, and is collected. The residual exhaust gas after passing through the liquid sulfur collecting device 10 is recycled under the action of the catalytic reduction device 12, then a part of exhaust gas is heated by the reheater 8 and then is sent back to the active coke in the carbothermal reduction section 4 of the analytical reduction tower 1, and residual sulfur-containing byproducts (H 2 S、COS、CS 2 Etc.) inhibit the generation of new sulfur-containing byproducts in the tower, and the other part enters the post-treatment device 13 for deacidification, dust removal and purification to clean exhaust gas and then is discharged.
As shown in fig. 1 and 2, in the analytical reduction column 1, before the preheating section 2, a gas leading-out and homogenizing device 15 is provided between the preheating section 2 and the analytical section 3, between the analytical section 3 and the carbothermic reduction section 4, and between the carbothermic reduction section 4 and the cooling section 6.
As shown in fig. 3 and 4, the gas-guiding-out and homogenizing device 15 is formed by combining a supporting plate 18, a material conveying funnel 19, a porous mesh plate 20 and an exhaust pipe 21, wherein the material conveying funnel 19 penetrates through the porous mesh plate 20, an opening part of the material conveying funnel 19 is positioned above the porous mesh plate 20, and a closing part of the material conveying funnel 19 is positioned at the lower side of the porous mesh plate 20; the supporting plate 18 plays a role of fixing the material conveying hopper 19 and bearing part of the weight of the material; the upper ends of the open parts of the adjacent material conveying funnels 19 are tightly connected, a gas space is formed above the porous mesh plate 20, below the supporting plate 18 and between the adjacent material conveying funnels 19, the exhaust pipe 21 is positioned on the inner wall of one side of the analysis tower of the gas space, and the lower end of the closing part of the material conveying funnels 19 is positioned below the material layer. The material conveying hopper 19 is used for collecting and distributing materials, the porous net plate 20 is used for inertial separation of powdery adsorption materials, and the cleanliness of collected gas is improved; the lower material pipe of the material conveying hopper 19 is positioned below the material layer and is used for preventing the precipitated gas from reversely flowing to form a gas plug, and a gas space is formed between the adjacent material conveying hoppers 19 and is connected with the gas exhaust pipe 8 so as to exhaust the precipitated gas.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application are intended to be included within the scope of the present application.

Claims (12)

1. An active burnt sulfur dioxide analysis reduction sulfur integrated device which characterized in that: the device comprises an analytic reduction tower and a cooling tower connected with a gas outlet of the analytic reduction tower, wherein the top of the analytic reduction tower is a material inlet, and the bottom of the analytic reduction tower is a material outlet; the inside of the analytic reduction tower is sequentially provided with a preheating section, an analytic section, a carbothermic reduction section and a cooling section from top to bottom; the cooling tower consists of a high-temperature separator, a reheater, a condenser and a liquid sulfur collector from top to bottom in sequence; the gas outlet of the analytic reduction tower is connected with the top of the high-temperature separator; the exhaust gas outlet of the liquid sulfur collector is sequentially connected with a catalytic reducer and a post-processor; a sulfur storage tank is arranged below the side of the liquid outlet of the liquid sulfur collector; the outer wall of the analytic reduction tower is provided with heat exchange medium pipe boxes corresponding to the preheating section, the analytic section, the carbothermic reduction section and the cooling section;
a gas guiding and homogenizing device is arranged above the preheating section, the analysis section, the carbothermic reduction section and the cooling section; a diversion cone is arranged at the inlet of the analytic reduction tower;
the gas guiding and homogenizing device is formed by combining a supporting plate, a conveying funnel, a porous mesh plate and an exhaust pipe; the material conveying funnel penetrates through the porous mesh plate, the opening part of the material conveying funnel is positioned above the porous mesh plate, the closing part of the material conveying funnel is positioned at the lower side of the porous mesh plate, and the supporting plate is used for fixing the material conveying funnel and bearing the weight of part of materials; a gas space is formed above the porous reticular plate, below the supporting plate and between adjacent material conveying funnels;
the gas outlet of the analysis section and the gas outlet of the cooling section are connected with a burner, and the outlet of the burner is connected with the bottom of the carbothermic reduction section;
the catalytic reducer is connected with the post-processor through a pipeline provided with a waste gas branch pipeline, and the waste gas branch pipeline is sequentially connected with a waste gas inlet pipeline and a waste gas outlet pipeline of the reheater; the exhaust gas branch pipeline is connected with an exhaust gas inlet pipeline of the reheater to form a first connecting port, and the exhaust gas branch pipeline is connected with an exhaust gas outlet pipeline of the reheater to form a second connecting port; a valve is arranged between the first connecting port and the second connecting port; the outlet of the exhaust gas pipeline is connected with the bottom of the carbothermic reduction section.
2. The device for resolving and reducing sulfur integrated with active coke sulfur dioxide according to claim 1, wherein the device is characterized in that: the gas outlet of the analysis section and the gas outlet of the cooling section are connected with the bottom of the carbothermic reduction section; the heat exchange medium enters the cooling section from the opening at the lower part of the cooling section of the heat exchange medium pipe box, heated air moves upwards, and the opening at the upper part of the cooling section of the heat exchange medium pipe box is connected with the burner; the flue gas of the burner enters a heat exchange medium pipe box of the carbothermic reduction section; finally, the heat exchange medium is discharged from the opening of the preheating section of the heat exchange medium pipe box, and the heat exchange medium and the adsorption material exchange heat reversely.
3. The device for resolving and reducing sulfur integrated with active coke sulfur dioxide according to claim 1, wherein the device is characterized in that: the heat exchange medium enters the cooling section from the opening at the lower part of the cooling section of the heat exchange medium pipe box, heated air moves upwards, and flows out from the opening at the upper part of the cooling section of the heat exchange medium pipe box; the heat exchange medium enters from the opening of the carbothermic reduction section of the heat exchange medium pipe box and flows out from the opening of the preheating section of the heat exchange medium pipe box.
4. The device for resolving and reducing sulfur integrated with active coke sulfur dioxide according to claim 1, wherein the device is characterized in that: the inner space of the preheating section, the analysis section, the carbothermic reduction section and the cooling section is provided with heat exchange tubes which are horizontally or vertically staggered.
5. The device for resolving and reducing sulfur integrated with active coke sulfur dioxide according to claim 1, wherein the device is characterized in that: the reheater and the condenser are internally provided with heat exchange tubes which are vertically staggered.
6. An integrated method for analyzing and reducing sulfur by active coke sulfur dioxide is characterized in that: the method comprises the following specific steps:
1) The sulfur-carrying active coke adsorbent is heated in a preheating section of the analytic reduction tower to separate out water in the adsorbent, and separated out water vapor is led out by a gas leading-out and homogenizing device positioned at the upper part of the preheating section, so that the pressure in the tower is ensured to be in a normal range; the sulfur dioxide absorbed in the desorption section adsorbent is desorbed and leaves the desorption section to be sent to a carbothermic reduction section; desorption of SO 2 Active coke adsorbent in carbothermic reduction stage and resolved SO 2 The gas undergoes carbothermal reduction reaction to generate elemental sulfur, and the elemental sulfur leaves the analytical reduction tower in a gas phase form and enters a cooling tower; analysis of SO 2 The active coke adsorbent of (2) is regenerated active coke, and residual SO is left in the cooling section 2 The gas is released and led out and enters a carbothermic reduction section to be reduced into sulfur, and the regenerated active coke leaves the desorption reduction tower and returns to the desulfurization tower to continuously adsorb SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The heating and cooling processes of the adsorbent are both indirectly heated by a heat exchanger, and the adsorbent and a heat exchange medium are subjected to reverse heat exchange;
the carbothermic reduction section mainly reacts to C+SO 2 =CO 2 +S;
Other side reactions are also involved:
C+CO 2 =2CO;
C+H 2 O=CO+H 2
2CO+SO 2 =2CO 2 +S;
2H 2 +SO 2 =2H 2 O+S;
2) The sulfur-containing mixed gas generated by the analytic reduction tower is sent into a cooling tower, active coke adsorbent, sulfur-containing mixed gas heat and sulfur in sulfur steam are recovered through a high-temperature separator, a reheater, a condenser and a liquid sulfur collecting device in sequence, and finally the sulfur is stored in a liquid sulfur storage tank in a liquid form; recovering active coke adsorbent particles entrained in the sulfur-containing mixed gas by a high-temperature separator; the reheater recovers heat in the sulfur-containing mixed gas, and the exhaust gas is heated; condensing the sulfur vapor by a condenser; the condensed liquid sulfur flows into a liquid sulfur collecting device along the wall of a condenser tube, the liquid sulfur collecting device guides the liquid sulfur into a sulfur storage tank, the exhaust gas is sent into a catalytic reduction device, part of the liquid sulfur in the exhaust gas is recovered again by the catalytic reduction device, then part of the exhaust gas is heated by a reheater and then sent back into active coke in a carbothermic reduction section of an analytical reduction tower, the generation of new sulfur-containing byproducts in the tower is inhibited by utilizing residual sulfur-containing byproducts, and the other part of the exhaust gas enters a post-treatment device for deacidification, dust removal and purification to clean exhaust gas and is discharged.
7. The method for integrating active coke sulfur dioxide resolution reduction with sulfur according to claim 6, which is characterized in that: the active coke is heated to 105-150 ℃ in a preheating section.
8. The method for integrating active coke sulfur dioxide resolution reduction with sulfur according to claim 6, which is characterized in that: the active coke is heated to 300-500 ℃ in the resolving section.
9. The method for integrating active coke sulfur dioxide resolution reduction with sulfur according to claim 6, which is characterized in that: the active coke is heated to 600-1000 ℃ in the carbothermic reduction section.
10. The method for integrating active coke sulfur dioxide resolution reduction with sulfur according to claim 6, which is characterized in that: the temperature of the active coke after being cooled in the cooling section is 50-90 ℃.
11. The method for integrating active coke sulfur dioxide resolution reduction with sulfur according to claim 6, which is characterized in that: the temperature of the sulfur-containing mixed gas at the outlet of the reheater is 400-700 ℃.
12. The method for integrating active coke sulfur dioxide resolution reduction with sulfur according to claim 6, which is characterized in that: the temperature of the exhaust gas at the outlet of the reheater is 300-600 ℃; the exhaust temperature at the outlet of the condenser is 120-160 ℃.
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