CN108726487B - Burn H2S, carbothermic reduction of SO2Device and process for recovering sulfur resources - Google Patents

Burn H2S, carbothermic reduction of SO2Device and process for recovering sulfur resources Download PDF

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CN108726487B
CN108726487B CN201810675074.3A CN201810675074A CN108726487B CN 108726487 B CN108726487 B CN 108726487B CN 201810675074 A CN201810675074 A CN 201810675074A CN 108726487 B CN108726487 B CN 108726487B
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gas
sulfur
incinerator
carbon
exhaust gas
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CN108726487A (en
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赵希强
马春元
冯太
夏霄
李军
张世珍
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Shandong University
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2206/00—Waste heat recuperation
    • F23G2206/10—Waste heat recuperation reintroducing the heat in the same process, e.g. for predrying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G2209/00—Specific waste
    • F23G2209/14—Gaseous waste or fumes

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  • Environmental & Geological Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention discloses a method for burning H2S, carbothermic reduction of SO2The device and the process for recovering sulfur resources comprise the following steps: providing circulating fluidizationA carbon bed reduction tower to be rich in H2Burning S gas to generate high-temperature gas, mixing the high-temperature gas with circulating gas to reduce the temperature of the high-temperature gas, conveying the high-temperature gas to a carbon thermal reduction tower of a circulating fluidized bed, and carrying out SO (sulfur oxide) reduction under the action of a carbon-based reducing agent2Reducing to form mixed gas, separating the mixed gas to obtain a circulating carbon-based reducing agent and gas containing sulfur, cooling and separating the gas containing sulfur to obtain sulfur and exhaust gas, and heating part of the exhaust gas containing sulfur to serve as the circulating gas. The invention is achieved by burning H2S obtaining high concentration SO2And heat, and the reaction gas circulation method is adopted to realize SO2And (3) inhibiting the generation of new by-products by utilizing the sulfur-containing by-products in the circulating gas while carrying out multiple reduction and conversion, and realizing the standard-reaching emission of the sulfur-containing gas and the efficient recovery of sulfur resources.

Description

Burn H2S, carbothermic reduction of SO2Device and process for recovering sulfur resources
Technical Field
The invention belongs to the field of atmospheric pollutant treatment and recycling, and particularly relates to incineration H2S, carbothermic reduction of SO2A device and a process for recovering sulfur resources.
Background
Coal chemical refers to the process of converting coal into gas, liquid and solid fuels and chemicals by chemical processing using coal as a raw material. Mainly comprises coal gasification, liquefaction, dry distillation, tar processing, calcium carbide acetylene chemical industry and the like. Petrochemical refers to the process of producing petroleum products and petrochemical products from petroleum and natural gas. Petroleum products are also called oil products, and mainly comprise various fuel oils (gasoline, kerosene, diesel oil and the like), lubricating oil, liquefied petroleum gas, petroleum coke, paraffin, asphalt and the like. The first step in the production of petrochemical products is the cracking of raw oil and gas (such as propane, gasoline, diesel, etc.) to produce basic chemical materials, typically ethylene, propylene, butadiene, benzene, toluene, xylene. The second step is to produce various organic chemical materials (about 200 kinds) and synthetic materials (plastics, synthetic fibers, synthetic rubbers) from basic chemical materials. The natural gas chemical industry is a process of generating chemical products by using natural gas as a raw material.
In oil gas chemical industry and coal chemical industry, numerous pollutants are generated, and H2S is the major sulfur-containing contaminant. H2S has the defects of high toxicity, stink, corrosion on equipment, poisoning of a catalyst and the like, and can generate acid pollution when being directly discharged into the atmosphere. At present H2The S treatment technology is mainly based on Claus (Claus) process. The Claus process used at present needs a multistage catalytic conversion device and tail gas treatment equipment to realize high-efficiency recovery of sulfur and standard emission of tail gas, and has higher process cost. However, there are no other mature H available to replace Claus process2S treatment and sulfur recovery process.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for incinerating H2S, carbothermic reduction of SO2Process for recovering sulfur resources by combustion of H2S obtaining high concentration SO2And heat, and the reaction gas circulation method is adopted to realize SO2And (3) inhibiting the generation of new by-products by utilizing the sulfur-containing by-products in the circulating gas while carrying out multiple reduction and conversion, and realizing the standard-reaching emission of the sulfur-containing gas and the efficient recovery of sulfur resources.
In order to achieve the purpose, the technical scheme of the invention is as follows:
burn H2S, carbothermic reduction of SO2Process for recovering sulfur resources to provide H2S incinerator, circulating fluidized bed carbon thermal reduction tower, and H-rich gas generated in oil gas chemical industry and/or coal chemical industry2S gas passes through H2S incinerator burns S to produce 1000-1500 deg.C SO with 5-30% (mass)2The high-temperature gas is mixed with the circulating gas, the temperature of the high-temperature gas is reduced to 600-1000 ℃, the high-temperature gas is conveyed to a carbon thermal reduction tower of a circulating fluidized bed, and SO is reduced in the carbon thermal reduction tower of the circulating fluidized bed under the action of a carbon-based reducing agent2Reducing to form a mixed gas containing sulfur vapor and a carbon-based reducing agentThe gas containing sulfur steam is cooled and separated to obtain liquid sulfur and exhaust gas, and part of the exhaust gas heated by the gas containing sulfur steam is used as circulating gas.
The invention firstly adopts H2S incineration to produce SO2And using the heat of incineration as heat source, adding carbon-based reducing agent to reduce SO2The sulfur is prepared, thereby realizing the standard emission of sulfur-containing gas and the high-efficiency recovery of sulfur resources, and reducing the existing H2Complexity and cost of the S remediation process.
Another object of the present invention is to provide a device for implementing the above process, comprising H2S incinerator, circulating fluidized bed carbon thermal reduction tower, high temperature separator, reheater, sulfur condenser, steam condenser, H2The S incinerator and the circulating fluidized bed carbon thermal reduction tower are both vertically arranged, H2The bottom of the S incinerator is provided with a mixed gas chamber H2The gas phase outlet at the bottom of the S incinerator is connected with the top inlet of the mixing gas chamber, the bottom outlet of the mixing gas chamber is connected with the bottom inlet of the carbon thermal reduction tower of the circulating fluidized bed, the top outlet of the carbon thermal reduction tower of the circulating fluidized bed is connected with the high-temperature separator, the gas phase outlet of the high-temperature separator is connected with the sulfur-containing gas inlet of the reheater, the sulfur-containing gas outlet of the reheater is connected with the sulfur condenser, the gas outlet of the sulfur cooler is connected with the exhaust gas inlet of the steam condenser, the exhaust gas outlet of the steam condenser is connected with the exhaust gas inlet of the reheater, the exhaust gas outlet of the reheater is connected with the exhaust gas pipeline, the exhaust gas pipeline is provided with a circulating gas pipeline, and the outlet.
The invention has the beneficial effects that:
the invention provides a method for burning H2S, carbothermic reduction of SO2A process for recovering sulfur resources using a carbon-based material and H2High concentration SO generated by S incineration2The high-temperature gas is used as a raw material, and H is realized by accurately controlling the carbothermic reduction reaction conditions2High-efficiency treatment of S and resource recovery of sulfur. Combines the exhaust gas incineration process to realize the system waste heat recovery and the simultaneous treatment processThe waste generated in the process. Can replace Claus process to realize sulfur resource recovery, and has wide market application prospect.
Drawings
The accompanying drawings, which 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 are not intended to limit the application.
FIG. 1 is a schematic diagram of the apparatus of the present invention;
1.H2s incinerator, 2 exhaust gas incinerator, 3 air heat exchanger, 4 circulating fluidized bed carbon heat reduction tower, 5 high temperature separator, 6 blanking hopper, 7 reheater, 8 reaction gas cooler, 9 sulfur condenser, 10 sulfur storage tank, 11 steam condenser, 12 SO2A removing tower, 13 a dust remover and 14 a chimney.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. 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 according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The carbon thermal reduction tower of the circulating fluidized bed is tower type circulating fluidized bed equipment.
The carbon-based reducing agent is a sulfur-carbon-based material with high sulfur content, such as petroleum coke and the like. The material is a byproduct in oil gas chemical industry and coal chemical industry, is not suitable for being used as fuel due to high sulfur content, and is limited in application, and by adopting the material, sulfur in the carbon-based material can be partially converted into sulfur in the carbothermic reduction process, so that the recovery rate of the sulfur can exceed 100%. Realizes the utilization of sulfur-carbon based materials with higher sulfur content, such as petroleum coke.
As described in the background, there is an existing process H in the prior art2S has the defects of complex process, high cost and the like, and in order to solve the technical problems, the application provides a method for incinerating H2S, carbothermic reduction of SO2A device and a process for recovering sulfur resources.
In an exemplary embodiment of the present application, an incineration H is provided2S, carbothermic reduction of SO2Process for recovering sulfur resources to provide H2S incinerator, circulating fluidized bed carbon thermal reduction tower, and H-rich gas generated in oil gas chemical industry and/or coal chemical industry2S gas passes through H2S incinerator burns S to produce 1000-1500 deg.C SO with 5-30% (mass)2The high-temperature gas is mixed with the circulating gas, the temperature of the high-temperature gas is reduced to 600-1000 ℃, the high-temperature gas is conveyed to a carbon thermal reduction tower of a circulating fluidized bed, and SO is reduced in the carbon thermal reduction tower of the circulating fluidized bed under the action of a carbon-based reducing agent2Reducing to form mixed gas containing sulfur steam and a carbon-based reducing agent, separating the mixed gas to obtain a circulating carbon-based reducing agent and gas containing the sulfur steam, cooling and separating the gas containing the sulfur steam to obtain liquid sulfur and exhaust gas, and heating part of the exhaust gas containing the sulfur steam to be used as the circulating gas.
This application begins with H2S incineration to produce SO2And using the heat of incineration as heat source, adding carbon-based reducing agent to reduce SO2The sulfur is prepared, thereby realizing the standard emission of sulfur-containing gas and the high-efficiency recovery of sulfur resources, and reducing the existing H2Complexity and cost of the S remediation process.
Preferably, a portion of the exhaust gas heated by the gas containing sulphur vapour is used as conditioning gas, which is fed to the circulating fluidized bed carbothermic tower. Due to the residual sulfur-containing by-product (H) contained in the exhaust gas2S、COS、CS2Etc.) can suppress the generation of new sulfur-containing by-products in the columnAnd (4) obtaining.
Preferably, a waste gas incinerator is provided, and a part of the waste gas heated by the gas containing sulfur steam is used as a conveying gas, and the conveying gas enters the waste gas incinerator for incineration.
Preferably, the bottom of the exhaust gas incinerator is provided with an air heat exchanger, the flue gas generated in the incinerator is used as a heat source to preheat the air in the air heat exchanger, and part of the preheated air enters H2And the other part of the S incinerator enters an exhaust gas incinerator. Further preferably, the flue gas after passing through the air heat exchanger is discharged after being desulfurized and dedusted.
Preferably, a part of the circulating carbon-based reducing agent obtained by separating the mixed gas is mixed with the conveying gas and then enters the exhaust gas incinerator for incineration.
Preferably, a part of the circulating carbon-based reducing agent obtained by separating the mixed gas is mixed with the carbon-based reducing agent and then enters a carbon thermal reduction tower of the circulating fluidized bed to reduce SO2。
Preferably, the particle size of the carbon-based reducing agent is 60 mu m-5 mm.
Preferably, after the gas containing the sulfur steam is subjected to exhaust gas cooling separation to obtain liquid sulfur and exhaust gas, the temperature of the sulfur is 120-160 ℃, and the temperature of the exhaust gas is 130-180 ℃.
Preferably, the temperature of the exhaust gas after the gas containing sulfur steam is heated is 300-600 ℃.
Preferably, the gas containing sulfur steam is cooled by adopting exhaust gas at 50-90 ℃. And heating the cooled exhaust gas to 300-600 ℃.
Said H2The high-temperature reaction gas at the outlet of the S incinerator is N2、SO2、H2O, and the like. The exhaust gas is N2、SO2、COS、H2S、CS2、CO、H2、CO2And H2O, and the like.
In another embodiment of the present application, there is provided an apparatus for performing the above process, comprising H2S incinerator, circulating fluidized bed carbon thermal reduction tower and high temperature separatorSeparator, reheater, sulfur condenser, steam condenser, H2The S incinerator and the circulating fluidized bed carbon thermal reduction tower are both vertically arranged, H2The bottom of the S incinerator is provided with a mixed gas chamber H2The gas phase outlet at the bottom of the S incinerator is connected with the top inlet of the mixing gas chamber, the bottom outlet of the mixing gas chamber is connected with the bottom inlet of the carbon thermal reduction tower of the circulating fluidized bed, the top outlet of the carbon thermal reduction tower of the circulating fluidized bed is connected with the high-temperature separator, the gas phase outlet of the high-temperature separator is connected with the sulfur-containing gas inlet of the reheater, the sulfur-containing gas outlet of the reheater is connected with the sulfur condenser, the gas outlet of the sulfur cooler is connected with the exhaust gas inlet of the steam condenser, the exhaust gas outlet of the steam condenser is connected with the exhaust gas inlet of the reheater, the exhaust gas outlet of the reheater is connected with the exhaust gas pipeline, the exhaust gas pipeline is provided with a circulating gas pipeline, and the outlet.
Preferably, the exhaust pipeline is provided with a regulating gas pipeline, and an outlet of the regulating gas pipeline is connected to a gas phase inlet on the side wall of the carbon thermal reduction tower of the circulating fluidized bed. Further preferably, 3-7 side wall inlets of the circulating fluidized bed carbothermic reduction tower are arranged from bottom to top.
Preferably, the waste gas incinerator comprises a waste gas pipeline, wherein a conveying gas pipeline is arranged on the waste gas pipeline, and an outlet of the conveying gas pipeline is connected with a fuel inlet of the waste gas incinerator.
Preferably, the bottom of the exhaust gas incinerator is provided with an air heat exchanger, a smoke outlet of the exhaust gas incinerator is connected with a smoke inlet of the air heat exchanger, and an air outlet of the air heat exchanger is respectively connected with an air inlet and an H of the exhaust gas incinerator2S incinerator air inlet. More preferably, the flue gas outlet of the air heat exchanger is sequentially connected with the SO2A desorption tower and a dust remover.
It is further preferred that the recycle carbon-based reductant outlet of the high temperature separator is connected to the transport gas line.
Preferably, the outlet of the carbon-based reducing agent circulating the high-temperature separator is connected to the inlet of the carbon-based reducing agent circulating the fluidized bed carbothermic tower.
Preferably, the bottom of the carbon thermal reduction tower of the circulating fluidized bed is provided with a Venturi tube，H2And high-temperature gas incinerated by the S incinerator enters the carbon thermal reduction tower of the circulating fluidized bed through the Venturi tube.
Preferably, a reaction gas cooler is arranged between the reheater and the sulphur condenser.
This application prefers a kind of incineration H2S, carbothermic reduction of SO2Sulfur resource recovery plant from H2The system comprises an S incinerator, an exhaust gas incinerator, a tail heating surface of the exhaust gas incinerator, a carbon thermal reduction device, a reaction gas cooling and sulfur recovery device, a tail gas purification device and the like. Is characterized in that H2S incinerator burning H2S, converting it to high-temperature high SO2Concentration of the reactive gas. The exhaust gas incinerator and the tail heating surface thereof are composed of a burner, an incinerator body and an air heater, the burner, the incinerator body and the air heater are sequentially arranged from upstream to downstream, and the air heater is an air-gas heat exchanger. The carbothermic reduction device comprises a fluidized bed carbothermic reduction tower, a high-temperature separator, a blanking hopper, a related material pipeline and the like. The lower part of the carbothermic reduction tower body is provided with a Venturi tube, and the tower body is provided with 3-7 air nozzles from bottom to top along the way. A material returning pipe is arranged between the high-temperature separator and the carbon thermal reduction tower body. The upper stream of the material returning pipe is provided with a slag discharging pipe, the lower stream is provided with a blanking hopper and a feeding pipe, and the feeding pipe and the slag discharging pipe are both provided with a gas locking feeder. The reaction gas cooling and sulfur recovery device comprises a reheater, a reaction gas cooler, a sulfur condenser, a sulfur storage tank and the like, which are arranged from top to bottom in sequence. The reheater is a gas-gas heat exchanger, and the reaction gas cooler and the sulfur condenser are gas-liquid heat exchangers. A water vapor condenser is arranged at the gas outlet of the sulfur condenser. The tail gas purifying device consists of SO2The device comprises a desorption tower, a dust remover, a chimney and the like, which are arranged from the upstream of the tail gas to the downstream in sequence. The acid gas removal tower is a circulating fluidized bed semi-dry desulfurization tower, and the dust remover is a bag type dust remover.
The air is led to the air heater by the draught fan and then divided into two paths to respectively provide H2S combustion air of an incinerator and a waste gas incinerator; the flue gas pipeline is led out from the exhaust gas incinerator, and the flue gas passes through the tail heating surface and SO2The removing tower and the dust remover are led to a chimney through a draught fan to be discharged into the atmosphere. The reaction gas pipeline is led out from the carbothermic reduction tower, and the reaction gas isSequentially passing through a high-temperature separator, a reheater cooling side, a sulfur condenser and a steam condenser, and leading to a reheater heating side through a draught fan. The outlet pipeline at the heating side of the reheater is divided into three paths: the conveying gas pipeline is connected with the slag discharge pipe, carries the discharged carbon-based reducing agent without reactivity, and leads the carbon-based reducing agent to the exhaust gas incinerator through the Venturi tube; adjusting an air pipeline to lead to an air jet of the carbothermic reduction tower; circulating gas pipeline in H2And adding the S into the incinerator, and introducing the mixed reaction gas to the bottom of the carbothermic reduction tower through a venturi tube and a mixed reaction gas heater. Condensed water in the steam condenser is sprayed into SO by a water pump2And (4) a removal tower. The gas-water pipelines are all provided with flow regulating valves.
The implementation process according to the preferred device is as follows:
(1)H2s is in H2S is burnt in an incinerator to generate SO at 1000-1500 DEG C2And mixing the high-temperature reaction gas with the concentration of 2-13% with the circulating gas, reducing the temperature to 600-1000 ℃, and then feeding the mixture into a carbothermic reduction tower.
(2) Burning the exhaust gas and the waste carbon-based reducing agent in an exhaust gas incinerator, enabling the temperature of outlet flue gas to be 1000-1500 ℃, performing brief introduction heat exchange with normal-temperature air in an air heater, and finally performing SO (sulfur oxide) introduction heat exchange2The purified gas is discharged from a chimney after being purified by the removing tower and the bag-type dust remover. Wherein air is heated to 200-500 ℃ in an air heater as H2And the S incinerator and the exhaust gas incinerator are used for supporting combustion.
(3) Fluidized bed carbothermic tower is SO2The reaction place is reduced into sulfur by C, the reaction temperature is 600-1000 ℃, and C/SO2The molar ratio is 10-100, the gas velocity in the tower is 4-8 m, and the contact time of the gas in the tower is 2-12 s. And (3) introducing the conditioning gas with the temperature of 300-600 ℃ into a carbon thermal reduction tower in sections, and adjusting the temperature and the gas speed in the tower.
(4) The reaction gas firstly enters a high-temperature separator after leaving the reduction tower, most of the separated carbon-based reducing agent returns to the reduction tower to continue reacting, and part of the carbon-based reducing agent losing reactivity is discharged and does not return to the reduction tower. And cooling the gas separated from the carbon-based reducing agent to 130-150 ℃ in a sulfur recovery device after the gas is cooled by a reheater and a reaction gas cooler, and enabling the sulfur to be changed from a gas state to a liquid state and to flow into a sulfur storage tank for storage. The exhaust gas leaving the sulphur recovery unit is further cooled to below 100 ℃ to condense water from the exhaust gas. The condensed water together with the acid gas dissolved in the water is sprayed into the acid gas removal tower. After the exhaust gas with the moisture removed enters a reheater and is heated to 300-600 ℃, the exhaust gas is divided into three paths of circulating gas, adjusting gas and conveying gas, wherein the conveying gas carries carbon thermal reduction combustible byproducts and carbon-based reducing agents discharged from a reduction tower, and the carbon-based reducing agents enter an incinerator for combustion, so that the byproducts which are difficult to treat are eliminated, energy is released, and the input of external energy is reduced; and (3) respectively introducing the recycle gas and the conditioning gas into a carbon thermal reduction tower according to the steps (1) and (3).
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
Example 1
As shown in FIG. 1, H2The S incinerator 1 has vertical furnace body, gas burner in the top and high concentration H2S gas flows through H2The S incinerator 1 is fully combusted in the hearth to convert the S into SO2And then is led out to a carbon thermal reduction tower 4 of the circulating fluidized bed through a mixed reaction gas pipeline. The gas in the circulating fluidized bed carbon heat reduction tower 4 flows through the high-temperature separator 5, the reheater 7, the reaction gas cooler 8 and the sulfur recovery device 9, and the internal space of the heat exchange pipeline, the internal space of the steam cooler and the space between the shell of the reheater and the heat exchange pipeline are provided with conveying power by a draught fan. Then divided into three gas pipelines: the conveying gas enters the exhaust gas incinerator 2 from the combustor after passing through the Venturi tube; the adjusting gas enters the reduction tower from the gas inlet of the fluidized bed carbon thermal reduction tower in a subsection manner; recycle gas in H2S incinerator 1 tail and H2And mixing the S burned gas and then feeding the gas into a circulating fluidized bed carbon thermal reduction tower 4. Newly added petroleum coke particles enter the carbon thermal reduction tower 4 of the circulating fluidized bed from an air locking feeder above the moving bed reduction tower 4, slowly move from top to bottom, pass through the petroleum coke cooler 5, and are discharged from the air locking feeder below the moving bed reduction tower 4. The furnace body of the exhaust gas incinerator 2 is vertically arranged, the top of the exhaust gas incinerator is provided with a gas burner, and the exhaust gas after reaction is in the exhaust gas incinerator2, the flue gas at the outlet of the exhaust gas incinerator 2 exchanges heat with the ambient air in the air heat exchanger 3 and is led out by a flue gas pipeline and sequentially passes through SO2The purified product is discharged to the atmosphere through a stack 14 via a stripping tower 12 and a dust collector 13. The air is supplied with power by the induced draft fan, and the air heated in the air heater 3 is respectively led to H through the high-temperature air pipelines2And burners of the S incinerator 1 and the exhaust gas incinerator 2.
An upper annular air chamber and a lower annular air chamber are arranged outside a tower body of a circulating fluidized bed carbon thermal reduction tower 4, an inner air chamber is arranged in the middle of the tower body, a petroleum coke particle layer is arranged between the inner air chamber and the outer air chamber, and a heat preservation layer is arranged outside the tower body.
The high temperature separator 6 is in the form of a cyclone separator, an axial flow separator, a ceramic cartridge filter or a combination of separators.
Comprises a sulfur storage tank 10, and the condensed liquid sulfur in a sulfur condenser 9 flows into the sulfur storage tank 10 for storage.
Comprises a water vapor condenser 11, condensed water in the water vapor condenser 11 is sprayed into SO by a water pump2A stripping column 12.
The adopted process comprises the following steps: the grain size of the petroleum coke is 2-5 mm, and the sulfur content is 4.5-5.5%.
One, H2S incinerating H with concentration of 60-80% in incinerator2S gas, which generates 1000-1200 ℃ high temperature gas, SO2The concentration is 8-10%, and the temperature is 650-900 ℃ after mixing with the circulating gas at the temperature of 300-600 ℃ according to the standard volume ratio of 1: 1.
Secondly, the mixed reaction gas enters a moving bed reduction tower, the reaction time is 3-5 s, the reaction temperature is 700-900 ℃, and SO is added2The conversion rate and the sulfur yield are respectively 90-98% and 90-98%, and the sulfur content of the petroleum coke after the reaction is reduced to 2-3.5%.
And thirdly, separating dust from the exhaust gas through a high-temperature filter, cooling the exhaust gas through a reheater, and condensing the exhaust gas through a sulfur condenser to recover sulfur. The purity of the recovered sulfur reaches more than 99.8 percent and meets the first-class standard of industrial sulfur.
Fourthly, the flue gas of the exhaust gas incinerator passes through a circulating fluidized bed semi-dry desulfurization tower and a bag-type dust removerSO at outlet of bag-type dust collector2The concentration is lower than 30mg/Nm3Dust less than 5mg/Nm3。
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (8)

1. Burn H2S, carbothermic reduction of SO2A process for recovering sulfur resources, characterized by providing H2S incinerator, circulating fluidized bed carbon thermal reduction tower, and H-rich gas generated in oil gas chemical industry and/or coal chemical industry2S gas passes through H2S incinerator burns S to produce 1000-1500 deg.C SO with 5-30% (mass)2The high-temperature gas is mixed with the circulating gas, the temperature of the high-temperature gas is reduced to 600-1000 ℃, the high-temperature gas is conveyed to a carbon thermal reduction tower of a circulating fluidized bed, and SO is reduced in the carbon thermal reduction tower of the circulating fluidized bed under the action of a carbon-based reducing agent2Reducing to form mixed gas containing sulfur steam and a carbon-based reducing agent, separating the mixed gas to obtain a circulating carbon-based reducing agent and gas containing the sulfur steam, cooling and separating the gas containing the sulfur steam to obtain liquid sulfur and exhaust gas, and heating part of the exhaust gas containing the sulfur steam to be used as the circulating gas; one part is used as adjusting gas, and the adjusting gas is conveyed into the carbon thermal reduction tower of the circulating fluidized bed;
providing a waste gas incinerator, wherein a part of the waste gas heated by the gas containing sulfur steam is used as conveying gas, and the conveying gas enters the waste gas incinerator for incineration;
after the gas containing sulfur steam is subjected to exhaust gas cooling separation to obtain liquid sulfur and exhaust gas, the temperature of the sulfur is 120-150 ℃, and the temperature of the exhaust gas is 130-180 ℃;
the temperature of the exhaust gas after the gas containing sulfur steam is heated is 300-600 ℃;
and cooling the gas containing the sulfur steam by adopting exhaust gas at the temperature of 50-90 ℃.
2. The process as claimed in claim 1, wherein the bottom of the exhaust gas incinerator is provided with an air heat exchanger, the flue gas generated in the incinerator is used as a heat source to preheat the air in the air heat exchanger, and a part of the preheated air enters H2S, the other part of the waste gas enters an incinerator;
and (3) mixing part of the circulating carbon-based reducing agent obtained by separating the mixed gas with the conveying gas, and then burning the mixture in the exhaust gas incinerator.
3. The process as set forth in claim 1, wherein the carbon-based reducing agent obtained by separating the mixed gas is partially mixed with the carbon-based reducing agent and then introduced into the circulating fluidized bed carbothermic reduction tower to reduce SO2。
4. An apparatus for use in the process of any one of claims 1 to 3, comprising H2S incinerator, circulating fluidized bed carbon thermal reduction tower, high temperature separator, reheater, sulfur condenser, steam condenser, H2The S incinerator and the circulating fluidized bed carbon thermal reduction tower are both vertically arranged, H2The bottom of the S incinerator is provided with a mixed gas chamber H2The gas phase outlet at the bottom of the S incinerator is connected with the top inlet of the mixing gas chamber, the bottom outlet of the mixing gas chamber is connected with the bottom inlet of the carbon thermal reduction tower of the circulating fluidized bed, the top outlet of the carbon thermal reduction tower of the circulating fluidized bed is connected with the high-temperature separator, the gas phase outlet of the high-temperature separator is connected with the sulfur-containing gas inlet of the reheater, the sulfur-containing gas outlet of the reheater is connected with the sulfur condenser, the gas outlet of the sulfur condenser is connected with the exhaust gas inlet of the steam condenser, the exhaust gas outlet of the steam condenser is connected with the exhaust gas inlet of the reheater, the exhaust gas outlet of the reheater is connected with the exhaust gas pipeline, the exhaust gas pipeline is provided with a circulating gas pipeline, and the.
5. The apparatus of claim 4, wherein the exhaust line is provided with a conditioning gas line, and an outlet of the conditioning gas line is connected to a gas phase inlet on a side wall of the circulating fluidized bed carbothermic tower.
6. The device as claimed in claim 4, which comprises a waste gas incinerator, wherein the waste gas pipeline is provided with a conveying gas pipeline, and an outlet of the conveying gas pipeline is connected with a fuel inlet of the waste gas incinerator;
the bottom of the exhaust gas incinerator is provided with an air heat exchanger, a smoke outlet of the exhaust gas incinerator is connected with a smoke inlet of the air heat exchanger, and an air outlet of the air heat exchanger is respectively connected with an air inlet and an H of the exhaust gas incinerator2S, an air inlet of the incinerator;
the outlet of the circulating carbon-based reducing agent of the high-temperature separator is connected to the conveying gas pipeline.
7. The apparatus of claim 6, wherein the circulating carbon-based reducing agent outlet of the high temperature separator is connected to the carbon-based reducing agent inlet of the circulating fluidized bed carbothermic tower.
8. The apparatus as claimed in claim 7, wherein a venturi tube is provided at the bottom of the carbon thermal reduction column of the circulating fluidized bed, and H is provided2S, high-temperature gas incinerated by the incinerator enters the circulating fluidized bed carbon thermal reduction tower through the Venturi tube;
a reactor cooler is arranged between the reheater and the sulphur condenser.
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