CN114561232A - Blast furnace gas fine desulfurization system and method - Google Patents
Blast furnace gas fine desulfurization system and method Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 138
- 230000023556 desulfurization Effects 0.000 title claims abstract description 138
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000007789 gas Substances 0.000 claims abstract description 203
- 238000001179 sorption measurement Methods 0.000 claims abstract description 69
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 60
- 239000011593 sulfur Substances 0.000 claims abstract description 60
- 230000008929 regeneration Effects 0.000 claims abstract description 37
- 238000011069 regeneration method Methods 0.000 claims abstract description 37
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- 238000004064 recycling Methods 0.000 claims abstract description 18
- 238000003860 storage Methods 0.000 claims abstract description 17
- 239000003034 coal gas Substances 0.000 claims abstract description 15
- 239000002918 waste heat Substances 0.000 claims abstract description 10
- 239000002912 waste gas Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 66
- 239000007788 liquid Substances 0.000 claims description 43
- 238000004458 analytical method Methods 0.000 claims description 42
- 238000002485 combustion reaction Methods 0.000 claims description 36
- 239000003546 flue gas Substances 0.000 claims description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 33
- 238000009833 condensation Methods 0.000 claims description 30
- 230000005494 condensation Effects 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000003795 desorption Methods 0.000 claims description 24
- 230000001172 regenerating effect Effects 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 238000001514 detection method Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 238000004868 gas analysis Methods 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000011010 flushing procedure Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 150000003568 thioethers Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 31
- 239000000047 product Substances 0.000 abstract description 17
- 239000006227 byproduct Substances 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000003245 coal Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 description 10
- 125000001741 organic sulfur group Chemical group 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 230000003009 desulfurizing effect Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000011268 retreatment Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 241000607479 Yersinia pestis Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
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- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- 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
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0447—Separation of the obtained sulfur
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/22—Methods of steam generation characterised by form of heating method using combustion under pressure substantially exceeding atmospheric pressure
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28B—STEAM OR VAPOUR CONDENSERS
- F28B7/00—Combinations of two or more condensers, e.g. provision of reserve condenser
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- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Thermal Sciences (AREA)
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Abstract
The invention discloses a blast furnace gas fine desulfurization system and a blast furnace gas fine desulfurization method, and belongs to the technical field of environmental protection. The system comprises a coal gas adsorption desulfurization unit, a waste gas waste heat recycling unit, a desulfurization adsorbent regeneration unit, a desorbed gas collection and storage unit, a flow control unit, a desorbed gas treatment unit and a resource product collection unit which are sequentially connected, and by organically combining an adsorption-method fine desulfurization process and a Claus process, a desulfurization byproduct which is difficult to utilize is converted into a resource product which can be directly utilized, so that the harmless and resource treatment of the blast furnace gas fine desulfurization byproduct is realized. Meanwhile, the organic combination and the reasonable configuration in the system can greatly reduce the operation cost of the system and the influence on the stable production of the blast furnace, and are beneficial to improving the use ratio of the blast furnace to high-sulfur ores and high-sulfur coal and reducing the coal blending and ore blending cost of the blast furnace.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a blast furnace gas fine desulfurization system and a blast furnace gas fine desulfurization method.
Background
At present, blast furnace gas fine desulfurization modification projects of various domestic iron and steel enterprises are in planning or implementation stages, and there are operating projects in the industry, aiming at the current main flow process of blast furnace gas fine desulfurization, which is to perform fine desulfurization on blast furnace gas by adopting a hydrolysis conversion retreatment mode or a direct adsorption desulfurization retreatment mode. The two technical routes can remove the sulfide in the blast furnace gas. Because the blast furnace gas contains a certain amount of COS, organic sulfur and H2S, the hydrolysis method is to convert organic sulfur in the coal gas into H2And (S) removing hydrogen sulfide. The adsorption method is to adsorb and regenerate sulfide in coal gas through adsorbing material and to convert organic sulfur into H during regeneration and desorption2And S. Thus, the principle of both hydrolysis and desorption is to convert organic sulfur into H2And processing after S.
Although the two process routes can remove the sulfide in the coal gas, certain problems still exist in the treatment of the desulfurization by-products, such as a hydrolysis conversion retreatment process in which organic sulfur in the coal gas is hydrolyzed and converted into H2After S, hydrogen sulfide is generally fixed in a desulfurizing agent by a dry or wet process to remove H2The waste desulfurizing agent (liquid) produced by S needs further treatment. The high-sulfur waste gas generated by adopting the adsorption desulfurization retreatment mode is also treated by adopting the same mode. The two existing blast furnace gas fine desulfurization processes have the same problem that the desulfurization by-product is not generatedThe utilization of the resource is also a pollutant transfer behavior in a certain form.
Through retrieval, patents related to blast furnace gas fine desulfurization have been published, for example, chinese patent publication No. 213141938U discloses a fine desulfurization system, and in the patent, a desulfurizing agent regeneration tower is provided, so that a desulfurization waste liquid generated by a reaction in a desulfurization absorption tower can be reacted again to generate a desulfurizing agent, and the desulfurizing agent is circulated and returned to the desulfurization absorption tower for recycling, but the problem of full utilization of resources with respect to a desulfurization byproduct still cannot be realized. For another example, chinese patent publication No. 212800255U discloses a blast furnace gas adsorption desulfurization apparatus, which aims to solve the problems of easy catalyst failure, high input cost and unstable sulfide removal effect when the blast furnace gas is purified by using the current catalytic hydrolysis or catalytic hydrogenolysis organic sulfur removal process route, but still has the same disadvantages as the above-mentioned patents in the resource treatment of desulfurization by-products. For another example, chinese patent publication nos. 210544386U and 113072983a are designed mainly for the desulfurization process of blast furnace gas, and there is no clear description about how to treat the desulfurized by-product after the fine desulfurization.
In summary, the search of the prior art for the desulfurization treatment of blast furnace gas basically focuses on the fine desulfurization process of blast furnace gas, and the resource utilization of the desulfurization by-products is rarely involved. Therefore, an environment-friendly blast furnace gas fine desulfurization system is urgently needed, so that harmless and recycling treatment of blast furnace gas fine desulfurization byproducts is realized.
Disclosure of Invention
1. Problems to be solved
The invention mainly aims to solve the problem that the blast furnace gas fine desulfurization process cannot be fully recycled in the desulfurization process, and develops a novel blast furnace gas fine desulfurization system and a novel method for recycling desulfurization products.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the blast furnace gas fine desulfurization system provided by the invention comprises a gas adsorption desulfurization unit, a desulfurization adsorbent regeneration unit, a desorbed gas collection and storage unit, a flow control unit, a desorbed gas treatment unit, a resource product collection unit and a waste gas waste heat recycling unit. The gas adsorption desulfurization unit at least comprises two desulfurization adsorption towers which are connected in parallel, and each desulfurization adsorption tower is respectively connected with the blast furnace gas pipeline through an independent connecting pipeline and is used for adsorbing and removing sulfides in the blast furnace gas and providing clean gas for downstream users.
The desulfurization adsorbent regeneration unit is used for regeneration and cyclic utilization of the adsorbent, so that the service life of the system is prolonged, and the replacement period of the adsorbent is shortened. Meanwhile, the desorption gas is produced, and the regeneration desorption gas outlet is connected with the desorption gas collecting and storing unit through a pipeline, so that the subsequent resource utilization of the components in the desorption gas is facilitated.
And the analysis gas collecting and storing unit is mainly used for storing the regenerated analysis gas desulfurized by the adsorption method so as to supply the regenerated analysis gas to the subsequent analysis gas treatment unit.
The flow control unit is used for controlling the flow distribution and the reaction rate of the analytic gas treatment unit;
the analysis gas treatment unit is used for treating a reaction device for analyzing gas and recycling the analysis gas;
the resource product collecting unit is used for collecting and processing resource products and converting the resource products into available resources;
the waste gas waste heat recycling unit is used for recycling waste heat in high-temperature flue gas, and is mainly used for heating the feed gas.
As a further improvement of the invention, the analysis gas treatment unit consists of a plurality of desulfurization adsorption towers, all the desulfurization adsorption towers are designed in parallel and have a standby design, fine desulfurization adsorption materials are filled in the towers, and each desulfurization adsorption tower has the independent working capacity. The desulfurization adsorption tower is designed in a circular shape, specific design parameters are formulated according to the amount of blast furnace gas to be treated, and certain margin is provided. Each desulfurization adsorption tower is provided with a blast furnace gas inlet, a purified gas outlet, a back-blowing regeneration gas inlet and an adsorbent filling discharge port, and the connecting pipelines at the material inlet and the material outlet are respectively provided with a control valve, so that the pipelines can be opened and closed independently.
As a further improvement of the invention, the desulfurization adsorbent regeneration unit consists of a control valve, a regeneration heat exchanger and a steam boiler, wherein the gas inlet of the regeneration heat exchanger is respectively connected with a blast furnace gas pipeline and the steam boiler through connecting pipelines, and the gas outlet of the regeneration heat exchanger is connected with the back-blowing regeneration gas inlet of the desulfurization adsorption tower through a connecting pipeline. The regenerative heat exchanger adopts blast furnace gas and steam for heat exchange, the high-temperature gas after heat exchange enters the adsorption desulfurization tower through a pipeline to sweep out sulfide in the adsorption material, and the high-temperature gas is conveyed to the desorption gas collection and storage unit through the pipeline. Furthermore, it is more preferred that the present invention combines a steam boiler with the combustion furnace of the Claus system, thereby facilitating the steam boiler to utilize the heat released by the combustion in the subsequent Claus process to generate steam.
As a further improvement of the invention, the analysis gas collecting and storing unit consists of a pressure pump and a gas holder, wherein one end of the pressure pump is connected with an analysis gas outlet of the desulfurization adsorption tower through a pipeline, the pipeline is provided with a control valve, the other end of the pressure pump is connected with the gas holder through a pipeline, the gas holder is connected with a flow controller of the flow control unit through a pipeline, and the pipeline is also provided with a control valve. The model of the booster pump and the specific parameters of the gas holder are determined according to the regeneration gas quantity of the desulfurization system, the selection of the booster pump needs to have a margin of 2-3 kPa, and the design of the booster pump is provided with a standby design, so that all the analysis gas generated by the gas fine desulfurization regeneration system can be conveyed into the gas holder without being discharged outside. The gas holder in the unit mainly has two functions, namely, the function of storing the analysis gas and the function of ensuring the stability of the pressure of the analysis gas in the subsequent treatment process. These two points are parameters that are of paramount importance to the parsing unit. Because the fine desulfurization process is continuous, and the regeneration process of the adsorbent is periodic, the generation of the analysis gas is not necessarily continuous, and the pressure and the flow can not be effectively controlled, but the pressure and the flow can be conveniently controlled after the analysis gas collecting and storing unit is added, so that the method plays an extremely important role in the stable operation of a subsequent analysis gas treatment unit. Preferably, the booster pump and the gas holder are designed according to a gas facility, and the size and the capacity of the gas holder are required to ensure that the normal production operation of a subsequent analysis gas treatment unit in the gas adsorption and desulfurization unit in a certain period of maintenance process is kept under the condition that no analysis gas enters the gas holder when the front-stage gas adsorption and desulfurization unit is maintained. Meanwhile, when the analysis gas treatment unit is overhauled, the analysis gas generated in the overhauling period can be ensured to completely enter the gas cabinet in a certain period and is not discharged outside.
As a further improvement of the present invention, the flow control unit adopts a flow controller, an air inlet of the flow controller is respectively connected with the gas holder and the air conveying pipeline, and an air outlet of the flow controller is connected with the analysis gas processing unit, more precisely, the flow controller is directly connected with the combustion furnace on one hand, and is connected with the combustion furnace through the second heat exchanger on the other hand. The unit is mainly divided into a control valve and a flow control loop, and the controlled parameter is flow, because the subsequent resourceful reaction of the analysis gas utilizes H contained in the analysis gas2S reacts with oxygen in the air, and different products are generated by utilizing different flow rates.
The above-mentioned analytic gas processing unit mainly comprises burning furnace, Claus reactor and condensation separator triplex, and is specific, fires burning furnace and links to each other through first heat exchanger and Claus reactor, and first heat exchanger passes through the pipeline and links to each other with first condensation separator, and the gas outlet of first condensation separator passes through the pipeline and links to each other with first heat exchanger, and the liquid sulfur discharge gate of first condensation separator links to each other with the liquid sulfur collecting vat. When the desorption gas is introduced into a combustion furnace for combustion, the main reactions generated in the desorption gas are as follows:
the main function of the combustion furnace is to remove a part of H in the decomposed gas2Conversion of S to SO2Is the next step H2Conversion of S to elemental sulfur provides SO for reaction2And simultaneously generating high-temperature flue gas, wherein the high-temperature flue gas passes through a heat exchanger and a condensation separator to convert gas-phase sulfur generated in the combustion process into liquid phase. And (4) after separation, the flue gas enters a Claus reactor for next catalytic reaction after heat exchange and temperature rise. The waste gas after condensation heat exchange is further catalytically converted in a Claus reactor to ensure H in the flue gas2S and SO2Fully reacting, wherein the reaction is as follows:
the Claus reactor is filled with a nickel-based catalyst, and the front part and the rear part of a catalyst bed layer are provided with inert balls to prevent flame from directly burning the catalyst. The gas-state sulfur produced by the reaction is converted into a liquid phase in a condensation separator through the heat exchanger by the flue gas after the reaction. It should be noted that the size of the furnace, the capacity of the Claus reactor and the capacity of the condensation separator are designed according to the capacity of the stripping gas, and a certain margin is required in the design process to ensure sufficient capacity support in the subsequent capacity of the pulling plant. Furthermore, it is preferred that the combustion furnace and the Claus reactor should be equipped with atmosphere measuring means, the measuring parameter being at least H2S、O2、SO2Three, but not limited to three, the detected parameters should be fed back to the flow control system in real time, and the flow control system adjusts the flow rate according to the detection result of the atmosphere so as to achieve the optimal reaction rate.
As a further improvement of the invention, the resource product collection unit mainly comprises a liquid sulfur collection tank, a solidification device and a sulfur storage bin, wherein the liquid sulfur collection tank is used for collecting and storing liquid sulfur separated by each stage of condensation separator, the liquid sulfur collection tank is sealed to prevent various chemical components in air from polluting the liquid sulfur, so that the quality of the liquid sulfur is influenced, the storage capacity of the liquid sulfur collection tank is designed according to the reaction rate of a production line, and 20% of allowance is provided to prevent the liquid sulfur from being incapable of being stored due to emergency. The curing device is mainly used for converting liquid sulfur into solid sulfur, the sulfur has extremely high economic value, can be used for industrial production and pest control, disinfection and sterilization and the like, and the sulfur generated by the curing device is sent to a sulfur storage bin for storage (the liquid sulfur can also be directly sold as a product, and the curing device is omitted). The purity of the sulfur produced by the process can reach more than 99 percent, and a plurality of Claus reactors can be added, and two adjacent Claus reactors are connected in series, so that the purity of the product can be further improved.
The waste gas waste heat recycling unit mainly comprises two heat exchangers, wherein the first heat exchanger (namely the first heat exchanger) exchanges heat between high-temperature flue gas (900-1200 ℃) combusted by a combustion furnace and low-temperature flue gas subjected to condensation separation to raise the temperature (200-400 ℃), the raised flue gas is sent to a Claus reactor to perform catalytic reaction, the temperature of the flue gas is raised after heat exchange, a reheating furnace is not needed for heat supplement, and the energy consumption is reduced; the second heat exchanger (namely the second heat exchanger) exchanges heat with air entering the combustion furnace by utilizing the flue gas reacted from the Claus reactor, preheats the air and raises the temperature, and can effectively reduce the energy consumption of the combustion furnace.
Secondly, the invention also provides a blast furnace gas fine desulfurization method, wherein the blast furnace gas is introduced into a desulfurization adsorption tower, sulfides in the gas are removed due to the adsorption desulfurization effect of the desulfurization adsorption tower, and the removed clean gas (namely purified gas) is conveyed to a downstream user unit for utilization. When a certain desulfurization adsorption tower is about to reach a saturated state, the desulfurization adsorption tower is stopped to be regenerated, the standby desulfurization adsorption tower is put into use, other desulfurization adsorption towers normally operate in the regeneration process, high-temperature coal gas is used for desorption in the regeneration process, and after the fine desulfurization system generates the desorption gas through regeneration and desorption, the booster pump is opened to collect the desorption gas into the gas holder. When gas in the gas holderAfter the capacity reaches the production requirement, the flow control unit gives out corresponding air flow and gas analysis flow, and the air flow and the gas analysis flow are sent into the combustion furnace for combustion, the heat generated during combustion is used for heating a steam boiler to generate high-quality steam, wherein, a part of steam is conveyed to a regenerative heat exchanger to exchange heat with coal gas, the rest steam is conveyed to a pipe network, the internal atmosphere change is monitored in real time in the combustion process, the atmosphere change parameters are fed back to a flow control unit in real time to form feedback control, the combusted flue gas passes through the heat exchanger and a condensation separator, and (3) separating the generated gas-phase sulfur, feeding the separated liquid sulfur into a liquid sulfur collecting tank through a pipeline for storage, carrying out heat exchange between low-temperature flue gas and high-temperature flue gas to 200-400 ℃ (the actual temperature determines the optimal process temperature according to actual production), and then feeding the flue gas into a Claus reactor for catalytic reaction, wherein H is left in the combustion flue gas.2S and SO2Carry out the abundant reaction, the flue gas obtains liquid sulphur behind heat exchanger (hot flue gas preheats combustion furnace air), the condensation separator after the reaction, this part liquid sulphur gets into the liquid sulphur collecting vat equally and stores, when liquid sulphur reaches a certain amount in the liquid sulphur collecting vat, carry the liquid sulphur to the solidification ware and solidify, turn into solid-state with liquid sulphur, can obtain high-purity sulphur, the sulphur that produces through the solidification ware is carried to sulphur warehouse again and is stored, and the whole flow is ended so far. Because the resource process of the analysis gas is continuous, high-quality sulfur can be continuously generated. Therefore, the process has a very high economic value.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through organically combining the Claus process with the coal gas fine desulfurization system, the desulfurization byproducts which are generated in the blast furnace coal gas fine desulfurization project and are difficult to utilize can be converted into resource products which can be directly utilized, so that the harmless and resource treatment of the blast furnace coal gas fine desulfurization byproducts is realized, the use ratio of a blast furnace to high-sulfur ores and high-sulfur coal is favorably improved, the coal blending and ore blending cost of the blast furnace is reduced, and the blast furnace coal gas fine desulfurization system and the method for recycling the desulfurization products are formed. The process route is convenient and feasible, meets the requirements of harmlessness and resource utilization, and particularly can directly convey the blast furnace gas fine desulfurization and decomposition gas through a process pipeline if a Claus furnace (namely a Claus reactor) is built in a coking area in a steel coking combined enterprise, thereby greatly saving investment and operation cost.
Meanwhile, according to the system and the production method, on one hand, the Claus process is adopted, so that sulfides in the analysis gas can be further converted into sulfur products with high added values, no waste is produced in the whole treatment process, and the resource requirement is completely met. On the other hand, the fine desulfurization system designed by the invention can not influence the blast furnace during damping down or maintenance of the fine desulfurization unit, ensures stable production of the blast furnace and stable operation of the fine desulfurization unit, and reduces the interference between the operation of the blast furnace and the operation of the fine desulfurization unit to the minimum. The blast furnace gas fine desulfurization unit also considers the efficient utilization of waste heat, ensures the stable operation of the whole system, and can generate abundant steam for power generation, heating and the like, thereby effectively reducing the operation cost of the system and having high application value.
Drawings
FIG. 1 is a schematic view of the overall structure of a blast furnace gas fine desulfurization system according to the present invention;
in the figure:
1. a control valve; 2. a regenerative heat exchanger; 3. a desulfurization adsorption tower; 4. a pressure pump; 5. a gas holder; 6. a flow controller; 7. a combustion furnace; 8. a steam boiler; 9. a first heat exchanger; 10. a first condensate separator; 11. a Claus reactor; 12. a second heat exchanger; 13. a second condensate separator; 14. a liquid sulfur collecting tank; 15. a curing device; 16. a sulfur storage bin; 17. and (4) a chimney.
Detailed Description
The invention is further described with reference to specific examples.
Example 1
As shown in fig. 1, when the blast furnace gas fine desulfurization system for recycling desulfurization products is put into use, the specific operation steps are as follows:
a) before the coal gas adsorption desulfurization unit operates, the control valve 1 is closed, meanwhile, the regeneration gas inlet and outlet valve (namely the control valve 1 at the back flushing regeneration gas inlet and the analysis gas outlet) on the desulfurization adsorption tower 3 to be operated and the control valve 1 at the adsorbent filling outlet are closed, the coal gas inlet and outlet valve is opened, and the valve on the standby desulfurization adsorption tower is completely closed.
b) After determining that the earlier-stage work is ready, introducing the blast furnace gas into a fine desulfurization system (namely, the gas adsorption desulfurization unit of the invention) to perform adsorption fine desulfurization, opening a regeneration system (namely, the desulfurization adsorbent regeneration unit of the invention) when the adsorbent in the desulfurization adsorption tower 3 reaches a certain saturation state, switching in the standby desulfurization adsorption tower 3 for use before the regeneration starts, and switching off the desulfurization adsorption tower 3 to be regenerated (namely, the last desulfurization adsorption tower 3 in the saturation state) after opening a gas inlet and outlet valve on the standby desulfurization adsorption tower 3.
c) When the desulfurization adsorption tower 3 is regenerated, a valve for back flushing the regenerated gas is opened, meanwhile, a control valve 1 at the air inlet of the regenerative heat exchanger 2 is opened, a part of blast furnace gas is introduced into the regenerative heat exchanger 2, the blast furnace gas exchanges heat with steam generated by a steam boiler 8 in the regenerative heat exchanger 2, the heat exchanged gas enters the desulfurization adsorption tower 3 to be regenerated, and the regenerated gas can be generated.
d) When the blast furnace gas adsorption method fine desulfurization adsorbent is regenerated to generate the desorption gas, the booster pump 4 is opened to pressurize the desorption gas conveyed from the desulfurization adsorbent regeneration unit and send the desorption gas to the gas holder 5 for storage, because the regeneration is a periodic process, and the regeneration period and the desorption gas amount generated by each regeneration are determined by the design amount of the fine desulfurization device and the actual desorption gas amount. Therefore, when the flow rate of the analysis gas generated by the fine desulfurization regeneration device is unstable and discontinuous, the problem can be solved by feeding the analysis gas to the gas holder 5. When the subsequent analysis gas is subjected to resource treatment, the feed gas is required to have stable pressure and flow, and 5 is used as a transfer, so that the problem can be effectively solved.
e) When the desorption gas in the gas holder 5 reaches a certain amount, the gas holder 6 is started, the combustion furnace 7 is ignited, supporting equipment such as a Claus reactor 11 is started, a control valve of the flow controller 6 is opened, the desorption gas and air in the gas holder 5 are introduced into the combustion furnace 7 according to a certain proportion and a proper flow rate for reaction (the reaction temperature is 900-1200 ℃), heat generated by combustion is used for heating a steam boiler 8 to generate high-quality steam, one part of steam is used for heat exchange of the regenerative heat exchanger 2, and the other part of steam is conveyed to the outside of the system for utilization.
f) The high-temperature flue gas generated by the reaction in the combustion furnace 7 firstly passes through the first heat exchanger 9 for energy exchange, and after the temperature is reduced, the flue gas is conveyed to the first condensation separator 10 by a pipeline for separation.
g) The flue gas after heat exchange by the first heat exchanger 9 is separated in the first condensation separator 10, and the separated low-temperature flue gas after condensation and part of liquid sulfur are generated, the part of liquid sulfur is formed by reducing the temperature of gas-phase sulfur generated by reaction in the combustion furnace 7 and changing the gas phase into a liquid phase, the separated liquid sulfur is conveyed to a liquid sulfur collecting tank 14 through a pipeline, and the liquid sulfur collecting tank 14 is responsible for collecting and storing the liquid sulfur generated by condensation after conversion at each stage in the system.
h) Returning the low-temperature flue gas separated in the first condensation separator 10 to the first heat exchanger 9, exchanging heat with the high-temperature flue gas, increasing the temperature to 200-400 ℃, and then entering the Claus reactor 11 for catalytic reaction, wherein the reaction in the Claus reactor 11 is to carry out H in the flue gas2S and SO2The reaction is converted into elemental sulfur, the flue gas after the reaction is introduced into a second heat exchanger 12 to exchange heat with cold air introduced into the combustion furnace 7 to heat up, the energy consumption of the combustion furnace 7 can be reduced by preheating air, the flue gas after the heat exchange is introduced into a second condensation separator 13, the second condensation separator 13 and the first condensation separator 10 have the same working principle, and after sulfur in the flue gas is separated out, the flue gas is conveyed to a liquid sulfur collecting tank 14 through a pipeline to be stored. The separated flue gas is introduced into a chimney 17 for emission, and an emission detection system is arranged at an emission outlet of the chimney 17 for monitoring and recording emission data in real time.
i) When the total amount of the liquid sulfur stored in the liquid sulfur collecting tank 14 reaches a certain degree, the curing device 15 is started, the liquid sulfur in the liquid sulfur collecting tank 14 is conveyed to the curing device 15 through a pipeline for curing, after the liquid sulfur is cured, the liquid sulfur is converted into high-quality elemental sulfur (sulfur), and the sulfur generated by the curing device 15 is conveyed to the sulfur storage bin 16 for storage.
The system and the method can convert the desulphurization by-product which is generated in the operation of the blast furnace gas fine desulphurization system and is difficult to utilize into a resource product which can be directly utilized, realize the harmless and resource treatment of the blast furnace gas fine desulphurization by-product, are beneficial to improving the use ratio of the blast furnace to the high-sulfur ore and the high-sulfur coal and reduce the coal blending and blending cost of the blast furnace. Meanwhile, the sulfur compounds in the analysis gas can be further converted into sulfur products with high added values by adopting a Claus process. No waste is produced in the whole treatment process, and the resource requirement is completely met.
Claims (10)
1. A blast furnace gas fine desulfurization system is characterized in that: including coal gas adsorption desulfurization unit and consecutive desulfurization adsorbent regeneration unit, analytic gas collection storage unit, flow control unit, analytic gas processing unit and resource product collection unit, wherein:
the gas adsorption desulfurization unit at least comprises two desulfurization adsorption towers (3) which are connected in parallel, each desulfurization adsorption tower (3) is respectively connected with a blast furnace gas pipeline through an independent connecting pipeline, and a fine desulfurization adsorption material is filled in the desulfurization adsorption towers and is used for adsorbing and removing sulfides in the blast furnace gas; the desulfurization adsorbent regeneration unit is used for regenerating and recycling the adsorbent and generating the analytic gas, and an analytic gas outlet is connected with the analytic gas collection and storage unit through a pipeline;
the flow control unit is used for controlling the flow distribution and the reaction rate of the analysis gas treatment unit, and the analysis gas treatment unit comprises a Claus reactor (11) for catalyzing the analysis gas to perform resource reaction; the resource product collection unit is used for collecting the gas analysis resource product.
2. The blast furnace gas fine desulfurization system according to claim 1, characterized in that: each desulfurization adsorption tower (3) is provided with a blast furnace gas inlet, a purified gas outlet, a back-blowing regeneration gas inlet, a desorption gas outlet and an adsorbent filling discharge hole, and the connecting pipelines at the gas inlets and the gas outlets of the materials are respectively provided with a control valve (1).
3. The blast furnace gas fine desulfurization system according to claim 1, characterized in that: the desulfurization adsorbent regeneration unit comprises a regenerative heat exchanger (2), a control valve (1) and a steam boiler (8), wherein the air inlet of the regenerative heat exchanger (2) is respectively connected with a blast furnace gas pipeline and the steam boiler (8) through connecting pipelines, the air outlet of the regenerative heat exchanger (2) is connected with the back-blowing regeneration gas inlet of the desulfurization adsorption tower (3) through a connecting pipeline, and the connecting pipelines at the air inlet and the air outlet of the regenerative heat exchanger (2) are respectively provided with the control valve (1); the steam boiler (8) is combined with a combustion furnace (7) of the analysis gas treatment unit.
4. The blast furnace gas fine desulfurization system according to claim 1, characterized in that: the analysis gas collecting and storing unit comprises a pressure pump (4) and a gas holder (5), one end of the pressure pump (4) is connected with an analysis gas outlet of the desulfurization adsorption tower (3) through a pipeline, a control valve (1) is arranged on the pipeline, and the other end of the pressure pump (4) is connected with the gas holder (5) through a pipeline; the gas holder (5) is connected with a flow controller (6) of the flow control unit through a pipeline, and the pipeline is also provided with a control valve (1); and after the air inlet of the flow controller (6) is connected with the air conveying pipeline, the air outlet of the flow controller is connected with the analysis gas processing unit.
5. The blast furnace gas fine desulfurization system according to any one of claims 1 to 4, characterized in that: the system also comprises a waste gas waste heat recycling unit, wherein the waste gas waste heat recycling unit comprises a first heat exchanger (9) and a second heat exchanger (12) and is used for recycling the waste heat of the high-temperature flue gas in the whole system; the gas analysis treatment unit comprises a Claus reactor (11), a combustion furnace (7) and a condensation separator, wherein a gas outlet of a flow controller (6) is connected with the combustion furnace (7) through a pipeline, the combustion furnace (7) is connected with a gas inlet of the Claus reactor (11) through a first heat exchanger (9), a gas outlet of the Claus reactor (11) is connected with a second condensation separator (13) through a second heat exchanger (12), and the second condensation separator (13) is respectively connected with a resource product collection unit and a chimney (17) through pipelines.
6. The blast furnace gas fine desulfurization system according to claim 5, characterized in that: the flow controller (6) is also connected with the combustion furnace (7) through a second heat exchanger (12); the first heat exchanger (9) is also connected with an air inlet of a first condensation separator (10) through a pipeline, an air outlet of the first condensation separator (10) is connected with the first heat exchanger (9) through a pipeline, and a discharge hole of the first condensation separator (10) is respectively connected with a liquid sulfur collecting tank (14) through a pipeline; the resource product collecting unit comprises a liquid sulfur collecting tank (14), and a feed inlet of the liquid sulfur collecting tank (14) is connected with the second condensation separator (13) through a pipeline.
7. The blast furnace gas fine desulfurization system according to claim 5, characterized in that: the Claus reactor (11) is filled with a catalyst, the front part and the rear part of a catalyst bed layer are respectively provided with an inert ball, the Claus reactor (11) and the combustion furnace (7) are respectively provided with an atmosphere detection device, the atmosphere detection devices are respectively and electrically connected with the flow control unit, and parameters detected by the atmosphere detection devices at least comprise H2S、O2、SO2The size of the flow rate.
8. The blast furnace gas fine desulfurization system according to claim 5, characterized in that: the Claus reactors (11) are arranged as multistage Claus reactors, and two adjacent Claus reactors (11) are connected in series; the liquid sulfur collecting tank (14) is also connected with a sulfur storage bin (16) through a solidification device (15).
9. A blast furnace gas fine desulfurization method is characterized in that: the fine desulfurization of blast furnace gas using the system according to any one of claims 1 to 8, comprising the steps of:
step one, early preparation work is carried out, and an operating desulfurization adsorption tower (3) is determined;
step two, operating a gas adsorption desulfurization unit, introducing blast furnace gas into a desulfurization adsorption tower (3) for adsorption, and opening a standby desulfurization adsorption tower (3) for adsorption after adsorption saturation;
when the standby desulfurization adsorption tower (3) is used for adsorption, starting a desulfurization adsorbent regeneration unit to work, carrying out heat exchange on part of blast furnace gas and part of steam generated by a boiler through a regeneration heat exchanger (2), then carrying out back flushing on the blast furnace gas and the part of steam to the desulfurization adsorption tower (3), and introducing generated desorption gas into a desorption gas collection and storage unit for treatment;
step four, a booster pump (4) of the analysis gas collecting and storing unit is used for carrying out pressurization treatment on the collected analysis gas and conveying the analysis gas into a gas holder (5) for storage so as to stabilize the pressure and flow of the analysis gas for subsequent treatment of the analysis gas;
and step five, starting the flow control unit to distribute the proportion and the flow of the analytic gas and the air, then conveying the analytic gas to the analytic gas treatment unit for recycling treatment, and conveying the generated liquid sulfur to a recycling product collection unit for collection.
10. The blast furnace gas fine desulfurization method according to claim 9, characterized in that:
in the first step, after the operation of the desulfurization adsorption tower (3) is determined, the early preparation work is as follows: closing control valves (1) at a back-blowing regeneration gas inlet, a desorption gas outlet and an adsorbent filling outlet on the desulfurization adsorption tower (3), opening a coal gas inlet and outlet valve, and closing all the control valves (1) on the standby desulfurization adsorption tower (3);
in the second step, after the standby desulfurization adsorption tower (3) is saturated in adsorption, the next standby tower is opened to work, and meanwhile, the standby desulfurization adsorption tower (3) saturated in adsorption repeats the operations from the second step to the fourth step;
in the fifth step, the analysis gas and the air are conveyed to enter a combustion furnace (7) for reaction, the heat of combustion is used for heating a steam boiler (8) to generate steam, one part of steam is used for heat exchange of a regenerative heat exchanger (2), and the other part of steam is conveyed to the outside of the system for utilization; high-temperature flue gas generated by combustion in the combustion furnace (7) is subjected to heat exchange by a first heat exchanger (9) of the waste gas waste heat recycling unit, and then enters a condensation separator to separate liquid sulfur; meanwhile, the low-temperature flue gas in the condensation separator returns to the first heat exchanger (9) to be heated and then enters the Claus reactor (11) to be subjected to catalytic reaction, the flue gas after reaction enters the second heat exchanger (12) to be subjected to heat exchange and then enters the condensation separator to be separated, and the separated flue gas is led to the chimney (17).
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