CN113877553A - Regeneration process of activated carbon for blast furnace gas desulfurization - Google Patents
Regeneration process of activated carbon for blast furnace gas desulfurization Download PDFInfo
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- CN113877553A CN113877553A CN202111254963.0A CN202111254963A CN113877553A CN 113877553 A CN113877553 A CN 113877553A CN 202111254963 A CN202111254963 A CN 202111254963A CN 113877553 A CN113877553 A CN 113877553A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 175
- 238000011069 regeneration method Methods 0.000 title claims abstract description 68
- 230000008929 regeneration Effects 0.000 title claims abstract description 67
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 23
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 230000001172 regenerating effect Effects 0.000 claims abstract description 6
- 239000012530 fluid Substances 0.000 claims description 13
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 230000009967 tasteless effect Effects 0.000 abstract description 3
- 239000003895 organic fertilizer Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 61
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- 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
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention relates to a regeneration process of activated carbon for blast furnace gas desulfurization, belonging to the field of chemical industry and environmental protection and adopting supercritical CO2Regenerating the activated carbon in the same tower, stopping feeding blast furnace gas and turning on CO when the activated carbon in the adsorber needs to be regenerated2Storage tank, supercritical CO2Flowing into adsorber to be regenerated, diffusing into active carbon pore canal to dissolve sulfur elementary substance small particles therein, wherein supercritical CO2The flow velocity is 100-300 m3The regeneration time is 8-18 h, the temperature is 25-45 ℃, the pressure is 25-35 Mpa; the invention uses supercritical CO2As a solvent for regenerating activated carbon, CO2The chemical property of the water-soluble organic fertilizer is inactive,the regenerated activated carbon adsorbent is colorless, tasteless, nontoxic, good in safety, capable of avoiding secondary pollution, environment-friendly and pollution-free, the original structure of the activated carbon is not changed and damaged in the regeneration process, the carbon loss rate is negligible, and the adsorption performance after regeneration is close to that of a fresh adsorbent.
Description
Technical Field
The invention belongs to the fields of chemical industry and environmental protection, and relates to a regeneration process of activated carbon for blast furnace gas desulfurization.
Background
The blast furnace gas is a combustible gas byproduct in the blast furnace smelting process, is a gas fuel with low calorific value, and can be used as a self-used gas of metallurgical enterprises, such as coal gasHot rolled steel ingots, preheated ladles, etc., and can also be supplied for civil use. The blast furnace gas contains a small amount of organic sulfur and H2S, after the gas is burnt, organic sulfur and inorganic sulfur are converted into SO2Is discharged into the atmosphere along with the flue gas. In view of the fact that downstream users of blast furnace gas are numerous and dispersed, if terminal treatment equipment is adopted, the investment is large, the operation and management are difficult, and desulfurization byproducts are difficult to treat. Therefore, in recent years, technicians are always seeking a feasible technology for directly desulfurizing blast furnace gas to enhance the source treatment of atmospheric pollutants, namely, starting from the source treatment of the blast furnace gas and reducing SO of downstream users2The amount of discharge of (c). The low-concentration sulfide in the gas purified by the activated carbon adsorption method has the advantages of low operation temperature, simple process, good effect, low cost and the like, thereby having wide application in the field of chemical industry and environmental protection.
For the treatment after the desulfurization activated carbon is used, one method is to directly use the activated carbon as fuel to burn, SO as to generate heat, but SO is generated in the burning process2Not only pollutes the environment and corrodes the equipment, but also wastes resources and increases the cost. Therefore, from the viewpoint of environmental protection and economy, the regeneration and recycling of the catalyst are required, and the regeneration methods which are widely applied at present are thermal regeneration and solvent regeneration. The thermal regeneration is to introduce high-temperature steam to regenerate the desulfurization activated carbon, although the regeneration efficiency of the method is higher, the carbon loss rate is also higher, generally 5-10%, and the mechanical strength of the regenerated carbon is reduced, in addition, energy sources are required to be added for heating in the thermal regeneration process, so that the investment and the operation cost are higher; the solvent regeneration utilizes the phase equilibrium relationship among the active carbon, the solvent and the adsorbed substance, breaks the adsorption equilibrium by changing the conditions of temperature, pH value of the solvent and the like, and desorbs the adsorbed substance from the active carbon.
Disclosure of Invention
In view of the above, the present invention aims to provide a regeneration process of activated carbon for blast furnace gas desulfurization by using supercritical CO2As a solvent for regenerating activated carbon to realize activityRegeneration of charcoal, supercritical CO2Low cost and no pollution, and solves the problems of high cost, large pollution, incomplete activated carbon regeneration and the like in the conventional activated carbon regeneration.
In order to achieve the purpose, the invention provides the following technical scheme:
a process for regenerating the desulfurizing activated carbon used to regenerate blast furnace gas includes such steps as providing several adsorbers, adsorbing the hydrogen sulfide in blast furnace gas by activated carbon to become elemental sulfur, and supercritical CO adsorption2The adsorption and regeneration can be carried out in the same adsorber, and the adsorption and regeneration can be alternately carried out among different adsorbers through high-pressure valve control;
the regeneration process of the blast furnace gas desulfurization activated carbon comprises the following steps:
s1, desulfurization and adsorption: opening part of the adsorbers to directly feed the blast furnace gas subjected to COS hydrolysis into the adsorbers to enable the adsorbers to enter a desulfurization adsorption state, and performing desulfurization treatment on the blast furnace gas through activated carbon in the adsorbers;
the desulfurization reaction is as follows: 2H2S+O2→2S↓+2H2O；
S2, starting activated carbon regeneration: when the activated carbon in one adsorber needs to be regenerated, stopping feeding blast furnace gas, and turning on CO2Storage tank, supercritical CO2Flowing into an adsorber to be regenerated, diffusing into the inside of the active carbon pore canal to dissolve small sulfur particles therein, simultaneously opening the standby adsorber, feeding blast furnace gas into a desulfurization adsorption state to participate in a desulfurization treatment process, wherein supercritical CO2The flow velocity is 100-300 m3The regeneration time of the activated carbon is 8-18 h, the temperature is 25-45 ℃, the pressure is 25-35 Mpa;
s3, elemental sulfur separation: supercritical CO with dissolved elemental sulfur2Reducing the pressure through a pressure reducing valve, and flowing into a separator to separate out elemental sulfur;
S4.CO2and (3) recycling: separation ofLow pressure CO from the vessel2The fluid is compressed by a compressor and then enters CO2The storage tank is recycled;
s5, completing the regeneration of the activated carbon: step S2 is carried out by subjecting activated carbon to supercritical CO2After the regeneration of the activated carbon of the adsorber is finished under the washing, CO is closed2Storage tank stopping feeding of supercritical CO2After the regeneration of the activated carbon is finished, continuously feeding the blast furnace gas;
s6, circulating steps S1-S5.
Further, in step S3, the supercritical CO dissolved with elemental sulfur2The pressure is reduced to 10-15 Mpa through a pressure reducing valve, the temperature is heated to 50-65 ℃ through a first heat exchanger, and then the gas flows into a separator.
Further, in step S4, the CO compressed by the compressor2The fluid pressure is 25-35 Mpa, the temperature is cooled to 35-45 ℃ by the second heat exchanger, and then CO flows in2A storage tank.
The invention has the beneficial effects that:
1. the invention has simple process, can finish adsorption desulfurization and regeneration of the active carbon in one set of equipment, saves space and equipment investment, can regulate and control the regeneration process by changing temperature and pressure, and has simple operation.
2. The invention overcomes the technical prejudice in the field of blast furnace gas desulfurization activated carbon, and creatively selects supercritical CO2As a regeneration solvent, the critical temperature is only 31.26 ℃, the critical pressure is 72.9atm, the critical condition is easy to reach, the chemical property is inactive, the solvent is colorless, tasteless and nontoxic, the safety is good, the secondary pollution can be avoided, the separated sulfur simple substances can be collected and utilized in a centralized manner, the environment is protected, the pollution is avoided, the regeneration temperature is lower, the original structure of the activated carbon is not changed and damaged in the regeneration process, the carbon loss rate is negligible, and the adsorption performance after regeneration is close to that of a fresh adsorbent.
3. Supercritical CO2The price is cheap and easy to obtain, and the activated carbon can be recycled through simple process regulation and control, so that the regeneration cost of the activated carbon is greatly reduced.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
fig. 1 is a schematic flow chart of a process for regenerating activated carbon by desulfurization of blast furnace gas according to an embodiment of the present invention.
Reference numerals: 1-CO2A storage tank, 2-a first adsorber, 3-a second adsorber, 4-a pressure reducing valve, 5-a first heat exchanger, 6-a separator, 7-a compressor and 8-a second heat exchanger.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Wherein the showings are for the purpose of illustrating the invention only and not for the purpose of limiting the same, and in which there is shown by way of illustration only and not in the drawings in which there is no intention to limit the invention thereto; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "front", "rear", etc., based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not an indication or suggestion that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes, and are not to be construed as limiting the present invention, and the specific meaning of the terms may be understood by those skilled in the art according to specific situations.
Referring to fig. 1, it is a schematic flow diagram of a process for regenerating activated carbon for desulphurization of blast furnace gas, the whole desulphurization system has two sets of adsorbers, wherein the second adsorber 3 is for standby use, during the operation process, the blast furnace gas to be treated passes through the first adsorber 2, the hydrogen sulfide in the gas is adsorbed by the activated carbon and converted into elemental sulfur, when the activated carbon in the first adsorber 2 is saturated by adsorption, supercritical CO is used2The adsorption and regeneration can be carried out in the same adsorber, and the adsorption and regeneration can be alternately carried out among different adsorbers through high-pressure valve control;
the regeneration process of the blast furnace gas desulfurization activated carbon comprises the following steps:
s1, desulfurization and adsorption: opening a first air inlet valve of the first adsorber 2, directly feeding the blast furnace gas subjected to COS hydrolysis into the first adsorber 2, enabling the blast furnace gas to enter a desulfurization adsorption state, and performing desulfurization treatment on the blast furnace gas through activated carbon in the first adsorber 2;
the desulfurization reaction is as follows: 2H2S+O2→2S↓+2H2O
S2, starting activated carbon regeneration: when the activated carbon in the first adsorber 2 needs to be regenerated, the first air inlet valve of the first adsorber 2 is closed, and the second air inlet valve of the first adsorber 2 is opened, so that the supercritical CO is generated2From CO2The storage tank 1 flows into a first adsorber 2 to be regenerated by active carbon, diffuses into the pore canal of the active carbon, dissolves small elemental sulfur particles in the active carbon, and opens a first air inlet valve of a second adsorber 3 to enable the sulfur particles to enter a desorption deviceSulfur adsorption state, and participating in desulfurization treatment process, wherein supercritical CO is adopted2The flow velocity is 100-300 m3The regeneration time of the activated carbon is 8-18 h, the temperature is 25-45 ℃, the pressure is 25-35 Mpa;
s3, elemental sulfur separation: supercritical CO with dissolved elemental sulfur2Reducing the pressure through a pressure reducing valve 4, and flowing into a separator 6 to separate out elemental sulfur;
S4.CO2and (3) recycling: low pressure CO from separator 62The fluid is compressed by the compressor 7 and enters CO2The storage tank 1 is recycled;
s5, completing the regeneration of the activated carbon: step S2 is carried out by subjecting activated carbon to supercritical CO2After the regeneration of the activated carbon in the first adsorber 2 is completed under the flushing of (3), the second air inlet valve of the first adsorber 2 is closed, and the supercritical CO is generated2The gas does not flow into the first adsorber 2 any more, and after the regeneration of the activated carbon is finished, the first gas inlet valve of the first adsorber 2 is opened to continue feeding the blast furnace gas;
s6, circulating steps S1-S5.
Further, in step S3, the supercritical CO with elemental sulfur dissolved therein2The pressure is reduced to 10-15 Mpa through a pressure reducing valve 4, the temperature is heated to 50-65 ℃ through a first heat exchanger 5, and then the gas flows into a separator 6.
Further, in step S4, the high pressure CO compressed by the compressor 72The pressure is 25-35 Mpa, the temperature is cooled to 35-45 ℃ by the second heat exchanger 8, and then CO flows in2A storage tank.
Example 1
(1) The composition of a certain blast furnace gas is as follows:
| composition (I) | H2S | O2 | N2 | CO2 | H2O |
| Concentration of | 120ppm | 0.101％ | 80.169％ | 14.740％ | 4.978％ |
(2) Space velocity: 1000h-1
(3) Temperature: 40 deg.C
(4) Pressure: 0.166Mpa
Under the working conditions, the blast furnace gas after pretreatment and hydrolysis is directly sent into the first adsorber 2, the gas with the hydrogen sulfide content less than or equal to 10ppm is obtained at the blast furnace gas outlet of the first adsorber 2, and then the desulfurized gas enters a pressure reducing valve bank or a TRT and then enters a clean gas pipe network.
When the first adsorber 2 is saturated or nearly saturated, the supply of blast furnace gas is stopped, the activated carbon regeneration is prepared and the second adsorber 2 is activated as a spare adsorber, so that the operation is alternated and continuous treatment can be realized.
The active carbon regeneration steps are as follows:
s1, desulfurization and adsorption: opening a first air inlet valve of the first adsorber, directly feeding the blast furnace gas subjected to COS hydrolysis into the first adsorber to enable the blast furnace gas to enter a desulfurization adsorption state, and performing desulfurization treatment on the blast furnace gas through activated carbon in the first adsorber;
s2, starting activated carbon regeneration: when the activated carbon in the first adsorber needs to be regenerated, the first air inlet valve of the first adsorber is closed and the activated carbon is openedOpening the second air inlet valve of the first adsorber to ensure that the supercritical CO is generated2From CO2The storage tank 1 flows into a first adsorber to be regenerated of active carbon, diffuses into the pore canal of the active carbon, dissolves small elemental sulfur particles in the active carbon, and opens a first air inlet valve of a second adsorber to enable the second adsorber to enter a desulfurization adsorption state to participate in a desulfurization treatment process, wherein supercritical CO2Flow rate of 150m3The temperature is 30 ℃, the pressure is 35Mpa, and the regeneration time of the active carbon is 18 h;
s3, elemental sulfur separation: supercritical CO with dissolved elemental sulfur2Reducing the pressure to 15Mpa by a pressure reducing valve 4, and passing through a first heat exchanger 5, and supercritical CO2Heating the fluid to 55 ℃, then flowing into a separator 6 to separate elemental sulfur, wherein the decomposed elemental sulfur can be recycled;
S4.CO2and (3) recycling: low pressure CO from separator 62The fluid is compressed by the compressor 7, the pressure is increased to 35Mpa, and the fluid passes through the second heat exchanger 8 and is subjected to supercritical CO2Cooling the fluid to 35 deg.C, introducing CO2The storage tank 1 is recycled;
s5, completing the regeneration of the activated carbon: step S2 is carried out by subjecting activated carbon to supercritical CO2After the regeneration of the activated carbon in the first adsorber 2 is completed under the flushing of (3), the second air inlet valve of the first adsorber 2 is closed, and the supercritical CO is generated2The gas does not flow into the first adsorber 2 any more, after the regeneration of the activated carbon is finished, the first gas inlet valve of the first adsorber 2 is opened, the blast furnace gas is continuously fed, and the activated carbon regeneration is carried out on the second adsorber 3;
s6, circulating steps S1-S5.
Example 2
(1) The composition of a certain blast furnace gas is as follows:
| composition (I) | H2S | O2 | N2 | CO2 | H2O |
| Concentration of | 50ppm | 0.504％ | 79.773％ | 15.240％ | 4.478％ |
(2) Space velocity: 2000h-1
(3) Temperature: 40 deg.C
(4) Pressure: 0.183MPa
Under the working conditions, the blast furnace gas after pretreatment and hydrolysis is directly sent into the first adsorber 2, the gas with the hydrogen sulfide content less than or equal to 10ppm is obtained at the blast furnace gas outlet of the first adsorber 2, and then the desulfurized gas enters a pressure reducing valve bank or a TRT and then enters a clean gas pipe network.
When the first adsorber 2 is saturated or nearly saturated, the supply of blast furnace gas is stopped, the activated carbon regeneration is prepared and the second adsorber 2 is activated as a spare adsorber, so that the operation is alternated and continuous treatment can be realized.
The active carbon regeneration steps are as follows:
s1, desulfurization and adsorption: opening a first air inlet valve of the first adsorber, directly feeding the blast furnace gas subjected to COS hydrolysis into the first adsorber to enable the blast furnace gas to enter a desulfurization adsorption state, and performing desulfurization treatment on the blast furnace gas through activated carbon in the first adsorber;
s2, activated carbon is addedThe method comprises the following steps of (1) raw starting: when the activated carbon in the first adsorber needs to be regenerated, the first air inlet valve of the first adsorber is closed, and the second air inlet valve of the first adsorber is opened, so that the supercritical CO is generated2From CO2The storage tank 1 flows into a first adsorber to be regenerated of active carbon, diffuses into the pore canal of the active carbon, dissolves small elemental sulfur particles in the active carbon, and opens a first air inlet valve of a second adsorber to enable the second adsorber to enter a desulfurization adsorption state to participate in a desulfurization treatment process, wherein supercritical CO2Flow velocity of 200m3The temperature is 25 ℃, the pressure is 30Mpa, and the regeneration time is 12 hours;
s3, elemental sulfur separation: supercritical CO with dissolved elemental sulfur2Reducing the pressure to 12Mpa by a pressure reducing valve 4, and passing through a first heat exchanger 5, and supercritical CO2Heating the fluid to 50 ℃, then flowing into a separator 6 to separate elemental sulfur, wherein the decomposed elemental sulfur can be recycled;
S4.CO2and (3) recycling: low pressure CO from separator 62The fluid is compressed by the compressor 7, the pressure is increased to 30Mpa, and the fluid passes through the second heat exchanger 8 and the supercritical CO2Cooling the fluid to 40 deg.C, introducing CO2The storage tank 1 is recycled;
s5, completing the regeneration of the activated carbon: step S2 is carried out by subjecting activated carbon to supercritical CO2After the regeneration of the activated carbon in the first adsorber 2 is completed under the flushing of (3), the second air inlet valve of the first adsorber 2 is closed, and the supercritical CO is generated2The gas does not flow into the first adsorber 2 any more, after the regeneration of the activated carbon is finished, the first gas inlet valve of the first adsorber 2 is opened, the blast furnace gas is continuously fed, and the activated carbon regeneration is carried out on the second adsorber 3;
s6, circulating steps S1-S5.
The invention uses supercritical CO2As a regeneration solvent, the critical temperature is only 31.26 ℃, the critical pressure is 72.9atm, the critical condition is easy to reach, the chemical property is inactive, the solvent is colorless, tasteless and nontoxic, the safety is good, the secondary pollution can be avoided, the separated sulfur simple substances can be collected and utilized in a centralized manner, the environment is protected, the pollution is avoided, the regeneration temperature is lower, the original structure of the activated carbon is not changed and damaged in the regeneration process, the carbon loss rate is negligible, the absorption after regeneration is negligible, and the regeneration is carried outClose to fresh adsorbent in terms of adsorption performance and use of supercritical CO2Greatly reduces the cost of activated carbon regeneration.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (3)
1. A regeneration process of activated carbon for blast furnace gas desulfurization comprises the following steps of S1, desulfurization adsorption: directly feeding the blast furnace gas subjected to COS hydrolysis into an adsorber to enable the blast furnace gas to enter a desulfurization adsorption state, and performing desulfurization treatment on the blast furnace gas through activated carbon in the adsorber; the method is characterized by further comprising the following steps:
s2, starting activated carbon regeneration: when the activated carbon in the adsorber needs to be regenerated, stopping feeding blast furnace gas, and opening CO2Storage tank, supercritical CO2Flowing into adsorber to be regenerated, diffusing into active carbon pore canal to dissolve sulfur elementary substance small particles therein, wherein supercritical CO2The flow velocity is 100-300 m3The regeneration time of the activated carbon is 8-18 h, the temperature is 25-45 ℃, the pressure is 25-35 Mpa;
s3, elemental sulfur separation: supercritical CO with dissolved elemental sulfur2Reducing the pressure through a pressure reducing valve, and flowing into a separator to separate out elemental sulfur;
S4.CO2and (3) recycling: low pressure CO from the separator2The fluid is compressed by a compressor and then enters CO2The storage tank is recycled;
s5, completing the regeneration of the activated carbon: step S2 is carried out by subjecting activated carbon to supercritical CO2After the regeneration of the activated carbon of the adsorber is finished under the washing, CO is closed2Storage tank stopping feeding of supercritical CO2A fluid;
s6, circulating steps S1-S5.
2.The regeneration process of the blast furnace gas desulfurization activated carbon according to claim 1, characterized in that: in step S3, supercritical CO with elemental sulfur dissolved therein2The pressure is reduced to 10-15 MPa through a pressure reducing valve, the temperature is heated to 50-65 ℃ through a first heat exchanger, and then the gas flows into a separator.
3. The process for regenerating activated carbon for blast furnace gas desulfurization according to claim 2, characterized in that: in step S4, CO compressed by compressor2Increasing the pressure to 25-35 Mpa, cooling the temperature to 35-45 ℃ by a second heat exchanger, and then performing supercritical CO2Then inflow of CO2The storage tank is recycled.
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