CN113908797A - Adsorbent for blast furnace gas desulfurization and heavy metal capture, preparation and application thereof - Google Patents
Adsorbent for blast furnace gas desulfurization and heavy metal capture, preparation and application thereof Download PDFInfo
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- CN113908797A CN113908797A CN202111259191.XA CN202111259191A CN113908797A CN 113908797 A CN113908797 A CN 113908797A CN 202111259191 A CN202111259191 A CN 202111259191A CN 113908797 A CN113908797 A CN 113908797A
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- heavy metal
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 66
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 57
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 40
- 230000023556 desulfurization Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 115
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000000197 pyrolysis Methods 0.000 claims abstract description 27
- 239000002028 Biomass Substances 0.000 claims abstract description 25
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims description 36
- 230000001105 regulatory effect Effects 0.000 claims description 31
- 239000002002 slurry Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000853 adhesive Substances 0.000 claims description 17
- 230000001070 adhesive effect Effects 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 239000003245 coal Substances 0.000 claims description 4
- 230000003009 desulfurizing effect Effects 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000002594 sorbent Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000011269 tar Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002910 solid waste Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 18
- 239000000428 dust Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 229910005084 FexOy Inorganic materials 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910014569 C—OOH Inorganic materials 0.000 description 1
- 241001190694 Muda Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
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Classifications
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
- C10K1/002—Removal of contaminants
- C10K1/007—Removal of contaminants of metal compounds
-
- 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
-
- 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
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Industrial Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention belongs to the technical field of solid waste resource utilization and flue gas pollution treatment, and particularly provides an adsorbent for blast furnace gas desulfurization and heavy metal capture, and preparation and application thereof. Overcomes the problems of poor effects of blast furnace gas desulfurization and heavy metal capture, high cost, low utilization rate of red mud and easy pollution in the prior artFully utilizes the coupling characteristic of the effective components in the red mud and the biomass pyrolysis reaction, develops the adsorbent meeting the purification requirement of the blast furnace gas and the matched process, and recovers SO in the blast furnace gas2The adsorbent is used for preparing acid, and the prepared adsorbent can be pyrolyzed and regenerated in an inert gas atmosphere or a vacuum atmosphere after being adsorbed and saturated and can be repeatedly put into use.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization and flue gas pollution treatment, and particularly relates to an adsorbent for blast furnace gas desulfurization and heavy metal capture, and a preparation method and a use method thereof.
Background
With the increasing demand of energy and the increasing requirement of environmental protection, the problems of heavy metal and desulfurization caused in the process of resource utilization of blast furnace gas are more and more prominent. The current common wet desulphurization process is used for SO2Has better removal effect, but can remove carbonyl sulfide (COS) and H in blast furnace gas2S has poor removal effect; techniques such as activated carbon adsorption or polycrystalline adsorption material for COS and H2S, in the process of adsorption treatment, the cost is high, and effective removal can be carried out only by matching with a wet desulphurization unit; in addition, there is a need for a sufficiently efficient treatment of heavy metals in blast furnace gas, which greatly increases the cost of blast furnace gas treatment.
The red mud is used for industrial production of Al2O3The solid waste slag discharged in the process mainly comprises alpha-Fe2O3(21.3％～45.9％)、Al2O3(18.9％～28.6％)、SiO2(14.5％～23.8％)、TiO2(3.8% -8.5%), CaO (1.3% -4.5%), and the like. Because the red mud is produced in large quantity and the application means is limited, a large amount of red mud cannot be effectively utilized and can only be stacked in a yard, so that a large amount of land resources are occupied, and because the red mud is strong-alkaline solid waste residues, the pH of a leaching solution can reach 10-13, when chemical components of the red mud are immersed in the land, the land can be alkalized, the surface water and underground water body are seriously polluted, and how to realize the efficient and large-scale resource utilization of the red mud becomes a difficult problem to be solved urgently in the aluminum-making industry.
Therefore, through reasonable and effective formula design and systematic process design, the effective components in the red mud and the characteristics of the pyrolysis reaction of the effective components and the biomass are fully utilized, and the blast furnace gas purification material and the matched process which meet the requirements are researched, so that the method has important significance in view of environmental protection and resource recycling.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the effects of blast furnace gas desulfurization and heavy metal capture are poor, the cost is high, the utilization rate of red mud is low, and pollution is easily caused.
Therefore, the invention provides an adsorbent for blast furnace gas desulfurization and heavy metal capture, which comprises the following components: red mud powder, biomass and a binder; wherein the red mud powder is prepared by removing SO from red mud-water slurry2Drying and grinding the product to prepare; (ii) a The mass ratio of the red mud powder, the biomass and the adhesive is 10: (10-50): (1-10).
Specifically, the biomass comprises at least one of straw, wood chips and coal powder.
Specifically, the adhesive comprises at least one of starch, tar and asphalt.
The invention also provides a preparation method of the adsorbent, which comprises the following steps: mixing red mud with water to obtain red mudA mud-water slurry, mixing the red mud-water slurry with SO2And (3) fully contacting, drying and grinding to obtain red mud powder, mixing the red mud powder with biomass and an adhesive, pressing into granules, and pyrolyzing in an inert gas atmosphere or a vacuum atmosphere to obtain the adsorbent for blast furnace gas desulfurization and heavy metal capture.
Specifically, the pyrolysis temperature is 550-750 ℃, and the time is 30-70 min.
The invention also provides a method for blast furnace gas desulfurization and heavy metal capture, which comprises the following steps:
(1) mixing red mud and water to prepare red mud slurry and placing the red mud slurry into a wet desulphurization tank;
(2) introducing blast furnace gas into the wet desulphurization tank, and utilizing SO in the blast furnace gas2Preparing the adsorbent for blast furnace gas desulfurization and heavy metal capture according to any one of claims 1 to 5;
(3) putting the adsorbent into a catalytic conversion tower, introducing blast furnace gas into the catalytic conversion tower, and utilizing the adsorbent to complete catalytic hydrolysis and H of COS2S, adsorbing heavy metals;
(4) cooling the blast furnace gas treated in the step (3), introducing the blast furnace gas into the wet desulphurization tank in the step (1), and removing SO2And the removal of sulfur and heavy metals in the blast furnace gas is completed.
Specifically, the method for removing sulfur from blast furnace gas and capturing heavy metals further comprises the following steps: and (4) desorbing the sulfide and heavy metal of the adsorbent saturated in the step (3) in a nitrogen atmosphere at 150-400 ℃, and returning the desorbed adsorbent to the catalytic conversion tower for secondary use.
Specifically, the step (2) further comprises recycling gas generated by pyrolysis in the process of preparing the adsorbent.
The invention also provides a system for the method for desulfurizing and trapping the heavy metal by the blast furnace gas, which comprises a catalytic conversion tower inlet and a temperature regulating device inlet which are connected with a blast furnace gas outlet in parallel; the outlet of the catalytic conversion tower is connected with the inlet of the temperature regulating device, and the adsorbent is placed in the catalytic conversion tower; the outlet of the temperature adjusting device is connected with a gas inlet of the wet desulphurization tank; the red mud-water slurry is placed in the wet desulphurization tank; all structures in the system are connected through pipelines, and each pipeline is provided with a regulating valve.
Specifically, the system for blast furnace gas desulfurization and heavy metal capture further comprises an adsorbent pyrolysis device, wherein the adsorbent pyrolysis device is used for pyrolyzing the red mud-water slurry desulfurization product collected in the wet desulfurization tank to prepare the adsorbent.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the adsorbent for blast furnace gas desulfurization and heavy metal capture provided by the invention is used with SO2The acidic red mud is formed after reaction and then mixed with biomass and a binder for pyrolysis, so that the effective components in the red mud and the coupling characteristic of the pyrolysis reaction of the effective components and the biomass in the red mud are fully utilized, the hole expansion is facilitated, the specific surface area of adsorbent particles is increased, and the H-component ratio is improved2S, adsorbing pollutants such as heavy metals and the like; hg and the like in blast furnace gas can react with active S generated by pyrolysis and is removed on the surface of the adsorbent through adsorption; because the red mud is added in the preparation process of the adsorbent, the surfaces of the adsorbent particles contain a large amount of FexOyActive components such as the like are favorable for catalytic hydrolysis of COS; the adsorbent can be pyrolyzed and regenerated in an inert gas atmosphere after being saturated in adsorption, can be repeatedly put into use, and saves the cost.
(2) The method for desulfurizing blast furnace gas and trapping heavy metals provided by the invention utilizes the alkalinity of the red mud which is solid waste to carry out SO treatment on the blast furnace gas2Removing, pyrolyzing the reacted red mud (containing generated sulfate) with biomass and adhesive to prepare adsorbent, and releasing SO in the pyrolysis process2Can be recycled to an acid making system of a steel mill for recycling and preparing H2SO4The prepared adsorbent can be used for treating COS and H in blast furnace gas2And removing S, heavy metal and other pollutants. The method and the matching system provided by the invention not only can complete the removal of sulfur and heavy metals in blast furnace gas,and can recover SO2The acid production is of great significance from the viewpoint of environmental protection and resource recycling.
The present invention will be described in further detail below with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic diagram of a system for desulfurizing blast furnace gas and capturing heavy metals according to an embodiment of the present invention.
Reference numerals: 1. a blast furnace; 2. a gravity dust collector; 3. a bag-type dust collector; 4. adjusting a valve; 5. a catalytic converter; 6. a heat exchanger; 7. a wet desulfurization tank; 8. an adsorbent pyrolysis unit; 9. a blast furnace gas main pipe; 10. blast furnace hot blast stove.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Although representative embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that various modifications and changes may be made thereto without departing from the scope of the invention. Therefore, the scope of the present invention should not be limited to the embodiments, but should be defined by the appended claims and equivalents thereof.
The invention provides an adsorbent for blast furnace gas desulfurization and heavy metal capture, which comprises the following components: the red mud powder, the biomass and the adhesive are prepared by the following steps: mixing red mud and water to prepare red mud-water slurry with pH of about 8-9, and mixing the red mud-water slurry with SO2Sufficient contact occurs when the main reactions take place as follows:
2Al(OH)3+3SO2＝Al2(SO3)3+3H2O
2Fe(OH)3+3SO2＝Fe2(SO3)3+3H2O
2Ca(OH)2+SO2＝CaSO3+2H2O
4Al(OH)3+6SO2+O2＝2Al2(SO4)3+6H2O
4Fe(OH)3+6SO2+O2＝Fe2(SO4)3+3H2O
2Ca(OH)2+2SO2+O2＝2CaSO4+2H2O
will react with SO2Drying and grinding the red mud-water slurry after reaction to obtain red mud powder, wherein the particle diameter of the red mud powder is preferably below 100 meshes, and mixing and pressing the red mud powder, the biomass and the adhesive into particles, wherein the mass ratio of the red mud powder, the biomass and the adhesive is 10: (10-50): (1-10); the biomass comprises at least one of straw, wood chips and coal powder, and the particle diameter of the biomass is preferably below 100 meshes; the adhesive comprises at least one of starch, tar and asphalt. Pyrolyzing the particles obtained after pressing in an inert gas atmosphere or a vacuum atmosphere at the pyrolysis temperature of 550-750 ℃ for 30-70 min, wherein the main reactions in the pyrolysis process are as follows:
Fe2(SO4)3＝Fe2O3+SO3
Al2(SO4)3＝Al2O3+SO3
CaSO4＝CaO+SO3
SO3＝SO2+O2
[CxHyOz]+H2SO4→H2O↑+S*+[CxHyOz+3]
[CxHyOz]→CO+H2+[Cx-1Hy-2Oz-1]
Fe2O3+CO＝2FeO+CO2
Fe2O3+H2＝2FeO+H2O
the solid substance obtained by the pyrolysis reaction is an adsorbent for blast furnace gas desulfurization and heavy metal capture, and the gas generated by decomposition in the pyrolysis process is mainlyThe essential component is SO2Can be used for recovering and preparing H2SO4。
The invention also provides a method for blast furnace gas desulfurization and heavy metal capture, which comprises the following steps:
(1) mixing red mud and water to prepare red mud slurry and placing the red mud slurry into a wet desulphurization tank;
(2) introducing blast furnace gas into the wet desulphurization tank, and utilizing SO in the blast furnace gas2Preparing the adsorbent for blast furnace gas desulfurization and heavy metal capture; for SO generated by pyrolysis in the preparation process of the adsorbent2Recycling and reusing; at this time, SO is generated due to iron ion pairs present in the blast furnace gas2The absorption of the red mud has catalysis/promotion effect, SO that the red mud-water slurry can more fully absorb SO in blast furnace gas2；
(3) Putting the adsorbent into a catalytic conversion tower, introducing blast furnace gas into the catalytic conversion tower, and hydrolyzing COS under the catalytic action of the iron oxide on the surface of the adsorbent; hg and the like in blast furnace gas react with active S generated by pyrolysis in the preparation process of the adsorbent; due to the coupling characteristic of the effective components in the red mud and the biomass pyrolysis reaction, the adsorbent with the increased specific surface area completes the reaction on H2S, adsorbing pollutants such as heavy metals and the like; the main reactions taking place in this step are as follows:
COS+H2O→H2S+CO2
C-OOH+Mn+→C-OOM(n-1)++H+
S*+Hg→HgS
in addition, the adsorbent is rich in FexOyCan promote H2S、SO2Waiting for the adsorption of the acid gas, the main reactions occurring at this time are as follows:
FexOy+H2S→FexOy-1S+H2O
FeO+SO2→FeSO3
the adsorbent after saturated adsorption can be used for desorbing sulfides and heavy metals in a nitrogen atmosphere at the temperature of 150-400 ℃, and the desorbed adsorbent is returned to the catalytic conversion tower for secondary use; the reaction in the desorption column takes place as follows:
C-OOM(n-1)+→COO++Mn+
FexOy-1S+H2O→FexOy+H2S
FeSO3→FeO+SO2
(4) cooling the blast furnace gas treated in the step (3), introducing the blast furnace gas into the wet desulphurization tank in the step (1), and removing SO2And the removal of sulfur and heavy metals in the blast furnace gas is completed.
The invention also provides a system for completing the blast furnace gas desulfurization and heavy metal capture method. The system for the desulfurization of the blast furnace gas and the collection of the heavy metal comprises a catalytic conversion tower inlet and a temperature regulating device inlet which are connected with a blast furnace gas outlet in parallel; the outlet of the catalytic conversion tower is connected with the inlet of the temperature regulating device; the outlet of the temperature adjusting device is connected with a gas inlet of the wet desulphurization tank; all structures in the system are connected through pipelines, and each pipeline is provided with a regulating valve. When the device is used, red mud slurry prepared by mixing red mud and water is injected into the wet desulphurization tank, and the regulating valves on the connecting pipelines between the blast furnace gas outlet and the temperature regulating device and between the temperature regulating device and the wet desulphurization tank are opened, so that the blast furnace gas cooled by the temperature regulating device enters the wet desulphurization tank to be fully contacted with the red mud slurry. Preferably, the bottom of the wet desulphurization tank is connected with an adsorbent pyrolysis device, and a pipeline below the wet desulphurization tank is opened to be connected with SO2Introducing the reacted red mud slurry into an adsorbent pyrolysis device, drying and grinding the reacted red mud slurry to obtain powder, adding biomass and an adhesive into the adsorbent pyrolysis device, mixing the biomass and the adhesive with the powder, pressing the mixture into particles, pyrolyzing the particles in an inert atmosphere, putting the obtained adsorbent for blast furnace gas desulfurization and heavy metal capture into a catalytic conversion tower, closing regulating valves on connecting pipelines between a blast furnace gas outlet and a temperature regulating device as well as between the temperature regulating device and a wet desulfurization tank, opening the regulating valve on the connecting pipeline between the blast furnace gas outlet and an inlet of the catalytic conversion tower, and introducing the regulating valves into the catalytic conversion towerThe catalytic hydrolysis of COS and H are completed by the adsorbent after the blast furnace gas is fed2S, adsorbing heavy metals. Opening regulating valves on connecting pipelines between the outlet of the catalytic conversion tower and the inlet of the temperature regulating device, and between the outlet of the temperature regulating device and the gas inlet of the wet desulphurization tank, cooling the blast furnace gas treated by the adsorbent, then feeding the blast furnace gas into the wet desulphurization tank to fully contact with the red mud slurry, and removing SO2。
Preferably, the temperature control device is a heat exchanger.
In order to avoid the influence of dust particles in the blast furnace gas on the subsequent desulfurization and heavy metal trapping efficiency, a gravity dust collector and a bag-type dust collector can be sequentially connected to the blast furnace gas outlet, and the bag-type dust collector outlet is respectively connected with the inlet of the catalytic conversion tower and the inlet of the temperature regulating device.
Furthermore, a blast furnace gas main pipe and a purified blast furnace gas utilization device are connected in parallel with a gas outlet of the wet desulphurization tank. The regulating valve between the gas outlet of the wet desulphurization tank and the blast furnace gas main pipe is opened, SO that only SO is finished2The removed gas is returned to the blast furnace gas pipe. And opening a regulating valve between the gas outlet of the wet desulphurization tank and the purified blast furnace gas utilization device, so that the purified blast furnace gas from which the sulfur and the heavy metal are removed can be utilized subsequently.
The effect of the sorbent, the method and the system provided by the invention on the desulfurization of blast furnace gas and the collection of heavy metals is studied by specific examples.
Example 1:
in the embodiment, a system for coal gas desulfurization and heavy metal capture as shown in fig. 1 is built, and comprises a gravity dust collector and a bag-type dust collector which are sequentially connected with a blast furnace; the outlet of the bag-type dust collector is respectively connected with the inlet of the catalytic conversion tower and the inlet of the heat exchanger; the outlet of the catalytic conversion tower is connected with the inlet of the heat exchanger; the outlet of the heat exchanger is respectively connected with the blast furnace gas main pipe and the gas inlet of the wet desulphurization tank; the gas outlet of the wet desulphurization tank is connected with the blast furnace gas main pipe and the blast furnace hot blast stove in parallel, and the bottom of the wet desulphurization tank is connected with an adsorbent pyrolysis device; the gas outlet of the wet desulphurization tank is connected with the gas inlet of the catalytic conversion tower; all structures in the system are connected through pipelines, and each pipeline is provided with a regulating valve.
In the system shown in fig. 1, the blast furnace gas is desulfurized and heavy metal is captured by the following specific steps:
(1) mixing red mud and water to prepare red mud slurry and placing the red mud slurry into a wet desulphurization tank;
(2) opening regulating valves on connecting pipelines between the bag-type dust remover and the heat exchanger and between the heat exchanger and the wet-process desulfurization tank, and cooling blast furnace gas by the heat exchanger after the blast furnace gas is dedusted by the gravity deduster and the bag-type dust remover, and the blast furnace gas enters the wet-process desulfurization tank to be fully contacted with the red mud slurry; opening the regulating valve between the gas outlet of the wet desulphurization tank and the blast furnace gas main pipe to only complete SO2Returning the removed coal gas to the blast furnace gas pipe; opening a pipeline below the wet desulphurization tank to react with SO2Introducing the reacted red mud slurry into an adsorbent pyrolysis device, drying and grinding the reacted red mud slurry to obtain powder, wherein the weight ratio of the powder: biomass: the adhesive is 10: 25: 5, adding biomass and an adhesive into an adsorbent pyrolysis device, mixing the biomass and the adhesive with the powder, pressing the mixture into granules, and pyrolyzing the granules for 50min at 650 ℃ in an inert atmosphere to obtain an adsorbent; wherein the biomass is a mixture of straw, wood chips and coal powder, and the adhesive is starch;
(3) putting the obtained adsorbent into a catalytic conversion tower, closing regulating valves on connecting pipelines between a bag-type dust remover and a heat exchanger and between the heat exchanger and a wet desulphurization tank, opening the regulating valves on the connecting pipelines between the bag-type dust remover and an inlet of the catalytic conversion tower, and introducing blast furnace gas into the catalytic conversion tower to ensure that the adsorbent finishes catalytic hydrolysis of COS and H2S, adsorbing heavy metals;
(4) opening regulating valves on connecting pipelines between the catalytic conversion tower and the heat exchanger and between the heat exchanger and the wet desulphurization tank to ensure that the blast furnace gas treated by the adsorbent is cooled by the heat exchanger and then enters the wet desulphurization tank to be fully contacted with the red mud slurry to remove SO2(ii) a Opening a regulating valve on a connecting pipeline between a gas outlet of the wet desulphurization tank and the blast furnace hot blast stove, and introducing the purified blast furnace gas subjected to sulfur and heavy metal removal into the blast furnace hot blast stove for subsequent operationAnd (4) utilizing.
The above examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention, which is intended to be covered by the claims and any design similar or equivalent to the scope of the invention.
Claims (10)
1. An adsorbent for blast furnace gas desulfurization and heavy metal capture, comprising: red mud powder, biomass and a binder; wherein the red mud powder is prepared by removing SO from red mud-water slurry2Drying and grinding the product to prepare; the mass ratio of the red mud powder, the biomass and the adhesive is 10: (10-50): (1-10).
2. The sorbent for blast furnace gas desulfurization and heavy metal capture according to claim 1, characterized in that: the biomass comprises at least one of straw, wood chips and coal powder.
3. The sorbent for blast furnace gas desulfurization and heavy metal capture according to claim 1, characterized in that: the adhesive comprises at least one of starch, tar and asphalt.
4. The method for preparing the adsorbent for desulfurization and heavy metal capture of blast furnace gas according to any one of claims 1 to 3, characterized by comprising the steps of: mixing red mud and water to prepare red mud-water slurry, and mixing the red mud-water slurry with SO2And (3) fully contacting, drying and grinding to obtain red mud powder, mixing the red mud powder with biomass and an adhesive, pressing into granules, and pyrolyzing in an inert gas atmosphere or a vacuum atmosphere to obtain the adsorbent for blast furnace gas desulfurization and heavy metal capture.
5. The sorbent for blast furnace gas desulfurization and heavy metal capture according to claim 4, characterized in that: the pyrolysis temperature is 550-750 ℃, and the time is 30-70 min.
6. The method for desulfurizing blast furnace gas and trapping heavy metals is characterized by comprising the following steps of:
(1) mixing red mud and water to prepare red mud slurry and placing the red mud slurry into a wet desulphurization tank;
(2) introducing blast furnace gas into the wet desulphurization tank, and utilizing SO in the blast furnace gas2Preparing the adsorbent for blast furnace gas desulfurization and heavy metal capture according to any one of claims 1 to 3;
(3) putting the adsorbent into a catalytic conversion tower, introducing blast furnace gas into the catalytic conversion tower, and utilizing the adsorbent to complete catalytic hydrolysis and H of COS2S, adsorbing heavy metals;
(4) cooling the blast furnace gas treated in the step (3), introducing the blast furnace gas into the wet desulphurization tank in the step (1), and removing SO2And the removal of sulfur and heavy metals in the blast furnace gas is completed.
7. The method for blast furnace gas desulfurization and heavy metal capture according to claim 6, further comprising: and (4) desorbing the sulfide and heavy metal of the adsorbent saturated in the step (3) in a nitrogen atmosphere at 150-400 ℃, and returning the desorbed adsorbent to the catalytic conversion tower for secondary use.
8. The method for blast furnace gas desulfurization and heavy metal capture according to claim 6, characterized in that: and (2) recycling the gas generated in the preparation process of the adsorbent.
9. A system for blast furnace gas desulfurization and heavy metal capture is characterized by comprising: the catalytic conversion tower inlet and the temperature regulating device inlet are connected with the blast furnace gas outlet in parallel; the outlet of the catalytic conversion tower is connected with the inlet of the temperature regulating device, and the adsorbent as defined in any one of claims 1 to 3 is placed in the catalytic conversion tower; the outlet of the temperature adjusting device is connected with a gas inlet of the wet desulphurization tank; the red mud-water slurry is placed in the wet desulphurization tank; all structures in the system are connected through pipelines, and each pipeline is provided with a regulating valve.
10. The system for blast furnace gas desulfurization and heavy metal capture according to claim 9, characterized in that: the wet desulphurization device further comprises an adsorbent pyrolysis device, wherein the adsorbent pyrolysis device is used for pyrolyzing the red mud-water slurry desulphurization product collected in the wet desulphurization tank to prepare the adsorbent according to any one of claims 1 to 3.
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