CN113908797B - Adsorbent for desulfurizing blast furnace gas and capturing heavy metals as well as preparation and application thereof - Google Patents
Adsorbent for desulfurizing blast furnace gas and capturing heavy metals as well as preparation and application thereof Download PDFInfo
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- CN113908797B CN113908797B CN202111259191.XA CN202111259191A CN113908797B CN 113908797 B CN113908797 B CN 113908797B CN 202111259191 A CN202111259191 A CN 202111259191A CN 113908797 B CN113908797 B CN 113908797B
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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 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 230000003009 desulfurizing effect Effects 0.000 title claims description 30
- 239000007789 gas Substances 0.000 claims abstract description 113
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 54
- 230000023556 desulfurization Effects 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000000197 pyrolysis Methods 0.000 claims abstract description 28
- 239000002028 Biomass Substances 0.000 claims abstract description 25
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 230000003197 catalytic effect Effects 0.000 claims description 36
- 230000001105 regulatory effect Effects 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000428 dust Substances 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 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
- 239000002817 coal dust Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003825 pressing Methods 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
- 238000001035 drying Methods 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
- 239000002594 sorbent Substances 0.000 claims 3
- 230000002378 acidificating effect Effects 0.000 claims 2
- 230000008569 process Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000003546 flue gas Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910014569 C—OOH Inorganic materials 0.000 description 1
- 229910002596 FexO Inorganic materials 0.000 description 1
- 241000338240 Parallela Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 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
Classifications
-
- 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
Abstract
The invention belongs to the technical field of solid waste recycling and flue gas pollution treatment, and particularly provides an adsorbent for blast furnace gas desulfurization and heavy metal trapping, and preparation and application thereof. Overcomes the problems of bad desulfurization and heavy metal trapping effect, high cost, low utilization rate of red mud and easy pollution of the blast furnace gas in the prior art, fully utilizes the coupling characteristic of the effective components in the red mud and the pyrolysis reaction of biomass, develops an adsorbent meeting the purification requirement of the blast furnace gas and a matched process, and recovers SO in the blast furnace gas 2 The adsorbent used for preparing the acid can be pyrolyzed and regenerated in an inert gas atmosphere or a vacuum atmosphere after being adsorbed and saturated, and is repeatedly put into use.
Description
Technical Field
The invention belongs to the technical field of solid waste recycling and flue gas pollution treatment, and particularly relates to an adsorbent for desulfurizing blast furnace gas and capturing heavy metals, and a preparation method and a use method thereof.
Background
Along with the continuous increase of energy demand and the continuous improvement of environmental protection requirements, the problems of heavy metal and desulfurization caused in the recycling process of blast furnace gas are more and more prominent. The wet desulfurization process commonly used at present is applicable to SO 2 Has better removal effect, but has better removal effect on carbonyl sulfide (COS) and H in blast furnace gas 2 The S removing effect is poor; the active carbon adsorption or polycrystalline adsorption material and other technology are used for preparing the catalyst for COS and H 2 S, in the adsorption treatment process, the cost is high, and the wet desulfurization unit is matched for use to effectively remove the S; in addition, the heavy metals in the blast furnace gas need to be treated sufficiently and effectively, which greatly increases the cost of blast furnace gas treatment.
Red mud is used for industrial production of Al 2 O 3 The main component of the solid waste residue discharged in the process is a-Fe 2 O 3 (21.3％～45.9％)、Al 2 O 3 (18.9％～28.6％)、SiO 2 (14.5％～23.8％)、TiO 2 (3.8% -8.5%), caO (1.3% -4.5%), etc. The method has the advantages that the production amount of the red mud is large, the application means are limited, a large amount of the red mud can not be effectively utilized, and the red mud can only be stacked in a storage yard, so that a large amount of land resources are occupied, the pH of the leaching solution can reach 10-13 because the red mud is strong alkaline solid waste residues, the land is alkalized when chemical components of the red mud are immersed in the land, the surface water and groundwater are seriously polluted, and the problem that the aluminum smelting industry needs to be solved is solved in a great deal of time when the efficient and large-scale recycling of the red mud is realized.
Therefore, by reasonable and effective formula design and systematic process design, the characteristics of effective components in the red mud and the pyrolysis reaction of the effective components with biomass are fully utilized, and the blast furnace gas purifying material and the matched process which meet the requirements are researched, so that the method has important significance from the aspects of environmental protection and resource recycling.
Disclosure of Invention
The invention aims to solve the problems of poor desulfurization and heavy metal trapping effects, high cost, low red mud utilization rate and easiness in pollution in the prior art.
To this end, the invention provides an adsorbent for desulfurization and heavy metal trapping of blast furnace gas, comprising: red mud powder, biomass and a binder; wherein the red mud powder is used for removing SO from red mud-water slurry 2 The obtained product is dried and ground to prepare; the method comprises the steps of carrying out a first treatment on the surface of the The mass ratio of the red mud powder to the biomass to the binder is 10: (10-50): (1-10).
Specifically, the biomass comprises at least one of straw, wood dust and coal dust.
Specifically, the binder includes 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 and water to prepare red mud-water slurry, and mixing the red mud-water slurry with SO 2 Fully contacting, drying and grinding to obtain red mud powder, mixing the red mud powder with biomass and a binder, pressing into particles, and pyrolyzing under inert gas atmosphere or vacuum atmosphere to obtain the adsorbent for desulfurizing blast furnace gas and capturing heavy metals.
Specifically, the pyrolysis temperature is 550-750 ℃ and the pyrolysis time is 30-70 min.
The invention also provides a method for desulfurizing the blast furnace gas and capturing heavy metals, which comprises the following steps:
(1) Mixing red mud and water to prepare red mud slurry, and placing the red mud slurry in a wet desulfurization tank;
(2) Introducing blast furnace gas into the wet desulfurization tank, and utilizing SO in the blast furnace gas 2 Preparing the adsorbent for desulfurizing blast furnace gas and capturing heavy metals according to any one of claims 1 to 5;
(3) The adsorbent is put into a catalytic conversion tower, blast furnace gas is introduced into the catalytic conversion tower, and the adsorbent is utilized to complete the catalytic hydrolysis of COS and H 2 S, adsorbing heavy metals;
(4) Cooling the blast furnace gas treated in the step (3), and then introducing the cooled blast furnace gas into the wet desulfurization tank in the step (1) to remove SO 2 And (5) removing sulfur and heavy metals in the blast furnace gas.
Specifically, the method for desulfurizing the blast furnace gas and capturing heavy metals further comprises the following steps: and (3) desorbing sulfide and heavy metal from the adsorbent subjected to adsorption saturation 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 the gas generated by pyrolysis in the process of preparing the adsorbent.
The invention also provides a system for the method for desulfurizing the blast furnace gas and capturing heavy metals, which comprises a catalytic converter inlet and a temperature regulating device inlet which are connected in parallel with the blast furnace gas outlet; 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 regulating device is connected with a gas inlet of the wet desulfurization tank; the wet desulfurization tank is internally provided with red mud-water slurry; all structures in the system are connected through pipelines, and regulating valves are arranged on all the pipelines.
Specifically, the system for desulfurizing blast furnace gas and capturing heavy metals further comprises an adsorbent pyrolysis device, wherein the adsorbent pyrolysis device is used for pyrolyzing red mud-water slurry desulfurization products 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 desulfurizing blast furnace gas and capturing heavy metals provided by the invention uses SO 2 The acid red mud is obtained after the reaction, and then mixed with biomass and binder for pyrolysis, so that the effective components in the red mud and the biomass are fully utilizedCoupling characteristic of pyrolysis reaction, favorability for reaming, increase of specific surface area of adsorbent particles, and improvement of H 2 S, adsorbing pollutants such as heavy metals; hg and the like existing in the blast furnace gas can react with active S generated by pyrolysis and are removed on the surface of the adsorbent through adsorption; because red mud is added in the preparation process of the adsorbent, the surface of the adsorbent particles contains a large amount of Fe x O y The active components are equal, which is beneficial to the catalytic hydrolysis of COS; the adsorbent can be pyrolyzed and regenerated in an inert gas atmosphere after adsorption saturation, can be repeatedly put into use, and saves cost.
(2) The method for desulfurizing the blast furnace gas and trapping the heavy metals utilizes the alkalinity of the solid waste red mud to treat SO in the blast furnace gas 2 Removing, pyrolyzing the red mud (containing generated sulfate) after reaction with biomass and binder to prepare adsorbent, and releasing SO in the pyrolysis process 2 Can be recycled to an acid making system of a steel plant for recycling and preparing H 2 SO 4 The prepared adsorbent can be used for treating COS and H in blast furnace gas 2 S, removing pollutants such as heavy metals. The method and the matched system provided by the invention not only can complete the removal of sulfur and heavy metals in blast furnace gas, but also can recycle SO 2 The acid production has important significance from the aspects of environmental protection and resource recycling.
The present invention will be described in further detail 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 remover; 3. a bag-type dust collector; 4. a regulating valve; 5. a catalytic converter; 6. a heat exchanger; 7. a wet desulfurizing tank; 8. an adsorbent pyrolysis device; 9. a blast furnace gas main pipe; 10. blast furnace hot blast stove.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following examples, and it is obvious that the described examples are only some examples of the present invention, but not all examples. Although representative embodiments of the present invention have been described in detail, those skilled in the art to which the invention pertains will appreciate that various modifications and changes can be made without departing from the scope of the invention. Accordingly, the scope of the 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 desulfurizing blast furnace gas and capturing heavy metals, which comprises the following components: the red mud powder, biomass and adhesive are prepared by the following steps: mixing red mud and water to prepare red mud-water slurry, wherein the pH of the slurry is about 8-9, mixing the red mud-water slurry with SO 2 The main reactions occurring at this time are as follows:
2Al(OH) 3 +3SO 2 ＝Al 2 (SO 3 ) 3 +3H 2 O
2Fe(OH) 3 +3SO 2 ＝Fe 2 (SO 3 ) 3 +3H 2 O
2Ca(OH) 2 +SO 2 ＝CaSO 3 +2H 2 O
4Al(OH) 3 +6SO 2 +O 2 ＝2Al 2 (SO 4 ) 3 +6H 2 O
4Fe(OH) 3 +6SO 2 +O 2 ＝Fe 2 (SO 4 ) 3 +3H 2 O
2Ca(OH) 2 +2SO 2 +O 2 ＝2CaSO 4 +2H 2 O
will be combined with SO 2 The reacted red mud-water slurry is dried and ground to obtain red mud powder, the particle diameter of the red mud powder is preferably below 100 meshes, the red mud powder, biomass and an adhesive are mixed and pressed into particles, wherein the mass ratio of the red mud powder to the biomass to the adhesive is 10: (10-50): (1-10); the biomass comprises at least one of straw, wood dust and coal dust, and the particle diameter of the biomass is preferably below 100 meshes; the binder comprises at least one of starch, tar and asphalt. Pyrolyzing the pressed particles in inert gas atmosphere or vacuum atmosphere, and heatingThe temperature is 550-750 ℃ and the time is 30-70 min, and the main reactions in the pyrolysis process are as follows:
Fe 2 (SO 4 ) 3 ＝Fe 2 O 3 +SO 3
Al 2 (SO 4 ) 3 ＝Al 2 O 3 +SO 3
CaSO 4 ＝CaO+SO 3
SO 3 ＝SO 2 +O 2
[C x H y O z ]+H 2 SO 4 →H 2 O↑+S*+[C x H y O z+3 ]
[C x H y O z ]→CO+H 2 +[C x-1 H y-2 O z-1 ]
Fe 2 O 3 +CO＝2FeO+CO 2
Fe 2 O 3 +H 2 ＝2FeO+H 2 O
the solid matter obtained by pyrolysis reaction is the adsorbent for desulfurizing blast furnace gas and capturing heavy metals, and the main component of the gas generated by decomposition in the pyrolysis process is SO 2 Can be used for recycling and preparing H 2 SO 4 。
The invention also provides a method for desulfurizing the blast furnace gas and capturing heavy metals, which comprises the following steps:
(1) Mixing red mud and water to prepare red mud slurry, and placing the red mud slurry in a wet desulfurization tank;
(2) Introducing blast furnace gas into the wet desulfurization tank, and utilizing SO in the blast furnace gas 2 Preparing the adsorbent for desulfurizing the blast furnace gas and trapping heavy metals; for SO generated by pyrolysis in adsorbent preparation process 2 Recycling and reutilizing; at this time, the SO is paired by iron ions present in the blast furnace gas 2 Has catalytic/promoting effect, SO that the red mud-water slurry can more fully absorb SO in blast furnace gas 2 ；
(3) The adsorbent is put into a catalytic conversion tower, and blast furnace gas is introduced into the catalytic conversion towerCOS is hydrolyzed under the catalysis of iron oxide on the surface of the adsorbent; hg and the like existing in the 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 pyrolysis reaction of biomass, the adsorbent with increased specific surface area completes H reaction 2 S, adsorbing pollutants such as heavy metals; the main reactions that occur in this step are as follows:
COS+H 2 O→H 2 S+CO 2
C-OOH+M n+ →C-OOM (n-1)+ +H +
S*+Hg→HgS
in addition, the adsorbent contains rich Fe x O y Can promote H 2 S、SO 2 Adsorption of the acid gases, the main reactions that occur at this time are as follows:
Fe x O y +H 2 S→FexO y-1 S+H 2 O
FeO+SO 2 →FeSO 3
the adsorbent after saturation adsorption can be subjected to desorption of sulfides and heavy metals in a nitrogen atmosphere at 150-400 ℃, and the adsorbent after desorption is returned to the catalytic conversion tower for secondary use; the reaction takes place in the desorption column as follows:
C-OOM (n-1)+ →COO + +M n+
Fe x O y-1 S+H 2 O→Fe x O y +H 2 S
FeSO 3 →FeO+SO 2
(4) Cooling the blast furnace gas treated in the step (3), and then introducing the cooled blast furnace gas into the wet desulfurization tank in the step (1) to remove SO 2 And (5) removing sulfur and heavy metals in the blast furnace gas.
The invention also provides a system for completing the method for desulfurizing the blast furnace gas and capturing heavy metals. The system for desulfurizing the blast furnace gas and capturing heavy metals comprises a catalytic converter inlet and a temperature regulating device inlet which are connected in parallel with a blast furnace gas outlet; the outlet of the catalytic converter is in phase with the inlet of the temperature regulating deviceConnecting; the outlet of the temperature regulating device is connected with a gas inlet of the wet desulfurization tank; all structures in the system are connected through pipelines, and regulating valves are arranged on all the pipelines. When the wet desulfurization device is used, red mud slurry prepared by mixing red mud and water is injected into the wet desulfurization tank, and a blast furnace gas outlet and a temperature regulating device and a regulating valve on a connecting pipeline between the temperature regulating device and the wet desulfurization tank are opened, so that the blast furnace gas cooled by the temperature regulating device enters the wet desulfurization tank to fully contact with the red mud slurry. Preferably, the bottom of the wet desulfurization tank is connected with an adsorbent pyrolysis device, and a pipeline below the wet desulfurization tank is opened to be connected with SO 2 Introducing the reacted red mud slurry into an adsorbent pyrolysis device, drying and grinding the reacted red mud slurry to obtain powder, adding biomass and adhesive into the adsorbent pyrolysis device, mixing the powder with the biomass and adhesive, pressing the mixture into particles, pyrolyzing the particles under an inert atmosphere, putting the obtained adsorbent for desulfurizing blast furnace gas and capturing heavy metals into a catalytic conversion tower, closing a regulating valve on a connecting pipeline between a blast furnace gas outlet and a temperature regulating device and 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 blast furnace gas into the catalytic conversion tower to ensure that the adsorbent completes catalytic hydrolysis and H of COS 2 S, adsorption of heavy metals. Opening a regulating valve on a connecting pipeline between an outlet of the catalytic conversion tower and an inlet of a temperature regulating device, and between an outlet of the temperature regulating device and a gas inlet of the wet desulfurization tank, SO that the blast furnace gas treated by the adsorbent enters the wet desulfurization tank after being cooled, and fully contacts with red mud slurry to remove SO 2 。
Preferably, the temperature adjusting device is a heat exchanger.
In order to avoid dust particles in the blast furnace gas from affecting the subsequent desulfurization and heavy metal trapping efficiency, a gravity dust remover and a cloth bag dust remover can be sequentially connected to a blast furnace gas outlet, and the cloth bag dust remover outlet is respectively connected with an inlet of a catalytic converter and an inlet of a temperature regulating device.
Further, a blast furnace gas main pipe is connected with a gas outlet of the wet desulfurization tank and is connected with the blast furnace gas main pipe and the purified blast furnace in parallelA gas utilization device. The regulating valve between the gas outlet of the wet desulfurizing tank and the main blast furnace gas pipe is opened to complete SO only 2 The removed gas is returned to the blast furnace gas pipe. And opening a regulating valve between a gas outlet of the wet desulfurization tank and the purified blast furnace gas utilization device to enable the purified blast furnace gas for removing sulfur and heavy metals to enter into subsequent utilization.
The effect of the adsorbent, the method and the system provided by the invention on desulfurization of blast furnace gas and heavy metal trapping will be studied by specific examples.
Example 1:
the embodiment builds a system for desulfurizing the furnace gas and capturing heavy metals as shown in fig. 1, and comprises a gravity dust remover and a cloth bag dust remover 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 converter and the inlet of the heat exchanger; the outlet of the catalytic converter is connected with the inlet of the heat exchanger; the outlet of the heat exchanger is respectively connected with a blast furnace gas main pipe and a gas inlet of the wet desulfurization tank; the gas outlet of the wet desulfurization 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 desulfurization tank is connected with an adsorbent pyrolysis device; the wet desulfurizing tank gas outlet is connected with the catalytic converter gas inlet; all structures in the system are connected through pipelines, and regulating valves are arranged on all the pipelines.
On the system shown in fig. 1, the blast furnace gas is desulfurized and heavy metal is trapped, and the specific steps are as follows:
(1) Mixing red mud and water to prepare red mud slurry, and placing the red mud slurry in a wet desulfurization 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 through the heat exchanger after dust removal of the gravity dust remover and the bag-type dust remover, and entering the wet-process desulfurization tank to fully contact with red mud slurry; opening a regulating valve between a gas outlet of the wet desulfurization tank and a main pipe of the blast furnace gas to only finish SO 2 The removed coal gas returns to the blast furnace gas pipe again; opening a pipeline below the wet desulfurization tank to be connected with SO 2 The reacted red mud slurry is led into an adsorbent pyrolysis device to react red mudDrying and grinding the slurry to obtain powder, wherein the powder is prepared by the following steps of: biomass: the adhesive is 10:25:5, adding biomass and an adhesive into an adsorbent pyrolysis device according to the mass ratio, mixing with the powder, pressing into particles, and pyrolyzing for 50min in an inert atmosphere at 650 ℃ to obtain an adsorbent; wherein the biomass is a mixture of straw, wood dust and coal dust, and the adhesive is starch;
(3) Putting the obtained adsorbent into a catalytic converter, closing a regulating valve on a connecting pipeline between a bag-type dust collector and a heat exchanger as well as between the heat exchanger and a wet desulfurization tank, opening the regulating valve on the connecting pipeline between the bag-type dust collector and an inlet of the catalytic converter, and introducing blast furnace gas into the catalytic converter to ensure that the adsorbent completes the catalytic hydrolysis and H of COS 2 S, adsorbing heavy metals;
(4) Opening a regulating valve on a connecting pipeline between the catalytic conversion tower and the heat exchanger, and between the heat exchanger and the wet desulfurization tank, SO that the blast furnace gas treated by the adsorbent enters the wet desulfurization tank after being cooled by the heat exchanger, and fully contacts with red mud slurry to remove SO 2 The method comprises the steps of carrying out a first treatment on the surface of the And opening a regulating valve on a connecting pipeline between a gas outlet of the wet desulfurization tank and the blast furnace hot blast stove, and introducing purified blast furnace gas with sulfur and heavy metals removed into the blast furnace hot blast stove for subsequent utilization.
The foregoing examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention, and all designs that are the same or similar to the present invention are within the scope of the present invention.
Claims (9)
1. The adsorbent for desulfurizing blast furnace gas and trapping heavy metals is characterized by comprising red mud powder, biomass and an adhesive; the mass ratio of the red mud powder to the biomass to the binder is 10: (10-50): (1-10);
the adsorbent is prepared by the following steps: mixing red mud and water to prepare red mud-water slurry, and mixing the red mud-water slurry with SO in blast furnace gas 2 Fully contacting, drying and grinding to obtain red mud powder, mixing the red mud powder with biomass and a binder, pressing into particles, and pyrolyzing in an inert gas atmosphere or a vacuum atmosphere to obtain the red mud powderAn adsorbent for desulfurizing blast furnace gas and capturing heavy metals.
2. The sorbent for desulfurization and heavy metal capture of blast furnace gas of claim 1, wherein: the biomass comprises at least one of straw, wood dust and coal dust.
3. The sorbent for desulfurization and heavy metal capture of blast furnace gas of claim 1, wherein: the adhesive comprises at least one of starch, tar and asphalt.
4. The sorbent for desulfurization and heavy metal capture of blast furnace gas of claim 1, wherein: the pyrolysis temperature is 550-750 ℃ and the pyrolysis time is 30-70 min.
5. The method for desulfurizing the blast furnace gas and trapping the 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 in a wet desulfurization tank;
(2) Introducing blast furnace gas into the wet desulfurization tank to enable red mud-water slurry and SO in the blast furnace gas to be mixed 2 Reacting to generate acidic red mud, and then mixing and pyrolyzing the acidic red mud with biomass and a binder to prepare the adsorbent for desulfurizing blast furnace gas and capturing heavy metals according to any one of claims 1 to 3;
(3) The adsorbent is put into a catalytic conversion tower, blast furnace gas is introduced into the catalytic conversion tower, and the adsorbent is utilized to complete the catalytic hydrolysis of COS and H 2 S, adsorbing heavy metals;
(4) Cooling the blast furnace gas treated in the step (3), and then introducing the cooled blast furnace gas into the wet desulfurization tank in the step (1) to remove SO 2 And (5) removing sulfur and heavy metals in the blast furnace gas.
6. The method for desulfurizing blast furnace gas and capturing heavy metals according to claim 5, further comprising: and (3) desorbing sulfide and heavy metal from the adsorbent subjected to adsorption saturation in the step (3) in a nitrogen atmosphere at 150-400 ℃, and returning the desorbed adsorbent to the catalytic conversion tower for secondary use.
7. The method for desulfurizing blast furnace gas and capturing heavy metals according to claim 5, wherein: the step (2) also comprises the step of recycling the gas generated in the adsorbent preparation process.
8. A system for desulfurizing blast furnace gas and capturing heavy metals, comprising: a catalytic converter inlet and a temperature regulating device inlet connected in parallel with the blast furnace gas outlet; the outlet of the catalytic converter is connected with the inlet of the temperature regulating device, and the adsorbent as set forth in any one of claims 1-4 is placed in the catalytic converter; the outlet of the temperature regulating device is connected with a gas inlet of the wet desulfurization tank; the wet desulfurization tank is internally provided with red mud-water slurry; all structures in the system are connected through pipelines, and regulating valves are arranged on all the pipelines.
9. The blast furnace gas desulfurization and heavy metal capturing system according to claim 8, wherein: the method also 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 according to any one of claims 1-4.
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