CN117070256A - Process method and device for removing organic sulfur in blast furnace gas - Google Patents
Process method and device for removing organic sulfur in blast furnace gas Download PDFInfo
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- CN117070256A CN117070256A CN202311000385.7A CN202311000385A CN117070256A CN 117070256 A CN117070256 A CN 117070256A CN 202311000385 A CN202311000385 A CN 202311000385A CN 117070256 A CN117070256 A CN 117070256A
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- blast furnace
- desulfurizing agent
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- 125000001741 organic sulfur group Chemical group 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 62
- 230000008569 process Effects 0.000 title claims abstract description 44
- 238000010521 absorption reaction Methods 0.000 claims abstract description 140
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 130
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 129
- 238000006243 chemical reaction Methods 0.000 claims abstract description 84
- 229910052717 sulfur Inorganic materials 0.000 claims description 182
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 170
- 239000011593 sulfur Substances 0.000 claims description 170
- 238000011069 regeneration method Methods 0.000 claims description 101
- 239000000463 material Substances 0.000 claims description 99
- 230000008929 regeneration Effects 0.000 claims description 94
- 239000000126 substance Substances 0.000 claims description 56
- 238000007599 discharging Methods 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 15
- 239000006096 absorbing agent Substances 0.000 claims description 14
- 239000000428 dust Substances 0.000 claims description 13
- 238000003860 storage Methods 0.000 claims description 9
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000003034 coal gas Substances 0.000 claims description 5
- 230000001172 regenerating effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000006298 dechlorination reaction Methods 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 abstract description 54
- 238000006477 desulfuration reaction Methods 0.000 abstract description 36
- 230000023556 desulfurization Effects 0.000 abstract description 34
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 228
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 48
- 229910052742 iron Inorganic materials 0.000 description 25
- 239000003054 catalyst Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 description 13
- 229910000831 Steel Inorganic materials 0.000 description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 238000004064 recycling Methods 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- -1 halogen ions Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005493 condensed matter Effects 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- 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
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/101—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids with water only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/485—Sulfur compounds containing only one sulfur compound other than sulfur oxides or hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- 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
- C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
- C10K1/10—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids
- C10K1/12—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors
- C10K1/14—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic
- C10K1/143—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors with aqueous liquids alkaline-reacting including the revival of the used wash liquors organic containing amino groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/308—Carbonoxysulfide COS
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Treating Waste Gases (AREA)
- Industrial Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention discloses a process method and a device for removing organic sulfur in blast furnace gas, which relate to the field of blast furnace gas fine desulfurization, wherein the process method comprises the steps of pretreating the blast furnace gas, and then carrying out desulfurization treatment, wherein the desulfurization treatment is to carry out desulfurization treatment on carbonyl sulfide COS and CS contained in the blast furnace gas 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, obtaining the purified gas and outputting the purified gas to a downstream pipe network. The device comprises a pretreatment system and an organic sulfur absorption and conversion system, wherein the pretreatment is carried out in the pretreatment system, and the desulfurization treatment is carried out in the organic sulfur absorption and conversion system. The process flow adopts the integrated desulfurizing agent for absorption and conversion, so that the desulfurizing process flow is simplified, the number of process devices is reduced, the efficiency is improved, and the cost is reduced; the desulfurizing agent is recycled, so that the resource waste is reduced and the cost is lowered; the desulfurization process does not need an extra heat source, and is more energy-saving.
Description
Technical Field
The invention relates to the field of blast furnace gas desulfurization, in particular to a process method and a device for removing organic sulfur in blast furnace gas.
Background
The blast furnace gas is a byproduct combustible gas with low heat value containing carbon monoxide, carbon dioxide, nitrogen and hydrogen in the iron-making process of iron and steel enterprises, has high yield and wide application, and can be used as fuel of blast furnace hot blast stoves, steel rolling heating furnaces and self-contained electric boilers of steel plants. The raw blast furnace gas also contains a large amount of dust and sulfides, which are mainly classified into organic sulfur and inorganic sulfur, and the organic sulfur content is about 70-85% higher than that of the inorganic sulfur. The main component of organic sulfur is carbonyl sulfide (COS), carbon disulfide (CS) 2 ) Sulfide, mercaptan, etc., wherein COS accounts for about 60-85% of the total sulfur; the main component of inorganic sulfur is mainly hydrogen sulfide, and also comprises a small amount of sulfur dioxide and the like. The discharge of sulfur dioxide in the untreated blast furnace gas and the flue gas is out of standard, and SO in the flue gas discharged by the untreated blast furnace gas is common 2 The content is greater than 50mg/Nm 3 Sometimes even up to 200mg/Nm 3 The above.
At present, the blast furnace gas desulfurization of iron and steel enterprises basically adopts end treatment, namely, the blast furnace gas is subjected to dust removal purification and TRT power generation and then is sent to subsequent devices such as a hot blast stove, a steel rolling heating furnace, a power plant boiler and the like, and organic sulfur is converted into inorganic Sulfur (SO) after combustion 2 ) Then desulfurization treatment, also called post desulfurization process, is carried out. However, the sulfur content after the end treatment does not meet the national latest ultra-clean emission requirements (below 50 mg/Nm) 3 Part of the area requires less than 35mg/Nm 3 The latest environmental policy requires that the steel industry all reach below 35mg/Nm by the end of 2025 3 ). The main technologies of end treatment at present are SDS, semi-dry method of circulating fluidized bed, active carbon method and the like, which need to arrange desulfurization facilities (hot blast stove, heating furnace, gas boiler and the like) at multiple points, thus not only having large occupied area and more equipment maintenance points, but also being characterized in that because of the desulfurization at the end, the blast furnace gas contains H 2 S has serious corrosion to TRT facilities and conveying pipelines, and can shorten the service life of the generator, and the early investment cost and the later maintenance cost are relatively high. And each tail end is required to be additionally provided with a whole set of desulfurization equipment, so that the investment cost is high.
Therefore, the sulfide in the blast furnace gas is directly removed before the blast furnace gas is combusted, and the combustion is carried out after sulfur removal, so that the content of sulfur dioxide in the combusted flue gas can reach the national ultra-low emission requirement, and a post-desulfurization process is not needed, and the method is called as a pre-desulfurization process and also called as source management. The front desulfurization process is simple, the occupied area is small, the operation cost is low, no refractory byproducts are generated, the purified coal gas is directly supplied to each production unit at the downstream to be used as energy for combustion, the national ultra-low emission requirement can be directly met, the direct emission is avoided, the solid waste is not generated, the service life of a coal gas pipeline can be prolonged due to the reduction of corrosion, the economic benefit and the social benefit are greatly improved, and the desulfurization cost is greatly reduced.
The sulfur in the blast furnace gas is mainly COS, and the desulfurization of the blast furnace gas is mainly performed by removing COS. Because the carbonyl sulfide has stable property, the carbonyl sulfide is difficult to directly react with other compounds in the oxygen-free environment of blast furnace gas, is not easy to dissociate or liquefy, and is difficult to remove.
Sulfur dioxide is a main environmental protection treatment object in the exhaust emission of industrial production, and sulfur dioxide can be oxidized into sulfuric acid mist or sulfate aerosol in the atmosphere, so that the sulfur dioxide is an important source of environmental acidification. The acid gas desulfurizing technology is divided into inorganic sulfur eliminating and organic sulfur eliminating, and has been mature in petrochemical industry, natural gas industry, coal chemical industry and other industry. However, in the steel industry, inorganic sulfur removal technology is continuously used, and with the help of the national policy, the steel enterprises in the next years can finish the source management of coal gas, namely the removal of organic sulfur. Because of the particularity of the iron making process in the steel industry, the organic sulfur removal (fine desulfurization) technical scheme referred to from the chemical industry is not ideal, the engineering cost is high, the operation cost is expensive, and the problem of ultra-low emission cannot be really solved.
The existing technology for removing COS mainly comprises the steps of catalyzing and hydrolyzing COS by using a catalyst, and absorbing H by using a desulfurizing agent 2 S, S. The method has complex process flow, more types of needed devices, large occupied area and high cost.
Accordingly, those skilled in the art have focused on developing a simpler, less costly pre-desulfurization process.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to solve the technical problem of how to develop a pre-desulfurization process with simpler process and apparatus and lower cost.
In order to achieve the above purpose, the invention provides a process method for removing organic sulfur in blast furnace gas, which comprises the following steps:
pretreating blast furnace gas to obtain gas to be desulfurized, wherein the blast furnace gas is gas generated by blast furnace ironmaking, and the gas to be desulfurized contains COS and CS 2 ；
Desulfurizing the gas to be desulfurized, wherein the gas to be desulfurized is mixed and contacted with an absorption and conversion integrated desulfurizing agent so as to mix COS and CS contained in the gas to be desulfurized 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, obtaining sulfur-rich substances and clean gas; and outputting the clean gas to a downstream pipe network.
Further, the pretreatment of the blast furnace gas comprises: receiving and conveying the blast furnace gas; and/or carrying out dust removal treatment on the blast furnace gas; and/or dechlorinating the blast furnace gas.
Further, the method further comprises the following steps: and circularly mixing and contacting the sulfur-rich substance with the gas to be desulfurized, wherein the sulfur-rich substance contains the unconsumed integrated desulfurizing agent for absorption and conversion.
Further, the method further comprises the following steps: regenerating the sulfur-rich material to separate tail gas and regenerated desulfurizing agent, wherein the tail gas contains H 2 S gas, the regenerated desulfurizing agent contains the absorbing and converting integrated desulfurizing agent.
Further, before the regeneration treatment of the sulfur-rich material, the sulfur-rich material is subjected to a heat exchange treatment with the regenerated desulfurizing agent that has been separated before.
Further, the method further comprises the following steps: and carrying out post-treatment on the tail gas.
And a device for removing organic sulfur in blast furnace gas, which comprises a pretreatment system and an organic sulfur absorption and conversion system,
the pretreatment system comprises a pretreatment device, a blast furnace gas inlet channel and a gas outlet channel to be desulfurized, which are arranged on the pretreatment device;
the blast furnace gas inlet channel is connected with an upstream device so as to input the blast furnace gas from upstream into the pretreatment device for pretreatment to obtain gas to be desulfurized, wherein the blast furnace gas is gas generated by blast furnace ironmaking, and the gas to be desulfurized contains COS and CS 2 ；
The organic sulfur absorption and conversion system comprises an absorption tower, and a gas inlet channel, a desulfurizing agent inlet channel, a clean gas outlet channel and a sulfur-rich substance outlet channel which are arranged on the absorption tower, wherein a cavity is formed in the absorption tower;
the gas inlet channel of the organic sulfur absorption and conversion system to be desulfurized is connected with the gas outlet channel of the pretreatment system to be desulfurized so as to input the gas to be desulfurized into a cavity in the absorption tower;
the desulfurizing agent feeding channel is connected with the desulfurizing agent feeding device so as to input the desulfurizing agent integrated with the absorption and conversion into a cavity in the absorption tower;
in the cavity inside the absorption tower, the gas to be desulfurized is mixed and contacted with the integrated desulfurizing agent for absorption and conversion so as to mix COS and CS contained in the gas to be desulfurized 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, obtaining sulfur-rich substances and clean gas;
the clean gas outlet channel is used for outputting the clean gas to a downstream pipe network; the method comprises the steps of,
the sulfur-rich material discharging channel is used for discharging the sulfur-rich material.
Further, the pretreatment system comprises a conveying pipeline, a dust removing system and/or a chlorine removing system.
Further, the gas inlet channel and the sulfur-rich material outlet channel are arranged at the lower part of the absorption tower, the clean gas outlet channel and the desulfurizing agent inlet channel are arranged at the upper part of the absorption tower, so that the absorption and conversion integrated desulfurizing agent enters the cavity inside the absorption tower from the upper part of the absorption tower, the gas to be desulfurized enters the cavity inside the absorption tower from the lower part of the absorption tower, the sulfur-rich material obtained after the gas to be desulfurized and the absorption and conversion integrated desulfurizing agent are mixed and contacted in the cavity inside the absorption tower is discharged from the lower part of the absorption tower, and the clean gas is output to a downstream pipe network from the upper part of the absorption tower.
Further characterized in that the organic sulfur absorbing and converting system also comprises a sulfur-rich material circulating system,
the sulfur-rich substance circulating system comprises a sulfur-rich substance circulating pump and a circulating pipeline, one end of the circulating pipeline is connected with the sulfur-rich substance discharging channel of the organic sulfur absorption and conversion system, the other end of the circulating pipeline is connected with a sulfur-rich substance feeding channel arranged on the absorption tower, and the sulfur-rich substance circulating pump is arranged on the circulating pipeline so as to pump the sulfur-rich substance from the sulfur-rich substance discharging channel to the sulfur-rich substance feeding channel, so that the sulfur-rich substance enters a cavity inside the absorption tower to be in circulating mixed contact with the coal gas to be desulfurized, wherein the sulfur-rich substance contains unconsumed integrated desulfurizing agent for absorption and conversion.
Further, the sulfur-rich material circulation system further includes a sulfur-rich material cooler provided on the circulation pipe to cool the sulfur-rich material.
Further, the device also comprises a regeneration system, wherein the regeneration system comprises a regeneration tower, and a sulfur-rich substance regeneration feeding channel, a regeneration desulfurizing agent discharging channel and a tail gas discharging channel which are arranged on the regeneration tower, wherein a cavity is formed in the regeneration tower;
the sulfur-rich material regeneration feed channel is connected with the sulfur-rich material discharge channel of the absorption tower so as to input the sulfur-rich material from the absorption tower into the cavity inside the regeneration tower for regeneration treatment, therebySeparating off the tail gas and the regenerated desulfurizing agent, wherein the tail gas contains H 2 S gas, the regenerated desulfurizing agent contains the absorbing and converting integrated desulfurizing agent;
the regenerated desulfurizing agent discharging channel is connected with the desulfurizing agent feeding channel of the absorption tower so as to convey the separated regenerated desulfurizing agent from the regeneration tower to a cavity in the absorption tower for repeated use;
the tail gas is connected with the tail gas receiving device through the tail gas outlet channel, so that the separated tail gas is conveyed to the tail gas receiving device.
Further, the sulfur-rich material regeneration feed channel is connected with the sulfur-rich material discharge channel through a first pipeline, and the regenerated desulfurizing agent discharge channel is connected with the desulfurizing agent feed channel through a second pipeline.
Further, the regeneration system further comprises a first heat exchanger connected with the first pipeline and the second pipeline respectively, so that the sulfur-rich substances in the first pipeline and the regenerated desulfurizing agent in the second pipeline exchange heat in the first heat exchanger.
Further, a regenerated desulfurizing agent cooler is arranged on the second pipeline and used for cooling the regenerated desulfurizing agent.
Further, a storage tank is arranged on the second pipeline and used for storing the absorbing and converting integrated desulfurizing agent and the regenerated desulfurizing agent.
Further, the regeneration system also includes an exhaust gas cooler coupled to the exhaust gas outlet of the regeneration tower configured to cool the exhaust gas to a condensed material.
Further, the regeneration system also comprises a tail gas separator connected with the tail gas cooler for separating H in the condensed substances 2 S gas and a reflux material, wherein the reflux material contains the sulfur-rich material.
Further, the regeneration system also comprises a reflux pump which is respectively connected with the tail gas separator and the regeneration tower and is used for conveying the reflux substance to the regeneration tower.
Further, the device also comprises an exhaust gas treatment system, wherein the exhaust gas treatment system is arranged at the downstream of the regeneration system and is used for treating H generated after the regeneration treatment 2 And (5) carrying out post-treatment on the S gas.
The invention has the following technical effects:
(1) The invention adopts the integrated desulfurizing agent for absorption and conversion, thereby simplifying the prior desulfurization process flow, reducing the number of process devices, improving the efficiency and reducing the cost.
(2) By recycling the working substances, the resource waste is reduced and the cost is reduced.
(3) The desulfurization process is carried out at normal temperature and normal pressure, no extra heat source is needed, no energy consumption is generated, and the energy is saved.
The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.
Drawings
FIG. 1 is a schematic illustration of a process according to a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of a pretreatment system in accordance with a preferred embodiment of the present invention;
FIG. 3 is a schematic diagram of an absorption conversion system and regeneration system according to a preferred embodiment of the present invention;
FIG. 4 is a schematic diagram of an exhaust treatment system according to a preferred embodiment of the present invention.
Reference numerals illustrate:
1.1-pretreatment tower, 1.2-pretreatment circulating pump;
the device comprises a 1-absorption tower, a 2-sulfur-rich substance circulating pump, a 3-sulfur-rich substance filter, a 4-first heat exchanger, a 5-regeneration tower, a 6-reboiler, a 7-tail gas cooler, an 8-tail gas separator, a 9-reflux pump, a 10-storage tank, a 11-regeneration desulfurizing agent pump, a 12-regeneration desulfurizing agent cooler, a 13-regeneration desulfurizing agent filter, a 14-to-be-desulfurized gas separator, a 15-clean gas separator, a 16-sulfur-rich substance cooler, a 17-sulfur-rich substance pump, an 18-tail gas treatment system air inlet, a 19-purified gas separating tank, a 20-desulfurization reactor, a 21-air inlet channel, a 22-sulfur melting kettle, a 23-steam inlet channel, a 24-condensate output channel, a 25-sulfur melting channel and a 26-medicament tank.
Detailed Description
The following description of the preferred embodiments of the present invention refers to the accompanying drawings, which make the technical contents thereof more clear and easy to understand. The present invention may be embodied in many different forms of embodiments and the scope of the present invention is not limited to only the embodiments described herein.
In the drawings, like structural elements are referred to by like reference numerals and components having similar structure or function are referred to by like reference numerals. The dimensions and thickness of each component shown in the drawings are arbitrarily shown, and the present invention is not limited to the dimensions and thickness of each component. The thickness of the components is exaggerated in some places in the drawings for clarity of illustration.
FIG. 1 is a schematic diagram of a process for removing organic sulfur from blast furnace gas according to the present invention, and as shown in FIG. 1, the process provided by the present invention may include:
pretreating blast furnace gas to obtain a gas containing COS and CS 2 Wherein, the blast furnace gas is gas generated by blast furnace ironmaking, the gas generated by blast furnace ironmaking is low heat value combustible energy gas, and the gas is one of main energy supplies of iron and steel plants due to larger gas quantity;
desulfurizing the gas to be desulfurized, wherein the desulfurizing is to mix and contact the gas to be desulfurized with an absorption and conversion integrated desulfurizing agent so as to mix COS and CS contained in the gas to be desulfurized 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, obtaining sulfur-rich substances and clean gas; and outputting the clean gas to a downstream pipe network.
In some embodiments, the pretreatment of the blast furnace gas may include: receiving and conveying blast furnace gas; and/or dust removal treatment is carried out on the blast furnace gas; and/or the blast furnace gas is subjected to chlorine removal treatment to effectively remove dust and/or halogen ions (chlorine Cl, bromine Br and the like) in the blast furnace gas.
In some embodiments, the dedusting and/or dechlorination treatment is an alkaline wash to reduce particulate matter and/or dechlorination.
In some embodiments, the absorption-conversion integrated desulfurization agent is an alcohol amine compound, the reaction mechanism is: COS+H 2 O＝
H 2 S+CO 2 ，CS 2 +2H 2 O＝2H 2 S+CO 2 ，
In some embodiments, the process for removing organic sulfur in blast furnace gas may further comprise circulating, mixing and contacting a sulfur-rich material with the gas to be desulfurized, wherein the sulfur-rich material contains an unconsumed integrated absorbent and conversion desulfurizing agent, and may be continuously used for recycling COS and CS contained in the gas to be desulfurized 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, recycling improves the utilization rate of the integrated desulfurizing agent for absorption and conversion.
In some embodiments, the process for removing organic sulfur from blast furnace gas may further comprise regenerating the sulfur-rich material to separate a tail gas and a regenerated desulfurizing agent, wherein the tail gas contains H 2 S and CO 2 The gas, regenerated desulfurizing agent contains the absorbing and converting integrated desulfurizing agent, thereby realizing the recycling of the desulfurizing agent.
In some embodiments, the process method for removing organic sulfur in blast furnace gas can further comprise heat exchange treatment of the sulfur-rich material and the regenerated desulfurizing agent separated before the regeneration treatment of the sulfur-rich material, so that heat generated in the process flow is fully utilized, and the effects of energy conservation and environmental protection are achieved by increasing the heat exchange efficiency.
In some embodiments, the process for removing organic sulfur from blast furnace gas may further comprise post-treating the tail gas.
In some embodiments, the tail gas is post-treated to convert elemental sulfur therein to sulfur.
In some embodiments, the process for converting sulfur element in the tail gas into sulfur is as follows:
the complex iron desulfurization process utilizes the redox property of the alkaline GLT complex iron catalyst to absorb H in tail gas 2 S。H 2 S is directly oxidized by a complex iron catalyst to generate elemental sulfur, the complex iron is converted into complex ferrous iron to form a catalyst rich solution, then air is blown in the regeneration process, and the complex ferrous iron in the catalyst rich solution is oxidized by the air to convert the complex ferrous iron in the catalyst rich solution into complex iron, so that the complex ferrous iron is regenerated and reused. The generated sulfur is treated by a sulfur recovery system.
The principle of the GLT complex iron desulfurization reaction is as follows:
(1) Absorption reaction
H 2 S(g)+2Fe 3+ L(a)→2H + (a)+S↓+2Fe 2+ L(a)
(2) Regeneration reaction
1/2O 2 (g)+H 2 O(a)+2Fe 2+ L(a)→2OH - (a)+2Fe 3+ L(a)
(3) Total reaction of desulfurization
H 2 S+1/2O 2 →H 2 O+S↓
In the overall reaction, the effect of the complex iron ions is to transfer the electrons obtained in the absorption reaction to elemental oxygen in the regeneration reaction. The production of each elemental sulphur atom requires two ferric ions to participate in the reaction. Thus, the iron ions, although taking part in the reaction, are not consumed in the overall reaction, but rather act as intermediate electron transfer species for the reaction of hydrogen sulfide and oxygen, and are part of the catalyst system.
Fig. 2-4 are schematic diagrams of an apparatus for removing organic sulfur from blast furnace gas, which may include a pretreatment system and an organic sulfur absorption conversion system, in which a process for removing organic sulfur from blast furnace gas may be performed.
In some embodiments, the organic sulfur absorbing conversion system may further comprise a sulfur-rich species recycle system.
In some embodiments, the means for removing organic sulfur from the blast furnace gas may further comprise a regeneration system.
In some embodiments, the means for removing organic sulfur from the blast furnace gas may further comprise a tail gas treatment system.
As shown in fig. 2, the pretreatment may be performed in a pretreatment system of a device for removing organic sulfur in blast furnace gas, and the pretreatment system may include a pretreatment device, and a blast furnace gas inlet channel and a gas outlet channel to be desulfurized provided on the pretreatment device; wherein the blast furnace gas inlet channel is connected with an upstream device to input blast furnace gas into a pretreatment device from upstream for pretreatment to obtain gas to be desulfurized, wherein the blast furnace gas is gas generated by blast furnace ironmaking, and the gas to be desulfurized contains COS (carbonyl sulfide) and CS (CS) 2 。
In some embodiments, the preprocessing system has two main functions: dedusting and/or chlorine removal. For the dust removal of the upstream of a residual pressure power generation system (TRT) which contains a large amount of particles (smoke dust) in the gas, the production requirement cannot be met, in addition, for the blast furnace gas which contains a large amount of halogen (chloride ions), the chloride ions are in the form of gaseous HCl in the gas, condensed water is formed after the temperature of the gas is reduced, so that hydrochloric acid is formed, and the corrosion to a gas pipe network and equipment is high, so that dust removal and/or chlorine removal pretreatment are required.
In some embodiments, the pretreatment system can comprise a pretreatment tower 1.1, blast furnace gas enters the pretreatment tower 1.1 from the lower part, and is in countercurrent contact with absorption liquid sprayed from the top of the tower (NaOH aqueous solution with a certain concentration) in the tower to perform sufficient mass transfer absorption, most HCl and smoke dust (particles) in the gas are absorbed, and the entrained liquid is removed through a gas-liquid separation section in the tower and then sent to the next procedure. The absorption liquid enters the pretreatment tower 1.1 from the top, contacts with gas from the bottom of the tower in a countercurrent way to absorb HCl and smoke dust therein, and automatically flows to the bottom of the pretreatment tower 1.1 to form a tower bottom rich liquid.
In some embodiments, the pretreatment system may further include a pretreatment substance circulation system, and the pretreatment substance circulation system may include a pretreatment circulation pump 1.2 and a third pipeline, where the pretreatment substance circulation system is connected to the pretreatment column 1.1, and the rich liquid at the bottom of the column is sent to the top of the pretreatment column 1.1 through the third pipeline via the pretreatment circulation pump 1.2 for circulation absorption.
In some embodiments, after the salt concentration or the specific gravity of the solution in the rich liquid at the bottom reaches a set value, part of the rich liquid is discharged outside the boundary and the fresh solution is supplemented at the same time, so that the absorption liquid has enough absorption capacity.
In some embodiments, the pretreatment system may further comprise an alkali distribution tank, wherein the alkali distribution tank is connected with the pretreatment circulating pump 1.2 of the pretreatment substance circulating system, the alkali distribution tank is a subsurface tank, the original starting and the supplementing of soft water are completed in the alkali distribution tank, and the supplementing of the fresh alkali solution is continuously added by the pretreatment circulating pump 1.2 of the pretreatment substance circulating system.
In some embodiments, the pretreatment system is established downstream of a blast furnace residual pressure power generation system (TRT).
As shown in fig. 3, the desulfurization treatment can be performed in an organic sulfur absorption and conversion system of a device for removing organic sulfur in blast furnace gas, and the organic sulfur absorption and conversion system can comprise an absorption tower 1, and a gas inlet channel to be desulfurized, a desulfurizing agent feeding channel, a clean gas outlet channel and a sulfur-rich substance discharging channel which are arranged on the absorption tower 1, wherein a cavity is formed inside the absorption tower 1; the gas inlet channel of the organic sulfur absorption and conversion system to be desulfurized is connected with the gas outlet channel of the pretreatment system to be desulfurized so as to lead the gas containing COS and CS to be contained 2 Is input into a cavity inside the absorption tower 1.
The desulfurizing agent feeding channel is connected with the desulfurizing agent feeding device so as to input the desulfurizing agent integrated with the absorption and conversion into a cavity in the absorption tower 1; in the cavity of the absorption tower 1, the gas to be desulfurized is mixed and contacted with an integrated desulfurizing agent for absorption and conversion to mix COS and CS contained in the gas to be desulfurized 2 Absorption and conversion to H 2 S, and absorbs H generated by conversion 2 S, obtaining sulfur-rich substances and clean gas.
The clean gas outlet channel is used for outputting clean gas to a downstream pipe network. The clean gas contains low-heat-value combustible gas of carbon monoxide, carbon dioxide, nitrogen and hydrogen, has large yield and wide application, and can be used as fuel of a blast furnace hot blast stove, a steel rolling heating furnace and a steel mill self-provided electric boiler, so that the clean gas can be supplied for downstream use.
The sulfur-rich material discharging channel is used for discharging the sulfur-rich material.
In some embodiments, the gas inlet channel and the sulfur-rich material outlet channel of the organic sulfur absorption and conversion system are arranged at the lower part of the absorption tower 1, the purified gas outlet channel and the desulfurizing agent inlet channel are arranged at the upper part of the absorption tower 1, so that the absorption and conversion integrated desulfurizing agent enters into the cavity inside the absorption tower 1 from the upper part and the gas to be desulfurized from the lower part, and the gas to be desulfurized can be fully contacted with the absorption and conversion integrated desulfurizing agent entering from the upper part in the cavity inside the absorption tower 1 to form purified gas which is output to a downstream pipe network from the upper part of the absorption tower 1, and the obtained sulfur-rich material is discharged from the lower part of the absorption tower.
In some embodiments, the integrated desulfurizing agent for absorption and conversion is liquid, such as liquid containing alcohol amine compound, the integrated desulfurizing agent for absorption and conversion is sprayed into the absorption tower 1 from top to bottom from a desulfurizing agent feeding channel positioned at the upper part of the absorption tower 1, and the gas to be desulfurized is fully contacted with the integrated desulfurizing agent for absorption and conversion flowing reversely from bottom to top in the inner cavity of the absorption tower 1, so that COS and CS in the gas to be desulfurized are fully contacted 2 、H 2 S and other gases are converted and absorbed and enter a liquid phase, and the gas after washing and absorption is clean gas which can be directly fed into a clean gas pipe network for supplying.
In some embodiments, the organic sulfur absorbing and converting system may further include a clean gas separator 15, where the clean gas separator 15 is connected to the clean gas outlet channel, and the clean gas is defogged by the clean gas separator 15 to remove entrained fine droplets and then sent to the clean gas pipe network to supply downstream, and the clean gas separator 15 is connected to the clean gas outlet channel of the organic sulfur absorbing and converting system.
In some embodiments, the gas to be desulfurized is purified by the gas separator 14 to be desulfurized and then sent to the organic sulfur absorption and conversion system, the gas separator 14 to be desulfurized is connected with a gas inlet channel of the gas to be desulfurized of the organic sulfur absorption and conversion system, and the purification treatment is used for removing impurities such as particles in the gas to be desulfurized.
As shown in FIG. 3, the circulating mixing contact of the sulfur-rich material and the gas to be desulfurized can be performed in a sulfur-rich material circulating system of a device of the organic sulfur absorption and conversion system, the sulfur-rich material circulating system can comprise a sulfur-rich material circulating pump 2 and a circulating pipeline, one end of the circulating pipeline is connected with a sulfur-rich material discharging channel of the organic sulfur absorption and conversion system, the other end of the circulating pipeline is connected with a sulfur-rich material feeding channel arranged on the absorption tower 1, the sulfur-rich material circulating pump 2 is arranged on the circulating pipeline so as to pump the sulfur-rich material from the sulfur-rich material discharging channel to the sulfur-rich material feeding channel, and thus the sulfur-rich material enters into a cavity inside the absorption tower 1 to be in circulating mixing contact with the gas to be desulfurized, the sulfur-rich material contains unconsumed integrated desulfurizing agent for absorption and conversion, and COS and CS contained in the gas to be desulfurized can be continuously carried out 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S。
In some embodiments, the sulfur-rich species circulation system may further include a sulfur-rich species cooler 16, the sulfur-rich species cooler 16 being disposed on the circulation conduit to cool the sulfur-rich species. The sulfur-rich material is discharged from the sulfur-rich material discharging channel and enters the circulating pipeline, and is pumped by the sulfur-rich material circulating pump 2 and cooled to a proper temperature by the sulfur-rich material cooler 16, and then is sent into the absorption tower 1 from the sulfur-rich material feeding channel.
In some embodiments, the sulfur-rich material feed channel is arranged in the middle of the absorber tower 1 and is matched with the integrated desulfurizing agent for absorption and conversion entering from the desulfurizing agent feed channel in the upper part of the absorber tower 1, and the gas to be desulfurized is mixed and contacted with the sulfur-rich material entering from the middle of the absorber tower 1 from bottom to top (the unconsumed integrated desulfurizing agent for absorption and conversion contained in the sulfur-rich material is used for mixing and contacting COS and CS contained in the gas to be desulfurized 2 First, the H generated by the primary absorption and conversion is absorbed and converted 2 S), and then mixing and contacting with an integrated desulfurizing agent for absorption and conversion (integrated desulfurizing agent for absorption and conversion is used for treating COS and CS contained in the gas to be desulfurized) entering through a desulfurizing agent feeding channel at the upper part of the absorption tower 1 2 Performing the absorption and conversion again, and absorbing H generated by the conversion 2 S), thereby achieving a more efficient desulfurization, and finally for COS and CS 2 Is effective in removing (1)The rate is more than 90 percent.
In some embodiments, the absorber 1 comprises a lower packing and an upper packing, the sulfur-rich material is passed through the sulfur-rich material circulation pump 2, and the regenerated desulfurizing agent is passed through the regenerated desulfurizing agent pump 11, and sprayed into the absorber 1 from the top of the lower packing and the top of the upper packing, respectively.
As shown in fig. 3, the sulfur-rich material regeneration treatment may be performed in a regeneration system of a device for removing organic sulfur in blast furnace gas, and the regeneration system may include a regeneration tower 5, and a sulfur-rich material regeneration feed channel, a regeneration desulfurizing agent discharge channel and a tail gas outlet channel disposed on the regeneration tower 5, wherein a cavity is formed inside the regeneration tower 5;
the sulfur-rich material regeneration feed channel is connected with the sulfur-rich material discharge channel of the absorption tower 1 to input the sulfur-rich material from the absorption tower 1 into the cavity inside the regeneration tower 5 for regeneration treatment so as to separate the tail gas and the regenerated desulfurizing agent, wherein the tail gas contains H 2 S and CO 2 The gas contains the integrated desulfurizing agent for absorption and conversion;
the regenerated desulfurizing agent discharging channel is connected with the desulfurizing agent feeding channel of the absorption tower so as to input the regenerated desulfurizing agent from the regeneration tower 5 into the cavity inside the absorption tower 1 for repeated use;
The tail gas is conveyed to be connected with the tail gas receiving device through the tail gas outlet channel so as to convey the separated tail gas to the tail gas receiving device.
In some embodiments, the sulfur-rich material regeneration feed passage is connected to the sulfur-rich material discharge passage by a first conduit and the regenerated sulfur-scavenger discharge passage is connected to the sulfur-scavenger feed passage by a second conduit. The sulfur-rich material is discharged from the sulfur-rich material discharging channel and then enters the regeneration tower 5 from the sulfur-rich material regeneration feeding channel through the first pipeline, and H-containing is separated 2 S and CO 2 The tail gas of the gas and the regenerated desulfurizing agent are discharged from a discharging channel of the regenerated desulfurizing agent and then enter an absorption tower 1 from a desulfurizing agent feeding channel through a second pipeline, and H is contained 2 S and CO 2 And the tail gas of the gas is discharged from the tail gas outlet channel to the tail gas receiving device.
In some embodiments, the regeneration system may further include a first heat exchanger 4, where the first heat exchanger 4 is connected to the first conduit and the second conduit, respectively, such that the sulfur-rich material in the first conduit and the regenerated sulfur-removing agent in the second conduit are heat exchanged in the first heat exchanger. For the regenerated desulfurizing agent through thermal regeneration, the temperature of the regenerated desulfurizing agent from the regenerated desulfurizing agent discharging channel is higher, the sulfur-rich substance firstly passes through the first heat exchanger 4 to exchange heat with the regenerated desulfurizing agent from the regenerated desulfurizing agent discharging channel after coming out of the regenerated desulfurizing agent discharging channel at the first heat exchanger 4, the regenerated desulfurizing agent is cooled and the sulfur-rich substance is heated, and the heated sulfur-rich substance enters the regeneration tower 5 from the sulfur-rich substance regeneration feeding channel of the regeneration tower 5 for thermal regeneration, so that the waste heat in the regeneration process is fully utilized, and the energy-saving effect is better.
In some embodiments, a regenerated desulfurization agent cooler 12 is provided on the second conduit, the regenerated desulfurization agent cooler 12 being configured to cool the temperature of the regenerated desulfurization agent such that the temperature of the regenerated desulfurization agent entering the absorption tower 1 reaches a suitable absorption conversion temperature.
In some embodiments, a storage tank 10 is arranged on the second pipeline and is used for storing the integrated desulfurizing agent for absorption and conversion and/or the integrated desulfurizing agent for regeneration, facilitating the preparation of the integrated desulfurizing agent for absorption and conversion, adjusting the water balance of the system and recovering the integrated desulfurizing agent for absorption and conversion during the stopping process.
In some embodiments, the first heat exchanger 4 is disposed upstream of the storage tank 10, and the regenerated desulfurizing agent enters the storage tank 10 after being subjected to heat exchange and temperature reduction by the first heat exchanger 4.
In some embodiments, the storage tank 10 is a defoamer storage tank 10 to prevent foaming of the easily foamable absorption and conversion integrated desulfurizer and to quickly foam during foaming.
In some embodiments, a sulfur-rich material pump 7 is provided on the first conduit for pumping the sulfur-rich material into the regeneration column 5.
In some embodiments, a sulfur-rich material filter 3 is disposed on the first pipe, and the sulfur-rich material passes through the first filter to filter out trace impurities in the sulfur-rich material, and then enters the regeneration tower 5.
In some embodiments, a regenerated desulfurizing agent pump 11 is arranged on the second pipeline, and is used for pumping the regenerated desulfurizing agent to the absorption tower 1 for recycling.
In some embodiments, the regenerated desulfurizing agent pump 11 is used to pump the integrated desulfurizing agent for absorption and conversion stored in the storage tank 10 and/or the regenerated desulfurizing agent to the absorption tower 1 for use.
In some embodiments, the second pipeline is provided with a regenerated desulfurizing agent filter 13, and the regenerated desulfurizing agent is firstly subjected to online filtration through the second filter to ensure the cleanliness of the regenerated desulfurizing agent, and then enters the absorption tower 1 for recycling.
In some embodiments, the regeneration treatment may be a steam stripping treatment, the regeneration tower 5 is a steam stripping tower for steam stripping treatment, the sulfur-rich material regeneration feed channel is arranged at the upper part of the steam stripping tower, and the sulfur-rich material passes through the steam stripping tower from top to bottom to be fully contacted with the countercurrent steam stripping steam from the sulfur-rich material regeneration feed channel to fully contact H in the sulfur-rich material 2 S and CO 2 The gas is resolved to form H-containing 2 S and CO 2 The tail gas of the gas contains about 95% CO 2 And less than 1% H 2 S。
In some embodiments, the lower part of the regeneration column 5 is provided with two reboilers 6 for providing the heat source of the stripping column.
In some embodiments, the heat source for the stripper is provided by off-line low pressure steam or electrical heating.
In some embodiments, the regeneration system may further comprise an exhaust cooler 7, the exhaust cooler 7 being connected to the exhaust outlet of the regeneration tower and configured to cool the exhaust to condensed matter.
In some embodiments, the regeneration system may further comprise an off-gas separator 8, the off-gas separator 8 being connected to the off-gas cooler 7 for separating H from the condensed material 2 S and CO 2 A gas and a reflux substance, wherein the reflux substance contains a sulfur-rich substance, H 2 S and CO 2 The gas is delivered to the tail gas receiving device.
In some embodiments, a reflux pump 9 may be further included, where the reflux pump 9 is connected to the tail gas separator 8 and the regeneration tower 5, respectively, for delivering reflux materials to the regeneration tower 5 for further regeneration.
In some embodiments, the pretreatment circulation pump 1.2, the sulfur-rich material circulation pump 2, the reflux pump 9, the regenerative desulfurizing agent pump 11, and the sulfur-rich material pump 17 function as pressurization conveyance.
In some embodiments, the exhaust gas receiving device is an exhaust gas treatment system, and the exhaust gas aftertreatment is performed in the exhaust gas treatment system. The exhaust treatment system is disposed downstream of the regeneration system. Containing H 2 S and CO 2 The tail gas of the gas enters the tail gas treatment system for tail gas aftertreatment after exiting from the tail gas outlet channel of the regeneration system.
As shown in fig. 4, the exhaust treatment system may include four sections: the absorption-regeneration part, the sulfur filtering refining part and the medicament supplementing part are specifically as follows:
1) Absorption-regeneration section:
the main function of the absorption-regeneration part is to remove H in the tail gas 2 S, the regeneration of the absorbent is realized to meet the requirement of recycling, and the cost is reduced, wherein the absorbent is a complex iron catalyst.
H-containing from regeneration system 2 S and CO 2 The tail gas of the gas enters an absorption compartment of an absorption oxidation tank of a desulfurization reactor 20 through a gas inlet 18 of the tail gas treatment system to be subjected to bubbling absorption to directly absorb and convert hydrogen sulfide into HS - Then the purified tail gas is separated out of the system through a purified gas liquid separating tank 19, ferric iron in the complex iron catalyst is reduced into ferrous iron to form a complex iron catalyst rich solution, and the complex iron catalyst rich solution enters a regeneration compartment of an absorption oxidation tank.
In the regeneration compartment of the absorption oxidation tank, the rich solution of the complex iron catalyst is fully contacted and reacted with the air entering the regeneration compartment from the air inlet channel 21, so that the ferrous iron in the rich solution of the complex iron catalyst is oxidized into ferric iron, the regenerated complex iron catalyst is obtained, and the regenerated complex iron catalyst enters the absorption oxidation tank from the regeneration compartment.
And the elemental sulfur realizes sedimentation separation through the density difference between the liquid and the elemental sulfur to form sulfur slurry sediment which enters a sedimentation zone. And (3) conveying the sulfur slurry sediment in the sedimentation zone to a sulfur recovery part through a sulfur slurry pump for solid-liquid separation.
In order to maintain the temperature of the system constant, the solution of the complex iron catalyst is continuously pumped out by a circulating solution pump and sent to a solution second heat exchanger so as to control the temperature of the system to be about 50 ℃.
2) Sulfur filtering and refining part:
the sulfur slurry conveyed by the sulfur slurry pump is conveyed to a plate-and-frame filter press to separate a sulfur cake with the solid content of about 60wt% and filtrate (complex iron catalyst), the separated filtrate is circulated back to the system through the filtrate pump, the sulfur cake with the solid content of about 60wt% is subjected to sulfur refining through a sulfur melting kettle 22 with the height difference falling under a bin under the bin to obtain industrial grade qualified sulfur, and the sulfur melting kettle 22 is communicated with a steam input channel 23, a condensate output channel 24 and a sulfur melting channel 25.
3) Medicament supplementing part:
in the desulfurization process, the complex iron catalyst is consumed, and fresh complex iron catalyst needs to be timely replenished so that the absorption dosage and concentration of the whole system do not greatly fluctuate, and the complex iron catalyst is input into the absorption oxidation tank through the medicament tank 26.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (20)
1. The process method for removing the organic sulfur in the blast furnace gas is characterized by comprising the following steps of:
pretreating blast furnace gas to obtain gas to be desulfurized, wherein the blast furnace gas is gas generated by blast furnace ironmaking, and the gas to be desulfurized contains COS and CS 2 ；
Desulfurizing the gas to be desulfurized, wherein the gas to be desulfurized is mixed and contacted with an absorption and conversion integrated desulfurizing agent so as to mix COS and CS contained in the gas to be desulfurized 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, obtaining sulfur-rich substances and clean gas; and outputting the clean gas to a downstream pipe network.
2. The process for removing organic sulfur from blast furnace gas according to claim 1, wherein the pretreatment of the blast furnace gas comprises:
Receiving and conveying the blast furnace gas; and/or
Dust removal treatment is carried out on the blast furnace gas; and/or
And (3) performing dechlorination treatment on the blast furnace gas.
3. The process for removing organic sulfur from blast furnace gas as set forth in claim 1, further comprising:
and circularly mixing and contacting the sulfur-rich substance with the gas to be desulfurized, wherein the sulfur-rich substance contains the unconsumed integrated desulfurizing agent for absorption and conversion.
4. The process for removing organic sulfur from blast furnace gas as set forth in claim 1, further comprising:
regenerating the sulfur-rich material to separate tail gas and regenerated desulfurizing agent, wherein the tail gas contains H 2 S gas, the regenerated desulfurizing agent contains the absorbing and converting integrated desulfurizing agent.
5. The process for removing organic sulfur from blast furnace gas according to claim 4, wherein said sulfur-rich material is heat exchanged with said regenerated desulfurizing agent which has been separated before said sulfur-rich material is subjected to a regeneration treatment.
6. The process for removing organic sulfur from blast furnace gas as set forth in claim 4, further comprising: and carrying out post-treatment on the tail gas.
7. The device for removing the organic sulfur in the blast furnace gas is characterized by comprising a pretreatment system and an organic sulfur absorption and conversion system,
the pretreatment system comprises a pretreatment device, a blast furnace gas inlet channel and a gas outlet channel to be desulfurized, which are arranged on the pretreatment device;
the blast furnace gas inlet channel is connected with an upstream device so as to input the blast furnace gas from upstream into the pretreatment device for pretreatment to obtain gas to be desulfurized, wherein the blast furnace gas is gas generated by blast furnace ironmaking, and the gas to be desulfurized contains COS and CS 2 ；
The organic sulfur absorption and conversion system comprises an absorption tower, and a gas inlet channel, a desulfurizing agent inlet channel, a clean gas outlet channel and a sulfur-rich substance outlet channel which are arranged on the absorption tower, wherein a cavity is formed in the absorption tower;
the gas inlet channel of the organic sulfur absorption and conversion system to be desulfurized is connected with the gas outlet channel of the pretreatment system to be desulfurized so as to input the gas to be desulfurized into a cavity in the absorption tower;
the desulfurizing agent feeding channel is connected with the desulfurizing agent feeding device so as to input the desulfurizing agent integrated with the absorption and conversion into a cavity in the absorption tower;
In the cavity inside the absorption tower, the gas to be desulfurized is mixed and contacted with the integrated desulfurizing agent for absorption and conversion so as to mix COS and CS contained in the gas to be desulfurized 2 Absorbing and converting to H 2 S, and absorbs H generated by conversion 2 S, obtaining sulfur-rich substances and clean gas;
the clean gas outlet channel is used for outputting the clean gas to a downstream pipe network; the method comprises the steps of,
the sulfur-rich material discharging channel is used for discharging the sulfur-rich material.
8. The apparatus for removing organic sulfur from blast furnace gas according to claim 7, wherein said pretreatment system comprises a transfer line, a dust removing system and/or a chlorine removing system.
9. The apparatus for removing organic sulfur from blast furnace gas according to claim 7, wherein said gas inlet passage for gas to be desulfurized and said sulfur-rich material outlet passage are provided in a lower portion of said absorber tower, said gas outlet passage for clean gas and said desulfurizing agent inlet passage are provided in an upper portion of said absorber tower, so that said integrated desulfurizing agent for absorption and conversion enters into a cavity inside said absorber tower from said upper portion of absorber tower, and said gas to be desulfurized enters into a cavity inside said absorber tower from said lower portion of absorber tower, said sulfur-rich material obtained after said gas to be desulfurized and said integrated desulfurizing agent for absorption and conversion are mixed and contacted in said cavity inside said absorber tower is discharged from said lower portion of absorber tower, and said clean gas is outputted from said upper portion of absorber tower to a downstream pipe network.
10. The apparatus for removing organic sulfur from blast furnace gas according to claim 7, wherein said organic sulfur absorbing and converting system further comprises a sulfur-rich material circulating system,
the sulfur-rich substance circulating system comprises a sulfur-rich substance circulating pump and a circulating pipeline, one end of the circulating pipeline is connected with the sulfur-rich substance discharging channel of the organic sulfur absorption and conversion system, the other end of the circulating pipeline is connected with a sulfur-rich substance feeding channel arranged on the absorption tower, and the sulfur-rich substance circulating pump is arranged on the circulating pipeline so as to pump the sulfur-rich substance from the sulfur-rich substance discharging channel to the sulfur-rich substance feeding channel, so that the sulfur-rich substance enters a cavity inside the absorption tower to be in circulating mixed contact with the coal gas to be desulfurized, wherein the sulfur-rich substance contains unconsumed integrated desulfurizing agent for absorption and conversion.
11. The apparatus for removing organic sulfur from blast furnace gas as set forth in claim 10, wherein said sulfur-rich material circulation system further comprises a sulfur-rich material cooler provided on said circulation line for cooling said sulfur-rich material.
12. The apparatus for removing organic sulfur from blast furnace gas according to claim 7, further comprising a regeneration system, wherein the regeneration system comprises a regeneration tower, and a sulfur-rich material regeneration feed channel, a regeneration desulfurizing agent discharge channel and a tail gas discharge channel which are arranged on the regeneration tower, wherein the regeneration tower is internally provided with a cavity;
The sulfur-rich material regeneration feed channel is connected with the sulfur-rich material discharge channel of the absorption tower so as to input the sulfur-rich material from the absorption tower into a cavity in the regeneration tower for regeneration treatment, so as to separate tail gas and a regenerated desulfurizing agent, wherein the tail gas contains H 2 S gas, the regenerated desulfurizing agent contains the absorbing and converting integrated desulfurizing agent;
the regenerated desulfurizing agent discharging channel is connected with the desulfurizing agent feeding channel of the absorption tower so as to convey the separated regenerated desulfurizing agent from the regeneration tower to a cavity in the absorption tower for repeated use;
the tail gas is connected with the tail gas receiving device through the tail gas outlet channel, so that the separated tail gas is conveyed to the tail gas receiving device.
13. The apparatus for removing organic sulfur from blast furnace gas according to claim 12, wherein said sulfur-rich material regeneration feed passage is connected to said sulfur-rich material discharge passage through a first pipe, and said regenerated desulfurizing agent discharge passage is connected to said desulfurizing agent feed passage through a second pipe.
14. The apparatus for removing organic sulfur from blast furnace gas according to claim 13, wherein said regeneration system further comprises a first heat exchanger connected to said first conduit and said second conduit, respectively, for heat exchanging said sulfur-rich material in said first conduit and said regenerated sulfur-removing agent in said second conduit at said first heat exchanger.
15. The apparatus for removing organic sulfur from blast furnace gas as set forth in claim 13, wherein said second pipe is provided with a regenerated desulfurizing agent cooler for cooling said regenerated desulfurizing agent.
16. The apparatus for removing organic sulfur from blast furnace gas according to claim 13, wherein said second pipe is provided with a storage tank for storing said integrated desulfurizing agent for absorption and conversion and said regenerated desulfurizing agent.
17. The apparatus for removing organic sulfur from blast furnace gas as set forth in claim 12, wherein said regeneration system further comprises a tail gas cooler, said tail gas cooler being connected to a tail gas outlet passage of said regeneration tower and configured to cool said tail gas to a condensed material.
18. The apparatus for removing organic sulfur from blast furnace gas as set forth in claim 17, wherein said regeneration system further comprises a tail gas separator connected to said tail gas cooler for separating H from said condensed material 2 S gas and a reflux material, wherein the reflux material contains the sulfur-rich material.
19. The apparatus for removing organic sulfur from blast furnace gas as set forth in claim 18, wherein said regeneration system further comprises a reflux pump connected to said tail gas separator and said regeneration tower, respectively, for delivering said reflux material to said regeneration tower.
20. The apparatus for removing organic sulfur from blast furnace gas as set forth in claim 12, further comprising an exhaust gas treatment system disposed downstream of said regeneration system for producing after said regeneration processH of (2) 2 And (5) carrying out post-treatment on the S gas.
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| CN202311000385.7A CN117070256A (en) | 2023-08-09 | 2023-08-09 | Process method and device for removing organic sulfur in blast furnace gas |
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