CN115245729B - Steel process CO 2 Conversion recycling method and system - Google Patents
Steel process CO 2 Conversion recycling method and system Download PDFInfo
- Publication number
- CN115245729B CN115245729B CN202210150952.6A CN202210150952A CN115245729B CN 115245729 B CN115245729 B CN 115245729B CN 202210150952 A CN202210150952 A CN 202210150952A CN 115245729 B CN115245729 B CN 115245729B
- Authority
- CN
- China
- Prior art keywords
- steel
- conversion
- steps
- gas
- recycling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 618
- 230000008569 process Effects 0.000 title claims abstract description 352
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 320
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 314
- 239000010959 steel Substances 0.000 title claims abstract description 314
- 238000004064 recycling Methods 0.000 title claims abstract description 129
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 331
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 168
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 168
- 229910052742 iron Inorganic materials 0.000 claims abstract description 165
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 71
- 238000003723 Smelting Methods 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims description 245
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 216
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 95
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 95
- 239000004571 lime Substances 0.000 claims description 95
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 65
- 239000001257 hydrogen Substances 0.000 claims description 65
- 230000009467 reduction Effects 0.000 claims description 61
- 238000005245 sintering Methods 0.000 claims description 58
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 53
- 239000003546 flue gas Substances 0.000 claims description 53
- 239000002803 fossil fuel Substances 0.000 claims description 49
- 238000001179 sorption measurement Methods 0.000 claims description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 31
- 239000000571 coke Substances 0.000 claims description 31
- 239000001301 oxygen Substances 0.000 claims description 31
- 239000003245 coal Substances 0.000 claims description 27
- 230000009466 transformation Effects 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 238000004939 coking Methods 0.000 claims description 24
- 238000000926 separation method Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000005868 electrolysis reaction Methods 0.000 claims description 20
- 239000000446 fuel Substances 0.000 claims description 18
- 238000005453 pelletization Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000428 dust Substances 0.000 claims description 15
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 13
- 238000002485 combustion reaction Methods 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002250 absorbent Substances 0.000 claims description 10
- 230000002745 absorbent Effects 0.000 claims description 10
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000008188 pellet Substances 0.000 claims description 7
- -1 alcohol amine Chemical class 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000002912 waste gas Substances 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 239000013335 mesoporous material Substances 0.000 claims description 4
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims 1
- 238000010310 metallurgical process Methods 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 20
- 239000012084 conversion product Substances 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 241000894007 species Species 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000005272 metallurgy Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007781 pre-processing Methods 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- 241000203069 Archaea Species 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 239000002802 bituminous coal Substances 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
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000004449 solid propellant Substances 0.000 description 2
- 238000001926 trapping method Methods 0.000 description 2
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 101000872083 Danio rerio Delta-like protein C Proteins 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/0462—Temperature swing adsorption
-
- 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
- B01D53/346—Controlling the process
-
- 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
- B01D53/62—Carbon oxides
-
- 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
- B01D53/76—Gas phase processes, e.g. by using aerosols
-
- 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
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8696—Controlling the catalytic process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/202—Hydrogen
-
- 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
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20753—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/025—Other waste gases from metallurgy plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Dispersion Chemistry (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
Steel process CO 2 A method of conversion recycling, the method comprising the steps of: 1) CO 2 Is trapped: CO generated by one or more procedures of iron and steel enterprises 2 Capturing to obtain enriched CO 2 A gas; 2) CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center (Z) and to CO 2 Introducing a reducing medium into the conversion center (Z) to obtain CO; 3) CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to one or more working procedures of an iron and steel enterprise for recycling. The invention takes the whole process of iron and steel smelting as a research object for the first time, and proposes CO according to the characteristics of carbon emission and energy input at the tail end of each process of iron and steel enterprises 2 Is CO 2 Conversion of (C) to CO 2 And a steel smelting system for realizing carbon chain circulation is provided, and a hydrocarbon composite metallurgical process is formed by reconstructing C, H, O dynamic balance, so that the carbon emission of the steel process is greatly reduced.
Description
Technical Field
The present invention relates to CO 2 In particular to a recycling process of steel process CO 2 A method and a system for conversion and recycling, belonging to the technical field of steel smelting.
Background
The fossil energy consumed in the steel industry in China is close to 13% of the total national consumption, and the carbon emission proportion also reaches 15%. In order to achieve the aim of 2030 carbon peak reaching and 2060 carbon neutralization in China, the action of emission reduction in the steel industry is imperative. CO 2 Emission reduction can be realized from energy structure adjustment at source end, energy and process efficiency improvement at process end and terminal CO 2 The trapping is realized by utilizing. Renewable energy sources replace the main process to be revolutionized for the traditional industry, and therefore this path is difficult to achieve in a short period of time. The requirements of sintering, pelletizing and other processes in steel on liquid solid fuels can be hardly met, because the C in fossil fuels plays three roles in the steel field: fuels, reducing agents and materials (carbon steel, less 0.0218-2.11%) are not just used as energy input media. In the blast furnace smelting process, coke plays a framework role besides being used as fuel, so that the ventilation property in the blast furnace is ensured, and the molten iron permeation is smooth, so that a certain amount of C is needed in the metallurgical process. H 2 Is a good reducing agent in iron making, but H 2 The reduction is an endothermic reaction process, pure hydrogen metallurgy is not sustainable in energy, and C fuel is needed to be supplemented, so that the metallurgy is ensured to be continuously carried out.
The scholars predict that the carbon emission reduction contribution brought by energy efficiency improvement reaches 50% by 2060, and the end CO 2 The contribution of the trapping utilization technology is predicted to be 17%, which is an indispensable technical route and a bridge for the transition of the prior art to the future technology. At present, the carbon trapping technology has been applied commercially, and the trapped CO 2 The method is mainly used for oil displacement or direct geological landfill, the former needs enterprises to be positioned at the periphery of an oil field, and the latter is only used as a means for long-term carbon fixation and is used for CO 2 The waste of resources and the long-term impact on geology after landfill have not been fully demonstrated. In contrast, CO 2 The transformation and recycling can be realizedEffectively reduce the fossil energy consumption of enterprises and end CO 2 The emission is not limited by geography and geological environment, and CO is realized 2 Is expected to become a preferable route for industrial carbon emission reduction by on-site utilization. Along with the rapid progress of photoelectric and wind power technologies, the cost of green energy sources can be greatly reduced in the future, and the CO can be driven by green energy 2 Transformation will be one of the best choices. Compared with pure hydrogen smelting, H 2 The storage and transportation of the steel are high in safety risk and easy to explode; secondly, pure hydrogen metallurgy needs to change the existing main body ironmaking process, the time period is long, and the technical reliability in large-scale production is also uncertain; finally, for the reduced iron reaction, the theoretical optimum reducing gas composition is 20% CO and 80% H 2 The participation of C is required for both blast furnaces and direct furnaces.
The use condition of fossil energy in China is that about 85% of the fossil energy is used as fuel for energy supply, and only about 15% of the fossil energy is used as production raw materials of chemical products. Therefore, from the whole C cycle, the chemical product demand of people cannot completely consume CO 2 The vast majority of the conversion products will still be used as fuel, thus CO 2 Conversion to energy products is the primary means of future large-scale carbon recycling. CO 2 The methanol which is the conversion product of hydrogenation can be used as fuel and is H at the same time 2 Can be processed by simple process to prepare H when needed 2 For the steel industry, the method can be used as fuel or reducing agent in each working procedure of iron and steel making, realizes complete digestion and recycling, and is an ideal conversion product.
At present, no CO aiming at the whole process of steel exists 2 Recycling process, reported industrial flue gas CO 2 The main types of trapping and utilization can be divided into three types:
1) Bioconversion, i.e. conversion of CO by microorganisms or plants 2 Converting into methane, ethanol, and the like, such as methane archaea of Electrochaea converting into methane CN113227389A, fermenting and converting industrial flue gas of brown into ethanol CN107099556B by yeast, preparing methanol tail gas of new ao coal into biodiesel CN106434778B by microalgae carbon fixation, and the like. First microbial transformation to air intake The methane archaea is usually anaerobic and cannot treat oxygen-containing gas, and then CO and H are treated 2 Gas contaminants such as S are severely required, which can otherwise lead to bacterial death or stop the methanation reaction. Secondly, the conversion rate is difficult to reach the conversion amount, the microbial conversion is mostly in tens of L/L reactors per day, and the tail gas generated by the lime kiln only in the steel working procedure reaches millions of Nm 3 Day.
2)CO 2 CO is produced by carbon conversion, requiring carbon participation.Recovery of CO with Ammonia Water as in CN106139838A 2 Then heat CO 2 And (3) carrying out fusion reaction on the gas and red coke, and then spraying the gas into the bottom of the blast furnace to generate the energy-containing gas mainly containing CO. CN106748655B, CO in blast furnace gas 2 The water vapor reacts with carbon to generate CO and H 2 And then synthesizing methanol with the hydrogen-rich coke oven gas. Using high temperature environment (such as coked high Wen Chijiao, carbon in blast furnace converter environment) of existing process, using coke and CO 2 And the reaction is carried out, so that the gas yield is improved. The carbon conversion path depends on the coking, the carbon and the high temperature environment of the blast furnace process, and is normalizedIs an endothermic reaction, is not energetically sustainable and therefore overall convertible CO 2 The amount is relatively limited.
3) The biggest problem with methane reforming and carbon dioxide reforming is the high energy consumption (due to its strong endothermic reaction). Calculations indicate that the energy required for carbon dioxide reforming is greater than the energy emitted by the chemical it converts as an energy source. That is, if the energy it consumes is provided by fossil fuel combustion, emissions are increased as well as emissions are not reduced. So the expert suggested that this technology would only be of value in combination with solar or industrial waste heat technology. Secondly, for steel smelting, raw gas methane mainly comes from coke oven gas, the methane yield is difficult to meet the conversion demand, and the self-circulation conversion in enterprises cannot be achieved.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a steel process CO 2 A method for converting and recycling. The method is characterized by capturing CO in flue gas of one or more procedures in a steel flow path 2 And through CO 2 The conversion center converts CO 2 The reducing medium is added to be converted into energetic products such as CO, methanol and the like, and then the CO products are conveyed to one or more working procedures of steel enterprises for recycling, so that a carbon conversion recycling chain is realized, and the carbon emission of the steel flow is greatly reduced. The invention also regulates and controls the proportion of the conversion products by matching the cost requirement and the carbon emission reduction requirement of the iron and steel enterprises, thereby realizing the comprehensive control of the conversion cost and the carbon emission reduction of the iron and steel enterprises. Based on the above, the invention also provides a catalyst for the reaction with CO 2 A system matched with a conversion recycling method. The system effectively connects each procedure of the steel flow in series and introduces CO 2 Conversion center for realizing CO 2 The conversion and recycling of the steel and iron smelting process can greatly reduce the carbon emission.
According to a first embodiment of the present invention, there is provided a steel process CO 2 A method for converting and recycling.
Steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 Is trapped: CO generated by one or more procedures of iron and steel enterprises 2 Capturing to obtain enriched CO 2 And (3) gas.
2)CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center, and to CO 2 And introducing a reducing medium into the conversion center to obtain CO.
3)CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to one or more working procedures of an iron and steel enterprise for recycling.
In the present invention, the reducing medium in step 2) is a reducing solid or a reducing gas. Preferably, the reducing solid is carbon and the reducing gas is H 2 。
In the present invention, step 2) hasThe body is as follows: to enrich CO 2 Gas delivery to CO 2 Conversion center, and to CO 2 H is introduced into the transformation center 2 CO and methanol are obtained. Wherein: methanol is used as a raw material, fuel for one or more processes in iron and steel enterprises, or is output as a product.
Preferably, the step 1) further comprises pretreatment of flue gas of each process of the iron and steel enterprises. The step 1) specifically comprises the following steps: firstly, carrying out dust removal, desulfurization and dehydration pretreatment on flue gas generated by one or more procedures of an iron and steel enterprise to obtain purified flue gas. And then CO is carried out on the purified flue gas of each procedure 2 Is trapped to obtain enriched CO 2 And (3) gas.
Preferably, the humidity of the cleaned flue gas is < 1%, preferably < 0.5%. The sulfide content in the purified flue gas is less than 35mg/Nm 3 Preferably < 30mg/Nm 3 . The dust content in the purified flue gas is less than 10mg/Nm 3 Preferably < 5mg/Nm 3 。
In the present invention, the CO described in step 1) 2 Is captured by a temperature and pressure swing adsorption device. The temperature and pressure swing adsorption device is internally provided with a porous material loaded with chemical absorbent. Preferably, the porous material is an aluminosilicate mesoporous material. The chemical absorbent is an alcohol amine reagent.
In the present invention, the CO described in step 2) 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a conversion substance gas-liquid separation and conversion gas allocation device. The hydrogen outlet of the hydrogen generating device is connected to CO 2 The hydrogen inlet of the reformer. CO 2 The converter outlet of the converter is connected to the converter inlet of the converter gas-liquid separation and conversion gas distribution device. Preferably, the hydrogen generating device is green electricity-H 2 O electrolysis unit.
In the present invention, green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy. Green electricity-H 2 The O electrolyzer electrolyzes water to produce hydrogen and oxygen, and the hydrogen is conveyed to CO 2 Transformation center asThe reducing medium, oxygen, is delivered to one or more processes of the iron and steel enterprise.
Preferably, the oxygen is fed to a blast furnace or converter for oxyfuel combustion or injection, or to a sintering machine for oxyfuel sintering.
Preferably, in step 1), high concentration CO generated for each process of the iron and steel industry 2 Capturing low concentration CO 2 And discharging. Wherein, high concentration CO 2 The volume fraction of (2) is more than or equal to 12%, and low concentration CO 2 Is < 12% by volume. Preferably, high concentration CO 2 The volume fraction of (2) is more than or equal to 15%, and low concentration CO 2 Is < 15% by volume.
In step 1) of the present invention, CO generated for n processes of the iron and steel enterprise 2 And (5) collecting. Wherein: n is 1 to 10, preferably 3 to 6.
In the step 3) of the invention, the CO obtained in the step 2) is conveyed to m working procedures of an iron and steel enterprise for recycling. Wherein: m is 1 to 12, preferably 3 to 8.
In the present invention, one or more of the processes of the iron and steel enterprises in the steps 1) and 3) are one or more of a blast furnace process, a converter process, a lime kiln process, a sintering process, a pellet process, a coking process, and a direct return process.
In the present invention, CO 2 CO is contained in the conversion center 2 A conversion catalyst. The CO 2 The conversion catalyst is a nickel-based or copper-based mesoporous catalytic material.
Preferably, the one or more processes of the iron and steel industry in the step 1) are one or more of a blast furnace process, a converter process and a lime kiln process.
Preferably, the one or more processes of the iron and steel enterprise in the step 3) are one or more of a blast furnace process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct return process.
In the present invention, CO generated in a certain process of an iron and steel enterprise 2 When the volume concentration of (a) is less than 20% (preferably less than 15%), CO generated in the process is reduced 2 Is transported after the enrichment processTo CO 2 A transformation center.
Preferably, the enrichment step is as follows: CO generated in one or more of a blast furnace process, a converter process, a sintering process, a pelletizing process, a coking process, and a direct recovery process 2 Delivering the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 And then concentrating the CO 2 Delivery to CO 2 A transformation center.
In the invention, the control of CO in the whole steel smelting process 2 The selectivity of converting the gas into CO is realized, thereby realizing the CO conversion of iron and steel enterprises 2 Conversion cost and carbon emission control. The method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc 。
(2) According to CO 2 The selectivity of the conversion of the gas into CO, the amount M of CO produced in the conversion in step 2) is calculated co 。
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco 。
(4) Calculating the carbon emission reduction amount in the whole steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The gas is converted to a cost difference deltac of CO and methanol.
(6) According to the cost target and/or the carbon emission reduction target of the iron and steel enterprise, calculating to obtain CO 2 Selectivity of gas to CO, and controlling CO in step 2) based on the obtained selectivity of CO 2 The process conditions of the transformation are realized, thereby realizing the CO of the iron and steel enterprises 2 Conversion cost and carbon emission control.
In the substep (1) of the present invention, the enriched CO obtained in step 1) is calculated 2 The total amount of gas is specifically:
the consumption amount of the g-th fossil fuel at the carbon input end of the i-th working procedure is F i,g . CO of fossil fuel of type g 2 Direct exhaustPut factor D g . The consumption amount of the h power medium at the carbon input end of the ith procedure is DM i,h . CO of the h power medium 2 Indirect emission factor ID h . The number of the outer pins of the j-th energetic product at the carbon output end of the i-th working procedure is P i,j . CO of the j-th energetic product 2 The direct emission factor is ND j . Accounting is carried out according to the material energy balance of the input end and the output end, and then the method is that:
wherein: m is m cc Enriched CO from step 1) 2 Total amount of gas. n is CO 2 The number of trapping steps. x is the number of fossil fuel species. y is the number of kinds of power media. z is the number of species of energetic product.
In the present application, the amount of consumption of the g-th fossil fuel and the CO of the g-th fossil fuel 2 The product of the direct emission factors is in units of mass (e.g., kg). For example, when the consumption amount of a certain fossil fuel is in kg, the CO of the fossil fuel 2 The unit of the direct carbon emission factor is 1; when the consumption amount of a certain fossil fuel is in Nm 3 At this time, the CO of the fossil fuel 2 The unit of the direct carbon emission factor is kg/Nm 3 . Likewise, the consumption amount of the h power medium and the CO of the h power medium 2 The product of the indirect emission factor is in units of mass (e.g., kg). The number of outer pins of the j th energetic product and the CO of the j th energetic product 2 The product of the direct emission factors is in units of mass (e.g., kg).
In the substep (2) of the present invention, CO is set 2 The selectivity of the gas to CO is S co . The method comprises the following steps:
setting CO 2 Conversion toThe equilibrium constant of the reaction in the methanol path is K 1 ，CO 2 The equilibrium constant of the reaction for conversion to CO is K 2 . According to CO 2 The reaction formula for converting into methanol and CO is as follows:
wherein: reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)；K 2 ＝f 2 (T). The method comprises the following steps:
combining (3) - (6) to obtain X CO 、X MeOH . Then combining the formula (2) to obtain S co 。
The amount of CO thus formed by the conversion in step 2) is:
in formulas (2) - (7): x is X CO Is CO 2 Conversion to CO. X is X MeOH Is CO 2 Conversion to methanol. Beta is H 2 /CO 2 Is a ratio of (2). P (P) Total (S) Is the total reaction pressure. T is the reaction temperature. m is m co The amount of CO produced for the conversion in step 2). a, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 A, a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants.
In the sub-step (3) of the present invention, the amount of CO entering the recycling process in the step 3) is:
the consumption amount of the g-th fossil fuel at the s-th working procedure carbon input end is F s,g . The conversion standard coal coefficient of the g-th fossil fuel is C g . The consumption amount of the h power medium at the carbon input end of the s-th procedure is DM s,h . Converting the h power medium into DC h . The consumption amount of the No. w irreplaceable fossil fuel of the No. s working procedure carbon input end is IF s,w . Conversion of the w-th irreplaceable fossil fuel into standard coal coefficient as IC w . The number of the outer pins of the jth energy-containing product at the carbon output end of the s-th working procedure is P s,j . The conversion coal marking coefficient of the j-th energy-containing product is PC j . Accounting is performed according to the material energy balance of the input end and the output end, and the method comprises the following steps:
the preparation method comprises the following steps:
wherein: m is m Lco The amount of CO entering the recycling step in step 3). ΔcH CO Is the heat of combustion of CO. ΔcH Standard coal The heat value of the standard coal. m is the number of CO recycling processes. x is the number of fossil fuel species. y is the number of kinds of power media. l is the number of types of fossil fuels that are not replaceable. z is the number of species of energetic product.
In the present application, the unit of the product of the amount of consumption of the g-th fossil fuel and the standard coal coefficient converted from the g-th fossil fuel is a unit of mass (for example, kg). Likewise, the product of the amount of consumption of the h-th power medium and the conversion of the h-th power medium to the coal index is in units of mass (e.gkg). The product of the consumption amount of the w-th irreplaceable fossil fuel and the conversion standard coal coefficient of the w-th irreplaceable fossil fuel is expressed in mass units (for example, kg). The number of outer pins of the j th energetic product and the CO of the j th energetic product 2 The product of the direct emission factors is in units of mass (e.g., kg).
In the substep (4) of the invention, the carbon emission reduction in the whole iron and steel smelting process is as follows:
if m is co ≤m Lco At this time
If m is co ＞m Lco At this time
Wherein:the method is used for reducing the carbon emission in the whole steel smelting process.
In the substep (5) of the present invention, CO is contained in the whole iron and steel smelting process 2 The cost difference of the gas conversion into CO and methanol is:
wherein: ΔC is CO in the whole steel smelting process 2 The gas is converted to a cost difference of CO and methanol. ΔP is the unit CO 2 Converted to a cost difference of CO and methanol.
In the substep (6) of the invention, the carbon emission reduction target of the iron and steel enterprise is set to delta E min The cost saving goal is delta C min 。
The method comprises the following steps:
i.e. < ->
ΔC≥ΔC min I.e.
Preferably, if the value Δc=Δc min I.e. take the valueCombining (2) - (6), calculating to obtain CO 2 Reaction conditions at the conversion center. The reaction condition realizes the lowest CO for iron and steel enterprises on the premise of achieving the aim of saving cost 2 The discharged process conditions.
If take valueI.e. take the value +.>Combining (2) - (6), calculating to obtain CO 2 Reaction conditions at the conversion center. The reaction condition is the most cost-saving process condition for iron and steel enterprises on the premise of achieving the aim of carbon emission reduction.
If take valueCombining (2) - (6), calculating to obtain CO 2 Reaction conditions at the conversion center. The reaction condition realizes CO for iron and steel enterprises on the premise of achieving the aims of saving cost and reducing carbon emission 2 And (3) comprehensively controlling conversion cost and carbon emission.
According to a second embodiment of the present invention, there is provided a steel process CO 2 A system for conversion and recycling.
A CO as described in the first embodiment 2 A system for a method of conversion recycling, the system comprising CO 2 Conversion center, blast furnace, lime kiln. CO 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device,A device for separating and blending the gas and the liquid of the converted substance. The gas outlet of the blast furnace and the gas outlet of the lime kiln are both connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln. The hydrogen outlet of the hydrogen generating device is connected to CO 2 The hydrogen inlet of the reformer. CO 2 The converter outlet of the converter is connected to the converter inlet of the converter gas-liquid separation and conversion gas distribution device.
In the invention, the system also comprises a sintering machine, a rotary kiln, a coke oven, a converter and a straight ring furnace. The gas outlet of the blast furnace, the gas outlet of the lime kiln and the gas outlet of the converter are all connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln and/or sintering machine and/or rotary kiln and/or coke oven and/or straight-loop furnace.
Preferably, the system further comprises CO 2 A preprocessing system. CO 2 The pretreatment system is used for carrying out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more procedures of the iron and steel enterprises.
Preferably, the system further comprises a temperature and pressure swing adsorption device. The gas outlets of the blast furnace, the lime kiln and the converter are all connected to CO 2 A preprocessing system. CO 2 The gas outlet of the pretreatment system is connected to a temperature and pressure swing adsorption device. CO of temperature and pressure swing adsorption device 2 The gas outlet is connected to CO 2 CO of conversion center 2 A gas inlet.
In the present invention, the gas outlet of the optional blast furnace, sintering machine, rotary kiln, coke oven, converter, straight ring furnace is connected to the gas inlet of the lime kiln. The gas outlet of the lime kiln is connected to CO 2 A preprocessing system. CO 2 The gas outlet of the pretreatment system is connected to a temperature and pressure swing adsorption device.
In the invention, the hydrogen generating device is green electricity-H 2 O electrolysis unit. Green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to a blast furnace, a converter or a sintering machine.
In order to achieve the aim of carbon peak reaching in 2030 and carbon neutralization in 2060, the action of carbon emission reduction in the steel industry in China is imperative at present. However, in the prior art, this path of replacing carbon in fossil fuels by renewable energy is difficult to achieve in a short period of time, and carbon in fossil fuels plays several roles in the iron and steel field, such as fuel, reducing agent and material, so that a certain amount of carbon is required to participate in metallurgical processes. In addition, if pure hydrogen metallurgy is adopted, but hydrogen reduction is an endothermic reaction process, the pure hydrogen metallurgy is not sustainable in energy, and the carbon fuel is needed to be supplemented, so that the metallurgy can be ensured to be continuously carried out.
Based on the above, the invention provides a steel process CO 2 A method for converting and recycling. The method adopts green energy driven CO 2 Method for recycling conversion coupled steel processes by capturing CO in flue gas from one or more processes in the steel process 2 And through CO 2 The conversion center converts CO 2 Adding a reducing medium to convert into energetic products such as CO, methanol and the like, and then conveying the CO products to one or more working procedures of a steel enterprise for recycling, thereby realizing a carbon conversion recycling chain, namely, CO 2 The method of conversion and recycling is used for partially replacing the source carbon input and reducing the tail end carbon emission, so that the carbon emission of the steel process is greatly reduced. The invention also regulates and controls the proportion of the conversion products by matching the cost requirement and the carbon emission reduction requirement of the iron and steel enterprises, thereby realizing the comprehensive control of the conversion cost and the carbon emission reduction of the iron and steel enterprises. Correspondingly, the invention also provides a method for preparing the catalyst and CO 2 A system matched with a conversion recycling method. The system effectively connects each procedure of the steel flow in series and introduces CO 2 Conversion center for realizing CO 2 The conversion and recycling of the steel and iron smelting process can greatly reduce the carbon emission.
The invention takes the whole process of iron and steel smelting as a research object for the first time, and proposes CO according to the characteristics of carbon emission and energy input at the tail end of each process of iron and steel enterprises 2 Is CO 2 Conversion of (C) to CO 2 The recycling technology of the steel process realizes the great reduction of carbon emission of the steel process. Specifically, the method first makes the iron and steel enterprisesCO in the tail gas produced by one or more processes (e.g., a blast furnace process and/or a lime kiln process and/or a converter process) 2 Capturing to obtain enriched CO 2 And (3) gas. Then, the enriched CO 2 Gas delivery to CO 2 Conversion center, and to CO 2 Introducing a reducing medium into a conversion center to generate CO 2 To obtain CO. Wherein CO 2 The transformation center can maintain the required high temperature by utilizing the waste heat of the factory, and can maintain the high pressure environment by being assisted by green energy, and CO 2 A catalyst bed layer is arranged in the conversion center to ensure the process conditions of the high-temperature high-pressure catalyst required by the conversion reaction. Finally, the CO converted from the reaction is sent to one or more processes (such as a blast furnace process and/or a lime kiln process and/or a sintering process) of the iron and steel enterprises for recycling. The invention uses CO 2 The capture, conversion and recycling of the iron and steel enterprises are realized, namely, a plurality of working procedures of the iron and steel enterprises are effectively connected in series, so that a carbon conversion and recycling chain is realized, and the carbon emission of the iron and steel flow is greatly reduced.
In the present invention, enriched CO 2 Delivery of gas and reducing Medium to CO 2 Conversion center, and CO 2 The transformation center maintains a high-temperature and high-pressure environment and simultaneously generates CO 2 The conversion center is internally provided with a catalyst, namely, the catalyst is used for realizing CO 2 The conversion reaction takes place. The reducing medium comprises a reducing solid or a reducing gas. Among them, the reducing solid mainly contains carbon. The reducing gas being predominantly H 2 . Generally, CO 2 Gas and reducing medium (e.g. H 2 ) The catalytic reaction products of (a) are CO, methanol and a small amount of byproducts. Wherein CO 2 The conversion product methanol of (a) can be used as raw material for one or more processes in a steel enterprise, fuel (e.g. methanol can be supplied as fuel to hot blast stoves in a steel process), or methanol can be output as product.
Generally, CO in flue gas (or tail gas) generated by each process of iron and steel enterprises 2 Collecting the collected CO 2 The gas tends to have a higher water content while CO 2 The gas is doped with sulfuration in tail gas of each process Other impurities such as matters and dust, and the like, thus the invention performs CO 2 Before the collection of the flue gas, the flue gas generated in each process of the iron and steel enterprises needs to be pretreated. The pretreatment mainly comprises the pretreatment of dust removal, desulfurization and dehydration of the flue gas in each procedure, and purified flue gas is obtained after the pretreatment is completed. Then CO is carried out on the purified flue gas of each procedure 2 Is trapped to obtain enriched CO 2 And (3) gas. To ensure the collection of the enriched CO 2 Purity of gas (e.g. CO 2 The purity of the purified flue gas obtained after the pretreatment is less than 1%, preferably less than 0.5%, and the subsequent conversion reaction is smoothly carried out and has higher conversion rate. The sulfide content in the purified flue gas is less than 35mg/Nm 3 Preferably < 30mg/Nm 3 . The dust content in the purified flue gas is less than 10mg/Nm 3 Preferably < 5mg/Nm 3 。
In the present invention, CO generated in each process of iron and steel enterprises 2 The trapping method adopts a synergistic separation method of chemical absorption and physical absorption, and the absorption material is a porous material modified by a chemical absorbent. Wherein the porous material is an aluminosilicate mesoporous material, such as an aluminosilicate molecular sieve or aluminosilicate sepiolite. The chemical absorbent is an alcohol amine reagent, such as primary amine (ethanolamine) MEA, secondary amine (diethanolamine) DEA, tertiary amine (N-methyl glycol amine) MDEA, polyazamine TETA (triethylene tetramine) or TEA (triethanolamine), or a mixture of several of the foregoing alcohol amine reagents. The trapping device is a temperature and pressure swing adsorption device connected in parallel, and the adsorption and desorption periods of the adsorption devices are staggered. The trapping method and the trapping device provided by the invention can reduce CO 2 Difficulty of trapping and speed up CO 2 Increase the capture rate of the captured CO 2 Is beneficial to the purity of CO in the subsequent steps 2 Is transformed and recycled.
CO as described in the present invention 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a conversion substance gas-liquid separation and conversion gas allocation device. The hydrogen generating device is mainly used for generating H 2 ，H 2 Entering CO 2 Conversion device and enrichmentCO 2 The gas undergoes catalytic hydrogenation conversion reaction. In CO 2 In the conversion device, CO 2 、H 2 Under the action of catalyst, it is converted into CO and methanol (CH) 3 OH) and small amounts of by-products (e.g., methane), the conversion products also being doped with small amounts of unreacted CO 2 And H 2 Is a mixed gas of (a) and (b). The conversion products enter a conversion product gas-liquid separation and conversion gas allocation device, firstly, the liquid phase mainly containing methanol is separated, most of the methanol is used as a hydrogen-carrying product or chemical raw material to be conveyed outwards, and the other part of the methanol can be used as fuel to be returned to each process of a steel enterprise (for example, used as fuel to be supplied to a hot blast stove of a steel process), and when the methanol is used as fuel in the blast furnace process, the methanol is preferably burnt with pure oxygen, which is beneficial to CO 2 Is a trapping cycle of (a). Second, CO 2 The crude product is separated and recycled to CO 2 Conversion center, continue to participate in CO 2 Is the conversion of CO in the present invention 2 The conversion center adopts a tail gas circulation reaction mode, the single-pass conversion rate is generally more than 25%, and the total conversion rate of multiple passes is more than 70%. Finally remaining CO, H 2 The mixed gas (namely gas phase mainly comprising CO) is used as fuel to be distributed to one or more working procedures of the steel process for recycling, and can also be used as a reducing agent to enter a blast furnace or a straight-ring furnace for reducing iron after hydrogenation proportion adjustment. CO 2 CO of conversion center 2 The conversion device contains CO 2 Conversion catalyst, said CO 2 The conversion catalyst is a nickel-based or copper-based mesoporous catalytic material.
Preferably, the hydrogen generating device may be selected from green electricity-H 2 O electrolysis unit. Green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy. Green electricity-H 2 O electrolyzer for generating H by electrolyzing water 2 CO supply 2 Conversion device for promoting CO 2 Conversion to O 2 The oxygen-enriched air is supplied to a blast furnace or a converter for oxygen-enriched combustion or oxygen-enriched blowing, and can also be supplied to a sintering machine for oxygen-enriched sintering.
In the present invention, CO 2 The trapped object is mainly high-concentration tail gas generated by each process of the iron and steel enterprises. Generally speaking, for steel enterprisesHigh concentration CO produced by each process in industry 2 Capturing low concentration CO 2 The discharge is carried out, but the total amount of discharge does not exceed 500kg/t steel. Wherein, high concentration CO 2 The volume fraction of (2) is more than or equal to 12%, and low concentration CO 2 Is < 12% by volume. Preferably, high concentration CO 2 The volume fraction of (2) is more than or equal to 15%, and low concentration CO 2 Is < 15% by volume. Further preferably, the low concentration CO generated in a certain process of the iron and steel industry 2 CO can be enriched without discharging 2 After the concentration is increased, the mixture is conveyed to CO 2 A transformation center. Alternatively, higher concentrations of CO generated for each process of the iron and steel enterprise 2 After the trapping, the CO can be further improved through the enrichment procedure 2 Concentration is then delivered to CO 2 A transformation center. For example, CO generated in a certain process of an iron and steel enterprise 2 When the volume concentration of (a) is less than 20% (preferably less than 15%), CO generated in the process is reduced 2 After the enrichment procedure, the mixture is conveyed to CO 2 A transformation center. This can further reduce CO 2 Is ensured to be CO 2 The total emission amount is not more than a specified range (for example, the total emission amount is not more than 500kg/t steel), thereby realizing the low carbon emission reduction of the whole steel process.
The invention takes the whole steel process as a research object for the first time, effectively connects each process in the steel process in series according to the characteristics of carbon emission and energy input at the tail end of each process in the steel enterprise, and introduces CO 2 Conversion center for realizing CO 2 Recycling, and greatly reducing carbon emission in the steel smelting process. In step 1) of the present invention, CO generated in n processes (one or more processes) of the iron and steel enterprise 2 Trapping is performed wherein n is 1-10, preferably 3-6, e.g. n=2 or 3 or 4 or 5. In step 3) of the present invention, the CO obtained in step 2) is sent to m processes (one or more processes) of the iron and steel enterprise for recycling. Wherein m is 1-12, preferably 3-8, e.g. m=1 or 2 or 3 or 4 or 5 or 6 or 7. In the present invention, one or more of the procedures of the iron and steel enterprises in the steps 1) and 3) are a blast furnace procedure, a converter procedure, a lime kiln procedure, a sintering procedure, a pelletizing procedure, and a coking procedureOne or more of a blast furnace process, a converter process, a lime kiln process, a sintering process, a pellet process and a coking process are one or more of a direct reduction process (namely, a direct reduction process and a smelting reduction process), wherein the blast furnace process, the converter process, the lime kiln process, the sintering process, the pellet process and the coking process are processes in a long process of steel smelting, and the direct reduction process is a short process of steel smelting. Preferably, step 1) CO 2 One or more processes of the iron and steel enterprises are one or more of a blast furnace process, a converter process, a lime kiln process and a direct return process, namely CO generated by the blast furnace process and/or the converter process and/or the lime kiln process and/or the direct return process 2 Capturing to obtain enriched CO 2 And (3) gas. Step 3) CO 2 The one or more processes of the iron and steel enterprises are one or more of a blast furnace process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct recovery process, namely, the conversion product CO obtained in the step 2) is conveyed to the blast furnace process and/or the lime kiln process and/or the sintering process and/or the pelletizing process and/or the coking process and/or the direct recovery process for recycling. Wherein, CO in tail gas generated by each working procedure of iron and steel enterprises 2 The volume concentration of (2) is respectively: CO in tail gas generated by blast furnace procedure 2 Is about 15% by volume; CO in the tail gas generated in the converter process 2 Is about 18% by volume; CO in tail gas generated in lime kiln process 2 The volume concentration of (2) is generally > 20%; CO in the tail gas generated in the sintering process 2 Is about 6% by volume; CO in tail gas generated in the pelletizing process 2 Is about 6% by volume; CO in tail gas generated in coking process 2 Is about 3% by volume; CO in tail gas generated in direct recovery process 2 Is about 20% by volume.
In the present invention, CO generated in a certain process of an iron and steel enterprise 2 When the volume concentration of (a) is less than 20% (preferably less than 15%), CO generated in the process is reduced 2 After the enrichment procedure, the mixture is conveyed to CO 2 A transformation center. The enrichment step as used herein refers to a step of adding CO generated in one or more of a blast furnace step, a converter step, a sintering step, a pelletizing step, a coking step, and a direct recovery step 2 Conveying to lime kilnCollecting CO in the flue gas discharged from the lime kiln process 2 Obtaining enriched CO 2 And then concentrating the CO 2 Delivery to CO 2 A conversion center, i.e. one or more of which produce CO 2 CO is processed by lime kiln process in the process of lower volume concentration 2 Enriching to improve CO 2 Concentration to reduce CO 2 Is beneficial to improving the subsequent CO 2 Is also further reduced by CO 2 The total emission amount of the steel can be reduced, and the low carbon emission reduction of the whole steel process can be realized. In the enrichment process, CO can be generated 2 The flue gas discharged by one or more procedures with lower volume concentration is directly conveyed to a lime kiln procedure, and then CO in the flue gas is discharged to the lime kiln procedure 2 Capturing to obtain enriched CO 2 . Preferably, in consideration of the matching of the smoke amounts, CO is generated 2 When the number of the procedures with lower volume concentration is multiple, the lime kiln procedure can be difficult to enrich the smoke of the multiple procedures, and at the moment, CO in the smoke is discharged to each procedure firstly 2 Collecting the collected CO 2 Delivering the waste gas to a lime kiln process, and discharging CO in the flue gas to the lime kiln process 2 Capturing to obtain enriched CO 2 Thereby improving CO 2 Concentration.
The invention also regulates and controls the proportion of the conversion products by matching the cost requirement and the carbon emission reduction requirement of the iron and steel enterprises, thereby realizing the comprehensive control of the conversion cost and the carbon emission reduction of the iron and steel enterprises. In the present invention, the conversion reaction involved mainly includes the following three reactions:
of the three reactions, the first two reactions are thermodynamically independent and competing reactions, and are the main two paths for determining the selectivity of the catalyst, so that the subsequent reactions (one) and (two) are controlled as independent reactions, wherein the reactants and the products are all in the form of gases. The selectivity of the products of the two conversion paths can be controlled between 20% and 80%. According to the reaction heat and the change of the reaction volume, generally, the temperature and the pressure are raised to facilitate the reaction in the CO direction, and the temperature and the pressure are lowered to facilitate CH 3 The reaction proceeds in the OH direction. According to the reactant metering ratio, H 2 /CO 2 The lower the ratio, the more advantageous the CO production.
By controlling CO in the whole steel smelting process 2 The selectivity of converting the gas into CO is realized, thereby realizing the CO conversion of iron and steel enterprises 2 Conversion cost and carbon emission control; the method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc ；
(2) According to CO 2 The selectivity of the conversion of the gas into CO, the amount m of CO produced in the conversion in step 2) is calculated co ；
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco ；
(4) Calculating the carbon emission reduction amount in the whole steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The cost difference delta C of the gas conversion into CO and methanol;
(6) according to the cost target and/or the carbon emission reduction target of the iron and steel enterprise, calculating to obtain CO 2 Selectivity of gas to CO, and controlling CO in step 2) based on the obtained selectivity of CO 2 The process conditions of the transformation are realized, thereby realizing the CO of the iron and steel enterprises 2 Conversion cost and carbon emission control.
Wherein in the substep (1), the substance, energy are circulated by a carbon chainCalculation of the equilibrium, reckoning the enriched CO obtained in step 1) 2 Total amount of gas. The method is characterized by comprising the following steps of calculating the carbon emission and the material energy balance of fossil fuel, power medium and energy-containing product at the carbon input end and the carbon output end of each process, and obtaining:
wherein: m is m cc Enriched CO from step 1) 2 Total amount of gas. n is CO 2 The number of capturing processes, the CO 2 The collecting step is one or more of a blast furnace step, a converter step, a lime kiln step, a sintering step, a pelletizing step, a coking step, and a direct recovery step, and preferably one or more of a blast furnace step, a converter step, and a lime kiln step. x is the type number of fossil fuel, and the fossil fuel is one or more of coke, coal dust, standard coal, anthracite, bituminous coal, clean coal, coke oven gas and natural gas. y is the type number of the power mediums, and the power mediums are other power mediums such as electric power or steam. z is the number of kinds of energetic products, and the energetic products are one or more of molten iron, gas ash, residual energy power generation, blast furnace gas, tar, crude benzene, coke oven gas and coke.
In sub-step (2), CO is set 2 The selectivity of the gas to CO is S co . The method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for conversion to methanol is K 1 ，CO 2 The equilibrium constant of the reaction for conversion to CO is K 2 According to the CO 2 The reaction formulas (I) and (II) for converting into methanol and CO are as follows:
in CO 2 In the reaction for converting into methanol or CO, the partial pressure of each component is based on the total pressure P of the reaction Total (S) 、H 2 /CO 2 Ratio beta of (C) to CO 2 Conversion to methanol X MeOH 、CO 2 Conversion to CO conversion X CO Obtaining:
and the reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)，K 2 ＝f 2 And (T) fitting the specific relation by experimental tests, wherein the specific relation is as follows:
wherein: a, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 A, a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants. The value of each fitting coefficient and CO 2 Conversion catalyst correlation, i.e. selection of CO 2 After conversion of the catalyst, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 A, a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 The value of (2) is a fixed value. For example, select CO 2 The conversion catalyst is copper-based mesoporous catalytic material, and the value of each fitting coefficient is a 1 ＝-152.7,b 1 ＝27169.2,d 1 ＝0.152,g 1 ＝-4.17,c 1 ＝h 1 ＝j 1 =0; a 2 ＝79.1,b 2 ＝-56500.7,c 2 ＝14.3,g 2 ＝-2.36,d 2 ＝h 2 ＝j 2 ＝0。
K (T) and X are established according to formulas (3) - (6) CO 、X MeOH 、β、P Total (S) The functional relation between them is obtained CO And X MeOH Respectively about T, beta, P Total (S) Is to change the reaction temperature T, H 2 /CO 2 Ratio beta of (2) and total reaction pressure P Total (S) Can obtain X under different conditions CO And X MeOH Is a value of (2). And then combining the formula (2) to obtain S co 。
Thus, the amount m of CO converted in step 2) co The method comprises the following steps:
in the substep (3), calculating the material energy balance of the fossil fuel, the power medium, the irreplaceable fossil fuel and the energy-containing product at the carbon output end of each process, and obtaining the energy-saving agent by:
wherein: m is m Lco The amount of CO entering the recycling step in step 3). m is the number of CO recycling processes, and the CO recycling processes are one or more of a blast furnace process, a lime kiln process, a sintering process, a pellet process, a coking process and a direct return process. x is the number of fossil fuels, and as mentioned above, the fossil fuels are coke, pulverized coal, standard coal, anthracite, bituminous coal, clean coal, One or more of coke oven gas and natural gas. y is the type number of the power mediums, and the power mediums are other power mediums such as electric power or steam. l is the number of types of non-replaceable fossil fuels mainly considering coke of the blast furnace process, solid fuel of the sintering process (e.g. coke breeze). And z is the number of types of energetic products, and as mentioned above, the energetic products are one or more of molten iron, gas ash, residual energy power generation, blast furnace gas, tar, crude benzene, coke oven gas and coke.
In substep (4), if m co ≤m Lco At this timeI.e. when the amount m of CO converted in step 2) co Not more than the amount m of CO entering the recycling process in step 3) Lco At this time, the amount of CO generated by conversion is fully recycled and used for meeting the energy required by one or more procedures (such as a blast furnace procedure and a lime kiln procedure) of the iron and steel enterprises, and the residual CO 2 Are all converted into methanol for fixation without additional carbon emission, namely CO trapped in the step 1) 2 The total amount of the gas is not required to be discharged, so that the minimum carbon emission of the iron and steel enterprises is realized.
If m is co ＞m Lco At this time
I.e. when the amount m of CO converted in step 2) co An amount m of CO greater than that of the step 3) of the cyclic utilization process Lco At this time, a part of the CO converted at this time is recycled to one or more processes of the iron and steel enterprises, and a part of the CO not recycled is corresponding to the recycled CO 2 The amount of CO discharged at this time is required to be discharged 2 The amount of (2) isThis results in the carbon emission reduction by the passage (10).
In sub-step (5)According to the above equations (I) and (II), considering that the CO and methanol reaction paths are both reaction directions in which the gas volumes are reduced, high temperature and high pressure conditions are required, and both are usually present as main and side reactions at the same time, and the reaction conditions can be approximately regarded as the same. The CO path absorbs 41kJ/mol while consuming 1 unit H 2 The methanol route gives off heat 49kJ/mol consuming 3 units of H 2 . From the energy perspective, the cost of the CO path is lower and the energy efficiency is higher. Thereby according to the unit CO 2 The cost difference delta P of CO and methanol can be converted to obtain the CO in the whole steel smelting process 2 The cost difference deltac of the gas conversion to CO and methanol is:
in sub-step (6), it is considered that the CO product will eventually remain as CO when it enters some process other than the blast furnace, lime kiln 2 In the form of (2) carbon emissions, the CO is still considered comprehensively based on the low cost of the aforementioned analysis of the CO path 2 Emission reduction. By combining (10) and (11), the cost difference DeltaC and the carbon emission reduction can be seenRespectively with CO 2 Selectivity S for conversion to CO co In inverse proportion, as shown in FIG. 6, the CO selectivity S is determined after the limited range of cost savings and carbon reduction for a given iron and steel enterprise co Range.
Setting the carbon emission reduction target of the iron and steel enterprise as delta E min The carbon emission reduction target Δe here min The method is a lower limit of an enterprise carbon emission reduction target, namely the minimum carbon emission reduction required to be achieved by the enterprise. Setting the cost saving target as delta C min At this time, the cost target delta C is saved min The lower limit of the cost goal for the enterprise, i.e., the lowest cost savings the enterprise wants to achieve. The method comprises the following steps:
i.e. < ->
ΔC≥ΔC min I.e.
If the value Δc=Δc min I.e. take the valueAnd combining the formulas (2) - (6) to calculate CO 2 Reaction conditions at the conversion center. At this time, CO in iron and steel enterprises 2 As can be seen from FIG. 6, the cost difference between CO and methanol reaches the lower limit of the cost saving target, and the carbon emission reduction in the steel process reaches the maximum value, i.e. the reaction condition is that the iron and steel enterprise realizes the lowest CO on the premise of achieving the cost saving target 2 The discharged process conditions.
CO as described herein 2 The reaction conditions of the conversion center mainly comprise total reaction pressure, reaction temperature and H 2 /CO 2 For example, in the ratio of the total reaction pressure to H 2 /CO 2 When the ratio of (C) is determined, the reaction temperature range can be obtained.
If take valueI.e. take the value +.>Combining (2) - (6), and calculating to obtain CO 2 Reaction conditions at the conversion center. At this time, the carbon emission reduction amount of the iron and steel enterprise just reaches the lower limit of the carbon emission reduction target of the enterprise, and as can be seen from fig. 6, the carbon emission reduction amount is at the lower limit of the carbon emission reduction target, and at this time, the carbon emission reduction amount is CO in the iron and steel process 2 The cost difference value of the CO and the methanol reaches the maximum value, namely the reaction condition is the most cost-saving process condition realized by the iron and steel enterprises on the premise of achieving the aim of carbon emission reduction, namely the reaction conditionThe process condition of the lowest hydrogen consumption is realized for iron and steel enterprises.
If take valueCombining (2) - (6), and calculating to obtain CO 2 Reaction conditions at the conversion center. At the moment, the iron and steel enterprises realize the proportion regulation of conversion products by matching the self cost requirement and the carbon emission reduction requirement, so as to reach the balance optimal value of the conversion cost and the carbon emission reduction, namely the iron and steel enterprises realize the CO on the premise that the reaction conditions reach the cost saving target and the carbon emission reduction target 2 And (3) comprehensively controlling conversion cost and carbon emission.
The invention also provides a method for using the CO 2 A system for a method of conversion recycling, the system comprising CO 2 Conversion center, blast furnace, lime kiln. CO 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a conversion substance gas-liquid separation and conversion gas allocation device. The gas outlet of the blast furnace and the gas outlet of the lime kiln are both connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln. The hydrogen outlet of the hydrogen generating device is connected to CO 2 The hydrogen inlet of the reformer. CO 2 The converter outlet of the converter is connected to the converter inlet of the converter gas-liquid separation and conversion gas distribution device. In this system, CO produced by the blast furnace and lime kiln 2 Is trapped and then is conveyed to CO 2 Conversion center, CO 2 In CO 2 CO of conversion center 2 H generated in conversion device and hydrogen generating device 2 CO is carried out 2 Conversion reaction of CO 2 And the CO product obtained by conversion is supplied to a blast furnace or a lime kiln for recycling through the separation of a conversion substance gas-liquid separation and conversion gas allocation device. By CO 2 The conversion recycling mode partially replaces the source carbon input and reduces the tail end carbon emission, thereby realizing the great reduction of the carbon emission of the steel process.
The CO described in the present invention 2 TransformationCentral CO 2 The gas inlet being CO 2 CO of conversion device 2 Gas inlet, CO 2 The CO gas outlet of the conversion center is the CO gas outlet of the conversion substance gas-liquid separation and conversion gas allocation device.
Preferably, the system further comprises a sintering machine, a rotary kiln, a coke oven, a converter and a straight ring furnace. The gas outlet of the blast furnace, the gas outlet of the lime kiln and the gas outlet of the converter are all connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln and/or sintering machine and/or rotary kiln and/or coke oven and/or straight-loop furnace. The invention takes the whole process of steel smelting as a research object, effectively connects each process of the steel process in series according to the characteristics of carbon emission and energy input at the tail end of each process of a steel enterprise, and realizes a carbon conversion recycling chain, thereby greatly reducing the carbon emission in the steel smelting process.
In the present invention, the system further comprises CO 2 A preprocessing system. CO 2 The pretreatment system is mainly used for carrying out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more working procedures of the iron and steel enterprises, and purifying the flue gas after pretreatment. CO as described in the present invention 2 The trapping of the flue gas is carried out by a temperature and pressure swing adsorption device, and the temperature and pressure swing adsorption device carries out CO on the purified flue gas 2 Is trapped to obtain enriched CO with high purity 2 And (3) gas. The pretreatment, trapping and enrichment of the flue gas are beneficial to the smooth proceeding of the subsequent conversion reaction and the improvement of the conversion efficiency.
In the present invention, CO generated in one or more steps of an iron and steel enterprise 2 When the concentration is low, the CO can be discharged without being trapped, and the CO with low concentration can also be discharged through a lime kiln process 2 Enriching and then taking part in the subsequent CO 2 And (5) capturing and converting the gas for recycling. In the system of the invention, CO is carried out by a lime kiln process 2 Is about to produce lower concentration CO 2 The gas outlet of the device corresponding to the step (for example, the gas of a blast furnace, a sintering machine, a rotary kiln, a coke oven, a converter, a straight-ring furnace is selectedOutlet) is connected with a gas inlet of the lime kiln, enriched by the lime kiln process and then connected with the subsequent CO 2 A pretreatment system and a temperature and pressure swing adsorption device. This arrangement achieves a low concentration of CO 2 Is used to reduce CO 2 Further ensuring the low carbon emission of the steel process.
In the present invention, the hydrogen generating apparatus is preferably green electricity-H 2 O electrolysis unit. Green electricity-H 2 The oxygen outlet of the O electrolyzer is connected to a blast furnace or converter for oxyfuel combustion/injection. Alternatively, green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to the sintering machine for oxygen-enriched sintering.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention takes the whole process of iron and steel smelting as a research object for the first time, and proposes CO according to the characteristics of carbon emission and energy input at the tail end of each process of iron and steel enterprises 2 Is CO 2 Conversion of (C) to CO 2 The recycling technology of the steel process realizes the great reduction of carbon emission of the steel process.
2. The invention proposes and CO 2 The system matched with the conversion recycling method effectively connects each procedure of the steel flow in series and introduces CO 2 And the conversion center realizes a carbon conversion recycling chain and greatly reduces carbon emission in the steel smelting process.
3. The invention realizes CO by matching the cost requirement and/or carbon emission requirement of the iron and steel enterprises 2 The proportion of the conversion products is regulated and controlled, so that the comprehensive control of the conversion cost and the carbon emission of steel enterprises is realized, and the balance optimal value of the conversion cost and the carbon emission of the enterprises is reached.
4. The technology is suitable for CO in the traditional steel smelting process 2 Emission reduction by CO 2 The conversion recycling mode is used for partially replacing source carbon input and reducing tail end carbon emission, and has wide application range and great market potential.
5. CO in the present technique 2 The trapped object is mainly the high concentration tail gas of each process, and the converted product returns to each process for circulationThe utilization of the ring can reduce the trapping difficulty, flexibly regulate and control the conversion product direction, and is easy to realize in engineering implementation.
Drawings
FIG. 1 shows a steel process CO according to the invention 2 A flow chart of a method of conversion recycling;
FIG. 2 is a CO of the process of the invention 2 A flow chart comprising methanol in the conversion product;
FIG. 3 is a flow chart of the pretreatment steps of the method of the present invention including flue gas;
FIG. 4 is a full flow CO of the steel in the invention 2 A flow chart of conversion and cyclic utilization;
FIG. 5 is a flow chart of the control of conversion cost and carbon emissions for a steel enterprise in accordance with the present invention;
FIG. 6 is a graph of CO in the present invention 2 A relation diagram of the selectivity of the converted CO and the conversion cost difference and the carbon emission;
FIG. 7 shows a steel process CO according to the invention 2 A structural schematic diagram of a system for conversion and recycling;
FIG. 8 is a schematic diagram of another steel process CO according to the invention 2 A structural schematic diagram of a system for conversion and recycling;
FIG. 9 is a schematic diagram of a system of the present invention with CO 2 Schematic structural diagrams of a pretreatment system and a temperature and pressure swing adsorption device;
FIG. 10 shows the production of lower concentration CO in the system of the present invention 2 CO is carried out by lime kiln process 2 Schematic of the structure of the enrichment.
Reference numerals:
a1: a blast furnace; a2: lime kiln; a3: a sintering machine; a4: a rotary kiln; a5: coke oven; a6: a converter; a7: a straight ring furnace; a8: CO 2 A pretreatment system; a9: a temperature and pressure swing adsorption device; z: CO 2 A transformation center; 1: a hydrogen generating device; 2: CO 2 A conversion device; 3: a device for separating and blending the gas and the liquid of the converted substance.
Detailed Description
The following examples illustrate the technical aspects of the invention, and the scope of the invention claimed includes but is not limited to the following examples.
According to a second embodiment of the present invention, there is provided a steel process CO 2 A system for conversion and recycling.
A CO as described in the first embodiment 2 A system for a method of conversion recycling, the system comprising CO 2 A conversion center Z, a blast furnace A1 and a lime kiln A2.CO 2 The conversion center Z comprises a hydrogen generating device 1 and CO 2 A conversion device 2, a conversion material gas-liquid separation and conversion gas allocation device 3. The gas outlet of the blast furnace A1 and the gas outlet of the lime kiln A2 are connected to CO 2 CO of conversion center Z 2 A gas inlet. CO 2 The CO gas outlet of the conversion centre Z is connected to the gas inlet of the blast furnace A1 and/or lime kiln A2. The hydrogen outlet of the hydrogen generating device 1 is connected to CO 2 The hydrogen inlet of the reformer 2. CO 2 The converter outlet of the converter 2 is connected to the converter inlet of the converter gas-liquid separation and conversion gas distribution device 3.
In the invention, the system also comprises a sintering machine A3, a rotary kiln A4, a coke oven A5, a converter A6 and a straight-ring furnace A7. The gas outlet of the blast furnace A1, the gas outlet of the lime kiln A2 and the gas outlet of the converter A6 are all connected to CO 2 CO of conversion center Z 2 A gas inlet. CO 2 The CO gas outlet of the conversion center Z is connected to the gas inlet of the blast furnace A1 and/or lime kiln A2 and/or sintering machine A3 and/or rotary kiln A4 and/or coke oven A5 and/or straight-loop furnace A7.
Preferably, the system further comprises CO 2 Pretreatment system A8.CO 2 The pretreatment system A8 is used for carrying out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more procedures of the iron and steel enterprises.
Preferably, the system further comprises a temperature and pressure swing adsorption apparatus A9. The gas outlets of the blast furnace A1, the lime kiln A2 and the converter A6 are all connected to CO 2 Pretreatment system A8.CO 2 The gas outlet of the pretreatment system A8 is connected to a temperature and pressure swing adsorption device A9. CO of temperature and pressure swing adsorption device A9 2 The gas outlet is connected to CO 2 CO of conversion center Z 2 A gas inlet.
In the present inventionIn the invention, the gas outlets of the optional blast furnace A1, the sintering machine A3, the rotary kiln A4, the coke oven A5, the converter A6 and the straight-ring furnace A7 are connected to the gas inlet of the lime kiln A2. The gas outlet of the lime kiln A2 is connected to CO 2 Pretreatment system A8.CO 2 The gas outlet of the pretreatment system A8 is connected to a temperature and pressure swing adsorption device A9.
In the present invention, the hydrogen generating apparatus 1 is green electricity-H 2 O electrolysis unit. Green electricity-H 2 The oxygen outlet of the O electrolyzer is connected to a blast furnace A1, a converter A6 or a sintering machine A3.
Example 1
As shown in FIG. 7, a steel process CO 2 A system for conversion recycling, the system comprising CO 2 A conversion center Z, a blast furnace A1 and a lime kiln A2.CO 2 The conversion center Z comprises a hydrogen generating device 1 and CO 2 A conversion device 2, a conversion material gas-liquid separation and conversion gas allocation device 3. The gas outlet of the blast furnace A1 and the gas outlet of the lime kiln A2 are connected to CO 2 CO of conversion center Z 2 A gas inlet. CO 2 The CO gas outlet of the conversion center Z is connected to the gas inlets of the blast furnace A1 and the lime kiln A2. The hydrogen outlet of the hydrogen generating device 1 is connected to CO 2 The hydrogen inlet of the reformer 2.CO 2 The converter outlet of the converter 2 is connected to the converter inlet of the converter gas-liquid separation and conversion gas distribution device 3. The CO 2 CO of conversion center Z 2 The gas inlet being CO 2 CO of the conversion apparatus 2 2 Gas inlet, CO 2 The CO gas outlet of the conversion center Z is the CO gas outlet of the conversion substance gas-liquid separation and conversion gas allocation device 3.
Example 2
As shown in fig. 8, example 1 is repeated except that the system further includes a sintering machine A3, a rotary kiln A4, a coke oven A5, a converter A6, and a straight-ring furnace A7. The gas outlet of the blast furnace A1, the gas outlet of the lime kiln A2 and the gas outlet of the converter A6 are all connected to CO 2 CO of conversion center Z 2 A gas inlet. CO 2 The CO gas outlet of the conversion center Z is connected to the gas inlets of the blast furnace A1, the lime kiln A2, the sintering machine A3, the rotary kiln A4, the coke oven A5 and the straight-ring furnace A7.
Example 3
As shown in FIG. 9, example 2 is repeated except that the system also includes CO 2 Pretreatment system A8.CO 2 The pretreatment system A8 carries out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by the blast furnace process, the lime kiln process and the converter process of the iron and steel enterprises.
Example 4
Example 3 is repeated except that the system further comprises a temperature and pressure swing adsorption unit A9. The gas outlets of the blast furnace A1, the lime kiln A2 and the converter A6 are all connected to CO 2 Pretreatment system A8.CO 2 The gas outlet of the pretreatment system A8 is connected to a temperature and pressure swing adsorption device A9. CO of temperature and pressure swing adsorption device A9 2 The gas outlet is connected to CO 2 CO of conversion center Z 2 A gas inlet.
Example 5
As shown in fig. 10, example 4 was repeated except that the gas outlets of the sintering machine A3, the rotary kiln A4, the coke oven A5, and the straight-ring furnace A7 were connected to the gas inlet of the lime kiln A2. The gas outlet of the lime kiln A2 is connected to CO 2 Pretreatment system A8.CO 2 The gas outlet of the pretreatment system A8 is connected to a temperature and pressure swing adsorption device A9.
Example 6
Example 4 was repeated except that the hydrogen-generating apparatus 1 was green electricity-H 2 O electrolysis unit. Green electricity-H 2 The oxygen outlets of the O electrolyzer are respectively connected to a blast furnace A1 and a converter A6.
Example 7
Example 5 was repeated except that the hydrogen-generating apparatus 1 was green electricity-H 2 O electrolysis unit. Green electricity-H 2 The oxygen outlet of the O-electrolysis device is connected to the sintering machine A3.
Example 8
As shown in FIG. 1, a steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 is trapped: CO generated by one or more procedures of iron and steel enterprises 2 Capturing to obtain enriched CO 2 And (3) gas.
2)CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center Z and to CO 2 And introducing a reducing medium into the conversion center Z to obtain CO.
3)CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to one or more working procedures of an iron and steel enterprise for recycling.
Example 9
As shown in FIG. 2, a steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 is trapped: CO generated by one or more procedures of iron and steel enterprises 2 Capturing to obtain enriched CO 2 And (3) gas.
2)CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center Z and to CO 2 And introducing a reducing medium into the conversion center Z to obtain CO and methanol. Wherein: methanol is used as a raw material and fuel for one or more processes in iron and steel enterprises.
3)CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to one or more working procedures of an iron and steel enterprise for recycling.
Example 10
As shown in fig. 3, a steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 is trapped: firstly, carrying out dust removal, desulfurization and dehydration pretreatment on flue gas generated by one or more procedures of an iron and steel enterprise to obtain purified flue gas. And then CO is carried out on the purified flue gas of each procedure 2 Is trapped to obtain enriched CO 2 And (3) gas.
The humidity of the purified flue gas is less than 0.5%. The sulfide content in the purified flue gas is less than 30mg/Nm 3 . The dust content in the purified flue gas is less than 5mg/Nm 3 。
2)CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center Z and to CO 2 And introducing a reducing medium into the conversion center Z to obtain CO and methanol. Wherein: methanol asAnd outputting a product.
3)CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to one or more working procedures of an iron and steel enterprise for recycling.
Example 11
Example 10 was repeated except that in step 2) the reducing medium was carbon.
Example 12
Example 10 was repeated except that the reducing medium in step 2) was a reducing gas H 2 。
Example 13
Example 12 was repeated except that the CO described in step 1) 2 Is captured by a temperature and pressure swing adsorption device. The temperature and pressure swing adsorption device is internally provided with a porous material loaded with chemical absorbent. The porous material is an aluminosilicate molecular sieve. The chemical absorbent is primary amine (ethanolamine) MEA in an alcohol amine reagent.
Example 14
Example 13 was repeated except that the porous material was aluminosilicate sepiolite.
Example 15
Example 13 was repeated except that the CO described in step 2) was used 2 The conversion center Z comprises a hydrogen generating device 1 and CO 2 A conversion device 2, a conversion material gas-liquid separation and conversion gas allocation device 3. The hydrogen outlet of the hydrogen generating device 1 is connected to CO 2 The hydrogen inlet of the reformer 2. CO 2 The converter outlet of the converter 2 is connected to the converter inlet of the converter gas-liquid separation and conversion gas distribution device 3. The hydrogen generating device 1 is green electricity-H 2 O electrolysis unit. CO 2 The conversion center Z contains CO 2 A conversion catalyst. The CO 2 The conversion catalyst is a copper-based mesoporous catalytic material.
Example 16
Example 15 was repeated except that the CO 2 The conversion catalyst is a nickel-based mesoporous catalytic material.
Example 17
As shown in fig. 4, example 15 is repeated except that the one or more processes of the iron and steel enterprises described in step 1) and step 3) include a blast furnace process, a converter process, a lime kiln process, a sintering process, a pellet process, a coking process, and a return-to-direct process.
Example 18
Example 17 was repeated except that in step 1), CO was produced at a high concentration in each step of the iron and steel industry 2 Capturing low concentration CO 2 And discharging. Wherein, high concentration CO 2 The volume fraction of (2) is more than or equal to 12%, and low concentration CO 2 Is < 12% by volume.
Example 19
Example 17 was repeated except that in step 1), CO was produced at a high concentration in each step of the iron and steel industry 2 Capturing low concentration CO 2 And discharging. Wherein, high concentration CO 2 The volume fraction of (2) is more than or equal to 15%, and low concentration CO 2 Is < 15% by volume.
Example 20
Example 18 was repeated except that in step 1), CO was produced in 2 steps, namely, the blast furnace step and the lime kiln step, of the iron and steel industry 2 And (5) collecting.
In the step 3), the CO obtained in the step 2) is recycled to 2 steps, namely, a blast furnace step and a lime kiln step of the iron and steel industry.
Example 21
Example 19 was repeated except that in step 1), CO was produced in 3 steps of the blast furnace step, the lime kiln step, and the converter step of the iron and steel industry 2 And (5) collecting.
In the step 3), the CO obtained in the step 2) is recycled to 6 steps of a blast furnace step, a lime kiln step, a sintering step, a pelletizing step, a coking step, and a direct recovery step of the iron and steel industry.
Example 22
Example 19 was repeated except that in step 1), CO was produced in 4 steps of the blast furnace step, the lime kiln step, the converter step, and the return step of the iron and steel industry 2 And (5) collecting.
In the step 3), the CO obtained in the step 2) is recycled to 6 steps of a blast furnace step, a lime kiln step, a sintering step, a pelletizing step, a coking step, and a direct recovery step of the iron and steel industry.
Example 23
Example 22 was repeated except that CO was produced in each of the sintering step, the pelletizing step and the coking step in the iron and steel industry 2 The volume concentration of (2) is lower than 15%, and CO generated in corresponding working procedure 2 After the enrichment procedure, the mixture is conveyed to CO 2 Transformation center Z. CO generated in the sintering process, the pelletizing process and the coking process 2 Delivering the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 And then concentrating the CO 2 Delivery to CO 2 Transformation center Z.
Example 24
Example 15 was repeated except green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing solar energy and wind energy. Green electricity-H 2 The O electrolyzer electrolyzes water to produce hydrogen and oxygen, and the hydrogen is conveyed to CO 2 The conversion center Z is used as a reducing medium, and oxygen is conveyed to a blast furnace and a converter of a steel enterprise for oxygen-enriched combustion and oxygen-enriched blowing.
Example 25
Example 24 was repeated except that oxygen was fed to the sintering machine for oxygen-enriched sintering.
Example 26
Steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 is trapped: CO generated by one or more procedures of iron and steel enterprises 2 Capturing to obtain enriched CO 2 And (3) gas.
2)CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center Z and to CO 2 H is introduced into the conversion center Z 2 CO is obtained.
3)CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to one or more working procedures of an iron and steel enterprise for recycling.
As shown in fig. 5, in the wholeIn the individual steel smelting flow, by controlling CO 2 The selectivity of converting the gas into CO is realized, thereby realizing the CO conversion of iron and steel enterprises 2 Conversion cost and carbon emission control. The method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc 。
(2) According to CO 2 The selectivity of the conversion of the gas into CO, the amount m of CO produced in the conversion in step 2) is calculated co 。
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco 。
(4) Calculating the carbon emission reduction amount in the whole steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The gas is converted to a cost difference deltac of CO and methanol.
(6) According to the cost target and the carbon emission reduction target of the iron and steel enterprise, calculating to obtain CO 2 Selectivity of gas to CO, and controlling CO in step 2) based on the obtained selectivity of CO 2 The process conditions of the transformation are realized, thereby realizing the CO of the iron and steel enterprises 2 Conversion cost and carbon emission control.
Example 27
Example 26 was repeated except that in substep (1), the enriched CO obtained in step 1) was calculated 2 The total amount of gas is specifically:
the consumption amount of the g-th fossil fuel at the carbon input end of the i-th working procedure is F i,g . CO of fossil fuel of type g 2 Direct emission factor D g . The consumption amount of the h power medium at the carbon input end of the ith procedure is DM i,h . CO of the h power medium 2 Indirect emission factor ID h . The number of the outer pins of the j-th energetic product at the carbon output end of the i-th working procedure is P i,j . CO of the j-th energetic product 2 The direct emission factor is ND j . Accounting is carried out according to the material energy balance of the input end and the output end, and then the method is that:
wherein: m is m cc Enriched CO from step 1) 2 Total amount of gas. n is CO 2 The number of trapping steps. x is the number of fossil fuel species. y is the number of kinds of power media. z is the number of species of energetic product.
Example 28
Example 27 was repeated except that in sub-step (2) CO was set 2 The selectivity of the gas to CO is S co . The method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for conversion to methanol is K 1 ，CO 2 The equilibrium constant of the reaction for conversion to CO is K 2 . According to CO 2 The reaction formula for converting into methanol and CO is as follows:
wherein: reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)；K 2 ＝f 2 (T). The method comprises the following steps:
/>
combining (3) - (6) to obtain X CO 、X MeOH . Then combining the formula (2) to obtain S co 。
The amount of CO thus formed by the conversion in step 2) is:
in formulas (2) - (7): x is X CO Is CO 2 Conversion to CO. X is X MeOH Is CO 2 Conversion to methanol. Beta is H 2 /CO 2 Is a ratio of (2). P (P) Total (S) Is the total reaction pressure. T is the reaction temperature. m is m co The amount of CO produced for the conversion in step 2). a, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 A, a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants.
Example 29
Example 28 was repeated except that in substep (3), the amount of CO entering the recycling process in step 3) was:
the consumption amount of the g-th fossil fuel at the s-th working procedure carbon input end is F s,g . The conversion standard coal coefficient of the g-th fossil fuel is C g . The consumption amount of the h power medium at the carbon input end of the s-th procedure is DM s,h . Converting the h power medium into DC h . The consumption amount of the No. w irreplaceable fossil fuel of the No. s working procedure carbon input end is IF s,w . Conversion of the w-th irreplaceable fossil fuel into standard coal coefficient as IC w . The number of the outer pins of the jth energy-containing product at the carbon output end of the s-th working procedure is P s,j . The conversion coal marking coefficient of the j-th energy-containing product is PC j . Accounting is performed according to the material energy balance of the input end and the output end, and the method comprises the following steps:
the preparation method comprises the following steps:
wherein: m is m Lco The amount of CO entering the recycling step in step 3). ΔcH CO Is the heat of combustion of CO. ΔcH Standard coal The heat value of the standard coal. m is the number of CO recycling processes. x is the number of fossil fuel species. y is the number of kinds of power media. l is the number of types of fossil fuels that are not replaceable. z is the number of species of energetic product.
Example 30
Example 29 was repeated except that in substep (4), the carbon emission reduction in the whole iron and steel smelting process was:
if m is co ≤m Lco At this time
If m is co ＞m Lco At this time
Wherein:the method is used for reducing the carbon emission in the whole steel smelting process.
Example 31
Example 30 was repeated except that in sub-step (5), CO was present in the entire iron and steel smelting process 2 The cost difference of the gas conversion into CO and methanol is:
wherein: ΔC is CO in the whole steel smelting process 2 The gas is converted to a cost difference of CO and methanol. ΔP is the unit CO 2 Conversion to CO and methanolCost difference.
Example 32
Example 31 was repeated except that in sub-step (6), the carbon emission reduction target of the iron and steel enterprise was set to ΔE min The cost saving goal is delta C min . The method comprises the following steps:
i.e. < ->
ΔC≥ΔC min I.e.
Example 33
Example 32 was repeated except that the value Δc=Δc was taken min I.e. take the valueCombining (2) - (6), calculating to obtain CO 2 Reaction conditions at the conversion center Z. The reaction condition realizes the lowest CO for iron and steel enterprises on the premise of achieving the aim of saving cost 2 The discharged process conditions.
Example 34
Example 32 is repeated, except that the value is takenI.e. take the value +.>Combining (2) - (6), calculating to obtain CO 2 Reaction conditions at the conversion center Z. The reaction condition is the most cost-saving process condition for iron and steel enterprises on the premise of achieving the aim of carbon emission reduction.
Example 35
Example 32 is repeated, except that the value is takenCombining (2) - (6), calculating to obtain CO 2 Reaction conditions at the conversion center Z. The reaction condition realizes CO for iron and steel enterprises on the premise of achieving the aims of saving cost and reducing carbon emission 2 And (3) comprehensively controlling conversion cost and carbon emission.
Application example 1
The iron and steel works CO described in example 33 2 The method for converting and recycling is used for Zhanjiang certain steel smelting plants, and comprises the following steps of:
1)CO 2 is trapped: according to the existing production level, CO generated by blast furnace process, lime kiln process and converter process of iron and steel enterprises is reduced 2 Capturing to obtain enriched CO 2 And (3) gas.
2)CO 2 Is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center Z and to CO 2 H is introduced into the conversion center Z 2 CO is obtained.
3)CO 2 Is recycled: and (3) conveying the CO obtained in the step (2) to a blast furnace process and a lime kiln process of an iron and steel enterprise for recycling.
By controlling CO in the whole steel smelting process 2 The selectivity of the gas to CO is realized, thereby realizing the CO conversion of the iron and steel enterprises 2 Conversion cost and carbon emission control. The method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc 。
m cc ＝380×3.12+150×2.93+12×0.78+25×0.33+180×0.33+28.8×2.775+1000×0.1-1000×0.15-15×1.1-35×0.33-1000×0.35＝1353.98kg。
In the above table, since carbon input is brought about by scrap steel/molten iron corresponding to the converter step, the enriched CO is calculated 2 The total amount of gas was calculated together.
(2) According to CO 2 The selectivity of the conversion of the gas into CO, the amount m of CO produced in the conversion in step 2) is calculated co 。
Setting CO 2 The selectivity of the gas to CO is S co . The method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for conversion to methanol is K 1 ，CO 2 The equilibrium constant of the reaction for conversion to CO is K 2 According to CO 2 The reaction formula for converting into methanol and CO is as follows:
and the reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)，K 2 ＝f 2 And (T) fitting the specific relation by experimental tests, wherein the specific relation is as follows:
wherein: a, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 A, a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants. The value of each fitting coefficient and CO 2 TransformationCatalyst-related. In the present embodiment, CO is selected 2 The conversion catalyst is copper-based mesoporous catalytic material, and the value of each fitting coefficient is a 1 ＝-152.7,b 1 ＝27169.2,d 1 ＝0.152,g 1 ＝-4.17,c 1 ＝h 1 ＝j 1 =0; a 2 ＝79.1,b 2 ＝-56500.7,c 2 ＝14.3,g 2 ＝-2.36,d 2 ＝h 2 ＝j 2 ＝0。
Combining (3) - (6) to obtain X CO And X MeOH . And then combining the formula (2) to obtain S co 。
Thus, the amount m of CO converted in step 2) co The method comprises the following steps:
/>
(3) calculating the amount m of CO entering the recycling process in the step 3) Lco 。
The preparation method comprises the following steps:
m Lco ＝71.31kg。
wherein: ΔcH CO Delta cH, the heat of combustion of CO CO ＝283kJ/mol。ΔcH Standard coal For the calorific value of standard coal, deltacH Standard coal ＝29307kJ/kg；
(4) Calculating the carbon emission reduction amount in the whole steel smelting process
If m is co ≤m Lco At this time
If m is co ＞m Lco At this time
(5) Calculating CO in the whole steel smelting process 2 The gas is converted to a cost difference deltac of CO and methanol.
Wherein: ΔP is the unit CO 2 Conversion to cost difference of CO and methanol, Δp=60 yuan/kmol.
(6) According to the cost target and the carbon emission reduction target of the iron and steel enterprise, calculating to obtain CO 2 Selectivity of gas to CO, and controlling CO in step 2) based on the obtained selectivity of CO 2 The process conditions of the transformation are realized, thereby realizing the CO of the iron and steel enterprises 2 Conversion cost and carbon emission control.
Setting carbon emission reduction target delta E of iron and steel enterprises min ＝400kg CO 2 T steel, cost saving target delta C min =600 yuan/t steel. The method comprises the following steps:
i.e. < ->
ΔC≥ΔC min I.e.
The steel plant takes the value deltac=deltac min I.e. take the valueThe method comprises the following steps: />
Wherein: ΔP is the unit CO 2 Conversion to cost difference of CO and methanol, Δp=60 yuan/kmol.
Combining (2) - (6), calculating to obtain CO 2 The reaction condition of the conversion center Z, and adjusting CO according to the calculated reaction condition 2 Various parameters of the conversion center Z are measured at the total reaction pressure P Total (S) ＝3Mpa，H 2 /CO 2 When β=3, the reaction temperature is t=195℃. The reaction condition realizes the lowest CO for iron and steel enterprises on the premise of achieving the aim of saving cost 2 The discharged process conditions.
At this time, the reduction of carbon emission in the iron and steel smelting process of the iron and steel plant is that And (3) steel.
Therefore, compared with the carbon emission of the traditional process, the whole process of steel smelting is taken as a research object in the iron and steel plant, and CO is adopted 2 Is CO 2 Conversion of (C) to CO 2 The recycling technology of the steel process realizes the great reduction of carbon emission of the steel process.
Application example 2
The iron and steel flow CO of example 34 2 The method of conversion recycling was used in Zhanjiang certain iron and steel smeltery, example 1 was repeated except that the iron and steel plant had taken valueI.e. take the value +.>The method comprises the following steps:
combining (2) - (6), calculating to obtain CO 2 The reaction condition of the conversion center Z, and adjusting CO according to the calculated reaction condition 2 Various parameters of the conversion center Z are measured at the total reaction pressure P Total (S) ＝3Mpa，H 2 /CO 2 When β=3, the reaction temperature is t=236℃. The reaction condition is the most cost-saving process condition for iron and steel enterprises on the premise of achieving the aim of carbon emission reduction.
At this time, the reduction of carbon emission in the iron and steel smelting process of the iron and steel plant is that And (3) steel.
Application example 3
The iron and steel process CO of example 35 2 The method of conversion recycling was used in Zhanjiang certain iron and steel smeltery, example 1 was repeated except that the iron and steel plant had taken valueThe method comprises the following steps:
0.325＜S co ＜0.787。
combining (2) - (6), calculating to obtain CO 2 The reaction condition of the conversion center Z, and adjusting CO according to the calculated reaction condition 2 Various parameters of the conversion center Z are measured at the total reaction pressure P Total (S) ＝3Mpa，H 2 /CO 2 When the ratio beta=3, the reaction temperature is 195 ℃ < T < 236 ℃. The reaction condition realizes CO for iron and steel enterprises on the premise of achieving the aims of saving cost and reducing carbon emission 2 And (3) comprehensively controlling conversion cost and carbon emission.
As can be seen from the above application examples, the present invention, by matching the cost requirements and/or carbon emission requirements of the iron and steel enterprises themselves,realization of CO 2 The proportion of the conversion products is regulated and controlled, so that the comprehensive control of the conversion cost and the carbon emission of steel enterprises is realized, and the balance optimal value of the conversion cost and the carbon emission of the enterprises can be reached.
Claims (44)
1. Steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 is trapped: CO generated by one or more procedures of iron and steel enterprises 2 Capturing to obtain enriched CO 2 A gas;
2)CO 2 is converted into: to enrich CO 2 Gas delivery to CO 2 Conversion center (Z) and to CO 2 Introducing a reducing medium into the conversion center (Z) to obtain CO;
3)CO 2 is recycled: delivering the CO obtained in the step 2) to one or more working procedures of an iron and steel enterprise for recycling;
by controlling CO in the whole steel smelting process 2 The selectivity of converting the gas into CO is realized, thereby realizing the CO conversion of iron and steel enterprises 2 Conversion cost and carbon emission control; the method specifically comprises the following substeps:
calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc ；
According to CO 2 The selectivity of the conversion of the gas into CO, the amount m of CO produced in the conversion in step 2) is calculated co ；
Calculating the amount m of CO entering the recycling process in the step 3) Lco ；
Calculating the carbon emission reduction amount in the whole steel smelting process
Calculating CO in the whole steel smelting process 2 The cost difference delta C of the gas conversion into CO and methanol;
according to the cost target and/or the carbon emission reduction target of the iron and steel enterprise, calculating to obtain CO 2 Selectivity of gas to CO, and controlling CO in step 2) based on the obtained selectivity of CO 2 The process conditions of the transformation are realized, thereby realizing the CO of the iron and steel enterprises 2 Conversion cost and carbon emission control.
2. The steel process CO according to claim 1 2 The method for converting and recycling is characterized by comprising the following steps of: the reducing medium in the step 2) is a reducing solid or a reducing gas;
the step 2) is specifically as follows: to enrich CO 2 Gas delivery to CO 2 Conversion center (Z) and to CO 2 H is introduced into the transformation center (Z) 2 CO and methanol are obtained; wherein: methanol is used as a raw material, fuel for one or more processes in iron and steel enterprises, or is output as a product.
3. Steel process CO according to claim 2 2 The method for converting and recycling is characterized by comprising the following steps of: the reducing solid is carbon, and the reducing gas is H 2 。
4. A steel process CO according to any one of claims 1-3 2 The method for converting and recycling is characterized by comprising the following steps of: the step 1) also comprises pretreatment of flue gas of each procedure of the iron and steel enterprises; the step 1) specifically comprises the following steps: firstly, carrying out dust removal, desulfurization and dehydration pretreatment on flue gas generated by one or more procedures of an iron and steel enterprise to obtain purified flue gas; and then CO is carried out on the purified flue gas of each procedure 2 Is trapped to obtain enriched CO 2 And (3) gas.
5. The steel process CO of claim 4 2 The method for converting and recycling is characterized by comprising the following steps of: the humidity of the purified flue gas is less than 1%; the sulfide content in the purified flue gas is less than 35mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the The dust content in the purified flue gas is less than 10mg/Nm 3 。
6. The steel process CO of claim 5 2 The method for converting and recycling is characterized by comprising the following steps of: the humidity of the purified flue gas is less than 0.5%; net for cleaningSulfide content in chemical fume is less than 30mg/Nm 3 The method comprises the steps of carrying out a first treatment on the surface of the The dust content in the purified flue gas is less than 5mg/Nm 3 。
7. Steel process CO according to any one of claims 1-3, 5-6 2 The method for converting and recycling is characterized by comprising the following steps of: CO as described in step 1) 2 Is captured by a temperature and pressure swing adsorption device; a porous material loaded with a chemical absorbent is arranged in the temperature and pressure swing adsorption device;
CO as described in step 2) 2 The conversion center (Z) comprises a hydrogen generating device (1) and CO 2 A conversion device (2), a conversion material gas-liquid separation and conversion gas allocation device (3); the hydrogen outlet of the hydrogen generating device (1) is connected to CO 2 A hydrogen inlet of the reformer (2); CO 2 The converter outlet of the converter (2) is connected to the converter inlet of the converter gas-liquid separation and converter gas distribution device (3).
8. The steel process CO of claim 4 2 The method for converting and recycling is characterized by comprising the following steps of: CO as described in step 1) 2 Is captured by a temperature and pressure swing adsorption device; a porous material loaded with a chemical absorbent is arranged in the temperature and pressure swing adsorption device;
CO as described in step 2) 2 The conversion center (Z) comprises a hydrogen generating device (1) and CO 2 A conversion device (2), a conversion material gas-liquid separation and conversion gas allocation device (3); the hydrogen outlet of the hydrogen generating device (1) is connected to CO 2 A hydrogen inlet of the reformer (2); CO 2 The converter outlet of the converter (2) is connected to the converter inlet of the converter gas-liquid separation and converter gas distribution device (3).
9. The steel process CO according to claim 7 2 The method for converting and recycling is characterized by comprising the following steps of: the porous material is an aluminosilicate mesoporous material; the chemical absorbent is an alcohol amine reagent; and/or
The hydrogen generating device (1) is green electricity-H 2 O electrolysis deviceAnd (5) placing.
10. The steel process CO according to claim 8 2 The method for converting and recycling is characterized by comprising the following steps of: the porous material is an aluminosilicate mesoporous material; the chemical absorbent is an alcohol amine reagent; and/or
The hydrogen generating device (1) is green electricity-H 2 O electrolysis unit.
11. The steel process CO according to claim 7 2 The method for converting and recycling is characterized by comprising the following steps of: green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy; green electricity-H 2 The O electrolyzer electrolyzes water to produce hydrogen and oxygen, and the hydrogen is conveyed to CO 2 The conversion center (Z) serves as a reducing medium, and oxygen is delivered to one or more processes of the iron and steel enterprise.
12. Steel process CO according to any one of claims 8-10 2 The method for converting and recycling is characterized by comprising the following steps of: green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy; green electricity-H 2 The O electrolyzer electrolyzes water to produce hydrogen and oxygen, and the hydrogen is conveyed to CO 2 The conversion center (Z) serves as a reducing medium, and oxygen is delivered to one or more processes of the iron and steel enterprise.
13. The steel process CO according to claim 11 2 The method for converting and recycling is characterized by comprising the following steps of: oxygen is delivered to a blast furnace or converter for oxyfuel combustion or blowing, or oxygen is delivered to a sintering machine for oxyfuel sintering.
14. Steel process CO according to claim 12 2 The method for converting and recycling is characterized by comprising the following steps of: delivering oxygen to a blast furnace or converter for oxyfuel combustion or injection, or delivering oxygen toThe sintering machine is used for oxygen-enriched sintering.
15. The steel process CO according to any one of claims 1-3, 5-6, 8-11, 13-14 2 The method for converting and recycling is characterized by comprising the following steps of: in step 1), high concentration CO generated for each process of the iron and steel enterprises 2 Capturing low concentration CO 2 Discharging; wherein, high concentration CO 2 The volume fraction of (2) is more than or equal to 12%, and low concentration CO 2 Is < 12% by volume.
16. The steel process CO of claim 4 2 The method for converting and recycling is characterized by comprising the following steps of: in step 1), high concentration CO generated for each process of the iron and steel enterprises 2 Capturing low concentration CO 2 Discharging; wherein, high concentration CO 2 The volume fraction of (2) is more than or equal to 12%, and low concentration CO 2 Is < 12% by volume.
17. The steel process CO according to claim 15 2 The method for converting and recycling is characterized by comprising the following steps of: high concentration CO 2 The volume fraction of (2) is more than or equal to 15%, and low concentration CO 2 Is < 15% by volume.
18. The steel process CO according to claim 16 2 The method for converting and recycling is characterized by comprising the following steps of: high concentration CO 2 The volume fraction of (2) is more than or equal to 15%, and low concentration CO 2 Is < 15% by volume.
19. The steel process CO according to any one of claims 1-3, 5-6, 8-11, 13-14, 16-18 2 The method for converting and recycling is characterized by comprising the following steps of: in step 1), CO generated in n processes of the iron and steel enterprise 2 Capturing; wherein: n is 1-10;
in the step 3), delivering the CO obtained in the step 2) to m working procedures of a steel enterprise for recycling; wherein: m is 1-12.
20. The steel process CO of claim 4 2 The method for converting and recycling is characterized by comprising the following steps of: in step 1), CO generated in n processes of the iron and steel enterprise 2 Capturing; wherein: n is 1-10;
in the step 3), delivering the CO obtained in the step 2) to m working procedures of a steel enterprise for recycling; wherein: m is 1-12.
21. The steel process CO of claim 19 2 The method for converting and recycling is characterized by comprising the following steps of: n is 3-6; m is 3-8.
22. The steel process CO according to claim 20 2 The method for converting and recycling is characterized by comprising the following steps of: n is 3-6; m is 3-8.
23. The steel process CO of claim 19 2 The method for converting and recycling is characterized by comprising the following steps of: the one or more procedures of the iron and steel enterprises in the step 1) and the step 3) are one or more of a blast furnace procedure, a converter procedure, a lime kiln procedure, a sintering procedure, a pelletizing procedure, a coking procedure and a direct return procedure;
CO 2 the conversion center (Z) contains CO 2 A conversion catalyst; the CO 2 The conversion catalyst is a nickel-based or copper-based mesoporous catalytic material.
24. Steel process CO according to any one of claims 20-22 2 The method for converting and recycling is characterized by comprising the following steps of: the one or more procedures of the iron and steel enterprises in the step 1) and the step 3) are one or more of a blast furnace procedure, a converter procedure, a lime kiln procedure, a sintering procedure, a pelletizing procedure, a coking procedure and a direct return procedure;
CO 2 the conversion center (Z) contains CO 2 A conversion catalyst; the CO 2 The conversion catalyst is a nickel-based or copper-based mesoporous catalytic material.
25. The steel process CO of claim 23 2 The method for converting and recycling is characterized by comprising the following steps of: the one or more procedures of the iron and steel enterprises in the step 1) are one or more of a blast furnace procedure, a converter procedure and a lime kiln procedure; and/or
The one or more procedures of the iron and steel enterprises in the step 3) are one or more of a blast furnace procedure, a lime kiln procedure, a sintering procedure, a pellet procedure, a coking procedure and a direct return procedure.
26. The steel process CO of claim 24 2 The method for converting and recycling is characterized by comprising the following steps of: the one or more procedures of the iron and steel enterprises in the step 1) are one or more of a blast furnace procedure, a converter procedure and a lime kiln procedure; and/or
The one or more procedures of the iron and steel enterprises in the step 3) are one or more of a blast furnace procedure, a lime kiln procedure, a sintering procedure, a pellet procedure, a coking procedure and a direct return procedure.
27. The steel process CO of claim 23 2 The method for converting and recycling is characterized by comprising the following steps of: CO generated in certain working procedure of iron and steel enterprises 2 When the volume concentration of (2) is less than 20%, CO generated in the process 2 After the enrichment procedure, the mixture is conveyed to CO 2 Transformation center (Z).
28. The steel process CO of claim 24 2 The method for converting and recycling is characterized by comprising the following steps of: CO generated in certain working procedure of iron and steel enterprises 2 When the volume concentration of (2) is less than 20%, CO generated in the process 2 After the enrichment procedure, the mixture is conveyed to CO 2 Transformation center (Z).
29. Steel process CO according to claim 27 or 28 2 The method for converting and recycling is characterized by comprising the following steps of: CO generated in certain working procedure of iron and steel enterprises 2 When the volume concentration of (2) is less than 15%, CO generated in the process 2 By enrichment ofAfter the process of collection, the mixture is conveyed to CO 2 Transformation center (Z).
30. Steel process CO according to claim 27 or 28 2 The method for converting and recycling is characterized by comprising the following steps of: the enrichment procedure is as follows: CO generated in one or more of a blast furnace process, a converter process, a sintering process, a pelletizing process, a coking process, and a direct recovery process 2 Delivering the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 And then concentrating the CO 2 Delivery to CO 2 Transformation center (Z).
31. The steel process CO of claim 29 2 The method for converting and recycling is characterized by comprising the following steps of: the enrichment procedure is as follows: CO generated in one or more of a blast furnace process, a converter process, a sintering process, a pelletizing process, a coking process, and a direct recovery process 2 Delivering the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 And then concentrating the CO 2 Delivery to CO 2 Transformation center (Z).
32. The steel process CO according to claim 1 2 The method for converting and recycling is characterized by comprising the following steps of: in sub-steps, the calculation step 1) results in enriched CO 2 The total amount of gas is specifically:
the consumption amount of the g-th fossil fuel at the carbon input end of the i-th working procedure is F i,g The method comprises the steps of carrying out a first treatment on the surface of the CO of fossil fuel of type g 2 Direct emission factor D g The method comprises the steps of carrying out a first treatment on the surface of the The consumption amount of the h power medium at the carbon input end of the ith procedure is DM i,h The method comprises the steps of carrying out a first treatment on the surface of the CO of the h power medium 2 Indirect emission factor ID h The method comprises the steps of carrying out a first treatment on the surface of the The number of the outer pins of the j-th energetic product at the carbon output end of the i-th working procedure is P i,j The method comprises the steps of carrying out a first treatment on the surface of the CO of the j-th energetic product 2 The direct emission factor is ND j The method comprises the steps of carrying out a first treatment on the surface of the Accounting is carried out according to the material energy balance of the input end and the output end, and then the method is that:
wherein: m is m cc Enriched CO from step 1) 2 The total amount of gas; n is CO 2 The number of trapping steps; x is the number of fossil fuel species; y is the type number of the power medium; z is the number of species of energetic product.
33. Steel process CO according to claim 1 or 32 2 The method for converting and recycling is characterized by comprising the following steps of: in the substep, CO is set 2 The selectivity of the gas to CO is S co The method comprises the steps of carrying out a first treatment on the surface of the The method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for conversion to methanol is K 1 ，CO 2 The equilibrium constant of the reaction for conversion to CO is K 2 The method comprises the steps of carrying out a first treatment on the surface of the According to CO 2 The reaction formula for converting into methanol and CO is as follows:
wherein: reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)；K 2 ＝f 2 (T); the method comprises the following steps:
combining (3) - (6) to obtain X CO 、X MeOH The method comprises the steps of carrying out a first treatment on the surface of the Then combining the formula (2) to obtain S co ；
The amount of CO thus formed by the conversion in step 2) is:
in formulas (2) - (7): x is X CO Is CO 2 Conversion to CO; x is X MeOH Is CO 2 Conversion to methanol; beta is H 2 /CO 2 Is a ratio of (2); p (P) Total (S) Is the total reaction pressure; t is the reaction temperature; m is m co The amount of CO generated for the conversion in step 2); a, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 A, a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants.
34. Steel process CO according to claim 1 or 32 2 The method for converting and recycling is characterized by comprising the following steps of: in the substep, the amount of CO entering the recycling process in the step 3) is:
the consumption amount of the g-th fossil fuel at the s-th working procedure carbon input end is F s,g The method comprises the steps of carrying out a first treatment on the surface of the The conversion standard coal coefficient of the g-th fossil fuel is C g The method comprises the steps of carrying out a first treatment on the surface of the The consumption amount of the h power medium at the carbon input end of the s-th procedure is DM s,h The method comprises the steps of carrying out a first treatment on the surface of the Converting the h power medium into DC h The method comprises the steps of carrying out a first treatment on the surface of the The consumption amount of the No. w irreplaceable fossil fuel of the No. s working procedure carbon input end is IF s,w The method comprises the steps of carrying out a first treatment on the surface of the Conversion of the w-th irreplaceable fossil fuel into standard coal coefficient as IC w The method comprises the steps of carrying out a first treatment on the surface of the The number of the outer pins of the jth energy-containing product at the carbon output end of the s-th working procedure is P s,j The method comprises the steps of carrying out a first treatment on the surface of the The conversion coal marking coefficient of the j-th energy-containing product is PC j The method comprises the steps of carrying out a first treatment on the surface of the Accounting is performed according to the material energy balance of the input end and the output end, and the method comprises the following steps:
the preparation method comprises the following steps:
wherein: m is m Lco The amount of CO entering the recycling process in the step 3); ΔcH CO Is the combustion heat of CO; ΔcH Standard coal The heat value of the standard coal; m is the number of CO recycling processes; x is the number of fossil fuel species; y is the type number of the power medium; l is the number of types of irreplaceable fossil fuels; z is the number of species of energetic product.
35. Steel process CO according to claim 1 or 32 2 The method for converting and recycling is characterized by comprising the following steps of: in the substep, the carbon emission reduction in the whole steel smelting process is as follows:
if m is co ≤m Lco At this time
If m is co ＞m Lco At this timeWherein: />The method is used for reducing the carbon emission in the whole steel smelting process.
36. The steel process CO of claim 35 2 The method for converting and recycling is characterized by comprising the following steps of: in the substep, CO in the whole steel smelting process 2 The cost difference of the gas conversion into CO and methanol is:
wherein: ΔC is CO in the whole steel smelting process 2 The cost difference of the gas conversion into CO and methanol; ΔP is the unit CO 2 Converted to a cost difference of CO and methanol.
37. The steel process CO of claim 36 2 The method for converting and recycling is characterized by comprising the following steps of: in the substep, the carbon emission reduction target of the iron and steel enterprise is set to be delta E min The cost saving goal is delta C min The method comprises the steps of carrying out a first treatment on the surface of the The method comprises the following steps:
i.e. < ->
38. The steel process CO of claim 37 2 The method for converting and recycling is characterized by comprising the following steps of:
if the value Δc=Δc min I.e. take the valueCombining (2) - (6), calculating to obtain CO 2 Reaction conditions of the conversion center (Z); the reaction condition realizes the lowest CO for iron and steel enterprises on the premise of achieving the aim of saving cost 2 The discharged process conditions;
if take valueI.e. take the value +.>Combining (2) - (6), calculating to obtain CO 2 Reaction conditions of the conversion center (Z); the reaction condition is the process condition which can save the cost most for iron and steel enterprises on the premise of achieving the aim of carbon emission reduction;
if take valueCombining (2) - (6), calculating to obtain CO 2 Reaction conditions of the conversion center (Z); the reaction condition realizes CO for iron and steel enterprises on the premise of achieving the aims of saving cost and reducing carbon emission 2 And (3) comprehensively controlling conversion cost and carbon emission.
39. The steel process CO according to claim 1 2 The method for converting and recycling is characterized by comprising the following steps of: steps 1) to 3) are implemented by the following system; the system includes CO 2 A conversion center (Z), a blast furnace (A1) and a lime kiln (A2); CO 2 The conversion center (Z) comprises a hydrogen generating device (1) and CO 2 A conversion device (2), a conversion material gas-liquid separation and conversion gas allocation device (3); the gas outlet of the blast furnace (A1) and the gas outlet of the lime kiln (A2) are connected to CO 2 CO of conversion center (Z) 2 A gas inlet; CO 2 The CO gas outlet of the conversion center (Z) is connected to the gas inlet of the blast furnace (A1) and/or the lime kiln (A2); the hydrogen outlet of the hydrogen generating device (1) is connected to CO 2 A hydrogen inlet of the reformer (2); CO 2 The converter outlet of the converter (2) is connected to the converter inlet of the converter gas-liquid separation and converter gas distribution device (3).
40. The steel process CO of claim 39 2 The method for converting and recycling is characterized by comprising the following steps of: the system also comprises a sintering machine (A3), a rotary kiln (A4), a coke oven (A5), a converter (A6) and a straight-ring furnace (A7); the gas outlet of the blast furnace (A1), the gas outlet of the lime kiln (A2) and the gas outlet of the converter (A6) are all connected to CO 2 CO of conversion center (Z) 2 A gas inlet; CO 2 The CO gas outlet of the conversion center (Z) is connected to the blast furnace (A1) and/or limeGas inlets of the kiln (A2) and/or the sintering machine (A3) and/or the rotary kiln (A4) and/or the coke oven (A5) and/or the straight-ring oven (A7).
41. The steel process CO of claim 40 2 The method for converting and recycling is characterized by comprising the following steps of: the system also includes CO 2 A pretreatment system (A8); CO 2 The pretreatment system (A8) carries out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more working procedures of the iron and steel enterprises.
42. The steel process CO of claim 41 2 The method for converting and recycling is characterized by comprising the following steps of: the system also includes a temperature and pressure swing adsorption device (A9); the gas outlets of the blast furnace (A1), the lime kiln (A2) and the converter (A6) are all connected to CO 2 A pretreatment system (A8); CO 2 The gas outlet of the pretreatment system (A8) is connected to a temperature and pressure swing adsorption device (A9); CO of temperature and pressure swing adsorption device (A9) 2 The gas outlet is connected to CO 2 CO of conversion center (Z) 2 A gas inlet.
43. The steel process CO according to claim 42 2 The method for converting and recycling is characterized by comprising the following steps of: connecting a gas outlet of one or more of a blast furnace (A1), a sintering machine (A3), a rotary kiln (A4), a coke oven (A5), a converter (A6) and a straight-ring furnace (A7) to a gas inlet of a lime kiln (A2); the gas outlet of the lime kiln (A2) is connected to CO 2 A pretreatment system (A8); CO 2 The gas outlet of the pretreatment system (A8) is connected to a temperature and pressure swing adsorption device (A9).
44. Steel process CO according to any one of claims 39 to 43 2 The method for converting and recycling is characterized by comprising the following steps of: the hydrogen generating device (1) is green electricity-H 2 An O electrolysis device; green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to a blast furnace (A1), a converter (A6) or a sintering machine (A3).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210150952.6A CN115245729B (en) | 2022-02-18 | 2022-02-18 | Steel process CO 2 Conversion recycling method and system |
| PCT/CN2022/116611 WO2023155417A1 (en) | 2022-02-18 | 2022-09-01 | Steel process co2 conversion and cyclic utilization method and system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210150952.6A CN115245729B (en) | 2022-02-18 | 2022-02-18 | Steel process CO 2 Conversion recycling method and system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115245729A CN115245729A (en) | 2022-10-28 |
| CN115245729B true CN115245729B (en) | 2023-10-27 |
Family
ID=83698982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210150952.6A Active CN115245729B (en) | 2022-02-18 | 2022-02-18 | Steel process CO 2 Conversion recycling method and system |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115245729B (en) |
| WO (1) | WO2023155417A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603104A (en) * | 2009-07-15 | 2009-12-16 | 北京大学 | CO in blast furnace and the coal gas of converter 2Separation and Recovery and cyclic utilization method |
| WO2012013485A1 (en) * | 2010-07-29 | 2012-02-02 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Process for reuse of co2-containing offgases |
| CN103611408A (en) * | 2013-10-28 | 2014-03-05 | 北京工业大学 | Comprehensive grading selection method for control mode of nitrogen oxide emission reduction in cement plant |
| RU2598062C2 (en) * | 2011-03-17 | 2016-09-20 | Прайметалз Текнолоджиз Аустриа ГмбХ | Method of controlling combustion heat of exhaust gases from plants for production of cast iron or for synthetic gas |
| CN106748655A (en) * | 2016-11-27 | 2017-05-31 | 华北理工大学 | It is a kind of efficiently to reduce integrated iron and steel works CO2The method of discharge |
| CN111841271A (en) * | 2019-04-28 | 2020-10-30 | 中冶长天国际工程有限责任公司 | Flue gas desulfurization and denitrification method and system by utilizing co-treatment of carbon monoxide |
| WO2021037700A1 (en) * | 2019-08-23 | 2021-03-04 | Schultes John W | Method and a direct reduction plant for producing direct reduced iron |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1218916C (en) * | 2000-09-04 | 2005-09-14 | 成都华西化工研究所 | Method for expanding production of methyl alcohol synthesis equipment by using natural gas as raw material |
| CA2685609A1 (en) * | 2007-05-04 | 2008-11-13 | Principle Energy Solutions, Inc. | Production of hydrocarbons from carbon and hydrogen sources |
| DE102011077819A1 (en) * | 2011-06-20 | 2012-12-20 | Siemens Aktiengesellschaft | Carbon dioxide reduction in steelworks |
| US11181062B2 (en) * | 2019-11-14 | 2021-11-23 | GM Global Technology Operations LLC | Exhaust gas recirculation control systems and methods |
| CN212357095U (en) * | 2020-03-16 | 2021-01-15 | 明阳智慧能源集团股份公司 | Renewable energy methanol synthesis system of thermal power plant |
-
2022
- 2022-02-18 CN CN202210150952.6A patent/CN115245729B/en active Active
- 2022-09-01 WO PCT/CN2022/116611 patent/WO2023155417A1/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101603104A (en) * | 2009-07-15 | 2009-12-16 | 北京大学 | CO in blast furnace and the coal gas of converter 2Separation and Recovery and cyclic utilization method |
| WO2012013485A1 (en) * | 2010-07-29 | 2012-02-02 | Deutsches Zentrum für Luft- und Raumfahrt e.V. | Process for reuse of co2-containing offgases |
| RU2598062C2 (en) * | 2011-03-17 | 2016-09-20 | Прайметалз Текнолоджиз Аустриа ГмбХ | Method of controlling combustion heat of exhaust gases from plants for production of cast iron or for synthetic gas |
| CN103611408A (en) * | 2013-10-28 | 2014-03-05 | 北京工业大学 | Comprehensive grading selection method for control mode of nitrogen oxide emission reduction in cement plant |
| CN106748655A (en) * | 2016-11-27 | 2017-05-31 | 华北理工大学 | It is a kind of efficiently to reduce integrated iron and steel works CO2The method of discharge |
| CN111841271A (en) * | 2019-04-28 | 2020-10-30 | 中冶长天国际工程有限责任公司 | Flue gas desulfurization and denitrification method and system by utilizing co-treatment of carbon monoxide |
| WO2021037700A1 (en) * | 2019-08-23 | 2021-03-04 | Schultes John W | Method and a direct reduction plant for producing direct reduced iron |
Non-Patent Citations (1)
| Title |
|---|
| 烧结烟气COx的生成机理及减排措施;王兆才 等;烧结球团;第46卷(第1期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115245729A (en) | 2022-10-28 |
| WO2023155417A1 (en) | 2023-08-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101705115B (en) | Poly-generation system and method of catalyzed and gasified coal-based energy chemical product | |
| CN103160296B (en) | Pyrolysis gasification coupling integrated poly-generation system and process for coal chemical industry | |
| WO2011029283A1 (en) | Method for composite utilizing coal and system thereof | |
| CN111547678B (en) | Method and system for preparing methanol by full-component thermal catalysis of marsh gas | |
| CN101760248B (en) | Coal-based energy chemical product poly-generation system and method | |
| CN102531835B (en) | Method for synthesizing methanol through low-carbon technology | |
| CN103898265A (en) | System device and method for modifying coke oven gas to directly reduce iron ore | |
| CN112725034A (en) | Renewable energy power-to-gas system coupled with biomass gasification | |
| CN115784840A (en) | Methanol preparation process coupling organic solid waste gasification and water electrolysis hydrogen production | |
| KR101953550B1 (en) | An Hydrogen Manufacturing Apparatus and a Method of Producing Hydrogen using Thereof | |
| CN208182929U (en) | A kind of system by gasification and electrolysis coupling symphysis production of synthetic gas | |
| CN107446635A (en) | A kind of coke-stove gas utilizes new method | |
| CN102732317A (en) | Technological process for preparing synthetic gas by using biomass | |
| CN101760249A (en) | Underground gasification coal derived energy chemical product poly-generation system and method | |
| CN219429725U (en) | Coupling system for household garbage incineration power plant and hydro-ammonia alcohol preparation | |
| CN210635950U (en) | Biogas preparation device combining biogas purification and carbon dioxide methanation | |
| CN115245729B (en) | Steel process CO 2 Conversion recycling method and system | |
| CN105623761B (en) | A kind of method of coke-stove gas biosynthesis natural gas | |
| CN116283490A (en) | CO is realized to garbage power generation and photovoltaic power generation gas production coupling 2 Method and apparatus for recovering and producing methanol | |
| JP2024509639A (en) | How to control a gas fermentation platform for improved conversion of carbon dioxide to products | |
| CN106929107B (en) | With coke cutting gasification combination oven gas partial oxidation and dry reforming inhibition and generation chemical product system | |
| CN219621111U (en) | CO is realized to garbage power generation and photovoltaic power generation gas production coupling 2 Device for recovering and producing methanol | |
| CN220926680U (en) | System for preparing liquid fuel by complementation of biogas and green hydrogen | |
| CN108299158A (en) | A kind of integrated chemical chain and carbon dioxide utilize the ammonia from coal system and method for technology | |
| CN215886933U (en) | Zero carbon of rich CO tail gas/low carbon emission production carbon base compound's device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |