CN114790396B - Dry quenching method with high efficiency and emission reduction and system for producing carbon monoxide - Google Patents
Dry quenching method with high efficiency and emission reduction and system for producing carbon monoxide Download PDFInfo
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- CN114790396B CN114790396B CN202210464053.3A CN202210464053A CN114790396B CN 114790396 B CN114790396 B CN 114790396B CN 202210464053 A CN202210464053 A CN 202210464053A CN 114790396 B CN114790396 B CN 114790396B
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- 238000010791 quenching Methods 0.000 title claims abstract description 185
- 230000000171 quenching effect Effects 0.000 title claims abstract description 185
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 91
- 230000009467 reduction Effects 0.000 title description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 298
- 239000000571 coke Substances 0.000 claims abstract description 226
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 149
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 149
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims description 371
- 238000001816 cooling Methods 0.000 claims description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000002918 waste heat Substances 0.000 claims description 43
- 238000007599 discharging Methods 0.000 claims description 41
- 238000009826 distribution Methods 0.000 claims description 38
- 239000000428 dust Substances 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 36
- 239000001301 oxygen Substances 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 36
- 238000002309 gasification Methods 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 27
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 238000000605 extraction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 125000001741 organic sulfur group Chemical group 0.000 claims description 13
- 238000006477 desulfuration reaction Methods 0.000 claims description 12
- 230000023556 desulfurization Effects 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 11
- 230000003009 desulfurizing effect Effects 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical group S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 8
- 238000004891 communication Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003546 flue gas Substances 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000012084 conversion product Substances 0.000 claims description 3
- 238000005235 decoking Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 238000011001 backwashing Methods 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 238000011946 reduction process Methods 0.000 abstract description 2
- 239000003570 air Substances 0.000 description 154
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000013461 design Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000008901 benefit Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
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- 230000006872 improvement Effects 0.000 description 7
- 238000004321 preservation Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 241000183024 Populus tremula Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
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- 230000009466 transformation Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000009924 canning Methods 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B39/00—Cooling or quenching coke
- C10B39/02—Dry cooling outside the oven
-
- 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
- B01D53/0454—Controlling 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
- B01D53/047—Pressure swing adsorption
- B01D53/0476—Vacuum pressure swing adsorption
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B41/00—Safety devices, e.g. signalling or controlling devices for use in the discharge of coke
- C10B41/08—Safety devices, e.g. signalling or controlling devices for use in the discharge of coke for the withdrawal of the distillation gases
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
- C10J3/56—Apparatus; Plants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/86—Other features combined with waste-heat boilers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/22—Apparatus, e.g. dry box purifiers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/20—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0969—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Coke Industry (AREA)
Abstract
The invention provides a high-efficiency emission-reduction dry quenching method, which adopts carbon dioxide gas and carbon dioxide-rich gas as the air intake of a dry quenching circulating air flow; the dry quenching circulating gas flow exchanges heat with the red coke, and part of carbon dioxide contained in the dry quenching circulating gas flow reacts with the high-temperature red coke to generate carbon monoxide, so that the volume content of the carbon monoxide in the circulating gas flow reaches 30-80%; the endothermic reaction of carbon dioxide and high-temperature red coke to generate carbon monoxide reasonably utilizes the heat of the high-temperature red coke, and ensures the stability of the coke quality in the dry quenching process. The system for producing carbon monoxide is characterized in that the produced gas flow of the dry quenching device is further purified and separated to obtain carbon monoxide product gas for external supply, and the separated carbon dioxide-rich gas is returned to the circulating gas system of the dry quenching device for utilization. The dry quenching method is a technically feasible and economically reasonable carbon emission reduction process.
Description
Technical Field
The invention belongs to the technical field of coal chemical industry, and particularly relates to a high-efficiency emission-reduction dry quenching method and a system for producing carbon monoxide.
Background
In the coking process, the process of cooling high-temperature red coke is called coke quenching, and the coke quenching method comprises a wet coke quenching method and a dry coke quenching method.
The wet quenching method is a process of directly spraying water on the high-temperature red coke to cool, and has simple process technology and little investment, but can not recover the sensible heat of the coke, and has great pollution to the environment.
The dry quenching method is a process of utilizing low-temperature airflow to exchange heat with red-hot red Jiao Niliu in a dry quenching furnace with a vertical structure and cooling red coke; the coke layer of the dry quenching furnace is provided with a pre-storing section at the middle upper part, the red coke is subjected to heat preservation and quality improvement at the pre-storing section, a cooling section is provided at the middle lower part, and the countercurrent heat exchange process of the low-temperature airflow and the red coke mainly occurs at the cooling section. In the dry quenching process, red coke with the temperature of 950-1100 ℃ is intermittently filled from the top of the dry quenching furnace, continuously moves downwards along with the discharging of the bottom of the dry quenching furnace after the average residence time of a pre-storing section is about 1h, enters a cooling section, exchanges heat with countercurrent circulating air flow to a temperature lower than 200 ℃ and is discharged from the bottom of the dry quenching furnace; circulating air flow with low temperature of about 130 ℃ flows into a coke layer at the bottom of a cooling section generally and uniformly through an air flow distribution part at the bottom of the dry quenching furnace, flows upwards and absorbs sensible heat of the coke layer, is discharged out of the dry quenching furnace from an annular flue at the upper part outside a chute area between a pre-storing section and a cooling section after being heated to about 950 ℃, is subjected to heat exchange by a primary dust collector to generate medium-high pressure steam after most of coke powder, particularly the coke powder with the external dimension of more than 0.8mm is collected by a waste heat boiler, is subjected to heat exchange to generate low-pressure steam, is subjected to pressure by a circulating fan after being cooled to about 160 ℃, is subjected to heat exchange by a water preheater of the waste heat boiler to cool to about 130 ℃ and enters the air flow distribution part at the bottom of the dry quenching furnace again to form air flow circulation. The dry quenching method has the advantages that firstly, the coke oven has higher productivity and operation elasticity due to the heat preservation and quality improvement effects of high-temperature red coke produced by the coke oven; and secondly, the circulating air flow brings over 70% of red Jiao Xianre out, and medium-high pressure steam generated by the waste heat boiler can be supplied to the outside and/or generated by a steam turbine, so that certain economic benefit is generated. The existing dry quenching device in China has more than three hundred sets, the energy yield is higher than that of the wet quenching device, and the pollution is relatively light.
The composition condition and the control method of the circulating air flow are important contents of the operation control of the dry quenching device; the content of carbon monoxide and hydrogen relates to the operation safety of a dry quenching device, and the content of carbon dioxide and oxygen is closely related to the coke burning loss rate. The components and the content of the circulating air flow when entering the coke layer at the bottom of the cooling section of the dry quenching furnace are generally 3-15v% of carbon monoxide, less than or equal to 5v% of hydrogen, 7-20v% of carbon dioxide, less than or equal to 0.5v% of methane, less than or equal to 0.5v% of oxygen and the balance of nitrogen; according to the device equipment level and the high-temperature red coke charging condition, and different purposes of process control such as system safety, coke burning rate and the like, the control of each dry quenching device on the content range of each component of the circulating air flow is quite different. The components and contents of the circulating gas flow are derived from the carbon monoxide and a small amount of hydrogen and methane released by the continuous pyrolysis and residual volatile matter conversion in the pre-stored Duan Gongjiao heat preservation upgrading process, and the residual of the continuous reaction product and nitrogen of oxygen, water vapor and high-temperature circulating gas flow components contained in the air which is mainly continuously introduced into the annular flue. The upper part of a pre-existing section of the dry quenching furnace of many conventional dry quenching methods is also provided with an air inlet, a small amount of air is continuously or intermittently introduced, and carbon monoxide and hydrogen released in the pre-existing Duan Gongjiao upgrading process are completely or partially burnt out so as to control the concentration of combustible components in the material layer and the upper space of the pre-existing section and reduce the explosion risk of gas leakage at the top of the dry quenching furnace; the device also increases the air flow of the air inlet before and/or during the red coke loading process, controls the concentration of combustible components in the upper space of the pre-storage section, and further reduces the explosion risk when the high-temperature gas escapes or exchanges with air after the loading port is opened.
The control method of the circulating air flow component generally mainly comprises continuously introducing nitrogen and/or air with required flow rate into a high-temperature annular flue, and considering and controlling the air leakage amount between a primary dust remover and a circulating fan by some devices, and continuously discharging a small part of the balance allowance of the circulating air flow at a rotary sealing valve of a discharging component under a dry quenching furnace, and continuously discharging a large part of the balance allowance of the circulating air flow after the temperature of a water preheater of a waste heat boiler is reduced. For example, the circulating gas flow of the dry quenching device with the red coke treatment capacity of 140t/h is about 190000-220000Nm 3 /h; the air flow rate continuously introduced into the annular flue in the operation of each manufacturer varies greatly depending on the device conditions and the purpose of process control, and is 8000Nm in some cases 3 About/h, some 10000Nm 3 About/h, some of which are 15000Nm 3 About/h; the exhaust flow of the rotary seal valve is typically 1000-2000Nm 3 And/h, discharging the rest part of the balance margin after the water supply preheater of the waste heat boiler. Some dry quenching devices are operated from the annular flue to the inlet of the circulating fan under a micro negative pressure condition, and a small amount of air can be continuously leaked in the period of poor air tightness of the negative pressure section.
The dry quenching furnace and circulating air flow system adopts equipment explosion-proof grade design and process control with medium or lower level, and comprises electric design with medium or lower grade below IIBT 2.
One disadvantage of the conventional dry quenching method is that the nitrogen content in the produced gas or the discharged gas of the circulating gas flow is high, the carbon monoxide and the hydrogen are low, the heat value is low, the utilization is difficult, and even if the volume content of the carbon monoxide is 10-15%, the carbon monoxide is not easy to be reasonably utilized. Therefore, some improved dry quenching technical schemes are proposed by manufacturers.
CN102031126a discloses a dry quenching method comprising taking a low heating value gas containing carbon monoxide and a certain amount of carbon dioxide generated in an industrial process as a cooling gas stream or circulating gas stream, such as blast furnace gas from a steel plant, converter gas or air generated by an underground coal gasification processThe gas is used as the gas for dry quenching, and the sensible heat released by the red coke in the quenching process is recovered, and partial chemical reaction mainly occurs, so that the contained carbon dioxide and the red coke react to generate more carbon monoxide, the carbon monoxide content and the heat value in the air flow or the circulating air flow are improved, and the subsequent utilization of the exhaust gas is facilitated. But the main components of blast furnace gas in the iron and steel plant have the volume contents of CO20-30% and H 2 ≤8％、CO 2 13-25％、N 2 50-55%; the main components of the converter gas have the volume content of CO50-65 percent and CO 2 15-20％、N 2 10-20%. The main components and the content of coal gas produced by the coal underground gasification process of the oxygen-enriched air of 65 percent are between blast furnace gas and converter gas. Due to CO 2 Lower content and no concern for CO 2 The specific control method for conversion to CO should result in limited increases in CO content.
CN111057560a discloses a method for coupling energy of a coke dry quenching furnace and an ironmaking blast furnace, which uses the heat absorption of heating and reaction of blast furnace gas and an external carbon source such as coal dust or compressed straw biomass particles to convert and transfer the heat in hot coke, so that H in the gas 2 The CO content and the heat value are improved by 10-30 percent; before entering the dry quenching furnace, the blast furnace gas can be supplemented with water vapor and/or CO accounting for 5-20% of the volume of the blast furnace gas 2 The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the additional carbon source is 5-15% of the mass of the hot coke, and CO is utilized 2 Compressed gas or high-pressure steam is taken as power to be carried and sprayed into a dry quenching furnace, coke powder or biochar is formed after pyrolysis of high-temperature coke, and high-pressure steam or CO which is taken as external carbon source to spray pushing gas is taken as external carbon source 2 The gas flow is 10-20% of the mass of the additional carbon source. But the process does not involve CO 2 More specific control methods for conversion to CO; the steam fed in will produce the same content of H 2 Higher equipment explosion-proof grade design and process control are needed, and the equipment explosion-proof grade design comprises electric designs with the grade of II CT2 which is higher than II BT2, and the electric designs with the middle and low grades below II BT2 cannot meet the requirements.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-efficiency emission-reduction dry quenching method which adoptsCarbon dioxide gas which is captured by carbon dioxide such as flue gas of a coke oven device, carbon dioxide gas which is a byproduct of low-temperature methanol washing of a coal-to-methanol device or a coal-to-ammonia device is used as air inlet of a dry quenching circulating air flow; the dry quenching circulating gas flow exchanges heat with the red coke, and part of carbon dioxide contained in the dry quenching circulating gas flow reacts with the high-temperature red coke to generate carbon monoxide, so that the volume content of the carbon monoxide in the circulating gas flow reaches 30-80%; the heat of the high-temperature red coke is reasonably utilized by the endothermic reaction of carbon dioxide and the carbon monoxide generated by the high-temperature red coke, so that the stability of the coke dry quenching process and the quality of the coke product is ensured; the equipment explosion-proof grade design and process control requirements of the dry quenching device are the same as those of the conventional dry quenching method which maintains the circulating air flow composition and controls the explosion risk by introducing a large amount of air, and the electrical design can be of a grade below IIBT 2; the produced gas of the dry quenching device has higher carbon monoxide content and heat value, is easy to use, can be used as heat source gas such as being supplied to a coke oven, can be supplied to devices such as synthesizing methanol and the like with the coke oven gas respectively or in a mixed manner, and can be further purified and separated to prepare carbon monoxide product gas for external supply. The carbon dioxide-rich gas containing less than or equal to 10% of carbon monoxide in the process of separating and preparing the carbon monoxide can be returned to the circulating gas system of the dry quenching device for use. The dry quenching method of the invention reasonably utilizes a larger amount of 5000Nm 3 The carbon dioxide gas above/h is a technically feasible and economically reasonable carbon emission reduction process.
The main unit equipment of the dry quenching method comprises a dry quenching furnace, a coke inlet device, a coke outlet device, a primary dust remover, a waste heat boiler, a secondary dust remover, a circulating air flow fan, a waste heat boiler water supply preheater and an optional coke powder gas making unit; the coke feeding device and the coke discharging device are respectively arranged above and below the coke dry quenching furnace and are respectively communicated with the coke dry quenching furnace in a sealing way, and the coke discharging device comprises a vibration feeder and a rotary sealing valve; the coke layer in the dry quenching furnace is provided with a pre-storing section for improving quality of red Jiao Baowen, a cooling section in countercurrent contact with circulating air flow is provided at the middle upper part, a chute for discharging high-temperature circulating air flow out of the coke layer is provided at the furnace wall between the pre-storing section and the cooling section, and an annular flue for collecting high-temperature circulating air flow is arranged outside the chute; the bottom Jiao Cengna of the cooling section is provided with an air flow distribution component which is communicated with a low-temperature circulating air flow inlet arranged at the bottom of the dry quenching furnace; the top and/or the side wall of the space above the highest position of the pre-storing section Jiao Ceng are provided with an atmosphere control air flow inlet and an optional air distribution component of the space above the pre-storing section; the annular flue gas flow outlet, the primary dust remover, the waste heat boiler, the secondary dust remover, the circulating gas flow fan, the waste heat boiler water supply preheater and the low-temperature circulating gas flow inlet are respectively provided with a circulating gas flow sequentially communicated pipeline;
The communication pipeline between the outlet of the circulating air flow fan and the low-temperature circulating air flow inlet is preferably connected with the produced air pipeline with the circulating air flow allowance at the air outlet of the water supply preheater of the waste heat boiler and the communication pipeline between the low-temperature circulating air flow inlet;
in the normal application process of the dry quenching method, red coke at 950-1100 ℃ from a coke oven is intermittently or continuously loaded into a pre-stored section from the top of the dry quenching oven through a coke feeding device, continuously moves downwards along with the discharging of a coke discharging device, and the average temperature of discharged coke is less than or equal to 200 ℃ and is easy to reach less than or equal to 160 ℃; the inlet temperature of the low-temperature circulating gas flow is controlled to be less than or equal to 130 ℃, more preferably less than or equal to 110 ℃;
the method is characterized in that carbon dioxide gas with the hydrogen and water content less than or equal to 4v percent and carbon dioxide-rich gas with the carbon monoxide content less than or equal to 10v percent are adopted as carbon dioxide gas inlet of the circulating gas flow; the flow rate of the carbon dioxide inlet air is 3-15v percent of circulating air flow such as air flow of an outlet of a fan, preferably 5-10v percent;
wherein, 0-30% of the flow of the carbon dioxide gas is used as upper air inlet, and the upper air inlet is used for controlling the flow inlet of the air flow through the upper atmosphere of the pre-storing section and introducing the air flow into the space above the pre-storing section Jiao Ceng, so that the combustible component in the space gas is controlled below the required concentration level, for example, the carbon monoxide content is less than or equal to 3v%; the flow of the oxygen-containing gas is 0-10% of the flow of the carbon dioxide gas;
A coke-discharging atmosphere control part is arranged between the inlet of the vibration feeder and the outlet of the rotary sealing valve, and is provided with a plurality of air inlet pipes with regulating valves; taking 20-40% of the carbon dioxide gas flow as coke outlet atmosphere control air inlet, and introducing the coke outlet atmosphere control part as coke outlet atmosphere control air flow; a part of the control gas flow of the coke-out atmosphere, such as 30-50% of the control gas flow is lost along with the normal leakage of the coke-out carrying and rotary sealing valve, and the rest plays a role of backwash gas flow, and the main components except carbon dioxide contained in the coke particle inner hole and Jiao Lijian gas, such as more than 80% by volume, preferably more than 90% by volume, more preferably more than 95% by volume, of combustible components and sulfides are blown back to the circulation gas flow of the cooling section Jiao Ceng;
the optional coke powder gas making unit is arranged outside or inside the dry quenching furnace, all or part of the obtained coke powder and optional other source coke powder are separated by utilizing a primary dust remover and a secondary dust remover, and the carbon dioxide gas and/or the carbon dioxide-rich gas with required flow and the oxygen with required flow are used as gasifying agents, and the carbon monoxide-rich gas flow with carbon monoxide content of more than 60v% generated by combustion is combined into the circulating gas flow; wherein the carbon monoxide-rich gas flow generated by the coke powder gas making unit outside the dry quenching furnace is merged into the circulating gas flow before the inlet of the waste heat boiler; the coke powder gas making unit in the dry quenching furnace is arranged in a temperature zone of 500-1000 ℃, preferably 700-1000 ℃, more preferably 750-1000 ℃ of the cooling section Jiao Ceng, and the discharged carbon monoxide-rich gas flow is distributed into a circulating gas flow of 800-1000 ℃, preferably 850-1000 ℃ of a coke layer;
Taking the carbon dioxide gas and/or the carbon dioxide-rich gas with the rest flow as lower inlet gas, primarily mixing the lower inlet gas with circulating gas from a low-temperature circulating gas inlet, and entering a coke layer from the bottom of a cooling section through the gas flow distribution component;
the backwash gas, the lower inlet gas and the recycle gas flow from the low-temperature recycle gas flow inlet are mixed to more than 80% of the mixing degree under half height of the cooling section Jiao Ceng in the vertical direction or under a curved surface at 800 ℃, preferably 700 ℃;
the average height of the coke layer at the temperature of the cooling section is more than or equal to 800 ℃ and is 25-35% of the average height of the coke layer at the cooling section on the airflow distribution component.
In the dry quenching method, the ventilation and gas mixing structures of the coke outlet atmosphere control part and the lower coke layer of the cooling section are matched with the structures of the coke outlet device, so that the uniform distribution of the gas flow and the gas mixing effect of the lower coke layer in the cooling section are ensured, the leakage quantity and the leakage concentration of the combustible components, sulfide and other highly toxic peculiar smell components in the coke outlet process are controlled, and only a lower explosion-proof safety level design and process control are needed at the lower part of the dry quenching furnace.
The structure of the air flow distribution component or the air supply component comprising the air flow distribution component can comprise a cross air duct and a plurality of layers of air distribution hoods which are communicated with each other on the cross air duct.
The preliminary mixing of the lower inlet air and the circulating air flow can be performed before the low-temperature circulating air flow enters the air flow distribution component, for example, a single-flow direction air mixer is arranged in a communication pipeline between a low-temperature circulating air flow inlet and a water supply preheater of the waste heat boiler; the single-flow direction gas mixer is internally provided with a plurality of spray pipes with openings facing the low-temperature circulating gas flow inlet of the dry quenching furnace and parallel to the circulating gas flow direction, and the lower inlet gas and the low-temperature circulating gas flow are mixed by utilizing the pressure head of the carbon dioxide gas and/or the carbon dioxide-rich gas and flow to the dry quenching furnace and the gas flow distribution component, so that the reflux of the lower inlet gas is avoided; at the moment, the extraction pipeline of the circulating air flow allowance can be communicated with the circulating air flow pipeline between the circulating air flow fan and the water supply preheater of the waste heat boiler, and also can be communicated with the circulating air flow pipeline between the water supply preheater of the waste heat boiler and the single-flow gas mixer, so that the influence of the reverse flow of the lower inlet air on the extraction of the circulating air flow allowance can be avoided.
The primary mixing of the lower inlet air and the circulating air flow can also be carried out in an air flow channel of the dry quenching furnace bottom before the two air flows enter the air flow distribution component, and then enter the air flow distribution component; the air flow channel can be provided with a proper structure, and the flow directions and the pressure heads of the two air flows are utilized for preliminary mixing. The air flow channel is simultaneously connected with the lower air inlet pipeline and the low-temperature circulating air flow inlet.
In the dry quenching method, the hydrogen content in the circulating gas flow, such as the hydrogen content in the outlet gas flow of a circulating gas flow fan, is controlled to be less than or equal to 5v percent, preferably less than or equal to 3v percent, more preferably less than or equal to 2v percent, and is mainly realized by controlling the water content of the carbon dioxide gas and the hydrogen release amount of the red coke entering the furnace.
The upper carbon dioxide inlet and the oxygen-containing gas enter an upper space of a coke layer of the pre-existing section through an air flow inlet controlled by the upper atmosphere of the pre-existing section, and the components such as carbon monoxide, hydrogen, sulfides and the like which are released by the pre-existing section and diffused by circulating air flow at the upper part of the cooling section are diluted, combusted and pressed down, so that under the condition that the temperature of red coke at the upper layer of the pre-existing section is not lower than a required value such as 950 ℃ and/or the quality improvement effect is ensured, the concentration of combustible components in the space above the pre-existing section Jiao Ceng and in the coke layer is controlled to be lower than the concentration level of the required explosion protection level, for example, the carbon monoxide content is controlled to be less than or equal to 10v percent and the hydrogen content is controlled to be less than or equal to 3v percent, so as to reduce the explosion risk of gas leakage at the top of the dry quenching furnace, particularly the explosion risk of gas exchange when the cover plate is opened and closed during the red coke loading process; before and/or during red coke loading, the carbon monoxide content in the space gas above the pre-stored section Jiao Ceng is preferably controlled to be less than or equal to 5v percent or even less than or equal to 2v percent, and the hydrogen content is preferably controlled to be less than or equal to 2v percent or even less than or equal to 1v percent. The pre-stored Duan Gongjiao heat preservation and quality improvement process can release a certain amount of combustible and toxic peculiar smell components such as carbon monoxide, hydrogen, sulfide and the like, and if the combustible and toxic peculiar smell components are not properly treated, the safety level is difficult to control. Before and during the charging process of the red coke, carbon dioxide with proper large flow rate can be introduced for air intake. The advantage of introducing oxygen-containing gas is that most of carbon monoxide, hydrogen, sulfide and the like contained in the space gas are burnt, and the upper space of the coke layer of the preheating section and the temperature of the coke layer can be controlled to be not lower than 950 ℃ or higher, so that the heat preservation and quality improvement effects of red coke are ensured. Introducing a proper amount or flow of carbon dioxide into an operation gap of twice red coke feeding of the dry quenching furnace, and pressing the gas in the upper space of the coke layer of the pre-storing section into the pre-storing section Jiao Ceng and the annular flue, wherein the coke feeding temperature is higher than 1000 ℃; however, when more carbon dioxide enters the coke layer, the temperature is reduced due to the endothermic reaction of generating carbon monoxide, the quality improving effect of red coke is reduced when the coke inlet temperature is lower, such as 950 ℃, and oxygen is simultaneously or independently fed, so that the combustible components are burnt, the temperature of the upper space of the pre-stored section is maintained by heat generation, and the quality improving effect and the explosion-proof safety effect of the red coke are both facilitated.
The carbon dioxide gas and the carbon dioxide-rich gas are all high carbon dioxide content gases which are economically available in industry. In the carbon dioxide gas, the total content of carbon monoxide and hydrogen is less than or equal to 0.5% by volume, preferably less than or equal to 0.2% by volume, the content of hydrocarbon such as methane is less than or equal to 0.5% by weight, and the carbon dioxide in the components except water accounts for more than 98% by volume; other non-mentioned impurity components should be not higher than conventional values, for example, the oxygen content should be 1% by volume or less, more preferably 0.5% by volume or less; further, for example, the sulfur content of the sulfide-folded sulfur should be not more than 0.1% by weight, more preferably not more than 0.05% by weight. The carbon dioxide gas comprises flue gas such as carbon dioxide gas recovered from coke oven flue gas by an amine method or a PSA method, and low-temperature methanol washing byproduct carbon dioxide gas of a coal-to-methanol device; the carbon dioxide gas obtained by the wet organic amine absorption-steam analysis process is controlled to have the volume content of carbon dioxide more than or equal to 96 percent and the volume content of water gas less than or equal to 4 percent; the carbon dioxide gas obtained by the dry pressure swing adsorption process can be controlled to have the carbon dioxide volume content of more than or equal to 99 percent and the water gas volume content of less than or equal to 1 percent; the byproduct carbon dioxide gas of low-temperature methanol washing of the coal-to-methanol device does not contain water. In the carbon dioxide-rich gas, the carbon dioxide should account for 95% or more by volume, preferably 98% or more by volume, of the components other than hydrogen, water vapor and carbon monoxide.
The oxygen content in the oxygen-enriched air can be 30-60v%; the oxygen content of the oxygen-containing gas can be 18-100v%, the water-containing gas is less than or equal to 5v%, and the rest is mainly nitrogen.
The coke dry quenching device using the method of the invention moves coke in the dry quenching furnace from top to bottom and flows air flow from bottom to top in the normal operation process. The red coke at 950-1100 ℃ is put into a dry quenching furnace through a coke feeding device, the average residence time in a pre-storing section can be more than 1h, heat preservation and quality improvement are carried out, the red coke continuously moves downwards along with the discharging of the bottom of the dry quenching furnace, and reacts with countercurrent air flow to consume heat and exchange heat to cool after entering a cooling section, and the red coke is discharged through a coke discharging device after cooling. After entering the coke layer at the bottom of the cooling section, the low-temperature air flow at the temperature of less than or equal to 130 ℃ flows upwards and absorbs sensible heat of the coke layer, carbon dioxide contained in the air flows to react with red coke to generate carbon monoxide after the temperature is raised to about 750 ℃, the reaction of the carbon dioxide and the red coke to generate carbon monoxide after the temperature is raised to 800 ℃ is accelerated, and the reaction of the carbon dioxide and the red coke to generate carbon monoxide after the temperature is raised to 850 ℃ is further accelerated; the reaction of carbon dioxide and red coke to generate carbon monoxide is a high endothermic reaction, and the heat absorption capacity of the reaction after 850 ℃ is obviously higher than the heat absorption capacity of the temperature rise of physical heat exchange. And discharging high-temperature circulating air flow of the dry quenching furnace at about 950 ℃ from an annular flue in a chute area between the pre-storing section and the cooling section, collecting most of coke powder, especially coke powder with the external dimension of more than 0.8mm, generating steam by heat exchange of a waste heat boiler through primary dust removal, collecting the rest small part of coke powder and ash powder when a coke powder gas making unit is adopted through secondary dust removal after cooling, and pressurizing by a circulating fan to re-blow into the bottom of the dry quenching furnace to form air flow circulation.
In the dry quenching method, the carbon dioxide accounts for more than 95% by volume and even more than 98% by volume of the circulating gas stream except carbon monoxide and hydrogen. The carbon monoxide content in the circulating gas flow mainly depends on three factors, namely the charging temperature and the particle size distribution of red coke, the reactivity with carbon dioxide, the ratio of the flow of the circulating gas flow to the red coke treatment capacity, and the ratio of the inlet flow of the carbon dioxide gas to the red coke treatment capacity, wherein the influence of the first two factors is more remarkable; the reactivity of red coke with carbon dioxide is mainly dependent on the coke variety and quality requirements. When the device is used for dry quenching treatment of metallurgical coke, the concentration of carbon monoxide in the circulating gas flow can reach 30-50% by volume due to lower reactivity with carbon dioxide, and the concentration of carbon monoxide in the circulating gas flow at the outlet of a fan can reach 45-60% by volume when a coke powder gas making unit is adopted. When the device is used for dry quenching treatment of gas-making coke, the concentration of carbon monoxide in the circulating gas flow can reach more than 50% by volume and even 80% by volume due to higher reactivity with carbon dioxide, and the concentration of carbon monoxide in the circulating gas flow at the outlet of a fan can reach 60-80% by volume when a coke powder gas-making unit is adopted.
The primary dust remover can be provided with a gravity type dust removing structure, can be provided with a retaining wall or not, and mainly collects coke powder with the external dimension of more than 0.8mm, and prevents the coke powder from depositing in a circulating airflow channel of the waste heat boiler so as to ensure the heat exchange efficiency and the steam production capacity of the waste heat boiler; the dust content of the gas stream is generally treated to, for example, 8g/m 3 The following is given.
The secondary dust remover can adopt a dust remover with a plurality of axial-flow cyclone separation structures, and generally treats the dust content of the air flow to be as 1g/m 3 The following is given.
The waste heat boiler reduces the temperature of the circulating air flow and recovers heat, and the produced steam can be externally supplied and/or generate economic benefit through a steam turbine for power generation; the waste heat boiler water supply preheater is used for further cooling the circulating air flow and recovering heat, the waste heat boiler water such as desalted water is preheated and then sent to the waste heat boiler, and the desalted water after preheating can be treated by the deoxidizer and then sent to the waste heat boiler.
In the dry quenching method, the average height of the coke layer at the cooling section temperature of more than or equal to 800 ℃ can be controlled to be more than 25-35% of the average height of the coke layer at the cooling section on the airflow distribution component, and the reasons include: (1) The specific heat of the carbon dioxide is higher than that of nitrogen and carbon monoxide, and the atmospheric specific heat of the carbon dioxide, the nitrogen and the carbon monoxide are respectively 300 ℃ 46.5, 29.9 and 30.3J/mol.K and 600℃:52.4, 31.9, 32.4J/mol.K, 900 ℃ 56.1, 33.6, 34.1J/mol.K, thus the cooling capacity of the recycle gas stream in the process of the invention is greater, especially at carbon dioxide contents above 40% by volume; (2) Adopting a lower cooling section air-material ratio, namely the ratio of the circulating air flow of the cooling section to the red coke feeding amount; (3) The better mixing distribution of the air inlet at the lower part of the cooling section can adopt the structure such as CN205653397U, CN208266112U and the like and the corresponding control method. The operation control purpose of the conventional dry quenching method is to adopt a higher gas-material ratio, control the average height of the coke layer at the temperature of the cooling section of more than or equal to 800 ℃ to be less than 20 percent, generally less than 15 percent and even less than 10 percent of the average height of the coke layer at the cooling section above the gas flow distribution component so as to reduce the average residence time of the circulating gas flow at the temperature of more than or equal to 800 ℃ and the carbon monoxide generation amount, and only the circulating gas flow and the distribution thereof are adopted at the lower inlet gas of the cooling section, so that the mixing distribution problem of the back washing gas, the lower inlet gas and the low-temperature circulating gas flow is avoided.
Compared with the conventional dry quenching method, the dry quenching method provided by the invention has the advantages that the average residence time of the circulating air flow in the coke layer at the temperature of more than or equal to 800 ℃ is doubled or even tripled under the condition that the coke inlet temperature of the dry quenching furnace and the coke inlet amount per hour are the same, the inner surface of the coke particles becomes a more important reaction place, and the carbon monoxide production amount is obviously increased because the required supplementary air flow with higher carbon dioxide content is adopted and the circulating air flow basically contains no nitrogen, the carbon monoxide content in the circulating air flow can reach more than 30v%, and the red coke heat with a larger proportion is converted into the chemical energy of CO.
The dry quenching method of the invention, when being used in a dry quenching device with red coke treatment capacity of about 140t/h, can realize the circulating gas flow of about 120000-170000Nm 3 /h; when the coke powder gas making unit is not adopted, the allowance of circulating air flow continuously extracted after a boiler water-feeding preheater or after a fan, namely the extracted air flow can be 13000-20000Nm 3 And/h. The annular flue no longer introduces air. The nitrogen content in the extracted gas of the circulating gas flow is less than or equal to 5v percent and even less than or equal to 1v percent, thereby being convenient for the separation and the utilization of the purified gas flow.
Based on the running data and the small test result of the existing dry quenching device, the technical effects can be completely proved and described through the simulation calculation of Aspen and Fluent software and the effect condition when changing the carbon dioxide. Through simulation calculation, the temperature segregation degree of red Jiao Cengna above 850 ℃ of the cooling section can be obviously reduced, because the carbon monoxide generation amount in the region with small excess is high, the heat absorption is more, and the carbon monoxide generation amount in the region with large excess is low, so that the distribution requirement and the requirement on the particle size distribution of red coke when the red coke is put into a dry quenching furnace are reduced to a certain extent.
The dry quenching energy-saving and emission-reducing device disclosed in CN101845307A comprises a fan, a reduction cooler, a dust remover and a waste heat boiler which are connected through a sequential air duct, wherein the fan is arranged in front of the reduction cooler, and is characterized in that: the reduction cooler is divided into a combustion chamber, a reduction section and a cooling section from top to bottom, the top of the combustion chamber is provided with a furnace cover, and the furnace wall at the middle lower part of the combustion chamber is provided with an air inlet; a gas outlet is formed in the upper furnace wall of the reduction section and is communicated with a waste heat boiler through a dust remover; the cooling section is gradually contracted downwards to form a coke discharging outlet, the discharger is a spiral discharger, and the coke discharging outlet is communicated with the spiral discharger of the water seal. The furnace wall of the cooling section is a water-cooled wall, water-cooled pipes which are arranged and distributed are arranged in the water-cooled wall, cooling water is filled in the water-cooled wall, and wear-resistant materials are coated in the water-cooled wall. The cooling section is internally provided with an internal water-cooling wall which is arranged in a crisscross or horizontal row, and the water pipe in the internal water-cooling wall is communicated with the water pipe of the furnace body. The inner water cooling wall is provided with fins at certain intervals, the width of each fin is 50-100 mm, the interval between every two adjacent fins is 50-80 mm, and the length of each fin is the height of the cooling section.
CN101845307a discloses an endothermic reaction and thought of using carbon dioxide and red coke to produce carbon monoxide, but the technical scheme and effect are significantly different from the present invention. The cooling section is equivalent to the middle lower section of the cooling section, the reduction section is equivalent to the coke layer with the temperature of more than or equal to 800 ℃ of the cooling section, the carbon dioxide gas directly reacts once without circulation, and the front-mounted fan only plays a role of blowing in the carbon dioxide gas. The coke with the cooling section of 250-350 ℃ can generate a large amount of steam (150-250 Nm) when finally falling into the water seal 3 Atmospheric steam/t coke) and all the steam enters a carbon dioxide gas flow, because the endothermic reaction of the steam and the coke to generate hydrogen and 1 carbon monoxide can be carried out in a large quantity at a temperature below 800 ℃ in a coke layer, and the reaction speed of the coke layer is obviously higher than that of the endothermic reaction of the carbon dioxide and the coke to generate 2 carbon monoxide at a temperature above 800 ℃, the generation of the steam not only leads to the generation of hydrogen which is more than or equal to 10% by volume, so that the carbon monoxide yield per unit weight of red coke is obviously lower than that of the invention when the temperature of the top red coke is the same.
The CN101845307A process also has the problems of low coke cooling speed, low capacity of the dry quenching furnace unit space and the like, and is not suitable for large-scale devices. The coke cooling speed of the dry quenching method is high, the productivity of the dry quenching furnace per unit space is high, and the dry quenching method is suitable for a large-scale device; one or more of air, oxygen-enriched air, oxygen and carbon dioxide are introduced into the top of the dry quenching furnace, and the combustible components in the gas in the upper space of the pre-stored coke layer are limited below the concentration level of the required guaranteed safety level under the condition that the heat preservation and quality improvement effects of red coke are not reduced, so that the direct oxidation burning loss of the red coke is not caused.
In the dry quenching method, the coke powder separated by the primary dust remover and the secondary dust remover accounts for about 1.5 to 3 weight percent of the total yield of coke, and the coke powder yield is similar to that of the conventional dry quenching method. Because the price of the coke powder is far lower than that of the coke product and the environmental pollution in the outward transportation process is serious, the coke powder is utilized by a coke powder gasification furnace and the carbon monoxide is increased.
The first scheme of the coke powder gas making unit is that the main equipment is an independent gas making furnace, the temperature of the reaction area of the gas making furnace is 900-1100 ℃, one or more gasification nozzles are arranged in the side wall or the hearth, the gasification nozzles adopt three-sleeve burners with cooling jackets, the outer sleeve and the central tube are respectively fed with oxygen with required pressure and flow, the middle sleeve is fed with carbon dioxide with required pressure and flow and is used as carrier gas to convey coke powder or ground coke powder into the gas making furnace, the coke powder, the carbon dioxide and the oxygen are sprayed into the hearth at high speed, mixed and rapidly reacted, and the produced gas flow contains 60-80v% of carbon monoxide and the temperature is 850-1000 ℃ together with ash powder and is combined into circulating gas flow before the inlet of the waste heat boiler through the gas outlet at the top or the side wall of the gas making furnace; the ash is mainly separated in a secondary dust remover.
The second scheme of the coke powder gas making unit is that the main equipment is a combined gas making furnace arranged below the primary dust remover, the top of the gas making furnace is connected with an ash bucket below the primary dust remover, a coke powder feeding valve is arranged between the gas making furnace and the ash bucket, coke powder falls into the gas making furnace from the ash bucket by gravity, a certain coke powder level is maintained in the ash bucket, air flow in the gas making furnace is prevented from being blown into the ash bucket, and the level in the ash bucket is controlled by the coke powder feeding valve; the side wall of the gas making furnace is provided with a carbon dioxide inlet and an oxygen inlet, and the other side is provided with a gas making outlet; the bottom of the gas making furnace is provided with a slag discharging port for regularly discharging furnace ash; the temperature of the reaction area of the gas making furnace is 900-1000 ℃, and the reaction pressure is micro positive pressure; the gas-making furnace outlet gas flow contains 65-85% of carbon monoxide, and its temperature is about 900-950 deg.C, and is combined into the circulating gas flow before the inlet of waste heat boiler by means of gas outlet on top of gas-making furnace or side wall.
The third scheme of the coke powder gas making unit is that the main equipment is a gasification channel arranged in the dry quenching furnace, the gasification channel is horizontally arranged and transversely crosses the dry quenching furnace, one end is closed, one end is provided with one or more gasification nozzles, and the top is an inverted V-shaped peak to prevent coke accumulation; the side wall or the bottom is provided with a plurality of exhaust holes. The temperature of the reaction area of the gasification channel is 900-1100 ℃, the gasification nozzle adopts a three-sleeve burner with a cooling jacket, the outer sleeve and the central tube are respectively fed with oxygen with required pressure and flow, the middle sleeve is fed with carbon dioxide gas with required pressure and flow and is used as carrier gas to convey coke powder or ground coke powder into the gasification channel, the coke powder, the carbon dioxide gas and the oxygen are sprayed into the gasification channel at high speed, mixed and rapidly reacted, and the produced gas flow contains 60-80v% of carbon monoxide and the temperature is 850-1000 ℃. The scheme has the advantages that the gas contained in the produced gas flow passes through the coke bed layer, unreacted carbon dioxide can further react with red coke, ash powder and ash particles contained in the produced gas flow can be filtered and adhered by the coke bed layer, and most of ash powder and ash particles are discharged from the bottom of the dry quenching furnace along with downward movement of coke.
Under the condition of the invention, the heat absorption of the upper reaction of the cooling section of the dry quenching furnace accelerates the cooling speed, but the influence on the quality of the coke product is estimated to be small by combining with practical experience. When the coke powder gas making unit is not adopted, the steam yield of the waste heat boiler is reduced to some extent, but the overall thermal efficiency of the dry quenching device is improved, and the overall economic benefit is improved. When the coke powder gas making unit is adopted, the steam yield of the waste heat boiler can be compensated, and the overall economic benefit of the dry quenching device is further improved.
The dry quenching method has obvious economic benefit, is easy to implement and has a certain application prospect; the method is suitable for low-cost transformation of the existing dry quenching device and transformation by utilizing the wet quenching device; the method is particularly suitable for the transformation of the conventional dry quenching device which is formed by supplementing air into an annular flue to control the circulating air flow, and greatly improves the operation elasticity and the productivity of the dry quenching device and the coke oven device. Under the condition that the coke productivity is basically unchanged, the coke discharge temperature of the dry quenching device is more stable and can be obviously reduced, the heat recovery rate of red coke is improved, and the circulating air flow or the power consumption of a circulating air flow fan can be obviously reduced. Because the heat recovery rate of the cooling section is improved, the coke yield of the dry quenching device can be improved to a certain extent under the condition of keeping the coke discharge temperature not to be increased, and the coke oven device can be conveniently operated in a high yield state or properly expanded.
The invention also provides a system for producing carbon monoxide on the basis of the dry quenching method, which sequentially carries out treatment operations such as dry desulfurization, compression, PSA decarbonation, PSA carbon monoxide extraction and the like on the circulating air flow allowance led out by the produced air pipeline, and separates and obtains product gas of carbon monoxide with purity of more than or equal to 98v percent and carbon dioxide-rich gas with carbon monoxide content of less than or equal to 10v percent, and returns the product gas to the dry quenching device to serve as carbon dioxide air intake of the circulating air flow.
The system for producing carbon monoxide comprises the dry quenching device and a produced gas flow purifying and separating device; the unit equipment of the produced gas flow purifying and separating device comprises a sulfur dioxide removal tower, a first cooler, an optional gas holder, a compressor, an optional heater, an organic sulfur hydrolysis tower, a fine desulfurization tower, a second cooler, a PSA carbon dioxide removal unit and a PSA carbon monoxide extraction unit which are sequentially communicated;
the produced gas pipeline with the allowance of the circulating gas flow led out by the dry quenching device is communicated with the gas inlet of the sulfur dioxide removal tower, so that part of the required flow of the circulating gas flow flows to the produced gas flow purifying and separating device; separating carbon dioxide-rich gas with carbon monoxide content less than or equal to 10v% by the PSA carbon dioxide removal unit, and returning the carbon dioxide-rich gas to a dry quenching device to serve as carbon dioxide gas inlet of the circulating gas flow; the CO replacement tail gas of the PSA carbon monoxide extraction unit is returned to the air inlet of the compressor for use; the hydrogen-containing tail gas of the PSA carbon monoxide extraction unit is burnt and utilized in a decoking furnace.
The flow direction of the produced gas flow purifying and separating device or the basic sequence of the treatment process is as follows: the device comprises a sulfur dioxide removal tower, a first cooler, a gas holder, a compressor, a heater, an organic sulfur hydrolysis tower, a fine desulfurization tower, a second cooler, a PSA carbon dioxide removal unit and a PSA carbon monoxide extraction unit.
The sulfur dioxide removal tower is filled with a desulfurizing agent taking calcium oxide, calcium hydroxide and calcium carbonate as main desulfurizing components.
The organic sulfur hydrolysis tower is filled with hydrolysis catalysts HB-SJ3 and HB-SJ2 of Qingdao Hua Sunyaka new materials science and technology Co., ltd, and the two catalysts are filled in upper and lower layers; wherein HB-SJ3 is a first-stage hydrolytic agent, and plays roles mainly in the crude conversion of organic sulfur, the removal of oxygen and the conversion of cyanide; HB-SJ2 is a secondary agent and plays a role in the deep hydrolysis of the residual organic sulfur; the temperature of the catalyst bed layer is 130-300 ℃, and the conversion product of the organic sulfur is hydrogen sulfide.
The fine desulfurization tower can be filled with zinc oxide desulfurizing agent HB-ZT201 of Qingdao Hua Summit New Material science and technology Co., ltd, the temperature of the desulfurizing agent bed is 130-300 ℃, the fine desulfurization tower is opened and prepared, can be connected in series, and the total sulfur of outlet is below 0.1 ppm.
The main exhaust pressure of the compressor is 1.0-2.0MPa, the pressure is the basic operating pressure of the PSA carbon dioxide removal unit and the PSA carbon monoxide extraction unit, and the operation procedures of the two PSA units can comprise vacuumizing operation procedures.
The invention relates to a dry quenching method and a system for producing carbon monoxide, which also comprise detection/control components such as temperature, flow, pressure and the like which are arranged on each unit equipment and pipelines according to the requirements, including meters, automatic valves and DCS for performing system control.
Drawings
FIG. 1 is a schematic diagram of a process flow of a dry quenching device and a carbon monoxide gas production system designed in example 1.
Detailed Description
The invention is further illustrated, but is not to be construed as being limited, by the following examples.
Example 1
A coke plant is built with a 2X 60 hole tamping coke oven and a matched dry quenching device, and the annual production of the coke is 120 ten thousand tons and the operation is carried out for 6 years. The main unit equipment of the dry quenching device comprises a dry quenching furnace, a coke inlet device, a coke outlet device, a primary dust remover, a waste heat boiler, a secondary dust remover, a circulating air flow fan and a waste heat boiler water supply preheater; the coke feeding device and the coke discharging device are respectively arranged above and below the coke dry quenching furnace and are respectively communicated with the coke dry quenching furnace in a sealing way, and the coke discharging device comprises a vibration feeder and a rotary sealing valve; the coke layer in the dry quenching furnace is provided with a pre-storing section for improving quality of red Jiao Baowen, a cooling section in countercurrent contact with circulating air flow is provided at the middle upper part, a chute for discharging high-temperature circulating air flow out of the coke layer is provided at the furnace wall between the pre-storing section and the cooling section, and an annular flue for collecting high-temperature circulating air flow is arranged outside the chute; the bottom Jiao Cengna of the cooling section is provided with an air flow distribution component which is communicated with a low-temperature circulating air flow inlet arranged at the bottom of the dry quenching furnace; the side wall of the space above the highest position of the pre-storing section Jiao Ceng is provided with a plurality of air inflow ports and porous nozzles for controlling the atmosphere of the space above the pre-storing section; a plurality of air flow distribution pipes with spray holes are arranged in the annular flue; the annular flue gas flow outlet, the primary dust remover, the waste heat boiler, the secondary dust remover, the circulating gas flow fan, the waste heat boiler water supply preheater and the low-temperature circulating gas flow inlet are respectively provided with a circulating gas flow sequentially communicated pipeline; a communication pipeline between an air outlet of a water supply preheater and a low-temperature circulating air flow inlet of the waste heat boiler is connected with an extracted air pipeline with circulating air flow allowance; the intake distribution member at the lower part of the cooling section has a structure described in CN 205653397U. The main coke products of the plant are metallurgical coke and chemical coke, and the production is switched according to market demands.
The diameter of the cooling section of the dry quenching furnace is 9.0m, and the height is about 7.8m (measured from the top surface of the hood on the air inlet distribution part at the lower part of the cooling section).
Typical normal operating conditions of the dry quenching device in the metallurgical coke production process are as follows: the coke feeding amount is 140t/h, the coke is intermittently fed into a pre-storing section from the top of the coke dry quenching furnace through a coke feeding device, and continuously moves downwards along with the discharging of a coke discharging device, and the coke discharging temperature is 190-200 ℃; the flow rate of the circulating gas at the inlet of the low-temperature circulating gas flow is about 200000-210000Nm 3 Air flow rate of annular flue is 8000-9000Nm 3 /h (average 1.8v% moisture), low temperature recycle gas stream inlet temperature 125-130 ℃; coke equivalent diameter 5.6cm, porosity 0.47; the gas components of the low-temperature circulating gas flow inlet are 15.7v% of carbon dioxide, 3.2v% of carbon monoxide, 2.1v% of hydrogen, 0.1v% of oxygen, 0.06v% of water vapor, 0.05v% of methane and 700mg/m of sulfur dioxide 3 230mg/m hydrogen sulfide 3 180mg/m of carbonyl sulfide 3 330mg/m of carbon disulfide 3 The remainder was about 79v% nitrogen.
Typical normal operating conditions of the dry quenching device in the chemical coke production process are as follows: the red coke of the dry quenching furnace is fed into the furnace at 950-1100 ℃, the coke feeding amount is 140t/h, the red coke is intermittently fed into a pre-stored section from the top of the dry quenching furnace through a coke feeding device, and continuously moves downwards along with the discharging of a coke discharging device, and the coke discharging temperature is 190-200 ℃; the flow rate of the recycle gas stream at the low temperature recycle gas stream inlet is about 210000-220000Nm 3 /h, annular smokeThe air flow rate of the channel is 10000-11000Nm 3 /h (average moisture content 2.0 v%) at a low temperature recycle gas stream inlet temperature of 125-130 ℃; coke equivalent diameter 5.1cm, porosity 0.41; the gas components at the inlet of the low-temperature circulating gas flow are 11.3v% of carbon dioxide, 5.6v% of carbon monoxide, 2.8v% of hydrogen, 0.1v% of oxygen, 0.0v% of water vapor, 0.0v% of methane and 900mg/m of sulfur dioxide 3 340mg/m of hydrogen sulfide 3 170mg/m of carbonyl sulfide 3 290mg/m of carbon disulfide 3 The remainder was about 80v% nitrogen.
The dry quenching device adopts equipment explosion-proof grade design and process control with medium or lower level for each unit equipment, and comprises II BT2 lower medium and low grade electrical design, and the dry quenching device runs stably and safely in the past 6 years.
And carrying out carbon dioxide reaction activity experiments on the typical metallurgical coke and the red coke before quenching of chemical Jiao Jingan by using a set of self-made small test device. The main body of the test device is a cylindrical carbon steel tank, the volume is 100L, the height-diameter ratio is 1.0, and the outer wall is insulated; the temperature of red coke after canning is 980-1000 ℃; introducing a 99.8v% carbon dioxide gas flow which is electrically heated to the red coke temperature through a top wall vent pipe; and detecting the carbon monoxide content in the gas flow discharged by the exhaust pipe at the bottom of the cylinder when the residence time of the carbon dioxide gas flow is 2.5 s. The results of three parallel experiments were that the component content of the metallurgical coke reaction exhaust gas was 34.2v% carbon monoxide and 65.7v% carbon dioxide, and the component content of the chemical coke reaction exhaust gas was 75.7v% carbon monoxide and 24.0v% carbon dioxide.
Based on the existing operation data and small test results of the dry quenching device, a system for preparing carbon monoxide by utilizing the dry quenching device, changing air supplemented by circulating air flow into carbon dioxide and further purifying and separating produced air is designed by combining with analog calculation of Aspen and Fluent software; the system comprises a dry quenching device and a produced gas flow purifying and separating device; the dry quenching device is based on the existing industrial device, and an air distribution pipe and air inlet arranged in the annular flue are canceled; the top wall and the side wall of the space above the highest position of the pre-storing section Jiao Ceng are respectively provided with a plurality of paths of inlets with regulating valves for controlling the atmosphere of the space above the pre-storing sectionThe air pipes extend into the hearth by 20-25cm and are provided with a plurality of air distribution nozzles, and are used as upper air inlet parts, and 20-30% of the carbon dioxide air flow is used as upper air inlet; a coke-discharging atmosphere control part is arranged between an inlet of the vibration feeder and an outlet of the rotary sealing valve, the coke-discharging atmosphere control part is provided with a plurality of air inlet pipes with regulating valves, 30-40% of the carbon dioxide air flow is used as coke-discharging atmosphere control air inlet, and the carbon dioxide air flow is introduced into the coke-discharging atmosphere control part; a single-flow gas mixer is arranged in a communication pipeline between a low-temperature circulating gas inlet and a water supply preheater of the waste heat boiler, a plurality of spray pipes with openings facing the low-temperature circulating gas inlet of the dry quenching furnace and parallel to the circulating gas flow direction are arranged in the single-flow gas mixer, the lower inlet gas is mixed with the low-temperature circulating gas by utilizing the pressure head of the carbon dioxide gas and/or the carbon dioxide-rich gas, and the rest carbon dioxide gas and all the carbon dioxide-rich gas are supplemented into the circulating gas through the single-flow gas mixer. In the design, the temperature of the dry quenching furnace red Jiao Jin furnace is 1000 ℃, the coke feeding amount is 140t/h, and the carbon dioxide supplementing amount is 5000-8000Nm 3 And/h, the carbon dioxide-rich gas comes from a PSA decarbonation unit of the produced gas flow purifying and separating device; the circulating gas flow is about 120000-170000Nm 3 And/h, the flow rate of produced gas is 10000-20000Nm 3 /h。
The unit equipment of the produced gas flow purifying and separating device comprises a sulfur dioxide removal tower, a first cooler, a gas holder, a compressor, a heater, an organic sulfur hydrolysis tower, a fine desulfurization tower, a second cooler, a PSA carbon dioxide removal unit and a PSA carbon monoxide extraction unit which are sequentially communicated;
the produced gas pipeline with the allowance of the circulating gas flow led out by the dry quenching device is communicated with the gas inlet of the sulfur dioxide removal tower, so that part of the required flow of the circulating gas flow flows to the produced gas flow purifying and separating device; separating carbon dioxide-rich gas with carbon monoxide content less than or equal to 5v% by the PSA carbon dioxide removal unit, and returning the carbon dioxide-rich gas to a dry quenching device to serve as carbon dioxide gas inlet of the circulating gas flow; the CO replacement tail gas of the PSA carbon monoxide extraction unit is returned to the air inlet of the compressor for use; the hydrogen-containing tail gas of the PSA carbon monoxide extraction unit is burnt and utilized in a decoking furnace.
The flow direction of the produced air flow purifying and separating device or the sequence of the treatment process is as follows: the device comprises a sulfur dioxide removal tower, a first cooler, a gas holder, a compressor, a heater, an organic sulfur hydrolysis tower, a fine desulfurization tower (2), a second cooler, a PSA carbon dioxide removal unit and a PSA carbon monoxide extraction unit.
The sulfur dioxide removal tower is filled with a desulfurizing agent taking superfine calcium carbonate as a main desulfurizing component.
The organic sulfur hydrolysis tower is filled with 30m of hydrolysis catalysts HB-SJ3 and HB-SJ2 of Qingdao Hua Sunyaka New Material technology Co., ltd 3 The two are filled in upper and lower layers; wherein HB-SJ3 is a first-stage hydrolytic agent, and plays roles mainly in the crude conversion of organic sulfur, the removal of oxygen and the conversion of cyanide; HB-SJ2 is a secondary agent and plays a role in the deep hydrolysis of the residual organic sulfur; the temperature of the catalyst bed layer is 200-230 ℃, and the conversion product of the organic sulfur is hydrogen sulfide.
The fine desulfurization towers are respectively filled with zinc oxide desulfurizing agent HB-ZT201 of Qingdao Hua surface new material science and technology Co., ltd, the temperature of the desulfurizing agent bed layer is 200-230 ℃, the desulfurization towers can be connected in series or be opened and prepared, and the total sulfur of the outlet is below 0.1 ppm.
The main exhaust pressure of the compressor is 1.0MPa; the operation procedures of the PSA carbon dioxide removal unit and the PSA carbon monoxide extraction unit comprise a vacuumizing operation process.
The designed dry quenching device and the produced gas flow purifying and separating device also comprise detection/control components such as temperature, flow, pressure and the like which are arranged on each unit equipment and pipelines according to the requirements, wherein the detection/control components comprise instruments, automatic valves and DCS for performing system control.
The new design of a dry quenching device and a system for preparing carbon monoxide gas by further purifying and separating produced gas adopts two types of carbon dioxide gas of 100v% and 96v% carbon dioxide and 4v% water gas, and under the limiting condition that the vertical direction of a cooling section Jiao Ceng is below half of the height or below the curved surface at 800 ℃ and 700 ℃, backwash gas, lower inlet gas and circulating gas flow from a low-temperature circulating gas flow inlet are mixed to be more than 80% of the mixing degree, and the simulation calculation results of Aspen and Fluent software of the system are based on the existing operation data and small test results of the dry quenching device and comprise:
the average temperature of the coke outlet is less than or equal to 160 ℃, and the inlet temperature of the low-temperature circulating air flow is 110-115 ℃;
the carbon dioxide gas flow entering the coke-discharging atmosphere control component can blow back the most of components except carbon dioxide contained in the coke granule inner hole and Jiao Lijian gas, such as more than 85v% of combustible components and sulfides, to the circulating gas flow of the cooling section Jiao Ceng;
the average height of the coke layer at the temperature of the cooling section is more than or equal to 800 ℃ and is 30-31% of the average height of the coke layer at the cooling section above the airflow distribution component;
the component content of the produced gas is 30-40% by volume of carbon monoxide during the dry quenching of metallurgical coke, and the 98.5% by volume of carbon monoxide gas output of the produced gas flow purifying and separating device can reach 7000Nm 3 /h; the component content of the produced gas is 65-78% by volume of carbon monoxide during the dry quenching of chemical coke, and the 98.5% by volume of carbon monoxide gas output of the produced gas flow purifying and separating device can reach 11000Nm 3 /h; when the carbon dioxide gas is 100v percent and chemical coke and 96v percent carbon dioxide+4v percent water gas and metallurgical coke are adopted, the hydrogen content in the produced gas is less than or equal to 5v percent;
the temperature segregation degree of the red Jiao Cengna above 850 ℃ of the cooling section can be obviously reduced.
The original medium or lower level equipment explosion-proof grade design and process control of each unit equipment of the dry quenching device comprise the medium and lower level electrical design below II BT2, the new design can meet the requirements, and the old device is convenient to reform.
Example 2
On the basis of the newly designed dry quenching device in embodiment 1, a system for further purifying and separating the produced gas to prepare carbon monoxide gas in the dry quenching device in embodiment 2 is designed, and the main difference is that: the height of the cooling section of the dry quenching furnace is increased by 1.0m, a coke powder gasification channel is additionally arranged in a temperature zone of 800-950 ℃ of the cooling section Jiao Ceng, the gasification channel is horizontally arranged and transversely penetrates through the dry quenching furnace, one end of the gasification channel is closed, one end of the gasification channel is provided with one or more gasification nozzles, the top of the gasification channel is an inverted V-shaped pointed top, the external dimension is 1.2m high, 1.0m wide, 10.5m long, the bore dimension is 0.7m wide, 0.5m long and 9.5m long, and 20 exhaust holes are arranged on the side wall of the gasification channel. The temperature of the reaction area in the gasification channel is 900-1100 ℃, the gasification nozzle adopts a three-sleeve burner with a cooling jacket, the pressure of each of the outer sleeve and the central tube is 0.4MPa, the flow of oxygen is required, the pressure of each of the middle sleeve and the central tube is 0.4MPa, the flow of carbon dioxide-rich gas is required, the carbon dioxide-rich gas is used as carrier gas to convey finely ground coke powder into the gasification channel, the coke powder, carbon dioxide inlet gas and oxygen are sprayed into the gasification channel at a high speed, mixed and rapidly reacted, the produced gas flow contains 73-75v% of carbon monoxide, the rest is basically carbon dioxide, and the temperature is 900-950 ℃. The carbon dioxide-rich gas is separated by a PSA carbon dioxide removal unit, and the carbon monoxide content is less than or equal to 5% by volume. The coke powder is all the coke powder obtained by separating the primary dust remover and the secondary dust remover and other source coke powder.
Simulation calculation was performed on the system for preparing carbon monoxide gas by further purifying and separating the dry quenching device and the produced gas in this example 2, and the results include: the gas making amount of the coke powder gasification channel is 2000-6000Nm calculated by carbon monoxide 3 And/h, the influence on the temperature distribution of the cooling section of the dry quenching furnace is small, and the temperature of the cooling section is more than or equal to 800 ℃ and the average height of the coke layer is 33% of the average height of the cooling section on the airflow distribution component; the average temperature of the coke outlet is less than or equal to 160 ℃, and the inlet temperature of the low-temperature circulating air flow is 115-120 ℃; the component content of the produced gas is 35-55v% of carbon monoxide during the dry quenching of metallurgical coke, and the upper limit of the yield of 98.5v% of carbon monoxide gas is 13000Nm 3 /h; the component content of the produced gas is 67-77v% of carbon monoxide, and the upper limit of the yield of 98.5v% of carbon monoxide gas is 17000Nm during the dry quenching of chemical coke 3 /h。
Claims (9)
1. A dry quenching method comprises a dry quenching furnace, a coke inlet device, a coke outlet device, a primary dust remover, a waste heat boiler, a secondary dust remover, a circulating air flow fan, a waste heat boiler water supply preheater and a coke powder gas making unit; the coke feeding device and the coke discharging device are respectively arranged above and below the coke dry quenching furnace and are respectively communicated with the coke dry quenching furnace in a sealing way, and the coke discharging device comprises a vibration feeder and a rotary sealing valve; the coke layer in the dry quenching furnace is provided with a pre-storing section for improving quality of red Jiao Baowen, a cooling section in countercurrent contact with circulating air flow is provided at the middle upper part, a chute for discharging high-temperature circulating air flow out of the coke layer is provided at the furnace wall between the pre-storing section and the cooling section, and an annular flue for collecting high-temperature circulating air flow is arranged outside the chute; the bottom Jiao Cengna of the cooling section is provided with an air flow distribution component which is communicated with a low-temperature circulating air flow inlet arranged at the bottom of the dry quenching furnace; the top and/or the side wall of the space above the highest position of the pre-storing section Jiao Ceng are provided with an atmosphere control air flow inlet and an optional air distribution component of the space above the pre-storing section; the annular flue gas flow outlet, the primary dust remover, the waste heat boiler, the secondary dust remover, the circulating gas flow fan, the waste heat boiler water supply preheater and the low-temperature circulating gas flow inlet are respectively provided with a circulating gas flow sequentially communicated pipeline;
A communication pipeline between the outlet of the circulating air flow fan and the low-temperature circulating air flow inlet is connected with an extracted air pipeline with the allowance of the circulating air flow;
in the normal application process of the dry quenching method, red coke at 950-1100 ℃ from a coke oven is intermittently or continuously loaded into a pre-stored section from the top of the dry quenching oven through a coke feeding device, and continuously moves downwards along with the discharging of a coke discharging device, wherein the average temperature of discharged coke is less than or equal to 200 ℃; the inlet temperature of the low-temperature circulating air flow is less than or equal to 130 ℃;
the method is characterized in that carbon dioxide gas with the hydrogen and water content less than or equal to 4v percent and carbon dioxide-rich gas with the carbon monoxide content less than or equal to 10v percent are adopted as carbon dioxide gas inlet of the circulating gas flow; the flow of the carbon dioxide inlet air is 3-15% of the circulating air flow; the carbon dioxide gas is industrially and economically available gas with high carbon dioxide content, the total content of carbon monoxide and hydrogen is less than or equal to 0.5 percent by weight, the content of hydrocarbon is less than or equal to 0.5 percent by weight, and the carbon dioxide in the components except water accounts for more than 98 percent by weight; the carbon dioxide-rich gas is obtained by sequentially carrying out dry desulfurization, compression and PSA carbon dioxide removal and separation on the circulating gas flow allowance led out by the produced gas pipeline, wherein the carbon dioxide accounts for more than 95% of the components except hydrogen, water vapor and carbon monoxide;
Wherein, 0-30% of the carbon dioxide gas flow is taken as an upper gas inlet flow, and the upper gas inlet flow is connected with one or more oxygen-containing gases of air, oxygen-enriched air and oxygen in the required quantity, and the upper gas inlet flow is controlled by the atmosphere of the upper space of the pre-storing section and is introduced into the space above the pre-storing section Jiao Ceng, so that the combustible components in the gas in the space are controlled below the required concentration level; the flow rate of the oxygen-containing gas is 0-10% of the flow rate of the carbon dioxide gas;
a coke-discharging atmosphere control part is arranged between the inlet of the vibration feeder and the outlet of the rotary sealing valve, and is provided with a plurality of air inlet pipes with regulating valves; taking 20-40% of the carbon dioxide gas flow as coke outlet atmosphere control air inlet, and introducing the coke outlet atmosphere control part as coke outlet atmosphere control air flow; the coke-discharging atmosphere controls 50-70% of the air flow, plays a role of backwashing air flow, and blows more than 80% of the carbon dioxide contained in the inner hole of the coke particles and Jiao Lijian gas back to the circulating air flow of the cooling section Jiao Ceng;
the coke powder gas making unit is arranged outside or inside the dry quenching furnace, all or part of the obtained coke powder and optional other source coke powder are separated by utilizing a primary dust remover and a secondary dust remover, and the carbon dioxide gas with required flow and the oxygen with required flow are used as gasifying agents, and a carbon monoxide-rich gas stream with carbon monoxide content of more than 60% generated by combustion is merged into a circulating gas stream; wherein the carbon monoxide-rich gas flow generated by the coke powder gas making unit outside the dry quenching furnace is merged into the circulating gas flow before the inlet of the waste heat boiler; the coke powder gas making unit in the dry quenching furnace is arranged in the temperature zone of 500-1000 ℃ of the cooling section Jiao Ceng, and the discharged carbon monoxide-rich gas flow is distributed into the circulating gas flow of the coke layer of 800-1000 ℃;
The rest flow of the carbon dioxide gas and the carbon dioxide-rich gas are taken as lower air inlet flows, are initially mixed with circulating air flow from a low-temperature circulating air flow inlet, and enter a coke layer from the bottom of a cooling section through the air flow distribution component;
the backwash airflow, the lower inlet airflow and the circulating airflow from the low-temperature circulating airflow inlet are mixed to more than 80% of the mixing degree under half height of the cooling section Jiao Ceng in the vertical direction or under a 800 ℃ temperature curved surface;
the average height of the coke layer at the temperature of the cooling section is more than or equal to 800 ℃ and is 25-35% of the average height of the coke layer at the cooling section on the airflow distribution component.
2. The dry quenching method as claimed in claim 1, wherein the air flow distribution part or the air supply part comprising the air flow distribution part comprises a cross air duct and a multi-layer air distribution hood which is communicated with the cross air duct.
3. The dry quenching method as claimed in claim 1, wherein the preliminary mixing of the lower inlet gas stream and the recycle gas stream is performed in a single-flow gas mixer provided in a communication line between the low-temperature recycle gas stream inlet and the feed water preheater of the waste heat boiler; the single-flow direction gas mixer is internally provided with a plurality of spray pipes with openings facing to a low-temperature circulating gas flow inlet of the dry quenching furnace and parallel to the flowing direction of the circulating gas flow, and the lower gas inlet flow is mixed with the low-temperature circulating gas flow by utilizing the pressure heads of the carbon dioxide gas and the carbon dioxide-rich gas and flows to the dry quenching furnace and the gas flow distribution component.
4. The method of dry quenching as claimed in claim 1, wherein the hydrogen content in the outlet air stream of the circulating air stream blower is controlled to be less than or equal to 3% by volume; the carbon monoxide content in the space gas above the pre-storing section Jiao Ceng is controlled to be less than or equal to 5% by volume, and the hydrogen content is controlled to be less than or equal to 2% by volume.
5. The dry quenching method as claimed in claim 1, wherein the communication pipeline between the air outlet of the water preheater of the waste heat boiler and the inlet of the low-temperature circulating air flow is connected with an extracted air pipeline with the allowance of circulating air flow.
6. The dry quenching method as claimed in claim 1, wherein the main equipment of the coke powder gas making unit is an independent gas making furnace, the temperature of the reaction area of the gas making furnace is 900-1100 ℃, one or more gasification nozzles are arranged in the side wall or the hearth, the gasification nozzles adopt three-sleeve nozzles with cooling jackets, the outer sleeve and the central tube respectively feed oxygen with required pressure and flow, the middle sleeve feeds carbon dioxide gas with required pressure and flow as carrier gas to convey the coke powder into the gas making furnace, the coke powder, the carbon dioxide gas and the oxygen are sprayed into the hearth at high speed, mixed and rapidly reacted, and the produced gas flow contains 60-80v% of carbon monoxide and has the temperature of 850-1000 ℃ together with ash powder and is merged into the circulating gas flow before the inlet of the waste heat boiler through the gas outlet at the top or the side wall of the gas making furnace; or the main equipment of the coke powder gas making unit is a combined gas making furnace arranged below the primary dust remover, the top of the gas making furnace is connected with an ash bucket below the primary dust remover, a coke powder feeding valve is arranged between the gas making furnace and the ash bucket, coke powder falls into the gas making furnace from the ash bucket by gravity, a certain coke powder level is maintained in the ash bucket, and the level in the ash bucket is controlled by the coke powder feeding valve; the side wall of the gas making furnace is provided with a carbon dioxide gas inlet and a oxygen gas inlet, and the other side is provided with a gas making outlet; the bottom of the gas making furnace is provided with a slag discharging port for regularly discharging furnace ash; the temperature of the reaction area of the gas making furnace is 900-1000 ℃, and the reaction pressure is micro positive pressure; the outlet gas flow of the gas making furnace contains 65-85% of carbon monoxide, the temperature is 900-950 ℃, and the gas flow is merged into the circulating gas flow before the inlet of the waste heat boiler through the exhaust port at the top or on the side wall of the gas making furnace; or the main equipment of the coke powder gas making unit is a gasification channel arranged in the dry quenching furnace, the gasification channel is horizontally arranged and transversely crosses the dry quenching furnace, one end is closed, one end is provided with one or more gasification nozzles, and the top is an inverted V-shaped peak to prevent coke accumulation; the side wall and/or the bottom are provided with a plurality of exhaust holes; the temperature of the reaction area of the gasification channel is 900-1100 ℃, the gasification nozzle adopts a three-sleeve burner with a cooling jacket, the outer sleeve and the central tube are respectively fed with oxygen with required pressure and flow, the middle sleeve is fed with carbon dioxide gas with required pressure and flow and is used as carrier gas to convey coke powder into the gasification channel, the coke powder, the carbon dioxide gas and the oxygen are sprayed into the gasification channel at high speed, mixed and rapidly reacted, and the produced gas flow contains 60-80v% of carbon monoxide and has the temperature of 850-1000 ℃.
7. A system for producing carbon monoxide, comprising a dry quenching apparatus according to the dry quenching method of claim 1, and a produced gas stream purification and separation apparatus; the unit equipment of the produced gas flow purifying and separating device comprises a sulfur dioxide removal tower, a first cooler, an optional gas holder, a compressor, an optional heater, an organic sulfur hydrolysis tower, a fine desulfurization tower, a second cooler, a PSA carbon dioxide removal unit and a PSA carbon monoxide extraction unit which are sequentially communicated; the produced gas pipeline with the allowance of the circulating gas flow led out by the dry quenching device is communicated with the gas inlet of the sulfur dioxide removal tower, so that part of the required flow of the circulating gas flow flows to the produced gas flow purifying and separating device; separating carbon dioxide-rich gas with carbon monoxide content less than or equal to 10v% by the PSA carbon dioxide removal unit, and returning the carbon dioxide-rich gas to a dry quenching device for use; the CO replacement tail gas of the PSA carbon monoxide extraction unit is returned to the air inlet of the compressor for use; the hydrogen-containing tail gas of the PSA carbon monoxide extraction unit is burnt and utilized in a decoking furnace.
8. The system for producing carbon monoxide according to claim 7, wherein the upper and lower layers of the organosulfur hydrolysis column are packed with organosulfur hydrolysis catalysts HB-SJ3 and HB-SJ2, respectively, and the catalyst bed temperature is 130 to 300 ℃, and the conversion product of the organosulfur is hydrogen sulfide; the fine desulfurization tower is filled with zinc oxide desulfurizing agent HB-ZT201, and the temperature of a desulfurizing agent bed layer is 130-300 ℃.
9. The system for producing carbon monoxide according to claim 7, wherein the PSA decarbonation unit and PSA carbon monoxide extraction unit are operated at a pressure of 1.0 to 2.0MPa.
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