CN-117181145-B - Device and process for producing high-value products by self-production and self-sales sectional type light-heat synergistic catalysis of metallurgical furnace gas

CN117181145BCN 117181145 BCN117181145 BCN 117181145BCN-117181145-B

Abstract

The invention discloses a device and a process for producing high-value products by self-produced self-sell sectional type utilizing metallurgical furnace gas photo-thermal synergistic catalysis, which belong to the technical field of furnace gas carbon negative emission in smelting processes. The invention can effectively utilize the waste heat of high-temperature converter/blast furnace gas generated in the smelting process, and simultaneously, the industrial grade CO 2 and the high-purity H 2 and N 2 generated in the short chemical-looping process are produced, so that the defect that raw gas is required to be additionally introduced when chemical CO-production is used for manufacturing high-added-value chemical products is overcome, the cooperation of the light-heat synergistic catalysis process is flexible, the raw gas can be coordinated according to the actual working condition, the energy utilization rate and the economic benefit are effectively improved, and the high-value utilization of the metallurgical furnace gas is realized.

Inventors

LI KONGZHAI
Zuo Huicong
CAI JUN
HE LUN
JIANG LEI
LI YUELUN
HUANG LINAN

Assignees

昆明理工大学

Dates

Publication Date: 20260512
Application Date: 20230414

Claims (10)

1. The system for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis in a self-produced and segmented mode is characterized by comprising an exhaust fan, a furnace gas purifying and dedusting device, a vaporization cooling tower, a waste heat utilization temperature control device, a gas cabinet, a chemical chain reactor unit, a CO 2 /N 2 purifying and separating unit, a steam generator, an air cabinet, a methane photocatalytic reactor, a methanol/low-carbon olefin catalytic reactor, a pressurizing device, first to third heat exchangers, first to fourth gas storage cabinets, a product storage cabinet, first to tenth control valves, first to seventh electromagnetic flowmeters, first to second condensers, first to second flue gas analyzers and first to second chromatograph; the chemical chain reactor unit comprises a combustion reactor, a steam reactor and an air reactor which are sequentially communicated through pipelines; The exhaust fan, the furnace gas purifying and dedusting device, the vaporization cooling tower, the waste heat utilization temperature control device, the gas cabinet, the first control valve, the first electromagnetic flowmeter, the first heat exchanger, the combustion reactor, the second control valve, the first condenser, the first flue gas analyzer and the CO 2 /N 2 purifying and separating unit are sequentially communicated through pipelines, and the CO 2 /N 2 purifying and separating unit is respectively communicated with the first gas storage cabinet and the second gas storage cabinet through pipelines; the steam generator, the third control valve, the second electromagnetic flowmeter, the steam reactor, the fourth control valve, the second condenser, the second flue gas analyzer and the third gas storage cabinet are sequentially communicated through pipelines; The air cabinet, the fifth control valve, the third electromagnetic flowmeter, the second heat exchanger, the air reactor and the sixth control valve are sequentially communicated through pipelines; the steam generator, the seventh control valve, the fourth electromagnetic flowmeter and the methane photocatalytic reactor are sequentially communicated through pipelines; the first gas storage cabinet, the eighth control valve, the fifth electromagnetic flowmeter, the methane photocatalytic reactor, the first chromatographic analyzer and the fourth gas storage cabinet are sequentially communicated through pipelines; The third gas storage cabinet, the ninth control valve, the sixth electromagnetic flowmeter, the third heat exchanger and the methanol/light olefin catalytic reactor are sequentially communicated through pipelines; The fifth electromagnetic flowmeter, the tenth control valve, the seventh electromagnetic flowmeter, the third heat exchanger, the methanol/light olefin catalytic reactor, the second chromatographic analyzer and the product storage cabinet are sequentially communicated through pipelines; the pressurizing device is communicated with the methanol/light olefin catalytic reactor through a pipeline.
2. The system for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis in a self-produced and self-produced manner according to claim 1, wherein the chemical chain reactor unit is internally filled with oxygen, the methane photocatalytic reactor is internally filled with catalyst, and the methanol/low-carbon olefin catalytic reactor is internally filled with catalyst.
3. The system for producing high-value products by self-produced and self-pinned sectional type utilizing metallurgical furnace gas photo-thermal synergistic catalysis according to claim 2, wherein the oxygen carrier is one or a mixture of several of Fe-based oxygen carriers, co-based oxygen carriers, mn-based oxygen carriers, ni-based oxygen carriers or perovskite oxygen carriers.
4. The system for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis in a self-produced-from-a-segment manner according to claim 2, wherein the methane photocatalytic reactor is internally filled with one or a mixture of a Fe, ti, zn, cu, bi, br, pt, cd, W or g-C 3 N 4 oxide, a composite catalyst or a MOF structure.
5. The system for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis In a self-produced and self-produced manner according to claim 2, wherein the internal filling catalyst of the methanol/light olefin catalytic reactor is Zn, ce, zr, mn, fe, cu, al, ti, cr, ga, cd, Y or In oxide or one or a mixture of several of ZSM-5/SiO 2 composite catalysts is introduced.
6. The system for producing high-value products by self-produced and self-pinned sectional type utilizing metallurgical furnace gas photo-thermal synergistic catalysis according to claim 1, wherein the exhaust fan air inlet is connected with a converter or a blast furnace tower through a furnace gas pipeline.
7. A system for the staged photo-thermal co-catalysis of metallurgical furnace gas production of high value products from self-produced and self-produced according to claim 1, wherein the steam generator is provided with a make-up water inlet.
8. A process for producing high-value products by self-produced and self-sold sectional type utilizing metallurgical furnace gas photo-thermal synergistic catalysis, which is characterized by comprising the following steps of: (1) The system for producing high-value products by utilizing the self-produced self-selling sectional type metallurgical furnace gas photo-thermal synergistic catalysis is used for sending converter/blast furnace smelting purge gas to a furnace gas purifying and dedusting device for purifying and preprocessing, and the working procedures of the system are that the converter/blast furnace gas after the purifying and preprocessing is subjected to dedusting, decarburization, deoxidization and desulfurization, enters a vaporization cooling tower for cooling, and is sent to a gas tank for waste heat utilization after the high-temperature furnace gas is cooled to a preset temperature within a range of 500-800 ℃ by a waste heat utilization temperature control device; (2) The converter/blast furnace gas is sent to a first heat exchanger for heat preservation and preheating, then is sent to a first stage chemical looping combustion reactor, reacts with oxygen carriers filled in the combustion reactor to generate CO 2 /N 2 mixed gas, and after passing through a CO 2 /N 2 purification and separation unit, CO 2 and N 2 are respectively stored; (3) Conveying the water vapor of the vapor generator into a first-stage chemical-looping vapor reactor, reacting with an internal oxygen-losing oxygen carrier to generate hydrogen containing water vapor, condensing and separating H 2 and condensed water, storing H 2 , and refluxing the condensed water to the vapor generator for circulation; (4) Preheating cold anhydrous air through a second heat exchanger, and then sending the preheated cold anhydrous air into a first-stage chemical-looping air reactor to react with an internal non-complete oxidation state oxygen carrier to a complete oxidation state; (5) Delivering water vapor of a steam generator into a second-stage methane photocatalytic reactor, delivering CO 2 obtained in the step (2) into the methane photocatalytic reactor, and reacting the two feeding atmospheres with an internal filling catalyst under the illumination condition to generate methane as a product; (6) And (3) conveying the H 2 obtained in the step (3) to a third-stage methanol/low-carbon olefin catalytic reactor, conveying the CO 2 obtained in the step (2) to the third-stage methanol/low-carbon olefin catalytic reactor, and reacting the two feeding atmospheres H 2 and CO 2 with an internal filling catalyst to generate the product methanol/low-carbon olefin.
9. The process for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis in a self-produced and self-pinned sectional manner according to claim 8, wherein in the step (5), the reaction condition is 300W xenon lamp simulated sunlight, 0.1MPa and constant temperature of 20 ℃, or the reaction condition is 300W xenon lamp simulated sunlight, 0.07MPa and constant temperature of 20 ℃.
10. The process for producing high-grade products by utilizing the photo-thermal synergistic catalysis of the metallurgical furnace gas, which is produced by self-production and has the advantages of being characterized in claim 8, wherein in the step (6), the reaction condition is 380 ℃ and 3.0 MPa, the molar ratio H 2 /CO 2 =3 and the space velocity 14400 mL-g -1 ·h -1 , or the reaction condition is 320 ℃ and 4.0 MPa, the molar ratio H 2 /CO 2 =3 and the space velocity 6000 mL-g -1 ·h -1 , or the reaction condition is 400 ℃ and 3.0 MPa, the molar ratio H 2 /CO 2 =3 and the space velocity 9000 mL-g -1 ·h -1 .

Description

Device and process for producing high-value products by self-production and self-sales sectional type light-heat synergistic catalysis of metallurgical furnace gas Technical Field The invention belongs to the technical field of furnace gas carbon emission in a smelting process, and relates to a device and a process for producing high-value products by utilizing light-heat synergistic catalysis of metallurgical furnace gas in a self-produced and self-sold sectional mode. Background The converter gas in the metallurgical furnace gas is a main byproduct in the converter smelting process, generally contains CO (55-60 vol%), CO 2 (15-20 vol%) and N 2 (10-20 vol%) as well as trace H 2 and O 2, has an average heat value of 8500-10000 kJ/m 3, and is a gas fuel with a medium heat value. The blast furnace smelting process also produces blast furnace gas rich in CO (20-25 vol%), CO 2 (18-22 vol%) and N 2 (50-55 vol%) and has an average heat value of 3300-4100 kJ/m 3, and is a gas fuel with a lower heat value. In addition to the self-use of the steel smelting process, a considerable part of the steel smelting process is used for direct combustion or power generation, even partial emptying treatment, so that environment 'colorless' pollution and valuable gas resource waste are caused. In the traditional flue gas waste heat recovery process, waste heat is recovered through a vaporization cooling flue for power generation, but only about 25-35% of waste heat of high-temperature steam is converted into electric energy, the energy conversion efficiency is low, and the yield of power generation is far lower than that of the chemical product which is treated by the high-temperature steam and is used as the chemical raw material for producing the high-added-value chemical product. At present, in order to solve the high-value efficient utilization of converter gas/blast furnace gas with larger generation amount in the metallurgical steel industry, the maximization of resource allocation striving for by the prior art becomes a development key. The main component CO/CO 2 of the byproduct furnace gas in the converter/blast furnace smelting process is the main raw material of C1 chemical industry, and when the byproduct furnace gas is directly used as raw material gas for synthesizing high-added-value chemical products (such as methane, methanol, ethanol, ethylene, urea and the like), H 2 is additionally introduced for gas quality adjustment and denitrification treatment to meet the synthesis requirement, the byproduct furnace gas cannot be fully and efficiently utilized, and the energy consumption for preparing H 2 is increased. On the other hand, some industrial operations that achieve gas separation under high pressure/pressure conditions require higher operating energy consumption resulting in higher capital and operating costs. The chemical product with high added value is an important energy chemical raw material, and has wide market prospect and wide application. In summary, to fully utilize the characteristic of high content of CO and CO 2 in the converter gas/blast furnace gas components and improve the resource allocation rate and economic benefit, a device and a process for specially and sectionally capturing CO 2 in the converter gas/blast furnace gas and simultaneously taking self-produced and self-sold H 2 as raw material gas for synthesizing chemical products and producing high-added-value chemical products (such as methane, methanol and low-carbon olefin) through photo-thermal synergistic catalysis are the problems to be solved by the technicians in the field. Disclosure of Invention In view of the above, the invention provides a device and a process for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis in a self-produced and self-sold sectional mode. In order to achieve the above purpose, the present invention adopts the following technical scheme: The system for producing high-value products by utilizing metallurgical furnace gas photo-thermal synergistic catalysis in a self-produced and segmented mode is characterized by comprising an exhaust fan, a furnace gas purifying and dedusting device, a vaporization cooling tower, a waste heat utilization temperature control device, a gas cabinet, a chemical chain reactor unit, a CO 2/N2 purifying and separating unit, a steam generator, an air cabinet, a methane photocatalytic reactor, a methanol/low-carbon olefin catalytic reactor, a pressurizing device, first to third heat exchangers, first to fourth gas storage cabinets, a product storage cabinet, first to tenth control valves, first to seventh electromagnetic flowmeters, first to second condensers, first to second flue gas analyzers and first to second chromatograph; the chemical chain reactor unit comprises a combustion reactor, a steam reactor and an air reactor which are sequentially communicated through pipelines; The exhaust fan, the furnace gas purifying and