CN115245729A - Steel process CO 2 Method and system for conversion and cyclic utilization - Google Patents
Steel process CO 2 Method and system for conversion and cyclic utilization Download PDFInfo
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- CN115245729A CN115245729A CN202210150952.6A CN202210150952A CN115245729A CN 115245729 A CN115245729 A CN 115245729A CN 202210150952 A CN202210150952 A CN 202210150952A CN 115245729 A CN115245729 A CN 115245729A
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- 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
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- 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
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Abstract
Steel process CO 2 A method of conversion recycling, the method comprising the steps of: 1) CO 2 2 The trapping: CO generated by one or more processes of iron and steel enterprises 2 Collecting to obtain enriched CO 2 A gas; 2) CO 2 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Transformation ofCentral (Z) and to CO 2 Introducing a reducing medium into the conversion center (Z) to obtain CO; 3) CO 2 2 The recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling. The invention takes the whole process of iron and steel smelting as a research object for the first time, and provides CO according to the characteristics of carbon emission and energy input at the tail end of each process of an iron and steel enterprise 2 Capture → CO 2 Transformation of → CO 2 The recycling process and the steel smelting system for realizing carbon chain circulation form a hydrocarbon composite metallurgy process by reconstructing C, H, O dynamic balance, thereby greatly reducing the carbon emission in the steel process.
Description
Technical Field
The invention relates to CO 2 The recycling process of the process, in particular to a CO recycling process in the steel process 2 A method and a system for conversion and cyclic utilization belong to the technical field of steel smelting.
Background
The fossil energy consumed by the steel industry in China is close to 13 percent of the total national consumption, and the carbon emission proportion also reaches 15 percent. In order to achieve the targets of 2030 carbon peak reaching and 2060 carbon neutralization in China, the action of reducing emission in the steel industry is imperative. CO 2 2 The emission reduction can be realized from the energy structure adjustment of a source end, the energy and process efficiency improvement of a process end and the tail end CO 2 Trapping is realized by utilization. Renewable energy alternatives for the traditional industry require a revolutionary body process, and therefore this route is difficult to implement in the short term. The requirements of sintering, pelletizing and other processes in steel on liquid solid fuel are difficult to meet, and green energy is difficult to meet, because C in fossil fuel plays three roles in the steel field: fuel, reducing agent and material (carbon steel, the dosage is 0.0218-2.11 percent less) are not only used as energy input media. For example, in the blast furnace smelting process, coke not only serves as fuel but also plays a role of a skeleton, the air permeability in the blast furnace is guaranteed, and molten iron infiltration is smooth, so that a certain amount of C is required in the metallurgical process. H 2 Is a good reducing agent in ironmaking, but H 2 The reduction is an endothermic reactionPure hydrogen metallurgy is not sustainable in energy, and C fuel is required to be supplemented, so that continuous metallurgy is ensured.
The scholars predict that the carbon emission reduction contribution brought by energy efficiency improvement reaches 50% by 2060 years, and the tail end CO is 2 The contribution of the capture utilization technology is predicted to be 17%, and the method is an indispensable technical route and a bridge for the transition of the prior art to the future technology. At present, the carbon capture technology is commercially applied, and CO after capture 2 The method is mainly used for oil displacement or direct geological landfill, the former needs enterprises to be positioned at the periphery of an oil field, and the latter is only used as a means for long-term carbon sequestration, namely for CO 2 The waste of resources and the long-term influence on the geology after the landfill are not fully demonstrated. In contrast, CO 2 The conversion and cyclic utilization can effectively reduce the consumption of fossil energy of enterprises and reduce the terminal CO 2 Emission is not limited by geographical and geological environment, and CO is realized 2 The method is used on site, and is expected to become an optimal route for industrial carbon emission reduction. With the rapid progress of photoelectric and wind power technologies, the cost of green energy can be greatly reduced in the future, and CO is driven by green energy 2 Transformation will be one of the best choices. Compared with pure hydrogen smelting, H 2 The storage and the transportation of the explosive have larger safety risks and are easy to explode; secondly, pure hydrogen metallurgy needs to change the existing main iron making process, the time period is long, and the technical reliability in large-scale production is uncertain; finally, for the reduced iron reaction, the theoretically optimal reducing gas composition is 20% CO and 80% H 2 Whether blast furnace or direct return furnace, all require the participation of C.
The use condition of fossil energy in China is that about 85 percent of fossil energy is used as fuel for energy supply, and only about 15 percent of fossil energy is used as production raw materials of chemical products. Thus, the demand for chemical products from the perspective of the overall C cycle cannot completely eliminate CO 2 The conversion products of (a) and the vast majority of the conversion products will still be used as fuel, and therefore CO will be used 2 Conversion to energy products is the primary means of future large-scale carbon recycling. CO 2 2 The hydrogenated conversion product methanol can be used as fuel and is H 2 A good carrier of (2) can be subjected to a simple process when necessaryProcess for preparing H 2 For the steel industry, the method can be used as fuel or reducing agent in various processes of iron making and steel making, realizes complete consumption and recycling, and is an ideal conversion product.
At present, CO aiming at the whole process of steel does not exist 2 Recycling Process, reported Industrial flue gas CO 2 The main categories of capture and utilization can be divided into three categories:
1) Bioconversion, i.e. CO conversion by microorganisms or plants 2 The methane, the ethanol and the like are prepared by conversion, for example, archaea methane of Electrochaea is converted to produce methane CN113227389A, the first industrial flue gas is converted to produce ethanol CN107099556B by yeast fermentation, and the tail gas of methanol prepared from Xinao coal is prepared to produce biodiesel CN106434778B by microalgae carbon fixation. Firstly, the microbial conversion has certain requirements on the components of the inlet gas, such as that the archaea is generally anaerobic and can not process oxygen-containing gas, and secondly, the conversion has certain requirements on CO and H 2 S and other gas pollutants are strictly required, otherwise, bacteria can die or methanation reaction can be stopped. Secondly, the conversion rate is difficult to reach the conversion amount, the microbial conversion is mostly in dozens of L/L reactors/day, and the tail gas generated by a lime kiln in the steel working procedure reaches million Nm 3 The day is.
2)CO 2 The carbon conversion process to produce CO requires the participation of carbon.
For example CN106139838A, ammonia is used to recover CO 2 Then heating CO 2 The gas is mixed with red coke to react and then sprayed into the bottom of the blast furnace to generate the energetic gas mainly containing CO. CN106748655B, CO in blast furnace gas 2 And steam and carbon react to form CO and H 2 Then the methanol is synthesized with the hydrogen-rich coke oven gas. Utilizing high temperature environment (such as high temperature red coke after coking and carbon in blast furnace converter environment) of existing process, utilizing coke and CO 2 The reaction improves the yield of coal gas. The carbon conversion path depends on the carbon and high temperature environment of coking and blast furnace processes, and the reaction is normalized
Is an endothermic reaction and is not energetically sustainableContinuous, thus totally convertible CO 2 The amount is relatively limited.
3) Methane reforming, the biggest problem with carbon dioxide reforming, is high energy consumption (because it is a strongly endothermic reaction). Calculations show that the energy required for carbon dioxide reforming is greater than the energy given off by the chemicals it converts as an energy source. That is, if the energy it consumes is provided by the combustion of fossil fuels, it increases emissions, not only but also emissions. Experts therefore propose that this technique is of value only in combination with solar or industrial waste heat techniques that do not make use of. Secondly, for steel smelting, raw material gas methane mainly comes from coke oven gas, and the yield of methane is difficult to meet the conversion demand and cannot reach the self-circulation conversion in enterprises.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a CO steel process 2 A method for converting and recycling. The method is used for trapping CO in the flue gas of one or more working procedures in the steel process 2 And through CO 2 Conversion center converts CO 2 Reducing medium is added to convert the carbon into energy-containing products such as CO, methanol and the like, and then the CO products are conveyed to one or more working procedures of the steel enterprises for cyclic utilization, so that a carbon conversion cyclic utilization chain is realized, and the carbon emission of the steel process is greatly reduced. The invention also regulates and controls the proportion of the conversion product by matching the cost requirement and the carbon emission reduction requirement of the iron and steel enterprise, thereby realizing the comprehensive control of the iron and steel enterprise on the conversion cost and the carbon emission reduction. Based on the above, the invention also provides a catalyst and CO 2 A system matched with the method for converting and recycling. The system effectively connects all the working procedures of the steel process in series and introduces CO 2 Conversion center, realization of CO 2 The conversion and the cyclic utilization of the steel greatly reduce the carbon emission in the steel smelting process.
According to a first embodiment of the present invention, there is provided a CO iron and steel process 2 A method for converting and recycling.
Steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 the collection: of iron and steel enterprisesCO produced by one or more of the processes 2 Collecting to obtain enriched CO 2 A gas.
2)CO 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of the center to CO 2 And introducing a reducing medium into the conversion center to obtain CO.
3)CO 2 The recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling.
In the present invention, the reducing medium in step 2) is a reducing solid or a reducing gas. Preferably, the reducing solid is carbon and the reducing gas is H 2 。
In the invention, the step 2) is specifically as follows: enriched CO 2 Gas delivery to CO 2 Conversion of the center to CO 2 Introducing H into the conversion center 2 To obtain CO and methanol. Wherein: methanol is used as raw material and fuel for one or more processes in steel enterprises, or is output as a product.
Preferably, the step 1) further comprises pretreatment of flue gas of each process of iron and steel enterprises. The step 1) is specifically as follows: firstly, the flue gas generated in one or more procedures of iron and steel enterprises is subjected to dust removal, desulfurization and dehydration pretreatment to obtain purified flue gas. Then the purified flue gas of each procedure is subjected to CO 2 To obtain enriched CO 2 A gas.
Preferably, the humidity of the purified flue gas is < 1%, preferably < 0.5%. The content of sulfide in the purified flue gas is less than 35mg/Nm 3 Preferably < 30mg/Nm 3 . The dust content in the purified flue gas is less than 10mg/Nm 3 Preferably < 5mg/Nm 3 。
In the present invention, CO described in step 1) 2 The trapping is carried out by a temperature and pressure swing adsorption device. And a porous material loaded with a chemical absorbent is arranged in the temperature and pressure swing adsorption device. Preferably, the porous material is an aluminosilicate mesoporous material. The chemical absorbent is an alcamines reagent.
In the present invention, the step 2) is describedCO of (2) 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a converted substance gas-liquid separation and converted gas blending device. The hydrogen outlet of the hydrogen generating device is connected to CO 2 Hydrogen inlet of the reformer. CO 2 2 The converted substance outlet of the conversion device is connected to the converted substance inlet of the converted substance gas-liquid separation and converted gas blending device. Preferably, the hydrogen generating device is a green power-H 2 And (4) an O electrolysis device.
In the present invention, a green electron-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy. Green power-H 2 The O electrolysis device electrolyzes water to generate hydrogen and oxygen, and the hydrogen is conveyed to CO 2 The conversion center is used as a reducing medium, and oxygen is conveyed to one or more working procedures of the steel enterprises.
Preferably, oxygen is fed to a blast furnace or converter for oxyfuel combustion or injection, or oxygen is fed to a sintering machine for oxyfuel sintering.
Preferably, in step 1), high concentration CO is generated for each process of a steel enterprise 2 Trapping to remove low concentration CO 2 And discharging. Wherein the high concentration of CO 2 The volume fraction of the carbon dioxide is more than or equal to 12 percent, and the low concentration CO is 2 Volume fraction of < 12%. Preferably, high concentration of CO 2 Volume fraction of the carbon dioxide is more than or equal to 15 percent, and low concentration CO 2 Volume fraction of (2) is < 15%.
In step 1) of the present invention, CO generated in n processes of a steel enterprise 2 And (4) collecting. Wherein: n is 1 to 10, preferably 3 to 6.
In step 3) of the present invention, the CO obtained in step 2) is transported to m processes of the steel enterprise for recycling. Wherein: m is 1 to 12, preferably 3 to 8.
In the invention, the one or more processes of the steel enterprises in the steps 1) and 3) are one or more of a blast furnace process, a converter process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct reduction process.
In the present invention, CO 2 The conversion center containsWith CO 2 A conversion catalyst. The CO is 2 The conversion catalyst is a nickel-based or copper-based mesoporous catalytic material.
Preferably, the one or more steps of the iron and steel works in step 1) are one or more of a blast furnace step, a converter step, and a lime kiln step.
Preferably, the one or more steps of the iron and steel enterprise in step 3) are one or more of a blast furnace step, a lime kiln step, a sintering step, a pelletizing step, a coking step, and a straightening and reducing step.
In the present invention, CO generated in a certain process of a steel enterprise 2 Is less than 20% (preferably less than 15%) by volume, with respect to the CO produced in the process 2 Passing through an enrichment process and then delivering to CO 2 And (4) transformation centers.
Preferably, the enrichment process comprises: CO generated in one or more of blast furnace process, converter process, sintering process, pelletizing process, coking process and direct reduction process 2 Conveying the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 Then the enriched CO is added 2 To CO 2 A transformation center.
In the invention, CO is controlled in the whole steel smelting process 2 The selectivity of converting gas into CO is realized, thereby realizing CO conversion of iron and steel enterprises 2 Conversion cost and carbon emission control. The method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc 。
(2) According to CO 2 Selectivity of gas conversion to CO, calculating the amount M of CO produced by conversion in step 2) co 。
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco 。
(4) Calculating the discharge reduction amount of carbon in the whole steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The difference in cost Δ C of the conversion of the gas to CO and methanol.
(6) Calculating to obtain CO according to the cost target and/or the carbon emission reduction target of the iron and steel enterprise 2 The selectivity of the gas conversion into CO is controlled according to the obtained selectivity of CO in the step 2) 2 The technological conditions of the conversion are adopted, thereby realizing the CO-separation of the iron and steel enterprises 2 Conversion cost and carbon emission control.
In substep (1) of the present invention, said calculating the enriched CO obtained in step 1) is carried out 2 The total amount of gas is specifically as follows:
the consumption quantity of the g fossil fuel at the carbon input end of the ith process is F i,g . CO of the g-th fossil fuel 2 Direct emission factor of D g . The consumption quantity of the h power medium at the carbon input end of the ith procedure is DM i,h . CO of h-th power medium 2 Indirect emission factor is ID h . The number of the external pins of the jth energetic product at the ith procedure carbon output end is P i,j . CO of jth energetic product 2 Direct emission factor ND j . And (3) carrying out accounting according to the material energy balance of the input end and the output end to obtain:
in the formula: m is cc For the enriched CO obtained in step 1) 2 Total amount of gas. n is CO 2 The number of trapping steps. x is the number of fossil fuel types. And y is the type number of the power medium. z is the number of types of energetic products.
It should be noted that, in the present application, the amount of consumption of the g-th fossil fuel and the CO of the g-th fossil fuel 2 The unit of the product of the direct emission factors is a unit of mass (e.g., kg). For example, when the consumption amount of a certain fossil fuel is in kg, the CO of the fossil fuel is 2 The unit of the direct carbon emission factor is 1; when the consumption amount of a certain fossil fuel is in Nm 3 When CO of the fossil fuel 2 Direct carbonThe unit of the emission factor is kg/Nm 3 . Similarly, the consumed amount of the h-th power medium is equal to the amount of CO of the h-th power medium 2 The unit of the product of the indirect emission factors is mass units (e.g., kg). The export quantity of the jth energetic product and the CO of the jth energetic product 2 The unit of the product of the direct emission factors is a unit of mass (e.g., kg).
In substep (2) of the present invention, CO is set 2 The selectivity of the conversion of gas to CO being S co . Namely, the method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for the conversion to methanol path is K 1 ，CO 2 The equilibrium constant of the reaction for the conversion to CO route is K 2 . According to CO 2 The reaction formula for converting methanol and CO into methanol and CO comprises the following steps:
wherein: reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)；K 2 ＝f 2 (T). Comprises the following steps:
combining formulae (3) to (6) to give X CO 、X MeOH . Then combining the formula (2) to obtain S co 。
The amount of CO converted in step 2) is thus:
in formulae (2) to (7): x CO Is CO 2 Conversion to CO. X MeOH Is CO 2 Conversion to methanol. Beta is H 2 /CO 2 The ratio of (a) to (b). P General assembly Is the total reaction pressure. T is the reaction temperature. m is co The amount of CO formed in step 2). a is a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 And a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants.
In substep (3) of the present invention, the amount of CO entering the recycling step in step 3) is:
the consumption quantity of the g fossil fuel at the carbon input end of the s procedure is F s,g . The g-th fossil fuel conversion standard coal coefficient is C g . The consumption quantity of the h power medium at the carbon input end of the s procedure is DM s,h . The h power medium converts the standard coal coefficient into DC h . The amount of consumption of the w-th non-replaceable fossil fuel at the carbon input of the s-th process is IF s,w . The w type irreplaceable fossil fuel reduced standard coal coefficient is IC w . The number of the external pins of the jth energetic product at the carbon output end of the s procedure is P s,j . The conversion standard coal coefficient of the jth energetic product is PC j . The accounting is carried out according to the material energy balance of the input end and the output end, and the method comprises the following steps:
thus obtaining the following components:
in the formula: m is Lco The amount of CO entering the recycling process in step 3). Δ cH CO Is the heat of combustion of CO. Δ cH Marking coal The calorific value of the standard coal. And m is the number of CO recycling processes. x is the number of fossil fuel types. And y is the number of the types of the power media. l is the number of types of fossil fuels that cannot be replaced. z is the number of types of energetic products.
In the present application, the unit of the product of the consumed amount of the g-th fossil fuel and the reduced standard coal coefficient of the g-th fossil fuel is a unit of mass (for example, kg). Similarly, the unit of the product of the consumed amount of the h-th power medium and the h-th power medium converted standard coal coefficient is a mass unit (for example, kg). The unit of the product of the consumption quantity of the w-th irreplaceable fossil fuel and the converted standard coal coefficient of the w-th irreplaceable fossil fuel is a mass unit (for example, kg). The export quantity of the jth energetic product and the CO of the jth energetic product 2 The unit of the product of the direct emission factors is a unit of mass (e.g., kg).
In the substep (4) of the present invention, the carbon emission reduction amount in the whole steel smelting process is:
if m co ≤m Lco At this time
If m is co ＞m Lco At this time
In the formula:
the method is used for reducing the emission of carbon in the whole steel smelting process.
In substep (5) of the present invention, CO is introduced into the entire steelmaking process 2 The difference in the cost of converting the gas to CO and methanol is:
in the formula: delta C is CO in the whole steel smelting process 2 The difference in cost of converting the gas to CO and methanol. Δ P as unit CO 2 The cost difference of conversion to CO and methanol.
In substep (6) of the present invention, a target for carbon reduction of iron and steel enterprises is set to Δ E min The cost saving goal is Δ C min 。
Comprises the following steps:
ΔC≥ΔC min I.e. by
Preferably, the value Δ C = Δ C min Instant value of
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions at the conversion center. The reaction condition is that the iron and steel enterprises realize the lowest CO on the premise of achieving the aim of saving cost 2 The process conditions of the discharge.
If taking a value
Namely taking value
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions at the conversion center. The reaction condition is the process condition which can realize the most cost saving of steel enterprises on the premise of achieving the aim of carbon emission reduction.
If taking a value
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions at the conversion center. The reaction condition is to realize the CO treatment of the iron and steel enterprises on the premise of achieving the aim of saving cost and reducing carbon emission 2 The conversion cost and the carbon emission are comprehensively controlled.
According to a second embodiment of the present invention, there is provided a CO iron and steel process 2 And (4) a conversion and recycling system.
A CO as described for the first embodiment 2 System for converting a cyclic process, the system comprising CO 2 Conversion center, blast furnace, limekiln. CO 2 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a converted substance gas-liquid separation and converted gas blending device. The gas outlet of the blast furnace and the gas outlet of the lime kiln are both connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln. The hydrogen outlet of the hydrogen generating device is connected to CO 2 Hydrogen inlet of the reformer. CO 2 2 The converted substance outlet of the conversion device is connected to the converted substance inlet of the converted substance gas-liquid separation and converted gas blending device.
In the invention, the system also comprises a sintering machine, a rotary kiln, a coke oven, a converter and a straight ring furnace. The gas outlet of the blast furnace, the gas outlet of the lime kiln and the gas outlet of the converter are connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln and/or sintering machine and/or rotary kiln and/or coke oven and/or straight-ring furnace.
Preferably, the system further comprises CO 2 A pretreatment system. CO 2 2 The pretreatment system carries out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more procedures of iron and steel enterprises.
Preferably, the system further comprises a temperature and pressure swing adsorption unit. The gas outlets of the blast furnace, the lime kiln and the converter are all connected to CO 2 A pretreatment system. CO 2 2 Pretreatment ofThe gas outlet of the system is connected to the temperature and pressure swing adsorption device. CO of temp. -changing and pressure-changing adsorber 2 The gas outlet is connected to CO 2 CO of conversion center 2 A gas inlet.
In the invention, the gas outlet of the optional blast furnace, sintering machine, rotary kiln, coke oven, converter, straight ring furnace is connected to the gas inlet of the lime kiln. The gas outlet of the lime kiln is connected to CO 2 A pretreatment system. CO 2 2 The gas outlet of the pretreatment system is connected to the temperature and pressure swing adsorption device.
In the invention, the hydrogen generating device is a green electricity-H 2 And (4) an O electrolysis device. Green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to a blast furnace, a converter or a sintering machine.
In order to achieve the goals of 2030 year carbon peak reaching and 2060 year carbon neutralization, the action of carbon emission reduction in the steel industry of China is imperative at present. However, in the prior art, the path of replacing carbon in fossil fuel by renewable energy is difficult to realize in a short time, and the carbon in the fossil fuel plays several roles of fuel, reducing agent and material in the field of steel, so that a certain amount of carbon is required to participate in the metallurgical process. In addition, if pure hydrogen metallurgy is adopted, hydrogen reduction is an endothermic reaction process, so that the pure hydrogen metallurgy cannot be continued on the energy source, and carbon fuel supplement is needed to ensure that the metallurgy is continuously carried out.
Based on the method, the invention provides the CO in the steel process 2 A method for converting and recycling. The method adopts green energy driven CO 2 The method for converting and coupling the recycling of the steel working procedure is to collect CO in the smoke of one or more working procedures in the steel working procedure 2 And through CO 2 Conversion center converts CO 2 Adding reducing medium to convert into energy-containing products such as CO, methanol and the like, and then conveying the CO products to one or more working procedures of steel enterprises for recycling, thereby realizing the carbon conversion recycling chain, namely, by CO 2 And the conversion recycling mode partially replaces the source carbon input and reduces the tail end carbon emission, thereby greatly reducing the carbon emission of the steel process. The invention also matches the cost requirement and carbon emission reduction requirement of iron and steel enterprises to the conversion productThe proportion of the carbon-containing carbon is regulated and controlled, and further the comprehensive control of the steel enterprises on the conversion cost and the carbon emission reduction is realized. Correspondingly, the invention also provides a catalyst which is mixed with CO 2 A system matched with the method for converting and recycling. The system effectively connects all the working procedures of the steel process in series and introduces CO 2 Conversion center, realization of CO 2 The conversion and the cyclic utilization of the steel greatly reduce the carbon emission in the steel smelting process.
The invention takes the whole process of iron and steel smelting as a research object for the first time, and provides CO according to the characteristics of carbon emission and energy input at the tail end of each process of an iron and steel enterprise 2 Capture → CO 2 Transformation of → CO 2 The recycling process realizes the great reduction of carbon emission in the steel process. Specifically, the method comprises the steps of firstly, mixing CO in tail gas generated in one or more processes (such as a blast furnace process, a lime kiln process and a converter process) of a steel enterprise 2 Collecting to obtain enriched CO 2 A gas. Then, the enriched CO is introduced 2 Gas delivery to CO 2 Conversion of the center to CO 2 Introducing reducing medium into the conversion center to generate CO 2 CO is obtained by the conversion reaction of (1). Wherein, CO 2 The conversion center can utilize the waste heat of the plant to maintain the required high temperature, and is assisted by green energy to maintain the high-pressure environment, and CO 2 The conversion center is internally provided with a catalyst bed layer to ensure the process conditions of the high-temperature high-pressure catalyst required by the conversion reaction. Finally, the conversion product CO obtained by the reaction is conveyed to one or more processes (such as a blast furnace process and/or a lime kiln process and/or a sintering process) of the steel enterprise for recycling. The invention passes CO 2 The method has the advantages that the processes of the capture, the conversion and the cyclic utilization are realized, namely, a plurality of processes of the iron and steel enterprises are effectively connected in series, so that the conversion and cyclic utilization chain of carbon is realized, and the carbon emission of the iron and steel process is greatly reduced.
In the present invention, the enriched CO is 2 Gas and reducing medium delivery to CO 2 Conversion center, and CO 2 The conversion center maintains a high-temperature and high-pressure environment while in CO 2 The catalyst is arranged in the conversion center, i.e. for the purpose of CO 2 The conversion reaction takes place. The reducing medium comprising a reducing solid or reductionAnd (4) a sex gas. Wherein the reducing solid is mainly carbon. The reducing gas having predominantly H 2 . In general, CO 2 Gas and reducing medium (e.g. H) 2 ) The catalytic reaction product of (A) comprises CO, methanol and a small amount of by-products. Wherein, CO 2 The methanol conversion product of (a) can be used as a feedstock for one or more processes of a steel plant, as a fuel (e.g., methanol can be used as a fuel to supply hot blast stoves of a steel process), or alternatively, methanol can be exported as a product.
Generally, the CO in the flue gas (or tail gas) generated by each process of the steel enterprise is directly treated 2 Collecting the obtained CO 2 The gas tends to have a higher water content, while the CO is 2 The gas may be contaminated with other impurities such as sulfide and dust in the off-gas of each step, so that the present invention is carried out in the presence of CO 2 Before the capture, the flue gas generated in each process of the steel enterprise needs to be pretreated. The pretreatment mainly comprises the steps of dedusting, desulfurizing and dehydrating the flue gas in each process, and the purified flue gas is obtained after the pretreatment is finished. Then carrying out CO treatment on the purified flue gas of each procedure 2 To obtain enriched CO 2 A gas. To ensure capture of the resulting enriched CO 2 Purity of gas (e.g. CO) 2 Purity > 95%) and a smooth subsequent conversion reaction with a high conversion rate, in the present invention the humidity of the purified flue gas obtained after said pretreatment is < 1%, preferably < 0.5%. The content of sulfide in the purified flue gas is less than 35mg/Nm 3 Preferably < 30mg/Nm 3 . The dust content in the purified flue gas is less than 10mg/Nm 3 Preferably < 5mg/Nm 3 。
In the present invention, CO generated in each process of a steel enterprise 2 The trapping is carried out by adopting a chemical absorption and physical absorption cooperative separation method, and the adsorption material is a chemical absorbent modified porous material. Wherein the porous material is aluminosilicate mesoporous material, such as aluminosilicate molecular sieve or aluminosilicate sepiolite. The chemical absorbent is an alcohol amine reagent, such as primary amine (ethanolamine) MEA, secondary amine (diethanolamine) DEA, tertiary amine (N-methyl glycol amine) MDEA, polyNitrogen amine TETA (triethylene tetramine) or TEA (triethanolamine), or a mixture of several of the foregoing alcohol amine agents. The catching device is a temperature and pressure swing adsorption device connected in parallel, and the adsorption and desorption periods of the adsorption devices are staggered. The trapping method and the trapping device provided by the invention can reduce CO 2 Difficulty in trapping and acceleration of CO 2 The capture rate of (2) and the capture of CO 2 Is favorable for CO in the subsequent step 2 The conversion is recycled.
CO described in the present invention 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a converted substance gas-liquid separation and converted gas blending device. The hydrogen generating device is mainly used for generating H 2 ，H 2 Into CO 2 Conversion plant and enriched CO 2 The gas undergoes a conversion reaction of catalytic hydrogenation. In CO 2 In the conversion unit, CO 2 、H 2 Under the action of catalyst, converting into CO and methanol (CH) 3 OH) and small amounts of by-products (e.g. methane), the conversion product also being contaminated with small amounts of unreacted CO 2 And H 2 The mixed gas of (2). The converted product enters a converted substance gas-liquid separation and converted gas blending device, liquid phase mainly comprising methanol is separated firstly, most of the methanol is taken as hydrogen-carrying products or chemical raw materials and is conveyed outwards, a small part of the methanol can be taken as fuel and returned to each process of the steel enterprise (for example, the methanol is taken as fuel and is supplied to a hot blast stove of a steel process), and when the methanol is taken as the fuel in the blast furnace process, the methanol is preferably pure oxygen for combustion, which is beneficial to CO combustion 2 The capture cycle of (2). Second, CO is mixed 2 Roughly separated and recycled to CO 2 Transformation center, continued participation in CO 2 Conversion of (2), i.e. CO in the present invention 2 The conversion center adopts a tail gas circulation reaction mode, the conversion rate per pass is generally more than 25 percent, and the total conversion rate of multiple passes is more than 70 percent. Finally, CO and H remain 2 The mixed gas (i.e. gas phase mainly containing CO) is used as fuel to be distributed to one or more working procedures of the steel process for recycling, and can also be used as reducing agent to enter a blast furnace or a straight-ring furnace for reducing iron after being hydrogenated and proportioned. CO 2 2 CO of conversion center 2 The conversion device contains CO 2 Conversion catalyst of said CO 2 The conversion catalyst isA nickel-based or copper-based mesoporous catalytic material.
Preferably, the hydrogen generating device can select LVELECTRO-H 2 And (4) an O electrolysis device. Green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy. Green electricity-H 2 O electrolysis device for electrolyzing water to generate H 2 Supplying CO 2 Conversion plant for promoting CO 2 Conversion of the resulting O 2 The oxygen-enriched air is supplied to a blast furnace or a converter for oxygen-enriched combustion or oxygen-enriched blowing, and can also be supplied to a sintering machine for oxygen-enriched sintering.
In the present invention, CO 2 The trapped objects are mainly high-concentration tail gas generated in each process of iron and steel enterprises. Generally, high concentration CO generated in each process of a steel enterprise 2 Trapping to remove low concentration CO 2 The discharge is carried out, but the total amount of discharge does not exceed 500kg/t steel. Wherein the high concentration of CO 2 The volume fraction of the carbon dioxide is more than or equal to 12 percent, and the low concentration CO is 2 The volume fraction of (a) is less than 12%. Preferably, high concentration of CO 2 The volume fraction of the carbon dioxide is more than or equal to 15 percent, and the low concentration CO is 2 Volume fraction of (2) is < 15%. More preferably, the low concentration CO generated in a certain process of a steel enterprise 2 It is also possible to carry out CO by means of an enrichment process without venting 2 Increased concentration before delivery to CO 2 And (4) transformation centers. Or CO with higher concentration generated in each process of iron and steel enterprises 2 After the capture, the CO can be further improved through an enrichment process 2 After concentration, is delivered to CO 2 And (4) transformation centers. For example, CO produced in a certain process of a steel enterprise 2 Is less than 20% (preferably less than 15%) by volume, with respect to the CO produced in the process 2 Passing through an enrichment process and then delivering to CO 2 And (4) transformation centers. Thereby, CO can be further reduced 2 Ensuring CO in the total amount of emissions 2 The total emission amount does not exceed a specified range (for example, the total emission amount does not exceed 500kg/t steel), so that the low-carbon emission reduction of the whole steel process is realized.
The invention takes the whole steel process as a research object for the first time, and according to the carbon emission and energy output of each process end of the steel enterpriseThe characteristics that all the working procedures in the steel flow are effectively connected in series and CO is introduced 2 Conversion center, realization of CO 2 The carbon emission in the steel smelting process is greatly reduced by recycling. In step 1) of the present invention, CO generated in n process (one or more process) of a steel enterprise 2 Trapping is performed wherein n is 1-10, preferably 3-6, e.g. n =2 or 3 or 4 or 5. In step 3) of the present invention, the CO obtained in step 2) is transported to m processes (one or more processes) of the steel works and recycled. Wherein m is 1 to 12, preferably 3 to 8, for example m =1 or 2 or 3 or 4 or 5 or 6 or 7. In the invention, one or more of the processes of the steel enterprises in the steps 1) and 3) are one or more of a blast furnace process, a converter process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct reduction process (namely, a direct reduction process comprising a melting reduction process), wherein the blast furnace process, the converter process, the lime kiln process, the sintering process, the pelletizing process and the coking process are processes in a long steel smelting process, and the direct reduction process is a short steel smelting process. Preferably, step 1) CO 2 The one or more processes of the iron and steel enterprises in the collection process are one or more of a blast furnace process, a converter process, a lime kiln process and a direct reduction process, namely CO generated by the blast furnace process and/or the converter process and/or the lime kiln process and/or the direct reduction process 2 Collecting to obtain enriched CO 2 A gas. Step 3) CO 2 The recycling of the steel enterprises comprises one or more of a blast furnace process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct reduction process, namely, the conversion product CO obtained in the step 2) is conveyed to the blast furnace process and/or the lime kiln process and/or the sintering process and/or the pelletizing process and/or the coking process and/or the direct reduction process for recycling. Wherein, CO in tail gas generated in each process of iron and steel enterprises 2 The volume concentrations of (A) are respectively as follows: CO in tail gas generated by blast furnace process 2 Is about 15% by volume; CO in tail gas generated in converter process 2 Is about 18% by volume; CO in tail gas generated in lime kiln process 2 The volume concentration of (A) is generally > 20%; sintering stepCO in the generated tail gas 2 Is about 6% by volume; CO in tail gas generated in pelletizing process 2 Is about 6% by volume; CO in tail gas generated in coking process 2 Is about 3% by volume; CO in tail gas generated in direct reduction process 2 Is about 20% by volume.
In the present invention, CO generated in a certain process of a steel enterprise 2 At a concentration of less than 20% (preferably less than 15%) by volume, CO generated for this process 2 Passing through an enrichment process and then delivering to CO 2 And (4) transformation centers. The enrichment step herein refers to a step of generating CO in one or more of a blast furnace step, a converter step, a sintering step, a pelletizing step, a coking step, and a straightening step 2 Conveying the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 Then the enriched CO is added 2 To CO 2 Conversion centres, i.e. producing CO from one or more than one 2 CO is treated by the working procedure of the lime kiln in the working procedure with lower volume concentration 2 Enrichment is carried out, thereby increasing CO 2 Concentration to reduce CO 2 The trapping difficulty is favorable for improving the subsequent CO 2 The conversion efficiency of (2) and further reducing CO 2 The total emission amount of the steel can realize low carbon emission reduction of the whole steel process. In the enrichment process, CO may be produced 2 Directly conveying the flue gas discharged by one or more working procedures with lower volume concentration to a lime kiln working procedure, and then discharging CO in the flue gas discharged by the lime kiln working procedure 2 Collecting to obtain enriched CO 2 . Preferably, the CO is generated in consideration of the matching of the amount of flue gas 2 When the number of working procedures with low volume concentration is multiple, the working procedures of the lime kiln are difficult to enrich smoke of the multiple working procedures, and at the moment, CO in the smoke discharged by each working procedure is discharged firstly 2 Performing capture, and then collecting the captured CO 2 Conveying the flue gas to a lime kiln process, and discharging CO in the flue gas to the lime kiln process 2 Collecting to obtain enriched CO 2 Thereby increasing CO 2 And (4) concentration.
The invention also regulates and controls the proportion of the conversion products by matching the cost requirement and the carbon emission reduction requirement of the iron and steel enterprises, thereby realizing the comprehensive control of the iron and steel enterprises on the conversion cost and the carbon emission reduction. In the present invention, the conversion reactions involved mainly include the following three reactions:
of the three reactions, the first two are thermodynamically independent and competing with each other, and are the main two paths for determining the selectivity of the catalyst, so that the subsequent reactions (one) and (two) are controlled as independent reactions, wherein the reactants and the products are all in the form of gas. The selectivity of the products of the two conversion paths can be controlled between 20% and 80%. According to the reaction heat and the change of the reaction volume, generally speaking, the temperature rise and pressure reduction is beneficial to the reaction in the CO direction, and the temperature fall and pressure rise is beneficial to the CH direction 3 The OH direction reaction proceeds. In terms of the reactant metering ratio, H 2 /CO 2 The lower the ratio, the more favorable the CO production.
In the whole steel smelting process, CO is controlled 2 The selectivity of converting gas into CO is realized, thereby realizing CO conversion of iron and steel enterprises 2 Control of conversion cost and carbon emissions; the method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc ；
(2) According to CO 2 Selectivity of gas conversion to CO, calculating the amount m of CO generated by conversion in step 2) co ；
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco ；
(4) Computer wholeCarbon emission reduction amount in steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The cost difference delta C of the CO and the methanol converted from the gas;
(6) calculating to obtain CO according to the cost target and/or the carbon emission reduction target of the iron and steel enterprise 2 The selectivity of the gas conversion into CO is controlled according to the obtained selectivity of CO in the step 2) 2 The technological conditions of the conversion are adopted, thereby realizing the CO-separation of the iron and steel enterprises 2 Conversion cost and carbon emission control.
Wherein, in the substep (1), the enriched CO obtained in the step 1) is calculated by calculating carbon chain circulating substances and energy balance 2 Total amount of gas. The carbon emission accounting and the material energy balance accounting of the fossil fuel at the carbon input end, the power medium and the energetic product at the carbon output end of each process are carried out, and the method comprises the following steps:
in the formula: m is cc For the enriched CO obtained in step 1) 2 Total amount of gas. n is CO 2 Number of capturing processes, the CO 2 The collecting process is one or more of a blast furnace process, a converter process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct reduction process, and preferably one or more of a blast furnace process, a converter process and a lime kiln process. x is the type number of fossil fuel, and the fossil fuel is one or more of coke, coal powder, standard coal, anthracite, bituminous coal, clean coal, coke oven gas and natural gas. y is the type and number of the power media, and the power media are other power media such as electric power or steam. z is the variety and the number of energy-containing products, and the energy-containing products are one or more of molten iron, coal gas ash, residual energy power generation, blast furnace gas, tar, crude benzene, coke oven gas and coke.
In the substep (2), CO is set 2 Gas conversionSelectivity to CO being S co . Namely, the method comprises the following steps:
setting of CO 2 The equilibrium constant of the reaction for the conversion to methanol path is K 1 ，CO 2 The equilibrium constant of the reaction for the conversion to CO route is K 2 According to the aforementioned CO 2 The reaction formulas (I) and (II) for converting methanol and CO into methanol and CO are as follows:
in CO 2 In the reaction of conversion to methanol or CO, the partial pressure of each component is determined by the total reaction pressure P General assembly 、H 2 /CO 2 Ratio of beta to CO 2 Conversion X into methanol MeOH 、CO 2 Conversion X to CO CO Obtaining the following components:
and reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)，K 2 ＝f 2 (T), the specific relational expression is obtained by experimental test fitting and comprises the following components:
in the formula: a is 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 And a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants. Value of each fitting coefficient and CO 2 Associated with conversion catalysts, i.e. selection of CO 2 After conversion of the catalyst, a 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 And a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 The value of (b) is a constant value. For example, selecting CO 2 The conversion catalyst is a copper-based mesoporous catalytic material, and the value of each fitting coefficient is a 1 ＝-152.7,b 1 ＝27169.2,d 1 ＝0.152,g 1 ＝-4.17,c 1 ＝h 1 ＝j 1 =0; and a 2 ＝79.1,b 2 ＝-56500.7,c 2 ＝14.3,g 2 ＝-2.36,d 2 ＝h 2 ＝j 2 ＝0。
Establishing K (T), X according to formulas (3) - (6) CO 、X MeOH 、β、P General assembly Functional relationship between them, namely X CO And X MeOH With respect to T, beta, P, respectively General assembly By changing the reaction temperature T, H 2 /CO 2 Beta and total reaction pressure P General assembly Namely X under different conditions can be obtained CO And X MeOH The value of (c). Then combining with the formula (2) to obtain S co 。
Thus, the amount m of CO formed by the conversion in step 2) co Comprises the following steps:
in substep (3), the mass energy balance calculation of the carbon input end fossil fuel, the power medium, the irreplaceable fossil fuel and the carbon output end energetic product of each process is carried out, and then the following steps are obtained:
in the formula: m is Lco The amount of CO entering the recycling process in step 3). m is the number of CO recycling procedures, and the CO recycling procedures are one or more of a blast furnace procedure, a lime kiln procedure, a sintering procedure, a pelletizing procedure, a coking procedure and a direct reduction procedure. x is the type and quantity of fossil fuel, and as mentioned above, the fossil fuel is one or more of coke, pulverized coal, standard coal, anthracite, bituminous coal, clean coal, coke oven gas and natural gas. y is the type and number of the power media, and the power media are other power media such as electric power or steam. l is the number of types of irreplaceable fossil fuels, which mainly consider the coke of the blast furnace process, the solid fuel of the sintering process (e.g. coke powder). z is the type and number of the energy-containing products, and as mentioned above, the energy-containing products are one or more of molten iron, coal gas ash, residual energy power generation, blast furnace gas, tar, crude benzene, coke oven gas and coke.
In substep (4), if m co ≤m Lco At this time
I.e. the amount m of CO formed when converting in step 2) co Not more than the amount m of CO entering the recycling process in the step 3) Lco In the process, the total amount of CO generated by conversion is recycled to meet the energy supply required by one or more processes (such as a blast furnace process and a lime kiln process) of the steel enterprises, and the rest CO is recycled 2 Are all converted to methanol for sequestration without additional carbon emissions, i.e. CO captured in step 1) 2 The total amount of gas does not need to be discharged, thereby realizing the lowest carbon emission of steel enterprises.
If m co ＞m Lco At this time
I.e. when the amount m of CO formed by conversion in step 2) co More than m of CO entering the recycling process in the step 3) Lco In the meantime, the amount of CO converted at this time is partly recycled in one or more steps of the iron and steel enterprise, and the CO corresponding to the part of CO which is not recycled in the recycling step 2 The amount of (C) is then required to be discharged, in which case the CO discharged is 2 In an amount of
Thus, the carbon reduction amount at this time is obtained by equation (10).
In the substep (5), according to the aforementioned equations (one) and (two), it is considered that both the CO and methanol reaction paths are in the reaction direction of gas volume reduction, and high-temperature and high-pressure conditions are required, and both of them generally exist together as a main and side reaction, and the reaction conditions of both can be approximately considered to be equal. The CO pathway endotherms 41kJ/mol while consuming 1 unit of H 2 The methanol route exothermed 49kJ/mol and consumed 3 units of H 2 . From the energy perspective, the CO path is lower in cost and higher in energy efficiency. Thus, according to the unit CO 2 The cost difference delta P of the CO and the methanol is converted to obtain the CO in the whole steel smelting process 2 The difference in cost Δ C of the gas converted to CO and methanol is:
in substep (6), it is considered that when the CO product enters some process other than the blast furnace and the lime kiln, the CO will be finally used 2 The form of (A) produces carbon emissions, and therefore, on the basis of the aforementioned lower cost analysis of the CO pathway, there is still a need to consider CO in combination therewith 2 And (5) emission reduction. The cost difference Δ C and carbon emission reduction can be seen by combining the formulas (10) and (11)
Respectively with CO 2 Selective conversion of S to CO co Is in direct inverse proportion, as shown in figure 6When the cost saving and carbon emission reduction limit range of a given steel enterprise is given, the selectivity S of CO is determined co And (3) a range.
Setting the carbon emission reduction target of iron and steel enterprises to be delta E min Here, the carbon reduction target Δ E min The method is the lower limit of the carbon emission reduction target of the enterprise, namely the minimum carbon emission reduction amount required by the enterprise. Setting a cost saving target to Δ C min At this time, the cost saving target Δ C min The lower limit of the cost saving target for the enterprise, namely the lowest cost saving that the enterprise wants to achieve. Namely, the method comprises the following steps:
ΔC≥ΔC min I.e. by
If the value is Δ C = Δ C min Instant value of
By combining the above formulas (2) to (6), CO can be calculated 2 Reaction conditions in the conversion center. At this time, CO in iron and steel enterprises 2 The cost difference of the converted CO and the methanol just reaches the lower limit of the cost saving target of the enterprise, and the attached figure 6 shows that when the cost difference is at the lower limit of the cost saving target, the carbon emission reduction in the steel process reaches the maximum value, namely the reaction condition is that the lowest CO is realized by the steel enterprise on the premise of reaching the cost saving target 2 The process conditions of the discharge.
CO as described herein 2 The reaction conditions of the conversion center mainly comprise total reaction pressure, reaction temperature and H 2 /CO 2 In the ratio of (A) to (B), e.g. in total reaction pressure and H 2 /CO 2 When the ratio of (A) to (B) is determined, the range of the reaction temperature can be determined.
If taking a value
Namely taking value
Combining the formulas (2) to (6) again, and calculating to obtain CO 2 Reaction conditions at the conversion center. At this time, the carbon emission reduction amount of the iron and steel enterprise just reaches the lower limit of the carbon emission reduction target of the enterprise, and as can be seen by combining with the attached figure 6, when the carbon emission reduction amount is at the lower limit of the carbon emission reduction target, at this time, CO in the iron and steel process flows 2 The difference value of the cost of converting into CO and methanol reaches the maximum value, namely the reaction condition is the process condition which realizes the lowest cost saving for the steel enterprises on the premise of reaching the carbon emission reduction target, namely the reaction condition is the process condition which realizes the lowest hydrogen consumption for the steel enterprises.
If taking a value
Then combining the formulas (2) - (6), calculating to obtain CO 2 Reaction conditions in the conversion center. At the moment, the steel enterprise realizes the proportion regulation of the conversion product by matching the cost requirement and the carbon emission reduction requirement of the steel enterprise, so that the balance optimal value of the conversion cost and the carbon emission reduction is achieved, namely the steel enterprise realizes the CO regulation on the premise that the reaction condition is that the cost saving goal and the carbon emission reduction goal are achieved 2 The conversion cost and the carbon emission are comprehensively controlled.
The invention also provides a method for preparing the CO 2 System for converting a cyclic process, the system comprising CO 2 Conversion center, blast furnace, limekiln. CO 2 2 The conversion center comprises a hydrogen generating device and CO 2 A conversion device, a converted substance gas-liquid separation and converted gas blending device. The gas outlet of the blast furnace and the gas outlet of the lime kiln are both connected to CO 2 CO of the conversion center 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln. The hydrogen outlet of the hydrogen generating device is connected to CO 2 Hydrogen inlet of the reformer. CO 2 2 The converted substance outlet of the conversion device is connected with the converted substance inlet of the converted substance gas-liquid separation and converted gas blending device. In the system, CO produced by blast furnace and lime kiln 2 Collected and then transported to CO 2 Center of transformation, CO 2 In CO 2 CO of the conversion center 2 H generated by the hydrogen generator in the converter 2 Carrying out CO 2 Conversion reaction of CO 2 And the product CO obtained by conversion is separated and blended by a converted substance gas-liquid separation and converted gas blending device and is supplied to a blast furnace or a lime kiln for recycling. By CO 2 And the conversion recycling mode partially replaces the source carbon input and reduces the tail end carbon emission, thereby greatly reducing the carbon emission in the steel process.
It is to be noted that CO described in the present invention 2 CO of conversion center 2 The gas inlet means CO 2 CO of the conversion plant 2 Gas inlet, CO 2 The CO gas outlet of the conversion center is the CO gas outlet of the converted product gas-liquid separation and converted gas blending device.
Preferably, the system further comprises a sintering machine, a rotary kiln, a coke oven, a converter and a straight ring furnace. The gas outlet of the blast furnace, the gas outlet of the lime kiln and the gas outlet of the converter are connected to CO 2 CO of conversion center 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion center is connected to the gas inlet of the blast furnace and/or lime kiln and/or sintering machine and/or rotary kiln and/or coke oven and/or straight-ring furnace. The invention takes the whole steel smelting process as a research object, effectively connects all the processes of the steel smelting process in series according to the characteristics of carbon emission and energy input at the tail end of each process of a steel enterprise, realizes a carbon conversion recycling chain, and greatly reduces the carbon emission in the steel smelting process.
In the present invention, the system further comprises CO 2 A pretreatment system. CO 2 2 The pretreatment system is mainly used for carrying out dust removal, desulfurization and dehydration pretreatment on the flue gas generated in one or more working procedures of iron and steel enterprises, and obtaining purified flue gas after pretreatment. CO described in the present invention 2 The trapping is carried out by a temperature and pressure swing adsorption device which carries out CO on the purified flue gas 2 To obtain high-purity enriched CO 2 A gas. The pretreatment, the capture and the enrichment of the flue gas are beneficial to the smooth proceeding of the subsequent conversion reaction and the improvement of the conversion efficiency.
In the present invention, CO produced in one or more steps of a steel enterprise 2 When the concentration is low, the CO may be discharged without being trapped, or CO of a low concentration may be discharged through a lime kiln process 2 Enrichment is carried out, and then the subsequent CO is participated in 2 And (4) capturing and converting the gas for cyclic utilization. In the system of the present invention, CO is carried out by a lime kiln process 2 Enrichment of (i) that will produce a lower concentration of CO 2 The gas outlet of the device corresponding to the working procedure (for example, the gas outlet of an optional blast furnace, a sintering machine, a rotary kiln, a coke oven, a converter or a straight-ring furnace) is connected with the gas inlet of the lime kiln, and the gas is enriched in the lime kiln and then connected with the subsequent CO 2 A pretreatment system and a temperature and pressure swing adsorption device. This arrangement enables the use of lower concentrations of CO 2 Utilization of, CO is reduced 2 The total emission amount of the steel is further ensured, and the low-carbon emission of the steel process is further ensured.
In the present invention, the hydrogen generating device is preferably a green power-H 2 And (4) an O electrolysis device. Green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to a blast furnace or a converter for oxygen-enriched combustion/blowing. Or, green electricity-H 2 And an oxygen outlet of the O electrolysis device is connected to the sintering machine and used for oxygen-enriched sintering.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention takes the whole process of iron and steel smelting as a research object for the first time, and provides CO according to the characteristics of carbon emission and energy input at the tail end of each process of an iron and steel enterprise 2 Capture → CO 2 Transformation of → CO 2 The recycling process realizes the great reduction of carbon emission in the steel process.
2. The invention proposes to react with CO 2 The system is matched with a conversion recycling method, and effectively connects all working procedures of the steel process in series and introduces CO 2 The conversion center realizes the conversion and cyclic utilization chain of carbon and greatly reduces the carbon emission in the steel smelting process.
3. The invention realizes CO by matching the cost requirement and/or the carbon emission requirement of the iron and steel enterprise 2 The proportion of the conversion product is regulated and controlled, so that the comprehensive control of the iron and steel enterprises on the conversion cost and the carbon emission is realized, and the balance optimal value of the conversion cost and the carbon emission of the enterprises is reached.
4. The technology of the invention is suitable for CO in the traditional steel smelting process 2 Reduction of emission by CO 2 The conversion and cyclic utilization mode partially replaces the source carbon input and reduces the tail end carbon emission, and has wide application range and large market potential.
5. CO in the present invention 2 The trapping object is mainly high-concentration tail gas of each process, and the conversion product returns to each process for recycling, so that the trapping difficulty can be reduced, the direction of the conversion product is flexibly regulated and controlled, and the method is easy to realize in engineering implementation.
Drawings
FIG. 1 shows a CO process for producing steel according to the present invention 2 A flow diagram of a method of conversion recycling;
FIG. 2 is CO of the process of the present invention 2 A flow diagram for including methanol in the conversion product;
FIG. 3 is a flow chart of the method of the present invention including the steps of pretreatment of the flue gas;
FIG. 4 shows the total process CO of steel production in the present invention 2 A flow chart of conversion and cyclic utilization;
FIG. 5 is a flow chart of the conversion cost and carbon emission control of the iron and steel enterprises of the present invention;
FIG. 6 shows CO in the present invention 2 The selectivity of the CO, the conversion cost difference and the carbon emission are converted into a relational graph;
FIG. 7 shows a process for producing CO 2 The structural schematic diagram of the system for conversion recycling;
FIG. 8 shows another CO production process for steel according to the present invention 2 The structural schematic diagram of the system for conversion recycling;
FIG. 9 shows a system of the present invention with CO 2 The structure schematic diagram of the pretreatment system and the temperature and pressure swing adsorption device;
FIG. 10 shows the production of lower concentrations of CO in the system of the present invention 2 The step (2) is to carry out CO by a lime kiln step 2 Schematic diagram of enrichment.
Reference numerals:
a1: a blast furnace; a2: a lime kiln; a3: sintering machine; a4: a rotary kiln; a5: a coke oven; a6: a converter; a7: a straight-ring furnace; a8: CO 2 2 A pre-treatment system; a9: a temperature and pressure swing adsorption unit; z: CO 2 2 A transformation center; 1: a hydrogen generating device; 2: CO 2 2 A conversion device; 3: a converted substance gas-liquid separation and converted gas blending device.
Detailed Description
The technical solution of the present invention is illustrated below, and the claimed scope of the present invention includes, but is not limited to, the following examples.
According to a second embodiment of the present invention, there is provided a CO iron and steel process 2 And (4) a conversion and recycling system.
A CO as described for the first embodiment 2 System for converting a cyclic process, the system comprising CO 2 A conversion center Z, a blast furnace A1 and a lime kiln A2.CO 2 2 The reforming center Z comprises a hydrogen generating device 1 and CO 2 A conversion device 2 and a converted substance gas-liquid separation and converted gas blending device 3. The gas outlet of the blast furnace A1 and the gas outlet of the lime kiln A2 are connected to CO 2 CO conversion of center Z 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion centre Z is connected to the gas inlet of the blast furnace A1 and/or the lime kiln A2. The hydrogen outlet of the hydrogen generating device 1 is connected to CO 2 Hydrogen inlet of the reformer 2.CO 2 2 The converted substance outlet of the conversion device 2 is connected to the converted substance inlet of the converted substance gas-liquid separation and converted gas blending device 3.
In the invention, the system also comprises a sintering machine A3, a rotary kiln A4, a coke oven A5, a converter A6 and a straight-ring furnace A7. The gas outlet of the blast furnace A1, the gas outlet of the lime kiln A2 and the gas outlet of the converter A6 are connected to CO 2 CO conversion of center Z 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion center Z is connected to the gas of a blast furnace A1 and/or a lime kiln A2 and/or a sintering machine A3 and/or a rotary kiln A4 and/or a coke oven A5 and/or a straight-ring furnace A7A body inlet.
Preferably, the system further comprises CO 2 Pretreatment system A8.CO 2 2 The pretreatment system A8 is used for carrying out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more procedures of iron and steel enterprises.
Preferably, the system further comprises a temperature and pressure swing adsorption unit A9. The gas outlets of the blast furnace A1, the lime kiln A2 and the converter A6 are all connected to CO 2 Pretreatment system A8.CO 2 2 The gas outlet of the pretreatment system A8 is connected to the temperature and pressure swing adsorption device A9. CO of temperature and pressure swing adsorption plant A9 2 The gas outlet is connected to CO 2 CO conversion of the centre Z 2 A gas inlet.
In the present invention, the gas outlets of the optional blast furnace A1, sintering machine A3, rotary kiln A4, coke oven A5, converter A6, and straight-ring furnace A7 are connected to the gas inlet of the lime kiln A2. The gas outlet of the lime kiln A2 is connected to CO 2 Pretreatment system A8.CO 2 2 The gas outlet of the pretreatment system A8 is connected to the temperature and pressure swing adsorption device A9.
In the present invention, the hydrogen generating apparatus 1 is a green power-H 2 And (4) an O electrolysis device. Green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to a blast furnace A1, a converter A6 or a sintering machine A3.
Example 1
As shown in FIG. 7, a process for producing steel CO 2 A system for conversion recycling, the system comprising CO 2 A conversion center Z, a blast furnace A1 and a lime kiln A2.CO 2 2 The reforming center Z comprises a hydrogen generating device 1 and CO 2 A conversion device 2 and a converted substance gas-liquid separation and converted gas blending device 3. The gas outlet of the blast furnace A1 and the gas outlet of the lime kiln A2 are connected to CO 2 CO conversion of center Z 2 A gas inlet. CO 2 2 The CO gas outlet of the conversion center Z is connected to the gas inlets of the blast furnace A1 and the lime kiln A2. The hydrogen outlet of the hydrogen generating device 1 is connected to CO 2 Hydrogen inlet of the reformer 2.CO 2 2 The converted substance outlet of the conversion device 2 is connected to the converted substance inlet of the converted substance gas-liquid separation and converted gas blending device 3. The CO is 2 CO conversion of center Z 2 Gas inlet means CO 2 CO of the conversion plant 2 2 Gas inlet, CO 2 The CO gas outlet of the reforming center Z is the CO gas outlet of the reformate gas-liquid separation and reformed gas blending device 3.
Example 2
As shown in fig. 8, example 1 was repeated except that the system further included a sintering machine A3, a rotary kiln A4, a coke oven A5, a rotary kiln A6, and a straight ring furnace A7. The gas outlet of the blast furnace A1, the gas outlet of the lime kiln A2 and the gas outlet of the converter A6 are connected to CO 2 CO conversion of center Z 2 A gas inlet. CO 2 2 And a CO gas outlet of the conversion center Z is connected with gas inlets of a blast furnace A1, a lime kiln A2, a sintering machine A3, a rotary kiln A4, a coke oven A5 and a straight-loop furnace A7.
Example 3
Example 2 is repeated, as shown in FIG. 9, except that the system further comprises CO 2 Pretreatment system A8.CO 2 2 The pretreatment system A8 carries out dust removal, desulfurization and dehydration pretreatment on the flue gas generated in the blast furnace process, the lime kiln process and the converter process of the iron and steel enterprise.
Example 4
Example 3 was repeated except that the system further included a temperature and pressure swing adsorption unit A9. The gas outlets of the blast furnace A1, the lime kiln A2 and the converter A6 are all connected to CO 2 Pretreatment system A8.CO 2 2 The gas outlet of the pretreatment system A8 is connected to the temperature and pressure swing adsorption device A9. CO of temperature and pressure swing adsorption plant A9 2 The gas outlet is connected to CO 2 CO conversion of center Z 2 A gas inlet.
Example 5
As shown in fig. 10, example 4 was repeated except that the gas outlets of the sintering machine A3, rotary kiln A4, coke oven A5, and straight-ring furnace A7 were connected to the gas inlet of lime kiln A2. The gas outlet of the lime kiln A2 is connected to CO 2 Pretreatment system A8.CO 2 2 The gas outlet of the pretreatment system A8 is connected to the temperature and pressure swing adsorption device A9.
Example 6
Example 4 was repeated except that the hydrogen generating apparatus 1 was a green power-H 2 And (4) an O electrolysis device. Green power-H 2 Oxygen outlet of O electrolysis deviceAre connected to blast furnace A1 and converter A6, respectively.
Example 7
Example 5 was repeated except that the hydrogen generating apparatus 1 was a green power-H 2 And (4) an O electrolysis device. Green electricity-H 2 The oxygen outlet of the O electrolysis device is connected to the sintering machine A3.
Example 8
As shown in figure 1, a steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 the collection: CO generated by one or more processes of iron and steel enterprises 2 Collecting to obtain enriched CO 2 A gas.
2)CO 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of center Z to CO 2 And introducing a reducing medium into the transformation center Z to obtain CO.
3)CO 2 The recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling.
Example 9
As shown in FIG. 2, a process for producing steel CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 the collection: CO generated by one or more processes of iron and steel enterprises 2 Collecting to obtain enriched CO 2 A gas.
2)CO 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of center Z to CO 2 And introducing a reducing medium into the conversion center Z to obtain CO and methanol. Wherein: methanol is used as a raw material and a fuel for one or more processes in iron and steel enterprises.
3)CO 2 The recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling.
Example 10
As shown in FIG. 3, a steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 the collection: firstly, the flue gas generated in one or more procedures of iron and steel enterprises is subjected to dust removal, desulfurization and dehydration pretreatment to obtain purified flue gas. Then the purified flue gas of each procedure is subjected to CO 2 To obtain enriched CO 2 A gas.
The humidity of the purified flue gas is less than 0.5%. The content of sulfide in the purified flue gas is less than 30mg/Nm 3 . The dust content in the purified flue gas is less than 5mg/Nm 3 。
2)CO 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of center Z to CO 2 And introducing a reducing medium into the conversion center Z to obtain CO and methanol. Wherein: methanol is output as a product.
3)CO 2 The recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling.
Example 11
Example 10 was repeated, except that in step 2) the reducing agent was carbon.
Example 12
Example 10 is repeated, except that in step 2) the reducing medium is a reducing gas H 2 。
Example 13
Example 12 is repeated, except that the CO described in step 1) 2 The trapping is carried out by a temperature and pressure swing adsorption device. And a porous material loaded with a chemical absorbent is arranged in the temperature and pressure swing adsorption device. The porous material is an aluminosilicate molecular sieve. The chemical absorbent is primary amine (ethanolamine) MEA in the alcohol amine reagent.
Example 14
Example 13 is repeated except that the porous material is an aluminosilicate sepiolite.
Example 15
Example 13 is repeated, except that the CO described in step 2) 2 The reforming center Z comprises a hydrogen generating device 1 and CO 2 A conversion device 2 and a converted substance gas-liquid separation and converted gas blending device 3. The hydrogen outlet of the hydrogen generating device 1 is connected to CO 2 Hydrogen inlet of the reformer 2.CO 2 2 The converted substance outlet of the conversion device 2 is connected to the converted substance inlet of the converted substance gas-liquid separation and converted gas blending device 3. The hydrogen generating device 1 is a green power-H 2 And (4) an O electrolysis device. CO 2 2 The conversion center Z contains CO 2 A conversion catalyst. The CO is 2 The conversion catalyst is a copper-based mesoporous catalytic material.
Example 16
Example 15 was repeated except that the CO was 2 The conversion catalyst is a nickel-based mesoporous catalytic material.
Example 17
As shown in fig. 4, example 15 is repeated except that one or more processes of the iron and steel works in step 1) and step 3) include a blast furnace process, a converter process, a lime kiln process, a sintering process, a pelletizing process, a coking process, and a straightening and returning process.
Example 18
Example 17 was repeated except that in step 1), high concentration CO was generated for each process of the iron and steel works 2 Trapping to remove low concentration CO 2 And discharging. Wherein the high concentration of CO 2 The volume fraction of the carbon dioxide is more than or equal to 12 percent, and the low concentration CO is 2 Volume fraction of < 12%.
Example 19
Example 17 was repeated except that in step 1), high concentration CO was generated for each process of the iron and steel works 2 Trapping to remove low concentration CO 2 And discharging. Wherein the high concentration of CO 2 Volume fraction of the carbon dioxide is more than or equal to 15 percent, and low concentration CO 2 Volume fraction of (2) is < 15%.
Example 20
Example 18 was repeated except that in step 1), CO generated in 2 steps of the blast furnace step and the lime kiln step of the iron and steel works was used 2 And (4) collecting.
In step 3), the CO obtained in step 2) is transported to 2 steps of a blast furnace step and a lime kiln step of the steel enterprise for recycling.
Example 21
Example 19 was repeated except that in step 1), steel was treatedCO produced in 3 steps of blast furnace process, lime kiln process and converter process of enterprises 2 And (4) collecting.
In the step 3), the CO obtained in the step 2) is conveyed to 6 processes of a blast furnace process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct reduction process of the iron and steel enterprise for recycling.
Example 22
Example 19 was repeated except that in step 1), CO generated in 4 steps of the blast furnace step, lime kiln step, converter step and direct reduction step of the iron and steel works was used 2 And (4) collecting.
In the step 3), the CO obtained in the step 2) is conveyed to 6 processes of a blast furnace process, a lime kiln process, a sintering process, a pelletizing process, a coking process and a direct reduction process of the iron and steel enterprise for recycling.
Example 23
Example 22 was repeated except that CO generated in each of the sintering step, the pelletizing step and the coking step of the iron and steel works was used 2 Is less than 15% by volume, with respect to the CO produced in the corresponding process 2 Passing through an enrichment process and then delivering to CO 2 The transformation center Z. Namely CO generated in the sintering process, the pelletizing process and the coking process 2 Conveying the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 Then the enriched CO is added 2 To CO 2 The transformation center Z.
Example 24
Example 15 was repeated except that the electron-H was changed to green 2 The O electrolysis device is a device for electrolyzing water by utilizing solar energy and wind energy. Green electricity-H 2 The O electrolysis device electrolyzes water to generate hydrogen and oxygen, and the hydrogen is conveyed to CO 2 The conversion center Z is used as a reducing medium, and oxygen is conveyed to a blast furnace and a converter of a steel enterprise for oxygen-enriched combustion and oxygen-enriched blowing.
Example 25
Example 24 was repeated except that oxygen was fed to the sintering machine for oxygen-rich sintering.
Example 26
A kind ofIron and steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 the trapping: CO generated by one or more processes of iron and steel enterprises 2 Collecting to obtain enriched CO 2 A gas.
2)CO 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of centre Z to CO 2 Introduction of H into the transformation center Z 2 And obtaining CO.
3)CO 2 The recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling.
As shown in FIG. 5, CO is controlled in the whole iron and steel smelting process 2 The selectivity of converting gas into CO is realized, thereby realizing CO conversion of iron and steel enterprises 2 Conversion cost and carbon emission control. The method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc 。
(2) According to CO 2 Selectivity of gas conversion to CO, calculating the amount m of CO generated by conversion in step 2) co 。
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco 。
(4) Calculating the carbon emission reduction in the whole steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The difference in cost Δ C of the conversion of the gas to CO and methanol.
(6) Calculating to obtain CO according to the cost target and the carbon emission reduction target of the iron and steel enterprise 2 The selectivity of the gas conversion into CO is controlled according to the obtained selectivity of CO in the step 2) 2 The technological conditions of the conversion are realized, thereby realizing the CO treatment of the iron and steel enterprises 2 Conversion cost and carbon emission control.
Example 27
Example 26 was repeated except that in substep (1),calculating the enriched CO obtained in step 1) 2 The total amount of gas is specifically as follows:
the consumption quantity of the g fossil fuel at the carbon input end of the ith process is F i,g . CO of the g-th fossil fuel 2 Direct discharge factor is D g . The consumption quantity of the h power medium at the carbon input end of the ith procedure is DM i,h . CO of h-th power medium 2 Indirect emission factor is ID h . The external sales quantity of the jth energetic product at the ith procedure carbon output end is P i,j . CO of jth energetic product 2 Direct emission factor ND j . And (3) carrying out accounting according to the material energy balance of the input end and the output end to obtain:
in the formula: m is cc For the enriched CO obtained in step 1) 2 Total amount of gas. n is CO 2 The number of trapping steps. x is the number of fossil fuel types. And y is the number of the types of the power media. z is the number of types of energetic products.
Example 28
Example 27 was repeated except that in substep (2), CO was set 2 The selectivity of the conversion of gas to CO being S co . Namely, the method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for the conversion to methanol path is K 1 ，CO 2 The equilibrium constant of the reaction for the conversion to CO route is K 2 . According to CO 2 The reaction formula for converting methanol and CO into methanol and CO comprises the following steps:
wherein: reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)；K 2 ＝f 2 (T). Comprises the following steps:
combining formulae (3) to (6) to give X CO 、X MeOH . Then combining the formula (2) to obtain S co 。
The amount of CO converted in step 2) is thus:
in formulae (2) to (7): x CO Is CO 2 Conversion to CO. X MeOH Is CO 2 Conversion to methanol. Beta is H 2 /CO 2 The ratio of (a) to (b). P General assembly Is the total reaction pressure. T is the reaction temperature. m is co The amount of CO formed in step 2). a is 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 And a is 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants.
Example 29
Example 28 was repeated except that in substep (3), the amount of CO entering the recycling step in said substep 3) was:
the consumption quantity of the g fossil fuel at the carbon input end of the s procedure is F s,g . The g-th fossil fuel conversion standard coal coefficient is C g . The s thThe consumption quantity of the h power medium at the carbon input end of the working procedure is DM s,h . The h power medium converts the standard coal coefficient into DC h . The amount of consumption of the w-th non-replaceable fossil fuel at the carbon input of the s-th process is IF s,w . The w type irreplaceable fossil fuel conversion standard coal coefficient is IC w . The number of the external pins of the jth energetic product at the carbon output end of the s procedure is P s,j . The conversion standard coal coefficient of the jth energetic product is PC j . The accounting is carried out according to the material energy balance of the input end and the output end, and the method comprises the following steps:
thus obtaining the following components:
in the formula: m is Lco The amount of CO entering the recycling process in step 3). Δ cH CO Is the heat of combustion of CO. Δ cH Marking coal The calorific value of the standard coal. And m is the number of CO recycling procedures. x is the number of fossil fuel types. And y is the type number of the power medium. l is the number of types of fossil fuels that cannot be replaced. z is the number of types of energetic products.
Example 30
Example 29 was repeated except that in substep (4), the amount of carbon reduction in the entire steelmaking process was:
if m co ≤m Lco At this time
If m co ＞m Lco At this time
In the formula:
the method is used for reducing the discharge of carbon in the whole steel smelting process.
Example 31
Example 30 was repeated except that in substep (5), CO was introduced into the entire steelmaking process 2 The difference in the cost of converting the gas to CO and methanol is:
in the formula: delta C is CO in the whole steel smelting process 2 The difference in cost of converting the gas to CO and methanol. Δ P as unit CO 2 The cost difference of conversion to CO and methanol.
Example 32
Example 31 was repeated except that in substep (6), the carbon reduction target of the iron and steel company was set to Δ E min The cost saving goal is Δ C min . Comprises the following steps:
ΔC≥ΔC min I.e. by
Example 33
Example 32 is repeated, except if the value Δ C = Δ C min Instant value of
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions for converting the center Z. The reaction condition is that the iron and steel enterprises realize the lowest CO on the premise of achieving the aim of saving cost 2 The process conditions of the discharge.
Example 34
Example 32 is repeated, except that values are given
Namely taking value
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions for converting the center Z. The reaction condition is the process condition which can realize the most cost saving of steel enterprises on the premise of achieving the aim of carbon emission reduction.
Example 35
Example 32 is repeated, except that values are given
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions for converting the center Z. The reaction condition is to realize the CO treatment of the iron and steel enterprises on the premise of achieving the aim of saving cost and reducing carbon emission 2 The conversion cost and the carbon emission are comprehensively controlled.
Application example 1
CO of the Steel works described in example 33 2 The method for conversion recycling is used in Zhanjiang certain steel smelting plant, and comprises the following steps:
1)CO 2 the collection: according to the existing production level, the CO generated in the blast furnace process, the lime kiln process and the converter process of the iron and steel enterprises 2 Collecting to obtain enriched CO 2 A gas.
2)CO 2 The transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of center Z to CO 2 Introduction of H into the transformation center Z 2 And obtaining CO.
3)CO 2 The recycling of (2): conveying the CO obtained in the step 2) to a blast furnace process and a lime kiln process of a steel enterprise for recycling.
In the whole steel smelting process, CO is controlled 2 The selectivity of converting gas into CO is realized, thereby realizing CO conversion of the iron and steel enterprise 2 Conversion cost and carbon emission control. The method specifically comprises the following substeps:
(1) calculating stepEnriched CO obtained in step 1) 2 Total amount of gas m cc 。
m cc ＝380×3.12+150×2.93+12×0.78+25×0.33+180×0.33+28.8×2.775+1000×0.1-1000×0.15-15×1.1-35×0.33-1000×0.35＝1353.98kg。
In the above table, since the scrap/hot metal corresponding to the converter process can bring about carbon input, the enriched CO is calculated 2 The total amount of gas was calculated.
(2) According to CO 2 Selectivity of gas conversion to CO, calculating the amount m of CO generated by conversion in step 2) co 。
Setting of CO 2 The selectivity of the conversion of gas to CO being S co . Namely, the method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for the conversion to methanol path is K 1 ，CO 2 The equilibrium constant of the reaction for the conversion to CO route is K 2 According to CO 2 The reaction formula for converting methanol and CO into methanol and CO comprises the following steps:
and reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)，K 2 ＝f 2 (T), the specific relational expression is obtained by experimental test fitting and comprises the following components:
in the formula: a is 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 And a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants. Value of each fitting coefficient and CO 2 The conversion catalyst is relevant. In this embodiment, the CO is selected 2 The conversion catalyst is a copper-based mesoporous catalytic material, and the value of each fitting coefficient is a 1 ＝-152.7,b 1 ＝27169.2,d 1 ＝0.152,g 1 ＝-4.17,c 1 ＝h 1 ＝j 1 =0; and a 2 ＝79.1,b 2 ＝-56500.7,c 2 ＝14.3,g 2 ＝-2.36,d 2 ＝h 2 ＝j 2 ＝0。
Combining formulae (3) to (6) to give X CO And X MeOH . Then combining with the formula (2) to obtain S co 。
Thus, the amount m of CO formed by the conversion in step 2) co Comprises the following steps:
(3) calculating the amount m of CO entering the recycling process in the step 3) Lco 。
Thus obtaining the following components:
m Lco ＝71.31kg。
in the formula: Δ cH CO Is the heat of combustion of CO,. DELTA.cH CO ＝283kJ/mol。ΔcH Marking coal As heat value of standard coal,. DELTA.cH Marking coal ＝29307kJ/kg；
(4) Calculating the carbon emission reduction in the whole steel smelting process
If m co ≤m Lco At this time
If m co ＞m Lco At this time
(5) Calculating CO in the whole steel smelting process 2 The difference in cost Δ C of the conversion of the gas to CO and methanol.
In the formula: Δ P as unit CO 2 Cost difference for conversion to CO and methanol, Δ P =60 yuan/kmol.
(6) Calculating to obtain CO according to the cost target and the carbon emission reduction target of the iron and steel enterprise 2 The selectivity of the gas to CO is controlled in step 2) depending on the CO selectivity determined 2 The technological conditions of the conversion are realized, thereby realizing the CO treatment of the iron and steel enterprises 2 Conversion cost and carbon emission control.
Setting a carbon emission reduction target delta E of an iron and steel enterprise min ＝400kg CO 2 T steel, cost saving target Delta C min Steel no =600 yuan/t. Comprises the following steps:
ΔC≥ΔC min I.e. by
The value of the iron and steel plant is Delta C = Delta C min Instant value of
Namely, the method comprises the following steps:
in the formula: Δ P as unit CO 2 Cost difference for conversion to CO and methanol, Δ P =60 yuan/kmol.
Combining the formulas (2) to (6), calculating to obtain CO 2 Converting the reaction conditions of the center Z and adjusting CO according to the calculated reaction conditions 2 Conversion of various parameters of the center Z at the total reaction pressure P General assembly ＝3Mpa，H 2 /CO 2 At a ratio β =3, the reaction temperature is T =195 ℃. The reaction condition is that the iron and steel enterprises realize the lowest CO on the premise of achieving the aim of saving cost 2 The process conditions of the discharge.
At this time, the steel plant reduces the carbon emission in the steel smelting process to
And (3) steel.
Therefore, compared with the carbon emission of the traditional process, the steel plant takes the whole process of steel smelting as a research object and adopts CO 2 Capture → CO 2 Conversion of → CO 2 The recycling process realizes the great reduction of carbon emission in the steel process.
Application example 2
CO of the Steel works described in example 34 2 The method of conversion recycling is used in Zhanjiang certain steel smelting plant, and example 1 is repeatedly applied, except that the steel smelting plant takes values
Namely the value of
Namely, the method comprises the following steps:
combining the formulas (2) to (6), calculating to obtain CO 2 Converting the reaction conditions of the center Z and adjusting CO according to the calculated reaction conditions 2 Conversion of various parameters of the center Z at the total reaction pressure P General assembly ＝3Mpa，H 2 /CO 2 At a ratio β =3, the reaction temperature is T =236 ℃. The reaction condition is the process condition which can realize the most cost saving of steel enterprises on the premise of achieving the aim of carbon emission reduction.
At this time, the steel plant reduces the carbon emission in the steel smelting process to
And (3) steel.
Application example 3
CO of the Steel works described in example 35 2 The method of conversion recycling is used in Zhanjiang certain steel smelting plant, and example 1 is repeatedly applied, except that the steel smelting plant takes values
Namely, the method comprises the following steps:
0.325＜S co ＜0.787。
combining the formulas (2) to (6), calculating to obtain CO 2 Converting the reaction conditions of the center Z and adjusting CO according to the calculated reaction conditions 2 Conversion of various parameters of the center Z at the total reaction pressure P General assembly ＝3Mpa，H 2 /CO 2 The reaction temperature is 195 ℃ and < T < 236 ℃ when the ratio of beta = 3. The reaction condition is that the iron and steel enterprises realize the CO treatment on the premise of achieving the goal of saving cost and reducing carbon emission 2 The conversion cost and the carbon emission are comprehensively controlled.
As can be seen from the above application examples, the present invention realizes CO by matching the cost requirements and/or carbon emission requirements of the iron and steel enterprises themselves 2 The proportion of the conversion products is regulated, so that the comprehensive control of the iron and steel enterprises on the conversion cost and the carbon emission is realized, and the balance optimal value of the conversion cost and the carbon emission of the enterprises can be reached.
Claims (24)
1. Steel process CO 2 A method of conversion recycling, the method comprising the steps of:
1)CO 2 the collection: CO generated by one or more processes of iron and steel enterprises 2 Collecting to obtain enriched CO 2 A gas;
2)CO 2 the transformation of (2): enriched CO 2 Gas delivery to CO 2 Conversion of the center (Z) to CO 2 Introducing a reducing medium into the conversion center (Z) to obtain CO;
3)CO 2 the recycling of (2): conveying the CO obtained in the step 2) to one or more working procedures of the iron and steel enterprises for recycling.
2.CO according to claim 1 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: the reducing medium in the step 2) is a reducing solid or a reducing gas; preferably, the reducing solid is carbon and the reducing gas is H 2 (ii) a And/or
The step 2) is specifically as follows: enriched CO 2 Gas delivery to CO 2 Conversion of the center (Z) to CO 2 Introduction of H into the transformation center (Z) 2 Obtaining CO and methanol; wherein: methanol is used as a raw material and a fuel for one or more processes in iron and steel enterprises, or is output as a product.
3. CO according to claim 1 or 2 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: the step 1) also comprises the pretreatment of the flue gas of each procedure of the iron and steel enterprises; the step 1) is specifically as follows: firstly, carrying out dust removal, desulfurization and dehydration pretreatment on flue gas generated by one or more procedures of iron and steel enterprises to obtain purified flue gas; then the purified flue gas of each procedure is subjected to CO 2 To obtain enriched CO 2 A gas;
preferably, the humidity of the purified flue gas is less than 1%, preferably less than 0.5%; the content of sulfide in the purified flue gas is less than 35mg/Nm 3 Preferably < 30mg/Nm 3 (ii) a The dust content in the purified flue gas is less than 10mg/Nm 3 Preferably < 5mg/Nm 3 。
4. CO according to any of claims 1-4 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: CO described in step 1) 2 The trapping is carried out by a temperature and pressure swing adsorption device; a porous material loaded with a chemical absorbent is arranged in the temperature and pressure swing adsorption device; preferably, the porous material is an aluminosilicate mesoporous material; the chemical absorbent is an alcamines reagent; and/or
CO described in step 2) 2 The conversion center (Z) comprises a hydrogen generating device (1) and CO 2 A conversion device (2), a converted substance gas-liquid separation and converted gas blending device (3); the hydrogen outlet of the hydrogen generating device (1) is connected to CO 2 A hydrogen inlet of the reformer (2); CO 2 2 A converted substance outlet of the conversion device (2) is connected to a converted substance inlet of the converted substance gas-liquid separation and converted gas blending device (3); preferably, the hydrogen generating device (1) is a green power-H 2 And (4) an O electrolysis device.
5. CO according to claim 4 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: green electricity-H 2 The O electrolysis device is a device for electrolyzing water by utilizing one or more of solar energy, wind energy, biological energy, water energy, geothermal energy or ocean energy; green electricity-H 2 The O electrolysis device electrolyzes water to generate hydrogen and oxygen, and the hydrogen is conveyed to CO 2 The conversion center (Z) is used as a reducing medium, and oxygen is conveyed to one or more working procedures of the steel enterprise;
preferably, oxygen is fed to a blast furnace or converter for oxyfuel combustion or injection, or oxygen is fed to a sintering machine for oxyfuel sintering.
6. CO according to any of claims 1-5 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in step 1), high concentration CO generated for each process of a steel enterprise 2 Trapping to remove low concentration CO 2 Discharging; wherein the high concentration of CO 2 The volume fraction of the carbon dioxide is more than or equal to 12 percent, and the low concentration CO is 2 The volume fraction of (A) is less than 12%; preferably, high concentration of CO 2 The volume fraction of the carbon dioxide is more than or equal to 15 percent, and the low concentration CO is 2 The volume fraction of (a) is < 15%.
7. CO according to any of claims 1-6 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in step 1), CO generated from n processes of a steel enterprise 2 Carrying out trapping; wherein: n is 1 to 10, preferably 3 to 6;
in the step 3), delivering the CO obtained in the step 2) to m processes of a steel enterprise for recycling; wherein: m is 1 to 12, preferably 3 to 8.
8.CO according to claim 7 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: the one or more working procedures of the iron and steel enterprises in the steps 1) and 3) are one or more of a blast furnace working procedure, a converter working procedure, a lime kiln working procedure, a sintering working procedure, a pelletizing working procedure, a coking working procedure and a direct reduction working procedure; and/or
CO 2 The conversion center (Z) contains CO 2 Conversion catalysisAn agent; the CO is 2 The conversion catalyst is a nickel-based or copper-based mesoporous catalytic material.
9. CO according to claim 8 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: the one or more working procedures of the iron and steel enterprises in the step 1) are one or more of a blast furnace working procedure, a converter working procedure and a lime kiln working procedure; and/or
The one or more working procedures of the iron and steel enterprises in the step 3) are one or more of a blast furnace working procedure, a lime kiln working procedure, a sintering working procedure, a pelletizing working procedure, a coking working procedure and a direct reduction working procedure.
10. CO according to claim 8 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: CO generated in a certain process of a steel enterprise 2 Is less than 20% (preferably less than 15%) by volume, with respect to the CO produced in the process 2 Passing through an enrichment process and then delivering to CO 2 A transformation center (Z);
preferably, the enrichment process comprises: CO generated in one or more of blast furnace process, converter process, sintering process, pelletizing process, coking process and direct reduction process 2 Conveying the waste gas to a lime kiln process, and capturing CO in the flue gas discharged by the lime kiln process 2 Obtaining enriched CO 2 Then the enriched CO is added 2 To CO 2 Transformation center (Z).
11. CO according to any of claims 1-10 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in the whole steel smelting process, CO is controlled 2 The selectivity of converting gas into CO is realized, thereby realizing CO conversion of iron and steel enterprises 2 Control of conversion cost and carbon emissions; the method specifically comprises the following substeps:
(1) calculating the enriched CO obtained in step 1) 2 Total amount of gas m cc ；
(2) According to CO 2 Selectivity of gas conversion to CO, calculating the amount m of CO generated by conversion in step 2) co ；
(3) Calculating the amount m of CO entering the recycling process in the step 3) Lco ；
(4) Calculating the carbon emission reduction in the whole steel smelting process
(5) Calculating CO in the whole steel smelting process 2 The cost difference delta C of the CO and the methanol converted from the gas;
(6) calculating to obtain CO according to the cost target and/or the carbon emission reduction target of the iron and steel enterprise 2 The selectivity of the gas conversion into CO is controlled according to the obtained selectivity of CO in the step 2) 2 The technological conditions of the conversion are realized, thereby realizing the CO treatment of the iron and steel enterprises 2 Conversion cost and carbon emission control.
12. CO according to claim 11 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in substep (1), the enriched CO obtained in step 1) is calculated 2 The total amount of gas is specifically as follows:
the consumption quantity of the g fossil fuel at the carbon input end of the ith process is F i,g (ii) a CO of the g-th fossil fuel 2 Direct emission factor of D g (ii) a The consumption amount of the h power medium at the ith procedure carbon input end is DM i,h (ii) a CO of h-th power medium 2 Indirect emission factor is ID h (ii) a The number of the external pins of the jth energetic product at the ith procedure carbon output end is P i,j (ii) a CO of jth energetic product 2 Direct emission factor ND j (ii) a And (3) carrying out accounting according to the material energy balance of the input end and the output end to obtain:
in the formula: m is cc For the enriched CO obtained in step 1) 2 Total amount of gas; n is CO 2 The number of trapping processes; x is the number of fossil fuel types; with y being the motive mediumNumber of species; z is the number of types of energetic products.
13. CO according to claim 11 or 12 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in the substep (2), CO is set 2 The selectivity of the conversion of gas to CO being S co (ii) a Namely, the method comprises the following steps:
setting CO 2 The equilibrium constant of the reaction for the conversion to methanol path is K 1 ，CO 2 Conversion to CO pathway has a reaction equilibrium constant of K 2 (ii) a According to CO 2 The reaction formula for converting methanol and CO into methanol and CO comprises the following steps:
wherein: reaction equilibrium constant K 1 、K 2 Is a function of the reaction temperature T, i.e. K 1 ＝f 1 (T)；K 2 ＝f 2 (T); comprises the following steps:
combining formulae (3) to (6) to give X CO 、X MeOH (ii) a Then combining the formula (2) to obtain S co ；
The amount of CO converted in step 2) is thus:
in formulae (2) to (7): x CO Is CO 2 Conversion to CO; x MeOH Is CO 2 Conversion to methanol; beta is H 2 /CO 2 The ratio of (A) to (B); p General assembly The total reaction pressure is used; t is the reaction temperature; m is a unit of co The amount of CO produced in step 2); a is 1 、b 1 、c 1 、d 1 、g 1 、h 1 、j 1 And a 2 、b 2 、c 2 、d 2 、g 2 、h 2 、j 2 Fitting coefficients for reaction equilibrium constants.
14. CO according to any of claims 11-13 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in the substep (3), the amount of CO entering the recycling process in the step 3) is:
the consumption quantity of the g fossil fuel at the carbon input end of the s procedure is F s,g (ii) a The g-th fossil fuel conversion standard coal coefficient is C g (ii) a The consumption quantity of the h power medium at the carbon input end of the s procedure is DM s,h (ii) a The h power medium converts the standard coal coefficient into DC h (ii) a The amount of consumption of the w-th non-replaceable fossil fuel at the carbon input of the s-th process is IF s,w (ii) a The w type irreplaceable fossil fuel conversion standard coal coefficient is IC w (ii) a The number of the external pins of the jth energetic product at the carbon output end of the s procedure is P s,j (ii) a The conversion standard coal coefficient of the jth energetic product is PC j (ii) a According to the input end and the output end material energy balance, the method comprises the following steps:
obtaining the following components:
in the formula: m is Lco The amount of CO entering the recycling process in step 3); Δ cH CO Is the heat of combustion of CO; Δ cH Marking coal The heat value of the standard coal is used; m is the number of CO recycling procedures; x is the number of fossil fuel types; y is the number of the types of the power media; l is the number of types of fossil fuels that cannot be replaced; z is the number of types of energetic products.
15. CO according to any of claims 11-14 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in the substep (4), the carbon emission reduction in the whole steel smelting process is:
if m co ≤m Lco At this time
If m co ＞m Lco At this time
In the formula:
the method is used for reducing the emission of carbon in the whole steel smelting process.
16. CO according to claim 15 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in the substep (5), CO is contained in the whole iron and steel smelting process 2 The difference in the cost of converting the gas into CO and methanol is:
in the formula: Δ C is wholeCO in steel smelting process 2 The difference in cost of converting the gas to CO and methanol; Δ P as unit CO 2 The cost difference of conversion to CO and methanol.
17. CO according to claim 16 2 The method for conversion and cyclic utilization is characterized by comprising the following steps: in substep (6), the carbon reduction target of the iron and steel enterprise is set to Δ E min The cost saving goal is Δ C min (ii) a Comprises the following steps:
ΔC≥ΔC min I.e. by
18. CO according to claim 17 2 The method for conversion and cyclic utilization is characterized by comprising the following steps:
if the value is Δ C = Δ C min Instant value of
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions of the transformation center (Z); the reaction condition is that the iron and steel enterprises realize the lowest CO on the premise of achieving the aim of saving cost 2 Process conditions of the discharge;
if taking a value
Namely taking value
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions of the transformation center (Z); the reaction condition is to achieve carbon emission reductionOn the premise of the target, the steel enterprises realize the most cost-saving process condition;
if taking a value
Combining the formulas (2) to (6), calculating to obtain CO 2 Reaction conditions of the transformation center (Z); the reaction condition is to realize the CO treatment of the iron and steel enterprises on the premise of achieving the aim of saving cost and reducing carbon emission 2 The conversion cost and the carbon emission are comprehensively controlled.
19. Use of a CO according to any one of claims 1 to 18 2 System for converting a cyclic process, the system comprising CO 2 A conversion center (Z), a blast furnace (A1) and a lime kiln (A2); CO 2 2 The conversion center (Z) comprises a hydrogen generating device (1) and CO 2 A conversion device (2), a converted substance gas-liquid separation and converted gas blending device (3); the gas outlet of the blast furnace (A1) and the gas outlet of the lime kiln (A2) are both connected to CO 2 CO of transformation center (Z) 2 A gas inlet; CO 2 2 The CO gas outlet of the conversion center (Z) is connected to the gas inlet of the blast furnace (A1) and/or the lime kiln (A2); the hydrogen outlet of the hydrogen generating device (1) is connected to CO 2 A hydrogen inlet of the reformer (2); CO 2 2 The transforming substance outlet of the transforming device (2) is connected to the transforming substance inlet of the transforming substance gas-liquid separation and transforming gas blending device (3).
20. The system of claim 19, wherein: the system also comprises a sintering machine (A3), a rotary kiln (A4), a coke oven (A5), a converter (A6) and a straight-ring furnace (A7); the gas outlet of the blast furnace (A1), the gas outlet of the lime kiln (A2) and the gas outlet of the converter (A6) are all connected to CO 2 CO of transformation center (Z) 2 A gas inlet; CO 2 2 The CO gas outlet of the conversion centre (Z) is connected to the gas inlet of the blast furnace (A1) and/or lime kiln (A2) and/or sintering machine (A3) and/or rotary kiln (A4) and/or coke oven (A5) and/or straight ring oven (A7).
21. The system of claim 20The system is characterized in that: the system also includes a CO 2 A pretreatment system (A8); CO 2 2 The pretreatment system (A8) carries out dust removal, desulfurization and dehydration pretreatment on the flue gas generated by one or more procedures of the iron and steel enterprises.
22. The system of claim 21, wherein: the system also includes a temperature and pressure swing adsorption apparatus (A9); the gas outlets of the blast furnace (A1), the lime kiln (A2) and the converter (A6) are all connected to CO 2 A pretreatment system (A8); CO 2 2 A gas outlet of the pretreatment system (A8) is connected to a temperature and pressure swing adsorption device (A9); CO of temperature and pressure swing adsorption unit (A9) 2 The gas outlet is connected to CO 2 CO of transformation center (Z) 2 A gas inlet.
23. The system of claim 22, wherein: optionally connecting gas outlets of a blast furnace (A1), a sintering machine (A3), a rotary kiln (A4), a coke oven (A5), a converter (A6) and a straight-ring furnace (A7) to a gas inlet of a lime kiln (A2); the gas outlet of the lime kiln (A2) is connected to CO 2 A pretreatment system (A8); CO 2 2 The gas outlet of the pretreatment system (A8) is connected to a temperature and pressure swing adsorption device (A9).
24. The system according to any one of claims 19-23, wherein: the hydrogen generating device (1) is a green power-H 2 An O electrolysis device; green power-H 2 The oxygen outlet of the O electrolysis device is connected to a blast furnace (A1), a converter (A6) or a sintering machine (A3).
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| PCT/CN2022/116611 WO2023155417A1 (en) | 2022-02-18 | 2022-09-01 | Steel process co2 conversion and cyclic utilization method and system |
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