CN110577847B - Synergistic removal of sulfide and CO in blast furnace gas by composite calcium ferrite2Method (2) - Google Patents
Synergistic removal of sulfide and CO in blast furnace gas by composite calcium ferrite2Method (2) Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/005—Carbon dioxide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
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Abstract
The invention relates to the removal of organic sulfur and CO from blast furnace gas2The field, in particular to the synergistic removal of sulfide and CO in blast furnace gas by functional composite calcium ferrite2The method of (1); the method is characterized in that: the functional composite calcium ferrite is used for synergistically removing sulfide and CO in blast furnace gas2The method of (1): the blast furnace gas after dust removal enters a desulfurization and decarbonization device, and is subjected to CO after being compounded with calcium ferrite2Is absorbed and carbonated by functional composite calcium ferrite; carbonyl sulfide is hydrolyzed in the basic center of functional composite calcium ferrite to generate H2S，H2S reacts with the active center of the metal oxide of the functional composite calcium ferrite to be converted into metal sulfide; by CO2The chemical reaction of the adsorption carbonation and the carbonyl sulfide realizes the synergistic removal of sulfide and CO in the blast furnace gas2The functional composite calcium ferrite can be recycled after oxidation regeneration under the oxygen atmosphere.
Description
Technical Field
The invention relates to the removal of organic sulfur and CO from blast furnace gas2The field, in particular to the synergistic removal of sulfide and CO in blast furnace gas by functional composite calcium ferrite2The method of (1).
Background
The iron and steel industry is an important basic industry in China, and the refined iron and steel has the characteristics of large process energy consumption, high emission, serious environmental pollution and the like. Blast furnace gas as important by-product of blast furnace ironmaking process in steel production process is preheated air and CO and H produced in combustion process of coke and iron ore2、CO2、N2And CH4And the like, and generally accounts for more than 50% of the energy supply amount in blast furnace ironmaking. The main components of blast furnace gas are CO and N2、CO2、H2、CH4Sulfides, wherein CO accounts forAbout 25% of CO2、N2About 16% and 58% respectively, and the total sulfur content is about 200mg/m3。
The sulfur in the blast furnace gas mainly comprises carbonyl sulfide (COS) and hydrogen sulfide (H)2S), carbon disulfide (CS)2) Mainly, the three sulfur components account for about 95 percent of the total sulfur, wherein carbonyl sulfur accounts for about 68 percent of the total sulfur, hydrogen sulfide accounts for about 28 percent of the total sulfur, and carbon disulfide accounts for about 19 percent of the total sulfur.
With the improvement of the environmental protection standard and the implementation of the greenhouse gas emission reduction policy, the efficient, reasonable and clean utilization of the blast furnace gas is the key for realizing energy conservation, consumption reduction, low carbon and emission reduction of steel enterprises. The method has low cost, large-scale removal of sulfides in blast furnace gas and high efficiency CO capture2The method is two major technical problems for realizing the resource utilization of the blast furnace gas in the steel industry.
Aiming at the blast furnace gas desulfurization technology, no mature and accepted technical route exists at present. The main technical problems are as follows: the existence form of sulfur in blast furnace gas is complex, and the existing inorganic sulfur H2S, COS and CS2And the like, and high-temperature treatment easily causes a series of problems of reactor corrosion, catalyst poisoning and the like, thereby seriously restricting the resource utilization of the blast furnace gas.
In general, the process for removing organic sulfur is more SO than SO2、H2The removal process of S is complex and has higher cost, and the blast furnace gas desulfurization also relates to the safety problem, so the blast furnace gas desulfurization technology is more complex than the common flue gas desulfurization technology. The removal method of COS mainly comprises catalytic hydrolysis, namely carbonyl sulfide is converted into H under the condition of catalyst2And S. Common catalytic systems include transition metal oxides such as Fe2O3、MoO3、ZrO2、ZnO、TiO2、SnO2Etc., alkaline earth metal carbonate-modified metal oxides and rare earth metal oxides such as CeO2、La2O3And the like. Generation of H2S is removed through the sulfurization reaction of metal oxide and can be used for H2The metal oxides removed by S include CaO and Fe2O3And ZnO and the like。
Chinese patent application CN108315070A discloses a method for removing carbonyl sulfide in liquefied petroleum gas by metal-doped KP type molecular sieve, which provides an alkaline center for carbonyl sulfide hydrolysis by a method for loading metal on KP type molecular sieve. The method is carried out by physical adsorption of carbonyl sulfide and H2And the chemical adsorption synergistic effect of the S realizes the high-efficiency removal of carbonyl sulfide in the liquefied petroleum gas. The method has high removal efficiency, but the method has small amount of purified gas and short service life of the metal-doped KP molecular sieve, needs continuous hydrothermal regeneration, and has long and complicated regeneration process.
The development of green and low carbon is a common consensus and trend. Worldwide, projects around Low carbon Steel manufacturing are started in succession, including the Ultra-Low CO2 Steelmarking (ULCOS) of the European Union, American Iron and Steel Institute with technology roadmap Programme (AISI) of the United states, and CO2 Multi Reduction in Steelmarking Process by innovative technology for cool Earth 2050 (COARSE) of Japan. The research on the carbon dioxide capture of blast furnace gas is the focus of the research on the carbon dioxide capture in the industrial sector.
Existing blast furnace gas CO2The trapping technology is mainly divided into three categories: 1) decarburization in front of the furnace, and iron making by adopting non-carbon (such as hydrogen) or zero-carbon (such as biomass) fuels; 2) carbon dioxide enrichment in the furnace is realized by adopting top gas recirculation, pure oxygen and vacuum pressure swing absorption to realize blast furnace tail gas CO2Enriching; 3) gas CO after furnace2And (4) separating, namely separating the carbon dioxide in the blast furnace gas by adopting solution absorption or a solid absorbent. The technology of decarburization in the front of the furnace and carbon dioxide enrichment in the furnace has the problems of high cost, large-scale transformation of the existing iron-making process and the like, and is difficult to popularize in a short period. After-furnace CO2The separation technology has strong flexibility and simpler popularization, and can be designed to be novel with CO2The blast furnace for trapping energy supply can be reformed based on the original blast furnace, and is the most promising blast furnace gas CO2Separation techniques. Patent CN 108970332a discloses a "decarbonization method for converter and/or blast furnace gas", which completes decarbonization of converter and/or blast furnace gas by two steps of pressure swing adsorption coarse decarbonization and MDEA solution fine decarbonization. TheThe method can not only convert CO2The content of the phosphorus is removed to PPM level, and meanwhile, the phosphorus hydride in the converter and blast furnace gas can be removed. However, the method has the defects of complicated steps, high investment, high energy consumption, high solvent consumption and the like, and has an unclear industrial prospect.
In conclusion, the near zero emission of blast furnace ironmaking is not separated from each other and the CO is cooperated with the desulfurization2There is no solution to capture the support of two important technologies. Aiming at the problems that calcium, iron, copper and other metal oxides are frequently used in the desulfurization and decarburization processes, and the calcium and iron oxides are common raw materials for steel production, the method can not only solve the problem of removing sulfur-containing gas in blast furnace gas, but also can efficiently capture CO2The multifunctional synergistic catalytic system can form an integrated technology of low-cost desulfurization and decarbonization of blast furnace gas.
Disclosure of Invention
The invention aims to provide the method for removing sulfide and CO in blast furnace gas by using functional composite calcium ferrite2The method can remove the sulfide in the blast furnace gas in a large scale with low cost and can efficiently capture CO2。
The technical scheme adopted by the invention for solving the technical problems is as follows: synergistic removal of sulfide and CO in blast furnace gas by functional composite calcium ferrite2The method of (2), characterized by: the functional composite calcium ferrite is used for synergistically removing sulfide and CO in blast furnace gas2The method of (1): the blast furnace gas after dust removal enters a desulfurization and decarbonization device, and is subjected to CO after being compounded with calcium ferrite2Is absorbed and carbonated by functional composite calcium ferrite; carbonyl sulfide is hydrolyzed in the basic center of functional composite calcium ferrite to generate H2S，H2S reacts with the active center of the metal oxide of the functional composite calcium ferrite to be converted into metal sulfide; by CO2The chemical reaction of the adsorption carbonation and the carbonyl sulfide realizes the synergistic removal of sulfide and CO in the blast furnace gas2The functional composite calcium ferrite can be recycled after oxidation regeneration under the oxygen atmosphere.
Specifically, the invention relates to a preparation method of composite calcium ferrite, which is characterized by comprising the following steps:
(1) mixing a ferric nitrate solution and a calcium nitrate solution to obtain a mixed solution A, wherein the ferric nitrate and the calcium nitrate are added according to a molar ratio of Ca to Fe (0.5-1.5): 1, preferably (0.8-1): 1;
(2) adding an ammonium oxalate solution into the solution A, uniformly stirring to obtain a mixed solution B, heating the mixed solution B to 50-80 ℃, and adjusting the pH value with an alkaline reagent to generate an emulsion C; wherein the adding amount of the ammonium oxalate is 0.5-3 times of the molar amount of (Ca + Fe) in the mixed solution A, and preferably 1-3 times; the PH value is 6-10;
(3) placing the emulsion C in a microwave reactor at 100-300 ℃ for 0.5-2 h, washing with water, washing with alcohol, drying and grinding to obtain solid powder D;
(4) and (3) placing the solid powder D in a muffle furnace, heating to 500-850 ℃ at a heating rate of 3-5 ℃/min, calcining at a constant temperature for 2-6 h, and grinding the calcined solid powder D to finally obtain the composite calcium ferrite.
Preferably, the concentration of the ferric nitrate and calcium nitrate solution in the step (1) is 0.25-1.0 mol/L.
Preferably, the concentration of the ammonium oxalate solution in the step (2) is 0.25-1.0 mol/L, and more preferably 0.35-0.85 mol/L.
More preferably, the ammonium oxalate solution is added dropwise to the mixed solution a.
Preferably, the alkaline reagent in the step (2) is one or more of urea, ammonia water, NaOH and monoethanolamine, and the pH is 7.5-10.
Preferably, the temperature in the step (4) is 550-750 ℃, and the calcination time is 3-6 h.
The invention also relates to the composite calcium ferrite obtained by the preparation method.
The invention also relates to the synergistic removal of sulfide and CO in blast furnace gas by the composite calcium ferrite obtained by the preparation method2The method of (1).
Preferably, the composite calcium ferrite is crushed into 5-10 meshes of catalyst particles after being pressed and formed.
Preferably, the present invention relates to the aboveThe compound calcium ferrite obtained by any one of the preparation methods synergistically removes sulfides and CO in blast furnace gas2The method of (2), characterized by: filling the composite calcium ferrite in a desulfurization and decarbonization device at the middle part of a desulfurization and decarbonization reactor, feeding the blast furnace gas subjected to dust removal into the desulfurization and decarbonization device, and performing synergistic removal of sulfide and CO in the blast furnace gas after the composite calcium ferrite2。
More preferably, the composite calcium ferrite synergistically removes sulfide and CO in blast furnace gas2The reaction temperature of (a) is 200 to 500 ℃, preferably 250 to 500 ℃; the airspeed is 500-5000 h-1Preferably 2500-5000 h-1(ii) a The pressure is 6 to 20Kpa, preferably 8 to 16 Kpa.
The invention also relates to a regeneration method of the composite calcium ferrite, which is characterized by comprising the following steps: and regenerating the inactivated composite calcium ferrite in an oxygen atmosphere at 850 ℃ and preferably at 800 ℃ and 500 ℃ for 0.5-6h, preferably 0.5-1.5 h to obtain the regenerated composite calcium ferrite.
The invention has the beneficial effects that:
(1) the invention adopts a multifunctional composite calcium ferrite material to circulate the carbon carrier and the sulfur carrier and creatively realizes the synergistic desulfurization and decarburization of blast furnace gas, the removal rate of carbonyl sulfide in the blast furnace gas treated by the composite calcium ferrite is 60-90 percent, and H is2The removal rate of S is 80-98%, and CO is removed2The removal rate is 30-70%;
(2) the preparation method of the multifunctional composite calcium ferrite is simple, and the materials used for synthesis are cheap and easy to obtain, so that the multifunctional composite calcium ferrite has a wide industrial application prospect;
(3) the multifunctional composite calcium ferrite has simple regeneration process, can realize the recycling by oxidizing regeneration in the oxygen atmosphere, and reduces the investment cost.
Detailed Description
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
Example 1
A kind ofFunctional composite calcium ferrite for synergistically removing sulfide and CO in blast furnace gas2The method specifically comprises the following steps:
(1) preparing ferric nitrate (analytically pure) and calcium nitrate (analytically pure) into a ferric nitrate solution with the concentration of 1.0mol/L and a calcium nitrate solution with the concentration of 1.0mol/L respectively by using a 1L volumetric flask; (2) transferring 300ml of ferric nitrate solution and 300ml of ferric nitrate solution, and uniformly mixing to obtain a mixed solution A; wherein the molar ratio of Ca to Fe in the mixed solution A is 1: 1; (3) dropwise adding 0.45mol/L ammonium oxalate solution into the mixed solution A, and uniformly stirring for 25min to obtain a mixed solution B; wherein, ammonium oxalate in the mixed solution B: the molar ratio of (Ca + Fe) is 2.5: 1; (4) heating the mixed solution B in a water bath, maintaining the constant temperature of 60 ℃, and dropwise adding ammonia water into the mixed solution B to adjust the pH value to 8 to obtain emulsion C; (5) placing the emulsion C in a microwave reactor at 200 ℃ for 1h, washing with water, washing with alcohol, drying and grinding to obtain solid powder D; (6) placing the solid powder D in a muffle furnace, heating to 650 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 4h, and grinding the calcined solid powder D to finally obtain functional composite calcium ferrite; (7) the functional composite calcium ferrite is pressed and molded and then crushed into catalyst particles with 5-10 meshes, the prepared catalyst particles are filled in the middle of a desulfurization and decarbonization reactor, the reaction temperature is 400 ℃, the reaction pressure is 10Kpa, and the space velocity is 5000h-1The reaction was carried out with the blast furnace gas composition as shown in Table 1. The reaction results show that: the content of carbonyl sulfide in blast furnace gas is reduced to 18.3ppm, and the removal rate is 77.1 percent; h2The S content is reduced to 4.4ppm, and the removal rate is 89.0 percent; carbonyl sulfide and H2The total sulfur removal rate of S is 80.9%; CO22The content is reduced to 9.5 percent, and the removal rate is 40.6 percent.
After 48H of reaction, carbonyl sulfide and H2The total sulfur removal rate of S is lower than 70%, the functional composite calcium ferrite catalyst is regenerated, and the regenerated functional composite calcium ferrite catalyst is obtained after regeneration for 1h in the oxygen atmosphere at 700 ℃.
Example 2
Synergistic removal of sulfide and CO in blast furnace gas by functional composite calcium ferrite2The method specifically comprises the steps ofThe following steps:
(1) preparing ferric nitrate (analytically pure) and calcium nitrate (analytically pure) into a ferric nitrate solution with the concentration of 0.5mol/L and a calcium nitrate solution with the concentration of 0.5mol/L respectively by using a 1L volumetric flask; (2) transferring 400ml of ferric nitrate solution and 500ml of ferric nitrate solution, and uniformly mixing to obtain a mixed solution A; wherein the molar ratio of Ca to Fe in the mixed solution A is 0.8: 1; (3) dropwise adding 0.80mol/L ammonium oxalate solution into the mixed solution A, and uniformly stirring for 25min to obtain a mixed solution B; wherein, ammonium oxalate in the mixed solution B: the molar ratio of (Ca + Fe) is 1: 1; (4) heating the mixed solution B in a water bath, maintaining the constant temperature of 80 ℃, and dropwise adding ammonia water into the mixed solution B to adjust the pH value to 10 to obtain emulsion C; (5) placing the emulsion C in a microwave reactor at 150 ℃ for 2h, washing with water, washing with alcohol, drying and grinding to obtain solid powder D; (6) placing the solid powder D in a muffle furnace, heating to 550 ℃ at the heating rate of 3 ℃/min, calcining at constant temperature for 6h, and grinding the calcined solid powder D to finally obtain functional composite calcium ferrite; (7) the functional composite calcium ferrite is pressed and molded and then crushed into catalyst particles with 5-10 meshes, and the prepared catalyst particles are filled in the middle of a desulfurization and decarbonization reactor, and the reaction temperature is 250 ℃, the reaction pressure is 12Kpa, and the space velocity is 2500h-1The reaction was carried out with the blast furnace gas composition as shown in Table 1. The reaction results show that: the content of carbonyl sulfide in blast furnace gas is reduced to 24.6ppm, and the removal rate is 69.3 percent; h2The S content is reduced to 6.2ppm, and the removal rate is 84.5 percent; carbonyl sulfide and H2The total sulfur removal rate of S was 74.1%; CO22The content is reduced to 11.0 percent, and the removal rate is 31.3 percent.
After 16H of reaction, carbonyl sulfide and H2The total sulfur removal rate of S is lower than 70%, the functional composite calcium ferrite catalyst is regenerated, and the regenerated functional composite calcium ferrite catalyst is obtained after regeneration is carried out for 1.5h in the oxygen atmosphere at the temperature of 600 ℃.
Example 3
Synergistic removal of sulfide and CO in blast furnace gas by functional composite calcium ferrite2The method specifically comprises the following steps:
(1) separately, ferric nitrate (analytically pure) and calcium nitrate (analytically pure)Preparing a ferric nitrate solution with the concentration of 0.25mol/L and a calcium nitrate solution with the concentration of 0.25mol/L by using a 1L volumetric flask; (2) transferring 500ml of ferric nitrate solution and 550ml of ferric nitrate solution, and uniformly mixing to obtain a mixed solution A; wherein the molar ratio of Ca to Fe in the mixed solution A is 1: 1.1; (3) dropwise adding 0.35mol/L ammonium oxalate solution into the mixed solution A, and uniformly stirring for 25min to obtain a mixed solution B; wherein, ammonium oxalate in the mixed solution B: the molar ratio of (Ca + Fe) is 3: 1; (4) heating the mixed solution B in a water bath, maintaining the constant temperature of 60 ℃, and dropwise adding ammonia water into the mixed solution B to adjust the pH value to 9 to obtain emulsion C; (5) placing the emulsion C in a microwave reactor at 300 ℃ for 0.5h, washing with water, washing with alcohol, drying and grinding to obtain solid powder D; (6) placing the solid powder D in a muffle furnace, heating to 750 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 3h, and grinding the calcined solid powder D to finally obtain functional composite calcium ferrite; (7) the functional composite calcium ferrite is pressed and molded and then crushed into catalyst particles with 5-10 meshes, and the prepared catalyst particles are filled in the middle of a desulfurization and decarbonization reactor, and the reaction temperature is 500 ℃, the reaction pressure is 8Kpa, and the space velocity is 4000h-1The reaction was carried out with the blast furnace gas composition as shown in Table 1. The reaction results show that: the content of carbonyl sulfide in the blast furnace gas is reduced to 9.3ppm, and the removal rate is 88.4 percent; h2The S content is reduced to 2.8ppm, and the removal rate is 93.0 percent; carbonyl sulfide and H2The total sulfur removal rate of S was 89.8%; CO22The content is reduced to 5.7 percent, and the removal rate is 64.4 percent.
After 36H of reaction, carbonyl sulfide and H2The total sulfur removal rate of S is lower than 70%, the functional composite calcium ferrite catalyst is regenerated, and the regenerated functional composite calcium ferrite catalyst is obtained after regeneration is carried out for 0.5h in the oxygen atmosphere at 800 ℃.
Example 4
Synergistic removal of sulfide and CO in blast furnace gas by functional composite calcium ferrite2The method specifically comprises the following steps:
(1) preparing ferric nitrate (analytically pure) and calcium nitrate (analytically pure) into a ferric nitrate solution with the concentration of 0.5mol/L and a calcium nitrate solution with the concentration of 0.5mol/L respectively by using a 1L volumetric flask; (2) moving 50Uniformly mixing 0ml of ferric nitrate solution and 500ml of ferric nitrate solution to prepare a mixed solution A; wherein the molar ratio of Ca to Fe in the mixed solution A is 1: 1; (3) dropwise adding 0.6mol/L ammonium oxalate solution into the mixed solution A, and uniformly stirring for 25min to obtain a mixed solution B; wherein, ammonium oxalate in the mixed solution B: the molar ratio of (Ca + Fe) is 2: 1; (4) heating the mixed solution B in a water bath, maintaining the constant temperature of 50 ℃, and dropwise adding ammonia water into the mixed solution B to adjust the pH value to 7.5 to obtain emulsion C; (5) placing the emulsion C in a microwave reactor at 200 ℃ for 1.5h, washing with water, washing with alcohol, drying and grinding to obtain solid powder D; (6) placing the solid powder D in a muffle furnace, heating to 650 ℃ at the heating rate of 5 ℃/min, calcining at constant temperature for 6h, and grinding the calcined solid powder D to finally obtain functional composite calcium ferrite; (7) the functional composite calcium ferrite is pressed and molded and then crushed into catalyst particles with 5-10 meshes, and the prepared catalyst particles are filled in the middle of a desulfurization and decarbonization reactor, and the reaction temperature is 450 ℃, the reaction pressure is 16Kpa, and the space velocity is 3000h-1The reaction was carried out with the blast furnace gas composition as shown in Table 1. The reaction results show that: the content of carbonyl sulfide in blast furnace gas is reduced to 12.7ppm, and the removal rate is 88.4 percent; h2The S content is reduced to 3.9ppm, and the removal rate is 90.0 percent; carbonyl sulfide and H2The total sulfur removal rate of S was 86.1%; CO22The content is reduced to 7.8 percent, and the removal rate is 51.3 percent.
After 42H of reaction, carbonyl sulfide and H2The total sulfur removal rate of S is lower than 70%, the functional composite calcium ferrite catalyst is regenerated, and the regenerated functional composite calcium ferrite catalyst is obtained after regeneration for 1h in the oxygen atmosphere at 750 ℃.
TABLE 1 blast furnace gas composition table (V/V)
| Composition (I) | Average content (%) |
| CO | 25.5 |
| CO2 | 14.5 |
| H2 | 1.5 |
| N2 | 58 |
| O2 | 0.8 |
| CH4 | 0.5 |
| H2S | 40ppm |
| COS | 80ppm |
| Total sulfur | 120ppm |
Claims (10)
1. Synergistic removal of sulfide and CO in blast furnace gas by using composite calcium ferrite2The method for preparing the composite calcium ferrite is characterized by comprising the following steps:
(1) mixing a ferric nitrate solution and a calcium nitrate solution to obtain a mixed solution A, wherein the ferric nitrate and the calcium nitrate are added according to the molar ratio of Ca to Fe (0.8-1): 1; the concentrations of the ferric nitrate and the calcium nitrate in the step (1) are 0.25-1.0 mol/L;
(2) adding an ammonium oxalate solution into the solution A, uniformly stirring to obtain a mixed solution B, heating the mixed solution B to 50-80 ℃, and adjusting the pH value with an alkaline reagent to generate an emulsion C; wherein the adding amount of the ammonium oxalate is 0.5-3 times of the molar amount of (Ca + Fe) in the mixed solution A; the pH is 6-10; the concentration of the ammonium oxalate solution in the step (2) is 0.25-1.0 mol/L; the alkaline reagent in the step (2) is one or more of urea, ammonia water, NaOH and monoethanolamine;
(3) placing the emulsion C in a microwave reactor at 100-300 ℃ for 0.5-2 h, washing with water, washing with alcohol, drying and grinding to obtain solid powder D;
(4) placing the solid powder D in a muffle furnace, heating to 500-850 ℃ at a heating rate of 3-5 ℃/min, calcining at a constant temperature for 2-6 h, and grinding the calcined solid powder D to finally obtain the composite calcium ferrite;
the compound calcium ferrite synergistically removes sulfide and CO in blast furnace gas2The reaction temperature is 200-500 ℃; the airspeed is 500-5000 h-1(ii) a The pressure is 6-20 Kpa;
the removal rate of carbonyl sulfide in blast furnace gas treated by the composite calcium ferrite is 60-90%, and H is2The removal rate of S is 80-98%, and CO is removed2The removal rate is 30-70%.
2. The method according to claim 1, wherein the ammonium oxalate added in step (2) is 1 to 3 times the molar amount of (Ca + Fe) in the mixed solution A.
3. The method of claim 1, wherein: the concentration of the ammonium oxalate solution in the step (2) is 0.35-0.85 mol/L.
4. The method of claim 1, wherein: and (3) the pH value in the step (2) is 7.5-10.
5. The method of claim 1, wherein: and (4) the temperature is 550-750 ℃, and the calcining time is 3-6 h.
6. The method of claim 1, wherein: the composite calcium ferrite is crushed into 5-10 mesh catalyst particles after being pressed and formed.
7. The method of claim 1, wherein: filling the composite calcium ferrite in a desulfurization and decarburization device at the middle part of a desulfurization and decarburization reactor, feeding the blast furnace gas subjected to dust removal into the desulfurization and decarburization reactor, and performing synergistic removal of sulfide and CO in the blast furnace gas after the composite calcium ferrite2。
8. The method of claim 1, wherein the composite calcium ferrite synergistically removes sulfide and CO from blast furnace gas2The reaction temperature is 250-500 ℃; the airspeed is 2500-5000 h-1(ii) a The pressure is 8 to 16 Kpa.
9. The method of claim 1, wherein the complex calcium ferrite is regenerated by: and regenerating the inactivated composite calcium ferrite for 0.5 to 6 hours in the oxygen atmosphere at 500-850 ℃ to obtain the regenerated composite calcium ferrite.
10. The method of claim 1, wherein the complex calcium ferrite is regenerated by: and regenerating the inactivated composite calcium ferrite in an oxygen atmosphere at the temperature of 600-800 ℃ for 0.5-1.5 h to obtain regenerated composite calcium ferrite.
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| CN114196448B (en) * | 2022-02-16 | 2022-05-10 | 北京中航天业科技有限公司 | Full-flow dry type blast furnace gas fine desulfurization system and method |
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