CN112708477B - Method for improving combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur - Google Patents
Method for improving combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur Download PDFInfo
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- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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- 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
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- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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Abstract
The invention relates to a method for improving the combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur, which aims at the low heat value and desulfurization requirement of the blast furnace gas, and introduces a certain amount of coke oven gas with high heat value into the blast furnace gas to improve the heat value of the blast furnace gas so as to achieve the purposes of resource utilization and process cost reduction; in addition, hydrogen in coke oven gas can be used as hydrogen source, and organic sulfur (COS, CS) in blast furnace gas can be reacted by hydrogenation under the action of catalyst 2 ) Conversion to inorganic Sulfur (H) 2 S), finally, inorganic sulfur removal is realized through a desulfurization catalyst; the method has the advantages of no waste gas and byproducts, low operation cost, good desulfurization effect and high practical application prospect.
Description
Technical Field
The invention relates to a method for improving the combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur, belonging to the technical field of industrial waste gas purification.
Background
In order to reduce the energy consumption of enterprises, the blast furnace gas can be used as fuel for steel plants after being purified. Non-combustible components (in N 2 And CO 2 Mainly) is more (about 70 percent), and the calorific value is low (3500 kJ/m) 3 Left and right). Coke oven gas, which is also present in steel plants, is composed mainly of hydrogen (56%) and methane (27%), and has a calorific value as high as 18250kJ/m 3 . The heating value of the coke oven gas is much higher than that of the blast furnace gas with the same volume. In general, low heating value blast furnace gas is not easy to burn, and in order to increase the thermal effect of combustion, the blast furnace gas must be preheated in addition to the air. Therefore, when the blast furnace gas is used for heating, one half of the regenerators of the updraft of the combustion system are used for preheating air, and the other half are used for preheating the gas. Therefore, in order to make the blast furnace gas burn better, enterprises can invest certain funds for preheating the blast furnace gas, which is contrary to the concept of recycling the blast furnace gas.
With the increasing environmental protection requirements of iron and steel enterprises, the iron-making process becomes an important link of energy conservation and emission reduction, and blast furnace gas generated in the iron and steel smelting process is taken as an important pollutant in the iron and steel smelting industry and contains organic sulfur (COS, CS) 2 、C 4 H 4 S, etc.), inorganic sulfur (H 2 S) and other harmful gases, and the existence of the harmful gases severely restricts the recycling of the blast furnace gas. COS and H 2 S is the main component in pollutants in blast furnace gas, and accounts for more than 95%, so that the research on the removal technology of the two substances is particularly critical.
Patent CN201610971597.3 discloses a modified activated carbon, a modification method and application thereof, and the method uses the activated carbon modified by saturated copper sulfate solution as an activated carbon column, and adsorbs hydrogen sulfide in gas by using the activated carbon column. However, the method requires carrying water treatment on the dried modified activated carbon, and a large amount of wastewater is generated in the process, so that the cost of industrial application is increased.
The patent CN201710791711.9 discloses a method for recycling hydrogen sulfide and carbonyl sulfide based on molten salt, which is characterized in that liquid functional molten salt is heated to 450-750 ℃ and then carbon powder is added into the liquid functional molten salt; then introducing hydrogen sulfide and carbonyl sulfide gas into molten salt for full contact and then absorbing by reaction; after stopping introducing gas, supplementing calcium salt or barium salt into the reacted molten salt system, stirring and mixing, and then leading sulfide generated by standing precipitation reaction out of the molten salt system at high temperature for recovery. The reaction has high temperature requirement, secondary pollutants such as wastewater, solid waste and the like can be generated in the reaction process, and the process cost is indirectly increased.
COS removal can be generally classified into dry and wet processes; the dry method mainly comprises a hydro-conversion method, a hydrolysis conversion method, an oxidation conversion method and the like. The wet method for removing carbonyl sulfide can be divided into a physical absorption method, a chemical absorption method and a physical and chemical method, such as an organic amine solvent absorption method, a liquid phase catalytic hydrolysis conversion method and the like. Because of the poor activity of organic sulfur, although the traditional solution absorption method and solid adsorption method can remove certain organic sulfur, the conversion process has better hydrolysis effect on organic sulfur, but the requirement of fine desulfurization is far from being met.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a method for improving the combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur with low cost and high efficiency, which introduces coke oven gas into the blast furnace gas to improve the heat value of the blast furnace gas, reduces the process cost and improves the hydrogen content in the blast furnace gas at the same time, so that the organic sulfur is easier to be converted into the inorganic sulfur in the purification process, and the inorganic sulfur is more similar to the original H 2 S together realizes the removal of the hydrogen sulfide gas under the action of a desulfurization catalyst.
The method of the invention is as follows:
(1) Improving the heat value of blast furnace gas: by utilizing the characteristics of high ratio of combustible components and high heat value of the coke oven gas, a certain volume of coke oven gas is introduced into the blast furnace gas, so that the volume ratio of the coke oven gas to the blast furnace gas is 6:1-12:1, the combustible components in the blast furnace gas components are improved to increase the heat value, the process cost of the blast furnace gas in combustion is reduced, and the hydrogen ratio in the blast furnace gas is correspondingly improved after the coke oven gas is introduced;
(2) Dedusting, deoxidizing and chlorine removing: dedusting, deoxidizing and dechlorinating the mixed gas in the step (1) to remove dust, oxygen and chlorine in the gas; in order to protect the hydrolytic agent, prevent the hydrolytic agent from poisoning and inactivating, improve the service life, reduce the corrosion to pipelines and TRT blades, so as to eliminate the influence of the substances on the subsequent process; after dust removal, the dust concentration in the flue gas is 5mg/m 3 The following are set forth; after deoxidization and dechlorination, the concentrations of oxygen and hydrogen chloride are respectively reduced to 0.05 percent and 10mg/m 3 The following are set forth;
(3) Conversion of organic sulfur to inorganic sulfur: by using H in gas 2 O and H brought by introducing coke oven gas 2 Under the action of an organic sulfur hydrolysis catalyst, organic sulfur in the mixed gas is subjected to catalytic hydrolysis reaction and hydroconversion reaction at 100-200 ℃ to generate inorganic sulfur, the conversion efficiency of the inorganic sulfur is improved by introducing hydrogen, the conversion rate is stably maintained to be more than 95%, CO gas is generated in the hydroconversion process, and the recycling of coal gas is facilitated; the reaction principle equation of this step is as follows: COS+H 2 →H 2 S+CO；COS+H 2 O→H 2 S+CO 2 ；CS 2 +H 2 O→H 2 S+CO 2 ；
(4) Cooling and oxygenation of the heat exchanger: the mixed gas is converted into organic sulfur (COS, CS) through hydrolysis 2 ) Then, the temperature of the mixed gas is reduced to 80-150 ℃ by utilizing a heat exchanger;
(5) And (3) removing inorganic sulfur: before the mixed gas is sent into a hydrogen sulfide removal tower, adding a certain amount of oxygen into the gas to control the oxygen content to be 0.05-0.8%; under the action of desulfurizing agent, original H in gas 2 S and H converted in step (3) 2 S generates elemental sulfur, metal sulfide and sulfate through catalytic oxidation reaction at 80-150 ℃ and is adsorbed on a catalyst, and the total sulfur content in the purified gas is 20mg/m 3 The following are set forth; the reaction principle equation of this step is as follows: h 2 S+O 2 →S+H 2 O；H 2 S+MO→MS+H 2 O；H 2 S+O+MO→sulfate+H 2 O (M is the metal supported by the catalyst);
(6) Regenerating a desulfurizing agent: and (3) after the desulfurization catalyst in the step (5) is deactivated, regenerating by a chemical method to realize the recycling of the desulfurizing agent.
The organic sulfur hydrolysis catalyst takes one of active carbon, alumina and a molecular sieve as a carrier, and takes one or more solutions of molybdenum salt, potassium salt, magnesium salt, cerium salt, cobalt salt, magnesium salt and aluminum salt as impregnant; the impregnant (M) is added to the carrier according to the constant volume impregnation method X ：M Carrier body =1 to 10%; x is the metal loaded by the catalyst), soaking for 6-24 hours at 20-60 ℃, filtering, drying the solid for 6-12 hours at 80-120 ℃, and roasting for 2-5 hours at 300-400 ℃ to obtain the organic sulfur hydrolysis catalyst.
The desulfurization catalyst takes one of active carbon, alumina and molecular sieve as a carrier, takes one or more solutions of copper salt, cerium salt, ferric salt, cobalt salt, manganese salt, lanthanum salt and silver salt as impregnant, and adds the impregnant (M) into the carrier at one time or in multiple times according to an equal volume impregnation method X :M Carrier body =1 to 10%; x is the metal supported by the catalyst)Soaking for 6-24 hours at 20-60 ℃, filtering, drying for 6-12 hours at 80-120 ℃, and roasting for 2-5 hours at 300-400 ℃ to obtain the desulfurization catalyst.
The catalyst regeneration is to take potassium hydroxide or sodium hydroxide solution with the mass concentration of 2-10% as regeneration liquid, put the deactivated desulfurization catalyst into the regeneration liquid to soak for 2-5 hours, soak for 2-5 times until the color of the soaking liquid is colorless, and then wash the regeneration liquid on the surface of the desulfurizing agent with deionized water at 15-40 ℃; and (5) drying at 80-120 ℃ for 6-15 h to obtain the regenerated desulfurizing agent.
The invention has the advantages that:
(1) According to the method, coke oven gas is introduced into blast furnace gas, so that the heat value of the blast furnace gas is improved, and hydrogen required by tail gas treatment is brought to the blast furnace gas; the process and tail gas treatment cost is reduced, and the resource utilization is realized to a certain extent;
(2) The method comprises the steps of selecting a proper catalyst to obtain organic sulfur (COS, CS) 2 ) Conversion to inorganic Sulfur (H) 2 S) after the catalyst is converted into elemental sulfur, sulfate and sulfide metal by a fine desulfurization catalyst; so that in the exhaust emission, COS and H 2 The S content is reduced to 20.0mg/m 3 Meanwhile, the fine desulfurization catalyst is regenerated, so that the environmental pollution caused by exhaust gas discharged into the air is eliminated, and the resource utilization rate is improved;
(3) The method of the invention is simple, low in investment and low in operation cost.
Drawings
FIG. 1 is a schematic flow chart of the method of the invention.
Detailed Description
The present invention will be further described in detail by the following drawings and examples, but the scope of the present invention is not limited to the above description, and the deoxidization and dechlorination processes in examples 1 to 4 use a conventional adsorption method to remove oxygen and hydrogen chloride in the mixed gas with a commercial deoxidization dechlorination adsorbent.
Example 1
1. Adding a molybdenum nitrate solution into a carrier by using active carbon as the carrier and using the molybdenum nitrate solution as an impregnating solution according to an isovolumetric impregnation method, wherein M Mo :M Carrier body =5%; soaking for 20 hours at 20 ℃, filtering, drying the solid at 80 ℃ for 6 hours, and roasting at 300 ℃ for 5 hours to obtain an organic sulfur hydrolysis catalyst A;
2. taking aluminum oxide as a carrier, taking a solution containing ferric nitrate and cobalt nitrate as an impregnating solution, and respectively adding the ferric nitrate and the cobalt nitrate solution into the carrier according to an equal volume impregnation method, wherein M Fe +M Co :M Carrier body =5%，M Fe :M Co =3:1, impregnating at room temperature for 12h, filtering, drying the solid at 80 ℃ for 6h, and then roasting at 300 ℃ for 5h to obtain a desulfurization catalyst a;
3. according to volume ratio V Blast furnace ：V Coke oven The ratio of =6:1, coke oven gas is introduced into blast furnace gas, and the smoke amount of the mixed gas is 4000m through measurement and calculation 3 And/h, the concentration of COS in the flue gas is 130mg/m 3 10mg/m of carbon disulfide 3 Hydrogen sulfide 40mg/m 3 Oxygen concentration is 0.5%, hydrogen concentration is 8.6%, and hydrogen chloride concentration is 50mg/m 3 The flue gas temperature is 130 ℃, and the dust concentration is 400mg/m 3 A heat value of 5000kJ/m 3 ；
4. As shown in FIG. 1, the mixed flue gas is firstly dedusted by a bag-type dust remover, and the dust concentration is reduced to 4mg/m after the dedusting 3 The method comprises the steps of carrying out a first treatment on the surface of the Before entering the catalytic hydrolysis process, the fixed bed adsorbent deoxidizing and dechlorinating are carried out, and the concentrations of oxygen and hydrogen chloride are respectively reduced to 0.03 percent and 8mg/m 3 Then feeding the mixture into a desulfurizing tower 1 filled with an organic sulfur hydrolysis catalyst, and converting carbonyl sulfur and carbon disulfide into hydrogen sulfide through hydrogenation conversion and catalytic hydrolysis under the condition of 130 ℃, wherein the total conversion efficiency reaches 95%; after the temperature of the converted flue gas is reduced to 100 ℃ by a heat exchanger, the flue gas is sent into a desulfurizing tower 2 filled with a desulfurizing catalyst to purify hydrogen sulfide, meanwhile, oxygen is added into the mixed gas, the oxygen concentration is increased to 0.1%, and the hydrogen sulfide is catalytically oxidized and converted into elemental sulfur, metal sulfide and sulfate under the action of the desulfurizing catalyst; the total sulfur content in the purified flue gas is 15mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then sending the purified flue gas into a smelting furnace for combustion; soaking the deactivated desulfurizing agent in 5wt% concentration sodium hydroxide solution for 3 times until the sodium hydroxide solution is colorless,washing off the regenerated liquid on the surface of the desulfurizing agent by using deionized water at 20 ℃, drying for 14 hours at 80 ℃, and controlling the total sulfur discharge to 20mg/m after 3 times of cyclic regeneration use 3 The following is given.
Example 2
1. Adding a molybdenum nitrate solution into a carrier by using a ZSM-5 molecular sieve as the carrier, using a molybdenum nitrate solution and a potassium carbonate solution as impregnating solution according to an isovolumetric impregnation method, wherein M Mo ：M Carrier body =5%; soaking at room temperature for 8 hr, filtering, oven drying at 100deg.C for 8 hr, adding the dried solid into potassium carbonate solution according to isovolumetric soaking method, wherein M K ：M Carrier body =3%; soaking for 15h at 30 ℃, drying the filtered solid at 90 ℃ for 8h, and roasting at 350 ℃ for 4h to obtain an organic sulfur hydrolysis catalyst B;
2. taking a 3A molecular sieve as a carrier, taking a solution containing copper acetate and cerium acetate as an impregnating solution, and respectively adding the copper acetate and cerium acetate solution into the carrier according to an equal volume impregnation method, wherein M Cu +M Ce :M Carrier body =5%，M Fe :M Co =2:1, impregnating at 30 ℃ for 15h, filtering, drying the solid at 80 ℃ for 6h, and then roasting at 350 ℃ for 4h to obtain a desulfurization catalyst B;
3. according to volume ratio V Blast furnace ：V Coke oven A ratio of =8:1, introducing coke oven gas into the blast furnace gas; the smoke volume of the mixed gas is 5000m through measurement and calculation 3 And/h, the concentration of COS in the flue gas is 135mg/m 3 Carbon disulfide concentration is 8mg/m 3 Hydrogen sulfide concentration of 45mg/m 3 Oxygen concentration is 0.8%, hydrogen concentration is 7.6%, and hydrogen chloride concentration is 35mg/m 3 The flue gas temperature is 150 ℃ and the dust concentration is 500mg/m 3 Heat value of 5700kJ/m 3 ；
4. The mixed flue gas is firstly dedusted by a bag-type dust remover, and the dust concentration is reduced to 3mg/m after dedusting 3 The method comprises the steps of carrying out a first treatment on the surface of the Before entering the catalytic hydrolysis process, the fixed bed adsorbent deoxidizing and dechlorinating are carried out, and the concentrations of oxygen and hydrogen chloride are respectively reduced to 0.04 percent and 10mg/m 3 Then, the mixture was fed into a desulfurizing tower 1 containing an organic sulfur hydrolysis catalyst, and carbonyl sulfide and disulfide were obtained at a temperature of 150 DEG CThe carbon is converted into hydrogen sulfide through hydroconversion and catalytic hydrolysis, and the total conversion efficiency reaches 98%; the converted flue gas is cooled to 120 ℃ by a heat exchanger, and then is sent into a desulfurizing tower 2 filled with a desulfurizing catalyst to purify hydrogen sulfide, and the hydrogen sulfide is converted into elemental sulfur, metal sulfide and sulfate by catalytic oxidation under the action of a desulfurizing agent; the total sulfur content in the purified flue gas is 10mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then sending the purified flue gas into a smelting furnace for combustion; soaking in 5wt% potassium hydroxide solution for 4 times until the color of potassium hydroxide solution is colorless, washing off the regenerated liquid on the surface of desulfurizing agent with 30 deg.c deionized water, stoving at 80 deg.c for 14 hr, and 3 times of cyclic regeneration to control the total sulfur discharge to 20mg/m 3 The following is given.
Example 3
1. Taking aluminum oxide as a carrier, taking magnesium nitrate and potassium carbonate as impregnating solution, adding a magnesium nitrate solution into the carrier according to an isovolumetric impregnation method, wherein M Mg ：M Carrier body =3%, standing at room temperature for 12 hr, oven drying at 100deg.C for 12 hr, adding the dried solid into potassium carbonate solution according to isovolumetric impregnation method, wherein M K ：M Carrier body =1%; standing for 7h at 55 ℃, drying for 12h at 100 ℃, and roasting for 3h at 300 ℃ to obtain the organic sulfur hydrolysis catalyst C;
2. adding cerium acetate solution into a carrier by using a 5A molecular sieve as the carrier and cerium acetate as an impregnating solution according to an isovolumetric impregnation method, wherein M Mg ：M Carrier body =3%; standing at 55 ℃ for 24 hours, drying at 100 ℃ for 12 hours, and roasting at 400 ℃ for 2 hours to obtain a desulfurization catalyst C;
3. according to volume ratio V Blast furnace ：V Coke oven The method comprises the steps of (1) introducing coke oven gas into blast furnace gas, and measuring and calculating the smoke amount of the mixed gas to be 8000m 3 And/h, the concentration of COS in the flue gas is 125mg/m 3 Carbon disulfide concentration is 5mg/m 3 Hydrogen sulfide concentration of 35mg/m 3 Oxygen concentration is 0.7%, hydrogen concentration is 6.2%, and hydrogen chloride concentration is 40mg/m 3 The flue gas temperature is 180 ℃ and the dust concentration is 550mg/m 3 A heat value of 5000kJ/m 3 ；
4. The mixed flue gas is firstly removed by a cloth bagThe dust collector removes dust, and the dust concentration is reduced to 3mg/m after the dust removal 3 The method comprises the steps of carrying out a first treatment on the surface of the Before entering the catalytic hydrolysis process, the fixed bed adsorbent deoxidizes and removes chlorine, the concentrations of oxygen and hydrogen chloride are respectively reduced to 0.03 percent and 7 mg/m 3 Then feeding the mixture into a desulfurizing tower 1 filled with an organic sulfur hydrolysis catalyst, and converting carbonyl sulfur and carbon disulfide into hydrogen sulfide through hydrogenation conversion and catalytic hydrolysis under the condition of 180 ℃ with the total conversion efficiency reaching 96%; the converted flue gas is cooled to 120 ℃ by a heat exchanger, and then is sent into a desulfurizing tower 2 filled with a desulfurizing catalyst to purify hydrogen sulfide, and the hydrogen sulfide is converted into elemental sulfur, metal sulfide and sulfate by catalytic oxidation under the action of a desulfurizing agent; the total sulfur content in the purified flue gas is 10mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the Then sending the purified flue gas into a smelting furnace for combustion; soaking in 8wt% sodium hydroxide solution for 5 times until the color of sodium hydroxide solution is colorless, washing off the regenerated solution on the surface of the desulfurizing agent with 20deg.C deionized water, oven drying at 80deg.C for 14 hr, and circulating and regenerating the desulfurizing catalyst for 3 times to control total sulfur discharge to 20mg/m 3 The following is given.
Example 4
1. Sequentially adding a magnesium nitrate solution, a potassium carbonate solution and a molybdenum nitrate solution into a carrier by using aluminum oxide as a carrier and magnesium nitrate, potassium carbonate and molybdenum nitrate as impregnating solutions according to an equal volume impregnation method, standing for 6 hours after adding one solution each time, and drying for 8 hours at 100 ℃ until adding the last solution; wherein M is Mg +M K +M Mo :M Carrier body =4%，M Mg :M K :M Mo Impregnating for 12h at 40 ℃, drying for 24h at 100 ℃, and roasting for 4h at 350 ℃ to obtain the organic sulfur hydrolysis catalyst;
2. taking a 10X molecular sieve as a carrier, taking copper acetate as an impregnating solution, and adding a copper acetate solution into the carrier according to an isovolumetric impregnation method, wherein M Cu :M Carrier body =5%, soaking at 40 deg.c for 12 hr, stoving at 100 deg.c for 24 hr, and roasting at 350 deg.c for 4 hr to obtain desulfurizing catalyst;
3. laboratory preparation of a mixture (V) simulating blast furnace gas and coke oven gas Blast furnace :V Coke oven =12:1) gas flow was 500mL/min, smokeThe concentration of COS in the gas is 115mg/m 3 Carbon disulfide concentration is 5mg/m 3 Hydrogen sulfide concentration of 30mg/m 3 Oxygen concentration is 0.6%, hydrogen concentration is 5.7%, and hydrogen chloride concentration is 45mg/m 3 CO concentration is 20%, CO 2 Concentration 20% and methane concentration 3%;
4. deoxidizing and dechlorinating the organic sulfur by using an adsorbent in a fixed bed before converting the organic sulfur, and reducing the oxygen concentration and the hydrogen chloride to 0.02% and 5mg/m respectively 3 Then feeding the mixture into a fixed bed filled with an organic sulfur hydrolysis catalyst, and converting carbonyl sulfide and carbon disulfide into hydrogen sulfide at the temperature of 200 ℃, wherein the total conversion efficiency reaches 99%; then the mixed gas is sent into a fixed bed filled with a desulfurization catalyst through cooling by a cooling bottle, the reaction temperature is 120 ℃, and hydrogen sulfide is converted into elemental sulfur, metal sulfide and sulfate through catalytic oxidation under the action of a desulfurizing agent; the total sulfur content in the purified flue gas is 5mg/m 3 。
Claims (1)
1. A method for improving the combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur is characterized in that: mixing blast furnace gas and coke oven gas according to the volume ratio of 6-12:1, dedusting, deoxidizing and dechlorinating the mixed gas, then under the action of an organic sulfur hydrolysis catalyst, making the organic sulfur in the mixed gas undergo the processes of catalytic hydrolysis reaction and hydro-conversion reaction at 100-200 ℃ to produce inorganic sulfur, after the mixed gas is hydrolyzed and converted into organic sulfur, utilizing a heat exchanger to reduce the temperature of the mixed gas to 80-150 ℃, introducing oxygen into the mixed gas to make the oxygen content be 0.05-0.8% by volume, under the action of a desulfurization catalyst, making H in the mixed gas 2 S generates sulfur simple substance, metal sulfide and sulfate through catalytic oxidation reaction at 80-150 ℃ and is adsorbed on a catalyst, so that the aim of improving the combustion heat value of blast furnace gas and simultaneously removing organic sulfur and inorganic sulfur is fulfilled;
the dust concentration after dust removal is less than 5mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the After deoxidization and dechlorination, the concentrations of oxygen and hydrogen chloride are respectively reduced to 0.05 percent and 10mg/m 3 The following are set forth;
the organic sulfur hydrolysis catalyst is prepared from active carbon, alumina and moleculesOne of the sieves is used as a carrier, and one or more solutions of molybdenum salt, potassium salt, magnesium salt, cerium salt, cobalt salt, magnesium salt and aluminum salt are used as impregnant; adding impregnant into the carrier according to the constant volume impregnation method at one time or in multiple times, M X ∶M Carrier body =1 to 10%; x is the metal loaded by the catalyst, after soaking for 6-24 hours at 20-60 ℃, filtering, drying the solid for 6-12 hours at 80-120 ℃, and then roasting for 2-5 hours at 300-400 ℃ to obtain the organic sulfur hydrolysis catalyst;
the desulfurization catalyst takes one of active carbon, alumina and molecular sieve as a carrier, takes one or more solutions of copper salt, cerium salt, ferric salt, cobalt salt, manganese salt, lanthanum salt and silver salt as impregnant, and adds the impregnant into the carrier at one time or in multiple times according to an equal volume impregnation method, M X ∶M Carrier body =1 to 10%; x is the metal loaded by the catalyst, after soaking for 6-24 hours at 20-60 ℃, filtering, drying for 6-12 hours at 80-120 ℃, and then roasting for 2-5 hours at 300-400 ℃ to obtain the desulfurization catalyst;
the catalyst regeneration is to take potassium hydroxide or sodium hydroxide solution with the mass concentration of 2-10% as regeneration liquid, put the deactivated desulfurization catalyst into the regeneration liquid to soak for 2-5 hours, soak for 2-5 times until the color of the soaking liquid is colorless, and then wash the regeneration liquid on the surface of the desulfurizing agent with deionized water with the temperature of 15-40 ℃; drying at 80-120 deg.c for 6-15 hr to obtain regenerated desulfurizing agent.
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