阅读说明：本技术 脱硫剂再生方法和脱硫-再生方法及系统 (Desulfurizing agent regeneration method and desulfurization-regeneration method and system ) 是由 刘时球 于 2021-08-06 设计创作，主要内容包括：本发明实施例提出了脱硫剂再生方法和脱硫-再生方法以及系统。所述脱硫剂再生方法例如包括：(1)将预设温度的再生气体以指定的体积空速导入脱硫装置内的催化剂床层的一侧,催化剂床层所包括的固体脱硫剂包含多孔性材料载体和负载于多孔性材料载体孔内的络合铁催化剂,多孔性材料载体孔内因固体脱硫剂应用于脱硫而吸附有单质硫,以及预设温度低于络合铁催化剂的热解温度且高于单质硫的熔点；(2)由再生气体将单质硫从多孔性材料载体孔内吹出,以得到位于催化剂床层的另一相对侧且含有单质硫的再生后气体；以及(3)将再生后气体自催化剂床层的所述另一相对侧排出脱硫装置。本发明实施例可以对脱硫剂性能进行再生,有利于实现较高的脱硫效率。(The embodiment of the invention provides a desulfurizing agent regeneration method, a desulfurizing-regenerating method and a desulfurizing-regenerating system. The desulfurizing agent regeneration method includes, for example: (1) introducing regeneration gas with preset temperature into one side of a catalyst bed layer in a desulfurization device at a designated volume space velocity, wherein a solid desulfurizer included in the catalyst bed layer comprises a porous material carrier and a complex iron catalyst loaded in pores of the porous material carrier, elemental sulfur is adsorbed in the pores of the porous material carrier due to the fact that the solid desulfurizer is applied to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the complex iron catalyst and higher than the melting point of the elemental sulfur; (2) blowing the elemental sulfur out of the pores of the porous material carrier by using the regenerated gas to obtain regenerated gas which is positioned on the other opposite side of the catalyst bed and contains the elemental sulfur; and (3) discharging the regenerated gas from the other opposite side of the catalyst bed out of the desulfurization device. The embodiment of the invention can regenerate the performance of the desulfurizer, and is beneficial to realizing higher desulfurization efficiency.)

1. A method for regenerating a desulfurizing agent, comprising:

introducing regeneration gas with a preset temperature into one side of a catalyst bed layer (310) in a desulfurization device (300) at a specified volume space velocity, wherein the catalyst bed layer (310) comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and a complex iron catalyst loaded in pores of the porous material carrier, elemental sulfur is adsorbed in the pores of the porous material carrier due to the solid desulfurizer applied to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the complex iron catalyst and higher than the melting point of the elemental sulfur;

blowing the elemental sulfur out of pores of the porous material carrier by the regeneration gas to obtain a regenerated gas which is positioned at the other opposite side of the catalyst bed (310) in the desulfurization device (300) and contains the elemental sulfur; and

discharging the regenerated gas from the other opposite side of the catalyst bed (310) out of the desulfurization unit (300).

2. The desulfurizing agent regeneration method according to claim 1, wherein the preset temperature is 150 ℃ to 220 ℃, and the volume space velocity is 50 h to 1000h^-1。

3. According to the rightThe desulfurizing agent regeneration method according to claim 2, wherein the volume space velocity is 200 to 500 hours^-1The regeneration gas is nitrogen, or the regeneration gas is desulfurized blast furnace gas or coke oven gas.

4. The desulfurizing agent regenerating method according to claim 1, further comprising:

and when the breakthrough sulfur capacity of the solid desulfurizing agent is not lower than 70% of the initial breakthrough sulfur capacity before the solid desulfurizing agent is applied to desulfurization, stopping introducing the regeneration gas.

5. The desulfurizing agent regeneration method according to any one of claims 1 to 4, wherein the complex iron catalyst of the solid desulfurizing agent is derived from a complex iron solution containing 0.01 to 0.06mol/L of complex iron ions, and the raw materials of the complex iron solution comprise: the iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to iron in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron in the iron source is 1.0-2.0, the pH value of the complexing iron solution is adjusted to 8.0-12.0 by the pH regulator, and the organic complexing agent is an aminocarboxylic acid complexing agent.

6. A desulfurization-regeneration method, characterized by comprising:

a desulfurization step comprising:

introducing a gas to be desulfurized, which comprises hydrogen sulfide and oxygen, to one side of a first catalyst bed layer loaded in a first desulfurization device, wherein the first catalyst bed layer comprises a first solid desulfurizing agent, and the first solid desulfurizing agent comprises a first porous material carrier and a first complex iron catalyst loaded in pores of the first porous material carrier;

carrying out oxidation-reduction reaction on the first complex iron catalyst loaded in the pores of the first porous material carrier and the hydrogen sulfide to generate elemental sulfur and complex ferrous ions, oxidizing and regenerating the complex ferrous ions into complex ferric ions by the oxygen, and obtaining desulfurized gas positioned on the other opposite side of the first catalyst bed layer; and

discharging the desulfurized gas from the first desulfurization unit from the other opposite side of the first catalyst bed; and

a regeneration step comprising:

heating the desulfurized gas discharged from the first desulfurization device to a preset temperature, and introducing the desulfurized gas into one side of a second catalyst bed layer in a second desulfurization device at a designated volume space velocity to serve as regeneration gas, wherein the second catalyst bed layer comprises a second solid desulfurizing agent, the second solid desulfurizing agent comprises a second porous material carrier and a second complex iron catalyst loaded in pores of the second porous material carrier, elemental sulfur is adsorbed in the pores of the second porous material carrier due to the fact that the second solid desulfurizing agent is applied to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the second complex iron catalyst and higher than the melting point of the elemental sulfur;

blowing the elemental sulfur out of the pores of the second porous material carrier by the regeneration gas to obtain a regenerated gas which is positioned at the other opposite side of the second catalyst bed layer in the second desulfurization device and contains the elemental sulfur; and

and discharging the regenerated gas out of the second desulfurization device from the other opposite side of the catalyst bed.

7. The desulfurization-regeneration method according to claim 6, wherein the preset temperature is 150 ℃ to 220 ℃, and the volume space velocity is 50 to 1000h^-1The complex iron catalyst of the second solid desulfurizing agent is derived from a complex iron solution containing 0.01-0.06 mol/L complex iron ions, and the raw materials of the complex iron solution comprise: the iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to iron elements in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron elements in the iron source is 1.0-2.0, and the pH regulator regulates the pH value of the complexing iron solution to be 8.0 ℃upto c12.0。

8. The desulfurization-regeneration method according to claim 6 or 7, wherein the first porous material support and the second porous material support are activated carbon, and the desulfurization-regeneration method further comprises:

throwing the used first solid desulfurizer into a furnace kiln for producing blast furnace gas or coke-oven gas for combustion;

and when the breakthrough sulfur capacity of the second solid desulfurizing agent is not lower than 70% of the initial breakthrough sulfur capacity before the second solid desulfurizing agent is applied to desulfurization, stopping introducing the regeneration gas.

9. A desulfurization-regeneration system (30), characterized by comprising: the system comprises a plurality of desulfurization devices (300), a heat exchanger (400), an air pump (500), a first gas input pipeline (301), a first gas output pipeline (303), a second gas input pipeline (305) and a second gas output pipeline (307) which are connected in parallel;

wherein the gas inlets (330) of the plurality of desulfurization devices (300) are connected with the same first gas input pipeline (301), the gas outlets (350) of the plurality of desulfurization devices (300) are connected with the same first gas output pipeline (303), the gas inlets (330) of the plurality of desulfurization devices (300) are sequentially connected with the same second gas input pipeline (305) through the heat exchanger and the gas pump, and the gas outlets (350) of the plurality of desulfurization devices (300) are connected with the same second gas output pipeline (307);

a catalyst bed layer (310) is arranged in each desulfurization device (300), the catalyst bed layer (310) comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and a complex iron catalyst loaded in pores of the porous material carrier, the solid desulfurizer is used for desulfurizing a gas to be desulfurized, which is sequentially introduced through the first gas input pipeline (301) and the gas inlet (330) and contains hydrogen sulfide and oxygen, so that the complex iron catalyst reacts with the hydrogen sulfide to generate elemental sulfur and complex ferrous ions, the oxygen oxidizes the complex ferrous ions into complex iron ions, and the obtained desulfurized gas is sequentially discharged through the gas outlet (350) and the first gas output pipeline (303);

the gas inlet (330) connected with the second gas input pipeline (305) is used for leading in the desulfurization device (300) with a specified volume space velocity through the second gas input pipeline (305), the gas pump (500) and the heat exchanger (400) in sequence to generate a regeneration gas with a preset temperature, the regeneration gas is used for blowing out the elemental sulfur adsorbed in the porous material carrier holes due to the application of the solid desulfurizer in desulfurization so as to obtain a regenerated gas containing the elemental sulfur, and the gas outlet (350) connected with the second gas output pipeline (307) is used for discharging the regenerated gas through the second gas output pipeline (307), and the preset temperature is lower than the pyrolysis temperature of the complex iron catalyst and higher than the melting point of the elemental sulfur.

10. The desulfurization-regeneration system according to claim 9, wherein said second gas input line (305) is connected to said first gas output line (303), and said volumetric space velocity is 50-1000 h^-1The complex iron catalyst of the solid desulfurizer is derived from a complex iron solution containing 0.01-0.06 mol/L complex iron ions, and the raw materials of the complex iron solution comprise: the iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to iron in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron in the iron source is 1.0-2.0, the pH value of the complexing iron solution is adjusted to 8.0-12.0 by the pH regulator, and the organic complexing agent is an aminocarboxylic acid complexing agent.

Technical Field

The invention relates to the technical field of gas purification and environmental protection, in particular to a desulfurizing agent regeneration method, a desulfurizing-regenerating method and a desulfurizing-regenerating system.

Background

Raw material gases such as blast furnace gas or coke oven gas (also called coke oven gas) and the like, which contain hydrogen sulfide (H) with different concentrations, can be generated in the production processes of steel smelting, coal chemical industry and the like₂S) gases, even organic sulfides (e.g. carbonyl sulfide), which, after hydrolysis, produce H₂S), high concentration of H₂The presence of S not only contaminates the ringEnvironmental and corrosive pipeline equipment, influence on product quality and cause catalyst poisoning and inactivation in subsequent process production, thereby removing H in gas phase₂S is a very important process. However, the conventional desulfurization method has low desulfurization efficiency and poor regeneration performance of the desulfurizing agent.

Disclosure of Invention

Therefore, embodiments of the present invention provide a desulfurizing agent regeneration method, a desulfurization-regeneration method, and a desulfurization-regeneration system, which can regenerate the desulfurization performance of a desulfurizing agent used after desulfurization, and are advantageous for achieving higher desulfurization efficiency.

Specifically, the embodiment of the invention discloses a method for regenerating a desulfurizing agent, which comprises the following steps: (i) introducing regeneration gas with a preset temperature into one side of a catalyst bed layer in a desulfurization device at a specified volume space velocity, wherein the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and a complex iron catalyst loaded in pores of the porous material carrier, elemental sulfur is adsorbed in the pores of the porous material carrier due to the application of the solid desulfurizer to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the complex iron catalyst and higher than the melting point of the elemental sulfur; (ii) blowing the elemental sulfur out of the pores of the porous material carrier by the regeneration gas to obtain a regenerated gas which is positioned on the other opposite side of the catalyst bed layer in the desulfurization device and contains the elemental sulfur; and (iii) discharging the regenerated gas from the other opposite side of the catalyst bed out of the desulfurization unit.

In one embodiment of the invention, the preset temperature is 150-220 ℃, and the volume space velocity is 50-1000 h^-1。

In one embodiment of the invention, the volume space velocity is 200-500 h^-1The regeneration gas is nitrogen, or the regeneration gas is desulfurized blast furnace gas or coke oven gas.

In one embodiment of the present invention, the desulfurizing agent regenerating method further comprises: and when the breakthrough sulfur capacity of the solid desulfurizing agent is not lower than 70% of the initial breakthrough sulfur capacity before the solid desulfurizing agent is applied to desulfurization, stopping introducing the regeneration gas.

In one embodiment of the invention, the complex iron catalyst of the solid desulfurizing agent is derived from a complex iron solution containing 0.01-0.06 mol/L complex iron ions, and the raw materials of the complex iron solution comprise: the iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to iron in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron in the iron source is 1.0-2.0, the pH value of the complexing iron solution is adjusted to 8.0-12.0 by the pH regulator, and the organic complexing agent is an aminocarboxylic acid complexing agent.

In another aspect, an embodiment of the present invention provides a desulfurization-regeneration method, including: (a) a desulfurization step comprising: (a-1) introducing a gas to be desulfurized, which comprises hydrogen sulfide and oxygen, to one side of a first catalyst bed loaded in a first desulfurization device, wherein the first catalyst bed comprises a first solid desulfurizing agent, and the first solid desulfurizing agent comprises a first porous material carrier and a first complex iron catalyst loaded in pores of the first porous material carrier; (a-2) carrying out redox reaction on the first complex iron catalyst loaded in the pores of the first porous material carrier and the hydrogen sulfide to generate elemental sulfur and complex ferrous ions, oxidizing and regenerating the complex ferrous ions into complex ferric ions by the oxygen, and obtaining desulfurized gas positioned on the other opposite side of the first catalyst bed layer; and (a-3) discharging the desulfurized gas from said first desulfurization unit from said opposite side of said first catalyst bed; and (b) a regeneration step comprising: (b-1) heating the desulfurized gas discharged from the first desulfurization device to a preset temperature, and introducing the desulfurized gas into one side of a second catalyst bed layer in a second desulfurization device at a designated volume space velocity to serve as regeneration gas, wherein the second catalyst bed layer comprises a second solid desulfurizer, the second solid desulfurizer comprises a second porous material carrier and a second complex iron catalyst loaded in pores of the second porous material carrier, elemental sulfur is adsorbed in the pores of the second porous material carrier due to the second solid desulfurizer applied to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the second complex iron catalyst and higher than the melting point of the elemental sulfur; (b-2) blowing out the elemental sulfur from the pores of the second porous material carrier by the regeneration gas to obtain a regenerated gas which is located on the other opposite side of the second catalyst bed in the second desulfurization device and contains the elemental sulfur; and (b-3) discharging the regenerated gas from the other opposite side of the catalyst bed out of the second desulfurization unit.

In one embodiment of the invention, the preset temperature is 150-220 ℃, and the volume space velocity is 50-1000 h^-1The complex iron catalyst of the second solid desulfurizing agent is derived from a complex iron solution containing 0.01-0.06 mol/L complex iron ions, and the raw materials of the complex iron solution comprise: the iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to iron in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron in the iron source is 1.0-2.0, and the pH value of the complexing iron solution is regulated to 8.0-12.0 by the pH regulator.

In one embodiment of the present invention, the first porous material support and the second porous material support are activated carbon, and the desulfurization-regeneration method further includes: throwing the used first solid desulfurizer into a furnace kiln for producing blast furnace gas or coke-oven gas for combustion; and/or stopping introducing the regeneration gas when the breakthrough sulfur capacity of the second solid desulfurizing agent is not lower than 70% of the initial breakthrough sulfur capacity before the second solid desulfurizing agent is applied to desulfurization.

In another aspect, an embodiment of the present invention provides a desulfurization-regeneration system, including: the system comprises a plurality of desulfurization devices, a heat exchanger, an air pump, a first gas input pipeline, a first gas output pipeline, a second gas input pipeline and a second gas output pipeline which are connected in parallel; the gas inlets of the plurality of desulfurization devices are connected with the same first gas input pipeline, the gas outlets of the plurality of desulfurization devices are connected with the same first gas output pipeline, the gas inlets of the plurality of desulfurization devices are sequentially connected with the same second gas input pipeline through the heat exchanger and the gas pump, and the gas outlets of the plurality of desulfurization devices are connected with the same second gas output pipeline; each desulfurization device is internally provided with a catalyst bed layer, the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and a complex iron catalyst loaded in pores of the porous material carrier, the solid desulfurizer is used for desulfurizing a gas to be desulfurized, which is sequentially led in through the first gas input pipeline and the gas inlet and contains hydrogen sulfide and oxygen, so that the complex iron catalyst and the hydrogen sulfide react to generate elemental sulfur and complex ferrous ions, the oxygen oxidizes the complex ferrous ions into complex iron ions, and the obtained desulfurized gas is sequentially discharged through the gas outlet and the first gas output pipeline; wherein, connect the second gas input pipeline the air inlet is used for passing through in proper order the second gas input pipeline the air pump with heat exchanger is with appointed volume airspeed to leading-in regeneration gas of predetermineeing the temperature in the desulphurization unit, just regeneration gas is used for will because of solid desulfurizer is applied to the desulfurization and adsorbs porous material carrier hole's elemental sulfur blows out in order to obtain and contains the regeneration back gas of elemental sulfur, and connects the second gas output pipeline the gas outlet be used for with regeneration back gas via the second gas output pipeline discharges, predetermine the temperature and be less than the pyrolysis temperature of complex iron catalyst and be higher than the melting point of elemental sulfur.

In one embodiment of the invention, the second gas input pipeline (305) is connected with the first gas output pipeline (303), and the volume space velocity is 50-1000 h^-1The complex iron catalyst of the solid desulfurizer is derived from a complex iron solution containing 0.01-0.06 mol/L complex iron ions, and the raw materials of the complex iron solution comprise: an iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to the iron element in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron element in the iron source is 1.0-2.0,the pH value of the complexing iron solution is adjusted to 8.0-12.0 by the pH regulator, and the organic complexing agent is an aminocarboxylic acid complexing agent.

The technical scheme can have the following advantages or beneficial effects: according to the desulfurizer regeneration method, the desulfurization-regeneration method and the desulfurization-regeneration system provided by the embodiment of the invention, the elemental sulfur in the porous material carrier pores can be blown out by introducing the regeneration gas with the preset temperature at the designated volume airspeed, so that the blocked pore channels are reopened, and the performance regeneration of the solid desulfurizer is realized, so that the regenerated solid desulfurizer can be desulfurized again, and the higher desulfurization efficiency is favorably realized. Moreover, the desulfurization and regeneration of different desulfurization units can be performed simultaneously, which is favorable for further improving the desulfurization efficiency. In addition, the solid desulfurizing agent is obtained by adsorbing and complexing the iron solution through a porous material carrier such as activated carbon, can be used for desulfurizing a gas to be desulfurized containing hydrogen sulfide and oxygen, i.e. oxidizing hydrogen sulfide into elemental sulfur, and can realize a desulfurization-regeneration cycle process, thereby having higher desulfurization efficiency. In addition, harmful impurity anions such as chloride ions and nitrate ions are not introduced into the iron complex solution, so that the problems of serious corrosion of chloride ions to equipment, easy explosion when the nitrate ions meet carbon, difficult wastewater treatment and the like can be avoided. Finally, the activated carbon left after the desulfurization of the solid desulfurizer in the embodiment of the invention can be directly burned in a furnace, the treatment is convenient, and the solid waste pollution to the environment is avoided.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a flow chart of a method for regenerating a desulfurizing agent according to an embodiment of the present invention.

FIG. 2 is a schematic view showing the structure of a desulfurizing device suitable for the desulfurizing agent regenerating method shown in FIG. 1.

Fig. 3 is a schematic structural diagram of a desulfurization-regeneration system according to an embodiment of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the invention described herein are, for example, capable of operation in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

Referring to fig. 1 and 2, fig. 1 is a flow chart of a method for regenerating a desulfurizing agent according to an embodiment of the present invention, and fig. 2 is a schematic structural diagram of a desulfurizing device suitable for the method for regenerating a desulfurizing agent shown in fig. 1. Specifically, as shown in fig. 1, the desulfurizing agent regenerating method includes:

step S31: introducing regeneration gas with a preset temperature into one side of a catalyst bed layer in a desulfurization device at a specified volume space velocity, wherein the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and a complex iron catalyst loaded in pores of the porous material carrier, elemental sulfur is adsorbed in the pores of the porous material carrier due to the application of the solid desulfurizer to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the complex iron catalyst and higher than the melting point of the elemental sulfur;

step S33: blowing the elemental sulfur out of the pores of the porous material carrier by the regeneration gas to obtain a regenerated gas which is positioned on the other opposite side of the catalyst bed layer in the desulfurization device and contains the elemental sulfur; and

step S35: and discharging the regenerated gas out of the desulfurization device from the other opposite side of the catalyst bed.

For example, the desulfurization unit 300 in step S31 is shown in fig. 2, for example, and includes a catalyst bed 310, an inlet 330, and an outlet 350. Wherein, the catalyst bed layer 310 is loaded inside the desulfurization device 300 (for example, inside the reaction tank of the desulfurization device 300), and comprises a solid desulfurizing agent, and the solid desulfurizing agent comprises a porous material carrier and a complex iron catalyst loaded in the pores of the porous material carrier. Of course, the catalyst bed 310 further includes, for example, a grid plate or a pore plate for supporting the solid desulfurizing agent, so that the solid desulfurizing agent can be sandwiched between two oppositely disposed grid plates or pore plates. Furthermore, the gas inlet 330 can be used for introducing the gas to be desulfurized and also can be used for introducing the regeneration gas; the number of the regeneration gas and the desulfurization gas can be one, so that the gas to be desulfurized and the regeneration gas are reused in time; or two gas inlets are provided for introducing the gas to be desulfurized and the regeneration gas, respectively, and the two gas inlets may be located on the same side of the catalyst bed 310 or on opposite sides of the catalyst bed 310. The gas outlet 350 may be used for discharging desulfurized gas or regenerated gas; the number of the gas-liquid separation device can be one, so that the desulfurized gas and the regenerated gas are reused in a time-sharing manner; or two gas outlets are respectively used for discharging the desulfurized gas and the regenerated gas, and the two gas outlets can be positioned on the same side of the catalyst bed layer 310 or respectively arranged on two opposite sides of the catalyst bed layer 310. Of course, it is understood that the gas inlet for introducing the gas to be desulfurized and the gas outlet for discharging the desulfurized gas are disposed on opposite sides of the catalyst bed 310, and the gas inlet for introducing the regeneration gas and the gas outlet for discharging the regenerated gas are disposed on opposite sides of the catalyst bed 310. Further, it is understood that the inlet port 330 and the outlet port 350 are respectively provided with valves. In addition, for the solid desulfurizing agent of the embodiment, the desulfurization performance parameters are as follows:

(x1) the reaction temperature is 20-150 ℃, preferably 40-110 ℃, and the temperature of the gas to be desulfurized is self-carried;

(x2) water vapor content of 0 to 90% of saturated steam of water at a specific temperature (e.g., reaction temperature), with water vapor carried by the gas to be desulfurized;

(x3) the volume space velocity of the gas to be desulfurized in contact with the solid desulfurizing agent is 100-3000 h^-1The volume space velocity here is the ratio of the volume of the gas to be desulfurized per hour passing through the catalyst bed 310 to the volume of the solid desulfurizing agent;

(x4) the reaction pressure is 0.1MPa to 8.0MPa (megapascals);

(x5) oxygen (O) in the gas to be desulfurized₂): hydrogen sulfide (H)₂S) the concentration ratio is 2-50, preferably 3-20;

(x6) the breakthrough sulfur capacity of the solid desulfurizer (i.e. the initial breakthrough sulfur capacity before the solid desulfurizer is applied to desulfurization, or the breakthrough sulfur capacity of the fresh solid desulfurizer) is 15-35%, where the breakthrough sulfur capacity is the capacity of the solid desulfurizer per unit volume capable of absorbing sulfur while ensuring the process purification degree index, which is the H content in the desulfurized gas₂The S concentration is, for example, less than or equal to 1mg/m³(mg/cubic meter);

(x7) the gas to be desulfurized is itself a mixed gas, which is derived from raw gas such as blast furnace gas or coke oven gas, for example, raw gas after hydrolyzing organic sulfide (such as carbonyl sulfide), although the case of raw gas without hydrolysis is not excluded;

(x8) concentration of oxygen in the gas to be desulphurized: when the porous material carrier is activated carbon, the oxygen concentration is less than 0.3%, and correspondingly, the concentration of hydrogen sulfide in the gas to be desulfurized is 5-1500 ppm (Parts Per Million ), preferably 50-1000 ppm; when the porous material carrier is other porous material such asAlumina (Al)₂O₃) Or silicon dioxide (SiO)₂) The oxygen concentration may suitably be higher than 0.3%, such as lower than 0.8%, and correspondingly the concentration of hydrogen sulphide in the gas to be desulphurised may be 4000ppm and below.

In step S31, the condition parameters for the performance regeneration process design of the solid desulfurizing agent with elemental sulfur adsorbed in the pores of the porous material carrier are as follows:

(y1) the regeneration temperature (corresponding to the preset temperature in step S31) is, for example, 150 ℃ to 220 ℃, too high temperature is likely to cause pyrolysis of the organic complex iron catalyst, and too low temperature cannot blow out elemental sulfur, so the design requirement of the regeneration temperature is: lower than the pyrolysis temperature of the organic complex iron catalyst and higher than the melting point of elemental sulfur;

(y2) regeneration time: the penetration sulfur capacity of the solid desulfurizer after the first regeneration is not less than 70% of the penetration sulfur capacity of the fresh solid desulfurizer (namely before the first desulfurization) according to the determination of the elemental sulfur adsorption quantity, and in the same way, the penetration sulfur capacity after the Nth (N is more than or equal to 2) regeneration is not less than 70% of the penetration sulfur capacity before the Nth desulfurization;

(y3) regeneration gas: nitrogen, or desulfurized blast furnace gas or coke oven gas;

(y4) regeneration space velocity: 50 to 1000 hours^-1Preferably 200 to 500 hours^-1；

(y5) the regenerated effluent is predominantly elemental sulphur.

In summary, the process of applying the solid desulfurizing agent to desulfurization is roughly as follows: taking a porous material carrier as active carbon as an example, when a gas to be desulfurized at a certain temperature and humidity (part of water vapor in the gas to be desulfurized) passes through the solid desulfurizer of the catalyst bed 310 according to a certain volume space velocity, hydrogen sulfide in the gas to be desulfurized and a complex iron catalyst (ferric iron) loaded in pores of the active carbon undergo an oxidation-reduction reaction to generate elemental sulfur and complex ferrous iron ions (ferrous iron ions), and oxygen molecules in the gas to be desulfurized can rapidly oxidize the complex ferrous iron ions reduced by the hydrogen sulfide into complex iron ions to regenerate the complex iron ions, thereby realizing a desulfurization-regeneration cycle process. The gas to be desulfurized is here itself a mixed gas,the main components including, for example, CO and CO₂、H₂S and N₂The oxygen source of less than 0.3% in the gas to be desulfurized can be oxygen carried by the raw material gas such as blast furnace gas or coke oven gas, and can also be oxygen supplemented according to the concentration of hydrogen sulfide in the raw material gas when no oxygen exists in the raw material gas. Moreover, in the desulfurization-regeneration cycle process, the microporous structure of the activated carbon provides a reaction site for desulfurization reaction, enhances the contact probability of hydrogen sulfide and ferric ions as well as oxygen to ferrous ions, and provides reaction performance; meanwhile, the high specific surface area of the activated carbon provides a loading place for the generated elemental sulfur. The solid desulfurizing agent is considered to be penetrated only when most of the pore channels in the activated carbon are blocked by the generated elemental sulfur and most of the gas to be desulfurized can not enter the pore channels to contact with the complex iron catalyst.

Therefore, in step S33, for the penetrated or near penetrated solid desulfurizing agent (elemental sulfur is adsorbed in the pores of the porous material carrier), the elemental sulfur adsorbed in the pores of the porous material carrier such as activated carbon needs to be blown out at a certain temperature, specifically: the elemental sulfur is blown out from the pores of the porous material carrier by the regeneration gas, so as to obtain a regenerated gas which is located on the other opposite side of the catalyst bed 310 in the desulfurization device 300 and contains the elemental sulfur. Thereby, the pore channels of the blocked porous material carrier can be reopened, so that the solid desulfurizing agent with regenerated performance can be applied to desulfurization again.

Thereafter, in step S35, the regenerated gas is discharged from the gas outlet 350 of the desulfurization device 300 located at the other opposite side of the catalyst bed 310 to enter other sections, for example, the regenerated gas is discharged to a flue gas treatment system. The regeneration time of the solid desulfurizing agent can be designed as follows: when the breakthrough sulfur capacity of the solid desulfurizing agent is not less than 70% of the initial breakthrough sulfur capacity before the solid desulfurizing agent is applied to desulfurization, the introduction of the regeneration gas is stopped.

In other embodiments, to further improve desulfurization efficiency, multiple desulfurization units may be connected together in parallel to form a desulfurization-regeneration system as shown in fig. 3. Specifically, as shown in fig. 3, the desulfurization-regeneration system 30 includes: a plurality of desulfurization devices 300, a heat exchanger 400, an air pump 500, a first gas input line 301, a first gas output line 303, a second gas input line 305, and a second gas output line 307, which are connected in parallel.

The gas inlets 330 of the plurality of desulfurization devices 300 are connected to the same first gas input pipeline (or called a gas input pipeline to be desulfurized) 301, the gas outlets 350 of the plurality of desulfurization devices 300 are connected to the same first gas output pipeline (or called a desulfurized gas output pipeline) 303, the gas inlets 330 of the plurality of desulfurization devices 300 are connected to the same second gas input pipeline (or called a regenerated gas input pipeline) 305 through the heat exchanger 400 and the gas pump 500 in sequence, and the gas outlets 350 of the plurality of desulfurization devices 300 are connected to the same second gas output pipeline (or called a regenerated gas output pipeline) 307.

Wherein, each be provided with catalyst bed 310 in desulphurization unit 300, catalyst bed 310 includes solid desulfurizer, just solid desulfurizer contains porous material carrier and load in the downthehole complex iron catalyst of porous material carrier, solid desulfurizer be used for in proper order via first gas input pipeline 301 with the leading-in and the waiting of containing hydrogen sulfide and oxygen of air inlet 330 is desulfurized with by complex iron catalyst with hydrogen sulfide reacts and generates simple substance sulphur and complex ferrous ion and by oxygen will complex ferrous ion is oxidized to complex ferric ion, and obtains the gas after the desulfurization via gas outlet 350 with first gas output pipeline 303 discharges in proper order.

Wherein the gas inlet 330 connected to the second gas input line 305 is used for sequentially passing through the second gas input line 305, the gas pump 500 and the heat exchanger 400 at a specified volume space velocity (for example, 50-1000 h)^-1Preferably 200 to 500 hours^-1) Introducing a regeneration gas having a predetermined temperature (e.g., 150 to 220 ℃) into the desulfurization apparatus 300, wherein the regeneration gas is used to adsorb elemental sulfur in the pores of the porous material carrier due to the application of the solid desulfurizing agent to desulfurizationBlown out to obtain a regenerated gas containing the elemental sulfur, and the gas outlet 350 connected to the second gas output pipeline 307 is used for discharging the regenerated gas through the second gas output pipeline 307, and the preset temperature is lower than the pyrolysis temperature of the complex iron catalyst and higher than the melting point of the elemental sulfur.

As mentioned above, in fig. 3, the second gas input pipeline 305 is connected to the first gas output pipeline 303, so that a part of the desulfurized gas flowing through the first gas output pipeline 303 is connected to the second gas input pipeline 305 to be sent to the heat exchanger 400 through the gas pump 500 for heating to obtain the regeneration gas, and the other part is connected to the flue gas treatment system; thus, an additional supply of regeneration gas is not required. Of course, it is understood that in other embodiments, the second gas input line 305 may not be connected to the first gas output line 303, so that the source of the regeneration gas may have more options, such as from a nitrogen source, and of course, may also be from desulfurized blast furnace gas or coke oven gas.

Further, it is worth mentioning that although fig. 3 shows that the number of the gas inlets 330 of each desulfurization device 300 is one, the gas inlets 330 introduce the gas to be desulfurized or the regeneration gas in a time-division multiplexing manner; and fig. 3 shows that the number of the gas outlets 350 of each desulfurization device 300 is one, so that the gas outlets 350 discharge the desulfurized gas or the regenerated gas in a time-division multiplexing manner. In other embodiments, the number of the gas inlets 330 of each desulfurization device 300 can also be two, and the two gas inlets are respectively used for introducing the gas to be desulfurized and the regeneration gas; and/or, the number of the gas outlets 350 of each desulfurization device 300 may be two, and the two gas outlets are used for discharging the desulfurized gas and the regenerated gas, respectively.

In addition, based on the desulfurization-regeneration system 30 shown in fig. 3, an embodiment of the present invention further provides a desulfurization-regeneration method, for example, including: a desulfurization step and a regeneration step.

Wherein the step of desulfurizing comprises, for example:

a substep (t1) of introducing a gas to be desulfurized, which comprises hydrogen sulfide and oxygen, to one side of a first catalyst bed loaded in a first desulfurization device, wherein the first catalyst bed comprises a first solid desulfurizing agent, and the first solid desulfurizing agent comprises a first porous material carrier and a first complex iron catalyst loaded in pores of the first porous material carrier;

a substep (t2) of performing a redox reaction between the first complex iron catalyst loaded in the pores of the first porous material carrier and the hydrogen sulfide to generate elemental sulfur and complex ferrous ions, and oxidizing and regenerating the complex ferrous ions into complex ferric ions by the oxygen, and obtaining a desulfurized gas located at the other opposite side of the first catalyst bed; and

and the substep (t3) of discharging the desulfurized gas from the first desulfurization unit from the other opposite side of the first catalyst bed.

Wherein the regenerating step comprises, for example:

a substep (r1) of heating the desulfurized gas discharged from the first desulfurization device to a preset temperature and introducing the desulfurized gas into one side of a second catalyst bed in a second desulfurization device at a designated volume space velocity to serve as a regeneration gas, wherein the second catalyst bed comprises a second solid desulfurizing agent, the second solid desulfurizing agent comprises a second porous material carrier and a second complex iron catalyst loaded in pores of the second porous material carrier, elemental sulfur is adsorbed in the pores of the second porous material carrier due to the second solid desulfurizing agent applied to desulfurization, and the preset temperature is lower than the pyrolysis temperature of the second complex iron catalyst and higher than the melting point of the elemental sulfur;

sub-step, (r2) blowing the elemental sulfur from the pores of the second porous material carrier by the regeneration gas to obtain a regenerated gas containing the elemental sulfur and located at the other opposite side of the second catalyst bed in the second desulfurization device; and

sub-step, (r3) discharging the regenerated gas from the other opposite side of the catalyst bed out of the second desulfurization unit.

As described above, the first desulfurization device may be one desulfurization device 300 of the plurality of desulfurization devices 300 of the desulfurization-regeneration system 30 shown in fig. 3, and the second desulfurization device may be another one desulfurization device 300 of the plurality of desulfurization devices 300 of the desulfurization-regeneration system 30 shown in fig. 3. The first solid desulfurizing agent and the second solid desulfurizing agent may be solid desulfurizing agents having the same composition as the solid desulfurizing agent included in the catalyst bed 310. In addition, when the first solid desulfurizing agent is applied to desulfurization for a limited number of times (i.e. when the desulfurization performance deteriorates to an unsatisfactory level), the first solid desulfurizing agent (corresponding to the first porous material carrier, which is activated carbon) which is used up is thrown into a kiln which generates blast furnace gas or coke-oven gas for combustion, thereby overcoming the disadvantage that the solid waste formed after desulfurization pollutes the environment through secondary treatment. In addition, with respect to the aforementioned second solid desulfurizing agent, the regeneration time thereof may be designed to be: and when the breakthrough sulfur capacity of the second solid desulfurizing agent is not lower than 70% of the initial breakthrough sulfur capacity before the second solid desulfurizing agent is applied to desulfurization, stopping introducing the regeneration gas.

Furthermore, it is worth to be noted that, for the plurality of desulfurization units 300 connected in parallel in the desulfurization-regeneration system 30 shown in fig. 3, desulfurization can be performed in a mostly normal-open manner and a small standby manner; alternatively, different desulfurization apparatuses 300 may be used to sequentially perform desulfurization and sequential regeneration. At the time of regeneration, a single desulfurization apparatus 300 to be regenerated may be switched off and regenerated individually by using a regeneration system.

In order to facilitate a clearer understanding of the examples of the present invention, the preparation of the solid desulfurizing agent used in the foregoing examples will be described in detail.

Specifically, the complex iron catalyst of the solid desulfurizing agent is derived from a complex iron solution containing 0.01-0.06 mol/L complex iron ions, and the raw materials of the complex iron solution comprise: the iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, wherein the molar ratio of the organic complexing agent to iron in the iron source is 1.0-2.0, the molar ratio of the stabilizer to the iron in the iron source is 1.0-2.0, and the pH value of the complexing iron solution is regulated to 8.0-12.0 by the pH regulator.

Wherein the iron source includes, for example: ferrous sulfate (FeSO)₄·7H₂O), ferrous ammonium sulfate ((NH)₄)₂Fe(SO₄)₂·6H₂O), iron (Fe) sulfate₂(SO₄)₃) And ferric ammonium sulfate (NH)₄Fe(SO₄)₂·12H₂O). It is understood herein that the iron source of the present embodiment does not contain chloride ions and nitrate ions; for example, the iron source of the embodiment does not include iron salts including chloride ions and nitrate ions, such as ferric chloride, ferric nitrate, and ferrous nitrate, so that harmful impurity anions, such as chloride ions and nitrate ions, are not introduced into the iron complex solution, thereby avoiding the serious corrosion problem of chloride ions to equipment, and avoiding the problems of easy explosion and difficult wastewater treatment when nitrate ions and carbon meet.

The organic complexing agent is, for example, an aminocarboxylic acid type complexing agent. For example, the aminocarboxylic acid complexing agent includes, for example: at least one of ethylenediaminetetraacetic acid (EDTA), disodium EDTA (disodium EDTA), nitrilotriacetic acid (NTA), and trisodium nitrilotriacetate (trisodium NTA).

Wherein the pH adjusting agent includes, for example: at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and ammonia water. Wherein the pH regulator is used for regulating the pH value of the solution, such as adjusting the pH value of the complexing iron solution to be alkaline.

Wherein the stabilizer is, for example, any one of sorbitol and sodium benzoate, and is mainly used for stabilizing ferrous ions.

Furthermore, the solid desulfurizing agent of the present embodiment is not limited to a specific shape, and may be in a granular shape or a pressed shape such as a honeycomb shape, a cylindrical shape, etc.; the pore diameter of the activated carbon as the porous material carrier is, for example, 1nm to 5nm, preferably 1nm to 4 nm. The inventor tests and verifies that the aperture of the active carbon is 1 nm-4 nm, and the solid desulfurizing agent has better desulfurizing activity.

Taking activated carbon as an example of a porous material carrier, the preparation method of the solid desulfurizing agent of the embodiment of the invention comprises the following steps:

(a) weighing an iron source containing sulfate radicals, a stabilizer and an organic complexing agent, dissolving the iron source, the stabilizer and the organic complexing agent in water to obtain a dissolved solution, stirring the dissolved solution, and continuously adding a pH regulator into the dissolved solution during stirring to prepare a complex iron solution;

(b) placing the activated carbon and the complexing iron solution in a sugar coating machine or a double-cone rotary impregnator to roll, so that the complexing iron solution is absorbed by the activated carbon to obtain loaded activated carbon; and

(c) and taking out the loaded active carbon, filling the loaded active carbon into a sealing bag, and drying the loaded active carbon to obtain the solid desulfurizer.

Wherein, the active carbon and the complex iron solution are placed in a sugar coating machine or a double-cone rotary impregnator to roll, for example, the method comprises the following steps: placing the activated carbon in a sugar coating machine or a double-cone rotary impregnator, and spraying a complexing iron solution to the activated carbon; or comprises the following steps: the activated carbon is placed in a sugar-coating machine, and the complex iron solution is poured into the sugar-coating machine so that the activated carbon is impregnated in the complex iron solution. In short, the complex iron solution can be efficiently adsorbed on a porous material carrier such as activated carbon by spraying the complex iron solution onto the activated carbon or immersing the activated carbon in the complex iron solution.

Wherein, taking out the loaded activated carbon, filling the loaded activated carbon into a sealed bag and drying the loaded activated carbon, for example, the method comprises the following steps: and (3) putting the loaded activated carbon into a sealing bag, preserving for 6-24 h, and drying the loaded activated carbon at the temperature of 80-120 ℃.

When the iron source contains divalent iron ions, the stirring solution includes, for example: stirring the dissolved solution, introducing air or oxygen, and controlling the temperature to be 20-60 ℃ so as to oxidize ferrous ions into ferric ions. It is understood herein that the rate of oxidation of ferrous ions to ferric ions can be further increased by controlling the temperature while agitating the solution to introduce air or oxygen.

Example one:

firstly, preparing 1000L (liter) of complex iron solution with the concentration of complex iron ions of 0.03mol/L (mol per liter), which specifically comprises the following steps: weighing 6.7Kg (Kg) of sorbitol, 24Kg of disodium EDTA and 10Kg of ferrous sulfate, dissolving in 1000L of deionized water to form a solution, stirring the solution for 12h to make the internal raw materials fully contact and oxidize ferrous ions, continuously adding sodium carbonate into the solution during stirring to adjust the pH value of the solution, so that the final pH value of the complexing iron solution is 9.2, and obtaining a dark red solution, namely the complexing iron solution.

Then weighing 100Kg of active carbon with water absorption rate of 60%, pouring the active carbon into a sugar-coating machine, spraying or dipping 60Kg of the prepared complex iron solution (0.03mol/L) on the active carbon, controlling the sugar-coating machine to overturn and roll for 10-30 min, enabling all the complex iron solution to be completely absorbed by the active carbon to obtain loaded active carbon, taking out the loaded active carbon, filling the loaded active carbon into a sealing bag, standing for 6-12 h, and drying the active carbon at 80-120 ℃ to obtain the solid desulfurizer.

Example two:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03mol/L, which specifically comprises the following steps: weighing 6.7Kg of sorbitol, 24Kg of EDTA disodium and 15.1Kg of ammonium ferrous sulfate, dissolving in 1000L of deionized water, stirring the solution for 12 hours to ensure that the internal raw materials fully contact and oxidize ferrous ions, and continuously adding sodium carbonate into the solution during stirring to adjust the pH value of the solution so as to ensure that the final pH value of the complexing iron solution is 9.2, thus obtaining a dark red solution, namely the complexing iron solution.

Then weighing 100Kg of active carbon with water absorption rate of 60%, pouring the active carbon into a sugar-coating machine, spraying or dipping 60Kg of the prepared complex iron solution (0.03mol/L) on the active carbon, controlling the sugar-coating machine to overturn and roll for 10-30 min, enabling all the complex iron solution to be completely absorbed by the active carbon to obtain loaded active carbon, taking out the loaded active carbon, filling the loaded active carbon into a sealing bag, standing for 6-12 h, and drying the active carbon at 80-120 ℃ to obtain the solid desulfurizer.

Example three:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03mol/L, which specifically comprises the following steps: weighing 6.7Kg of sorbitol, 24Kg of EDTA disodium and 11.6Kg of ferric ammonium sulfate, dissolving in 1000L of deionized water to obtain a solution, stirring the solution for 2h, and continuously adding sodium carbonate into the solution during stirring to adjust the pH value of the solution so as to make the final pH value of the iron complex solution be 10.2, thus obtaining a dark red solution, namely the iron complex solution.

Then, weighing 1000Kg of activated carbon with water absorption rate of 60%, pouring the activated carbon into a double-cone rotary impregnator, spraying or impregnating 600Kg of the prepared complex iron solution (0.03mol/L) on the activated carbon, controlling the double-cone rotary impregnator to roll for 10-30 min in a turnover manner, enabling all the complex iron solution to be completely absorbed by the activated carbon to obtain loaded activated carbon, taking out the loaded activated carbon, filling the loaded activated carbon into a sealing bag, standing for 6-12 h, and drying the activated carbon at 80-120 ℃ to obtain the solid desulfurizer.

Example four:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03mol/L, which specifically comprises the following steps: weighing 6.7Kg of sorbitol, 24Kg of EDTA disodium and 4.7Kg of ferric sulfate, dissolving in 1000L of deionized water to obtain a solution, stirring the solution for 2h, and continuously adding sodium carbonate into the solution during stirring to adjust the pH value of the solution so as to make the final pH value of the iron complex solution be 10.2, thus obtaining a dark red solution, namely the iron complex solution.

Then weighing 100Kg of active carbon with water absorption rate of 60%, pouring the active carbon into a sugar-coating machine, spraying or dipping 60Kg of the prepared complex iron solution (0.03mol/L) on the active carbon, controlling the sugar-coating machine to overturn and roll for 10-30 min, enabling all the complex iron solution to be completely absorbed by the active carbon to obtain loaded active carbon, taking out the loaded active carbon, filling the loaded active carbon into a sealing bag, standing for 6-12 h, and drying the active carbon at 80-120 ℃ to obtain the solid desulfurizer.

It should be noted that, for the first example and the second example, the divalent iron ions are oxidized, that is, air is introduced during stirring, oxygen in the air and the divalent iron ions undergo a chemical reaction to obtain trivalent iron ions, and in addition, in order to accelerate the oxidation rate of the divalent iron ions in the solution, the temperature can be controlled to be 20 to 60 ℃ while the air is introduced; or pure oxygen can be introduced during stirring, and the temperature is controlled to be 20-60 ℃ so as to accelerate the oxidation rate of the ferrous ions.

For the first to fourth examples, an isometric method is adopted for preparing the solid desulfurizer, that is, the mass of the solution which can be absorbed by the pores of the activated carbon at most is calculated based on the weighed mass and the water absorption of the activated carbon, and then the complexing iron solution with the same mass is taken for preparing the solid desulfurizer, so that the loaded activated carbon is taken out after all the complexing iron solution is completely absorbed by the activated carbon.

Further, in the existing desulfurization method:

the Lo-cat process can treat a large amount of hydrogen sulfide gas, but the related desulfurization system is complex, the investment cost is high, a large amount of solution is needed for circulation, and the operation cost is high;

2. in addition, the solubility of the gas in the liquid film is reduced along with the rise of the reaction temperature, so the high reaction temperature can also cause the reduction of the penetrating sulfur capacity of the traditional active carbon sodium silicate desulfurizer, so the desulfurizer is only suitable for being used under the conditions of low temperature, low space velocity and high water vapor concentration, and the applicable desulfurization environment is relatively limited;

3. the low-temperature desulfurization process of the solid ferric oxide can directly utilize the combination of ferric ions and hydrogen sulfide, does not need to supplement oxygen in the reaction process, but after the ferric oxide absorbs sulfur and is converted into the ferric sulfide, because S^2-Ionic radius greater than O^2-The radius of the catalyst can further cause the catalyst to swell, and the catalyst is easy to pulverize; in addition, a large amount of solid waste iron sulfide formed after desulfurization needs secondary treatment, and the operation is complicated.

Compared with the prior desulfurization process, the desulfurization method disclosed in the embodiment utilizes the organic complexing agent to stabilize iron ions, and highly disperses the iron complex catalyst in the microporous channels of the porous material carrier (such as activated carbon), so that H in the gas to be desulfurized is highly dispersed₂The S gas diffuses into the microchannels,upon complexation with trivalent iron ion (Fe)³⁺) When in contact, the sulfur can be immediately oxidized into elemental sulfur (2 Fe)³⁺L+S^2-＝2Fe²⁺L + S) when traces of O are present in the gas to be desulfurized₂When is, O₂But also can rapidly mix Fe²⁺L is oxidized and regenerated into Fe³⁺L, and then the circulation of the hydrogen sulfide catalyzed and oxidized by the complex iron ions is completed, the reaction process can be completed in a liquid film, and can also be completed directly through gas-solid contact, so that the catalyst can be used in a wider saturated steam concentration and a wider temperature range. When the solid desulfurizer is penetrated or is close to penetrating, the regeneration gas with preset temperature can be introduced at a designated volume airspeed to blow out elemental sulfur in the porous material carrier pores, so that the blocked pore channels are reopened, and the performance regeneration of the solid desulfurizer is realized, so that the regenerated solid desulfurizer can be desulfurized again. When the porous material carrier is active carbon, the desulfurized solid desulfurizer can be directly burned in a furnace, the operation is convenient, and the environment is not polluted greatly by solid waste.

In summary, in the desulfurizing agent regeneration method, the desulfurizing-regenerating method and the system according to the embodiments of the present invention, the regenerating gas with the predetermined temperature is introduced at the designated volume airspeed to blow out the elemental sulfur in the pores of the porous material carrier, so that the blocked pores are reopened, thereby realizing the performance regeneration of the solid desulfurizing agent, and the regenerated solid desulfurizing agent can be desulfurized again, which is beneficial to realizing higher desulfurizing efficiency. Moreover, the desulfurization and regeneration of different desulfurization units can be performed simultaneously, which is favorable for further improving the desulfurization efficiency. In addition, the solid desulfurizing agent is obtained by adsorbing and complexing the iron solution through a porous material carrier such as activated carbon, can be used for desulfurizing a gas to be desulfurized containing hydrogen sulfide and oxygen, i.e. oxidizing hydrogen sulfide into elemental sulfur, and can realize a desulfurization-regeneration cycle process, thereby having higher desulfurization efficiency. In addition, harmful impurity anions such as chloride ions and nitrate ions are not introduced into the iron complex solution, so that the problems of serious corrosion of chloride ions to equipment, easy explosion when the nitrate ions meet carbon, difficult wastewater treatment and the like can be avoided. Finally, the activated carbon left after the desulfurization of the solid desulfurizer in the embodiment of the invention can be directly burned in a furnace, the treatment is convenient, and the solid waste pollution to the environment is avoided.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.