阅读说明：本技术 固态脱硫剂及其制备方法 (Solid desulfurizing agent and preparation method thereof ) 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一种固态脱硫剂和一种固态脱硫剂的制备方法,所述固态脱硫剂的原料包括：活性炭和络合铁溶液,其中所述络合铁溶液的原料包括：含有硫酸根的铁源、有机络合剂、pH调节剂和稳定剂,所述有机络合剂与所述铁源中的铁元素的摩尔比为1.0～2.0,所述稳定剂与所述铁源中的所述铁元素的摩尔比为1.0～2.0,所述pH调节剂将所述络合铁溶液的pH值调整为8.0～12.0。本发明实施例公开的固态脱硫剂用于含硫化氢气体的原料气脱硫,可以将硫化氢气体氧化为硫单质,提高脱硫效率。(The embodiment of the invention provides a solid desulfurizing agent and a preparation method thereof, wherein the solid desulfurizing agent comprises the following raw materials: the method comprises the following steps of (1) activated carbon and a complex iron solution, wherein the complex iron solution comprises the following raw materials: 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. The solid desulfurizing agent disclosed by the embodiment of the invention is used for desulfurizing raw material gas containing hydrogen sulfide gas, can oxidize the hydrogen sulfide gas into elemental sulfur, and improves the desulfurization efficiency.)

1. A solid desulfurizing agent is characterized in that the raw materials comprise: activated carbon and complex iron solution; wherein the raw materials of the complexing 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.

2. The solid desulfurization agent according to claim 1, wherein the iron source comprises: at least one of ferrous sulfate, ammonium ferrous sulfate, ferric sulfate, and ammonium ferric sulfate.

3. The solid desulfurization agent according to claim 1, wherein the organic complexing agent comprises: at least one of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, nitrilotriacetic acid, and trisodium nitrilotriacetic acid.

4. The solid desulfurization agent according to claim 1, wherein the pH regulator comprises: at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and ammonia; and the stabilizer is any one of sorbitol and sodium benzoate.

5. The solid desulfurizing agent according to claim 1, wherein the solid desulfurizing agent is used for desulfurizing a raw material gas containing hydrogen sulfide gas, wherein the raw material gas is blast furnace gas or coke oven gas.

6. A solid desulfurization agent, comprising: activated carbon and complex iron ions adsorbed on the surface of the activated carbon; the complexing iron ions are derived from a complexing iron solution containing 0.01-0.06 mol/L complexing iron ions, and the raw materials of the complexing 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.

7. A preparation method of a solid desulfurizing agent, which is used for preparing the solid desulfurizing agent according to any one of claims 1 to 6, and which comprises:

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

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 taking out the loaded active carbon, putting the loaded active carbon into a sealed container for storage, and drying the loaded active carbon to obtain the solid desulfurizing agent.

8. The method for preparing the solid desulfurizing agent according to claim 7, wherein the placing the activated carbon and the complex iron solution in a sugar coating machine or a double-cone rotary impregnator for rolling comprises:

placing the activated carbon in the sugar coater or the double cone rotary impregnator and spraying the complex iron solution to the activated carbon so that the activated carbon is impregnated in the complex iron solution.

9. The method for preparing the solid desulfurizing agent according to claim 7, wherein the step of taking out the loaded activated carbon, placing the loaded activated carbon in a sealed container for storage, and then drying the loaded activated carbon comprises the steps of:

and (3) putting the loaded activated carbon into the sealed container, preserving for 6-24 h, and drying the loaded activated carbon at the temperature of 80-120 ℃.

10. The method for preparing a solid desulfurizing agent according to claim 7, wherein, when said iron source contains ferrous ions, said stirring said dissolved solution includes: and stirring the dissolved solution, introducing air or oxygen, and controlling the temperature to be 20-60 ℃ so that the ferrous ions are oxidized into ferric ions.

Technical Field

The invention relates to the technical field of gas purification, in particular to a solid desulfurizing agent and a preparation method thereof.

Background

Waste gas is generated in the chemical production processes of petroleum refining, natural gas processing, coal gasification and the like, and the waste gas contains H with different concentrations₂S gas, high concentration H₂The existence of S not only pollutes the environment, corrodes pipeline equipment and influences the quality of chemical products, but also can cause the catalyst poisoning and inactivation in the subsequent process production, thereby removing H in a gas phase₂S is a very important chemical process. At present, the existing desulfurizer has the defects of low desulfurization efficiency, limitation to desulfurization environment such as only being suitable for conditions of low temperature, low space velocity and high water vapor concentration, environmental pollution caused by secondary treatment of solid waste formed after desulfurization and the like.

Therefore, the invention provides a novel desulfurizer to make up the defects of the existing desulfurizer, and the technical problem to be solved is needed.

Disclosure of Invention

The embodiment of the invention discloses a solid desulfurizing agent and a preparation method thereof, which are used for desulfurizing feed gas containing hydrogen sulfide gas, can oxidize the hydrogen sulfide gas into elemental sulfur, improve the desulfurization efficiency, are suitable for various desulfurization environments, and avoid the condition that the environment is polluted by treating solid wastes.

Specifically, the embodiment of the invention discloses a solid desulfurizing agent, which comprises the following raw materials: activated carbon and complex iron solution; wherein the raw materials of the complexing 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 8-12 by the pH regulator.

In one embodiment of the present invention, the iron source includes: at least one of ferrous sulfate, ammonium ferrous sulfate, ferric sulfate, and ammonium ferric sulfate.

In one embodiment of the present invention, the organic complexing agent comprises: at least one of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, nitrilotriacetic acid, and trisodium nitrilotriacetic acid.

In one embodiment of the present invention, the pH adjusting agent includes: at least one of sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and ammonia; and the stabilizer is any one of sorbitol and sodium benzoate.

In one embodiment of the invention, the solid desulfurizing agent is applied to desulfurizing raw material gas containing hydrogen sulfide gas, wherein the raw material gas is blast furnace gas or coke oven gas.

In addition, the embodiment of the invention discloses a solid desulfurizing agent, which comprises: activated carbon and complex iron ions adsorbed on the surface of the activated carbon; the complexing iron ions are derived from a complexing iron solution containing 0.01-0.06 mol/L complexing iron ions, and the raw materials of the complexing 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 addition, the embodiment of the invention also discloses a preparation method of the solid desulfurizing agent, which is used for preparing any one of the solid desulfurizing agents disclosed in the foregoing, and the preparation method comprises the following steps: weighing the sulfate-containing iron source, the stabilizer and the organic complexing agent, dissolving the sulfate-containing iron source, the stabilizer and the organic complexing agent in water to obtain a dissolved solution, stirring the dissolved solution, and adding the pH regulator into the dissolved solution during stirring to prepare the iron complex solution; 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 taking out the loaded active carbon, putting the loaded active carbon into a sealed container for storage, and drying the loaded active carbon to obtain the solid desulfurizing agent.

In one embodiment of the present invention, the placing the activated carbon and the complex iron solution in a sugar coating machine or a double-cone rotary impregnator for rolling comprises: placing the activated carbon in the sugar coater or the double cone rotary impregnator and spraying the complex iron solution to the activated carbon so that the activated carbon is impregnated in the complex iron solution.

In one embodiment of the present invention, the removing the loaded activated carbon, placing in a sealed container for preservation, and then drying the loaded activated carbon comprises: and (3) putting the loaded activated carbon into the sealed container, preserving for 6-24 h, and drying the loaded activated carbon at the temperature of 80-120 ℃.

In one embodiment of the present invention, when the iron source includes divalent iron ions, the stirring the dissolution liquid includes: and stirring the dissolved solution, introducing air or oxygen, and controlling the temperature to be 20-60 ℃ so that the ferrous ions are oxidized into ferric ions.

The technical scheme can have the following advantages or beneficial effects: according to the solid desulfurizer and the preparation method thereof disclosed by the embodiment of the invention, an iron solution is subjected to adsorption complexing by active carbon, raw materials of the iron solution comprise an iron source containing sulfate radicals, an organic complexing agent, a pH regulator and a stabilizer, 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 iron solution is regulated to 8-12 by the pH regulator, the iron solution can be used for desulfurizing raw material gas containing hydrogen sulfide gas, namely oxidizing the hydrogen sulfide gas into elemental sulfur, wherein harmful impurity anions such as chloride ions and nitrate ions are not introduced into the iron solution, so that the problem that equipment is seriously corroded by chloride ions is avoided, the problems that the nitrate ions and carbon are easy to explode when meeting each other and the wastewater is difficult to treat are avoided, and the desulfurization efficiency can be improved; the solid desulfurizing agent disclosed by the embodiment can complete desulfurization in a liquid film and can also be directly completed through gas-solid contact, so that the solid desulfurizing agent is suitable for wider saturated steam concentration and wider temperature range, namely is suitable for various desulfurization environments and is more widely applied; the active carbon left after the solid desulfurizer disclosed by the embodiment is desulfurized can be directly burned in a furnace, the treatment is convenient, and the environment is not polluted greatly; the solid desulfurizing agent disclosed by the embodiment has the advantages of wide raw material source range, low price and suitability for large-scale production; the preparation method of the solid desulfurizing agent disclosed by the embodiment is simple, and the solid desulfurizing agent is convenient to store and transport.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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 capable of operation in sequences other than those described or illustrated 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.

Specifically, one embodiment of the present invention discloses a solid desulfurizing agent, which comprises the following raw materials: activated carbon and complex iron solution; the raw materials of the complexing 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.

Further, the iron source includes: 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 should be understood that the iron source disclosed in this embodiment does not contain chloride ions and nitrate ions, for example, the iron source disclosed in this embodiment does not contain iron salts containing 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 explosion problem and wastewater treatment difficulty problem when nitrate ions and carbon meet, and thus the desulfurization efficiency can be improved.

Further, the organic complexing agent is an aminocarboxylic acid 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).

Further, the pH adjusting agent includes: 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.

Further, the stabilizer is any one of sorbitol and sodium benzoate, and is mainly used for stabilizing divalent iron ions.

Furthermore, 1000L of the complex iron solution contains complex iron ions with the concentration range of 0.01-0.06 mol/L. The complex iron ions mentioned are, for example, ferric ions.

Further, the solid desulfurizing agent is applied to the desulfurization of raw material gas containing hydrogen sulfide gas, wherein the raw material gas is blast furnace gas or coke oven gas.

Further, the pore diameter of the activated carbon is 1nm to 5nm, more specifically, the pore diameter of the activated carbon is, for example, 1nm to 4nm, and experiments prove that the pore diameter of the activated carbon is 1nm to 4nm, and the solid desulfurizing agent has the highest desulfurization activity.

In addition, one embodiment of the present invention discloses a solid desulfurizing agent, comprising: activated carbon and complex iron ions adsorbed on the surface of the activated carbon; the complexing iron ions are derived from a complexing iron solution containing 0.01-0.06 mol/L complexing iron ions, and the raw materials of the complexing 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 8-12 by the pH regulator.

The solid desulfurizing agent mentioned in the embodiments of the present invention is not limited to a specific shape, and for example, is in the form of a granule or is synthesized by pressing into a specific shape such as a honeycomb shape, a cylindrical shape, etc.

In addition, another embodiment of the present invention discloses a preparation method of a solid desulfurizing agent, for preparing the solid desulfurizing agent disclosed in the previous embodiment, the preparation method comprising:

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

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

and taking out the loaded activated carbon, putting the loaded activated carbon into a sealed container for storage, and drying the loaded activated carbon to obtain the solid desulfurizing agent.

Further, the placing the activated carbon and the complexing iron solution in a sugar coating machine or a double-cone rotary impregnator for rolling comprises the following steps: placing the activated carbon in the sugar coater or the double cone rotary impregnator and spraying the complex iron solution to the activated carbon so that the activated carbon is impregnated in the complex iron solution.

The complex iron solution can be efficiently adsorbed by the activated carbon by spraying the complex iron solution to the activated carbon.

Further, the taking out the loaded activated carbon, putting the loaded activated carbon into a sealed container for storage, and then drying the loaded activated carbon comprises the following steps: and (3) putting the loaded activated carbon into the sealed container, preserving for 6-24 h, and drying the loaded activated carbon at the temperature of 80-120 ℃.

Further, when the iron source includes ferrous ions, the stirring the dissolution liquid includes: and stirring the dissolved solution, introducing air or oxygen, and controlling the temperature to be 20-60 ℃ so that the ferrous ions are oxidized 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.

The preparation of the solid desulfurizing agent is described below with reference to specific examples.

Example 1:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03 mol/L: weighing 6.7Kg of sorbitol, 24Kg of EDTA disodium and 10Kg of ferrous sulfate, dissolving in 1000L of deionized water to form a solution, stirring the solution for 12 hours to make the internal raw materials fully contact and oxidize ferrous ions, 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, putting the loaded active carbon into a sealed container (such as a sealed bag) for 6-12 h, and drying the active carbon at 80-120 ℃ to obtain the solid desulfurizer.

Example 2:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03 mol/L: 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, adding sodium carbonate into the solution during stirring to adjust the pH value of the solution and 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, placing the loaded active carbon into a sealed container, standing for 6-12 h, and drying the active carbon at 80-120 ℃ to obtain the solid desulfurizer.

Example 3:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03 mol/L: 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, adding sodium carbonate into the solution during stirring to adjust the pH value of the solution, so that the final pH value of the iron complex solution is 10.2, thus obtaining a deep red solution, namely the iron complex solution.

Then, weighing 1000Kg of activated carbon with water absorption 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, placing the loaded activated carbon into a sealed container, standing for 6-12 h, and drying the activated carbon at 80-120 ℃ to obtain the solid desulfurizer.

Example 4:

firstly, preparing 1000L of complex iron solution with the complex iron ion concentration of 0.03 mol/L: 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, adding sodium carbonate into the solution during stirring to adjust the pH value of the solution, so that the final pH value of the iron complex solution is 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, placing the loaded active carbon into a sealed container, standing for 6-12 h, and drying the active carbon at 80-120 ℃ to obtain the solid desulfurizer.

It should be noted that, for example 1 and example 2, 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 introducing the air; 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 foregoing embodiments 1 to 4, an isometric method is adopted for preparing the solid desulfurizing agent, that is, the mass of the solution that 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 iron complex solution with the same mass is taken to prepare the solid desulfurizing agent, so that the loaded activated carbon needs to be taken out after all the iron complex solution is completely absorbed by the activated carbon.

It is worth mentioning that through the experiments of the inventor, the solid desulfurizer disclosed by the embodiment of the invention is used for desulfurizing blast furnace gas or coke oven gas in a steel mill, when the concentration of hydrogen sulfide in the blast furnace gas or coke oven gas is 5-5000 ppm, the reaction temperature is 20-150 ℃, and the air space velocity is controlled, namely the gas flow per hour in 1 cubic meter of the solid desulfurizer is 100-3000 h^-1In the meantime, the penetration sulfur capacity (the capacity of sulfur that can be absorbed by a desulfurizing agent per unit volume while ensuring the process purification degree index, i.e., the sulfur capacity that can be absorbed for the first time, which is H in the desulfurized gas) of the solid desulfurizing agent disclosed in the embodiment of the present invention₂The S concentration is, for example, less than or equal to 1mg/m³(mg/cubic meter)) is 15-35%, and in addition, after the solid desulfurizing agent disclosed by the embodiment of the invention is regenerated, the penetrating sulfur capacity of the solid desulfurizing agent can be not lower than 70% of that of the solid desulfurizing agent at the beginning (15-35%). From this, it can be seen that the solid desulfurizing agent disclosed in the present example has a high desulfurizing efficiency and a high regeneration capability.

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 existing desulfurizer, the solid desulfurizer disclosed in the embodiment utilizes the organic complexing agent to stabilize iron ions, highly disperses the complexed iron ions in the activated carbon micro-channels, and has H in the raw material gas₂S gas diffuses into the microchannels, once complexed with ferric ions (Fe)³⁺) When in contact, the sulfur can be immediately oxidized into elemental sulfur (2 Fe)³⁺L+S^2-＝2Fe²⁺L + S) when trace O exists in the raw material gas₂When is, O₂But also can rapidly mix Fe²⁺L is oxidized and regenerated into Fe³⁺L, further completing the circulation of the hydrogen sulfide catalyzed and oxidized by the complex iron ions, wherein the reaction process can be completed in a liquid film or directly completed through gas-solid contact, so that the catalyst can be used in a wider saturated steam concentration and a wider temperature range; in addition, the desulfurization system related to the solid desulfurizing agent disclosed by the embodiment is simple, and the investment cost is reduced; the active carbon left after the solid desulfurizer disclosed by the embodiment is desulfurized can be directly returned to the furnace for combustion, the operation is convenient, and the environment is not greatly polluted.

In summary, the solid desulfurizing agent and the preparation method thereof disclosed in the embodiments of the present invention adsorb and complex iron solution through activated carbon, and the raw material of the complexing iron solution comprises an iron source containing sulfate radical, an organic complexing agent, a pH regulator and a stabilizing agent, 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 stabilizing agent 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, the composite material can be used for desulfurizing the feed gas containing the hydrogen sulfide gas, namely oxidizing hydrogen sulfide gas into elemental sulfur, wherein harmful impurity anions such as chloride ions and nitrate ions are not introduced into the complex iron solution, thereby avoiding the problems of serious corrosion of chloride ions to equipment, easy explosion when nitrate ions meet carbon, difficult wastewater treatment and the like, and improving the desulfurization efficiency; the solid desulfurizing agent disclosed by the embodiment can complete desulfurization in a liquid film and can also be directly completed through gas-solid contact, so that the solid desulfurizing agent is suitable for wider saturated steam concentration and wider temperature range, namely is suitable for various desulfurization environments and is more widely applied; the active carbon left after the solid desulfurizer disclosed by the embodiment is desulfurized can be directly burned in a furnace, the treatment is convenient, and the environment is not polluted greatly; the solid desulfurizing agent disclosed by the embodiment has the advantages of wide raw material source range, low price and suitability for large-scale production; the preparation method of the solid desulfurizing agent disclosed by the embodiment is simple, and the solid desulfurizing agent is convenient to store and transport.

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.