阅读说明：本技术 脱硫方法、装置及系统 (Desulfurization method, device 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方法、装置以及系统。所述脱硫方法例如包括：从脱硫进气口导入包含硫化氢和氧气的待脱硫气体至装载于脱硫装置内的催化剂床层的一侧,其中催化剂床层包括固体脱硫剂、且固体脱硫剂包括多孔性材料载体和负载在多孔性材料载体孔壁的络合铁离子,固体脱硫剂的穿透硫容为15％～35％；由负载在多孔性材料载体孔壁的络合铁离子与硫化氢进行氧化还原反应生成单质硫和络合亚铁离子以及由氧气将络合亚铁离子氧化再生为络合铁离子,并得到脱硫后混合气体；以及从脱硫装置的位于催化剂床层的另一相对侧的脱硫出气口排出脱硫后混合气体。本发明实施例在将H-(2)S氧化为单质硫的脱硫过程中可以实现脱硫-再生循环,脱硫效率较佳。(The embodiment of the invention provides a desulfurization method, a desulfurization device and a desulfurization system. The desulfurization method includes, for example: introducing a gas to be desulfurized containing hydrogen sulfide and oxygen from a desulfurization gas inlet to one side of a catalyst bed layer loaded in a desulfurization device, wherein the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and complex ferric ions loaded on the wall of the hole of the porous material carrier, and the sulfur penetration capacity of the solid desulfurizer is 15-35%; carrying out redox reaction on complex ferric ions loaded on the pore wall of the porous material carrier and hydrogen sulfide to generate elemental sulfur and complex ferrous ions, oxidizing and regenerating the complex ferrous ions into complex ferric ions by oxygen, and obtaining a desulfurized mixed gas; and discharging the desulfurized mixed gas from a desulfurization gas outlet of the desulfurization device, which is positioned on the other opposite side of the catalyst bed layer. In the embodiment of the invention, H 2 The desulfurization-regeneration cycle can be realized in the desulfurization process of S being oxidized into elemental sulfur, and the desulfurization efficiencyPreferably.)

1. A method of desulfurization, comprising:

introducing a gas to be desulfurized, which comprises hydrogen sulfide and oxygen, from a desulfurization gas inlet of a desulfurization device to one side of a catalyst bed layer loaded in the desulfurization device, wherein the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and complex iron ions loaded on the wall of the pore of the porous material carrier, and the sulfur penetration capacity of the solid desulfurizer is 15-35%;

carrying out redox reaction on the complex ferric ions loaded on the porous material carrier hole wall 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 to obtain a desulfurized mixed gas; and

and discharging the desulfurized mixed gas from a desulfurization gas outlet of the desulfurization device, which is positioned at the other opposite side of the catalyst bed layer.

2. The desulfurization method according to claim 1, wherein the concentration ratio of the oxygen to the hydrogen sulfide in the gas to be desulfurized is 2 to 50, the concentration of the hydrogen sulfide in the gas to be desulfurized is 5 to 1500ppm, and the concentration of the oxygen in the gas to be desulfurized is less than 0.3%.

3. The desulfurization method of claim 2, wherein the reaction temperature of the solid desulfurizing agent is 20-150 ℃ and is provided by the temperature of the gas to be desulfurized, the water vapor content of the gas to be desulfurized is 0-90% of saturated steam of water at the reaction temperature, the reaction pressure of the solid desulfurizing agent is 0.1-8.0 MPa, and the gas space velocity when the gas to be desulfurized is in contact with the solid desulfurizing agent is 100-3000 h^-1。

4. The desulfurization method according to claim 3, wherein the concentration ratio of the oxygen gas to the hydrogen sulfide in the gas to be desulfurized is 3 to 20, the concentration of the hydrogen sulfide in the gas to be desulfurized is 50 to 1000ppm, and the reaction temperature is 40 to 110 ℃.

5. The desulfurization method according to claim 1, wherein the gas to be desulfurized is derived from blast furnace gas or coke oven gas, the porous material support is activated carbon, and the desulfurization method further comprises:

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

6. The desulfurization method according to any one of claims 1 to 5, wherein the complex iron ions of the solid desulfurizing agent are 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, and the pH value of the complexing iron solution is regulated to 8.0-12.0 by the pH regulator.

7. A desulfurization apparatus, comprising:

the catalyst bed layer comprises a solid desulfurizer with the penetrating sulfur capacity of 15-35%, wherein the solid desulfurizer comprises a porous material carrier and complex ferric ions loaded on the hole wall of the porous material carrier, and the complex ferric ions are used for reacting with hydrogen sulfide in the gas to be desulfurized to generate elemental sulfur and obtain the desulfurized mixed gas;

the desulfurization gas inlet is positioned on one side of the catalyst bed layer and is used for introducing the gas to be desulfurized; and

and the desulfurization gas outlet is positioned on the other opposite side of the catalyst bed layer and is used for discharging the desulfurized mixed gas.

8. The desulfurization apparatus according to claim 7, wherein the complex iron ions of the solid desulfurizing agent are derived from a complex iron solution containing 0.01-0.06 mol/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, and the pH value of the complexing iron solution is regulated to 8.0-12.0 by the pH regulator.

9. A desulfurization system, comprising: a plurality of desulfurization units connected in parallel;

wherein each of the desulfurization units comprises:

the catalyst bed layer comprises a solid desulfurizer with the penetrating sulfur capacity of 15-35%, wherein the solid desulfurizer comprises a porous material carrier and complex ferric ions loaded on the hole wall of the porous material carrier, and the complex ferric ions are used for reacting with hydrogen sulfide in the gas to be desulfurized to generate elemental sulfur and obtain the desulfurized mixed gas;

the desulfurization gas inlet is positioned on one side of the catalyst bed layer and is used for introducing the gas to be desulfurized; and

the desulfurization gas outlet is positioned on the other opposite side of the catalyst bed layer and is used for discharging the desulfurized mixed gas;

the desulfurization gas inlets of the desulfurization devices are connected to the same input pipeline of the gas to be desulfurized, and the desulfurization gas outlets of the desulfurization devices are connected to the same output pipeline of the mixed gas.

10. The desulfurization system according to claim 9, wherein the complex iron ions of the solid desulfurizing agent are derived from a complex iron solution containing 0.01-0.06 mol/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, and the pH value of the complexing iron solution is regulated to 8.0-12.0 by the pH regulator.

Technical Field

The invention relates to the technical field of gas purification and environmental protection, in particular to a desulfurization method, a desulfurization device and a desulfurization 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 existence of S not only pollutes the environment, corrodes pipeline equipment and influences the product quality, but also canCause the catalyst in the subsequent process to be poisoned and deactivated, thereby removing H in gas phase₂S is a very important process. However, the conventional desulfurization method has disadvantages that desulfurization efficiency is low, desulfurization environment is limited, for example, only suitable for conditions of low temperature, low space velocity and high water vapor concentration, or solid waste formed after desulfurization pollutes the environment by secondary treatment.

Disclosure of Invention

Therefore, the embodiment of the invention provides a desulfurization method, a desulfurization device and a desulfurization system, which are used for desulfurization of a gas to be desulfurized, which contains hydrogen sulfide, can oxidize hydrogen sulfide into elemental sulfur, have high desulfurization efficiency, and even can avoid the environment pollution caused by secondary treatment of solid waste.

Specifically, the embodiment of the invention discloses a desulfurization method, which comprises the following steps: (i) introducing a gas to be desulfurized, which comprises hydrogen sulfide and oxygen, from a desulfurization gas inlet of a desulfurization device to one side of a catalyst bed layer loaded in the desulfurization device, wherein the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and complex iron ions loaded on the wall of the pore of the porous material carrier, and the sulfur penetration capacity of the solid desulfurizer is 15-35%; (ii) carrying out redox reaction on the complex ferric ions loaded on the porous material carrier hole wall 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 to obtain a desulfurized mixed gas; and (iii) discharging the desulfurized mixed gas from a desulfurization gas outlet of the desulfurization unit located on the other opposite side of the catalyst bed.

In one embodiment of the invention, the concentration ratio of the oxygen to the hydrogen sulfide in the gas to be desulfurized is 2-50, the concentration of the hydrogen sulfide in the gas to be desulfurized is 5-1500 ppm, and the concentration of the oxygen in the gas to be desulfurized is less than 0.3%.

In one embodiment of the invention, the reaction temperature of the solid desulfurizing agent is 20-150 ℃ and is provided by the temperature of the gas to be desulfurized, and the reaction temperature isThe water vapor content of the gas to be desulfurized is 0-90% of saturated steam of water at the reaction temperature, the reaction pressure of the solid desulfurizer is 0.1-8.0 MPa, and the gas space velocity when the gas to be desulfurized is contacted with the solid desulfurizer is 100-3000 h^-1。

In one embodiment of the invention, the concentration ratio of the oxygen to the hydrogen sulfide in the gas to be desulfurized is 3-20, the concentration of the hydrogen sulfide in the gas to be desulfurized is 50-1000 ppm, and the reaction temperature is 40-110 ℃.

In one embodiment of the present invention, the gas to be desulfurized is derived from blast furnace gas or coke oven gas, the porous material carrier is activated carbon, and the desulfurization method further comprises: and throwing the used solid desulfurizer into a kiln for producing blast furnace gas or coke-oven gas for combustion.

In one embodiment of the invention, the complex ferric ions of the solid desulfurizing agent are derived from a complex ferric solution containing 0.01-0.06 mol/L of complex ferric ions, and the raw materials of the complex ferric 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.

Furthermore, an embodiment of the present invention provides a desulfurization apparatus, including: the catalyst bed layer comprises a solid desulfurizer with the penetrating sulfur capacity of 15-35%, wherein the solid desulfurizer comprises a porous material carrier and complex ferric ions loaded on the hole wall of the porous material carrier, and the complex ferric ions are used for reacting with hydrogen sulfide in the gas to be desulfurized to generate elemental sulfur and obtain the desulfurized mixed gas; the desulfurization gas inlet is positioned on one side of the catalyst bed layer and is used for introducing the gas to be desulfurized; and a desulfurization gas outlet which is positioned at the other opposite side of the catalyst bed layer and is used for discharging the desulfurized mixed gas.

In one embodiment of the invention, the complex ferric ions of the solid desulfurizing agent are derived from a complex ferric solution containing 0.01-0.06 mol/L of complex ferric ions, and the raw materials of the complex ferric 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, a desulfurization system provided by an embodiment of the present invention includes: a plurality of desulfurization units connected in parallel. Wherein each of the desulfurization units comprises: the catalyst bed layer comprises a solid desulfurizer with the penetrating sulfur capacity of 15-35%, wherein the solid desulfurizer comprises a porous material carrier and complex ferric ions loaded on the hole wall of the porous material carrier, and the complex ferric ions are used for reacting with hydrogen sulfide in the gas to be desulfurized to generate elemental sulfur and obtain the desulfurized mixed gas; the desulfurization gas inlet is positioned on one side of the catalyst bed layer and is used for introducing the gas to be desulfurized; and a desulfurization gas outlet which is positioned at the other opposite side of the catalyst bed layer and is used for discharging the desulfurized mixed gas. In addition, the desulfurization gas inlets of the plurality of desulfurization devices are connected to the same input pipeline of the gas to be desulfurized, and the desulfurization gas outlets of the plurality of desulfurization devices are connected to the same output pipeline of the mixed gas.

In one embodiment of the invention, the complex ferric ions of the solid desulfurizing agent are derived from a complex ferric solution containing 0.01-0.06 mol/L of complex ferric ions, and the raw materials of the complex ferric 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.

The technical scheme can have the following advantages or beneficial effects: the desulfurization method, device and system of the embodiment of the invention adopt a porous material carrier, such as activityThe solid desulfurizer prepared by complexing iron solution through carbon adsorption can be used for desulfurizing gas to be desulfurized containing hydrogen sulfide, namely hydrogen sulfide (H)₂S) is oxidized into elemental sulfur, and a desulfurization-regeneration cyclic process can be realized, so that the desulfurization efficiency is high. 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. In addition, the solid desulfurizing agent provided by the embodiment of the invention can be used for desulfurizing in a liquid film or directly by gas-solid contact, so that the desulfurizing agent is suitable for a wider saturated steam concentration and a wider temperature range, namely is suitable for various desulfurizing environments and is more widely applied. In addition, when the porous material carrier is activated carbon, the activated carbon left after desulfurization of the solid desulfurizer of the embodiment of the invention can be directly burned in a furnace, the treatment is convenient, and the environment is not polluted by relatively large solid wastes.

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 desulfurization method according to an embodiment of the present invention.

FIG. 2 is a schematic view showing a desulfurization apparatus suitable for use in the desulfurization method shown in FIG. 1.

Fig. 3 is a schematic structural diagram of a desulfurization 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 desulfurization method according to an embodiment of the present invention, and fig. 2 is a schematic structural diagram of a desulfurization apparatus suitable for use in the desulfurization method shown in fig. 1. Specifically, as shown in fig. 1, the desulfurization method includes:

step S11: introducing a gas to be desulfurized, which comprises hydrogen sulfide and oxygen, from a desulfurization gas inlet of a desulfurization device to one side of a catalyst bed layer loaded in the desulfurization device, wherein the catalyst bed layer comprises a solid desulfurizer, the solid desulfurizer comprises a porous material carrier and complex iron ions loaded on the wall of the pore of the porous material carrier, and the sulfur penetration capacity of the solid desulfurizer is 15-35%;

step S13: carrying out redox reaction on the complex ferric ions loaded on the porous material carrier hole wall 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 to obtain a desulfurized mixed gas;

step S15: and discharging the desulfurized mixed gas from a desulfurization gas outlet of the desulfurization device, which is positioned at the other opposite side of the catalyst bed layer.

For example, the desulfurization device 100 in step S11 is shown in fig. 2, and includes a catalyst bed 110, a desulfurization gas inlet 130, and a desulfurization gas outlet 150. The catalyst bed layer 110 is loaded inside the desulfurization device 100, and includes a solid desulfurizing agent, and the solid desulfurizing agent includes a porous material carrier and complex iron ions loaded on a pore wall of the porous material carrier. Of course, the catalyst bed layer 110 further includes, for example, a grid plate for supporting the solid desulfurizing agent, so that the solid desulfurizing agent can be sandwiched between two oppositely disposed grid plates. Furthermore, the desulfurization gas inlet 130 and the desulfurization gas outlet 150 are respectively disposed at two opposite sides of the catalyst bed 110, and the desulfurization gas inlet 130 is used for introducing a gas to be desulfurized, which contains hydrogen sulfide and oxygen, to one side of the catalyst bed 110. Further, typically, the desulfurization inlet 130 and the desulfurization outlet 150 are respectively provided with valves. In addition, for the solid desulfurizing agent of the embodiment, the desulfurization performance parameters are as follows:

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

(2) the water vapor content is 0-90% of saturated steam of water at a specific temperature (such as reaction temperature), and the gas to be desulfurized carries the water vapor;

(3) the gas airspeed when the desulfurized gas is contacted with the solid desulfurizer is 100-3000 h^-1Where the gas space velocity is the ratio of the volume of the gas to be desulfurized per hour passing through the catalyst bed 110 to the volume of the solid desulfurizing agent;

(4) the reaction pressure is 0.1MPa to 8.0 MPa;

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

(6) the penetrating sulfur capacity of the solid desulfurizer is 15-35%, the penetrating sulfur capacity is the capacity of the solid desulfurizer in unit volume capable of absorbing sulfur when ensuring the process purification degree index, and the process purification degree index is H in the desulfurized gas₂The S concentration is, for example, less than or equal to 1mg/m³(mg/cubic meter);

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

(8) concentration of oxygen in the gas to be desulfurized: 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 as alumina (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 S13, taking the porous material carrier as the activated carbon as an example, when the 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 110 at a certain gas space velocity, the hydrogen sulfide in the gas to be desulfurized and the complex ferric ions (ferric ions) loaded on the wall of the activated carbon pore undergo an oxidation-reduction reaction to generate elemental sulfur and complex ferrous ions (ferrous ions), and the oxygen molecules in the gas to be desulfurized can rapidly oxidize the complex ferrous ions reduced by the hydrogen sulfide into complex ferric ions to regenerate the complex ferric ions, thereby implementing the desulfurization-regeneration cycle process. The gas to be desulfurized is a mixed gas, and the main components include, 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. Only when the majority of the activated carbon isThe pore channels 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 ions, so that the solid desulfurizing agent is considered to be penetrated. The penetrated solid desulfurizer can subsequently execute desulfurizer regeneration to reopen the blocked pore channel so as to carry out desulfurization again, and then can be thrown into a furnace kiln for producing raw material gas such as blast furnace gas or coke-oven gas and the like for combustion after the solid desulfurizer can not be used for desulfurization again, thereby overcoming the defect that the environment is polluted by secondary treatment of solid waste formed after desulfurization.

After the step S13, the gas to be desulfurized is desulfurized by the solid desulfurizing agent in the catalyst bed 110, and a desulfurized mixed gas is obtained at the other opposite side of the catalyst bed 110, so that in the step S15, the desulfurized mixed gas is discharged from the desulfurization gas outlet 150 of the desulfurization device 100 at the other opposite side of the catalyst bed 110 to enter other sections, for example, the desulfurized mixed gas is discharged to a flue gas treatment system.

In other embodiments, to further improve the desulfurization efficiency, a plurality of desulfurization units may be connected in parallel to form a desulfurization system as shown in fig. 3. Specifically, as shown in fig. 3, the desulfurization system 10 includes: a plurality of desulfurization devices 100 connected in parallel, and a gas to be desulfurized input pipeline 101 and a mixed gas output pipeline 103.

Wherein each of the desulfurization devices 100 includes: catalyst bed 110, sweet gas inlet 130, and sweet gas outlet 150. The catalyst bed layer 110 comprises a solid desulfurizer with a penetrating sulfur capacity of 15-35%, wherein the solid desulfurizer comprises a porous material carrier and complex iron ions loaded on the pore wall of the porous material carrier, and the complex iron ions are used for reacting with hydrogen sulfide in a gas to be desulfurized to generate elemental sulfur and obtain a desulfurized mixed gas; of course, the catalyst bed layer 110 further includes, for example, a grid plate for supporting the solid desulfurizing agent, so as to sandwich the solid desulfurizing agent between two oppositely disposed grid plates. The desulfurization gas inlet 130 is located at one side of the catalyst bed 110 and is used for introducing the gas to be desulfurized, and the desulfurization gas outlet 150 is located at the other opposite side of the catalyst bed 110 and is used for discharging the desulfurized gas mixture.

In addition, the desulfurization gas inlets 130 of the plurality of desulfurization devices 100 are connected to the same input line 101 for the gas to be desulfurized, and the desulfurization gas outlets 150 of the plurality of desulfurization devices 100 are connected to the same output line 103 for the mixed gas.

Note that, when the gas to be desulfurized is desulfurized by the desulfurization system 10 shown in fig. 3, the gas to be desulfurized fed through the gas-to-be-desulfurized pipeline 101 may be fed into all or a part of the plurality of desulfurization apparatuses 100, and may be specifically determined as necessary. For the desulfurization method of a single desulfurization device 100, the desulfurization method described above with reference to fig. 1 can be referred to, and thus, the description thereof is omitted.

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 ions of the solid desulfurizing agent are derived from a complex iron solution containing 0.01-0.06 mol/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, and the pH value of the complexing iron solution is regulated to 8-12 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 present embodiment does not include chloride ions such as ferric chloride, ferric nitrate, and ferrous nitrateAnd ferric salt of nitrate ions, so harmful impurity anions such as chloride ions and nitrate ions are not introduced into the iron complexing solution, thereby avoiding the problems of serious corrosion of chloride ions to equipment, easy explosion when the nitrate ions meet carbon, difficult wastewater treatment and the like.

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 disperse the complexed iron ions in the microporous channels of the porous material carrier (such as activated carbon), so that H in the gas to be desulfurized is highly dispersed₂S 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 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, 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 device and the desulfurization system related to the desulfurization method are simple, and the investment cost can be reduced; when in useWhen the porous material carrier is activated carbon, the desulfurized solid desulfurizer of the desulfurization method can be directly burned in a furnace, the operation is convenient, and the environment is not polluted by large solid wastes.

In summary, the desulfurization method, the desulfurization device and the desulfurization system according to the embodiments of the present invention obtain the solid desulfurizing agent by adsorbing and complexing the iron solution with the porous material carrier, such as activated carbon, which can be used for desulfurizing the 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 a high 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. In addition, the solid desulfurizing agent provided by the embodiment of the invention can be used for desulfurizing in a liquid film or directly by gas-solid contact, so that the desulfurizing agent is suitable for a wider saturated steam concentration and a wider temperature range, namely is suitable for various desulfurizing environments and is more widely applied. In addition, 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 environment is not polluted by large solid wastes.

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.