CN113856451B - A kind of hydrogen sulfide removal agent and its preparation method, hydrogen sulfide removal method - Google Patents

Abstract

The invention relates to a hydrogen sulfide removing agent, a preparation method thereof and a hydrogen sulfide removing method. The hydrogen sulfide remover is amino carboxylic acid chelating agent and Fe ³⁺ Is a chelate compound of (a). The preparation method of the hydrogen sulfide removing agent according to the invention is amino carboxylic acid chelating agent and Fe-containing ³⁺ And chelating the compound, wherein the obtained chelate is used as a hydrogen sulfide removing agent. The hydrogen sulfide removal method according to the present invention employs the hydrogen sulfide removal agent of the present invention. The hydrogen sulfide remover of the invention contains a large amount of amino and carboxyl, thus chelating a large amount of Fe ³⁺ The method comprises the steps of carrying out a first treatment on the surface of the And due to amino and carboxyl groups and Fe ³⁺ Is very strong in chelating force of Fe ³⁺ Is not easy to fall off; therefore, when the hydrogen sulfide removing agent is used for removing hydrogen sulfide, the efficiency of removing hydrogen sulfide is high and stable.

Description

A kind of hydrogen sulfide removal agent and its preparation method, hydrogen sulfide removal method

technical field

The invention relates to the field of hydrogen sulfide removal, in particular to a hydrogen sulfide removal agent, a preparation method thereof, and a hydrogen sulfide removal method.

Background technique

Oil and gas, coal bed methane and biogas often corrode equipment due to hydrogen sulfide gas, and poison workers in it due to hydrogen sulfide gas. Therefore, the removal of hydrogen sulfide gas has economic, safety and environmental value.

At present, the methods of removing hydrogen sulfide gas by redox method include dry method and wet method, also known as heterogeneous catalytic oxidation method and homogeneous catalytic oxidation method.

However, the removal agent used in the dry removal of hydrogen sulfide generally has the problems of low stability of the removal agent, low efficiency of hydrogen sulfide removal and instability.

For example, Chinese patent CN112717931A discloses an iron-based composite hydrogen sulfide remover and a preparation method thereof. The specific preparation method is as follows: preparing a certain concentration of iron salt solution, adding a certain proportion of carbon nanotubes, stirring to obtain a mixed solution, adding a precipitant solution at a certain temperature to adjust the pH of the solution to 3-11, forming a suspension and then aging, after the aging is completed, suction filtration is performed, and the precipitate is collected and washed with deionized water to obtain an iron-based composite hydrogen sulfide remover.

This method mainly uses the Fe-O-C chemical bond interaction between carbon nanotubes and hydrated iron oxide to promote the electron mobility of the hydrogen sulfide removal agent when removing hydrogen sulfide, thereby improving its ability to remove hydrogen sulfide.

However, the bond energy between C-O bonds in the Fe-O-C chemical bond formed between carbon nanotubes and hydrated iron oxide is low, and it is easy to break under acidic conditions; and the treatment process of hydrogen sulfide is more acidic, which will make the hydrated iron oxide gradually fall off on the surface of carbon nanotubes, thereby causing the ability of the hydrogen sulfide remover to remove hydrogen sulfide.

Based on this, it is urgent to provide a hydrogen sulfide removal agent with high hydrogen sulfide removal efficiency and stability.

Contents of the invention

The invention provides a hydrogen sulfide removal agent, a preparation method thereof, and a hydrogen sulfide removal method to solve the problem of low and unstable removal efficiency of the hydrogen sulfide removal agent in the prior art.

According to one aspect of the present invention, a hydrogen sulfide removal agent is provided, the hydrogen sulfide removal agent is an aminocarboxylic acid chelating agent and a chelate of Fe ³⁺ .

According to the hydrogen sulfide removing agent of the present invention, the aminocarboxylic acid chelating agent is a cross-linked product of polyaspartic acid and spheres with amino groups at their ends.

According to the hydrogen sulfide removing agent of the present invention, the spheres containing amino groups at the ends are conjugated products of spheres containing hydroxyl groups and silane coupling agents containing amino groups.

According to the hydrogen sulfide removing agent of the present invention, the hydroxyl-containing spheres are hydroxyl-containing glass microspheres.

According to another aspect of the present invention, a kind of preparation method of hydrogen sulfide removal agent is provided, comprising the preparation step of chelate: aminocarboxylic acid chelating agent and the compound chelation containing Fe3 ⁺ , obtain chelate as hydrogen sulfide removal agent;

Preferably, the mass ratio of the aminocarboxylic acid chelating agent to the Fe ³⁺ -containing compound is 1:5˜1:20.

According to the preparation method of the present invention, comprising the preparation steps of the aminocarboxylic acid chelating agent:

Polyaspartic acid is cross-linked with spheres including amino groups at the end through a cross-linking agent to obtain the aminocarboxylic acid chelating agent;

Preferably, the mass ratio of the sphere including the amino group at the end to the polyaspartic acid is 1:5˜1:20.

According to the preparation method of the present invention, the steps of preparing the spheres whose ends include amino groups are included:

The hydroxyl-containing sphere is coupled with the amino-containing silane coupling agent to obtain a sphere whose terminal includes an amino group.

Preferably, the mass ratio of the hydroxyl-containing sphere to the amino-containing silane coupling agent is 1:1˜1:2.

According to the preparation method of the present invention, comprising the preparation steps of the hydroxyl-containing spheres:

The hollow glass microspheres are treated with an alkaline solution to obtain the hydroxyl-containing spheres.

According to another aspect of the present invention, a method for removing hydrogen sulfide is provided, using the hydrogen sulfide removing agent described in the present invention as the removing agent for dry removal of hydrogen sulfide.

According to another aspect of the present invention, a method for removing hydrogen sulfide is provided, comprising:

Pass the gas containing hydrogen sulfide into the absorption tower containing the alkaline solution, until the hydrogen sulfide in the alkaline solution can penetrate to form the solution to be treated;

The solution to be treated is transported to the regeneration tower containing the hydrogen sulfide removal agent of the present invention, and oxygen is introduced at the same time to remove hydrogen sulfide and regenerate the hydrogen sulfide removal agent at the same time.

Compared with the prior art, the beneficial effects produced by the technical solution of the present invention are as follows:

According to the hydrogen sulfide removal agent of the present invention, on the one hand, because the chelating ability of aminocarboxylic acid chelating agent and Fe ³⁺ is very strong, so the Fe ³⁺ used for removing hydrogen sulfide is not easy to fall off, so ^{that the efficiency of removing hydrogen sulfide is stable; 2+ is oxidized to Fe 3+ ) to} reuse the hydrogen sulfide removal agent.

According to the preparation method of the hydrogen sulfide removing agent of the present invention, the hydrogen sulfide removing agent of the present invention ^has been prepared. On the one hand, because the chelating ability of the aminocarboxylic acid ^{chelating agent and Fe is very strong, the Fe for removing hydrogen sulfide is not easy to fall off, so that the removal of hydrogen sulfide is efficient and stable; In the present invention, the hydrogen sulfide removing agent can be regenerated by oxygen (that is, Fe 2+ is} oxidized to Fe ³⁺ by oxygen ⁾ , so that the hydrogen sulfide removing agent can be reused.

According to the hydrogen sulfide removal method of the present invention, the hydrogen sulfide removal agent of the present invention is used, and has high and stable hydrogen sulfide removal efficiency.

According to another hydrogen sulfide removal method of the present invention, since the hydrogen sulfide is reacted with the alkaline solution contained in the absorption tower to form a solution to be treated, the problem in the prior art that when the absorption tower directly removes hydrogen sulfide in a homogeneous solution containing iron ions, the problem that the formed sulfur powder blocks the pipeline of the absorption tower is solved; on the other hand, the hydrogen sulfide removal agent of the present invention is used in the regeneration tower to treat the solution to be treated, and the removal efficiency is high and stable.

Description of drawings

Fig. 1 shows the infrared spectrum of the product generated in each step of the hydrogen sulfide removal agent preparation method in Example 1 of the present invention;

Reference numerals: hydroxyl group-containing sphere a, terminal end-containing sphere b, aminocarboxylic acid chelating agent c, chelate d.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and embodiments. Apparently, the described embodiments are only a part of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

According to one aspect of the present invention, a kind of hydrogen sulfide removal agent is provided, and the hydrogen sulfide removal agent is the chelate of aminocarboxylic acid chelating agent and Fe ³⁺ .

According to the hydrogen sulfide removal agent of the present invention, on the one hand, due to the strong chelating ability of the aminocarboxylic acid chelating agent and Fe ³⁺ , the amino group and carboxyl group and Fe ³⁺ can form a very strong coordination bond ^, so the Fe ³⁺ used to remove hydrogen sulfide is not easy to fall off, and its removal efficiency for hydrogen sulfide ^is strong and stable ^;

Wherein, aminocarboxylic acid chelating agent refers to the chelating agent that contains amino group and carboxyl group in chelating agent.

Wherein, the aminocarboxylic acid chelating agent is selected from at least one of the following: a cross-linked product of polyaspartic acid and a sphere including an amino group at the end, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminediacetic acid (EDDHA).

The compound containing Fe ³⁺ is preferably iron salt, more preferably at least one of the following: Fe ₂ (SO ₄ ) ₃ , FeCl ₃ ·6H ₂ O and Fe(NO ₃ ) ₃ .

The stability constant of aminocarboxylic acid chelating agent and Fe3 ⁺ is high, such as: the stability constant of ethylenediaminetetraacetic acid (EDTA) and Fe3 ⁺ is 25.1, and the stability constant of ethylenediaminediacetic acid (EDDHA) and Fe3 ⁺ is 29.6, because in this type of chelating agent, it is chelated with Fe3 ⁺ by amino group and carboxyl group, in the same way, it can also be known that the cross-linked product of polyaspartic acid and the sphere including amino group at the end has good stability with Fe3 ^{+, and it can be seen that The chelate formed by aminocarboxylic acid chelating agent and Fe 3+ is} very stable.

According to the hydrogen sulfide removing agent of the present invention, the aminocarboxylic acid chelating agent is preferably a cross-linked product of polyaspartic acid and a sphere including an amino group at the terminal.

According to the hydrogen sulfide removal agent of the present invention, polyaspartic acid (abbreviated as PASP) is adopted in the chelating agent. PASP is a polymer formed by the polymerization of a single aspartic acid through an amide bond, naturally exists in snails and mollusk shells, and contains a large amount of carboxyl and amino groups in the structure.

Because the PASP structure contains abundant carboxyl groups and amino groups (mainly nitrogen atoms), it can chelate a large amount of Fe ³⁺ , so that the key groups for removing hydrogen sulfide increase and the efficiency of removing hydrogen sulfide increases.

In addition, due to the presence of amino groups in the PASP structure, it can be cross-linked with spheres containing amino groups at the end through a cross-linking agent to form an aminocarboxylic acid chelating agent.

Among them, the crosslinking agent is preferably glutaraldehyde and glyoxal.

According to the hydrogen sulfide removing agent of the present invention, the sphere including an amino group at the end is a conjugated product of a hydroxyl group-containing sphere and an amino group-containing silane coupling agent.

According to the hydrogen sulfide removing agent of the present invention, the hydroxyl-containing sphere and the amino-containing silane coupling agent form a coupled chemical bond through the hydroxyl and amino groups to form a conjugate, thereby providing a substrate for the cross-linked PASP.

According to the hydrogen sulfide removing agent of the present invention, the hydroxyl-containing spheres are hydroxyl-containing glass microspheres.

Among them, the glass microspheres are preferably hollow glass microspheres, and the diameter of the glass microspheres is generally 50-100 μm; more preferably 50um, 55um, 60um, 65um, 70um, 75um, 80um, 85um, 90um, 95um and 100um.

The reason why glass microspheres are selected is that glass microspheres contain Si-O-Si bonds. When treated with an alkaline solution, the chemical bonds can be opened to form Si-OH bonds, which provide conditions for coupling amino-containing silane coupling agents. In addition, the spheres have a larger specific surface area and can form more Si-OH bonds, thereby coupling more amino-containing silane coupling agents, which in turn can cross-link more PASP, so that the aminocarboxylic acid chelating agent contains more amino and carboxyl groups, and finally chelates more Fe ³⁺ .

According to another aspect of the present invention, a kind of preparation method of hydrogen sulfide removal agent is provided, comprising the preparation step of chelate: aminocarboxylic acid chelating agent and the compound chelation containing Fe3 ⁺ , obtain chelate as hydrogen sulfide removal agent;

Preferably, the mass ratio of the aminocarboxylic acid chelating agent to the Fe ³⁺ -containing compound is 1:5˜1:20.

Specifically, the aminocarboxylic acid chelating agent and the Fe3 ⁺ -containing compound are generally dispersed in the solution in a certain proportion, and the chelating reaction is performed at a certain temperature for a period of time. After the reaction is completed, the suction is filtered; after the filter residue is dried and roasted, the chelate is obtained as a hydrogen sulfide removal agent.

The mass ratio of the carboxyl-containing chelating agent to the Fe3 ⁺ -containing compound is preferably 1:5 to 1:20, specifically preferably 1:5, 1:6, 1:8, 1:10, 1:12, 1:14, 1:15, 1:17 and 1:20.

Among them, the aminocarboxylic acid chelating agent is preferably a cross-linked product of polyaspartic acid and a sphere including an amino group at the end, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminediacetic acid (EDDHA).

Among them, Fe ³⁺ -containing compounds are preferably iron salts, more preferably at least one of the following: Fe ₂ (SO ₄ ) ₃ , FeCl ₃ ·6H ₂ O, [FeNH ₄ (SO ₄ ) ₂ ·12H ₂ O] and Fe(NO ₃ ) ₃ .

Among them, the certain temperature is 60-70°C, specifically preferably 60°C, 63°C, 65°C, 68°C and 70°C.

Wherein, the certain time is 4-6 hours, specifically preferably 4 hours, 4.5 hours, 5 hours, 5.5 hours and 6 hours.

More specifically, in the following equation, the cross-linked product of polyaspartic acid and spheres with amino groups at the end is used as a chelating agent and iron chloride chelation as an example, and the specific operation method is as follows.

Prepare a ferric chloride solution with a mass fraction of 25% to 50%. According to the mass ratio of the chelating agent to the ferric chloride solution volume ratio of 1:20 to 40 (g/mL) (converted to a mass ratio of 1:5 to 1:20), weigh the chelating agent and disperse it in the iron salt solution; then heat up to 60 to 70°C for chelation reaction for 4 to 6 hours; after the reaction, vacuum filter and collect the filter residue and filtrate respectively; Utilization; the collected filter residue is sent into a vacuum drying oven, vacuum-dried for 4-8 hours at a temperature of 50-60°C and a vacuum degree of 40-50Pa, and then roasted at 300°C for 5 hours after taking it out to prepare a chelate as a hydrogen sulfide removal agent.

An exemplary reaction equation for this step is shown below.

According to preparation method of the present invention, comprise the preparation step of aminocarboxylic acid chelating agent:

Polyaspartic acid is cross-linked with spheres including amino groups at the end through a cross-linking agent to obtain a chelating agent of aminocarboxylic acid;

Preferably, the mass ratio of the sphere including the amino group at the end to the polyaspartic acid is 1:5-1:20;

Preferably, during the preparation of the aminocarboxylic acid chelating agent, a pore-forming agent is added.

Specifically, the spheres including amino groups at the end and polyaspartic acid are cross-linked by a cross-linking agent in a certain ratio to obtain an aminocarboxylic acid chelating agent.

The mass ratio of the spheres including amino groups at the end to polyaspartic acid is preferably 1:5-1:20, specifically 1:5, 1:8, 1:10, 1:13, 1:15, 1:18 and 1:20.

Preferably, when preparing the aminocarboxylic acid chelating agent, the pore-forming agent is preferably polyethylene glycol, wood powder and talcum powder.

The mass ratio of the crosslinking agent to the spheres including amino groups at the terminal is 0.05:1˜0.1:1, specifically preferably 0.05:1, 0.08:1 and 0.1:1.

The reaction temperature is preferably 60-70°C, specifically preferably 60°C, 63°C, 65°C, 68°C and 70°C.

The reaction time is preferably 4-6h, specifically preferably 4h, 4.5h, 5h, 5.5h and 6h.

Taking the reaction between a sphere with an amino group at its terminal and polyaspartic acid in the following equation as an example, the specific operation is as follows: first prepare a PASP solution with a mass fraction of 25% to 50%, and weigh polyethylene glycol into the PASP solution according to the mass ratio of PASP to polyethylene glycol at a ratio of 1:0.05 to 0.1 (g/g); ~1:20), weigh the spheres containing amino groups at the end and disperse them in the PASP solution, mix thoroughly; then prepare a glutaraldehyde solution with a mass fraction of 5%, add glutaraldehyde according to the ratio of the mass of the spheres containing amino groups at the end to the glutaraldehyde solution volume ratio of 1:1~2 (g/mL), heat to 60~70°C with a constant temperature water bath, after 4~6 hours of treatment, perform vacuum filtration, and wash repeatedly with water until no liquid drops flow out. Collect the filter residue and filtrate respectively, wherein the filtrate includes unreacted PASP solution, which can be used again to prepare the aminocarboxylic acid chelating agent; the filter residue is then placed in a vacuum drying oven, and vacuum-dried for 4 to 8 hours at a temperature of 50-60°C and a vacuum degree of 40-50Pa to obtain the aminocarboxylic acid chelating agent.

An exemplary reaction equation for a sphere including an amino group at the end and polyaspartic acid for this step is as follows:

According to the preparation method of the present invention, the preparation steps of spheres comprising amino groups at the end are included:

The hydroxyl-containing sphere is coupled with the amino-containing silane coupling agent to obtain a sphere whose terminal includes an amino group.

Preferably, the mass ratio of the hydroxyl-containing sphere to the amino-containing silane coupling agent is 1:1˜1:2.

Specifically, the amino group-containing silane coupling agent is preferably at least one of the following: (3-aminopropyltriethoxysilane) and (3-aminopropyltrimethoxysilane).

More specifically, the reaction equation of the hydroxyl-containing sphere and the amino-containing silane coupling agent is shown below as an example. The specific operation is: according to the mass ratio of the hydroxyl-containing sphere and the amino-containing silane coupling agent of 1:1-2 (g/g), weigh the hydroxyl-containing sphere and the silane coupling agent, and then according to the total mass of the hydroxyl-containing sphere and the silane coupling agent: The volume ratio of absolute ethanol is 1:100-200 (g/mL), and the hydroxyl-containing sphere The body and the silane coupling agent are dispersed in absolute ethanol, heated to 80-90°C with a constant temperature water bath, condensed and refluxed for 4-6 hours, taken out, vacuum filtered, and the filter residue and filtrate are collected respectively; the collected filtrate is used to recover ethanol; the collected filter residue is sent to a vacuum drying oven for 4-8 hours at a temperature of 50-60°C and a vacuum degree of 40-50Pa to obtain a sphere containing a hydroxyl group at the end.

The exemplary reaction equation of this step is as follows, wherein the amino group-containing silane coupling agent is 3-aminopropyltriethoxysilane.

According to the preparation method of the present invention, comprising the preparation steps of hydroxyl-containing spheres:

The hollow glass microspheres are treated with an alkaline solution to obtain hydroxyl-containing spheres.

Wherein, the alkaline solution is selected from at least one of the following solutions: sodium hydroxide, lithium hydroxide, potassium hydroxide and calcium hydroxide.

Preferably, the alkaline solution is sodium hydroxide solution, and the mass fraction of sodium hydroxide solution is preferably 25% to 50%, specifically preferably 25%, 30%, 35%, 40%, 45% and 50%.

Specifically, take the following reaction equation as an example, the specific operation is as follows: first prepare a sodium hydroxide solution with a mass fraction of 25% to 50%, according to the volume ratio of hollow glass microspheres (HGM) and sodium hydroxide solution of 1:10 to 30 (g/mL), weigh the HGM and disperse it in the sodium hydroxide solution, heat it to 80 to 100°C in a constant temperature water bath, take it out after treatment for 3 to 6 hours, wash it with pure water for several times until the washing solution is neutral, and dissolve the washing solution After being combined with the waste liquid after pretreatment of HGM, it is neutralized and discharged after reaching the standard, while the washed HGM is placed in an oven, dried at 40-60°C to constant weight, and then stored in a glass desiccator to prepare hydroxyl-containing spheres.

The mechanism of using hollow glass microspheres and sodium hydroxide solution in the preparation method of the present invention is as follows.

According to another aspect of the present invention, a method for removing hydrogen sulfide is provided, using the hydrogen sulfide removing agent of the present invention as the removing agent for dry removal of hydrogen sulfide.

The following takes a laboratory dry method of hydrogen sulfide removal as an example to describe the dry removal of hydrogen sulfide using the hydrogen sulfide removal agent of the present invention.

Take 0.2g to 1.0g of the hydrogen sulfide removal agent prepared by the present invention, place it in a U-shaped bubbling tube, and keep the temperature constant in a water bath. When the temperature of the U-shaped bubbling tube reaches 40°C to 50°C, use raw material gas with a hydrogen sulfide concentration of 200mg/m3 to enter the U-shaped bubbling tube at a flow rate of 40mL/ ^{min under normal pressure to react with the hydrogen sulfide removal agent. The hydrogen sulfide concentration at the outlet is detected by an LC-2 hydrogen sulfide detector. When it reaches 6mg/m 3 ,} stop the ventilation, and at this time, it is considered that the hydrogen sulfide removal agent has penetrated.

According to another aspect of the present invention, a method for removing hydrogen sulfide is provided, comprising:

Pass the gas containing hydrogen sulfide into the absorption tower containing the alkaline solution, until the hydrogen sulfide in the alkaline solution can penetrate to form the solution to be treated;

The solution to be treated is transported to the regeneration tower containing the hydrogen sulfide removal agent of the present invention, and oxygen is introduced at the same time to remove hydrogen sulfide and regenerate the hydrogen sulfide removal agent at the same time.

Wherein, the alkaline solution is preferably at least one of the following: sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.

Among them, the alkaline solution is more preferably sodium hydroxide solution, the solvent is preferably water, and the concentration is preferably 0.05-0.2 mol/L, more preferably 0.05 mol/L, 0.1 mol/L, 0.15 mol/L.

When hydrogen sulfide gas is passed into the alkaline solution in the absorption tower, salts (such as sodium sulfide and sodium hydrosulfide) will be formed and dissolved in water; the solution is passed into the regeneration tower, which contains the hydrogen sulfide removal agent of the present invention, which can oxidize HS- ^{and S2-} in the solution into sulfur powder.

Wherein, hydrogen sulfide in alkaline solution can penetrate means that hydrogen sulfide gas can no longer react with alkaline solution to form salt and dissolve in water, that is, the solution can no longer absorb hydrogen sulfide.

In the prior art, an iron-based hydrogen sulfide removal agent is contained in the absorption tower, and it is a homogeneous reaction, and the redox reaction between the iron-based ionic liquid and sulfur ions: 2Fe ³⁺ +S2-=2Fe ²⁺ +S.

The sulfur element produced by it is generally in the state of sulfur powder, which will block the absorption tower.

In this method, the solution containing iron ions is replaced with an alkaline solution, and sulfur powder will not be generated in the absorption tower, but a sulfur salt will be dissolved in water. For example, when the alkaline solution is sodium hydroxide solution, there may be two reaction modes with hydrogen sulfide. The equation of one reaction _mode is: 2NaOH+H ₂ S=Na ₂ S+ _{H 2 O} ;

The above-mentioned solution to be treated formed in the absorption tower is sent to the regeneration tower, which contains the hydrogen sulfide removal agent of the present invention, and the reaction equation between the hydrogen sulfide removal agent of the present invention and S ^2- in the solution is: 2Fe ³⁺ +S ^2- =2Fe ²⁺ +S.

After hydrogen sulfide is removed in the regeneration tower, the hydrogen sulfide removal agent and sulfur powder are released together, and the sulfur powder is dissolved by the extraction agent, so that the hydrogen sulfide removal agent can be recovered conveniently.

The main purpose of introducing oxygen is to regenerate the hydrogen sulfide removal agent, which can be reused. The regeneration principle is 4Fe ²⁺ +O ₂ +4H ⁺ =4Fe ³⁺ +2H ₂ O.

The efficiency of removing hydrogen sulfide by using the hydrogen sulfide removing agent of the invention is high and stable.

In order to prove the method, the applicant carried out laboratory operations. Taking sodium hydroxide solution as an example, the specific operation is as follows: according to the ratio of the mass of sodium hydroxide to the volume of water of 1:200-400 (g/mL), dissolve sodium hydroxide in water, and after fully dissolving, pour the sodium hydroxide solution into a U-shaped bubbling tube (equivalent to an absorption tower) and keep the temperature in a water bath at 40-50°C.₂S concentration is the raw material gas of 5% (mol%), passes in the above-mentioned solution with 30mL/min flow rate under normal pressure, carries out desulfurization reaction and starts timing, when tail gas H₂S concentration reaches 6mg/m³When (reaching this concentration means that sulfur breakthrough is achieved, the solution can no longer absorb H₂S) stop the aeration and count the time, that is, the solution to be treated is formed.

According to the ratio of the mass of the hydrogen sulfide removing agent of the present invention to the volume ratio of the solution to be treated as 1:20-40 (g/mL), add it into the above-mentioned U-shaped bubbling tube (equivalent to a regeneration tower) for desulfurization, react at 40°C under normal pressure conditions, and start timing, and at the same time feed oxygen to regenerate the hydrogen sulfide removing agent after desulfurization. .

What needs to be explained here is that the oxidation-reduction potential is an instrument for monitoring the redox reaction in the solution. If there is no redox reaction in the solution, the reading is 0; if there is a redox reaction, there is a reading; in the process of removing hydrogen sulfide and regeneration, because the redox reaction has been occurring, the reading of the redox potential has been increasing. When the redox has completed, the redox potential will not change.

According to the hydrogen sulfide removing agent of the present invention, the mechanism of hydrogen sulfide removal and oxygen regeneration is as follows.

The present invention will be described below in conjunction with specific examples. It should be noted here that the examples are only used to illustrate the present invention and do not limit the protection scope of the claims.

Wherein, embodiment 1～3 is the preparation method of hydrogen sulfide removal agent; Embodiment 4～6 is the method that adopts the hydrogen sulfide removal agent prepared in embodiment 1～3 to carry out the method for dry method of hydrogen sulfide removal; Embodiment 7～9 is the hydrogen sulfide removal method that adopts the hydrogen sulfide removal agent of the present invention, carries out combination of dry and wet. Comparative examples 1-3 are methods for removing hydrogen sulfide using the prior art.

Example 1

First carry out step S1: prepare the hollow glass microsphere containing hydroxyl group, the concrete operation of this step is as follows:

Prepare a sodium hydroxide solution with a mass fraction of 25%; according to the volume ratio of hollow glass microspheres (HGM) and sodium hydroxide solution of 1:10 (g/mL), weigh HGM and disperse it in the sodium hydroxide solution; heat it to 80°C with a constant temperature water bath, and take it out after 3 hours of treatment; wash it with pure water until the washing solution is neutral; Put it in an oven, dry it to a constant weight at 40°C, and store it in a glass desiccator to prepare hollow glass microspheres containing hydroxyl groups.

Carry out step S2 then: prepare the sphere that terminal comprises amino group, the concrete operation of this step is as follows:

According to the ratio of the mass ratio of hydroxyl-containing hollow glass microspheres to aminosilane coupling agent of 1:1 (g/g), weigh the hydroxyl-containing hollow glass microspheres and silane coupling agent; then according to the ratio of the total mass of hydroxyl-containing hollow glass microspheres and silane coupling agent: the volume ratio of absolute ethanol is 1:100 (g/mL), disperse the hydroxyl-containing glass microspheres and silane coupling agent in absolute ethanol; use a constant temperature water bath to heat to 80 ° C, Take it out after reflux treatment for 4 hours; perform vacuum filtration to collect the filter residue and filtrate respectively; the collected filtrate is used to recover ethanol; the collected filter residue is sent to a vacuum drying oven, and vacuum dried for 4 hours at a temperature of 50 ° C and a vacuum degree of 40 Pa to prepare a sphere containing an amino group at the end. Wherein the aminosilane coupling agent is 3-aminopropyltriethoxysilane.

Carry out step S3 afterwards: prepare aminocarboxylic acid chelating agent, the concrete operation of this step is as follows:

Prepare a PASP solution with a mass fraction of 25%. According to the ratio of the mass of spheres including amino groups at the end to the PASP solution volume ratio of 1:20 (g/mL), weigh the spheres including amino groups at the end and disperse them in the PASP solution. The volume ratio of the solution is 1:1 (g/mL), add glutaraldehyde solution, heat to 60°C with a constant temperature water bath, keep it for 4 hours, and then vacuum filter. Collect the filter residue and filtrate, wherein the filtrate includes unreacted PASP solution, which can be recycled again; the filter residue is placed in a vacuum drying oven, and vacuum-dried for 4 hours at a temperature of 50°C and a vacuum of 40Pa to prepare the aminocarboxylic acid chelating agent.

Finally carry out step S4: the preparation of hydrogen sulfide removal agent, the concrete operation of this step is as follows:

The preparation mass fraction is the iron salt solution of 25%, according to the ratio of the mass of carboxyl-containing chelating agent and the iron salt solution volume ratio of 1:20 (g/mL), take aminocarboxylic acid chelating agent and disperse in iron salt solution; Then heat up to 60 ℃, chelate reaction 4h; After vacuum suction filtration, collect filter residue and filtrate respectively; The hydrogen sulfide remover was prepared by vacuum drying for 4 hours under the condition of 45 Pa, and then roasted under the condition of 300°C for 5 hours after taking it out, and the iron salt used was FeCl ₃ ·6H ₂ O.

The applicant performed infrared spectrum characterization on the reaction products in each step of Example 1, and the characterization results are shown in FIG. 1 .

In Figure 1 curve a, 3500cm ^-1 is the stretching vibration peak of -OH, and around 1000cm ^-1 is the bending vibration peak of Si-OH, so it proves that hydroxyl groups are formed on the surface of the hollow glass microspheres treated with alkali.

In Figure 1 curve b, compared with curve a, a new peak appeared at 2900-3000cm ^-1 , which was attributed to the stretching vibration peaks of methyl and methylene groups, and two new peaks appeared around 1500 and 1350cm ^-1 , which were attributed to the vibration peaks of amino groups and -CN bonds, and the peak near 950cm ^- 1 was the stretching vibration peak of Si-O, all of which were due to the coupling of 3-aminopropyltriethoxysilane with hydroxyl-containing spheres. The termini include amino groups.

In Figure 1 curve c, the absorption peak around 1400cm ^-1 is enhanced, and a new peak also appears around 900cm ^-1 , which is attributed to the vibration absorption peak of the hydroxyl group in the carboxyl group in the introduced PASP. In addition, the reason why the absorption peak around 1600cm ^-1 does not change greatly after crosslinking is that the amino group in the sphere including the amino group at the end overlaps with the amino group introduced after crosslinking, but there is the formation of -C=N-, so at 1600cm ^-1 The left and right absorption peaks are red-shifted.

In the curve d of Fig. 1, the peaks related to the amino group and the carboxyl group in the curve c all weaken or disappear, which is due to the chelation of iron ions by the aminocarboxylic acid chelating agent.

Example 2

First carry out step S1: prepare the hollow glass microsphere containing hydroxyl group, the concrete operation of this step is as follows:

Prepare a sodium hydroxide solution with a mass fraction of 40%; according to the volume ratio of hollow glass microspheres (HGM) and sodium hydroxide solution of 1:20 (g/mL), weigh HGM and disperse it in the sodium hydroxide solution; heat it to 90°C with a constant temperature water bath, take it out after 4 hours of treatment; wash it with pure water until the washing solution is neutral; Put it in an oven, dry it to constant weight at 50°C, and store it in a glass desiccator to prepare hollow glass microspheres containing hydroxyl groups.

Carry out step S2 then: prepare the sphere that terminal comprises amino group, the concrete operation of this step is as follows:

According to the ratio of the mass ratio of the hydroxyl-containing hollow glass microspheres to the aminosilane coupling agent of 1:1.5 (g/g), weigh the hydroxyl-containing hollow glass microspheres and the silane coupling agent; then according to the ratio of the total mass of the hydroxyl-containing hollow glass microspheres and the silane coupling agent: the volume ratio of absolute ethanol is 1:150 (g/mL), disperse the hydroxyl-containing glass microspheres and the silane coupling agent in absolute ethanol; heat to 85°C with a constant temperature water bath , taken out after 5 hours of condensing and reflux treatment; vacuum filtration was carried out to collect the filter residue and filtrate respectively; the collected filtrate was used to recover ethanol; the collected filter residue was sent into a vacuum drying oven, and vacuum dried for 5 hours at a temperature of 55 ° C and a vacuum degree of 45 Pa to prepare a sphere containing an amino group at the end. Wherein the aminosilane coupling agent is 3-aminopropyltrimethoxysilane.

Carry out step S3 afterwards: prepare aminocarboxylic acid chelating agent, the concrete operation of this step is as follows:

Prepare a PASP solution with a mass fraction of 40%. According to the ratio of the mass of spheres including amino groups at the end to the PASP solution volume ratio of 1:30 (g/mL), weigh the spheres including amino groups at the end and disperse them in the PASP solution. The solution volume ratio is 1:1.5 (g/mL), add glutaraldehyde solution, heat to 70°C with a constant temperature water bath, keep for 5h, and then vacuum filter. Collect the filter residue and filtrate, wherein the filtrate is unreacted PASP solution, which can be recycled again; the filter residue is placed in a vacuum drying oven, and vacuum-dried for 5 hours at a temperature of 55 ° C and a vacuum degree of 45 Pa to prepare the aminocarboxylic acid chelating agent.

Finally carry out step S4: the preparation of hydrogen sulfide removal agent, the concrete operation of this step is as follows:

Preparation mass fraction is the iron salt solution of 40%, according to the mass ratio of carboxyl-containing chelating agent and iron salt solution volume ratio is 1:30 (g/mL), weighs aminocarboxylic acid chelating agent and is dispersed in iron salt solution; Then heat up to 65 ℃, chelation reaction 5h; After vacuum suction filtration, collect filter residue and filtrate respectively; The hydrogen sulfide remover was prepared by vacuum drying at 45 Pa for 6 hours, and then roasting at 300°C for 5 hours after taking it out. The iron salt used was Fe ₂ (SO ₄ ) ₃ .

Example 3

First proceed to step S1: prepare hollow glass microspheres containing hydroxyl groups, the specific operation of this step is as follows:

Prepare a sodium hydroxide solution with a mass fraction of 50%; according to the volume ratio of hollow glass microspheres (HGM) and sodium hydroxide solution of 1:30 (g/mL), weigh HGM and disperse it in the sodium hydroxide solution; heat it to 100°C in a constant temperature water bath, and take it out after treatment for 6 hours; wash it with pure water until the washing liquid is neutral; M is placed in an oven, dried at 60°C to constant weight, and then stored in a glass desiccator to prepare hollow glass microspheres containing hydroxyl groups.

Carry out step S2 then: prepare the sphere that terminal comprises amino group, the concrete operation of this step is as follows:

According to the ratio of the mass ratio of hydroxyl-containing hollow glass microspheres to aminosilane coupling agent of 1:2 (g/g), weigh the hydroxyl-containing hollow glass microspheres and silane coupling agent; then according to the ratio of the total mass of hydroxyl-containing hollow glass microspheres and silane coupling agent: the volume ratio of absolute ethanol is 1:200 (g/mL), disperse the hydroxyl-containing glass microspheres and silane coupling agent in absolute ethanol; heat to 90 ° C with a constant temperature water bath, condense Take it out after reflux treatment for 6 hours; perform vacuum filtration to collect the filter residue and filtrate respectively; the collected filtrate is used to recover ethanol; the collected filter residue is sent to a vacuum drying oven, and vacuum dried at a temperature of 60°C and a vacuum degree of 50Pa for 8 hours to prepare a sphere containing an amino group at the end. Wherein the aminosilane coupling agent is 3-aminopropyltrimethoxysilane.

Carry out step S3 afterwards: prepare aminocarboxylic acid chelating agent, the concrete operation of this step is as follows:

Prepare a PASP solution with a mass fraction of 50%. According to the ratio of the mass of spheres including amino groups at the end to the PASP solution volume ratio of 1:40 (g/mL), weigh the spheres including amino groups at the end and disperse them in the PASP solution. The volume ratio is 1:2 (g/mL), add glutaraldehyde solution, heat to 70°C with a constant temperature water bath, keep it for 6h, and then vacuum filter. Collect the filter residue and filtrate, wherein the filtrate is unreacted PASP solution, which can be recycled again; the filter residue is placed in a vacuum drying oven, and vacuum-dried for 8 hours at a temperature of 60°C and a vacuum of 50Pa to prepare a carboxyl-containing chelating agent.

Finally carry out step S4: the preparation of hydrogen sulfide removal agent, the concrete operation of this step is as follows:

The preparation mass fraction is the iron salt solution of 50%, according to the mass ratio of the carboxyl-containing chelating agent and the iron salt solution volume ratio of 1:40 (g/mL), the aminocarboxylic acid chelating agent is weighed and dispersed in the iron salt solution; then the temperature is raised to 70°C, and the chelation reaction is carried out for 6h; after vacuum filtration, the filter residue and the filtrate are collected respectively; The hydrogen sulfide removal agent was prepared by vacuum drying at a temperature of 50 Pa for 8 hours, and then roasting at 300°C for 5 hours after taking it out. The iron salt used was Fe₂(SO₄)₃.

Example 4

Take 0.2 g of the hydrogen sulfide removal agent prepared in Example 1, place it in a U-shaped bubbling tube, and keep the temperature constant in a water bath. When the temperature of the U-shaped bubbling tube reaches 40° C., use raw material gas with a hydrogen sulfide concentration of 200 mg/ ^m3 under normal pressure to enter the U-shaped bubbling tube at a flow rate of 40 mL/min to react with the hydrogen sulfide removal agent. The outlet hydrogen sulfide concentration is detected by an LC-2 hydrogen sulfide detector. When the outlet hydrogen sulfide concentration reaches 6 mg/ ^m3 , stop ventilation, at this time, it is considered that the hydrogen sulfide remover penetrates.

Example 5

In this example, the hydrogen sulfide removal agent prepared in Example 2 was used to remove hydrogen sulfide, and other conditions were the same as in Example 4.

Example 6

In Example 6, the hydrogen sulfide removal agent prepared in Example 3 was used to remove hydrogen sulfide, and other conditions were the same as in Example 4.

Example 7

According to the ratio of the mass of sodium hydroxide to the volume of water of 1:250 (g/mL) (that is, the concentration is 0.1mol/L), dissolve the sodium hydroxide in the aqueous solution. After fully dissolving, pour the sodium hydroxide solution into a U-shaped bubbling tube (equivalent to an absorption tower) and keep the temperature in a water bath at 40°C.₂S concentration is the raw material gas of 5% (mol%), passes in the above-mentioned solution with 30mL/min flow rate under normal pressure, carries out desulfurization reaction and starts timing, when tail gas H₂S concentration reaches 6mg/m³When (reaching this concentration means that sulfur breakthrough is achieved, the solution can no longer absorb H₂S) stop the aeration and count the time, that is, the solution to be treated is formed.

According to the ratio of the mass of the hydrogen sulfide removing agent in Example 1 to the volume ratio of the solution to be treated at 1:20 (g/mL), add it into the above-mentioned U-shaped bubbling tube (equivalent to a regeneration tower) for desulfurization, and simultaneously feed oxygen to regenerate the hydrogen sulfide removing agent after desulfurization. The oxygen flow rate is 200mL/min. The ORP of the upper liquid is continuously monitored.

Example 8

Embodiment 8 has adopted the hydrogen sulfide removing agent in embodiment 2, and other conditions are identical with embodiment 7.

Example 9

Embodiment 9 has adopted the hydrogen sulfide removal agent in embodiment 3, and other conditions are the same as embodiment 7.

Comparative example 1

In Comparative Example 1, the composite of carbon nanotubes and hydrated iron oxide disclosed in CN112717931A was used as the hydrogen sulfide removal agent, and other conditions were the same as in Example 4.

Comparative example 2

In Comparative Example 2, except that the sodium hydroxide solution was replaced by an imidazolium chloride iron-based ion (Fe-IL:[Bmim]FeCl ₄ ) solution, and the regeneration tower was not connected, the others were the same as in Example 7.

Comparative example 3

In Comparative Example 3, except that the sodium hydroxide solution was replaced by N-butylpyridine ferric tetrachloride ([BPy]FeCl ₄ ) solution, and the step of regeneration tower was not connected, the others were the same as in Example 8.

Comparative example 4

In Comparative Example 4, except that the hydrogen sulfide removal agent in the regeneration tower is the composite of carbon nanotubes and hydrated iron oxide disclosed in CN112717931A as the hydrogen sulfide removal agent, the others are the same as in Example 7.

In order to clearly illustrate the hydrogen sulfide removal efficiency and stability of the hydrogen sulfide removal agent of the present invention, the applicant tested the breakthrough sulfur capacity of Examples 4-9 and Comparative Examples 1-3.

The detection method and calculation method of the breakthrough sulfur capacity of embodiment 4～6 and comparative example 1 are as follows:

The breakthrough sulfur capacity is calculated by the mass fraction of sulfur in the hydrogen sulfide removal agent, and the value is expressed in %, calculated according to the following formula: In the formula, C represents the mass concentration of sulfur in the feed gas (kg/m ³ ); V ₁ and V ₂ represent the gas volume values (mL) at the start and end of the wet gas flowmeter; m represents the mass (kg) of the hydrogen sulfide removal agent in the reactor.

The sulfur capacity testing conditions of Examples 4 to 6 and Comparative Example 1 are as follows: temperature is 40°C, pressure is normal pressure (usually 1 atmosphere), and breakthrough concentration is 6 mg/m ³ ;

The detection steps are:

Take 0.2g of hydrogen sulfide remover, place it in a U-shaped bubbling tube, and keep the temperature constant in a water bath. When the temperature of the U-shaped bubbling tube reaches 40°C, use raw material gas with a hydrogen sulfide concentration of 200mg/ ^m3 under normal pressure to enter the U-shaped bubbling tube at a flow rate of 40mL/ ^min to react with the hydrogen sulfide removing agent. The hydrogen sulfide concentration at the outlet is detected by an LC-2 hydrogen sulfide detector. At this time, it is considered that the hydrogen sulfide removal agent penetrates; use the wet gas flow meter to start and end the value of the gas volume, and record the removal time of hydrogen sulfide at the end of the reaction.

Calculated according to the above formula, the obtained test data are shown in Table 1.

Table 1

breakthrough sulfur capacity H2S removal time (min) Example 4 22.5% 25 Example 5 25.7% 29 Example 6 27.1% 32 Comparative example 1 144.2mg/g (14.42%) 19

Through the comparison of Example 4 and Comparative Example 1, it can be seen that the hydrogen sulfide removal agent prepared in Example 1, because the aminocarboxylic acid chelating agent and Fe ³⁺ have a strong chelating force, Fe ³⁺ is not easy to fall off, and because the abundant Fe ³⁺ is chelated, more hydrogen sulfide can be removed, so the breakthrough sulfur capacity of Example 4 is much higher than that of Comparative Example 1. It can be seen that the hydrogen sulfide removal efficiency of the hydrogen sulfide removal agent of the present invention is high.

However, Examples 4-6 using the hydrogen sulfide removing agent of the present invention all maintained a high and similar breakthrough sulfur capacity, which also shows that the efficiency of removing hydrogen sulfide using the hydrogen sulfide desulfurizing agent of the present invention is high and stable.

Compared with the removal time of Examples 4-6 and Comparative Example 1, it can also be seen that the hydrogen sulfide removal agent of the present invention has a long and stable removal time; the removal time of Comparative Example 1 is shorter, so it can be seen that the efficiency of the hydrogen sulfide removal agent of the present invention is high and stable.

The detection and calculation method of the sulfur capacity of embodiments 7～9 and comparative examples 2 and 3 are as follows:

The detection conditions are: temperature 40°C, pressure at normal pressure (usually 1 atmosphere), and breakthrough hydrogen sulfide concentration at 6 mg/m ³ .

The detection steps are:

Take 100mL of the solutions of Examples 7-9 and Comparative Examples 2 and ³ and pour them into a U-shaped bubbling tube (equivalent to an absorption _tower ), keep the temperature constant in a water bath at 40° C., and use feed gas containing H2S at a flow rate of 5% (mol%) to pass it into the above solution at a flow rate of 30mL/min under normal pressure to carry out the desulfurization reaction and start timing. When the concentration of _H2S in the tail gas reaches 6mg/m (reabsorption of H ₂ S) stop aeration and record the time, that is to calculate the breakthrough sulfur capacity of the solution. The calculation formula is: In the formula, S _L represents the liquid sulfur capacity of the solution (g/L), P represents the pressure of hydrogen sulfide gas (100kPa), Q _H2S represents the gas flow rate of hydrogen sulfide (mL/min), t represents the desulfurization reaction time (min), R represents the gas state constant, 8.314Pa· ^m3 /(mol·K); T represents the reaction temperature (315K), and V is the liquid volume (L).

On this basis, add the solution to be treated in Examples 7 to 9 into the U-shaped bubbling tube equipped with 0.2 g of the hydrogen sulfide removal agent prepared in Example 1, (wherein the reaction volume of the solution to be treated is excessive compared with the hydrogen sulfide removal agent) at 40 ° C, under normal pressure conditions, and start timing. , the removal of hydrogen sulfide is completed, and the reaction time is recorded. The longer the reaction time, the better the effect of hydrogen sulfide desulfurization. The detection and calculation results are shown in Table 2.

Observe whether sulfur powder is precipitated in the absorption tower, the results are shown in Table 2.

Table 2

By comparative examples 2 and 3, it can be seen that compared with embodiments 7 to 9, in embodiments 7 and 8, no sulfur powder is produced in the absorption tower, so the absorption tower is not blocked; and comparative examples 3 and 4, because sulfur powder is produced in the absorption tower, so the absorption tower can be blocked.

At the same time, it can also be seen from Table 2 that the hydrogen sulfide removal agent in Examples 1 to 3 was used in Examples 7 to 9, and the hydrogen sulfide removal time was longer than that of Comparative Example 4, which shows that the hydrogen sulfide removal efficiency is high.

It can also be seen from Table 2 that the absorption tower has adopted sodium hydroxide solution in Examples 7-9, and the breakthrough sulfur capacity in the solution will be higher than the traditional iron-containing hydrogen sulfide removal agent in Comparative Examples 2 and 3.

It can also be seen from Table 2 that the hydrogen sulfide removal time in the regeneration tower in Examples 7-9 is not more than 1 h, and is relatively stable, indicating that the hydrogen sulfide removal agent of the present invention has high and stable hydrogen sulfide removal efficiency.

Apparently, those skilled in the art can make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention also intends to include these modifications and variations.

Claims (9)

1. A method of removing hydrogen sulfide comprising:

introducing hydrogen sulfide-containing gas into an absorption tower containing alkaline solution until the hydrogen sulfide in the alkaline solution can penetrate to form solution to be treated;

conveying the solution to be treated to a regeneration tower containing a hydrogen sulfide removing agent, simultaneously introducing oxygen, removing hydrogen sulfide and simultaneously regenerating the hydrogen sulfide removing agent;

the hydrogen sulfide remover is amino carboxylic acid chelating agent and Fe ³⁺ Is a chelate of (a);

the amino carboxylic acid chelating agent is a cross-linked product of polyaspartic acid and a sphere with an amino end;

the sphere with the tail end comprising the amino group is a conjugate of a sphere containing the hydroxyl group and a silane coupling agent containing the amino group;

the hydroxyl-containing spheres are hydroxyl-containing glass microspheres.

2. The method of claim 1, wherein the hydrogen sulfide removal agent is prepared by:

(1) Treating the hollow glass microspheres by an alkaline solution to obtain spheres containing hydroxyl groups;

(2) Coupling the sphere containing the hydroxyl group with the silane coupling agent containing the amino group to obtain a sphere with the tail end comprising the amino group;

(3) The polyaspartic acid is crosslinked with a sphere with the tail end comprising amino groups through a crosslinking agent to obtain an amino carboxylic acid chelating agent;

(4) Aminocarboxylic acid chelating agent and Fe-containing ³⁺ The chelate is obtained by chelating the compound of (2) to obtain the chelate, namely the hydrogen sulfide remover.

3. The method according to claim 2, wherein the alkaline solution is selected from at least one of the following solutions: sodium hydroxide, lithium hydroxide, potassium hydroxide, and calcium hydroxide.

4. The method according to claim 2, wherein the amino group-containing silane coupling agent is selected from at least one of the following: 3-aminopropyl triethoxysilane and 3-aminopropyl trimethoxysilane;

the mass ratio of the hydroxyl-containing spheres to the amino-containing silane coupling agent is 1:1-1:2.

5. The method of claim 2, wherein the cross-linking agent is glutaraldehyde or glyoxal.

6. The method according to claim 2, wherein the mass ratio of the polyaspartic acid to the sphere having the amino group at the end is 1:5 to 1:20.

7. The method according to claim 2, wherein the Fe-containing component is ³⁺ Is selected from at least one of the following: fe (Fe) ₂ (SO ₄ ) ₃ 、FeCl ₃ ·6H ₂ O and Fe (NO) ₃ ) ₃ 。

8. The method of claim 2, wherein the aminocarboxylic acid chelating agent and Fe-containing ³⁺ The mass ratio of the compounds is 1:5-1:20.

9. A hydrogen sulfide removal agent prepared by the following method:

(1) Treating the hollow glass microspheres by an alkaline solution to obtain spheres containing hydroxyl groups;

(2) Coupling the sphere containing the hydroxyl group with the silane coupling agent containing the amino group to obtain a sphere with the tail end comprising the amino group;

(3) The polyaspartic acid is crosslinked with a sphere with the tail end comprising amino groups through a crosslinking agent to obtain an amino carboxylic acid chelating agent;

(4) Aminocarboxylic acid chelating agent and Fe-containing ³⁺ The chelate is obtained by chelating the compound of (2) to obtain the chelate, namely the hydrogen sulfide remover.