CN113856451A

CN113856451A - Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method

Info

Publication number: CN113856451A
Application number: CN202111361477.9A
Authority: CN
Inventors: 邱奎; 刘露微; 江文; 董雨; 刘志豪; 金肇波; 程地奎; 罗世杰
Original assignee: Sichuan Xinchuangneng Petroleum Engineering Technology Co ltd; Chongqing University of Science and Technology
Current assignee: Sichuan Xinchuangneng Petroleum Engineering Technology Co ltd; Chongqing University of Science and Technology
Priority date: 2021-11-17
Filing date: 2021-11-17
Publication date: 2021-12-31
Anticipated expiration: 2041-11-17
Also published as: CN113856451B

Abstract

The invention relates to a hydrogen sulfide remover, a preparation method thereof and a hydrogen sulfide removing method. The hydrogen sulfide removing agent is aminocarboxylic acid chelating agent and Fe³⁺The chelate of (2). The hydrogen sulfide removing agent according to the present invention is prepared by a method of using an aminocarboxylic acid chelating agent and Fe³⁺The compound is chelated, and the obtained chelate is used as a hydrogen sulfide remover. The hydrogen sulfide removal method according to the present invention employs the hydrogen sulfide removal agent of the present invention. The hydrogen sulfide remover contains a large amount of amino and carboxyl, so a large amount of Fe is chelated³⁺(ii) a And isDue to amino and carboxyl groups with Fe³⁺Has strong chelating power of Fe³⁺Is not easy to fall off; therefore, when the hydrogen sulfide is removed by adopting the hydrogen sulfide removing agent disclosed by the invention, the efficiency of removing the hydrogen sulfide is high and stable.

Description

Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method

Technical Field

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

Background

The petroleum, natural gas, coal bed gas and methane often corrode equipment due to the hydrogen sulfide gas, and operators in the petroleum, natural gas, coal bed gas and methane are poisoned due to the hydrogen sulfide gas, so that the hydrogen sulfide gas removed from the petroleum, natural gas, coal bed gas and methane has economic, safe and environment-friendly values.

At present, methods for removing hydrogen sulfide gas by using a redox method include dry and wet methods, also referred to as heterogeneous catalytic oxidation and homogeneous catalytic oxidation.

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 removing hydrogen sulfide and instability.

For example, chinese patent CN112717931A discloses an iron-based composite hydrogen sulfide remover and a preparation method thereof. The preparation method comprises the following steps: preparing an iron salt solution with a certain concentration, adding a carbon nano tube in a certain proportion, stirring to prepare a mixed solution, adding a precipitator solution at a certain temperature to adjust the pH of the solution to 3-11, aging after forming a suspension, performing suction filtration after aging, collecting precipitates, and washing with deionized water to obtain the iron-based composite hydrogen sulfide remover.

The method mainly utilizes the interaction of Fe-O-C chemical bonds formed between the carbon nano tubes and the hydrated ferric oxide to promote the electron mobility of the hydrogen sulfide remover in the removal of the hydrogen sulfide, thereby improving the capability of the hydrogen sulfide remover.

However, the C-O bond between the carbon nano tube and the hydrated ferric oxide which forms Fe-O-C chemical bond has lower bond energy and is easy to break under the acidic condition; and the strong acidity of the treatment process of the hydrogen sulfide can lead the hydrated ferric oxide to gradually fall off on the surface of the carbon nano tube, thereby causing the reduction of the capability of the hydrogen sulfide removing agent for removing the hydrogen sulfide.

In view of the above, it is urgently needed to provide a hydrogen sulfide removing agent which is high in hydrogen sulfide removing efficiency and stable.

Disclosure of Invention

The invention provides a hydrogen sulfide remover, a preparation method thereof and a hydrogen sulfide removing method, which aim to solve the problems of low removing efficiency and instability of the hydrogen sulfide remover in the prior art.

According to an aspect of the present invention, there is provided a hydrogen sulfide removing agent which is an aminocarboxylic acid chelating agent and Fe³⁺The chelate of (2).

According to the hydrogen sulfide removing agent, the aminocarboxylic acid chelating agent is a cross-linked product of polyaspartic acid and a sphere with the tail end comprising an amino group.

According to the hydrogen sulfide removing agent of the present invention, the sphere having an amino group at the terminal is a conjugate of a hydroxyl group-containing sphere and an amino group-containing silane coupling agent.

According to the hydrogen sulfide remover, the spheres containing hydroxyl are glass microspheres containing hydroxyl.

According to another aspect of the present invention, there is provided a method for preparing a hydrogen sulfide removing agent, comprising the steps of: aminocarboxylic acid chelating agents and Fe-containing compounds³⁺Chelating the compound to obtain a chelate serving as a hydrogen sulfide removing agent;

preferably, the aminocarboxylate chelant and Fe-containing³⁺The mass ratio of the compounds (A) to (B) is 1:5 to 1: 20.

The preparation method comprises the following steps:

crosslinking polyaspartic acid with a sphere of which the tail end comprises an amino group through a crosslinking agent to obtain the aminocarboxylic acid chelating agent;

preferably, the mass ratio of the sphere with the terminal comprising the amino group to the polyaspartic acid is 1: 5-1: 20.

The preparation method comprises the following steps of:

and coupling the hydroxyl-containing spheres with an amino-containing silane coupling agent to obtain the spheres with the tail ends including amino groups.

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

The preparation method comprises the following steps of:

and (3) treating the hollow glass microspheres with an alkaline solution to obtain the hydroxyl-containing spheres.

According to another aspect of the invention, a method for removing hydrogen sulfide is provided, and the hydrogen sulfide removing agent is used as a removing agent for removing hydrogen sulfide by a dry method.

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

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

and conveying the solution to be treated to a regeneration tower containing the hydrogen sulfide removing agent, and introducing oxygen simultaneously to remove hydrogen sulfide and regenerate the hydrogen sulfide removing agent.

Compared with the prior art, the technical scheme of the invention has the following beneficial effects:

the hydrogen sulfide removal agent according to the present invention is due, on the one hand, to the aminocarboxylic acid chelating agent and Fe³⁺Has very strong chelating capacity, so that Fe is used for removing hydrogen sulfide³⁺The hydrogen sulfide is not easy to fall off, so that the hydrogen sulfide removal efficiency is stable; on the other hand, because the chelating agent adopts polyaspartic acid, the polyaspartic acid contains abundant amino and carboxyl, and can chelate a large amount of Fe³⁺Therefore, the efficiency of removing hydrogen sulfide is improved; in still another aspect, the hydrogen sulfide removing agent of the present inventionThe Fe can be regenerated by oxygen (i.e. by oxygen²⁺Oxidation to Fe³⁺) The hydrogen sulfide remover can be reused.

According to the preparation method of the hydrogen sulfide remover, the hydrogen sulfide remover is prepared, on one hand, due to the amino carboxylic acid chelating agent and Fe³⁺Has very strong chelating capacity, so that Fe is used for removing hydrogen sulfide³⁺The hydrogen sulfide is not easy to fall off, so that the hydrogen sulfide removing efficiency is high and stable; on the other hand, because the chelating agent adopts polyaspartic acid, the polyaspartic acid contains abundant amino and carboxyl, and can chelate a large amount of Fe³⁺Thus improving the efficiency of removing hydrogen sulfide; in yet another aspect, the hydrogen sulfide removal agent of the present invention can be regenerated by oxygen (i.e., by oxygen to regenerate Fe²⁺Oxidation to Fe³⁺) So that the hydrogen sulfide remover can be repeatedly used.

According to the hydrogen sulfide removal method, the hydrogen sulfide removal agent provided by the invention is adopted, and the hydrogen sulfide removal efficiency is high and stable.

According to another hydrogen sulfide removal method, the hydrogen sulfide and the contained alkaline solution react in the absorption tower to form a solution to be treated, so that the problem that the pipeline of the absorption tower is blocked by the formed sulfur powder when the absorption tower directly removes the hydrogen sulfide in the homogeneous solution containing iron ions in the prior art is solved; on the other hand, the solution to be treated is treated by the hydrogen sulfide removing agent in the regeneration tower, and the removing efficiency is high and stable.

Drawings

FIG. 1 shows an infrared spectrum of the product formed at each step of the process for producing a hydrogen sulfide removing agent in example 1 of the present invention;

reference numerals: a sphere a containing hydroxyl, a sphere b with an amino group at the tail end, an aminocarboxylic acid chelating agent c and a chelate d.

Detailed Description

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

According to one aspect of the present invention, there is provided a hydrogen sulfide removing agent comprising an aminocarboxylic acid chelating agent and Fe³⁺The chelate of (2).

The hydrogen sulfide removal agent according to the present invention is due, on the one hand, to the aminocarboxylic acid chelating agent and Fe³⁺Has very strong chelating ability, and amino and carboxyl groups and Fe³⁺Can form very strong coordinate bond, and is used for removing Fe of hydrogen sulfide³⁺The hydrogen sulfide is not easy to fall off, and the hydrogen sulfide removal efficiency is strong and stable; on the other hand, Fe³⁺Can be regenerated by oxygen (i.e. Fe)²⁺Can be oxidized into Fe by oxygen³⁺) The hydrogen sulfide remover is reused.

The aminocarboxylic acid chelating agent is a chelating agent containing an amino group and a carboxyl group in the chelating agent.

Wherein the aminocarboxylate chelant is selected from at least one of the following: cross-linked polyaspartic acid with spheres having amino groups at the ends, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminediacetic acid (EDDHA).

Containing Fe³⁺The compound is preferably an iron salt, and further preferably at least one of the following: fe₂(SO₄)₃、FeCl₃·6H₂O and Fe (NO)₃)₃。

Aminocarboxylic acid chelating agent and Fe³⁺High stability constants such as: ethylenediaminetetraacetic acid (EDTA) and Fe³⁺Has a stability constant of 25.1, ethylenediamine diacetic acid (EDDHA) and Fe³⁺Has a stability constant of 29.6, since in this class of chelating agents the iron is bonded to the iron via the amino and carboxyl groups³⁺Chelation, similarly, a cross-linked product of polyaspartic acid and a sphere having an amino group at the end, and Fe³⁺Is good, and it can be seen that the aminocarboxylic acid chelating agent and Fe³⁺The chelate formed is very stable.

According to the hydrogen sulfide removing agent of the present invention, the aminocarboxylic acid chelating agent is preferably a crosslinked product of polyaspartic acid and a sphere having an amino group at the end.

According to the hydrogen sulfide remover, polyaspartic acid (abbreviated as PASP in English) is adopted as a chelating agent, the PASP is a polymer formed by polymerizing single aspartic acid through an amido bond, the PASP naturally exists in shells of snails and mollusks, and the structure of the PASP contains a large amount of carboxyl and amino.

Because the PASP structure contains abundant carboxyl and amino (mainly nitrogen atoms), a large amount of Fe can be chelated³⁺Therefore, the key groups for removing the hydrogen sulfide are increased, and the efficiency for removing the hydrogen sulfide is improved.

In addition, due to the presence of the amino group in the PASP structure, the amino carboxylic acid chelating agent can be formed by crosslinking with a sphere having an amino group at the end by a crosslinking agent.

Among them, glutaraldehyde and glyoxal are preferable as the crosslinking agent.

According to the hydrogen sulfide remover, the sphere with the amino group at the tail end is a coupling product of a sphere containing a hydroxyl group and a silane coupling agent containing an amino group.

According to the hydrogen sulfide removing agent, the sphere containing the hydroxyl and the silane coupling agent containing the amino form a coupling chemical bond through the hydroxyl and the amino to form a coupling product, so that a substrate is provided for crosslinking PASP.

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

The glass microspheres are selected because the glass microspheres contain Si-O-Si bonds, and after the glass microspheres are treated by alkaline solution, the chemical bonds can be opened to form Si-OH bonds, so that conditions are provided for coupling silane coupling agents containing amino groups; in addition, the sphere has large specific surface area, can form more Si-OH bonds, thereby coupling more amino-containing silane coupling agents, further crosslinking more PASP, leading the aminocarboxylic acid chelating agent to contain more amino and carboxyl, and finally chelating more Fe³⁺。

preferably, the aminocarboxylic acid chelating agent and the Fe-containing compound³⁺The mass ratio of the compounds (A) to (B) is 1:5 to 1: 20.

Specifically, the aminocarboxylate chelant is typically combined with the Fe-containing compound³⁺Dispersing the compound in a solution according to a certain proportion, carrying out chelation reaction for a period of time at a certain temperature, and carrying out suction filtration after the reaction is finished; drying and roasting the filter residue to obtain a chelate serving as a hydrogen sulfide removing agent.

Chelating agents containing carboxyl groups and containing Fe³⁺The mass ratio of the compound (b) is preferably 1:5 to 1:20, and more 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 crosslinked product of polyaspartic acid and a sphere having an amino group at the end, ethylenediaminetetraacetic acid (EDTA) and ethylenediaminediacetic acid (EDDHA).

Wherein, contains Fe³⁺The compound is preferably an iron salt, and further preferably at least one of the following: fe₂(SO₄)₃、FeCl₃·6H₂O、[FeNH₄(SO₄)₂·12H₂O]And Fe (NO)₃)₃。

Wherein the certain temperature is 60-70 ℃, and the specific preference is 60 ℃, 63 ℃, 65 ℃, 68 ℃ and 70 ℃.

The certain time is 4-6 hours, and particularly preferably 4 hours, 4.5 hours, 5 hours, 5.5 hours and 6 hours.

More specifically, the following equation shows an example in which the cross-linked product of polyaspartic acid and a sphere having an amino group at the end is chelated with iron chloride, and the specific operation method is as follows.

Preparing 25-50% by mass of ferric chloride solution, and weighing and dispersing the chelating agent in the ferric salt solution according to the proportion (converted into the mass ratio of 1: 5-1: 20) of the mass of the chelating agent to the volume ratio of 1: 20-40 (g/mL) of the ferric chloride solution; then heating to 60-70 ℃, and carrying out chelation reaction for 4-6 h; after the reaction is finished, carrying out vacuum filtration, and respectively collecting filter residue and filtrate; the collected filtrate is the recovered ferric salt solution which can be reused; and (3) conveying the collected filter residues into a vacuum drying oven, vacuum-drying for 4-8 h under the conditions that the temperature is 50-60 ℃ and the vacuum degree is 40-50 Pa, taking out, and roasting for 5h under the condition of 300 ℃ to obtain the chelate serving as the hydrogen sulfide removing agent.

An exemplary reaction equation for this step is shown below.

The preparation method comprises the following steps of:

crosslinking polyaspartic acid with a sphere of which the tail end comprises an amino group through a crosslinking agent to obtain a chelating agent of aminocarboxylic acid;

preferably, the mass ratio of the sphere with the tail end comprising the amino group to the polyaspartic acid is 1: 5-1: 20;

preferably, the pore-forming agent is added during the preparation of the aminocarboxylate chelant.

Specifically, the amino carboxylic acid chelating agent is obtained by crosslinking a sphere with an amino group at the end and polyaspartic acid according to a certain proportion by a crosslinking agent.

The mass ratio of the sphere with the terminal amino group to the polyaspartic acid is preferably 1: 5-1: 20, and specifically preferably 1:5, 1:8, 1:10, 1:13, 1: 15. 1:18 and 1: 20.

Preferably, in the preparation of the aminocarboxylic acid chelating agent, the pore-forming agent is preferably polyethylene glycol, wood dust and talcum powder.

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

The reaction temperature is preferably 60-70 ℃, and particularly preferably 60 ℃, 63 ℃, 65 ℃, 68 ℃ and 70 ℃.

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

Taking the reaction of a sphere with an amino group at the end and polyaspartic acid in the following equation as an example, the operation is as follows: firstly, preparing a PASP solution with the mass fraction of 25-50%, wherein the mass ratio of PASP to polyethylene glycol is 1: weighing polyethylene glycol at a ratio of 0.05-0.1 (g/g) and adding the polyethylene glycol into the PASP solution; then, weighing spheres with the tail ends comprising amino groups according to the ratio of the mass of the spheres with the tail ends comprising the amino groups to the volume of the PASP solution of 1: 20-40 (g/mL) (the mass ratio is 1: 5-1: 20), dispersing the spheres into the PASP solution, and fully mixing; and preparing a glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde according to the ratio of the mass of the sphere with the tail end comprising the amino group to the volume of the glutaraldehyde solution of 1: 1-2 (g/mL), heating to 60-70 ℃ by using a constant-temperature water bath kettle, treating for 4-6 h, then carrying out vacuum filtration, and repeatedly washing with water until no liquid drops flow out. Respectively collecting filter residue and filtrate, wherein the filtrate comprises unreacted PASP solution and can be used for preparing the aminocarboxylate chelating agent again; and putting the filter residue into a vacuum drying oven, and carrying out vacuum drying for 4-8 h under the conditions that the temperature is 50-60 ℃ and the vacuum degree is 40-50 Pa to obtain the aminocarboxylic acid chelating agent.

An exemplary reaction equation for spheres with terminal amino groups and polyaspartic acid is as follows:

the preparation method comprises the following steps of:

the hydroxyl-containing spheres and the amino-containing silane coupling agent are coupled to obtain spheres with the tail ends including amino groups.

Preferably, the mass ratio of the hydroxyl-containing spheres to the amino-containing silane coupling agent is 1:1 to 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 following reaction equation of the hydroxyl group-containing sphere and the amino group-containing silane coupling agent is given as an example, and the specific operation is: according to the mass ratio of the hydroxyl-containing spheres to the amino-containing silane coupling agent of 1: 1-2 (g/g), weighing a hydroxyl-containing sphere and a silane coupling agent, and then according to the total mass of the hydroxyl-containing sphere and the silane coupling agent: dispersing a hydroxyl-containing sphere and a silane coupling agent in absolute ethyl alcohol at a volume ratio of 1: 100-200 (g/mL), heating to 80-90 ℃ with a constant-temperature water bath kettle, carrying out condensation reflux treatment for 4-6 h, taking out, carrying out vacuum filtration, and collecting filter residue and filtrate respectively; recovering ethanol from the collected filtrate; and (3) conveying the collected filter residues into a vacuum drying oven, and carrying out vacuum drying for 4-8 h under the conditions that the temperature is 50-60 ℃ and the vacuum degree is 40-50 Pa, so as to obtain the sphere with the hydroxyl at the tail end.

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

The preparation method comprises the following steps of:

and (3) treating the hollow glass microspheres by using an alkaline solution to obtain spheres containing hydroxyl groups.

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

Specifically, the following reaction equation is taken as an example, and the specific operation is as follows: firstly, preparing a sodium hydroxide solution with the mass fraction of 25-50%, and mixing the sodium hydroxide solution and the Hollow Glass Microspheres (HGM) according to the volume ratio of 1: weighing HGM according to a ratio of 10-30 (g/mL), dispersing the weighed HGM in a sodium hydroxide solution, heating the mixture to 80-100 ℃ by using a constant-temperature water bath kettle, treating the mixture for 3-6 hours, taking out the mixture, washing the mixture for several times by using purified water until the washing liquid is neutral, combining the washing liquid and the waste liquid after the HGM is pretreated, neutralizing the mixture, discharging the mixture after the mixture reaches the standard, putting the washed HGM in a drying oven, drying the HGM at the temperature of 40-60 ℃ to constant weight, and storing the HGM in a glass dryer to prepare the hydroxyl-containing sphere.

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

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

The following description will exemplarily describe the dry removal of hydrogen sulfide by using the hydrogen sulfide remover of the present invention, taking a laboratory dry removal procedure for hydrogen sulfide as an example.

Taking 0.2g to 1.0g of the hydrogen sulfide remover prepared by the invention, placing the hydrogen sulfide remover in a U-shaped bubbling tube, keeping the temperature of the U-shaped bubbling tube constant in a water bath kettle, and using the hydrogen sulfide-containing solution with the concentration of 200mg/m when the temperature of the U-shaped bubbling tube reaches 40 ℃ to 50 DEG C³The raw material gas enters a U-shaped bubbling tube at the flow rate of 40mL/min under normal pressure to react with a hydrogen sulfide removing agent, the concentration of the outlet hydrogen sulfide is detected by an LC-2 type hydrogen sulfide detector, and when the concentration of the outlet hydrogen sulfide reaches 6mg/m³At that time, the aeration was stopped, and at this time, the hydrogen sulfide removing agent was considered to have penetrated.

the solution to be treated is conveyed to a regeneration tower containing the hydrogen sulfide removing agent, and oxygen is introduced simultaneously to remove hydrogen sulfide and regenerate the hydrogen sulfide removing agent simultaneously.

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

When hydrogen sulfide gas is introduced into the alkaline solution in the absorption tower, salts (such as sodium sulfide and sodium hydrosulfide) are formed and dissolved in water; the solution is introduced into a regeneration tower, and the regeneration tower contains the hydrogen sulfide remover and can remove HS in the solution^-And S^2-Oxidized to sulfur powder.

The hydrogen sulfide penetrability of the alkaline solution means that the hydrogen sulfide gas can not react with the alkaline solution to form salt and is dissolved in water, namely the solution can not absorb the hydrogen sulfide again.

In the prior art, an absorption tower contains an iron-based hydrogen sulfide remover, and the iron-based ionic liquid and sulfur ions are subjected to oxidation-reduction reaction in a homogeneous reaction: 2Fe³⁺+S2-＝2Fe²⁺+S。

The generated sulfur simple substance is generally in a sulfur powder state and can block the absorption tower.

In the method, the solution containing iron ions is replaced by the alkaline solution, sulfur powder is not generated in the absorption tower, but the generated sulfur salt is dissolved in water, for example, when the alkaline solution is sodium hydroxide solution, two reaction modes can exist between the alkaline solution and hydrogen sulfide, and the equation of one reaction mode is as follows: 2NaOH + H₂S＝Na₂S+H₂O; another reaction scheme is the equation: NaOH + H₂S＝NaHS+H₂O。

Conveying the solution to be treated formed in the absorption tower to a regeneration tower, wherein the regeneration tower comprises the hydrogen sulfide remover, the hydrogen sulfide remover and S in the solution^2-The reaction equation of (a) is: 2Fe³⁺+S^2-＝2Fe²⁺+S。

After hydrogen sulfide is removed in the regeneration tower, the hydrogen sulfide remover and sulfur powder are discharged together, and the sulfur powder is dissolved by an extracting agent, so that the hydrogen sulfide remover can be conveniently recovered.

The oxygen is introduced mainly for regenerating the hydrogen sulfide removing agent and can be recycled. The regeneration principle is 4Fe²⁺+O₂+4H⁺＝4Fe³⁺+2H₂O。

The hydrogen sulfide removing agent has high and stable efficiency for removing hydrogen sulfide.

In order to prove the method, the applicant carries out laboratory operation, and the specific operation taking sodium hydroxide solution as an example is as follows: dissolving sodium hydroxide into water according to the mass ratio of the sodium hydroxide to the water being 1: 200-400 (g/mL), pouring the sodium hydroxide solution into a U-shaped bubbling tube (equivalent to an absorption tower) after the sodium hydroxide solution is fully dissolved, keeping the temperature of the solution constant in a water bath kettle at 40-50 ℃, and using H-containing solution₂Introducing raw material gas with S concentration of 5% (mol%) into the above solution at normal pressure at flow rate of 30mL/min, performing desulfurization reaction, and timing when tail gas H₂The concentration of S reaches 6mg/m³When (reaching this concentration means that sulfur breakthrough is reached and the solution is no longer able to absorb H₂S) stopping aeration and recording time, namely forming the solution to be treated.

Adding the hydrogen sulfide removing agent into the U-shaped bubbling tube (equivalent to a regeneration tower) according to the ratio of the mass of the hydrogen sulfide removing agent to the volume of the solution to be treated being 1: 20-40 (g/mL) for desulfurization, reacting at 40 ℃ under normal pressure, starting timing, introducing oxygen at the same time to regenerate the desulfurized hydrogen sulfide removing agent, wherein the flow rate of the oxygen is 200mL/min, monitoring the oxidation-reduction potential (ORP) of the solution in the process until the oxidation-reduction potential is not increased any more, and removing hydrogen sulfide is completed.

It should be noted here that the redox potential is an instrument for monitoring the redox reaction in the solution, and if no redox reaction occurs in the solution, it is indicated as 0; if the redox reaction occurs, the indication is given; during the hydrogen sulfide removal and regeneration processes, as the oxidation-reduction reaction is always generated, the indication number of the oxidation-reduction potential is always increased, and the oxidation-reduction potential is not changed after the oxidation-reduction reaction is completed.

The mechanism of hydrogen sulfide removal and regeneration by introducing oxygen according to the hydrogen sulfide removing agent of the present invention is as follows.

The present invention will be described with reference to specific examples, which are to be construed as merely illustrative and not limitative of the remainder of the disclosure.

Wherein, the embodiment 1-3 is a preparation method of the hydrogen sulfide remover; examples 4 to 6 are methods for removing hydrogen sulfide by a dry process using the hydrogen sulfide removing agent prepared in examples 1 to 3; examples 7 to 9 are dry-wet combined hydrogen sulfide removal methods using the hydrogen sulfide removal agent of the present invention. Comparative examples 1 to 3 are methods for removing hydrogen sulfide using the prior art.

Example 1

Firstly, step S1 is carried out, the hollow glass microsphere containing hydroxyl is prepared, and the specific operation of the step is as follows:

preparing a sodium hydroxide solution with the mass fraction of 25%; according to the volume ratio of Hollow Glass Microspheres (HGM) to sodium hydroxide solution of 1:10 (g/mL), weighing HGM, and dispersing in a sodium hydroxide solution; heating to 80 deg.C with a constant temperature water bath, treating for 3 hr, and taking out; washing with purified water until the washing liquid is neutral; combining the washing liquid with the waste liquid after HGM treatment, and then carrying out neutralization and other treatments, and discharging after reaching the standard; and (3) putting the washed HGM into an oven, drying the HGM at the temperature of 40 ℃ to constant weight, and storing the HGM in a glass drier to prepare the hollow glass microsphere containing hydroxyl.

Then, step S2 is carried out, wherein the method comprises the following steps:

according to the mass ratio of the hollow glass microspheres containing hydroxyl groups to the amino silane coupling agent of 1: 1(g/g), weighing hollow glass microspheres containing hydroxyl and a silane coupling agent; and then according to the total mass of the hollow glass microspheres containing hydroxyl and the silane coupling agent: dispersing the glass microspheres containing hydroxyl groups and the silane coupling agent in absolute ethyl alcohol at the volume ratio of 1:100 (g/mL); heating to 80 deg.C with a constant temperature water bath, performing condensation reflux treatment for 4 hr, and taking out; carrying out vacuum filtration, and respectively collecting filter residue and filtrate; collecting filtrate for recovering ethanol; and (3) conveying the collected filter residue into a vacuum drying oven, and performing vacuum drying for 4h under the conditions that the temperature is 50 ℃ and the vacuum degree is 40Pa, thus preparing the sphere with the tail end comprising the amino. Wherein the amino silane coupling agent is 3-aminopropyl triethoxysilane.

Then, step S3 is performed: the preparation method of the aminocarboxylic acid chelating agent comprises the following specific steps:

preparing a PASP solution with the mass fraction of 25%, weighing spheres with the tail ends comprising amino groups according to the proportion that the volume ratio of the spheres with the tail ends comprising the amino groups to the PASP solution is 1:20(g/mL), and fully mixing the spheres with the tail ends comprising the amino groups in the PASP solution; according to the mass ratio of PASP to polyethylene glycol of 1: 0.05(g/g), weighing polyethylene glycol and adding into PASP solution; preparing a glutaraldehyde solution with the mass fraction of 5%, adding the glutaraldehyde solution according to the proportion that the volume ratio of the mass of the sphere with the tail end comprising the amino group to the glutaraldehyde solution is 1:1(g/mL), heating the mixture to 60 ℃ by using a constant-temperature water bath kettle, keeping the temperature for 4 hours, and then carrying out vacuum filtration. Collecting filter residue and filtrate, wherein the filtrate comprises unreacted PASP solution which can be recycled; and putting the filter residue into a vacuum drying oven, and carrying out vacuum drying for 4h under the conditions that the temperature is 50 ℃ and the vacuum degree is 40Pa, thus preparing the aminocarboxylic acid chelating agent.

And finally, step S4, the preparation of the hydrogen sulfide removing agent is carried out, and the specific operation of the step is as follows:

preparing an iron salt solution with the mass fraction of 25%, and weighing and dispersing an aminocarboxylic acid chelating agent into the iron salt solution according to the ratio of the mass of the carboxyl-containing chelating agent to the volume of the iron salt solution of 1:20 (g/mL); then heating to 60 ℃, and carrying out chelation reaction for 4 h; after vacuum filtration, respectively collecting filter residue and filtrate; recovering the ferric salt solution from the collected filtrate for re-preparation; sending the collected filter residue into a vacuum drying oven, vacuum drying at 55 deg.C and 45Pa for 4 hr, taking out, and calcining at 300 deg.C for 5 hr to obtain hydrogen sulfide remover, wherein the ferric salt is FeCl₃·6H₂O。

The applicant carried out infrared spectrum characterization on the reaction products in each step of example 1, and the characterization results are shown in fig. 1.

In curve a of FIG. 1, 3500cm^-1Is the stretching vibration peak of-OH at 1000cm^-1The left and right are bending vibration peaks of Si-OH, so that the hydroxyl groups are formed on the surface of the hollow glass microsphere subjected to alkali treatment.

In the curve b of FIG. 1, it is at 2900-3000cm^-1A new peak appeared, which was attributed to the stretching vibration peaks of methyl and methylene groups, and further at 1500 and 1350cm^-1Two new peaks are formed nearby, and are attributed to the vibration peaks of amino and-C-N bond, 950cm^-1The nearby peak is the stretching vibration peak of Si-O, which is caused by the coupling of 3-aminopropyltriethoxysilane to the hydroxyl group-containing sphere, and is indicated to include an amino group at the terminal.

In curve c of FIG. 1, at 1400cm^-1The absorption peak nearby is enhanced and is 900cm^-1A new peak was also appeared in the vicinity due to the vibration absorption peak of hydroxyl group in carboxyl group in PASP introduced, and further, 1600cm after crosslinking^-1The reason why the absorption peaks on the left and right sides did not change greatly was that the amino group in the sphere having an amino group at the terminal overlapped with the amino group introduced after crosslinking, but C-N-was formed, and thus the peak was 1600cm^-1The left and right absorption peaks are red-shifted.

In fig. 1, curve d, the peaks associated with both amino and carboxyl groups in curve c are diminished or eliminated due to the chelation of iron ions by the aminocarboxylic acid chelating agent.

Example 2

preparing a sodium hydroxide solution with the mass fraction of 40%; according to the volume ratio of Hollow Glass Microspheres (HGM) to sodium hydroxide solution of 1:20(g/mL), weighing HGM, and dispersing in a sodium hydroxide solution; heating to 90 deg.C with a constant temperature water bath, treating for 4 hr, and taking out; washing with purified water until the washing liquid is neutral; combining the washing liquid with the waste liquid after HGM treatment, and then carrying out neutralization and other treatments, and discharging after reaching the standard; and (3) putting the washed HGM into an oven, drying the HGM at the temperature of 50 ℃ to constant weight, and storing the HGM in a glass drier to prepare the hollow glass microsphere containing hydroxyl.

Then, step S2 is carried out, wherein the method comprises the following steps:

according to the mass ratio of the hollow glass microspheres containing hydroxyl groups to the amino silane coupling agent of 1:1.5 (g/g), weighing hollow glass microspheres containing hydroxyl and a silane coupling agent; and then according to the total mass of the hollow glass microspheres containing hydroxyl and the silane coupling agent: dispersing the glass microspheres containing hydroxyl groups and the silane coupling agent in absolute ethyl alcohol at the volume ratio of 1:150 (g/mL); heating to 85 deg.C with a constant temperature water bath, performing condensation reflux treatment for 5 hr, and taking out; carrying out vacuum filtration, and respectively collecting filter residue and filtrate; collecting filtrate for recovering ethanol; and (3) conveying the collected filter residue into a vacuum drying oven, and carrying out vacuum drying for 5h under the conditions that the temperature is 55 ℃ and the vacuum degree is 45Pa, thus preparing the sphere with the tail end comprising the amino. Wherein the aminosilane coupling agent is 3-aminopropyltrimethoxysilane.

preparing a PASP solution with the mass fraction of 40%, weighing spheres with the tail ends comprising amino groups according to the proportion that the volume ratio of the spheres with the tail ends comprising the amino groups to the PASP solution is 1:30(g/mL), and fully mixing the spheres with the tail ends comprising the amino groups in the PASP solution; according to the mass ratio of PASP to polyethylene glycol of 1: 0.08(g/g), adding polyethylene glycol into PASP solution; preparing a glutaraldehyde solution with the mass fraction of 5%, adding the glutaraldehyde solution according to the proportion that the volume ratio of the mass of the sphere with the tail end comprising the amino group to the glutaraldehyde solution is 1:1.5(g/mL), heating to 70 ℃ by using a constant-temperature water bath kettle, keeping the temperature for 5 hours, and then filtering in vacuum. Collecting filter residue and filtrate, wherein the filtrate is unreacted PASP solution and can be recycled; and putting the filter residue into a vacuum drying oven, and carrying out vacuum drying for 5h under the conditions that the temperature is 55 ℃ and the vacuum degree is 45Pa, thus preparing the aminocarboxylic acid chelating agent.

Finally, step S4 is performed: the preparation of the hydrogen sulfide remover comprises the following specific operations:

preparing 40 mass percent of ironA salt solution, namely weighing and dispersing aminocarboxylic acid chelating agent into an iron salt solution according to the ratio of the mass of the carboxyl-containing chelating agent to the volume of the iron salt solution of 1:30 (g/mL); then heating to 65 ℃, and carrying out chelation reaction for 5 h; after vacuum filtration, respectively collecting filter residue and filtrate; recovering the ferric salt solution from the collected filtrate for re-preparation; feeding the collected filter residue into a vacuum drying oven, vacuum drying at 60 deg.C and 45Pa for 6 hr, taking out, and calcining at 300 deg.C for 5 hr to obtain hydrogen sulfide remover, wherein the ferric salt is Fe₂(SO₄)₃。

Example 3

Step S1 is first performed: the preparation method of the hollow glass microsphere containing hydroxyl comprises the following specific steps:

preparing a sodium hydroxide solution with the mass fraction of 50%; according to the volume ratio of Hollow Glass Microspheres (HGM) to sodium hydroxide solution of 1:30(g/mL), weighing HGM, and dispersing in a sodium hydroxide solution; heating to 100 ℃ by using a constant-temperature water bath kettle, treating for 6h, and taking out; washing with purified water until the washing liquid is neutral; combining the washing liquid with the waste liquid after HGM treatment, and then carrying out neutralization and other treatments, and discharging after reaching the standard; and (3) putting the washed HGM into an oven, drying the HGM at the temperature of 60 ℃ to constant weight, and storing the HGM in a glass drier to prepare the hollow glass microsphere containing hydroxyl.

Then, step S2 is carried out, wherein the method comprises the following steps:

weighing the hollow glass microspheres containing hydroxyl groups and the silane coupling agent according to the mass ratio of the hollow glass microspheres containing hydroxyl groups to the aminosilane coupling agent of 1:2 (g/g); and then according to the total mass of the hollow glass microspheres containing hydroxyl and the silane coupling agent: dispersing the glass microspheres containing hydroxyl groups and the silane coupling agent in absolute ethyl alcohol at the volume ratio of 1:200 (g/mL); heating to 90 deg.C with a constant temperature water bath, performing condensation reflux treatment for 6 hr, and taking out; carrying out vacuum filtration, and respectively collecting filter residue and filtrate; collecting filtrate for recovering ethanol; and (3) conveying the collected filter residue into a vacuum drying oven, and carrying out vacuum drying for 8h under the conditions that the temperature is 60 ℃ and the vacuum degree is 50Pa, thus preparing the sphere with the tail end comprising the amino. Wherein the aminosilane coupling agent is 3-aminopropyltrimethoxysilane.

preparing a PASP solution with the mass fraction of 50%, weighing spheres with the tail ends comprising amino groups according to the proportion that the volume ratio of the spheres with the tail ends comprising the amino groups to the PASP solution is 1:40(g/mL), and fully mixing the spheres with the tail ends comprising the amino groups in the PASP solution; according to the mass ratio of PASP to polyethylene glycol of 1: 0.1(g/g), weighing polyethylene glycol and adding into PASP solution; preparing a glutaraldehyde solution with the mass fraction of 5%, adding the glutaraldehyde solution according to the proportion that the volume ratio of the mass of the sphere with the tail end comprising the amino group to the glutaraldehyde solution is 1:2(g/mL), heating to 70 ℃ by using a constant-temperature water bath kettle, keeping the temperature for 6 hours, and then carrying out vacuum filtration. Collecting filter residue and filtrate, wherein the filtrate is unreacted PASP solution and can be recycled; and putting the filter residue into a vacuum drying oven, and carrying out vacuum drying for 8h under the conditions that the temperature is 60 ℃ and the vacuum degree is 50Pa, thus preparing the chelating agent containing carboxyl.

preparing an iron salt solution with the mass fraction of 50%, weighing and dispersing an aminocarboxylic acid chelating agent into the iron salt solution according to the ratio of the mass of the carboxyl-containing chelating agent to the volume of the iron salt solution of 1:40 (g/mL); then heating to 70 ℃, and carrying out chelation reaction for 6 h; after vacuum filtration, respectively collecting filter residue and filtrate; recovering the ferric salt solution from the collected filtrate for re-preparation; feeding the collected filter residue into a vacuum drying oven, vacuum drying at 60 deg.C and 50Pa for 8 hr, taking out, and calcining at 300 deg.C for 5 hr to obtain hydrogen sulfide remover, wherein the ferric salt is Fe₂(SO₄)₃。

Example 4

0.2g of the hydrogen sulfide removing agent prepared in example 1 was placed in a U-shaped bubbling tube and kept at a constant temperature in a water bath, and when the temperature of the U-shaped bubbling tube reached 40 ℃, the hydrogen sulfide removing agent was usedThe concentration of the hydrogen sulfide is 200mg/m³The raw material gas enters a U-shaped bubbling tube at the flow rate of 40mL/min under normal pressure to react with a hydrogen sulfide removing agent, the concentration of the outlet hydrogen sulfide is detected by an LC-2 type hydrogen sulfide detector, and when the concentration of the outlet hydrogen sulfide reaches 6mg/m³The aeration was stopped, at which point the hydrogen sulfide removal agent breakthrough was considered.

Example 5

In this example, hydrogen sulfide was removed by using the hydrogen sulfide remover prepared in example 2, and the other conditions were the same as in example 4.

Example 6

In example 6, hydrogen sulfide was removed by using the hydrogen sulfide remover prepared in example 3, and the other conditions were the same as in example 4.

Example 7

Dissolving sodium hydroxide in water solution at a ratio of sodium hydroxide mass to water volume of 1:250(g/mL) (concentration of 0.1mol/L), pouring the solution into U-shaped bubbling tube (equivalent to absorption tower), maintaining the temperature in water bath at 40 deg.C, and adding H₂Introducing raw material gas with S concentration of 5% (mol%) into the above solution at normal pressure at flow rate of 30mL/min, performing desulfurization reaction, and timing when tail gas H₂The concentration of S reaches 6mg/m³When (reaching this concentration means that sulfur breakthrough is reached and the solution is no longer able to absorb H₂S) stopping aeration and recording time, namely forming the solution to be treated.

According to the proportion that the mass ratio of the hydrogen sulfide removing agent in the embodiment 1 to the volume of the solution to be treated is 1:20(g/mL), the solution is added into the U-shaped bubbling tube (equivalent to a regeneration tower) for desulfurization, oxygen is introduced to regenerate the desulfurized hydrogen sulfide removing agent at the same time, the flow rate of the oxygen is 200mL/min, ORP is continuously monitored for the upper layer liquid, and after the oxidation-reduction potential is stable, the removal of hydrogen sulfide is completed.

Example 8

Example 8 the hydrogen sulfide removing agent of example 2 was used, and the other conditions were the same as in example 7.

Example 9

Example 9 the hydrogen sulfide removing agent of example 3 was used, and the other conditions were the same as those of example 7.

Comparative example 1

In comparative example 1, a composite of carbon nanotubes and hydrated iron oxide disclosed in CN112717931A was used as a hydrogen sulfide removing agent, and the other conditions were the same as in example 4.

Comparative example 2

In comparative example 2, except that the sodium hydroxide solution was treated with imidazolium chloride-based ion (Fe-IL: [ Bmim ]]FeCl₄) The solution was replaced and no regeneration column step was introduced, otherwise the same as in example 7.

Comparative example 3

In comparative example 3, except that the sodium hydroxide solution was treated with N-butylpyridinium iron tetrachloride ([ BPy ]]FeCl₄) The solution was replaced and no regeneration column step was introduced, otherwise the same as in example 8.

Comparative example 4

In comparative example 4, the same procedure as in example 7 was repeated except that the hydrogen sulfide removing agent in the regeneration column was a composite of carbon nanotubes and hydrated iron oxide disclosed in CN112717931A as the hydrogen sulfide removing agent.

In order to clearly illustrate the efficiency and stability of the hydrogen sulfide removal agent of the present invention in removing hydrogen sulfide, the applicant examined the breakthrough sulfur capacities of examples 4 to 9 and comparative examples 1 to 3.

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

the breakthrough sulfur capacity is expressed in% as the mass fraction of sulfur in the hydrogen sulfide removal agent and is calculated as follows:

wherein C represents the mass concentration (kg/m) of sulfur in the feed gas³)；V₁，V₂A value (mL) representing the volume of gas at the start and end of the wet gas flow meter; m represents the mass (kg) of the hydrogen sulfide removing agent in the reactor.

The sulfur capacity detection conditions of examples 4 to 6 and comparative example 1 were: the temperature is 40 deg.C, the pressure is normal pressure (usually 1 atm), and the penetration concentration is 6mg/m³；

The detection steps are as follows:

placing 0.2g hydrogen sulfide remover in U-shaped bubbling tube, maintaining the temperature in water bath, and adding hydrogen sulfide at concentration of 200mg/m when the temperature of U-shaped bubbling tube reaches 40 deg.C³The raw material gas enters a U-shaped bubbling tube at the flow rate of 40mL/min under normal pressure to react with a hydrogen sulfide removing agent, the concentration of the outlet hydrogen sulfide is detected by an LC-2 type hydrogen sulfide detector, and when the concentration of the outlet hydrogen sulfide reaches 6mg/m³Stopping ventilation, and considering that the hydrogen sulfide remover penetrates through the ventilation; values for gas volume at start and end of the reaction were measured using a wet gas flow meter and the hydrogen sulfide removal time at the end of the reaction was recorded.

The calculation was performed according to the above formula, and the obtained detection data are shown in table 1.

TABLE 1

	Penetration sulfur capacity	Hydrogen sulfide 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

As can be seen from comparison of example 4 with comparative example 1, the hydrogen sulfide removing agent prepared in example 1 was used because of the aminocarboxylic acid chelating agent and Fe³⁺Has strong chelating power, Fe³⁺Is not easy to fall off and is chelated with abundant Fe³⁺More hydrogen sulfide can be removed, so that the breakthrough sulfur capacity of example 4 is much higher than that of comparative example 1, and thus it can be seen that the efficiency of removing hydrogen sulfide using the hydrogen sulfide removing agent of the present invention is high.

Examples 4 to 6 using the hydrogen sulfide removal agent of the present invention all maintained high and comparable breakthrough sulfur capacities, which also indicates that the hydrogen sulfide removal efficiency using the hydrogen sulfide desulfurization agent of the present invention is high and stable.

Compared with the removal time of the comparative example 1, the removal time of the hydrogen sulfide removal agent is long and stable as can be seen in the examples 4-6; the removal time of comparative example 1 was short, and it can be seen that the hydrogen sulfide removing agent of the present invention was high in efficiency and stable.

The method for detecting and calculating the sulfur capacity of examples 7 to 9 and comparative examples 2 and 3 is as follows:

the detection conditions are as follows: at a temperature of 40 ℃, at a pressure of atmospheric pressure (generally 1 atm), and at a concentration of 6mg/m of hydrogen sulfide³。

The detection steps are as follows:

100mL of the solutions of examples 7 to 9 and comparative examples 2 and 3 were poured into a U-shaped bubbling tube (corresponding to an absorption column) and kept at a constant temperature in a water bath at 40 ℃ and then charged with a solution containing H₂Introducing raw material gas with S concentration of 5% (mol%) into the above solution at normal pressure at flow rate of 30mL/min, performing desulfurization reaction, and timing when tail gas H₂The concentration of S reaches 6mg/m³When (reaching this concentration means that sulfur breakthrough is reached and the solution is no longer able to absorb H₂S) stopping the aeration and recording the time, i.e. calculating the penetration of the solutionAnd (4) sulfur permeability. The calculation formula is as follows:

in the formula S_LDenotes the liquid sulfur capacity (g/L) of the solution, P denotes the pressure of hydrogen sulfide gas (100kPa), Q_H2SRepresents the gas flow rate (mL/min) of hydrogen sulfide, t represents the desulfurization reaction time (min), R represents the gas state constant, 8.314Pa · m³V (mol. K); t represents the reaction temperature (315K), and V represents the liquid volume (L).

On the basis, the solution to be treated in examples 7 to 9 is added into a U-shaped bubbling tube filled with 0.2g of the hydrogen sulfide removing agent prepared in example 1, (wherein the reaction amount of the solution to be treated is excessive compared with the hydrogen sulfide removing agent), the reaction is carried out at 40 ℃ and normal pressure, timing is started, oxygen is introduced to regenerate the desulfurized hydrogen sulfide removing agent, the flow rate of the oxygen is 200mL/min, the oxidation-reduction potential (ORP) of the upper layer liquid is continuously monitored, after the oxidation-reduction potential is stabilized, the removal of hydrogen sulfide is completed, the reaction time is recorded, and the longer the reaction time is, the better the desulfurization effect of the hydrogen sulfide is. The results of the detection and calculation are shown in table 2.

Whether or not sulfur powder was precipitated in the absorption tower was observed, and the results are shown in table 2.

TABLE 2

As can be seen from comparison of comparative examples 2 and 3 with examples 7 to 9, in examples 7 and 8, no sulfur powder was generated in the absorption tower and thus the absorption tower was not clogged; in contrast, comparative examples 3 and 4, the absorption tower was clogged due to the generation of sulfur powder in the absorption tower.

Meanwhile, as can be seen from table 2, the hydrogen sulfide removal agents in examples 1 to 3 are used in examples 7 to 9, and the hydrogen sulfide removal time is longer than that in comparative example 4, thus indicating that the hydrogen sulfide removal efficiency is high.

As can be seen from Table 2, in examples 7 to 9 in which the absorption tower used a sodium hydroxide solution, the breakthrough sulfur capacity was higher than that of the conventional 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 towers in examples 7 to 9 did not exceed 1 hour, and was relatively stable, which indicates that the hydrogen sulfide removal efficiency of the hydrogen sulfide removal agent of the present invention is high and stable.

It will be apparent to those skilled in the art that various changes and modifications may be made in the embodiments of the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims

1. The hydrogen sulfide remover is characterized in that the hydrogen sulfide remover is aminocarboxylic acid chelating agent and Fe³⁺The chelate of (2).

2. The hydrogen sulfide removing agent according to claim 1, wherein the aminocarboxylic acid chelating agent is a crosslinked product of polyaspartic acid and a sphere having an amino group at the end.

3. The hydrogen sulfide removing agent according to claim 2, wherein the sphere having an amino group at the terminal is a coupling product of a hydroxyl group-containing sphere and an amino group-containing silane coupling agent.

4. The hydrogen sulfide removing agent according to claim 3, wherein the hydroxyl group-containing spheres are hydroxyl group-containing glass microspheres.

5. The preparation method of the hydrogen sulfide remover is characterized by comprising the preparation steps of: aminocarboxylic acid chelating agents and Fe-containing compounds³⁺Chelating the compound to obtain a chelate serving as a hydrogen sulfide removing agent;

6. The method of claim 5, comprising the step of preparing an aminocarboxylate chelant:

preferably, the mass ratio of the polyaspartic acid to the spheres with the tail ends including the amino groups is 1: 5-1: 20.

7. The method of claim 6, comprising a step of preparing a sphere having an amino group at the terminal thereof:

coupling the hydroxyl-containing sphere with an amino-containing silane coupling agent to obtain the sphere with the tail end containing the amino;

8. The method of claim 7, comprising the step of preparing the hydroxyl group-containing spheres by:

9. A method for removing hydrogen sulfide, characterized in that the hydrogen sulfide removing agent of any one of claims 1 to 4 is used as a removing agent for removing hydrogen sulfide by a dry method.

10. A method for removing hydrogen sulfide, comprising:

conveying the solution to be treated to a regeneration tower containing the hydrogen sulfide removing agent as defined in any one of claims 1 to 5, and introducing oxygen simultaneously to remove hydrogen sulfide and regenerate the hydrogen sulfide removing agent simultaneously.