CN113856451B - Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method - Google Patents
Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method Download PDFInfo
- Publication number
- CN113856451B CN113856451B CN202111361477.9A CN202111361477A CN113856451B CN 113856451 B CN113856451 B CN 113856451B CN 202111361477 A CN202111361477 A CN 202111361477A CN 113856451 B CN113856451 B CN 113856451B
- Authority
- CN
- China
- Prior art keywords
- hydrogen sulfide
- agent
- sphere
- amino
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
- C10L3/103—Sulfur containing contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/306—Alkali metal compounds of potassium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/604—Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/24—Hydrocarbons
- B01D2256/245—Methane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/304—Hydrogen sulfide
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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
Technical Field
The invention relates to the field of hydrogen sulfide removal, in particular to a hydrogen sulfide remover, a preparation method thereof and a hydrogen sulfide removal method.
Background
Equipment is corroded by hydrogen sulfide gas in petroleum and natural gas, coal bed gas and methane, and operators in the equipment are poisoned by the hydrogen sulfide gas, so that the hydrogen sulfide gas removal has economic, safe and environment-friendly values.
Currently, methods for removing hydrogen sulfide gas using a redox method include dry and wet methods, also referred to as heterogeneous catalytic oxidation and homogeneous catalytic oxidation.
The removal agent adopted in the dry method for removing the hydrogen sulfide generally has the problems of low stability, low efficiency and instability of the removal agent.
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 ferric salt solution with a certain concentration, adding a certain proportion of carbon nano tubes, stirring to prepare mixed solution, adding precipitant solution at a certain temperature to regulate the pH value of the solution to 3-11, forming suspension, aging, carrying out suction filtration after the aging is finished, collecting precipitate, and washing with deionized water to prepare the iron-based composite hydrogen sulfide remover.
The method mainly utilizes the interaction of Fe-O-C chemical bonds formed between the carbon nano tube and the hydrated ferric oxide to promote the electron mobility of the hydrogen sulfide removing agent in the process of removing the hydrogen sulfide, thereby improving the capability of removing the hydrogen sulfide.
However, the bond energy between C-O bonds in Fe-O-C chemical bonds formed between the carbon nano tube and the hydrated ferric oxide is low, and the carbon nano tube is easy to break under the acidic condition; the hydrogen sulfide is treated with stronger acidity, so that the hydrated ferric oxide gradually falls off on the surface of the carbon nano tube, thereby reducing the capability of the hydrogen sulfide remover for removing hydrogen sulfide.
Based on this, it is highly desirable to provide a hydrogen sulfide removal agent which is highly efficient and stable in hydrogen sulfide removal.
Disclosure of Invention
The invention provides a hydrogen sulfide removing agent, a preparation method thereof and a hydrogen sulfide removing method, which are used for solving the problems of low removing efficiency and instability of the hydrogen sulfide removing agent in the prior art.
According to an aspect of the present invention, there is provided a hydrogen sulfide remover which is an aminocarboxylic acid chelating agent and Fe 3+ Is a chelate compound of (a).
According to the hydrogen sulfide removing agent, the amino carboxylic acid chelating agent is a cross-linked product of polyaspartic acid and a sphere with an amino end.
According to the hydrogen sulfide removing agent of the present invention, the sphere having an amino group at the end is a conjugate of a sphere having a hydroxyl group and a silane coupling agent having an amino group.
According to the hydrogen sulfide removing agent disclosed by the invention, the hydroxyl-containing spheres are hydroxyl-containing glass microspheres.
According to another aspect of the present invention, there is provided a method for preparing a hydrogen sulfide remover, comprising the steps of: aminocarboxylic acid chelating agent and Fe-containing 3+ The chelate compound is obtained to be used as a hydrogen sulfide remover;
preferably, the aminocarboxylic acid chelating agent and the Fe-containing agent 3+ The mass ratio of the compounds is 1:5-1:20.
The preparation method comprises the following preparation steps of the amino carboxylic acid chelating agent:
the polyaspartic acid is crosslinked with a sphere with the tail end comprising amino groups through a crosslinking agent, so that the amino carboxylic acid chelating agent is obtained;
preferably, the mass ratio of the sphere with the tail end comprising the amino group to the polyaspartic acid is 1:5-1:20.
The preparation method according to the invention comprises the steps of preparing a sphere comprising an amino group at the end:
and coupling the sphere containing the hydroxyl group with the silane coupling agent containing the amino group to obtain the sphere with the tail end comprising the amino group.
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:
the hollow glass microspheres are treated by alkaline solution to obtain the hydroxyl-containing spheres.
According to another aspect of the present invention, there is provided a method for removing hydrogen sulfide, using the hydrogen sulfide remover of the present invention as a remover 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 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;
And conveying the solution to be treated into a regeneration tower containing the hydrogen sulfide removing agent, introducing oxygen at the same time, removing hydrogen sulfide and regenerating the hydrogen sulfide removing agent at the same time.
Compared with the prior art, the beneficial effects generated by utilizing the technical scheme of the invention are as follows:
the hydrogen sulfide removal agent according to the present invention is based on one hand on an aminocarboxylic acid chelating agent and Fe 3+ Is very strong and therefore Fe for removing hydrogen sulfide 3+ The hydrogen sulfide is not easy to fall off, so that the efficiency of removing the hydrogen sulfide is stable; on the other hand, since polyaspartic acid is used as the chelating agent, the polyaspartic acid contains rich amino groups and carboxyl groups, and can chelate a large amount of Fe 3+ Thus, the efficiency of removing hydrogen sulfide is improved; in yet another aspect, the hydrogen sulfide removal agent of the present invention may be regenerated by oxygen (i.e., fe by oxygen) 2+ Oxidation to Fe 3+ ) The hydrogen sulfide removing agent is reused.
According to the preparation method of the hydrogen sulfide remover, the hydrogen sulfide remover is prepared, and on one hand, due to the aminocarboxylic acid chelating agent and Fe 3+ Is very strong and therefore Fe for removing hydrogen sulfide 3+ The hydrogen sulfide is not easy to fall off, so that the hydrogen sulfide removal efficiency is high and stable; on the other hand, since polyaspartic acid is used as the chelating agent, the polyaspartic acid contains rich amino groups and carboxyl groups, and can chelate a large amount of Fe 3+ Thus improving the efficiency of removing the hydrogen sulfide; in yet another aspect of the present invention,the hydrogen sulfide removal agent of the present invention may be regenerated by oxygen (i.e., fe is regenerated by oxygen 2+ Oxidation to Fe 3+ ) The hydrogen sulfide removing agent is reused.
According to the hydrogen sulfide removal method, the hydrogen sulfide removal agent provided by the invention is adopted, so that the hydrogen sulfide removal efficiency is high and stable.
According to the other method for removing hydrogen sulfide, 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 formed sulfur powder blocks the absorption tower pipeline 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 hydrogen sulfide remover is adopted to treat the solution to be treated in the regeneration tower, so that the removal efficiency is high and stable.
Drawings
FIG. 1 shows an infrared spectrum of the product produced at each step of the process for producing a hydrogen sulfide removal agent according to example 1 of the present invention;
reference numerals: a sphere a containing hydroxyl, a sphere b containing amino 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 clearly and completely described below with reference to the drawings and examples of the specification, and it is apparent that the described examples are only some of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to an aspect of the present invention, there is provided a hydrogen sulfide remover which is an aminocarboxylic acid chelating agent and Fe 3+ Is a chelate compound of (a).
The hydrogen sulfide removal agent according to the present invention is based on one hand on an aminocarboxylic acid chelating agent and Fe 3+ Is very strong, amino and carboxyl groups and Fe 3+ Can form very strong coordination bonds, thus Fe for removing hydrogen sulfide 3+ Is not easy to fall off, has strong removal efficiency on hydrogen sulfide and is suitable for the hydrogen sulfideStabilizing; on the other hand, fe 3+ Can be regenerated by oxygen (i.e. Fe 2+ Can be oxidized into Fe by oxygen 3+ ) The hydrogen sulfide removal agent is reused.
The aminocarboxylic acid chelating agent is a chelating agent containing an amino group and a carboxyl group.
Wherein the aminocarboxylic acid chelating agent is selected from at least one of the following: cross-links of polyaspartic acid with spheres comprising an amino group at the end, ethylenediamine tetraacetic acid (EDTA) and ethylenediamine diacetic acid (EDDHA).
Containing Fe 3+ The compound is preferably an iron salt, and more preferably at least one of the following: fe (Fe) 2 (SO 4 ) 3 、FeCl 3 ·6H 2 O and Fe (NO) 3 ) 3 。
Aminocarboxylic acid chelating agents and Fe 3+ High stability constants, such as: ethylenediamine tetraacetic acid (EDTA) and Fe 3+ Has a stability constant of 25.1, ethylenediamine diacetic acid (EDDHA) and Fe 3+ Has a stability constant of 29.6, since in this class of chelating agents the amino and carboxyl groups are used in combination with Fe 3+ Chelating, and the same can be known that the cross-linked product of polyaspartic acid and a sphere having an amino group at the end and Fe 3+ Is good in stability, and it can be seen that the aminocarboxylic acid chelating agent and Fe 3+ 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 removing agent of the present invention, polyaspartic acid (abbreviated as PASP in english) is adopted in the chelating agent, and PASP is a polymer polymerized from single aspartic acid through amide bond, and naturally exists in snail and mollusk shells, and the structure of PASP contains a large amount of carboxyl and amino.
As PASP contains rich carboxyl and amino (mainly nitrogen atoms), a large amount of Fe can be chelated 3+ 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 amino groups in the PASP structure, the amino carboxylic acid chelator may be formed by cross-linking with spheres that include amino groups at their ends by a cross-linking agent.
Among them, glutaraldehyde and glyoxal are preferable as the crosslinking agent.
According to the hydrogen sulfide removing agent of the present invention, the sphere having an amino group at the end is a conjugate of a sphere having a hydroxyl group and a silane coupling agent having an amino group.
The hydrogen sulfide removing agent according to the present invention, wherein the hydroxyl group-containing spheres and the amino group-containing silane coupling agent form a conjugate through the chemical bond of the hydroxyl group and the amino group, thereby providing a substrate for cross-linked PASP.
According to the hydrogen sulfide remover, the hydroxyl-containing spheres are hydroxyl-containing glass microspheres.
Wherein the glass microspheres are preferably hollow glass microspheres, and the diameter of the glass microspheres is generally 50-100 mu m; further preferred are 50um, 55um, 60um, 65um, 70um, 75um, 80um, 85um, 90um, 95um and 100um.
Glass microspheres are selected because the glass microspheres contain Si-O-Si bonds, and after being treated by alkaline solution, the chemical bonds can form Si-OH bonds after being opened, thereby providing conditions for coupling amino-containing silane coupling agents; in addition, the sphere has large specific surface area, more Si-OH bonds can be formed, more amino-containing silane coupling agents can be coupled, more PASP can be crosslinked, more amino groups and carboxyl groups are contained in the aminocarboxylic acid chelating agent, and more Fe is finally chelated 3+ 。
According to another aspect of the present invention, there is provided a method for preparing a hydrogen sulfide remover, comprising the steps of: aminocarboxylic acid chelating agent and Fe-containing 3+ The chelate compound is obtained to be used as a hydrogen sulfide remover;
preferably, the aminocarboxylic acid chelating agent and the Fe-containing agent 3+ The mass ratio of the compounds is 1:5-1:20.
Specifically, an aminocarboxylic acid chelating agent is generally combined with a Fe-containing material 3+ Dispersing the compound in the 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; and drying and roasting filter residues to obtain chelate serving as a hydrogen sulfide remover.
Chelating agent containing carboxyl group and Fe containing 3+ The mass ratio of the compounds of (3) is preferably 1:5 to 1:20, particularly 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 having an amino group at the end, ethylenediamine tetraacetic acid (EDTA) and ethylenediamine diacetic acid (EDDHA).
Wherein, contains Fe 3+ The compound is preferably an iron salt, and more preferably at least one of the following: fe (Fe) 2 (SO 4 ) 3 、FeCl 3 ·6H 2 O、[FeNH 4 (SO 4 ) 2 ·12H 2 O]And Fe (NO) 3 ) 3 。
Wherein the certain temperature is 60-70deg.C, preferably 60deg.C, 63deg.C, 65deg.C, 68deg.C and 70deg.C.
Wherein, the certain time is 4-6 h, and particularly preferably 4h, 4.5h, 5h, 5.5h and 6h.
More specifically, the following formula shows an example of chelating agent and ferric chloride as a cross-linked product of polyaspartic acid and a sphere having an amino group at the end, and the specific operation method is as follows.
Preparing an iron chloride solution with the mass fraction of 25% -50%, and weighing and dispersing the chelating agent in an iron salt solution according to the proportion (converted into the mass ratio of 1:5-1:20) of the chelating agent to the volume ratio of 1:20-40 (g/mL) of the iron chloride solution; then heating to 60-70 ℃ and chelating for 4-6 h; after the reaction is finished, vacuum suction filtration is carried out, and filter residues and filtrate are respectively collected; the collected filtrate is a reclaimed ferric salt solution and can be reused; and (3) sending the collected filter residues into a vacuum drying oven, vacuum drying for 4-8 hours at the temperature of 50-60 ℃ and the vacuum degree of 40-50 Pa, taking out, and roasting for 5 hours at the temperature of 300 ℃ to obtain the chelate serving as a hydrogen sulfide removing agent.
An exemplary reaction equation for this step is shown below.
The preparation method according to the invention comprises the preparation steps of an aminocarboxylic acid chelating agent:
polyaspartic acid is crosslinked with a sphere with the tail end comprising amino groups through a crosslinking agent to obtain a chelating agent of amino carboxylic 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 former is added during the preparation of the aminocarboxylic acid chelating agent.
Specifically, a sphere with an amino group at the tail end and polyaspartic acid are crosslinked through a crosslinking agent according to a certain proportion, so that the aminocarboxylic acid chelating agent is obtained.
The mass ratio of the sphere having the amino group at the end and the polyaspartic acid is preferably 1:5 to 1:20, particularly 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 powder, or talc.
The mass ratio of the crosslinking agent to the spheres having amino groups at the ends is 0.05:1 to 0.1:1, particularly preferably 0.05:1, 0.08:1 and 0.1:1.
The reaction temperature is preferably 60 to 70℃and particularly preferably 60℃63℃65℃68℃and 70 ℃.
The reaction time is preferably from 4 to 6 hours, particularly preferably 4 hours, 4.5 hours, 5 hours, 5.5 hours and 6 hours.
Taking the reaction of a sphere having an amino group at the end and polyaspartic acid as an example in the following equation, the specific procedure is as follows: firstly, preparing PASP solution with mass fraction of 25% -50%, wherein the mass ratio of PASP to polyethylene glycol is 1: weighing polyethylene glycol according to the proportion of 0.05-0.1 (g/g) and adding the polyethylene glycol into the PASP solution; then weighing and dispersing the spheres with the tail ends comprising amino groups in PASP solution according to the proportion of the mass of the spheres with the tail ends comprising amino groups to the volume ratio of the PASP solution of 1:20-40 (g/mL) (the mass ratio is 1:5-1:20), and fully mixing; preparing 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 amino to the volume ratio of glutaraldehyde solution of 1:1-2 (g/mL), heating to 60-70 ℃ by using a constant-temperature water bath, treating for 4-6 h, performing vacuum filtration, and repeatedly washing with water until no liquid drops flow out. Respectively collecting filter residues and filtrate, wherein the filtrate comprises unreacted PASP solution, and the unreacted PASP solution can be used for preparing an aminocarboxylic acid chelating agent again; and (3) placing the filter residues into a vacuum drying box, and vacuum drying for 4-8 hours at the temperature of 50-60 ℃ and the vacuum degree of 40-50 Pa to obtain the aminocarboxylic acid chelating agent.
An exemplary reaction equation for a sphere with an amino group at the end of this step and polyaspartic acid is as follows:
the preparation method according to the invention comprises the preparation steps of a sphere comprising an amino group at the end:
and coupling the sphere containing the hydroxyl group with the silane coupling agent containing the amino group to obtain the sphere with the tail end comprising the amino group.
Preferably, the mass ratio of the hydroxyl-containing spheres 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-aminopropyl triethoxysilane) and (3-aminopropyl trimethoxysilane).
More specifically, the following reaction equation showing a hydroxyl group-containing sphere and an amino group-containing silane coupling agent is exemplified, and the specific operation is: the mass ratio of the sphere containing hydroxyl to the silane coupling agent containing amino is 1: 1-2 (g/g), weighing the sphere containing hydroxyl and the silane coupling agent, and then according to the total mass of the sphere containing hydroxyl and the silane coupling agent: dispersing hydroxyl-containing spheres and a silane coupling agent in absolute ethyl alcohol according to the volume ratio of 1:100-200 (g/mL), heating to 80-90 ℃ by using a constant-temperature water bath kettle, condensing and refluxing for 4-6 hours, taking out, carrying out vacuum suction filtration, and collecting filter residues and filtrate respectively; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a vacuum drying oven, and vacuum drying for 4-8 hours 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-containing silane coupling agent is 3-aminopropyl triethoxysilane.
The preparation method comprises the following steps of:
the hollow glass microsphere is treated by alkaline solution to obtain a sphere containing hydroxyl.
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, preferably 25% to 50% by mass, particularly preferably 25%, 30%, 35%, 40%, 45% and 50% by mass.
Specifically, the following reaction equation is taken as an example, and the specific operation is: firstly, preparing sodium hydroxide solution with the mass fraction of 25% -50%, wherein the volume ratio of Hollow Glass Microspheres (HGM) to the sodium hydroxide solution is 1: 10-30 (g/mL), weighing HGM, dispersing in sodium hydroxide solution, heating to 80-100 ℃ by a constant temperature water bath, treating for 3-6 h, taking out, washing with purified water for several times until the washing liquid is neutral, combining the washing liquid with the waste liquid after pretreatment of the HGM, neutralizing, discharging after reaching standards, putting the washed HGM into an oven, drying to constant weight at 40-60 ℃, and preserving in a glass dryer to prepare the hydroxyl-containing sphere.
The mechanism of treatment with 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, there is provided a method for removing hydrogen sulfide, using the hydrogen sulfide remover of the present invention as a remover for removing hydrogen sulfide by a dry method.
The hydrogen sulfide removal by the hydrogen sulfide removal agent of the present invention is exemplified by a laboratory dry process.
Taking 0.2 g-1.0 g of the hydrogen sulfide remover prepared by the invention, placing the hydrogen sulfide remover into a U-shaped bubbling pipe, and keeping the temperature in a water bath kettle, when the temperature of the U-shaped bubbling pipe reaches 40-50 ℃, using the hydrogen sulfide with the concentration of 200mg/m 3 The raw material gas of (2) enters a U-shaped bubbling pipe at the flow rate of 40mL/min to react with a hydrogen sulfide removing agent under normal pressure, 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/m 3 When the aeration is stopped, the hydrogen sulfide removal agent is considered to penetrate.
According to another aspect of the present invention, there is provided a method for 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;
The solution to be treated is conveyed to a regeneration tower containing the hydrogen sulfide removing agent, oxygen is simultaneously introduced, hydrogen sulfide is removed, and the hydrogen sulfide removing agent is simultaneously regenerated.
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 a sodium hydroxide solution, the solvent is preferably water, and the concentration is preferably 0.05 to 0.2mol/L, still more preferably 0.05mol/L, 0.1mol/L, 0.15mol/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 which contains the hydrogen sulfide removing agent of the invention, and HS in the solution can be removed - And S is 2- Oxidized into sulfur powder.
Wherein the hydrogen sulfide in the alkaline solution is penetrable in the sense that the hydrogen sulfide gas is no longer able to react with the alkaline solution to form a salt and dissolve in water, i.e. the solution is no longer able to absorb hydrogen sulfide.
In the prior art, an iron-based hydrogen sulfide remover is contained in an absorption tower and is a homogeneous reaction, and the oxidation-reduction reaction of iron-based ionic liquid and sulfur ions: 2Fe 3+ +S2-＝2Fe 2+ +S。
The generated sulfur simple substance is in a sulfur powder state generally, and can block the absorption tower.
In the method, alkaline solution is used for replacing solution containing iron ions, sulfur powder is not generated in an absorption tower, but sulfur salt is generated and dissolved in water, for example, when sodium hydroxide solution is used as alkaline solution, two reaction modes can exist between the alkaline solution and hydrogen sulfide, and one reaction mode is as follows: 2NaOH+H 2 S＝Na 2 S+H 2 O; the equation for the other reaction scheme is: naOH+H 2 S＝NaHS+H 2 O。
Delivering 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 (2) is: 2Fe 3+ +S 2- ＝2Fe 2+ +S。
After hydrogen sulfide is removed in the regeneration tower, the hydrogen sulfide removing agent and the sulfur powder are discharged together, and the sulfur powder is dissolved by the extracting agent, so that the hydrogen sulfide removing agent can be conveniently recovered.
The oxygen is introduced mainly for regenerating the hydrogen sulfide removing agent, and can be recycled. The regeneration principle is 4Fe 2+ +O 2 +4H + ＝4Fe 3+ +2H 2 O。
The hydrogen sulfide removing agent has high and stable hydrogen sulfide removing efficiency.
In order to prove the method, the applicant carried out laboratory operations, the specific operations exemplified by sodium hydroxide solution being the steps of: dissolving sodium hydroxide in water according to the mass ratio of the sodium hydroxide to water of 1:200-400 (g/mL), pouring sodium hydroxide solution into a U-shaped bubbling pipe (equivalent to an absorption tower) after the sodium hydroxide solution is fully dissolved, and keeping the temperature in a water bath kettle at 40-50 ℃ at constant temperature, wherein the water bath kettle contains H 2 The raw material gas with S concentration of 5% (mol%) is introduced into the solution at the flow rate of 30mL/min under normal pressureIn the process, desulfurization reaction is carried out and timing is started, when tail gas H 2 S concentration reaches 6mg/m 3 When this concentration is reached (meaning that sulfur breakthrough is reached, the solution is no longer able to absorb H 2 S) stopping ventilation and recording time to form the solution to be treated.
According to the invention, the ratio of the mass of the hydrogen sulfide removing agent to the volume ratio of the solution to be treated is 1:20-40 (g/mL), the hydrogen sulfide removing agent is added into the U-shaped bubbling pipe (equivalent to a regeneration tower) for desulfurization, the reaction is carried out at 40 ℃ and normal pressure, the timing is started, meanwhile, oxygen is introduced for regenerating the desulfurized hydrogen sulfide removing agent, the flow rate of the oxygen is 200mL/min, the oxidation-reduction potential (ORP) of the solution is monitored in the process until the oxidation-reduction potential is not increased, and the hydrogen sulfide is removed.
It should be noted that, the oxidation-reduction potential is an instrument for monitoring oxidation-reduction reaction in the solution, and if oxidation-reduction reaction does not occur in the solution, the indication is 0; if a redox reaction occurs, an indication is provided; in the processes of removing hydrogen sulfide and regenerating, the oxidation-reduction reaction always occurs, the oxidation-reduction potential indication is always increased, and the oxidation-reduction potential is not changed after the oxidation-reduction is completed.
The mechanism of hydrogen sulfide removal and oxygen regeneration by the hydrogen sulfide removal agent according to the present invention is as follows.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not limiting to the scope of the claims.
Wherein, examples 1 to 3 are the preparation method of the hydrogen sulfide remover; examples 4 to 6 are methods for dry removal of hydrogen sulfide using the hydrogen sulfide removal agents prepared in examples 1 to 3; examples 7 to 9 are dry-wet combined hydrogen sulfide removal methods using the hydrogen sulfide removal agents of the present invention. Comparative examples 1 to 3 are methods for removing hydrogen sulfide using the prior art.
Example 1
Firstly, preparing hollow glass microspheres containing hydroxyl, wherein the specific operation of the step S1 is as follows:
preparing sodium hydroxide solution with mass fraction of 25%; according to the volume ratio of the Hollow Glass Microspheres (HGM) to the sodium hydroxide solution of 1:10 (g/mL), weighing HGM and dispersing in sodium hydroxide solution; heating to 80 ℃ by using a constant-temperature water bath kettle, treating for 3 hours, and taking out; washing with purified water until the washing liquid is neutral; combining the washing liquid with the waste liquid after HGM treatment, then carrying out neutralization treatment, and discharging after reaching the standard; and (3) placing the washed HGM into an oven, drying the HGM to constant weight at 40 ℃, and storing the HGM in a glass dryer to prepare the hydroxyl-containing hollow glass microspheres.
Then, a step S2 is carried out, wherein a sphere with an amino group at the tail end is prepared, and the specific operation of the step is as follows:
the mass ratio of the hollow glass microsphere containing hydroxyl to the aminosilane coupling agent is 1:1 (g/g), weighing hollow glass microspheres containing hydroxyl and a silane coupling agent; and then according to the total mass of the hydroxyl-containing hollow glass microsphere and the silane coupling agent: the volume ratio of the absolute ethyl alcohol is 1:100 (g/mL), and glass microspheres containing hydroxyl and a silane coupling agent are dispersed in the absolute ethyl alcohol; heating to 80 ℃ by using a constant-temperature water bath kettle, condensing and refluxing for 4 hours, and taking out; vacuum filtering, and collecting filter residues and filtrate respectively; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a vacuum drying box, and vacuum drying for 4 hours at the temperature of 50 ℃ and the vacuum degree of 40Pa to prepare the sphere with the tail end comprising the amino group. Wherein the aminosilane coupling agent is 3-aminopropyl triethoxysilane.
Then, step S3 is performed: the preparation of the aminocarboxylic acid chelating agent is carried out as follows:
preparing PASP solution with mass fraction of 25%, weighing and dispersing the spheres with the tail end comprising amino groups in the PASP solution according to the proportion of the mass of the spheres with the tail end comprising amino groups to the volume ratio of the PASP solution of 1:20 (g/mL), and fully mixing; the mass ratio of PASP to polyethylene glycol is 1:0.05 The (g/g) proportion is that the polyethylene glycol is weighed and added into the PASP solution; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution according to the ratio of the mass of the sphere with the tail end comprising amino group to the glutaraldehyde solution volume of 1:1 (g/mL), heating to 60 ℃ by using a constant-temperature water bath kettle, keeping for 4 hours, and vacuum filtering. Collecting filter residues and filtrate, wherein the filtrate comprises unreacted PASP solution and can be recycled; and (3) placing the filter residues into a vacuum drying oven, and vacuum drying for 4 hours at the temperature of 50 ℃ and the vacuum degree of 40Pa to prepare the aminocarboxylic acid chelating agent.
Finally, the preparation of the hydrogen sulfide removing agent is carried out in the step S4, 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 in the iron salt solution according to the ratio of the mass of the chelating agent containing carboxyl to the volume ratio of the iron salt solution of 1:20 (g/mL); then heating to 60 ℃, and carrying out chelation reaction for 4 hours; after vacuum filtration, respectively collecting filter residues and filtrate; the collected filtrate is used for recovering ferric salt solution for preparing again; the collected filter residues are sent into a vacuum drying oven to be dried for 4 hours under the conditions of 55 ℃ and 45Pa of vacuum degree, and then are taken out and baked for 5 hours under the conditions of 300 ℃ to prepare the hydrogen sulfide removing agent, wherein the iron salt is FeCl 3 ·6H 2 O。
The applicant carried out an infrared spectrum characterization of the reaction products in each step of example 1, the characterization results being shown in fig. 1.
In curve a of FIG. 1, 3500cm -1 Is a stretching vibration peak of-OH at 1000cm -1 The bending vibration peak of Si-OH is shown on the left and right, so that the surface of the hollow glass microsphere subjected to alkali treatment is proved to form hydroxyl groups.
In FIG. 1, curve b, which is between 2900 and 3000cm compared to curve a -1 A new peak appears, which is due to the stretching vibration peak of methyl and methylene, and furthermore at 1500 and 1350cm -1 Two new peaks are shown nearby, 950cm due to the vibrational peaks of the amino and-C-N bonds -1 The nearby peak is the stretching vibration peak of Si-O, which is all the reason that 3-aminopropyl triethoxy silane is coupled with a sphere containing hydroxyl groupThus, and stated to include an amino group at the terminus.
In curve c of FIG. 1, at 1400cm -1 The absorption peak in the vicinity is enhanced and is 900cm -1 A new peak also appears nearby, due to the vibration absorption peak of the hydroxyl groups in the carboxyl groups of the PASP introduced, furthermore, at 1600cm after crosslinking -1 The reason why the absorption peaks do not change greatly is that the amino group in the sphere having the amino group at the end is overlapped with the amino group introduced after crosslinking, but-C=N-is formed, and thus 1600cm -1 The left and right absorption peaks are red shifted.
In curve d of FIG. 1, the peak associated with the amino and carboxyl groups in curve c is reduced or eliminated due to the chelation of iron ions by the aminocarboxylic acid chelating agent.
Example 2
Firstly, preparing hollow glass microspheres containing hydroxyl, wherein the specific operation of the step S1 is as follows:
preparing a sodium hydroxide solution with the mass fraction of 40%; according to the volume ratio of the Hollow Glass Microspheres (HGM) to the sodium hydroxide solution of 1:20 (g/mL), weighing HGM and dispersing in sodium hydroxide solution; heating to 90 ℃ by using a constant-temperature water bath kettle, treating for 4 hours, and taking out; washing with purified water until the washing liquid is neutral; combining the washing liquid with the waste liquid after HGM treatment, then carrying out neutralization treatment, and discharging after reaching the standard; and (3) placing the washed HGM into an oven, drying the HGM to constant weight at 50 ℃, and storing the HGM in a glass dryer to prepare the hydroxyl-containing hollow glass microspheres.
Then, a step S2 is carried out, wherein a sphere with an amino group at the tail end is prepared, and the specific operation of the step is as follows:
the mass ratio of the hollow glass microsphere containing hydroxyl to the aminosilane coupling agent is 1:1.5 (g/g), weighing the hollow glass microspheres containing hydroxyl and the silane coupling agent; and then according to the total mass of the hydroxyl-containing hollow glass microsphere and the silane coupling agent: dispersing glass microspheres containing hydroxyl and a silane coupling agent in absolute ethyl alcohol in a volume ratio of 1:150 (g/mL); heating to 85 ℃ by using a constant-temperature water bath kettle, condensing and refluxing for 5 hours, and taking out; vacuum filtering, and collecting filter residues and filtrate respectively; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a vacuum drying box, and vacuum drying for 5 hours at the temperature of 55 ℃ and the vacuum degree of 45Pa to prepare the sphere with the tail end comprising the amino group. Wherein the aminosilane coupling agent is 3-aminopropyl trimethoxy silane.
Then, step S3 is performed: the preparation of the aminocarboxylic acid chelating agent is carried out as follows:
preparing PASP solution with the mass fraction of 40%, weighing and dispersing the spheres with the tail ends comprising amino groups in the PASP solution according to the proportion of the mass of the spheres with the tail ends comprising amino groups to the volume ratio of the PASP solution of 1:30 (g/mL), and fully mixing; the mass ratio of PASP to polyethylene glycol is 1:0.08 The (g/g) proportion is that the polyethylene glycol is weighed and added into the PASP solution; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution according to the ratio of the mass of the sphere with the tail end comprising amino to the glutaraldehyde solution volume of 1:1.5 (g/mL), heating to 70 ℃ by using a constant-temperature water bath, maintaining for 5h, and vacuum filtering. Collecting filter residues and filtrate, wherein the filtrate is unreacted PASP solution and can be recycled again; and (3) putting the filter residues into a vacuum drying oven, and vacuum drying for 5 hours at the temperature of 55 ℃ and the vacuum degree of 45Pa to prepare the aminocarboxylic acid chelating agent.
Finally, step S4 is carried out: the preparation of the hydrogen sulfide removing agent comprises the following specific operations:
preparing an iron salt solution with the mass fraction of 40%, and weighing and dispersing an aminocarboxylic acid chelating agent in the iron salt solution according to the ratio of the mass of the chelating agent containing carboxyl to the volume ratio of the iron salt solution of 1:30 (g/mL); then heating to 65 ℃ and carrying out chelation reaction for 5 hours; after vacuum filtration, respectively collecting filter residues and filtrate; the collected filtrate is used for recovering ferric salt solution for preparing again; the collected filter residues are sent into a vacuum drying oven to be dried for 6 hours under the conditions of 60 ℃ and 45Pa of vacuum degree, and then are taken out and baked for 5 hours under the conditions of 300 ℃ to prepare the hydrogen sulfide removing agent, wherein the iron salt is iron salt of Fe 2 (SO 4 ) 3 。
Example 3
Step S1 is first performed: the preparation method comprises the following specific operation steps of:
preparing a sodium hydroxide solution with the mass fraction of 50%; according to the volume ratio of the Hollow Glass Microspheres (HGM) to the sodium hydroxide solution of 1:30 (g/mL), weighing HGM and dispersing in sodium hydroxide solution; heating to 100deg.C with a constant temperature water bath, treating for 6 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, then carrying out neutralization treatment, and discharging after reaching the standard; and (3) placing the washed HGM into an oven, drying the HGM to constant weight at 60 ℃, and storing the HGM in a glass dryer to prepare the hydroxyl-containing hollow glass microspheres.
Then, a step S2 is carried out, wherein a sphere with an amino group at the tail end is prepared, and the specific operation of the step is as follows:
weighing the hollow glass microspheres containing hydroxyl and the silane coupling agent according to the mass ratio of the hollow glass microspheres containing hydroxyl to the aminosilane coupling agent of 1:2 (g/g); and then according to the total mass of the hydroxyl-containing hollow glass microsphere and the silane coupling agent: dispersing glass microspheres containing hydroxyl and a silane coupling agent in absolute ethyl alcohol in a volume ratio of 1:200 (g/mL); heating to 90 ℃ by using a constant-temperature water bath kettle, condensing and refluxing for 6 hours, and taking out; vacuum filtering, and collecting filter residues and filtrate respectively; the collected filtrate is used for recovering ethanol; and (3) sending the collected filter residues into a vacuum drying box, and vacuum drying for 8 hours at the temperature of 60 ℃ and the vacuum degree of 50Pa to prepare the sphere with the tail end comprising the amino group. Wherein the aminosilane coupling agent is 3-aminopropyl trimethoxy silane.
Then, step S3 is performed: the preparation of the aminocarboxylic acid chelating agent is carried out as follows:
preparing PASP solution with the mass fraction of 50%, weighing and dispersing the spheres with the tail ends comprising amino groups in the PASP solution according to the proportion of the mass of the spheres with the tail ends comprising amino groups to the volume ratio of the PASP solution of 1:40 (g/mL), and fully mixing; the mass ratio of PASP to polyethylene glycol is 1:0.1 The (g/g) proportion is that the polyethylene glycol is weighed and added into the PASP solution; preparing glutaraldehyde solution with the mass fraction of 5%, adding glutaraldehyde solution according to the ratio of the mass of the sphere with the tail end comprising amino group to the glutaraldehyde solution volume ratio of 1:2 (g/mL), heating to 70 ℃ by using a constant-temperature water bath kettle, maintaining for 6 hours, and vacuum filtering. Collecting filter residues and filtrate, wherein the filtrate is unreacted PASP solution and can be recycled again; and (3) placing the filter residues into a vacuum drying oven, and vacuum drying for 8 hours at the temperature of 60 ℃ and the vacuum degree of 50Pa to prepare the chelating agent containing carboxyl.
Finally, step S4 is carried out: the preparation of the hydrogen sulfide removing agent comprises the following specific operations:
preparing 50% ferric salt solution by mass fraction, and weighing aminocarboxylic acid chelating agent to be dispersed in the ferric salt solution according to the ratio of the mass of the chelating agent containing carboxyl to the ferric salt solution volume of 1:40 (g/mL); then heating to 70 ℃, and carrying out chelation reaction for 6 hours; after vacuum filtration, respectively collecting filter residues and filtrate; the collected filtrate is used for recovering ferric salt solution for preparing again; the collected filter residues are sent into a vacuum drying oven to be dried for 8 hours under the conditions of 60 ℃ and 50Pa of vacuum degree, and are taken out and then are roasted for 5 hours under the conditions of 300 ℃ to prepare the hydrogen sulfide removing agent, wherein the iron salt is iron salt of Fe 2 (SO 4 ) 3 。
Example 4
Taking 0.2g of the hydrogen sulfide removing agent prepared in the example 1, placing the hydrogen sulfide removing agent into a U-shaped bubbling pipe, keeping the temperature in a water bath kettle, and when the temperature of the U-shaped bubbling pipe reaches 40 ℃, using the hydrogen sulfide containing catalyst with the concentration of 200mg/m 3 The raw material gas of (2) enters a U-shaped bubbling pipe at a 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/m 3 The aeration is stopped and the hydrogen sulfide removal agent is considered to penetrate.
Example 5
In this example, the hydrogen sulfide removal agent prepared in example 2 was used to remove hydrogen sulfide, and the other conditions were the same as in example 4.
Example 6
The hydrogen sulfide removal agent prepared in example 3 was used in example 6 to remove hydrogen sulfide, with the other conditions being the same as in example 4.
Example 7
Sodium hydroxide is dissolved in aqueous solution according to the mass to water volume ratio of 1:250 (g/mL) (namely, the concentration is 0.1 mol/L), after the sodium hydroxide is fully dissolved, the sodium hydroxide solution is poured into a U-shaped bubbling pipe (equivalent to an absorption tower) and is kept at constant temperature in a water bath kettle at 40 ℃, and the solution containing H is used 2 Introducing raw material gas with S concentration of 5% (mol%) into the solution at a flow rate of 30mL/min under normal pressure, performing desulfurization reaction, starting timing, and collecting tail gas H 2 S concentration reaches 6mg/m 3 When this concentration is reached (meaning that sulfur breakthrough is reached, the solution is no longer able to absorb H 2 S) stopping ventilation and recording time to form the solution to be treated.
According to the proportion of the mass of the hydrogen sulfide removing agent to the volume ratio of the solution to be treated of 1:20 (g/mL) in the embodiment 1, the hydrogen sulfide removing agent is added into the U-shaped bubbling pipe (equivalent to a regeneration tower) for desulfurization, meanwhile, oxygen is introduced to regenerate the desulfurized hydrogen sulfide removing agent, the flow rate of the oxygen is 200mL/min, the ORP is continuously monitored on the upper liquid, and the removal of hydrogen sulfide is completed after the oxidation-reduction potential is stabilized.
Example 8
Example 8 the hydrogen sulfide remover of example 2 was used, with the other conditions being the same as in example 7.
Example 9
Example 9 the hydrogen sulfide remover of example 3 was used, with the same exception that the conditions were the same as in example 7.
Comparative example 1
In comparative example 1, a composite of carbon nanotubes and hydrous 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 an imidazolyl chloride iron-based ion (Fe-IL: [ Bmim]FeCl 4 ) The solution was replaced and the regeneration column step was not accessed, the other being the same as in example 7.
Comparative example 3
In comparative example 3, except that sodium hydroxide solution was used with NButylpyridine iron tetrachloride ([ BPy)]FeCl 4 ) The solution was replaced and the regeneration column step was not accessed, the other being the same as in example 8.
Comparative example 4
In comparative example 4, the same as in example 7 was conducted except that the hydrogen sulfide removing agent in the regenerator was a composite of carbon nanotubes and hydrous iron oxide as disclosed in CN112717931 a.
The applicant has examined the penetrating sulfur capacities of examples 4 to 9 and comparative examples 1 to 3 in order to clearly demonstrate the efficiency and stability of the hydrogen sulfide removal by the hydrogen sulfide removal agent of the present invention.
The detection method and calculation method of the penetrating sulfur capacities of examples 4 to 6 and comparative example 1 are as follows:
the breakthrough sulfur capacity is calculated as the mass fraction of sulfur in the hydrogen sulfide removal agent, the values are expressed in%, calculated as follows:wherein C represents the mass concentration (kg/m) of sulfur in the feed gas 3 )；V 1 ，V 2 A value (mL) representing the gas volume at the start and stop 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 ℃, the pressure is normal pressure (usually 1 atmosphere), and the penetration concentration is 6mg/m 3 ；
The detection steps are as follows:
taking 0.2g of hydrogen sulfide removing agent, placing into a U-shaped bubbling pipe, and keeping the temperature in a water bath kettle, when the temperature of the U-shaped bubbling pipe reaches 40 ℃, using a catalyst containing 200mg/m of hydrogen sulfide 3 The raw material gas of (2) enters a U-shaped bubbling pipe at the flow rate of 40mL/min to react with a hydrogen sulfide removing agent under normal pressure, 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/m 3 Stopping ventilation when the hydrogen sulfide remover penetrates; the values of the gas volumes at the start and stop of the reaction were recorded by a wet gas flow meter, and the removal time of hydrogen sulfide at the end of the reaction was recorded.
The calculation was performed according to the above formula, and the detection data were obtained as shown in table 1.
TABLE 1
| Penetrating sulfur capacity | Time to Hydrogen sulfide removal (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 a comparison of example 4 and comparative example 1, the hydrogen sulfide remover prepared in example 1 was used because of the aminocarboxylic acid chelating agent and Fe 3+ Has strong chelating force, fe 3+ Is not easy to fall off and is chelated with rich Fe 3+ More hydrogen sulfide was removed and thus the penetrating sulfur Rong Yuan of example 4 was higher than that of comparative example 1, and it can be seen that the use ofThe hydrogen sulfide removing agent has high efficiency of removing hydrogen sulfide.
While examples 4 to 6 using the hydrogen sulfide removal agent of the present invention all maintained high and slightly different penetrating sulfur capacities, also demonstrated that the hydrogen sulfide removal efficiency was high and stable using the hydrogen sulfide removal agent of the present invention.
It can also be seen from examples 4 to 6 that the hydrogen sulfide remover of the present invention has a long and stable removal time compared with the removal time of comparative example 1; the hydrogen sulfide removal agent of the present invention was found to be efficient and stable in comparison with comparative example 1, since the removal time was short.
The method for measuring and calculating the sulfur capacities of examples 7 to 9 and comparative examples 2 and 3 is as follows:
The detection conditions are as follows: the temperature is 40 ℃, the pressure is normal pressure (usually 1 atmosphere), and the concentration of penetrating hydrogen sulfide is 6mg/m 3 。
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℃using a solution containing H 2 Introducing raw material gas with S concentration of 5% (mol%) into the solution at a flow rate of 30mL/min under normal pressure, performing desulfurization reaction, starting timing, and collecting tail gas H 2 S concentration reaches 6mg/m 3 When this concentration is reached (meaning that sulfur breakthrough is reached, the solution is no longer able to absorb H 2 S) stopping ventilation and recording time, namely calculating the penetrating sulfur capacity of the solution. The calculation formula is as follows:s in L Represents the liquid sulfur capacity (g/L) of the solution, P represents the pressure of hydrogen sulfide gas (100 kPa), Q H2S The flow rate (mL/min) of hydrogen sulfide gas, t the desulfurization reaction time (min), and R the gas state constant (8.314 Pa.m) 3 /(mol.K); t represents the reaction temperature (315K) and V is the liquid volume (L).
On the basis, the solution to be treated in examples 7 to 9 is added into a U-shaped bubbling pipe filled with 0.2g of the hydrogen sulfide removing agent prepared in example 1, the reaction is carried out at 40 ℃ under normal pressure (the reaction amount of the solution to be treated is excessive compared with the hydrogen sulfide removing agent), the timing is started, meanwhile, oxygen is introduced to regenerate the desulfurated hydrogen sulfide removing agent, wherein the flow rate of the oxygen is 200mL/min, the oxidation-reduction potential (ORP) is continuously monitored on the upper liquid, the hydrogen sulfide removal is completed after the oxidation-reduction potential is stabilized, the reaction time is recorded, and the longer the reaction time is, the better the desulfurated hydrogen sulfide effect is indicated. The detection and calculation results are shown in table 2.
Whether sulfur powder was precipitated in the absorption column was observed, and the results are shown in table 2.
TABLE 2
As can be seen from comparison of examples 2 and 3 with examples 7 to 9, in examples 7 and 8, sulfur powder was not generated in the absorption column, and thus the absorption column was not plugged; in contrast, in comparative examples 3 and 4, since sulfur powder was generated in the absorption column, the absorption column was clogged.
Meanwhile, as can be seen from Table 2, examples 7 to 9 use the hydrogen sulfide removing agents of examples 1 to 3, which have a longer hydrogen sulfide removing time than comparative example 4, thus demonstrating high hydrogen sulfide removing efficiency.
It can also be seen from Table 2 that in examples 7-9 the absorber column used sodium hydroxide solution, the breakthrough sulfur capacity in the solution was higher than in comparative examples 2 and 3 for the conventional iron-containing hydrogen sulfide removal agent.
As can be seen from Table 2, the hydrogen sulfide removal time in the regeneration towers in examples 7 to 9 is not more than 1h, and is relatively stable, which indicates that the hydrogen sulfide removal agent of the present invention has high and stable hydrogen sulfide removal efficiency.
It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments of the present invention without departing from the spirit and scope of the invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111361477.9A CN113856451B (en) | 2021-11-17 | 2021-11-17 | Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111361477.9A CN113856451B (en) | 2021-11-17 | 2021-11-17 | Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113856451A CN113856451A (en) | 2021-12-31 |
| CN113856451B true CN113856451B (en) | 2023-07-25 |
Family
ID=78984768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111361477.9A Active CN113856451B (en) | 2021-11-17 | 2021-11-17 | Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113856451B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09221654A (en) * | 1996-02-14 | 1997-08-26 | Mitsubishi Chem Corp | Chelating agent |
| JP2002515922A (en) * | 1995-08-30 | 2002-05-28 | ザ ダウ ケミカル カンパニー | Polyaminomonosuccinic acid derivative-degradable chelating agent, its use and composition thereof |
| CN107088349A (en) * | 2017-06-28 | 2017-08-25 | 重庆科技学院 | One kind compounding ion liquid reclaiming agent and preparation method |
| EP3581257A1 (en) * | 2018-06-11 | 2019-12-18 | HeidelbergCement AG | Method using recycled concrete fines for co2/sox removal from exhaust gas |
| CN112456944A (en) * | 2020-11-30 | 2021-03-09 | 山西大学 | Amino modified SiO2Thermal insulation building material prepared by aerogel synergistic solid waste carbonization and method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT411227B (en) * | 2002-02-15 | 2003-11-25 | Lindner Wolfgang | ENANTIOSELECTIVE CATION EXCHANGE MATERIALS |
| JP2004261670A (en) * | 2003-02-28 | 2004-09-24 | Research Institute Of Innovative Technology For The Earth | Method for treating exhaust gas |
| CN112619609B (en) * | 2020-11-26 | 2022-12-09 | 上海绿强新材料有限公司 | Adsorbent for synergistically removing sulfur and mercury and preparation method and application thereof |
-
2021
- 2021-11-17 CN CN202111361477.9A patent/CN113856451B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002515922A (en) * | 1995-08-30 | 2002-05-28 | ザ ダウ ケミカル カンパニー | Polyaminomonosuccinic acid derivative-degradable chelating agent, its use and composition thereof |
| JPH09221654A (en) * | 1996-02-14 | 1997-08-26 | Mitsubishi Chem Corp | Chelating agent |
| CN107088349A (en) * | 2017-06-28 | 2017-08-25 | 重庆科技学院 | One kind compounding ion liquid reclaiming agent and preparation method |
| EP3581257A1 (en) * | 2018-06-11 | 2019-12-18 | HeidelbergCement AG | Method using recycled concrete fines for co2/sox removal from exhaust gas |
| CN112456944A (en) * | 2020-11-30 | 2021-03-09 | 山西大学 | Amino modified SiO2Thermal insulation building material prepared by aerogel synergistic solid waste carbonization and method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113856451A (en) | 2021-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104226095B (en) | Based on the synchronous denitrating technique of flue gas wet ammonia process desulfurizing | |
| EP2383030A1 (en) | Method for removing h2s from gaseous stream at normal temperature | |
| CN103111177B (en) | Method and device for removing hydrogen sulfide in gas phase through oxidation | |
| CN103599682B (en) | Method and the special equipment thereof of hydrogen sulfide are removed in a kind of hypergravity liquid phase oxidation reduction | |
| CN105032389B (en) | Mn Ce bimetal-doped activated carbon base desulphurization catalysts and preparation method thereof | |
| CN109499334B (en) | Efficient trapping and separating H2S and CO2And resource utilization method | |
| CN107812450A (en) | A kind of method of alkaline nonaqueous phase wet method catalysis oxidation hydrogen sulfide | |
| CN100469420C (en) | Method for cleansing exhaust gas of sulfureted hydrogen in low concentration | |
| CN101318099B (en) | Process for removing organic sulfur in low-temperature condition | |
| CN102658002A (en) | Method for absorbing and purifying hydrogen sulfide with EDTA (ethylene diamine tetraacetic acid) chelated iron copper compound system | |
| CN113856451B (en) | Hydrogen sulfide removing agent, preparation method thereof and hydrogen sulfide removing method | |
| CN111905549A (en) | Absorb H2S desulfurization solution, desulfurization system and desulfurization method | |
| CN105498491B (en) | It is heat-treated reaction end gas cleaning and recovering process and system | |
| CN114029040B (en) | Iron disulfide resin composite material and preparation method and application thereof | |
| CN109550367A (en) | A kind of ionic liquid desulphurization system and method | |
| CN116020434A (en) | Sulfur accumulation-free and deactivation-resistant carbonyl sulfide hydrolysis catalyst and application thereof | |
| CN114053859B (en) | Hydrogen sulfide remover and preparation method thereof | |
| CN109381985A (en) | A kind of purifying treatment method of natural gas | |
| CN105642096B (en) | The method and device of ionic liquid at room temperature, removing sulfur dioxide in tail gas and carbon dioxide | |
| CN109908706B (en) | Ionic liquid microcapsule, preparation method thereof and application thereof in removing low-concentration gas | |
| CN110510631B (en) | Application of modified NaY type molecular sieve in desulfurization process of regenerated rubber | |
| CN105107380A (en) | Super-gravity oxygen-enriched oxidation regeneration method by wet oxidation desulfurization process and special equipment | |
| CN109534297B (en) | Method for desulfurizing hydrogen sulfide and sulfur dioxide through reaction | |
| CN106744714A (en) | A kind of technique that sulfur dioxide Sulphuric acid is reclaimed from flue gas | |
| CN204952672U (en) | Super dead -weight loading oxidization regeneration equipment of wet -type oxidative desulfurization technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |