CN116059812A - Synthesis method of complex iron ion desulfurizing agent - Google Patents
Synthesis method of complex iron ion desulfurizing agent Download PDFInfo
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- CN116059812A CN116059812A CN202211567277.3A CN202211567277A CN116059812A CN 116059812 A CN116059812 A CN 116059812A CN 202211567277 A CN202211567277 A CN 202211567277A CN 116059812 A CN116059812 A CN 116059812A
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- 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
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- 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
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- 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
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Abstract
The invention belongs to the technical field of hydrogen sulfide-containing gas purification, and in particular relates to a synthesis method of a complex iron ion desulfurizer, which comprises the steps of mixing nitrilotriacetic acid and ethylenediamine tetraacetic acid according to a molar ratio of 1:1-1:2, mixing ferric oxide and the mixture according to a molar ratio of 1:1-1:2, adding water as a solvent, heating the mixed solution to 95-100 ℃, gradually adding an accelerator into the mixed solution, stirring the solution, and ending the reaction after all solids in the solution are dissolved.
Description
Technical Field
The invention belongs to the technical field of hydrogen sulfide-containing gas purification, and particularly relates to a synthesis method of a complex iron ion desulfurizing agent.
Background
The wet oxidation-reduction complex iron desulfurization technology adopts ferric ions to directly convert hydrogen sulfide in natural gas into elemental sulfur, the ferric ions are reduced into ferrous ions, the ferrous ions can be regenerated by adopting air, and the ferric ions are oxidized into the ferric ions by oxygen in the air, so that the wet oxidation-reduction complex iron desulfurization technology is a novel environment-friendly and nontoxic desulfurization technology with simple process and high working sulfur capacity, and overcomes the defects of low sulfur capacity, complex desulfurization process, high byproduct salt generation rate, serious environmental pollution and the like in the traditional desulfurization technology. At present, the conventional iron ion desulfurizing agent is prepared by compounding a chelating agent with ferric chloride or ferric ammonium sulfate, and the iron ions synthesized by the method have weak chelating force, are easy to wear and have low effective content, so that the sulfur capacity is lower.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the complex iron ion desulfurizing agent with good stability and high content.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a method for synthesizing a complex iron ion desulfurizing agent comprises the following steps: mixing nitrilotriacetic acid and ethylenediamine tetraacetic acid according to a molar ratio of 1:1-1:2, and mixing ferric oxide and the mixture according to a molar ratio of 1:1-1: 2 mixing, adding water as solvent, heating the mixed solution to 95-100 ℃, gradually adding accelerator into the mixed solution, stirring the solution, and after all solids in the solution are dissolved, finishing the reaction to form the complex iron ion desulfurizing agent.
In the above scheme, the ferric oxide is Fe 2 O 3 ·H 2 O or Fe 2 O 3 。
In the scheme, the accelerator comprises a mixture of sodium carbonate and ammonia water, wherein the molar ratio of the sodium carbonate to the ammonia water is 1:2, and the stirring speed is 60-120 revolutions per minute.
The beneficial effects of the invention are as follows:
the conventional complex iron ion desulfurizing agent is compounded with ferric chloride or ferric ammonium sulfate by utilizing a chelating agent, and the produced chelate iron can not completely form a stable chelate covalent bond structure with iron, so that iron ions are easy to form a complex bond with OH in an alkaline solution - Or CO 3 2- And reacting to generate ferric hydroxide or ferric carbonate precipitate, thereby causing the loss of iron ions. Aiming at the problems, the invention adopts a method of synthesizing ferric oxide, nitrilotriacetic acid and ethylenediamine tetraacetic acid by chemical reaction to generate nitrilotriacetic acid and ethylenediamine tetraacetic acid, the chelated iron ions are of a space three-dimensional structure, and can lead the iron ions to exist in an ion form in an alkaline solution stably through a three-dimensional covalent bond, thereby avoiding generating ferric hydroxide or carbonic acidIron precipitation greatly reduces iron ion loss, so that the desulfurizing agent has higher content, larger sulfur capacity and higher desulfurizing efficiency.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrated, but are not limited to the following examples.
EXAMPLE 1 preparation of conventional desulfurizing agent
The ferric ammonium sulfate and the ethylenediamine tetraacetic acid are prepared into aqueous solutions, and the concentrations are prepared as shown in the table below. The concentration of iron ions in the desulfurizing agent is 10g/L, naOH is added to adjust the pH value of the solution to 8-9, and the preparation mode is shown in the table below.
The composition of the desulfurizing agent is shown in the following table:
| component (A) | Dosage of |
| Ammonium iron sulfate | 47.5g |
| Water and its preparation method | 900g |
| Ethylenediamine tetraacetic acid | 100g |
| NaOH | 5g |
A nitrogen mixture containing 1000ppm of hydrogen sulfide was introduced into the above desulfurizing agent solution, and after the outlet hydrogen sulfide content exceeded 10pppm and the aeration was stopped, and then air (1L/min) was introduced into the solution for 30 minutes, the above steps were repeated for a total of 3 cycles, and the iron ion concentration was detected as follows to be 7.5g/L, and the iron ion loss ratio was (10-7.5)/10X 100% = 25%.
EXAMPLE 2 preparation of the desulfurizing agent of the present invention
Mixing ferric oxide, nitrilotriacetic acid and ethylenediamine tetraacetic acid, adding water, heating to 95 ℃, stirring at a rotation speed of 60 r/min, and adding sodium carbonate and ammonia water (molar ratio of 1:2) accelerators at a constant speed within 2 hours to produce the complex iron ion desulfurizing agent. The concentrations were formulated as shown in the following table. The concentration of iron ions in the desulfurizing agent is 10g/L, naOH is added to adjust the pH value of the solution to 8-9, and the preparation mode is shown in the table below.
The composition of the desulfurizing agent is shown in the following table:
| component (A) | Dosage of |
| Iron oxide | 14.29g |
| Nitrilotriacetic acid | 17.05g |
| Ethylenediamine tetraacetic acid | 26.07g |
| Sodium carbonate and ammonia water mixture (molar ratio 1:2) | 45g |
| Water and its preparation method | 945g |
| NaOH | 5g |
A nitrogen mixture containing 1000ppm of hydrogen sulfide was introduced into the above desulfurizing agent solution, and after the outlet hydrogen sulfide content exceeded 10pppm and the aeration was stopped, and then air (1L/min) was introduced into the solution for 30 minutes, the above steps were repeated for a total of 3 cycles, and the iron ion concentration was detected as follows to be 9.95g/L, and the iron ion loss ratio was (10-9.95)/10X100% = 0.5%.
EXAMPLE 3 preparation of the desulfurizing agent of the present invention
Mixing ferric oxide, nitrilotriacetic acid and ethylenediamine tetraacetic acid, adding water, heating to 98 ℃, stirring at a speed of 100 rpm, and adding sodium carbonate and ammonia water (molar ratio of 1:2) accelerators at a constant speed within 2.5 hours to produce the complex iron ion desulfurizing agent. The concentrations were formulated as shown in the following table. The concentration of iron ions in the desulfurizing agent is 10g/L, naOH is added to adjust the pH value of the solution to 8-9, and the preparation mode is shown in the table below.
The composition of the desulfurizing agent is shown in the following table:
a nitrogen mixture containing 1000ppm of hydrogen sulfide was introduced into the above desulfurizing agent solution, and after the outlet hydrogen sulfide content exceeded 10pppm and the aeration was stopped, and then air (1L/min) was introduced into the solution for 30 minutes, the above steps were repeated for a total of 3 cycles, and the iron ion concentration was detected as follows to be 9.93g/L, and the iron ion loss ratio was (10-9.93)/10X100% = 0.7%.
EXAMPLE 4 preparation of the desulfurizing agent of the present invention
Examples of complex iron ions according to the invention. Mixing ferric oxide, nitrilotriacetic acid and ethylenediamine tetraacetic acid, adding water, heating to 100 ℃, stirring at 120 r/min, and adding sodium carbonate and ammonia water (molar ratio 1:2) accelerators at uniform speed within 3 hours to produce the complex iron ion desulfurizing agent. The concentrations were formulated as shown in the following table. The concentration of iron ions in the desulfurizing agent is 10g/L, naOH is added to adjust the pH value of the solution to 8-9, and the preparation mode is shown in the table below.
The composition of the desulfurizing agent is shown in the following table:
| component (A) | Dosage of |
| Iron oxide | 14.29g |
| Nitrilotriacetic acid | 8.52g |
| Ethylenediamine tetraacetic acid | 13.03g |
| Sodium carbonate and ammonia water mixture (molar ratio 1:2) | 45g |
| Water and its preparation method | 966g |
| NaOH | 5g |
A nitrogen mixture containing 1000ppm of hydrogen sulfide was introduced into the above desulfurizing agent solution, and after the outlet hydrogen sulfide content exceeded 10pppm and the aeration was stopped, and then air (1L/min) was introduced into the solution for 30 minutes, the above steps were repeated for a total of 3 cycles, and the iron ion concentration was detected as follows to be 9.91g/L, and the iron ion loss ratio was (10-9.93)/10X100% = 0.9%.
Through the above examples, the loss of the complex iron ion desulfurizer of the invention is greatly reduced compared with that of the traditional iron ion desulfurizer, thereby reducing production consumption and improving product quality.
Claims (3)
1. The synthesis method of the complex iron ion desulfurizing agent is characterized by comprising the following steps of: mixing nitrilotriacetic acid and ethylenediamine tetraacetic acid according to a molar ratio of 1:1-1:2, and mixing ferric oxide and the mixture according to a molar ratio of 1:1-1: 2 mixing, adding water as solvent, heating the mixed solution to 95-100 ℃, gradually adding accelerator into the mixed solution, stirring the solution, and finishing the reaction after all solids in the solution are dissolved.
2. The method according to claim 1, wherein the iron oxide is Fe 2 O 3 ·H 2 O or Fe 2 O 3 。
3. The method of claim 1, wherein the accelerator comprises a mixture of sodium carbonate and aqueous ammonia, the molar ratio of sodium carbonate to aqueous ammonia is 1:2, and the stirring rate is 60-120 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211567277.3A CN116059812A (en) | 2022-12-07 | 2022-12-07 | Synthesis method of complex iron ion desulfurizing agent |
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| CN202211567277.3A CN116059812A (en) | 2022-12-07 | 2022-12-07 | Synthesis method of complex iron ion desulfurizing agent |
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| CN116059812A true CN116059812A (en) | 2023-05-05 |
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| CN202211567277.3A Pending CN116059812A (en) | 2022-12-07 | 2022-12-07 | Synthesis method of complex iron ion desulfurizing agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116422382A (en) * | 2023-06-13 | 2023-07-14 | 山东秋水化学科技有限公司 | Wet desulfurization complex iron catalyst and preparation method thereof |
| CN117654640A (en) * | 2024-02-01 | 2024-03-08 | 成都华阳兴华化工有限公司 | Iron ion catalytic desulfurizing agent and preparation method and application thereof |
-
2022
- 2022-12-07 CN CN202211567277.3A patent/CN116059812A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116422382A (en) * | 2023-06-13 | 2023-07-14 | 山东秋水化学科技有限公司 | Wet desulfurization complex iron catalyst and preparation method thereof |
| CN117654640A (en) * | 2024-02-01 | 2024-03-08 | 成都华阳兴华化工有限公司 | Iron ion catalytic desulfurizing agent and preparation method and application thereof |
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