CN117654640A - Iron ion catalytic desulfurizing agent and preparation method and application thereof - Google Patents
Iron ion catalytic desulfurizing agent and preparation method and application thereof Download PDFInfo
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- CN117654640A CN117654640A CN202410139483.7A CN202410139483A CN117654640A CN 117654640 A CN117654640 A CN 117654640A CN 202410139483 A CN202410139483 A CN 202410139483A CN 117654640 A CN117654640 A CN 117654640A
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- iron
- iron ion
- desulfurizing agent
- complex
- stabilizer
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 746
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 570
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 247
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 245
- 230000003009 desulfurizing effect Effects 0.000 title claims abstract description 184
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- -1 iron ion Chemical class 0.000 claims abstract description 401
- 239000003381 stabilizer Substances 0.000 claims abstract description 145
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 96
- 230000023556 desulfurization Effects 0.000 claims abstract description 96
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 74
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002738 chelating agent Substances 0.000 claims abstract description 37
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 36
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000003345 natural gas Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 57
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 30
- 150000007529 inorganic bases Chemical class 0.000 claims description 29
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 22
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 20
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 20
- 239000011736 potassium bicarbonate Substances 0.000 claims description 20
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 20
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 20
- 235000011181 potassium carbonates Nutrition 0.000 claims description 20
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 20
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 20
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 20
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 19
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 19
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 19
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 19
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 19
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 19
- 229960002413 ferric citrate Drugs 0.000 claims description 16
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- 230000008929 regeneration Effects 0.000 claims description 12
- 238000011069 regeneration method Methods 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 11
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000012670 alkaline solution Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 30
- 239000007789 gas Substances 0.000 description 13
- 230000001590 oxidative effect Effects 0.000 description 12
- PMODATROEZUNCM-UHFFFAOYSA-N CN(CCO)CCO.[N] Chemical compound CN(CCO)CCO.[N] PMODATROEZUNCM-UHFFFAOYSA-N 0.000 description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 230000001172 regenerating effect Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- JTPLPDIKCDKODU-UHFFFAOYSA-N acetic acid;2-(2-aminoethylamino)ethanol Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.NCCNCCO JTPLPDIKCDKODU-UHFFFAOYSA-N 0.000 description 9
- 239000001476 sodium potassium tartrate Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 description 5
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 5
- 229940043237 diethanolamine Drugs 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 238000007429 general method Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 3
- 229960004887 ferric hydroxide Drugs 0.000 description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
-
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to the technical field of hydrogen sulfide removal of natural gas, and particularly discloses an iron ion catalytic desulfurizing agent and a preparation method and application thereof. The iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water; the concentration of the iron ions in the catalytic desulfurizing agent is 1000 mg/L-20000 mg/L; the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is 5% -20%; the complex iron stabilizer consists of the following raw materials in percentage by mass: 5-15% of low carbon alcohol amine, 5-20% of carboxylic acid chelating agent, 1-5% of inorganic alkali, 3-8% of antioxidant and 52-86% of water. The invention can improve the stability of iron ions in alkaline solution and reduce the loss of iron ions, thereby reducing the treatment cost of complex desulfurization, reducing the impurity concentration of iron ions in byproduct sulfur paste and improving the running stability, reliability and desulfurization efficiency of desulfurization process.
Description
Technical Field
The invention relates to the technical field of natural gas hydrogen sulfide removal, in particular to an iron ion catalytic desulfurizing agent, and a preparation method and application of the iron ion catalytic desulfurizing agent.
Background
Natural gas produced from gas wells contains hydrogen sulfide components. The hydrogen sulfide in the natural gas can cause corrosion of equipment and pipelines, pollute the environment and have harm to human health, thereby affecting the gathering, the processing and the use of the natural gas, and in order to solve the technical problems, the natural gas needs to be subjected to desulfurization treatment.
Complex iron desulfurization is a common method for natural gas desulfurization, and iron ions in the complex iron desulfurizing agent are used as an oxidant to adsorb and remove hydrogen sulfide in natural gas. The iron ions can directly oxidize hydrogen sulfide in the natural gas into elemental sulfur, and then the iron ions in the complex iron desulfurizing agent are oxidized through air to restore the oxidizing capacity of the complex iron desulfurizing agent for recycling.
In order to improve the absorption effect of the complex iron desulfurizing agent, the pH value of the complex iron desulfurizing agent is alkaline. However, iron ions tend to form iron sulfide and iron hydroxide precipitates in alkaline solutions. The stable performance of the iron ions is characterized by the cycle times and the iron ion loss rate of the complex iron desulfurizing agent in the industry, and the iron ion content of the common complex iron desulfurizing agent is lower and is generally less than 0.5g/L, and the 10-cycle loss rate of the iron ions is about 20%; as the concentration of iron ions increases, the stability of iron ions in alkaline solutions decreases more significantly. Therefore, a large amount of supplementary iron ions are required in the existing complex iron desulfurizing agent to maintain the concentration of iron ions in the desulfurizing agent, which tends to affect the stability of the desulfurizing process and increase the desulfurizing cost.
Disclosure of Invention
The technical purpose of the invention is that: aiming at the particularity of the natural gas complex desulfurization and the defects of the prior art, an iron ion catalytic desulfurization agent capable of effectively reducing the loss of iron ions in alkaline solution is provided, and a preparation method and application of the iron ion catalytic desulfurization agent.
The technical aim of the invention is achieved by the following technical scheme that the iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
the concentration of the iron ions in the catalytic desulfurizing agent is 1000 mg/L-20000 mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is 5% -20%;
the complex iron stabilizer consists of the following raw materials in percentage by mass:
5-15% of low-carbon alcohol amine,
5 to 20 percent of carboxylic acid chelating agent,
1 to 5 percent of inorganic alkali,
3-8% of antioxidant,
52-86% of water.
Preferably, the complex iron stabilizer consists of the following raw materials in percentage by mass:
10-15% of low-carbon alcohol amine,
15-20% of carboxylic acid chelating agent,
3 to 5 percent of inorganic alkali,
3-8% of antioxidant,
52-69% of water.
The low-carbon alcohol amine is at least one of azomethyl diethanolamine and 2-amino-2-methyl-1-propanol.
The carboxylic acid chelating agent is at least one of nitrilotriacetic acid, hydroxyethylidene diphosphonic acid and potassium sodium tartrate.
The inorganic base is at least one of potassium carbonate and potassium bicarbonate.
The antioxidant is at least one of sodium thiosulfate and potassium thiosulfate.
The iron ion is at least one of ferric citrate and hydroxyethyl ethylenediamine triacetic acid.
The water is industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.5-9.5, thereby obtaining the complex iron stabilizer;
And step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The application of the iron ion catalytic desulfurizing agent is that the iron ion catalytic desulfurizing agent is used as a complex iron desulfurizing process of natural gas;
the application method comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into a reactor for absorption reaction;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
The beneficial technical effects of the invention are as follows: aiming at the technical characteristics of poor iron ion stability in common complex iron desulfurizing agents, the complex iron stabilizer is developed, the stability of iron ions in alkaline solution can be improved by adding the complex iron stabilizer in the complex iron desulfurizing agents, the loss of the iron ions is reduced, namely, the chelating capacity of the iron ions is synergistically improved through the complex iron stabilizer, the iron ion loss is reduced, and the generation of iron ion precipitation is reduced and even prevented, so that the processing cost of complex desulfurization is reduced, the impurity concentration of the iron ions in byproduct sulfur paste is reduced, and the running stability, reliability and desulfurization efficiency of a desulfurization process are improved.
Specifically, the low-carbon alcohol amine in the complex iron stabilizer is an organic solvent capable of improving the solubility of iron ions, has certain chelating capacity, can prevent iron ions from reacting with sulfur ions to produce ferrous sulfide, and can soften and stabilize calcium-magnesium-containing water. The carboxylic acid chelating agent in the complex iron stabilizer has strong chelating ability, can form a plurality of coordinate covalent bonds with iron ions, and prevents the iron ions from being combined with hydroxide by adopting a covalent bond stable structure of a multi-ring, thereby preventing the generation of ferric hydroxide precipitation, and even under the condition that the pH value of a solution is 13, the ferric hydroxide precipitation can not occur. The antioxidant in the complex iron stabilizer has reducibility, can be combined with hydroxyl radicals, and avoids the excessive hydroxyl radicals from decomposing the complex iron stabilizer, thereby avoiding the loss of iron ions caused by the consumption of the complex iron stabilizer. Therefore, the complex iron stabilizer can effectively reduce, even prevent the generation of iron sulfide and iron hydroxide precipitation, effectively reduce the loss of iron ions, reduce the iron ion consumption cost, reduce the production cost and increase the operation stability and reliability.
The iron ion catalytic desulfurizing agent containing the complex iron stabilizer has stable iron ion performance, high iron ion content and high hydrogen sulfide purification degree, and under the action of the complex iron stabilizer, the iron ions do not produce ferric sulfide and ferric hydroxide precipitation, the medicament is stable, the byproduct sulfur paste iron impurities are low, and the operation cost is low. Experiments show that the highest concentration of iron ions in the iron ion catalytic desulfurizing agent provided by the application can reach 20000mg/L, natural gas is desulfurized by using the iron ion catalytic desulfurizing agent, the 10-time cycle loss rate of iron ions is less than 1.0%, and the concentration of hydrogen sulfide in purified gas is less than 4mg/Nm 3 Meets the technical requirements of treatment indexes.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to examples by different types of research analyses.
1. When the complex iron stabilizer is not added in the iron ion catalytic desulfurization agent (namely, the proportion of the complex iron stabilizer to the iron ion catalytic desulfurization agent is 0%), the performance of the iron ion catalytic desulfurization agent is studied.
Preparation of iron ion catalytic desulfurization agent: the iron ion catalytic desulfurizing agent is prepared by adopting ferric citrate, hydroxyethyl ethylenediamine ferric acetate and water.
The preparation method comprises the following steps: according to the proportion in Table 1, ferric citrate and hydroxyethyl ethylenediamine ferric acetate are dissolved in water to prepare 9 iron ion solutions with different proportions, and industrial desalted water is used for fixing the volume to 1L.
Table 1 iron ion catalytic desulfurization components without Complex iron stabilizer and amounts thereof
Will H 2 S and nitrogen gas mixture (H 2 The molar fraction of S is 4 percent) is respectively introduced into the iron ion catalytic desulfurizing agent 1-1 (namely the mixture ratio 1-1) to the iron ion catalytic desulfurizing agent 9-1 (namely the mixture ratio 9-1) to absorb hydrogen sulfide. The flow is 1L/min, and the concentration of the directly-discharged hydrogen sulfide is more than or equal to 6mg/m 3 And stopping, then blowing air according to the flow of 5L/min, wherein the air is blown for 60min, repeating the above operation for 10 times, and then testing the concentration of the iron ions in the solution (a general method 1, 10-phenanthroline spectrophotometry for measuring the iron content of a chemical product for GB/T3049-2006 industrial use), so as to obtain the concentration of the iron ions and the loss rate, wherein the concentration and the loss rate are shown in a table 2.
TABLE 2 concentration of iron ions and loss ratio of iron ion catalyst desulfurizing agents 1-1 to 9-1 after absorbing Hydrogen sulfide
The iron ion catalytic desulfurizing agents 1-1 to 9-1 show that the iron ion loss rate in the iron ion catalytic desulfurizing agents is large and ranges from 21.5% to 23.83% under the condition that the complex iron stabilizer is not added.
2. And adding a complex iron stabilizer into the iron ion catalytic desulfurization agent, and researching the stabilizing effect of the complex iron stabilizer on the iron ion catalytic desulfurization agents with different concentrations.
The complex iron stabilizer is prepared from azomethyl diethanolamine, 2-amino-2-methyl-1-propanol, nitrilotriacetic acid, hydroxyethylidene diphosphonic acid, potassium sodium tartrate, potassium thiosulfate, sodium thiosulfate, potassium carbonate and potassium bicarbonate, and industrial desalted water, and the specific formula is shown in table 3.
The preparation method of the complex iron stabilizer comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine (azomethine diethanolamine, 2-amino-2-methyl-1-propanol) and water according to the formula amount;
sequentially adding carboxylic chelating agent (nitrilotriacetic acid, hydroxyethylidene diphosphonic acid, potassium sodium tartrate) and antioxidant (potassium thiosulfate, sodium thiosulfate) into the mixed solution in the step (1), and uniformly mixing;
And (3) adding the inorganic base (potassium carbonate and potassium bicarbonate) with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 9.5, thereby obtaining the complex iron stabilizer.
TABLE 3 composition and amounts of Complex iron stabilizers
The complex iron stabilizer prepared in table 3 was added on the basis of the iron ion catalytic desulfurization agent shown in table 1 to obtain an iron ion catalytic desulfurization agent containing the complex iron stabilizer, as shown in table 4.
The preparation method of the iron ion catalytic desulfurizing agent containing the complex iron stabilizer comprises the following steps: the formula amount of iron ions, the complex iron stabilizer and the industrial desalted water are uniformly mixed to obtain the iron ion catalytic desulfurizing agent containing the complex iron stabilizer (the volume is fixed to 1L by the industrial desalted water).
Table 4 contains the components and amounts of the iron ion catalyst desulfurization agent containing the complex iron stabilizer shown in Table 3
Will H 2 S and nitrogen gas mixture (H 2 The mole fraction of S is 4 percent) is respectively introduced into the iron ion catalytic desulfurizing agent 1-2 (namely the mixture ratio 1-2) to the iron ion catalytic desulfurizing agent 9-2 (namely the mixture ratio 9-2) to absorb hydrogen sulfide. The flow is 1L/min, and the concentration of the directly-discharged hydrogen sulfide is more than or equal to 6mg/m 3 Stopping, and then blowing air at a flow rate of 5L/min for 60min The above operation is repeated 10 times, and then the concentration of iron ions in the solution is tested (general method 1, 10-phenanthroline spectrophotometry for measuring the iron content of industrial chemical products of GB/T3049-2006), so that the concentration of iron ions and the loss rate are shown in Table 5.
TABLE 5 concentration of iron ions and loss ratio of iron ion catalyst desulfurizing agent 1-2 to iron ion catalyst desulfurizing agent 9-2 after absorbing Hydrogen sulfide
The iron ion catalytic desulfurizing agents 1-2 to 9-2 show that the complex iron stabilizer has remarkable effect on stabilizing iron ions, and the loss rate of the iron ions in the iron ion catalytic desulfurizing agents with the concentration ranging from 1000mg/L to 20000mg/L can be reduced to below 1% through the complex iron stabilization. In addition, the stabilizing effect of the complex iron stabilizer on low-concentration iron ions is slightly better than that of high-concentration iron ions.
3. Research on influence of different concentrations of complex iron stabilizer on performance of iron ion catalytic desulfurization agent
The complex iron stabilizer is prepared from azomethyl diethanolamine, 2-amino-2-methyl-1-propanol, nitrilotriacetic acid, hydroxyethylidene diphosphonic acid, potassium sodium tartrate, potassium thiosulfate, sodium thiosulfate, potassium carbonate and potassium bicarbonate, and industrial desalted water, and the specific formula is shown in Table 6.
The preparation method of the complex iron stabilizer comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine (nitrogen methyl diethanolamine, 2-amino-2-methyl-1-propanol) and industrial desalted water according to the formula amount;
sequentially adding carboxylic chelating agent (nitrilotriacetic acid, hydroxyethylidene diphosphonic acid, potassium sodium tartrate) and antioxidant (potassium thiosulfate, sodium thiosulfate) into the mixed solution in the step (1), and uniformly mixing;
and (3) adding the inorganic base (potassium carbonate and potassium bicarbonate) with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 9.5, thereby obtaining the complex iron stabilizer.
TABLE 6 composition and amounts of Complex iron stabilizers
The complex iron stabilizer prepared in table 6 was added to the following table 7 to obtain the corresponding iron ion catalyst desulfurizing agent containing the complex iron stabilizer.
The preparation method of the iron ion catalytic desulfurizing agent containing the complex iron stabilizer comprises the following steps: the formula amount of iron ions (ferric citrate, hydroxyethyl ethylenediamine ferric acetate), the complex iron stabilizer and the industrial desalted water are uniformly mixed to obtain the iron ion catalytic desulfurizing agent containing the complex iron stabilizer (the industrial desalted water is used for fixing the volume to 1L, and the concentration of the iron ions is 12000 mg/L).
Table 7 contains the components and amounts of the iron ion catalyst desulfurization agent containing the complex iron stabilizer shown in Table 6
Will H 2 S and nitrogen gas mixture (H 2 The molar fraction of S is 4 percent) is respectively introduced into the iron ion catalytic desulfurizing agent 10 (namely the mixture ratio 10) to the iron ion catalytic desulfurizing agent 12 (namely the mixture ratio 12) to absorb hydrogen sulfide. The flow is 1L/min, and the concentration of the directly-discharged hydrogen sulfide is more than or equal to 6mg/m 3 And stopping, then blowing air according to the flow of 5L/min, wherein the air is blown for 60min, repeating the above operation for 10 times, and then testing the concentration of the iron ions in the solution (a general method 1, 10-phenanthroline spectrophotometry for measuring the iron content of chemical products for GB/T3049-2006 industrial use), so as to obtain the concentration of the iron ions and the loss rate, which are shown in Table 8.
Table 8 concentration of iron ions and loss ratio of iron ion catalyst desulfurizing agent 10 to iron ion catalyst desulfurizing agent 12 after absorbing hydrogen sulfide
| Proportion 10 | Proportion 11 | Proportion 12 | |
| Iron ion concentration mg/l | 11889 | 11943 | 11945 |
| Iron ion loss rate | 0.93% | 0.48% | 0.46% |
The above iron ion catalytic desulfurization agents 10 to 12 show that as the concentration of the complex iron stabilizer in the iron ion catalytic desulfurization agent is higher, the loss rate of iron ions is lower, and when the addition amount of the complex iron stabilizer is in the range of 5% -20%, the loss rate of iron ions is less than 1%.
4. In the complex iron stabilizer, the influence of the change of the ratio of the low-carbon alcohol amine, the carboxylic acid chelating agent, the inorganic base and the antioxidant on the performance of the iron ion catalytic desulfurizing agent is studied.
The complex iron stabilizer is prepared from azomethyl diethanolamine, 2-amino-2-methyl-1-propanol, nitrilotriacetic acid, hydroxyethylidene diphosphonic acid, potassium sodium tartrate, potassium thiosulfate, sodium thiosulfate, potassium carbonate and potassium bicarbonate, and industrial desalted water, and the specific formula is shown in Table 9.
The preparation method of the complex iron stabilizer comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine (nitrogen methyl diethanolamine, 2-amino-2-methyl-1-propanol) and industrial desalted water according to the formula amount;
sequentially adding carboxylic chelating agent (nitrilotriacetic acid, hydroxyethylidene diphosphonic acid, potassium sodium tartrate) and antioxidant (potassium thiosulfate, sodium thiosulfate) into the mixed solution in the step (1), and uniformly mixing;
and (3) adding the inorganic base (potassium carbonate and potassium bicarbonate) with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 9.5, thereby obtaining the complex iron stabilizer.
Table 9 composition ratios of nine Complex iron stabilizers
The complex iron stabilizer prepared in table 9 was added to the following table 10 to obtain the corresponding iron ion catalyst desulfurizing agent containing the complex iron stabilizer.
The preparation method of the iron ion catalytic desulfurizing agent containing the complex iron stabilizer comprises the following steps: the formula amount of iron ions (ferric citrate, hydroxyethyl ethylenediamine ferric acetate), the complex iron stabilizer and the industrial desalted water are uniformly mixed to obtain the iron ion catalytic desulfurizing agent containing the complex iron stabilizer (the industrial desalted water is used for fixing the volume to 1L, and the concentration of the iron ions is 12000 mg/L).
Table 10 contains the iron ion catalytic desulfurization components and amounts of the complex iron stabilizers shown in Table 9
Will H 2 S and nitrogen gas mixture (H 2 The molar fraction of S is 4 percent) is respectively introduced into the iron ion catalytic desulfurizing agent 13-2 (namely the proportion 13-2) to the iron ion catalytic desulfurizing agent 21-2 (namely the proportion 21-2) to absorb hydrogen sulfide. The flow is 1L/min, and the concentration of the directly-discharged hydrogen sulfide is more than or equal to 6mg/m 3 Stop, followed by a flow of 5L/minAir is blown in, the air is blown in for 60min, the operation is repeated for 10 times, then the concentration of the iron ions in the solution is tested (the general method for measuring the iron content of chemical products in GB/T3049-2006 industry, namely 1, 10-phenanthroline spectrophotometry), and the concentration of the iron ions and the loss rate are obtained as shown in a table 11.
TABLE 11 concentration of iron ions and loss ratio of iron ion catalyst desulfurizing agent 13-2 to iron ion catalyst desulfurizing agent 21-2 after absorbing Hydrogen sulfide
Comparing the iron ion catalytic desulfurizing agent 13-1 with the iron ion catalytic desulfurizing agent 13-2, the iron ion catalytic desulfurizing agent 14-1 with the iron ion catalytic desulfurizing agent 14-2, the iron ion catalytic desulfurizing agent 15-1 with the iron ion catalytic desulfurizing agent 15-2, it is clear that the iron ion loss rate decreases with increasing the proportion of the low carbon alcohol amine.
Comparing the iron ion catalytic desulfurizing agent 15-1 with the iron ion catalytic desulfurizing agent 15-2, the iron ion catalytic desulfurizing agent 16-1 with the iron ion catalytic desulfurizing agent 16-2, the iron ion catalytic desulfurizing agent 17-1 with the iron ion catalytic desulfurizing agent 17-2, the iron ion loss rate is obviously reduced along with the increase of the proportion of the carboxylic acid chelating agent.
Comparing the above-mentioned iron ion catalytic desulfurizing agent 17-1 and iron ion catalytic desulfurizing agent 17-2, iron ion catalytic desulfurizing agent 18-1 and iron ion catalytic desulfurizing agent 18-2, iron ion catalytic desulfurizing agent 19-1 and iron ion catalytic desulfurizing agent 19-2, it is clear that the iron ion loss rate increases slightly as the proportion of inorganic base increases.
Comparing the above-mentioned iron ion catalytic desulfurizing agent 19-1 and iron ion catalytic desulfurizing agent 19-2, iron ion catalytic desulfurizing agent 20-1 and iron ion catalytic desulfurizing agent 20-2, iron ion catalytic desulfurizing agent 21-1 and iron ion catalytic desulfurizing agent 21-2, it is clear that the iron ion loss rate is reduced slightly as the proportion of antioxidant increases.
5. In the complex iron stabilizer, the composition of different low-carbon alcohol amine, carboxylic acid chelating agent, inorganic base and antioxidant is changed, and the performance influence of the iron ion catalytic desulfurizing agent is studied.
The specific formulations selected for the different components of the complex iron stabilizer are shown in table 12 and the continuation of table 12.
Composition ratio of thirteen complex iron stabilizers in Table 12
Table 12 the composition ratio of thirteen complex iron stabilizers
The complex iron stabilizer prepared in table 12 and table 12 was added to the following table 13 to obtain the corresponding iron ion catalyst desulfurization agent containing the complex iron stabilizer.
The preparation method of the iron ion catalytic desulfurizing agent containing the complex iron stabilizer comprises the following steps: the formula amount of iron ions (ferric citrate, hydroxyethyl ethylenediamine ferric acetate), the complex iron stabilizer and the industrial desalted water are uniformly mixed to obtain the iron ion catalytic desulfurizing agent containing the complex iron stabilizer (the industrial desalted water is used for fixing the volume to 1L, and the concentration of the iron ions is 12000 mg/L).
Table 13 contains the composition and amount of the iron ion catalyst desulfurizing agent containing the complex iron stabilizer shown in Table 12 and tables 12
Will H 2 S and nitrogen gas mixture (H 2 The molar fraction of S is 4%) is respectively introduced into the iron ion catalytic desulfurizing agent 22-2 (namely the proportion 22-2) to the iron ion catalytic desulfurizing agent 34-2 (the proportion 34-2) for absorbing hydrogen sulfide. The flow is 1L/min, and the concentration of the directly-discharged hydrogen sulfide is more than or equal to 6mg/m 3 Stopping, then blowing air at a flow rate of 5L/min for 60min, repeating the above operation for 10 times, and assaying the concentration of iron ions in the solution (general method 1, 10-phenanthrene for measuring iron content of industrial chemical products of GB/T3049-2006)And a spectrophotometric method of the indoline), and the obtained iron ion concentration and loss rate are shown in a table 14.
TABLE 14 concentration of iron ions and loss ratio of iron ion catalyst desulfurizing agent 22-2 to iron ion catalyst desulfurizing agent 34-2 after absorbing Hydrogen sulfide
Comparing the iron ion catalytic desulfurizer 22-1 and the iron ion catalytic desulfurizer 22-2, the iron ion catalytic desulfurizer 23-1 and the iron ion catalytic desulfurizer 23-2, and the iron ion catalytic desulfurizer 24-1 and the iron ion catalytic desulfurizer 24-2, the nitrogen methyl diethanolamine and the 2-amino-2-methyl-1-propanol can reduce the iron ion loss rate, and the two combined use effects are more excellent.
Comparing the iron ion catalytic desulfurizer 24-1 with the iron ion catalytic desulfurizer 24-2, the iron ion catalytic desulfurizer 25-1 with the iron ion catalytic desulfurizer 25-2, the iron ion catalytic desulfurizer 26-1 with the iron ion catalytic desulfurizer 26-2, the iron ion catalytic desulfurizer 27-1 with the iron ion catalytic desulfurizer 27-2, the iron ion catalytic desulfurizer 28-1 with the iron ion catalytic desulfurizer 28-2, the iron ion catalytic desulfurizer 29-1 with the iron ion catalytic desulfurizer 29-2, the iron ion catalytic desulfurizer 30-1 with the iron ion catalytic desulfurizer 30-2, the effect is optimal when three combinations are used, and the effect is clearly shown that the nitrilotriacetic acid, the hydroxyethylidene diphosphonic acid and the potassium sodium tartrate can reduce the iron ion loss rate along with the combination of one or more of carboxylic acid chelating agents.
Comparing the above-mentioned iron ion catalytic desulfurizing agent 30-1 and iron ion catalytic desulfurizing agent 30-2, iron ion catalytic desulfurizing agent 31-1 and iron ion catalytic desulfurizing agent 31-2, iron ion catalytic desulfurizing agent 32-1 and iron ion catalytic desulfurizing agent 32-2, it is clear that the combination of one or two of potassium carbonate and potassium bicarbonate can reduce the iron ion loss rate, and the iron ion loss rate is higher when potassium carbonate is used alone than when potassium bicarbonate is used alone and both are used simultaneously.
Comparing the above-mentioned iron ion catalytic desulfurizing agent 32-1 and iron ion catalytic desulfurizing agent 32-2, iron ion catalytic desulfurizing agent 33-1 and iron ion catalytic desulfurizing agent 33-2, iron ion catalytic desulfurizing agent 34-1 and iron ion catalytic desulfurizing agent 34-2, it is clear that the effect difference of using either potassium thiosulfate or sodium thiosulfate alone or a combination of both is not obvious, and the iron ion loss rate can be reduced by one or a combination of several of potassium thiosulfate and sodium thiosulfate.
6. Engineering application.
The JT1 well complex iron desulfurization device for the middle and southwest petroleum gas field has the gas flow of 20 square/d (the hydrogen sulfide content is 0.8%), the initial iron ion concentration is 4500mg/l, and the iron ion loss rate is continuously examined for 40 hours.
The iron ion catalyst desulfurizing agent is added with 20% of complex iron stabilizer, the desulfurizing liquid circulates once every hour, and the iron ion concentration is sampled every 10 hours, namely, in 40 hours of continuous investigation, the iron ion concentration is marked as the number 1 in the table 17 in the first 10 hours of sampling test, the iron ion concentration is marked as the number 2 in the table 17 in the second 10 hours of sampling test, the iron ion concentration is marked as the number 3 in the table 17 in the third 10 hours of sampling test, and the iron ion concentration is marked as the number 4 in the table 17 in the fourth 10 hours of sampling test.
The proportion of each component in the complex iron stabilizer is shown in table 15, the dosage of each component in the iron ion catalytic desulfurizing agent is shown in table 16, and the concentration and loss rate of iron ions are shown in table 17.
Table 15 complex iron stabilizer composition and proportion
TABLE 16 iron ion catalytic desulfurization compositions and amounts
Table 17 iron ion concentration and loss ratio of the iron ion catalyst desulfurization agent of table 16 after absorbing hydrogen sulfide
The results show that the complex iron stabilizer can obviously reduce the iron ion loss rate, reduce the iron ion consumption cost, reduce the production cost and increase the running stability and reliability.
Thus, based on the above research analysis, the present invention forms the following examples.
Example 1
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions in the catalytic desulfurization agent is about 12000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 12%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low-carbon alcohol amine (10% of nitrogen methyl diethanolamine, 5.0% of 2-amino-2-methyl-1-propanol), 20% of carboxylic chelating agent (3% of nitrilotriacetic acid, 7% of hydroxyethylidene diphosphonic acid, 10% of potassium sodium tartrate), 5% of inorganic base (2.5% of potassium carbonate, 2.5% of potassium bicarbonate), 8% of antioxidant (4% of sodium thiosulfate and 4% of potassium thiosulfate) and 52% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution to be 9.4, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
Oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 2
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 12000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 10%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 5% of low carbon alcohol amine (3.0% of nitrogen methyl diethanol amine, 2.0% of 2-amino-2-methyl-1-propanol), 5% of carboxylic acid chelating agent (2.5% of nitrilotriacetic acid, 1.5% of hydroxyethylidene diphosphonic acid, 1.0% of sodium potassium tartrate), 1% of inorganic base (0.4% of potassium carbonate and 0.6% of potassium bicarbonate),
3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 86% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
Step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.7, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
The regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 3
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 10000mg/L;
wherein the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 15%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 10% of low carbon alcohol amine (6.0% of nitrogen methyl diethanolamine, 4.0% of 2-amino-2-methyl-1-propanol), 5% of carboxylic acid chelating agent (2.5% of nitrilotriacetic acid, 1.5% of hydroxyethylidene diphosphonic acid, 1.0% of sodium potassium tartrate), 1% of inorganic base (0.4% of potassium carbonate, 0.6% of potassium bicarbonate), and,
3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 81% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
Adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution to be 9.1, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 4
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
Wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 20000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 20%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low carbon alcohol amine (9.0% of nitrogen methyl diethanol amine, 6.0% of 2-amino-2-methyl-1-propanol), 5% of carboxylic acid chelating agent (2.5% of nitrilotriacetic acid, 1.5% of hydroxyethylidene diphosphonic acid, 1.0% of sodium potassium tartrate), 1% of inorganic base (0.4% of potassium carbonate and 0.6% of potassium bicarbonate), and,
3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 76% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.9, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 5
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 1000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 5%;
The complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low-carbon alcohol amine (9.0% of nitrogen methyl diethanolamine, 6.0% of 2-amino-2-methyl-1-propanol), 12.0% of carboxylic chelating agent (6.0% of nitrilotriacetic acid, 3.6% of hydroxyethylidene diphosphonic acid, 2.4% of sodium potassium tartrate), 1% of inorganic alkali (0.4% of potassium carbonate, 0.6% of potassium bicarbonate), 3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 69% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.8, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
Step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 6
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 3000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 7%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low-carbon alcohol amine (9.0% of nitrogen methyl diethanolamine, 6.0% of 2-amino-2-methyl-1-propanol), 20% of carboxylic chelating agent (10.0% of nitrilotriacetic acid, 6.0% of hydroxyethylidene diphosphonic acid, 4.0% of sodium potassium tartrate), 1% of inorganic base (0.4% of potassium carbonate, 0.6% of potassium bicarbonate), 3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 61% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution to be 9.3, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
Oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 7
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 7500mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 9%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low-carbon alcohol amine (9.0% of nitrogen methyl diethanolamine, 6.0% of 2-amino-2-methyl-1-propanol), 20% of carboxylic chelating agent (10% of nitrilotriacetic acid, 6.0% of hydroxyethylidene diphosphonic acid, 4.0% of sodium potassium tartrate), 3% of inorganic base (1.2% of potassium carbonate, 1.8% of potassium bicarbonate), 3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 59% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
Step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.6, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
The regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 8
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 18000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurization agent is about 17%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low carbon alcohol amine (9.0% of nitrogen methyl diethanolamine, 6.0% of 2-amino-2-methyl-1-propanol), 20% of carboxylic acid chelating agent (10% of nitrilotriacetic acid, 6% of hydroxyethylidene diphosphonic acid, 4% of sodium potassium tartrate), 5% of inorganic base (2.0% of potassium carbonate and 3.0% of potassium bicarbonate), and,
3% of antioxidant (1.5% of sodium thiosulfate, 1.5% of potassium thiosulfate) and 57% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
Adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution to be 9.0, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 9
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
Wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 15000mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurization agent is about 13%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low-carbon alcohol amine (9.0% of nitrogen methyl diethanolamine, 6.0% of 2-amino-2-methyl-1-propanol), 20% of carboxylic chelating agent (10% of nitrilotriacetic acid, 6% of hydroxyethylidene diphosphonic acid, 4% of potassium sodium tartrate), 5% of inorganic base (2.0% of potassium carbonate, 3.0% of potassium bicarbonate), 5% of antioxidant (2.5% of sodium thiosulfate, 2.5% of potassium thiosulfate) and 55% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution to be 9.5, thereby obtaining the complex iron stabilizer;
And step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
Example 10
An iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
wherein the concentration of iron ions (a mixture of ferric citrate and ferric hydroxyethyl ethylenediamine triacetate) in the catalytic desulfurization agent is about 20000mg/L;
The mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is about 20%;
the complex iron stabilizer consists of the following raw materials in percentage by mass: 15% of low carbon alcohol amine (9.0% of nitrogen methyl diethanolamine, 6.0% of 2-amino-2-methyl-1-propanol), 20% of carboxylic acid chelating agent (10% of nitrilotriacetic acid, 6% of hydroxyethylidene diphosphonic acid, 4% of sodium potassium tartrate), 5% of inorganic base (2.0% of potassium carbonate and 3.0% of potassium bicarbonate), and,
8% of antioxidant (sodium thiosulfate 4.0%, potassium thiosulfate 4.0%) and 52% of industrial desalted water.
The preparation method of the iron ion catalytic desulfurization agent comprises the following steps:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.5, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
The complex iron desulfurization process for natural gas by using the iron ion catalytic desulfurization agent comprises the following steps:
Step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into the reactor for absorption reaction;
iron ions in the iron ion catalytic desulfurizing agent react with hydrogen sulfide to absorb the hydrogen sulfide in the gas, the hydrogen sulfide is oxidized into elemental sulfur by the iron ions, and the valence state of the iron ions is reduced from trivalent to divalent;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
oxidizing ferrous iron into ferric iron by utilizing oxygen in the air, and regenerating the iron ion catalytic desulfurizing agent;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. An iron ion catalytic desulfurizing agent, which is characterized in that:
the iron ion catalytic desulfurizing agent is prepared from iron ions, a complex iron stabilizer and water;
The concentration of the iron ions in the catalytic desulfurizing agent is 1000 mg/L-20000 mg/L;
the mass ratio of the complex iron stabilizer in the catalytic desulfurizing agent is 5% -20%;
the complex iron stabilizer consists of the following raw materials in percentage by mass:
5-15% of low-carbon alcohol amine,
5 to 20 percent of carboxylic acid chelating agent,
1 to 5 percent of inorganic alkali,
3-8% of antioxidant,
52-86% of water.
2. The iron ion catalytic desulfurization agent according to claim 1, wherein the complex iron stabilizer is composed of the following raw materials in percentage by mass:
10-15% of low-carbon alcohol amine,
15-20% of carboxylic acid chelating agent,
3 to 5 percent of inorganic alkali,
3-8% of antioxidant,
52-69% of water.
3. The iron ion catalytic desulfurization catalyst according to claim 1 or 2, characterized in that:
the low-carbon alcohol amine is at least one of azomethyl diethanolamine and 2-amino-2-methyl-1-propanol.
4. The iron ion catalytic desulfurization catalyst according to claim 1 or 2, characterized in that:
The carboxylic acid chelating agent is at least one of nitrilotriacetic acid, hydroxyethylidene diphosphonic acid and potassium sodium tartrate.
5. The iron ion catalytic desulfurization catalyst according to claim 1 or 2, characterized in that:
the inorganic base is at least one of potassium carbonate and potassium bicarbonate.
6. The iron ion catalytic desulfurization catalyst according to claim 1 or 2, characterized in that:
the antioxidant is at least one of sodium thiosulfate and potassium thiosulfate.
7. The iron ion catalytic desulfurization agent according to claim 1, characterized in that:
the iron ion is at least one of ferric citrate and hydroxyethyl ethylenediamine triacetic acid.
8. The iron ion catalytic desulfurization agent according to claim 1, characterized in that:
the water is industrial desalted water.
9. A method for producing the iron ion catalyst desulfurization agent according to any one of claims 1 to 8, characterized by comprising the steps of:
step 1, preparation of a complex iron stabilizer, which comprises the following steps:
step (1), uniformly mixing low-carbon alcohol amine with water according to the formula amount;
step (2), adding the carboxylic chelating agent and the antioxidant into the mixed solution in the step (1) according to the formula amount, and uniformly mixing;
Adding the inorganic base with the formula amount into the mixed solution in the step (2), and uniformly mixing to keep the pH value of the dissolved solution at 8.5-9.5, thereby obtaining the complex iron stabilizer;
and step 2, uniformly mixing the formula amount of iron ions, the complex iron stabilizer and water to obtain the iron ion catalytic desulfurizing agent.
10. Use of an iron ion catalytic desulfurization agent according to any one of claims 1 to 8, characterized in that it is used as a complex iron desulfurization process for natural gas;
the application method comprises the following steps:
step 1, loading an iron ion catalytic desulfurizing agent into a reactor;
step 2, introducing natural gas containing hydrogen sulfide into a reactor for absorption reaction;
step 3, when the iron ion catalytic desulfurization agent in the reactor is absorbed and reacted to a saturated state, air is blown into the reactor for regeneration reaction;
the regenerated iron ion catalytic desulfurizing agent can repeat the step 2 to perform new hydrogen sulfide absorption reaction.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009251A (en) * | 1973-08-27 | 1977-02-22 | Rhodia, Inc. | Process for the removal of hydrogen sulfide from gaseous streams by catalytic oxidation of hydrogen sulfide to sulfur while inhibiting the formation of sulfur oxides |
| WO2015088342A1 (en) * | 2013-12-11 | 2015-06-18 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process and apparatus for hydrogen sulfide removal |
| WO2019191249A1 (en) * | 2018-03-28 | 2019-10-03 | Bionomic Industries Inc. | Process for hydrogen sulfide scrubbing and method for ferric ion regeneration |
| CN111495148A (en) * | 2020-04-01 | 2020-08-07 | 陕西省石油化工研究设计院 | Chelating agent for complex iron method desulfurization |
| CN113649078A (en) * | 2021-08-06 | 2021-11-16 | 德微科技有限公司 | Complex iron catalyst solution and preparation method thereof |
| CN114558622A (en) * | 2022-03-22 | 2022-05-31 | 东南大学 | Desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide and preparation method thereof |
| CN116059812A (en) * | 2022-12-07 | 2023-05-05 | 成都华阳兴华化工有限公司 | Synthesis method of complex iron ion desulfurizing agent |
| CN116832873A (en) * | 2023-07-25 | 2023-10-03 | 西北大学 | Complex iron catalyst for removing hydrogen sulfide in industrial gas and preparation method thereof |
| CN117358027A (en) * | 2022-06-30 | 2024-01-09 | 中国石油化工股份有限公司 | Desulfurizing agent for removing hydrogen sulfide and carbonyl sulfide, and preparation method and application thereof |
-
2024
- 2024-02-01 CN CN202410139483.7A patent/CN117654640A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009251A (en) * | 1973-08-27 | 1977-02-22 | Rhodia, Inc. | Process for the removal of hydrogen sulfide from gaseous streams by catalytic oxidation of hydrogen sulfide to sulfur while inhibiting the formation of sulfur oxides |
| WO2015088342A1 (en) * | 2013-12-11 | 2015-06-18 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process and apparatus for hydrogen sulfide removal |
| WO2019191249A1 (en) * | 2018-03-28 | 2019-10-03 | Bionomic Industries Inc. | Process for hydrogen sulfide scrubbing and method for ferric ion regeneration |
| CN111495148A (en) * | 2020-04-01 | 2020-08-07 | 陕西省石油化工研究设计院 | Chelating agent for complex iron method desulfurization |
| CN113649078A (en) * | 2021-08-06 | 2021-11-16 | 德微科技有限公司 | Complex iron catalyst solution and preparation method thereof |
| CN114558622A (en) * | 2022-03-22 | 2022-05-31 | 东南大学 | Desulfurization catalyst for synergistically removing hydrogen sulfide and carbonyl sulfide and preparation method thereof |
| CN117358027A (en) * | 2022-06-30 | 2024-01-09 | 中国石油化工股份有限公司 | Desulfurizing agent for removing hydrogen sulfide and carbonyl sulfide, and preparation method and application thereof |
| CN116059812A (en) * | 2022-12-07 | 2023-05-05 | 成都华阳兴华化工有限公司 | Synthesis method of complex iron ion desulfurizing agent |
| CN116832873A (en) * | 2023-07-25 | 2023-10-03 | 西北大学 | Complex iron catalyst for removing hydrogen sulfide in industrial gas and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王志衡: "螯合铁法脱硫液的稳定性", 《曲阜师范大学学报》, vol. 4, 31 December 1986 (1986-12-31), pages 1 - 2 * |
| 黄佩武: "脱硫液组成对EDTA-Fe稳定性和选择性的影响", 《江汉大学学报》, vol. 50, 26 April 2022 (2022-04-26), pages 25 * |
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