Preparation method and application of ferric fulvic acid-based metal-organic framework material
By preparing fulvic acid iron-based metal-organic framework materials and combining them with multiphysics field technology, the problem of efficient removal and resource utilization of thiophene sulfur in fuel oil was solved, realizing deep purification and resource recycling of fuel oil, and reducing energy consumption and equipment investment.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- SHANXI YONGDONG CHEM IND CO LTD
- Filing Date
- 2026-04-03
- Publication Date
- 2026-06-05
AI Technical Summary
Existing desulfurization technologies are unable to efficiently remove thiophene-type organic sulfur compounds with stable aromatic ring structures from fuel oil, and they also suffer from problems such as high energy consumption, high equipment investment, and significant octane number loss. Traditional desulfurizing agents are not very targeted at thiophene-type sulfides, and the desulfurization products are difficult to separate and utilize.
Using fulvic acid iron-based metal-organic framework (Fe-FA-MOF) materials, a dynamic MOF system is formed through electrochemical synthesis. Combined with ultrasonic, swirling flow field and viscosity sensing technologies, efficient capture and oxidation of thiophene organic sulfur is achieved. Furanic acid is used as an inducer to simplify the separation process, and a multi-physics field synergistic enhancement of the desulfurization process is constructed.
It achieves efficient and targeted removal and resource utilization of thiophene sulfur in fuel oil, simplifies the separation process, reduces energy consumption and equipment investment, improves desulfurization efficiency and resource recovery rate, and is suitable for deep purification of coal tar, carbon black oil and diesel.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of refining and desulfurization technology, and more specifically, to a method for preparing humic acid iron-based metal-organic framework materials and their applications. Background Technology
[0002] With increasingly stringent environmental regulations, higher requirements are being placed on the deep removal of thiophene-based organic sulfur compounds from fuel oils such as coal tar, carbon black, and diesel. Existing desulfurization technologies are mainly divided into two categories: hydrodesulfurization and non-hydrodesulfurization.
[0003] While hydrodesulfurization technology can effectively remove simple sulfides such as mercaptans and thioethers, it has low removal efficiency for thiophenes and their derivatives (such as benzothiophene and dibenzothiophene) with stable aromatic ring structures. In addition, it is usually carried out under high temperature and high pressure (300-400℃, 3-10MPa), which has problems such as high hydrogen consumption, high investment and operating costs, easy loss of oil octane number and large carbon emissions.
[0004] While non-hydrodesulfurization technologies such as oxidative desulfurization and adsorption desulfurization can be carried out under relatively mild conditions, they still face many challenges. For example, Chinese patent CN109439366 A discloses a method for removing thiophene sulfur from gasoline, using formic acid, propionic acid, and citric acid as an oxidation system. Although it can achieve the oxidative removal of thiophene, it suffers from problems such as high oxidant consumption, complex processes, difficulty in separating desulfurization products, and ineffective utilization. Furthermore, existing desulfurizing agents, such as the MIL-100(Fe) catalyst disclosed in invention patent CN108948366 A, while exhibiting excellent performance in H2S removal, are not particularly effective against the more structurally stable thiophene-based organic sulfur compounds. Various triazine-based desulfurizing agents (such as CN202510200689.0, CN118852036A, and CN111808036B) are mainly designed for H2S gas removal and are difficult to apply to the complex thiophene-based sulfur compounds in fuel systems.
[0005] In summary, there is an urgent need to develop a new desulfurization technology that integrates high-efficiency desulfurization, high-value recovery of sulfur resources, intelligent separation, and process enhancement, in order to break through existing technological bottlenecks and achieve deep purification of fuel oil and recycling of resources. Summary of the Invention
[0006] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, one aspect of the present invention is to provide a method for preparing iron-based metal-organic framework materials of fulvic acid, wherein the specific steps of the preparation method are as follows: Fe, Fe3O4, Fe2O3, coal fulvic acid (FA), H2SO4, H4SiO4 and H4SiO4 are mixed. 12MoO3 is placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction is carried out. Fe-MOF is synthesized at the anode and FA-MOF is synthesized at the cathode, thus forming Fe-FA-MOF, which is a humic acid iron-based metal-organic framework material.
[0007] Preferably, the constituents are Fe, Fe3O4, Fe2O3, coal humic acid (FA), H2SO4, H4SiO4, and H4SiO4. 12 The mass ratio of MoO3 is 1~3:0.2~6:0.8~2.5:0.6~1.8:0.1~0.3:0.3~0.9.
[0008] Preferably, the electrolysis reaction temperature is 35-65℃, the electrolysis reaction frequency is 50-106kHz, the wavenumber is 1.0-1.5km / s, the electrolysis reaction time is 1-10min, and the electrolysis reaction ultrasonic rotation speed is 1000-3000r / min.
[0009] Another objective of this invention is to provide an application of an iron humate-based metal-organic framework material for the removal of thiophene sulfur from coal tar, carbon black oil, and diesel oil mixtures.
[0010] Another aspect of this invention aims to provide an application of an iron humate-based metal-organic framework material, wherein coal tar, carbon black oil, and a diesel oil mixture are added to the iron humate-based metal-organic framework material for a catalytic oxidation-reduction desulfurization reaction to form C8H6S@FA.Fe3O4, and the [HSO4] in the iron humate-based metal-organic framework material... - ,HSiMo 12 O 40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12 H8S) and thiophene carboxylic acid (C5H4O2S) are converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), and then the thiophene compounds are extracted by solvent extraction for continued recycling.
[0011] Preferably, the mass ratio of the humate iron-based metal-organic framework material, coal tar, carbon black oil and diesel oil is 1~3:0.2~1:0.5~2:0.1~2.5.
[0012] Preferably, the [HSO4] - ,HSiMo 12 O 40 - HSiO 2-Benzothiophine (C8H6S), dibenzothiophene (C 12 The molar ratio of H8S and thiophene carboxylic acid (C5H4O2S) is 0.001~0.005: 0.001~0.003: 0.001~0.01: 0.0001~0.0005: 0.0001~0.001: 0.0001~0.002.
[0013] Preferably, the electrode potential of the catalytic redox desulfurization reaction is (Fe2+ / Fe) = -0.440~-0.650V, which generates ion exchange or hydrogen bonding interactions, playing a role in immobilization, dispersion, and synergistic catalytic effect, allowing C8H6S and C to react. 12 The removal efficiency of H8S and the recycling rate of C5H4O2S gradually increased from 17.89%, 18.01%, and 18.43% to 99.99-100%.
[0014] Preferably, the solvent is one or a mixture of two of the following: butanone, cyclohexanone, toluene, and kerosene.
[0015] The beneficial effects of this invention are as follows: Constructing a dynamic MOF system to achieve efficient targeted desulfurization and resource utilization: This invention innovatively utilizes the electrochemical properties of iron oxides (Fe3O4, Fe2O3) and coal humic acid (HA) to construct a system containing ionic [HSO4] - Heteropolyacids HSiMo 12 O 40 The dynamic metal-organic framework (MOF) system of HSiO2- not only possesses an extremely high specific surface area and abundant active sites, enabling efficient capture and oxidation of thiophene-based organic sulfur compounds in coal tar, carbon black oil, and diesel oil, but also achieves selective adsorption and conversion of thiophenes by regulating the dynamic structure of the MOF. More importantly, this process does not simply remove sulfur, but rather recovers the removed thiophene compounds as high-value-added chemicals, turning waste into treasure and greatly improving the economic efficiency of the process.
[0016] This invention introduces furanoic acid (C5H4O2S) as an inducing agent to simplify the separation process: Addressing the challenge of separating catalysts from oil products in traditional desulfurization processes, this invention innovatively introduces C5H4O2S as an inducing separation agent. Utilizing its unique molecular structure, it can induce a liquid-solid phase transition or aggregation of sulfur-loaded MOF materials after the reaction, thereby achieving efficient and rapid material separation. This method avoids complex physical separation steps such as traditional filtration and centrifugation. Combined with the ferromagnetism inherent in the MOF material due to Fe3O4, the separation effect can be controlled through simple magnetic and sedimentation monitoring, significantly simplifying the process and reducing equipment investment and energy consumption.
[0017] Multi-physics field synergistic regulation enhances reaction and process control: This invention comprehensively utilizes ultrasonic waves, swirling flow fields, and viscosity sensing technologies to construct a multi-physics field synergistic enhancement system. Frequency variations in ultrasound can generate cavitation effects, effectively dispersing MOF materials and preventing agglomeration, while also enhancing the oxidation reaction of thiophene through localized high temperature and pressure. Swirling flow fields enhance material mixing and mass transfer processes, improving reaction efficiency. Online viscosity sensing technology can monitor the physical state of the reaction system in real time, precisely controlling the reaction process and inducing separation timing. This multi-parameter, multi-dimensional regulation method ensures the controllability and stability of the entire desulfurization process, providing technical support for continuous production.
[0018] Promoting a circular production model: This process is designed with a complete recycling system. After desulfurization and induced separation, the dynamic MOF material can be efficiently regenerated and recycled. The removed thiophene compounds are recycled, and the extraction solvent can also be recycled, thus maximizing the utilization of resources. The entire process operates at a low temperature and avoids the high-energy-consuming hydrogenation process, significantly reducing carbon emissions and energy consumption.
[0019] Additional aspects and advantages of the invention will become apparent from the description which follows, or may be learned by practice of the invention. Detailed Implementation
[0020] To better understand the above-mentioned objectives, features, and advantages of the present invention, the present invention will be further described in detail below with reference to specific embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in these embodiments can be combined with each other.
[0021] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be implemented in other ways different from those described herein. Therefore, the scope of protection of the invention is not limited to the specific embodiments disclosed below.
[0022] Example 1 Mix 1 part Fe, 1 part Fe3O4, 1 part Fe2O3, 0.2 parts FA, 0.1 part H2SO4, 0.6 parts 0.1 H4SiO4 and 0.3 parts H4SiO4. 12 MoO3 is placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction is carried out at a temperature of 35℃, a frequency of 50 kHz, a wave number of 1.0 km / s, an electrolytic reaction time of 1 min, and an ultrasonic rotation speed of 1000 r / min. Fe-MOF is synthesized at the anode and FA-MOF is synthesized at the cathode, forming Fe-FA-MOF.
[0023] 1 part Fe-FA-MOF is mixed with 1000 parts coal tar, 200 parts carbon black oil, and 500 parts diesel oil ([HSO4]). - ,HSiMo 12 O 40 - HSiO 2- Benzothiophane (C8H6S), dibenzothiophene (C 12 The molar ratio of H8S and thiophenecarboxylic acid (C5H4O2S) is 0.001:0.001:0.001:0.0001:0.0001:0.0002. A catalytic redox desulfurization reaction is carried out on the oil, with an electrode potential of (Fe2+ / Fe) 0.350V, forming C8H6S@FA.Fe3O4, which is [HSO4] in the humic acid iron-based metal-organic framework material. - ,HSiMo 12 O 40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12 H8S) and thiophene carboxylic acid (C5H4O2S) are converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), and then extracted by mixing butanone and cyclohexanone in a 1:1 ratio to continue recycling. The removal efficiencies are 17.89%, 18.01%, and 18.43%, respectively. The results are shown in Table 1 below.
[0024] Table 1. Desulfurization Results of Example 1 Example 2 Mix 1 part Fe, 1 part Fe3O4, 1 part Fe2O3, 1 part FA, 2.5 parts H2SO4, 0.3 parts H4SiO4 and 0.3 parts 0.6H4SiO4. 12 MoO3 is placed in an electrolytic synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction is carried out at a temperature of 65℃, a frequency of 106 kHz, a wave number of 1.5 km / s, an electrolytic reaction time of 10 min, and an ultrasonic rotation speed of 3000 r / min. Fe-MOF is synthesized at the anode and FA-MOF is synthesized at the cathode, forming Fe-FA-MOF.
[0025] Mix 2 parts Fe-FA-MOF with 1000 parts coal tar, 200 parts carbon black oil, and 500 parts diesel oil ([HSO4]). - ,HSiMo 12 O 40 - HSiO 2- Mixed benzothiophenol (C8H6S) and dibenzothiophene (C12 The molar ratio of H8S and thiophene carboxylic acid (C5H4O2S) is 0.005:0.003:0.01:0.0001:0.0001:0.0002. A catalytic redox desulfurization reaction is carried out on the oil, with an electrode potential of (Fe2+ / Fe) = -0.650V, forming C8H6S@FA.Fe3O4, which is [HSO4] in the humic acid iron-based metal-organic framework material. - ,HSiMo 12 O 40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12 H8S) and thiophene carboxylic acid (C5H4O2S) are converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), and then regenerated by ferromagnetism, redox properties, and liquid-solid separation. Thiophene compounds are extracted and recycled. The removal efficiencies are 99.992%, 99.996%, and 100.0%, respectively. The results are shown in Table 2 below.
[0026] Table 2. Desulfurization Results of Example 2 Example 3 Mix 1 part Fe, 1 part Fe3O4, 3 parts Fe2O3, 5 parts FA, 2.5 parts H2SO4, 0.3 parts H4SiO4 and 0.9 parts H4SiO4. 12 MoO3 was placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction was carried out at a temperature of 65℃, a frequency of 106 kHz, a wavenumber of 1.5 km / s, an electrolytic reaction time of 5 min, an ultrasonic rotation speed of 3000 r / min, and a viscosity sensing value of 3.75 μ (mPa·s). Fe-MOF was synthesized at the anode and FA-MOF was synthesized at the cathode, forming Fe-FA-MOF.
[0027] 3 parts Fe-FA-MOF were mixed with 1000 parts coal tar, 200 parts carbon black oil, and 500 parts diesel oil ([HSO4]). - ,HSiMo 12 O 40 - HSiO 2- Removal of benzothiophene (C8H6S) and dibenzothiophene (C8H6S) from oil products 12The molar ratio of H8S and thiophene carboxylic acid (C5H4O2S) is 0.005:0.003:0.01:0.0005:0.0001:0.0002. The oil undergoes a catalytic redox desulfurization reaction with an electrode potential of (Fe2+ / Fe) = -0.650V, forming C8H6S@FA.Fe3O4, which is [HSO4] in the humic acid iron-based metal-organic framework material. - ,HSiMo 12 O 40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12 H8S) and thiophene carboxylic acid (C5H4O2S) are converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), resulting in a removal efficiency of 99.992% for benzothiophene and dibenzothiophene organic sulfur compounds. The thiophene compounds are then extracted by mixing butanone and cyclohexanone in a 2:1 ratio and recycled, achieving a removal efficiency of 90.0%.
[0028] Example 4 Mix 1 part Fe, 1 part Fe3O4, 1 part Fe2O3, 1 part FA, 2 parts H2SO4, 0.3 parts H4SiO4 and 0.6 parts H4SiO4. 12 MoO3 was placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction was carried out at a temperature of 65℃, a frequency of 106 kHz, a wavenumber of 1.5 km / s, an electrolytic reaction time of 10 min, an ultrasonic rotation speed of 3000 r / min, and a viscosity sensing value of 1.20 μ (mPa·s). Fe-MOF was synthesized at the anode and FA-MOF was synthesized at the cathode, forming Fe-FA-MOF.
[0029] 3 parts Fe-FA-MOF were mixed with 1000 parts coal tar, 200 parts carbon black oil, and 500 parts diesel oil ([HSO4]). - ,HSiMo 12 O 40 - HSiO 2- Benzothiophine (C8H6S), dibenzothiophene (C 12 The molar ratio of H8S and thiophenecarboxylic acid (C5H4O2S) is 0.005:0.003:0.01:0.0005:0.0001:0.0002. A catalytic redox desulfurization reaction is carried out on the oil, with an electrode potential of (Fe2+ / Fe) = -0.650V, forming C8H6S@FA.Fe3O4, which is [HSO4] in the humic acid iron-based metal-organic framework material. - ,HSiMo 12 O40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12 H8S) and thiophene carboxylic acid (C5H4O2S) are converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), resulting in a removal efficiency of 99.996% for benzothiophene and dibenzothiophene organic sulfur compounds. The thiophene compounds are then extracted by mixing kerosene and cyclohexanone in a 1:1 ratio and recycled, achieving a removal efficiency of 95.0%.
[0030] Example 5 Mix 1 part Fe, 1 part Fe3O4, 1 part Fe2O3, 5 parts FA, 2.5 parts H2SO4, 0.3 parts H4SiO4 and 0.9 parts H4SiO4. 12 MoO3 is placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction is carried out at a temperature of 65℃, a frequency of 106 kHz, a wave number of 1.5 km / s, an electrolytic reaction time of 10 min, and an ultrasonic rotation speed of 3000 r / min. Fe-MOF is synthesized at the anode and FA-MOF is synthesized at the cathode, forming Fe-FA-MOF.
[0031] 3 parts Fe-FA-MOF were mixed with 1000 parts coal tar, 200 parts carbon black oil, and 500 parts diesel oil ([HSO4]). - ,HSiMo 12 O 40 - HSiO 2- Benzothiophine (C8H6S), dibenzothiophene (C 12 The molar ratio of H8S and thiophene carboxylic acid (C5H4O2S) is 0.005:0.003:0.01:0.0001:0.0001:0.0002. A catalytic redox desulfurization reaction is carried out on the oil, with an electrode potential of (Fe2+ / Fe) = -0.650V, forming C8H6S@FA.Fe3O4, which is [HSO4] in the humic acid iron-based metal-organic framework material. - ,HSiMo 12 O 40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12H8S) and thiophene carboxylic acid (C5H4O2S) are converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), making the removal efficiency of benzothiophene and dibenzothiophene organic sulfur 100%. The thiophene compounds are then extracted and recycled, achieving a removal efficiency of 100%. This is used in high-quality rubber reinforcing carbon black, increasing the product's pigment performance by 57.0% and improving product profit by 35.9%.
[0032] Example 6 Mix 3 parts Fe, 3 parts 3Fe3O4, 3 parts Fe2O3, 3 parts FA, 2.5 parts H2SO4, 0.3 parts H4SiO4, and 0.6 parts H4SiO4. 12 MoO3 is placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction is carried out at a temperature of 65℃, a frequency of 106 kHz, a wave number of 1.5 km / s, an electrolytic reaction time of ~ min, and an ultrasonic rotation speed of 3000 r / min. Fe-MOF is synthesized at the anode and FA-MOF is synthesized at the cathode, forming Fe-FA-MOF.
[0033] 3 parts Fe-FA-MOF were mixed with 1000 parts coal tar, 200 parts carbon black oil, and 500 parts diesel oil ([HSO4]). - ,HSiMo 12 O 40 - HSiO 2- Benzothiophine (C8H6S), dibenzothiophene (C 12 The molar ratio of H8S and thiophenecarboxylic acid (C5H4O2S) is 0.005:0.003:0.01:0.0005:0.0001:0.0002. A catalytic redox desulfurization reaction is carried out on the oil, with an electrode potential of (Fe2+ / Fe) = -0.650V, forming C8H6S@FA.Fe3O4, which is [HSO4] in the humic acid iron-based metal-organic framework material. - ,HSiMo 12 O 40 - HSiO 2- With benzothiophene (C8H6S) and dibenzothiophene (C 12 The removal of benzothiophene (H8S) and thiophene carboxylic acid (C5H4O2S) is converted into sulfone (RS(=O)2-R') and sulfoxide (RS(=O)-R'), resulting in a 100% removal efficiency for benzothiophene and dibenzothiophene organic sulfur compounds. Coal tar, carbon black oil, and diesel products purified by MOF dynamic composites are used in the production of carbon black and needle coke. The former can be used for high-quality conductive carbon black, high-pigment carbon black, and rubber-reinforcing carbon black, while the latter can be used for high-power and ultra-high-power electrodes and carbon materials for aerospace applications.
[0034] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the invention by those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the invention should be included within the scope of protection of the invention.
Claims
1. A method for preparing an iron humate-based metal-organic framework material, characterized in that: The specific steps of the preparation method are as follows: Fe, Fe3O4, Fe2O3, coal humic acid, H2SO4, H4SiO4 and H4SiO4 are added. 12 MoO3 is placed in an electrochemical synthesis cell, with metallic iron forming the anode and coal humic acid forming the cathode, and an electrolytic reaction is carried out. Fe-MOF is synthesized at the anode and FA-MOF is synthesized at the cathode, thus forming Fe-FA-MOF, which is a humic acid iron-based metal-organic framework material.
2. The method for preparing an iron-based metal-organic framework material of fulvic acid according to claim 1, characterized in that: The components are Fe, Fe3O4, Fe2O3, coal humic acid, H2SO4, H4SiO4, and H4SiO4. 12 The mass fraction of MoO3 is 1~3:1~5:0.2~6:0.1~2.5:0.6~1.8:0.1~0.3:0.3~0.
9.
3. The method for preparing an iron-based metal-organic framework material of fulvic acid according to claim 1, characterized in that: The electrolysis reaction temperature is 35-65℃, the electrolysis reaction frequency is 50-106kHz, the wavenumber is 1.0-1.5km / s, the electrolysis reaction time is 1-10min, and the ultrasonic rotation speed of the electrolysis reaction is 1000-3000r / min.
4. The application of the humate-based metal-organic framework material according to claim 1, characterized in that: The iron-based metal-organic framework material of fulvic acid is used for the removal of thiophene sulfur from coal tar, carbon black oil and diesel oil mixtures.
5. The application of the humate-based metal-organic framework material according to claim 1, characterized in that: The iron-based fulvic acid metal-organic framework material is subjected to a catalytic redox desulfurization reaction by adding a mixture of coal tar, carbon black oil, and diesel oil to form C8H6S@FA.Fe3O4. The [HSO4] in the iron-based fulvic acid metal-organic framework material... - ,HSiMo 12 O 40 - HSiO 2- It is converted into sulfones and sulfoxides by benzothiophenol, dibenzothiophene and thiophene carboxylic acid, and then the thiophene compounds are extracted by solvent extraction for continued recycling.
6. The application of the humate-based metal-organic framework material according to claim 5, characterized in that: The mass ratio of the iron-based metal-organic framework material, coal tar, carbon black oil and diesel oil is 1~3:0.2~1:0.5~2:0.1~2.
5.
7. The application of the humate-based metal-organic framework material according to claim 5, characterized in that: The [HSO4] - ,HSiMo 12 O 40 - HSiO 2- The molar ratio of benzothiophenol, dibenzothiophene and thiophene carboxylic acid is 0.001~0.005: 0.001~0.003: 0.001~0.01: 0.0001~0.0005: 0.0001~0.001: 0.0001~0.
002.
8. The application of the humate-based metal-organic framework material according to claim 5, characterized in that: The electrode potential of the catalytic oxidation-reduction desulfurization reaction is (Fe2+ / Fe) = -0.440~-0.650V.
9. The application of the humate-based metal-organic framework material according to claim 5, characterized in that: The solvent is one or a mixture of two of the following: butanone, cyclohexanone, toluene, and kerosene.