A method for regenerating permanganate ions and in-situ coupling organic matter oxidation using pulse potential

Abstract

The present invention provides a method for regenerating permanganate ions and coupling in situ oxidation of organic matter using pulse potential. The method comprises the following steps: (1) introducing an anolyte containing divalent manganese ions and organic matter into an electrochemical reaction device; (2) applying a pulse voltage between the anode and cathode of the electrochemical reaction device to obtain an electrolyte containing divalent manganese ions and oxides of organic matter. The technical solution of the present invention adopts a pulse potential, wherein the positive potential oxidizes the divalent manganese ions into permanganate ions and couples in situ oxidation of organic matter, and the negative potential reduces the manganese dioxide deposited on the electrode surface into divalent manganese ions, thereby realizing the circulation of a redox couple composed of divalent manganese ions and permanganate ions, and greatly reducing the amount of permanganate ions used; a one-step method is used to regenerate permanganate ions and couple in situ oxidation of organic matter, thereby avoiding the separation and purification steps in the traditional regeneration process of potassium permanganate.

Description

Technical Field

[0001] The invention relates to the technical field of organic electrochemical synthesis, in particular to a method for regenerating permanganate ions by using pulse potential and in-situ coupling oxidation of organic matter. Background Art

[0002] Stoichiometric oxidation reactions play a vital role in the production of fine chemicals. Commonly used chemical oxidants include potassium dichromate, potassium permanganate, sodium hypochlorite and sodium periodate, which have the advantages of high selectivity and good functional group compatibility. Recycling used oxidants can reduce environmental pollution and production costs.

[0003] Potassium permanganate is a strong oxidant that can be used to oxidize a variety of organic molecules, such as olefins, alcohols, sulfides, etc., and is reduced to manganese dioxide. The process of recycling manganese dioxide to oxidize potassium permanganate in the current industry is as follows: first, the manganese dioxide produced by potassium permanganate oxidation of organic matter is separated and purified, and the obtained manganese dioxide is added to high-temperature molten potassium hydroxide, and oxygen is introduced to oxidize the manganese dioxide to potassium manganate; after separation and purification, the obtained potassium manganate is oxidized to potassium permanganate in an electrochemical reactor; the obtained potassium permanganate is separated and purified for the oxidation of organic matter (CN116478027, CN104862730). How to simplify the potassium permanganate regeneration process and in-situ coupling with organic oxidation reactions still faces great challenges.

[0004] The above prior art faces the disadvantages of large potassium permanganate dosage, high energy consumption in the regeneration process and many separation and purification steps. Since potassium permanganate regeneration is a two-step process and the reaction conditions are different from those of organic matter oxidation, it cannot be coupled in the same reactor, resulting in the need for stoichiometric potassium permanganate oxidation of organic matter. In addition, due to the poor conductivity and high oxidation potential of manganese dioxide precipitation, it is difficult to directly oxidize to potassium permanganate in one step by an electrochemical method.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] The object of the present invention is to provide a method for regenerating permanganate ions and coupling in-situ oxidation of organic matter by using pulse potential, which regenerates permanganate ions and couples in-situ oxidation of organic matter in one step at normal temperature and pressure.

[0007] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0008] The present invention provides a method for regenerating permanganate ions and in-situ coupling organic matter oxidation using pulse potential, the method comprising the following steps:

[0009] (1) introducing an anolyte containing divalent manganese ions and organic matter into an electrochemical reaction device;

[0010] (2) A pulse voltage is applied between the anode and cathode of the electrochemical reaction device to obtain an electrolyte containing divalent manganese ions and an oxide of an organic substance.

[0011] Preferably, in step (1), the divalent manganese ions are derived from divalent manganese salts.

[0012] Preferably, in step (1), the divalent manganese salt is selected from any one or a combination of at least two of manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese chloride or manganese phosphate.

[0013] Preferably, in step (1), in the anolyte, the concentration of the divalent manganese ions is 0.0001 to 1 mol / L.

[0014] Preferably, in step (1), the organic matter is selected from any one of cyclic sulfites, thioethers, alcohols or aldehydes.

[0015] Preferably, in step (1), the structural formula of the cyclic sulfite is Wherein, R is selected from any one of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and n is an integer between 0 and 2.

[0016] Preferably, in step (1), the structural formula of the thioether is Wherein, R1 and R2 are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0017] Preferably, in step (1), the alcohol has a structural formula of R′-OH, wherein R′ is selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0018] Preferably, in step (1), the structural formula of the aldehyde is R"-CHO, wherein R" is selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0019] Preferably, in step (1), the concentration of the organic matter in the anolyte is 0.001 to 10 mol / L.

[0020] Preferably, in step (1), the anolyte further comprises an inorganic acid and / or a polar organic solvent.

[0021] Preferably, in step (1), the inorganic acid is selected from any one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or perchloric acid, or a combination of at least two thereof.

[0022] Preferably, in step (1), the polar organic solvent is selected from any one of methanol, ethanol, isopropanol, ethylene glycol, acetone, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane or N,N-dimethylformamide, or a combination of at least two thereof.

[0023] Preferably, in step (1), in the anolyte, the concentration of the inorganic acid is 0 to 10 mol / L.

[0024] Preferably, in step (1), in the anode electrolyte, the volume ratio of the inorganic acid to the polar organic solvent is (0-100):1.

[0025] Preferably, step (1) further comprises introducing a cathode electrolyte.

[0026] Preferably, the catholyte comprises a mineral acid.

[0027] Preferably, in the cathode electrolyte, the concentration of the inorganic acid is 0 to 10 mol / L.

[0028] Preferably, in the cathode electrolyte, the inorganic acid is selected from any one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or perchloric acid, or a combination of at least two thereof.

[0029] Preferably, in step (2), the anode comprises any one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foam titanium, titanium fiber felt or powder sintered porous titanium, or a combination of at least two thereof.

[0030] Preferably, in step (2), the cathode comprises any one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foam titanium, titanium fiber felt or powder sintered porous titanium, or a combination of at least two thereof.

[0031] Preferably, in step (2), the cathode is loaded with a platinum catalyst.

[0032] Preferably, in step (2), the platinum loading in the cathode is 0.01 to 4 mg / cm 2 .

[0033] Preferably, in step (2), applying the pulse voltage includes applying a positive potential and applying a negative potential;

[0034] Wherein, the forward potential is 1.0 to 2.5 V, and the duration is 1 to 600 s;

[0035] The negative potential is -2.0 to -0.1 V, and the duration is 1 to 60 s.

[0036] Preferably, in step (2), the total cycle time of applying the pulse voltage is 0.1 to 10 hours.

[0037] Preferably, in step (2), the divalent manganese ions are derived from divalent manganese salts.

[0038] Preferably, the divalent manganese salt is selected from any one or a combination of at least two of manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese chloride or manganese phosphate.

[0039] Preferably, in step (2), in the electrolyte, the concentration of the divalent manganese ions is 0.0001 to 1 mol / L.

[0040] Preferably, in step (2), the oxide of the organic matter is selected from any one of cyclic sulfate, sulfone or acid.

[0041] Preferably, the structural formula of the cyclic sulfate is Wherein, R is selected from any one of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and n is an integer between 0 and 2.

[0042] Preferably, the structural formula of the sulfone is Wherein, R1 and R2 are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0043] Preferably, the acid has a structural formula of R′-COOH or R″-COOH, wherein R′ and R″ are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0044] Preferably, in step (2), the concentration of the oxide of the organic matter in the electrolyte is 0.001 to 10 mol / L.

[0045] Preferably, the method further comprises step (3) post-processing;

[0046] When the oxide of the organic matter is solid, the post-treatment is: concentrating, filtering, washing and drying the electrolyte containing the divalent manganese ions and the oxide of the organic matter in sequence to obtain the oxide of the organic matter;

[0047] When the oxide of the organic matter is liquid, the post-treatment is: extracting the electrolyte containing the divalent manganese ions and the oxide of the organic matter to obtain an organic phase, and then concentrating the organic phase to obtain the oxide of the organic matter.

[0048] [Term explanation]

[0049] Various aspects and features of the present invention are further described below.

[0050] As mentioned in the present invention, the term "alkyl" refers to an alkyl group having a specified number of carbon atoms, which can be a straight-chain alkyl group or a branched alkyl group. For example, the "C1-C20 alkyl group" refers to a straight-chain alkyl group or a branched alkyl group having 1 to 20 carbon atoms. For example, the number of carbon atoms can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc. Specific groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, etc., and similar groups.

[0051] As mentioned in the present invention, the term "alkenyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having at least one carbon-carbon double bond, such as the "C2-C20 alkenyl", for example, the number of carbon atoms can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., referring to a straight or branched alkenyl with 2 to 20 carbon atoms, specific groups such as vinyl, allyl, isopropenyl, 2-butenyl, etc., and similar groups.

[0052] As mentioned in the present invention, the term "alkynyl" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having at least one carbon-carbon triple bond, such as the "C2-C20 alkynyl", for example, the number of carbon atoms can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., referring to a straight or branched alkynyl group with 2 to 20 carbon atoms, specific groups such as ethynyl, 2-propynyl, etc., and similar groups.

[0053] As mentioned in the present invention, the term "aryl" includes monocyclic, polycyclic or condensed aromatic groups, and the rings may be interrupted by short non-aromatic units, including but not limited to phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylene, pyrene, naphthphenyl, perylene, chrysene, condensed tetraphenyl, fluoranthenyl or spirobifluorenyl, and derivatives thereof.

[0054] As mentioned in the present invention, the term "halogen atom" includes F, Cl, Br, and I.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) The technical solution of the present invention adopts a pulse potential. The positive potential oxidizes the divalent manganese ions into permanganate ions and couples the oxidation of organic matter in situ. The negative potential reduces the manganese dioxide deposited on the electrode surface into divalent manganese ions, thereby realizing the circulation of the redox couple composed of divalent manganese ions and permanganate ions, and greatly reducing the amount of permanganate ions.

[0057] (2) The present invention adopts a one-step method to regenerate permanganate ions and couples the oxidation of organic matter in situ, thereby avoiding the separation and purification steps in the traditional potassium permanganate regeneration process.

[0058] (3) The method of the present invention is carried out at room temperature and pressure, with low energy consumption and low carbon emissions. BRIEF DESCRIPTION OF THE DRAWINGS

[0059] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0060] Figure 1 Schematic diagram of the in situ coupling of electrochemical regeneration of permanganate ions with organic matter oxidation.

[0061] Figure 2 1 is a curve diagram of the change of current density over time in Example 1 and Comparative Example 1.

[0062] Figure 3 This is a scanning electron microscope image of the anode carbon paper after electrolysis in Example 1.

[0063] Figure 4 This is a scanning electron microscope image of the anode carbon paper after electrolysis in Comparative Example 1. DETAILED DESCRIPTION

[0064] Unless otherwise defined herein, scientific and technological terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0065] It should be noted that specific details are described in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in a variety of other ways different from those described herein, and those skilled in the art can make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0066] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but it will be appreciated by those skilled in the art that the following embodiments and examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified, proceed according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0067] In a first aspect, the present invention provides a method for regenerating permanganate ions using a pulse potential and in-situ coupling organic oxidation, the method comprising the following steps:

[0068] (1) introducing an anolyte containing divalent manganese ions and organic matter into an electrochemical reaction device;

[0069] (2) A pulse voltage is applied between the anode and cathode of the electrochemical reaction device to obtain an electrolyte containing divalent manganese ions and an oxide of an organic substance.

[0070] The invention provides a pulse potential method, which regenerates permanganate ions and couples in-situ oxidation of organic matter in one step at room temperature and pressure, thereby solving the problems of large amount of permanganate used, high energy consumption in the regeneration process and many separation steps.

[0071] like Figure 1 As shown in the figure, taking the organic raw material as cyclic sulfite and the oxidation product as cyclic sulfate as an example, in the process of applying a pulse voltage between the anode and the cathode of the electrochemical reaction device, when a positive potential is applied, most of the divalent manganese ions (Mn 2+ ) is oxidized to permanganate ions (MnO4 - ), a small part is oxidized to manganese dioxide (MnO2); at the same time, in the process of applying the pulse voltage forward potential, permanganate ions (MnO4 - ) as an oxidant, in situ coupled with organic matter to produce an oxidation reaction to obtain the oxide of the organic matter, and at the same time, permanganate ions (MnO4 - ) is reduced to divalent manganese ions (Mn 2+ When a negative potential is applied, manganese dioxide (MnO2) is reduced to divalent manganese ions (Mn 2+), realizing the circulation of the redox couple composed of divalent manganese ions and permanganate ions.

[0072] As an optional embodiment, in step (1), the divalent manganese ions are derived from divalent manganese salts.

[0073] As an optional embodiment, in step (1), the divalent manganese salt is selected from any one or a combination of at least two of manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese chloride or manganese phosphate.

[0074] As an optional embodiment, in step (1), in the anode electrolyte, the concentration of the divalent manganese ions is 0.0001 to 1 mol / L, for example, it can be 0.0001 mol / L, 0.0002 mol / L, 0.0004 mol / L, 0.0005 mol / L, 0.0006 mol / L, 0.0008 mol / L, 0.001 mol / L, 0.005 mol / L, 0.01 mol / L, 0.05 mol / L, 0.1 mol / L, 0.5 mol / L, 1 mol / L, etc.

[0075] As an optional embodiment, in step (1), the organic matter is selected from any one of cyclic sulfites, thioethers, alcohols or aldehydes.

[0076] As an optional embodiment, in step (1), the structural formula of the cyclic sulfite is Wherein, R is selected from any one of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and n is an integer between 0 and 2.

[0077] As an optional embodiment, in step (1), the structural formula of the cyclic sulfite is Among them, R is selected from any one of a hydrogen atom, a halogen atom, a C1-C20 alkyl group (for example, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, a C7 alkyl group, a C8 alkyl group, a C9 alkyl group, a C10 alkyl group, a C12 alkyl group, a C14 alkyl group, a C16 alkyl group, a C18 alkyl group, and a C20 alkyl group), a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a C6-C12 aryl group, and n is an integer between 0 and 2, for example, it can be 0, 1, or 2.

[0078] As an optional embodiment, in step (1), the structural formula of the thioether is Wherein, R1 and R2 are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0079] As an optional embodiment, in step (1), the structural formula of the thioether is wherein R1 and R2 are each independently selected from C1-C20 alkyl (e.g., C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C12 alkyl, C14 alkyl, C16 alkyl, C18 alkyl, C20 alkyl), C2-C20 alkenyl (e.g., C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl, C7 alkenyl, C8 alkenyl, C9 alkenyl, C10 alkenyl, C12 alkyl, C14 alkyl, C16 alkyl, C18 alkyl, C20 alkyl), The present invention can be any one of a C2-C20 alkynyl group (for example, a C2 alkynyl group, a C3 alkynyl group, a C4 alkynyl group, a C5 alkynyl group, a C6 alkynyl group, a C7 alkynyl group, a C8 alkynyl group, a C9 alkynyl group, a C10 alkynyl group, a C12 alkynyl group, a C14 alkynyl group, a C16 alkynyl group, a C18 alkynyl group, and a C20 alkynyl group) or a C6-C12 aryl group (for example, a C6 aryl group, a C8 aryl group, a C10 aryl group, and a C12 aryl group).

[0080] As an optional embodiment, in step (1), the structural formula of the alcohol is R′-OH, wherein R′ is selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0081] As an optional embodiment, in step (1), the structural formula of the alcohol is R′-OH, wherein R′ is selected from C1-C20 alkyl (for example, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C12 alkyl, C14 alkyl, C16 alkyl, C18 alkyl, C20 alkyl), C2-C20 alkenyl (for example, C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl, C7 alkenyl, C The present invention can be any one of a C2-C20 alkynyl group (for example, a C2 alkynyl group, a C3 alkynyl group, a C4 alkynyl group, a C5 alkynyl group, a C6 alkynyl group, a C7 alkynyl group, a C8 alkynyl group, a C9 alkynyl group, a C10 alkynyl group, a C12 alkynyl group, a C14 alkynyl group, a C16 alkynyl group, a C18 alkynyl group, and a C20 alkynyl group) or a C6-C12 aryl group (for example, a C6 aryl group, a C8 aryl group, a C10 aryl group, and a C12 aryl group).

[0082] As an optional embodiment, in step (1), the structural formula of the aldehyde is R"-CHO, wherein R" is selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0083] As an optional embodiment, in step (1), the structural formula of the aldehyde is R″-CHO, wherein R″ is selected from C1-C20 alkyl (for example, C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, C10 alkyl, C12 alkyl, C14 alkyl, C16 alkyl, C18 alkyl, C20 alkyl), C2-C20 alkenyl (for example, C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl, C7 alkenyl, C The present invention can be any one of a C2-C20 alkynyl group (for example, a C2 alkynyl group, a C3 alkynyl group, a C4 alkynyl group, a C5 alkynyl group, a C6 alkynyl group, a C7 alkynyl group, a C8 alkynyl group, a C9 alkynyl group, a C10 alkynyl group, a C12 alkynyl group, a C14 alkynyl group, a C16 alkynyl group, a C18 alkynyl group, and a C20 alkynyl group) or a C6-C12 aryl group (for example, a C6 aryl group, a C8 aryl group, a C10 aryl group, and a C12 aryl group).

[0084] As an optional embodiment, in step (1), in the anode electrolyte, the concentration of the organic matter is 0.001-10 mol / L, for example, it can be 0.001 mol / L, 0.002 mol / L, 0.004 mol / L, 0.005 mol / L, 0.006 mol / L, 0.008 mol / L, 0.01 mol / L, 0.02 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.08 mol / L, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, etc.

[0085] As an optional embodiment, in step (1), the electrolyte further includes an inorganic acid and / or a polar organic solvent.

[0086] As an optional embodiment, in step (1), the inorganic acid is selected from any one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or perchloric acid, or a combination of at least two thereof.

[0087] As an optional embodiment, in step (1), the polar organic solvent is selected from any one or a combination of at least two of methanol, ethanol, isopropanol, ethylene glycol, acetone, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane or N,N-dimethylformamide.

[0088] As an optional embodiment, in step (1), in the anode electrolyte, the concentration of the inorganic acid is 0 to 10 mol / L, for example, it can be 0 mol / L, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L, 5 mol / L, 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, 10 mol / L, etc.

[0089] As an optional embodiment, in step (1), in the anode electrolyte, the volume ratio of the inorganic acid to the polar organic solvent is (0-100):1, for example, it can be 0:1, 1:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, etc.

[0090] As an optional embodiment, step (1) further comprises introducing a cathode electrolyte.

[0091] As an alternative embodiment, the catholyte comprises an inorganic acid.

[0092] As an optional embodiment, in the cathode electrolyte, the concentration of the inorganic acid is 0 to 10 mol / L, for example, it can be 0 mol / L, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L, 5 mol / L, 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, 10 mol / L and the like.

[0093] As an optional embodiment, in the cathode electrolyte, the inorganic acid is selected from any one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or perchloric acid, or a combination of at least two thereof.

[0094] As an optional embodiment, in step (2), the anode includes any one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foam titanium, titanium fiber felt or powder sintered porous titanium, or a combination of at least two thereof.

[0095] As an optional embodiment, in step (2), the cathode includes any one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foam titanium, titanium fiber felt or powder sintered porous titanium, or a combination of at least two thereof.

[0096] As an optional embodiment, in step (2), the cathode is loaded with a platinum catalyst.

[0097] As an optional embodiment, in step (2), the platinum loading in the cathode is 0.01 to 4 mg / cm 2 , for example, it can be 0.01 mg / cm 2 , 0.05mg / cm 2 , 0.1mg / cm 2 , 0.5mg / cm 2 , 1mg / cm 2 , 1.5mg / cm 2 , 2mg / cm 2 , 2.5mg / cm 2 、3mg / cm 2 、3.5mg / cm 2 , 4mg / cm 2 wait.

[0098] As an optional embodiment, in step (2), the electrochemical reaction device also includes a proton exchange membrane.

[0099] As an optional embodiment, in step (2), the proton exchange membrane is Nafion117.

[0100] As an optional embodiment, in step (2), applying the pulse voltage includes applying a positive potential and applying a negative potential;

[0101] Wherein, the forward potential is 1.0-2.5V, for example, it can be 1.0V, 1.2V, 1.4V, 1.5V, 1.6V, 1.8V, 2.0V, 2.4V, 2.5V, etc., and the duration is 1-600s, for example, it can be 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 150s, 200s, 250s, 300s, 350s, 400s, 450s, 500s, 550s, 600s, etc.

[0102] Among them, the negative potential is -2.0 to -0.1V, for example, it can be -2.0V, -1.8V, -1.6V, -1.5V, -1.4V, -1.2V, -1.0V, -0.8V, -0.6V, -0.4V, -0.2V, -0.1V, etc., and the duration is 1 to 60s, for example, it can be 1s, 5s, 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, etc.

[0103] Preferably, in step (2), the total cycle time of applying the pulse voltage is 0.1 to 10 h, for example, it can be 0.1 h, 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, etc.

[0104] As an optional embodiment, in step (2), the divalent manganese ions are derived from divalent manganese salts.

[0105] As mentioned above, when a negative potential is applied, manganese dioxide (MnO2) will be reduced to divalent manganese ions (Mn 2+ ), therefore, the electrolyte obtained in the final step (2) still contains the same concentration of divalent manganese ions, realizing the cyclic conversion of manganese elements between low-valent state-high-valent state-low-valent state, so that permanganate ions can be regenerated by pulse potential, so that the manganese elements can be reused, that is, solving the problems of large amount of permanganate usage, high energy consumption in the regeneration process and many separation steps.

[0106] As an optional embodiment, in step (2), the divalent manganese salt is selected from any one or a combination of at least two of manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese chloride or manganese phosphate.

[0107] As an optional embodiment, in step (2), in the electrolyte, the concentration of the divalent manganese ions is 0.0001 to 1 mol / L, for example, 0.0001 mol / L, 0.0002 mol / L, 0.0004 mol / L, 0.0005 mol / L, 0.0006 mol / L, 0.0008 mol / L, 0.001 mol / L, 0.002 mol / L, 0.004 mol / L, / L, 0.005mol / L, 0.006mol / L, 0.008mol / L, 0.01mol / L, 0.02mol / L, 0.04mol / L, 0.05mol / L, 0.06mol / L, 0.08mol / L, 0.1mol / L, 0.2mol / L, 0.4mol / L, 0.5mol / L, 0.6mol / L, 0.8mol / L, 1mol / L, etc.

[0108] As an optional embodiment, in step (2), the oxide of the organic matter is selected from any one of cyclic sulfate, sulfone or acid.

[0109] As an optional embodiment, in step (2), the structural formula of the cyclic sulfate is Wherein, R is selected from any one of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and n is an integer between 0 and 2.

[0110] As an optional embodiment, when the organic raw material in step (1) is selected from cyclic sulfite, in step (2), cyclic sulfate is prepared by oxidation, and the reaction formula is as follows:

[0111]

[0112] Preferably, the structural formula of the sulfone is Wherein, R1 and R2 are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0113] As an optional embodiment, when the organic raw material in step (1) is selected from sulfide, in step (2), sulfone is prepared by oxidation, and the reaction formula is as follows:

[0114]

[0115] As an optional embodiment, the acid has a structural formula of R′-COOH or R″-COOH, wherein R′ and R″ are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group.

[0116] As an optional embodiment, when the organic raw material in step (1) is selected from alcohol or aldehyde, in step (2), an acid is prepared by oxidation, and the reaction formula is as follows:

[0117]

[0118] As an optional embodiment, in step (2), in the electrolyte, the concentration of the oxide of the organic matter is 0.001 to 10 mol / L, for example, it can be 0.001 mol / L, 0.002 mol / L, 0.004 mol / L, 0.005 mol / L, 0.006 mol / L, 0.008 mol / L, 0.01 mol / L, 0.02 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.08 mol / L, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, etc.

[0119] As an optional embodiment, the method further comprises step (3) post-processing;

[0120] When the oxide of the organic matter is solid, the post-treatment is: concentrating, filtering, washing and drying the electrolyte containing the divalent manganese ions and the oxide of the organic matter in sequence to obtain the oxide of the organic matter;

[0121] When the oxide of the organic matter is liquid, the post-treatment is: extracting the electrolyte containing the divalent manganese ions and the oxide of the organic matter to obtain an organic phase, and then concentrating the organic phase to obtain the oxide of the organic matter.

[0122] As an optional embodiment, the extraction agent used in the extraction is dichloromethane.

[0123] The present invention is further described below by means of specific examples and comparative examples. However, it should be understood that these examples are only used for more detailed description and should not be construed as limiting the present invention in any form.

[0124] Example 1

[0125] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling oxidation of organic matter, the method comprising the following steps:

[0126] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2), the proton exchange membrane is Nafion 117. An anolyte is introduced from the anode of the electrochemical reaction device at a flow rate of 20 mL / min, and the anolyte comprises: 0.0005 mol / L manganese sulfate, 0.5 mol / L ethylene sulfite, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile; a catholyte is introduced from the cathode of the electrochemical reaction device at a flow rate of 20 mL / min, and the catholyte comprises: 10 mL 0.5 mol / L sulfuric acid.

[0127] (2) A pulse voltage (1.8 V for 60 s, -2.0 V for 10 s) was applied between the anode and cathode electrodes of the electrochemical reaction device and the voltage was stopped after 1 hour.

[0128] Record the current of the device and draw a graph of the current density versus time, such as Figure 2 As shown by the solid line, the oxidation current density is between 85 and 50 mA / cm 2 The scanning electron microscope image of the anode carbon paper after electrolysis is shown in Figure 2. Figure 3 As shown, there is no manganese dioxide deposition on the electrode surface.

[0129] (3) The above-mentioned anolyte containing divalent manganese ions and organic oxides is subjected to reduced pressure distillation, filtration, washing and drying to obtain vinyl sulfate, with a product yield of 85% and a purity of 99%.

[0130] Example 2

[0131] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling oxidation of organic matter, the method comprising the following steps:

[0132] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2 ), the proton exchange membrane is Nafion 117. An anolyte is introduced from the anode of the electrochemical reaction device at a flow rate of 20 mL / min, and the anolyte comprises: 0.0005 mol / L manganese sulfate, 0.5 mol / L ethylene sulfite, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile; a catholyte is introduced from the cathode of the electrochemical reaction device at a flow rate of 20 mL / min, and the catholyte comprises: 10 mL 0.5 mol / L sulfuric acid.

[0133] (2) A pulse voltage (1.8 V for 60 s, -2.0 V for 2 s) was applied between the anode and cathode electrodes of the electrochemical reaction device and the voltage was stopped after 1 h.

[0134] (3) The above-mentioned anolyte containing divalent manganese ions and organic oxides is subjected to reduced pressure distillation, filtration, washing and drying to obtain vinyl sulfate, with a product yield of 60% and a purity of 99%.

[0135] Example 3

[0136] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling oxidation of organic matter, the method comprising the following steps:

[0137] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2 ), the proton exchange membrane is Nafion 117. The anolyte is introduced from the anode of the electrochemical reaction device at a flow rate of 20 mL / min, and the anolyte comprises: 0.0005 mol / L manganese sulfate, 0.5 mol / L ethylene sulfite, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile. The catholyte is introduced from the cathode of the electrochemical reaction device at a flow rate of 20 mL / min, and the catholyte comprises: 10 mL 0.5 mol / L sulfuric acid.

[0138] (2) A pulse voltage (1.8 V for 300 s, -2.0 V for 10 s) was applied between the anode electrode and the cathode electrode of the electrochemical reaction device and the voltage was stopped after 1 hour.

[0139] (3) The above-mentioned anolyte containing divalent manganese ions and organic oxides is subjected to reduced pressure distillation, filtration, washing and drying to obtain vinyl sulfate, with a product yield of 51% and a purity of 99%.

[0140] Example 4

[0141] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling oxidation of organic matter, the method comprising the following steps:

[0142] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2 ), the proton exchange membrane is Nafion 117. The anolyte is introduced from the anode of the electrochemical reaction device at a flow rate of 20 mL / min, and the anolyte comprises: 0.0005 mol / L manganese sulfate, 0.5 mol / L dimethyl sulfide, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile. The catholyte is introduced from the cathode of the electrochemical reaction device at a flow rate of 20 mL / min, and the catholyte comprises: 10 mL 0.5 mol / L sulfuric acid.

[0143] (2) A pulse voltage (1.8 V for 60 s, -2.0 V for 10 s) was applied between the anode and cathode electrodes of the electrochemical reaction device and the voltage was stopped after 1 hour.

[0144] (3) The anolyte containing the divalent manganese ions and the organic oxide is extracted with dichloromethane and distilled under reduced pressure to obtain dimethyl sulfone, with a product yield of 95% and a purity of 98%.

[0145] Example 5

[0146] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling oxidation of organic matter, the method comprising the following steps:

[0147] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2 ), the proton exchange membrane is Nafion 117. The anolyte is introduced from the anode of the electrochemical reaction device at a flow rate of 20 mL / min, and the anolyte comprises: 0.0005 mol / L manganese sulfate, 0.5 mol / L benzyl alcohol, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile. The catholyte is introduced from the cathode of the electrochemical reaction device at a flow rate of 20 mL / min, and the catholyte comprises: 10 mL 0.5 mol / L sulfuric acid.

[0148] (2) A pulse voltage (1.8 V for 60 s, -2.0 V for 10 s) was applied between the anode electrode and the cathode electrode of the electrochemical reaction device for 1 hour and then stopped.

[0149] (3) The above-mentioned anolyte containing divalent manganese ions and organic oxides is subjected to reduced pressure distillation, filtration, washing and drying to obtain benzoic acid, with a product yield of 90% and a purity of 99%.

[0150] Example 6

[0151] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling oxidation of organic matter, the method comprising the following steps:

[0152] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2), the proton exchange membrane is Nafion 117. The anolyte is introduced from the anode of the electrochemical reaction device at a flow rate of 20 mL / min, and the anolyte comprises: 0.0005 mol / L manganese sulfate, 0.5 mol / L benzaldehyde, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile. The catholyte is introduced from the cathode of the electrochemical reaction device at a flow rate of 20 mL / min, and the catholyte comprises: 10 mL 0.5 mol / L sulfuric acid.

[0153] (2) A pulse voltage (1.6 V for 60 s, -2.0 V for 10 s) was applied between the anode electrode and the cathode electrode of the electrochemical reaction device for 1 hour and then stopped.

[0154] (3) The anolyte containing divalent manganese ions and organic oxides is subjected to reduced pressure distillation, filtration, washing and drying to obtain benzoic acid, with a product yield of 95% and a purity of 99%.

[0155] Example 6

[0156] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation, which is different from Example 1 only in that the anolyte contains: 0.005 mol / L manganese sulfate, 0.5 mol / L vinyl sulfite, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile; other settings are exactly the same as Example 1.

[0157] Result: Ethylene sulfate was obtained with a yield of 85% and a purity of 96%.

[0158] Example 7

[0159] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation. The only difference from Example 1 is that the anolyte contains: 0.001 mol / L manganese sulfate, 1 mol / L vinyl sulfite, 5 mL 1 mol / L sulfuric acid and 5 mL acetonitrile; other settings are exactly the same as Example 1.

[0160] Result: Ethylene sulfate was obtained with a yield of 78% and a purity of 98%.

[0161] Example 8

[0162] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation. The only difference from Example 1 is that the anode electrolyte contains: 0.0005 mol / L manganese nitrate, 0.5 mol / L vinyl sulfite, 5 mL 0.5 mol / L nitric acid and 5 mL 1,4-dioxane; other settings are exactly the same as Example 1.

[0163] Result: Ethylene sulfate was obtained with a yield of 80% and a purity of 99%.

[0164] Example 9

[0165] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation, which is different from Example 1 only in that the anolyte contains: 0.0005 mol / L manganese acetate, 0.5 mol / L vinyl sulfite, 5 mL 0.5 mol / L acetic acid and 5 mL N,N-dimethylformamide; other settings are exactly the same as Example 1.

[0166] Result: Ethylene sulfate was obtained with a yield of 72% and a purity of 98%.

[0167] Example 10

[0168] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation. The only difference from Example 1 is that the forward potential is 1.6V and the duration is 60s; the negative potential is -2V and the duration is 10s; the other settings are exactly the same as Example 1.

[0169] Result: Ethylene sulfate was obtained with a yield of 31% and a purity of 99%.

[0170] Embodiment 11

[0171] This embodiment provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation. The only difference from Example 1 is that the forward potential is 1.8V and the duration is 60s; the negative potential is -1V and the duration is 10s; the other settings are exactly the same as Example 1.

[0172] Result: Ethylene sulfate was obtained with a yield of 60% and a purity of 99%.

[0173] Comparative Example 1

[0174] This comparative example provides a method for regenerating permanganate ions using pulse potential and in-situ coupling organic oxidation, the method comprising the following steps:

[0175] (1) Preparation of an electrochemical reaction device, with carbon paper as the anode and platinum-coated titanium felt as the cathode (the platinum loading is 0.5 mg / cm 2), the proton exchange membrane is Nafion 117. Anode electrolyte is introduced from the anode at a flow rate of 20 mL / min, and the anode electrolyte contains: 0.0005 mol / L manganese sulfate, 0.5 mol / L ethylene sulfite, 5 mL 0.5 mol / L sulfuric acid and 5 mL acetonitrile; cathode electrolyte is introduced from the cathode at a flow rate of 20 mL / min, and the cathode electrolyte contains: 10 mL 0.5 mol / L sulfuric acid.

[0176] (2) A constant voltage of 1.8 V was applied between the anode and cathode electrodes of the electrochemical reaction device and the reaction was stopped after 1 hour.

[0177] Record the current of the device and draw a graph of the current density versus time, such as Figure 2 As shown by the dotted line, the oxidation current density is 85 mA / cm 2 Reduced to 32mA / cm 2 . Scanning electron microscope image of anode carbon paper after electrolysis, such as Figure 4 As shown, a large amount of manganese dioxide is deposited on the electrode surface.

[0178] (3) The anolyte containing divalent manganese ions and organic oxides is subjected to reduced pressure distillation, filtration, washing and drying to obtain vinyl sulfate, with a product yield of 56% and a purity of 99%.

[0179] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for regenerating permanganate ions and in-situ coupling organic oxidation using pulse potential, characterized in that: The method comprises the following steps: (1) introducing an anolyte containing divalent manganese ions and organic matter into an electrochemical reaction device; (2) A pulse voltage is applied between the anode and cathode of the electrochemical reaction device to obtain an electrolyte containing divalent manganese ions and an oxide of an organic substance.

2. The method for regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (1), the divalent manganese ions are derived from divalent manganese salts; Preferably, the divalent manganese salt is selected from any one or a combination of at least two of manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese chloride or manganese phosphate; Preferably, in step (1), in the anolyte, the concentration of the divalent manganese ions is 0.0001 to 1 mol / L.

3. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (1), the organic matter is selected from any one of cyclic sulfites, thioethers, alcohols or aldehydes; Preferably, the structural formula of the cyclic sulfite is Wherein, R is selected from any one of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and n is an integer between 0 and 2; Preferably, the structural formula of the thioether is Wherein, R1 and R2 are each independently selected from any one of alkyl, alkenyl, alkynyl or aryl; Preferably, the alcohol has a structural formula of R′-OH, wherein R′ is selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group; Preferably, the structural formula of the aldehyde is R″-CHO, wherein R″ is selected from any one of alkyl, alkenyl, alkynyl or aryl; Preferably, in step (1), the concentration of the organic matter in the anolyte is 0.001 to 10 mol / L.

4. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (1), the anolyte further comprises an inorganic acid and / or a polar organic solvent; Preferably, the inorganic acid is selected from any one or a combination of at least two of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or perchloric acid; Preferably, the polar organic solvent is selected from any one or a combination of at least two of methanol, ethanol, isopropanol, ethylene glycol, acetone, acetonitrile, dimethyl sulfoxide, tetrahydrofuran, 1,4-dioxane or N,N-dimethylformamide; Preferably, in the anolyte, the concentration of the inorganic acid is 0 to 10 mol / L; Preferably, in the anode electrolyte, the volume ratio of the inorganic acid to the polar organic solvent is (0-100):

1.

5. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: Step (1) further comprises introducing a cathode electrolyte; Preferably, the catholyte comprises an inorganic acid; Preferably, in the cathode electrolyte, the concentration of the inorganic acid is 0 to 10 mol / L; Preferably, in the cathode electrolyte, the inorganic acid is selected from any one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or perchloric acid, or a combination of at least two thereof.

6. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (2), the anode comprises any one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foam titanium, titanium fiber felt or powder sintered porous titanium, or a combination of at least two thereof; Preferably, in step (2), the cathode comprises any one of carbon fiber paper, carbon fiber cloth, carbon fiber felt, titanium mesh, foam titanium, titanium fiber felt or powder sintered porous titanium, or a combination of at least two thereof; Preferably, the cathode is loaded with a platinum catalyst; Preferably, the platinum loading in the cathode is 0.01 to 4 mg / cm 2 .

7. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (2), applying the pulse voltage includes applying a positive potential and applying a negative potential; Wherein, the forward potential is 1.0 to 2.5 V, and the duration is 1 to 600 s; Wherein, the negative potential is -2.0 to -0.1 V, and the duration is 1 to 60 s; Preferably, in step (2), the total cycle time of applying the pulse voltage is 0.1 to 10 hours.

8. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (2), the divalent manganese ions are derived from divalent manganese salts; Preferably, the divalent manganese salt is selected from any one or a combination of at least two of manganese sulfate, manganese nitrate, manganese acetate, manganese oxalate, manganese chloride or manganese phosphate; Preferably, in step (2), in the electrolyte, the concentration of the divalent manganese ions is 0.0001 to 1 mol / L.

9. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: In step (2), the oxide of the organic compound is selected from any one of cyclic sulfate, sulfone or acid; Preferably, the structural formula of the cyclic sulfate is Wherein, R is selected from any one of a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group, and n is an integer between 0 and 2; Preferably, the structural formula of the sulfone is Wherein, R1 and R2 are each independently selected from any one of alkyl, alkenyl, alkynyl or aryl; Preferably, the acid has a structural formula of R′-COOH or R″-COOH, wherein R′ and R″ are each independently selected from any one of an alkyl group, an alkenyl group, an alkynyl group or an aryl group; Preferably, in step (2), the concentration of the oxide of the organic matter in the electrolyte is 0.001 to 10 mol / L.

10. The method of regenerating permanganate ions by pulse potential and in-situ coupling organic oxidation according to claim 1, characterized in that: The method further comprises step (3) post-processing; When the oxide of the organic matter is solid, the post-treatment is: concentrating, filtering, washing and drying the electrolyte containing the divalent manganese ions and the oxide of the organic matter in sequence to obtain the oxide of the organic matter; When the oxide of the organic matter is liquid, the post-treatment is: extracting the electrolyte containing the divalent manganese ions and the oxide of the organic matter to obtain an organic phase, and then concentrating the organic phase to obtain the oxide of the organic matter.

Images