CN108866821B - Preparation method of high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane - Google Patents

Preparation method of high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane Download PDF

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CN108866821B
CN108866821B CN201810840101.8A CN201810840101A CN108866821B CN 108866821 B CN108866821 B CN 108866821B CN 201810840101 A CN201810840101 A CN 201810840101A CN 108866821 B CN108866821 B CN 108866821B
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ortho
cardanol modified
fiber membrane
cardanol
thermosetting phenolic
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CN108866821A (en
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曹健
张彩云
杨凯
刘淑萍
魏朋
何建新
拱荣华
李洁
任东雪
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Zhongyuan University of Technology
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
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    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
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    • D06C7/04—Carbonising or oxidising

Abstract

The invention discloses a preparation method of a high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane, which comprises the following steps: reacting phenols, aldehyde compounds and cardanol under the action of a catalyst, and performing reduced pressure dehydration to prepare high-ortho cardanol modified phenolic resin; dissolving the thermosetting phenolic resin into alcohols and aldehyde compounds to react under the action of a catalyst to prepare high-ortho cardanol modified thermosetting phenolic resin; the modified high-ortho-cardanol modified high-ortho-thermosetting phenolic fiber membrane is used as a carbon precursor solution, coaxial electrostatic spinning is adopted, and heating and curing are carried out to obtain a high-ortho-cardanol modified high-ortho-thermosetting phenolic fiber membrane with a partially compatible skin-core structure; then in N2Carbonizing and activating under protection to obtain the high-ortho cardanol modified thermosetting phenolic group hollow nano gradient activated carbon fiber membrane. Compared with the prior art, the method has the advantages of simplicity, easiness in implementation, environmental friendliness, controllable hollowness, high curing efficiency and high mechanical property.

Description

Preparation method of high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane
Technical Field
The invention belongs to the field of preparation of special carbon materials, and particularly relates to a preparation method of a high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane.
Background
Phenolic resin has many advantages as a carbon precursor, but the heat resistance is relatively poor, wherein the problems of long curing period, more processes, high cost, environmental pollution, low molecular weight and poor spinnability of thermosetting phenolic aldehyde can not be avoided. In order to improve the heat resistance of phenolic fiber, resin is modified by chemical method, cardanol mainly has a structure that a monoene or diolefin long chain with 15 carbons is substituted by phenol in meta position, so that the cardanol has not only the characteristics of phenolic compound but also the flexibility of aliphatic compound, the modified phenolic resin can obviously improve the heat resistance of material, and C is C15The side chain can obviously improve the toughness of the material. The phenolic resin is modified by cardanol, so that the toughness of the phenolic resin is increased, and the high-temperature hot brittleness of the phenolic resin is reduced. The method is simple to operate, environment-friendly and low in production cost.
The prior methods for preparing the phenolic aldehyde-based hollow activated carbon fiber comprise a semi-curing-dissolving method and a profiled spinneret spinning method, but the prepared fiber is thick, complicated in preparation, high in cost, heavy in environmental pollution and difficult to apply in a large area. The coaxial electrostatic spinning method can well solve the problems, and although the coaxial electrostatic spinning method is widely applied to the preparation and production of various polymer-based micro-nano hollow fibers at present, the coaxial electrostatic spinning method is not applied to the spinning of high-ortho thermosetting phenolic resin. Meanwhile, the hollow activated carbon fiber obtained by the traditional spinning method or electrostatic spinning method has uniform pore size distribution, and the sizes of pores on the inner wall and the outer wall of the fiber are not changed, so that the adsorption performance of the activated carbon material is influenced. The preparation method for preparing the high-ortho thermosetting phenolic aldehyde-based hollow nano gradient activated carbon fiber membrane by the coaxial electrostatic spinning method simplifies the preparation steps, improves the curing efficiency, and can further improve the adsorption property, the mechanical property, the electrochemical property, the heat-insulating property and the like, so that the high-ortho thermosetting phenolic aldehyde-based hollow nano gradient activated carbon fiber membrane can be widely applied to the fields of hydrogen storage industry, environmental protection, water purification, electrochemistry and the like.
Disclosure of Invention
Aiming at the problems, cardanol is added in the synthesis process of phenolic resin to obtain high-ortho-position cardanol modified phenolic resin, the high-ortho-position cardanol modified thermosetting phenolic resin is obtained through reaction with aldehydes, and the continuous, flexible and high-carbon-residue-rate preparation method of the high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano activated carbon fiber is prepared through a coaxial electrostatic spinning method.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane comprises the following steps:
(1) boiling cardanol, phenols and aldehyde compounds for 2-6h under the action of a first catalyst, then dropwise adding an acid catalyst, continuing to carry out boiling reaction for 0.5-4h, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 105-165 ℃, and continuing to react for 0.1-4h to obtain high-ortho cardanol modified phenolic resin;
(2) dissolving high-ortho cardanol modified phenolic resin in an alcohol compound, adding an aldehyde compound and a second catalyst, reacting for 3-7h at 45-85 ℃, cooling to room temperature, adjusting the pH value to be 5-8.0, performing suction filtration, removing impurities, then performing reduced pressure dehydration, wherein the termination temperature of the reduced pressure dehydration is 50-90 ℃, and the time of the reduced pressure dehydration is 0.5-3h, so as to prepare the high-ortho cardanol modified thermosetting phenolic resin;
(3) dissolving the high-ortho cardanol modified thermosetting phenolic resin and the high-molecular linear polymer in a solvent to prepare a shell solution, dissolving the high-molecular linear polymer in the solvent to prepare a core solution, and heating and curing by adopting coaxial electrostatic spinning to obtain a high-ortho cardanol modified high-ortho thermosetting phenolic fiber membrane with a partially compatible skin-core structure; then in N2Carbonizing and activating under protection to obtain the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane。
In the step (1), the phenolic compound is phenol, p-cresol or xylenol; the aldehyde compound is formaldehyde, acetaldehyde or furfural, and the first catalyst is zinc acetate, cadmium acetate or zinc oxide; the acid catalyst is phosphoric acid, nitric acid, sulfuric acid with the mass fraction of 98% or hydrochloric acid with the mass fraction of 37%; wherein the molar ratio of the phenols to the aldehydes is 1 (0.6-2), the mass ratio of the phenolic compounds to the first catalyst is 100 (0.8-3), and the mass ratio of the phenolic compounds to the acid catalyst is 100 (0.2-2); the mass ratio of phenols to cardanol is 100 (5-35).
In the step (2), the alcohol compound is methanol or ethanol; the aldehyde compound is at least one of formaldehyde, acetaldehyde and furfural, and the second catalyst is triethanolamine, barium carbonate or barium acetate; the acid used for adjusting the pH is one of hydrochloric acid, oxalic acid or sulfuric acid with the mass fraction of 98%; wherein the mass ratio of the high-ortho-cardanol modified phenolic resin to the alcohols is 1:1-3, the molar ratio of the high-ortho-cardanol modified phenolic resin to the aldehydes is 1:1-10, and the mass ratio of the high-ortho-cardanol modified phenolic resin to the second catalyst is 100: 1-5.
In the step (3), the high molecular linear polymer is PVB, PVA or PVP, the solvent is at least one of ethanol, methanol, tetrahydrofuran, distilled water and N.N-dimethylformamide, wherein the mass fraction ratio of the components of the shell liquid is high-ortho cardanol modified thermosetting phenolic resin to the high molecular linear polymer and the solvent is = (18-75) = (15-0): (67-25), and the mass fraction ratio of the components of the core liquid is high molecular linear polymer and the solvent is = (1-15): (99-85).
In the step (3), the coaxial electrostatic spinning parameters comprise temperature T =15-30 ℃, relative humidity RH =35-70%, receiving distance d =12-25cm, spinning voltage U =13-28kV, and inner and outer axis spinning speed Vin: Vout =1: 1-3.
In the step (3), the heating curing temperature is 120-.
In the step (3), the activating agent is water vapor and CO2、KOH、ZnCl2One of KCl。
In the step (3), during one-step activation, the mass ratio of the solid activating agent to the high-ortho cardanol modified phenolic fiber membrane is 0.5-8: 1; when carbonizing and activating are carried out firstly, the mass ratio of the solid activating agent to the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane is 0.5-8: 1; the flow rate of the gas activating agent is 10-30 ml/min.
In the step (3), the temperature rise rate of carbonization and activation is 1-10 ℃/min, the carbonization temperature is 400-1100 ℃, the carbonization time is 0.5-2.5h, the activation temperature is 400-1000 ℃, and the activation time is 0.1-2h, so that the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is obtained.
The invention has the beneficial effects that: 1. according to the high-ortho-position cardanol modified thermosetting phenolic resin prepared by the invention, as the cardanol has a main structure that a monoene or diolefin long chain with 15 carbons is substituted in the meta position of phenol, the ablation resistance, the thermal stability, the mechanical property and the like of the high-ortho-position cardanol modified thermosetting phenolic fiber membrane and the activated carbon fiber membrane are improved, and in addition, natural cardanol is used, so that the production process is more environment-friendly, the cost is greatly reduced, and the processing is simple; the high-efficiency epoxy resin has higher para-position activity, is beneficial to further reacting with formaldehyde to generate high-ortho thermosetting phenolic resin, and simultaneously the residual para-position can be reacted more quickly in the primary fiber curing, so that the reaction efficiency is improved, the energy consumption is reduced, and the high-efficiency epoxy resin has the characteristics of environmental friendliness and high efficiency; 2. when the high-ortho thermosetting phenolic resin is synthesized, triethanolamine, barium carbonate and barium acetate are used as catalysts, so that the removal (precipitation or volatilization) of the catalysts is facilitated when the pH value is adjusted, the content of the catalysts/reaction products in the resin is reduced, and the stability of the resin in use is improved; the prepared high-ortho thermosetting phenolic resin has the characteristics of high molecular weight and high spinnability of the thermoplastic phenolic resin, has the characteristic that the thermosetting phenolic resin can be directly carbonized only by simple heating and curing, and solves the problems of low molecular weight and poor spinnability of the thermosetting phenolic resin, long curing time of the thermoplastic phenolic resin, multiple curing processes, high cost and environmental pollution; 3. the high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane prepared by adopting a coaxial electrostatic spinning method has the characteristics of simple preparation process, environmental friendliness, low energy consumption, controllable diameter, designable hollowness and the like; in the thermal curing process, the sheath-core layers are mutually diffused, so that a phenolic aldehyde concentration gradient is generated from the surface to the center, the phenolic aldehyde aperture gradient is generated after activation, and the larger the distance from the surface, the larger the macropores are. 4. Compared with the common phenolic aldehyde based active carbon fiber, the phenolic aldehyde based active carbon fiber has higher specific surface area and better toughness due to the hollow gradient structure, so the adsorption performance and the electrochemical performance are greatly improved, and the heat insulation performance is also greatly improved due to the fact that a large amount of static air is wrapped in the hollow cavity inside the phenolic aldehyde based active carbon fiber. Compared with the common phenolic aldehyde-based hollow activated carbon fiber, the hollow fiber has the advantages that the hollow fiber has uniform micro-nano size, the pore diameter of the cortex is distributed in a gradient manner, and meanwhile, the hollow fiber has a complete and continuous hollow structure, so that the development of the preparation of micro-nano hollow gradient structure materials is greatly promoted.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the following examples are illustrative only and are not intended to limit the scope of the invention, which is to be given numerous insubstantial modifications and adaptations by those skilled in the art based on the teachings set forth above.
Example 1
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling phenol, formaldehyde and cardanol under the action of zinc acetate for 2 hours, dropwise adding concentrated sulfuric acid to continuously react for 0.5 hour, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 105 ℃, reacting at constant temperature for 0.1 hour to obtain the high-ortho-position cardanol modified phenolic resin, wherein the molar ratio of phenol to formaldehyde is 1:0.7, the mass ratio of phenol to zinc acetate to concentrated sulfuric acid is 100:0.8: 0.2, and the mass ratio of phenol to cardanol is 100: 5;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in methanol, adding formaldehyde to react for 3 hours at 45 ℃ under the action of triethanolamine, cooling to room temperature, dropwise adding hydrochloric acid to adjust the pH value to =5, and performing suction filtration. Decompressing and dehydrating, heating to 45 ℃, and keeping the temperature for 0.5h to obtain the high-ortho cardanol modified thermosetting phenolic resin; wherein the mass ratio of the high-ortho-cardanol modified phenolic resin to the methanol is 1:1, the molar ratio of the high-ortho-cardanol modified phenolic resin to the formaldehyde is 1:1, and the mass ratio of the high-ortho-cardanol modified phenolic resin to the triethanolamine is 100: 1;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the mass fraction ratio of the shell liquid is high-ortho-position cardanol modified thermosetting phenolic resin and ethanol =75:25, the mass fraction ratio of the core liquid is PVB and ethanol =1:99, the coaxial electrostatic spinning parameters are T =15 ℃, RH =35%, d =12cm, U =13kV, and Vin: Vout =1:1. Curing the mixture for 0.5h in air at 120 ℃; heating to 400 ℃ at the heating rate of 1 ℃/min under the protection of nitrogen, carbonizing for 0.5h, introducing steam with the flow rate of 30ml/min, and activating for 0.1h to obtain the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 85 percent, the diameter distribution range of the activated carbon fiber of 690-1900nm, the inner diameter of 290-1120nm, the thermal conductivity coefficient of 141W/m.K and the specific surface area of 2400m2The iodine value is 179mg/g, the average micropore diameter is 0.7nm, the internal mesoporous diameter is 5nm, and the pore diameter is in gradient distribution. The specific capacitance in the Et4NBF4/PC electrolyte of 1 mol/L is 298F/g, and after the current density is increased from 50mA/g to 10A/g, the specific capacitance can still maintain 279F/g.
Example 2
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) and carrying out boiling reaction on phenol, acetaldehyde and cardanol for 2.5h under the action of chromium acetate, dropwise adding hydrochloric acid to continue reacting for 1h, carrying out reduced pressure dehydration, cooling to 40 ℃, slowly heating to 115 ℃, and carrying out constant temperature reaction for 0.5h to obtain the high-ortho-cardanol modified thermoplastic phenolic resin. Wherein the molar ratio of phenol to acetaldehyde is 1:0.8, the mass ratio of phenol to chromium acetate to hydrochloric acid is 100:1:0.5, and the mass ratio of phenol to cardanol is 100: 8;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in ethanol, adding acetaldehyde to react at 50 ℃ for 4h under the action of a catalyst barium acetate, cooling to room temperature, dropwise adding sulfuric acid to enable the pH to be =5.5, and performing suction filtration. Decompressing, dehydrating and heating to 55 ℃, and keeping the temperature for 1h to obtain the high-ortho cardanol modified thermosetting phenolic resin; the mass ratio of the high-ortho-cardanol modified phenolic resin to ethanol is 1:1.5, the molar ratio of the high-ortho-cardanol modified phenolic resin to acetaldehyde is 1:2, and the mass ratio of the high-ortho-cardanol modified phenolic resin to barium acetate is 100: 5;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the mass fraction ratio of the shell liquid is high-ortho-position cardanol modified thermosetting phenolic resin PVB: ethanol =70:0.05:29.95, the mass fraction ratio of the core liquid is PVB: ethanol =2:98, the coaxial electrostatic spinning parameters are T =20 ℃, RH =40%, d =16cm, U =15kV, and Vin: Vout =1:1. Curing the mixture for 1 hour at 140 ℃ in nitrogen; heating to 600 deg.C at a heating rate of 2 deg.C/min under nitrogen protection, carbonizing for 0.7h, introducing CO2The flow rate is 20ml/min, and the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is obtained after activation for 0.3 h.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 85 percent, the diameter distribution range of the activated carbon fiber is 500-940nm, the inner diameter is 245-510nm, the heat conductivity coefficient is 132W/m.K, and the specific surface area is 2698m2The iodine value is 199mg/g, the average micropore diameter is 1.7nm, the internal mesoporous diameter is 15nm, and the pore diameter is in gradient distribution. The specific capacitance of the Et4NBF4/PC electrolyte at 1 mol/L is 355F/g, and the specific capacitance can still maintain 334F/g after the current density is increased from 50mA/g to 10A/g.
Example 3
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling phenol, furfural and cardanol under the action of zinc oxide for 3 hours, dropwise adding phosphoric acid to continue reacting for 1.5 hours, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 125 ℃, and reacting at constant temperature for 1 hour to obtain the high-ortho-cardanol modified thermoplastic phenolic resin, wherein the molar ratio of phenol to furfural is 1:0.8, the mass ratio of phenol to zinc oxide to phosphoric acid is 100:1.5: 0.7, and the mass ratio of phenol to cardanol is 100: 10;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in methanol, adding furfural to react at 55 ℃ for 5h under the action of a catalyst barium carbonate, cooling to room temperature, dropwise adding oxalic acid to enable the pH to be =6, and performing suction filtration. Decompressing and dehydrating, heating to 60 ℃, and keeping the temperature for 1.5h to obtain the high-ortho cardanol modified thermosetting phenolic resin; the mass ratio of the high-ortho cardanol modified phenolic resin to the methanol is 1:2, the molar ratio of the high-ortho cardanol modified phenolic resin to the furfural is 1:3, and the mass ratio of the high-ortho cardanol modified phenolic resin to the barium carbonate is 100: 2;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the mass fraction ratio of the shell liquid is high-ortho-position cardanol modified thermosetting phenolic resin to PVB to methanol =50:0.1:49.9, the mass fraction ratio of the core liquid is PVB to methanol =3:97, the coaxial electrostatic spinning parameters are T =25 ℃, RH =45%, d =19cm, U =20kV, and Vin to Vout =1: 1.2. Curing for 1.5h at 160 ℃ under vacuum condition; heating to 700 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, carbonizing for 0.9h to obtain a high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane, weighing the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane and KOH, wherein the mass ratio of the two is 1:0.5, adding distilled water, soaking for 1h, drying, heating to 700 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen, and activating for 0.5h to obtain the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 76%, the diameter distribution range of the activated carbon fiber is 290-710nm, the inner diameter is 101-320nm, the heat conductivity coefficient is 113W/m.K, and the specific surface area is 2890m2The iodine value is 291mg/g, the average micropore diameter is 1.2nm, the internal mesoporous diameter is 25nm, and the pore diameter is in gradient distribution. Et4NBF4/PC at 1 mol/LThe specific capacitance in the electrolyte is 384F/g, and after the current density is increased from 50mA/g to 10A/g, the specific capacitance can still maintain 343F/g.
Example 4
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling phenol, formaldehyde and cardanol under the action of zinc acetate for 3.3h, dropwise adding nitric acid to continue reacting for 2h, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 135 ℃, and reacting at constant temperature for 2h to obtain the high-ortho-position cardanol modified thermoplastic phenolic resin, wherein the molar ratio of phenol to formaldehyde is 1:1, the mass ratio of phenol to zinc acetate to nitric acid is 100:1.8: 0.9, and the mass ratio of phenol to cardanol is 100: 12;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in ethanol, adding formaldehyde and acetaldehyde to react at 60 ℃ for 5.5h under the action of catalyst triethanolamine, cooling to room temperature, dropwise adding hydrochloric acid to enable the pH to be =6.5, and performing suction filtration. Decompressing and dehydrating, heating to 65 ℃, and keeping the temperature for 2 hours to obtain the high-ortho cardanol modified thermosetting phenolic resin; the mass ratio of the high-ortho-cardanol modified phenolic resin to ethanol is 1:2.5, the molar ratio of the high-ortho-cardanol modified phenolic resin to formaldehyde to acetaldehyde is 1:3:2, and the mass ratio of the high-ortho-cardanol modified phenolic resin to triethanolamine is 100: 3.5;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; wherein the shell liquid comprises the following components in percentage by mass: high-ortho cardanol modified thermosetting phenolic resin: PVB: tetrahydrofuran =30:0.5:69.5, and the mass fraction ratio of the core liquid is PVB: tetrahydrofuran =4:96, coaxial electrospinning parameters T =30 ℃, RH =50%, d =21cm, U =23kV, Vin: vout =1:1.6, and cured at 180 ℃ under nitrogen for 2h, heating to 800 ℃ at the heating rate of 4 ℃/min under the protection of nitrogen, carbonizing for 1h, obtaining the high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane, weighing the high-ortho-position cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane and ZnCl2, the mass ratio of the two is 1:2, the two are soaked in distilled water for 3h and dried, then the temperature is raised to 800 ℃ at the heating rate of 4 ℃/min under the protection of nitrogen, and the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is obtained after activation for 0.7 h.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 65 percent, the diameter distribution range of the activated carbon fiber is 183-450nm, the inner diameter is 69-156nm, the heat conductivity coefficient is 101W/m.K, and the specific surface area is 3750m2The iodine value is 351mg/g, the average micropore diameter is 1.4nm, the internal mesoporous diameter is 32nm, and the pore diameter is in gradient distribution. The specific capacitance in the Et4NBF4/PC electrolyte of 1 mol/L is 398F/g, and the specific capacitance can still maintain 364F/g after the current density is increased from 50mA/g to 10A/g.
Example 5
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling m-cresol, formaldehyde and cardanol under the action of zinc acetate for 4 hours, dropwise adding concentrated sulfuric acid, continuing to react for 2 hours, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 145 ℃, reacting at constant temperature for 2.5 hours to obtain the high-ortho-cardanol modified thermoplastic phenolic resin, wherein the molar ratio of m-cresol to formaldehyde is 1:1.2, the mass ratio of m-cresol to zinc acetate to concentrated sulfuric acid is 100:1.8:1.1, and the mass ratio of m-cresol to cardanol is 100: 15;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in methanol, adding formaldehyde to react for 6h at 70 ℃ under the action of barium carbonate serving as a catalyst, cooling to room temperature, dropwise adding sulfuric acid to enable the pH to be =7, and performing suction filtration. Decompressing and dehydrating, heating to 70 ℃, and keeping the temperature for 2 hours to obtain the high-ortho cardanol modified thermosetting phenolic resin; the mass ratio of the high-ortho-cardanol modified phenolic resin to the methanol is 1:2.5, the molar ratio of the high-ortho-cardanol modified phenolic resin to the formaldehyde is 1:7, and the mass ratio of the high-ortho-cardanol modified phenolic resin to the barium carbonate is 100: 4;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the shell liquid comprises high-ortho-cardanol modified thermosetting phenolic resin, PVB, ethanol and tetra-n-butyl phenol resin in percentage by massTetrahydrofuran =20:1:16:63, the mass fraction ratio of the core liquid is PVB to ethanol to tetrahydrofuran =5: 76:19, the coaxial electrostatic spinning parameters are T =30 ℃, RH =55%, d =23cm, U =25kV, Vin to Vout =1:2, the core liquid is solidified for 2.5 hours in vacuum at 200 ℃, the core liquid is heated to 900 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen and carbonized for 1.2 hours to obtain the high-ortho-cardanol modified thermosetting phenolic aldehyde group hollow nano-gradient carbon fiber membrane, and the high-ortho-cardanol modified thermosetting phenolic aldehyde group hollow nano-gradient carbon fiber membrane KCl is weighed2Adding distilled water to soak for 5h and drying, heating to 900 ℃ at the heating rate of 5 ℃/min under the protection of nitrogen, and activating for 0.8h to obtain the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 55 percent, the diameter distribution range of the activated carbon fiber is 93-210nm, the inner diameter is 41-112nm, the heat conductivity coefficient is 102W/m.K, and the specific surface area is 3735m2The iodine value is 596mg/g, the average micropore diameter is 1.4nm, the internal mesoporous diameter is 32nm, and the pore diameter is in gradient distribution. The specific capacitance of the Et4NBF4/PC electrolyte at 1 mol/L is 409F/g, and the specific capacitance can still be 464F/g after the current density is increased from 50mA/g to 10A/g.
Example 6
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling m-cresol, furfural and cardanol under the action of zinc oxide for 4.5 hours, dropwise adding concentrated sulfuric acid, continuing to react for 2.5 hours, decompressing and dehydrating, reducing the temperature to 40 ℃, slowly heating to 150 ℃, and reacting at constant temperature for 3 hours to obtain the high-ortho-cardanol modified thermoplastic phenolic resin, wherein the molar ratio of m-cresol to furfural is 1:4, the mass ratio of m-cresol to zinc oxide to concentrated sulfuric acid is 100:2:1.3, and the mass ratio of m-cresol to cardanol is 100: 20;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in ethanol, adding acetaldehyde to react at 80 ℃ for 6.5h under the action of catalyst triethanolamine, cooling to room temperature, dropwise adding oxalic acid to enable the pH to be =7.5, and performing suction filtration. Decompressing and dehydrating, heating to 80 ℃, and keeping the temperature for 2.5 hours to obtain the high-ortho cardanol modified thermosetting phenolic resin; wherein the mass ratio of the high-ortho-cardanol modified phenolic resin to ethanol is 1:3, the molar ratio of the high-ortho-cardanol modified phenolic resin to acetaldehyde is 1:8, and the mass ratio of the high-ortho-cardanol modified phenolic resin to triethanolamine is 100: 5;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the shell liquid comprises high-ortho cardanol modified thermosetting phenolic resin, PVB, methanol and tetrahydrofuran =18:2:70:10, the core liquid comprises PVB, methanol and tetrahydrofuran =4:76.8:19.2, coaxial electrostatic spinning parameters are T =15 ℃, RH =60%, d =25cm, U =28kV and Vin, Vout =1:2.3, the shell liquid is solidified in air at 160 ℃ for 3 hours, the shell liquid is heated to 1100 ℃ at the heating rate of 6 ℃/min under the protection of nitrogen and carbonized for 1.5 hours to obtain the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane, the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane and KOH are weighed, the mass ratio of the two is 1:4, distilled water is added for soaking for 7 hours and drying, the shell liquid is heated to 1000 ℃ at the heating rate of 6 ℃/min under the protection of nitrogen and activated for 1 hour, obtaining the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 53 percent, the diameter distribution range of the activated carbon fiber is 87-154nm, the inner diameter is 40-51nm, the heat conductivity coefficient is 97W/m.K, and the specific surface area is 4245m2The iodine value is 819mg/g, the average micropore diameter is 1.6nm, the internal mesoporous diameter is 38nm, and the pore diameter is in gradient distribution. The specific capacitance of the Et4NBF4/PC electrolyte at 1 mol/L is 418F/g, and after the current density is increased from 50mA/g to 10A/g, the specific capacitance can still be maintained at 383F/g.
Example 7
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling m-cresol, acetaldehyde and cardanol under the action of cadmium acetate for 5 hours, dropwise adding concentrated sulfuric acid, continuing to react for 3 hours, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 155 ℃, and reacting at constant temperature for 3 hours to obtain the high-ortho-cardanol modified thermoplastic phenolic resin. Wherein the molar ratio of m-cresol to acetaldehyde is 1:1.6, the mass ratio of m-cresol to zinc oxide to concentrated sulfuric acid is 100:2:1.5, and the mass ratio of m-cresol to cardanol is 100: 25;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in methanol, adding formaldehyde to react at 85 ℃ for 7h under the action of barium carbonate serving as a catalyst, cooling to room temperature, dropwise adding hydrochloric acid to enable the pH to be =8, and performing suction filtration. Decompressing and dehydrating, heating to 85 ℃, and keeping the temperature for 3 hours to obtain the high-ortho cardanol modified thermosetting phenolic resin; the mass ratio of the high-ortho-cardanol modified phenolic resin to the methanol is 1:2.5, the molar ratio of the high-ortho-cardanol modified phenolic resin to the formaldehyde is 1:10, and the mass ratio of the high-ortho-cardanol modified phenolic resin to the barium carbonate is 100: 5;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the shell liquid is composed of high-ortho-cardanol modified thermosetting phenolic resin, PVA and ethanol =60:5:35, core liquid is composed of PVA and ethanol =5:95, coaxial electrostatic spinning parameters are T =15 ℃, RH =35%, d =14cm, U =16kV and Vin: Vout =1:1.2, the shell liquid is solidified for 0.5h in air at 120 ℃, the shell liquid is heated to 500 ℃ at the heating rate of 7 ℃/min under the protection of nitrogen, carbonized for 2h, steam is introduced at the flow rate of 15ml/min, and the high-ortho-cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is obtained after 2h of activation.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 79 percent, the diameter distribution range of the activated carbon fiber is 242-330nm, the inner diameter is 82-120nm, the heat conductivity coefficient is 90W/m.K, and the specific surface area is 3810m2Iodine value of 373mg/g, average micropore diameter of 1nm, internal mesoporous diameter of 22nm, and gradient distribution of pore diameter. The specific capacitance of the Et4NBF4/PC electrolyte at 1 mol/L is 459F/g, and the specific capacitance can still be kept at 398F/g after the current density is increased from 50mA/g to 10A/g.
Example 8
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) heating xylenol, formaldehyde and cardanol to boiling reaction for 5 hours under the action of zinc acetate, dropwise adding concentrated sulfuric acid to react for 3.5 hours, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 160 ℃, reacting at constant temperature for 3.5 hours to obtain the high-ortho-cardanol modified thermoplastic phenolic resin, wherein the molar ratio of xylenol to formaldehyde is 1:1.8, the mass ratio of xylenol to zinc acetate to concentrated sulfuric acid is 100:2.5:1.7, and the mass ratio of xylenol to cardanol is 100: 30;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in ethanol, adding acetaldehyde to react at 80 ℃ for 6.5h under the action of catalyst triethanolamine, cooling to room temperature, dropwise adding oxalic acid to enable the pH to be =7.5, and performing suction filtration. Decompressing and dehydrating, heating to 80 ℃, and keeping the temperature for 2.5 hours to obtain the high-ortho cardanol modified thermosetting phenolic resin; wherein the mass ratio of the high-ortho-cardanol modified phenolic resin to ethanol is 1:3, the molar ratio of the high-ortho-cardanol modified phenolic resin to acetaldehyde is 1:8, and the mass ratio of the high-ortho-cardanol modified phenolic resin to triethanolamine is 100: 5;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the mass fraction ratio of the shell liquid is high ortho thermosetting phenolic resin to PVA to distilled water =50:7:43, the mass fraction ratio of the core liquid is PVA to distilled water =12:88, the coaxial electrostatic spinning parameters are T =30 ℃, RH =35%, d =25cm, U =18kV, and Vin: Vout =1: 1.4. Curing the mixture in nitrogen at 140 ℃ for 1h, raising the temperature to 600 ℃ at the heating rate of 8 ℃/min under the protection of nitrogen, carbonizing the mixture for 2.5h, and introducing CO2The flow rate is 10ml/min, and the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is obtained after activation for 0.8 h.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 70 percent, the diameter distribution range of the activated carbon fiber is 132-290nm, the inner diameter is 110-132nm, the heat conductivity coefficient is 78W/m.K, and the specific surface area is 4970m2Iodine value of 587mg/g, average micropore diameter of 1.8nm, internal mesopore diameter of 36nm, and poresThe diameter has gradient distribution. The specific capacitance of the Et4NBF4/PC electrolyte at 1 mol/L was 468F/g, and the specific capacitance remained 429F/g after the current density was increased from 50mA/g to 10A/g.
Example 9
The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nanometer gradient activated carbon fiber membrane comprises the following steps:
(1) boiling phenol, formaldehyde and cardanol under the action of zinc acetate for 6 hours, dropwise adding concentrated sulfuric acid, continuing to react for 4 hours, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 165 ℃, and reacting at constant temperature for 4 hours to obtain the high-ortho-position cardanol modified thermoplastic phenolic resin. Wherein the molar ratio of phenol to formaldehyde is 1:2, the mass ratio of phenol to zinc acetate to concentrated sulfuric acid is 100:3: 2, and the mass ratio of phenol to cardanol is 100: 12;
(2) dissolving the obtained high-ortho cardanol modified phenolic resin in methanol, adding formaldehyde to react at 85 ℃ for 7h under the action of barium carbonate serving as a catalyst, cooling to room temperature, dropwise adding hydrochloric acid to enable the pH to be =8, and performing suction filtration. Decompressing and dehydrating, heating to 85 ℃, and keeping the temperature for 3 hours to obtain the high-ortho cardanol modified thermosetting phenolic resin; the mass ratio of the high-ortho-cardanol modified phenolic resin to the methanol is 1:2.5, the molar ratio of the high-ortho-cardanol modified phenolic resin to the formaldehyde is 1:10, and the mass ratio of the high-ortho-cardanol modified phenolic resin to the barium carbonate is 100: 5;
(3) adopting coaxial electrostatic spinning, heating and curing to obtain a high-ortho cardanol modified thermosetting phenolic fiber membrane with a partially compatible skin-core structure; the shell liquid is prepared from high-ortho cardanol modified thermosetting phenolic resin, PVA, N.N-dimethylformamide =28:12:60 core liquid, coaxial electrostatic spinning parameters of T =25 ℃, RH =70%, d =25cm, U =28kV and Vin, Vout =1:3, through curing for 1.5h in vacuum at 160 ℃, heating to 700 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen, carbonizing for 1.2h to obtain the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane, weighing the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane KOH, wherein the mass ratio of the two is 1:8, adding distilled water, soaking for 9h, drying, heating to 700 ℃ at a heating rate of 9 ℃/min under the protection of nitrogen, activating for 0.5h, obtaining the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane.
The obtained high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane has the carbon residue rate of 65 percent, the diameter distribution range of the activated carbon fiber is 32-65nm, the inner diameter is 20-32nm, the heat conductivity coefficient is 66W/m.K, and the specific surface area is 4460m2The iodine value is 590mg/g, the average micropore diameter is 1.4nm, the internal mesoporous diameter is 38nm, and the pore diameter is in gradient distribution. The specific capacitance of Et4NBF4/PC electrolyte at 1 mol/L is 467F/g, and after the current density is increased from 50mA/g to 10A/g, the specific capacitance can still maintain 389F/g.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (9)

1. A preparation method of a high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is characterized by comprising the following steps:
(1) boiling cardanol, phenols and aldehyde compounds for 2-6h under the action of a first catalyst, then dropwise adding an acid catalyst, continuing to carry out boiling reaction for 0.5-4h, decompressing and dehydrating, cooling to 40 ℃, slowly heating to 105-165 ℃, and continuing to react for 0.1-4h to obtain high-ortho cardanol modified phenolic resin;
(2) dissolving high-ortho cardanol modified phenolic resin in an alcohol compound, adding an aldehyde compound and a second catalyst, reacting for 3-7h at 45-85 ℃, cooling to room temperature, adjusting the pH value to be 5-8.0, performing suction filtration, removing impurities, then performing reduced pressure dehydration, wherein the termination temperature of the reduced pressure dehydration is 50-90 ℃, and the time of the reduced pressure dehydration is 0.5-3h, so as to prepare the high-ortho cardanol modified thermosetting phenolic resin;
(3) dissolving the high-ortho cardanol modified thermosetting phenolic resin and the high-molecular linear polymer in a solvent to prepare a shell solution, dissolving the high-molecular linear polymer in the solvent to prepare a core solution, and heating and curing by adopting coaxial electrostatic spinning to obtain a high-ortho cardanol modified high-ortho thermosetting phenolic fiber membrane with a partially compatible skin-core structure; then in N2Carbonizing and activating under protection to obtain the high-ortho cardanol modified thermosetting phenolic group hollow nano gradient activated carbon fiber membrane.
2. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (1), the phenolic compound is phenol, p-cresol or xylenol; the aldehyde compound is formaldehyde, acetaldehyde or furfural, and the first catalyst is zinc acetate, cadmium acetate or zinc oxide; the acid catalyst is phosphoric acid, nitric acid, sulfuric acid with the mass fraction of 98% or hydrochloric acid with the mass fraction of 37%; wherein the molar ratio of the phenols to the aldehydes is 1 (0.6-2), the mass ratio of the phenolic compounds to the first catalyst is 100 (0.8-3), and the mass ratio of the phenolic compounds to the acid catalyst is 100 (0.2-2); the mass ratio of phenols to cardanol is 100 (5-35).
3. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (2), the alcohol compound is methanol or ethanol; the aldehyde compound is at least one of formaldehyde, acetaldehyde and furfural, and the second catalyst is triethanolamine, barium carbonate or barium acetate; the acid used for adjusting the pH is one of hydrochloric acid, oxalic acid or sulfuric acid with the mass fraction of 98%; the mass ratio of the high-ortho-cardanol modified phenolic resin to the alcohols is 1 (1-3), the molar ratio of the high-ortho-cardanol modified phenolic resin to the aldehydes is 1 (1-10), and the mass ratio of the high-ortho-cardanol modified phenolic resin to the second catalyst is 100 (1-5).
4. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), the high molecular linear polymer is PVB, PVA or PVP, the solvent is at least one of ethanol, methanol, tetrahydrofuran, distilled water and N.N-dimethylformamide, wherein the mass fraction ratio of the components of the shell liquid is high-ortho cardanol modified thermosetting phenolic resin to the high molecular linear polymer and the solvent is = (18-75) = (15-0): (67-25), and the mass fraction ratio of the components of the core liquid is high molecular linear polymer and the solvent is = (1-15): (99-85).
5. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), the coaxial electrostatic spinning parameters comprise temperature T =15-30 ℃, relative humidity RH =35-70%, receiving distance d =12-25cm, spinning voltage U =13-28kV, and inner and outer axis spinning speed Vin: Vout =1: 1-3.
6. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), the heating curing temperature is 120-.
7. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), the activating agent is water vapor and CO2、KOH、ZnCl2And KCl.
8. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), during one-step activation, the mass ratio of the solid activating agent to the high-ortho cardanol modified phenolic fiber membrane is 0.5-8: 1; when carbonizing and activating are carried out firstly, the mass ratio of the solid activating agent to the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient carbon fiber membrane is 0.5-8: 1; the flow rate of the gas activating agent is 10-30 ml/min.
9. The preparation method of the high-ortho cardanol modified thermosetting phenolic aldehyde based hollow nano gradient activated carbon fiber membrane as claimed in claim 1, wherein the preparation method comprises the following steps: in the step (3), the temperature rise rate of carbonization and activation is 1-10 ℃/min, the carbonization temperature is 400-1100 ℃, the carbonization time is 0.5-2.5h, the activation temperature is 400-1000 ℃, and the activation time is 0.1-2h, so that the high-ortho cardanol modified thermosetting phenolic aldehyde group hollow nano gradient activated carbon fiber membrane is obtained.
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