WO2021068449A1 - Membrane cnf modifiée capable de dégrader catalytiquement le 4-nitrophénol, son procédé de préparation et son application - Google Patents

Membrane cnf modifiée capable de dégrader catalytiquement le 4-nitrophénol, son procédé de préparation et son application Download PDF

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WO2021068449A1
WO2021068449A1 PCT/CN2020/076726 CN2020076726W WO2021068449A1 WO 2021068449 A1 WO2021068449 A1 WO 2021068449A1 CN 2020076726 W CN2020076726 W CN 2020076726W WO 2021068449 A1 WO2021068449 A1 WO 2021068449A1
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cnf
modified
preparation
nitrophenol
cuo
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PCT/CN2020/076726
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Chinese (zh)
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林兆云
杨桂花
陈嘉川
和铭
戢德贤
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齐鲁工业大学
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Publication of WO2021068449A1 publication Critical patent/WO2021068449A1/fr

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    • B01J35/59—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4007—Regeneration or reactivation of catalysts containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/403—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to the technical field of nano cellulose fiber catalysts, in particular to a modified nano cellulose fiber membrane capable of catalytically degrading 4-nitrophenol, and a preparation method and application thereof.
  • 4-Nitrophenol is a stubborn water impurity, widely derived from dyes, pesticides and pharmaceutical industries, and is a toxic organic pollutant.
  • the conversion of 4-nitrophenol to 4-aminophenol can not only reduce the toxicity of 4-nitrophenol, but also 4-aminophenol, as a fine organic chemical intermediate with a wide range of applications, can be used in the pharmaceutical industry to synthesize paracetamol, etc. It can also be used to prepare products such as developers, antioxidants and petroleum additives.
  • Photocatalytic degradation is mainly when semiconductors (such as nano TiO 2 , nano ZnO, etc.) are irradiated by ultraviolet light with a wavelength of less than 387.5 nm, the electrons in the valence band are excited, and the transition enters the conduction band, thus generating negative charge on the conduction band electronic high activity (E -), leaving a hole in the valence band of positively charged (h +), under the action of the electric field, electrons and holes are separated and migrate to different parts of the surface of the particle, form an oxidation - reduction
  • 4-nitrophenol is used as a sacrificial agent to be catalytically reduced.
  • the technical problems to be solved/objectives achieved by the present invention include at least: (1) Preparation of a green and renewable catalyst capable of treating 4-nitrophenol (such as in wastewater); (2) High catalytic efficiency; (3) Recycling The catalytic efficiency is high; in order to reduce the problem of large usage of the degrading 4-nitrophenol chemicals in the existing method, and the unsatisfactory treatment effect.
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol and a preparation method and application thereof; the present invention uses nano cellulose fibers (CNF) as raw materials, and nano CuO particles are grown in situ On the nano-cellulose fiber, and the surface of the nano-cellulose fiber is coupled and grafted with amine groups, so that it has the ability to catalyze the degradation of 4-nitrophenol, and is mixed with polyvinyl alcohol to form a film for sewage treatment, and it can be recycled , Which can provide a new direction for the industrial application of CNF.
  • CNF nano cellulose fibers
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, comprising: nano cellulose fibers (CNF) and nano CuO particles, the nano CuO particles being grown in situ on the nano cellulose fibers , And the surface of the nanocellulose fiber is coupled and grafted with an amine group; the amine group is an alcohol amine group.
  • CNF nano cellulose fibers
  • nano CuO particles being grown in situ on the nano cellulose fibers
  • the surface of the nanocellulose fiber is coupled and grafted with an amine group; the amine group is an alcohol amine group.
  • the mass ratio of the CNF and the nano CuO particles is 1:1-2.
  • the amine group in the nanocellulose fiber is provided by glycol amine.
  • the CNF has a length of 500-2000 nm and a diameter of 10-50 nm.
  • the present invention also provides a method for preparing the above-mentioned modified nano-cellulose fiber membrane, which includes the following steps:
  • step (2) After mixing the CNF treated in step (1), the water-soluble copper source, and the lye, the reaction is carried out under stirring conditions until black appears to obtain CNF@CuO;
  • a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
  • the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
  • the mass ratio of the two in the hydrogen peroxide-ammonia mixture is 1:1-2.
  • the water-soluble copper source includes any one of copper sulfate, copper nitrate and copper chloride.
  • the lye is an aqueous sodium hydroxide solution or ammonia water.
  • the stirring temperature is 60-90°C.
  • the temperature of the water bath is 50-85°C.
  • the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1.
  • the silane coupling agent includes 3-aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -(2,3-cyclic Any one of oxypropoxy)propyltrimethoxysilane.
  • the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
  • the amount of glycol amine is 1-30 wt%.
  • the amount of glycol amine is 5-20 wt%.
  • the temperature of the water bath is 45-60°C.
  • the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
  • the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0 wt%, 1.2 wt% or 1.5 wt%.
  • the present invention also provides a method for catalytic degradation of 4-nitrophenol: adding the modified nano cellulose fiber membrane to the 4-nitrophenol solution, and at the same time adding NaBH 4 for stirring, to catalytically degrade the 4-nitrophenol. ⁇ phenol.
  • the mass ratio of the modified nanocellulose fiber membrane to NaBH 4 is 1-10:6.
  • the modified nanocellulose fiber membrane is recovered by centrifugal separation.
  • the modified nano cellulose membrane obtained after the recovery is used to catalyze the degradation of 4-nitrophenol.
  • the invention also provides the application of the modified nano cellulose fiber in the fields of environment, chemical industry and medicine.
  • the present invention has achieved the following beneficial effects:
  • the present invention uses CNF as a raw material, and the modification is carried out under water system conditions, so that it has the advantages of green, environmental protection and renewable.
  • the modified CNF membrane of the present invention has excellent catalytic degradation ability for degradable 4-nitrophenol, the degradation rate can reach more than 94% when used for the first time, and it can efficiently catalyze and degrade 4-nitrophenol in a short time.
  • the high-efficiency catalytic degradation ability of the present invention enables the modified CNF membrane of the present invention to significantly reduce the dosage compared with the traditional chemical treatment of 4-nitrophenol.
  • the modified CNF membrane of the present invention can convert 4-nitrophenol into 4-aminophenol, not only can reduce the toxicity of 4-nitrophenol, but also 4-aminophenol can be used as a fine organic chemical intermediate.
  • the modified CNF membrane of the present invention can be recovered by washing with deionized water, which is a clean product; and after multiple use-recovery-use, the degradation rate of 4-nitrophenol still remains above 85% .
  • the preparation method of the present invention is simple, has strong degradation ability, strong practicability, and is easy to popularize.
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol and a preparation method thereof.
  • the present invention provides a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol, comprising: nano cellulose fibers and nano CuO particles, the nano CuO particles are grown in situ on the nano cellulose fibers, and The surface of the nano cellulose fiber is coupled and grafted with an amine group.
  • the CNF in the modified nanocellulose fiber membrane has a length of 500-2000 nm and a diameter of 10-50 nm;
  • the mass ratio of CNF and nano CuO particles in the modified nanocellulose fiber membrane is 1:1 to 2, and an excessive amount of nano CuO particles will cause nano CuO particles dispersed in the CNF network structure Increase and loss in the washing process.
  • the amine group in the modified nanocellulose fiber membrane is provided by glycol amine.
  • the present invention also provides a method for preparing the modified nanocellulose fiber membrane, which is characterized in that it comprises the following steps:
  • step (2) After mixing the nanocellulose fibers treated in step (1), the water-soluble copper source and the lye, the reaction is carried out under stirring conditions until black appears, and CNF@CuO is obtained;
  • a suspension of CNF is prepared by a sulfuric acid method, and ultrasonic treatment is performed.
  • the addition ratio of the CNF suspension and the hydrogen peroxide-ammonia mixed liquid is 1 to 2 g: 10 mL.
  • the mass ratio of the two in the hydrogen peroxide ammonia water mixture is 1:1-2.
  • the main purpose of adding the hydrogen peroxide-ammonia mixture is to remove the sulfonic acid groups attached to the surface of the CNF and increase the hydroxyl content, thereby increasing the surface activity of the CNF, which is beneficial to the subsequent modification process.
  • the water-soluble copper source includes copper sulfate, copper nitrate or copper chloride.
  • the lye in the step (2), is an aqueous sodium hydroxide solution or ammonia water.
  • the stirring temperature is 60-90°C.
  • the temperature of the water bath is 50-85°C.
  • the mass ratio of CNF@CuO and the silane coupling agent is 10-5:1.
  • the silane coupling agent is mainly grafted on the surface of CNF to improve its hydrophobicity, and the silane coupling agent can be coupled and grafted with glycol amine, but the mass ratio of CNF@CuO and silane coupling agent exceeding 5:1 will cause The hydrophobicity of CNF is obviously increased, which is not conducive to the catalytic degradation of modified CNF membrane in water.
  • the silane coupling agent includes 3-aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane and ⁇ -(2 Any one of ,3-glycidoxy)propyltrimethoxysilane.
  • the method for removing oxygen in the reaction system is to continuously pass nitrogen into the reaction system.
  • the amount of the glycol amine is 1-30 wt%.
  • the main purpose of adding glycol amine is to graft the catalytically active alcohol amine group to replace -Cl on the silane group.
  • the amount of the glycol amine is 5-20 wt%. Further research of the present invention found that when the amount of glycolamine is less than 5wt%, the modified CNF membrane has a poor catalytic degradation effect on 4-nitrophenol; when the amount of glycolamine is greater than 20wt%, continue to increase the amount of glycol amine The amount of amine has little effect on the catalytic degradation of 4-nitrophenol.
  • the temperature of the water bath is 45-60°C.
  • the volume ratio of the modified nanocellulose fiber suspension grafted with amine groups to the polyvinyl alcohol is 2 to 4:1.
  • the concentration of the modified nanocellulose fiber suspension grafted with amine groups is 1.0 wt%, 1.2 wt%, or 1.5 wt%.
  • the present invention also provides a method for catalytic degradation of 4-nitrophenol: adding the modified nano cellulose fiber membrane to the 4-nitrophenol solution, and at the same time adding NaBH 4 for stirring, to catalytically degrade the 4-nitrophenol. ⁇ phenol.
  • the mass ratio of the modified CNF membrane to NaBH 4 in the method for catalytic degradation of 4-nitrophenol is 1-10:6, and the removal rate of 4-nitrophenol is improved by more than 10:6. Not obvious.
  • the modified nanocellulose membrane can be recovered by centrifugal separation; or the modified CNF membrane can be recovered by washing with deionized water and reused for 4-nitro Catalytic degradation of phenol.
  • the invention also provides the application of the modified nano cellulose fiber in the fields of environment, chemical industry and medicine.
  • a modified nano-cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e) Take 8g of CNF treated in step d) in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask, stir at 60°C for 4h until the solution turns black. Get CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step f) Take 6g of CNF@CuO-APTS of step f) in a three-necked flask, add 1wt% glycol amine (relative to CNF@CuO-APTS of step f)), and continue to pour in nitrogen, and react in a 45°C water bath 12h, centrifuge and wash until the filtrate does not contain chloride ions, and collect the precipitate to obtain the modified CNF suspension;
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration.
  • the modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e) Take 8g of CNF treated in step d) in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask, stir at 60°C for 4h until the solution turns black.
  • the obtained precipitate is CNF@CuO, and the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and apply it to UV-visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e Take 8g of the nanocellulose fiber treated in step d) and place it in a three-necked flask. Disperse 0.2M CuSO 4 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 60°C for 4h. The solution is black, and the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.2 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 4:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 100mg of modified CNF membrane and 600mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and apply it to UV-visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step e Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol into a beaker, add 100mg of modified CNF membrane, and at the same time add 200mg of NaBH 4 , mechanically stir for 5 minutes, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 20g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 2) at room temperature with mechanical stirring IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 200mg of NaBH 4 at the same time, mechanically stir for 5 min, centrifuge to wash and recover the modified CNF membrane, and collect the upper liquid and spectroscopy in UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration.
  • the modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 20g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 2) at room temperature with mechanical stirring IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step e Take 8g of CNF treated in step d) and place it in a three-necked flask. Disperse 0.2M CuCl 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 70°C for 4h until the solution turns black. , The resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:2.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol in a volume of 3:1, and cast into a film to obtain.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask. Disperse 0.2M Cu(NO 3 ) 2 and 1.0M NaOH in 100mL deionized water and transfer to a three-necked flask. Stir at 80°C for 4h Until the solution turns black, the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.0 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 2:1, and cast into a film to obtain it.
  • modified CNF membrane Take 50mL of 1mmol/L 4-nitrophenol and place it in a beaker, add 400mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5 min, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M Cu(NO 3 ) 2 and 1.0M NH 3 ⁇ H 2 O in 100 mL deionized water and transfer to the three-necked flask, Stir at 80°C for 4h until the solution turns black.
  • the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • step g) The modified CNF suspension (concentration of 1.5 wt%) of step g) is mixed with polyvinyl alcohol according to a volume of 2:1, and cast into a film to obtain.
  • modified CNF membrane Take 50mL of 1.5mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 100mg of NaBH 4 at the same time, mechanically stir for 5min, centrifuge and wash to recover the modified CNF membrane, and collect the upper layer liquid and apply it to ultraviolet visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step c) Take 10g of step c) CNF suspension was placed in three-necked flask, was added 100mLH 2 O 2 and NH 3 ⁇ H 2 O mixed solution (mass ratio 1: 1), stirred at room temperature mechanical IH, deionized water, centrifugation Wash to neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M Cu(NO 3 ) 2 and 1.0M NH 3 ⁇ H 2 O in 100 mL deionized water and transfer to the three-necked flask, Stir at 80°C for 4h until the solution turns black.
  • the resulting precipitate is CNF@CuO, where the mass ratio of CNF to CuO is 1:1.
  • modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step d) Take 20g of the CNF suspension of step c) and place it in a three-necked flask, add 100 mL of a mixture of H 2 O 2 and NH 3 ⁇ H 2 O (mass ratio 1:2), mechanically stir for 1 hour at room temperature, deionized water Centrifuge and wash until neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF processed in step d) and place it in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NH 3 ⁇ H 2 O in 100mL deionized water and transfer to the three-necked flask, stir at 90 °C 4h until the solution turns black, the precipitate obtained is CNF@CuO, and the mass ratio of CNF to CuO is 1:2.
  • modified CNF membrane Take 50mL of 2.5mmol/L 4-nitrophenol and place it in a beaker, add 200mg of modified CNF membrane and 60mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper layer liquid and apply it to ultraviolet visible light. Scan under a spectrophotometer, record the absorbance at a wavelength of 400nm, and calculate its concentration. The modified CNF membrane is recovered by washing with deionized water and reused.
  • a modified nano cellulose fiber membrane capable of catalytic degradation of 4-nitrophenol the specific steps are as follows:
  • step d) Take 20g of the CNF suspension of step c) and place it in a three-necked flask, add 100 mL of a mixture of H 2 O 2 and NH 3 ⁇ H 2 O (mass ratio 1:2), mechanically stir for 1 hour at room temperature, deionized water Centrifuge and wash until neutral, collect the precipitate and measure the moisture.
  • step d) Take 8g of CNF treated in step d) and place it in a three-necked flask, disperse 0.2M CuSO 4 and 1.0M NH 3 ⁇ H 2 O in 100 mL of deionized water and transfer to the three-necked flask, stir at 90°C for 4h Until the solution turns black, the precipitate obtained is CNF@CuO, and the mass ratio of CNF to CuO is 1:2.
  • modified CNF membrane Place 50mL of 3mmol/L 4-nitrophenol in a beaker, add 200mg of modified CNF membrane and 60mg of NaBH 4 at the same time, stir mechanically for 5 minutes, centrifuge and wash to recover the modified CNF membrane, and collect the upper liquid and spectroscopy it under UV-visible light. Scan under a photometer, record the absorbance at a wavelength of 400nm, and calculate its concentration.
  • the modified CNF membrane is recovered by washing with deionized water and reused.
  • the concentration of 4-nitrophenol in the filtrate after the 4-nitrophenol was treated with the modified nanocellulose filaments prepared in Examples 1-11 was measured.
  • the test method is: configure the 4-nitrophenol standard samples of 0.005g/L, 0.001g/L, 0.0015g/L, 0.002g/L, 0.0025g/L, and place them in an ultraviolet-visible spectrophotometer to measure the absorbance. And determine the standard curve, as shown in Table 1.
  • Example number 1 2 3 4 5 Absorbance/T% 0.14632 0.12931 0.07269 0.06153 0.05425 Concentration/mmol/L 0.05651 0.04883 0.02462 0.01985 0.01674 Removal rate/% 94.35 95.12 97.54 98.02 98.33 Reuse times 25 25 25 25 25 Removal rate after reuse/% 85.08 85.46 86.12 88.15 88.67
  • Example number 6 7 8 9 10 11 Absorbance/T% 0.03260 0.01611 0.06780 0.11058 0.25929 0.36335 Concentration/mmol/L 0.00748 0.00443 0.02253 0.04082 0.10440 0.14889 Removal rate/% 99.26 99.56 98.50 97.96 95.83 95.04 Reuse times 25 25 25 25 25 25 25 25 Removal rate after reuse/% 89.88 90.12 89.75 89.53 89.42 89.13

Abstract

La présente invention concerne le domaine technique des catalyseurs à membrane de nanofibres de cellulose, et concerne en particulier une membrane CNF modifiée capable de dégrader catalytiquement le 4-nitrophénol, son procédé de préparation et son application. La membrane CNF modifiée comprend : des nanofibres de cellulose et des nanoparticules de CuO, les nanoparticules de CuO étant cultivées in situ sur les nanofibres de cellulose, et les surfaces des nanofibres de cellulose étant greffées avec des groupes amine. La membrane CNF modifiée de la présente invention présente d'excellentes capacités de dégradation catalytique pour le 4-nitrophénol dégradable, et peut dégrader catalytiquement de manière efficace le 4-nitrophénol dans une courte période de temps.
PCT/CN2020/076726 2019-10-09 2020-02-26 Membrane cnf modifiée capable de dégrader catalytiquement le 4-nitrophénol, son procédé de préparation et son application WO2021068449A1 (fr)

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