CN113368838A - Biomass nano-cellulose porous material with surface loaded with nano-transition metal oxide and preparation method thereof - Google Patents
Biomass nano-cellulose porous material with surface loaded with nano-transition metal oxide and preparation method thereof Download PDFInfo
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- CN113368838A CN113368838A CN202110662882.8A CN202110662882A CN113368838A CN 113368838 A CN113368838 A CN 113368838A CN 202110662882 A CN202110662882 A CN 202110662882A CN 113368838 A CN113368838 A CN 113368838A
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- metal oxide
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- cellulose
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
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- 238000004132 cross linking Methods 0.000 claims description 21
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- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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Abstract
The invention relates to a biomass nanocellulose/nano transition metal oxide porous material, a preparation method and application, wherein a nano transition metal oxide is loaded on the surface of the biomass nanocellulose through non-covalent interaction. The biomass nano-cellulose/nano-transition metal oxide porous material has both adsorption and catalysis effects, and can be used as a recyclable adsorption degradation material; the composite material is used as an adsorption catalytic degradation material, has the advantages of high adsorption catalytic degradation efficiency, environmental protection, excellent regeneration capacity, easy separation, recycling and no repeated pollution, and has considerable application prospect.
Description
Technical Field
The invention belongs to the technical field of biomass material resource utilization and sewage treatment materials, and particularly relates to a high-efficiency, rapid and recyclable porous material prepared by a high internal phase Pickering emulsion template method and a preparation method thereof.
Background
The biomass material is a natural biological material with the most abundant natural amount, including green plants, marine animals, bacteria and other organisms, and the biomass nano-cellulose extracted from the biomass material has the advantages of large specific surface area, reactable surface, light weight, environmental protection and the like, so the biomass nano-cellulose has potential application value in the field of sewage treatment. However, the biomass nano-cellulose adsorption material only has adsorption capacity, so that secondary pollution is easily caused.
The nanometer transition metal oxide has stronger effect of catalyzing, oxidizing and degrading organic pollutants. However, the method has the defects of easy agglomeration of nano particles, difficult solid-liquid separation, leaching with treated wastewater and the like, and is greatly limited in the treatment application of industrial sewage. The preparation of the three-dimensional material with the adsorption and degradation functions by combining the biomass nanocellulose with the adsorption function and the nano transition metal oxide with the catalytic organic pollutant degradation is expected to realize the high-efficiency treatment of industrial sewage, and the preparation of the three-dimensional material is expected to realize the recycling of the biomass nanocellulose/nano transition metal oxide. For example, in the Chinese invention patent with the application number of CN202010023064, sodium alginate, cellulose nanocrystal and manganese dioxide are combined to prepare the sodium alginate/cellulose nanocrystal/manganese dioxide ternary composite gel for dye treatment, and the prepared adsorption degradation material has the advantages of easy separation, no repeated pollution and the like. However, the ternary composite gel prepared by the invention has small specific surface area, so that the application effect of the ternary composite gel cannot be brought into the best play. Therefore, the development of a method which can combine the excellent adsorption performance of the biomass nanocellulose and the strong catalytic oxidation performance of the nano transition metal oxide and realize the efficient, rapid and recyclable biomass porous material has important significance.
The high internal phase Pickering emulsion is an emulsion with the volume fraction of the stable internal phase of more than or equal to 74% which is prepared by amphiphilic solid nano particles or micro particles replacing surfactants, wherein the amphiphilic solid particles are positioned at an oil-water interface and can be used for constructing the pore wall of a porous material, and the porous polymer material prepared by taking the high internal phase Pickering emulsion as a template has the advantages of high specific surface area, high porosity, light weight, rich surface functional groups and the like, and has important application in the fields of filtration, adsorption, catalyst loading and the like.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Disclosure of Invention
Object of the Invention
The invention aims to provide a biomass nano-cellulose/nano-transition metal oxide porous material which is efficient, rapid and recyclable, and a preparation method and application thereof. The invention takes biomass nanocellulose as a carrier, nano transition metal oxide is uniformly loaded on the surface of the biomass nanocellulose, a high internal phase Pickering emulsion template method is adopted to combine the adsorption capacity of the biomass nanocellulose and the strong catalytic oxidation capacity of the metal oxide to prepare the biomass nanocellulose/nano transition metal oxide porous material, wherein the inherent amphipathy of the biomass nanocellulose and the nano transition metal oxide enables the biomass nanocellulose and the nano transition metal oxide to be used as a solid emulsifier for preparing the high internal phase Pickering, and the biomass nanocellulose/nano transition metal oxide at the oil-water interface forms the pore wall of the porous material together at the later stage so as to be convenient for the biomass nanocellulose/nano transition metal oxide to be in full contact with sewage and realize the fast adsorption and the catalytic degradation of the industrial sewage. The application prospect is considerable.
Solution scheme
In order to achieve the above object, an embodiment of the present invention provides a preparation method of a biomass nanocellulose porous material with a surface loaded with a nano transition metal oxide, which includes the following steps:
(1) preparing mixed solution of biomass nanocellulose/nano transition metal oxide, water-soluble carboxyl organic matter, olefin monomer, olefin polymerization initiator and surfactant;
(2) adding an organic solvent into the mixed solution obtained in the step (1) and then emulsifying at a high speed to obtain an oil-in-water type biomass nanocellulose/nano transition metal oxide high internal phase Pickering emulsion;
(3) shaping the biomass nanocellulose/nano transition metal oxide high internal phase Pickering emulsion obtained in the step (2), and then carrying out ion crosslinking to obtain a biomass nanocellulose/nano transition metal oxide hydrogel;
(4) and (4) initiating the olefin monomer in the biomass nano-cellulose/nano-transition metal oxide hydrogel obtained in the step (3) to polymerize, so as to prepare the biomass nano-cellulose/nano-transition metal oxide hydrogel with better toughness.
(5) And (4) drying the biomass nano-cellulose/nano-transition metal oxide hydrogel obtained in the step (4) to prepare the biomass nano-cellulose/nano-transition metal oxide porous material.
In one possible embodiment, the nano transition metal oxide is loaded on the surface of the biomass nanocellulose by adopting a non-covalent interaction mode, wherein the nano transition metal oxide loaded on the biomass nanocellulose accounts for 10% -60% of the total mass of the biomass nanocellulose/nano transition metal oxide binary composite material; alternatively from 20% to 50%, further alternatively from 30% to 40%;
when the loading mode of the nanometer transition metal oxide is physical mixing, adding the nanometer transition metal oxide into the biomass nanometer cellulose water suspension, and uniformly stirring, wherein the mass ratio of the nanometer transition metal oxide to the biomass nanometer cellulose is 1:9-3: 2;
when the loading mode of the nano transition metal oxide is in-situ generation, a certain amount of transition metal salt with strong oxidizing property is added into the biomass nano cellulose suspension, and the mixture is rapidly stirred and reacted for a certain time under the conditions of a certain pH value and temperature, so that the nano transition metal oxide can be generated on the surface of the biomass nano cellulose in-situ, wherein the mass ratio of the transition metal salt to the biomass nano cellulose is 1:1-1:40, the pH value of a reaction system is 1-14, the reaction temperature is 30-100 ℃, and the reaction time is 1-10 hours.
In one possible embodiment, the bio-based nanofibers comprise one or more of cellulose nanocrystals, cellulose nanofibers, chitin nanocrystals, chitin nanofibers, bacterial cellulose;
in one possible embodiment, the transition metal oxide comprises one or more of manganese dioxide, titanium dioxide, zinc oxide, iron sesquioxide, iron tetroxide, copper oxide, cuprous oxide, manganese dioxide;
in one possible embodiment, the water-soluble carboxyl organic substance comprises one or more of citric acid, oxalic acid, sodium alginate, sodium carboxymethyl cellulose, formic acid, acetic acid, butyric acid, caproic acid, caprylic acid, capric acid and benzoic acid;
in one possible embodiment, the surfactant comprises one or more of polyvinyl alcohol, polyethylene glycol, sodium a-alkenyl sulfonate, sodium linear alkyl benzene sulfonate, sodium stearate, dodecyl dimethyl ammonium oxide, alkyl alcohol amide, alkyl polyglycoside and glucamide; the surfactant used in the present invention is not limited thereto.
In one possible embodiment, the olefin monomer comprises one or more of acrylamide, acrylic acid, acrylonitrile, methyl methacrylate, styrene, ethylene, octene, hexene, cyclohexene, cyclopentadiene, norbornene; the olefin monomer used in the present invention is not limited thereto.
In one possible embodiment, the oil phase organic solvent comprises one or more of n-hexane, cyclohexane, ethyl acetate, pentane, hexane and octane; the oil phase organic solvent used in the present invention is not limited thereto.
In one possible embodiment, the mass ratio of the biomass nanocellulose/nano transition metal oxide to the water-soluble carboxyl organic substance is 1: 0.01-0.5.
In one possible embodiment, the mass ratio of biomass nanocellulose/nano transition metal oxide to surfactant is 1: 0.01-0.5.
In one possible embodiment, the mass ratio of biomass nanocellulose/nano transition metal oxide to olefin monomer is 1: 0.05-0.5.
In one possible embodiment, the volume ratio of the oil phase organic solvent to water is 3-49:1
In one possible embodiment, the high-speed emulsification rate is 1000-.
In one possible embodiment, the ion used in the ionic crosslinking is Ca2+、Mg2+、Ba2+、Al3+、Fe2 +、Fe3+、Zn2+、Cu2+Wherein the addition amount of the ionic salt is 1-20% of the amount of the water-soluble carboxyl organic substance.
In one possible embodiment, the initiating means for initiating the polymerization of the olefin monomer may be one or more of ultraviolet initiation and thermal initiation.
When the initiating manner of initiating the olefin monomer polymerization is ultraviolet initiating free radical polymerization, the initiator is one or more of benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin dimethyl ether, benzophenone, amine compounds, thioxanthone, camphorquinone, bisimidazole, diaryl iodonium salt and triaryl sulfonium salt;
wherein the addition amount of the initiator is 0.01-0.5% of the mass of the olefin monomer, the power of an ultraviolet lamp is 100-;
when the initiation mode for initiating the polymerization of the olefin monomer is thermal initiation polymerization, the initiator is one or more of ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, potassium persulfate, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide;
wherein the addition amount of the free radical initiator is 0.01-0.5% of the mass of the olefin monomer, the initiation temperature is 20-100 ℃, and the polymerization time is 1-24 h.
In a possible embodiment, the drying mode is one or more of ordinary oven drying, vacuum oven drying, freeze drying and supercritical drying.
In one possible embodiment, the high internal phase Pickering emulsion may be shaped by extrusion or injection into any shape, such as any of a sphere, cube, cuboid, cylinder, cone, etc.;
in a possible embodiment, the biomass nano-cellulose/nano-transition metal oxide porous material prepared by the preparation method of any one of 1 to 9 can be repeatedly regenerated for industrial sewage treatment.
In one possible embodiment, the industrial wastewater comprises one or more of dye wastewater, cotton pulp black liquor, coke quenching water, heavy metal wastewater, heated polluted wastewater and the like.
Advantageous effects
1. The biomass nano-cellulose porous material with the surface loaded with the nano-transition metal oxide prepared by the invention takes the biomass nano-cellulose as the carrier, and the nano-transition metal oxide is loaded on the surface of the biomass nano-cellulose to jointly form the pore wall of the porous material, thereby not only solving the problem that the secondary pollution is easily caused because the biomass nano-cellulose can not degrade pollutants only by adsorbing, but also solving the problem that nano-transition metal oxide particles are easy to gather, while the biomass nano-cellulose/nano-transition metal oxide binary composite material is recycled, the specific surface area of the biomass nano-cellulose/nano-transition metal oxide binary composite material is increased, more organic binding sites are exposed, the biomass nano-cellulose/nano-transition metal oxide binary composite material is convenient to fully and quickly contact with pollutants in sewage, and stronger adsorption, catalytic oxidation and degradation capacities are shown.
2. The porous material prepared by the invention has better structural stability after ionic crosslinking and olefin monomer polymerization, wherein the olefin monomer can mutually wind and connect the biomass nanocellulose/nano transition metal oxide forming the pore wall after being polymerized into a corresponding polymer molecular chain, so that the shaped biomass nanocellulose/nano transition metal oxide hydrogel is not easy to collapse and close pores in the drying process; in addition, the amount of the added olefin monomer is small, the amount of the generated corresponding polymer molecular chain is small, the biomass nanocellulose/nano transition metal oxide of the small amount of polymer molecular chain is intertwined with each other, the contact of the biomass nanocellulose/nano transition metal oxide with pollutants in sewage is not influenced, the biomass nanocellulose/nano transition metal oxide can be separated from the wastewater solution by simple filtration while the excellent adsorption catalytic oxidation degradation capability is shown, the recycling of materials is facilitated, and the problem of difficult solid-liquid separation is solved to a great extent.
3. The porous material prepared by the invention combines the adsorption of the biomass nanocellulose and the catalytic degradation capability of the nano transition metal oxide, solves the problem that the traditional adsorption material is only adsorbed but not degraded, can be recycled after adsorption and degradation through natural drying, solves the problem that the traditional adsorption material needs a desorption process using an organic solvent such as ethanol and the like to cause secondary pollution, and has the advantages of excellent recycling capability and no secondary repeated pollution in use.
4. According to the invention, the biomass nanocellulose/nano transition metal oxide porous material is prepared by using a high internal phase Pickering emulsion template method, and by using the emulsion template method, the biomass nanocellulose and the nano transition metal oxide which are positioned at an oil-water interface in the emulsion can form the pore wall of the porous material together after being subjected to molding, crosslinking and other processes, so that the biomass nanocellulose/nano transition metal oxide binary composite material is expected to be easily recycled and reused, the specific surface area of the biomass nanocellulose/nano transition metal oxide binary composite material is greatly increased, the biomass nanocellulose and the nano transition metal oxide can be in full contact with sewage, and the task of rapid degradation after adsorption is completed.
5. The biomass nano-cellulose/nano-transition metal oxide porous material prepared by adopting the high internal phase Pickering emulsion template method has the advantages of fast adsorption, high degradation efficiency, easy separation, excellent cyclic regeneration capacity, no secondary pollution and the like, and provides a new way for purifying high-concentration industrial wastewater.
Drawings
One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting.
FIG. 1 is a photograph taken by a polarizing microscope of a high internal phase Pickering emulsion prepared in example 1 of the present invention (a), a photograph of a cross-linked and shaped hydrogel thereof (b), a photograph of a corresponding porous material after drying of the hydrogel (c), and a photograph of a corresponding porous material under a scanning electron microscope at different magnifications (d-f);
FIG. 2 is a comparison graph of the effect of adsorption and degradation of black liquor of cotton pulp by biomass nano-cellulose/nano-transition metal oxide microspheres prepared in example 1, comparative example 2 and comparative example 3 of the present invention.
FIG. 3 is a diagram showing the effect of cellulose nanofiber/nanocarbon dioxide porous microspheres in recycling.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
Any of the following examples should not necessarily be construed as preferred or advantageous over other examples unless explicitly supported.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some instances, methods, means, elements well known to those skilled in the art have not been described in detail so as not to obscure the present invention.
Example 1
(1) Preparing a mixed solution of biomass nano-cellulose/nano-transition metal oxide, a carboxyl organic matter, an olefin monomer, an olefin polymerization initiator and a surfactant:
s1: preparing cellulose nano-fibers by an ammonium persulfate oxidation method: adding 5g of cotton pulp cellulose into 150mL of sodium hydroxide dimethyl sulfoxide solution with the concentration of 4% to be soaked for 24h for swelling, then washing the cotton pulp cellulose with deionized water until the pH value of the cotton pulp cellulose is the same as that of the deionized water, dispersing the pretreated cellulose raw material into an aqueous solution consisting of 200mL of deionized water, 5g of ammonium persulfate and 8g of sodium hydroxide, stirring the solution at 50 ℃, oxidizing and hydrolyzing the solution for 0.5h, and then carrying out ultrasonic treatment on the cellulose hydrolysate to obtain a cellulose nano-fiber suspension;
s2: in-situ generation of nano transition metal oxide on the surface of cellulose nanofiber: heating 200mL of 1 wt.% cellulose nanofiber suspension obtained in the step S1 to 70 ℃, slowly dropwise adding 1mL of titanium tetrachloride solution under a rapid stirring state, reacting for 6 hours, and centrifuging and washing with water to obtain a cellulose nanofiber/nano titanium dioxide binary composite material;
s3: to 200mL of 1 wt.% cellulose nanofiber/nano titanium dioxide suspension obtained in step S2, 0.1g of citric acid, 0.1g of polyvinyl alcohol solution, 0.5g of acrylamide, and 0.01g of benzoyl peroxide are sequentially added and uniformly stirred to obtain a mixed solution.
(2) Adding 2000mL of normal hexane into the mixed solution obtained in the step (1), and rapidly stirring at the rotating speed of 15000rpm/min to form the oil-in-water cellulose nanofiber/nano titanium dioxide Pickering emulsion with the internal phase volume of 83%.
(3) And (3) injecting the cellulose nanofiber/nano titanium dioxide high internal phase Pickering emulsion obtained in the step (2) into a 1000mL shower type push rod injector, and dropping the emulsion into 2000mL of 2 wt.% magnesium chloride solution by using an automatic injection device to slowly stir for 20min to obtain the cellulose nanofiber/nano titanium dioxide hydrogel microspheres.
(4) And (4) stirring the cellulose nano-fiber/nano-titanium dioxide hydrogel microspheres obtained in the step (3) at 50 ℃ for 2 hours to initiate acrylamide monomer polymerization, so as to prepare the cellulose nano-fiber/nano-titanium dioxide hydrogel microspheres with better toughness.
(5) And (4) freeze-drying the cellulose nanofiber/nano titanium dioxide hydrogel microspheres with better toughness obtained in the step (4) to obtain the cellulose nanofiber/nano titanium dioxide porous microspheres.
As shown in figure 1a, the prepared high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion droplets are tightly stacked, clear droplet edges can be observed, an oil phase is wrapped in the middle of a water phase, the emulsion has good overall stability, the emulsion breaking phenomenon is avoided, the droplet size of the emulsion is 10-50 μm, and the average droplet size is 28 μm; from FIG. 1b it can be observed that a spherical hydrogel with a regular shape can be obtained; as can be seen from FIGS. 1c and 1d, the obtained hydrogel microspheres can maintain the spherical shape of the original hydrogel microspheres after drying, and no structural collapse occurs during the drying processCollapsing; brittle fracture is carried out on the prepared cellulose nanofiber/nano titanium dioxide microspheres by using liquid nitrogen, and the fracture surface is sprayed with gold and then is observed under a scanning electron microscope, and the result is shown in figure 1e, clear porous structure can be observed from the figure, the structure collapse does not occur in the interior of the microspheres due to the winding of polymers obtained by ionic crosslinking and olefin polymerization on the cellulose nanofiber/nano titanium dioxide, and a multi-stage pore structure exists; the pore walls of FIG. 1e are further enlarged, and as a result, as shown in FIG. 1f, the cellulose nanofibers/nano titanium dioxide jointly form the pore walls of the porous microspheres, and the specific surface area is 16m measured by the BET method2/g。
In addition, the nanocellulose in this embodiment may be prepared by other methods such as an acid hydrolysis method and an oxidation method; similar effects are shown when the nano-cellulose prepared in the embodiment is compounded with nano transition metal oxides such as manganese dioxide, zinc oxide, ferric oxide, ferroferric oxide, copper oxide, cuprous oxide, manganese heptaoxide and the like.
Example 2
The addition of the surfactant polyvinyl alcohol was varied, the addition of the polyvinyl alcohol was 0.02g, and all other conditions (e.g., the types and amounts of raw materials, the process flow, etc.) were the same as in example 1, to obtain a stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion having an internal phase volume of 75%, the emulsion droplet size was between 40-100 μm, and the average droplet size was 70 μm. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 12m2/g。
Example 3
The addition of the surfactant polyvinyl alcohol was varied, the addition of the polyvinyl alcohol was 0.4g, and all other conditions (e.g., the type and amount of raw materials, and the process flow) were the same as in example 1, to obtain a stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion having an internal phase volume of 90%, the droplet size of the emulsion was 2-20 μm, and the average droplet size was 11 μm. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 20m2/g。
Example 4
The surfactant was sodium dodecylbenzenesulfonate, the amount of sodium dodecylbenzenesulfonate solution added was 0.1g, and all other conditions (e.g., type, amount of raw materials, and process flow) were the same as in example 1, to obtain a stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with an internal phase volume of 78%, the emulsion droplet size was between 10-50 μm, and the average droplet size was 30 μm. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano titanium dioxide porous microsphere is obtained, and the specific surface area is 15m2/g。
Example 5
The addition amount of the carboxyl organic matter citric acid is different, the addition amount of the citric acid is 0.05g, all other conditions (such as the types and the amounts of raw materials, the process flow and the like) are the same as those of the example 1, and the stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with the internal phase volume of 83 percent is obtained, the droplet size of the emulsion is between 10 and 50 mu m, and the average droplet size is 28 mu m. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 13m2/g。
Example 6
The addition of the carboxyl organic citric acid was varied, the addition of citric acid was 0.4g, and all other conditions (e.g., type of raw material, amount of used raw material, and process flow) were the same as in example 1, to obtain a stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with an internal phase volume of 83%, the droplet size of the emulsion was between 10-50 μm, and the average droplet size was 28 μm. After drying, a stable porous material with a specific surface area of 18m can be obtained2/g。
Example 7
The carboxy organic substance was sodium carboxymethylcellulose, the amount of sodium carboxymethylcellulose added was 0.1g, and all other conditions (e.g., type, amount, and process flow of raw materials) were the same as in example 1, to obtain a stable high internal phase cellulose nanofiber/nano-titania Pickering emulsion having an internal phase volume of 83%, the droplet size of the emulsion being within the range of10-50 μm and the average size of the liquid drops is 30 μm. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 17m2/g。
Example 8
Preparing cellulose nanofiber/nano titanium dioxide tough gel microspheres by adopting an ultraviolet-initiated free radical polymerization mode, wherein an initiator is benzoin dimethyl ether, the addition amount of the benzoin dimethyl ether is 0.01g, all other conditions (such as the types and the amounts of raw materials, the process flow and the like) are the same as those of the embodiment 1, shaping and ion crosslinking the prepared high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with the internal phase volume of 83 percent, placing the emulsion under an ultraviolet lamp with the power of 300W and the wavelength of 600nm for irradiation reaction for 30min, and freezing and drying the emulsion to obtain the cellulose nanofiber/nano titanium dioxide porous microspheres, wherein the specific surface area of the porous microspheres is 15m2/g。
Example 9
The initiator is ammonium persulfate, all other conditions (such as the types, the dosage, the process flow and the like of the raw materials) are the same as those in the example 1, the prepared high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with the internal phase volume of 83 percent is shaped and subjected to ion crosslinking, then the high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion is placed in a water bath with the temperature of 80 ℃ for reaction for 8 hours, and the cellulose nanofiber/nano titanium dioxide porous microspheres are obtained after freeze drying, wherein the specific surface area is 16m2/g。
Example 10
The addition of the olefin monomer acrylamide is different, the addition of the acrylamide is 0.1g, all other conditions (such as the types and the amounts of raw materials, the process flow and the like) are the same as those of the example 1, and the stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with the internal phase volume of 83 percent is obtained, the droplet size of the emulsion is between 10 and 50 mu m, and the average droplet size is 28 mu m. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano titanium dioxide porous microsphere is obtained, and the specific surface area is 15m2/g。
Example 11
The amount of acrylamide as olefin monomer is different, and the amount of acrylamide is 1g, and the rest conditions (such as: the types, the amounts and the process flow of the raw materials, etc.) are the same as those in example 1, and a stable high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with an internal phase volume of 83% is obtained, the droplet size of the emulsion is 10-50 μm, and the average droplet size is 28 μm. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 21m2/g。
Example 12
The olefin monomer is acrylonitrile, the addition amount of the acrylonitrile is 1g, all other conditions (such as the types and the amounts of raw materials, the process flow and the like) are the same as those of the example 1, and the high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with the stable internal phase volume of 83 percent is obtained, the droplet size of the emulsion is between 10 and 50 mu m, and the average droplet size is 30 mu m. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 20m2/g。
Example 13
The addition amount of the oil phase n-hexane is different, the addition amount is 1000mL, all other conditions (such as the types and the use amounts of raw materials, the process flow and the like) are the same as those of the example 1, and the high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with the stable internal phase volume of 83 percent is obtained, the droplet size of the emulsion is between 10 and 40 mu m, and the average droplet size is 20 mu m. After post-treatment such as shaping, crosslinking and the like, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere is obtained, and the specific surface area is 16m2/g。
Example 14
The nano titanium dioxide is added into 200mL of 2 wt.% cellulose nano fiber water suspension in an amount of 4000mL, and the rest conditions (such as raw material types, dosage, process flow and the like) are the same as those in example 1, so as to obtain a stable high internal phase cellulose nano fiber/nano titanium dioxide Pickering emulsion with an internal phase volume of 83%, wherein the droplet size of the emulsion is 10-45 μm, and the average droplet size is 30 μm. Through shaping and cross-linkingAfter the post-treatment, the stable cellulose nano-fiber/nano-titanium dioxide porous microsphere with the specific surface area of 16m is obtained2/g。
Comparative example 1
The conditions (such as the types and the amounts of raw materials, the process flow and the like) are the same as those in example 1 except that no surfactant is added, and the volume of the internal phase of the obtained cellulose nanofiber/nano carbon dioxide Pickering emulsion is 30 percent and is lower than the requirement that the volume of the internal phase required by the high internal phase is more than 74 percent. After the obtained emulsion is molded, crosslinked and dried, the obtained nano-cellulose/titanium dioxide microspheres have few internal pores and collapse, and the specific surface area is 2m2/g。
Comparative example 2
The high internal phase cellulose nanofiber/nano titanium dioxide Pickering emulsion with an internal phase volume of 83% was obtained by the same conditions (e.g., types, amounts of raw materials, and process flow) as in example 1, except that no carboxyl organic substance was added. The emulsion droplet size is between 5-40 μm. Because of the existence of the ion-free cross-linking agent carboxyl organic matter, ion cross-linking cannot be carried out subsequently, collapse and closed pores are easy to occur in the drying process after the cellulose nano-fiber/nano-titanium dioxide high internal phase emulsion is shaped, and the specific surface area of the finally obtained nano-cellulose/titanium dioxide microsphere is 1m2/g。
Comparative example 3
The olefin monomer is not added, and all other conditions (such as the types and the dosage of raw materials, the process flow and the like) are the same as those in the example 1, so that the high internal phase cellulose nano-fiber/nano titanium dioxide Pickering emulsion with the internal phase volume of 83 percent is obtained. After the prepared intermediate-internal phase emulsion is subjected to ion cross-linking in a shaping manner, the strength of the prepared porous microspheres is improved without further free radical polymerization, collapse and closed pores are easy to generate in the drying process after the nano-cellulose/titanium dioxide high-internal phase emulsion is subjected to shaping, and the specific surface area of the finally obtained nano-cellulose/titanium dioxide microspheres is 4m2/g。
Test examples
1. The experimental method for measuring the decolorizing effect of the cotton pulp black liquor comprises the following steps:
respectively taking 2L of 500mg/L cotton pulp black liquor, putting the cotton pulp black liquor into 4 beakers, and respectively adding 1g of the porous microspheres obtained in the example 1, the comparative example 2 and the comparative example 3 into the 4 beakers, and respectively stirring the mixture for 30min at 25 ℃ for adsorption and degradation. The treatment results are shown in figure 2, the cellulose nanofiber/nano titanium dioxide porous microspheres obtained in example 1 show good adsorption degradation effects, the chromatic value of the cotton pulp black liquor is reduced to 70cpu from undetectable, the TOC value is reduced to 600mg/L from the original 72000mg/L, the COD value is reduced to 265mg/L from 14850mg/L, and the BOD value is reduced to 130mg/L from 6000mg/L, and the results completely meet the grade standard of the quality of sewage discharged into town sewers. The cellulose nanofiber/nano titanium dioxide microspheres prepared in the comparative example 1 without adding the surfactant have the advantages that when the cellulose nanofiber/nano titanium dioxide microspheres are used for treating cotton pulp black liquor, the colorimetric value of the cotton pulp black liquor at night is reduced to 1000cpu from undetectable, the TOC value is reduced to 5000mg/L from the original 72000mg/L, the COD value is reduced to 1250mg/L from 14850mg/L, and the BOD value is reduced to 600mg/L from 6000 mg/L; the cellulose nanofiber/nano titanium dioxide microspheres prepared in the comparative example 2 without adding carboxyl are used for treating cotton pulp black liquor, the colorimetric value of the cotton pulp black liquor at night is reduced to 1500cpu from undetectable, the TOC value is reduced to 6000mg/L from the original 72000mg/L, the COD value is reduced to 1400mg/L from 14850mg/L, and the BOD value is reduced to 780mg/L from 6000 mg/L; comparative example 3 cellulose nanofiber/nano titanium dioxide microspheres prepared without adding olefin monomers, when the cellulose nanofiber/nano titanium dioxide microspheres are used for treating cotton pulp black liquor, the chroma value of the cotton pulp black liquor is reduced to 800cpu from undetectable, the TOC value is reduced to 3050mg/L from the original 72000mg/L, the COD value is reduced to 1000mg/L from 14850mg/L, and the BOD value is reduced to 510mg/L from 6000 mg/L; the results of the comparative example 1, the comparative example 2 and the comparative example 3 are all higher than the highest value requirement of the grade standard of the quality of the sewage discharged into the urban sewer.
2. The experimental method for measuring the repeated utilization rate of the cellulose nanofiber/nano titanium dioxide porous microspheres comprises the following steps:
(1) 2L of 500mg/L cotton pulp black liquor is taken and put into a beaker, then 1g of the porous microspheres obtained in the example 1 are added into the beaker and stirred for 30min at 25 ℃ for carrying out adsorption and degradation experiments, and the TOC, COD and BOD values of the cotton pulp black liquor after the porous microspheres are treated are measured.
(2) Filtering and taking out the cellulose nano-fiber/titanium dioxide porous microspheres subjected to adsorption degradation, and drying.
(3) And (4) putting the dried porous microspheres into 2L of 500mg/L cotton pulp black liquor again, and measuring the TOC, COD and BOD values of the cotton pulp black liquor after the porous microspheres are treated under the same conditions as in the step one.
(4) And (4) repeating the step (2) and the step (3) until the porous microspheres have no capacity of adsorbing and degrading the cotton pulp black liquor.
The experimental result of the repeated utilization rate of the cellulose nano-fiber/nano-titanium dioxide porous microspheres is shown in figure 3. As can be seen from fig. 3, the cellulose nanofiber/nano titanium dioxide porous microspheres can ensure high adsorption degradation efficiency after being recycled for 16 times. The reason is that the transition metal catalyst has the characteristics of toxicity resistance, good thermal stability, developed pore structure, more oxygen vacancies, long service life and high selective oxidation, so that the cellulose nano-fiber/nano-titanium dioxide porous microspheres still maintain high efficiency in the recycling from 2 nd to 16 th.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
The internal phase volumes and corresponding porous material specific surface areas of the biomass nanocellulose/nano transition metal oxide high internal phase Pickering emulsions prepared in examples 1 to 14 and comparative examples 1 to 3, and the treatment results on cotton pulp black liquor (TOC value: 72000 mg/L; COD value: 14850 mg/L; BOD value: 6000mg/L) are shown in Table 1.
TABLE 1
As can be seen from the comparison of example 1 with comparative examples 1 to 3, the obtained nanocellulose/titanium dioxide high internal phase emulsion is easy to have closed pores or collapse during drying process if the obtained shaped spheres are not crosslinked after being shaped, so that the specific surface area of the finally obtained nanocellulose/titanium dioxide microspheres is small.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A surface-supported nano transition metal oxide biomass nano cellulose porous material is characterized in that:
uniformly mixing biomass nanocellulose water suspension loaded with nano transition metal oxide on the surface, a water-soluble organic matter containing carboxyl, a small amount of surfactant, an olefin monomer and an initiator capable of initiating polymerization of the olefin monomer, adding an organic solvent into the mixture, and preparing an oil-in-water biomass nanocellulose/nano transition metal oxide high internal phase Pickering emulsion by taking the organic solvent as an oil phase; and shaping the obtained high internal phase Pickering emulsion, sequentially carrying out ion crosslinking, initiating polymerization of olefin monomers in the high internal phase Pickering emulsion, and drying to obtain the biomass nano-cellulose/nano-transition metal oxide porous material with the porous structure. The nanometer transition metal oxide is loaded on the surface of the biomass nanometer cellulose through non-covalent interaction, and the polymerization mode of the olefin monomer is free radical initiated polymerization.
2. A method of making the porous material of claim 1, wherein: the preparation method comprises the following steps of preparing a biomass nano cellulose porous material with a surface loaded with a nano transition metal oxide by using a high internal phase Pickering emulsion as a template:
(1) preparing mixed solution of biomass nanocellulose/nano transition metal oxide, carboxyl organic matter, olefin monomer, olefin polymerization initiator and surfactant;
(2) adding an organic solvent into the mixed solution obtained in the step (1) and then emulsifying at a high speed to obtain an oil-in-water type biomass nanocellulose/nano transition metal oxide high internal phase Pickering emulsion;
(3) shaping the biomass nanocellulose/nano transition metal oxide high internal phase Pickering emulsion obtained in the step (2), and then carrying out ion crosslinking to obtain a biomass nanocellulose/nano transition metal oxide hydrogel;
(4) and (4) initiating the olefin monomer in the biomass nano-cellulose/nano-transition metal oxide hydrogel obtained in the step (3) to polymerize, so as to prepare the biomass nano-cellulose/nano-transition metal oxide hydrogel with better toughness.
(5) And (4) drying the biomass nano-cellulose/nano-transition metal oxide hydrogel obtained in the step (4) to prepare the biomass nano-cellulose/nano-transition metal oxide porous material.
3. The method of claim 1, wherein:
the nanometer transition metal oxide is loaded on the surface of the biomass nanocellulose in a non-covalent interaction manner, wherein the loading manner of the nanometer transition metal oxide is to physically mix the nanometer transition metal oxide and the biomass nanocellulose in water, carry out loading by virtue of interaction between functional groups on the surface of the biomass nanocellulose and the nanometer transition metal oxide, and/or generate the nanometer transition metal oxide on the surface of the biomass nanocellulose in situ;
the nanometer transition metal oxide loaded on the biomass nanocellulose accounts for 10-60% of the total mass of the biomass nanocellulose/nanometer transition metal oxide binary composite material; alternatively from 20% to 50%, further alternatively from 30% to 40%;
the bio-based nano cellulose comprises one or more of cellulose nanocrystals, cellulose nano fibers and bacterial cellulose;
and/or the transition metal oxide comprises one or more of manganese dioxide, titanium dioxide, zinc oxide, ferric oxide, ferroferric oxide, copper oxide, cuprous oxide and manganese heptaoxide;
and/or the water-soluble carboxyl organic substance comprises one or more of citric acid, oxalic acid, sodium alginate, sodium carboxymethylcellulose, formic acid, acetic acid, butyric acid, caproic acid, caprylic acid, capric acid and benzoic acid;
and/or the surfactant comprises one or more of polyvinyl alcohol, polyethylene glycol, sodium a-alkenyl sulfonate, linear alkyl benzene sulfonate, sodium stearate, dodecyl dimethyl ammonium oxide, alkylolamide, alkyl polyglycoside and glucamide; the surfactant used in the present invention is not limited thereto.
And/or the olefin monomer comprises one or more of acrylamide, acrylic acid, acrylonitrile, methyl methacrylate, styrene, ethylene, octene, hexene, cyclohexene, cyclopentadiene and norbornene; the olefin monomer used in the present invention is not limited thereto.
And/or the oil phase organic solvent comprises one or more of n-hexane, cyclohexane, ethyl acetate, pentane, hexane and octane; the oil phase organic solvent used in the present invention is not limited thereto.
4. The method of claim 2, wherein: the mass ratio of the biomass nanocellulose/nano transition metal oxide to the water-soluble carboxyl organic matter is 1: 0.01-0.5.
And/or the mass ratio of the biomass nanocellulose/nano transition metal oxide to the surfactant is 1: 0.01-0.5.
And/or the mass ratio of the biomass nanocellulose/nano transition metal oxide to the olefin monomer is 1: 0.05-0.5.
The volume ratio of the oil phase organic solvent to the water is 3-49: 1.
5. The method of claim 2, wherein: the high-speed emulsification speed is 1000-.
6. The method of claim 2, wherein: the ion used in the ionic crosslinking is Ca2+、Mg2+、Ba2 +、Al3+、Fe2+、Fe3+、Zn2+、Cu2+Wherein the addition amount of the ionic salt is 1-20% of the amount of the water-soluble carboxyl organic substance.
The initiating mode for initiating the polymerization of the olefin monomer can be one or more of ultraviolet initiation and thermal initiation.
When the initiating manner of initiating the olefin monomer polymerization is ultraviolet initiating free radical polymerization, the initiator is one or more of benzoin, benzoin ethyl ether, benzoin butyl ether, benzoin dimethyl ether, benzophenone, amine compounds, thioxanthone, camphorquinone, bisimidazole, diaryl iodonium salt and triaryl sulfonium salt;
wherein the addition amount of the initiator is 0.01-0.5% of the mass of the olefin monomer, the power of an ultraviolet lamp is 100-;
when the initiation mode for initiating the polymerization of the olefin monomer is thermal initiation polymerization, the initiator is one or more of ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, potassium persulfate, benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide;
wherein the addition amount of the free radical initiator is 0.01-0.5% of the mass of the olefin monomer, the initiation temperature is 20-100 ℃, and the polymerization time is 1-24 h.
7. The method of claim 2, wherein: the drying mode is one or more of common oven drying, vacuum oven drying, freeze drying and supercritical drying.
8. The method of claim 2, wherein: the shaping of the high internal phase Pickering emulsion can be carried out in an extrusion or injection mode to obtain any shape, such as any one of a sphere, a cube, a cuboid, a cylinder, a cone and the like.
9. The method of claim 3, wherein:
when the loading mode of the nanometer transition metal oxide is physical mixing, adding the nanometer transition metal oxide into the water suspension of the biomass nanocellulose and uniformly stirring;
when the loading mode of the nano transition metal oxide is in-situ generation, a certain amount of transition metal salt with strong oxidizing property is added into the biomass nano cellulose suspension, and the mixture is rapidly stirred and reacts for a certain time under the conditions of certain pH and temperature, so that the nano transition metal oxide can be generated on the surface of the biomass nano cellulose in situ; wherein the mass ratio of the transition metal salt to the biomass nano-cellulose is 1:1-1:40, the pH value of a reaction system is 1-14, the reaction temperature is 30-100 ℃, and the reaction time is 1-10 h.
10. The biomass nano-cellulose/nano-transition metal oxide porous material prepared by the preparation method according to any one of claims 1 to 9 can be repeatedly regenerated for industrial sewage treatment, wherein the industrial sewage comprises one or more of dye sewage, cotton pulp black liquor, coke quenching water, heavy metal wastewater, heated polluted wastewater and the like.
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