CN107353352B - A kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film - Google Patents
A kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film Download PDFInfo
- Publication number
- CN107353352B CN107353352B CN201710671228.7A CN201710671228A CN107353352B CN 107353352 B CN107353352 B CN 107353352B CN 201710671228 A CN201710671228 A CN 201710671228A CN 107353352 B CN107353352 B CN 107353352B
- Authority
- CN
- China
- Prior art keywords
- cellulose
- nano
- preparation
- added
- water purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/12—Cellulose derivatives
- B01D71/20—Esters of inorganic acids, e.g. cellulose nitrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/40—Fibre reinforced membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2397/00—Characterised by the use of lignin-containing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
- C08J2401/16—Esters of inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention belongs to water-purifying material technical fields, more particularly to a kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film, the nano-cellulose preparation method is the following steps are included: pretreatment of raw material, preparing chemical cellulose, preparing nano-cellulose.The nano-cellulose is prepared by the preparation method, the water purification film includes the nano-cellulose, the preparation method of the water purification film is the following steps are included: prepare lignin base, prepare polyether sulfone ultrafiltration layer, preparation water purification film, and wherein the raw material wood element of lignin base is by the product isolated in the preparation method of nano-cellulose.Above-mentioned preparation method mild condition provided by the invention, non-pollution discharge object, and the nano-cellulose finally prepared meets the requirement of preparation water purification film, further makes nanofiber cellulose content in the preparation method water purification film obtained of the water purification film provided high, the service life is longer, and purifying water effect is more preferable.
Description
Technical field
The invention belongs to water-purifying material technical field more particularly to a kind of preparation methods of nano-cellulose, nanofiber
The preparation method of element and water purification film, water purification film.
Background technique
Membrane Separation for Water Treatment is the important technology for solving resource-type water shortage problem, is the advanced skill for guaranteeing drinking water safety
Art is the core technology of Drinking Water processing, is widely used in water purification product.The capacity and the output value in Chinese film market occupy generation
Boundary's second was possible to surmount the U.S. after several years, became the big film market of the first in the world.Currently, domestic reverse osmosis membrane has 90% to be
Imported product；And the raw material for being used to make film have 50%-70% to rely on import.Our national membrane product manufacturing enterprises have 300
Yu Jia, but due to lacking core technology, in international market almost without any status.Even Haier beauty the country such as Gree know
Name appliance brand, can all use " selected U.S.'s ×× water filter membrane " when publicizing the water purification product of oneself.So film product is domestic
Change the leading market situation that can fundamentally change foreign brand name.
Currently, the raw materials for production of global water filter membrane are all chemical materials, these water filter membranes while crossing drainage,
It can be chemically reacted with water, some pairs of unfavorable chemical components of human body in raw material are dissolved into water, and these ingredients are not
With scientific detection means, we are daily to can't see at all, can't smell.So if the water filter membrane made of chemical materials with
It in drinking water treatment field, is especially used in drinking-water processing, there is certain side effect, drinking water treatment industry is expected natural
Reproducible organic film material overturns the situation that Drinking Water Filtration film in the world selects chemical materials.
Water filter membrane belongs to consumptive material, and the water filter membrane for needing to regularly replace, and replace can generally be used as house refuse quilt
It abandons.Huge and difficult to degrade " white pollution " object as caused by synthetic material and synthetic fibers has given the living environment of the mankind
Bring crisis, and natural fiber film is easy to the advantages of degrading with it positive meaning to environmental protection, so, utilize day
Right fiber film makes Drinking Water Filtration film and product, will can become the development trend of drinking water treatment industry.
The development and utilization of natural fiber resource have extremely important meaning.It is burnt in previous Chinese alpine rush primarily as dried firewood
Fall the raw material with papermaking, do not developed and utilized deeper into ground, virtually forms a kind of waste of resource.By to Dracaena
The understanding of the biological characteristics and Planting characteristic of grass, it is known that Chinese alpine rush it is adaptable it is wide, easily plant easily pipe, small investment, high efficiency,
Quick and ecological benefits significantly etc. are different from the characteristics of general economic plants, are worth on vast hills, mountain area Devoting Major Efforts To Developing benefit
With.
Research and the patent of invention for extracting cellulose in Chinese alpine rush at present are quite a lot, but are only limited to extract or make
Until the products such as standby cellulose acetate, nitrocellulose, the native cellulose extracted is used to prepare the technology of membrane for water treatment
It is still immature.The native cellulose preparation water treatment technology extracted using straw plants is gradually increased in China in recent years, is extracted
Cellulose out is mixed in a certain proportion and prepares membrane for water treatment in casting solution, but this kind of method has the following problems.
Firstly, existing such as native cellulose preparation water purification film mostly uses chemical method to be pre-processed, and use alkaline process
Lignocellulosic is decomposed, it is made to resolve into lignin, cellulose, hemicellulose.Such as application publication number is
The patent of invention of CN103143269A discloses a kind of Chitosan/cellulose composite separation membrane and preparation method thereof, uses chlorine
Changing zinc aqueous solution is to be immersed gel method after solvent directly dissolves chitosan and cellulose and compound point of Chitosan/Cellulose is made
From film.In another example the patent of invention that application publication number is CN102517971A uses mixing slurrying of the soda processes to wheat straw reed；
The patent of invention that application publication number is CN106192514A is using NaOH solution to containing lignin, hemicellulose and cellulose
Biomass carries out alkali and extracts in advance, and lignin, hemicellulose and cellulose are efficiently separated purification；Hebei Ji ligusticumic chemical fibre Limited Liability
Company (publication number CN1936175A) pulping method using high active alkali method uses high-alkali progress boiling hydrolysis.Wherein all use alkaline process
Lignocellulosic is decomposed, it is made to resolve into lignin, cellulose, hemicellulose.Such method is although easy to operate, place
Manage high-efficient, but this method is strong to the corrosivity of equipment, reduces the service life of equipment, increases operation cost；After processing
Waste liquid soda acid content it is high, when discharge, causes serious pollution to environment.
Secondly, it is not high by the cellulose quality that plant is extracted as raw material, it is unable to satisfy film and requires.Art technology
Personnel are well known can be divided into chemical cellulose and hemicellulose for cellulose again, wherein chemical cellulose is defined as: cellulose original
Expect 20 DEG C immerse 17.5% or 18% NaOH solution in after 45 minutes undissolved part.And the polymerization of chemical cellulose
Spend it is very big, its content really in staple fibre and paper industry cellulosic material important indicator.Existing extraction process is adopted
With in plant cellulose extraction process, dissociateed from plant material by chemically or physically pre-processing chemical cellulose.Dissociation
Chemical cellulose by filtering, cleaning etc. techniques obtain final film raw material.But it, can only be by α by above-mentioned pretreating process
Cellulose and lignin and non-cellulose carry out the separation in classification, and isolated chemical cellulose is the shape of high molecular polymer
State, size is inhomogenous, is easy to be mingled with the impurity such as mother liquor between particle, can not thoroughly clean separation.The aperture of its film of chemical cellulose simultaneously
All within 1-10 nanometer range.The polymer materials of macromolecular are unable to satisfy the such high-end water purification film requirement of manufacture.
Finally, hydrophilic run-inflation effect of the existing natural cellulose membrane due to native cellulose, the natural fibre for water process
Dimension membrane durability is poor, and the service life is low.Therefore in order to improve the durability of film, natural fiber content is usually lower, often less than 1%.
Such as application publication number is the patent of invention of CN103816817A, in a kind of alkali resistant cellulose film provided and preparation method thereof,
The weight percent of casting solution containing cellulose pulp is 0.1-2%；In another example application publication number is the invention of CN103816819A
Patent provides a kind of doughnut and nanofiltration membrane and its preparation process is blended, wherein weight amount ratio of the casting solution containing ethyl cellulose
For 0.2-0.6%.
It can be seen that can be based on deficiency in the prior art, provide a kind of improved nano-cellulose preparation method,
And using the method based on nano-cellulose preparation water purification film, make its method mild condition, non-pollution discharge object, and final system
Standby nano-cellulose meets the requirement of preparation water purification film, further makes the preparation method water purification obtained of the water purification film provided
Film nanofiber cellulose content is high, becomes those skilled in the art's technical problem urgently to be resolved.
Summary of the invention
The present invention for the above technical issues, proposes the preparation method of nano-cellulose a kind of, nano-cellulose and net
The preparation method of moisture film, water purification film.Make to prepare nano-cellulose with more preferably performance, while preparation process condition is mild, nothing
Corrosive raw materials, and non-pollutant discharge.Be additionally based on preparation nano-cellulose preparation water purification film in content of cellulose more
Height, obtained water purification film patience is more preferable, and the service life is longer.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of nano-cellulose, comprising the following steps:
Step 1: pretreatment of raw material: crushing Chinese alpine rush powder after taking Chinese alpine rush shear treatment, takes Chinese alpine rush powder investment hair
Biodegrade is carried out in ferment pond obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Ionic liquid is added in dewatered degradation treatment raw material of learning from else's experience, and is stirred laggard
Row is separated by solid-liquid separation, and obtains filtrate A and filter residue B, after taking filter residue B that ionic liquid is added, is dissolved by heating, is filtered after being separated by solid-liquid separation
Liquid C and filter residue D is added after ethyl alcohol into liquor C and obtains chemical cellulose through solid-liquid separation treatment；
Step 3: it prepares nano-cellulose: taking anhydrous phosphoric acid that anhydrous phosphoric acid solution is prepared, the α for taking step 2 to prepare
Cellulose and anhydrous phosphoric acid solution mix to obtain mixed solution, adjust pH value to alkalinity, pure water are added, esterification occurs, instead
Acid adding neutralizes after answering, and obtains nano-cellulose after cleaning treatment.
Preferably, hemicellulase of the enzyme that uses of the biodegrade for hemicellulase, in the fermentation vat
Concentration is 0.05~1.2g/L, and the temperature in fermentation vat is 35~50 DEG C, a length of 24~28h when biodegradable；
The solid-to-liquid ratio of the degradation treatment raw material and ionic liquid is 1:1, and the condition that is stirred is to stir 2 at 50~70 DEG C
~5h；
The recovered processing of the filtrate obtained after ethyl alcohol through solid-liquid separation treatment is added in the liquor C and obtains ionic liquid.
Preferably, the ionic liquid that the degradation treatment raw material is added are as follows: 2- methoxyethyl -1- crassitude relies
Propylhomoserin salt, 2- methoxyethyl -1- crassitude acetate, 2- methoxyethyl -1- crassitude propionate or 2- first
Oxygen ethyl -1- crassitude glycinate；The ionic liquid that the filter residue B is added are as follows: the double ethyl dimethylamines third of methoxyethyl
The double ethyl dimethylamine amino acids salt of propylhomoserin salt, methoxyethyl or the double ethyl dimethylamine propionates of methoxyethyl.
Preferably, the ionic liquid that the degradation treatment raw material is added are as follows: 2- methoxyethyl -1- crassitude relies
Propylhomoserin salt；The ionic liquid that the filter residue B is added are as follows: the double ethyl dimethylamine alanine salt of methoxyethyl.
Preferably, the preparation method of anhydrous phosphoric acid solution is to take anhydrous phosphoric acid that pure water dissolution is added while cooling, obtain
Concentration is the anhydrous phosphoric acid solution of 0.02~0.1mol/L；
The molar ratio of the chemical cellulose and anhydrous phosphoric acid is 5~20:1；
The alkaline solution for adjusting pH value to alkalinity is 1N- sodium hydroxide solution, alkaline ph values 11.0；
The volume that pure water is added in esterification is 0.2~1 times of mixed liquor volume；
The esterification condition is that 0.5~2h is reacted at a temperature of 30~50 DEG C；
Hydrochloric acid is added after reaction to neutralize, cleans after processing removes phosphoric acid and chloride ion and obtains nano-cellulose.
More preferably, the anhydrous phosphoric acid solution concentration is 0.06mol/L；
More preferably, the molar ratio of the chemical cellulose and anhydrous phosphoric acid is 10:1；
More preferably, the volume of the pure water is 0.5 times of mixed liquor volume；
More preferably, the esterification condition is to react 1h at a temperature of 40 DEG C.
A kind of nano-cellulose is prepared by the preparation method of above-mentioned nano-cellulose.
A kind of water purification film, including separating layer include nano-cellulose in the separating layer, and the nano-cellulose is upper
The nano-cellulose stated.
Preferably, the content of nano-cellulose is 1%~20% in the separating layer.
More preferably, the content of nano-cellulose is 10% in the separating layer.
Preferably, the water purification film further includes lignin base and polyether sulfone ultrafiltration layer, the separating layer of the water purification film,
Polyether sulfone ultrafiltration layer and lignin base are sequentially connected；
The lignin base with a thickness of 100~300 μm；The polyether sulfone ultrafiltration layer with a thickness of 70~150 μm；
The separating layer with a thickness of 10~40 μm.
More preferably, the lignin base with a thickness of 200 μm；The polyether sulfone ultrafiltration layer with a thickness of 100 μm；
The separating layer with a thickness of 20 μm.
A kind of preparation method of above-mentioned water purification film, comprising the following steps:
Step 1: it prepares lignin base: taking the filtrate A obtained when preparing nano-cellulose, second is added into filtrate A
After alcohol, makes the solute in solution that precipitating be precipitated, obtain lignin through solid-liquid separation treatment, the lignin is prepared as lignin
Base；
Step 2: preparing polyether sulfone ultrafiltration layer: polyether sulfone being taken to be dissolved in organic solvent, ultrasonic deaeration, standing after dissolving
Polyether sulfone ultrafiltration layer casting solution is obtained, lignin-base is taken to be placed on flat support face, polyether sulfone ultrafiltration layer casting solution is cast
In lignin base upper surface, and striking forms a film, and the lignin-base for being covered with film is placed in hydrogel and is impregnated, and takes out dry
To polyether sulfone ultrafiltration layer interconnected and lignin base；
Step 3: polyether sulfone ultrafiltration layer interconnected and lignin-base preparation water purification film: are placed on flat support face
On, take nano-cellulose to be dissolved in organic solvent, ultrasonic deaeration, standing obtain separating layer casting solution after dissolving, and take separating layer
Casting solution, which pours, casts from polyether sulfone ultrafiltration layer upper surface, and striking forms a film, and will be covered with polyether sulfone ultrafiltration layer and the lignin base of film
It is placed in hydrogel and impregnates, cleaned after taking-up, be dried to obtain water purification film.
Preferably, the organic solvent is DMAC.
Preferably, being added in the filtrate A, the filtrate obtained after ethyl alcohol through solid-liquid separation treatment is recovered to be handled
To ionic liquid.
Preferably, a length of 1~4h when the ultrasound deaeration, when standing a length of 20~40h.
Compared with prior art, the advantages and positive effects of the present invention are:
1, the preparation method of nano-cellulose provided by the invention using Chinese alpine rush as raw material sources, energy conservation and environmental protection, and
Preparation cost is low, and the nano-cellulose of high-purity, while intermediate product filtrate A and liquor C energy are obtained using comprehensive extraction
It is enough to recycle, have the advantages that energy-saving and emission-reduction.
2, the preparation method of nano-cellulose provided by the invention utilizes selection of the ionic liquid to chemical cellulose and lignin
Specificity carries out fractional extraction, operates determining preparation method smooth, separation operating method is more safely, conveniently.
3, water purification film provided by the invention includes nano-cellulose, there is 3 hydroxyls in chemical cellulose saccharide ring, wherein 2 straight
Be connected to relatively stiff saccharide ring in succession, since the freedom degree of hydroxyl has received biggish limitation so that cellulose show it is thin
Water and hydrophilic dual character；Therefore the nano-cellulose has hydrophobic and hydrophilic double grading, will include nano-cellulose
Separating layer and solution contact surface be prepared as hydrophobic surface, reduce the degrees of fusion of film surface and water, reduce pollution of the inorganic matter to film,
Extend the service life of water purification film.
4, water purification film provided by the invention is multilayer composite separation, and substrate is lignin base, the lignin of raw material
By-product in alpine rush cellulose extraction process efficiently uses waste, further reduces the discharge of waste；
Since lignin density is low, is not easy hydrolyzed characteristic, for can be very good to play as the lignin base in water purification film
Permeable and support effect.
5, water purification film provided by the invention is multilayer composite separation, by the charge effect of polyether sulfone ultrafiltration layer, is made point
Towards combining inside water purification film with polyether sulfone ultrafiltration layer, hydrophobic surface is outwardly formed hydrophobic the hydrophilic surface of the nano-cellulose of absciss layer
Cortex reduces the degrees of fusion of water purification film surface and water.
6, the preparation method of water purification film provided by the invention, the macromolecular that will be extracted in Chinese alpine rush using inorganic acid esterification process
Chemical cellulose Shu Jinhang esterification treatment；Alpine rush cellulose beam after esterification is due to electrostatic repulsion effect, the chemical cellulose of macromolecular
Beam is separated into nanoscale cellulose, obtains nano-cellulose；This method is realized using easy technique and mechanical milling method
The preparation of same nano-grade cellulosic particle, and the nano-cellulose granular size stable homogeneous prepared, improve mechanical grinding
Mill method prepares that nano-cellulose granular size is uncontrollable, is distributed wide non-uniform disadvantage, while making in the water purification film of preparation, nanometer
Content of cellulose is higher, and content can reach 10~15%.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method of nano-cellulose provided by the embodiment of the present invention；
Fig. 2 is nano-cellulose grain size distribution provided by the embodiment of the present invention；
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The embodiment of the invention provides a kind of preparation methods of nano-cellulose, as shown in Figure 1, comprising the following steps:
Step 1: pretreatment of raw material: crushing Chinese alpine rush powder after taking Chinese alpine rush shear treatment, takes Chinese alpine rush powder investment hair
Biodegrade is carried out in ferment pond obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Ionic liquid is added in dewatered degradation treatment raw material of learning from else's experience, and is stirred laggard
Row is separated by solid-liquid separation, and obtains filtrate A and filter residue B, after taking filter residue B that ionic liquid is added, is dissolved by heating, is filtered after being separated by solid-liquid separation
Liquid C and filter residue D is added after ethyl alcohol into liquor C and obtains chemical cellulose through solid-liquid separation treatment；
Step 3: it prepares nano-cellulose: taking anhydrous phosphoric acid that anhydrous phosphoric acid solution is prepared, the α for taking step 2 to prepare
Cellulose and anhydrous phosphoric acid solution mix to obtain mixed solution, adjust pH value to alkalinity, pure water are added, esterification occurs, instead
Acid adding neutralizes after answering, and obtains nano-cellulose after cleaning treatment.
The invention firstly uses Mechanical Methods to crush Chinese alpine rush, makes its largest surface area, so that it is subsequent
It is come into full contact in biodegrade with hemicellulase, lignin is scattered between chemical cellulose fiber in Chinese alpine rush, but the two is usual
Without direct chemistry key connection, lignin mainly plays resistance to compression effect；Hemicellulose is through lignin and chemical cellulose fiber
Between, effect connecting the two is played, and then form very firm chemical cellulose-hemicellulose-lignin network structure.This
Invention, to the degradation of hemicellulose, cuts off linking between chemical cellulose and lignin, Dracaena grass meal using hemicellulase
End adequately absorbs moisture profit in biodegradable pond and rises, and under the action of hemicellulase, becomes loose cotton-shaped knot
Structure.Its preparation cost is low, and raw material sources environmental protection is easy to get, entire preparation step mild condition, while being directed to intermediate product filtrate A
It can be recycled with liquor C, have the advantages that energy-saving and emission-reduction.In addition the nano-cellulose granular size of this method preparation is uniform
Stablize, provides more reliable raw material for subsequent further preparation water purification film and support.Filter residue D therein is ash content, as general useless
Gurry processing.
Nano-cellulose grain diameter test experience:
Take the nano-cellulose of the above-mentioned preparation of 5g in 350ml beaker, be added dispersing agent DMSO 200ml be stirred to
It is completely dispersed.The mixed liquor is tested using laser particle size analyzer.Test results are shown in figure 2, can by Fig. 2 data
Know, this experiment is tested the partial size of nano-cellulose within the scope of 0~300nm, can be seen that from partial size test result
Nano-cellulose granular size is concentrated mainly within the scope of 50-110nm, accounts for 90% of overall ratio or more, and is in similar normal state
Distribution.
In an alternative embodiment, the enzyme that the biodegrade uses for hemicellulase, in the fermentation vat half
Cellulase concentration is 0.05~1.2g/L, and the temperature in fermentation vat is 35~50 DEG C, a length of 24~28h when biodegradable；
In an alternative embodiment, the solid-to-liquid ratio of the degradation treatment raw material and ionic liquid is 1:1, is stirred condition
It is 2~5h of stirring at 50~70 DEG C；
In a preferred embodiment, being stirred condition is to stir 3h at 60 DEG C；
It is recovered that the filtrate obtained after ethyl alcohol through solid-liquid separation treatment is added in an alternative embodiment, in the liquor C
Processing obtains ionic liquid.
In a preferred embodiment, the ionic liquid that the degradation treatment raw material is added are as follows: 2- methoxyethyl -1- methyl
Pyrrolidines lysine salt, 2- methoxyethyl -1- crassitude acetate, 2- methoxyethyl -1- crassitude third
Hydrochlorate or 2- methoxyethyl -1- crassitude glycinate；The ionic liquid that the filter residue B is added are as follows: methoxyethyl is double
The double ethyl dimethylamine amino acids salt of ethyl dimethylamine alanine salt, methoxyethyl or the double ethyl dimethylamine propionates of methoxyethyl.
In a preferred embodiment, the ionic liquid that the degradation treatment raw material is added are as follows: 2- methoxyethyl -1- methyl
Pyrrolidines lysine salt；The ionic liquid that the filter residue B is added are as follows: the double ethyl dimethylamine alanine salt of methoxyethyl.
In an alternative embodiment, the preparation method of anhydrous phosphoric acid solution is molten to take anhydrous phosphoric acid that pure water is added while cooling
Solution obtains the anhydrous phosphoric acid solution that concentration is 0.02~0.1mol/L；
In a preferred embodiment, the concentration of anhydrous phosphoric acid solution is 0.06mol/L；
In an alternative embodiment, the molar ratio of the chemical cellulose and anhydrous phosphoric acid is 5~20:1；
In a preferred embodiment, the molar ratio of the chemical cellulose and anhydrous phosphoric acid is 10:1；
In an alternative embodiment, the alkaline solution for adjusting pH value to alkalinity is 1N- sodium hydroxide solution, and alkaline ph values are
11.0；
In an alternative embodiment, the volume that pure water is added in esterification is 0.2~1 times of mixed liquor volume；
In a preferred embodiment, the volume that pure water is added in esterification is 0.5 times of mixed liquor volume；
In an alternative embodiment, the esterification condition is that 0.5~2h is reacted at a temperature of 30~50 DEG C；
In a preferred embodiment, the esterification condition is to react 1h at a temperature of 40 DEG C；
The present embodiment additionally provides a kind of meter of cellulose, is prepared by the preparation method of above-mentioned nano-cellulose.
Have 3 hydroxyls in the cellulose saccharide ring of finally obtained nano-cellulose, wherein 2 be directly connected in it is relatively stiff
Saccharide ring, since the freedom degree of hydroxyl has received biggish limitation so that nano-cellulose show it is hydrophobic with hydrophilic two sides
Property.
The present embodiment additionally provides a kind of water purification film, including separating layer, includes nano-cellulose in the separating layer, institute
Stating nano-cellulose is above-mentioned nano-cellulose.
It include the separating layer and solution of nano-cellulose by the nano-cellulose with hydrophobic and hydrophilic double grading
Contact surface is prepared as hydrophobic surface, reduces the degrees of fusion of film surface and water, reduces pollution of the inorganic matter to film, extends making for water purification film
Use the service life.
In an alternative embodiment, the content of nano-cellulose is 1%~20% in the separating layer.
In an alternative embodiment, the water purification film further includes lignin base and polyether sulfone ultrafiltration layer, the water purification film
Separating layer, polyether sulfone ultrafiltration layer and lignin base be sequentially connected；
The polyether sulfone ultrafiltration ultrafiltration layer of preferred hydrophilic and good water permeability is as transition zone, since Chinese alpine rush is as raw material system
The viscosity of standby nano-cellulose is high, when 10% nano-cellulose hydrophobic membrane of preferred content is separating layer, by separating layer and gathers
The charge effect of ether sulfone ultrafiltration ultrafiltration layer makes the nano-cellulose hydrophilic surface of separating layer towards water purification film inside and polyether sulfone ultrafiltration
Ultrafiltration layer combines, and hydrophobic surface is outwardly formed hydrophobic cortex.To further improve the purifying water effect of water purification film, water purification is improved
Film service life.
In a preferred embodiment, the content of nano-cellulose is 10% in the separating layer.
In an alternative embodiment, the lignin base with a thickness of 100~300 μm；The polyether sulfone ultrafiltration layer
With a thickness of 70~150 μm；The separating layer with a thickness of 10~40 μm.
In a preferred embodiment, the lignin base with a thickness of 200 μm；The polyether sulfone ultrafiltration layer with a thickness of
100μm；The separating layer with a thickness of 20 μm.
The present embodiment also provides a kind of preparation method of above-mentioned water purification film, comprising the following steps:
Step 1: it prepares lignin base: taking the filtrate A obtained when preparing nano-cellulose, second is added into filtrate A
After alcohol, makes the solute in solution that precipitating be precipitated, obtain lignin through solid-liquid separation treatment, the lignin is prepared as lignin
Base；
Step 2: preparing polyether sulfone ultrafiltration layer: polyether sulfone being taken to be dissolved in organic solvent, ultrasonic deaeration, standing after dissolving
Polyether sulfone ultrafiltration layer casting solution is obtained, lignin-base is taken to be placed on flat support face, polyether sulfone ultrafiltration layer casting solution is cast
In lignin base upper surface, and striking forms a film, and the lignin-base for being covered with film is placed in hydrogel and is impregnated, and takes out dry
To polyether sulfone ultrafiltration layer interconnected and lignin base；
Step 3: polyether sulfone ultrafiltration layer interconnected and lignin-base preparation water purification film: are placed on flat support face
On, take nano-cellulose to be dissolved in organic solvent, ultrasonic deaeration, standing obtain separating layer casting solution after dissolving, and take separating layer
Casting solution, which pours, casts from polyether sulfone ultrafiltration layer upper surface, and striking forms a film, and will be covered with polyether sulfone ultrafiltration layer and the lignin base of film
It is placed in hydrogel and impregnates, cleaned after taking-up, be dried to obtain water purification film.
Water purification film prepared by the present invention, substrate are lignin base, and the lignin of raw material derives from alpine rush cellulose
By-product in extraction process efficiently uses waste, further reduces the discharge of waste；Due to lignin density is low,
It being not easy hydrolyzed characteristic, playing the role of permeable and support for can be very good as the lignin base in water purification film.
In an alternative embodiment, the organic solvent is DMAC.
The filtrate obtained after ethyl alcohol through solid-liquid separation treatment is added in an alternative embodiment, in the filtrate A to pass through back
Receipts handle to obtain ionic liquid；
In an alternative embodiment, a length of 1~4h when the ultrasound deaeration, when standing a length of 20~40h.
In a preferred embodiment, a length of 2h when the ultrasonic deaeration, when standing, are a length of for 24 hours.
In order to become apparent from the preparation method for introducing nano-cellulose provided by the embodiment of the present invention in detail, nanofiber
The preparation method of element and water purification film, water purification film, is described below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of nano-cellulose, comprising the following steps:
Step 1: pretreatment of raw material: crushing Chinese alpine rush powder after taking Chinese alpine rush shear treatment, takes Chinese alpine rush powder investment hair
In ferment pond, and hemicellulase is added, makes the hemicellulose concentration 0.05g/L in fermentation vat, the temperature in fermentation vat is 50
DEG C, when biodegradable it is a length of for 24 hours；It carries out biodegrade and obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Learn from else's experience dewatered degradation treatment raw material according to solid-to-liquid ratio be 1:1 be added 2- methoxy
Ethyl -1- crassitude lysine salt, mixing condition are to stir 2h at 50 DEG C, are separated by solid-liquid separation, are obtained after being stirred
It is dissolved by heating, after being separated by solid-liquid separation after taking filter residue B that the double ethyl dimethylamine alanine salt of methoxyethyl are added to filtrate A and filter residue B
Liquor C and filter residue D are obtained, is added into liquor C after ethyl alcohol and obtains chemical cellulose through solid-liquid separation treatment, added in the liquor C
Enter the recovered processing of the filtrate obtained after ethyl alcohol through solid-liquid separation treatment and obtains 2- methoxyethyl -1- crassitude lysine
Salt；
Step 3: it prepares nano-cellulose: taking anhydrous phosphoric acid that pure water dissolution is added while cooling, obtaining concentration is
The anhydrous phosphoric acid solution of 0.02mol/L, the chemical cellulose and anhydrous phosphoric acid solution for taking step 2 to prepare are mixed for 5:1 according to molar ratio
Conjunction obtains mixed solution, continuously adds 1N- sodium hydroxide solution and adjusts pH value to 11.0, mixes and pure water hair is added in solution
Life esterification, acid adding neutralizes after reaction, cleans after cleaning processing removing phosphoric acid and chloride ion after obtaining nano-cellulose
Obtain nano-cellulose.
A kind of nano-cellulose is prepared by the preparation method of above-mentioned nano-cellulose.
Embodiment 2
A kind of preparation method of nano-cellulose, comprising the following steps:
Step 1: pretreatment of raw material: crushing Chinese alpine rush powder after taking Chinese alpine rush shear treatment, takes Chinese alpine rush powder investment hair
In ferment pond, and hemicellulase is added, makes the hemicellulose concentration 0.1g/L in fermentation vat, the temperature in fermentation vat is 45
DEG C, a length of 26h when biodegradable；It carries out biodegrade and obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Learn from else's experience dewatered degradation treatment raw material according to solid-to-liquid ratio be 1:1 be added 2- methoxy
Ethyl -1- crassitude lysine salt, mixing condition are to stir 3h at 60 DEG C, are separated by solid-liquid separation, are obtained after being stirred
To filtrate A and filter residue B, takes filter residue B that the double ethyl dimethylamine alanine salt of methoxyethyl are added, dissolve by heating, after being separated by solid-liquid separation
To liquor C and filter residue D, it is added into liquor C after ethyl alcohol and obtains chemical cellulose through solid-liquid separation treatment, second is added in the liquor C
The recovered processing of the filtrate obtained after alcohol through solid-liquid separation treatment obtains the double ethyl dimethylamine alanine salt of methoxyethyl；
Step 3: prepare nano-cellulose: taking 0.3mol anhydrous phosphoric acid that pure water to volume is added while cooling is 5L progress
Dissolution, the chemical cellulose and anhydrous phosphoric acid solution for taking step 2 to prepare are that 10:1 is mixed to get mixed solution according to molar ratio, are added
Enter 1N- sodium hydroxide solution and adjusts pH value to 11.0, mixing and pure water to volume is added in solution is that esterification occurs for 7.5L,
Acid adding neutralizes after reaction, cleans after cleaning processing removing phosphoric acid and chloride ion after obtaining nano-cellulose and obtains nanofiber
Element.
A kind of nano-cellulose is prepared by the preparation method of above-mentioned nano-cellulose.
Embodiment 3
A kind of preparation method of nano-cellulose, comprising the following steps:
Step 1: pretreatment of raw material: crushing Chinese alpine rush powder after taking Chinese alpine rush shear treatment, takes Chinese alpine rush powder investment hair
In ferment pond, and hemicellulase is added, makes the hemicellulose concentration 1.2g/L in fermentation vat, the temperature in fermentation vat is 35
DEG C, a length of 28h when biodegradable；It carries out biodegrade and obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Learn from else's experience dewatered degradation treatment raw material according to solid-to-liquid ratio be 1:1 be added 2- methoxy
Ethyl -1- crassitude lysine salt, mixing condition are to stir 2h at 70 DEG C, are separated by solid-liquid separation, are obtained after being stirred
It is dissolved by heating, after being separated by solid-liquid separation after taking filter residue B that the double ethyl dimethylamine alanine salt of methoxyethyl are added to filtrate A and filter residue B
Liquor C and filter residue D are obtained, is added into liquor C after ethyl alcohol and obtains chemical cellulose through solid-liquid separation treatment, added in the liquor C
Enter the recovered processing of the filtrate obtained after ethyl alcohol through solid-liquid separation treatment and obtains the double ethyl dimethylamine alanine salt of methoxyethyl；
Step 3: it prepares nano-cellulose: taking anhydrous phosphoric acid that pure water dissolution is added while cooling, obtaining concentration is
The anhydrous phosphoric acid solution of 0.1mol/L, the chemical cellulose and anhydrous phosphoric acid solution for taking step 2 to prepare are mixed for 20:1 according to molar ratio
Conjunction obtains mixed solution, continuously adds 1N- sodium hydroxide solution and adjusts pH value to 11.0, mixes and pure water hair is added in solution
Life esterification, acid adding neutralizes after reaction, cleans after cleaning processing removing phosphoric acid and chloride ion after obtaining nano-cellulose
Obtain nano-cellulose.
A kind of nano-cellulose is prepared by the preparation method of above-mentioned nano-cellulose.
Embodiment 4
A kind of water purification film, including separating layer include nano-cellulose in the separating layer, and the nano-cellulose is real
Nano-cellulose described in example 1 is applied, the content of nano-cellulose is 10% in the separating layer.
Embodiment 5
A kind of water purification film, including separating layer, the water purification film further include lignin base and polyether sulfone ultrafiltration layer, described net
Separating layer, polyether sulfone ultrafiltration layer and the lignin base of moisture film are sequentially connected, and the content of nano-cellulose is in the separating layer
20%.
The lignin base with a thickness of 100 μm；The polyether sulfone ultrafiltration layer with a thickness of 70 μm；The separating layer
With a thickness of 40 μm.
A kind of preparation method of water purification film, comprising the following steps:
Step 1: lignin base is prepared: the filtrate A obtained when preparing nano-cellulose described in Example 1, to filter
After ethyl alcohol is added in liquid A, makes the solute in solution that precipitating be precipitated, lignin is obtained through solid-liquid separation treatment, by the lignin
It is prepared as lignin base, the filtrate obtained after addition ethyl alcohol through solid-liquid separation treatment in the filtrate A is recovered to be handled
To 2- methoxyethyl -1- crassitude lysine salt；
Step 2: preparing polyether sulfone ultrafiltration layer: polyether sulfone being taken to be dissolved in DMAC, and ultrasonic deaeration, standing obtain after dissolving
Polyether sulfone ultrafiltration layer casting solution, takes the lignin-base with a thickness of 100 μm to be placed on flat support face, and polyether sulfone ultrafiltration layer is cast
Film liquid, which is poured, casts from lignin-base layer upper surface, and the lignin-base for being covered with film is placed on water at the film with a thickness of 70 μm by striking
It is impregnated in gel, taking-up is dried to obtain polyether sulfone ultrafiltration layer interconnected and lignin base；
Step 3: polyether sulfone ultrafiltration layer interconnected and lignin-base preparation water purification film: are placed on flat support face
On, nano-cellulose prepared by Example 1 is dissolved in DMAC, and ultrasonic deaeration 1h, standing 40h obtain separating layer casting after dissolving
Film liquid takes separating layer casting solution to pour and casts from polyether sulfone ultrafiltration layer upper surface, and striking will be covered with film at the film with a thickness of 40 μm
Polyether sulfone ultrafiltration layer and lignin-base, which are placed in hydrogel, to be impregnated, and is cleaned after taking-up, is dried to obtain water purification film.
A kind of water purification film of embodiment 6, including separating layer, the water purification film further include lignin base and polyether sulfone ultrafiltration
Layer, separating layer, polyether sulfone ultrafiltration layer and the lignin base of the water purification film are sequentially connected, nano-cellulose in the separating layer
Content be 10%.
The lignin base with a thickness of 200 μm；The polyether sulfone ultrafiltration layer with a thickness of 100 μm；The separating layer
With a thickness of 20 μm.
A kind of preparation method of water purification film, comprising the following steps:
Step 1: lignin base is prepared: the filtrate A obtained when preparing nano-cellulose described in Example 1, to filter
After ethyl alcohol is added in liquid A, makes the solute in solution that precipitating be precipitated, lignin is obtained through solid-liquid separation treatment, by the lignin
It is prepared as lignin base, the filtrate obtained after addition ethyl alcohol through solid-liquid separation treatment in the filtrate A is recovered to be handled
To ionic liquid；
Step 2: preparing polyether sulfone ultrafiltration layer: polyether sulfone and its additive being taken to be dissolved in DMAC, and ultrasound is de- after dissolving
Bubble, standing obtain polyether sulfone ultrafiltration layer casting solution, take and are placed on flat support face with a thickness of 200 μm of lignin-bases, by polyethers
Sulfone ultrafiltration layer casting solution, which pours, casts from lignin-base layer upper surface, and striking will be covered with the lignin of film at the film with a thickness of 100 μm
Base, which is placed in hydrogel, impregnates, and taking-up is dried to obtain polyether sulfone ultrafiltration layer interconnected and lignin base；
Step 3: polyether sulfone ultrafiltration layer interconnected and lignin-base preparation water purification film: are placed on flat support face
On, nano-cellulose and additive prepared by Example 1 is dissolved in DMAC, and ultrasonic deaeration 2h, standing obtain for 24 hours after dissolving
Separating layer casting solution takes separating layer casting solution to pour and casts from polyether sulfone ultrafiltration layer upper surface, and striking is incited somebody to action at the film with a thickness of 20 μm
The polyether sulfone ultrafiltration layer and lignin-base for being covered with film are placed in hydrogel and impregnate, and clean after taking-up, are dried to obtain water purification film.
Embodiment 7
A kind of water purification film, including separating layer, the water purification film further include lignin base and polyether sulfone ultrafiltration layer, described net
Separating layer, polyether sulfone ultrafiltration layer and the lignin base of moisture film are sequentially connected, and the content of nano-cellulose is in the separating layer
1%.
The lignin base with a thickness of 300 μm；The polyether sulfone ultrafiltration layer with a thickness of 150 μm；The separating layer
With a thickness of 10 μm.
A kind of preparation method of water purification film, comprising the following steps:
Step 1: lignin base is prepared: the filtrate A obtained when preparing nano-cellulose described in Example 1, to filter
After ethyl alcohol is added in liquid A, makes the solute in solution that precipitating be precipitated, lignin is obtained through solid-liquid separation treatment, by the lignin
It is prepared as lignin base, the filtrate obtained after addition ethyl alcohol through solid-liquid separation treatment in the filtrate A is recovered to be handled
To ionic liquid；
Step 2: preparing polyether sulfone ultrafiltration layer: polyether sulfone and its additive being taken to be dissolved in DMAC, and ultrasound is de- after dissolving
Bubble, standing obtain polyether sulfone ultrafiltration layer casting solution, take the lignin-base with a thickness of 300 μm to be placed on flat support face, will gather
Ether sulfone ultrafiltration layer casting solution, which pours, casts from lignin-base layer upper surface, and striking will be covered with the wooden of film at the film with a thickness of 150 μm
Plain base, which is placed in hydrogel, impregnates, and taking-up is dried to obtain polyether sulfone ultrafiltration layer interconnected and lignin base；
Step 3: polyether sulfone ultrafiltration layer interconnected and lignin-base preparation water purification film: are placed on flat support face
On, nano-cellulose and additive prepared by Example 1 is dissolved in DMAC, and ultrasonic deaeration 4h, standing 20h are obtained after dissolving
Separating layer casting solution takes separating layer casting solution to pour and casts from polyether sulfone ultrafiltration layer upper surface, and striking is incited somebody to action at the film with a thickness of 10 μm
The polyether sulfone ultrafiltration layer and lignin-base for being covered with film are placed in hydrogel and impregnate, and clean after taking-up, are dried to obtain water purification film.
Wherein additive described in embodiment 5,6 and 7 can be acetone.
Those skilled in the art can be directly obtained based on screening is carried out.
Experimental example 1
Filter residue progress chromatography survey is obtained through solid-liquid separation treatment to after addition ethyl alcohol in liquor C by taking embodiment 2 as an example
Amount.
With efficient liquid phase chromatographic analysis, wherein glucan has corresponded to the content of chemical cellulose in experimental material, xylan and Ah
The summation of primary glycan is drawn to correspond to the hemicellulose level of experimental material.In order to improve the accuracy of experiment, a sugar damage is surveyed
Vector, a Standard for Sugars amount.Test result is calculated according to following numerical expression.
E%: extract content
A damage: loss high performance liquid chromatograph response
A matches: configuration solution high performance liquid chromatograph response
A sugar mark: standard solution high performance liquid chromatograph response
X: the high performance liquid chromatograph response of solution and standard solution is prepared
ODW: the example weight after dry
Three plain results after detection:
Respectively cellulose 93%, hemicellulose 2%, lignin 1%, other compositions 4%.
Experimental example 2
Water purification film described in Example 5,6 and 7 carries out performance measuring and evaluating experiment:
Experimental method: according to People's Republic of China's ocean professional standard (HY/T 113-2008) " nanofiltration membrane and its member
Part " in provide examination criteria, assessment can be carried out to water purification film property described in the embodiment of the present invention 5,6 and 7.Test condition:
1. water inlet: 1000g/L NaCl*, 2000mg/L MgSO4；
* the water inlet concentration of NaCl is 500mg/L in standard HY/T 113-2008
2. testing pressure: 0.4MPa
3. inflow temperature: 25 DEG C ± 1 DEG C
4. squeeze time: 0.5h
Test item:
Pure water flux, rejection (MgSO4, NaCl, bacterial virus)
Pure water flux is acquired by water yield and the ratio of effective membrane area.
The concentration of water outlet MgSO4 and NaCl are measured using atomic absorption spectrography (AAS) (AAS).Under the concentration measured is substituted into
Formula finds out rejection.
Rejection=(1- water outlet target substance concentration/water inlet target substance concentration) × 100%
Test result: as shown in table table 1, table 2 and table 3,
Water purification film properties test experience result described in 1 embodiment 5 of table
Water purification film properties test experience result described in 2 embodiment 6 of table
Water purification film properties test experience result described in 3 embodiment 7 of table
It is above standard HY/T by each performance indicator of water purification film prepared by the present invention known to table 1, table 2 and 3 data of table
The regulation of 113-2008.And specific regulation, water purification prepared by the present invention are not made to the ability of bacterial virus in the standard
Film reaches 100% to the rejection of bacterium and virus.
Claims (7)
1. a kind of preparation method of nano-cellulose, which comprises the following steps:
Step 1: pretreatment of raw material: Chinese alpine rush powder is crushed after taking Chinese alpine rush shear treatment, Chinese alpine rush powder is taken to put into fermentation vat
Middle progress biodegrade obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Ionic liquid is added in dewatered degradation treatment raw material of learning from else's experience, and is consolidated after being stirred
Liquid separation, obtains filtrate A and filter residue B, after taking filter residue B that ionic liquid is added, dissolves by heating, liquor C is obtained after being separated by solid-liquid separation
With filter residue D, it is added into liquor C after ethyl alcohol and obtains chemical cellulose through solid-liquid separation treatment；
Step 3: it prepares nano-cellulose: taking anhydrous phosphoric acid that anhydrous phosphoric acid solution is prepared, the alpha fibers for taking step 2 to prepare
Element mixes to obtain mixed solution with anhydrous phosphoric acid solution, adjusts pH value to alkalinity, pure water is added, esterification, reaction knot occurs
Acid adding neutralizes after beam, obtains nano-cellulose after cleaning treatment；
Wherein, the ionic liquid that the degradation treatment raw material is added are as follows: 2- methoxyethyl -1- crassitude lysine salt,
2- methoxyethyl -1- crassitude acetate, 2- methoxyethyl -1- crassitude propionate or 2- methoxyethyl -
1- crassitude glycinate；The ionic liquid that the filter residue B is added are as follows: the double ethyl dimethylamine alanine salt of methoxyethyl,
The double ethyl dimethylamine amino acids salt of methoxyethyl or the double ethyl dimethylamine propionates of methoxyethyl.
2. the preparation method of nano-cellulose according to claim 1, which is characterized in that the enzyme that the biodegrade uses
For hemicellulase, the hemicellulose enzyme concentration in the fermentation vat is 0.05~1.2g/L, and the temperature in fermentation vat is 35
~50 DEG C, a length of 24~28h when biodegradable；
The solid-to-liquid ratio of the degradation treatment raw material and ionic liquid be 1:1, be stirred condition be 50~70 DEG C at stirring 2~
5h；
The recovered processing of the filtrate obtained after ethyl alcohol through solid-liquid separation treatment is added in the liquor C and obtains ionic liquid.
3. the preparation method of nano-cellulose according to claim 1, which is characterized in that the preparation side of anhydrous phosphoric acid solution
Method is to take anhydrous phosphoric acid that pure water dissolution is added while cooling, obtains the anhydrous phosphoric acid solution that concentration is 0.02~0.1mol/L；
The molar ratio of the chemical cellulose and anhydrous phosphoric acid is 5~20:1；
The alkaline solution for adjusting pH value to alkalinity is 1N- sodium hydroxide solution, alkaline ph values 11.0；
The volume that pure water is added in esterification is 0.2~1 times of mixed liquor volume；
The esterification condition is that 0.5~2h is reacted at a temperature of 30~50 DEG C；
Hydrochloric acid is added after reaction to neutralize, cleans after processing removes phosphoric acid and chloride ion and obtains nano-cellulose.
4. a kind of preparation method of water purification film, which comprises the following steps:
Step 1: it prepares lignin base: taking the filtrate A obtained when preparing nano-cellulose, after ethyl alcohol is added into filtrate A,
Make the solute in solution that precipitating be precipitated, obtains lignin through solid-liquid separation treatment, the lignin is prepared as lignin base；
Step 2: preparing polyether sulfone ultrafiltration layer: polyether sulfone being taken to be dissolved in organic solvent, and ultrasonic deaeration, standing obtain after dissolving
Polyether sulfone ultrafiltration layer casting solution, takes lignin-base to be placed on flat support face, and polyether sulfone ultrafiltration layer casting solution is poured and casts from wood
Quality base upper surface, and striking forms a film, and the lignin-base for being covered with film is placed in hydrogel and is impregnated, taking-up is dried to obtain phase
The polyether sulfone ultrafiltration layer to connect and lignin base；
Step 3: preparation water purification film: polyether sulfone ultrafiltration layer interconnected and lignin-base are placed on flat support face, taken
Nano-cellulose is dissolved in organic solvent, and ultrasonic deaeration, standing obtain separating layer casting solution after dissolving, and takes separating layer casting solution
It pours and casts from polyether sulfone ultrafiltration layer upper surface, and striking forms a film, and the polyether sulfone ultrafiltration layer and lignin-base that are covered with film are placed on water
It is impregnated in gel, is cleaned after taking-up, is dried to obtain water purification film, in which:
Nano-cellulose is prepared by preparation method as described in any one of claims 1-3, is specifically included:
Step 1: pretreatment of raw material: Chinese alpine rush powder is crushed after taking Chinese alpine rush shear treatment, Chinese alpine rush powder is taken to put into fermentation vat
Middle progress biodegrade obtains degradation treatment raw material；
Step 2: chemical cellulose is prepared；Ionic liquid is added in dewatered degradation treatment raw material of learning from else's experience, and is consolidated after being stirred
Liquid separation, obtains filtrate A and filter residue B, after taking filter residue B that ionic liquid is added, dissolves by heating, liquor C is obtained after being separated by solid-liquid separation
With filter residue D, it is added into liquor C after ethyl alcohol and obtains chemical cellulose through solid-liquid separation treatment；
Step 3: it prepares nano-cellulose: taking anhydrous phosphoric acid that anhydrous phosphoric acid solution is prepared, the alpha fibers for taking step 2 to prepare
Element mixes to obtain mixed solution with anhydrous phosphoric acid solution, adjusts pH value to alkalinity, pure water is added, esterification, reaction knot occurs
Acid adding neutralizes after beam, obtains nano-cellulose after cleaning treatment；Wherein, the ionic liquid that the degradation treatment raw material is added are as follows:
2- methoxyethyl -1- crassitude lysine salt, 2- methoxyethyl -1- crassitude acetate, 2- methoxyethyl -
1- crassitude propionate or 2- methoxyethyl -1- crassitude glycinate；The ionic liquid that the filter residue B is added
Body are as follows: the double ethyl dimethylamine alanine salt of methoxyethyl, the double ethyl dimethylamine amino acids salt of methoxyethyl or the double ethyls of methoxyethyl
Methylamine propionate.
5. the preparation method according to claim 4, which is characterized in that be added after ethyl alcohol in the filtrate A through being separated by solid-liquid separation
It handles the recovered processing of obtained filtrate and obtains ionic liquid；A length of 1~4h when the ultrasound deaeration, when standing, are a length of
20~40h.
6. the preparation method according to claim 4, which is characterized in that nano-cellulose in the separating layer of the water purification film
Content is 1%~20%.
7. the preparation method according to claim 4, which is characterized in that the lignin base with a thickness of 100~300 μ
m；The polyether sulfone ultrafiltration layer with a thickness of 70~150 μm；The separating layer with a thickness of 10~40 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710671228.7A CN107353352B (en) | 2017-08-08 | 2017-08-08 | A kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710671228.7A CN107353352B (en) | 2017-08-08 | 2017-08-08 | A kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107353352A CN107353352A (en) | 2017-11-17 |
| CN107353352B true CN107353352B (en) | 2019-10-29 |
Family
ID=60286548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710671228.7A Active CN107353352B (en) | 2017-08-08 | 2017-08-08 | A kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107353352B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112064392B (en) * | 2019-06-10 | 2022-07-29 | 中国科学院化学研究所 | Biomass pretreatment composition and biomass pretreatment method |
| CN114605664B (en) * | 2020-12-17 | 2023-07-04 | 赣南师范大学 | Hydrogel and preparation method thereof |
| CN113215860B (en) * | 2021-05-12 | 2022-02-22 | 东北林业大学 | Lignin/cellulose composite film and preparation method thereof |
| CN115025642B (en) * | 2022-07-28 | 2024-01-19 | 渤海大学 | Phosphorylated nanocellulose film, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580522A (en) * | 2009-06-11 | 2009-11-18 | 大连工业大学 | Method for separating lignin and cellulose from lignocellulose by using ionic liquid solvent |
| CN102677510A (en) * | 2011-03-11 | 2012-09-19 | 中国科学院过程工程研究所 | Method for separating cellulose and lignin from plant fiber raw material by utilizing ion liquid |
| CN102698614A (en) * | 2012-06-16 | 2012-10-03 | 浙江大学 | Tubular nanofiltration membrane with multi-layer structure and preparation method thereof |
| CN103088692A (en) * | 2013-01-31 | 2013-05-08 | 河南科技大学 | Method for selectively separating lignin and cellulose from lignocellulose biomasses |
| CN105189857A (en) * | 2013-01-25 | 2015-12-23 | 文迪克斯环境股份有限公司 | Process for isolating cellulose from cellulosic biomass, isolated cellulose of type i and composite materials comprising same |
| CN105498550A (en) * | 2015-12-10 | 2016-04-20 | 华南理工大学 | Nonwoven cloth composite nanofiltration membrane and preparation method and application thereof |
-
2017
- 2017-08-08 CN CN201710671228.7A patent/CN107353352B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101580522A (en) * | 2009-06-11 | 2009-11-18 | 大连工业大学 | Method for separating lignin and cellulose from lignocellulose by using ionic liquid solvent |
| CN102677510A (en) * | 2011-03-11 | 2012-09-19 | 中国科学院过程工程研究所 | Method for separating cellulose and lignin from plant fiber raw material by utilizing ion liquid |
| CN102698614A (en) * | 2012-06-16 | 2012-10-03 | 浙江大学 | Tubular nanofiltration membrane with multi-layer structure and preparation method thereof |
| CN105189857A (en) * | 2013-01-25 | 2015-12-23 | 文迪克斯环境股份有限公司 | Process for isolating cellulose from cellulosic biomass, isolated cellulose of type i and composite materials comprising same |
| CN103088692A (en) * | 2013-01-31 | 2013-05-08 | 河南科技大学 | Method for selectively separating lignin and cellulose from lignocellulose biomasses |
| CN105498550A (en) * | 2015-12-10 | 2016-04-20 | 华南理工大学 | Nonwoven cloth composite nanofiltration membrane and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107353352A (en) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107353352B (en) | A kind of preparation method of nano-cellulose, the preparation method of nano-cellulose and water purification film, water purification film | |
| CN105860090A (en) | Method for extracting high-activity lignin from biomass and lignin extracted by same | |
| CN105568744B (en) | A kind of cornstalk nano-cellulose whisker and preparation method and application | |
| CN104558238B (en) | Process for extracting sodium alginate | |
| CN102995475B (en) | Extraction method of bagasse cellulose | |
| CN108299517A (en) | A method of extracting low-molecular weight lignin from biomass | |
| CN103360509B (en) | Alginic acid and the method for alginic acid salt is prepared for raw material with fresh sargassum | |
| Sterner et al. | Extraction of laminarin from Saccharina latissima seaweed using cross-flow filtration | |
| CN103342826A (en) | Preparation method of chitin nano-fiber/montmorillonite composite membrane material | |
| CN101906167B (en) | Method for preparing concrete water reducing agent by utilizing waste cellulose deposited in pulping black liquor | |
| CN105622980A (en) | Method for preparing wood fiber gel material from LiCl/DMSO dissolved lignocelluloses | |
| CN104939159A (en) | Kelp powder producing method | |
| ES2918154T3 (en) | Production method of lignin and hemicellulose from a plant lignocellulosic material | |
| CN1962686A (en) | Method for cleanly producing saponin by integrated utilization of yam | |
| CN110028624A (en) | Preparation method and application based on hemicellulose compound temperature-sensitive gel | |
| CN106148467B (en) | A kind of preparation method of mussel active peptide | |
| Gómez-Sánchez et al. | Production of cellulosic pulp from reed (Phragmites australis) to produce paper and paperboard | |
| CN110074418A (en) | A kind of extracting method of seaweed diet fiber | |
| CN102442795A (en) | Method for preparing water reducing agent by using solid wastes of biomass acidic hydrolysis industry | |
| Li et al. | Preparation and applications of soybean residue CNF films | |
| CN109208366A (en) | A kind of preparation method and application of micro-nano cellulose | |
| CN105558859B (en) | Method for producing donkey bone glue main material and method for producing donkey bone glue | |
| CN105502794B (en) | A kind of pH adjusting methods of anaerobic fermented liquid | |
| KR102073898B1 (en) | A physically pretreated biomass composition capable of membrane filtration | |
| CN109024034B (en) | Cooking agent for papermaking pulping |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |