CN106699904B - A kind of nitration mixture alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material - Google Patents
A kind of nitration mixture alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5263—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using natural chemical compounds
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- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
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Abstract
The present invention relates to a kind of nitration mixture alternately to hydrolyze the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material, comprising: using biomass cellulose as raw material, replaces hydrolysis process using nitration mixture, prepares the hyperbranched Cellulose nanocrystal of the more carboxyls in surface.Specific implementation step: preparing Cellulose nanocrystal material by nitration mixture hydrocellulose raw material first, then the hyperbranched Cellulose nanocrystal material of the last obtained more carboxyls in surface is alternately hydrolyzed by different nitration mixture.Preparation process cheap and simple of the present invention, Environmental compatibility are good, the hyperbranched Cellulose nanocrystal material of the resulting more carboxyls in surface, have efficient absorption property, it is recyclable repeatedly utilize, have in field of industrial waste water treatment and be widely applied.
Description
Technical field
The invention belongs to the preparation fields of hyperbranched nanofiber, and more particularly, to a kind of nitration mixture, alternately hydrolysis preparation is super
The method of branched fiber element sodium rice crystalline substance flocculation material.
Background technique
With being constantly progressive for science and technology, social economy is grown rapidly, and people's living standard increasingly improves, all can every year
A large amount of waste water is discharged into environment, causes serious water pollution, and water deficiency is further deepened, and causes to environment, society
Serious influence.The organic pollutants such as waste water from dyestuff bring high risks, such as people to people's lives and its health
If long-term drinking can cause slow poisoning by the water source that organic pollutant pollutes, occur Nausea and vomiting and memory loss,
The symptoms such as amentia, it is serious to will lead to death.The effective waste water and control water pollution administered is the important of water pollution control
Means.
The approach for administering sewage main at present includes being adsorbed using adsorbent to pollutant, is coagulated with flocculant
It is poly-, utilize the pollutant etc. in the metabolism degradation water of microorganism.But there are operating cost height, decontamination be not thorough for these approach
Bottom, use scope is narrow, recycles the disadvantages of difficult, so that developing the water that a kind of operating cost is low, environmentally protective and strong dirt-removing power
Pollution treatment method becomes more and more important.
Then, research finds that the easy acidolysis of cellulose extracts Cellulose nanocrystal, and its large specific surface area, surface group
The abundant and characteristics such as easy-regulating, biodegradability make Cellulose nanocrystal become possibility as flocculation material, and comform
Show one's talent in more adsorbent materials, has been played and its important role in the processing of the water pollutions such as waste water from dyestuff.Cellulose nanometer
Crystalline substance is used as a kind of bioflocculation material, and absorption property is good, and manufacture craft green non-pollution, biodegradable after absorption,
Secondary pollution will not be caused to environment.
For the adsorption capacity of reinforcing fiber element flocculation material,Et al. take the lead in having prepared double carboxylics
Base Cellulose nanocrystal, and to its to municipal wastewater flocculation treatment carried out using assessment (T,Liimatainen
H,HormOJ.Coagulation–flocculation treatment of municipal wastewater
based on anionized nanocelluloses[J].Chemical Engineering Journal.2013,231:
59-67).Result of study shows: when nanoscale DCC dosage is 25mg/L, turbidity of sewage reduces 40-80%, and flocculating effect is aobvious
It writes.But it was found that nanoscale DCC content increases, the increase of sewage flocculation effect is unobvious, this is because sodium periodate oxidation, it can only
Along with the fracture of glucosides ring, double carboxyls are generated, thus surface group is still limited；Excessive oxidation, can be to the rigid of cellulose
Property structure cause destruction, product yield significantly reduces, and is unfavorable for industrialized production.
Then, researcher has attempted the development of Cellulose nanocrystal of the surface with phosphate radical and its in heavy metal contaminants
The application of process field.Research is found: Cellulose nanocrystal surface phosphoric acid foundation group increases cellulose for heavy metal pollution
The adsorption rate and adsorption capacity of object.Research shows that being compared to Cellulose sulfate and carboxylated cellulose element, phosphorylation fiber
Element has better adsorption capacity for heavy metal, this is because electronegativity of its surface with anion is larger.However, due to
Cellulose surface group is than relatively limited, so that phosphorylated cellulose surface group content is few, absorption property is up for raising (Liu
P,Borrell PF,Bozic M,Kokol V,Oksman K,Mathew AP.Nanocelluloses and their
phosphorylated derivatives for selective adsorption of Ag(+),Cu(2+)and Fe(3+)
from industrial effluents[J].Journal of Hazardous Materials.2015,294:177-
185).Therefore, it develops surface and has abundant anion or hyper-branched Cellulose nanocrystal flocculation material as current industrial
A major challenge of wastewater treatment.
Summary of the invention
For overcome the deficiencies in the prior art, that the present invention provides a kind of preparation process is simple and fast, easily controllable, can grasp
The nitration mixture that the property made is strong, absorption property is good alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material.
The technical solution adopted by the present invention to solve the technical problems is: alternately hydrolysis prepares hyperbranched fiber for a kind of nitration mixture
The method of plain sodium rice crystalline substance flocculation material, comprising the following steps:
1) using biomass cellulose as raw material, using nitration mixture acidolysis process, 2-6h is reacted at 60-90 DEG C and obtains surface band
There is the carboxylated cellulose element nanocrystalline material of carboxylic group；
2) carboxylated cellulose element nanocrystalline material and ascorbic acid solution are mixed, 3-10mL hydrochloric acid is added dropwise in mixed liquor
With 1-5mL distilled water, 6-12h is stirred at 70-90 DEG C after mixing, washing is centrifuged to neutrality, the suspension that will be obtained
Freeze-drying, obtains the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid；
3) using hyperbranched Cellulose nanocrystal as raw material, using nitration mixture acidolysis process, it is carboxylic that surface richness is prepared
Hyperbranched Cellulose nanocrystal material.
Further, biomass cellulose is microcrystalline cellulose, waste wood pulp cellulose or waste cotton fiber in the step 1)
Element.
Further, the step 1) and the nitration mixture in nitration mixture acidolysis process in step 3) are the mixing of acid solution A and acid solution B
Liquid；Acid solution A is citric acid, formic acid, lactic acid, maleic acid or tartaric acid, and the concentration of acid solution A is 1-3mol/L；Acid solution B be hydrochloric acid,
Sulfuric acid or nitric acid, the concentration of acid solution B are 2-6mol/L.
Further, the volume ratio of acid solution A and acid solution B are 7-9:1-3 in the step 1).
Further, the volume ratio of acid solution A and acid solution B are 7:3 or 8:2 or 9:1 in the step 1).
Further, carboxylated cellulose element nanocrystalline material is in rodlike or needle-shaped, diameter 10- in the step 1)
40nm, length 100-1000nm.The surface group of carboxylated cellulose element nanocrystalline material has hydrophobic hydroxyl and a small amount of carboxylic
Base.
Further, the concentration of ascorbic acid solution is 0.1-0.8mol/L, concentration of hydrochloric acid 2- in the step 2)
6mol/L。
Further, the mass ratio of carboxylated cellulose element nanocrystalline material and ascorbic acid solution is 1- in the step 2)
3:3-5, hyperbranched Cellulose nanocrystal material are in corynebacterium or root shape, a diameter of 20-50nm, length 100-1000nm.
Further, the mass ratio of carboxylated cellulose element nanocrystalline material and ascorbic acid solution is 1 in the step 2):
3 or 2:4 or 3:5.
Further, the mass ratio of hyperbranched Cellulose nanocrystal material and acid solution A are 0.5-2 in the step 3):
1.5-5；Reaction temperature be 20-80 DEG C, reaction time 4-12h, hyperbranched Cellulose nanocrystal material be in ellipticity or fusiform,
Diameter is 20-50nm, length 100-900nm.
Further, in the step 3) mass ratio of hyperbranched Cellulose nanocrystal material and acid solution A be 0.5:1.5 or
1:3 or 2:5.
The present invention, as substrate, is designed using Cellulose nanocrystal by exquisite chemical structure, using hydrochloric acid as catalyst,
Surface carboxylation Cellulose nanocrystal is prepared first as macromole evocating agent, then with citric acid, formic acid, lactic acid, maleic acid,
One of tartaric acid is branching unit with ascorbic acid, has constructed surface multilevel structure and has been rich in the hyperbranched fiber of more carboxyls
Element is nanocrystalline, can be used as processing of the multifunctional efficient flocculation realization to trade effluent.Hyperbranched Cellulose nanocrystal is as a kind of
Novel adsorbent material, large specific surface area, biodegradability is good, good biocompatibility, and surface-bound carboxylic content is high, relative to
Common modified cellulose is nanocrystalline, and hyperbranched Cellulose nanocrystal is more preferable for the absorption property of waste water from dyestuff, degradation absorption
Ability is strong.Also, hyperbranched Cellulose nanocrystal raw material sources are wide, economical and easily available, and production is simple, do not use noxious material, very
Good solves the problems, such as that existing flocculant price or adsorption capacity are weak.Because its manufacture craft is simple, it is expected to realize and criticizes
Amount production.And the hyperbranched Cellulose nanocrystal after use can utilize again, will not generate secondary pollution, lead in water pollution control
Domain shows good use value and application potential.
The beneficial effects of the present invention are:
1) it can be carried out in Routine Test Lab, not need special instrument and equipment, preparation process is easy to convenient for operation
Control；Raw material are biodegradable material, will not generate pollution to environment, and from a wealth of sources；The chemical race for needing to use
Class is few and low in cost.
2) the hyperbranched Cellulose nanocrystal in surface obtained by has that surface group is more, degree of branching height, specific surface area
The advantages that big, especially surface, have a large amount of carboxyls, not only have a suction-operated to dyestuff, also because its branched structure play it is certain
The net effect of catching, absorption property are good；The flocculation material that can be used as a kind of great potential, in sewage treatment, filler, biological medicine etc.
Aspect, which has, to be more widely applied.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph (SEM) of Cellulose nanocrystal material of the invention, and wherein a is that carboxylated cellulose element is received
The brilliant electron microscope of rice, b are branched fiber element nanocrystalline material electron microscope, and c is hyperbranched Cellulose nanocrystal material electron microscope.
Specific embodiment
In order to make those skilled in the art better understand the present invention program, below in conjunction in the embodiment of the present invention
Attached drawing carries out clear, complete description to the technical solution in inventive embodiments, it is clear that described embodiment is only this
A part of the embodiment of invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without making creative work, should fall within the scope of the present invention.
Embodiment one
It 1) is that 1:50 is mixed by solid-to-liquid ratio with the mixed acid solution mixed by hydrochloric acid and citric acid by microcrystalline cellulose,
The volume ratio of middle citric acid and hydrochloric acid is 9:1, and the concentration of citric acid is 2mol/L, and the concentration of hydrochloric acid is 3mol/L.At 77 DEG C
Under the conditions of react 5h, after reaction with deionized water by solution be adjusted to pH be 7, through washing centrifugation after, freeze-drying, obtain
Carboxylated cellulose element nanocrystalline material.The carboxylated cellulose element nanocrystalline material that observation through scanning electron microscope obtains in rodlike,
Diameter is 20nm, length 400nm.
2) suspension containing 1g carboxylated cellulose element nanocrystalline material is mixed with 3g ascorbic acid solution, wherein anti-bad
The concentration of hematic acid solution is 0.3mol/L, reacts 12h at 80 DEG C, 3mL hydrochloric acid and 1mL distilled water is added as catalyst,
Middle concentration of hydrochloric acid is 2mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, after washing centrifugation, freeze-drying,
Obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid.
3) suspension containing the hyperbranched Cellulose nanocrystal material of 1g is reacted into 12h at 75 DEG C with 3g citric acid, added
Enter 3mL hydrochloric acid as catalyst, wherein concentration of hydrochloric acid is 3mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed,
After washing centrifugation, freeze-drying obtains the carboxylic hyperbranched Cellulose nanocrystal material (a) in surface, through scanning electron microscope
The hyperbranched Cellulose nanocrystal material that observation obtains is in rodlike, a diameter of 30nm, length 400nm.
Embodiment two
It 1) is that 1:80 is mixed by solid-to-liquid ratio with the mixed acid solution mixed by hydrochloric acid and citric acid by waste wood pulp cellulose,
Wherein the volume ratio of citric acid and hydrochloric acid is 7:3, and the concentration of citric acid is 2mol/L, and the concentration of hydrochloric acid is 3mol/L, at 75 DEG C
Under conditions of react 5h, after reaction with deionized water by solution be adjusted to pH be 7, through washing centrifugation after, freeze-drying, obtain
To carboxylated cellulose element nanocrystalline material.The carboxylated cellulose element nanocrystalline material that observation through scanning electron microscope obtains in rodlike,
A diameter of 20nm, length 600nm.
2) suspension containing 1g carboxylated cellulose element nanocrystalline material is mixed with 3g ascorbic acid solution, wherein anti-bad
The concentration of hematic acid solution is 0.4mol/L, reacts 12h at 80 DEG C, 5mL hydrochloric acid and 3mL distilled water is added as catalyst,
Middle concentration of hydrochloric acid is 4mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, after washing centrifugation, freeze-drying,
Obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid.
3) suspension containing the hyperbranched Cellulose nanocrystal material of 1g is reacted into 6h at 76 DEG C with 3g citric acid, be added
4mL hydrochloric acid is as catalyst, and wherein concentration of hydrochloric acid is 3mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, warp
After washing centrifugation, freeze-drying obtains the carboxylic hyperbranched Cellulose nanocrystal material (b) in surface, the sight through scanning electron microscope
The hyperbranched Cellulose nanocrystal material diameter for examining acquisition is 25nm, and in rodlike, the length is 600nm.
Embodiment three
It 1) is that 1:70 is mixed by solid-to-liquid ratio with the mixed acid solution mixed by hydrochloric acid and citric acid by waste wood pulp cellulose,
Wherein the volume ratio of citric acid and hydrochloric acid is 7:3, and the concentration of citric acid is 3mol/L, and the concentration of hydrochloric acid is 5mol/L, at 87 DEG C
Under conditions of react 5h, after reaction with deionized water by solution be adjusted to pH be 7, through washing centrifugation after, freeze-drying, obtain
To carboxylated cellulose element nanocrystalline material.The carboxylated cellulose element nanocrystalline material that observation through scanning electron microscope obtains in needle-shaped,
A diameter of 30nm, length 900nm.
2) suspension containing 1g carboxylated cellulose element nanocrystalline material is mixed with 3g ascorbic acid solution, wherein anti-bad
The concentration of hematic acid solution is 0.5mol/L, reacts 12h at 80 DEG C, 4mL hydrochloric acid and 5mL distilled water is added as catalyst,
Middle concentration of hydrochloric acid is 5mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, after washing centrifugation, freeze-drying,
Obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid.
3) suspension containing the hyperbranched Cellulose nanocrystal material of 1g is reacted into 4h at 80 DEG C with 3g citric acid, be added
2mL hydrochloric acid is as catalyst, and wherein concentration of hydrochloric acid is 5mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, warp
After washing centrifugation, freeze-drying obtains the carboxylic hyperbranched Cellulose nanocrystal material (c) in surface, the sight through scanning electron microscope
The hyperbranched Cellulose nanocrystal material diameter for examining acquisition is 30nm, and in rodlike, the length is 900nm.
Example IV
1) microcrystalline cellulose is mixed with the mixed acid solution mixed by hydrochloric acid and formic acid by solid-to-liquid ratio for 1:50, wherein
The volume ratio of formic acid and hydrochloric acid is 9:1, and the concentration of formic acid is 3mol/L, and the concentration of hydrochloric acid is 5mol/L, under conditions of 90 DEG C
4h is reacted, it is 7 that solution, which is adjusted to pH, with deionized water after reaction, and after washing centrifugation, freeze-drying obtains carboxylated
Cellulose nanocrystal material.The carboxylated cellulose element nanocrystalline material that observation through scanning electron microscope obtains is a diameter of in rodlike
40nm, length 800nm,.
2) suspension containing 1g carboxylated cellulose element nanocrystalline material is mixed with 3g ascorbic acid solution, wherein anti-bad
The concentration of hematic acid solution is 0.6mol/L, reacts 12h at 85 DEG C, 6mL hydrochloric acid and 4mL distilled water is added as catalyst,
Middle concentration of hydrochloric acid is 6mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, after washing centrifugation, freeze-drying,
Obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid.
3) suspension containing the hyperbranched Cellulose nanocrystal material of 1g is reacted into 12h at 76 DEG C with 3g citric acid, added
Enter 3mL hydrochloric acid as catalyst, wherein concentration of hydrochloric acid is 5mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed,
After washing centrifugation, freeze-drying obtains the carboxylic hyperbranched Cellulose nanocrystal material (d) in surface, through scanning electron microscope
The hyperbranched Cellulose nanocrystal material diameter that observation obtains is 45nm, and in needle-shaped, the length is 900nm.
Embodiment five
1) waste cotton cellulose is mixed with the mixed acid solution mixed by hydrochloric acid and formic acid by solid-to-liquid ratio for 1:60, wherein
The volume ratio of formic acid and hydrochloric acid is 8:2, and the concentration of formic acid is 1mol/L, and the concentration of hydrochloric acid is 6mol/L, under conditions of 86 DEG C
4h is reacted, it is 7 that solution, which is adjusted to pH, with deionized water after reaction, and after washing centrifugation, freeze-drying obtains carboxylated
Cellulose nanocrystal material.The carboxylated cellulose element nanocrystalline material that observation through scanning electron microscope obtains is a diameter of in rodlike
30nm, length 750nm.
2) suspension containing 1g carboxylated cellulose element nanocrystalline material is mixed with 3g ascorbic acid solution, wherein anti-bad
The concentration of hematic acid solution is 0.4mol/L, reacts 12h at 80 DEG C, 4mL hydrochloric acid and 3mL distilled water is added as catalyst,
Middle concentration of hydrochloric acid is 5mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, after washing centrifugation, freeze-drying,
Obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid.
3) suspension containing the hyperbranched Cellulose nanocrystal material of 2g is reacted into 8h at 80 DEG C with 3g citric acid, be added
4mL hydrochloric acid is as catalyst, and wherein concentration of hydrochloric acid is 3mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, warp
After washing centrifugation, freeze-drying obtains the carboxylic hyperbranched Cellulose nanocrystal material (e) in surface, the sight through scanning electron microscope
The hyperbranched Cellulose nanocrystal material diameter for examining acquisition is 40nm, and in rodlike, the length is 805nm.
Embodiment six
1) waste cotton cellulose is mixed with the mixed acid solution mixed by hydrochloric acid and formic acid by solid-to-liquid ratio for 1:70, wherein
The volume ratio of formic acid and hydrochloric acid is 8:2, and the concentration of formic acid is 3mol/L, and the concentration of hydrochloric acid is 6mol/L, under conditions of 83 DEG C
4h is reacted, it is 7 that solution, which is adjusted to pH, with deionized water after reaction, and after washing centrifugation, freeze-drying obtains carboxylated
Cellulose nanocrystal material.The carboxylated cellulose element nanocrystalline material that observation through scanning electron microscope obtains is a diameter of in rodlike
45nm, length 900nm.
2) suspension containing 1g carboxylated cellulose element nanocrystalline material is mixed with 3g ascorbic acid solution, wherein anti-bad
The concentration of hematic acid solution is 0.1mol/L, reacts 12h at 80 DEG C, 3mL hydrochloric acid and 1mL distilled water is added as catalyst,
Middle concentration of hydrochloric acid is 6mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, after washing centrifugation, freeze-drying,
Obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid.
3) suspension containing the hyperbranched Cellulose nanocrystal material of 1g is reacted into 4h at 70 DEG C with 3g citric acid, be added
2mL hydrochloric acid is as catalyst, and wherein concentration of hydrochloric acid is 4mol/L, and it is 7 that solution, which is adjusted pH, with deionized water after reaction was completed, warp
After washing centrifugation, freeze-drying obtains the carboxylic hyperbranched Cellulose nanocrystal material (f) in surface, the sight through scanning electron microscope
The hyperbranched Cellulose nanocrystal material diameter for examining acquisition is 45nm, and in needle-shaped, the length is 780nm.
Measure over-expense cellulose prepared by embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6
Sodium rice crystalline substance flocculation material, when flocculation material dosage is 20mg/L, when handling time 1h, to the wadding of the kaolin solution of different pH value
Solidifying effect.Six kinds of over-expense chemical fibres that table 1 is embodiment 1, prepared by embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6
Plain sodium rice crystalline substance flocculation material is tieed up, to the flocculating effect of the kaolin solution of different pH value.
By data in table 1 it is found that being flocculated using the hyperbranched cellulose sodium rice crystalline substance that preparation method of the present invention obtains
Material (a), (b), (c), (d), (e), (f) are applied to waste water flocculating processing, when flocculation material dosage is 20mg/L, processing time
When 1h, the turbidity value of the kaolin solution of different pH value is reduced to 14NTU hereinafter, illustrating that the hyperbranched cellulose sodium rice of preparation is brilliant
Flocculation material has preferable flocculation sedimentation effect to industrial wastewater.
Table 1
Above-mentioned specific embodiment is used to illustrate the present invention, rather than limits the invention, of the invention
In spirit and scope of protection of the claims, to any modifications and changes that the present invention makes, protection model of the invention is both fallen within
It encloses.
Claims (9)
1. a kind of nitration mixture alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material, which is characterized in that including with
Lower step:
1) using biomass cellulose as raw material, using nitration mixture acidolysis process, 2-6h is reacted at 60-90 DEG C and obtains surface with carboxylic
The carboxylated cellulose element nanocrystalline material of base group；The nitration mixture is the mixed liquor of acid solution A and acid solution B；Acid solution A be citric acid,
Formic acid, lactic acid, maleic acid or tartaric acid, the concentration of acid solution A are 1-3mol/L；Acid solution B be hydrochloric acid, sulfuric acid or nitric acid, acid solution B's
Concentration is 2-6mol/L；
2) carboxylated cellulose element nanocrystalline material and ascorbic acid solution are mixed, 3-10mL hydrochloric acid and 1- is added dropwise in mixed liquor
5mL distilled water stirs 6-12h at 70-90 DEG C after mixing, and washing is centrifuged to neutrality, and obtained suspension is freezed
It is dry, obtain the hyperbranched Cellulose nanocrystal material of surface grafting ascorbic acid；
3) using hyperbranched Cellulose nanocrystal as raw material, using citric acid acidolysis process, the carboxylic over-expense in surface is prepared
Cellulose nanocrystalline material.
2. nitration mixture according to claim 1 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
Be characterized in that: biomass cellulose is microcrystalline cellulose, waste wood pulp cellulose or waste cotton cellulose in the step 1).
3. nitration mixture according to claim 1 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
Be characterized in that: the volume ratio of acid solution A and acid solution B are 7-9:1-3 in the step 1).
4. nitration mixture according to claim 1 or 3 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
It is characterized by: the volume ratio of acid solution A and acid solution B are 7:3 or 8:2 or 9:1 in the step 1).
5. nitration mixture according to claim 1 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
Be characterized in that: carboxylated cellulose element nanocrystalline material is in rodlike or needle-shaped, diameter 10-40nm in the step 1), and length is
100-1000nm。
6. nitration mixture according to claim 1 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
Be characterized in that: the concentration of ascorbic acid solution is 0.1-0.8mol/L, concentration of hydrochloric acid 2-6mol/L in the step 2).
7. nitration mixture according to claim 1 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
Be characterized in that: the mass ratio of carboxylated cellulose element nanocrystalline material and ascorbic acid solution is 1-3:3-5 in the step 2), is surpassed
Branched fiber element nanocrystalline material is in corynebacterium or root shape, a diameter of 20-50nm, length 100-1000nm.
8. nitration mixture according to claim 1 or claim 7 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
It is characterized by: the mass ratio of carboxylated cellulose element nanocrystalline material and ascorbic acid solution is 1:3 or 2:4 in the step 2)
Or 3:5.
9. nitration mixture according to claim 1 alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material,
Be characterized in that: the mass ratio of hyperbranched Cellulose nanocrystal material and citric acid is 0.5-2:1.5-5 in the step 3)；Reaction
Temperature is 20-80 DEG C, reaction time 4-12h, and hyperbranched Cellulose nanocrystal material is in ellipticity or fusiform, diameter 20-
50nm, length 100-900nm.
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| 纳米纤维素微晶的制备、改性及其应用;刘颖,任学宏;《材料导报A:综述篇》;20150630;第29卷(第6期);第133-143页 |
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