CN107337764B - The preparation method and application of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group - Google Patents
The preparation method and application of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group Download PDFInfo
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Abstract
The present invention discloses a kind of preparation method of hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group, this method removes the peel air-dried corn stover, grind and screening obtains acceptable material, hemicellulose in hot-water extraction technology separation acceptable material is assisted using alkali, then pass through aqueous solution micellar copolymerization method, by n-isopropyl acrylamide and phenyl methacrylate graft copolymerization on hemicellulose macromolecular chain, and and N, N- methylene-bisacrylamide carries out cross-linking reaction, obtains hydrophobicity corn stalk stalks of rice, wheat, etc. hemicellulose group temperature-sensitive hydrogel；The white bulk of gel obtained, to pentachlorophenol, pentachlorodiphenyl and 3,4- BaP adsorption capacity with higher controls absorption and desorption by temperature, the gel is reusable without losing adsorption, belongs to environmentally friendly hydrophobic organic pollutant temperature control adsorbent material.
Description
Technical field
The present invention relates to a kind of, and the hemicellulose graft copolymerization hydrophobically modified based on the corn stalk stalks of rice, wheat, etc. prepares thermo-sensitive gel, is used for
The adsorption treatment of hydrophobic organic pollutant belongs to natural macromolecule modification field of material technology.
Background technique
With the fast development of China's chemical industry, a large amount of industrial wastewater especially persistence organic pollutant, without
Processing is discharged directly into water body, is caused water environment pollution problem to get worse, is also resulted in significant damage to human health.
Many organic pollutants, such as polycyclic aromatic hydrocarbon, aromatic compound, Polychlorinated biphenyls etc. have hydrophobicity, therefore these pollutants
Also referred to as hydrophobic organic pollutant (HOCs).HOCs majority has carcinogenic, teratogenesis, causes gene mutation effect, can be in biology
Cylinder accumulation finally causes health threat to animal and human body.By years of researches, it is believed that processing HOCs is more effective
Means first is that adsorption technology, i.e., separated HOCs using adsorbent material, then its concentrate is taken height from water body
The multistages such as grade oxidation or burning carry out harmless treatment.However, absorption method reagent apply present in due to HOCs water solubility
Difference and concentration is low causes the rate of adsorption slow, adsorbent reactivation difficulty causes economic cost high and secondary pollution problems limitation occurs
Its scale application.Therefore, according to the above-mentioned characteristic of HOCs in waste water, the adsorbent material of selection efficiently, economic practical answers its
Processing for HOCs seems most important.
In recent years, largely research shows that intelligent temperature-sensitive hydrogel is a kind of excellent water treatment absorbent material, this master
If being swollen after hydrogel and waste water, and then quickly form gel-water termination since it is especially fast to pollutant absorption
On concentration gradient, pollutant power the hydration and hydrogen bond the effects of drives lower pollutant to spread from solution to gel surface
And it is adsorbed；Its another big advantage is that regeneration is easy, when changing critical-temperature of the liquidus temperature above or below gel, hydrogen bond etc.
Active force reduces, and polymer chain, which retracts into, causes hydrone and pollutant to be extruded, and realizes the regeneration of hydrogel adsorbent.Temperature
In terms of quick hydrogel is concentrated mainly on the hydrophilies such as heavy metal, dyestuff pollutant process to the absorption of pollutant at present.But it is temperature sensitive
Hydrogel will can be realized must just introduce hydrophobic grouping to effective absorption of hydrophobic organic pollutant in hydrogel network,
So that gel surface is changed into hydrophobic property by hydrophily, the Adsorption to HOCs is realized and improved by heat resistance and salt tolerance.
Currently, most of hydrogels are prepared by petroleum-based products, these hydrogels are not only difficult to degrade, pollute ring
Border, and its source is non-renewable, therefore, prepares water using agricultural-forestry biomass resource part even replacing whole petroleum-based products
Gel is imperative.In nature, hemicellulose level very abundant, the content especially in gramineae plant are up to 1/
3 or more, it is only second to content of cellulose.Hemicellulose is the inhomogenous glycan being made of different glycan bases, is contained in molecular weight
A large amount of reactive hydroxyl can occur esterification, etherificate, graft copolymerization etc. and be modified, to prepare hemicellulose group function material
Material.Wherein, the application study of hemicellulose group gel in the treatment of waste water is commonplace.By acrylic graft copolymer in xylan
Class hemicellulose prepares xylan-g- acrylic hydrogel, the Pd in adsorbable aqueous solution2+、Cd2+, Zn2+Etc. heavy metal ion,
And there is good power of regeneration and heavy metal removal rate, when recycling, will not influence the adsorption energy of heavy metal ion
Power.The Organic-inorganic composite hydrogel prepared using hemicellulose and multi-walled carbon nanotube, also shows good methylene
Blue absorption property.In redox ammonium persulfate/tetramethylethylenediamine system, with N, N- diacrylamine is crosslinking agent, will
Xylan class hemicellulose and acrylic graft copolymer prepare hydrogel with good swelling behavior, and to pH, ion and have
Solvent has good responsiveness.It to sum up analyzes, as a kind of environmentally friendly water treatment absorbent, develops based on HOCs's
It is feasible for effectively removing the temperature-sensitive hydrogel of the hemicellulose group hydrophobically modified of research, and has highly important economic benefit
And social benefit.
China is corn planting big country, and corn stover yield up to 2.2 hundred million tons, remove in rural area by this huge living resources
Be used as outside domestic energy, most of abandoning in ground or on-site incineration.How this kind of agricultural wastes performance self-value is used
Promote the well-being of mankind the important topic for having become and studying now.Currently, corn stalk skin has been used as fibrous raw material in pulp and paper industry
In applied, alleviate the severe situation of China's Papermaking Resource shortage.However, the corn stalk stalks of rice, wheat, etc. (also known as cornstalk core) due to
Composition cell is mostly short and small, wall is thin, frangible non-fiber cell (or being heteroproteose cell), and the application in fiber industry receives
Serious limitation considerably reduces the application value of corn stover.Although the small part stalk stalks of rice, wheat, etc. has been developed that as feed processing
Or alcoholic fermentation industry, but the restriction by own characteristic and transformation technology, there are no large-scale industrial applications now.But no
Deniable to be, hemicellulose macromolecule rich in the corn stalk stalks of rice, wheat, etc., lignin content is lower, and the cell wall of the cornstalk stalks of rice, wheat, etc.
Short texture reacts large specific surface area, is conducive to the separation and extraction of high molecular component, therefore, from raw material components and structure
Prove that the corn stalk stalks of rice, wheat, etc. can be used as the initial feed of hemicellulose extraction.
The pollution problem of water body hydrophobic organic in conjunction with caused by modern industry, the application are described in detail using the corn stalk stalks of rice, wheat, etc. as raw material
The process flow for preparing environmentally friendly hemicellulose group hydrophobically modified thermo-sensitive gel, as pentachlorophenol, pentachlorodiphenyl, 3,4-
The adsorbent of the multiple types such as BaP HOCs.The vacancy that hemicellulose macromolecule is studied in heteroproteose cell is not made up only, and
The comprehensive utilization ratio of maize straw resource is improved, plays positive impetus for the high value added utilization of the corn stalk stalks of rice, wheat, etc..
Summary of the invention
For hemicellulose group thermo-sensitive gel, as the exploitation of hydrophobic Adsorption of Organic agent, there are no enough bases
With the support of technology, therefore have processing capacity ideal, effective reuse, the also non-scale of environmentally friendly attractive gel industry
Using and exploitation.Therefore, the present invention provides a kind of preparation method of hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group, the party
Method is raw material using the still shallow corn stalk stalks of rice, wheat, etc. of resourceful but Exploitation Depth, its hemicellulose of high efficiency extraction, then with hydrophobic list
Body, temperature sensitive monomer and crosslinking agent carry out graft copolymerization/cross-linking reaction, and hemicellulose group hydrophobically modified thermo-sensitive gel product is made；
The application field for further expanding hemicellulose, promotes corn stalk stalks of rice, wheat, etc. added value.
The process technology scheme for realizing that the object of the invention is taken is as follows:
(1) corn stover is removed the peel after air-drying, and straw stalks of rice, wheat, etc. partial mill and screening obtain acceptable material；
(2) qualified straw stalks of rice, wheat, etc. raw material carries out alkali under given conditions and assists hot-water extraction hemicellulose separating treatment, to processing
Material filter membrane separation afterwards, filtrate alcohol precipitation, centrifuge separation and washing, until cleaning solution is neutrality, sediment freeze-drying is made
Corn stalk stalks of rice, wheat, etc. hemicellulose, it is spare；
(3) graft copolymerization is carried out to corn stalk stalks of rice, wheat, etc. hemicellulose using aqueous solution micellar copolymerization method, that is, selected
Ammonium sulfate is promotor as initiator, N, N, N, N ,-tetramethylethylenediamine, and N, N ,-methylene-bisacrylamide is crosslinking agent,
N-isopropyl acrylamide is temperature sensitive monomer, and phenyl methacrylate is hydrophobic monomer, and ten disulfobenzene sodium sulfonates are living for surface
Property agent, carry out graft copolymerization/crosslinking inborn nature, copolymer products dehydrated alcohol and water are washed respectively, are freeze-dried, obtained
The hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group.
The preparation method of the above-mentioned hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group, concrete operations are as follows:
(1) melting process of the corn stalk stalks of rice, wheat, etc.: corn stover is after air-drying processing, wherein air-drying the moisture of raw material according to not
Different and different with season air humidity from different places, general moisture control is in the range of 5~30%, air dry matter peeling
Afterwards, straw stalks of rice, wheat, etc. part is obtained, grinding is mechanically pulverized, and screen by the sieve of 60~300 mesh, obtains acceptable material；
(2) qualified straw stalks of rice, wheat, etc. raw material hemicellulose separation process: air-dried straw stalks of rice, wheat, etc. raw material is sufficiently mixed with potassium hydroxide, water and is stirred
It after mixing uniformly, is transferred in cooker (sealed pressure vessel tank), seals completely, be put into rotation electric heater unit, providing
Hemicellulose extraction process, treatment conditions are carried out under conditions of temperature and time are as follows: potassium hydroxide dosage is the over dry corn stalk stalks of rice, wheat, etc.
The 1.0~10.0% of quality, water and the over dry corn stalk stalks of rice, wheat, etc. 5 ~ 15g:1g of mass ratio, 0.5~3.0h of reaction time in system, place
120~200 DEG C of temperature of reason；Material after being disposed is cooled to room temperature, and takes off from oxygen that be transferred to aperture in tank completely be 0.20
Be separated by solid-liquid separation in~1.00nm filter membrane, liquid portion pour into dehydrated alcohol until transparency liquid there is white emulsion state,
Illustrate that precipitating finishes, 10~20min is washed and be centrifuged at 7000~15000rpm with dehydrated alcohol, until cleaning solution is neutrality,
Freeze-drying is until material is completely dried to get corn stalk stalks of rice, wheat, etc. hemicellulose；
(3) preparation process of the hydrophobic thermo-sensitive gel of hemicellulose group: by corn stalk stalks of rice, wheat, etc. hemicellulose, N- isopropyl acrylamide
Amine and N, N- methylene-bisacrylamide dissolve in water, then inject phenyl methacrylate and ten disulfobenzene sodium sulfonates,
It is vigorously stirred 5 ~ 30min under the conditions of logical nitrogen, ammonium persulfate and N, N, N, N- tetramethylethylenediamine is added, initiation grafting copolymerization is anti-
It answers；Wherein, n-isopropyl acrylamide and corn stalk stalks of rice, wheat, etc. hemicellulose mass ratio are 1:1~10:1, phenyl methacrylate with
Corn stalk stalks of rice, wheat, etc. hemicellulose mass ratio is 3:1~15:1, ammonium persulfate and corn stalk stalks of rice, wheat, etc. hemicellulose mass ratio be 0.005:1~
0.025:1；N,N methylene bis acrylamide quality and the ratio between temperature sensitive monomer and hydrophobic monomer quality summation be 0.005:1~
0.02:1, N, N, N, N- tetramethylethylenediamine and ammonium persulfate mass ratio are 2:1 ~ 1:2, and reaction temperature is 40~70 DEG C, reaction
Time is 15.0~48.0h, and the ratio between corn stalk stalks of rice, wheat, etc. hemicellulose quality and reaction liquid total volume are controlled in 1g:50mL~1g:
In the range of 150mL, the mass concentration of ten disulfobenzene sodium sulfonates in the reaction system is 3 ~ 8%；After completion of the reaction, gel is cut
At 1.00~2.00cm × 1.00~2.00cm × 0.10~1.00cm fritter, fritter synthetic is carried out instead with dehydrated alcohol
After 12 ~ 72h is washed in after backwashing, continue to carry out washing 2 ~ 8 days with water, be freeze-dried to get based on the hydrophobic of corn stalk stalks of rice, wheat, etc. hemicellulose
Thermo-sensitive gel.
The present invention is another object is that the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group made from the above method is applied
In adsorption treatment organic pollutant.
The beneficial effects of the present invention are: using the agricultural wastes corn stalk stalks of rice, wheat, etc. as the source of hemicellulose, it is short using high temperature
When under the conditions of alkali assist the isolated hemicellulose of hot-water extraction technology, by aqueous solution micellar copolymerization method, by temperature sensitive list
Phenyl methacrylate graft copolymerization is in hemicellulose macromolecular chain for body --- n-isopropyl acrylamide and hydrophobic monomer ---
On, and and N, N- methylene-bisacrylamide carry out cross-linking reaction, obtain absorption HOCs corn stalk stalks of rice, wheat, etc. hemicellulose group it is hydrophobic
Thermo-sensitive gel.Hemicellulose is that " intelligence " attractive gel of matrix has the general character of synthesis high score subclass adsorbent material, can changed
It can be played in terms of the processing of organic pollutant waste liquid caused by multiple industries such as work, weaving, printing and dyeing, pharmacy, printing good
Application prospect.Meanwhile the attractive gel is also equipped with efficient absorption and desorption performance, reuse number are high, environmental-friendly etc. excellent
Gesture, is novel, the green functional material of one kind of mainstream development now, this attractive gel is embodied as corn stover high added value
One feasible scheme of offer is provided.
Specific embodiment
Below with reference to embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold, method used in the present embodiment is conventional method unless otherwise specified, and the reagent used is normal unless otherwise specified
Advise reagent.
Embodiment 1: the preparation method based on the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose, concrete operations are as follows:
(1) stock of the corn stalk stalks of rice, wheat, etc.
Corn stover is by air-drying processing, wherein the water content for air-drying raw material is 5%, after artificial peeling, the straw stalks of rice, wheat, etc. carries out machine
Then tool milled processed is acceptable material after 60 mesh but the only screening of 100 mesh screens；
(2) separation of corn stalk stalks of rice, wheat, etc. raw material hemicellulose
The condition that hemicellulose extracts are as follows: potassium hydroxide dosage is the 1.0% of over dry material quality, water and over dry in system
The ratio between material quality 5g:1g, reaction time 0.5h, 120 DEG C for the treatment of temperature.
Concrete operation step are as follows: 10.0g over dry straw stalks of rice, wheat, etc. raw material (if air-drying raw material moisture is 5%, is weighed into 10.5g
Air-dry the straw stalks of rice, wheat, etc.), the water (10 × 5=50mL) of 0.1g potassium hydroxide (10 × 1.0%=0.1g) and 50mL is sufficiently mixed uniformly, completely
It is transferred in cooker, seals, be put into rotation electric heater unit, start to react after being warming up to 120 DEG C, be reacted after 0.5h
Terminate, after material is cooled to room temperature, taken off from oxygen be transferred to completely in tank aperture be 0.20nm filter membrane in be separated by solid-liquid separation, liquid
Part pour into dehydrated alcohol until transparency liquid there is white emulsion state, washed with dehydrated alcohol and be centrifuged at 7000rpm
10min, cleaning to cleaning solution are neutrality, are freeze-dried to get corn stalk stalks of rice, wheat, etc. hemicellulose.
(3) preparation of the hydrophobic thermo-sensitive gel of hemicellulose group
Gel preparation condition: n-isopropyl acrylamide is 1:1, phenyl methacrylate and half with hemicellulose mass ratio
Cellulose mass ratio is 3:1, and ammonium persulfate and hemicellulose mass ratio are 0.005:1；N,N methylene bis acrylamide quality
It is 0.005:1, N, N with the ratio between temperature sensitive and hydrophobic two kinds of monomer mass summations, N, N- tetramethylethylenediamine and ammonium persulfate quality
Than for 2:1, reaction temperature is 40 DEG C, reaction time 15.0h, the ratio between hemicellulose quality and reaction liquid total volume, which control, to exist
In the range of 1g:50mL, the mass concentration of ten disulfobenzene sodium sulfonates in the reaction system is 3%.
Gel preparation course: equipped with reflux condensing tube, mechanical agitator three mouthfuls of reaction flasks in be added 5g hemicellulose,
5g n-isopropyl acrylamide (5 × 1=5g) and 0.1g N, N- methylene-bisacrylamide (0.005 × (5+15)=0.1g),
A certain amount of deionized water is added and sufficiently dissolves reactant, then injects 15g phenyl methacrylate (5 × 3=15g) and 7.5g
Reaction flask, is vigorously stirred by ten disulfobenzene sodium sulfonates (250 × 3%=7.5g) in 40 DEG C of water bath with thermostatic control under nitrogen protection
Be added after 5min 0.025g ammonium persulfate (0.005 × 5=0.025g) and 0.05g N, N, N, N- tetramethylethylenediamine (0.025 ×
2=0.05g), while deionized water is added, make reaction solution total volume 250mL(50 × 5=250mL), react 15h；Graft copolymerization
After reaction, network body gel is cut into 1.00cm × 1.00cm × 0.10cm fritter, and after washing 12h repeatedly with dehydrated alcohol,
Continue to be washed with water 2 days, be freeze-dried to get the hydrophobic thermo-sensitive gel of hemicellulose group.
(4) character of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group
HOCs determining adsorption method: it is 25mg/L's that measurement, which takes the desiccant gel of 2g or so to be immersed in 500mL concentration respectively,
Pentachlorophenol, pentachlorodiphenyl, in 3,4- BaP solution, shaking table rocks for 24 hours under the conditions of 25 DEG C, after adsorption equilibrium, takes out solidifying
Glue utilizes the content of remaining organic pollutant in each solution of high performance liquid chromatography detection.
The hydrophobic thermo-sensitive gel of the hemicellulose group being obtained by the above reaction has comparatively ideal HOCs adsorption capacity, to five
Chlorophenol, pentachlorodiphenyl, 3,4- BaP removal efficiency respectively reach 82%, 79% and 76%, physical behavior is white blocks
Shape.
Gel regeneration method: the gel for adsorbing HOCs is put into 50 DEG C of 300mL of deionized water, after for 24 hours, freezing
It is dry, namely regenerated gel；Rejuvenation gel continues adsorption experiment in above-mentioned hydrophobic Adsorption of Organic method.
As a result it can obtain: be obtained by the above reaction gel reusable 5 times, to pentachlorophenol, pentachlorodiphenyl, 3,4- benzene
And the removal efficiency of pyrene is without being decreased obviously.
Embodiment 2: the preparation method based on the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose, concrete operations are as follows:
(1) stock of the corn stalk stalks of rice, wheat, etc.
Corn stover is by air-drying processing, wherein the water content for air-drying raw material is 20%, after artificial peeling, the straw stalks of rice, wheat, etc. carries out machine
Then tool milled processed is acceptable material after 100 mesh but the only screening of 200 mesh screens；
(2) separation of corn stalk stalks of rice, wheat, etc. raw material hemicellulose
The condition that hemicellulose extracts are as follows: potassium hydroxide dosage is the 8.0% of over dry material quality, water and absolutely in system
Dry raw material mass ratio 10g:1g, reaction time 2.0h, 170 DEG C for the treatment of temperature.
Concrete operation step are as follows: 10.0g over dry straw stalks of rice, wheat, etc. raw material (if air-drying raw material moisture is 20%, is weighed into 12.5g
Air-dry the straw stalks of rice, wheat, etc.), the water (10 × 10=100mL) of 0.8g potassium hydroxide (10 × 8.0%=0.8g) and 100mL be sufficiently mixed uniformly, it is complete
Total transfer is into cooker, sealing, is put into rotation electric heater unit, starts to react after being warming up to 170 DEG C, anti-after 2.0h
Should terminate, after material is cooled to room temperature, taken off from oxygen be transferred to completely in tank aperture be 0.45nm filter membrane in be separated by solid-liquid separation, liquid
Body portion pour into dehydrated alcohol until transparency liquid there is white emulsion state, washed with dehydrated alcohol and at 10000rpm from
Heart 15min, cleaning to cleaning solution are neutrality, are freeze-dried to get corn stalk stalks of rice, wheat, etc. hemicellulose.
(3) preparation of the hydrophobic thermo-sensitive gel of hemicellulose group
Gel preparation condition: n-isopropyl acrylamide is 5:1, phenyl methacrylate and half with hemicellulose mass ratio
Cellulose mass ratio is 12:1, and ammonium persulfate and hemicellulose mass ratio are 0.015:1；N,N methylene bis acrylamide dosage
It is 0.010:1, N, N with the ratio between temperature sensitive and hydrophobic two kinds of monomer mass summations, N, N- tetramethylethylenediamine and ammonium persulfate quality
Than for 1:1, reaction temperature is 55 DEG C, reaction time 24.0h, the ratio between hemicellulose quality and reaction liquid total volume, which control, to exist
In the range of 1g:100mL, the mass concentration of ten disulfobenzene sodium sulfonates in the reaction system is 5%.
Gel preparation course: equipped with reflux condensing tube, mechanical agitator three mouthfuls of reaction flasks in be added 5g hemicellulose,
25g n-isopropyl acrylamide (5 × 5=25g) and 0.85g N,N methylene bis acrylamide (0.010 × (25+60)=
0.85g), a certain amount of deionized water is added and sufficiently dissolves reactant, then inject 60g phenyl methacrylate (5 × 12=
60g) and ten disulfobenzene sodium sulfonate (500 × 5%=25g) of 25g, under nitrogen protection by reaction flask in 55 DEG C of water bath with thermostatic control
0.025g ammonium persulfate (0.015 × 5=0.075g) and 0.075g N, N, N, N- tetramethylethylenediamine is added after acutely stirring 20min
(0.075 × 1=0.075g), while deionized water is added, make reaction solution total volume 250mL(100 × 5=500mL), reaction
24h；After graft copolymerization, network body gel is cut into 1.50cm × 1.50cm × 0.50cm fritter, and anti-with dehydrated alcohol
After after backwashing is washed for 24 hours, continue to be washed with water 5 days, be freeze-dried to get the hydrophobic thermo-sensitive gel of hemicellulose group.
(4) character of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group
HOCs determining adsorption method: it is 25mg/L's that measurement, which takes the desiccant gel of 2g or so to be immersed in 500mL concentration respectively,
Pentachlorophenol, pentachlorodiphenyl, in 3,4- BaP solution, shaking table rocks for 24 hours under the conditions of 25 DEG C, after adsorption equilibrium, takes out solidifying
Glue utilizes the content of remaining organic pollutant in each solution of high performance liquid chromatography detection.
The hydrophobic thermo-sensitive gel of the hemicellulose group being obtained by the above reaction has comparatively ideal HOCs adsorption capacity, to five
Chlorophenol, pentachlorodiphenyl, 3,4- BaP removal efficiency respectively reach 95%, 90% and 88%, physical behavior is white blocks
Shape.
Gel regeneration method: the gel for adsorbing HOCs is put into 50 DEG C of 300mL of deionized water, after for 24 hours, freezing
It is dry, namely regenerated gel；Rejuvenation gel continues adsorption experiment in above-mentioned hydrophobic Adsorption of Organic method.
As a result it can obtain: be obtained by the above reaction gel reusable 9 times, to pentachlorophenol, pentachlorodiphenyl, 3,4- benzene
And the removal efficiency of pyrene is without being decreased obviously.
Embodiment 3: the preparation method based on the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose, concrete operations are as follows:
(1) stock of the corn stalk stalks of rice, wheat, etc.
Corn stover is by air-drying processing, wherein the water content for air-drying raw material is 30%, after artificial peeling, the straw stalks of rice, wheat, etc. carries out machine
Then tool milled processed is acceptable material after 200 mesh but the only screening of 300 mesh screens；
(2) separation of corn stalk stalks of rice, wheat, etc. raw material hemicellulose
The condition that hemicellulose extracts are as follows: potassium hydroxide dosage is the 10.0% of over dry material quality, in system water with
The ratio between over dry material quality 15g:1g, reaction time 3.0h, 200 DEG C for the treatment of temperature.
Concrete operation step are as follows: 10.0g over dry straw stalks of rice, wheat, etc. raw material (if air-drying raw material moisture is 30%, is weighed into 14.3g
Air-dry the straw stalks of rice, wheat, etc.), the water (15 × 10=150mL) of 1.0g potassium hydroxide (10 × 10.0%=1.0g) and 150mL be sufficiently mixed uniformly,
It is transferred in cooker, seals completely, be put into rotation electric heater unit, start to react after being warming up to 200 DEG C, after 3.0h
Reaction terminates, after material is cooled to room temperature, taken off from oxygen be transferred to completely in tank aperture be 1.00nm filter membrane in be separated by solid-liquid separation,
Liquid portion pour into dehydrated alcohol until transparency liquid there is white emulsion state, washed with dehydrated alcohol and at 15000rpm
It is centrifuged 20min, cleaning to cleaning solution is neutrality, is freeze-dried to get hemicellulose.
(3) preparation of the hydrophobic thermo-sensitive gel of hemicellulose group
Gel preparation condition: n-isopropyl acrylamide dosage is 10:1, methacrylic acid benzene with hemicellulose mass ratio
Ester dosage and hemicellulose mass ratio are 15:1, and ammonium persulfate dosage and hemicellulose mass ratio are 0.025:1；N,N,Methylene
The ratio between base bisacrylamide dosage and temperature sensitive and hydrophobic two kinds of monomer mass summations are 0.020:1, N, N, N, N- tetramethyl second two
Amine and ammonium persulfate mass ratio are 1:2, and reaction temperature is 70 DEG C, reaction time 48.0h, hemicellulose quality and reaction solution
The ratio between body total volume controls in the range of 1g:150mL, and the mass concentration of ten disulfobenzene sodium sulfonates in the reaction system is
8%。
Gel preparation course: equipped with reflux condensing tube, mechanical agitator three mouthfuls of reaction flasks in be added 5g hemicellulose,
50g n-isopropyl acrylamide (10 × 5=50g) and 2.5g N,N methylene bis acrylamide (0.020 × (50+75)=
2.5g), a certain amount of deionized water is added and sufficiently dissolves reactant, then injects 75g phenyl methacrylate (5 × 15=75g)
It is under nitrogen protection that reaction flask is violent in 70 DEG C of water bath with thermostatic control with ten disulfobenzene sodium sulfonate (750 × 8%=60g) of 60g
0.125g ammonium persulfate (0.025 × 5=0.125g) and 0.063g N, N, N, N- tetramethylethylenediamine is added after stirring 30min
(0.125 × 1/2=0.063g), while deionized water is added, make reaction solution total volume 750mL(150 × 5=750mL), reaction
48h；After graft copolymerization, network body gel is cut into 2.00cm × 2.00cm × 1.00cm fritter, and anti-with dehydrated alcohol
After 72h is washed in after backwashing, continue to be washed with water 8 days, be freeze-dried to get the hydrophobic thermo-sensitive gel of hemicellulose group.
(4) character of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group
HOCs determining adsorption method: it is 25mg/L's that measurement, which takes the desiccant gel of 2g or so to be immersed in 500mL concentration respectively,
Pentachlorophenol, pentachlorodiphenyl, in 3,4- BaP solution, shaking table rocks for 24 hours under the conditions of 25 DEG C, after adsorption equilibrium, takes out solidifying
Glue utilizes the content of remaining organic pollutant in each solution of high performance liquid chromatography detection.
The hydrophobic thermo-sensitive gel of the hemicellulose group being obtained by the above reaction has comparatively ideal HOCs adsorption capacity, to five
Chlorophenol, pentachlorodiphenyl, 3,4- BaP removal efficiency respectively reach 91%, 94% and 90%, physical behavior is white blocks
Shape.
Gel regeneration method: the gel for adsorbing HOCs is put into 50 DEG C of 300mL of deionized water, after for 24 hours, freezing
It is dry, namely regenerated gel；Rejuvenation gel continues adsorption experiment in above-mentioned hydrophobic Adsorption of Organic method.
As a result it can obtain: be obtained by the above reaction gel reusable 7 times, to pentachlorophenol, pentachlorodiphenyl, 3,4- benzene
And the removal efficiency of pyrene is without being decreased obviously.
Claims (3)
1. a kind of preparation method of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group, it is characterised in that carry out as follows:
1. corn stover is removed the peel, ground after air-drying drying and screening process, qualified straw stalks of rice, wheat, etc. raw material assists hot water to take out using alkali
It proposes method and carries out hemicellulose separating treatment, material filter membrane separation that treated, filtrate alcohol precipitation, centrifuge separation and washing, until
Cleaning solution is neutrality, cleans sediment freeze-drying, corn stalk stalks of rice, wheat, etc. hemicellulose is made；
2. graft copolymerization is carried out to corn stalk stalks of rice, wheat, etc. hemicellulose using aqueous solution micellar copolymerization method, with corn stalk stalks of rice, wheat, etc. half fiber
Dimension element is response matrix, selects ammonium persulfate as initiator, N, N, N, N- tetramethylethylenediamine is promotor, N, N- methylene
Bisacrylamide is crosslinking agent, and n-isopropyl acrylamide is temperature sensitive monomer, and phenyl methacrylate is hydrophobic monomer, 12 sulphurs
Base benzene sulfonic acid sodium salt is surfactant, carries out graft copolymerization/crosslinking inborn nature, copolymer products dehydrated alcohol and water carry out respectively
Washing, freeze-drying, obtain the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group.
2. the preparation method of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group according to claim 1, it is characterised in that
Concrete operations are as follows:
1. will air-dry that treated, corn stover removed the peel, is ground, and be sieved by the sieve of 60~300 mesh, and qualified original is obtained
Material；
2. air-dried straw stalks of rice, wheat, etc. raw material and potassium hydroxide, water are sufficiently mixed after mixing evenly, it is transferred in cooker, seals completely,
It is put into rotation electric heater unit and carries out hemicellulose extraction process, wherein potassium hydroxide dosage is over dry corn stalk stalks of rice, wheat, etc. quality
1.0~10.0%, the mass ratio of water and the over dry corn stalk stalks of rice, wheat, etc. is 5 ~ 15:1,0.5~3.0h of reaction time, treatment temperature 120
~200 DEG C；Material after being disposed is cooled to room temperature, and being transferred to aperture completely is to be consolidated in 0.20~1.00nm filter membrane
Liquid separation, liquid portion pours into dehydrated alcohol until white emulsion state is presented in transparency liquid, and precipitating is finished, washed with dehydrated alcohol
It washs and is centrifuged at 7000~15000rpm, until cleaning solution is neutrality, freeze-drying is until material is completely dried to get corn stalk
Stalks of rice, wheat, etc. hemicellulose；
3. corn stalk stalks of rice, wheat, etc. hemicellulose, n-isopropyl acrylamide and N, N- methylene-bisacrylamide are dissolved in water, after
And phenyl methacrylate and ten disulfobenzene sodium sulfonates are injected, it is vigorously stirred 5 ~ 30min under the conditions of logical nitrogen, persulfuric acid is added
Ammonium and N, N, N, N- tetramethylethylenediamine, initiation grafting copolyreaction, wherein n-isopropyl acrylamide and corn stalk stalks of rice, wheat, etc. half fiber
The mass ratio of dimension element is 1:1~10:1, and phenyl methacrylate and corn stalk stalks of rice, wheat, etc. hemicellulose mass ratio are 3:1~15:1, mistake
Ammonium sulfate and corn stalk stalks of rice, wheat, etc. hemicellulose mass ratio are 0.005:1~0.025:1；N,N methylene bis acrylamide quality: temperature
The ratio between quick monomer and hydrophobic monomer quality summation are 0.005:1~0.02:1, N, N, N, N- tetramethylethylenediamine and ammonium persulfate
Mass ratio is 2:1 ~ 1:2, and reaction temperature is 40~70 DEG C, and the reaction time is 15.0~48.0h, corn stalk stalks of rice, wheat, etc. hemicellulose quality
With the control of the ratio between reaction liquid total volume in 1g:50mL~1g:150mL, ten disulfobenzene sodium sulfonates are in the reaction system
Mass concentration is 3 ~ 8%；After completion of the reaction, gel is cut into small pieces, with dehydrated alcohol to fritter synthetic carry out repeatedly washing 12 ~
After 72h, continue to carry out washing 2 ~ 8 days with water, is freeze-dried, obtains the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group.
3. corn stalk made from the preparation method of the hydrophobic thermo-sensitive gel of corn stalk stalks of rice, wheat, etc. hemicellulose group of any of claims 1 or 2
Application of the hydrophobic thermo-sensitive gel of stalks of rice, wheat, etc. hemicellulose group in adsorption treatment organic pollutant.
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| CN110028624A (en) * | 2019-04-16 | 2019-07-19 | 昆明理工大学 | Preparation method and application based on hemicellulose compound temperature-sensitive gel |
| CN110065988B (en) * | 2019-04-23 | 2022-03-01 | 中国石油大学(华东) | Application of composite hydrogel in heavy metal ion removal |
| CN110170303A (en) * | 2019-06-10 | 2019-08-27 | 陕西科技大学 | A kind of heavy-metal adsorption material and its preparation method and application |
| CN110372049B (en) * | 2019-07-12 | 2021-09-28 | 中国农业科学院农业环境与可持续发展研究所 | Preparation method and application of high-performance cadmium fixing agent |
| CN113318784B (en) * | 2021-05-27 | 2022-07-05 | 昆明理工大学 | Preparation method and application of corn straw loaded nano osmium composite filter column |
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