CN107081134A - A kind of modified hair keratin adsorbent and preparation method and application - Google Patents
A kind of modified hair keratin adsorbent and preparation method and application Download PDFInfo
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- CN107081134A CN107081134A CN201610085448.7A CN201610085448A CN107081134A CN 107081134 A CN107081134 A CN 107081134A CN 201610085448 A CN201610085448 A CN 201610085448A CN 107081134 A CN107081134 A CN 107081134A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4856—Proteins, DNA
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a kind of preparation method of modified hair keratin adsorbent, it is using hair as raw material, modification is carried out in two steps after the pretreatment of the NaOH aqueous solution with formaldehyde, dimethylamine respectively, compound to prepare a kind of modification keratin adsorbent containing quaternary ammonium salt, its outward appearance has no significant difference with procephalon hair.Compared with prior art, it is high to the clearance of anionic dye in dyeing waste water applied to treatment of dyeing wastewater field by hair keratin cation adsorbent modified made from the method for the present invention；By verification experimental verification, it, up to 537.6mg/g, is approximately more than ten times of unmodified hair keratin fiber to anthraquinone dye Reactive Brilliant Blue KN-R adsorption capacity；Extensively, method of modifying technique is simple for the raw material sources needed for the preparation method of the present invention simultaneously.
Description
Technical field
The invention belongs to modified adsorbent field of material preparation, and in particular to a kind of preparation of modified hair keratin adsorbent
Method.
Background technology
In recent years, as industrialization and urbanization are developed rapidly, various sanitary sewages, industrial wastewater discharge capacity increasingly
Increase, adjoint water environment pollution problem is increasingly serious.Wherein, waste water from dyestuff accounts for industrial wastewater than great, with color
The features such as degree is deep, biodegradability is poor, toxicity is big, pollution level is high.Such as charcoal absorption of common processing method, biological drop
The drawbacks of there are high price, low efficiency and easy formation harmful by-products in solution, chemical oxidation etc..Utilize abundance, price
Cheap biological material has cheap control expense, easily designed operation, to poisonous as sorbent treatment dyeing waste water
Pollutant is insensitive and does not produce the advantage of secondary pollution, and the extensive concern of people is caused at present.
The existence range of natural keratin is very wide, and application value is very high.Angle egg is extracted from poultry hair, human hair, animal coffin
It is white not only to reclaim keratin, and pollution of the keratin to environment can be reduced, while economic benefit is obtained
Obtain ecological benefits and environmental benefit.Mankind's keratin is mainly in the effective object of adsorbing domain pollutes extensive, harm
Big and conventional method is difficult to oils, heavy metal and the harmful dyestuff removed.
Be presented a beach greasy dirt around the birds often adrift covered on the sea of oil spill accident by greasy dirt, feather, the U.S. with
The oil suction bag " Hai Jing " of chicken feather filling is just born in the research to this phenomenon, and feather is put into nothing by patent CN96242403.X
Spin in cloth bag and prepare oil suction bag.Pen L are in article Influence of typical poultry feather structure and
It is 132 ° that chicken feather contact angle is pointed out in surface lipoid on wettability, with lipophilic-hydrophobic property, fine hair specific surface area
Big and intervillous space can produce capillarity, suitable for the removal of standing level oil slick, " chicken feather grid " ratio made with chicken feather
Fibrofelt sorbing material under equal adsorbance cheap 1/5th, Han Qingli " chicken feather as fume purifying filter
Chicken feather is made into " chicken feather plate " in the text of the experimental study of material " one can be removed 80% in oil smoke by intercepting with suction-operated
Pollutant, the especially particulate matter removal efficiencies to less than 0.3 μm are very considerable.
Keratin surface contains substantial amounts of amino acid residue (- NH2,-COOH) and disulfide bond sulfide linkage (- S-S-) these
All it is common adsorption site.Early in nineteen eighty-three, T.C.TAN etc. utilizes acid reagent such as HCI, H2SO4, alkalescence
Reagent such as NaOH and reproducibility reagent N a2S and NaOH mixed solution is pre-processed to human hair keratin, and
Investigate to Hg2+、Ag+、Pb2+Etc. the adsorption effect of heavy metal ion, compared to unmodified human hair fiber, adsorbance is equal
It is obviously improved, making human hair keratin fiber as industrial wastewater adsorbent becomes possibility.But not to inhaling in text
What random was managed is explained further.
Aman Ullah etc. dissolve feather in NaOH strong alkali environments at 150 DEG C, from the poly- second two of four kinds of dopants
Alcohol glycidol ether PEG, PNIPAM PNIPAM, propenyl AA, the silanol silsesquioxane of cyclohexyl three
Alkane POSS and carboxyl, sulfydryl, amino, hydroxyl reaction in solubilised state feather keratin, obtain NEW TYPE OF COMPOSITE keratin material
Material, AA doping adulterates keratin to As with POSS3+Adsorbance be respectively 11.5 × 10-2、11.0×10-2mg/g。
Solubilised state keratin functional group reactionses efficiency is the method increase, but dissolution conditions are harsh, and adsorption rate is not high.
Keratin also has certain adsorption effect to dyestuff, and Vinod K.Gupta etc. are soaked with hydrogen peroxide (30%w/v)
There are adsorption effect, but smaller of adsorbance after chicken feather 24h to anionic dye erythrosine and dye of positive ion malachite green
Reach 15.75mg/g and 26.11mg/g.Suctions of the M.Radetic et al. using reuse wool nonwoven materials as acid dyes
Attached dose has been inquired into the non-woven of untreated, corona treatment, chitosan processing and plasma and chitosan Combined Treatment
The Dye Adsorption performance of fleece material respectively to acid red AR27, acid red AR 88 and acid blue AB113.Research hair
Existing, reuse fleece material can effectively adsorb the acid dyes in dyeing waste water, the reuse wool especially handled through chitosan
It is greatly improved with the reuse wool nonwoven materials through plasma and chitosan Combined Treatment to acid dyes in dye liquor
Adsorption capacity.But the non-woven reuse wool through Low Temperature Plasma Treating or through plasma Yu chitosan Combined Treatment
Suction-operated of the material to acid blue AB113 be not obvious, awaits further further investigation.
Still rarely have discovery, only Zhu Xian for the use of hair is used for dyestuff removal as sorbent material in patent or paper
Younger brother has found hair to dye of positive ion methylene blue and alkalescence in " characterization of adsorption of the hair to water cationic dyestuff " one text
Pinkish red adsorption effect is substantially better than Congo red to anionic dye and eosin W or W S adsorption effect, but finds to use unmodified head
Break out for the effect of adsorbent adsorption treatment of dye waste water and bad, adsorbance is only 1~2mg/g.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of modified hair keratin adsorbent, to solve prior art presence
Adsorption effect it is not good the problem of.
The technical problem of the invention also to be solved is to provide the preparation method of above-mentioned modified hair keratin adsorbent.
The technical problem of the invention finally to be solved is to provide above-mentioned modified hair keratin adsorbent and contaminated in water body is removed
Application in material.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of preparation method of modified hair keratin adsorbent, it comprises the following steps：
(1) pretreatment shreds the hair after handling totally, and 1~2h is soaked in the 0.5mol/L NaOH aqueous solution
After take out, be washed to neutral and dry 3h, the hair keratin fiber pre-processed at 40 DEG C；
Above-mentioned processing can not only effectively remove the water insoluble class lipid layer of hair keratin surface, increase the wettability of hair with
Permeability, can also disconnect the part disulfide bond and salt type bond of hair surface, expose (- SO3) and amino acid residue
(-NH2,-COOH) more reaction sites, for follow-up dimethylamine be modified more reaction sites are provided.
(2) once it is modified：The hair keratin fiber of the pretreatment obtained in step (1) is immersed in formalin,
30~60min is stirred at 40~60 DEG C；
The hair keratin fiber of pretreatment is once modified using formaldehyde in above-mentioned steps；Because head alkali is to hair form
There is certain damage effect, on the one hand formaldehyde can repair keratin and be damaged, another aspect formaldehyde occurs aldehyde amine with amino and contracted
Symphysis is played a part of being crosslinked dimethylamine into methylol amine.
(3) it is twice-modified：Added into step (2) in the mixed system of gained at dimethylamine agueous solution, 40~60 DEG C
Solid portion is taken to be washed to neutrality after 60~120min of stirring, 3~5h of vacuum drying at 40~60 DEG C produces modified head
Send out keratin adsorbent；
Above-mentioned steps introduce amino using dimethylamine, and one side dimethylamine can be with carboxyl (- COOH) sulfonic group (- SO3)
Generation esterification generates quaternary ammonium salt, and the methylol amine of another aspect step (2) generation can continue to react with dimethylamine.
Second modified, can make these the generally negatively charged cationizations in aqueous of sulfonic group and carboxyl, convert it
For positively charged quaternary ammonium salt so that cellulose easily attracts negatively charged anionic dye, removal anion dye is reached
Expect the effect of waste water.
In step (1), the clean method of hair treatment is：After the hot soap lye water cleaning of Hair grooming, washing is dried i.e.
Can；Hair lengths after wherein shredding are 4~6mm.
In step (2), the hair keratin fiber of pretreatment and the solid-to-liquid ratio of formalin are 0.1g：2~6m.
In step (2), in formalin, the mass fraction of solute formaldehyde is 37%.
In step (3), the hair keratin fiber of pretreatment and the solid-to-liquid ratio of dimethylamine agueous solution are 0.1g：5~10mL.
In step (3), in dimethylamine agueous solution, the mass fraction of solute dimethylamine is 33%.
The modified hair keratin adsorbent that above-mentioned any one is prepared is also within protection scope of the present invention.
Above-mentioned modified hair keratin adsorbent remove dyes in application also protection scope of the present invention it
It is interior.
Wherein, described dyestuff is anionic dye.
The present invention is divided to two with formaldehyde, dimethylamine respectively using keratin material hair as material after the pretreatment of the NaOH aqueous solution
Step is modified, compound to prepare a kind of modification keratin adsorbent containing quaternary ammonium salt, and its outward appearance has no substantially with procephalon hair
Difference.
The present invention overcomes the deficiencies in the prior art and proposes a kind of preparation of the modified hair keratin adsorbent containing quaternary ammonium salt
Method, the present invention is by being modified to surface functional group hair keratin that is abundant and easily regenerating, obtaining containing quaternary ammonium salt
Modified hair keratin adsorbent, and using assign its specific physicochemical property removing water body in anionic dye, especially
It is for reactive brilliant blue K-GR KN-R in dyeing waste water removal effect it is notable.
Described anionic dye refers to that a class contains hydroxy, sulfonic group, carboxyl, can be with wool or silk fabric ion
The dyestuff that bond is closed and dyed, negatively charged soluble in water.The cation-modified hair keratin adsorbent containing quaternary ammonium salt
Add after waste water from dyestuff, because the electrostatic adsorption of zwitterion just be able to can be served well to Wastewater Dyes
Removal is acted on.Anthraquinone dye Reactive Brilliant Blue KN-R used in whole process of the test is a kind of typical case containing anthraquinone ring
Anionic dye, it is representative with anionic dye.
At room temperature, modified hair keratin cation adsorbent dosage is 0.5~2g/L, and regulation anionic aq dyestuff gives up
The pH of water is about 2~4, and oscillation rate is 160~180r/min, continues 2~3h, its clearance can be more than 95%.
Beneficial effect：
Compared with prior art, by hair keratin cation adsorbent modified made from the method for the present invention, application
It is high to the clearance of anionic dye in dyeing waste water in treatment of dyeing wastewater field；By verification experimental verification, it is to anthraquinone
Dye activity brilliant blue KN-R adsorption capacity, up to 537.6mg/g, is approximately more than ten times of unmodified hair keratin fiber；
Extensively, method of modifying technique is simple for the raw material sources needed for the preparation method of the present invention simultaneously.
Brief description of the drawings
Fig. 1 (is modified for the hair keratin in embodiment 5 before modified with modified hair keratin cation adsorbent
Hair keratin fiber afterwards) figure is influenceed by pH value on anionic dye Reactive Brilliant Blue KN-R in waste water；
Fig. 2 is that the dosage of modified hair keratin cation adsorbent made from embodiment 5 adsorbs anthraquinone dye work to it
The influence figure of property brilliant blue KN-R；
Fig. 3 is that modified hair keratin cation adsorbent adsorption time made from embodiment 5 adsorbs anthraquinone dye work to it
The influence figure of property brilliant blue KN-R；
Fig. 4 inhales for the hair keratin fiber in embodiment 5 before modified with modified hair keratin cation adsorbent
Anthraquinone dye Reactive Brilliant Blue KN-R is influenceed figure by dyestuff initial concentration in attached waste water；
Fig. 5 is the ESEM phenogram of the unmodified hair keratin fiber obtained by step one in embodiment 5, amplification
500 times of multiple；
Fig. 6 is the ESEM phenogram of the modified hair keratin cation adsorbent obtained by embodiment 5, multiplication factor
500 times；
Fig. 7 is the modified hair keratin cation adsorbent absorption anthraquinone dye Reactive Brilliant Blue KN-R obtained by embodiment 5
ESEM phenogram afterwards, 1000 times of multiplication factor；
Fig. 8 is the absorption property figure after modified hair keratin cation adsorbent desorption is multiple made from embodiment 5.
Embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the content described by example and be merely to illustrate the present invention, without should be also without limitation on described in detail in claims
The present invention.
Embodiment 1：
A kind of preparation method of modified hair keratin adsorbent, it comprises the following steps：
(1) pre-process：
After the hot soap lye water cleaning for several times of Hair grooming, cleaned to remove surface dirt with deionized water, be placed in ventilating kitchen and dry in the air
It is dry, then cut with scissors to 5mm or so, take 2g to be placed in beaker, adding 0.5M NaOH submerges it, room temperature
Lower magnetic stirrer reacts 2h, takes out to distill water wash to neutrality, 40 DEG C of dry 3h are standby after filtering.
(2) once it is modified：
It is 37% as mass fraction in constant temperature combined reactor, is added to take the hair keratin fiber that 0.1g is pre-processed
Formalin, every 0.1 gram of hair keratin adds 6mL formalin；Then in constant temperature whip modified at 40 DEG C
40min；
(3) it is twice-modified：
Mass fraction is directly added into once modified reactor for 33% dimethylamine solution, every 0.1 gram of hair angle egg
It is white to add 5ml, then in constant temperature whip modified 60min at 40 DEG C, then by modified hair keratin deionization
Neutrality is washed to, in vacuum drying 3~5 hours at 40 DEG C, twice-modified hair keratin fiber, as modified hair is obtained
Keratin sun adsorbent finished product.
Embodiment 2：
Preparation method is same as Example 1, except that, the operating method of step (2) is：
The hair keratin fiber 0.1g obtained in step (1) is taken in constant temperature combined reactor, adding mass fraction is
37% formalin, every 0.1 gram of hair keratin adds 4mL formalin；Then stirred in constant temperature at 50 DEG C
Modified 50min.
Embodiment 3：
Preparation method is same as Example 1, except that, the operating method of step (2) is：
The hair keratin fiber 0.1g obtained in step (1) is taken in constant temperature combined reactor, adding mass fraction is
37% formalin, every 0.1 gram of hair keratin adds 2mL formalin；Then stirred in constant temperature at 50 DEG C
Modified 60min.
Embodiment 4:
Preparation method is same as Example 1, except that, the operating method of step (3) is：
Mass fraction is directly added into once modified reactor for 33% dimethylamine solution, every 0.1 gram of hair angle egg
It is white to add 8ml, then in constant temperature whip modified 90min at 40 DEG C, then by modified hair keratin deionization
Neutrality is washed to, in vacuum drying 3~5 hours at 40 DEG C, twice-modified hair keratin fiber, as modified hair is obtained
Keratin cation adsorbent finished product.
Embodiment 5:
Preparation method is same as Example 1, except that, the operating method of step (3) is：
Mass fraction is directly added into once modified reactor for 33% dimethylamine solution, every 0.1 gram of hair angle egg
It is white to add 10ml, then in constant temperature whip modified 120min at 40 DEG C, then by modified hair keratin spend from
Son is washed to neutrality, in vacuum drying 3~5 hours at 40 DEG C, obtains twice-modified hair keratin fiber, is as modified head
Send out keratin cation adsorbent finished product.
Embodiment 6：
(1) pre-process：
After the hot soap lye water cleaning for several times of Hair grooming, cleaned to remove surface dirt with deionized water, be placed in ventilating kitchen and dry in the air
It is dry, then cut with scissors to 5mm or so, take 2g to be placed in beaker, adding 0.1M NaOH submerges it, room temperature
Lower magnetic stirrer reacts 2h, takes out to distill water wash to neutrality, 40 DEG C of dry 3h are standby after filtering.
(2) once it is modified：
It is 37% as mass fraction in constant temperature combined reactor, is added to take the hair keratin fiber that 0.1g is pre-processed
Formalin, every 0.1 gram of hair keratin adds 6mL formalin；Then in constant temperature whip modified at 40 DEG C
40min；
(3) it is twice-modified：
Mass fraction is directly added into once modified reactor for 33% dimethylamine solution, every 0.1 gram of hair angle egg
It is white to add 10ml, then in constant temperature whip modified 120min at 40 DEG C, then by modified hair keratin spend from
Son is washed to neutrality, in vacuum drying 3~5 hours at 40 DEG C, obtains twice-modified hair keratin fiber, is as modified head
Send out the positive adsorbent finished product of keratin.
Embodiment 7：
The use of hair keratin fiber made from the step of embodiment 5 (1) is that unmodified hair keratin is used to contrast absorption examination
Test, setting dosage is 0.5g/L, pH value of solution is adjusted to 3 or so, and Reactive Brilliant Blue KN-R dyestuff waste liquid concentration is 200mg/L,
Hunting speed is adjusted in constant temperature oscillator for 180rpm, dyestuff residual concentration is determined after vibration 180min and calculates to obtain adsorbent
Adsorbance.
Embodiment 8：
Adsorption activity brilliant blue KN-R experiment is carried out using modified cation adsorbent made from embodiment 5, takes adsorbent to throw
Dosage is 2g/L, and dyestuff initial concentration is 200mg/L, and pH is adjusted to 3 or so, fully after vibration adsorption equilibrium, mistake
Filter, is washed with deionized several times, adsorbent is taken out, for lower step desorption experiment.
It is as follows using desorption method：In conical flask, take 0.1g saturations adsorb after adsorbent be added to 20mL concentration and be
In 0.4mol/L NaOH solution, vibration desorption 5h, filtering, are washed with deionized several times in constant temperature oscillator,
Adsorption test again, adsorption capacity of the examination reproducing adsorbent to dyestuff can be carried out by taking out adsorbent.
Above step repeatedly, to inquire into the power of regeneration of modified cation adsorbent.
Utilize the Reactive Brilliant Blue KN-R in the modified cation adsorbent absorption waste water from dyestuff solution prepared in embodiment 1-8.
The adsorption test condition of each embodiment is as follows：
The dosage of modified hair keratin cation adsorbent is 0.5g/L, and pH value of solution is adjusted to 3 or so, reactive brilliant bule
KN-R dyestuff waste liquids concentration is 200mg/L, and modified hair keratin cation made from embodiment 1~7 is added into waste water
Adsorbent is 180rpm after vibrating 180min, hunting speed in 25 DEG C of constant temperature oscillators.
It is to be adsorbed to reach after balance, solution is taken out, and after being centrifuged with supercentrifuge, determine residual dye in supernatant
Concentration, according to following formulaObtain adsorbance.In formula：Q is adsorbance (mg/g), C0It is preceding molten for absorption
The concentration (mg/L) of dyestuff, C in liquideFor the concentration (mg/L) of dyestuff in solution after absorption, V is liquor capacity (L),
W is adsorbent mass (g).
Each adsorbent adsorption activity brilliant blue KN-R dye solution adsorbance of embodiment 1~8 is as shown in table 1.
Table 1
| Embodiment | Adsorbance (mg/g) |
| 1 | 345.7 |
| 2 | 331.0 |
| 3 | 325.3 |
| 4 | 360.6 |
| 5 | 389.7 |
| 6 | 245.6 |
| 7 | 23.8 |
| 8 | 380.8 |
Here is to be carried out by taking the positive adsorbent of the modified hair keratin of embodiment 5 as an example under different condition to waste water reactive brilliant bule
The experimental conditions of KN-R removal.
PH influence：
Experiment condition：At room temperature, to initial concentration 200mg/L Reactive Brilliant Blue KN-R solution, pH scopes are adjusted
Between 2~11, using modified hair keratin fiber, setting dosage is 0.5g/L, 160rpm vibration absorption 180min.
Modified hair keratin is influenceed larger to the absorption of dyestuff by the initial pH of solution, in addition, will hair keratin before modified
Fiber also carries out the experiment of the same terms, obtain Fig. 1 before modified after hair keratin fiber to Dye Adsorption amount size with pH
Value changes compare figure.Contrast finds that modified hair keratin fiber is significantly increased to the adsorbance of Reactive Brilliant Blue KN-R,
16 times of about unmodified hair keratin.
The influence of adsorbent dosage：
Experiment condition：At room temperature, to the Reactive Brilliant Blue KN-R solution that initial concentration is 200mg/L, under 160rpm
Vibrate and control adsorption time to be 180min, pH is 3.As shown in Fig. 2 as modified hair keratin fiber is added
The increase of amount, adsorbent also constantly increases the clearance of Reactive Brilliant Blue KN-R.
The influence of adsorption time：
Experiment condition：At room temperature, the pH of 200mg/L Reactive Brilliant Blue KN-R solution is adjusted into 3, control absorption
Agent dosage is 15~180min of vibration absorption under 0.5g/L, 160rpm.As shown in figure 3, modified hair keratin is to work
The clearance of property brilliant blue KN-R increases with the increase of adsorption time, and 0~40min rates of adsorption quickly, then gradually become
It is slow, adsorption equilibrium is basically reached after 120min, adsorbance is about 389mg/g.
The influence of dyestuff initial concentration：
Experiment condition：At room temperature, the pH for maintaining waste water from dyestuff is 3, and 160rpm vibrates 180min in constant temperature oscillator,
Dosage is 0.5g/L, sets initial concentration excursion as 25~600mg/L.As shown in figure 4, being in initial concentration
Modified adsorbent is rapid extremely with the increase of initial concentration to the adsorbance of anthraquinone dye Reactive Brilliant Blue KN-R during 0~300mg/L
About 466mg/g；Concentration is slowly increased by a small margin in 200~600mg/L；Mainly adsorption site reaches saturation.
Fig. 8 is the absorption property figure of the multiple post-modification hair keratin cation adsorbent of desorption, and the modification is learnt by figure
Adsorbent remains to adsorb 138mg/g after the 4th desorption to dyestuff progress processing, and desorption efficiency remains at more than 60%,
Illustrate that modified hair has preferable power of regeneration.
Claims (9)
1. a kind of preparation method of modified hair keratin adsorbent, it is characterised in that it comprises the following steps：
(1) pre-process：Hair after handling totally is shredded, 1~2h is soaked in the 0.5mol/L NaOH aqueous solution
After take out, be washed to neutral and dry, the hair keratin fiber pre-processed；
(2) once it is modified：The hair keratin fiber of the pretreatment obtained in step (1) is immersed in formalin,
30~60min is stirred at 40~60 DEG C；
(3) it is twice-modified：Added into step (2) in the mixed system of gained at dimethylamine agueous solution, 40~60 DEG C
Solid portion is taken to be washed to neutrality after 60~120min of stirring, 3~5h of vacuum drying at 40~60 DEG C produces modified head
Send out keratin adsorbent.
2. preparation method according to claim 1, it is characterised in that in step (1), hair treatment is clean
Method is：After the hot soap lye water cleaning of Hair grooming, washing is dried；Hair lengths after wherein shredding are 4~6mm.
3. preparation method according to claim 1, it is characterised in that in step (2), the hair angle of pretreatment
The solid-to-liquid ratio of azelon and formalin is 0.1g：2~6m.
4. preparation method according to claim 1, it is characterised in that in step (2), in formalin,
The mass fraction of solute formaldehyde is 37%.
5. preparation method according to claim 1, it is characterised in that in step (3), the hair angle of pretreatment
The solid-to-liquid ratio of azelon and dimethylamine agueous solution is 0.1g：5~10mL.
6. preparation method according to claim 1, it is characterised in that in step (3), in dimethylamine agueous solution,
The mass fraction of solute dimethylamine is 33%.
7. the modified hair keratin adsorbent that any one is prepared in claim 1~6.
8. application of the modified hair keratin adsorbent in dyes are removed described in claim 7.
9. application according to claim 8, it is characterised in that described dyestuff is anionic dye.
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| CN114768695A (en) * | 2022-04-20 | 2022-07-22 | 广东省科学院生物与医学工程研究所 | Formaldehyde-removing gel particles prepared based on waste keratin and preparation method thereof |
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| CN108046440A (en) * | 2017-12-14 | 2018-05-18 | 张松 | A kind of bath sewage cleanser and its preparation method and application |
| CN108554386A (en) * | 2018-03-21 | 2018-09-21 | 中国农业科学院农业资源与农业区划研究所 | Promote the new material and the preparation method and application thereof of efficient passivation Cadmium in Soil |
| CN108404875A (en) * | 2018-03-28 | 2018-08-17 | 齐鲁工业大学 | A kind of preparation method of ox hair protein sponge sorbing material for tanning dyeing waste liquid |
| CN108404875B (en) * | 2018-03-28 | 2020-11-06 | 齐鲁工业大学 | Preparation method of cow hair protein sponge adsorbing material for tanning dyeing waste liquid |
| CN110152621A (en) * | 2019-06-06 | 2019-08-23 | 安徽科技学院 | A kind of Enteromorpha that improves is to the new method of waste water dyestuff malachite green adsorption efficiency |
| CN113578278A (en) * | 2021-07-30 | 2021-11-02 | 陕西科技大学 | Amidoxime group functionalized feather fiber adsorption material and preparation method and application thereof |
| CN114768695A (en) * | 2022-04-20 | 2022-07-22 | 广东省科学院生物与医学工程研究所 | Formaldehyde-removing gel particles prepared based on waste keratin and preparation method thereof |
| CN114768695B (en) * | 2022-04-20 | 2023-07-25 | 广东省科学院生物与医学工程研究所 | Formaldehyde-removing gel particles prepared based on waste keratin and preparation method thereof |
| CN115055038A (en) * | 2022-06-02 | 2022-09-16 | 广东省科学院生物与医学工程研究所 | Method for preparing degradable air purification material by hydrolyzing waste feather through microbiological method |
| CN115055038B (en) * | 2022-06-02 | 2023-07-25 | 广东省科学院生物与医学工程研究所 | Method for preparing degradable air purification material by hydrolyzing waste feathers through microbiological method |
| CN116459807A (en) * | 2023-05-26 | 2023-07-21 | 广东省科学院生物与医学工程研究所 | Modified keratin-based formaldehyde adsorbent and preparation method thereof |
| CN116532099A (en) * | 2023-05-26 | 2023-08-04 | 广东省科学院生物与医学工程研究所 | Method for preparing adsorbent by modifying soluble keratin with diallylamine and application |
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