CN106925242B - A kind of basic fuchsin adsorbent and its preparation method and application - Google Patents
A kind of basic fuchsin adsorbent and its preparation method and application Download PDFInfo
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- CN106925242B CN106925242B CN201710166390.3A CN201710166390A CN106925242B CN 106925242 B CN106925242 B CN 106925242B CN 201710166390 A CN201710166390 A CN 201710166390A CN 106925242 B CN106925242 B CN 106925242B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a kind of basic fuchsin adsorbent and preparation method thereof, preparation method includes: that methylol occurs with formaldehyde and reacts using anionic polyacrylamide as parent, then graft reaction occurs with ligand niacinamide, obtains the basic fuchsin adsorbent.Preparation method of the present invention is simple, easy to operate, and yield is high.Anionic polyacrylamide is modified, high mechanical strength, the good feature of thermal stability are made it have.The invention also discloses application of the basic fuchsin adsorbent in processing waste water from dyestuff, basic fuchsin adsorbent of the present invention is the functional material of separable enrichment, containing more functional group, there is preferable adsorptivity to basic fuchsin, to the basic fuchsin high treating effect in waste water from dyestuff.
Description
Technical field
The invention belongs to field of waste water treatment, it is related to a kind of basic fuchsin adsorbent and its preparation method and application.
Background technique
As China's dye industry rapidly develops in recent years, the waste water discharged, which has become, endangers China's natural water water
One of maximum pollution sources of resource.A small amount of waste water from dyestuff discharge also results in large stretch of water body coloring, the knot that generation environment deteriorates
Fruit, this not only influences the safe mass of water body but also reduces light transmission capacity, influences various in the photosynthesis and water of aquatile
The vital movement of planktonic organism, while containing phenyl ring in a variety of dyestuffs, there is teratogenesis and carcinogenicity.
Dyeing is one of heavy polluted industry, is the object that waste water treatment field is paid close attention to, and dyeing waste water face
Color depth, complicated component, noxious material are more, are difficult to degrade, thus cause serious environmental pollution.The dye of weaving and printing and dyeing industry
A large amount of waste water can be generated during material processing and application, these waste water are generally acknowledged waste water that is toxic, being most difficult to improvement
One of, especially yellow and red dyeing waste water, wherein basic fuchsin is a kind of biggish dyestuff of dosage, is mainly used in artificial
The printing and dyeing of fiber, paper.
Basic fuchsin is widely present in dyeing waste water, this kind of waste water containing basic fuchsin, since its color is very bright-coloured,
So that even if the coloration of water body is also very high when levels are very low, thus severe jamming light transmission, the deeper waste water of coloration, no
It only will cause the displeased quick-drying of people aesthetically, while influencing the incident ray amount of water body, reduce water transparency, and then interfere
The self purification of water body influences the photosynthesis of water plant, interferes the metabolism of aquatile, influences the life of aquatic environment
State balance, if this waste water will cause influence difficult to the appraisal to entire aquatic ecosystem without processing.Therefore,
One of current urgent problem to be solved is had become to the processing of waste water neutral and alkali magenta.
The pinkish red most common method of removal waste water neutral and alkali is broadly divided into chemical method, physical method, bioanalysis three classes at present.Change
Method mainly includes conventional oxidation method, precipitation adsorption method, Coagulation Method etc., chemical method due to its is with high costs, energy consumption is high,
Chemical agent investment is more, still restricts it applied to industrialized production.Physical method mainly utilizes physical action, separates or goes
Except the pollutant in sewage.Currently, a variety of physical methods have been used widely, such as adsorption technology, UF membrane filtering technique, instead
Infiltration, electrodialysis, etc., but these technologies require high expense, and subsequent treatment process is complicated.In bioanalysis, such as: true
Bacterium decoloration, microbial degradation, biological adsorption, the biological prosthetic industrial applications that successfully obtained handle waste water from dyestuff, mainly
Many organisms, such as: bacterium, yeast, algae, fungi, water plant have the advantage for the pollutant that can degrade, be enriched with.Tradition is raw
Object method mainly applies anaerobic process and aerobic method to handle waste water from dyestuff, is method commonly used at present, but Traditional Method is run
Period is long.
Modified polyacrylamide can be used as a kind of hydrophilic polymer, currently be applied to organic industry, biomedical,
The purified treatment of water, food industry, heavy metal recovery, the wadding of suspended matter are heavy.This polymer has multiple functions functional group, such as carboxylic
Base, amino, hydroxyl or sulfonic group etc..Existed using Mannich reaction (Mannich reaction) i.e. methylol reaction and graft reaction
Amino-containing group is introduced on anionic polyacrylamide main chain, when the group of introducing is amino or other groups, so that it may
To promote the functionality of substance itself, the application in other respects of modified material is expanded.
Summary of the invention
It is an object of the invention to solve above-mentioned technology existing in the prior art and cost problem, a kind of alkaline product are provided
Red adsorbent and its preparation method and application, the present invention are reacted using polyacrylamide as parent with ligand niacinamide, can
The modified polyacrylamide with higher functionality base conversion ratio is obtained, gained modified polyacrylamide has basic fuchsin good
Selective absorption performance.
To solve above-mentioned technical problem, the invention adopts the following technical scheme:
A kind of basic fuchsin adsorbent includes the repetitive unit as shown in formula (I):
The inherent viscosity of the basic fuchsin adsorbent is 750~850mL/g.
Parent polyacrylamide is the linear polymer of energy adsorbent particles functional group, and particle can be attached together
Dough polyacrylamide Long carbon chain is formed, plays bridging action between particles.Polyacrylamide can be used as macromolecular scaffold
By reacting linkage function group with reagent, thus the functional material of the separable enrichment of preparation.With formaldehyde and ligand nicotinoyl
Amination graft reaction occurs for the amide groups on amine and branch, generates polyamine type anion organic macromolecule adsorbent, has and catches
Catch the function of basic fuchsin.
The preparation method of the basic fuchsin adsorbent, comprising: poly- with the anion with the repetitive unit as shown in (II)
Acrylamide is parent, and methylol occurs with formaldehyde and reacts, then graft reaction occurs with structure ligand as shown in (III), is obtained
The basic fuchsin adsorbent；
The preparation method specifically includes:
(1) anionic polyacrylamide is soluble in water, formalin is added and carries out methylol reaction, obtains mixture；
(2) ligand is added in the mixture that step (1) obtains and carries out graft reaction, obtains polymer；
(3) polymer for obtaining step (2) impregnates in a solvent, after water washing, is freeze-dried to obtain the alkaline product
Red adsorbent.
Preferably, in step (1), anionic polyacrylamide is soluble in water, and gained anionic polyacrylamide is water-soluble
The mass fraction of liquid is 0.5~5%.
Preferably, in step (1), the mass fraction of the formalin is 20~50%.
Preferably, in step (1), the anionic polyacrylamide and formalin add ratio be 1g:0.1~
8mL, in the proportional region, the utilization rate of formaldehyde first increases with the increase that formaldehyde adds ratio to be reduced afterwards, since anion is poly-
Acrylamide is reacted with formaldehyde generates hydroxymethyl polyacrylamide intermediate, then carries out graft reaction with ligand, if content of formaldehyde
It is excessively high, it easily crosslinks, the stability of product can be reduced；Further preferably, the anionic polyacrylamide and formaldehyde are water-soluble
The ratio that adds of liquid is 1g:2~8mL；Optimally, the anionic polyacrylamide and the ratio that adds of formalin are
1g:3mL, the utilization rate highest of formaldehyde, reaches 87.6% at this time.
Preferably, in step (1), the temperature of the methylol reaction is 25~35 DEG C.
Preferably, in step (1), the time of the methylol reaction is 2~5h.
Preferably, in step (2), anionic polyacrylamide and the ratio that adds of ligand are 1g:3 in the step (1)
~8mmol, as ligand adds the increase of ratio, the molecular weight of gained basic fuchsin adsorbent first increases, and then increases trend
It tends towards stability.Due to the increase with the reaction time, graft polymerization reaction is constantly carried out, and the strand of polymer constantly adds
It is long, increase the molecular weight of polymer constantly, and when reaction proceeds to certain time, due to molecule graftable on main chain
Chain limited amount, total molecular weight stop increasing.
Preferably, in step (2), the temperature of the graft reaction is 50~100 DEG C, the basic fuchsin adsorbent of preparation
Molecular weight is the raising with temperature and increases, and is finally tended to balance；Since the raising of graft reaction temperature can be improved in solution
Reactivity site diffusion of the ligand on parent (anionic polyacrylamide) main chain rate, and increase active sites
The concentration of point ligand, promotes the progress of polymerization reaction.
Further preferably, the temperature of the graft reaction is 90~100 DEG C.Within this temperature range, gained basic fuchsin
The molecular weight of adsorbent is maximum
Preferably, in step (2), the pH of the graft reaction is 6~8, the molecular weight of gained basic fuchsin adsorbent
With the raising first increases and then decreases of pH；Further preferably, the pH of the graft reaction is 7.5, under the pH, the trip of reaction environment
From hydrogen ion and hydroxide ion interaction do not interfere with polymerization reaction.
Preferably, in step (2), the time of the graft reaction is 8~15h.
Preferably, in step (3), the solvent is the formalin that mass fraction is 20~50%.
Preferably, in step (3), the temperature of the freeze-drying is -60~-40 DEG C.
The present invention also provides a kind of application of basic fuchsin adsorbent in processing waste water from dyestuff.
Preferably, the basic fuchsin adsorbent can adsorb the alkaline product in waste water from dyestuff in the range of pH is 5~8
It is red.
Preferably, the concentration of the waste water from dyestuff neutral and alkali magenta is 150~300mg/L.
Compared with prior art, the invention has the following beneficial effects:
(1) raw material sources are extensive, cheap；
(2) anionic polyacrylamide is modified, makes it have high mechanical strength, thermal stability is good；
(3) reaction dissolvent and reactant are green non-poisonous, save the cost, protect environment, reduce secondary pollution；
(4) present invention is that the functional material of separable enrichment has preferably basic fuchsin containing more functional group
Adsorptivity；
(5) nitrogen-atoms of present invention grafting up is more, and nitrogen content is high, and it is more to provide lone pair electrons, to basic fuchsin have compared with
Good adsorption effect；
(6) reaction route of basic fuchsin adsorbent provided by the invention is simple, and synthetic method is easy to operate, it is only necessary to female
Then with ligand two step of graft reaction, condition occur for body after reacting generation methylolation polyacrylamide intermediate with formaldehyde
It is easy to reach, is not necessarily to large-scale instrument and equipment, so batch production easy to accomplish and automation control, before there is good application
Scape；
(7) application method of the present invention is simple, simplifies adsorption step, conveniently, cost is small.
Detailed description of the invention
Fig. 1 is the infrared spectrum of basic fuchsin adsorbent prepared by embodiment 1；
The thermogravimetric curve for the NITMP that Fig. 2 is APAM and prepared by embodiment 1；
The thermal weight loss rate analysis figure for the NITMP that Fig. 3 is APAM and prepared by embodiment 1；
The scanning electron microscope (SEM) photograph for the NITMP that Fig. 4 is APAM and prepared by embodiment 1, wherein (a) is the scanning electron microscope (SEM) photograph of APAM,
(b) scanning electron microscope (SEM) photograph for being NITMP；
Fig. 5 is influence result figure of the absorption system pH to basic fuchsin removal rate；
Fig. 6 is influence result figure of the adsorption temp to basic fuchsin removal rate.
Specific embodiment
It is further depicted as the present invention combined with specific embodiments below, but the contents of the present invention are not limited to this.
In the present invention, the method for measuring polymer viscosity is as follows:
It accurately weighs 0.1g basic fuchsin adsorbent to be put into the beaker for filling 50mL deionized water, on magnetic stirring apparatus
Several minutes of heating stirring, turn off heater switch later, then remove beaker, be cooled to room temperature, then solution is transferred to 100mL and is done
Only in dry volumetric flask, a certain amount of deionized water is added and carries out constant volume, it is spare.
" polyacrylamide characteristic is viscous according to standard GB/T 12005.1-89 for the measurement method of experiment and specific measurement operation
Spend measuring method "；The intrinsic viscosity of experiment test high molecular polymer is according to standard GB/T PT 12005.10-92
" Molecular Weight for Polyacrylamide measurement --- viscosimetry ", calculates relevant data and obtains the viscous equal average molecular of high molecular polymer
Quality.
The relative molecular mass of polymer can be calculated according to by formula (1) (2) (3):
ηr=t/t0 (1)
ηr--- relative viscosity；
The flow time of t --- sample solution, s；
to--- the flow time of 1.00mol/L sodium chloride solution, s.
C=ms/v (2)
By the η acquiredrTable look-up accordingly [η] c value divided by sample solution concentration c up to inherent viscosity [η]
In formula: [η] --- inherent viscosity, mL/g；
The concentration of c --- sample solution, g/mL；
M --- sample mass, g；
S --- sample solid content, g；
The sample solution volume of V --- preparation, mL
The Mark-Houwink formula of this test condition is as follows:
[η]=kMa (3)
In formula:
The inherent viscosity of [η] --- solution, mL/g；
k——4.75×10-3, mL/g；
M --- relative molecular mass
a——0.80。
Embodiment 1
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) anionic polyacrylamide (APAM) 1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into,
It is sufficiently dissolved under room temperature, is added and adjusts pH to 7.5, the formalin that 3mL mass fraction is 36.69% is added, reacted 3h, obtain mixed
Close object；By measurement mixture in residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 87.6%.
(2) 0.005mol ligand niacinamide (NITM) is added in the mixture obtained by step (1), and at 90 DEG C, pH is
7.5, heating stirring reacts 10h under nitrogen protection, and mixing speed 300rpm/min obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 36.69% is impregnated, then with steaming
Distilled water is washed for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
Through detecting, the inherent viscosity of gained basic fuchsin adsorbent is 827.66mL/g, calculates to obtain the basic fuchsin suction
Attached dose of relative molecular mass 3.56 × 106。
The infrared spectrum of gained basic fuchsin adsorbent is as shown in Figure 1,1689cm-1Place is-C=O stretching vibration absworption peak
3315、3081cm-1Place is the N-H stretching vibration absworption peak of NITMP；3367,3172cm-1The N-H stretching vibration that place is NITM is inhaled
Receive peak；3406cm-1、3108cm-1Place is the N-H stretching vibration absworption peak of APAM；1621cm-1, 1594cm-1Place is C-N, and C-C stretches
Contracting vibration peak；609cm-1Place is the stretching vibration peak of pyridine ring.Compare basic fuchsin adsorbent (NITMP), anion pp
There are biggish difference, the 609cm especially in NITMP spectrogram between them known to the infrared spectrum curve of amide (APAM)-1,
1689cm-1There are strong absworption peak appearance, and 3000-3500cm in place-1Between peak value obviously reinforce, be indicated above in NITMP and increase
Pyridine ring and C=O are added, hence it is demonstrated that NITMP has the amino group abundant ,-NH of NITMP ratio APAM2Group characteristic peak
It is obvious to weaken.
The thermogravimetric curve of anionic polyacrylamide (APAM) and basic fuchsin adsorbent (NITMP) is as shown in Fig. 2, yin
The thermal weight loss rate analysis of cationic polyacrylamide (APAM) and basic fuchsin adsorbent (NITMP) is as shown in Figure 3.Macromolecule connects
The thermal decomposition process of graft copolymer is divided into three phases: the first stage is moisture content or small-molecule substance, and wherein moisture includes
Free water and Free water；Second stage is the fracture of copolymer functional group key；Phase III be the main chain weight change of copolymer not
Greatly.
APAM: the first stage originates in 25 DEG C, terminates at 145 DEG C or so, and thermal weight loss amount is 1.59%, and thermal weight loss rate is
0.000217%s-1；Second stage is the fracture COO of branch chain link on main chain-, CONH2In C=O, C-O, C-N, N-H occurs disconnected
It splits, the result is that APAM mass is substantially change, originates in 175~211 DEG C, terminate at 475 DEG C or so；Phase III is main chain in height
At a temperature of decompose.
NITMP: the first stage originates in 25 DEG C, terminates at 139 DEG C or so, weight-loss ratio 1.1%, and thermal weight loss rate rate is
0.00076%s-1；Second stage is the cracking i.e. COO of the branch on branch and grafting on original main chain-With,In C=O, C-O, C-N, N-H is broken, the result is that NITMP mass is substantially change, originate in 145~
193 DEG C terminate at 361 DEG C or so；Phase III is that main chain decomposes under high-temperature.
From the point of view of the thermal weight loss rate of Fig. 3,55 DEG C, 271 DEG C, 343 DEG C of APAM；67 DEG C, 163 DEG C, 283 DEG C of NITMP
There is hot rate peak value and shows that the fracture result that functional group occurs under corresponding temperature value is that weight changes very greatly in a short time.
By in two figures two curves the result shows that NITMP is stable at normal temperature, do not decompose.
The scanning electron microscope (SEM) photograph of anionic polyacrylamide (APAM) and basic fuchsin adsorbent (NITMP) as shown in figure 4, its
In, Fig. 4 (a) is the scanning electron microscope (SEM) photograph of APAM, and Fig. 4 (b) is the scanning electron microscope (SEM) photograph of NITMP.As seen from the figure, APAM and NITMP knot
Structure is significantly different, and rear material grains size is substantially change before modified, and NITMP is less than APAM；Surface area after before modified also with
Change.
Embodiment 2
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, sufficiently dissolution, is added at normal temperature
PH to 7.5 is adjusted, the formalin that 6mL mass fraction is 36.69% is added, 3h is reacted, obtains mixture；By measuring mixture
In residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 84.1%.
(2) 0.006mol ligand NITM is added in the mixture obtained by step (1), and at 90 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 10h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 30% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.41 × 10 of the basic fuchsin adsorbent6。
Embodiment 3
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, sufficiently dissolution, is added at normal temperature
PH to 7.5 is adjusted, the formalin that 8mL mass fraction is 36.69% is added, 3h is reacted, obtains mixture；By measuring mixture
In residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 83.6%.
(2) 0.008mol ligand NITM is added in the mixture obtained by step (1), and at 90 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 10h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 45% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.38 × 10 of the basic fuchsin adsorbent6。
Embodiment 4
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, sufficiently dissolution, is added at normal temperature
PH to 7.5 is adjusted, the formalin that 2mL mass fraction is 36.69% is added, 3h is reacted, obtains mixture；By measuring mixture
In residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 83.4%.
(2) 0.004mol ligand NITM is added in the mixture obtained by step (1), and at 90 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 10h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 25% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.31 × 10 of the basic fuchsin adsorbent6。
Embodiment 5
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM 1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, sufficiently dissolution, adds at normal temperature
Enter to adjust pH to 7.5, the formalin that 1mL mass fraction is 36.69% is added, reacts 3h, obtain mixture；It is mixed by measurement
The amount of residual formaldehyde in object, calculate analyze formaldehyde utilization rate be 81.1%.
(2) 0.003mol ligand NITM is added in the mixture obtained by step (1), and at 90 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 10h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 20% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.06 × 10 of the basic fuchsin adsorbent6。
Embodiment 6
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, sufficiently dissolution, is added at normal temperature
PH to 7.5 is adjusted, the formalin that 4mL mass fraction is 36.69% is added, 2h is reacted, obtains mixture；By measuring mixture
In residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 85.1%.
(2) 0.005mol ligand NITM is added in the mixture obtained by step (1), and at 60 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 13h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 50% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.14 × 10 of the basic fuchsin adsorbent6。
Embodiment 7
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 3% is made into, sufficiently dissolution, is added at normal temperature
PH to 7.5 is adjusted, the formalin that 4mL mass fraction is 20% is added, 4h is reacted, obtains mixture；By in measurement mixture
Residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 85.9%.
(2) 0.005mol ligand NITM is added in the mixture obtained by step (1), and at 50 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 15h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 35% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.08 × 10 of the basic fuchsin adsorbent6。
Embodiment 8
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 0.5% is made into, sufficiently dissolution, adds at normal temperature
Enter to adjust pH to 7.5, the formalin that 4mL mass fraction is 50% is added, reacts 5h, obtain mixture；By measuring mixture
In residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 84.4%.
(2) 0.005mol ligand NITM is added in the mixture obtained by step (1), and at 100 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 8h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 50% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -60 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.48 × 10 of the basic fuchsin adsorbent6。
Embodiment 9
A kind of preparation method of basic fuchsin adsorbent, successively follows the steps below:
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 5% is made into, sufficiently dissolution, is added at normal temperature
PH to 7.5 is adjusted, the formalin that 4mL mass fraction is 41% is added, 2.5h is reacted, obtains mixture；By measuring mixture
In residual formaldehyde amount, calculate analyze formaldehyde utilization rate be 84.9%.
(2) 0.005mol ligand NITM is added in the mixture obtained by step (1), and at 100 DEG C, pH 7.5, nitrogen
It protects lower heating stirring to react 8h, mixing speed 300rpm/min, obtains polymer；
(3) formalin that the resulting polymer mass fraction of step (2) is 50% is impregnated, then uses distilled water
Washing is for several times；
It is refrigerated to constant weight at a temperature of polymer after above-mentioned flushing is put into -40 DEG C, obtains the basic fuchsin adsorbent
(NITMP)。
It is calculated through detection, the relative molecular mass 3.48 × 10 of the basic fuchsin adsorbent6。
Embodiment 10
The application of basic fuchsin adsorbent prepared by embodiment 1 in processing waste water from dyestuff, includes the following steps:
(1) the resulting basic fuchsin adsorbent (NITMP) of 10.0mg embodiment 1 is weighed, clean and dry 100mL is placed in
In iodine flask, the deionized water of 100mL is added later, dissolves NITMP sufficiently；
(2) 30mL waste water from dyestuff to be processed, alkali in waste water from dyestuff to be processed are added in step (1) mixture obtained
Property pinkish red initial concentration be 200mg/L, system pH=7.5 is mixed up, with 300rpm/min's in 30 DEG C of constant temperature oscillator
Revolving speed shakes to balance and carries out adsorption test；
(3) step (2) resulting mixture is taken and is existed away from the supernatant at liquid level 30mm after high speed centrifugation 15min
The absorbance of solution is measured at basic fuchsin maximum absorption wavelength 542nm, residual alkalinity magenta is dense in the water phase of analytical solution
Degree.Then the removal rate of basic fuchsin is calculated with following formula:
D (%)=(Co-Ce)/Co
In formula: Ce is the concentration (mg/L) of solution neutral and alkali magenta after balance；Co is then that solution neutral and alkali is pinkish red before adsorbing
The concentration (mg/ml) of solution.
It is calculated through detection, NITMP is 84.3% to the removal rate of basic fuchsin.
Embodiment 11~14
The operation of embodiment 10 is repeated, difference is only that the pH value of system is adjusted to 5.0,6.0,7.0,8.0 respectively, to grind
Study carefully influence of the system pH to basic fuchsin removal rate, as a result as shown in Figure 5.
During basic fuchsin adsorbent handles waste water from dyestuff basic fuchsin, the initial pH of solution is that adsorption experiment is important
One of influence factor.Hydrogen ion is easily adsorbed in experiment reaction solution, and hydroxide ion also will affect adsorption site,
Therefore, it probes into pH and important meaning is adsorbed with to basic fuchsin.
As can be seen from FIG. 5, the continuous increase NITMP particle of system initial pH value also increases the value of basic fuchsin adsorbance
Greatly.Slowly increase when pH value increases to 7 rear decoloring rates by 6.In neutral conditions, the hydrogen ion in solution and hydroxide ion are dense
The equal progress for reaching balance and will not influence absorption is spent, so that adsorbent rises the adsorption capacity of basic fuchsin.Work as solution
Percent of decolourization highest when initial pH reaches 7.5.
Embodiment 15~18
The operation of embodiment 10 is repeated, difference is only that the temperature of system is changed to 15 DEG C, 20 DEG C, 30 DEG C, 35 DEG C, with research
Influence of the adsorption temp to basic fuchsin removal rate, as a result as shown in Figure 6.
It can be concluded that, after reaction proceeds to 30 DEG C, adsorption experiment basically reaches balance by curve in Fig. 6.Therefore 30 DEG C
It is decided to be optimal adsorption temperature.Before 30 DEG C the change of temperature can significantly affect percent of decolourization as a result, being influenced not after 30 DEG C
Greatly, reason is that the functional group of temperature raising adsorbent NITMP and adsorption site are more active, and molecular action is strong, promotees significantly
Gradually be diffused by boundary layer table in adsorbent into basic fuchsin molecule and and its it is internal.
Above-described embodiment is not limit the invention in any way, all to be obtained by the way of equivalent substitution or equivalent transformation
Technical solution fall within the scope of protection of the present invention.
Claims (5)
1. a kind of basic fuchsin adsorbent, which is characterized in that include the repetitive unit as shown in formula (I):
The inherent viscosity of the basic fuchsin adsorbent is 750~850mL/g；
The preparation method of the basic fuchsin adsorbent, comprising: with the anion poly- third with the repetitive unit as shown in (II)
Acrylamide is parent, and methylol occurs with formaldehyde and reacts, then graft reaction occurs with structure ligand as shown in (III), is had
There is the basic fuchsin adsorbent；
The anionic polyacrylamide and the ratio that adds of formalin are 1g:0.1~8mL；
The anionic polyacrylamide and the ratio that adds of ligand are 1g:3~8mmol.
2. basic fuchsin adsorbent according to claim 1, which is characterized in that the preparation method specifically includes:
(1) anionic polyacrylamide is soluble in water, formalin is added and carries out methylol reaction, obtains mixture；
(2) ligand is added in the mixture that step (1) obtains and carries out graft reaction, obtains polymer；
(3) polymer for obtaining step (2) impregnates in a solvent, after water washing, is freeze-dried to obtain the basic fuchsin suction
Attached dose.
3. basic fuchsin adsorbent according to claim 2, which is characterized in that in step (2), the temperature of the graft reaction
Degree is 50~100 DEG C.
4. basic fuchsin adsorbent according to claim 2, which is characterized in that in step (2), the pH of the graft reaction
It is 6~8.
5. a kind of application of basic fuchsin adsorbent according to claim 1 in processing waste water from dyestuff.
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