CN106925242A - 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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- CN106925242A CN106925242A CN201710166390.3A CN201710166390A CN106925242A CN 106925242 A CN106925242 A CN 106925242A CN 201710166390 A CN201710166390 A CN 201710166390A CN 106925242 A CN106925242 A CN 106925242A
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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
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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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
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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
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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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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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
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a kind of basic fuchsin adsorbent and preparation method thereof, its preparation method includes：With PAMA as parent, there is methylol reaction with formaldehyde, then graft reaction occurs with part niacinamide, obtain the basic fuchsin adsorbent.Preparation method of the present invention is simple, and easy to operate, yield is high.PAMA is modified, high mechanical strength is made it have, the characteristics of heat endurance is good.The invention also discloses application of the basic fuchsin adsorbent in waste water from dyestuff is processed, 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 technology
As China's dye industry is developed rapidly in recent years, the waste water for being discharged has become harm China 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
Really, this not only influences the safe mass of water body but also reduces light transmission capacity, various in the photosynthesis and water of influence aquatile
The vital movement of planktonic organism, while contain phenyl ring in various dyestuffs, with 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, be difficult to degrade, and thus result in serious environmental pollution.Weaving and the dye of printing and dyeing industry
A large amount of waste water can be produced during material processing and application, these waste water are generally acknowledged waste water that is poisonous, being most difficult to improvement
One of, especially yellow and red dyeing waste water, wherein basic fuchsin is a kind of dyestuff of large usage quantity, 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, because its color and luster is very bright-coloured,
Even if during so that levels are very low, the colourity of water body is also very high, thus severe jamming printing opacity, the deeper waste water of colourity, no
People's displeased quick-drying aesthetically can be only caused, while influenceing the incident ray amount of water body, water transparency is reduced, and then hinder
The self purification of water body, influences the photosynthesis of water plant, disturbs the metabolism of aquatile, influences the life of aquatic environment
State is balanced, if this waste water is not processed, will cause influence difficult to the appraisal to whole aquatic ecosystem.Therefore,
To waste water neutral and alkali, pinkish red treatment has become one of current problem demanding prompt solution.
The pinkish red most common method of removal waste water neutral and alkali is broadly divided into chemical method, Physical, the class of bioanalysis three at present.Change
Method mainly including conventional oxidation method, precipitation adsorption method, Coagulation Method etc., chemical method because its is with high costs, energy ezpenditure is high,
Chemical agent input is more, still restricts it and is applied to industrialized production.Physical mainly uses physical action, separates or goes
Except the pollutant in sewage.At present, various Physicals have been used widely, such as adsorption technology, UF membrane filtering technique, instead
Infiltration, electrodialysis, etc., but these technologies are required for high expense, and subsequent treatment process is complicated.In bioanalysis, such as：Very
Bacterium decolouring, microbial degradation, biological adsorption, the biological prosthetic industrial applications that successfully obtained process waste water from dyestuff, mainly
Many organisms, such as：Bacterium, yeast, algae, fungi, water plant have the advantage of the pollutant that can degrade, be enriched with.Tradition is raw
Thing method is mainly using anaerobic process and aerobic method to process waste water from dyestuff, is commonly used method at present, but Traditional Method runs
Cycle is long.
Modified polyacrylamide can currently be applied to organic industry as a kind of hydrophilic polymer, biomedical,
The purified treatment of water, food industry, heavy metal recovery, the wadding of suspension sink.This polymer has various function functional groups, such as carboxylic
Base, amino, hydroxyl or sulfonic group etc..It is that methylol reaction and graft reaction exist using Mannich reaction (Mannich reactions)
The group containing amino is introduced on PAMA main chain, when the group for introducing is amino or other groups, so that it may
To lift material feature in itself, the application in other respects of modified material is expanded.
The content of the invention
It is an object of the invention to solve above-mentioned technology and Cost Problems present in prior art, there is provided a kind of alkaline product
Red adsorbent and its preparation method and application, the present invention is reacted with polyacrylamide as parent with part niacinamide, can
The modified polyacrylamide with higher functionality base conversion ratio is obtained, gained modified polyacrylamide has good to basic fuchsin
Selective absorption performance.
To solve above-mentioned technical barrier, the present invention uses following technical scheme：
A kind of basic fuchsin adsorbent, comprising the repeat unit as shown in formula (I)：
The inherent viscosity of the basic fuchsin adsorbent is 750~850mg/mL.
, can be attached together for particulate by the linear polymer of parent polyacrylamide Shi Neng adsorbent particles functional group
Dough polyacrylamide Long carbon chain is formed, bridging action is played between particles.Polyacrylamide can be used as macromolecular scaffold
Reacted linkage function group by with reagent, so as to prepare the functional material of separable enrichment.With formaldehyde and part nicotinoyl
There is amination graft reaction in the amide groups on amine and side chain, generate polyamine type anion organic macromolecule adsorbent, with catching
Catch the function of basic fuchsin.
The preparation method of the basic fuchsin adsorbent, including：It is poly- with the anion with the repeat unit as shown in (II)
Acrylamide is parent, and methylol reaction, then the part generation graft reaction with structure as shown in (III) occur with formaldehyde, is obtained
The basic fuchsin adsorbent；
The preparation method is specifically included：
(1) it is PAMA is soluble in water, add formalin to carry out methylol reaction, obtain mixture；
(2) part is added in the mixture that step (1) is obtained carries out graft reaction, obtains polymer；
(3) in a solvent, after water washing, freeze-drying obtains the alkaline product for the polymer immersion for obtaining step (2)
Red adsorbent.
Preferably, in step (1), PAMA is soluble in water, and gained PAMA 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 ratio that adds of the PAMA and formalin is 1g：0.1~
8mL, in the proportion, the utilization rate of formaldehyde first increases with the increase that formaldehyde adds ratio and reduces afterwards, because anion is poly-
Acrylamide and formaldehyde reaction generation hydroxymethyl polyacrylamide intermediate, then graft reaction is carried out with part, if content of formaldehyde
It is too high, easily crosslink, the stability of product can be reduced；Further preferably, the PAMA is water-soluble with formaldehyde
The ratio that adds of liquid is 1g：2~8mL；Optimally, the ratio that adds of the PAMA and formalin is
1g：3mL, now the utilization rate highest of formaldehyde, reaches 87.6%.
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), PAMA adds ratio for 1g in the part and step (1)：3
~8mmol, the increase of ratio is added with part, and the molecular weight of gained basic fuchsin adsorbent first increases, and then increases trend
Tend towards stability.Due to constantly being carried out with the increase in reaction time, graft polymerization reaction, the strand of polymer constantly adds
Long, making the molecular weight of polymer constantly increases, and when reaction proceeds to certain hour, due to graftable molecule on main chain
Chain limited amount, total molecular weight stops 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 increased with the rising of temperature, is finally tended to balance；In solution being improved due to the rising of graft reaction temperature
The speed that is spread to the reactivity site on parent (PAMA) main chain of part, and increase active sites
The concentration of point part, promotes the carrying out of polymerisation.
Further preferably, the temperature of the graft reaction is 90~100 DEG C.In the 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 rising 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 interact do not interfere with polymerisation.
Preferably, in step (2), the time of the graft reaction is 8~15h.
Preferably, in step (3), the solvent is formalin that mass fraction is 20~50%.
Preferably, in step (3), the temperature of the freeze-drying is -60~-40 DEG C.
Present invention also offers a kind of application of basic fuchsin adsorbent in waste water from dyestuff is processed.
Preferably, the basic fuchsin adsorbent can be the alkaline product in adsorbing waste water from dyestuff in the range of 5~8 in pH
It is red.
Preferably, the pinkish red concentration of the waste water from dyestuff neutral and alkali is 150~300mg/L.
Compared with prior art, the present invention has the advantages that：
(1) raw material sources are extensively, cheap；
(2) PAMA is modified, makes it have high mechanical strength, heat endurance is good；
(3) reaction dissolvent and reactant are green non-poisonous, cost-effective, and environmental protection reduces secondary pollution；
(4) present invention is the functional material of separable enrichment, containing more functional group, is had preferably to basic fuchsin
Adsorptivity；
(5) present invention grafting up nitrogen-atoms it is more, nitrogen content is high, there is provided lone pair electrons are more, have to basic fuchsin compared with
Good adsorption effect；
(6) reaction scheme of the basic fuchsin adsorbent that the present invention is provided is simple, and synthetic method is easy to operate, it is only necessary to female
Then there is the step of graft reaction two, condition with part after body and formaldehyde reaction generation methylolation polyacrylamide intermediate
Easily reach, without large-scale instrument and equipment, so batch production and Automated condtrol are easily realized, it is preceding with good application
Scape；
(7) application process of the present invention is simple, simplifies adsorption step, convenience, and cost is small.
Brief description of the drawings
Fig. 1 is the infrared spectrum of basic fuchsin adsorbent prepared by embodiment 1；
Fig. 2 is APAM and the thermogravimetric curve of the NITMP of the preparation of embodiment 1；
Fig. 3 is APAM and the thermal weight loss rate analysis figure of the NITMP of the preparation of embodiment 1；
Fig. 4 is APAM and the scanning electron microscope (SEM) photograph of the NITMP of the preparation of embodiment 1, wherein, (a) is the scanning electron microscope (SEM) photograph of APAM,
B () is the scanning electron microscope (SEM) photograph of NITMP；
Fig. 5 is influence result figures of the absorption system pH to basic fuchsin clearance；
Fig. 6 is influence result figure of the adsorption temp to basic fuchsin clearance.
Specific embodiment
The present invention is further depicted as with reference to specific embodiment, but present disclosure is not limited to this.
In the present invention, the method for determining polymer viscosity is as follows：
Accurately weigh 0.1g basic fuchsin adsorbents to be put into the beaker for filling 50mL deionized waters, on magnetic stirring apparatus
Heating stirring several minutes, turn off heater switch afterwards, then remove beaker, be cooled to room temperature, then solution is transferred into 100mL and do
In net dry volumetric flask, a certain amount of deionized water is added to carry out constant volume, it is standby.
" polyacrylamide characteristic is glued according to standard GB/T 12005.1-89 for the measuring method of experiment and specific measurement operation
Degree assay method "；The intrinsic viscosity of experiment test high molecular polymer is according to standard GB/T PT 12005.10-92
" Molecular Weight for Polyacrylamide is determined --- viscosimetry ", calculate the viscous equal average molecular that related data obtain 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 solutions, s.
C=ms/v (2)
By the η for trying to achieverTable look-up accordingly [η] c values obtains final product inherent viscosity [η] divided by sample solution concentration c
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 are 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, follows the steps below successively：
(1) PAMA (APAM) 1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into,
Fully dissolved under normal temperature, add regulation pH to 7.5, add the formalin that 3mL mass fractions are 36.69%, react 3h, obtain mixed
Compound；By determining the amount of the residual formaldehyde in mixture, calculating analyze the utilization rate of formaldehyde is 87.6%.
(2) 0.005mol parts niacinamide (NITM) are added in step (1) gained mixture, and at 90 DEG C, pH is
7.5, the lower heating stirring reaction 10h of nitrogen protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 36.69%, then with steaming
Distilled water is washed for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
After testing, the inherent viscosity of gained basic fuchsin adsorbent is 827.66mg/mL, calculates the basic fuchsin and inhales
Attached dose of relative molecular mass 3.56 × 106。
The infrared spectrum of gained basic fuchsin adsorbent is as shown in figure 1,1689cm-1It is-C=O stretching vibration absworption peaks to locate
3315、3081cm-1Locate the N-H stretching vibration absworption peaks for NITMP；3367、3172cm-1Locate to be inhaled for the N-H stretching vibrations of NITM
Receive peak；3406cm-1、3108cm-1Locate the N-H stretching vibration absworption peaks for APAM；1621cm-1, 1594cm-1It is C-N to locate, and C-C stretches
Contracting vibration peak；609cm-1Locate the stretching vibration peak for pyridine ring.Compare basic fuchsin adsorbent (NITMP), anion pp
The infrared spectrum curve of acid amides (APAM) understands there is larger difference between them, especially the 609cm in NITMP spectrograms-1,
1689cm-1Place has strong absworption peak to occur, and 3000-3500cm-1Between peak value substantially strengthen, be indicated above increasing in NITMP
Pyridine ring and C=O are added, hence it is demonstrated that NITMP has abundant amino group ,-NHs of the NITMP than APAM2Group characteristic peak
Substantially weaken.
The thermogravimetric curve of PAMA (APAM) and basic fuchsin adsorbent (NITMP) is as shown in Fig. 2 the moon
The thermal weight loss rate analysis of cationic polyacrylamide (APAM) and basic fuchsin adsorbent (NITMP) are as shown in Figure 3.Macromolecule connects
The thermal decomposition process of graft copolymer is divided into three phases：First stage is moisture content or small-molecule substance, and wherein moisture includes
Free water and Free water；Second stage is the key fracture of copolymer functional group；Phase III be the main chain weight change of copolymer not
Greatly.
APAM：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 speed 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
Split, result is that APAM mass substantially changes, and originates in 175~211 DEG C, terminates at 475 DEG C or so；Phase III is main chain in height
At a temperature of decompose.
NITMP：First stage originates in 25 DEG C, terminates at 139 DEG C or so, and weight-loss ratio is 1.1%, and thermal weight loss rate speed is
0.00076%s-1；Second stage is the cracking i.e. COO of the side chain on side chain and grafting on original main chain-With,In C=O, C-O, C-N, N-H is broken, and result is that NITMP mass substantially changes, originate in 145~
193 DEG C terminate at 361 DEG C or so；Phase III is that main chain is decomposed under high-temperature.
From the point of view of the thermal weight loss speed 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
Hot speed peak value occur, to show that the fracture result that functional group occurs under corresponding temperature value is that weight changes in a short time very big.
Show that NITMP stablizes at normal temperatures by the result of two curves in two figures, do not decompose.
The scanning electron microscope (SEM) photograph of PAMA (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 is tied
Structure is significantly different, and rear material grainses size substantially changes 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, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, fully dissolving, adds at normal temperatures
Regulation pH to 7.5, adds the formalin that 6mL mass fractions are 36.69%, reacts 3h, obtains mixture；By determining mixture
In residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 84.1%.
(2) 0.006mol part NITM are added in step (1) gained mixture, and at 90 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 10h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 30%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.41 × 10 of the basic fuchsin adsorbent6。
Embodiment 3
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, fully dissolving, adds at normal temperatures
Regulation pH to 7.5, adds the formalin that 8mL mass fractions are 36.69%, reacts 3h, obtains mixture；By determining mixture
In residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 83.6%.
(2) 0.008mol part NITM are added in step (1) gained mixture, and at 90 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 10h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 45%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.38 × 10 of the basic fuchsin adsorbent6。
Embodiment 4
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, fully dissolving, adds at normal temperatures
Regulation pH to 7.5, adds the formalin that 2mL mass fractions are 36.69%, reacts 3h, obtains mixture；By determining mixture
In residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 83.4%.
(2) 0.004mol part NITM are added in step (1) gained mixture, and at 90 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 10h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 25%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.31 × 10 of the basic fuchsin adsorbent6。
Embodiment 5
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM 1.0g accurately are weighed, is made into the aqueous solution that mass fraction is about 1%, at normal temperatures fully dissolving, plus
Enter and adjust pH to 7.5, add the formalin that 1mL mass fractions are 36.69%, react 3h, obtain mixture；Mixed by determining
The amount of the residual formaldehyde in thing, calculating analyze formaldehyde utilization rate be 81.1%.
(2) 0.003mol part NITM are added in step (1) gained mixture, and at 90 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 10h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 20%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.06 × 10 of the basic fuchsin adsorbent6。
Embodiment 6
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 1% is made into, fully dissolving, adds at normal temperatures
Regulation pH to 7.5, adds the formalin that 4mL mass fractions are 36.69%, reacts 2h, obtains mixture；By determining mixture
In residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 85.1%.
(2) 0.005mol part NITM are added in step (1) gained mixture, and at 60 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 13h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 50%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.14 × 10 of the basic fuchsin adsorbent6。
Embodiment 7
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 3% is made into, fully dissolving, adds at normal temperatures
Regulation pH to 7.5, adds the formalin that 4mL mass fractions are 20%, reacts 4h, obtains mixture；In by determining mixture
Residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 85.9%.
(2) 0.005mol part NITM are added in step (1) gained mixture, and at 50 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 15h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 35%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -50 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.08 × 10 of the basic fuchsin adsorbent6。
Embodiment 8
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 0.5% is made into, at normal temperatures fully dissolving, plus
Enter and adjust pH to 7.5, add the formalin that 4mL mass fractions are 50%, react 5h, obtain mixture；By determining mixture
In residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 84.4%.
(2) 0.005mol part NITM are added in step (1) gained mixture, and at 100 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 8h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 50%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -60 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, the relative molecular mass 3.48 × 10 of the basic fuchsin adsorbent6。
Embodiment 9
A kind of preparation method of basic fuchsin adsorbent, follows the steps below successively：
(1) APAM1.0g is accurately weighed, the aqueous solution that mass fraction is about 5% is made into, fully dissolving, adds at normal temperatures
Regulation pH to 7.5, adds the formalin that 4mL mass fractions are 41%, reacts 2.5h, obtains mixture；By determining mixture
In residual formaldehyde amount, calculating analyze formaldehyde utilization rate be 84.9%.
(2) 0.005mol part NITM are added in step (1) gained mixture, and at 100 DEG C, pH is 7.5, nitrogen
The lower heating stirring reaction 8h of protection, mixing speed is 300rpm/min, obtains polymer；
(3) by the formalin immersion that the polymer mass fraction obtained by step (2) is 50%, distilled water is then used
Washing is for several times；
Constant weight is refrigerated at a temperature of polymer after above-mentioned flushing is put into -40 DEG C, the basic fuchsin adsorbent is obtained
(NITMP)。
Calculate after testing, 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 waste water from dyestuff is processed, comprises the following steps：
(1) the basic fuchsin adsorbent (NITMP) of the gained of 10.0mg embodiments 1 is weighed, clean dry 100mL is positioned over
In iodine flask, the deionized water of 100mL is added afterwards, NITMP is fully dissolved；
(2) the pending waste water from dyestuff of 30mL, alkali in pending waste water from dyestuff are added in the mixture that step (1) is 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
Rotating speed shakes to balance and carries out adsorption test；
(3) by the mixture obtained by step (2), exist by after high speed centrifugation 15min, taking the supernatant at liquid level 30mm
The absorbance of solution is determined at basic fuchsin maximum absorption wavelength 542nm, residual alkalinity magenta is dense in the water phase of analytical solution
Degree.Then the clearance of basic fuchsin is calculated with below equation：
D (%)=(Co-Ce)/Co
In formula：Ce is the concentration (mg/L) of solution neutral and alkali magenta after balance；Co is then solution neutral and alkali magenta before absorption
The concentration (mg/ml) of solution.
Calculate after testing, NITMP is 84.3% to the clearance of basic fuchsin.
Embodiment 11~14
The operation of embodiment 10 is repeated, the pH value for differing only in system is adjusted to 5.0,6.0,7.0,8.0, to grind respectively
Study carefully influences of the system pH to basic fuchsin clearance, as a result as shown in Figure 5.
During basic fuchsin sorbent treatment waste water from dyestuff basic fuchsin, the initial pH of solution is important adsorption experiment
One of influence factor.Hydrogen ion is easily adsorbed in experiment reaction solution, and hydroxide ion can also influence adsorption site,
Therefore, probe into pH and important meaning is adsorbed with to basic fuchsin.
It can be seen from Fig. 5, the continuous increase NITMP particles of system initial pH value also increase to 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 and hydroxide ion in solution are dense
Degree is equal to reach the carrying out that balance does not interfere with absorption so that adsorbent rises to 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, the temperature for differing only in system is changed to 15 DEG C, 20 DEG C, 30 DEG C, 35 DEG C, to study
Influence of the adsorption temp to basic fuchsin clearance, as a result as shown in Figure 6.
By that can be drawn in curve in Fig. 6, after reaction proceeds to 30 DEG C, adsorption experiment basically reaches balance.Therefore 30 DEG C
It is decided to be optimal adsorption temperature.The change of temperature can significantly affect the result of percent of decolourization before 30 DEG C, be influenceed not after 30 DEG C
Greatly, reason be temperature raise adsorbent NITMP functional group and adsorption site it is more active, molecular action is strong, promotees significantly
Entered basic fuchsin molecule be progressively diffused into table in adsorbent by boundary layer and and its it is internal.
Above-described embodiment limits the present invention never in any form, every to be obtained by the way of equivalent or equivalent transformation
Technical scheme all fall within protection scope of the present invention.
Claims (8)
1. a kind of basic fuchsin adsorbent, it is characterised in that comprising the repeat unit as shown in formula (I)：
The inherent viscosity of the basic fuchsin adsorbent is 750~850mg/mL.
2. a kind of preparation method of basic fuchsin adsorbent according to claim 1, it is characterised in that including：To have
The PAMA of repeat unit as shown in (II) is parent, and methylol reaction occurs with formaldehyde, then with structure such as
(III) there is graft reaction in the part shown in, obtain with the basic fuchsin adsorbent；
3. the preparation method of basic fuchsin adsorbent according to claim 2, it is characterised in that the preparation method is specific
Including：
(1) it is PAMA is soluble in water, add formalin to carry out methylol reaction, obtain mixture；
(2) part is added in the mixture that step (1) is obtained carries out graft reaction, obtains polymer；
(3) in a solvent, after water washing, freeze-drying obtains the basic fuchsin and inhales for the polymer immersion for obtaining step (2)
Attached dose.
4. the preparation method of basic fuchsin adsorbent according to claim 3, it is characterised in that in step (1), described the moon
The ratio that adds of cationic polyacrylamide and formalin is 1g：0.1~8mL.
5. the preparation method of basic fuchsin adsorbent according to claim 3, it is characterised in that described to match somebody with somebody in step (2)
PAMA adds ratio for 1g in body and step (1)：3~8mmol.
6. the preparation method of basic fuchsin adsorbent according to claim 3, it is characterised in that described to connect in step (2)
The temperature of branch reaction is 50~100 DEG C.
7. the preparation method of basic fuchsin adsorbent according to claim 3, it is characterised in that described to connect in step (2)
The pH of branch reaction is 6~8.
8. application of a kind of basic fuchsin adsorbent according to claim 1 in waste water from dyestuff is processed.
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| US5744563A (en) * | 1995-08-11 | 1998-04-28 | American Envirocare Inc | Mannich base copolymer and method for making it |
| CN103601279A (en) * | 2013-11-29 | 2014-02-26 | 天津市双洁化工技术有限公司 | Spray paint waste water treatment agent and treatment method thereof |
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