CN105174351B - Prevent and treat the method for pollution of chromium and chelate fibre used in blackish green glass production - Google Patents
Prevent and treat the method for pollution of chromium and chelate fibre used in blackish green glass production Download PDFInfo
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- CN105174351B CN105174351B CN201510567196.7A CN201510567196A CN105174351B CN 105174351 B CN105174351 B CN 105174351B CN 201510567196 A CN201510567196 A CN 201510567196A CN 105174351 B CN105174351 B CN 105174351B
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Abstract
The invention discloses a kind of chelate fibre NTHF synthetic method, comprise the following steps：Using grafted propylene acid polytetrafluoroethylene fibre as parent, N is placed on, is soaked in N dimethylformamides；Then add part and be stirred reaction；Reaction products therefrom is filtered, gained filter cake dries the chelate fibre NTHF for constant weight, obtaining having high-selectivity adsorption ability to Cr (VI) after flushing.The present invention further simultaneously discloses a kind of method for preventing and treating pollution of chromium in blackish green glass production：After adding chelate fibre NTHF in caused waste water into blackish green Improving Glass Manufacturing Processes, staticly settle, the heavy metal in waste water is adsorbed using chelate fibre NTHF；The heavy metal includes chromium.Absorption can effectively be realized using the method for the present invention and reclaim the chromium in chromate waste water caused by blackish green glass production.
Description
Technical field
The present invention relates to a kind of method of synthesizing new chelate fibre, and in particular to grafted propylene acid fibrillated polytetrafluoroethylene
It is parent to tie up (PTFE-g-AA), with hydroxyacyl hydroxyacyl hydrazine (NTH) for part, has high efficiency selected suction to Cr (VI) ion so as to synthesize
The chelate fibre NTHF of attached performance, the method for preventing and treating chromate waste water pollution problem in blackish green Improving Glass Manufacturing Processes.
Background technology
China can produce chrome ore slag nearly 300,000 every year.Both a large amount of places had been occupied, and have seriously polluted environment, to national economy
Build, ecological environmental protection and whole society's sustainable development cause certain pressure.In recent years, chrome ore slag has been used as producing flat board
The colouring agent of green glass and blackish green beer bottle, it is all or part of to replace chromium oxide, waste is utilized, is generated obvious
Economic benefit and social benefit, but preventing and treating is badly in need of in resulting pollution of chromium.
Chromium harm to the human body is larger.The toxic dose of crome metal is 200mg, and lethal dose 6g, chromium poisoning can be by dust
Enter from respiratory tract, or contaminated food is entered by alimentary canal.Skin, the mucous membrane of human body can be damaged because of contact, poisoning symptom table
Be now schneiderian membrance ulcer and perforation of nasal septum, multiple ulcer arranged at oral cavity bottom, pharyngitis, tonsillitis, dermatitis, at skinfold
Ulcer, headache, dizziness, gastricism.Chromium ion valence state is different, and the extent of injury is also different.Cr VI and its esters are in chromic salts
Poisoning is maximum.The toxicity of Cr VI is than 100 times of trivalent chromium.Cr VI has stimulation to alimentary canal and skin, and Cr VI has
Carcinogenesis.Chromate waste water and skin contact, the dermatitis to mostly occur based on erythematous papules, eczema can be changed into.
At present, the method for domestic and international heavy-metal ion removal has a lot, and main method has the precipitation method, displacement method, solvent extraction
Take partition method, extration resin partition method, ion-exchange-resin process and chelating resin absorption method etc..The precipitation method and displacement method are mainly
Using various metals in itself intrinsic Wuli-Shili-Renli system approach and carry out separation and Extraction.Shortcoming is obvious：Device configuration
And complex operation, reagent consumption is big, seriously polluted etc..In the separation and concentration of heavy metal, the application of solvent extraction technology
It is more and more extensive.The shortcomings that technology, essentially consists in used extractant price mostly costly, and organic solvent is more volatile,
Environmental pollution is serious, and another common problem is to need to adjust feed liquid group before each heavy metal is extracted in Extraction of Heavy Metals
Into, and multitple extraction process is also cumbersome, also easily forms third phase sometimes.Mechanical strength of resin, extraction be present in extration resin partition method
The problems such as agent is lost in, current practice is seldom.Although oneself extraction and separation technology be applied in many fields, Hen Duocui
It is still serious to take pollution caused by flow.Ion exchange is one of classical separation method with adsorbing separation.But still suffer from system
About some factors of the technology practical application, the poor selectivity of the metal ion similar with radius to ion electricity.It is several above
The all selective difference of method heavy metal ion, it is impossible to be used in the shortcomings that high poison of going out valence state heavy metal ion, chelating resin is inhaled
Attached law of segregation is that basis carries the functional group containing different coordination atoms, chelate can be formed with metal cation, due to gold
It is different to belong to interionic valence electron structure, therefore the absorption to ion has higher selectivity.Chelating resin is a kind of counterweight
Metal ion has the functional material of certain selective adsorption capacity.But because some adsorption reactions occur in microballoon when eluting
Inside, influenceed by cross-linked network, have the shortcomings that conditions of streaking during elution, being so greatly lowered the repetition of chelating resin makes
Use efficiency.
Polytetrafluoroethylene (PTFE) (PTFE) fiber has fabulous chemical stability and higher specific surface area, thus and adsorbate
Contact area is bigger, fluid resistance is smaller, diffusion admittance is shorter, is easier with the reaction of function base, and adsorption capacity is big, selectively
Also more preferable, absorption and elution rate are also higher, while have that plasticity is strong, can be made it is various required for shape the advantages that.Cause
This, makes it connect various chelating function groups, the PTFE chelatings being prepared into are fine if surface graft modification can be carried out to PTFE fiber
Dimension would is that a kind of novel adsorption separation material very promising available for removal of heavy metal ions processing in environment or food
Material.
Caused chromate waste water in blackish green Improving Glass Manufacturing Processes, its metal ingredient contained include：Co(II)、Ni
(II), Se (II), Fe (III), Cr (VI), Cr (III).
The content of the invention
The technical problem to be solved in the present invention is to provide one kind to have efficient selective energy of adsorption to Cr (VI) ion
The chelate fibre NTHF of power synthetic method and the method for preventing and treating pollution of chromium in blackish green glass production accordingly.Using the present invention
Method can effectively realize absorption and reclaim the chromium in chromate waste water caused by blackish green glass production.
The present invention provides a kind of chelate fibre NTHF synthetic method, comprises the following steps：
1), with grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA) for parent, by grafted propylene acid polytetrafluoroethylene (PTFE)
Fiber (PTFE-g-AA) is placed in 12~14h of immersion in N,N-dimethylformamide；
2) part, is added in the gains of step 1), (for example, 12 is small within 11~14 hours in 30~50 DEG C of stirring reactions
When)；The part is hydroxyacyl hydroxyacyl hydrazine, and the mol ratio of parent and part is 1：2~6；
3), step 2) products therefrom is filtered, gained filter cake is dried to constant weight after flushing, obtains having Cr (VI)
There is the chelate fibre NTHF of efficient selective adsorption capacity.
As the improvement of the chelate fibre NTHF of present invention synthetic method, the flushing in step 3) is：Gained filter cake passes through
N,N-dimethylformamide, ether, ethanol, deionized water are rinsed successively.
As the further improvement of the chelate fibre NTHF of present invention synthetic method, grafted propylene acid poly- four in step 1)
The solid-liquid ratio of PVF fiber (PTFE-g-AA) and N,N-dimethylformamide is 20.0mg：40~60ml.
As the further improvement of the chelate fibre NTHF of present invention synthetic method, the drying in step 3) is：In 40
~60 DEG C of (preferably 50 DEG C) freeze-day with constant temperature.
As the further improvement of the chelate fibre NTHF of present invention synthetic method, the rotating speed of stirring is in step 2)
250~350rpm/min.
It is blackish green that the present invention also provides the preventing and treating carried out using the chelate fibre NTHF of above method synthesis gained simultaneously
The method of pollution of chromium in glass production：Caused waste water (the preceding place through Ge Shan and regulating reservoir into blackish green Improving Glass Manufacturing Processes
Waste water after reason) in add chelate fibre NTHF after, staticly settle, utilize the heavy metal in chelate fibre NTHF absorption waste water；
The heavy metal includes chromium.
Improvement as the method for pollution of chromium in the blackish green glass production of preventing and treating of the present invention：0.8 is added in per 1L waste water
~1.2g (preferably 1g) chelate fibre NTHF, the time is staticly settled as 36~60 hours (preferably 48 hours).
The chelate fibre NTHF being synthesized into using the inventive method, it has to Cr (VI) in hybrid piles solution
There is high efficiency selected absorption property.
Inventor, with density functional theory, selects the Ligand Model of different polymer, optimizes these during invention
Part forms the geometry of complex with Cr (VI) ion, is calculated with reference to energy, it is established that polymer is inhaled to metal ion
The evaluation model of attached ability, and correction factor is introduced on this basis, realize the quick theoretical screening to target ligand.
Products therefrom of the present invention is new chelate fibre NTHF, according to the content of N in product, the chelate fibre of synthesis
NTHF function base conversion ratio can be calculated by formula below (1) and (2)：
In above formula (1) and (2), F0For grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA) functional group content
(mmol/g), x be chelate fibre function base conversion ratio, N0Contain for grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA)
Nitrogen quantity (%), NcFor chelate fibre after synthesis (NTHF) nitrogen content (%), nNFor the quantity of nitrogen-atoms in grafting part, MLFor
It is grafted the molal weight (mol/g) of part.
Calculate NTHF function base conversion ratio be 57.3%.
Contain carboxyl (- COOH) in grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA) molecule, can with amino (-
NH2) condensation reaction formation acid amides occurs.The PTFE-g-AA can according to Chunhua Xiong, Caiping Yao,
Preparation and application of acrylic acid grafted polytetrafluoroethylene
fiber as a weak acid cation exchanger for adsorption of Er(III).Journal of
It is prepared by Hazardous Material, 170 (2009) 1125-1132.
Remarks explanation：Also name polytetrafluoroethylene (PTFE) grafted propylene is sour for grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA)
Copolymer, acrylic acid modified polytetrafluoroethylene fibre etc..
In the present invention, the nitrogen atom straight chain organic ligand that there is excellent chelating ability to Cr (VI) ion heavy metal is introduced
Hydroxyacyl hydroxyacyl hydrazine, chelate fibre NTHF composition principle signal formula are as follows：
Rinse in step 3) of the present invention (will gained filter cake through N,N-dimethylformamide, ether, ethanol, deionized water
Rinse successively) for conventional backwashing manner, DMF, ether, ethanol, the basic phase of the volumetric usage of deionized water
Together.
Chelate fibre NTHF is synthesized using the method for the present invention, had the following advantages that：
1st, the chelate fibre NTHF of gained has that raw material sources are extensive, cheap characteristic；
2nd, heavy metal ion has the rate of adsorption fast, and time of equilibrium adsorption is short, wherein, have efficiently to Cr (VI) ion
Adsorptive selectivity, the shortcomings that overcoming former parent adsorption selectivity difference.
3rd, possesses excellent regenerability, reusability is good, cost-effective, environmental protection.
Brief description of the drawings
The embodiment of the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 is the reaction principle figure of the present invention；
Fig. 2 is the influence for reacting mol ratio to parent function base conversion ratio；
Fig. 3 is influence of the reaction temperature to parent function base conversion ratio；
Fig. 4 is influence of the reaction time to parent function base conversion ratio；
Fig. 5 be under different pH value NTHF to the shadow of the adsorption capacity of the different ions such as metal ion Cr (VI), Cr (III)
Ring；
Fig. 6 is the different time influences of PS-MPP to metal ion Cr (VI) adsorbance with a temperature of；
Fig. 7 is waste water treatment process figure.
Embodiment
The present invention is further depicted as with reference to specific embodiment and comparative example, but present disclosure is not limited to
This.
Embodiment 1, a kind of method for synthesizing chelate fibre NTHF, are followed the steps below successively：
1), will about 20.0mg parents --- grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA) be placed in the three of 100mL
In neck bottle, add DMF 50mL and soak 12 hours；
Remarks explanation：In grafted propylene acid polytetrafluoroethylene fibre (PTFE-g-AA) PTFE-g-AA functions base (that is ,-
COOH) content is 3.07mmol/g.
2) 0.246mmol part, is added into three-necked bottle again --- hydroxyacyl hydroxyacyl hydrazine (that is, PTFE-g-AA and part it is anti-
It is 1 to answer mol ratio：4), 35 DEG C of stirring reactions 12 hours, agitator speed 300rpm/min.
3), products therefrom in step 2) is filtered, gained filter cake through DMF, ether, ethanol, go
Ionized water rinses 3 times successively, every in：N,N-dimethylformamide, ether, ethanol, the dosage of deionized water are 100ml；
By the filter cake after above-mentioned flushing be put into vacuum drying chamber under 40~60 DEG C of drying temperature dry to constant weight (when
Between about 3~5 days), obtain chelate fibre NTHF.
4), according to the content of N in products therefrom, calculate chelate fibre NTHF function base conversion ratio is 56.8%.
Cr (VI) ion in the NTHF adsorption aqueous solutions that experiment 1, embodiment 1 are prepared
The NTHF 15.0mg for weighing the gained of embodiment 1 are placed in 100mL iodine flask, move into 25mL pH=4 vinegar
Acid-sodium acetate buffer soaks 24 hours, then adds 5mL standards Cr (VI) (concentration 2mg/mL) solion,
Under 308K, constant temperature oscillation adsorbs after 12 hours reaches balance, and wherein frequency of oscillation is 100rpm.It is dense that quality is made into distilled water water
The hydrazine of diphenyl phosphinylidyne two spent for 0.2% is developer, and iodine flask supernatant is detected at ultraviolet-visible spectrophotometer 542nm
Middle Cr (VI) ion concentration, it is 106.5mg/g to the adsorbance of Cr (VI) ion to extrapolate NTHF.
Remarks explanation：For NTHF, pH=4 NaAc_HAc buffer solution is optimal, remaining pH vinegar
NTHF after acid-sodium acetate buffer immersion is below 106.5mg/g to the adsorbance of Cr (VI) ion.
Comparative example 1, the part in embodiment 1 is changed to 2- aminobenzothiazoles, 3- sulfydryls -1,2,4- three by hydroxyacyl hydroxyacyl hydrazine
Nitrogen azoles, 2- thenoyls hydrazine, 4-aminopyridine formamide, remaining is equal to embodiment 1.
Finally using grafted propylene acid polytetrafluoroethylene fibre as parent, DMF is reaction dissolvent, 2- ammonia
Base benzothiazole, 3- sulfydryl -1,2,4- triazoles, 2- thenoyls hydrazine, the chelate fibre that 4-aminopyridine formamide is part
Function base conversion ratio is respectively 40.7%, 21.3%, 9.41%, 16.7%.
Comparative example 2, the part in embodiment 1 is changed to 2- aminobenzothiazoles, 3- sulfydryls -1,2,4- three by hydroxyacyl hydroxyacyl hydrazine
Nitrogen azoles, 2- thenoyls hydrazine, 4-aminopyridine formamide, reaction dissolvent are changed to toluene, Isosorbide-5-Nitrae-two by DMF
The ring of oxygen six, acetone, remaining is equal to embodiment 1.
Finally using grafted propylene acid polytetrafluoroethylene fibre as parent, toluene, Isosorbide-5-Nitrae-dioxane, acetone are molten for reaction
Agent, 2- aminobenzothiazoles, 3- sulfydryls -1,2,4- triazoles, 2- thenoyls hydrazine, the chela that 4-aminopyridine formamide is part
Condensating fiber function base conversion ratio see the table below 1：
Table 1, different ligands the gained chelate fibre function base conversion ratio under differential responses solvent
Contrast experiment 1-1, using hydroxyacyl hydroxyacyl hydrazine as the chelate fibre obtained by ligand reaction, it will be changed in experiment 1 with 2- amino
Benzothiazole, 3- sulfydryl -1,2,4- triazoles, 2- thenoyls hydrazine, 4-aminopyridine formamide are the chela obtained by ligand reaction
Condensating fiber, remaining is equal to experiment 1.
Finally measure using grafted propylene acid polytetrafluoroethylene fibre as parent, 2- aminobenzothiazoles, 3- sulfydryls -1,2,4-
Triazole, 2- thenoyls hydrazine, 4-aminopyridine formamide are suction of the chelate fibre to Cr (VI) ion obtained by ligand reaction
Attached amount is respectively 87.1mg/g, 37.6mg/ml, 17.6mg/ml, 29.8mg/ml.
Contrast experiment 1-2, using hydroxyacyl hydroxyacyl hydrazine as the chelate fibre obtained by ligand reaction, it will be changed in experiment 1 with 2- amino
Benzothiazole, 3- sulfydryl -1,2,4- triazoles, 2- thenoyls hydrazine, 4-aminopyridine formamide are the chela obtained by ligand reaction
Condensating fiber, the pH of cushioning liquid Acetic acid-sodium acetate used are changed to 2.5,3.5,5.5,6.5 by 4, and remaining is equal to experiment 1.
Finally measure with 2- aminobenzothiazoles, 3- sulfydryl -1,2,4- triazoles, 2- thenoyls hydrazine, 4-aminopyridine
Formamide be ligand reaction obtained by chelate fibre, be changed to 2.5,3.5,5.5,6.5 by 4 in cushioning liquid pH, to Cr (VI) from
The adsorbance of son see the table below 2：
Table 2
The NTHF that experiment 2, embodiment 1 are prepared is in Cr (VI) and Cr (III), Pb (II), Cd (II), Fe (III), Mg
(II), the confirmatory experiment of the selective absorption in Ca (II) mixed ion solutions to Cr (VI) ion：
Mixed solution is prepared with compound chromic nitrate, potassium bichromate, Cr (VI) and Cr (III) ion concentration in mixed solution
It is 2mg/ml, specific experiment content is as follows：
Accurately weigh 15.0mg NTHF to be placed in 100mL iodine flask, the Acetic acid-sodium acetate for moving into 25mL pH=4 delays
Solution immersion 24h is rushed, then adds 5mL mixed ion solutions, under 308K, constant temperature oscillation adsorbs after 1 day reaches balance, wherein
Frequency of oscillation is 100rpm.
Remarks explanation：The measure of Cr (VI) ion concentration in mixed solution：Phosphoric acid (1:1) (concentrated phosphoric acid deionized water is dilute
Release 1 times), 0.2% diphenylcarbazide developer (water is solvent), at 542nm with ultraviolet-visible scene photometer detect inhale
Luminosity；
Cr (VI) ion concentration after adsorbing is calculated with following formula：
Chinese style CeCr (VI) ion concentration (mg/ml) during to balance, C0For Cr before absorption (VI) ion concentration (mg/ml), Ae
To measure Cr (VI) ion absorbance, A during balance0To measure Cr (VI) ion absorbance before absorption.
Other ion concentrations measure also uses ICP (inductively coupled plasma).
Final acquired results are that NTHF is 106.3mg/g to the adsorbance of Cr (VI) ion, and other ions are not inhaled substantially
It is attached, illustrate that NTHF chelate fibres have in the case of other ions such as Cr (VI) and Cr (III) are simultaneous to Cr (VI) ion
There is efficient specific selection performance.
Contrast experiment 2-1, using hydroxyacyl hydroxyacyl hydrazine as part gained chelate fibre, it will be changed in experiment 2 with 2- amino benzo thiophenes
Azoles is chelate fibre obtained by part, and remaining is equal to experiment 2.
Final to measure using 2- aminobenzothiazoles as part gained chelate fibre, the adsorbance to Cr (VI) ion is
87.1mg/g, the adsorbance to Cr (III) ion are 68.2mg/g.Illustrate that the chelating obtained by part is fine using 2- aminobenzothiazoles
Tie up in the case of Cr (VI) and Cr (III) ion are simultaneous to the selectivity of Cr (VI) ion not as using hydroxyacyl hydroxyacyl hydrazine as with
Chelate fibre obtained by body.
Experiment 3
Every part of 3 parts of NTHF fiber for 30.0mg present invention gained is accurately weighed, 50ml HAc-NaAc is separately added into and delays
Rush in solution (pH 4.0) after soaking 24 hours, add 10.0ml, 0.700mg/mL Cr (VI) solion is (for using high
Potassium manganate is formulated), adsorbed respectively at 15 DEG C, 25 DEG C, 35 DEG C with 100r/min speed constant temperature oscillation, the timing of interval one
Between after a small amount of solution measure concentration of metal ions of quantitative taking-up, until adsorption equilibrium.Acquired results are as shown in Figure 6.
According to Fig. 6, learn：It is all bigger in the rate of adsorption of incipient stage resin；As the progress of absorption, speed are gradual
Reduce；Finally reach balance.And the adsorbance with the rise resin heavy metal ion Cr (VI) of temperature also increases, by scheming
6 it can be seen that the NTHF fibers of the present invention are 3h to the time of equilibrium adsorption of hexavalent chromium.
Experiment 4, Cr (VI) ion regeneration tests
The CBDF tested in 1 after adsorption equilibrium is filtered out, is rinsed 3~5 times and (removed with pH=4 NaAc_HAc buffer solutions
Remove to float on Cr (VI) ion on surface), it is placed in iodine flask and (adsorption equilibrium in an experiment 1 is only put in an iodine flask
NTHF fibers), the thiourea solution 30mL of various concentrations is separately added into, is placed under the conditions of 308K, constant temperature oscillation 24h, frequency of oscillation
For 100rmp/min.It is respectively 94.6%, 100%, 100%, 100% to measure NTHF regeneration rates.From environmental protection and reduce into
This angle considers that the thiourea solution from concentration 6% is optimum N THF regenerative agents.
NTHF adsorbs the desorption efficiency of Cr (VI) ion under 3 different thiourea concentrations of table
Experiment 5, NTHF fibers are used for blackish green glass production wastewater treatment
Xie Ruzhen etc. exists《Wastewater Treatment Technology for Glass Industry and research》One text proposes that a kind of glass manufactory waste water processing improves work
Skill, pollutant (oils, COD, suspension, fluorine-containing thing) concentration of waste discharge is effectively reduced, but article finally also indicates that now
There is the non-heavy metal pollution of handling process to carry out specific aim processing, therefore abundant to blackish green glass production wastewater treatment present situation
On the basis of grasp, using the NTHF fibers of the present invention, can Cr (VI) in the blackish green glass production waste water of specific aim Adsorption,
As shown in Figure 7：
Remarks explanation：Pre-treatment of the waste water through Ge Shan and regulating reservoir be prior art (that is, according to《Glass manufactory waste water processing
Analysis and research》Handled), after testing, Cr (VI) concentration (mg/L) is 92mg/L to the waste water of gained after pre-treatment；Also include
Other metals of following concentration：
| Co(II) | Ni(II) | Se(II) | Fe(III) | Cr(III) |
| 20mg/L | 83mg/L | 14mg/L | 57mg/L | 23mg/L |
Amount ratio after above-mentioned preceding processing in the waste water of gained according to " 1L waste water adapted 1g fibers " adds fiber, fiber
Waste water after adsorption treatment detects, acquired results such as following table through natural sedimentation 48 hours to Cr (VI) concentration in waste water
It is described.
Remarks explanation：After precipitation process without chrome waste water carry out subsequent treatment be prior art (that is, according to《Glass factory gives up
Water process is analyzed and research》Handled).
Blackish green glass production waste water (V/L)：Synthetic fibers quality (M/g)=1:1
Experiment shows, under concrete application environment, compared to other during the blackish green glass production waste water of NTHF fiber treatments
Fiber shows good stability, and absorption property is not disturbed by other environmental factors, and this is the crucial skill that this process is realized
Art, and the innovation of this patent.The concentration of Cr VI reaches in blackish green glass production waste water after NTHF fiber treatments
Standard when country discharges on high concentration chrome wastewater is arrived, so as to avoid producing hexavalent chromium polluted problem.
Finally, it is also necessary to it is noted that listed above is only several specific embodiments of the invention.Obviously, this hair
It is bright to be not limited to above example, there can also be many deformations.One of ordinary skill in the art can be from present disclosure
All deformations for directly exporting or associating, are considered as protection scope of the present invention.
Claims (7)
1. the chelate fibre NTHF synthetic method for preventing and treating pollution of chromium in blackish green glass production can be used for, it is characterized in that including with
Lower step：
1）, using grafted propylene acid polytetrafluoroethylene fibre as parent, grafted propylene acid polytetrafluoroethylene fibre is placed in N, N- bis-
12 ~ 14h is soaked in NMF；
2）, in step 1）Gains in add part, in 30 ~ 50 DEG C of stirring reactions 11 ~ 14 hours；The part is nicotinic acid acyl
The mol ratio of hydrazine, parent and part is 1：2~6；
3）, by step 2）Products therefrom is filtered, and gained filter cake is dried to constant weight after flushing, obtains having height to Cr (VI)
The chelate fibre NTHF of selective adsorption capacity.
2. chelate fibre NTHF according to claim 1 synthetic method, it is characterized in that：
Step 3）In flushing be：Gained filter cake rinses successively through N,N-dimethylformamide, ether, ethanol, deionized water.
3. chelate fibre NTHF according to claim 1 or 2 synthetic method, it is characterized in that：
Step 1）The solid-liquid ratio of middle grafted propylene acid polytetrafluoroethylene fibre and N,N-dimethylformamide is 20.0mg：40~
60mL。
4. chelate fibre NTHF according to claim 3 synthetic method, it is characterized in that：
Step 3）In drying be：In 40 ~ 60 DEG C of freeze-day with constant temperature.
5. chelate fibre NTHF according to claim 4 synthetic method, it is characterized in that：
Step 2）The rotating speed of middle stirring is 250 ~ 350rpm/min.
6. the blackish green glass production of preventing and treating of the chelate fibre NTHF progress of gained is synthesized using such as claim 1 ~ 5 either method
The method of middle pollution of chromium, it is characterized in that：After chelate fibre NTHF being added into blackish green Improving Glass Manufacturing Processes in caused waste water,
Staticly settle, the Cr (VI) in waste water is adsorbed using chelate fibre NTHF.
7. the method for pollution of chromium in the blackish green glass production of preventing and treating according to claim 6, it is characterized in that：Per in 1L waste water
0.8 ~ 1.2g chelate fibre NTHF are added, staticly settle the time as 36 ~ 60 hours.
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