CN105174351A - Method of preventing and controlling chromium pollution in dark green glass production and used chelate fiber - Google Patents
Method of preventing and controlling chromium pollution in dark green glass production and used chelate fiber Download PDFInfo
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- CN105174351A CN105174351A CN201510567196.7A CN201510567196A CN105174351A CN 105174351 A CN105174351 A CN 105174351A CN 201510567196 A CN201510567196 A CN 201510567196A CN 105174351 A CN105174351 A CN 105174351A
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Abstract
The invention discloses a synthetic method of a chelate fiber NTHF. The synthetic method comprises the steps of taking a grafting acrylic acid polytetrafluoroethylene fiber as a parent, and soaking the grafting acrylic acid polytetrafluoroethylene fiber into N,N-dimethyl formamide; then, adding a ligand for stirring and reacting; filtering a product obtained through reacting, washing an obtained filter cake and drying to constant weight, so as to obtain the chelate fiber NTHF which has high preferential adsorption capability to Cr(VI). The invention also discloses a method of preventing and controlling chromium pollution in dark green glass production. The method comprises the steps of after adding the chelate fiber NTHF into wastewater generated in a dark green glass production process, performing static settlement, and absorbing heavy metal in the wastewater by utilizing the chelate fiber NTHF; the heavy metal comprises chromium. By adopting the method provided by the invention, the chromium in chromate waste water generated in the dark green glass production can be absorbed and recycled effectively.
Description
Technical field
The present invention relates to a kind of method of synthesizing new chelate fibre, be specifically related to graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) as parent, with hydroxyacyl hydroxyacyl hydrazine (NTH) for part, thus synthesis has the chelate fibre NTHF of high efficiency selected absorption property to Cr (VI) ion, for preventing and treating the method for 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 occupy a large amount of place, again serious environment pollution, cause certain pressure to the development of the national economy, ecological environmental protection and whole society's Sustainable development.In recent years, chrome ore slag has been used as the tinting material producing dull and stereotyped green glass and blackish green Beer Bottle, and all or part of replacement chromic oxide, makes refuse obtain utilization, creates obvious economic benefit and social benefit, but control is badly in need of in consequent pollution of chromium.
Chromium is larger to harm.The toxic dose of chromium metal is 200mg, and lethal dose is 6g, and chromium poisoning can be entered from respiratory tract by dust, or contaminated food is entered by digestive tube.Skin, the mucous membrane of human body can be impaired because of contact, and toxicity symptom shows as nasal mucosa ulcer and perforation of nasal septum, has multiple ulcer bottom oral cavity, pharyngitis, tonsillitis, dermatitis, skinfold place ulcer, headache, dizziness, gastricism.Chromium ion valence state is different, and hazard rating is also different.Sexavalent chrome and its esters maximum in chromic salts toxic.Chromic toxicity ratio trivalent chromium 100 times.Sexavalent chrome has hormesis to digestive tube and skin, and sexavalent chrome has carcinogenesis.Chromate waste water and skin contact, the dermatitis mostly occurred based on erythematous papules, can change eczema into.
At present, the method for domestic and international heavy-metal ion removal has a lot, and main method has the precipitator method, substitution method, solvent extraction and separation method, extration resin partition method, ion-exchange-resin process and resin absorption method etc.The precipitator method and substitution method mainly utilize the intrinsic Wuli-Shili-Renli system approach of various metal itself and carry out separation and Extraction.Shortcoming is apparent: Equipments Setting and complex operation, and reagent consumption is large, seriously polluted etc.In the separation and concentration of heavy metal, the application of solvent extraction technology is more and more extensive.The shortcoming of this technology is mainly that used extraction agent price mostly costly, organic solvent is more volatile, environmental pollution is serious, in Extraction of Heavy Metals, another ubiquitous problem is before each heavy metal of extraction, need adjustment feed liquid composition, and multi-stage solvent extraction process is also more loaded down with trivial details, sometimes also easily forms third phase.There is the problem such as mechanical strength of resin, extraction agent loss in extration resin partition method, current practical application is little.Although extraction and separation technology oneself be applied in a lot of fields, the pollution that a lot of extraction procedure causes is still serious.Ion-exchange and fractionation by adsorption are one of separation methods of classics.But still there are some factors of this technology practical application of restriction, to the poor selectivity of the metal ion of ion electricity and similar radius.The all selective difference of above several method heavy metal ion, the shortcoming of high malicious valence state heavy metal ion can not be used for away, resin fractionation by adsorption rule is that basis is with the functional group containing different ligating atom, energy and metallic cation form inner complex, because the valence electron structure between metal ion is different, therefore to the absorption of ion, there is higher selectivity.Resin is the functional materials that a kind of heavy metal ion has certain selective adsorption capacity.But because some absorption reaction occurs in microballoon inside during wash-out, by the impact of cross-linked network, have the shortcomings such as conditions of streaking during wash-out, what so just greatly reduce resin reuses efficiency.
Tetrafluoroethylene (PTFE) fiber has fabulous chemical stability and higher specific surface area, thus with adsorbate contact area is larger, fluid resistance is less, diffusion admittance is shorter, easier with the reaction of function base, loading capacity is large, selectivity is also better, absorption and elution rate also higher, there is plasticity-strong simultaneously, the advantages such as various required shapes can be made.Therefore, make it connect various chelating function group if can carry out surface graft modification to PTFE fiber, then the PTFE chelate fibre be prepared into will be a kind ofly can be used for the very promising Novel adsorption parting material of removal of heavy metal ions process in environment or food.
The chromate waste water produced in blackish green Improving Glass Manufacturing Processes, its metal ingredient contained comprises: Co (II), Ni (II), Se (II), Fe (III), Cr (VI), Cr (III).
Summary of the invention
The technical problem to be solved in the present invention is to provide one in order to have the synthetic method of the chelate fibre NTHF of efficient selective adsorptive power and corresponding method of preventing and treating pollution of chromium in blackish green glass production to Cr (VI) ion.Adopt method of the present invention effectively can realize the chromium adsorbed and reclaim in the chromate waste water of blackish green glass production generation.
The invention provides the synthetic method of a kind of chelate fibre NTHF, comprise the following steps:
1), with graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) for parent, graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) is placed in DMF and soaks 12 ~ 14h;
2), in step 1) gains in add part, in 30 ~ 50 DEG C of stirring reactions 11 ~ 14 hours (being such as 12 hours); Described part is hydroxyacyl hydroxyacyl hydrazine, and the mol ratio of parent and part is 1:2 ~ 6;
3), by step 2) products therefrom filters, and gained filter cake is dried to constant weight after rinsing, and obtains chelate fibre NTHF Cr (VI) to efficient selective adsorptive power.
As the improvement of the synthetic method of chelate fibre NTHF of the present invention, step 3) in flushing be: gained filter cake rinses successively through DMF, ether, ethanol, deionized water.
As the further improvement of the synthetic method of chelate fibre NTHF of the present invention, step 1) in graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) be 20.0mg:40 ~ 60ml with the solid-liquid ratio of DMF.
As the further improvement of the synthetic method of chelate fibre NTHF of the present invention, step 3) in drying be: in 40 ~ 60 DEG C of (being preferably 50 DEG C) freeze-day with constant temperature.
As the further improvement of the synthetic method of chelate fibre NTHF of the present invention, step 2) in the rotating speed that stirs be 250 ~ 350rpm/min.
The present invention also provides the method for pollution of chromium in utilize aforesaid method the to synthesize blackish green glass production of control that the chelate fibre NTHF of gained carries out simultaneously: after adding chelate fibre NTHF in the waste water that produces in blackish green Improving Glass Manufacturing Processes (waste water after the pre-treatment of Ge Shan and equalizing tank), staticly settle, utilize the heavy metal in chelate fibre NTHF absorption waste water; Described heavy metal comprises chromium.
Improvement as the method for pollution of chromium in the blackish green glass production of control of the present invention: add 0.8 ~ 1.2g (being preferably 1g) chelate fibre NTHF in every 1L waste water, the time of staticly settling is 36 ~ 60 hours (being preferably 48 hours).
Adopt the chelate fibre NTHF that the inventive method is synthesized into, it has high efficiency selected absorption property to Cr (VI) in hybrid piles solution.
Contriver is in invention process, use density functional theory, select the Ligand Model of different polymkeric substance, optimize the geometry that these parts and Cr (VI) ion form title complex, calculate and combine energy, set up the evaluation model of polymkeric substance to adsorption of metal ions ability, and introduce correction factor on this basis, realize the quick theory screening to target ligand.
Products therefrom of the present invention is novel chelate fibre NTHF, and according to the content of N in product, the function base transformation efficiency of the chelate fibre NTHF of synthesis is by formula (1) and (2) calculating below:
In above formula (1) and (2), F
0for graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) functional group content (mmol/g), x is the function base transformation efficiency of chelate fibre, N
0for graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) nitrogen content (%), N
cfor synthesizing the nitrogen content (%) of rear chelate fibre (NTHF), n
nfor the quantity of nitrogen-atoms in grafting part, M
lfor the molar mass (mol/g) of grafting part.
The function base transformation efficiency calculating NTHF is 57.3%.
Containing carboxyl (-COOH) in graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) molecule, can with amino (-NH
2) there is condensation reaction formation acid amides.This PTFE-g-AA can according to ChunhuaXiong, CaipingYao, Preparationandapplicationofacrylicacidgraftedpolytetrafl uoroethylenefiberasaweakacidcationexchangerforadsorption ofEr (III) .JournalofHazardousMaterial, 170 (2009) 1125 – 1132 are prepared.
Remarks illustrate: graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) is name tetrafluoroethylene grafted propylene acid copolymer, acrylic acid modified polytetrafluoroethylene fiber etc. also.
In the present invention, introduce nitrogen atom straight chain organic ligand hydroxyacyl hydroxyacyl hydrazine Cr (VI) ion heavy metal to excellent chelating ability, the composition principle signal formula of chelate fibre NTHF is as follows:
Step 3 of the present invention) in rinse (by gained filter cake through N, dinethylformamide, ether, ethanol, deionized water rinse successively) be conventional backwashing manner, the volumetric usage of DMF, ether, ethanol, deionized water is substantially identical.
Adopt method of the present invention to synthesize chelate fibre NTHF, tool has the following advantages:
1, the chelate fibre NTHF of gained has raw material sources extensively, cheap characteristic;
2, heavy metal ion has adsorption rate soon, and time of equilibrium adsorption is short, wherein, has efficient adsorption selectivity to Cr (VI) ion, overcomes the shortcoming of former parent adsorption selectivity difference.
3, possess excellent regenerability, reusability is good, cost-saving, protection of the environment.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is reaction principle figure of the present invention;
Fig. 2 is that reaction mol ratio is on the impact of parent function base transformation efficiency;
Fig. 3 is the impact of temperature of reaction on parent function base transformation efficiency;
Fig. 4 is the impact of reaction times on parent function base transformation efficiency;
Fig. 5 be under different pH value NTHF on the impact of the loading capacity of the different ions such as metal ion Cr (VI), Cr (III);
Fig. 6 be at different time and temperature PS-MPP on the impact of the adsorptive capacity of metal ion Cr (VI);
Fig. 7 is waste water treatment process figure.
Embodiment
Describe the present invention further below in conjunction with specific embodiment and comparative example, but content of the present invention is not limited to this.
Embodiment 1, a kind of method of synthesizing chelate fibre NTHF, carry out following steps successively:
1), by about 20.0mg parent---graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) is placed in the three-necked bottle of 100mL, adds DMF 50mL and soaks 12 hours;
Remarks illustrate: PTFE-g-AA function base (that is ,-COOH) content in graft acrylic acid polytetrafluoroethylene fiber (PTFE-g-AA) is 3.07mmol/g.
2), in three-necked bottle, add part---the hydroxyacyl hydroxyacyl hydrazine (that is, the reaction mol ratio of PTFE-g-AA and part is 1:4) of 0.246mmol again, 35 DEG C of stirring reactions 12 hours, agitator speed is 300rpm/min.
3), by step 2) in products therefrom filter, gained filter cake is through N, dinethylformamide, ether, ethanol, deionized water rinse 3 times successively, often all in: the consumption of DMF, ether, ethanol, deionized water is 100ml;
Filter cake after above-mentioned flushing is put into vacuum drying oven under the drying temperature of 40 ~ 60 DEG C, be dried to constant weight (time is about 3 ~ 5 days), obtain chelate fibre NTHF.
4), according to the content of N in products therefrom, the function base transformation efficiency calculating chelate fibre NTHF is 56.8%.
Cr (VI) ion in the NTHF adsorption aqueous solution that experiment 1, embodiment 1 are prepared and obtained
The NTHF15.0mg taking embodiment 1 gained is placed in the iodine flask of 100mL, the NaAc_HAc buffer solution moving into the pH=4 of 25mL soaks 24 hours, then 5mL standard C r (VI) (concentration is 2mg/mL) solion is added, under 308K, constant temperature oscillation adsorbs after 12 hours and reaches balance, and wherein oscillation frequency is 100rpm.With distilled water water be made into mass concentration be 0.2% phenylbenzene phosphinylidyne two hydrazine be developer, Cr (VI) ionic concn in iodine flask supernatant liquor is detected at ultraviolet-visible spectrophotometer 542nm place, and extrapolating the adsorptive capacity of NTHF to Cr (VI) ion is 106.5mg/g.
Remarks illustrate: for NTHF, and the NaAc_HAc buffer solution of pH=4 be best, the NTHF after the NaAc_HAc buffer solution immersion of all the other pH to the adsorptive capacity of Cr (VI) ion all lower than 106.5mg/g.
Comparative example 1, change the part in embodiment 1 into 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide by hydroxyacyl hydroxyacyl hydrazine, all the other are equal to embodiment 1.
Final with graft acrylic acid polytetrafluoroethylene fiber for parent, N, dinethylformamide is reaction solvent, 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide are that the chelate fibre function base transformation efficiency of part is respectively 40.7%, 21.3%, 9.41%, 16.7%.
Comparative example 2, change the part in embodiment 1 into 2-aminobenzothiazole, 3-sulfydryl-1 by hydroxyacyl hydroxyacyl hydrazine, 2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide, reaction solvent is by N, dinethylformamide changes toluene, 1 into, 4-dioxane, acetone, all the other are equal to embodiment 1.
Final with graft acrylic acid polytetrafluoroethylene fiber for parent, toluene, Isosorbide-5-Nitrae-dioxane, acetone are reaction solvent, 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide are that the chelate fibre function base transformation efficiency of part sees the following form 1:
Table 1, different ligands be gained chelate fibre function base transformation efficiency under differential responses solvent
Contrast experiment 1-1, the chelate fibre in experiment 1 with hydroxyacyl hydroxyacyl hydrazine will being ligand reaction gained, change into 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide are the chelate fibre of ligand reaction gained, and all the other are equal to experiment 1.
Finally record with graft acrylic acid polytetrafluoroethylene fiber as parent, 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide are that the adsorptive capacity of chelate fibre to Cr (VI) ion of ligand reaction gained is respectively 87.1mg/g, 37.6mg/ml, 17.6mg/ml, 29.8mg/ml.
Contrast experiment 1-2, the chelate fibre in experiment 1 with hydroxyacyl hydroxyacyl hydrazine will being ligand reaction gained, change into 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide are the chelate fibre of ligand reaction gained, the pH of buffered soln Acetic acid-sodium acetate used changes 2.5,3.5,5.5,6.5 into by 4, and all the other are equal to experiment 1.
Finally record with 2-aminobenzothiazole, 3-sulfydryl-1,2,4-triazole, 2-thenoyl hydrazine, 4-aminopyridine methane amide are the chelate fibre of ligand reaction gained, change 2.5,3.5,5.5,6.5 at buffered soln pH into by 4, see the following form 2 to the adsorptive capacity of Cr (VI) ion:
Table 2
The confirmatory experiment of NTHF to the selective adsorption of Cr (VI) ion in Cr (VI) and Cr (III), Pb (II), Cd (II), Fe (III), Mg (II), Ca (II) mixed ion solutions that experiment 2, embodiment 1 are prepared and obtained:
With compound chromium nitrate, potassium bichromate preparation mixing solutions, in mixing solutions, Cr (VI) and Cr (III) ionic concn are 2mg/ml, and specific experiment content is as follows:
Accurately take the iodine flask that 15.0mgNTHF is placed in 100mL, the NaAc_HAc buffer solution moving into the pH=4 of 25mL soaks 24h, then adds 5mL mixed ion solutions, under 308K, constant temperature oscillation 1 day afterwards absorption reaches balance, and wherein oscillation frequency is 100rpm.
Remarks illustrate: the mensuration of Cr (VI) ionic concn in mixing solutions: phosphoric acid (1:1) (strong phosphoric acid deionized water dilutes 1 times), 0.2% diphenylcarbazide developer (water is solvent), detect absorbancy at 542nm place with ultraviolet-visible scene photometer;
Rear Cr (VI) ionic concn of absorption is calculated with following formula:
Chinese style C
efor Cr (VI) ionic concn (mg/ml) during balance, C
0for adsorbing front Cr (VI) ionic concn (mg/ml), A
ecr (VI) ion absorbancy is recorded, A for during balance
0for recording Cr (VI) ion absorbancy before absorption.
Other ionic concns measure and also use ICP (inductively coupled plasma).
Final acquired results is the adsorptive capacity of NTHF to Cr (VI) ion is 106.3mg/g, other ions are not adsorbed substantially, illustrates that NTHF chelate fibre has efficient specific selectivity to Cr (VI) ion in the simultaneous situations of other ions such as Cr (VI) and Cr (III).
Contrast experiment 2-1, will take hydroxyacyl hydroxyacyl hydrazine as part gained chelate fibre in experiment 2, change into 2-aminobenzothiazole for part gained chelate fibre, all the other be equal to experiment 2.
Finally recording with 2-aminobenzothiazole for part gained chelate fibre, is 87.1mg/g to the adsorptive capacity of Cr (VI) ion, is 68.2mg/g to the adsorptive capacity of Cr (III) ion.Illustrate with 2-aminobenzothiazole for part gained chelate fibre under Cr (VI) and the simultaneous situation of Cr (III) ion to the chelate fibre of the selectivity of Cr (VI) ion not as taking hydroxyacyl hydroxyacyl hydrazine as part gained.
Experiment 3
Accurately take the NTHF fiber 3 parts of the gained of the present invention that every part is 30.0mg, add respectively in 50mlHAc-NaAc buffered soln (pH is 4.0) and soak after 24 hours, add 10.0ml, Cr (VI) solion (for adopting potassium permanganate formulated) of 0.700mg/mL, adsorb with the speed constant temperature oscillation of 100r/min at 15 DEG C, 25 DEG C, 35 DEG C respectively, the measured in solution concentration of metal ions that taking-up quantitative after separated in time is a small amount of, until adsorption equilibrium.Acquired results as shown in Figure 6.
According to Fig. 6, learn: all larger in the adsorption rate of initial stage resin; Along with the carrying out of absorption, speed reduces gradually; Finally reach balance.And along with the adsorptive capacity of rising resin heavy metal ion Cr (VI) of temperature also increases, NTHF fiber of the present invention is 3h to the time of equilibrium adsorption of hexavalent chromium as seen from Figure 6.
Experiment 4, Cr (VI) ion regeneration tests
CBDF after adsorption equilibrium in experiment 1 is leached, rinse 3 ~ 5 times (removing floats on Cr (VI) ion on surface) with pH=4 NaAc_HAc buffer solution, be placed in iodine flask (iodine flask only puts the NTHF fiber of experiment 1 adsorption equilibrium), add the thiourea solution 30mL of different concns respectively, under being placed in 308K condition, constant temperature oscillation 24h, oscillation frequency is 100rmp/min.Record NTHF regeneration rate and be respectively 94.6%, 100%, 100%, 100%.From environment protection and reduce costs angle consider, select the thiourea solution of concentration 6% to be optimum N THF regenerator.
Under the different thiourea concentration of table 3, NTHF adsorbs the desorption efficiency of Cr (VI) ion
Experiment 5, NTHF fiber are used for blackish green glass production wastewater treatment
Xie Ruzhen etc. propose a kind of glass manufactory waste water process improving technique at " Wastewater Treatment Technology for Glass Industry and research " one literary composition, effectively reduce pollutent (oils, COD, suspended substance, the fluorine-containing thing) concentration of waste discharge, but article is finally also pointed out that the non-heavy metal of existing treatment process is polluted and is carried out specific aim process, therefore on the basis that blackish green glass production wastewater treatment present situation is fully grasped, adopt NTHF fiber of the present invention, Cr (VI) in the blackish green glass production waste water of energy specific aim Adsorption, as shown in Figure 7:
Remarks illustrate: waste water through the pre-treatment of Ge Shan and equalizing tank be prior art (namely, process according to " Wastewater Treatment Technology for Glass Industry and research "), after pre-treatment, the waste water of gained after testing, and Cr (VI) concentration (mg/L) is 92mg/L; Also comprise 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 |
After above-mentioned pre-treatment gained waste water in add fiber according to the amount ratio of " 1L waste water adapted 1g fiber ", waste water after fibers adsorption process was through natural sedimentation 48 hours, detect Cr (VI) concentration in waste water, acquired results as in the table below.
Remarks illustrate: after precipitation process to carry out subsequent disposal without chrome waste water be prior art (that is, processing according to " Wastewater Treatment Technology for Glass Industry and research ").
Blackish green glass production waste water (V/L): synthon quality (M/g)=1:1
Test shows, under embody rule environment, show satisfactory stability during the blackish green glass production waste water of NTHF fiber treatment compared to other fibers, absorption property is by the interference of other environmental factorss, this is the gordian technique of this process implementation, is also the innovation of this patent.In blackish green glass production waste water after NTHF fiber treatment, chromic concentration reaches standard when country discharges about high concentration chrome wastewater, thus avoids producing hexavalent chromium polluted problem.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (7)
1. the synthetic method of chelate fibre NTHF, is characterized in that comprising the following steps:
1), with graft acrylic acid polytetrafluoroethylene fiber for parent, graft acrylic acid polytetrafluoroethylene fiber is placed in DMF and soaks 12 ~ 14h;
2), in step 1) gains in add part, in 30 ~ 50 DEG C of stirring reactions 11 ~ 14 hours; Described part is hydroxyacyl hydroxyacyl hydrazine, and the mol ratio of parent and part is 1:2 ~ 6;
3), by step 2) products therefrom filters, and gained filter cake is dried to constant weight after rinsing, and obtains chelate fibre NTHF Cr (VI) to high-selectivity adsorption ability.
2. the synthetic method of chelate fibre NTHF according to claim 1, is characterized in that:
Step 3) in flushing be: gained filter cake rinses successively through DMF, ether, ethanol, deionized water.
3. the synthetic method of chelate fibre NTHF according to claim 1 and 2, is characterized in that:
Step 1) in the solid-liquid ratio of graft acrylic acid polytetrafluoroethylene fiber and DMF be 20.0mg:40 ~ 60ml.
4. the synthetic method of chelate fibre NTHF according to claim 3, is characterized in that:
Step 3) in drying be: in 40 ~ 60 DEG C of freeze-day with constant temperature.
5. the synthetic method of chelate fibre NTHF according to claim 4, is characterized in that:
Step 2) in stir rotating speed be 250 ~ 350rpm/min.
6. the method for pollution of chromium in the blackish green glass production of control utilizing the chelate fibre NTHF as Claims 1 to 5 either method synthesis gained to carry out, it is characterized in that: after adding chelate fibre NTHF in the waste water produced in blackish green Improving Glass Manufacturing Processes, staticly settle, utilize the heavy metal in chelate fibre NTHF absorption waste water; Described heavy metal comprises chromium.
7. the method for pollution of chromium in the blackish green glass production of control according to claim 6, is characterized in that: add 0.8 ~ 1.2g chelate fibre NTHF in every 1L waste water, the time of staticly settling is 36 ~ 60 hours.
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| CN115677883A (en) * | 2022-10-24 | 2023-02-03 | 中汽创智科技有限公司 | Modified polytetrafluoroethylene, preparation method thereof and application thereof in membrane electrode |
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| US20090274634A1 (en) * | 2008-05-05 | 2009-11-05 | Capture Technologies, Inc. | Novel crosslinked polymeric substrates methods of preparation and end use applications of the substrates |
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