CN107312178A - A kind of preparation method and applications of hydroxyl phosphonitrilic polymer - Google Patents
A kind of preparation method and applications of hydroxyl phosphonitrilic polymer Download PDFInfo
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- CN107312178A CN107312178A CN201710497653.9A CN201710497653A CN107312178A CN 107312178 A CN107312178 A CN 107312178A CN 201710497653 A CN201710497653 A CN 201710497653A CN 107312178 A CN107312178 A CN 107312178A
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- hydroxyl
- ammonia
- phosphonitrilic
- phosphonitrilic polymer
- polymer
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 49
- 229920000642 polymer Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 31
- 239000000975 dye Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 239000008096 xylene Substances 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 15
- -1 amino, imino group Chemical group 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 230000000640 hydroxylating effect Effects 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000003443 Unconsciousness Diseases 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000005499 phosphonyl group Chemical group 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/025—Polyphosphazenes
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a kind of preparation method and applications of hydroxyl phosphonitrilic polymer, this method is after hexachlorocyclotriph,sphazene addition xylene solvent is fully dissolved, in less than 5 DEG C, whisk and be at the uniform velocity passed through dry ammonia reaction, after 2 4h of reaction, stopping is filled with ammonia, the ammonia for making reactor be in air-tight state, bottle continues to react with hexachlorocyclotriph,sphazene, in placement 8 12 hours under normal temperature, then obtained mixture suction filtration removal solvent will be reacted, filter cake obtains white powdery solids after drying.By white solid in being taken out after high-temperature polycondensation 30min, it is put into air and is cooled to room temperature.Polycondensation product is distributed to after being washed repeatedly in deionized water, in being dried under vacuum to constant weight at 90 DEG C, that is, obtains water insoluble hydroxyl phosphonitrilic polymer.Material of the present invention prepares fairly simple, environmental protection, reliable and stable, material and is easy to get, implements easily, and prepared material has good adsorption effect to the dyestuff in waste water, heavy metal ion.
Description
Technical field
The present invention relates to the technical field of wastewater treatment sorbing material, a kind of preparation of hydroxyl phosphonitrilic polymer is referred in particular to
Method and its application.
Background technology
Current water pollution is a global problem, and particularly some developing countries for being directed to developing the economy come
Say, heavy contaminating enterprises concentrate, and the sewage disposal technology and the idea of backwardness that fall behind force them to be polluted in unconscious
Environment;But in face of the reality of scarcity of fresh water resources, increasing people takes up to try every possible means to look for solution, but due to
The discharge capacity of industrial wastewater is huge, and intractability is big, handles not thorough, ultimately results in many pollutants and more or less enters nature
In water body.The characteristics of dyeing waste water is that concentration is high, water is big, ingredient is complicated, colourity is big, and various chemical industry are contained among waste water
Dyestuff.Typically, since chemical dye belongs to the organic compound of difficult degradation, thus chemical dye in water body chemically
Matter is typically more stable, so can be stranded in water body environment, and is difficult in the short time by Institute of Micro-biology's drop in environment
Solution.Heavy metal can not be degraded, but it can be enriched with animals and plants, and the mankind are the tops of biological chain, so as the mankind eat
After the animals and plants of these heavy metal pollutions, its harmful heavy metal element is enriched with human body, most harmful to human at last it is strong
Health.According to the standard of China's sewage discharge, total cadmium, total lead belong to the first pollutant, and highest permission concentration of emission is respectively
0.1mg/L and 1.0mg/L;Total copper belongs to the second pollutant, it is allowed to one-level level discharge standard concentration be respectively 0.5mg/L.
Therefore, before discharge heavy metal wastewater thereby, it is necessary to strictly remove this metal ion (or being reduced under permission concentration of emission),
It so just can guarantee that the health of water environment.In numerous pollution treatment methods, absorption method is because having low cost, efficiency high and appearance
The advantages of easily operating continuously, it is considered to be comparatively ideal advanced treating dyestuff and Treatment On The Wasterwater of Containing Heavy Metalions.Adsorption material
The main organic and/or inorganic materials of matrix, organic polymer and the class of biomaterial three of material, these sorbing materials typically contain hydroxyl, carboxylic
The functional groups such as base, Ryukyu's base, phosphate radical, amido, but the research of the sorbing material containing phosphonyl group is relatively fewer, but its energy
Chelating ligands key is formed with cation (dye of positive ion, metal ion), so that with certain adsorption capacity.Existing absorption
Material has that adsorbance is small, the problem of each side such as separation is difficult, to recycle and reuse rate low, therefore design and exploitation are a kind of
Adsorbance is big, and removal efficiency is high, and the rate of adsorption is fast, high-performance adsorbent material that is efficiently easily reclaiming, can repeatedly regenerate is inevitable
Pursuit.The present invention for important source material, is developed a kind of new hydroxyl phosphonitrilic polymer and used with hexachlorocyclotriph,sphazene (HCCP)
Make sorbing material, and the dyestuff and heavy metal ion being applied in processing waste water.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of system of hydroxyl phosphonitrilic polymer with shortcoming
Preparation Method and its application, material of the present invention prepare fairly simple, environmental protection, reliable and stable, material and are easy to get, implement easily, institute
The material of preparation has good adsorption effect to the dyestuff in waste water, heavy metal ion, to different types of dyestuff, heavy metal
The adsorption capacity of ion is different, shows good adsorptive selectivity.
To achieve the above object, technical scheme provided by the present invention is as follows:
A kind of preparation method of hydroxyl phosphonitrilic polymer, comprises the following steps:
1) ammonia replaces
Hexachlorocyclotriph,sphazene by purification is added in the incomplete closed reactor for fill xylene solvent fully
After dissolving, 25~100g/L is configured to, is whisked in less than 5 DEG C and is at the uniform velocity continually fed into dry ammonia, course of reaction can engender
White precipitate material, after reaction 2-4h, stopping is filled with ammonia, reactor is in air-tight state, and ammonia in bottle after
Continuous to be reacted with hexachlorocyclotriph,sphazene, the suction filtration after being placed 8-12 hours under normal temperature, filter cake dries naturally, obtains white powder and consolidates
Body;
2) high-temperature polycondensation and hydroxylating
White powdery solids obtained above are put into drying baker, in taken out after 120~150 DEG C of polycondensation 30min into
Row is cooled down, crushed, and painting is then washed with deionized water, and removes accessory substance, while chlorine is optionally substituted by a hydroxyl group, by repeatedly washing after 90
Constant weight is dried under vacuum at DEG C, you can obtain water insoluble hydroxyl phosphonitrilic polymer, the hydroxyl phosphonitrilic polymer, which has, to be inhaled
Attached function, containing the active group of cation, including amino, imino group, hydroxyl can be chelated.
Obtained hydroxyl phosphonitrilic polymer is irregular graininess, and the powder of required size can be obtained after screening by grinding
End, to improve adsorption capacity.
In step 1) in, the flow velocity of the ammonia is 10~20ml/min.
Above-mentioned hydroxyl phosphonitrilic polymer can be used for removing Wastewater Dyes, heavy metal ion;Wherein, the dyestuff is crystallization
The combination of one or both of purple, methylene blue, the soluble-salt of the heavy metal ion is copper chloride, copper nitrate, copper sulphate, chlorination
One or more in cadmium, cadmium nitrate, plumbi nitras, lead chloride.
In use, by hydroxyl phosphonitrilic polymer be added in the aqueous solution containing dyestuff or heavy metal ion solubility
In the aqueous solution of salt, being stirred at room temperature after 0.5~2 hour just can complete absorption;Wherein, in solution the concentration of dyestuff for 40
~1000mg/L, and the concentration of heavy metal ion is 20~120mg/L;The dosage of hydroxyl phosphonitrilic polymer is 0.1 in solution
~0.4g/L.
Above-mentioned hydroxyl phosphonitrilic polymer can be used as the filler of adsorption tower.
The present invention compared with prior art, has the following advantages that and beneficial effect:
1st, the present invention uses hexachlorocyclotriph,sphazene to have obvious superiority for raw material.Hexachlorocyclotriph,sphazene contains stable knot
The very active easily generation substitution reaction of chlorine on the hexatomic ring of structure, abundant electron rich element (N, P), its molecule forms crosslinking
The advantages of macromolecular substances.
2nd, the molecular structure feature of hydroxyl phosphonitrilic polymer material prepared by the present invention:Containing it is a large amount of can chelate heavy metal from
The active group of son, including amino, imino group, hydroxyl.
3rd, the present invention is using part chlorine on ammonia substitution hexachlorocyclotriph,sphazene, so that laid a good foundation for polymerisation, because
For under the high temperature conditions, condensation reaction can occur for the chlorine on amino and another molecule on a molecule, multiple molecules that
Condensation around here just forms a water-soluble difficult high molecular polymer.
4th, present invention process process is simple, environment-friendly, instrument and equipment is cheap, with preferable feasibility.
5th, prepared by the present invention hydroxyl phosphonitrilic polymer (being porous carbon materials) has to the heavy metal ion in waste water
Good adsorption effect, the adsorption capacity to different types of heavy metal ion is different, shows good adsorptive selectivity;Inhale
It is attached test result indicates that, crystal violet, methylene blue, lead ion, cadmium ion, cupric ion adsorption are respectively reached
1795.49mg/g, 667.32mg/g, 424.45mg/g, 132.23mg/g and 109.97mg/g.
Brief description of the drawings
Fig. 1 is the stereoscan photograph (SEM) of hydroxyl phosphonitrilic polymer in embodiment 1.
Fig. 2 is the infrared spectrogram (FTIR) of hydroxyl phosphonitrilic polymer in embodiment 1.
Fig. 3 is the zero potential analysis (Zate) of hydroxyl phosphonitrilic polymer in embodiment 1.
Embodiment
With reference to multiple specific embodiments, the invention will be further described.
Embodiment 1
The preparation process for the hydroxyl phosphonitrilic polymer that the present embodiment is provided is as follows:
10.0g hexachlorocyclotriph,sphazenes (HCCP) by purification are added in 250mL boiling flasks, 150mL bis- is added
Toluene solvant is fully dissolved after HCCP, obtains 66.67g/L HCCP solution, flask is placed in frozen water, and control temperature is at 5 DEG C
Hereinafter, whisk down and be at the uniform velocity passed through after ammonia (ammonia flow velocity is 10~20ml/min) reaction, reaction 2-4h, stopping is filled with ammonia,
Closed reactor, is placed 8-12 hours.Then filter, filter cake obtains white powdery solids after drying.By obtained white powder
Shape solid is placed in drying box, in being taken out after 120~150 DEG C of polycondensation 30min, is cooled to room temperature.Obtained polycondensation product is used
Washcoated 3 times of substantial amounts of deionized water, is dried under vacuum to constant weight, you can obtain 6.81g water insoluble hydroxyl at 90 DEG C
Polyphosphazene polymer (HPP), it is then standby after milled 300 mesh sieve.Wherein, the ESEM of obtained hydroxyl phosphonitrilic polymer
Photo, infrared spectrogram, zero potential analysis are referred to shown in Fig. 1,2,3.
Hydroxyl phosphonitrilic polymer obtained above, which contains, can largely chelate the active group of cation, including amino, imido
Base, hydroxyl, available for Wastewater Dyes, heavy metal ion is removed, also can be used as the filler of adsorption tower;Wherein dyestuff is crystallization
The combination of one or both of purple, methylene blue, the soluble-salt of heavy metal ion is copper chloride, copper nitrate, copper sulphate, caddy,
One or more in cadmium nitrate, plumbi nitras, lead chloride.When in use, hydroxyl phosphonitrilic polymer is added to containing dyestuff
In the aqueous solution or heavy metal ion soluble-salt the aqueous solution in, be stirred at room temperature after 0.5~2 hour just can complete inhale
It is attached;Wherein, the concentration of dyestuff is for 40~1000mg/L in solution, and the concentration of heavy metal ion is 20~120mg/L;Solution
The dosage of middle hydroxyl phosphonitrilic polymer is 0.1~0.4g/L.
The adsorption experiment of heavy metal ion:The soluble-salt of heavy metal ion is dissolved in distilled water respectively, is configured to not
With the heavy metal ion solution of gradient concentration, Cu2+,Cd2+20~80mg/L of initial concentration (mg/L) scope.Pb2+It is initial dense
Spend (mg/L):20~120mg/L.The heavy metal ion solution for taking 50mL to be matched somebody with somebody respectively is put into 75mL centrifuge tube, is weighed
10mg hydroxyl phosphonitrilic polymers are added in above-mentioned heavy metal ion solution and adsorbed at 30 DEG C, are slowly stirred 2h.Using
Flame type atomic absorption spectrophotometer determines the initial concentration and residual concentration of heavy metal ion, and then it is poly- to calculate hydroxyl phosphonitrile
The adsorption capacity of compound heavy metal ion.Concrete outcome see the table below 1.
The hydroxyl phosphonitrilic polymer of table 1 is to Pb2+、Cd2+And Cu2+Adsorbance under conditions of different initial concentrations
Embodiment 2
The preparation process for the hydroxyl phosphonitrilic polymer that the present embodiment is provided is as follows:
7.5g hexachlorocyclotriph,sphazenes (HCCP) by purification are added in 250mL boiling flasks, 150mL diformazans are added
Benzene solvent is fully dissolved after HCCP, obtains 50g/L HCCP solution, flask is placed in frozen water, controls temperature below 5 DEG C,
Whisk down and be at the uniform velocity passed through ammonia reaction, after reaction 2-4h, stopping is filled with ammonia, and closed reactor is placed 8-12 hours.Then cross
Filter, filter cake obtains white powdery solids after drying.Obtained white powdery solids are placed in drying box, in 120~150 DEG C
Taken out after polycondensation 30min, be cooled to room temperature.By obtained polycondensation product washcoated 3 times with substantial amounts of deionized water, at 90 DEG C
It is dried under vacuum to constant weight, you can obtain the water insoluble hydroxyl polyphosphazene polymers (HPP) of 5.7g, then milled 300 mesh sieve
It is standby afterwards.
The adsorption experiment of dyestuff:Dyestuff is dissolved in distilled water respectively, the aqueous solution of different gradient concentrations is configured to, crystallized
Purple initial concentration (mg/L) 50~1000mg/L of scope, the initial concentration (mg/L) of methylene blue:40~300mg/L.Respectively
The dye solution for taking 50mL to be matched somebody with somebody is put into 75mL centrifuge tube, is weighed 10mg hydroxyl phosphonitrilic polymers and is added to above-mentioned dye
Adsorbed in the material aqueous solution at 30 DEG C, be slowly stirred 2h.The initial concentration of dyestuff is determined and residual using ultraviolet specrophotometer
Remaining concentration, and then calculate adsorption capacity of the hydroxyl phosphonitrilic polymer to dyestuff in water.Concrete outcome see the table below 2.
Adsorbance of the hydroxyl phosphonitrilic polymer of table 2 to crystal violet and methylene blue under conditions of different initial concentrations
Remarks:Adsorption capacity QeCalculation formula it is as follows:
QeThe adsorption capacity (mg/g) of one-adsorbent
C0One-dyestuff or the initial concentration of heavy metal ion (mg/L)
CeOne-dyestuff or heavy metal ion reach the concentration (mg/L) during adsorption equilibrium
The volume (L) of mono--solution of V
The quality (g) of mono--adsorbents of W
Clearance R calculation formula is as follows:
Examples of implementation described above are only the preferred embodiments of the invention, and the implementation model of the present invention is not limited with this
Enclose, therefore the change that all shape, principles according to the present invention are made, it all should cover within the scope of the present invention.
Claims (5)
1. a kind of preparation method of hydroxyl phosphonitrilic polymer, it is characterised in that comprise the following steps:
1) ammonia replaces
Hexachlorocyclotriph,sphazene by purification is added in the incomplete closed reactor for fill xylene solvent and fully dissolved
Afterwards, 25~100g/L is configured to, is whisked in less than 5 DEG C and is at the uniform velocity continually fed into dry ammonia, course of reaction can engender white
Deposit, after reaction 2-4h, stopping is filled with ammonia, reactor is in air-tight state, and ammonia in bottle continue with
Hexachlorocyclotriph,sphazene reacts, and the suction filtration after being placed 8-12 hours under normal temperature, filter cake dries naturally, obtains white powdery solids;
2) high-temperature polycondensation and hydroxylating
White powdery solids obtained above are put into drying baker, it is cold in taking out progress after 120~150 DEG C of polycondensation 30min
But, crush, painting is then washed with deionized water, remove accessory substance, while chlorine is optionally substituted by a hydroxyl group, by repeatedly washing after at 90 DEG C
It is dried under vacuum to constant weight, you can obtain water insoluble hydroxyl phosphonitrilic polymer, the hydroxyl phosphonitrilic polymer has absorption work(
Can, containing the active group of cation, including amino, imino group, hydroxyl can be chelated.
2. a kind of preparation method of hydroxyl phosphonitrilic polymer according to claim 1, it is characterised in that:Obtained hydroxyl phosphorus
Nitrile polymer is irregular graininess, the powder of required size can be obtained after screening by grinding, to improve adsorption capacity.
3. a kind of preparation method of hydroxyl phosphonitrilic polymer according to claim 1, it is characterised in that:In step 1) in,
The flow velocity of the ammonia is 10~20ml/min.
4. the application of hydroxyl phosphonitrilic polymer described in a kind of claim 1, it is characterised in that:For removing Wastewater Dyes, again
Metal ion;Wherein, the dyestuff is the combination of one or both of crystal violet, methylene blue, the solubility of the heavy metal ion
Salt is the one or more in copper chloride, copper nitrate, copper sulphate, caddy, cadmium nitrate, plumbi nitras, lead chloride.
In use, by hydroxyl phosphonitrilic polymer be added in the aqueous solution containing dyestuff or heavy metal ion soluble-salt
In the aqueous solution, being stirred at room temperature after 0.5~2 hour just can complete absorption;Wherein, in solution dyestuff concentration for 40~
1000mg/L, and the concentration of heavy metal ion is 20~120mg/L;In solution the dosage of hydroxyl phosphonitrilic polymer be 0.1~
0.4g/L。
5. the application of hydroxyl phosphonitrilic polymer described in a kind of claim 1, it is characterised in that:It is used as the filler of adsorption tower.
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CN113831527A (en) * | 2021-11-05 | 2021-12-24 | 万华化学集团股份有限公司 | Preparation method of methallyl alcohol polyoxyethylene ether |
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Cited By (5)
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CN109806851A (en) * | 2019-03-25 | 2019-05-28 | 东华大学 | A kind of cyclodextrin porous material and preparation method thereof |
CN109806851B (en) * | 2019-03-25 | 2022-08-09 | 东华大学 | Cyclodextrin porous material and preparation method thereof |
CN111548476A (en) * | 2020-06-12 | 2020-08-18 | 广东裕泰实业有限公司 | Flame-retardant environment-friendly polyurethane material and preparation method thereof |
CN111548476B (en) * | 2020-06-12 | 2021-03-30 | 广东裕泰实业有限公司 | Flame-retardant environment-friendly polyurethane material and preparation method thereof |
CN113831527A (en) * | 2021-11-05 | 2021-12-24 | 万华化学集团股份有限公司 | Preparation method of methallyl alcohol polyoxyethylene ether |
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