CN108671900A - A kind of disperse modified prepares the method and its application of high-specific surface area support type hydrous zirconium oxide(HZO) - Google Patents
A kind of disperse modified prepares the method and its application of high-specific surface area support type hydrous zirconium oxide(HZO) Download PDFInfo
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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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/06—Tubular membrane modules
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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Abstract
The present invention provides the method and its application that a kind of disperse modified prepares high-specific surface area support type hydrous zirconium oxide(HZO), and surface modification is carried out to the large hole cation exchanger resin for being adsorbed with zirconium ion using surfactant：Surfactant and sodium hydroxide are prepared into mixed solution；Large hole cation exchanger resin is added in zirconium chloride/hydrochloric acid solution and is reacted；The ion exchange resin for being adsorbed with zirconium ion is added in the mixed solution containing surfactant and is reacted；After having reacted, successively ion exchange resin is cleaned with distilled water, absolute ethyl alcohol, drying product.The present invention adjusts the dispersity of hydrous zirconium oxide(HZO) in cation exchange resin using surfactant, allow hydrous zirconium oxide(HZO) in ion exchange resin with nano-size dispersion, increase composite material specific surface area, improve material absorption heavy metal ion performance, product is for handling desulfurization wastewater, zinc ion and organic matter in waste water can be removed simultaneously, it reduces NF membrane to use, reduces cost.
Description
Technical field
The present invention relates to environment-friendly materials manufacturing technology fields, and in particular to a kind of disperse modified prepares high-specific surface area load
The method and its application of type hydrous zirconium oxide(HZO).
Background technology
Heat-engine plant desulfurized waste water is high with suspension content, calcium and magnesium salt amount is high, heavy metal ion is seriously polluted, change of water quality
It is big and contain a large amount of SO4 2-、Cl-The features such as, become reluctant sewage in thermal power plant.Power plant first to desulfurization wastewater into
Suspended particulate larger in sewage is carried out aggregate and precipitate by row flocculation treatment.But wastewater pH slant acidity when due to flocculation,
Still there are heavy metal ion, organic matter and the small suspension micelle of high level, thermal power plant to need to make in treated waste water
Deep purifying is carried out to the pretreated water that flocculates with embrane method.But microfiltration membranes can only organics removal, colloid, gold can not be removed
Belong to ion, therefore there is still a need for NF membranes to remove metal ion, but will increase cost in this way.
It is main at present to go the method for heavy metal ion in water removal to include：The precipitation method, absorption method, biochemical process, electrification
Method, ion-exchange and membrane filter method.Membrane filter method is with separative efficiency height, to object with advanced treating ability
Advantage, but membrane module is expensive.And absorption method has that easy to operate, effect stability, low energy consumption, non-secondary pollution, cost
The features such as low is one of the method that removing heavy metals are most effective and most have an economic benefit, with carrying for national wastewater discharge standard
Height becomes more and more important in the effect of heavy metal containing wastewater treatment.If the two can be combined, absorption method heavy-metal ion removal is first used,
Membrane filter method organics removal is used again, can reduce membrane module, is had complementary advantages, is reduced cost.
Hydrous zirconium oxide(HZO) (hydrated zirconium oxide) is one of common sorbing material, is had nontoxic, anti-
It aoxidizes, is stabilized in acid or alkali environment, is highly selective, the characteristics such as reproducible utilization.Hydrous zirconium oxide(HZO) has high-specific surface area
It is a kind of excellent heavy metal absorbent with a large amount of surface hydroxyl.But hydrous zirconium oxide(HZO) is generally powdered form, is actually answering
It is easy to be lost in, needs to be loaded to solve this problem and form composite material on porous material.Ion exchange resin is
High molecular material of the one kind with active function groups and with three-dimensional netted skeleton has preferable mechanical strength, durability, and
And its macroporous structure allows hydrous zirconium oxide(HZO) with nano-size dispersion, is a kind of excellent basis material.
Nano hydrated zirconium oxide has larger surface energy, thermodynamic instability, they can pass through particle since size is small
Between aggregation reduce surface energy, therefore nano hydrated zirconium oxide is easily reunited.If nano hydrated zirconium oxide is rolled into a ball in basis material
It is poly-, the adsorption potential of itself can be covered, and lead to the reduction of composite adsorbing material specific surface area due to largely blocking duct, make material
Adsorption capacity significantly weakens, it is therefore desirable to control the dispersity of hydrous zirconium oxide(HZO) in the base.
Hydrous zirconium oxide(HZO) is carried on styrene-divinylbenzene and is copolymerized sphere by patent CN102942236A, but in the material
Portion is positively charged quaternary ammonium group, has repulsive interaction with zinc ion, is unfavorable for removing the zinc ion in desulfurization wastewater.Patent
Zirconium oxide is fixed on ion exchange resin by CN103212383A using presoma diffusion-in situ deposition method, for leaded useless
Water process, but there is no corresponding research and report is done to dispersion of the hydrous zirconium oxide(HZO) in ion exchange resin, do not hand over
The parameter of hydrous zirconia particles size and the specific surface area of gained composite adsorbing material.Patent CN103752291A is by water
It closes zirconium oxide to be carried on sulfonic group styrene-divinylbenzene copolymerization sphere, lead containing wastewater treatment is used for, also without to water
Close dispersion of the zirconium oxide in ion exchange resin and do corresponding research and report, only rely on sulfonic group on copolymerization sphere to zirconium from
Son is attracted and is disperseed, but sulfonic acid group is unevenly distributed originally, therefore the patent can not effectively solve aqua oxidation
The agglomeration traits of zirconium, therefore the composite adsorbing material of high surface area can not be obtained.
It can be seen that these three patents do not carry out correlative study and report to the dispersion of hydrous zirconium oxide(HZO) in the base
Road, but hydrous zirconium oxide(HZO) has a significant impact to the specific surface area of composite material in the deployment conditions of matrix, and then influence its suction
Attached performance.The method that control hydrous zirconium oxide(HZO) disperses in the composite can be divided into physical method and chemical method.Physical method
Including ultrasonic disperse and mechanical agitation, but ultrasonic disperse needs additional energy consumption and can not act on the object in matrix cavity
Matter, and the most of generation in matrix cavity of hydrous zirconium oxide(HZO), it is difficult to by ultrasound and be dispersed with stirring.Chemical method is exactly to add
Enter surfactant, lyophily protective layer is formed on hydrous zirconium oxide(HZO) surface or increases the electrostatic reprimand between hydrous zirconia particles
Power.
Invention content
The object of the present invention is to provide a kind of disperse modified prepare high-specific surface area support type hydrous zirconium oxide(HZO) method and
It is applied, and the dispersity of hydrous zirconium oxide(HZO) in large hole cation exchanger resin is adjusted using surfactant, allows aqua oxidation
Zirconium, with nano-size dispersion, increases composite material specific surface area, improves material absorption heavy metal ion in ion exchange resin
Performance.Modified sorbing material is fitted into micro-filtration membrane tube and prepares Filter column, for handling desulfurization wastewater, can be removed simultaneously useless
Zinc ion and organic matter in water reduce NF membrane and use, reduce cost.
To achieve the goals above, the technical solution adopted by the present invention is as follows：
A kind of method that disperse modified prepares high-specific surface area support type hydrous zirconium oxide(HZO), using surfactant to absorption
There is the large hole cation exchanger resin of zirconium ion to carry out surface modification, includes the following steps：
1) surfactant is mixed with sodium hydroxide, the good mixed solution of compatibility is made；
2) large hole cation exchanger resin is added in zirconium chloride/hydrochloric acid solution and is reacted, obtain being adsorbed with zirconium from
The ion exchange resin of son；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and is reacted, to
Ion exchange resin through being adsorbed with zirconium ion carries out surface modification, is adsorbed in the zirconium ion in resin and is generated under alkali effect and is sunk
It forms sediment, under the action of surfactant, adjusts the deposition growing mechanism and dispersity of the hydrous zirconium oxide(HZO) that precipitation generates, to
So that hydrous zirconium oxide(HZO) is more evenly distributed in the channel surfaces of ion exchange resin, the ratio of composite adsorbing material can be significantly improved
The ability of surface area and absorption heavy metal ion；
4) after having reacted, successively ion exchange resin is cleaned with distilled water, absolute ethyl alcohol, is dried to get product.
According to above scheme, using nonionic surface active agent to being adsorbed with the large hole cation exchanger resin of zirconium ion
Surface modification is carried out, is included the following steps：
1) nonionic surface active agent is dissolved in distilled water at 60-80 DEG C, independent wiring solution-forming, then with sodium hydroxide
Solution mixes, and is uniformly mixing to obtain the good mixed solution of compatibility, the quality of nonionic surface active agent in mixed solution
Score is a concentration of 2mol/L of 5%-10%, sodium hydroxide；
2) zirconium chloride is dissolved in the hydrochloric acid solution that mass concentration is 0.4%, large hole cation exchanger resin reaction is added
12h obtains the ion exchange resin for being adsorbed with zirconium ion；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and carries out reaction 12h,
Ion exchange resin to being adsorbed with zirconium ion carries out surface modification, and the zirconium ion being adsorbed in resin produces under alkali effect
Raw precipitation, nonionic surface active agent form layer protecting film on hydrous zirconium oxide(HZO) surface, prevent the association between particle
And aggregation, reduce the reunion of hydrous zirconium oxide(HZO), keep hydrous zirconium oxide(HZO) evenly dispersed in the base, composite adsorption can be significantly improved
The ability of the specific surface area and absorption heavy metal ion of material；
4) after having reacted, first product is rinsed with distilled water, until supernatant liquor is without chlorion, then uses washes of absolute alcohol
It 2~3 times, is then dried to get product at 80 DEG C.
According to above scheme, the nonionic surface active agent include hydroxypropyl cellulose, fatty alcohol polyoxyethylene ether,
Any one in polyvinyl alcohol or more than one mixture.
According to above scheme, using cationic surface active agent to being adsorbed with the large hole cation exchanger resin of zirconium ion
Surface modification is carried out, is included the following steps：
1) cationic surface active agent is mixed with sodium hydroxide solution, is uniformly mixing to obtain the good mixing of compatibility
Solution, a concentration of 2mol/L of sodium hydroxide in mixed solution；
2) zirconium chloride is dissolved in the hydrochloric acid solution that mass concentration is 0.4%, large hole cation exchanger resin reaction is added
12h obtains the ion exchange resin for being adsorbed with zirconium ion；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and carries out reaction 12h,
Ion exchange resin to being adsorbed with zirconium ion carries out surface modification, and positively charged polar group is adsorbed in hydrous zirconium oxide(HZO) table
Hydrophobic interaction occurs for the hydrophobic group in face, nonpolar base and surfactant in liquid phase, forms the second of polarity basal orientation water phase
Adsorption layer or surface micella reduce reunion, it are made to be kept for good point since hydrous zirconium oxide(HZO) band identical charges are mutually exclusive
Bulk state can significantly improve the ability of the specific surface area and absorption heavy metal ion of composite adsorbing material；
4) after having reacted, first product is rinsed with distilled water, until supernatant liquor is without chlorion, then uses washes of absolute alcohol
It 2~3 times, is then dried to get product at 80 DEG C.
According to above scheme, the cationic surface active agent includes octadecyltrimethylammonium chloride, dodecyl
Any one in dimethyl benzyl ammonium chloride, cetylpyridinium chloride bell or more than one mixture.
According to above scheme, the cationic surface active agent is mixed in cationic surface active agent with sodium hydroxide
Concentration in solution is controlled in 60-200g/L.
According to above scheme, the high-specific surface area support type hydrous zirconium oxide(HZO) is loaded into prepare in micro-filtration membrane tube and is filtered
Column, for handling the desulfurization wastewater containing zinc ion.
The large hole cation exchanger resin of the present invention is a kind of height with active function groups and with three-dimensional netted skeleton
Molecularly Imprinted Polymer, active function groups are sulfonic group or carboxyl, and active function groups can carry out ion exchange with cation.Macropore sun from
Sub-exchange resin has porous structure, and aperture is tens to hundreds of nanometers, grain size about 0.2mm.
The beneficial effects of the invention are as follows：
(1) present invention adjusts the hydrous zirconium oxide(HZO) loaded on ion exchange resin by the peptizaiton of surfactant
Deposition growing and dispersity, solve the agglomeration traits of hydrous zirconium oxide(HZO) in the composite, make hydrous zirconium oxide(HZO) in base
" morely and smallly " disperse in body, the grain size for controlling hydrous zirconium oxide(HZO) is nanoscale, and grain size 20-100nm is high surface area, height
The composite material of absorption property, and composite adsorbing material can have very the zinc ion in desulfurization wastewater under conditions of slant acidity
High adsorbance；
(2) present invention has well solved hydration by the way that hydrous zirconium oxide(HZO) is loaded on large hole cation exchanger resin
The problem of zirconium oxide is easy to run off in practical applications, hardly possible recycles, and ion exchange resin is not only a carrier, and it also has
Have adsorption capacity, with hydrous zirconium oxide(HZO) it is compound after have good synergistic effect；
(3) matrix large hole cation exchanger resin of the invention derives from a wealth of sources, is cheap, hydrolysis methods operation letter
It is single, expensive, accurate instrument is not needed in actual production, is easy to produce in enormous quantities；
(4) composite adsorbing material of the present invention is loaded into micro-filtration membrane tube and prepares Filter column, handled for desulfurization wastewater
When, zinc ion and organic matter in waste water can be removed simultaneously, can be reduced NF membrane use, be reduced engineering cost；
(5) hydrofluoric acid, sodium hydroxide is used to carry out backwash to filter column, Filter column can recycle.
Description of the drawings
Fig. 1 is that the product of the present invention is used for equipment schematic diagram when desulfurization wastewater handles zinc ion；
Fig. 2 is transmission electron microscope (TEM) figure of 3 product of the embodiment of the present invention；
Fig. 3 is transmission electron microscope (TEM) figure of the hydrous zirconium oxide(HZO) composite adsorbing material without disperse modified；
Fig. 4 is the adsorption dynamics adsorption kinetics figure of 3 product of the embodiment of the present invention；
Fig. 5 is the adsorption isotherm map of 3 product of the embodiment of the present invention.
In figure：1, valve one；2, valve two；3, valve three；4, valve four；5, pipeline；6, Filter column；61, micro-filtration Membrane cover
Pipe；62, micro-filtration membrane tube；63, product of the present invention；7, pressure gauge.
Specific implementation mode
Technical scheme of the present invention is illustrated with embodiment below in conjunction with the accompanying drawings.
Embodiment 1, is shown in Fig. 1：
The present invention provides a kind of method that disperse modified prepares high-specific surface area support type hydrous zirconium oxide(HZO), including following step
Suddenly：
1) the NaOH solution 200mL of 4mol/L is prepared；20g hydroxypropyl celluloses are dissolved in 200mL distilled water at 80 DEG C,
It is individually made into mass fraction and is 10% solution, then mixed with sodium hydroxide solution, it is good mixed to be uniformly mixing to obtain compatibility
Close solution；
2) zirconium chloride is dissolved in the hydrochloric acid solution that hydrochloric acid mass concentration is 0.4%, 20g macroporous cations is added and exchange tree
Fat reacts 12h at 30 DEG C, obtains the ion exchange resin for being adsorbed with zirconium ion；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and carries out reaction 12h；
4) after having reacted, first product is rinsed with distilled water, until supernatant liquor (instills AgNO without chlorion3After solution
Without white precipitate), then with washes of absolute alcohol 3 times, finally at 80 DEG C drying to get product.The specific surface area of product is up to
17.2633m2The hydrous zirconium oxide(HZO) of/g/ion exchange resin composite adsorbing material, with the similar composite adsorption without decentralized processing
Material is compared, and specific surface area increases 1.8 times.
The present embodiment product is loaded into micro-filtration membrane tube and obtains Filter column 6, builds equipment (see Fig. 1), the Filter column 6
Include successively from outside to inside micro-filtration film casing 61, micro-filtration membrane tube 62, product of the present invention 63, is gone out by pipeline 5 and water inlet, micro-filtration
The mouth of a river, circulating outlet connection, and pressure is carried out to the different zones of the pipeline 5 by pressure gauge 7 and is shown.When operation, beat
It opens the valve 22 and valve 44, close valve 1 and valve 33, the supernatant after desulfurization wastewater is flocculated is from water inlet
Through the pipeline 5 by the Filter column 6, pressure is adjusted to 0.2MPa, carries out the removal of zinc ion, is flowed out from micro-filtration water outlet.
Zinc ion initial concentration is 2000mg/L in desulfurization wastewater, and removal rate reaches 98.4%.After treatment, to the Filter column 6
Backwash is carried out, the valve 1 and valve 33 is opened, closes valve 22 and valve 44, backwash liquor is from water inlet through the pipe
Then road 5 is flowed out by the Filter column 6 from circulating outlet, pressure is adjusted to 0.3MPa, is first carried out with 0.5wt% hydrofluoric acid
Backwash, then with water outlet is originally washed to be neutral；Then first backwash is carried out with 3wt%NaOH solution, then with being originally washed to out
Water is neutrality, and zinc ion desorption rate is more than 95.1%, and Filter column is recyclable.
Embodiment 2：
The present invention provides a kind of method that disperse modified prepares high-specific surface area support type hydrous zirconium oxide(HZO), basic with implementation
Example 1, the difference is that：In step 1)：40g polyvinyl alcohol is dissolved in 200mL distilled water at 80 DEG C, is individually made into quality point
Number is 20% solution, then is mixed with the sodium hydroxide solution of 200mL 4mol/L, and it is good mixed to be uniformly mixing to obtain compatibility
Close solution.
The specific surface area of product is 18.4352m2/ g, compared with the similar composite adsorbing material without decentralized processing, ratio
Surface area increases 2.0 times.
The present embodiment product is loaded into micro-filtration membrane tube and obtains Filter column, handles desulfurization wastewater, in desulfurization wastewater zinc from
Sub- initial concentration, equipment and operating method reach 99.1% with embodiment 1, zinc removal rate.After backwash, zinc ion desorption rate is more than
94.9%, Filter column is recyclable.
Embodiment 3 is shown in Fig. 2 to Fig. 4：
The present invention provides a kind of method that disperse modified prepares high-specific surface area support type hydrous zirconium oxide(HZO), basic with implementation
Example 1, the difference is that step 1)：It is first equipped with the sodium hydroxide solution of 2mol/L, then 25g ten is added toward sodium hydroxide solution
Eight alkyl trimethyl ammonium chlorides, stir evenly, and octadecyltrimethylammonium chloride is made fully to dissolve, and it is good mixed to obtain compatibility
Close solution.
The specific surface area of product is 21.7709m2/ g, compared with the similar composite adsorbing material without decentralized processing, ratio
Surface area increases 2.5 times.
The present embodiment product is loaded into micro-filtration membrane tube and obtains Filter column, handles desulfurization wastewater, in desulfurization wastewater zinc from
Sub- initial concentration, equipment and operating method reach 99.5% with embodiment 1, zinc removal rate.After backwash, zinc ion desorption rate is more than
95.6%, Filter column is recyclable.
The present embodiment product utilization Emission High Resolution rate transmission electron microscope (TEM) is measured to the pattern of zirconium oxide,
As a result see Fig. 2.It is prepared for the hydrous zirconium oxide(HZO) composite adsorbing material without disperse modified simultaneously, measuring its specific surface area is
6.1389m2/ g, TEM measurement result are shown in Fig. 3.
The present embodiment product is subjected to adsorption dynamics adsorption kinetics measurement, product adsorbs Zn2+Process can use pseudo-first-order dynamics
Model explanation, fitting coefficient R2It is 0.99769, the fitting result of pseudo-first-order kinetic model maximal absorptive capacity is
98.87164mg/g, and experiment value is 97.62mg/g, the two differs only by 1.27%.And as shown in figure 5, composite adsorbing material
To Zn2+Isotherm adsorption data accorded meet Langmuir models.
The above embodiments are only used to illustrate and not limit the technical solutions of the present invention, although above-described embodiment to the present invention into
Detailed description is gone, the related technical personnel of this field should understand that：It can modify to the present invention or replace on an equal basis, but
Any modification and part replacement for not departing from spirit and scope of the invention should all be covered in scope of the presently claimed invention.
Claims (7)
1. a kind of method that disperse modified prepares high-specific surface area support type hydrous zirconium oxide(HZO), which is characterized in that lived using surface
Property agent to be adsorbed with zirconium ion large hole cation exchanger resin carry out surface modification, include the following steps：
1) surfactant is mixed with sodium hydroxide, the good mixed solution of compatibility is made；
2) large hole cation exchanger resin is added in zirconium chloride/hydrochloric acid solution and is reacted, obtain being adsorbed with zirconium ion
Ion exchange resin；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and is reacted；
4) after having reacted, successively ion exchange resin is cleaned with distilled water, absolute ethyl alcohol, is dried to get product.
2. the method that disperse modified according to claim 1 prepares high-specific surface area support type hydrous zirconium oxide(HZO), feature
It is, surface modification, packet is carried out to the large hole cation exchanger resin for being adsorbed with zirconium ion using nonionic surface active agent
Include following steps：
1) nonionic surface active agent is dissolved in distilled water at 60-80 DEG C, independent wiring solution-forming, then with sodium hydroxide solution
Mixing, is uniformly mixing to obtain the good mixed solution of compatibility, the mass fraction of nonionic surface active agent in mixed solution
For 5%-10%, a concentration of 2mol/L of sodium hydroxide；
2) zirconium chloride is dissolved in the hydrochloric acid solution that mass concentration is 0.4%, large hole cation exchanger resin is added and reacts 12h,
Obtain the ion exchange resin for being adsorbed with zirconium ion；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and carries out reaction 12h；
4) after having reacted, first product is rinsed with distilled water, until supernatant liquor is without chlorion, then with washes of absolute alcohol 2~3
It is secondary, then dried to get product at 80 DEG C.
3. the method that disperse modified according to claim 2 prepares high-specific surface area support type hydrous zirconium oxide(HZO), feature
It is, the nonionic surface active agent includes arbitrary in hydroxypropyl cellulose, fatty alcohol polyoxyethylene ether, polyvinyl alcohol
One or more kinds of mixtures.
4. the method that disperse modified according to claim 1 prepares high-specific surface area support type hydrous zirconium oxide(HZO), feature
It is, surface modification, packet is carried out to the large hole cation exchanger resin for being adsorbed with zirconium ion using cationic surface active agent
Include following steps：
1) cationic surface active agent is mixed with sodium hydroxide solution, it is molten is uniformly mixing to obtain the good mixing of compatibility
Liquid, a concentration of 2mol/L of sodium hydroxide in mixed solution；
2) zirconium chloride is dissolved in the hydrochloric acid solution that mass concentration is 0.4%, large hole cation exchanger resin is added and reacts 12h,
Obtain the ion exchange resin for being adsorbed with zirconium ion；
3) ion exchange resin for being adsorbed with zirconium ion is immersed in mixed solution prepared by step 1) and carries out reaction 12h；
4) after having reacted, first product is rinsed with distilled water, until supernatant liquor is without chlorion, then with washes of absolute alcohol 2~3
It is secondary, then dried to get product at 80 DEG C.
5. the method that disperse modified according to claim 4 prepares high-specific surface area support type hydrous zirconium oxide(HZO), feature
Be, the cationic surface active agent include octadecyltrimethylammonium chloride, dodecyl benzyl dimethyl ammonium chloride,
Any one in cetylpyridinium chloride bell or more than one mixture.
6. the method that disperse modified according to claim 4 prepares high-specific surface area support type hydrous zirconium oxide(HZO), feature
It is, concentration of the cationic surface active agent in cationic surface active agent and sodium hydroxide mixed solution controls
In 60-200g/L.
7. the method that disperse modified according to claim 1,2 or 4 prepares high-specific surface area support type hydrous zirconium oxide(HZO),
It is characterized in that, the high-specific surface area support type hydrous zirconium oxide(HZO) is loaded into micro-filtration membrane tube and prepares Filter column, for handling
Desulfurization wastewater containing zinc ion.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN115850589A (en) * | 2023-02-24 | 2023-03-28 | 北京中科康仑环境科技研究院有限公司 | Resin containing active metal group and preparation method and application thereof |
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