CN107758739A - Micron order zirconium oxide, its preparation method and application - Google Patents

Micron order zirconium oxide, its preparation method and application Download PDF

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CN107758739A
CN107758739A CN201610707097.9A CN201610707097A CN107758739A CN 107758739 A CN107758739 A CN 107758739A CN 201610707097 A CN201610707097 A CN 201610707097A CN 107758739 A CN107758739 A CN 107758739A
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zirconium hydroxide
water
zirconium
filter residue
preparation
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董思言
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
    • 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
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    • B01J20/28078—Pore diameter
    • B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • 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
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/10—Inorganic compounds
    • C02F2101/101—Sulfur compounds
    • C—CHEMISTRY; METALLURGY
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    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
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Abstract

The invention discloses a kind of micron order zirconium hydroxide, 1.8 ~ 2.8nm of aperture；0.18 ~ 0.28cm of pore volume3/g；6 μm≤D of particle diameter10≤ 12 μm, 23 μm≤D50≤ 28 μm, 45 μm≤D10≤85µm；350 ~ 680m of specific surface area2/ g, the zirconium hydroxide are engraved structure.Application the invention also discloses the preparation method of the zirconium hydroxide and its in purified water and the suction-operated in haemodialysis.Phosphate radical, sulfate radical and fluorine ion in the adsorbable water of micron order of the present invention, the also phosphate radical in adsorbable haemodialysis.

Description

Micron order zirconium oxide, its preparation method and application
Technical field
The present invention relates to chemical field, more particularly to purification techniques field, and in particular to a kind of micron order zirconium hydroxide, its Preparation method and application.
Background technology
Sulfate radical, phosphate radical and fluorine ion are all anion common in Chemical Manufacture, and their presence is to production and ring Border can bring significant damage, polluted water.The phosphate anion too high levels in blood of human body, have a strong impact on health.Mesh Before be commercially used for removing the main method of sulfate radical, phosphate radical and fluorine ion in water and have chemical precipitation method, electric flocculation method, biology Method and absorption method.And the ratio of chemical precipitation method and the purification efficiency of bioanalysis is relatively low, electric flocculation rule can increase cost, energy consumption Greatly.Absorption method not only efficiency high, sorbing material also reusable edible.And zirconium hydroxide is nontoxic, available for preparing blood Dialysis material, the content of phosphorus in blood is adjusted, be primarily now to prepare a kind of appropriate big and big adsorption capacity hydrogen-oxygen of granularity Change zirconia material, and the stability of existing zirconium hydroxide material is insufficient, the also skewness of the grain hole for absorption, grain hole forming amount Few, adsorption capacity is relatively low when causing purified water with carrying out haemodialysis.
The content of the invention
To solve the above problems, the invention provides a kind of micron order zirconium hydroxide, its preparation method and application.
According to an aspect of the invention, there is provided a kind of micron order zirconium hydroxide, 1.8 ~ 2.8nm of aperture；Pore volume 0.18 ~ 0.28cm3/g；6 μm≤D of particle diameter10≤ 12 μm, 23 μm≤D50≤ 28 μm, 45 μm≤D10≤85µm；350 ~ 680m of specific surface area2/ G, the zirconium hydroxide are engraved structure.The adsorption capacity of such a zirconium hydroxide is 0.8mol/g ~ 2.0mol/g, and nontoxic nothing Evil.
According to another aspect of the present invention, there is provided the preparation method of micron order zirconium hydroxide, including step：
S1：Compound concentration scope is the aqueous slkali of 0.6 ~ 0.8mol/L sodium hydroxide；
S2:5-8g zirconium chlorides are added under conditions of heating, are stirred 0.5 hour, control pH value is 8 ~ 14, then 80 ~ 100oC Lower ageing 18 hours, then 80 ~ 100oFiltered under C and obtain filter residue；
S3：In the filter residue of acquisition plus water stirs, and the weight ratio of filter residue and water is 1:3, it is 0.8 ~ 8mol/L then to instill concentration Acetic acid, control pH value stands 3 hours 4 ~ 5, then filters and obtain solid；
S4：100 ~ 150oC, vacuum are that 30 ~ 40min is incubated under 0.6 ~ 07atm, obtain micron order zirconium hydroxide.
In the preparation method of the present invention, 80 ~ 100 in step S2oBe aged 18 hours under C, selection ageing 18 hours, be for The particle size and pore size of control zirconium hydroxide, to prevent the time is too short and, the time mistake too small with aperture that result in particle diameter Long, particle diameter is excessive, ensure that the adsorption capacity of zirconium hydroxide.In step S4, isothermal holding is in order that zirconium hydroxide is more steady It is fixed, and beneficial to the formation in grain hole, increase adsorption capacity, become hollow out ball.To ensure vacuum, during insulation Can be while vacuumize, while be passed through inert gas, such as argon gas.It is also to have asked guarantee hydroxide to have certain vacuum degree in insulating process The composition of zirconium is not destroyed.
In some embodiments, the filter residue in step S2 uses 80 ~ 90oC water washing 1 ~ 2 time.Simply need herein Washing 1 ~ 2 time, the number of cleaning is excessive, easily causes the yield reduction of zirconium hydroxide, and 80 ~ 90oWashed under C, Washing each time can be made all than more thoroughly.
In some embodiments, the solid that acquisition is filtered in step S3 uses 50 ~ 60oC water washing 1 ~ 2 time.
In some are embodiment, step S4 is 120oC, vacuum are that 30min is incubated under 0.6atm, obtain micron Level zirconium hydroxide.120 are selected hereinoC is to ensure the drying of zirconium hydroxide with the formation in grain hole with stably, also avoiding have selected more High-temperature causes the decomposition of zirconium hydroxide.
According to another aspect of the invention, application of the zirconium hydroxide in purified water is additionally provided, zirconium hydroxide is adsorbable Phosphate radical, sulfate radical and fluorine ion in water.Wherein, the process of zirconium hydroxide purification sulfate radical comprises the following steps：
A, the zirconium hydroxide of preparation and particle diameter are pressed 1 for 150 μm of silica:3 mass ratioes are well mixed, and are then charged into both ends The filter of opening；
B, compound concentration is 2.5mmol/L niter cakes, is injected with 5 ~ 15ml/min speed from one end of filter, another Hold the water body after being purified, HSO4 -、SO4 2-The clearance of ion reaches more than 98%.
In some embodiments, after step B, zirconium hydroxide is activated, by the zirconium hydroxide after step B uses 80 ~ 90oUnder C, filtered after soaking 40 ~ 50min containing 0.05 ~ 0.1mol/L sodium hydroxide solutions with 1L, then use deionized water Wash 1 ~ 2 time and obtain filter residue, then filter residue is mixed with deionized water and is tuned into suspension, then it is acid to adjust its pH value with acetic acid Property, it is recovered the high adsorption activity to sulfate radical, phosphate radical and fluorine ion.Thus, with the timing of sodium hydroxide solution immersion one Between after zirconium hydroxide can be made fully to activate, washing 1 ~ 2 time enough, and ensure that the rate of recovery of zirconium hydroxide.
Present invention also offers suction-operated of the zirconium hydroxide in haemodialysis to phosphate radical.
The principle of the inventive method is the hydroxyl and H by zirconium hydroxide microparticle surfaces2PO4 -/HPO4 2-/PO4 3-/HSO4 -/ SO4 2-/F-Ion exchange reaches the effect of adsorption cleaning water body.
The advantage of the invention is that：
（1）Prepared zirconium hydroxide is to H in water body2PO4 -、HPO4 2-、PO4 3-、HSO4 -、SO4 2-、F-Advantages of good adsorption effect, not by it The influence of his foreign ion, adsorption capacity can reach 0.8mol/g ~ 2.0mol/g.
（2）Prepared zirconium hydroxide has good biocompatibility, nontoxic, non-hazardous, with micron-sized titanium dioxide Silicon, which is used in mixed way, can effectively reduce dialysate pressure, reduce energy consumption.
（3）Whole preparation process is simple, can high efficiente callback zirconium hydroxide, recycle.
Figure of description
Fig. 1 is zirconium hydroxide of the present invention dialysis test schematic diagram；
Fig. 2 is the front view of the micron order zirconium oxide of the present invention.
Embodiment
With reference to specific embodiment, present disclosure is expanded on further.
Embodiment 1
Compound concentration is the aqueous slkali of 0.6mol/L sodium hydroxide；60o5g zirconium chlorides, stirring 0.5 are added under C heating conditions Hour, it is 8 to control pH value, then 80oIt is aged 18 hours under C, then 80oFiltered under C and obtain filter residue, filter residue uses 80oC Water washing 2 times；In the filter residue of acquisition plus water stirs, and the weight ratio of filter residue and water is 1:3, then instilling concentration is 0.8mol/L acetic acid, it is 4 to control pH value, stands 3 hours, then filters and obtains solid, uses 50oC water washing solid 2 It is secondary；100oC, vacuum are that 30min is incubated under 0.6atm, obtain micron order zirconium hydroxide.
Embodiment 2
Compound concentration is the aqueous slkali of 0.7mol/L sodium hydroxide；90o6g zirconium chlorides, stirring 0.5 are added under C heating conditions Hour, it is 9 to control pH value, then 90oIt is aged 18 hours under C, then 90oFiltered under C and obtain filter residue, filter residue uses 90oC Water washing 1 time；In the filter residue of acquisition plus water stirs, and the weight ratio of filter residue and water is 1:3, then instilling concentration is 2.5mol/L acetic acid, it is 5 to control pH value, stands 3 hours, then filters and obtains solid, uses 60oC water washing solid 2 It is secondary；120oC, vacuum are that 35min is incubated under 0.6atm, obtain micron order zirconium hydroxide.
Embodiment 3
Compound concentration is the aqueous slkali of 0.8mol/L sodium hydroxide；90o7g zirconium chlorides, stirring 0.5 are added under C heating conditions Hour, it is 11 to control pH value, then 100oIt is aged 18 hours under C, then 100oFiltered under C and obtain filter residue, filter residue uses 90oC water washing 2 times；In the filter residue of acquisition plus water stirs, and the weight ratio of filter residue and water is 1:3, then instilling concentration is 4.2mol/L acetic acid, it is 4 to control pH value, stands 3 hours, then filters and obtains solid, uses 60oC water washing solid 1 It is secondary；135oC, vacuum are that 40min is incubated under 0.65atm, obtain micron order zirconium hydroxide.
Embodiment 4
Compound concentration is the aqueous slkali of 0.8mol/L sodium hydroxide；80o8g zirconium chlorides, stirring 0.5 are added under C heating conditions Hour, it is 14 to control pH value, then 90oIt is aged 18 hours under C, then 80oFiltered under C and obtain filter residue, filter residue uses 90oC Water washing 1 time；In the filter residue of acquisition plus water stirs, and the weight ratio of filter residue and water is 1:3, it is 8mol/L then to instill concentration Acetic acid, control pH value be 5, stand 3 hours, then filter obtain solid, use 60oC water washing solid 1 time；150oC, Vacuum is that 30min is incubated under 0.7atm, obtains micron order zirconium hydroxide.
Table 1 is each physical index of the micron order zirconium hydroxide sample prepared by embodiment 1 ~ 4.
Table 1
The front view of the micron order zirconium oxide of the present invention is illustrated in figure 2, there are multiple holes 1 in the inside of zirconium oxide so that oxygen It is in Openworks shape to change zirconium.
Embodiment 5
A kind of application method of micron order zirconium hydroxide, the process of sulfate radical comprises the following steps in zirconium hydroxide purified water：
A, the zirconium hydroxide of preparation and particle diameter are pressed 1 for 150 μm of silica:3 mass ratioes are well mixed, and are then charged into both ends The filter of opening；
B, compound concentration is 2.5mmol/L niter cakes, is injected with 5ml/min speed from one end of filter, the other end Water body after being purified, HSO4 -、SO4 2-The clearance of ion reaches more than 98%.
C, by the zirconium hydroxide after step B uses 80oUnder C, soaked with 1L sodium hydroxide solutions containing 0.05mol/L Filtered after 40min, be then washed with deionized 2 times and obtain filter residue, then filter residue is mixed with deionized water and is tuned into suspension, It is acid to adjust its pH value with acetic acid again, it is recovered the high adsorption activity to sulfate radical, then filters and obtains filter residue use 60oC water washing solid 3 times, completes the recovery of zirconium hydroxide.
D, the zirconium hydroxide of recovery is repeated by step A-C, repeats 30 recovery and adsorption test.
The application method of phosphate radical and fluorine ion and the user of purification sulfate radical in micron order zirconium hydroxide purified water Method is identical.Difference is, it is sodium dihydrogen phosphate to filter prepared during phosphate radical, and when filtering fluorine ion, preparation is fluorination Sodium solution.
Table 2 is adsorbance and the relation table of recycling number of the micron order zirconium hydroxide to sulfate radical, wherein sharp again Initial sample is represented with number " 0 ".
Table 2
Recycle number 0 3 6 10 15 21 28 30
Sulfate radical adsorption capacity mmol/g 1.25 1.24 1.23 1.21 1.20 1.18 1.17 1.16
Embodiment 6
Suction-operated of the zirconium hydroxide in haemodialysis to phosphate radical, comprises the following steps：
1st, 0.41g sodium dihydrogen phosphates, 6.14g sodium chloride, 1.78g sodium acid carbonates and 0.16g sodium acetates are dissolved with water and mixed, so 37wt% concentrated hydrochloric acid 5ml is added afterwards, and with constant volume in 1L volumetric flasks, it is 7.1 ~ 7.2 to control the final PH of solution, is simulated with this solution Blood；
2nd, the solution prepared in step 1 is tested the zirconium hydroxide obtained by embodiment 4, its method of testing flow is same Embodiment 5, flow chart is as shown in figure 1, be that the solution containing phosphate prepared in step 1 enters hydrogen in test pole B, B through D pipes in container A Zirconium oxide presses 1 with silica:3 mass ratioes are well mixed, and after absorption, container C is flowed into by E pipes in B for solution containing phosphate In be collected, every 10 minutes of container C collects the liquid after primary purification, until having phosphonium ion seepage, then in test container C Phosphate ion concentration, finally calculate its adsorption capacity is 2.02mmol/g.Wherein E is managed with C pipes not on same axis, E pipes It is partial to test pole B one end respectively with C pipes, can so solution containing phosphate is fully adsorbed in B.
Above-described is only some embodiments of the present invention, it is noted that for one of ordinary skill in the art For, on the premise of the creation design of the present invention is not departed from, other modification and improvement can also be made, belong to the present invention's Protection domain.

Claims (9)

  1. A kind of 1. micron order zirconium hydroxide, it is characterised in that 1.8 ~ 2.8nm of aperture；0.18 ~ 0.28cm of pore volume3/g；6 μm of particle diameter≤ D10≤ 12 μm, 23 μm≤D50≤ 28 μm, 45 μm≤D10≤85µm；350 ~ 680m of specific surface area2/ g, the zirconium hydroxide are to engrave Hollow structure.
  2. 2. the preparation method of zirconium hydroxide according to claim 1, it is characterised in that including step：
    S1：Compound concentration scope is the aqueous slkali of 0.6 ~ 0.8mol/L sodium hydroxide；
    S2:5-8g zirconium chlorides are added under conditions of heating, are stirred 0.5 hour, control pH value is 8 ~ 14, then 80 ~ 100oC Lower ageing 18 hours, then 80 ~ 100oFiltered under C and obtain filter residue；
    S3：In the filter residue of acquisition plus water stirs, and the weight ratio of filter residue and water is 1:3, it is 0.8 ~ 8mol/L then to instill concentration Acetic acid, control pH value stands 3 hours 4 ~ 5, then filters and obtain solid；
    S4：100 ~ 150oC, vacuum are that 30 ~ 40min is incubated under 0.6 ~ 07atm, obtain micron order zirconium hydroxide.
  3. 3. the preparation method of zirconium hydroxide according to claim 2, it is characterised in that the filter residue in the step S2 uses 80~90oC water washing 1 ~ 2 time.
  4. 4. the preparation method of zirconium hydroxide according to claim 2, it is characterised in that filter what is obtained in the step S3 Solid uses 50 ~ 60oC water washing 1 ~ 2 time.
  5. 5. the preparation method of zirconium hydroxide according to claim 2, it is characterised in that the step S4 is 120oC, very Reciprocal of duty cycle is that 30min is incubated under 0.6atm, obtains micron order zirconium hydroxide.
  6. 6. application of the zirconium hydroxide according to claim 1 in purified water, it is characterised in that the zirconium hydroxide can be inhaled Phosphate radical, sulfate radical and fluorine ion in attached water.
  7. 7. application of the zirconium hydroxide according to claim 6 in purified water, it is characterised in that the zirconium hydroxide purification The process of sulfate radical comprises the following steps：
    A, the zirconium hydroxide of preparation and particle diameter are pressed 1 for 150 μm of silica:3 mass ratioes are well mixed, and are then charged into both ends The filter of opening；
    B, compound concentration is 2.5mmol/L niter cakes, is injected with 5 ~ 15ml/min speed from one end of filter, another Hold the water body after being purified.
  8. 8. application of the zirconium hydroxide according to claim 7 in purified water, it is characterised in that after step B, to hydrogen-oxygen Change zirconium to be activated, by the zirconium hydroxide after step B uses 80 ~ 90oIt is molten with 1L sodium hydroxides containing 0.05 ~ 0.1mol/L under C Liquid filters after soaking 40 ~ 50min, is then washed with deionized 1 ~ 2 time and obtains filter residue, then mixes filter residue with deionized water Suspension is tuned into, then it is acid to adjust its pH value with acetic acid, its high absorption recovered to sulfate radical, phosphate radical and fluorine ion is lived Property.
  9. 9. zirconium hydroxide according to claim 1 is in haemodialysis to the adsorption applications of phosphate radical.
CN201610707097.9A 2016-08-23 2016-08-23 Micron order zirconium oxide, its preparation method and application Withdrawn CN107758739A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108751331A (en) * 2018-07-07 2018-11-06 重庆大学 A kind of method and process system of processing waste water
CN110713284A (en) * 2019-10-14 2020-01-21 江苏省盐海化工有限公司 Sulfate radical removal process for circulating zero-emission brine system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108751331A (en) * 2018-07-07 2018-11-06 重庆大学 A kind of method and process system of processing waste water
CN110713284A (en) * 2019-10-14 2020-01-21 江苏省盐海化工有限公司 Sulfate radical removal process for circulating zero-emission brine system

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