CN1151970C - Micrometer level porous zirconium dioxide spherical granules - Google Patents
Micrometer level porous zirconium dioxide spherical granules Download PDFInfo
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- CN1151970C CN1151970C CNB011420235A CN01142023A CN1151970C CN 1151970 C CN1151970 C CN 1151970C CN B011420235 A CNB011420235 A CN B011420235A CN 01142023 A CN01142023 A CN 01142023A CN 1151970 C CN1151970 C CN 1151970C
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Abstract
The present invention relates to a preparation technique of zirconium dioxide, particularly to micrometer-level porous zirconium dioxide spheral granules, wherein more than 90 percent of the spheral granules have the granule diameters of 1 to 10 (+/-) 0.1 micrometer, and the pore diameters of the spheral granules are 1 to 150 nanometer. In the present invention, nanometer-class ZrO2 hydrosol is prepared from zirconium salt, and composite spheral granules are generated from the ZrO2 hydrosol and urea formaldehyde resin in a polymerization induced colloid coagulation method under the condition of pH=0.5 to 3; then, water and organic matter in the composite spheral granules are removed, and the micrometer-level porous zirconium dioxide spheral granules are obtained by sintering and strengthening by temperature programming. The present invention has the characteristics of narrow particle size distribution, adjustable pore diameters, sufficient rigidity and high chemical stability; the present invention can be used as HPLC column filler.
Description
Technical field
The present invention relates to the preparation of zirconium dioxide, particularly it is a kind of preparation that is used as the micrometer level porous zirconium dioxide spherical granules of performance liquid chromatographic column filler.
Background technology
High performance liquid chromatography (HPLC) all is widely used in science and production field, and as the analysis task in the industries such as oil, chemical industry, medicine, environmental protection, major part can be finished with HPLC; And in the purifying process of biotechnology derived product, handle as one-level with membrane sepn earlier often, and then separate as high resolution with HPLC; The preparative column that directly reaches tens centimetres when front pillar has replaced classical lock out operation in many high-tech enterprises, the high classical way of its usefulness is incomparable.
Column packing is one of key of restriction HPLC technology all the time, and it determines its range of application, separation efficiency, separating mechanism, moving phase to form, even detection method; And current widely used silica matrix column packing, because unstable in the medium of pH＞8, and second effect of remaining silicon hydroxyl, its application is restricted, perhaps can only use reluctantly under the condition in sacrificial posts life-span, this is particularly outstanding at life science.
Studies show that zirconium glue (ZrO
2) can be stable in the pH=1-13 scope, and the apparent alkalescence in surface, rigidity is strong, is considered to one of new separating medium that most possibly overcomes the silica gel defective.The method for preparing the zirconia-based cation exchanger microballoon mainly contains two kinds, and the one, oily emulsion process is (referring to Tr ü dingerU, etal., Chromatogr.1990,535:111; CarrPW, etal., USPat., 5015373,1991), this method is dispersed in the zirconium water-sol in the oil phase with micron order globule form, extracts moisture by chemical process from the globule again, and makes ZrO
2Separate out with gel form.The zirconium micelle that this method makes directly distributes wide, and the aperture is less, must just can be used for the HPLC column packing through screening.Other method, (Polymerization-InducedColloidAggregation, PICA), the starting raw material of this method is nano level ZrO to promptly so-called polymerisation induced coacervation of colloid method
2The water-sol, add urea and formaldehyde under certain condition and make it polymerization, induce the micelle sedimentation simultaneously, generate compound pellet,, make the micron order spherolite through sinter at last through handling moisture and the organism of removing in the compound ball, the zirconium glue that this method makes, narrow diameter distribution, the aperture variable range is big, can be directly used in the HPLC column packing.The PICA method is used for the preparation of porous silica gel the earliest, is used for the preparation of zirconium glue thereafter, (referring to llerRK, McQuestonHJ, USPat., 4010242,1977; CarrPW, etal., USPat., 5540834,1996).But these two pieces of used critical materialses of patent (the zirconium water-sol) all are outsourcings, and repeatability is undesirable, emphasize to use the reactor of polyethylene material such as the latter, and can only use once.
Summary of the invention
The purpose of this invention is to provide a kind of micrometer level porous zirconium dioxide spherical granules and preparation method, its particle diameter is: at 1-10 ± 0.1 μ m, aperture 1-150nm has enough rigidity and high chemical stability, can be used as the HPLC column packing more than 90%.
The preparation method of micrometer level porous zirconium dioxide spherical granules of the present invention comprises the steps:
(1) ZrO
2The preparation of the water-sol
With zirconates (ZrOY
2, Y=Cl
-Or NO
3 -) water-soluble and make ZrO with ammoniacal liquor reaction
2The water-sol, the reaction that relates to:
The zirconates hydrolysis is a slow step, also is a decisive step.The kind of alkali and add alkali speed, and temperature of reaction all has material impact.Zirconium colloidal sol is that a phase (disperse phase) is scattered in the heterogeneous system in another phase (dispersion medium), in order to obtain stable zirconium colloidal sol, also must add the stable complexation agent, comprise N.F,USP MANNITOL, ethylene glycol, quadrol, oxalic dialdehyde, glycine, citric acid, pyruvic acid or methyl ethyl diketone.The add-on of stablizer is 0.02-4/1, and this ratio refers to the mol ratio of stablizer and zirconium dioxide.The zirconium water-sol that this law makes: pH=0.5-3, concentration 5-40% (w/w), colloid diameter 10-300nm.This water-sol is highly stable, places not to be separated in 1 year.
(2) preparation ZrO
2-Precondensed UreaFormaldehyde Resin complex microsphere
With the ZrO that makes
2The water-sol is added in the round bottom there-necked flask that stirring is housed, and adds urea, regulates pH=0.5-2.5, temperature adds formalin to 10-40 ℃, stirs, and, add dilute alkaline soln or big water gaging then with termination reaction, pH=5-8 at this temperature standing and reacting 5-20h.ZrO
2The concentration of the water-sol is 5-40% (w/w), and the concentration of urea and formaldehyde is 0.5-3.0mol/L.The ZrO that produces
2-Precondensed UreaFormaldehyde Resin complex microsphere outward appearance is a white.
(3) pre-treatment
Behind the unreacted reactant and impurity in the water flush away complex microsphere, it is transferred in the four-hole bottle that agitator and water trap are housed, adds an amount of isoamyl acetate or dimethylbenzene, azeotropic water removing is treated white ZrO
2-Precondensed UreaFormaldehyde Resin complex microsphere becomes light yellow, and in the distillate no longer during entrapped moisture, stops heating, filters, and air-dry, this moment, sphere diameter did not have considerable change.
(4) thermal treatment
In order to remove ZrO fully
2Moisture in the-Precondensed UreaFormaldehyde Resin complex microsphere and organism also obtain suitable pore structure and enough rigidity, also tackle pretreated product and carry out a series of thermal treatments: 1. vacuum-drying, place vacuum drying oven to carry out drying with being lurid resin compounded ball after the pre-treatment, temperature 100-200 ℃, vacuum tightness 0.03-0.08MPa, time of drying 12-36h.By the light yellow brown that becomes, volume obviously shrinks through this step process after product.2. temperature programming sintering, product after vacuum-drying still contains large amount of organic and moisture, and physical strength is not high, must be through the temperature programming sintering: rise to 200 ℃ from room temperature with 2-5 ℃/min, rise to 300 ℃ with 0.5-2 ℃/min from 200 ℃, rise to 700 ℃ with 1-3 ℃/min from 300 ℃, and keep 2-5h.
The micrometer level porous zirconium dioxide spherical granules of the present invention's preparation, narrow diameter distribution, the aperture is adjustable, and almost full pH value scope is stable; Under dress column pressure 40-100MPa condition, spherolite is indeformable, not broken, is particularly suitable for as the performance liquid chromatographic column filler, also the useful as catalysts carrier.
The present invention can describe in detail by embodiment, but they are not that the present invention is imposed any restrictions.
Description of drawings
Fig. 1 is the ZrO that photon correlation spectrometer records
2The gel particle distribution figure of the water-sol; Fig. 2 is the stereoscan photograph of the zirconium dioxide spherical granules behind the sintering; Fig. 3 is the X-diffracting spectrum of 700 ℃ of zirconium dioxide spherical granules behind the sintering; Fig. 4 is the chromatographic fractionation figure of basic cpd on zirconium glue stationary phase.
Embodiment
The 100g zirconium oxychloride is added in the 500mL flask with three necks,round bottom, adds 280mL deionized water and 3mL methyl ethyl diketone, fully stir, drip 25% ammoniacal liquor and reactant is heated to 85 ℃ from room temperature, keep pH value of solution=1-2, continue to stir 10h, promptly make ZrO
2The water-sol.This water-sol concentration 20% (w/w), recording its average colloid diameter through photon correlation spectrometer is 79.8nm (referring to Fig. 1)
Embodiment 2
Get the ZrO of embodiment 1 preparation
2Water-sol 200mL is added in the 500mL flask with three necks,round bottom, regulates pH=1.2, adds 20g urea, stirring makes fully dissolving, and 15 ℃ add 38% formaldehyde solution 25mL, stir 2min fast after, stop to stir, 15 ℃ are reacted 12h down, add 1%NaOH solution to pH=8, termination reaction, ZrO
2-resin compounded ball is sunken to reactor bottom, appearance white, particle diameter 12-15 μ m.Filter, wash product with water, then it is transferred in the four-hole bottle, add the isoamyl acetate azeotropic water removing, this moment, white compound ball became light yellow.Again this product is placed vacuum drying oven, keep vacuum tightness 0.06MPa, 120 ℃ of dry 12h, 200 ℃ of dry 24h, light yellow compound ball becomes brown, after temperature programming thermal treatment: pretreated compound ball is placed High Temperature Furnaces Heating Apparatus, thickness≤5mm rises to 200 ℃ with 4 ℃/min from room temperature, rises to 300 ℃ with 1 ℃/min from 200 ℃ then, rise to 700 ℃ with 2 ℃/min from 300 ℃, and continue sintering 3h at 700 ℃.The zirconium dioxide microspherulite diameter 5 μ m that make, specific surface 123m
2/ g, mean pore size 15nm, pore volume 0.333mL/g, voidage 66%.Fig. 2 is its stereoscan photograph, and Fig. 3 is its x-ray diffraction spectra, proves that the zirconium dioxide microballoon of this method preparation mainly is a tetragonal crystal, with the ratio of monoclinic crystal be 9/1.
Place 6mol/L hydrochloric acid to soak 24h the micrometer level porous zirconium dioxide spherical granules that makes among the embodiment 2, be washed till neutrality with distilled water then; Soak 24h and be washed till neutrality with the 1mol/L sodium hydroxide solution again with distilled water; Be placed in the autoclave at last and add suitable quantity of water, 200 ℃ of heat treated 8h.Zirconium glue microballoon through above-mentioned processing can be directly used in normal-phase chromatography, is particularly suitable for the separation of basic cpd, and can be suitable for the moving phase of pH=1～13 scopes.Fig. 4 is the normal-phase chromatography separate instance of zirconium glue stationary phase.
The zirconium glue 10g that makes among the embodiment 3 is joined in the 100mL round-bottomed flask that water trap is housed, add 60mL dimethylbenzene, backflow 4h adds carbon 18 triethoxyl silane 1mL and tosic acid 0.3g, backflow 24h again; And then the adding 3mL trimethylchlorosilane and the 4h that refluxes.After the cooling, filter out the zirconium ball, use toluene, acetone and methanol wash successively, promptly get bonded carbon 18 zirconium glue column packings (ODZ), can be used for reversed-phase liquid chromatography.
Claims (5)
1. micrometer level porous zirconium dioxide spherical granules is characterized in that its diameter is: more than 90% at 1-10 μ m, aperture 1-150nm.
2. the preparation method of the described micrometer level porous zirconium dioxide spherical granules of claim 1 is characterized in that it comprises the steps:
(1) zirconates is added deionized water and complexing stablizer methyl ethyl diketone, dropping ammonia solution fully stirs, and reactant is heated to 85 ℃ from room temperature, keeps pH value of solution=0.5-3, continues to stir 10h, makes weight percent and be 5～40% ZrO
2The water-sol, described complexing stablizer and ZrO
2Mol ratio be 0.02-4/1;
(2) at ZrO
2Add urea in the water-sol, ZrO
2With the weight ratio of urea be 2: 1, pH=0.5-2.5, temperature is to 10-40 ℃, adds the formalin of mass percentage concentration 38%, ZrO
2With the formalin amount ratio be 1.6 the gram ZrO
2: the 1ml formalin, stir, and at this temperature standing and reacting 5-20h; ZrO
2The water-sol and Precondensed UreaFormaldehyde Resin generate complex microsphere;
(3) water flush away unreacted reactant adds the isoamyl acetate azeotropic water removing, filters airing;
(4) carry out drying in the vacuum drying oven, temperature 100-200 ℃, vacuum tightness 0.03-0.08MPa, time of drying 12-36h;
(5) the product temperature programming sintering after vacuum-drying rises to 200 ℃ with 2-5 ℃/min from room temperature, rises to 300 ℃ with 0.5-2 ℃/min from 200 ℃, rises to 700 ℃ with 1-3 ℃/min from 300 ℃, and keeps 2-5h, gets final product.
3. the preparation method of micrometer level porous zirconium dioxide spherical granules according to claim 2, described zirconates is ZrOCl
2Or ZrO (NO
3)
2
4. the preparation method of micrometer level porous zirconium dioxide spherical granules according to claim 2 keeps pH value of solution=1-2, described ZrO when described zirconates and ammonia soln reaction
2The mass percentage concentration 20% of the water-sol.
5. the preparation method of micrometer level porous zirconium dioxide spherical granules according to claim 2 is characterized in that adding entry or diluted alkaline termination reaction, pH=5-8 after the described standing and reacting.
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|---|---|---|---|
| CNB011420235A CN1151970C (en) | 2001-09-07 | 2001-09-07 | Micrometer level porous zirconium dioxide spherical granules |
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|---|---|---|---|
| CNB011420235A CN1151970C (en) | 2001-09-07 | 2001-09-07 | Micrometer level porous zirconium dioxide spherical granules |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060263291A1 (en) | 2004-11-23 | 2006-11-23 | Carmine Torardi | Mesoporous amorphous oxide of titanium |
| US7601326B2 (en) | 2004-11-23 | 2009-10-13 | E. I. Du Pont De Nemours And Company | Mesoporous oxide of zirconium |
| US7988947B2 (en) | 2004-11-23 | 2011-08-02 | E. I. Du Pont De Nemours And Company | Mesoporous oxide of titanium |
| US7601327B2 (en) | 2004-11-23 | 2009-10-13 | E.I. Du Pont De Nemours And Company | Mesoporous oxide of hafnium |
| CN102350325A (en) * | 2011-07-12 | 2012-02-15 | 北京化工大学 | Preparation method of high-purity monodisperse silica-based chromatographic packing |
| CN103288130B (en) * | 2012-03-02 | 2014-12-10 | 同济大学 | Method for preparing monodispersed zirconium dioxide microspheres with evenly distributed particle size |
| WO2017139987A1 (en) * | 2016-02-21 | 2017-08-24 | 肖丽芳 | Method for preparing graphene/zirconia hollow sphere/sulfur composite material |
| CN109761274A (en) * | 2019-01-31 | 2019-05-17 | 中锆纳米材料股份有限公司 | A kind of method of low temperature preparation self-stabilization nano zircite colloidal sol |
| CN110862106A (en) * | 2019-12-13 | 2020-03-06 | 江苏省无锡环境监测中心 | Preparation method of zirconium dioxide microspheres |
| CN114426307B (en) * | 2020-10-09 | 2024-04-02 | 中国石油化工股份有限公司 | Zirconium sol, preparation method thereof and heavy oil catalytic cracking catalyst |
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