The chromatographic material and method thereof

 

(57) Abstract:

The invention relates to sorbents for chromatography on the basis of zirconium dioxide and can be used in various types of chromatography, including gas and liquid. Features Staropromyslovsky chromatographic material composition: MexZr1-xO2-0,5 xn H2O, where Me is a metal of group III of the Periodic system of the elements; x=0,02 - 0,40; n=from 0.01 to 0.8, which is a solid solution with tetragonal or cubic lattice and is characterized by an average pore diameter of 3 to 100 nm and sorption pore volume of 0.04-0.6 cm3/the Average diameter of the granules of the material is 3 to 600 μm. The method of obtaining material includes the following stages: electrochemical synthesis Zola to achieve a pH of 1.6 - 2.2 dispersion Zola in generouse medium (gas or aqueous ammonia solution) by vibrating spray, separating the formed gel spheres, their washing and heat treatment. 2 S. and 6 C. p. F.-ly, 1 Il., 6 table.

The invention relates to sorbents for chromatography on the basis of zirconium dioxide and can be used in various types of chromatography, including high-performance liquid chromatography (HPLC) and gas chromatolysis methods of research and analysis of complex mixtures of organic and biologically active compounds. To solve some difficult problems in chromatography, especially in the variant HPLC, adsorbents and carriers must meet certain requirements to physical and chemical properties: form of pellets and particle size, porous structure (specific surface area, pore size and sorption pore volume), the mechanical strength of the granules, hydrolytic stability. On the one hand, it microspheric form of granules of uniform size and sufficiently high mechanical strength. For example, commercial adsorbents and carriers on the basis of silica granules of spherical shape with a size of 3-50 μm. On the other hand, the material must be sufficiently porous structure that provides efficient separation of organic substances with large molecular masses. The advantages of inorganic carriers are sufficiently high strength of granules and nanabahamutki matrix. Widely used in the chromatography stationary phase of silica-based, however they cannot be used for a long period of time when the medium pH is more than 8 due to low hydrolytic stability of siloxane matrix [1,2]

Hydrolytic stability of media, such as developed by industry Paris is to the dioxide of titanium or zirconium [3,4] This technique has allowed in some cases to raise the limit of applicability of such chromatographic materials only up to pH 10, which limits their use in more alkaline environments.

Known use as chromatographic materials individual of Zirconia or titanium, which have a fairly high hydrolytic stability at pH from 0 to 14. Along with hydrolytic stability provides other material characteristics: specific surface 30-62 m2/g; pore diameter of 9.5 to 15 nm; the form of spherical granules, and the granule size 5-50 μm [5]

The lack of individual Zirconia as the chromatographic material is that upon receipt of a given porous structure with thermal and hydrothermal modification of intensively are a variety of phase transitions, which leads to loss of mechanical strength and loss of strength of the granules.

Closest to the proposed method is a method of obtaining hydrated zirconium dioxide, according to which an aqueous solution of zirconium chloride is subjected to electrolysis to produce Zola, translated Sol in spherogel, washed it and thermoablative [6]

The task of the invention to provide a chromatographic material based on zirconium dioxide having high porosity and mechanical the crimson on the basis of zirconium dioxide, represents a solid solution with tetragonal or cubic lattice the General formula

IUxZr1-xO2-0,5.nH2O, where X 0,02-0,40;

IU metal of group III of the Periodic system;

n is from 0.01 to 0.8, and has an average pore diameter of 3-100 nm, sorption pore volume of 0.04-0.6 cm3/g, average diameter of the granules 3-600 μm. The unit cell parameters of the solid solutions of the claimed composition does not change during the heat treatment in the field of 400-1100aboutC. the High thermal stability of solid solution ZrO2-Me2O3with tetragonal or cubic lattice provides stability, strength characteristics and allows a wide range to adjust the parameters of the porous structure of the sorbent.

Introduction to chromatographic material stabilizing additive on M3+in the amount of less than 0.02 mole fractions leads to the formation of monoclinic modification of zirconium dioxide with a low mechanical strength of the granules. Additionally, during the heat treatment of the phase transition of monoclinic tetragonal occurs by crushing of the granules due to the sharp change of unit cell parameters. With the introduction of stabilizing additives on M3+more than 0.40 m is atora. This leads to reduced mechanical strength and violates the homogeneity of the sorbent.

The task is also solved by a method of obtaining material, according to which the chromatographic material of the proposed composition and porous structure with tetragonal or cubic lattice get the Sol-gel method. Prepare a water solution containing chloride of zirconium and at least one chloride of a metal of group III of the Periodic system D. I. Mendeleev when a molar ratio of Zr:Me= (0,60-0,98):(0-40-0,02). Electrolysis of a mixed solution is carried out at 40-100aboutWith up to a pH of 1.6 to 2.2. The electrolysis is subjected to a solution with a total concentration of these chlorides of metals from 0.8 mol/l and up to saturation.

The obtained Sol was dispersed in generouse environment depending on the desired fractional composition of the material. As the last to obtain pellets of a size of 100 to 600 μm and more, mainly used in gas chromatography, used liquid halirous Wednesday aqueous solution of ammonia. For more small spheres (diameter less than 100 μm) dispersion Zola is carried out in the gas medium is heated at 100 to 1000aboutBy using spray drying, using as a technical medium is by vibrating spray when the oscillation frequency 20-500 kHz. The resulting spherical particles are washed with water and subjected to heat treatment at 400-1000aboutC.

In the composition of the material, in addition to these trivalent rare-earth metals can enter and lanthanides with variable valence. For example, CEO2generated by calcining in air or other oxidizing atmosphere may be present alone or in mixture with CE2ABOUT3depending on the conditions of oxidation and thermal treatment.

For experimental validation of the chromatographic material of the inventive composition of the porous structure with tetragonal or cubic lattice were obtained 24 specimens (PL.1-4), 14 of which showed the best results on the mechanical strength of the granules.

P R I m e R s 1-5. An aqueous solution of chlorides of zirconium and aluminum containing 0,01, 0,02, 0,20, is 0.40 to 0.45 mol. for Al and 0.99, and 0.98, 0,80, of 0.60 and 0.55 mol. on Zr with a total concentration of metals of 1.5 mol/l was poured into the chamber of an electrolysis cell, in which the electrodes used: platinum anode, cathode titanium. The electrolysis was carried out at 75aboutWith a cathode current density of 450 a/m2. As a result of electrolysis has been stable in time sols with a pH of 1.8-2.0. Videostar ammonia. The dispersion was performed using ultrasonic source by vibrating spraying with a frequency of 44 kHz. The gel spheres were washed from the electrolyte with distilled water and dried at 150aboutAnd then there was heat treated at 800aboutWith over 6 hours of the Obtained pellets of the sorbent had a shape close to spherical, and the diameter predominantly 3-50 μm.

X-ray phase analysis (XRD) of the samples was performed on the diffractometer mark DRON-2 at room temperature using CuK-radiation. Abbreviated name of the phases: amorphous, T tetragonal To cubic. Parameters of porous structure of the samples were found as follows: specific surface area (SN2) was determined by isothermal nitrogen adsorption BET method; specific sorption volume VSthen, the average diameter dnbeen determined by full isothermal adsorption-desorption of benzene vapours. The mechanical strength of the Pm of the granules was determined by the maximum force at crushing the granules as elastic-brittle body between two rigid supports. The average value of Pmwas calculated by the test results of 20 pellets. The magnitude of the relative error of the measurements was 18-28% confidence likely the mental data for the system AlxZr1-xO2-0,5 x.nH2O are given in table. 1, from which it follows that the sorbent composition corresponds to the formula AlxZr1-xO2-0,5 x.nH2O, where X 0,02-0,04;

n 0,06, and represents a solid solution with a tetragonal lattice.

P R I m e R s 6-14. An aqueous solution of chlorides of zirconium and yttrium, with a total concentration of metals of 1.4 mol/l, containing 0,01, 0,02, 0,08, 0,16, 0,40, 0,45 mol. Y and 0,99, 0,98, 0,92, 0,84, 0,60, 0,55 mol. for Zr was poured into the chamber of the electrolytic cell and subjected to electrolysis, as described in examples 1-5. As a result of electrolysis has been stable sols with a pH of 1.7 to 2.0. The current output of the product in the electrolysis process was 85-90% at a temperature of 80 solutionaboutWith and a cathode current density of 550 a/m2.

The obtained sols were dispersively, the gel spheres were washed, dried, subjected to heat treatment and the product was investigated, as described in examples 1-5.

Experimental data for the system YxZr1-xO2-0,5 x.nH2O are given in table. 2, from which it follows that the sorbent composition corresponds to the formula YxZr1-xO2-0,5 x.nH2O, where x 0,02-0,40;

n is from 0.01 to 0.8, is a solid solution with tetragonal or cubic resh is S="ptx2">

P R I m e R s 15-19. An aqueous solution of chlorides of zirconium and lanthanum, with a total concentration of metals to 1.2 mol./l containing 0,01, 0,02, 0,04, is 0.40 to 0.45 mol. in La and 0.99, and 0.98, 0,96, 0,60, of 0.55 mol. for Zr was poured into the chamber of the electrolytic cell and subjected to electrolysis, as described in examples 1-14. As a result of electrolysis has been stable in time sols with a pH of 1.7 to 2.0. The current output of the product in the electrolysis process was 85-90% at a temperature of 80 solutionaboutWith and a cathode current density of 450 a/m2.

The obtained sols were dispersively, the gel spheres were washed, dried, subjected to heat treatment and the product was investigated, as described in examples 1-5.

Experimental data for the system LaxZr1-xO2-0,5 x.nH2O are given in table. 3, from which it follows that the sorbent composition corresponds to the formula LaxZr1-xO2-0,5 x.nH2O, where x 0,02-0,40;

n 0,06-0,07 and represents a solid solution with tetragonal or cubic lattice ZrO2.

P R I m e R s 20-24. An aqueous solution of chlorides of zirconium and cerium, with a total concentration of metals to 1.2 mol./l containing 0,01, 0,02, 0,04, is 0.40 to 0.45 mol. on Ce and 0.99, and 0.98, 0,96, 0,60, of 0.55 mol. for Zr was poured in a single-chamber electrolyzer and was also subjected to electric="ptx2">

The obtained sols were dispersively, the gel spheres were washed, dried, subjected to heat treatment and the product was investigated, as described in examples 1-5.

Experimental data for the system CexZr1-xO2-0,5 x.nH2O are given in table. 4, from which it follows that the sorbent composition corresponds to the formula CexZr1-xO2-0,5 x.nH2O, where x 0,02-0,40;

n 0,06-0,07, and represents a solid solution with tetragonal or cubic lattice Zr2.

Electrolysis of aqueous solutions of metal chlorides can be conducted in one, two - or three-chamber electrolyzer. In single-chamber apparatus of the simplification process.

In table. 5 experimental data (examples 25-33) the influence of temperature electrolysis, metal concentrations and pH Zola on the properties of the final product on the basis of Alof 0.2Zr0,8O1,9.

P R I m e R s 25-33. An aqueous solution of chlorides of zirconium, aluminum, containing 0.8 mol. for Zr and 0.2 mol. on Al with a total concentration of metals 0,7, 0,8, 1,5, 2,5 mol/l was poured into the cell and the electrolysis was carried out at a cathode current density of 450 a/m2as described in examples 1-5. The temperature of the electrolysis supported 35, 40, 75 and 100aboutC. Pprovodilis heat treatment and the product investigated, as described in examples 1-5.

As follows from the table.5, the end product with the mechanical strength of the granules more than 30 MPa should be obtained under the following optimal conditions of electrolysis of hydrochloric acid solutions of zirconium with one of the metals of group III: the temperature of the electrolysis of aqueous hydrochloric acid solutions of these metals to keep from 40 to 100aboutWith; the total concentration of metal chlorides from 0.8 mol./l and more. The final Sol was adjusted to a pH of 1.6 to 2.2.

Dispersion Sol of zirconium hydroxide with one of the metals of group III of the Periodic system D. I. Mendeleev produced by electrolysis was carried out by spray drying and vibration spraying.

P R I m e R s 34-42. The Sol containing 0.8 mol. for Zr and 0.2 mol. for Al, the total concentration of the metals of 1.5 mol./l and pH 1.8 was dispersively by using spray drying through a nozzle diameter of 0.8 mm in a cylindrical apparatus with air at 50, 100, 1000, 1100aboutC. When the air temperature 100aboutWith the addition to the reaction chamber has introduced a pair of ammonia. The same Sol was dispersively by vibrating spray when the oscillation frequency of 10, 20, 44, 500 kHz in the apparatus containing vapors of ammonia at the temperature of the reaction medium 300

Experimental data on the influence of the conditions of the dispersion Sol containing 0.2 mol. for Al and 0.8 mol. for Zr are shown in table.6.

From table. 6, when the dispersion Zola by spraying through a nozzle or a high-frequency vibration in the reaction gaseous environment significantly reduces the yield of granulated product at a temperature less than 100aboutC. When the temperature is among more than 1000aboutWith the decrease of the sorption properties of the final product by reducing the sorption volume of pores and the specific surface. The introduction of ammonia vapors in the reaction chamber when the dispersion Zola leads to increased release of granules with a spherical shape.

Chromatographic tests.

For chromatographic test was used sorbent composition Y0,025Zr0,975O1,9875.0,06 H2O, which has a tetragonal phase of ZrO2and is characterized by a pore diameter of 9.8 nm and sorption pore volume of 0.13 cm3/, Separation of organic substances (benzene, octane, nonane and dodecane) was performed on chrometm. The basic conditions of the separation were as follows: column diameter 1.2 mm; column length 1 m; bandwidth 100 cm3/h; the temperature of the media 222aboutC; detection by katharometer. The new sorbent was obtained chromatogram of the separation of organic substances in the above order with clear resolution and symmetric peaks. The chromatogram shown in the drawing.

1. Chromatographic material based on hydrated Zirconia spherical granulation, characterized in that it is a solid solution with tetragonal or cubic lattice structure

MexZr1-xO2-0,5 xn H2O,

where x=0,02 0,40;

Me is a metal of group III;

n=0,01 0,8,

and is characterized by an average pore diameter of 3 to 100 nm and sorption pore volume of 0.04 0.6 cm3/,

2. The material under item 1, characterized in that the spherical granules have an average diameter of 3 to 600 microns.

3. A method of obtaining a chromatographic material based on hydrated Zirconia spherical granulation, including the electrolysis of an aqueous solution of zirconium chloride with getting Zola, dispersion Zola in generouse environment, the Department formed a gel-spheres, their washing and the containing chloride of a metal of group III in a molar ratio of zirconium metal of group III of 0.60 to 0.98 0,40 0,02, sacralis carried out at 40 100oTo achieve a pH of 1.6 to 2.2, and the heat treatment is conducted at 400 to 1000oC.

4. The method according to p. 3, characterized in that the electrolysis is subjected to the specified solution with a total concentration of metal chlorides from 0.8 mol./l up to saturation.

5. The method according to PP.3 and 4, characterized in that as generouse environment using the gas phase and the dispersion Zola carried out by the method of spray drying at 100 to 1000oC.

6. The method according to PP.3 to 5, characterized in that Galereya gaseous medium further comprises a pair of ammonia.

7. The method according to PP.3 and 4, characterized in that as generouse environment using aqueous ammonia, and the dispersion Zola is carried out by vibrating spray.

8. The method according to PP.3,4 and 7, characterized in that, to increase the yield of particles with a radius of 3 to 50 μm, the dispersion is carried out by vibrating spray when the oscillation frequency of 20 to 500 kHz.

 

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