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 
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 
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 300Experimental 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;
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.
SUBSTANCE: invention relates to developing porous materials and adsorbents, including medicine-destination ones, as effective agents for hemo-, entero-, and vulneosorption, cosmetics, environment-oriented materials, enzyme and cell carriers, biologically active substances, and drugs. Alumina-based sorbent of invention is characterized by meso- and macroporous structure and contains modifying component: polyvinylpyrrolidone-silver complex with 0.05 to 0.3 wt % Ag.
EFFECT: increased adsorption capacity regarding toxins with different molecular weights and acquired bactericidal properties.
3 tbl, 5 ex
FIELD: water treatment.
SUBSTANCE: sorbent according to invention represents dispersion of ferric and ferrous hydroxides and a bivalent metal hydroxide, the latter, in particular, being magnesium hydroxide at magnesium-to-iron molar ratio between 1:2 and 1;2.2. Preparation of sorbent consists in coprecipitation of bivalent metal and ferric hydroxides at pH 10-11 followed by filtration (formation of precipitate), drying, granulation, and heat treatment of precipitate at 210-270°C.
EFFECT: increased heavy metal sorption capacity.
2 cl, 5 tbl, 6 ex
FIELD: methods of production of granulated inorganic sorbents on base of oxyhydrates of metals, mainly trivalent and tetravalent used in metallurgy and chemical industry; treatment of sewage and decontamination of solutions.
SUBSTANCE: proposed method includes precipitation of oxyhydrates of metals, filtration, washing and granulation of sediment; sediment is divided into two parts: larger part is subjected to treatment with sodium chloride solution at concentration of 250-300 g/dm3 NaCl; then sediment is dried and repulped at liquid-to-solid ratio =(5-10): 1; suspension is settled, filtered and washed with water; then it is repeatedly dried; after mixing the remaining moist part of sediment, paste is granulated by extrusion.
EFFECT: increased dynamic capacity of sorbents to "jump" of radio-nuclides into filtrate.
FIELD: water treatment.
SUBSTANCE: sorbent catalyst appropriate to produce drinking water contains, as carrier, filter material (ODM-2F), ground opokas with summary pore volume 0.45-0.55 cm3/g (98.0-99.5%) and manganese dioxide (0.5-2.0%). Sorption capacity of sorbent catalyst exceeds that of quartz sand-based "black sand" by a factor above 1.5.
EFFECT: increased sorption capacity.
1 tbl, 4 ex
SUBSTANCE: invention provides sorbent based on manganese oxides, which is prepared by a method comprising mixing of alkali metal permanganate solution with reducer in alkali medium to form slurry of manganese oxide precipitate followed by pause, during which suspension of organic binder in amount 0.5 to 10% of the weight of manganese oxide precipitate is added. Precipitate is then separated, dried on working surface, calcined, and subjected to decrepitation to produce granules. Organic binder is selected from polyvinyl alcohol, polyacrylamide, polyvinylacetate, carboxymethylcellulose, gelatin, and casein. Invention also disclose a method for liberating solutions of strontium radionuclides by passing solutions through sorbent prepared by above-described method.
EFFECT: extended choice of decontaminating agents.
9 cl, 3 tbl, 7 ex
SUBSTANCE: device comprises dust catcher, adsorber, and sucking device connected via the through passage for supplying air with inlet and outlet branch pipes and mounted on the individual section of the movable platform for permitting mutual connection. The device is provided with the additional section of the movable platform provided with the lock device for connecting with the main sections. The additional section is provided with the device for fine purification of air, which is mounted downstream of the adsorber. The device for fine purification is made of housing that receives vertical grids whose mesh size does not exceeds 0.6 mm. The layers of chemical absorbers are interposed between the grids. The layers catch harmful gases that are generated during welding. The thickness of each layer is 50-80 mm. The specific gas loading of each of the layers does not exceed 1.5 l/min cm2. The device for fine purification of air is provided with the mechanism for discharging of the exhaust chemical absorbers.
EFFECT: enhanced quality of purification.
1 cl, 1 dwg
FIELD: filtering materials, water treatment.
SUBSTANCE: invention relates to methods for preparing drinking water, namely to purification of water from manganese and iron and can be used in additional treatment of well-drilling water. Filtering material used in treatment of water from Mn and Fe comprises as a base the natural granular material with catalytically active layer formed on a base wherein catalytically active layer consists of a mixture of oxides MnO, Mn2O3 and MnO2 in their mass ratio = (5-6):(3-2):(2-1), respectively. This material is prepared by treatment of a base with reagent solution containing manganese salts and treatment is carried out successively with at least solutions of two reagents. Firstly, treatment is carried out in Mn (II) salt solution and then with potassium permanganate followed by additional treatment with reagent solution reducing Mn (VII) and providing the formation of a mixture of manganese oxide compounds on surface of granular material. Method for water treatment from manganese and iron involves passing water through a filtering material layer with catalytically active layer comprising a mixture of oxides MnO, Mn2O3 and MnO2. Method provides effective removal of manganese and iron from well-drilling and tap water, it doesn't require the preliminary treatment of water with oxidant and provides the possibility for regeneration of the filtering material also.
EFFECT: valuable properties of filtering material, improved preparing method.
14 cl, 7 tbl, 5 ex
SUBSTANCE: invention provides zirconium oxide-based mesoporous material with following composition: SO42-/ZrO2-EOx, where E represents group III or IV element, x = 1.5 or 2, content of sulfate ions 0.1-10 wt %, and molar ratio ZrO2/EOx = 1:(0.4-1.0), said material having specific surface 300-800 m2/g with total pore volume 0.3 to 0.8 cm3/g. Method involves preparation of composition consisted of hydrated zirconium sulfate, sulfate ions, and water via precipitation of hydrated oxide phase from soluble zirconium or zirconyl salts followed by hydrothermal reprecipitation in presence of cationic surfactants to form mesoporous structure, which is then stabilized by treatment with group III or IV element compounds taken is additive proportions to mesoporous crystalline structure.
EFFECT: achieved preparation of material with controlled acid-base properties, high specific surface, and elevated heat resistance.
7 cl, 2 dwg, 6 tbl, 13 ex
FIELD: composition of ion exchange component-sorbent on base of hydrated zirconium dioxide.
SUBSTANCE: organic cation polymer is introduced into hydrated zirconium dioxide; this polymer is polydemethyl diallylammonium chloride having molecular mass of 104-106; it is introduced in the amount of 0.01-0.04 g per gram of zirconium dioxide. Moisture content of sorbent is 0-60 mass-% determined through drying at 100°C and size of granules ranges from 0.1 to 2.0 mm.
EFFECT: increased selectivity of sorbent to cations and anions.
3 cl, 2 tbl, 10 ex
SUBSTANCE: invention relates to sorbents based on metal oxyhydrate gels, which can be used in sorption technologies to recover metals from process solutions, to treat waste waters originated from hydrometallurgical enterprises, and to prepare pure substance in chemical industry. Process of invention comprises following stages: alkali precipitation of metal oxyhydrate, ripening of precipitate, separation. Drying, and granulation of sorbent. Granulated sorbent is further exposed for 2 h to magnetic field 980 oersted, after which sorbent is kept for 7 days in air at room temperature.
EFFECT: considerably increased sorption capacity.
3 tbl, 3 ex
FIELD: chromatographic sorbents.
SUBSTANCE: invention relates to chromatographic sorbents, which can be used for analysis and preparative purification of optically active compounds. A novel sorbent for resolution of isomers of optically active compounds is developed containing, as chiral selector, macrocyclic glycopeptide antibiotic eremomycin, vancomycin, ristomycin A, teicoplanine, or their aglycons. Method of immobilization of macrocyclic glycopeptide antibiotics is also developed, which resides in that silica gel in aqueous buffer solution is first treated with 3-glycidoxypropyl(trialkoxy)silane and then, in alkaline aqueous or water-organic solution, above-indicated macrocyclic glycopeptide antibiotic is grafted to epoxy group-modified silica gel.
EFFECT: increased selectivity in enantiomer resolution and simplified preparation procedure.
9 cl, 12 dwg, 5 tbl, 9 ex
SUBSTANCE: specific area of silica surface reaches 300,2/g, porosity - up to 1,1 cm3/g, average pores diameter - 12,0-16,0 nm. For separating and property detection couples of substances and carrier gas are let through chromatography column, filled with silica powder, which is precipitated from hydrothermal solution, with receipt at output of column of sequence of special components, recorded in form of peaks. Absorbent, received on basis of silica, precipitated from hydro-thermal solution, in several cases has better separating ability then traditional absorbents.
EFFECT: higher efficiency.