RU2466933C1 - Colloid alumosilicate - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: claimed is colloid alumosilicate of formula: M₂O-(0.1-1.2)Al₂O₃·(4-12)SiO₂, where M represents cation of alkali metal or ammonium. Alumosilicate is in form of spherical particles with specific surface 300-450 m²/g. Surface of particles contains alumosilicate anionic centres in quantity from 1.2 to 2.5 aluminium anions Al³⁺ per 10 nm² of surface. Particles represent agglomerates with size from 60 to 610 nm. Obtained alumosilicate is characterized by specific diffractogram, presented in description.

EFFECT: obtaining novel colloid alumosilicate compound from available and cheap raw material components.

3 tbl, 3 dwg, 4 ex

Description

The invention relates to colloidal aluminosilicate, which can be used as an adsorbent, for example, for the purification of hydrocarbon fractions from sulfur-containing compounds, a catalyst for the conversion of hydrocarbons, a component for producing synthetic zeolites, a binder for the manufacture of foundry molds.

The level of technology.

Aluminosilicates have catalytic properties and are widely used in a wide variety of ion exchange, catalytic and adsorption processes (Schweiker G.C., Sodium silicates and sodium aluminosilicates, J. Am. Oil Chemists'soc., 1978, v. 55, p. 36-40).

Aluminosilicates are known which are produced in the form of colloidal solutions (sols) of silicon dioxide modified with aluminum ions of various trademarks, for example, Ludox-AM and Ludox-WP from Grace Davison. The particles of silicon dioxide modified by aluminum have an Al ₂ O ₃ content _of from 0.2 to 0.6 wt.%, Which corresponds to the formula: (0.042-0.2) Na ₂ O · (0.039-0.118) Al ₂ O ₃ · (10 -11.67) SiO ₂ . The method of obtaining aluminum-modified silica sols is described in the monograph (Euler R. Silica Chemistry: Transl. From English - M .: Mir, 1982, part 2).

Japanese Patent Abstract (WO / 2008/111383 Aluminum-modified colloidal silica and method for producing the same. IPC C01B 33/148, 09/18/2008) proposes aluminum-modified colloidal silica, acid pH stable, Al ₂ molar ratio O ₃ / SiO ₂ is 0.00005-0.01, with an alkali metal concentration of not more than 0.005 wt.% (50 ppm), which corresponds to the formula: 0.0016 Na ₂ O · (0.0005-0.1) Al ₂ O ₃ · 10SiO ₂ .

The closest to the proposed invention in technical essence are amorphous aluminosilicate derivatives, which are described in the abstract of the application for the invention (RU No. 97107016, 05.20.1999, IPC СВВ 33/46, applicant Dze University of Queensland, AU), having the chemical composition of the general formula: M _p Al _g Si ₂ O _r (OH) _s · uH ₂ O, where M is an ammonium ion or an alkali metal cation; p from 0.2 to 2.0; g from 0.5 to 2.5; r from 4.0 to 12; s from 0.5 to 4.0; u from 0.0 to 6.0, which corresponds to the formula: (0.1-1.0) Na ₂ O · (0.25-1.25) Al ₂ O ₃ · 2SiO ₂ · 2SiO ₂ · (0, 5-4.0) (OH) · (0-6) H ₂ O.

These amorphous aluminosilicate derivatives are obtained by reacting a starting material containing silicon dioxide and aluminum oxide (montmorillonite, kaolin, natural zeolite, illite, palygorskite and saponite) with an alkali metal or ammonium alkali solution and using an alkali metal or ammonium halide as an additional reagent, temperature reactions of 50-200 ° C, reaction time from 1 min to 100 hours, use less than 24 hours.

The objective of the present invention is to expand the range of colloidal aluminosilicates with the aim of using them as effective reagents: an adsorbent for the purification of hydrocarbon fractions from sulfur-containing compounds, a catalyst in the conversion of hydrocarbons, a component for producing synthetic zeolites, as a binder for the manufacture of foundry molds, etc.

The technical problem is solved by a new chemical compound, which is a colloidal aluminosilicate of the formula: M ₂ O · (0.1-1.2) Al ₂ O ₃ · (4-12) SiO ₂ , where M is an alkali metal or ammonium cation; the aluminosilicate is in the form of spherical particles with a specific surface of 300-450 m ² / g, the surface of the particles of which contains aluminosilicate anionic centers in an amount of 1.2 to 2.5 aluminum ions Al ³⁺ on 10 nm ² surface. The chemical compound is characterized by intermittent contact atomic force microscopy and a diffractogram, which are presented in figures 1, 2, 3.

The present invention provides colloidal aluminosilicate, the diffraction patterns (Fig. 1) of samples of which show that it is amorphous and cannot be assigned to the class of zeolites. The data of the X-ray phase analysis were obtained using a Bruker D8 Advance diffractometer, Cu Kα radiation in the shooting mode: 40 kV, 30 mA, scan step 0.01 °, exposure 2 ° / min, slits 0.6 * 0.6.

A brief description of the drawings.

The accompanying description of the drawings shows:

Figure 1 - x-ray diffraction patterns obtained by x-ray diffraction analysis of samples 1, 2, where sample No. 1 is obtained from colloidal aluminosilicate synthesized in accordance with example 1, sample No. 2 is obtained from colloidal aluminosilicate synthesized in accordance with example 2.

Table 1 presents the analysis of the mineral composition of samples of the inventive colloidal aluminosilicate (samples No. 1, 2).

The figure 2-3 shows electron microscopic images of the amorphous aluminosilicate according to the invention (samples No. 1, 2). The images were obtained by intermittent contact atomic force microscopy using a MultiMode V scanning probe microscope. A scale is plotted on each image. The obtained colloidal aluminosilicate of the averaged formula has a particle size (agglomerates) of 60 to 610 nm, determined by electron microscopy.

Colloidal aluminosilicate is obtained from a reaction mixture prepared from sources of aluminum oxide, silicon dioxide and alkali metal or ammonium ions in aqueous media. Sources of Al ₂ O ₃ , SiO ₂ and alkali metal or ammonium ions are taken in a molar ratio corresponding to the stoichiometry of the target product.

Sources of silicon dioxide are colloidal silica and silicates of alkali metals or ammonium.

Sources of alumina are alumina hydrosols.

Sources of alkali metal or ammonium ions are hydroxides, silicate salts of the corresponding alkali metals or ammonium.

Substances used to produce amorphous aluminosilicate: sodium liquid glass in accordance with GOST 13078-81, potassium glass liquid in accordance with GOST 18958-73, Silin-30 silicon dioxide hydrosol according to TU 2145-002-13002578-94, aluminum oxide hydrosol of the brand " Silin AL-30 "according to TU 2163-010-13002578-2005, aqueous ammonia according to GOST 3760-79.

An amorphous aluminosilicate of the specified formula is obtained by introducing a silica hydrosol into a 10-20% alkali metal silicate solution, and then an aluminum oxide hydrosol at a temperature of 20-90 ° C.

The invention is illustrated by the following examples.

Example 1

Take 20 g of a solution of sodium silicate (20 wt.% SiO ₂ , 7.37 wt.% Na ₂ O) with continuous stirring, add 13.4 g of a hydrosol of silicon dioxide (16 wt.% SiO ₂ ), then 1 , 4 g of an alumina hydrosol (18 wt.% Al ₂ O ₃ ) with a dosing rate of an alumina hydrosol of 1 dm ³ / h with continuous stirring at 50 ° C and with exposure at this temperature for 0.5 hours.

The composition of the obtained product corresponds to the formula:

Na ₂ O · 0, lAl ₂ O ₃ · 4,3SiO ₂ .

Example 2

Take 30 g of a solution of sodium silicate (10 wt.% SiO ₂ , 3.7 wt.% Na ₂ O) with stirring add 12.5 g of a solution of hydrochloric acid (5 wt.% HCl) until a pH of 11.0 ÷ 11.6. Then, 2.6 g of aluminum oxide hydrosol (18 wt.% Al ₂ O ₃ ) was added to the resulting mixture with continuous stirring at 70 ° C and with exposure at this temperature for 0.25 hours. The composition of the obtained product corresponds to the formula:

Na ₂ O · 0,5Al ₂ O ₃ · 5,4SiO ₂ contains NaCl as a side component.

Example 3

Take 20 g of a solution of potassium silicate (10 wt.% SiO ₂ , 4.75 wt.% K ₂ O) with stirring, add 25.4 g of a hydrosol of silicon dioxide (16 wt.% SiO ₂ ), then 4 are added to the resulting mixture. 6 g of aluminum oxide hydrosol (18 wt.% Al ₂ O ₃ ) with a dosing rate of aluminum oxide hydrosol of 1 dm ³ / h with continuous stirring at 90 ° C and with exposure at this temperature for 0.1 hours. The composition of the obtained product corresponds to the formula:

K ₂ O · 0.8Al ₂ O ₃ · 10SiO ₂ .

Example 4

Take 20 g of a solution of sodium silicate (10 wt.% SiO ₂ , 3.7 wt.% Na ₂ O) and produce carbonization of a solution of sodium silicate by passing carbon dioxide gases 34-40 vol.% To a pH value of 11.0- 11.6, 0.54 g of a solution of ammonium hydroxide (27 wt.% NH ₄ OH) is introduced into the resulting mixture, then 1.9 g of an aluminum oxide hydrosol (18 wt.% Al ₂ O ₃ ) is introduced at a rate of 1 dm ³ / h with continuous stirring at 50 ° C and with exposure at this temperature for 0.5 hours. The composition of the obtained product corresponds to the formula: (NH ₄ ) ₂ O · 1,2Al ₂ O ₃ · 12SiO ₂ , contains Na ₂ CO ₃ as a side component.

The ratio of components, operating conditions and properties of the obtained colloidal aluminosilicates are given in table 2.

The concentration of silicon dioxide in aluminosilicate is determined by the method described in the monograph (Euler R. Chemistry of silica. M: Mir, 1982, part 1, p.265).

The elemental composition of the obtained colloidal aluminosilicates is determined using physicochemical methods of analysis:

- the mass concentration of sodium ions Na ⁺ is determined by titration of aluminosilicate solutions;

- the mass concentration of silicon dioxide SiO ₂ is determined by the gravimetric method by converting silicon oxide into volatile silicon tetrafluoride by reaction with hydrofluoric acid;

- the mass concentration of alumina Al ₂ O ₃ is determined by the complexometric method by converting alumina by interaction with a mixture of hydrofluoric and sulfuric acids into complex compounds of aluminum with a disodium salt of ethylenediaminetetraacetic acid (Analytical chemistry of aluminum. Tikhonov VN Institute of Geochemistry and Analytical Chemistry named after B I.I. Vernadsky Publishing House: Nauka, 1971, 266 pp.).

As can be seen from examples of specific performance and data on the elemental composition, colloidal aluminosilicate has the structural formula: M ₂ O · (0.1 - 1.2) Al ₂ O ₃ · (4-12) SiO ₂ ,

where M denotes a cation of an alkali metal or ammonium.

The obtained colloidal aluminosilicate retains its structure and properties in the temperature range from plus 5 ° C to plus 80 ° C.

The obtained colloidal aluminosilicate can be used as an adsorbent for the purification of hydrocarbon fractions, including associated petroleum gas, from sulfur-containing compounds.

Case Study 5.

The process is carried out using a specially designed device that performs supercritical effects and allows the process of interaction of the liquid-gas-solid system described in the application "Device for conducting heterogeneous chemical reactions". The authors based on the inventive colloidal aluminosilicate developed a technical product with the trade name "Silin-S", a method for purifying associated petroleum gas using a reagent "Silin-S", and also a device for its implementation "Groundhog". The company Silin LLC (Ulyanovsk Region) produced pilot batches of Silin-S reagent and conducted pilot tests of the Groundhog device at the Yamashneft NGDU OAO Tatneft facility. Tests were conducted on a pilot plant with a capacity of 100 m ³ / h for the purification of associated petroleum gas from sulfur-containing compounds using a 2 wt.% Solution of colloidal aluminosilicate in the field. The test results are presented in table.3.

Thus, as can be seen from the application example, the reagent for purification of associated petroleum gas using the amorphous aluminosilicate based on the inventive amorphous silicate can be used as an adsorbent for the purification of associated petroleum gas from sulfur-containing compounds, which makes it possible to reduce the content of hydrogen sulfide in APG.

Table 1 Mineral Composition Analysis Sample No. Conclusion one The X-ray amorphous substance or crystalline structure is highly disordered. Diffuse reflections have conditional maxima d = 1.5-0.40 nm and a large half-width (Fig. 1). The CSRs for diffuse reflections are 43 Å (d = 1.5 nm) and 14 Å (d = 0.4 nm). The presence of small broadened reflections d = 0.27–0.26 nm is most likely associated with the presence of a crystalline phase similar to sample No. 1, but with a lower content and more dispersed (CSR about 100 Å). 2 X-ray amorphous phase (see sample No. 2) and NaCl.
An X-ray amorphous substance is characterized by a diffuse reflex in the angular range of 15-28 ° 2Θ with a conditional maximum d = 0.40 nm and CSR = 14 Å; background rise in the small-angle region (d = 1.5 nm) is very slight (Fig. 1). For comparison, the CSR values of sodium chloride are 360-380 Å. Note: OCD (conditionally we can talk about the average size of crystallites with an ordered structure) are calculated by the Scherrer formula.

Table 3 Results of purification of associated petroleum gas from sulfur-containing compounds using colloidal aluminosilicate and installation No. Gas components Mass concentration, g / m ³ Before cleaning After cleaning one Carbon dioxide 79.79 34.81 2 Oxygen 0.93 0.59 3 Nitrogen 355.89 369.00 four Hydrogen sulfide 43.04 0.00 5 Hydrocarbons 854.76 988.62

Claims (1)

A colloidal aluminosilicate having the formula M ₂ O · (0.1-1.2) Al ₂ O ₃ · (4-12) SiO ₂ , where M - denotes an alkali metal or ammonium cation, while the aluminosilicate is in the form of spherical particles with a specific surface area of 300-450 m ² / g, the surface of the particles contains aluminosilicate anionic centers in an amount of 1.2 to 2.5 aluminum ions Al ³⁺ per 10 nm ² surface and the aluminosilicate is characterized by a diffraction pattern shown in figure 1.

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