Method of sulfur dioxide oxidation

FIELD: chemical industry; methods of production of sulfuric acid.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of oxidation of sulfur dioxide and may be used in oxidation of sulfur dioxide into trioxide in production of sulfuric acid both from elemental sulfur and sulfur-containing minerals (pyrite), and at purification of sulfur-containing industrial gases outbursts. The method of oxidation of sulfur dioxide provides for a gating through of the gaseous reaction mixture containing even sulfur dioxide and oxygen through a catalyst layer providing oxidation of sulfur dioxide into sulfur trioxide. At that use the catalyst representing a geometrically structured system made out of microfilaments of a 5-20 microns diameter and having the active centers, which are characterized in IR spectrums of adsorbed ammonia by availability of an absorption band with the wave numbers in the range of v = 1410-1440 cm-1 containing an active component and a highly siliceous fibrous carrying agent defined characterized by availability in a spectrum of nuclear magnetic resonance (NMR)29 Si lines with chemical shifts - 100±3 m.d. (line Q3) and - 110±3 m.d. (line Q4) at a ratio of the integrated intensities of the lines Q3/Q4 0.7-1.2, in the IR spectrum of an absorption band of the hydroxyl groups with a wave number ν = 3620-3650 cm-1 and a half-width of 65-75 cm-1 having a specific surface measured by method BET by a thermal desorption of an argon, SAr = 0.5-30 m2 / g, the value of the surface, measured by a method alkaline titrating SNa= l0-250 m2 / g at the ratio of SNa/SAr = 5-30. An active component of the catalyst is one of the platinum group metals, mainly platinum. The invention allows to increase a conversion in one adiabatic layer of the catalyst up to 80-85 %, to increase a maximum permissible concentration of sulfur dioxide in the initial blend. At that a mechanical stability of a catalyst layer is also ensured making it possible to create different types of catalyst layers.

EFFECT: the invention ensures a significant increase of a conversion in one adiabatic layer of the catalyst, an increase of a maximum permissible concentration of sulfur dioxide in the initial blend and creation of different types of the catalyst layers.

4 cl, 2 ex

 

The invention relates to the field of chemistry, and in particular to methods of oxidation of sulfur dioxide, and can be used for oxidation of sulfur dioxide to trioxide in sulfuric acid production, as from elemental sulfur and sulfur-containing minerals (pyrite), and for cleaning of sulfur-containing industrial gas emissions.

Well-known traditional and widely used method for the oxidation of sulfur dioxide, comprising passing a gaseous reaction mixture containing at least sulfur dioxide and oxygen through the catalyst bed to ensure the oxidation of sulfur dioxide to sulfur trioxide through adiabatic layer of granular catalyst containing vanadium oxide (Agumentin. Technology sulfuric acid. M.: Chemistry, 1983, s-186).

The disadvantage of this method is limited to the maximum conversion of sulfur dioxide (due to the force equilibrium conditions), and also limited the maximum concentration of SO2in the source gases (and, accordingly, limited to specific performance of catalytic reactors), due to the relatively narrow range of temperatures vanadium catalysts (360-380 to 620-650° (C) and their relatively low activity.

Techno-economic performance of this method can be enhanced by using a catalyst in which platinum is at stake is the amount of 0.005-0.1% of applied onto the surface of the microfiber media, containing silicon oxide and/or aluminum oxide, in particular optical fibers the size of 1-20 microns with a content of silicon oxide is not less than 55% and a specific surface area of 1-200 m2/g (RF patent №2158633, priority from 02.11.99, publ. 10.11.00, IPC B 01 J 23/58, 35/06, 01 17/78). This catalyst has a high activity, a significant increase in the maximum allowable temperatures (up to 700-750° (C), as well as high stability and resistance to deactivation.

The disadvantages of this method include the low conversion of sulphur dioxide in the region of low temperatures and relatively high value of the minimum operating temperature (~350-400° (C)that limits the maximum equilibrium conversion of sulfur dioxide. In addition, during long-term operation, this catalyst shows a significant decrease in activity.

The authors sought to develop a method of oxidation of sulfur dioxide in achieving high conversion of sulfur dioxide and recyclability of the source gases with a high content of SO2provided high stability of the catalyst and the high life.

The problem is solved in that in the method of oxidation of sulfur dioxide, comprising passing a gaseous reaction mixture containing at least sulfur dioxide and oxygen through the catalyst bed to ensure the sustained oxidation of sulfur dioxide to sulfur trioxide, using a catalyst comprising a geometrically structured system of microfibers with a diameter of 5-20 μm, having active centers, which are characterized in the IR spectra of adsorbed ammonia in the presence of absorption bands with wave numbers in the range ν=1410-1440 cm-1containing the active ingredient and vysokokremnezemnstogo fibrous media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40,7-1,2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, SAr=0.5 to 30 m2/g, the magnitude of the surface, measured by the method of alkaline titration, SNa=10-250 m2/g at a ratio of SPA/SAG=5-30. The active component of the catalyst may be at least one platinum group metals, in particular platinum. As a catalyst of microfibers use fiberglass in the form of either non-woven or extruded material such as wool or Volga or threads with a diameter of 0.5 to 5 mm, or woven from the threads of the material with the weave type of the sat is n, leaf, openwork with a cell diameter of 0.5 to 5 mm

The technical effect of the proposed method is to reduce the minimum operating temperature conducive to the growth of the equilibrium conversion of sulfur dioxide to increase the overall range of operating temperatures and increase the service life of the catalyst.

For implementing the method of the original reaction mixture, containing at least sulfur dioxide and oxygen is passed through the catalyst layer containing the active component and glass fiber media, and IR spectra of adsorbed ammonia on the specified catalyst have a characteristic absorption band with wave numbers in the range ν=1410-1440 cm-1and as the active component uses at least one of platinum group metals, in particular platinum. The presence of these bands in the IR spectra of adsorbed ammonia is clear evidence of the presence on the surface of the specific catalyst active centers, providing a high activity and selectivity of the catalyst in the oxidation of sulfur dioxide, as well as high activity at low temperatures and the stability of the catalyst. The establishment of such centres can be carried out by targeted modification of the catalyst surface in a variety of ways at the stage of its preparation./p>

For implementing the method using a catalyst formed into flexible, permeable to flow of the reaction mixture, fiberglass structures, made in the form of yarns, woven or extruded materials. Such structuring facilitates the placement and fixation of the catalyst in the catalytic reactor and prevents entrainment of the microfibers of the catalyst from the reaction stream.

The oxidation of sulfur dioxide by the described method provides a reduction in the minimum operating temperature to values of the order of 300-350°C. due to this, the maximum conversion in a single adiabatic catalyst layer can be increased (for typical mixtures of sulfuric acid production) to level 80-85% compared to 65-70% for traditional vanadium systems and 70-75% for systems using well-known platinum catalyst. In addition, the extension of the operating temperature range (up from 300 to 750° (C) will increase the maximum allowable concentration of sulfur dioxide (and proportional - performance catalytic reactor) in the initial mixture in 2-3 times in comparison with traditional methods based on vanadium catalysts and 1.2 to 1.5 in comparison with the methods known for the platinum catalyst.

The proposed method has high stability of the catalyst and high crocomire service. It also provides mechanical stability of the catalyst layer, allowing you to create different types of catalyst (axial, radial, and others) and to have a catalytic reactor in any geometric orientation (vertical, horizontal etc), which significantly increases efficiency and extends the application of the method.

Example 1

The oxidation of sulfur dioxide is carried out in a laboratory isothermal reactor, skip mixture containing 10% (vol.) SO2and 10% O2(the rest is nitrogen) through the catalyst bed. The catalyst is a geometrically structured system of microfibers with a diameter of 10 microns in the form of a woven material. Contains fiberglass media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40,7-1,2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, SAr=0.5 to 30 m2/g, the magnitude of the surface, measured by the method of alkaline titration, SPA=10-250 m2/g at a ratio of SPA/SAG=5-30, and the active component (platinum) moreover, in the preparation of the pre-catalyst is modified so that the IR spectra of adsorbed ammonia on the specified catalyst had a characteristic absorption band with wave numbers in the range ν=1410-1440 cm-1. At 300°and flow rate of the source gas mixture 4000 h-1achieved conversion of sulfur dioxide to 61-71%. In similar conditions, the method using a known platinum catalyst provides conversion of no higher than 10-15%, the method using a vanadium catalyst is less than 1-2%.

Example 2

The oxidation of sulfur dioxide is carried out in four industrial adiabatic reactors with intermediate cooling of the reaction mixture between layers, omitting the initial mixture, containing 10% (vol.) SO2and 10% O2(the rest is nitrogen) through the catalyst layers. The catalyst is a geometrically structured system of microfibers with a diameter of 10 microns in the form of a woven material. Contains fiberglass media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40,7-1,2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1the full width at half maximum 65-75 cm -1having a specific surface area measured by the BET method by thermal desorption of argon, SAr=0.5 to 30 m2/g; the amount of the surface measured by the method of alkaline titration, SPA=10-250 m2/g at a ratio of SPA/SAG=5-30 (structured in the form of a woven material). It also contains the active ingredient (platinum), and in the preparation of the pre-catalyst is modified so that the IR spectra of adsorbed ammonia on the specified catalyst had a characteristic absorption band with wave numbers in the range ν=1410-1440 cm-1. When the input temperature of the mixture to 300°With (on each layer) is a total conversion of sulfur dioxide up to 99.7 99.8 per cent. In similar conditions, the method using a known platinum catalyst provides conversion of no higher than 99,0%, the method using a vanadium catalyst is not higher than 98.5 per cent.

1. The method of oxidation of sulfur dioxide, comprising passing a gaseous reaction mixture containing at least sulfur dioxide and oxygen through the catalyst bed to ensure the oxidation of sulfur dioxide to sulfur trioxide, wherein the used catalyst comprising a geometrically structured system of microfibers with a diameter of 5-20 μm, having active centers, which are characterized in IR-Spa is fucking adsorbed ammonia by the presence of absorption bands with wave numbers in the range ν =1410-1440 cm-1containing the active ingredient and vysokoglinozemistyj fibrous media, characterized by the presence of the NMR spectrum29Si lines with chemical shifts -100±3 ppm (line Q3and -110±3 ppm (line Q4) when the ratio of the integral intensities of the lines of Q3/Q40,7-1,2, in the infrared spectrum absorption band of hydroxyl groups with wave number ν=3620-3650 cm-1and the width of 65-75 cm-1having a specific surface area measured by the BET method by thermal desorption of argon, SAr=0.5 to 30 m2/g, the magnitude of the surface, measured by the method of alkaline titration, SNa=10-250 m2/g at a ratio of SNa/SAr=5-30.

2. The method according to claim 1, characterized in that the active component of the catalyst is one of the platinum group metals.

3. The method according to claim 2, characterized in that the active component of the catalyst is platinum.

4. The method according to any one of claims 1 to 3, characterized in that the catalyst of the microfibers used fiberglass in the form of either non-woven or extruded material such as wool or felt, or threads with a diameter of 0.5 to 5 mm, or woven from the threads of the material with the weave type : sateen, canvas, Agur with a cell diameter of 0.5 to 5 mm



 

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5 cl, 1 tbl, 4 ex

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FIELD: chemical industry; methods of production of sulfuric acid.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of oxidation of sulfur dioxide and may be used in oxidation of sulfur dioxide into trioxide in production of sulfuric acid both from elemental sulfur and sulfur-containing minerals (pyrite), and at purification of sulfur-containing industrial gases outbursts. The method of oxidation of sulfur dioxide provides for a gating through of the gaseous reaction mixture containing even sulfur dioxide and oxygen through a catalyst layer providing oxidation of sulfur dioxide into sulfur trioxide. At that use the catalyst representing a geometrically structured system made out of microfilaments of a 5-20 microns diameter and having the active centers, which are characterized in IR spectrums of adsorbed ammonia by availability of an absorption band with the wave numbers in the range of v = 1410-1440 cm-1 containing an active component and a highly siliceous fibrous carrying agent defined characterized by availability in a spectrum of nuclear magnetic resonance (NMR)29 Si lines with chemical shifts - 100±3 m.d. (line Q3) and - 110±3 m.d. (line Q4) at a ratio of the integrated intensities of the lines Q3/Q4 0.7-1.2, in the IR spectrum of an absorption band of the hydroxyl groups with a wave number ν = 3620-3650 cm-1 and a half-width of 65-75 cm-1 having a specific surface measured by method BET by a thermal desorption of an argon, SAr = 0.5-30 m2 / g, the value of the surface, measured by a method alkaline titrating SNa= l0-250 m2 / g at the ratio of SNa/SAr = 5-30. An active component of the catalyst is one of the platinum group metals, mainly platinum. The invention allows to increase a conversion in one adiabatic layer of the catalyst up to 80-85 %, to increase a maximum permissible concentration of sulfur dioxide in the initial blend. At that a mechanical stability of a catalyst layer is also ensured making it possible to create different types of catalyst layers.

EFFECT: the invention ensures a significant increase of a conversion in one adiabatic layer of the catalyst, an increase of a maximum permissible concentration of sulfur dioxide in the initial blend and creation of different types of the catalyst layers.

4 cl, 2 ex

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2 cl, 10 ex

FIELD: industrial organic synthesis catalysts.

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4 tbl, 12 ex

FIELD: hydrogenation-dehydrogenation catalysts.

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10 cl, 3 tbl, 5 ex

FIELD: chemical industry; methods of manufacture of the deposited polymetallic catalytic agents.

SUBSTANCE: the invention is pertaining to the methods of manufacture of the oxidation catalytic agents based on any solid carriers by deposition on them of the metals solid solutions. The catalytic agents may be used in the various fields of the catalysis, for example, for realization of the photocatalytic, electrocatalytic, catalytic and other reactions. The invention presents the description of the method of manufacture of the deposited polymetallic catalytic agents by deposition of the metals on ceramics, plastics materials, metals, composite materials, oxides of the transition metals, the carbonic material, which includes the sequential stages of deposition of the previous layers carrying the cationic and anionic parts and for recovery. In the capacity of the previous layer carrying the cationic part use the substances of the following composition: [М(NH3)xАyz, where M - Cr, Со, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; В - OH, F, Cl, Br, I, NO2, NO3, SO4; and as the previous layer carrying the anionic part use the substance of the following composition: Еx2[M'Dy2Cz2], where М' - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg; С - ОН, Н20, F, SCN, Cl, Br, I, NO, NO2; D - ОН, Н20, F, SCN, Cl, Br, I, NO, NO2; Е - Н, Li, Na, К, Rb, Cs, NH4; or as the previous layer carrying the cationic part use the substances having the following composition: [М(NH3)xАyz and/or [М1(NH3)x1Аy1z1, where M AND M1 - Cr, Со, Ni, Cu, Zn, Ru, Ag, CD, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; В - OH, F, Cl, Br, I, NO2, NO3, SO4; and as the previous layer carrying the anionic part use the substances having the following composition: Еx2[M'Dy2Cz2] and/or Еx3[M'1Dy3Cz3], where М' and М'1 - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Ag, Cd, Hf, Ta, W, Os, Ir, Pt, Au, Hg; С - ОН, Н20, F, Cl, Br, I, NO, NO2; D - ОН, Н20, F, Cl, Br, I, NO, NO2; Е - Н, Li, Na, К, Rb, Cs, NH4; or as the previous layer carrying both the cationic part and then anionic part use the substance having the following composition: [М(NH3)xАy]x1[M'Dy1Cz1]z, where: M - Cr, Со, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Ir, Pt, Au; А - ОН, Н20, C1, Br, I, NO, NO2; М' - Ti, Cr, Со, Ni, Cu, Zn, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, 0s, Ir, Pt, Au, Hg; С - ОН, Н20, F, Cl, Br, I, NO, NO2; D - ОН, Н20, F, Cl, Br, I, NO, NO2. The technical result of the invention is the high activity of the produced catalytic agents.

EFFECT: the invention ensures the high activity of the produced catalytic agents.

14 cl, 3 tbl, 97 ex

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